Liquid hand dishwashing composition

Abstract

To provide a liquid hand dishwashing detergent composition which, while providing good foaming properties, viscosity, and stability, still has high biodegradability and a high concentration of renewable components.SOLUTION: The need for a liquid hand dishwashing composition which, while including a surfactant derived from a more renewable supply source, still provides good performance, in particular foam longevity in the presence of oily and fatty particulate soils and hard water, as well as oily and fatty soil removal, is met by formulating the liquid hand dishwashing composition with an alkylalkanolamide sulfate anionic surfactant in combination with an alkyl sulfate anionic surfactant.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to liquid hand dish detergent compositions that provide good foaming, viscosity and stability while still having high biodegradability and a high concentration of renewable ingredients. [Background technology]

[0002] Hand dishwashing cleaning compositions have typically been formulated using alkyl ethoxylated sulfate surfactants as the primary anionic surfactant because they provide good grease removal, foam persistence in the presence of suspended greasy particulate soils, and good low temperature stability. In particular, grease removal and foam persistence are viewed as indicators of good, long-lasting performance.

[0003] During hand dishwashing, users typically rely on foam level as an indicator of the remaining cleaning effectiveness of a diluted detergent composition. A large foam volume and / or stable, long-lasting foam persistence (i.e., mileage) indicates to the user that sufficient active ingredients (e.g., surfactants) remain to provide the desired cleaning. Insufficient foam longevity typically leads users to add additional cleaning composition even when cleaning effectiveness remains. Furthermore, as soils are lifted from dishes and utensils, they become emulsified and / or suspended in the wash solution, further suppressing foaming even when sufficient surfactants are present for additional grease removal. Insufficient foam longevity in the presence of soils is exacerbated when hard water is used.

[0004] There is also a growing demand for detergent compositions with improved biodegradability and derived from renewable sources. Hand dishwashing detergent compositions have typically been formulated using alkyl ethoxylated sulfate surfactants as the primary anionic surfactant. However, the process for producing such alkyl ether sulfate anionic surfactants can result in trace amounts of residual 1,4-dioxane by-product. The amount of 1,4-dioxane by-product in alkoxylated alkyl sulfates, particularly ethoxylated alkyl sulfates, can be reduced. Based on recent technological advances, further reduction of 1,4-dioxane by-products can be achieved by subsequent stripping, distillation, solvent evaporation, centrifugation, microwave irradiation, molecular sieving, or catalytic or enzymatic degradation processes.

[0005] An alternative is to use alkyl sulfate anionic surfactants that contain only low levels of ethoxylation, or even no ethoxylation. However, the incorporation of such alkyl sulfate anionic surfactants with little or no ethoxylation reduces the performance of hand dishwashing detergent compositions, particularly with respect to foam longevity in the presence of greasy particulate soils, and reduces physical stability at low temperatures.

[0006] Thus, there remains a need for liquid hand dishwashing compositions that contain surfactants derived from more renewable sources and still provide good performance, particularly foam persistence and grease cleaning in the presence of greasy particulate soils and hard water.

[0007] European Patent No. 0780367(A) relates to an anionic detergent mixture obtained by co-sulfating a mixture of fatty acid alkanolamide and fatty alcohol polyalkylene glycol in a weight ratio of 5:95 to 70:30, followed by neutralization with aqueous base, and a process for co-sulfating the mixture and neutralizing the mixture with aqueous base. U.S. Patent No. 4116986(A) relates to a process for sulfating fatty alkanolamides prepared from the reaction of fatty acids and esters with low molecular weight alkanolamines by adding about 5 to 15% by weight of a low molecular weight alcohol to the fatty alkanolamide and consulfating with a sulfating agent. Japanese Patent Publication No. 10330783 relates to a detergent composition containing at least one amidosulfate ester surfactant. Korean Patent Publication No. 20120060485(A) relates to a liquid detergent composition containing an alkyl alkanolamide sulfate anionic surfactant. U.S. Patent No. 2,353,081(A) relates to sulfated monoethanolamide and a method for preparing same. U.S. Patent No. 2,843,550(A) relates to a detergent composition consisting essentially of an alkali metal sulfated C2-C3 alkylolamide of C14-C18 hydrogenated tallow fatty acid, an alkali metal C9-C18 monoalkylbenzene sulfonate detergent (the former being present in an amount of about 15% to 50% by weight of the total of the two, and the latter being present in an amount of 50% to 85% by weight), and about 5% to 70% by weight, based on the sulfated alkylolamide salt, of a straight-chain saturated C10-C18 fatty alcohol as a foam improver. EP 4253510(A) relates to a liquid hand dish detergent composition that contains a high proportion of ingredients derived from natural renewable sources without substantially changing the viscosity profile, ideally with improved biodegradability, while still providing good foaming, grease removal and low temperature stability, the composition comprising a surfactant system that includes an anionic surfactant that includes a combination of an alkyl sulfate anionic surfactant and an acyltaurate anionic surfactant.The synthesis of sulfated alkanolamides is described in "Synthesis and properties of sulfated alkanolamides," Journal of the American Oil Chemists' Society, volume 47, pages 91-93 (1970), and "Synthesis and Properties of N-Alkyl Amide Sulfates," Langmuir 1999, 15, 20, 6664-6670. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] European Patent No. 0780367(A) [Patent Document 2] U.S. Patent No. 4,116,986(A) [Patent Document 3] Japanese Patent Publication No. 10330783 [Patent Document 4] Korean Patent Publication No. 20120060485(A) [Patent Document 5] U.S. Patent No. 2,353,081(A) [Patent Document 6] U.S. Patent No. 2,843,550(A) [Patent Document 7] European Patent No. 4253510(A) [Non-patent literature]

[0009] [Non-Patent Document 1] "Synthesis and properties of sulfated alkanolamides" Journal of the American Oil Chemists'Society volume 47, pages 91-93(1970) [Non-patent document 2] "Synthesis and Properties of N-Alkyl Amide Sulfates" Langmuir 1999,15,20,6664-6670 Summary of the Invention [Means for solving the problem]

[0010] The present invention relates to a liquid hand dishwashing detergent composition comprising from 5.0% to 50% by weight of the liquid hand dishwashing detergent composition of a surfactant system, the surfactant system comprising an anionic surfactant, the anionic surfactant having the formula: R(CO)NXR'O-SO3- M+ (I) and wherein R is an alkyl chain containing an average of 7 to 17 carbon atoms, R' is an alkyl chain containing an average of 1 to 3 carbon atoms, X is H or C1-C3 alkyl, and M+ is a counter ion; and alkyl sulfate anionic surfactants having an average degree of alkoxylation of less than 0.1.

[0011] The present invention further provides a compound of formula: R(CO)NXR'O-SO3- M+ (I) and a method for preparing a concentrated surfactant blend comprising an alkyl alkanolamide sulfate anionic surfactant having the formula: The method comprises the step of reacting at least one compound of formula (II): R(CO)NXR'OH (II) providing a non-ionic stream comprising an alkyl alkanolamide of The method includes a sulfation step in which at least one alkyl alkanolamide of formula (II) in the nonionic stream is sulfated to form a sulfuric acid stream comprising at least one alkyl alkanolamide sulfuric acid; a step in which a neutralization stream comprising at least one neutralizing agent is provided; and a neutralization step in which the sulfuric acid stream and the neutralization stream are combined to neutralize the at least one alkyl alkanolamide sulfuric acid. DETAILED DESCRIPTION OF THE INVENTION

[0012] The liquid cleaning compositions described herein are formulated to provide hand dish detergent compositions that have good foam persistence and good grease removal in the presence of greasy particulate soils, which include a mixture of grease or oils and particles such as carbohydrates, while also providing compositions that are derived from more renewable sources.

[0013] As used herein, articles such as "a" and "an" used in the claims are understood to mean one or more of what is claimed or described.

[0014] As used herein, the term "comprising" means that steps and ingredients other than those specifically mentioned can be added. This term encompasses the terms "consisting of" and "consisting essentially of." The compositions of the present invention can include, consist of, or consist essentially of the essential elements and limitations of the invention described herein, as well as any additional or optional ingredients, components, steps, or limitations described herein.

[0015] As used herein, the term "dishware" includes, by way of non-limiting example, cookware and tableware made from ceramic, china, metal, glass, plastic (e.g., polyethylene, polypropylene, polystyrene, etc.), and wood.

[0016] As used herein, the terms "oil" or "oleaginous" mean that a substance comprises, at least in part (i.e., at least 0.5% by weight of the substance) saturated and unsaturated fats and oils, preferably oils and fats derived from animal sources such as beef, pork, and / or chicken.

[0017] The terms "include / includes / including" are meant to be non-limiting.

[0018] As used herein, the term "particulate soil" means inorganic and especially organic solid soil particles, especially food particles, non-limiting examples of which include ultrafine particulate elemental carbon, baked grease particles, and meat particles.

[0019] As used herein, the term "suds profile" refers to a characteristic of a cleaning composition related to the quality of foam during the dishwashing process. The term "suds profile" of a cleaning composition includes the initial foam volume generated upon dissolving and stirring the cleaning composition in an aqueous washing solution, typically by manual stirring, and the retention of foam during the dishwashing process. Preferably, hand dishwashing cleaning compositions characterized by having a "good suds profile" tend to have a high initial foam volume and / or a persistent foam volume, particularly throughout a significant portion or the entire dishwashing process. This is important because consumers use high sudsing as an indicator that sufficient cleaning composition has been dispensed. Furthermore, consumers also use sustained foam volume, even toward the end of the dishwashing process, as an indicator that sufficient active cleaning ingredients (e.g., surfactants) are present. Consumers typically refresh their washing solution when suds become low. Therefore, low-sudsing cleaning compositions tend to be replenished by consumers more frequently than necessary due to their low suds levels.

[0020] It will be understood that the test methods disclosed in the Test Methods section of this application must be used to determine the values ​​of each of the parameters of Applicants' inventions described and claimed herein.

[0021] Unless specifically stated otherwise, as is clear from the context, all percentages are by weight of the total composition, all ratios are by weight unless specifically stated otherwise, and all measurements are made at 25°C unless otherwise specified.

[0022] Liquid cleaning composition The cleaning composition is a liquid cleaning composition, preferably a liquid hand dishwashing cleaning composition, and is therefore in liquid form. The liquid cleaning composition is preferably an aqueous cleaning composition. Thus, the composition can contain 50% to 85% by weight, preferably 50% to 75% by weight, of water based on the total weight of the composition.

[0023] When measured as a 10% aqueous solution in demineralized water at 20° C., the liquid cleaning composition has a pH of 7.0 or greater, or from 7.0 to 12.0, preferably from 7.5 to 11.0, more preferably from 8.0 to 10.0.

[0024] The liquid cleaning compositions of the present invention may be Newtonian or non-Newtonian, but are preferably Newtonian. Preferably, the compositions have a viscosity of from 10 mPa·s to 10,000 mPa·s, preferably from 100 mPa·s to 5,000 mPa·s, more preferably from 300 mPa·s to 2,000 mPa·s, or most preferably from 500 mPa·s to 1,500 mPa·s, or alternatively a combination thereof.

[0025] The compositions of the present invention may contain renewable components and exhibit good performance, such as cleaning and foam persistence. The compositions disclosed herein may contain renewable components from 20%, 40%, or 50% by weight of the composition, up to 60%, 80%, or even 100% by weight. The compositions disclosed herein are at least partially or completely biobased. Thus, the compositions may contain 50% to 100% by weight of the composition, preferably 75% to 100%, most preferably 80% to 100%, and most preferably about 90% to about 100% by weight of the composition. Biobased means that the material is derived from biologically derived materials, such as cultivated plants, rather than from coal or petroleum. The percent biobased carbon content can be calculated as "percent modern carbon" (pMC), derived using the method of ASTM D6866-16. The compositions of the present disclosure may be substantially free of petroleum-derived solvents. The compositions of the present disclosure may be substantially free of surfactants or even polymers derived from petroleum-derived alcohols.

[0026] surfactant system The liquid cleaning composition comprises from 5.0% to 50%, preferably from 6.0% to 40%, most preferably from 15% to 35% by weight of the surfactant system, based on the weight of the total composition.

[0027] Anionic surfactants The surfactant system includes an anionic surfactant. The surfactant system may comprise at least 40% by weight of the anionic surfactant, preferably 60% to 90% by weight, more preferably 65% ​​to 85% by weight of the surfactant system. The surfactant system preferably does not contain fatty acids or salts thereof, since such fatty acids inhibit foam generation.

[0028] Alkyl Alkanolamide Sulfate Anionic Surfactants The surfactant system comprises an anionic surfactant, the anionic surfactant comprising an alkyl alkanolamide sulfate anionic surfactant. Preferably, the alkyl alkanolamide sulfate anionic surfactant is present at a concentration of 5.0% to 50%, preferably 10% to 40%, more preferably 15% to 30% by weight of the anionic surfactant system.

[0029] The alkyl alkanolamide sulfate anionic surfactant may be present in the range of 1.0% to 25% by weight of the composition, preferably 3.0% to 15% by weight, more preferably 5.0% to 10% by weight.

[0030] The alkyl alkanolamide sulfate anionic surfactants used in the present invention have the formula: R(CO)NXR'O-SO3 - M + (I) and During the ceremony, R is an alkyl chain containing, on a number average, 7 to 17 carbon atoms, preferably R is an alkyl chain containing, on a number average, 9 to 13 carbon atoms, more preferably 11 to 13 carbon atoms, and most preferably R is a blend of C11 and C13 alkyl chains; R' is an alkyl chain containing, on average, 1 to 3 carbon atoms, preferably R' is an alkyl chain containing, on average, 2 to 3 carbon atoms, more preferably R' is selected from the group consisting of -(CH2)2-, -CH2CH(CH3)-, and -CH(CH3)CH2-; X is H or C1-C3 alkyl, preferably X is H or C1 alkyl, more preferably H or methyl; M + is a counter ion, preferably M + is an alkali metal counterion or ammonium, ethanolamine, or isopropanolamine, more preferably Na + , or K + , Mg 2+ , or ethanolamine, most preferably Na+ is.

[0031] R can be derived from a suitable starting fatty acid, such as lauric acid (C12), myristic acid (C14), palmitic acid (C16), stearic acid (C18), oleic acid (C18:1), and mixtures thereof. When the starting fatty acid is naturally derived, it typically has a chain length distribution, such as 8 to 18 carbon atoms, or a narrower distribution when refined to achieve the desired alkyl chain length distribution. Lauric acid (C12), myristic acid (C14), and particularly mixtures thereof, are preferred. Because the carbon chain length of a fatty acid includes the carbon atoms of the carboxylic acid of the fatty acid, the carbon number of R in the alkyl alkanolamide sulfate surfactant formula (I) is one less than the carbon number of the fatty acid. For example, if the alkyl alkanolamide surfactant is formed using lauric acid (C12), R in the alkyl alkanolamide sulfate surfactant formula (I) is a C11 alkyl.

[0032] The alkyl chains R may have a molar percentage of C11-C13 chains relative to total alkyl chains of at least 60%, preferably at least 70%, more preferably at least 80%, and most preferably at least 90%. The molar ratio of C11 alkyl chains to C13 alkyl chains in R may be 1:2 to 6:1, preferably 1:1 to 5:1.

[0033] R may be a linear alkyl chain, for example to improve grease cleaning, and may therefore be naturally derived from renewable sources such as coconut oil, palm kernel oil, and mixtures thereof, with coconut oil being preferred.

[0034] Alternatively, but less preferably, the alkyl chain of R may be branched, for example, to improve the low-temperature stability of the resulting detergent composition. Using an alkyl chain with a weight-average branching degree of at least 15%, preferably 20% to 60%, and more preferably 30% to 50%, for R can achieve a combination of good grease removal and improved low-temperature stability of the detergent composition. The weight-average branching degree of the R group is calculated using the same method as described below for alkyl sulfate anionic surfactants. The weight-average branching degree and branching distribution can typically be obtained from the technical data sheets for the component fatty acids used to produce the alkyl alkanolamide sulfate anionic surfactants. Alternatively, the type of branching can be determined by analytical methods known in the art, including capillary gas chromatography with a flame ionization detector on a medium-polarity capillary column using hexane as the solvent.

[0035] The alkyl alkanolamide sulfate anionic surfactant preferably comprises a C12 alkyl alkanolamide sulfate anionic surfactant, a C14 alkyl alkanolamide sulfate anionic surfactant, and a mixture thereof, and a blend of a C12 alkyl alkanolamide sulfate anionic surfactant and a C14 alkyl alkanolamide sulfate anionic surfactant is preferred.Therefore, R in formula (I) is preferably C11 or C13, or a combination thereof.

[0036] Suitable C12 alkyl alkanolamide sulfate anionic surfactants may be selected from the group consisting of N-(2-hydroxyethyl)dodecanamide sulfate, N-(2-hydroxypropyl)dodecanamide sulfate, N-(2-hydroxyethyl)-N-methyldodecanamide sulfate, N-(1-hydroxypropan-2-yl)dodecanamide sulfate, and mixtures thereof, preferably N-(2-hydroxyethyl)dodecanamide sulfate, N-(2-hydroxypropyl)dodecanamide sulfate, N-(2-hydroxyethyl)-N-methyldodecanamide sulfate, and mixtures thereof.

[0037] Suitable C14 alkyl alkanolamide sulfate anionic surfactants may be selected from the group consisting of N-(2-hydroxyethyl)tetradecanamide sulfate, N-(2-hydroxypropyl)tetradecanamide sulfate, N-(2-hydroxyethyl)-N-methyltetradecanamide sulfate, N-(1-hydroxypropan-2-yl)tetradecanamide sulfate, and mixtures thereof, preferably N-(2-hydroxyethyl)tetradecanamide sulfate, N-(2-hydroxypropyl)tetradecanamide sulfate, N-(2-hydroxyethyl)-N-methyltetradecanamide sulfate, and mixtures thereof.

[0038] Alkyl sulfate anionic surfactants The anionic surfactant preferably further comprises an alkyl sulfate anionic surfactant, and the anionic surfactant may comprise at least 25% by weight of the anionic surfactant, preferably 30% to 90% by weight, more preferably 65% ​​to 85% by weight of the alkyl sulfate anionic surfactant.

[0039] The anionic surfactant may comprise at least 70% by weight of the anionic surfactant, more preferably at least 85% by weight, and most preferably 100% by weight of the alkyl sulfate anionic surfactant and the alkyl alkanolamide sulfate anionic surfactant. In a preferred composition, the anionic surfactant consists of the alkyl sulfate anionic surfactant and the alkanolamide sulfate anionic surfactant. The alkyl sulfate anionic surfactant and the alkyl alkanolamide sulfate anionic surfactant are preferably present in a weight ratio of 10:1 to 1:2, preferably 7:1 to 1:1, and most preferably 5:1 to 2:1.

[0040] Without being bound by theory, it is believed that the mixture provides a surfactant loading that exhibits a balance of grease cleaning and foam retention performance, especially in the presence of oily particulate soils, low temperature stability, and minimal impact on the viscosity of the target end product.

[0041] To provide a combination of improved grease removal and increased cleaning speed, the molar average alkyl chain length of the alkyl sulfate anionic surfactant can be from 8 to 18, preferably from 10 to 14, more preferably from 12 to 14, and most preferably from 12 to 13 carbon atoms.

[0042] The alkyl sulfate anionic surfactant may have a molar fraction of C12 and C13 alkyl chains of at least 50%, preferably at least 65%, more preferably at least 80%, and most preferably at least 90%. When the C13 / C12 alkyl chain molar ratio is at least 57 / 43, preferably 60 / 40 to 90 / 10, more preferably 60 / 40 to 80 / 20, and most preferably 60 / 40 to 70 / 30, foam persistence is particularly improved, particularly in the presence of greasy particulate soil, while not impairing foam persistence in the presence of particulate soil.

[0043] The relative molar amounts of C13 and C12 alkyl chains in alkyl sulfate anionic surfactants can be derived from the carbon chain length distribution of the anionic surfactant. The carbon chain length distribution of alkyl chains in alkyl sulfate anionic surfactants can be obtained from the technical data sheets of the surfactant or the alkyl alcohols that make them up. Alternatively, the chain length distribution and average molecular weight of the aliphatic alcohols used to make the alkyl sulfate anionic surfactants can be determined by methods known in the art. Such methods include capillary gas chromatography with a flame ionization detector on a medium polarity capillary column using hexane as the solvent. The chain length distribution is based on the starting alcohol and alkoxylated alcohol. Therefore, alkyl sulfate anionic surfactants must be hydrolyzed, for example, using hydrochloric acid, to return them to the corresponding alkyl alcohol and alkyl alkoxylated alcohol before analysis.

[0044] The alkyl sulfate anionic surfactant may have a weight average degree of branching of at least 15%, preferably 20% to 60%, more preferably 30% to 50%. Compositions containing such branched alkyl sulfate anionic surfactants typically have improved viscosity control and low temperature stability. More preferably, the alkyl sulfate anionic surfactant has an average degree of branching of less than 15%, more preferably less than 10%, and most preferably, the alkyl sulfate anionic surfactant is linear. The linear alkyl chain is typically derived from renewable sources.

[0045] The alkyl sulfate anionic surfactant may contain at least 5%, preferably at least 10%, and most preferably at least 25% by weight of branching at the C2 position of the alkyl sulfate anionic surfactant (measured by counting carbon atoms from the sulfate group for non-alkoxylated alkyl sulfate anionic surfactants and counting from the alkoxy group furthest from the sulfate group for alkoxylated alkyl sulfate anionic surfactants). More preferably, greater than 75%, and even more preferably greater than 90% by weight of the total branched alkyls are C1-C5 alkyl moieties, preferably C1-C2 alkyl moieties. Formulating compositions of the present invention using alkyl sulfate surfactants with the aforementioned branching levels has been found to result in improved low-temperature stability. Such compositions require less solvent to achieve good physical stability at low temperatures. Thus, the compositions may contain low concentrations of organic solvent, less than 5.0% by weight based on the weight of the liquid cleaning composition, while still having improved low-temperature stability. Higher surfactant branching also results in faster initial foam generation, but typically results in lower foam persistence. The weight average branching described herein has been found to provide improved low temperature stability, initial foam generation, and foam persistence.

[0046] The weight average degree of branching of the anionic surfactant mixture is calculated according to the following formula: Weight average branching degree (%) = [(x1 * Wt% of branched chain alcohol 1 in alcohol 1 + x2 * (wt% of branched-chain alcohol 2 in alcohol 2 + ....) / (x1 + x2 + ....)] × 100 can be calculated using where x1, x2, ... are the weights (in grams) of each alcohol in the total alcohol mixture used as a starting material before (alkoxylation and) sulfation to produce the alkyl(alkoxy) sulfate anionic surfactant. The weight average branching degree calculation includes the weight of the alkyl alcohol used to form the unbranched alkyl sulfate anionic surfactant.

[0047] The weight average degree of branching and branching distribution can usually be obtained from the technical data sheet of the surfactant or its constituent alkyl alcohol. Alternatively, branching can be determined through analytical methods known in the art, including capillary gas chromatography with a flame ionization detector on a medium polarity capillary column using hexane as the solvent. The weight average degree of branching and branching distribution are based on the starting alcohol used to produce the alkyl sulfate anionic surfactant.

[0048] The alkyl sulfate surfactant may be alkoxylated or non-alkoxylated.

[0049] If alkoxylated, the alkyl sulfate anionic surfactants may have an average degree of alkoxylation of less than 0.1, but are particularly preferably not alkoxylated. If alkoxylated, ethoxylation is preferred.

[0050] Thus, the alkyl sulfate anionic surfactant comprises less than 10%, preferably less than 5%, by weight of the alkyl sulfate anionic surfactant of alkoxylated alkyl sulfate surfactant, and more preferably the alkyl sulfate anionic surfactant is free of alkoxylated alkyl sulfate surfactant.

[0051] The average degree of alkoxylation is the molar average degree of alkoxylation of all alkyl sulfate anionic surfactants (i.e., the molar average degree of alkoxylation). Thus, when calculating the molar average degree of alkoxylation, the number of moles of non-alkoxylated sulfate anionic surfactants is included. Molar average degree of alkoxylation = (x1 * Alkoxylation degree of surfactant 1 + x2 * Alkoxylation degree of surfactant 2 +....) / (x1 + x2 +....) where x1, x2, ... are the number of moles of each alkyl (or alkoxy) sulfate anionic surfactant in the mixture, and the degree of alkoxylation is the number of alkoxy groups in each alkyl sulfate anionic surfactant.

[0052] If used, the preferred alkyl alkoxy sulfates are alkyl ethoxy sulfates.

[0053] Non-alkoxylated alkyl sulfate surfactants can be formed using naturally occurring alkyl chains, such as those derived from palm oil or coconut oil. Non-alkoxylated alkyl sulfate surfactants have also been found to be more easily biodegradable by microorganisms in soil and natural water. However, such naturally occurring alkyl chains are typically completely linear, resulting in completely linear non-alkoxylated alkyl sulfate surfactants. Liquid detergent compositions containing linear alkyl sulfates typically require more solvent to achieve the desired viscosity profile, providing the desired low-temperature phase stability and facilitating user administration. Increasing the amount of solvent also results in an environmentally unsustainable composition.

[0054] Suitable counterions include alkali metal cations, alkaline earth metal cations, alkanolammonium or ammonium or substituted ammonium, preferably sodium, as the use of alkanolammonium or ammonium or substituted ammonium may cause discoloration of the composition.

[0055] Suitable examples of commercially available alkyl sulfate anionic surfactants include those derived from alcohols sold by Shell under the trade name Neodol® or by Sasol under the trade names Lial®, Isalchem®, and Safol®, or some of the natural alcohols manufactured by Procter & Gamble Chemicals. Based on the relative fractions of C13 and C12 in the starting alcohol, obtained from the technical data sheet from the supplier or by analysis using methods known in the art, alcohols can be blended to achieve the desired mole fractions of C12 and C13 chains and the desired C13 / C12 ratio.

[0056] Performance, including grease cleaning, foaming, low temperature stability, and viscosity of the final product, can be affected by the breadth of the alkoxylation distribution of the alkoxylated alkyl sulfate anionic surfactant. The alkoxylation distribution, including its breadth, can be varied through the selection of catalysts and process conditions when making the alkoxylated alkyl sulfate anionic surfactant.

[0057] Without being bound by theory, when ethoxylated alkyl sulfates are present, the amount of 1,4-dioxane by-product in the alkoxylated, especially ethoxylated alkyl sulfates, can be reduced by strictly controlling the process conditions and raw material composition during both the alkoxylation, especially ethoxylation, and sulfation steps. Based on recent technological advances, further reduction of 1,4-dioxane by-products can be achieved by subsequent stripping, distillation, solvent evaporation, centrifugation, microwave irradiation, molecular sieving, or catalytic or enzymatic decomposition steps. Methods for controlling the 1,4-dioxane content in alkoxylated / ethoxylated alkyl sulfates are widely known in the art. Alternatively, the control of 1,4-dioxane levels in detergent formulations by adding 1,4-dioxane inhibitors such as 5,6-dihydro-3-(4-morpholinyl)-1-[4-(2-oxo-1-piperidinyl)-phenyl]-2-(1-H)-pyridone, the 3-alpha-hydroxy-7-oxo stereoisomeric mixture of cholanic acid, 3-(N-methylamino)-L-alanine, and mixtures thereof to formulations containing 1,4-dioxane has also been described in the art.

[0058] Additional anionic surfactants The anionic surfactant can include additional anionic surfactants such as those selected from the group consisting of alkyl(benzene)sulfonate surfactants, alkyl sulfosuccinate and dialkyl sulfosuccinate ester surfactants, and mixtures thereof.

[0059] Anionic alkyl sulfonate or sulfonic acid surfactants suitable for use herein include alkyl benzene sulfonates, alkyl ester sulfonates, primary and secondary alkane sulfonates (such as paraffin sulfonates), alpha or internal olefin sulfonates, alkyl sulfonated (poly)carboxylic acids, and mixtures thereof, in acid and salt form. Suitable anionic sulfonate or sulfonic acid surfactants include C5-C20 alkyl benzene sulfonates, more preferably C10-C16 alkyl benzene sulfonates, more preferably C11-C13 alkyl benzene sulfonates, C5-C20 alkyl ester sulfonates, especially C5-C20 methyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C5-C20 sulfonated (poly)carboxylic acids, and any mixtures thereof, but preferably C11-C13 alkyl benzene sulfonates. The surfactants can vary widely in their 2-phenyl isomer content. Compared to the sulfonation of alpha olefins, the sulfonation of internal olefins can occur at any position due to randomly positioned double bonds, resulting in a variety of twin-tail branched structures due to the hydrophilic sulfonate and hydroxyl groups of IOS being located in the middle of the alkyl chain. Alkanesulfonates include paraffin sulfonates and other secondary alkanesulfonates (such as Hostapur SAS60 from Clariant).

[0060] Alkyl sulfosuccinate and dialkyl sulfosuccinate esters are organic compounds having the formula MO3SCH(CO2R')CH2CO2R, where R and R' can be H or alkyl groups, and M is a counterion such as sodium (Na). The alkyl sulfosuccinate and dialkyl sulfosuccinate ester surfactants can be alkoxylated or non-alkoxylated, preferably non-alkoxylated. The surfactant system can contain additional anionic surfactants. However, the composition preferably contains less than 30% by weight, preferably less than 15% by weight, and more preferably less than 10% by weight of the surfactant system of additional anionic surfactants. Most preferably, the surfactant system does not contain additional anionic surfactants, preferably no anionic surfactants other than alkyl sulfate anionic surfactants and acyltaurate anionic surfactants.

[0061] Co-surfactant To improve surfactant loading after dilution and therefore improve lather persistence, the surfactant system may include a co-surfactant selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.

[0062] The weight ratio of the anionic surfactant to the co-surfactant may be from 1:1 to 8:1, preferably from 2:1 to 5:1, more preferably from 2.5:1 to 4:1.

[0063] The composition preferably comprises from 0.1% to 20%, more preferably from 0.5% to 15%, especially from 2% to 10% of a co-surfactant by weight of the cleaning composition.

[0064] The surfactant system of the cleaning composition of the present invention preferably comprises up to 50% co-surfactant by weight of the surfactant system, preferably from 10% to 40%, more preferably from 15% to 35%.

[0065] The co-surfactant is preferably an amphoteric surfactant, more preferably an amine oxide surfactant.

[0066] Amine oxide surfactants may be linear or branched, with linear being preferred. Suitable linear amine oxides are typically water-soluble and characterized by the formula R1-N(R2)(R3)O. R1 is a C8-18 alkyl, and R1 is preferably a linear alkyl chain, more preferably derived from a natural renewable source such as coconut or palm kernel, with coconut being particularly preferred. The R2 and R3 moieties are selected from the group consisting of C1-3 alkyl groups, C1-3 hydroxyalkyl groups, and mixtures thereof. For example, R2 and R3 can be selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl, and mixtures thereof, with one or both of R2 and R3 preferably being methyl. Linear amine oxide surfactants can include linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxyethyl dihydroxyethyl amine oxides, among others.

[0067] Preferably, the amine oxide surfactant is selected from the group consisting of alkyl dimethyl amine oxide, alkyl amidopropyl dimethyl amine oxide, and mixtures thereof. Alkyl dimethyl amine oxides such as C8-18 alkyl dimethyl amine oxide or C10-16 alkyl dimethyl amine oxide (e.g., cocodimethyl amine oxide) are particularly preferred. Suitable alkyl dimethyl amine oxides include C10 alkyl dimethyl amine oxide surfactants, C10-12 alkyl dimethyl amine oxide surfactants, C12-C14 alkyl dimethyl amine oxide surfactants, and mixtures thereof. C12-C14 alkyl dimethyl amine oxides are particularly preferred.

[0068] Alternative suitable amine oxide surfactants include mid-branched amine oxide surfactants. As used herein, "mid-branched" means that the amine oxide has one alkyl moiety with n1 carbon atoms, and one alkyl branch in the alkyl moiety has n2 carbon atoms. The alkyl branch is located on the alpha carbon from the nitrogen on the alkyl moiety. This type of branching of amine oxides is also known in the art as internal amine oxides. The sum of n1 and n2 may be 10 to 24, preferably 12 to 20, and more preferably 10 to 16 carbon atoms. The number of carbon atoms in one alkyl moiety (n1) is preferably the same as or similar to the number of carbon atoms in one alkyl branch (n2), thereby making the one alkyl moiety and the one alkyl branch symmetrical. As used herein, "symmetrical" means that in at least 50% by weight, more preferably at least 75% to 100% by weight of the mid-branched amine oxides used herein, |n1-n2| is 5 or less, preferably 4, and most preferably 0 to 4 carbon atoms. The amine oxide further comprises two moieties independently selected from a C1-3 alkyl, a C1-3 hydroxyalkyl group, or a polyethylene oxide group containing an average of about 1 to about 3 ethylene oxide groups. Preferably, these two moieties are selected from a C1-3 alkyl, and more preferably, both are selected as a C1 alkyl.

[0069] Alternatively, the amine oxide surfactant may be a mixture of amine oxides, including a mixture of low cut and mid cut amine oxides. Thus, the amine oxide of the composition of the present invention may be: a) about 10% to about 45% by weight of the amine oxide of a low cut amine oxide of the formula R1R2R3AO, wherein R1 and R2 are independently selected from hydrogen, C1-C4 alkyl, or mixtures thereof, and R3 is selected from C10 alkyl and mixtures thereof; b) 55% to 90% by weight of the amine oxide, a mid-cut amine oxide of formula R4R5R6AO, where R4 and R5 are independently selected from hydrogen, C1-C4 alkyl, or a mixture thereof, and R6 is selected from C12-C16 alkyl, or a mixture thereof.

[0070] In preferred low-cut amine oxides for use herein, R3 is n-decyl, and preferably both R1 and R2 are methyl. In mid-cut amine oxides of formula R4R5R6AO, preferably both R4 and R5 are methyl.

[0071] Preferably, the amine oxide comprises less than about 5% by weight of the amine oxide, more preferably less than 3% by weight of the amine oxide of formula R7R8R9AO, where R7 and R8 are selected from hydrogen, C1-C4 alkyl and mixtures thereof, and R9 is selected from C8 alkyl and mixtures thereof. By limiting the amount of amine oxide of formula R7R8R9AO, both physical stability and foam persistence are improved.

[0072] Suitable zwitterionic surfactants include betaine surfactants, including alkyl betaines, alkylamido betaines, amidoazolinium betaines, sulfobetaines (INCI sultaines), phosphobetaines, and mixtures thereof, preferably represented by formula (I): R 1 -[CO-X(CH2) n ] x -N + (R 2 )(R3)-(CH2) m -[CH(OH)-CH2] y -Y - Fulfilling In formula (I), R1 is selected from the group consisting of saturated or unsaturated C6-22 alkyl residues, preferably C8-18 alkyl residues, more preferably saturated C10-16 alkyl residues, and most preferably saturated C12-14 alkyl residues, and R1 is preferably a straight alkyl chain, preferably derived from a natural renewable source such as coconut or palm kernel, preferably coconut. X is selected from the group consisting of NH, NR4 (wherein R4 is a C1-4 alkyl residue), O, and S; n is an integer of 1 to 10, preferably 2 to 5, and more preferably 3; x is 0 or 1, preferably 1; R2 and R3 are independently selected from the group consisting of C1-4 alkyl residues, substituted hydroxy such as hydroxyethyl, and mixtures thereof, preferably both R2 and R3 are methyl; m is an integer from 1 to 4, preferably 1, 2, or 3; y is 0 or 1, Y is selected from the group consisting of COO, SO3, OPO(OR5)O, or P(O)(OR5)O, where R5 is H or a C1-4 alkyl residue.

[0073] Preferred betaines are the alkyl betaines of formula (Ia), the alkylamidopropyl betaines of formula (Ib), the sulfobetaines of formula (Ic), and the amidosulfobetaines of formula (Id): R 1 -N + (CH3)2-CH2COO - (IIa) R 1 -CO-NH-(CH2)3-N + (CH3)2-CH2COO - (IIb) R 1 -N + (CH3)2-CH2CH(OH)CH2SO3 - (IIc) R 1 -CO-NH-(CH2)3-N + (CH3)2-CH2CH(OH)CH2SO3 - (IId) and In the formula, R1 has the same meaning as in formula (I). Particularly preferred are carbobetaines of formula (Ia) and (Ib) [i.e., in formula (I), Y- is COO-], and more preferred are alkylamidobetaines of formula (Ib).

[0074] Suitable betaines may be selected from the group consisting of capryl / capramidopropyl betaine, cetyl betaine, cetylamidopropyl betaine, cocamidoethyl betaine, cocamidopropyl betaine, coco betaine, decyl betaine, decylamidopropyl betaine, hydrogenated tallow betaine / amidopropyl betaine, isostearamidopropyl betaine, lauramidopropyl betaine, lauryl betaine, myristylamidopropyl betaine, myristyl betaine, oleadopropyl betaine, oleyl betaine, palmamidopropyl betaine, palmitamidopropyl betaine, palm kernelamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, tallowamidopropyl betaine, tallow betaine, undecylenamidopropyl betaine, undecyl betaine, and mixtures thereof [or named according to INCI]. Preferred betaines are selected from the group consisting of cocamidopropyl betaine, cocobetaine, lauramidopropyl betaine, lauryl betaine, myristyl amidopropyl betaine, myristyl betaine, and mixtures thereof, with cocamidopropyl betaine and / or lauryl amidopropyl betaine being particularly preferred.

[0075] Nonionic surfactants The surfactant system may further comprise a nonionic surfactant. Suitable nonionic surfactants include alkoxylated alcohol nonionic surfactants, alkyl polyglucoside nonionic surfactants, and mixtures thereof. When the nonionic surfactant comprises a blend of alkyl polyglucoside and alkoxylated alcohol nonionic surfactant, the nonionic surfactant may comprise the alkyl polyglucoside and the alkoxylated alcohol nonionic surfactant in a weight ratio of 10:90 to 90:10, preferably 30:70 to 70:30, and more preferably 40:60 to 60:40.

[0076] The surfactant system of the compositions of the present invention may further comprise from 1.0% to 50%, preferably from 1.25% to 25%, more preferably from 1.5% to 15%, and most preferably from 1.5% to 5% by weight of the surfactant system of a nonionic surfactant.

[0077] Alkoxylated Alcohol Nonionic Surfactants Preferably, the alkoxylated alcohol nonionic surfactant is a linear or branched primary or secondary alkyl alkoxylated nonionic surfactant, preferably an alkyl ethoxylated nonionic surfactant, preferably containing an average of 9 to 15, preferably 10 to 14 carbon atoms in the alkyl chain and an average of 5 to 12, preferably 6 to 10, most preferably 7 to 8, units of ethylene oxide per mole of alcohol. The alkyl chain is preferably linear.

[0078] Suitable examples of commercially available alkoxylated alcohol nonionic surfactants include those derived from alcohols sold by Shell under the trade name Neodol®, or by Sasol under the trade names Lial®, Isalchem®, and Safol®, or some of the natural alcohols produced by Procter & Gamble Chemicals. The performance can be affected by the breadth of the alkoxylation distribution of the alkoxylated alcohol nonionic surfactant. The alkoxylation distribution, including its breadth, can be varied by the selection of catalysts and process conditions when making the alkoxylated alcohol nonionic surfactant.

[0079] Alkyl polyglucoside nonionic surfactants: Alkyl polyglucoside nonionic surfactants typically lather more than other nonionic surfactants such as alkyl ethoxylated alcohols.

[0080] The combination of alkyl polyglucosides with anionic surfactants (especially mixtures of alkyl sulfate and alkyl alkanolamide sulfate anionic surfactants) has been found to improve removal of polymerized grease, foam persistence, reduced viscosity change with surfactant and / or system changes, and more persistent Newtonian rheology.

[0081] The alkyl polyglucoside surfactant can be selected from C6 to C18 alkyl polyglucoside surfactants. The alkyl polyglucoside surfactant can have a number average degree of polymerization of 0.1 to 3.0, preferably 1.0 to 2.0, and more preferably 1.2 to 1.6. The alkyl polyglucoside surfactant can include a blend of short-chain alkyl polyglucoside surfactants having alkyl chains containing 10 or fewer carbon atoms and medium- to long-chain alkyl polyglucoside surfactants having alkyl chains containing more than 10 carbon atoms to 18 carbon atoms, preferably 12 to 14 carbon atoms. The alkyl chains are preferably linear.

[0082] Short-chain alkyl polyglucoside surfactants have a unimodal chain length distribution of C8 to C10, medium- to long-chain alkyl polyglucoside surfactants have a unimodal chain length distribution of C10 to C18, while medium-chain alkyl polyglucoside surfactants have a unimodal chain length distribution of C12 to C14. In contrast, C8 to C18 alkyl polyglucoside surfactants typically have a unimodal distribution of C8 to C18 alkyl chains, such as C8 to C16. Thus, a combination of a short-chain alkyl polyglucoside surfactant with a medium- to long-chain or medium-chain alkyl polyglucoside surfactant will have a broader chain length distribution, or even a bimodal distribution, than the unblended C8 to C18 alkyl polyglucoside surfactant. Preferably, the weight ratio of the short-chain alkyl polyglucoside surfactant to the long-chain alkyl polyglucoside surfactant is from 1:1 to 10:1, preferably from 1.5:1 to 5:1, more preferably from 2:1 to 4:1. Such a blend of short-chain alkyl polyglucoside surfactant and long-chain alkyl polyglucoside surfactant results in faster dissolution of the detergent solution in water and improved initial foaming combined with improved foam stability.

[0083] C8-C16 alkyl polyglucosides are commercially available from several sources (e.g., Simusol® surfactants from Seppic Corporation, and Glucopon® 600 CSUP, Glucopon® 650 EC, Glucopon® 600 CSUP / MB, and Glucopon® 650 EC / MB from BASF Corporation). Glucopon® 215UP is a preferred short-chain APG surfactant. Glucopon® 600CSUP is a preferred medium- to long-chain APG surfactant.

[0084] In preferred compositions, the surfactant system may comprise an alkyl sulfate anionic surfactant, an acyltaurate anionic surfactant having an average degree of branching of less than 10%, and an alkyl polyglucoside nonionic surfactant.

[0085] Further ingredients The present cleaning compositions may optionally contain many other adjunct ingredients such as builders (preferably citrates), chelating agents, conditioning polymers, other cleaning polymers, surface modifying polymers, structuring agents, emollients, humectants, skin rejuvenating actives, enzymes, carboxylic acids, scrubbing particles, fragrances, malodor control agents, pigments, dyes, opacifiers, pearlescent particles, inorganic cations such as alkaline earth metals such as Ca / Mg ions, antimicrobial agents, preservatives, viscosity modifiers (e.g., salts such as NaCl and other mono-, di-, and trivalent salts), and pH adjusters and buffering means (e.g., carboxylic acids such as citric acid, HCl, NaOH, KOH, alkanolamines, carbonates such as sodium carbonate, bicarbonates, sesquicarbonates, etc.).

[0086] Preferred additional ingredients include those selected from amphiphilic alkoxylated polyalkyleneimines, cyclic polyamines, triblock copolymers, hydroxypropyl cellulose polymers, salts, hydrotropes, organic solvents, and mixtures thereof.

[0087] Amphiphilic alkoxylated polyalkyleneimines: The compositions of the present invention may further comprise 0.05% to 2%, preferably 0.07% to 1% by weight of the total composition, of an amphiphilic polymer. Suitable amphiphilic polymers may be selected from the group consisting of amphiphilic alkoxylated polyalkyleneimines and mixtures thereof. Amphiphilic alkoxylated polyalkyleneimine polymers have been found to reduce gel formation on hard surfaces being cleaned when the liquid composition is added directly to a cleaning implement (such as a sponge) prior to cleaning and then contacted with a heavily oily surface, particularly when the cleaning implement contains little to no water, for example, when a lightly pre-moistened sponge is used.

[0088] Preferred amphiphilic alkoxylated polyethyleneimine polymers have the formula (I):

[0089] [ka] having the general structure wherein the polyethyleneimine backbone has a weight-average molecular weight of 600, n in formula (I) is an average of 10, m in formula (I) is an average of 7, and R in formula (I) is selected from hydrogen, C1-C4 alkyl, and mixtures thereof, preferably hydrogen. The degree of permanent quaternization in formula (I) may be 0% to 22% of the nitrogen atoms in the polyethyleneimine backbone. The molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer is preferably 10,000 to 15,000 Da.

[0090] More preferably, the amphiphilic alkoxylated polyethyleneimine polymer has the general structure of formula (I), except that the polyethyleneimine backbone has a weight-average molecular weight of 600 Da, n in formula (I) averages 24, m in formula (I) averages 16, and R in formula (I) is selected from hydrogen, C1-C4 alkyl, and mixtures thereof, preferably hydrogen. The degree of permanent quaternization of formula (I) may be 0% to 22% of the nitrogen atoms of the polyethyleneimine backbone, preferably 0%. The molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer is preferably 25,000 to 30,000, most preferably 28,000 Da.

[0091] Amphiphilic alkoxylated polyethyleneimine polymers can be made by the methods described in more detail in WO 2007 / 135645.

[0092] Alternatively, the composition may not include an amphiphilic polymer.

[0093] cyclic polyamines The composition may include a cyclic polyamine having an amine functionality to aid in cleaning. The composition of the present invention preferably comprises 0.1 to 3% by weight of the total composition of cyclic polyamine, more preferably 0.2 to 2%, especially 0.5 to 1%.

[0094] Cyclic polyamines have at least two primary amine functional groups. The primary amine may be located at any position within the cyclic amine, but it has been found that better performance is obtained from the viewpoint of grease cleaning when the primary amine is located at the 1- and 3-positions. It has also been found that cyclic amines in which one of the substituents is -CH3 and the remaining is H provide improved grease cleaning performance.

[0095] Thus, the most preferred cyclic polyamines for use in the cleaning compositions of the present invention are those selected from the group consisting of 2-methylcyclohexane-1,3-diamine, 4-methylcyclohexane-1,3-diamine, and mixtures thereof. These particular cyclic polyamines, when combined with the surfactant system of the compositions of the present invention, function to improve the foam and grease cleaning profile throughout the dishwashing process.

[0096] Suitable cyclic polyamines may be supplied by BASF under the trade name Baxxodur, with Baxxodur ECX-210 being particularly preferred.

[0097] A combination of a cyclic polyamine and magnesium sulfate is particularly preferred. Thus, the composition may further comprise magnesium sulfate at a concentration of 0.001% to 2.0% by weight of the composition, preferably 0.005% to 1.0% by weight, and more preferably 0.01% to 0.5% by weight.

[0098] triblock copolymer The compositions of the present invention can include a triblock copolymer. The triblock copolymer can be present at a level of 1% to 20%, preferably 3% to 15%, and more preferably 5% to 12% by weight of the total composition. Suitable triblock copolymers include alkylene oxide triblock copolymers, defined as triblock copolymers having alkylene oxide moieties according to formula (I): (EO)x(PO)y(EO)x, where EO represents ethylene oxide and each x represents the number of EO units in the EO block. Each x can independently average 5 to 50, preferably 10 to 40, and more preferably 10 to 30. Preferably, x is the same for both EO blocks, and "same" means that the difference in x between the two EO blocks is within a maximum of 2 units, preferably within a maximum of 1 unit, and more preferably both x's are the same number of units. PO represents propylene oxide and y represents the number of PO units in the PO block. The y's can be set to 28 to 60, preferably 30 to 55, and more preferably 30 to 48 on average.

[0099] Preferably, the ratio of y to each x in the triblock copolymer is 3:1 to 2:1. The ratio of y to the average x of the two EO blocks in the triblock copolymer is preferably 3:1 to 2:1. Preferably, the triblock copolymer has an average weight percentage of total EO that is 30% to 50% by weight of the triblock copolymer. Preferably, the triblock copolymer has an average weight percentage of total PO that is 50% to 70% by weight of the triblock copolymer. It is understood that the average total weight percentages of EO and PO for a triblock copolymer add up to 100%. The triblock copolymer can have an average molecular weight of 2060 to 7880, preferably 2620 to 6710, more preferably 2620 to 5430, and most preferably 2800 to 4700. The average molecular weight is determined using 1H NMR spectroscopy (see Thermo Scientific Application Note No. AN52907).

[0100] Triblock copolymers have the basic structure ABA, where A and B are different homopolymer and / or monomer units. In this case, A is ethylene oxide (EO) and B is propylene oxide (PO). Those skilled in the art will recognize that the term "block copolymer" is synonymous with this definition of "block polymer."

[0101] Triblock copolymers according to formula (I) having specific EO / PO / EO configurations and respective homopolymer lengths have been found to enhance the foam persistence performance of liquid hand dishwashing detergent compositions in the presence of greasy soils and / or foam consistency throughout dilution in the cleaning process.

[0102] Suitable EO-PO-EO triblock copolymers are commercially available from BASF, e.g., under the Pluronic® PE series, and from Dow Chemical Company, e.g., under the Tergitol® L series. Particularly preferred triblock copolymers from BASF are sold under the trade names Pluronic® PE6400 (MW about 2900, about 40 wt. % EO) and Pluronic® PE9400 (MW about 4600, 40 wt. % EO). Particularly preferred triblock copolymers from Dow Chemical Company are sold under the trade name Tergitol® L64 (MW about 2700, about 40 wt. % EO).

[0103] Preferred triblock copolymers are readily biodegradable under aerobic conditions.

[0104] salt: The composition of the present invention may contain, based on the weight of the total composition, about 0.05% by weight to about 2% by weight, preferably about 0.1% by weight to about 1.5% by weight, or more preferably about 0.5% by weight to about 1% by weight of a salt, preferably a monovalent or divalent inorganic salt, or a mixture thereof, more preferably a salt selected from sodium chloride, sodium sulfate, and a mixture thereof. Sodium chloride is most preferred.

[0105] Hydrotropes: The compositions of the present invention may comprise from about 0.1% to about 10%, or preferably from about 0.5% to about 10%, or more preferably from about 1% to about 10% by weight of a hydrotope or mixture thereof, preferably sodium cumene sulfonate, based on the weight of the total composition.

[0106] Organic solvents: The composition may contain about 0.1% to about 10% by weight of an organic solvent, based on the weight of the total composition, or preferably about 0.5% to about 10% by weight, or more preferably about 1% to about 10% by weight. Suitable organic solvents include those selected from the group consisting of alcohols, glycols, glycol ethers, and mixtures thereof, preferably alcohols, glycols, and mixtures thereof. Ethanol is a preferred alcohol. Polyalkylene glycols, particularly polypropylene glycols, are preferred glycols, with polypropylene glycols having a weight-average molecular weight of 750 Da to 1,400 Da being particularly preferred.

[0107] Packaged Products The hand dishwashing detergent composition can be packaged in a container, typically a plastic container. A suitable container includes an orifice. Typically, the container has a cap, and the orifice is typically provided on the cap. The cap can have an injection port, and the orifice is at the outlet of the injection port. The injection port can have a length of 0.5 mm to 10 mm.

[0108] The orifice is 3mm at the outlet. 2 ~20mm 2 , preferably 3.8 mm 2 ~12mm 2 , more preferably 5 mm 2 ~10mm 2 and the container further comprises a composition according to the present invention, the cross-sectional area being measured perpendicular to the liquid outlet from the container (i.e. perpendicular to the liquid flow during dispensing).

[0109] The container can typically contain 200 mL to 5,000 mL, preferably 350 mL to 2,000 mL, and more preferably 400 mL to 1,000 mL of the liquid hand dishwashing detergent composition.

[0110] Alternatively, the hand dishwashing detergent composition can be packaged in an inverted container. Such an inverted container typically includes a cap at the bottom of the container, the cap including either a lid or a self-sealing valve, or a combination thereof. Preferably, the cap includes a self-sealing valve. Suitable self-sealing valves include slit valves. The self-sealing valve defines an orifice that recoils open when pressure applied inside the valve exceeds pressure applied outside the valve. The bottom-shaped pouring container can include an impact-resistant system such as that described in WO2019108293A1.

[0111] Cleaning method The present invention is further directed to a method of manually washing dishware with the composition of the present invention, comprising the steps of dispensing the composition of the present invention into a volume of water to form a wash solution and immersing dishware in the solution, wherein the dishware is washed with the composition in the presence of water.

[0112] Optionally, the dishware may be rinsed. As used herein, "rinsing" refers to contacting the dishware washed by the method of the present invention with a substantial amount of a suitable solvent, typically water. "Substantial amount" typically refers to about 1 to about 20 L or under running water.

[0113] The compositions herein can be applied in their diluted form. Soiled dishware is contacted with an effective amount, typically about 0.5 mL to about 20 mL, preferably about 3 mL to about 10 mL (per about 25 dishes to be treated), of a detergent composition of the present invention diluted with water, preferably in liquid form. The actual amount of cleaning composition used is at the discretion of the user and typically depends on factors such as the specific product formulation of the cleaning composition, including the concentration of active ingredients in the cleaning composition, the number of soiled dishes to be cleaned, and the degree of soiling of the dishes. Generally, about 0.01 mL to about 150 mL, preferably about 3 mL to about 40 mL, of the cleaning composition of the present invention is combined with about 2,000 mL to about 20,000 mL, more typically about 5,000 mL to about 15,000 mL, of water in a sink. The soiled dishware is then immersed in the sink containing the diluted cleaning composition, and the soiled surface of the dishware is then contacted with a cloth, sponge, or similar cleaning implement. The cloth, sponge, or similar cleaning implement may be immersed in the cleaning composition and water mixture before contacting the dishware, typically for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user. Contacting the cloth, sponge, or similar cleaning implement with the dishware involves simultaneously scrubbing the dishware.

[0114] Alternatively, the compositions herein can be applied in their undiluted form to the utensils to be treated. As used herein, "in their undiluted form" means that the composition is applied directly to the surface to be treated or to a cleaning device or implement, such as a brush, sponge, nonwoven material, or woven material, without any significant dilution by the user immediately prior to application. "In their undiluted form" also includes slight dilution, for example, due to the presence of water on the surface of the cleaning device, or the addition of water by the consumer to remove residual amounts of the composition from a bottle. Thus, the undiluted form of the composition includes a mixture of the composition and water in a ratio ranging from 50:50 to 100:0, preferably 70:30 to 100:0, more preferably 80:20 to 100:0, and even more preferably 90:10 to 100:0, depending on the user's habits and cleaning tasks.

[0115] Another aspect of the present invention relates to the use of the liquid hand dishwashing cleaning compositions described herein to provide a good sudsing profile, including foam stabilization in the presence of soils, particularly greasy particulate soils, and good cleaning, while providing good low temperature stability, in a high bio-based surfactant content and biodegradability profile.

[0116] Methods for producing alkyl alkanolamide sulfate anionic surfactants and concentrate blends containing them The alkyl alkanolamide sulfate anionic surfactant can be prepared using any suitable method, for example, by reacting at least one alkyl alkanolamide sulfate compound of formula (II): R(CO)NXR'OH (II) a non-ionic stream comprising an alkyl alkanolamide of R, X, R' are as defined for formula (I).

[0117] The non-ionic stream forms the feedstock for a sulfation step, which produces a sulfuric acid stream containing at least one alkyl alkanolamide sulfate. In the sulfation step, the non-ionic stream feedstock containing at least one alkyl alkanolamide sulfate is sulfated to produce a sulfuric acid stream containing at least one alkyl alkanolamide sulfate. Sulfation involves the formation of a carbon-oxygen-sulfur bond. The resulting acid form of the alkyl alkanolamide sulfate is not hydrolytically stable. Unless neutralized, it decomposes to form sulfuric acid and other chemicals.

[0118] Similar methods for the sulfation of alcohols or alkoxylated alcohols to (alkoxylated) alkyl sulfates have been widely described. Further details of such sulfation processes are found in "Sulf(on)ation Technology in the Detergent Industry" (W. Herman de Groot, Springer-Science+Business Media, BV, 1991, ISBN 978-90-481-4088-6).

[0119] While various reagents can be used for the sulfation step, sulfur trioxide (SO3) is particularly preferred, at least in part due to its low cost. SO3 is an electrophilic reagent that reacts rapidly with any organic compound containing an electron-donating group. The resulting reaction is highly exothermic. Effective cooling of the reactants is essential because high temperatures promote side reactions that generate undesirable by-products. Precise control of the molar ratio of SO3 to alkyl alkanolamide (and alkyl alcohol, if present) is also essential, as excess SO3 contributes to side reactions and by-product formation due to its reactivity. Therefore, commercial-scale sulfation reactions require specialized equipment and instrumentation to tightly control the molar ratio of SO3 to alkyl alkanolamide (and alkyl alcohol, if present) and allow for rapid removal of the heat of reaction.

[0120] The problem of SO3 reactivity has typically been solved by diluting and / or complexing the SO3 to mitigate the reaction rate. Commercially available diluents or complexing agents include ammonia (sulfamic acid), hydrochloric acid (chlorosulfonic acid), and dry air (air / SO3 membrane sulfation). Using control of the ratio of SO3 to alkyl alkanolamide (and alkyl alcohol, if present), improved product quality can be achieved with the use of any of these reagents.

[0121] Air / SO3 membrane sulfation processes are typically carried out using membrane reactors, such as annular falling film reactors, such as a "Chemithon" reactor, or multi-tubular membrane reactors, such as a "Ballestra" reactor. In such processes, SO3 is first diluted with dry air. Such air / SO3 sulfation processes are direct processes in which SO3 gas is diluted with very dry air and reacted directly with the feedstock. The reaction of gaseous SO3 with alkyl alkanolamide (and alkyl alcohol, if present) is rapid and stoichiometric. Such processes are complicated by the possibility of side reactions; however, with strict process control, very high purity sulfate surfactants can be achieved.

[0122] In the air / SO3 membrane sulfation process, the sulfation step is typically carried out in a liquid-gas interfacial reactor, preferably a falling film reactor. Suitable falling film reactors include annular gap falling film ("Chemithon") reactors, (multi)tubular ("Ballestra") reactors, and the like.

[0123] The alkyl alkanolamide (and alkyl alcohol, if present) is converted to sulfuric acid via reaction with SO3 in a falling film reactor. Given the exothermic nature of the sulfonation reaction, cooling is again required after separating the air / gas from the liquid stream. Ideally, the reaction mixture is maintained at a temperature of 15°C to 50°C, preferably 30°C to 40°C, at the reactor outlet.

[0124] If necessary, a degassing step can be carried out.

[0125] The non-ionic stream fed to the sulfation reaction preferably contains less than 0.1%, preferably less than 0.05% water, and more preferably is free of water.

[0126] The nonionic stream further comprises at least one alkyl alcohol and / or at least one alkoxylated alkyl alcohol, and therefore the nonionic stream comprises at least one alkyl alcohol and / or at least one alkoxylated alkyl alcohol and at least one alkyl alkanolamide of formula (II). Using such a method, a concentrated surfactant blend can be produced, the concentrated surfactant blend comprising an alkyl sulfate anionic surfactant and an alkyl alkanolamide sulfate anionic surfactant of formula (I). The at least one alkyl alcohol has an average degree of alkoxylation of less than 0.1, and is preferably not alkoxylated.

[0127] During a subsequent sulfation step, the at least one alkyl alcohol and / or at least one alkoxylated alkyl alcohol and at least one alkyl alkanolamide of formula (II) in the nonionic stream are sulfated to form a sulfuric acid stream comprising at least one alkyl sulfuric acid and / or at least one alkoxylated alkyl sulfuric acid and at least one alkyl alkanolamide sulfuric acid. The sulfuric acid stream is then combined with a neutralization stream in a neutralization step to neutralize the at least one alkyl sulfuric acid and / or at least one alkoxylated alkyl sulfuric acid and at least one alkyl alkanolamide sulfuric acid.

[0128] The neutralizing agent in the neutralization stream may be an alkali metal hydroxide or ammonium hydroxide, ethanolamine, or isopropanolamine, more preferably sodium hydroxide, potassium hydroxide, magnesium hydroxide, or ethanolamine, and most preferably sodium hydroxide.

[0129] A buffering surfactant may be added before or during the neutralization step to provide a sulfated anionic surfactant that is more stable to hydrolysis. Such sulfated anionic surfactants can be maintained at a lower pH. Suitable buffering surfactants are amphoteric surfactants, zwitterionic surfactants, or mixtures thereof. Suitable buffering surfactants can be selected from the group consisting of amine oxide surfactants, betaine surfactants, and mixtures thereof, preferably amine oxide surfactants, more preferably C10-16 dimethylamine oxide surfactants. C12-14 dimethylamine oxide (lauryl dimethylamine oxide) is particularly preferred. Such buffering surfactants also contribute to the performance of the resulting liquid hand dishwashing detergent. In addition, the buffering surfactant results in the concentrated surfactant blend formed by the methods described herein having reduced viscosity, especially when an amine oxide surfactant is used as the buffering surfactant.

[0130] The buffer surfactant is preferably added as a separate buffer stream during the neutralization step, but is preferably added as part of the neutralization stream. Alternatively, the buffer surfactant can be added before the neutralization step. The alkyl alkanolamide sulfate (and, if present, the alkyl sulfate and / or alkoxylated alkyl sulfate) and the buffer surfactant can be combined in a weight ratio of the alkyl sulfate and / or alkoxylated alkyl sulfate and alkyl alkanolamide sulfate combination to the buffer surfactant of 10:1 to 1:1, preferably 8:1 to 2:1, and more preferably 6:1 to 3:1.

[0131] method Viscosity measurement Viscosity is measured using a controlled stress rheometer (such as Thermo Scientific's HAAKE MARS or equivalent) using a 60 mm 1° cone and a 52 micrometer gap size at 20° C. After 2 minutes of temperature equilibration, the sample is heated for 10 seconds. -1 The reported viscosity of the liquid hand dishwashing detergent composition is determined by shearing the average shear stress from 15 seconds to 30 seconds at 20°C for 10 seconds.-1 is defined as the shear rate at which the shear force is applied.

[0132] Foam persistence in the presence of greasy particulate soils The purpose of the foam persistence test is to compare the change in foam volume produced over time for different test agents at specified water hardness, solution temperature, and formulation concentration while under the influence of intermittent injections of greasy particulate soil. The data is compared and expressed as a foam persistence index relative to a reference composition (the reference composition has a foam persistence index of 100). The steps of the method are as follows: 1. 0.12% by weight of the test composition is dispensed into a stream of water with a water hardness of 2.67 mmol / L Ca equivalent (15 dH) and a temperature of 42°C at a flow rate of 0.67 mL / sec using a plastic pipette at a height of 37 cm above the bottom of a sink (dimensions: diameter 300 mm, height 288 mm), filling the sink to 4 L at a constant pressure of 4 bar. 2. Initial foam volume generated (measured as the average foam volume X above the liquid in the sink (cm 3 (represented by ) is recorded immediately after filling is completed. 3. Immediately pour a fixed amount of soil (6 mL) and one of the prescribed compositions below into the center of the sink. 4. Mix the resulting solution using a metal blade (10 cm x 5 cm) positioned at a 45° angle to the air-liquid interface in the center of the sink, rotating 20 times at 85 RPM. 5. Another measurement of the total lather volume is recorded immediately after the blade rotation has finished. 6. The measured total foam volume is 400 cm 3 Repeat steps 3-5 until you reach a level of 400cm 3 The amount of soil added required to reach a level of suds is considered the suds persistence of the test composition. 7. Each test composition is tested four times per test condition (i.e., water temperature, composition concentration, water hardness, soil type). 8. Calculate the average foam persistence as the average of four replicates per sample for the stated test conditions. 9. Compare the average persistence of the test composition samples to the reference composition samples and calculate the Lather Persistence Index. The calculation is as follows:

[0133]

number

[0134] The greasy particulate soil compositions used in the tests are prepared by standard mixing of the ingredients listed in Table 1.

[0135] [Table 1]

[0136] C) Grease cleaning The Grease Cleaning Performance Test Method is used to measure the relative grease removal efficacy of compositions at various dilution concentrations in water of a particular hardness and temperature (liquid detergent compositions at concentrations of 0.5%, 1.0%, 1.5%, 5.0%, and 10% by weight in water of hardness 0.356 mmol CaCO3 equivalent (2 dH), 2.67 mmol CaCO3 equivalent (15 dH), and 5.34 mmol CaCO3 equivalent (30 dH) and a temperature of 35°C) relative to a reference composition.

[0137] Homogenized lard (stain no. 44069, supplied by Warwick Equest Ltd. UK) is preheated to 50°C, mixed with purple dye to improve visibility, and held in an oven for 2 hours. A plastic syringe is then filled with 50 mL of the colored homogenized lard, ensuring there is no air in the syringe, and placed in a 60°C oven. The syringe is then left at 22°C for at least 24 hours to ensure the colored homogenized lard has solidified.

[0138] The colored homogenized lard is then heated to 55°C. Using a Liquidyn® P-Jet Series injection valve (product number 7825004, supplied by Nordson, Westlake, Ohio 44145-4551) with a valve pressure of 5 bar, a fluid pressure of 3 bar, and a valve open time of 2 minutes, the heated colored homogenized lard is injected onto three layers of juxtaposed polypropylene nonwoven substrate (14 cm x 9 cm, 60 g / m² sms nonwoven, manufactured by Avgol), and 96 circular stains (each 5 mm in diameter) are applied to the nonwoven to create stain circles approximately 5 mm in diameter, each containing about 5 mg of colored homogenized lard. The stained fabric is then dried at 21°C for 24 hours.

[0139] Fabric stains are then cut from the treated nonwoven fabric using a 5 mm diameter cutting die and a hydraulic ATOM1 press plate, and each cut fabric stain is then placed in the bottom of a well of a 96-well deep well microtiter plate (96-well plate, polystyrene, U-bottom, circular well shape, 1.1 mL, part number 391-0159, supplied by VWR).

[0140] Stain intensity is measured before and after treatment by imaging using a DigiEye® (supplied by Verivide UK, Z02791) equipped with a Nikon D7000 camera under D65 diffuse light, and the average grease stain intensity before and after washing is determined by converting the RGB values ​​to Lab measurements.

[0141] A cleaning solution is prepared with a target composition concentration, water hardness, and temperature.The cleaning solution is then dispensed into each well using a 96-channel pipetting head (950 μL of cleaning solution per well), and the contact time between the stained fabric and the cleaning solution is 10 minutes.The cleaning solution is then removed using a 96-channel pipetting head.Four rinse cycles are applied using a 96-channel pipetting head, each consisting of applying 950 μL of water with 0.356 mmol / L Ca calcium equivalent hardness and 35°C for 2 minutes, followed by removal of the rinse water using a pipetting head.The substrate is then dried at 30°C for 24 hours.

[0142] The stain intensity after treatment was then re-measured by imaging using a DigiEye® (supplied by Verivide UK, Z02791) and imaging software to determine the average grease stain intensity after washing.

[0143] The stain removal rate (SR%) is then calculated for each wash solution concentration as follows:

[0144]

number

[0145] The SR% is averaged for eight replicates for each test condition (cleaning concentration and water hardness) and plotted against the different cleaning concentrations. The resulting area under the curve is calculated and indexed against the area under the curve of the reference product. The SRI% index is calculated by comparing the area under the curve of the test composition to the area under the curve of the reference composition sample.

[0146]

number

[0147] The foam persistence and grease cleaning performance of compositions of the present invention containing an alkyl alkanolamide sulfate surfactant as part of the anionic surfactant were compared to comparative compositions containing only an alkyl sulfate anionic surfactant or an alkyl ethoxylated sulfate anionic surfactant as the anionic surfactant using the test methods described herein.

[0148] Lauryl (C12-C14) monoethanolamide sulfate was obtained by sulfation of lauryl monoethanolamide (CAS: 142-78-9). Lauryl monoisopropanolamide sulfate was obtained by sulfation of lauryl (C12-C14) monoisopropanolamide (CAS: 142-54-1). Alkyl sulfate anionic surfactants and ethoxylated alkyl sulfate anionic surfactants were obtained by sulfation of non-ethoxylated and ethoxylated alcohols, respectively. All sulfation reactions were performed in a pilot-scale sulfation unit.

[0149] The following inventive and comparative compositions were prepared by mixing the respective starting components, which in the inventive compositions contained a blend of linear alkyl alkanolamide sulfates in combination with branched alkyl sulfates as the anionic surfactant, and in the comparative examples contained a blend of linear ethoxylated sulfates or linear alkyl sulfates in combination with branched alkyl sulfates as the anionic surfactant.

[0150] [Table 2] * Comparative Example 1 C12-C13 branched alkyl sulfate anionic surfactant (54% branched) supplied by Procter & Gamble and derived from Safol® 23 alkyl alcohol supplied by Sasol 2 Tensagex® EOC970, supplied by KLK Tensachem 3 obtained by sulfation of lauryl (C12-C14) monoethanolamide (CAS: 142-78-9), sold under the trade name Ninol® LMP by Stepan 4 obtained by sulfation of lauryl (C12-C14) monoisopropanolamide (CAS: 142-54-1), sold under the trade name ColaMid® LMPA by Colonial Chemical. 5 Powered by Procter & Gamble 6 Polyethyleneimine supplied by BASF with a PEI backbone MW of 600 and 24 EO and 16 PO units per alkoxylated chain 7 Fragrances, dyes, preservatives

[0151] The foam persistence of the composition that comprises alkyl ethoxylated surfactants is increased, especially in the presence of greasy particulate soil, compared with the equivalent composition that all anionic surfactants are non-alkoxylated.In contrast, the removal of greasy soil is increased in the composition that comprises non-alkoxylated alkyl sulfate anionic surfactants, compared with the composition that comprises alkyl ethoxylated sulfate anionic surfactants.Therefore, the foam persistence of the composition of the present invention that comprises alkyl alkanolamide sulfate anionic surfactants is evaluated using the composition that comprises alkyl ethoxylated anionic surfactants as reference.

[0152] Because a linear (lauroyl) alkyl alkanolamide sulfate anionic surfactant was used in the compositions of the present invention, a C12-C14 linear alkyl ethoxylated alkyl sulfate anionic surfactant was used in the reference composition used to evaluate foam persistence.

[0153] Because the compositions of the present invention used linear (lauroyl) alkyl alkanolamide sulfate anionic surfactants, the reference composition used to evaluate grease cleaning contained a C12-C14 linear alkyl (non-ethoxylated) alkyl sulfate anionic surfactant.

[0154] The foam persistence index in hard water with a hardness of 2.67 mmol / L Ca equivalent (15 dH) was evaluated for both Inventive Examples 1 and 2 using Comparative Example A as a reference. The composition of Comparative Example A contained a combination of linear alkyl ethoxylated sulfate and branched alkyl sulfate anionic surfactants, with the concentration of the anionic surfactants being 2 wt % higher than that of Inventive Examples 1 and 2.

[0155] [Table 3]

[0156] The above results show that replacing the linear ethoxylated alkyl sulfate anionic surfactant with the alkyl alkanolamide sulfate anionic surfactant increased foam persistence in hard water, even when the linear ethoxylated alkyl sulfate anionic surfactant was replaced with a smaller amount of the alkyl alkanolamide sulfate anionic surfactant.

[0157] The grease cleaning performance of the compositions of Examples 1 and 2 of the present invention was evaluated using Comparative Example B (containing a linear non-ethoxylated alkyl sulfate anionic surfactant) as a reference.

[0158] [Table 4]

[0159] The above results show that replacing the linear alkyl sulfate with the alkyl alkanolamide sulfate anionic surfactant used in the present invention increased grease removal for all water hardness levels used.

[0160] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

Claims

1. 1. A liquid hand dishwashing detergent composition comprising from 5.0% to 50%, by weight of the composition, of a surfactant system, said surfactant system comprising an anionic surfactant, said anionic surfactant comprising: a. An alkyl alkanolamide sulfate anionic surfactant, said alkyl alkanolamide sulfate anionic surfactant having the formula: R(A)EER'O-O ３ － M ＋ (I), and During the ceremony, R is an alkyl chain containing, on average, 7 to 17 carbon atoms; R' is an alkyl chain containing, on average, 1 to 3 carbon atoms; X is H or C1-C3 alkyl; M ＋ is the counterion, an alkyl alkanolamide sulfate anionic surfactant; b. A liquid hand dish detergent composition comprising an alkyl sulfate anionic surfactant, wherein the alkyl sulfate anionic surfactant has an average degree of alkoxylation of less than 0.

1.

2. 2. The composition of claim 1, wherein the composition comprises from 6.0% to 40%, preferably from 15% to 35% by weight of the total composition of the surfactant system.

3. 3. A composition according to claim 1 or 2, wherein the surfactant system comprises at least 40% of said anionic surfactant by weight of the surfactant system, preferably from 60% to 90%, more preferably from 65% to 85%.

4. 4. The composition of any one of claims 1 to 3, wherein the anionic surfactant comprises at least 70%, more preferably at least 85%, and most preferably 100% of the alkyl sulfate anionic surfactant and the alkyl alkanolamide sulfate anionic surfactant by weight of the anionic surfactant.

5. In the alkyl alkanolamide sulfate anionic surfactant of formula (I), R is an alkyl chain containing, by number average, 9 to 13 carbon atoms, preferably 11 to 13 carbon atoms, most preferably R is a blend of C11 and C13 alkyl chains; R' is an alkyl chain containing, on average, 2 to 3 carbon atoms, and more preferably R' is -(CH ２ ) ２ -, -CH ２ CH (CH ３ ) -, -CH(CH ３ ) CH ２ - selected from the group consisting of X is H or C1 alkyl, preferably H or methyl; M ＋ is an alkali metal counterion or ammonium, ethanolamine, or isopropanolamine, more preferably Na ＋ , or K ＋ , Mg ２＋ , or ethanolamine, most preferably Na ＋ The composition according to any one of claims 1 to 4, wherein

6. 6. The composition of claim 5, wherein in the alkyl alkanolamide sulfate anionic surfactant, the alkyl chains R have a molar percentage of C11-C13 chains relative to total alkyl chains of at least 60%, preferably at least 70%, more preferably at least 80%, and most preferably at least 90%.

7. the alkyl alkanolamide sulfate anionic surfactant comprises a C12 alkyl alkanolamide sulfate anionic surfactant, a C14 alkyl alkanolamide sulfate anionic surfactant, and mixtures thereof, with a blend of a C12 alkyl alkanolamide sulfate anionic surfactant and a C14 alkyl alkanolamide sulfate anionic surfactant being preferred; The C12 alkyl alkanolamide sulfate anionic surfactant is preferably selected from the group consisting of N-(2-hydroxyethyl)dodecanamide sulfate, N-(2-hydroxypropyl)dodecanamide sulfate, N-(2-hydroxyethyl)-N-methyldodecanamide sulfate, N-(1-hydroxypropan-2-yl)dodecanamide sulfate, and mixtures thereof, preferably N-(2-hydroxyethyl)dodecanamide sulfate, N-(2-hydroxypropyl)dodecanamide sulfate, N-(2-hydroxyethyl)-N-methyldodecanamide sulfate, and mixtures thereof; The composition according to any one of claims 1 to 6, wherein the C14 alkyl alkanolamide sulfate anionic surfactant is preferably selected from the group consisting of N-(2-hydroxyethyl)tetradecanamide sulfate, N-(2-hydroxypropyl)tetradecanamide sulfate, N-(2-hydroxyethyl)-N-methyltetradecanamide sulfate, N-(1-hydroxypropan-2-yl)tetradecanamide sulfate, and mixtures thereof, preferably N-(2-hydroxyethyl)tetradecanamide sulfate, N-(2-hydroxypropyl)tetradecanamide sulfate, N-(2-hydroxyethyl)-N-methyltetradecanamide sulfate, and mixtures thereof.

8. A composition according to any one of claims 1 to 7, wherein the alkyl sulphate anionic surfactant has a number average alkyl chain length of from 8 to 18, preferably from 10 to 14, more preferably from 12 to 14, most preferably from 12 to 13 carbon atoms.

9. A composition according to any preceding claim, wherein the alkyl sulphate anionic surfactant is not alkoxylated.

10. 10. A composition according to any one of claims 1 to 9, wherein the alkyl sulphate anionic surfactant has an average degree of branching of at least 15%, preferably from 20% to 60%, more preferably from 30% to 50%.

11. 11. A composition according to any preceding claim, wherein the alkyl sulphate anionic surfactant and the alkyl alkanolamide sulphate anionic surfactant are present in a weight ratio of from 10:1 to 1:2, preferably from 7:1 to 1:1, most preferably from 5:1 to 2:

1.

12. 12. The composition of any one of claims 1 to 11, wherein the surfactant system further comprises a co-surfactant selected from the group consisting of amphoteric co-surfactants, zwitterionic co-surfactants, and mixtures thereof.

13. the anionic surfactant and the co-surfactant are present in a weight ratio of from 1:1 to 8:1, preferably from 2:1 to 5:1, more preferably from 2.5:1 to 4:1; The amphoteric surfactant is preferably an amine oxide surfactant, more preferably the amine oxide surfactant is selected from the group consisting of alkyl dimethyl amine oxide, alkyl amidopropyl dimethyl amine oxide, and mixtures thereof, most preferably alkyl dimethyl amine oxide; 13. The composition of claim 12, wherein the zwitterionic surfactant is preferably a betaine surfactant, more preferably a betaine surfactant selected from the group consisting of alkyl betaines, alkylamidoalkyl betaines, amidazolinium betaines, sulfobetaines (INCI sultaines), phosphobetaines, and mixtures thereof, and most preferably cocoamidopropyl betaine.

14. 1. A method for making a concentrated surfactant blend, the blend comprising: R(CO)NXR'O-SO3-M+ (I), an alkyl alkanolamide sulfate anionic surfactant having the formula: an alkyl sulfate anionic surfactant, wherein the alkyl sulfate anionic surfactant has an average degree of alkoxylation of less than 0.1; The method comprises the following steps: a. providing a non-ionic stream, said non-ionic stream comprising: At least one compound of formula (II): R(CO)NXR'OH (II), and an alkyl alkanolamide of at least one alkyl alcohol, wherein the at least one alkyl alcohol has an average degree of alkoxylation of less than 0.1; b. a sulfation step in which the at least one alkyl alkanolamide of formula (II) and at least one alkyl alcohol in the non-ionic stream are sulfated to form a sulfuric acid stream comprising at least one alkyl alkanolamide sulfuric acid and at least one alkyl sulfuric acid; c. providing a neutralization stream comprising at least one neutralizing agent; and (d) a neutralization step of combining said sulfuric acid stream with said neutralization stream to neutralize said at least one alkyl alkanolamide sulfuric acid and at least one alkyl sulfuric acid.

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