Single chamber unit dose laundry detergent capsule

Abstract

A single chamber unit dose laundry detergent capsule comprising a pair of substantially rectangular water-soluble membrane sheets sealed from one another about their respective peripheries to form a chamber between them, the chamber containing 5-13 g of a liquid detergent composition, when viewed in plan view, the liquid detergent composition having a unit dose of 5-10 g. The chamber includes first and second pairs of opposing sealing edges, each edge connected to an adjacent edge at a sealing corner, the chamber including a corner protrusion directed toward each of four sealing corners.

Description

Technical Field

[0001] The present invention relates to an improved laundry detergent capsule. Background Art

[0002] US2015 / 267155 (Brooker) discloses a multi-compartment water-soluble unit dose article comprising a water-soluble film and a liquid laundry detergent composition, wherein at least one compartment of the unit dose article comprises a liquid laundry detergent composition, and wherein the unit dose has a height, a width and a length, wherein the maximum length is between about 2 and about 5 cm; the maximum width is between about 2 and about 5 cm; and the maximum height is between about 3 and about 5 cm; and wherein the volume of the liquid laundry detergent composition within the water-soluble unit dose is between about 10 and about 20 ml.

[0003] WO 2020 / 109079 (Unilever) discloses a laundry or machine dishwashing or machine dishwashing product comprising a tray containing a plurality of water-soluble capsules, each capsule comprising at least two compartments containing a substrate treatment composition and positioned side by side extending laterally across the capsule, and the tray packaging comprising a substantially horizontal base whereby the capsules are positioned side by side on the base.

[0004] Despite the prior art, there remains a need for improved liquid laundry detergent capsules which are aesthetically pleasing yet effective.

[0005] Furthermore, there remains a need for improved liquid laundry capsules which are small and easily captured by fabrics in the wash liquor prior to dissolving.

[0006] Still further, there remains a need for improved laundry detergent capsules which exhibit less sticking during storage. Summary of the invention

[0007] The present invention provides a capsule, which contains a small volume of detergent and also occupies a significant footprint, and is designed to make it difficult to fold itself during use and before being completely dissolved. In addition, the capsule needs to have sufficient size to not be discarded from the fabric folds in the drum and therefore release the contents at the drum edge (e.g., the door of the drum). When the capsule releases its contents at the door of the drum, the detergent is released into the washing liquid away from the fabric, so the effect on cleaning is small. This is especially true when the capsule contains a small amount of detergent, wherein it is very beneficial to release a small amount of detergent into the folds of the fabric as much as possible. Capsules formed with a small volume footprint are considered to be less attractive to consumers because the capsules tend to lack physical entities and are less prone to manual handling.

[0008] Furthermore, there is a need to reduce the sticking of small capsules in their packaging during storage. We have found that small capsules of such size are less likely to stick to each other because the contact points are smaller and the relative surface area to volume ratio is higher. This also solves the problem of small capsules clumping together at the bottom of the container in which they are contained, thus giving a poor appearance to the consumer, and also avoids the consumer having to reach into the container to pick one out of many tightly grouped items.

[0009] However, there is a need for single chamber capsules to be smaller and more concentrated, and thus a need for better designs of such capsules. There is also a need to improve the aroma properties of capsules stored in their containers so that consumers experience the aroma emission during use of the capsules in the container when opened.

[0010] We have also found that new designs of single chamber capsules show improved dissolution properties, with those of the invention dissolving faster than simpler single chamber capsules.

[0011] Thus, in a first aspect, there is provided a single chamber unit dose detergent capsule comprising a pair of substantially rectangular water soluble film sheets sealed to each other about their respective peripheries to form a chamber therebetween, the chamber containing 5-13 g of a liquid detergent composition, the chamber comprising first and second pairs of opposed sealed edges when viewed in plan view, each edge connected to an adjacent edge at a sealed corner, the chamber comprising corner projections directed towards each of the four sealed corners.

[0012] The protrusion refers to a portion of the chamber that extends outward toward the corner when viewed in plan view.

[0013] Preferably, at least one edge of any pair of opposing edges comprises a notch, wherein the edge extends towards the interior of the chamber at the notch.

[0014] Preferably, both edges of any pair of opposing edges include a notch, wherein the edges extend towards the interior of the chamber at the notch.

[0015] Preferably, at least one of any pair of opposing edges includes a pair of notches, wherein the edge extends towards the interior of the chamber at the notches.

[0016] Preferably, both edges within any pair of opposing edges include a pair of notches, wherein the edges extend towards the interior of the chamber at the notches.

[0017] Preferably, at least one corner protrusion comprises an apex which is 2 to 7 mm from the nearest sealing corner.

[0018] Preferably, at least one of the corner protrusions comprises an apex which is 3 to 5 mm from the nearest sealing corner.

[0019] Preferably, the stretching ratio of the water-soluble film is 1.7 to 2.1.

[0020] More preferably, the stretching ratio of the water-soluble film is 1.8 to 2.05.

[0021] The stretch ratio refers to the ratio between the areas of the film before and after thermoforming into the mold cavity.

[0022] Preferably, liquid detergent compositions comprise from 2 to 10% water by weight of the composition.

[0023] Preferably, the unit dose detergent capsule comprises a display portion on at least one water soluble sheet, said display portion comprising ink.

[0024] Preferably, the ink comprises phthalocyanine ink.

[0025] Preferably, the water soluble film comprises a bittering agent.

[0026] Preferably, the membrane comprises a maleic acid derived polymer.

[0027] Preferably, the liquid detergent composition comprises water and a non-aqueous solvent and a surfactant, and wherein the weight ratio of total surfactant to total water and non-aqueous solvent is at least 1.6.

[0028] Unit dose products containing liquid laundry detergent compositions wherein the weight ratio between surfactant level and non-aqueous solvent is above 1.6 result in a more stable product. This is particularly relevant for formulations having a total dose of less than 15 g of detergent composition.

[0029] More preferably, the weight ratio of total surfactant to total water and non-aqueous solvent is at least 2.0, most preferably at least 2.5.

[0030] Preferably, the surfactant includes linear alkylbenzene sulfonate and a nonionic surfactant.

[0031] Preferably, the product comprises a chamber containing said detergent composition.

[0032] In a second aspect, there is provided a method for preparing a single-chamber unit-dose detergent capsule according to the first aspect, the method comprising: obtaining a mold cavity comprising four corner mold protrusions, thermoforming a first film in the mold, filling the thermoformed film in the mold cavity with a detergent liquid, covering the filled thermoformed film in the mold cavity with a second film and sealing.

[0033] Because of the end shape and resulting film tensile stresses, the capsule is formed using a die having such protrusions in the corners and preferably having further outwardly curved edges between the corner die protrusions. This is superior to using a straight edge die to form the capsule, whereby the corner protrusions are an artifact of film tensile stresses rather than being created as desired.

[0034] A mold protrusion refers to a portion of the cavity mold that extends outward toward a corner when viewed in plan view.

[0035] Preferably as defined with respect to the capsule, it is also preferred that the mould comprises between the mould protrusions and at least one edge within any pair of opposing edges comprises a notch, wherein the edge extends towards the interior of the mould cavity at the notch.

[0036] Preferably, both mould edges within any pair of opposing edges include a notch, wherein the edges extend towards the interior of the mould cavity at the notch.

[0037] Preferably, at least one of the mould edges within any pair of opposing edges comprises a pair of notches, wherein the edge extends towards the interior of the mould cavity at the notches.

[0038] Preferably, both edges within any pair of opposing edges include a pair of notches, wherein the edges extend towards the interior of the mold cavity at the notches.

[0039] Preferably, at least one corner mould protrusion comprises an apex which is 1 to 8 mm from the nearest sealing corner.

[0040] Preferably, at least one of the corner mould protrusions comprises an apex which is 2 to 6 mm from the nearest sealing corner.

[0041] Water-soluble film composition

[0042] Liquid detergent compositions are contained in water-soluble capsules.

[0043] Preferably, the capsule has one to four compartments.Preferably, the capsule is a unit dose product and may be 8 to 15 g in weight to represent a unit dose.

[0044] Water-soluble film compositions, optional ingredients therefor, and methods of making them are well known in the art, whether for use in preparing relatively thin water-soluble films (eg, as encapsulation materials) or otherwise.

[0045] PVA is a synthetic resin usually prepared by alcoholysis (commonly referred to as hydrolysis or saponification) of polyvinyl acetate. Fully hydrolyzed PVA (wherein almost all acetate groups have been converted to alcohol groups) is a strongly hydrogen-bonded, highly crystalline polymer that dissolves only in hot water - greater than about 140 degrees Fahrenheit (60 degrees Celsius). If a sufficient number of acetate groups are allowed to remain after the polyvinyl acetate is hydrolyzed, the PVA polymer is referred to as partially hydrolyzed, which is more weakly hydrogen-bonded and less crystalline, and is soluble in cold water below about 10 degrees Celsius. Intermediate cold or hot water soluble films may include, for example, intermediate partially hydrolyzed PVA (e.g., a degree of hydrolysis of about 94% to about 98%), and are only readily soluble in warm water, such as rapidly dissolving at temperatures of about 40 degrees Celsius and higher. Fully and partially hydrolyzed PVA types are usually referred to as PVA homopolymers, although the partially hydrolyzed types are technically vinyl alcohol-vinyl acetate copolymers.

[0046] In addition to PVA polymers and PVA copolymers, other water-soluble polymers used in the blend may include, but are not limited to, modified polyvinyl alcohols, polyacrylates, water-soluble acrylate copolymers, polyvinyl pyrrolidone, polyethylene imine, pullulan, 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), the above copolymers and any combination of the above. Other water-soluble polymers may include polyalkylene oxides, polyacrylamides, polyacrylic acids and salts thereof, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylates and salts thereof, polyamino acids, polyamides, gelatin, methylcellulose, carboxymethylcellulose and salts thereof, dextrins, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrins and polymethacrylates. Such water-soluble polymers, whether PVOH or otherwise, are commercially available from a variety of sources.

[0047] Any of the foregoing water-soluble polymers are generally suitable for use as the film-forming polymer. Typically, the water-soluble film may include copolymers and / or blends of the foregoing resins.

[0048] The weight ratio of the amount of all water-soluble polymers to the combined amount of all plasticizers, compatibilizers, and minor additives can range, for example, from about 0.5 to about 18, from about 0.5 to about 15, from about 0.5 to about 9, from about 0.5 to about 5, from about 1 to 3, or from about 1 to 2. 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 film flexibility and impart processing benefits in view of desired mechanical film properties.

[0049] It is well known in the art that the viscosity of a water-soluble polymer (PVA or other) is related to the weight average molecular weight (W) of the polymer, and viscosity is generally used as a proxy for Mw. Thus, the weight average molecular weight of the water-soluble polymer (including the first PVA copolymer and the second PVA polymer) may be, for example, in the range of about 30,000 to about 175,000, or about 30,000 to about 100,000, or about 55,000 to about 80,000.

[0050] The water-soluble film may contain other auxiliary agents and processing agents, such as but not limited to plasticizers, plasticizer extenders, surfactants, lubricants, mold release agents, fillers, extenders, crosslinking agents, anti-caking agents, antioxidants, anti-adhesive agents, defoamers, nanoparticles such as layered silicate nanoclays (e.g., sodium montmorillonite), bleaching agents (e.g., sodium metabisulfite, sodium bisulfite or others), aversive agents such as bittering agents (e.g., denatonium salts such as denatonium benzoate, denatonium sugar and denatonium chloride; sucrose octaacetate; quinine; flavonoids such as quercetin and naringenin; and quasinoids such as quasin and strychnine) and pungent agents (e.g., capsaicin, piperine, allyl isothiocyanate and resinferatoxin), and other functional ingredients, in amounts suitable for their intended purpose. An embodiment including a plasticizer is preferred. The amount of these agents may 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%, individually or collectively.

[0051] Plasticizer can include but is not limited to glycerol, diglycerol, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol at most 400MW, neopentyl glycol, trimethylolpropane, polyether polyol, sorbitol, 2-methyl-1,3-propylene glycol, ethanolamine and its mixture.Preferred plasticizer is glycerol, sorbitol, triethylene glycol, propylene glycol, dipropylene glycol, 2-methyl-1,3-propylene glycol, trimethylolpropane or its combination.Based on total film weight, the total amount of plasticizer can be in the range of about 10 weight % to about 40 weight %, or about 15 weight % to about 35 weight %, or about 20 weight % to about 30 weight %, for example, about 25 weight %.A combination of glycerol, dipropylene glycol and sorbitol can be used.Optionally, glycerol can be used in the amount of about 5 weight % to about 30 weight %, or 5 weight % to about 20 weight %, for example, about 13 weight %.

[0052] Optionally, dipropylene glycol can be used with about 1 % by weight to about 20 % by weight, or about 3 % by weight to about 10 % by weight, for example, 6 % by weight. Optionally, sorbitol can be used with about 1 % by weight to about 20 % by weight, or about 2 % by weight to about 10 % by weight, for example, about 5 % by weight. In a particular embodiment, the specific amount of plasticizer can be selected based on the film flexibility and processability characteristics required for water-soluble film. Under low plasticizer content, film may become brittle, be difficult to process or be easy to break. Under the plasticizer level that rises, film may be too soft, weak or be difficult to process for required purposes.

[0053] In a preferred embodiment, the water soluble film comprises a taste aversive agent such as denatonium benzoate and / or a pungent agent such as capsaicin.

[0054] Maleic acid modified polyvinyl alcohols are well known in the art and are commercially available from many water soluble film manufacturers.

[0055] Preferably, the maleic acid-modified PVA accounts for 10 to 70 wt %, more preferably 30 to 60 wt % of the water-soluble film.

[0056] Preferably, the film comprises less than 10 wt% acrylic-modified PVA.

[0057] Liquid unit dose compositions are preferably laundry compositions and contain a detergent (surfactant) as well as other ingredients described below to aid cleaning performance.

[0058] Surfactants

[0059] The liquid detergents of the present invention preferably comprise 2-60 wt% total surfactants, most preferably 4-30 wt%.Anionic and nonionic surfactants are preferred.

[0060] Anionic surfactants are discussed in Anionic Surfactants: Organic Chemistry by Helmut W. Stache (Marcel Dekker 1995), CRC Press, ed. Helmut W. Stache (Marcel Dekker 1995), Surfactant Science Series. 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.

[0061] Commonly used in laundry liquid compositions are C12-C14 alkyl ether sulfates having a straight or branched chain alkyl group containing 12 to 14 carbon atoms (C12-14) and containing an average of 1 to 3 EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES) in which the predominantly C12 lauryl alkyl group is ethoxylated with an average of 3 EO units per molecule.

[0062] Anionic surfactants are preferably added to the detergent composition in the form of salts. Preferred cations are alkali metal ions, such as sodium and potassium. However, the salt form of anionic surfactants can be formed in situ by neutralizing the acid form of the surfactant with a base such as sodium hydroxide or an amine such as monoethanolamine, diethanolamine or triethanolamine. The weight ratio is calculated with the protonated form of the surfactant.

[0063] Preferably, the composition comprises an alkyl ether sulfate as the monoisopropanolamine (MIPA) AES, more preferably a MIPA LES.

[0064] Preferably, the alkyl ether sulfate, more preferably MIPA AES, is present in 1-10 wt. % of the detergent composition.

[0065] Further examples of suitable anionic surfactants are rhamnolipids, α-olefinsulfonates, olefinsulfonates, alkenesulfonates, alkane-2,3-diylbis(sulfates), hydroxyalkanesulfonates and disulfonates, fatty alcohol sulfates (FAS), alkanesulfonates, ester sulfonates, sulfonated fatty acid glycerides, methyl ester sulfonates alkyl or alkenylsuccinic acid, dodecenyl / tetradecenylsuccinic acid (DTSA), fatty acid derivatives of amino acids, DATEM, CITREM and diesters and monoesters of sulfosuccinic acid.

[0066] Nonionic surfactants are discussed in Non-ionic Surfactants: Organic Chemistry, Nico M. van Os, ed. (Marcel Dekker 1998), Surfactant Science Series, published by CRC Press. Preferred nonionic surfactants are alkoxylated, preferably ethoxylated, preferred nonionic surfactants are alcohol ethoxylates and methyl ester ethoxylates, having C10-C18 alkyl chains. Commonly used in laundry liquid compositions are C12-C15 alcohol ethoxylates having a straight or branched chain alkyl group containing 12 to 15 carbon atoms and containing 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 the anionic and nonionic surfactants, the ethoxy units may be partially replaced by propoxy units.

[0068] The nonionic surfactant fraction is preferably greater than 50% by weight, more preferably greater than 80% by weight, most preferably greater than 95% by weight of alcohol ethoxylate.

[0069] Other examples of suitable nonionic surfactants include alkoxylated fatty acid alkyl esters, alkyl polyglycosides, alkoxylated amines, ethoxylated glycerides, fatty acid monoethanolamides, fatty acid diethanolamides, ethoxylated fatty acid monoethanolamides, propoxylated fatty acid monoethanolamides, polyhydroxyalkyl fatty acid amides or N-acyl N-alkyl derivatives of glucosamine, polysorbates (TWEENS).

[0070] The formulations may contain soaps and zwitterionic or cationic surfactants as minor components, preferably in an amount of 0.1-3% by weight. Betaines such as CAPB are preferred zwitterionic surfactants.

[0071] Preferred nonionic surfactants include narrow range ethoxylates. Preferably, the detergent composition comprises an alcohol ethoxylate of the formula RO-(CH2CH2O)qH, wherein q is the molar average degree of ethoxylation, the alcohol ethoxylate comprising greater than 70 wt.% RO-(CH2CH2O) X -H to RO-(CH2CH2O) y -H range, and x and y are absolute numbers, wherein x=qq / 2 and y=q+q / 2, and R is a C12-15 alkyl group.

[0072] Preferably, R is a linear or branched alkyl group and preferably has 12 to 14 carbon atoms. In the most preferred embodiment, R is C12 and / or C14. Most preferably, greater than 50% of the total alcohol ethoxylates are C12 or C14.

[0073] 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, most preferably 9 and 10.

[0074] Alcohol ethoxylate nonionic surfactants are discussed in Non-ionic Surfactants: Organic Chemistry, Nico M. van Os, ed. (Marcel Dekker 1998), Surfactant Science Series, published by CRC Press. Commonly used in laundry liquid compositions are C12-C15 alcohol ethoxylates having a straight or branched chain alkyl group containing from 12 to 15 carbon atoms and containing an average of 5 to 12 EO units per molecule.

[0075] Preferably the alcohol ethoxylate is present in 1 to 35 wt %, preferably 5 to 25 wt % of the composition.

[0076] Typically, the ethoxylation reaction to form alcohol ethoxylates is base catalyzed using NaOH, KOH or NaOCH3. 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 NaOCH3. Preferably, the narrow ethoxy distribution has greater than 70 wt%, more preferably greater than 80 wt%, of the ethoxy chain lengths in RO-(CH2CH2O). X Alcohol ethoxylates ranging from -H to RO-(CH2CH2O)yH RO-(CH2CH2O) q -H, wherein q is the molar average degree of ethoxylation, x and y are absolute numbers, wherein x=qq / 2 and y=q+q / 2. For example, when q=10, then more than 70% by weight of the alcohol ethoxylate should consist of ethoxylates having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15 ethoxylate groups.

[0077] Narrow range ethoxylation catalysts are described in EP 3289790 (Procter & Gamble), EP 1747183 (Hacros); Santacesatia et al. Ind. Eng. Chem. Res. 1992, 31, 2419-2421; US ​​4239917 (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 WO 2022 / 129374 (Unilever). Catalysts based on Ca or Ba are preferred, most preferably in combination with sulfuric acid.

[0078] Preferably, the nonionic surfactant is present in the liquid detergent in an amount of from 1 to 22% by weight of the composition, more preferably from 2 to 12% by weight of the composition.

[0079] C16 and / or C18 alcohol ether sulfates

[0080] Preferably, the composition comprises C16 and C18 ether sulfates of the formula:

[0081] R2-O-(CH2CH2O) p SO3H

[0082] Wherein R2 is selected from saturated, monounsaturated, polyunsaturated, linear C16 and C18 alkyl chains, and wherein p is 3 to 20, preferably 4 to 12, more preferably 5 to 10. The monounsaturation is preferably at position 9 of the chain, with the carbons counted from the end of the chain to which the ethoxylate is attached. The double bond may be in cis or trans configuration (oleyl or anti-oleyl), but is preferably cis. Cis or trans ether sulfate CH3(CH2)7-CH=CH-(CH2)8O-(OCH2CH2) n SO3H is described as C18:1 (Δ9) ether sulfate. This follows the nomenclature CX:Y (ΔZ), where X is the number of carbons in the chain, Y is the number of double bonds, and ΔZ is the position of the double bond on the chain, with the carbons counted from the end of the chain to which the OH is attached.

[0083] Preferably, R2 is selected from saturated C16, saturated C18 and monounsaturated C18. More preferably, saturated C16 is a linear alkyl group of at least 90 wt% of the C16 content. Regarding the C18 content, it is preferred that the main C18 part is C18:1, more preferably C18:1 (Δ9). Preferably, the proportion of monounsaturated C18 accounts for at least 50 wt% of the total C16 and C18 alkyl ether sulfate surfactants.

[0084] More preferably, the proportion of monounsaturated C18 is at least 60% by weight, most preferably at least 75% by weight of the total C16 and C18 alkyl ether sulfate surfactants.

[0085] Preferably, the C16 alcohol ethoxylate surfactant comprises at least 2 wt % of the total C16 and C18 alkyl ether sulfate surfactants, and more preferably 4 wt %.

[0086] Preferably, the saturated C18 alkyl ether sulfate surfactants comprise at most 20 wt %, more preferably at most 11 wt % of the total C16 and C18 alkyl ether sulfate surfactants. Preferably, the saturated C18 content is at least 2 wt % of the total C16 and C18 alkyl ether sulfate content.

[0087] Where the composition comprises a mixture of C16 / 18 source materials for the alkyl ether sulphate as well as the more traditional C12 alkyl chain length materials, it is preferred that the total C16 / 18 alkyl ether sulphate content should account for at least 10 wt % of the total alkyl ether sulphate in the composition, more preferably at least 50 wt %, even more preferably at least 70 wt %, particularly preferably at least 90 wt %, most preferably at least 95 wt % of the alkyl ether sulphate.

[0088] Ether sulfates are discussed in Anionic Surfactants: Organic Chemistry, edited by Helmut W. Stache, Surfactant Science Series, CRC Press (Marcel Dekker 1995).

[0089] Linear saturated or monounsaturated C20 and C22 ether sulfates may also be present. Preferably, the weight fraction of the sum of "C18 ether sulfates" / "C20 and C22 ether sulfates" is greater than 10.

[0090] Preferably, the C16 and C18 ether sulfates contain less than 15 wt %, more preferably less than 8 wt %, most preferably less than 4 wt % and most preferably less than 2 wt % polyunsaturated ether sulfates of ether sulfate. Polyunsaturated ether sulfates contain hydrocarbon chains with two or more double bonds.

[0091] Ether sulfates can be synthesized by sulfonation of the corresponding alcohol ethoxylates. Alcohol ethoxylates can be prepared by ethoxylation of alkyl alcohols. The alkyl alcohols used to produce alcohol ethoxylates can be produced by transesterification of triglycerides into methyl esters and then by distillation and hydrogenation into alcohols. Kreutzer, UR's Journal of American Oil Chemists' Society. 61 (2): 343-348 discusses this process. The preferred alkyl alcohol for the reaction is oleyl alcohol having an iodine value of 60 to 80, preferably 70 to 75, which can be obtained from BASF, Cognis, Ecogreen.

[0092] The polyunsaturation in the surfactant can be controlled by hydrogenation of triglycerides as described in A Practical Guide to Vegetable Oil Processing (Gupta MKAcademic Press 2017). Distillation and other purification techniques can be used. Ethoxylation is described in Non-Ionic Surfactant Organic Chemistry (NM van Os ed.), Surfactant Science Series Volume 72, CRC Press.

[0093] Preferably, the ethoxylation reaction is catalyzed using NaOH, KOH or NaOCH3 bases. More preferred are catalysts that provide a narrower ethoxyl distribution than NaOH, KOH or NaOCH3. Preferably, these narrower distribution catalysts involve Group II bases such as barium dodecanoate; Group II metal alkoxides; Group II hydrotalcites as described in WO2007 / 147866. Lanthanides may also be used. Such narrower distribution alcohol ethoxylates are available from Azo Nobel and Sasol.

[0094] Preferably, the narrow ethoxyl distribution has more than 70 wt. %, more preferably more than 80 wt. % in R2-O-(CH2CH2O) z SO3H to R2-O-(CH2CH2O) w Ether sulfates in the range of SO3H R2-O-(CH2CH2O) q SO3H, wherein q is the molar average degree of ethoxylation, and x and y are absolute numbers, wherein z=pp / 2, and w=p+p / 2. For example, when p=6, more than 70% by weight of the ether sulfates should consist of ether sulfates having 3, 4, 5, 6, 7, 8, 9 ethoxylate groups.

[0095] Ether sulfate weight is calculated based on the protonated form: R2-O-(CH2CH2O) p SO3H. In the formulation, it exists in the ionic form R2-O-(CH2CH2O)pSO3- with the corresponding counter ions, preferably the counter ions are Group I and II metals, amines, and most preferably sodium.

[0096] Preferred anionic surfactants are further described below.

[0097] C16 / C18 Alcohol Ethoxylate

[0098] Preferred alcohol ethoxylates have the formula:

[0099] R1-O-(CH2CH2O) q -H

[0100] Wherein R1 is selected from saturated, monounsaturated, polyunsaturated, linear C16 and C18 alkyl chains, and wherein q is 4 to 20, preferably 5 to 14, more preferably 8 to 12. The monounsaturation is preferably at position 9 of the chain, with the carbons counted from the end of the chain to which the ethoxylate is attached. The double bond may be in cis or trans configuration (oleyl or anti-oleyl), preferably cis. Cis or trans alcohol ethoxylates CH3(CH2)7-CH=CH-(CH2)8O-(OCH2CH2) nOH is described as C18:1 (Δ9) alcohol ethoxylate. This follows the nomenclature CX:Y (ΔZ), where X is the number of carbons in the chain, Y is the number of double bonds, and ΔZ is the position of the double bond on the chain, with the carbons counted from the end of the chain to which the OH is attached.

[0101] Preferably, R1 is selected from saturated C16, saturated C18 and monounsaturated C18. More preferably, saturated C16 alcohol ethoxylate is at least 90% by weight of C16 linear alcohol ethoxylate. Regarding the C18 alcohol ethoxylate content, it is preferred that the main C18 part is C18:1, more preferably C18:1 (Δ9). The proportion of monounsaturated C18 alcohol ethoxylate accounts for at least 50% by weight of the total C16 and C18 alcohol ethoxylate surfactants. Preferably, the proportion of monounsaturated C18 accounts for at least 60% by weight of the total C16 and C18 alcohol ethoxylate surfactants, most preferably at least 75% by weight.

[0102] Preferably, the C16 alcohol ethoxylate surfactant comprises at least 2 wt % of the total C16 and C18 alcohol ethoxylate surfactants, and more preferably 4 wt %.

[0103] Preferably, the saturated C18 alcohol ethoxylate surfactant comprises at most 20 wt%, more preferably at most 11 wt% of the total C16 and C18 alcohol ethoxylate surfactants.

[0104] Preferably, the saturated C18 content is at least 2 wt% of the total C16 and C18 alcohol ethoxylate content.

[0105] Alcohol ethoxylates are discussed in Non-ionic Surfactants: Organic Chemistry, edited by Nico M. van Os, Surfactant Science Series, CRC Press (Marcel Dekker 1998). Alcohol ethoxylates are often referred to as alkyl ethoxylates.

[0106] Preferably, the weight fraction of C18 alcohol ethoxylate / C16 alcohol ethoxylate is greater than 1, more preferably from 2 to 100, most preferably from 3 to 30. "C18 alcohol ethoxylate" is the sum of all C18 fractions in alcohol ethoxylate, and "C16 alcohol ethoxylate" is the sum of all C16 fractions in alcohol ethoxylate.

[0107] Linear saturated or monounsaturated C20 and C22 alcohol ethoxylates may also be present. Preferably, the weight fraction of the sum of "C18 alcohol ethoxylates" / "C20 and C22 alcohol ethoxylates" is greater than 10.

[0108] Preferably, the C16 / 18 alcohol ethoxylate contains less than 15 wt %, more preferably less than 8 wt %, most preferably less than 5 wt % of polyunsaturated alcohol ethoxylate of the alcohol ethoxylate. Polyunsaturated alcohol ethoxylates contain hydrocarbon chains with two or more double bonds.

[0109] C16 / 18 alcohol ethoxylates can be synthesized by ethoxylation of alkyl alcohols via the following reaction:

[0110] R1-OH+qethylene oxide→R1-O-(CH2CH2O) q -H

[0111] Alkyl alcohols can be prepared by transesterifying triglycerides into methyl esters, followed by distillation and hydrogenation to the alcohols. This process is discussed in Kreutzer, UR, Journal of the American Oil Chemists' Society 61(2): 343-348. The preferred alkyl alcohol for the reaction is oleyl alcohol having an iodine value of 60-80, preferably 70-75, which is available from BASF, Cognis, Ecogreen.

[0112] The production of fatty alcohols is further discussed in Sanchez MA et al. J. Chem. Technol. Biotechnol 2017; 92: 27-92 and Ullmann's Enzyclopaedie der technischen Chemie, Verlag Chemie, Weinheim, 4th edition, volume 11, page 436, etc.

[0113] Preferably, the ethoxylation reaction is base catalyzed using NaOH, KOH or NaOCH3. Even more preferred are catalysts that provide a narrower ethoxyl distribution than NaOH, KOH or NaOCH3. Preferably, these narrower distribution catalysts involve Group II bases such as barium dodecanoate; Group II metal alkoxides; Group II hydrotalcites as described in WO2007 / 147866. Lanthanides may also be used. Such narrower distribution alcohol ethoxylates are available from Azo Nobel and Sasol.

[0114] Preferably, the narrow ethoxyl distribution has greater than 70 wt%, more preferably greater than 80 wt% in RO-(CH2CH2O) x -H to RO-(CH2CH2O) y -H range alcohol ethoxylates RO-(CH2CH2O) q-H, where q is the molar average degree of ethoxylation, x and y are absolute numbers, where x = qq / 2 and y = q+q / 2. For example, when q = 10, then more than 70% by weight of the alcohol ethoxylate should be composed of ethoxylates having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15 ethoxylate groups.

[0115] Methyl Ester Ethoxylate (MEE)

[0116] Preferred methyl ester ethoxylate surfactants have the following form:

[0117] R3(-C=O)-O-(CH2CH2-O) n -CH3

[0118] Where R3COO is the fatty acid moiety, such as oleic acid, stearic acid, palmitic acid. Fatty acid nomenclature describes the fatty acid by using two numbers, A:B, where A is the number of carbons in the fatty acid and B is the number of double bonds it contains. For example, oleic acid is 18:1, stearic acid is 18:0, and palmitic acid is 16:0. The position of the double bond on the chain can be given in parentheses, oleic acid is 18:1 (9), linoleic acid is 18:2 (9, 12), where 9 is the carbon number from the COOH end.

[0119] The integer n is the molar average number of ethoxylates.

[0120] Methyl ester ethoxylate (MEE) is described in Chapter 8 of Biobased Surfactants (Second Edition) Synthesis, Properties, and Applications by G.A. Smith, pages 287-301 (AOCS Press 2019); J.Am.Oil.Chem.Soc.vol 74 (1997) by Cox M.E. and Weerasooriva U, pages 847-859; Tenside Surf.Det. Vol. 28 (2001) by Hreczuch et al., pages 72-80; C.Kolano.Household and Personal Care Today (2012), pages 52-55; J.Am.Oil.Chem.Soc. Vol. 72 (1995) by A.Hama et al., pages 781-784. MEE can be prepared by the reaction of methyl esters with ethylene oxide using calcium or magnesium-based catalysts. The catalyst may be removed or left in the MEE.

[0121] Alternative preparation routes are the transesterification of methyl esters or the esterification of carboxylic acids with polyethylene glycols terminated at one end of the chain with a methyl group.

[0122] Methyl esters can be prepared by the transesterification of methanol with triglycerides or the esterification of methanol with fatty acids. The transesterification of triglycerides to fatty acid methyl esters and glycerol is discussed in Fattah et al. (Front. Energy Res., June 2020, Vol. 8, Chapter 101) and references therein. Common catalysts for these reactions include sodium hydroxide, potassium hydroxide and sodium methoxide. Esterases and lipases can also be used. Triglycerides are naturally present in vegetable fats or oils, and preferred sources are rapeseed oil, castor oil, corn oil, cottonseed oil, olive oil, palm oil, safflower oil, sesame oil, soybean oil, high stearic acid / high oleic acid sunflower oil, high oleic acid sunflower oil, inedible vegetable oils, tall oil and any mixture thereof and any derivative thereof. Oil from trees is called tall oil. Used food cooking oil can be used. Triglycerides can also be obtained from algae, fungi, yeast or bacteria. Plant sources are preferred.

[0123] Distillation and fractionation processes can be used to produce the methyl esters or carboxylic acids to produce the desired carbon chain distribution.Preferred sources of triglycerides are those containing less than 35 weight percent polyunsaturated fatty acids in the oil prior to distillation, fractionation or hydrogenation.

[0124] Fatty acids and methyl esters can be obtained from oleochemical suppliers such as Wilmar, KLK Oleo, Unileveroleochemical Indonesia. Biodiesel is a methyl ester and these sources can be used.

[0125] When the ESB is MEE, it preferably has a molar average of 8 to 30, more preferably 10 to 20 ethoxylate groups (EO). The most preferred ethoxylates contain 12 to 18 EO. Preferably, at least 10 wt%, more preferably at least 30 wt% of the total C18: 1 MEE in the composition has 9 to 11 EO, and even more preferably at least 10 wt% has exactly 10 EO. For example, when the MEE has a molar average of 10 EO, then at least 10 wt% of the MEE should be composed of ethoxylates with 9, 10 and 11 ethoxylate groups.

[0126] The methyl ester ethoxylate preferably has a molar average of 8 to 13 ethoxylate groups (EO). The most preferred ethoxylates have a molar average of 9 to 11 EO, even more preferably 10 EO. When the MEE has a molar average of 10 EO, then at least 10 wt. % of the MEE should consist of ethoxylates having 9, 10 and 11 ethoxylate groups.

[0127] In the case of a broader MEE contribution, it is preferred that at least 40 wt% of the total MEE in the composition is C18:1.

[0128] Furthermore, it is preferred that the MEE component also comprises some C16 MEE.

[0129] Therefore, it is preferred that the total MEE component comprises 5-50 wt% C16 MEE of the total MEE.Preferably, the C16 MEE is greater than 90 wt%, more preferably greater than 95 wt% C16:0.

[0130] In addition, it is preferred that the total MEE component contains less than 15 wt %, more preferably less than 10 wt %, most preferably less than 5 wt % of polyunsaturated C18, i.e. C18:2 and C18:3, of the total MEE. Preferably, C18:3 is present at less than 1 wt %, more preferably less than 0.5 wt %, and most preferably substantially absent. The degree of polyunsaturation can be controlled by distillation, fractionation or partial hydrogenation of the feedstock (triglycerides or methyl esters) or MEE.

[0131] Furthermore, it is preferred that the C18:0 component is less than 10 wt % of the total MEE present.

[0132] Furthermore, it is preferred that components having carbon chains of 15 or less comprise less than 4 wt % of the total MEE present.

[0133] Particularly preferred MEEs have 2 to 26 wt. % MEE 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.

[0134] Preferred sources of the alkyl group for MEE include methyl esters derived from distilled palm oil and distilled high oleic methyl esters derived from palm kernel oil, partially hydrogenated methyl esters of canola oil, methyl esters of high oleic sunflower oil, methyl esters of high oleic safflower oil, and methyl esters of high oleic soybean oil.

[0135] 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.

[0136] Preferably, more than 80% by weight of the double bonds in MEE are in cis configuration. Preferably, the 18:1 component is oleic acid. Preferably, the 18:2 component is linoleic acid.

[0137] The methyl group of the methyl ester may be replaced by an ethyl group or a propyl group. The methyl group is most preferred.

[0138] Preferably, the pH of the composition is from 5 to 10, more preferably from 6 to 8, most preferably from 6.1 to 7.0.

[0139] Preferably the methyl ester ethoxylate comprises from 0.1 to 95 wt% of the composition. More preferably the composition comprises from 2 to 40 wt% MEE, most preferably from 4 to 30 wt% MEE.

[0140] Preferably, the methyl ester ethoxylate surfactant is used in combination with an anionic surfactant. Preferably, the weight fraction of methyl ester ethoxylate surfactant / total anionic surfactant is 0.1 to 9, more preferably 0.15 to 2, most preferably 0.2 to 1. Total anionic surfactant refers to the total content of any type of anionic surfactant, preferably ether sulfate, linear alkylbenzene sulfonate, alkyl ether carboxylate, alkyl sulfate, rhamnolipid and mixtures thereof.

[0141] Source of alkyl chains

[0142] The alkyl chains of the C16 / 18 surfactant are preferably obtained from renewable sources, preferably from triglycerides. A renewable source is one in which 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.

[0143] Preferred plant sources of oil are rapeseed, sunflower, corn, soybean, cottonseed, olive oil and trees. The oil from trees is known as tall oil. Most preferably palm oil and rapeseed oil are sources.

[0144] Saad MG et al., Energies 2019, 12, 1920Algal Biofuels: Current Status and Key Challenges discuss algal oil. Masri MA et al., Energy Environ. Sci., 2019, 12, 2717Austainable, high-performance process for the economic production of waste-free microbial oils that can replace plant-based equivalents, describes a method for producing triglycerides from biomass using yeast.

[0145] Inedible vegetable oils may be used and are preferably selected from the fruits and seeds of Jatropha curcas, Calophylluminophyllum, Sterculia feotida, Madhuca indica (mahua), Pongamia glabra (koroch seed), linseed, Pongamia pinnata (karanja), Hevea brasiliensis (rubber seed), Azadirachta indica (neem), Camelina sativa, Lesquerella fendleri, Nicotiana tabacum (tobacco), Deccan hemp, Ricinus communis L. (castor), Simmondsia chinensis (Jojoba), Eruca sativa.L.), Cerbera odollam (Sea mango), Coriandrum sativum L., Croton megalocarpus, Pilu, Crambe, Syringa, Scheleichera triguga (kusum), Stillingia, Shorearobusta (Sal), Terminalia belerica roxb, Cuphea, Camellia, Champaca, Simarouba glauca, Garcinia indica, Rice bran, Hingan (balanites), Desert date, Cardoon, Asclepias syriaca (Milkweed), Guizotia abyssinica), Radish Ethiopian mustard, Syagrus, Tung, Idesia polycarpa var. vestita, algae, Argemone mexicana L.)(Mexican prickly poppy), Putranjiva roxburghii(Lucky bean tree), Sapindus mukorossi(Soapnut), M.azedarach(syringe), Thevettiaperuviana(yellow oleander), Copaiba, Milk bush, Laurel, Cumaru, Andiroba, Piqui, B.napus, Zanthoxylumbungeanum. .

[0146] SLES and PAS

[0147] SLES and other such alkali metal alkyl ether sulfate anionic surfactants are generally obtainable by sulfating alcohol ethoxylates. These alcohol ethoxylates are generally obtainable by ethoxylating linear alcohols. Similarly, primary alkyl sulfate surfactants (PAS) can be obtained directly from linear alcohols by sulfating linear alcohols. Thus, the formation of linear alcohols is a central step in obtaining PAS and alkali metal alkyl ether sulfate surfactants.

[0148] Linear alcohols suitable as an intermediate step in the manufacture of alcohol ethoxylates and hence anionic surfactants such as sodium lauryl ether sulfate can be obtained from a number of different sustainable sources. These include:

[0149] Primary sugar

[0150] Primary sugars are extracted from sucrose or sugar beets, etc., and can be fermented to form bioethanol. The bioethanol is then dehydrated to form bioethylene, which then undergoes olefin metathesis to form alkenes. These alkenes are then processed into linear alcohols by hydroformylation or oxidation.

[0151] An alternative method can be used that also utilizes primary sugars to form linear alcohols, and in which the primary sugars are microbially converted by algae to form triglycerides. These triglycerides are subsequently hydrolyzed to linear fatty acids, which are then reduced to form linear alcohols.

[0152] Biomass

[0153] Biomass, such as forest products, rice husks and straw, can be processed into synthesis gas by gasification. Through the FischerTropsch reaction, these materials are processed into alkanes, which are then dehydrogenated to form alkenes. These alkenes can be treated in the same manner as the alkenes described above [primary sugars].

[0154] An alternative process converts the same biomass into polysaccharides by steam explosion, which can be enzymatically degraded into secondary sugars. These secondary sugars are then fermented to form bioethanol, which is subsequently dehydrated to form bioethylene. This bioethylene is then processed into linear alcohols as described above [primary sugars].

[0155] Waste plastics

[0156] Waste plastics are pyrolyzed to form pyrolysis oil. This is then fractionated to form linear alkanes, which are subsequently dehydrogenated to form alkenes. These alkenes are processed as described above [primary sugars].

[0157] Alternatively, the pyrolysis oil is cracked to form ethylene which is subsequently processed by olefin metathesis to form the desired alkenes. These are then processed as described above [primary sugars] to linear alcohols.

[0158] Municipal solid waste

[0159] MSW is converted to syngas by gasification. From the syngas, it can be processed as described above [primary sugars] or converted to ethanol by an enzymatic process before dehydrogenation to ethylene. The ethylene can then be converted to linear alcohols by the Ziegler process.

[0160] MSW can also be converted to pyrolysis oil by gasification, which is subsequently fractionated to form alkanes. These alkanes are then dehydrogenated to form olefins and then linear alcohols.

[0161] Ocean Carbon

[0162] There are various carbon sources from marine communities, such as seaweed and kelp. From these marine communities, triglycerides can be isolated from the source and subsequently hydrolyzed to form fatty acids, which are reduced to straight chain alcohols in the usual manner.

[0163] Alternatively, the feedstock can be separated into polysaccharides which are enzymatically degraded to form secondary sugars. These can be fermented to form bioethanol and then processed as described above [primary sugars].

[0164] Waste oil

[0165] Waste oils, such as used cooking oils, can be physically separated into triglycerides, which are broken down to form straight chain fatty acids and then straight chain alcohols as described above.

[0166] Alternatively, used cooking oil can be subjected to the Neste process, whereby the oil is catalytically cracked to form bio-ethylene. This is then processed as described above.

[0167] Methane capture

[0168] Methane capture processes capture methane from landfills or fossil fuel production. Methane can be gasified to form syngas. Syngas can be processed as described above, where the syngas is first converted to methanol (Fischer Tropsch reaction), then to olefins, and then to linear alcohols by hydroformylation oxidation.

[0169] Alternatively, the synthesis gas can be converted to alkanes and then to olefins via Fischer Tropsch and subsequent dehydrogenation.

[0170] Carbon capture

[0171] Carbon dioxide can be captured by any of a variety of well-known methods. Carbon dioxide can be converted to carbon monoxide by the reverse water-gas shift reaction, which is then converted to synthesis gas using hydrogen in an electrolysis reaction. The synthesis gas is then processed as described above and converted to methanol and / or alkanes before reacting to produce olefins.

[0172] Alternatively, the captured carbon dioxide is mixed with hydrogen before being enzymatically processed to form ethanol. This is the process developed by Lanzatech. Hereby, ethanol is converted to ethylene, then processed to olefins, and then to linear alcohols as described above.

[0173] The above process can also be used to obtain C16 / 18 chains of C16 / 18 alcohol ethoxylates and / or C16 / 18 ether sulfates.

[0174] Linear alkylbenzene sulfonate

[0175] LAS (linear alkylbenzene sulfonate) is the preferred anionic surfactant.

[0176] The key intermediate compounds in LAS production are the related alkenes. These alkenes (olefins) can be produced by any of the above methods and can be formed from primary sugars, biomass, waste plastics, MSW, carbon capture, methane capture, ocean carbon, etc.

[0177] While in the above process, the substituted olefin is processed by hydroformylation and oxidation to form a linear alcohol, the olefin is reacted with benzene and then with a sulfonate to form LAS.

[0178] Alkyl chain length is the linear alkylbenzene sulfonate of 10-18 carbon atoms. Commercially available LAS is a mixture of closely related isomers and homologous alkyl chain homologues, each containing an aromatic ring that is sulfonated in the "para-position" and is connected to the linear alkyl chain at any position except the terminal carbon. The linear alkyl chain preferably has a chain length of 11-15 carbon atoms, and the main material has a chain length of about C12. Each alkyl chain homologue is composed of a mixture of all possible sulfophenyl isomers except the 1-phenyl isomer. LAS is usually formulated in the composition in the form of acid (i.e. HLAS), then at least partially in situ neutralized.

[0179] Preferably the linear alkylbenzene sulphonate surfactant is present at 10-30% by weight, more preferably 15-25% by weight, most preferably 18-23% by weight of the detergent composition.

[0180] Surfactant ratio

[0181] Preferably, the weight ratio of total nonionic surfactant to total anionic surfactant (weight of nonionic surfactant / weight of anionic surfactant) is from 0 to 2, preferably from 0.2 to 1.5, most preferably from 0.3 to 1.

[0182] Preferably, the weight ratio of total nonionic surfactant to total alkyl ether sulfate surfactant (weight of nonionic surfactant / weight of alkyl ether sulfate surfactant) is from 0.5 to 2, preferably from 0.7 to 1.5, most preferably from 0.9 to 1.1.

[0183] Preferably the composition comprises less than 12 wt% water, but this will depend on the level of total surfactant and will be adjusted accordingly. More preferably the composition comprises less than 10 wt% water.

[0184] Preferably, the composition is visually clear.

[0185] Aminocarboxylates

[0186] Preferably the composition comprises an aminocarboxylate chelating agent.Preferably the aminocarboxylate chelating agent is selected from GLDA and MGDA.

[0187] Preferably, the aminocarboxylate is present in the composition at 0.1 to 15 wt %, more preferably 0.1 to 10 wt %, even more preferably 0.3 to 5 wt %, still more preferably 0.8 to 3 wt %, and most preferably 1 to 2.5 wt % (by weight of the composition).

[0188] Glutamic acid diacetic acid (GLDA)

[0189] GLDA can be present as a salt of GDLA or a mixture of GDLA and a GDLA salt. Preferred salt forms include mono-, di-, tri- or tetra-alkali metal and mono-, di-, tri- or tetra-ammonium salts of GLDA. The alkali metal salt of glutamic acid diacetic acid GDLA is preferably selected from the lithium salt, potassium salt, and more preferably the sodium salt of GLDA.

[0190] Glutamic acid diacetic acid can be partially or preferably completely neutralized with the corresponding base. Preferably, an average of 3.5 to 4 COOH groups of GLDA are neutralized with an alkali metal, preferably with sodium. Most preferably, the composition comprises the tetrasodium salt of GLDA.

[0191] GLDA is at least partially neutralized with an alkali metal, more preferably sodium or potassium, most preferably sodium.

[0192] The GLDA salt may be an alkali metal salt of L-GLDA, an alkali metal salt of D-GLDA, or an enantiomerically enriched mixture of isomers.

[0193] Preferably, the composition comprises a mixture of L- and D-enantiomers of glutamic acid diacetic acid (GLDA) or its corresponding mono-, di-, tri- or tetra-alkali metal salt or mono-, di-, tri- or tetra-ammonium salt or a mixture thereof, said mixture containing predominantly the corresponding L-isomer in an enantiomeric excess (ee) in the range of 10-95%.

[0194] Preferably the GLDA salt is essentially L-glutamic acid diacetic acid which is at least partially neutralized with an alkali metal.

[0195] The sodium salt of GLDA is preferred.

[0196] A suitable commercial source of GLDA in the tetrasodium salt form is available from Nouryon GL.

[0197] Preferably, GLDA is present in the composition at 0.1 to 15 wt%, more preferably 0.1 to 10 wt%, even more preferably 0.3 to 5 wt%, still more preferably 0.8 to 3 wt%, and most preferably 1 to 2.5 wt% (by weight of the composition).

[0198] Methylglycine diacetic acid (MGDA)

[0199] Preferred salt forms include mono-, di-, tri- or tetra-alkali metal and mono-, di-, tri- or tetra-ammonium salts of MGDA. The alkali metal salt is preferably selected from the lithium salt, potassium salt, and more preferably the sodium salt of MGDA.

[0200] The sodium salt of methylglycine diacetic acid is preferred. Especially preferred is the trisodium salt of MGDA.

[0201] MGDA can be partially or preferably completely neutralized with the corresponding alkali metals. Preferably, an average of 2.7 to 3 COOH groups per molecule of MGDA are neutralized with alkali metals, preferably with sodium.

[0202] MGDA may be selected from alkali metal salts of MGDA and racemic mixtures of pure enantiomers, such as alkali metal salts of L-MGDA, alkali metal salts of D-MGDA and mixtures of enantiomerically enriched isomers.

[0203] A suitable commercial source of MGDA in the trisodium form is available from BASF as M and purchased from Nouryon M-40.

[0204] Preferably, MGDA is present in the composition at 0.1 to 15 wt %, more preferably 0.1 to 10 wt %, even more preferably 0.3 to 5 wt %, still more preferably 0.8 to 3 wt %, and most preferably 1 to 2.5 wt % (based on the weight of the composition).

[0205] Small amounts of aminocarboxylates may carry cations other than alkali metals. It is thus possible that small amounts, such as 0.01 to 5 mol %, carry alkaline earth metal cations such as Mg2+ or Ca2+, or Fe(II) or Fe(III) cations. GLDA may contain small amounts of impurities originating from its synthesis, such as lactic acid, alanine, propionic acid, etc. In this case, "small amounts" means a total of 0.1 to 1 wt % of the chelating agent aminocarboxylates.

[0206] Organic Acid

[0207] The composition preferably comprises an organic acid. Preferably, the organic acid has the general structure R-CH(OH)-COOH, wherein R is a linear C1-C5, more preferably C2-C4, most preferably C4 alkyl.

[0208] Preferably at least two, more preferably all, carbon atoms in the linear C1-4 are substituted by OH groups. Preferably R comprises a terminal COOH group.

[0209] Preferred examples are lactic acid, tartaric acid, gluconic acid, mucic acid, glucoheptonic acid. Most preferably the organic acid is gluconic acid.

[0210] The organic acid may be in its D or L form.

[0211] Gluconic acid may 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 alkali metal salts of enantiomerically enriched isomeric mixtures. Preferred is the D-isomer form.

[0212] Preferably, the organic acid is present in the range of 0.1 to 15 wt%, more preferably 0.1 to 10 wt%, even more preferably 0.2 to 4 wt%, still more preferably 0.5 to 3 wt%, and most preferably 0.8 to 2 wt% (by weight of the composition), measured in its protonated form.

[0213] In a most preferred embodiment, the composition comprises GLDA and / or MGDA and gluconic acid, more preferably GLDA and gluconic acid.

[0214] Crystallizable glycerides

[0215] The composition preferably comprises a crystallizable glyceride.

[0216] Crystallizable glycerides can be used to form an external structuring system as described in WO2011 / 031940, the contents of which (particularly with respect to the manufacture of ESS) are incorporated by reference. When ESS is present, it is preferred that the ESS of the present invention preferably comprises: (a) crystallizable glyceride; (b) alkanolamine; (c) anionic surfactant; (d) additional components; and (e) optional components. Each of these components is discussed in detail below.

[0217] Crystallizable glycerides used herein include "hydrogenated castor oil" or "HCO". The HCO used herein can most generally be any hydrogenated castor oil, as long as it can be crystallized in the ESS premix. Castor oil can include glycerides, especially triglycerides, which contain C10 to C22 alkyl or alkenyl moieties, which contain hydroxyl groups. The hydrogenation of castor oil to prepare HCO converts the double bonds present in the raw oil as the ricinol acyl moiety into saturated hydroxyalkyl moieties, for example, 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 solid, molten state and mixtures thereof. The amount of HCO present in the ESS of the present invention is generally from about 2% to about 10%, from about 3% to about 8%, or from about 4% to about 6% by weight of the structured system. In some embodiments, the corresponding percentage of hydrogenated castor oil delivered to the final laundry detergent product is less than about 1.0%, typically from 0.1% to 0.8%.

[0218] Useful HCO may have the following properties: a melting point of about 40 degrees Celsius to about 100 degrees Celsius, or about 65 degrees Celsius to about 95 degrees Celsius; and / or an iodine value ranging from 0 to about 5, 0 to about 4, or 0 to about 2.6. The melting point of HCO can be measured using ASTM D3418 or ISO 11357; both tests utilize DSC: differential scanning calorimetry. HCO used in the present invention includes those that are commercially available. Non-limiting examples of commercially available HCO used in the present invention include: THIXCIN (R) from Rheox, Inc. Other examples of useful HCO can be found in U.S. Patent No. 5,340,390. The castor oil source used for hydrogenation to form HCO can have any suitable origin, such as from Brazil or India. In a suitable embodiment, castor oil is hydrogenated using a noble metal (e.g., a palladium catalyst), and the hydrogenation temperature and pressure are controlled to optimize the hydrogenation of the double bonds of natural castor oil while avoiding unacceptable levels of dehydroxylation.

[0219] The present invention is not intended to be limited to the use of hydrogenated castor oil. Any other suitable crystallizable glycerides may be used. In one embodiment, the structuring agent is a substantially pure triglyceride of 12-hydroxystearic acid. This molecule represents a pure form of a fully hydrogenated triglyceride of 12-hydroxy-9-cis-octadecenoic acid. In nature, the composition of castor oil is fairly constant, but may vary slightly. Likewise, the hydrogenation process may vary. Any other suitable equivalent material may be used, such as a mixture of triglycerides, at least 80% by weight of which is derived from castor oil. Exemplary equivalent materials mainly contain or consist essentially of triglycerides; or mainly contain or consist essentially of a mixture of diglycerides and triglycerides; or mainly contain or consist essentially of a mixture of triglycerides with diglycerides and a limited amount (e.g., less than about 20% by weight of the glyceride mixture) of monoglycerides; or mainly contain or consist essentially of a mixture of triglycerides with diglycerides and a limited amount (e.g., less than about 20% by weight of the glyceride mixture) of monoglycerides; or mainly contain or consist essentially of any of the foregoing glycerides with a limited amount (e.g., less than about 20% by weight) of the corresponding acid hydrolyzate of any of the foregoing glycerides. The above premise is that the major portion (usually at least 80% by weight) of any of the glycerides is chemically identical to the glyceride of fully hydrogenated ricinoleic acid, i.e., the glyceride of 12-hydroxystearic acid. For example, it is known in the art to modify hydrogenated castor oil so that in a given triglyceride, there are two 12-hydroxystearic acid moieties and one stearic acid moiety. Likewise, it is contemplated that hydrogenated castor oil may not be fully hydrogenated. Conversely, the present invention does not include poly(alkoxylated) castor oil when it does not meet the melting criteria.

[0220] The crystallizable glycerides used in the present invention may have a melting point of about 40 degrees Celsius to about 100 degrees Celsius.

[0221] fatty acid

[0222] Preferably the fatty acid is present in 1-6% by weight of the composition (measured relative to the acid added to the composition), more preferably 2-5% by weight.

[0223] In the context of the present invention, suitable fatty acids include aliphatic carboxylic acids of the formula RCOOH, wherein R is a straight or branched alkyl or alkenyl chain containing 6 to 24, more preferably 10 to 22, most preferably 12 to 18 carbon atoms and 0 or 1 double bonds. Preferred examples of such materials include saturated C12-18 fatty acids, such as lauric acid, myristic acid, palmitic acid or stearic acid; and fatty acid mixtures, wherein 50-100% by weight (based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures can typically be derived from natural fats and / or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow).

[0224] The fatty acids may be present in the form of their sodium, potassium or ammonium salts and / or in the form of soluble salts with organic bases such as mono-, di- or triethanolamine.

[0225] Mixtures of any of the above materials may also be used.

[0226] For formulation purposes, fatty acids and / or their salts (as defined above) are not included in the level of surfactant or in the level of builder in the formulation.

[0227] Chelating agents

[0228] Preferably, the detergent composition may also contain a chelating agent material. Examples include alkali metal citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid and citric acid. Other examples are DEQUEST TM , chelating agents of the organic phosphonate type sold by Monsanto, and alkane hydroxyphosphonates.

[0229] A preferred chelating agent is Dequest(R) 2066 (diethylenetriamine penta(methylenephosphonic acid) or heptasodium DTPMP). Preferably, HEDP (1-hydroxyethylidene-1,1-diphosphonic acid) is not present.

[0230] In a preferred embodiment, the composition comprises a fatty acid and a chelating agent.

[0231] The composition according to the invention is a low water composition. Preferably, the composition comprises less than 15% by weight of water, more preferably less than 10% by weight of water.

[0232] Alkoxylated cationic or zwitterionic polyamine polymers

[0233] Preferably, the composition comprises an alkoxylated cationic or zwitterionic di- or polyamine polymer in which the positive charge is provided by quaternization of the nitrogen atom of the amine and the anionic groups, if present, are provided by sulfation or sulfonation of the alkoxylated groups.

[0234] Preferably, the alkoxylate is selected from propoxy and ethoxy, most preferably ethoxy.

[0235] Preferably, greater than or equal to 50 mol % of the amine nitrogen is quaternized, preferably with methyl groups. Preferably, the polymer contains 3 to 10, more preferably 3 to 6, most preferably 3 to 5 quaternized amine nitrogen groups. Preferably, the alkoxylate group is selected from ethoxy and propoxy, most preferably ethoxy.

[0236] Preferably, the polymer contains ester (COO) or acid amide (CONH) groups in the structure, preferably these groups are arranged so that when all ester or acid amide groups are hydrolyzed, at least one, preferably all of the hydrolyzed fragments have a molecular weight of less than 4000, preferably less than 2000, most preferably less than 1000.

[0237] Preferably, the polymer has the following form:

[0238]

[0239] Where R1 is C3 to C8 alkyl, X is (C2H4O) n Y group, wherein n is 15 to 30, wherein m is 2 to 10, preferably 2, 3, 4 or 5, and wherein Y is selected from OH and SO3 - , and preferably SO3 - The number of groups is greater than the number of OH groups. Preferably, there are 0, 1 or 2 OH groups. X and R1 may contain ester groups therein. X may contain a carbonyl group, preferably an ester group. Preferably, there is 1 C2H4O unit separating the ester group from N, so that the structural unit N-C2H4O-ester-(C2H4O) n-1 Y is preferred.

[0240] Such polymers are described in WO 2021239547 (Unilever). Example polymers are sulfated ethoxylated hexamethylenediamine and Examples P1, P2, P3, P4, P5 and P6 of WO 2021239547. Ester groups can be included using lactones or sodium chloroacetate (modified Williamson synthesis), added to the OH or NH groups, followed by subsequent ethoxylation.

[0241] An exemplary reaction scheme involving an ester group is

[0242]

[0243] The addition of lactones is discussed in WO2021 / 165468.

[0244] Soil Release Polymers

[0245] Soil release polymers help improve the separation of soil from fabrics by modifying the fabric surface during the washing process. The adsorption of SRPs on the fabric surface is promoted by the affinity between the chemical structure of the SRP and the target fibers.

[0246] The SRP used in the present invention may include a variety of charged (e.g., anionic) and uncharged monomer units, and the structure may be linear, branched, or star-shaped. The SRP structure may also include end-capping groups for controlling molecular weight or changing polymer properties (e.g., surface activity). The weight average molecular weight (M) of the SRP w ) may suitably be in the range of about 1000 to about 20,000, and preferably in the range of about 1500 to about 10,000.

[0247] The SRP used in the present invention can be suitably selected from copolyesters of dicarboxylic acids (e.g. adipic acid, phthalic acid or terephthalic acid), diols (e.g. ethylene glycol or propylene glycol) and polyglycols (e.g. polyethylene glycol or polypropylene glycol). The copolyesters can also include monomer units substituted with anionic groups, such as, for example, sulfonated isophthaloyl units. Examples of such materials include oligomeric esters resulting from the transesterification / oligomerization of poly(ethylene glycol) methyl ether, dimethyl terephthalate ("DMT"), propylene glycol ("PG"), and polyethylene glycol ("PEG"); partially and fully anionically terminated oligomeric esters, such as oligomers of ethylene glycol ("EG"), PG, DMT, and Na-3,6-dioxa-8-hydroxyoctane sulfonic acid; nonionic terminated block polyester oligomers, such as those produced from DMT, Me terminated PEG, and EG and / or PG, or a combination of DMT, EG and / or PG, Me terminated PEG, and sodium 5-dimethylsulfonate, and copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.

[0248] Other types of SRPs useful in the present invention include cellulose derivatives such as hydroxyether cellulose polymers, C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses; polymers having poly(vinyl ester) hydrophobic segments, such as graft copolymers of poly(vinyl esters), for example, C1-C6 vinyl esters (e.g., poly(vinyl acetate)) grafted onto a polyethylene oxide backbone; poly(vinyl caprolactam) and related copolymers with monomers such as vinyl pyrrolidone and / or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam and polyethylene glycol.

[0249] Preferred SRPs for use in the present invention include copolyesters formed by the condensation of terephthalate and a diol, preferably 1,2-propylene glycol, and also include endcaps formed by repeating units of alkyl-terminated alkylene oxides. Examples of such materials have structures corresponding to general formula (I):

[0250]

[0251] Where R 1 and R 2 Independently of each other are X-(OC2H4) n -(OC3H6) m ;

[0252] Where X is C 1-4 Alkyl and preferably methyl;

[0253] n is a number from 12 to 120, preferably from 40 to 50;

[0254] m is a number from 1 to 10, preferably from 1 to 7; and

[0255] a is a number from 4 to 9.

[0256] Because they are average values, m, n and a are not necessarily integers for the polymer as a whole.

[0257] Mixtures of any of the above materials may also be used.

[0258] The overall level of SRP (when included) can range from 0.1 to 10%, depending on the polymer level intended for use in the final let-down composition, and is ideally 0.3 to 7%, more preferably 0.5 to 5% (by weight based on the total weight of the let-down composition).

[0259] Suitable soil release polymers are described in more detail in U.S. Patent Nos. 5,574,179; 4,956,447; 4,861,512; 4,702,857; WO 2007 / 079850 and WO 2016 / 005271. If used, soil release polymers will typically be incorporated into the liquid laundry detergent compositions herein at a concentration of from 0.01% to 10%, more preferably from 0.1% to 5%, by weight of the composition.

[0260] Hydrotrope

[0261] The compositions of the present invention may include non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids such as C1 to C5 monohydric alcohols (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); weight average molecular weight (M w ) ranges from about 200 to 600; C1 to C3 alkanolamines, such as monoethanolamine, diethanolamine, and triethanolamine; and alkylaryl sulfonates having up to 3 carbon atoms in the lower alkyl group (such as sodium and potassium xylene, toluene, ethylbenzene, and cumene (cumene) sulfonates).

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

[0263] The non-aqueous carrier (preferably included) may be present in an amount ranging from 1 to 50%, preferably 10 to 30%, 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 content to control the viscosity of such compositions. Preferred hydrotropes are monopropylene glycol and glycerol.

[0264] Co-surfactant

[0265] 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 (eg amphoteric (zwitterionic) and / or cationic surfactants).

[0266] Specific cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and derivatives thereof, wherein one or two hydroxyethyl groups replace one or two methyl groups, and mixtures thereof. Cationic surfactants (when included) may be present in an amount ranging from 0.1% to 5% (by weight based on the total weight of the composition).

[0267] Specific amphoteric (zwitterionic) surfactants include alkylamine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sultaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkyl amphoglycolates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, having an alkyl group containing from about 8 to about 22 carbon atoms, preferably selected from C12, C14, C16, C18 and C18:1, the term "alkyl" being used to include the alkyl portion of higher acyl groups. Amphoteric (zwitterionic) surfactants (when included) may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

[0268] Mixtures of any of the above materials may also be used.

[0269] Fluorescent agent

[0270] It may be advantageous to include a fluorescent agent in the composition. Typically, these fluorescent agents are provided and used in the form of their alkali metal salts (e.g., sodium salts). The total amount of one or more fluorescent agents used in the composition is typically 0.005 to 2% by weight, more preferably 0.01 to 0.5% by weight of the composition.

[0271] Preferred fluorescent agents are: distyryl biphenyl compounds, such as CBS-X, diaminobenzene disulfonic acid compounds, such as Tinopal DMS pure Xtra, Tinopal5BMGX and HRH, and pyrazoline compounds such as Blankophor SN.

[0272] Preferred fluorescent agents are: sodium 2-(4-phenylvinyl-3-sulfophenyl)-2H-naphthol[1,2-d]triazole, disodium 4,4'-bis{[(4-anilino-6-(N-methyl-N-2-hydroxyethyl)amino-1,3,5-triazine-2-yl)]amino}stilbene-2-2'-disulfonate, disodium 4,4'-bis{[(4-phenylvinyl-6-morpholino-1,3,5-triazine-2-yl)]amino}stilbene-2-2'-disulfonate and disodium 4,4'-bis(2-sulfonylstyryl)biphenyl.

[0273] Most preferably, the fluorescent agent is a distyrylbiphenyl compound, preferably sodium 2,2′-([1,1′-biphenyl]-4,4′-diylbis(ethylene-2,1-diyl))dibenzenesulfonate (CAS No 27344-41-8).

[0274] Color dye

[0275] Shading dyes can be used to improve the performance of the composition. Preferred dyes are violet or blue. It is believed that low levels of dyes of these shades deposited on fabrics mask the yellowing of the fabric. Another advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself.

[0276] Hueing dyes are well known in the art of laundry liquid formulations.

[0277] Suitable and preferred dye types 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 bonded to ethoxylated or propoxylated polyethylene imine as described in WO2011 / 047987 and WO2012 / 119859, alkoxylated monoazothiophenes, dyes of CAS-No72749-80-5, acid blue 59 and phenazine dyes selected from the group consisting of:

[0278]

[0279] in:

[0280] X3 is selected from: -H, -F, -CH3, -C2H5, -OCH3 and -OC2H5;

[0281] X4 is selected from: -H, -CH3, -C2H5, -OCH3 and -OC2H5;

[0282] Y2 is selected from: -OH, -OCH2CH2OH, -CH(OH)CH2OH, -OC(O)CH3 and C(O)OCH3.

[0283] Alkoxylated thiophene dyes are discussed in WO 2013 / 142495 and WO 2008 / 087497.

[0284] The hueing dye is preferably present in the composition in the range of 0.0001 to 0.1 wt%.Depending on the nature of the hueing dye there is a preferred range depending on the potency of the hueing dye, which depends on the species and the specific potency within any particular species.

[0285] External structurants

[0286] The compositions of the present invention can further modify their rheology by using one or more external structurants that form a structural network within the composition. Examples of such materials include hydrogenated castor oil, microfiber cellulose, and citrus pulp fibers. The presence of an external structurant can provide shear-thinning rheology and can also allow materials such as encapsulates and visual cues to be stably suspended in the liquid.

[0287] The composition preferably comprises a crystallizable glyceride.

[0288] Crystallizable glycerides can be used to form an external structuring system as described in WO2011 / 031940, the contents of which (particularly with respect to the manufacture of ESS) are incorporated by reference. When ESS is present, it is preferred that the ESS of the present invention preferably comprises: (a) crystallizable glyceride; (b) alkanolamine; (c) anionic surfactant; (d) additional components; and (e) optional components. Each of these components is discussed in detail below.

[0289] Crystallizable glycerides used herein include "hydrogenated castor oil" or "HCO". The HCO used herein can most generally be any hydrogenated castor oil, as long as it can be crystallized in the ESS premix. Castor oil can include glycerides, especially triglycerides, which contain C10 to C22 alkyl or alkenyl moieties, which contain hydroxyl groups. The hydrogenation of castor oil to prepare HCO converts the double bonds present in the raw oil as the ricinol acyl moiety into saturated hydroxyalkyl moieties, for example, 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 solid, molten state and mixtures thereof. The amount of HCO present in the ESS of the present invention is generally from about 2% to about 10%, from about 3% to about 8%, or from about 4% to about 6% by weight of the structured system. In some embodiments, the corresponding percentage of hydrogenated castor oil delivered to the final laundry detergent product is less than about 1.0%, typically 0.1% to 0.8%.

[0290] Useful HCO may have the following properties: a melting point of about 40 degrees Celsius to about 100 degrees Celsius, or about 65 degrees Celsius to about 95 degrees Celsius; and / or an iodine value ranging from 0 to about 5, 0 to about 4, or 0 to about 2.6. The melting point of HCO can be measured using ASTM D3418 or ISO 11357; both tests utilize DSC: differential scanning calorimetry. HCO used in the present invention includes those that are commercially available. Non-limiting examples of commercially available HCO used in the present invention include: THIXCIN (R) from Rheox, Inc. Other examples of useful HCO can be found in U.S. Patent No. 5,340,390. The castor oil source used for hydrogenation to form HCO can have any suitable origin, such as from Brazil or India. In a suitable embodiment, castor oil is hydrogenated using a noble metal (e.g., a palladium catalyst), and the hydrogenation temperature and pressure are controlled to optimize the hydrogenation of the double bonds of natural castor oil while avoiding unacceptable levels of dehydroxylation.

[0291] The present invention is not intended to be limited to the use of hydrogenated castor oil. Any other suitable crystallizable glycerides may be used. In one embodiment, the structuring agent is a substantially pure triglyceride of 12-hydroxystearic acid. This molecule represents a pure form of a fully hydrogenated triglyceride of 12-hydroxy-9-cis-octadecenoic acid. In nature, the composition of castor oil is fairly constant, but may vary slightly. Likewise, the hydrogenation process may vary. Any other suitable equivalent material may be used, such as a mixture of triglycerides, at least 80% by weight of which is derived from castor oil. Exemplary equivalent materials mainly contain or consist essentially of triglycerides; or mainly contain or consist essentially of a mixture of diglycerides and triglycerides; or mainly contain or consist essentially of a mixture of triglycerides with diglycerides and a limited amount (e.g., less than about 20% by weight of the glyceride mixture) of monoglycerides; or mainly contain or consist essentially of a mixture of triglycerides with diglycerides and a limited amount (e.g., less than about 20% by weight of the glyceride mixture) of monoglycerides; or mainly contain or consist essentially of any of the foregoing glycerides with a limited amount (e.g., less than about 20% by weight) of the corresponding acid hydrolyzate of any of the foregoing glycerides. The above premise is that the major portion (usually at least 80% by weight) of any of the glycerides is chemically identical to the glyceride of fully hydrogenated ricinoleic acid, i.e., the glyceride of 12-hydroxystearic acid. For example, it is known in the art to modify hydrogenated castor oil so that in a given triglyceride, there are two 12-hydroxystearic acid moieties and one stearic acid moiety. Likewise, it is contemplated that hydrogenated castor oil may not be fully hydrogenated. Conversely, the present invention does not include poly(alkoxylated) castor oil when it does not meet the melting criteria.

[0292] The crystallizable glycerides used in the present invention may have a melting point of about 40 degrees Celsius to about 100 degrees Celsius.

[0293] Enzymes

[0294] The composition preferably comprises an enzyme selected from the group consisting of cellulases, proteases and amylase / mannanase mixtures.

[0295] In addition, further enzymes may be present, such as those described below.

[0296] Preferably, the composition of the present invention may comprise an effective amount of one or more enzymes, preferably selected from lipase, hemicellulase, peroxidase, hemicellulase, xylanase, xantanase, lipase, phospholipase, esterase, cutinase, pectinase, carrageenase, pectate lyase, keratinase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanases, malic enzyme, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, tannase, nuclease (such as deoxyribonuclease and / or ribonuclease), phosphodiesterase or mixtures thereof.

[0297] Preferably, the enzyme is present in an amount of from 0.1 to 100, more preferably from 0.5 to 50, most preferably from 1 to 30 mg active enzyme protein per 100 g of finished laundry liquid composition.

[0298] Examples of preferred enzymes are sold under the following trade names: Purafect (DuPont), Stainzyme (Novozymes), Biotouch (ABEnzymes), (BASF).

[0299] Detergent enzymes are discussed in WO2020 / 186028 (Procter and Gamble), WO2020 / 200600 (Henkel), WO2020 / 070249 (Novozymes), WO2021 / 001244 (BASF) and WO2020 / 259949 (Unilever).

[0300] Nucleases are enzymes capable of cleaving phosphodiester bonds between nucleotide subunits of nucleic acids, and are preferably deoxyribonucleases or ribonucleases. Preferably, the nuclease is a deoxyribonuclease, preferably selected from the class EC3.1.21.x, wherein x=1, 2, 3, 4, 5, 6, 7, 8 or 9, EC3.1.22.y, wherein y=1, 2, 4 or 5, EC3.1.30.Z, wherein z=1 or 2, EC3.1.31.1 and any one of mixtures thereof.

[0301] Proteases hydrolyze bonds within peptides and proteins, which in the case of laundry results in enhanced removal of stains containing proteins or peptides. Examples of suitable protease families include aspartic proteases; cysteine ​​proteases; glutamic proteases; asparagine peptide lysing enzymes; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http: / / merops.sanger.ac.uk / ). Serine proteases are preferred. Subtilase-type serine proteases are more preferred. The term "subtilase" refers to a subgroup of serine proteases according to Siezen et al., Protein Engng.4 (1991) 719-737 and Siezen et al., Protein Science 6 (1997) 501-523. Serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate. Subtilases can be divided into six subclassifications, namely the subtilisin family, the thermophilic protease (Thermitase) family, the proteinase K family, the lanthionine bacteria (Lantibiotic) peptidase family, the Kexin family and the pyrolysin family.

[0302] Examples of subtilases are those derived from Bacillus, such as Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in US 7262042 and WO 09 / 021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO 89 / 06279, and protease PD138 described in WO 93 / 18140. Other useful proteases may be those described in WO 92 / 175177, WO 01 / 016285, WO 02 / 026024 and WO02 / 016547. Examples of trypsin-like proteases are trypsin (eg of porcine or bovine origin) and the Fusarium proteases described in WO 89 / 06270, WO 94 / 25583 and WO 05 / 040372, and the chymotrypsin derived from Cellumonas described in WO 05 / 052161 and WO 05 / 052146.

[0303] Most preferably, the protease is subtilisin (EC 3.4.21.62).

[0304] Examples of subtilases are those derived from Bacillus, such as Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in US 7262042 and WO 09 / 021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO 89 / 06279, and protease PD138 described in WO 93 / 18140. Preferably, the subtilisin is derived from Bacillus, preferably Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii, as described in US 6,312,936B1, US 5,679,630, US 4,760,025, US 7,262,042 and WO 09 / 021867. Most preferably, the subtilisin is derived from Bacillus gibsonii or Bacillus lentus.

[0305] Suitable commercially available proteases include those sold under the trade name DuralaseTm, DurazymTm, Ultra, Ultra, Ultra, Ultra, and Those sold, all available as or (Novozymes A / S) sales.

[0306] Suitable amylases (alpha and / or beta) include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, such as a special strain of Bacillus licheniformis described in more detail in GB 1,296,839, or Bacillus strains disclosed in WO95 / 026397 or WO 00 / 060060. Commercially available amylases are Duramyl TM Termamyl TM ,Termamyl Ultra TM 、Natalase TM 、Stainzyme TM 、Fungamyl TM and BAN TM (Novozymes A / S), Rapidase TM and PurastarTM (From Genencor International Inc.).

[0307] Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the following genera: Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, such as the fungal cellulases produced by Humicola insolens, Thielavia terrestris, Myceliophthora thermophila and Fusarium oxysporum disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, WO 89 / 09259, 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.

[0308] Lipase

[0309] Lipase is a lipid esterase, and the terms lipid esterase and lipase are used synonymously herein.

[0310] The composition preferably comprises 0.0005-0.5 wt%, preferably 0.005-0.2 wt% lipase.

[0311] Detergent lipid esterases are discussed in Enzymes in Detergency edited by Jan H. Van Ee, Onno Misset and Erik J. Baas (1997 Marcel Dekker, New York).

[0312] The lipid esterase may be selected from lipases of EC class 3.1 or 3.2 or a combination thereof.

[0313] Preferably, the cleaning lipid esterase is selected from:

[0314] (1) Triacylglycerol lipase (EC3.1.1.3)

[0315] (2) Carboxyl ester hydrolase (EC3.1.1.1)

[0316] (3) Cutinase (EC 3.1.1.74)

[0317] (4) Sterol esterase (EC3.1.1.13)

[0318] (5) Wax-ester hydrolase (EC 3.1.1.50)

[0319] Triacylglycerol lipase (EC 3.1.1.3) is most preferred.

[0320] Suitable triacylglycerol lipases may be selected from variants of Humicola lanuginosa (Thermomyces lanuginosa) lipase. Other suitable triacylglycerol lipases can be selected from variants of Pseudomonas lipases, for example from Pseudomonas alcaligenes or Pseudomonas pseudoalcaligenes (EP 218272), Pseudomonas cepacia (EP 331376), Pseudomonas stutzeri (GB 1,372,034), Pseudomonas fluorescens, Pseudomonas sp. strain SD705 (WO 95 / 06720 and WO 96 / 27002), P. wisconsinensis (WO 96 / 12012); Bacillus lipases, for example from Bacillus subtilis (B. subtilis) (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), Bacillus stearothermophilus (B. stearothermophilus) (JP 64 / 744992) or Bacillus pumilus (B. pumilus) (WO91 / 16422).

[0321] Suitable carboxyl ester hydrolases may be selected from wild-type or variant carboxyl ester hydrolases endogenous to Burkholderia gladioli, Pseudomonas fluorescens, Pseudomonas putida, B. acidocaldarius, Bacillus subtilis, Bacillus stearothermophilus, Streptomyces aurorassis, S. diastatochromogenes, and Saccharomyces cerevisiae.

[0322] Suitable Cutinases may be selected from the wild type or variants of a Cutinase endogenous to a strain of Aspergillus (particularly Aspergillus oryzae), a strain of Alternaria (particularly Alternaria brassicae), a strain of Fusarium (particularly Fusarium solani pisi, Fusarium oxysporum, Fusarium cepa, Fusarium rubrum or Fusarium roseum sambucium), a strain of Humicola (particularly Humicola insolens), a strain of Pseudomonas (particularly Pseudomonas mendocina or Pseudomonas putida), a strain of Rhizoctonia (particularly Rhizoctonia solani), a strain of Streptomyces (particularly Streptomyces scabies), a strain of Coprinus (particularly Coprinus cinerea), a strain of Thermospora (particularly Schistosporium thermophilum), a strain of Magnaporthe oryzae (particularly Magnaporthe oryzae) or a strain of Ulocladium consortiale.

[0323] In a preferred embodiment the Cutinase is selected from variants of the Pseudomonas mendocina Cutinase described in WO2003 / 076580 (Genencor), such as a variant having three substitutions at I178M, F180V and S205G.

[0324] In another preferred embodiment, the cutinase is the wild type or variant of the six cutinases endogenous to Coprinus cinereus described in H. Kontkanen et al. App. Environ. Microbiology, 2009, p2148-2157.

[0325] In another preferred embodiment, the Cutinase is a wild type or variant of the two Cutinases endogenous to Trichoderma reesei described in WO 2009007510 (VTT).

[0326] In a most preferred embodiment, the Cutinase is derived from a strain of Humicola insolens, in particular the strain DSM 1800 of Humicola insolens. Humicola insolens Cutinase is described in WO 96 / 13580, which is incorporated herein by reference. The Cutinase may be a variant, such as one of the variants disclosed in WO 00 / 34450 and WO 01 / 92502. Preferred Cutinase variants include the variants listed in Example 2 of WO 01 / 92502. Preferred commercial Cutinase includes Novozym 51032 (available from Novozymes, Bagsvaerd, Denmark).

[0327] Suitable sterol esterases may be derived from a strain of Ophiostoma (eg, Ophiostoma piceae), a strain of Pseudomonas (eg, Pseudomonas aeruginosa), or a strain of Melanocarpus (eg, Melanocarpus albomyces).

[0328] 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.

[0329] Suitable wax-ester hydrolases may be derived from Simmondsia chinensis.

[0330] The lipid esterase is preferably selected from the lipases of EC class 3.1.1.1 or 3.1.1.3 or a combination thereof, most preferably EC 3.1.1.3.

[0331] Examples of EC 3.1.1.3 lipases include those described in WIPO Publications WO 00 / 60063, WO 99 / 42566, WO 02 / 062973, WO 97 / 04078, WO 97 / 04079 and US 5,869,438. Preferred lipases are produced by Absidia reflexa, Absidia corymbefera, rhizmucormiehei, Rhizopus deleman, Aspergillus niger, Aspergillus tubigensis, Fusarium oxysporum, Fusarium heterosporum, Aspergillus oryzea, Penicilium camembertii, Aspergillus foetidus, Aspergillus niger, Thermomyces lanoginosus (synonym: Humicola lanuginosa) and Landerina penisapora, in particular Thermomyces lanoginosus. Certain preferred lipases are produced by Novozymes under the trade name Lipolase and (registered trade name of Novozymes) and LIPASE P Purchased from Areaio Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Available from Toyo Jozo Co., Tagata, Japan; and other Chromobacter viscosum lipases from Amersham Pharmacia Biotech., Piscataway, New Jersey, USA and Diosynth Co., Netherlands, and other lipases, such as Pseudomonas gladioli. Other useful lipases are described in WIPO Publications WO02062973, WO2004 / 101759, WO2004 / 101760 and WO2004 / 101763. In one embodiment, suitable lipases include "first cycle lipases" described in WO00 / 60063 and U.S. Pat. No. 6,939,702B1, preferably variants of SEQ ID No. 2, more preferably variants of SEQ ID No. 2 having at least 90% homology to SEQ ID No. 2 comprising substitutions of neutral or negatively charged amino acids with R or K at any of positions 3, 224, 229, 231 and 233, most preferably variants comprising T231R and N233R mutations, such most preferred variants being sold under the trade name (Novozymes) sales.

[0332] The above lipases can be used in combination (any lipase mixture can be used). Suitable lipases can be purchased from Novozymes, Bagsvaerd, Denmark; Areario Pharmaceutical Co. Ltd., Nagoya, Japan; Toyo Jozo Co., Tagata, Japan; Amersham Pharmacia Biotech., Piscataway, New Jersey, USA; Diosynth Co., Oss, Netherlands and / or prepared according to the examples contained herein.

[0333] Particularly preferred are lipases with reduced odor potential and good relative performance, as described in WO 2007 / 087243. These include (Novozyme).

[0334] Preferred commercially available lipases include Lipolase TM and Lipolase Ultra TM 、Lipex TM and Lipoclean TM (Novozymes A / S).

[0335] Fragrance

[0336] The composition comprises a fragrance and preferably the fragrance is present at from 0.01 wt % to 5 wt %, more preferably from 0.1 wt % to 1 wt % of the composition.

[0337] The fragrance is selected from ethyl-2-methylvalerate (manzanate), limonene, (4Z)-cyclopentadeca-4-en-1-one, dihydromyrcenol, dimethylbenzyl carbonate acetate, spiro[1,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'-methylenenaphthalene)], benzyl acetate, rose oxide, geraniol, methylnonyl acetaldehyde, decanal, octanal, undecanal, tricyclodecenyl acetate, tert-butyl cyclohexyl acetate, cyclamal, beta ionone, hexyl salicylate, tonalid, [2- [(cyclohexyloxy)ethyl]benzene (phenafleur), octahydrotetramethylacetophenone (OTNE), benzene, toluene, xylene (BTX) raw materials such as 2-phenylethanol, phenylpentyl alcohol and mixtures thereof, cyclododecanone raw materials such as habolonolide, phenol raw materials such as hexyl salicylate, raw materials containing C5 modules or oxygen heterocyclic moieties such as gamma-decanoic acid, methyl dihydrojasmonate and mixtures thereof, terpene raw materials such as dihydromyrcenol, linalool, terpineol, camphor, citronellol and mixtures thereof, alkyl alcohol raw materials such as ethyl-2-methylbutyrate, diacid raw materials such as ethylene glycol brazic acid, and mixtures thereof.

[0338] Preferably, the fragrance contains 0.5-30% by weight, more preferably 2-15% by weight, particularly preferably 6-10% by weight of the fragrance component ethyl-2-methylvalerate (matricarbide).

[0339] Preferably, the fragrance contains 0.5-30% by weight, more preferably 2-15% by weight, particularly preferably 6-10% by weight of the fragrance component limonene.

[0340] Preferably, the fragrance comprises 0.5-30% by weight, more preferably 2-15% by weight, particularly preferably 6-10% by weight of the fragrance component (4Z)-cyclopentadeca-4-en-1-one.

[0341] Preferably, the fragrance comprises 0.5-30% by weight, more preferably 2-15% by weight, particularly preferably 6-10% by weight of the fragrance combination dimethylbenzyl carbonate acetate.

[0342] Preferably, the fragrance contains 0.5-30% by weight, more preferably 2-15% by weight, particularly preferably 6-10% by weight of the fragrance component dihydromyrcenol.

[0343] Preferably, the fragrance contains 0.5-30% by weight, more preferably 2-15% by weight, particularly preferably 6-10% by weight of the fragrance component rose oxide.

[0344] Preferably, the fragrance contains 0.5-30% by weight, more preferably 2-15% by weight, particularly preferably 6-10% by weight of the fragrance component tert-butyl cyclohexyl acetate.

[0345] Preferably, the fragrance contains 0.5-30% by weight, more preferably 2-15% by weight, and particularly preferably 6-10% by weight of the fragrance component tricyclodecenyl acetate.

[0346] Preferably, the fragrance contains 0.5-30% by weight, more preferably 2-15% by weight, and particularly preferably 6-10% by weight of the fragrance component benzyl acetate.

[0347] Preferably, the fragrance comprises 0.5-30% by weight, more preferably 2-15% by weight, especially preferably 6-10% by weight of the fragrance component spiro[1,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'-methylenenaphthalene)].

[0348] Preferably, the fragrance contains 0.5-30% by weight, more preferably 2-15% by weight, particularly preferably 6-10% by weight of the fragrance component geraniol.

[0349] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance component methylnonyl acetaldehyde.

[0350] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance component cyclamen aldehyde.

[0351] Preferably, the fragrance comprises 0.5-30% by weight, more preferably 2-15% by weight, particularly preferably 6-10% by weight of the fragrance component beta ionone.

[0352] Preferably, the fragrance contains 0.5-30% by weight, more preferably 2-15% by weight, particularly preferably 6-10% by weight of the fragrance component hexyl salicylate.

[0353] Preferably, the fragrance contains 0.5-30% by weight, more preferably 2-15% by weight, particularly preferably 6-10% by weight of the fragrance component Musk Tonalite.

[0354] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance component [2-(cyclohexyloxy)ethyl]benzene.

[0355] Preferably, the fragrance comprises a component selected from the group consisting of benzene, toluene, xylene (BTX) raw materials. More preferably, the fragrance component is selected from the group consisting of 2-phenylethanol, phenylpentyl alcohol and mixtures thereof.

[0356] Preferably, the fragrance comprises a component selected from the class of cyclododecanone raw materials. More preferably, the fragrance component is habolonolide.

[0357] Preferably, the fragrance comprises a component selected from the class of phenolic raw materials. More preferably, the fragrance component is hexyl salicylate.

[0358] Preferably, the fragrance comprises a component selected from the class of raw materials containing heterocyclic moieties containing C5 moieties or oxygen. More preferably, the fragrance component is selected from gamma decalactone, methyl dihydrojasmonate and mixtures thereof.

[0359] Preferably, the fragrance comprises a component selected from the class of terpene raw materials. More preferably, the fragrance component is selected from linalool, terpineol, camphor, citronellol and mixtures thereof.

[0360] Preferably, the fragrance comprises a component selected from the class of alkyl alcohol raw materials. More preferably, the fragrance component is ethyl-2-methylbutyrate.

[0361] Preferably, the fragrance comprises a component selected from the class of diacid raw materials. More preferably, the fragrance component is ethylene glycol brazyl.

[0362] Preferably, the above listed fragrance components are present in the finished detergent composition in an amount of 0.0001 to 1 % by weight of the composition.

[0363] Microcapsules

[0364] A type of particulate suitable for use in the present invention is microcapsule. Microencapsulation can be defined as a method of surrounding or encapsulating a substance in another substance on a very small scale, thereby producing capsules ranging in size from less than one micron to hundreds of microns. The encapsulated material can be referred to as a core, active ingredient or agent, filler, payload, core or internal phase. The material encapsulating the core can be referred to as a coating, film, shell or wall material.

[0365] Microcapsules typically have at least one generally spherical continuous shell around a core. Depending on the materials and encapsulation techniques employed, the shell may contain holes, vacancies or interstitial openings. Multiple shells may be made of the same or different encapsulating materials and may be arranged in layers of varying thickness around the core. Alternatively, microcapsules may be asymmetrically and variably shaped and have a certain amount of smaller core material droplets embedded throughout the microcapsule.

[0366] The shell may have a barrier function to protect the core material from the environment outside the microcapsule, but it may also be used as a means to regulate the release of the core material, such as a fragrance. Thus, the shell may be water-soluble or water-swellable and may initiate fragrance release in response to exposure of the microcapsule to a humid environment. Similarly, if the shell is temperature-sensitive, the microcapsule may release the fragrance in response to elevated temperatures. The microcapsule may also release the fragrance in response to shear forces applied to the surface of the microcapsule.

[0367] A preferred type of polymer microparticle suitable for use in the present invention is a polymer core-shell microcapsule in which at least one continuous shell of a generally spherical polymer material surrounds a core containing a fragrance preparation (f2). The shell typically accounts for up to 20% by weight of the total weight of the microcapsule. The fragrance preparation (f2) typically accounts for about 10% to about 60% by weight of the total weight of the microcapsule, preferably about 20% to about 40% by weight. The amount of fragrance (f2) can be determined by taking a slurry of the microcapsule, extracting it into ethanol and measuring it by liquid chromatography.

[0368] The polymer core-shell microcapsules used in the present invention can be prepared using methods known to those skilled in the art such as coacervation, interfacial polymerization and polycondensation.

[0369] The coacervation process generally involves encapsulation of a core material, which is usually insoluble in water, by precipitation of a colloidal substance on the surface of a droplet. Coacervation can be simple, for example using one colloid, such as gelatin, or can be complex, where two or possibly more colloids of opposite charge are used under carefully controlled conditions of pH, temperature and concentration, such as gelatin and gum arabic or gelatin and carboxymethylcellulose.

[0370] Interfacial polymerization is usually carried out with the formation of a fine dispersion of 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 the dispersed phase (oil droplets) and the aqueous continuous phase and 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 prepared by this method is a polyurea microcapsule having a shell formed by the reaction of a diisocyanate or polyisocyanate with a diamine or polyamine.

[0371] The polycondensation comprises forming a dispersion or emulsion of the core material in an aqueous solution of a precondensate of the polymer material under appropriate stirring conditions to prepare capsules of the desired size, and adjusting the reaction conditions to cause the polycondensation of the precondensate by acid catalysis, resulting in the condensate separating from the solution and surrounding the dispersed core material to produce a coacervate film and the desired microcapsules. Examples of core-shell microcapsules produced by this method are aminoplast microcapsules having a shell formed by a polycondensation product of melamine (2,4,6-triamino-1,3,5-triazine) or urea and formaldehyde. Suitable crosslinking agents (e.g., toluene diisocyanate, divinylbenzene, butanediol diacrylate) may also be used, and secondary wall polymers, such as polymers and copolymers of anhydrides and their derivatives, particularly maleic anhydride, may also be used appropriately.

[0372] An example of a preferred polymer core-shell microcapsule for use in the present invention is an aminoplast microcapsule having an aminoplast shell surrounding a core containing the fragrance formulation (f2). More preferably, this aminoplast shell is formed from a polycondensation product of melamine and formaldehyde.

[0373] Polymer microparticles suitable for use in the present invention typically have an average particle size of 100 nanometers to 50 microns. Particles larger than this size enter the visible range. Examples of particles in the submicron range include latexes and microemulsions with a typical size range of 100 to 600 nanometers. Preferred particle size ranges are in the micrometer range. Examples of particles in the micrometer range include polymer core-shell microcapsules (such as those described further above) with a typical size range of 1 to 50 microns, preferably 5 to 30 microns. The average particle size can be determined by light scattering using a Malvern Mastersizer, wherein 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 microcapsules initially produced can be filtered or screened to produce a more uniformly sized product.

[0374] Polymer microparticles suitable for use in the present invention may be provided with a deposition aid on the outer surface of the microparticle. The deposition aid is used to modify the properties of the exterior of the microparticle, for example to make the microparticle more substantive to a desired substrate. Desired substrates include cellulose (including cotton) and polyester (including those used to make polyester fabrics).

[0375] The deposition aid may be provided at the outer surface of the microparticle, suitably by covalent bonding, entanglement or strong adsorption. Examples include polymer core-shell microcapsules (such as those described further above) in which the deposition aid is attached to the exterior of the shell, preferably by covalent bonding. Although it is preferred that the deposition aid is attached directly to the exterior of the shell, it may also be attached to the exterior of the shell via a linking substance.

[0376] The deposition aid for use in the present invention may be suitably 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 beta glycan (broadly defined) backbone structure having at least 4, preferably at least 10, β1-4 linked backbone residues, such as a glucan backbone (consisting of β1-4 linked glucose residues), a mannan backbone (consisting of β1-4 linked mannose residues) or a xylan backbone (consisting of β1-4 linked xylose residues). Examples of these β1-4 linked polysaccharides include xyloglucan, glucomannan, mannan, galactomannan, β(1-3), β(1-4) glucan and the xylan family comprising glucuronoxylan, arabinoxylan and glucuronoxylan. Preferred β1-4 linked polysaccharides for use in the present invention can be selected from plant-derived xyloglucans, such as pea xyloglucan and tamarind seed xyloglucan (TXG) (which have a β1-4 linked glucan backbone and side chains of α-D-xylopyranose and β-D-galactopyranosyl-(1-2)-α-D-xylopyranose, both of which are linked 1-6 to the backbone); and plant-derived galactomannans, such as locust bean gum (LBG) (which have a mannan backbone composed of β1-4 linked mannose residues and single unit galactose side chains linked α1-6 to the backbone).

[0377] Also suitable are polysaccharides which, appropriately upon hydrolysis, acquire an affinity for cellulose, such as cellulose monoacetate, or modified polysaccharides having an affinity for cellulose, such as hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl guar, hydroxyethyl ethyl cellulose and methyl cellulose.

[0378] The deposition aid for use in the present invention may also be selected from phthalate-containing polymers having an affinity for polyesters. Such phthalate-containing polymers may have one or more nonionic hydrophilic segments containing oxyalkylene groups (e.g., ethylene oxide, polyoxyethylene, propylene oxide, or polyoxypropylene groups) and one or more hydrophobic segments containing terephthalate groups. Typically, the oxyalkylene groups will have a degree of polymerization of from 1 to about 400, preferably from 100 to about 350, more preferably from 200 to about 300. A suitable example of a phthalate-containing polymer of this type is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide terephthalate.

[0379] Mixtures of any of the above materials may also be used.

[0380] The weight average molecular weight (M) of the deposition aid used in the present invention is w) is generally 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.

[0381] 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 polycondensation of melamine and formaldehyde, said shell surrounding a core containing the fragrance formulation (f2), wherein a deposition aid is attached to the outside of said shell by covalent bonding. Preferred deposition aids are selected from β1-4 linked polysaccharides, in particular xyloglucans of plant origin, as further described above.

[0382] The inventors have surprisingly observed that the total level of fragrance contained in the compositions of the present invention can be reduced without sacrificing the overall fragrance experience delivered to the consumer at a critical stage in the laundry process. A reduction in the total level of fragrance is advantageous for cost and environmental reasons.

[0383] Therefore, the total amount of fragrance formulation (f1) and fragrance formulation (f2) in the composition of the present invention is suitably in the range of 0.5 to 1.4%, preferably 0.5 to 1.2%, more preferably 0.5 to 1%, most preferably 0.6 to 0.9% (by weight based on the total weight of the composition).

[0384] The weight ratio of fragrance preparation (f1) to fragrance preparation (f2) in the composition of the present invention is preferably in the range of 60:40 to 45:55. Particularly good results are obtained when the weight ratio of fragrance preparation (f1) to fragrance preparation (f2) is about 50:50.

[0385] Fragrance (f1) and fragrance (f2) are usually added at different stages of the formation of the composition of the present invention. Typically, discrete polymer particles (e.g., microcapsules) encapsulating the fragrance formulation (f2) are added as a slurry to a warm base formulation containing other components of the composition (e.g., surfactants and solvents). Fragrance (f1) is usually added later after the base formulation has cooled.

[0386] Further optional ingredients

[0387] The compositions of the present invention may contain further optional ingredients to enhance performance and / or consumer acceptance. Examples of such ingredients include foam enhancers, preservatives (such as bactericides), polyelectrolytes, anti-shrinkage agents, anti-wrinkle agents, antioxidants, sunscreens, corrosion inhibitors, drape-imparting agents, antistatic agents, ironing aids, colorants, pearlescent agents and / or sunscreens and tinting dyes. Each of these ingredients is present in an amount effective to achieve its purpose. Typically, these optional ingredients are included individually in an amount of up to 5% (by weight based on the total weight of the diluted composition) and are adjusted according to the dilution ratio with water.

[0388] Many of the ingredients used in embodiments of the present invention can be obtained from so-called black carbon sources or more sustainable green sources. Provided below is a list of alternative sources for several of these ingredients and how they can be made into the feedstocks described herein.

[0389] Preferably, the unit dose detergent is packaged in a container such as a plastic tub. Such plastic tubs are typically hermetically sealed and include a child-resistant closure.

[0390] 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 may be virgin or recycled, but are preferably recycled.

[0391] Preferably, the container comprises at least 90% by weight of biodegradable material.

[0392] Preferred pulps include paperboard, especially corrugated paperboard. BRIEF DESCRIPTION OF THE DRAWINGS

[0393] Embodiments of the present invention will now be described with reference to the following non-limiting drawings, in which:

[0394] Figure 1 is a plan view of a unit dose capsule; and

[0395] Figure 2 is a side view of the same unit dose capsule. DETAILED DESCRIPTION

[0396] Figure 1 A unit dose detergent capsule is shown formed between a pair of substantially rectangular water soluble film sheets, the sheets being sealed to each other around their respective peripheries to form sealed edges (2) and a chamber therebetween, the chamber (7) containing 5 to 13 g of a liquid detergent composition, the chamber comprising, when viewed in plan view, first and second pairs (3) of opposed sealed edges, each edge being connected to an adjacent edge at a sealed corner (5), the chamber comprising a corner protrusion (6) directed toward each of the four sealed corners (5).

[0397] A protrusion refers to a portion of a chamber that extends outwardly toward a corner when viewed in plan view.

[0398] Figure 2 The sealing edge (2) and the corner protrusion (6) are shown as well as the sealing corner (5) and the capsule chamber (7).

[0399] Example

[0400] Example 1

[0401] The following are unit dose formulations for use in capsules according to embodiments of the present invention.

[0402] Table 1

[0403] Element 1 Total liquid weight (g) 10.9 Chamber rupture (g) 8.8g LAS 25.9 MIPA AES 14.1 NI 20.7 fatty acid 3.3 glycerin 0 MPG 15 water 8 Active substance:solvent ratio 2.78

[0404] Composition 1 is stable at lower dosages and can clean soiled loads.

[0405] Example 2

[0406] We compared the filling patterns of two capsules of different shapes but the same volume (8 ml). Figure 1 The shape of the control capsules was medium, while the control capsules had a pillow shape. 27 capsules were placed in a bucket of the same size and the settling pattern was observed.

[0407] The capsules of the present invention are spaced more widely from each other than the comparative pillow-shaped capsules. As a result, the capsules stick less to each other and the dead space above the capsule is reduced (i.e., the fill level is higher) when the consumer first opens it. This also affects the dispersion of the fragrance in the headspace.

[0408] The headspace for the capsule of the invention was 18.26, while the corresponding headspace for the comparative pillow shape was 31.3%.

[0409] Example 3

[0410] We further tested the dissolution rates of the two capsule shapes.

[0411] The dissolution rates of identical inventive and comparative capsules were measured and are reported in Table 2.

[0412] Table 2

[0413] Foaming of liquid Liquid Escape Liquid use Capsules of the present invention 45.7s 67.4s 149.9s Comparison capsules 63.8s 73.5s 155.1s

[0414] The data clearly demonstrate that the shape of the present invention results in improved capsule dissolution performance.

[0415] Example 4

[0416] Comparison between identical capsules of the invention and comparative capsules shows that the capsules of the invention are less likely to leave residue on clothes during use. This is because the capsules of the invention remain with the clothes during the wash process, whereas the comparative capsules are more likely to be pushed toward the drum door.

Claims

1. A single-chamber unit-dose laundry detergent capsule characterized by A sheet comprising a pair of substantially rectangular water-soluble films, the sheets being sealed to each other around their respective peripheries to form a chamber therebetween, the chamber containing 5-13 g of a liquid detergent composition, the chamber comprising first and second pairs of opposing sealed edges when viewed in plan view, each edge being connected to an adjacent edge at a sealed corner, the chamber comprising a corner protrusion directed toward each of the four sealed corners.

2. The single chamber unit dose laundry detergent capsule of claim 1, characterized in that At least one edge within any pair of opposing edges includes a notch, wherein the edge extends toward the interior of the chamber at the notch when viewed in plan view.

3. The single chamber unit dose laundry detergent capsule of claim 1, characterized in that Both edges within any pair of opposing edges include notches, wherein the edges extend toward the interior of the chamber at the notches when viewed in plan view.

4. The single chamber unit dose laundry detergent capsule of claim 1, wherein At least one edge within any pair of opposing edges includes a pair of notches, wherein the edges extend toward the interior of the chamber at the notches when viewed in plan view.

5. The single chamber unit dose laundry detergent capsule of claim 1, wherein Both edges within any pair of opposing edges include a pair of notches, wherein the edges extend toward the interior of the chamber at the notches when viewed in plan view.

6. A single chamber unit dose laundry detergent capsule according to any one of claims 1 to 5, characterised in that At least one corner protrusion includes an apex located 2 to 7 mm from the nearest sealing corner.

7. A single chamber unit dose laundry detergent capsule according to any one of claims 1 to 5, characterised in that At least one corner protrusion comprises an apex located 3 to 5 mm from the nearest sealing corner.

8. A single chamber unit dose laundry detergent capsule according to any one of claims 1 to 5, characterised in that The stretching ratio of the water-soluble film is 1.7 to 2.

1.

9. A single chamber unit dose laundry detergent capsule according to any one of claims 1 to 5, characterised in that The stretching ratio of the water-soluble film is 1.8 to 2.

05.

10. A single chamber unit dose laundry detergent capsule according to any one of claims 1 to 5, characterised in that The liquid detergent composition comprises from 2 to 10% water by weight of the liquid detergent composition.

11. A single chamber unit dose laundry detergent capsule according to any one of claims 1 to 5, characterised in that A display portion is included on at least one of the water-soluble sheets, the display portion containing ink.

12. The single chamber unit dose laundry detergent capsule of claim 11, wherein The ink includes phthalocyanine ink.

13. A single chamber unit dose laundry detergent capsule according to any one of claims 1 to 5, characterised in that The water soluble film comprises a bittering agent.

14. A single chamber unit dose laundry detergent capsule according to any one of claims 1 to 5, characterised in that The membrane comprises a maleic acid derived polymer.

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