Dishwashing detergent composition

Abstract

The present invention provides a liquid dishwashing composition that is more environmentally sustainable and, at the same time, exhibits good foaming persistence even in the presence of oily particulate matter. [Solution] A liquid dishwashing detergent composition is formulated using an alkyl glycol sulfate anionic surfactant and a betaine auxiliary surfactant.

Description

[Technical Field]

[0001] This invention relates to a liquid detergent composition for hand washing dishes. [Background technology]

[0002] In formulating liquid dishwashing detergent compositions, the selection of surfactants plays a crucial role in determining performance characteristics such as foam persistence, stain removal effectiveness, and low-temperature stability. In particular, grease removal and foam persistence are seen as indicators of good, long-lasting performance. In fact, during dishwashing, users typically rely on the foam level as an indicator of the remaining cleaning effect of the 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 perform the desired cleaning.

[0003] Typically, alkylethoxylated sulfates have been used as the main anionic surfactants in liquid dishwashing compositions because they provide good foaming, grease removal, and low-temperature stability. Alkylethoxylated sulfate anionic surfactants are typically formed via the reaction of alkyl alcohols with ethylene oxide, which results in a broad distribution of ethoxylation. The process of producing such alkyl ether sulfate anionic surfactants may result in the presence of trace amounts of residual 1,4-dioxane byproducts, the amount of dioxane formed being at least partially related to the proportion of alkylethoxylated sulfate anionic surfactants containing two or more ethoxy groups. The amount of 1,4-dioxane byproducts in alkoxylated alkyl sulfates, and especially ethoxylated alkyl sulfates, can be reduced. Based on recent technological advances, further reduction of 1,4-dioxane byproducts can be achieved by subsequent stripping, distillation, evaporation, centrifugation, microwave irradiation, molecular sieving, or catalytic or enzymatic decomposition steps.

[0004] One alternative to conventional alkyl ether sulfate anionic surfactants is the use of alkyl sulfate anionic surfactants that lack ethoxylation. These alkyl sulfate surfactants can provide certain advantages, including oil and grease cleaning, but their incorporation into formulations can negatively impact foam persistence performance and low-temperature stability, particularly when dealing with difficult cleaning tasks involving particulate and oily soils. This trade-off emphasizes the complexity of surfactant selection, as formulators must balance the need for effective foam generation and foam persistence with product stability under various conditions. The interaction between foam performance and temperature stability remains an important consideration in the development of high-performance dishwashing liquid detergent compositions.

[0005] Therefore, there remains a need for dishwashing compositions that are more environmentally sustainable, essentially free of 1,4-dioxane, and that provide persistent foaming, even in the presence of oily particulate soils, as well as good low-temperature stability.

[0006] International Publication No. 2024063990(A1) relates to an aqueous lightweight liquid detergent formulation comprising water, a zwitterionic surfactant, and an alcohol ethoxysulfate surfactant wherein 95 to 100 mol% of the alcohol ethoxysulfate surfactant has an ethoxylation degree of 1. International Publication No. 202463991(A1) relates to an aqueous laundry detergent composition comprising water and a cleaning surfactant, wherein the cleaning surfactant comprises a blend of a nonionic surfactant and an anionic surfactant, and the anionic surfactant comprises an alcohol ethoxysulfate surfactant, wherein 95 to 100 mol% of the alcohol ethoxysulfate surfactant has an ethoxylation degree of 1. Although referred to as alcohol “ethoxysulfate” surfactants, the surfactants described in International Publications 2024063990(A1) and 202463991(A1) are not derived through a process involving an ethoxylation step, but instead involve reacting an ethylene glycol monomer or oligomer with an alkene prior to sulfation. An exemplary process for producing such “alkyl glycol” sulfates is described in International Publication 202464645(A). In contrast to alkylethoxylated sulfate anionic surfactants, alkyl glycol sulfate anionic surfactants are typically formed via an acid-catalyzed addition of glycol, which results in a Markovnikov addition of hydrogen (typically the less substituted side) and an alkoxy group, leading to the addition of an ether bond, followed by the addition of SO3, i.e., a sulfation process, and subsequent neutralization to provide a counterion. This results in an alkyl glycol sulfate anionic surfactant containing an extremely narrow distribution of ethylene glycol units, typically 1 to 3 ethylene glycol units per molecule of the alkyl glycol sulfate anionic surfactant, or even 1 ethylene glycol unit per molecule of the alkyl glycol sulfate anionic surfactant.Alkyl glycol sulfate anionic surfactants formed using such a process also typically do not contain alkyl sulfated anionic surfactants that do not contain a glycol linking group between the alkyl chain and the sulfate group. International Publication No. 202464645 (A1) describes a process that involves contacting an olefin, an alcohol, and a metallosilicate catalyst to form an oligomer of an alcohol “ethoxylate” in which 95 to 100 mol% of the alcohol ethoxylate has an ethoxylation degree of 1, and then sulfating the oligomer.

[0007] Japanese Unexamined Patent Application Publication No. 2006104438 (A) provides a liquid detergent composition that provides detergency against oily stains, rinsability, handleability, and handling safety. The liquid detergent composition contains an anionic surfactant, a nonionic surfactant, and water, and the anionic surfactant contains a secondary alkyl ether sulfate. Japanese Unexamined Patent Application Publication No. 2006137872 provides a powder detergent composition that has good fluidity, detergency, and rinsability, has little odor, and has excellent dispersion solubility in cold water. The powder detergent composition contains a higher secondary alcohol alkoxylate sulfate and an anionic surfactant other than the higher secondary alcohol alkoxylate sulfate. European Patent Application Publication No. 0850907 (A1) relates to a higher secondary alcohol alkoxylate compound composition, a method for producing the same, and detergents and emulsifiers using the composition.

[0008] The following journal articles describe the process by which alkoxylate surfactants are derived from alpha-olefins: BAKKER PM: "Sulfonates and sulfates of sec-alkyl ethyl ether: detergents prepared by the addition of substituted alcohols to 1-alkenes", CHIMIE, PHYSIQUE ET APPLICATIONS PRATIQUES DES AGENTS DE SURFACT, XX, XX, September 9, 1968 (1968-09-09), pp. 157-165, XP002075332; JFKNIFTON: "Detergent-range alcohol alkoxylates via vicinal glycol additions to alpha-olefins", APPLIED CATALYSIS, A, Vol. 130, 1995, pp. 79-88, XP002075333; PMBAKKER: "An exploratory study of the addition reactions of ethyleneglycol, 2-chloroethanol and "1,3-dichloro-2-propanol to 1-dodecene," JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY, Vol. 44, September 1967, pp. 517-521, XP002058548. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] International Publication No. 2024063990(A1) [Patent Document 2] International Publication No. 202463991(A1) [Patent Document 3] International Publication No. 202464645(A) [Patent Document 4] International Publication No. 202464645(A1) [Patent Document 5] Japanese Patent Publication No. 2006104438(A) [Patent Document 6] Japanese Patent Publication No. 2006137872 [Patent Document 7] European Patent Application Publication No. 0850907(A1) [Non-patent literature]

[0010] [Non-Patent Document 1] BAKKER PM: "Sulfonates and sulfates of sec-alkyl ethyl ether:detergents prepared by the addition of substituted alcohols to 1-alkenes",CHIMIE,PHYSIQUE ET APPLICATIONS PRATIQUES DES AGENTS DE SURFACT, XX, XX, September 9, 1968 (1968-09-09), pp. 157-165, XP002075332 [Non-Patent Document 2] JFKNIFTON: "Detergent-range alcohol alkoxylates via vicinal glycol additions to alpha-olefins" APPLIED CATALYSIS, A, vol. 130, 1995, pp. 79-88, XP002075333 [Non-Patent Document 3] PMBAKKER: "An exploratory study of the addition reactions of ethyleneglycol,2-chloroethanol and 1,3-dichloro-2-propanol to 1-dodecene" JOURNAL OF THE AMERICAN OIL CHEMISTS'SOCIETY, Vol. 44, September 1967, pp. 517-521, XP002058548 [Overview of the project] [Means for solving the problem]

[0011] The present invention relates to a liquid detergent composition for hand washing dishes, comprising 5.0% to 50% by weight of a surfactant system, wherein the surfactant system comprises an anionic surfactant, the anionic surfactant comprises an alkyl glycol sulfate anionic surfactant, and the alkyl glycol sulfate anionic surfactant has the formula: R1CH(R2)(OCH2CH2) n OSO3 - M + (I) has, In the formula, R1 is independently H, alkyl, alkylene, or a mixture thereof, R2 is independently alkyl, alkylene, or a mixture thereof, the total number of carbon atoms present in R1 and R2 is, on average, 7 to 19, n is 1 to 3, 90 mol% or more of the surfactant molecules of structure (I) have an n of 1, and 10 mol% or less of the surfactant molecules of structure (I) have an n of 2 or more, M + The present invention relates to a liquid dishwashing detergent composition comprising an alkyl glycol sulfate anionic surfactant, which is a counterion, and an auxiliary surfactant, wherein the auxiliary surfactant is a zwitterionic surfactant, and the zwitterionic auxiliary surfactant is a betaine surfactant. [Modes for carrying out the invention]

[0012] As described herein, formulating a liquid dishwashing detergent composition using a combination of alkyl glycol sulfate anionic surfactant and betaine auxiliary surfactant has been found to provide good low-temperature stability, be essentially 1,4-dioxane-free, and good foam persistence even in the presence of oily particulate matter.

[0013] Since alkyl glycol sulfate anionic surfactants are produced through a process in which ethylene glycol monomers are added to alpha-olefins, the resulting alkyl glycol sulfate anionic surfactants can be prepared so that essentially all alkyl glycol sulfate anionic surfactants contain just one ethylene glycol unit. The extremely narrow distribution of ethylene glycol monomers in the alkyl glycol sulfate anionic surfactants used herein is thought to provide improved foaming persistence when combined with zwitterionic surfactants, particularly betaine surfactants, while simultaneously providing good low-temperature stability.

[0014] When used herein, articles such as "a" and "an" used in the claims are understood to mean one or more of the claims or descriptions.

[0015] As used herein, the term “comprising” means that additional steps and components may be added beyond those specifically mentioned. This term encompasses the terms “consisting of” and “essentially consisting of.” The compositions of the present invention may consist of, and may essentially consist of, any of the essential elements and limitations of the invention described herein, as well as any additional or optional components, elements, steps, or limitations described herein.

[0016] As used herein, the term “dishware” includes, in a non-limiting sense, cookware and tableware made from ceramics, porcelain, metal, glass, plastics (e.g., polyethylene, polypropylene, polystyrene, etc.) and wood.

[0017] As used herein, the terms “oils and fats” or “oil-based” mean that the substance contains, at least partially (i.e., at least 0.5% by weight of oils and fats in the substance), saturated and unsaturated fats and oils, preferably oils and fats derived from animal raw materials such as beef, pork, and / or chicken.

[0018] The term "include / includes / including" means that it is non-restrictive.

[0019] As used herein, the term “particulate matter” means inorganic and, in particular, organic solid contaminant particles, especially food particles, and, in non-limiting examples, ultrafine elemental carbon, calcined fat particles, and meat particles.

[0020] As used herein, the term “foaming profile” refers to the properties of a cleaning composition relating to the nature of the foam during the dishwashing process. The “foaming profile” of a cleaning composition includes the dissolution and agitation of the cleaning composition in an aqueous cleaning solution, the initial foaming volume typically generated during manual agitation, and the retention of foam during the dishwashing process. Preferably, a dishwashing cleaning composition characterized by having a “good foaming profile” tends to have a large initial foaming volume and / or persistent foaming volume, particularly over a significant portion or the entirety of the dishwashing process. This is important because consumers use high foaming as an indicator that sufficient cleaning composition has been added. Furthermore, consumers also use the persistence of foaming volume even towards the end of the dishwashing process as an indicator that sufficient active cleaning components (e.g., surfactants) are present. Consumers typically refresh the cleaning solution when foaming decreases. Therefore, low-foaming cleaning compositions tend to be replenished more frequently than necessary by consumers due to their low foaming level.

[0021] 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 parameter of the applicant's invention described herein and claimed.

[0022] Unless otherwise specified, all proportions are based on the total weight of the composition, as is evident from the context. Unless otherwise specified, all ratios are weight ratios, and all measurements are taken at 25°C.

[0023] Liquid cleaning compositions The cleaning composition is a liquid cleaning composition, preferably a liquid dishwashing cleaning composition, and is therefore in liquid form. The liquid cleaning composition is preferably an aqueous cleaning composition. Therefore, the composition may contain 50% to 85% by weight, preferably 50% to 75% by weight, of water in the total composition.

[0024] When measured as a 10% aqueous solution in desalinated water at 20°C, the pH of the liquid washing composition is 6.0 or higher, preferably 7.0 to 11.0, and more preferably 7.5 to 9.0.

[0025] The liquid cleaning composition of the present invention may be a Newtonian fluid or a non-Newtonian fluid, but is preferably a Newtonian fluid. Preferably, the composition has a viscosity of 10 mPa·s to 10,000 mPa·s, preferably 100 mPa·s to 5,000 mPa·s, more preferably 300 mPa·s to 2,000 mPa·s, or most preferably 500 mPa·s to 1,500 mPa·s, or alternatively a combination thereof.

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

[0027] Anionic surfactants The surfactant system includes an anionic surfactant. The surfactant system may contain at least 40% by weight, preferably 60% to 90% by weight, and more preferably 65% ​​to 85% by weight of anionic surfactant. Since fatty acids hinder foam formation, the surfactant system preferably does not contain fatty acids or their salts.

[0028] Alkyl glycol sulfate anionic surfactant The surfactant system includes an anionic surfactant, and the anionic surfactant includes an alkyl glycol sulfate anionic surfactant. Preferably, the alkyl glycol sulfate anionic surfactant is present in a concentration of 5.0% to 50% by weight, preferably 10% to 40% by weight, and more preferably 15% to 30% by weight of the anionic surfactant system.

[0029] Alkyl ethoxylated sulfate anionic surfactants are typically formed through a process in which the alkyl alcohol is first ethoxylated before sulfation. In contrast, alkyl glycol sulfate anionic surfactants are typically prepared by first reacting an ethylene glycol monomer or oligomer with an alkene before sulfation. Since the resulting sulfate surfactants are not formed using an ethoxylation step, it is not technically correct to call them alkyl ethoxylated surfactants. Therefore, since they are typically formed by reacting an alkene with a glycol (aliphatic diol), they are referred to herein as alkyl glycol sulfate anionic surfactants, e.g., alkyl ethylene glycol sulfates (AEGS). For example, a process such as that described in International Publication No. 202464645(A1) results in a much narrower distribution of glycol groups in the resulting alkyl glycol sulfate anionic surfactants, thus allowing for a significant reduction in the presence and formation of dioxanes in detergent formulations containing them. This is because little to no 1,4-dioxane is formed during the production of alkylethylene glycol sulfate. Furthermore, by limiting the amount of alkylethylene glycol sulfate having two or more glycol units present, the generation of 1,4-dioxane due to the decomposition of the surfactant is substantially reduced.

[0030] The alkyl glycol sulfate anionic surfactant has the formula (I): R1CH(R2)(OCH2CH2) n OSO3 - M + (I).

[0031] The value of n in structure (I) has a value of 1 to 3. For example, n may be 1, 2, or 3. 90 mol% or more of the surfactant molecules of structure (I) have n of 1, and 10 mol% or less of the surfactant molecules of structure (I) have n of 2 or more. More preferably, 92 mol% or more of the surfactant molecules of structure (I) have n of 1, and 8 mol% or less of the surfactant molecules of structure (I) have n of 2 or more. Most preferably, 95 mol% or more of the surfactant molecules of structure (I) have n of 1, and 5 mol% or less of the surfactant molecules of structure (I) have n of 2 or more.

[0032] In formula (I), the group (OCH2CH2) n can be derived from ethylene glycol (ethane-1,2-diol) or an oligomer of ethylene glycol, and suitable oligomers of ethylene glycol contain up to 3 monomer units of ethylene glycol. Preferably, in formula (I), the group (OCH2CH2) n is derived from ethylene glycol.

[0033] R1 is independently H, alkyl, alkylene, or a mixture thereof, preferably H, alkyl, or a mixture thereof, with a blend of H and alkyl being particularly preferred. Typically, alkyl glycol sulfate anionic surfactants are a blend of alkyl glycol sulfate anionic surfactants of formula (I) (wherein R1 is H and alkyl), with the majority being alkyl glycol sulfate anionic surfactant of formula (I) (wherein R1 is alkyl) and a relatively small portion being alkyl glycol sulfate anionic surfactant of formula (I) (wherein R1 is H). This is because alkyl glycol sulfate anionic surfactants of formula (I) are typically formed via addition reactions following Markovnikov's law, where induction and overconjugation lead to the formation of the most stable carbocation on the more substituted carbon atoms of the alkene bond. However, other less substituted, less stable carbocations still form as intermediates at certain residual concentrations, thus forming a residual amount of the alkyl glycol sulfate anionic surfactant of formula (I) where R1 is H. Preferably, in at least 50% by weight, more preferably at least 60% by weight, and most preferably at least 80% by weight of the alkyl glycol sulfate of formula (I), R1 is alkyl and the remainder is H. R1 preferably contains 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Preferably, in at least 80 mol%, more preferably at least 90 mol%, of the alkyl glycol sulfate anionic surfactant of formula (I), R1 contains 1 carbon atom, more preferably methyl. Thus, branching at the C1 position, particularly methyl branching, is preferably present in at least 80 mol%, or even more preferably at least 90 mol%, of the alkyl glycol sulfate anionic surfactant, where the C1 position is a carbon atom bonded to the oxygen atom of the glycol sulfate group.

[0034] R2 is independently an alkyl, alkylene, or a mixture thereof, preferably an alkyl. R2 preferably contains an average of 6 to 19 carbon atoms, preferably 8 to 17 carbon atoms, more preferably 9 to 15 carbon atoms, and most preferably 10 to 13 carbon atoms. R2 may be linear, branched, or a combination thereof, and R2 is preferably linear.

[0035] The total number of carbon atoms present in R1 and R2 is, on average, 7 to 19, preferably 9 to 17, more preferably 11 to 15, and most preferably 11 to 13.

[0036] Alkyl glycols can have a molar-average alkyl chain length of 8 to 18 carbon atoms, preferably 10 to 14, and most preferably 12 to 13 carbon atoms, as defined by R1CH(R2).

[0037] For both R1 and R2, alkyls are preferred over alkylenes because the presence of multiple double bonds in the starting alkene can lead to reduced selectivity for terminal double bonds during the reaction that forms the ether bond. Therefore, R1 and R2 can be independently saturated or unsaturated, but saturated is preferred.

[0038] Can the distributions of R1 and R2 be determined analytically? (For example, 1 1H NMR and / or 13 This can be determined (through 1C NMR) or from the starting materials used to produce alkyl glycol sulfate anionic surfactants.

[0039] Structure (I) M + is a counterion, preferably M + The alkali metal counterions or ammonium, ethanolamine, isopropanolamine, triethylamine, triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-dimethylpropanolamine, and combinations thereof, more preferably Na + , K+ Mg 2+ , or ethanolamine, most preferably Na + Therefore, different surfactant molecules are M + It will be understood that they may have different materials.

[0040] In formula (I), R1CH(R2) can be derived from a suitable alkene, particularly a linear alpha-olefin (LAO). Linear alpha-olefins are linear terminal alkenes and therefore contain a double bond at the alpha (α-, 1-, or primary) position and a linear (unbranched) hydrocarbon chain. Thus, they result in longer, less branched alkyl groups in the resulting alkyl glycol sulfate anionic surfactant compared to starting from a medium-chain unsaturated alkene. Suitable linear alpha-olefins can be selected from the group consisting of 1-dodecene, 1-tetradecene, 1-hexadecene, and mixtures thereof. Commercial sources of such alpha-olefins may contain small amounts of other long-chain olefins, branched-chain olefins, and vinylidene olefins.

[0041] Linear alpha-olefins can be produced using any known process, including oligomerization of ethylene, Fischer-Tropsch synthesis, dehydration of alcohols, or thermal decomposition of waxes. Alternatively, olefins can be “bio-derived” as described in International Publication No. 2011002284(A) or Yu, H., Wang, C., Lin, T. et al., “Direct production of olefins from syngas with ultrahigh carbon efficiency,” Nat. Commun. 13, 5987 (2022). Alkyl glycol sulfate anionic surfactants are similar to alkyl ethoxylated sulfate anionic surfactants, but have several important differences.

[0042] Alternatively, branched olefins can be used. The chemical and physical properties of the resulting alkyl glycol sulfate anionic surfactants can vary depending on the choice of linear or branched olefins, as well as the degree and type of branching. Suitable examples of branched olefins include propylene tetramers and butylene trimers (branched dodecenes), which are used in the production of oxo alcohols by Exxon (Exxal 13®) and BASF (Lutensol TDA®).

[0043] Residual amounts of other components may be present, such as secondary alcohols, secondary alcohol sulfates, unreacted or partially reacted alpha-olefins, unreacted ethylene glycols, and unsulfated alkyl glycols. Such residual amounts of other components are typically present at concentrations of less than 20% by weight, preferably less than 10% by weight, and more preferably less than 5% by weight of the alkyl glycol sulfate anionic surfactant.

[0044] Alkyl glycol sulfate anionic surfactants can be present in the composition in an amount of 1.0% to 25% by weight, preferably 3.0% to 15% by weight, and more preferably 5.0% to 10% by weight.

[0045] An exemplary process for producing the alkyl glycol sulfates used in the present invention is described in International Publication No. 202464645(A). In contrast to alkylethoxylated sulfate anionic surfactants, alkyl glycol sulfate anionic surfactants are typically formed via an acid-catalyzed addition of glycol, which results in a Markovnikov addition of hydrogen (typically the less substituted side) and an alkoxy group, leading to the addition of an ether bond, followed by the addition of SO3, i.e., a sulfation process, and subsequent neutralization to provide a counterion.

[0046] This results in alkyl glycol sulfate anionic surfactants containing an extremely narrow distribution of ethylene glycol units, typically 1 to 3 ethylene glycol units per molecule of the alkyl glycol sulfate anionic surfactant, or even 1 ethylene glycol unit per molecule of the alkyl glycol sulfate anionic surfactant. Alkyl glycol sulfate anionic surfactants formed using such a process also typically do not contain alkyl sulfate anionic surfactants that do not contain a glycol linking group between the alkyl chain and the sulfate group.

[0047] When alkyl glycol sulfate anionic surfactants are derived from the reaction of alpha-olefins with glycols, the methyl branching at the C1 position may be present in at least 90 mol%, or even more than 95 mol%, of the alkyl glycol sulfate anionic surfactant, where the C1 position is the carbon atom bonded to the oxygen atom of the glycol sulfate group.

[0048] Alkyl sulfated anionic surfactant The anionic surfactant preferably further comprises an alkyl sulfated anionic surfactant. The anionic surfactant may contain at least 25% by weight, preferably 30% to 90% by weight, and more preferably 70% to 85% by weight of the alkyl sulfated anionic surfactant.

[0049] The anionic surfactant may include at least 70% by weight, more preferably at least 85% by weight, and most preferably 100% by weight of alkyl sulfated anionic surfactant and alkyl glycol sulfate anionic surfactant. In a preferred composition, the anionic surfactant consists of alkyl sulfated anionic surfactant and alkyl glycol sulfate anionic surfactant. The alkyl sulfated anionic surfactant and alkyl glycol sulfate anionic surfactant are preferably present in a weight ratio of 19:1 to 1:2, preferably 7:1 to 1:1, and most preferably 5:1 to 2:1.

[0050] While not bound by theory, it is believed that the mixture provides a surfactant filler that strikes a balance between oil-removing properties and sustained foaming performance, particularly in the presence of oily particulate matter, exhibits low-temperature stability, and minimizes the impact on the viscosity of the target final product.

[0051] To provide a combination of improved grease removal and enhanced cleaning speed, the molar average alkyl chain length of the alkyl sulfate anionic surfactant or alkyl alkoxy sulfate anionic surfactant may be 8 to 18 carbon atoms, preferably 10 to 14, more preferably 12 to 14, and most preferably 12 to 13 carbon atoms.

[0052] The alkyl chain of an alkyl sulfate anionic surfactant or alkyl alkoxy sulfate anionic surfactant may have a mole fraction of C12 and C13 chains of at least 50%, preferably at least 65%, more preferably at least 80%, and most preferably at least 90%. When the C13 / C12 molar ratio of the alkyl chain 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, especially in the presence of oily contaminants, while foam persistence in the presence of particulate contaminants is not impaired.

[0053] The relative molar amounts of C13 alkyl chains and C12 alkyl chains in alkyl sulfate anionic surfactants or alkyl alkoxy sulfate anionic surfactants can be derived from the carbon chain length distribution of the surfactant. The carbon chain length distribution of the alkyl chains in alkyl sulfate surfactants and alkyl alkoxy sulfate surfactants can be obtained from the technical data sheets of the suppliers of the surfactants or the alkyl alcohols that constitute them. Alternatively, the chain length distribution and average molecular weight of the aliphatic alcohols used to prepare alkyl sulfate anionic surfactants or alkyl alkoxy sulfate anionic surfactants can also be determined by methods known in the art. Such methods include capillary gas chromatography with flame ionization detection in a medium-polarity capillary column using hexane as the solvent. The chain length distribution is based on the starting alcohol and the alkoxylated alcohol. Therefore, alkyl sulfate anionic surfactants must be hydrolyzed back to the corresponding alkyl alcohol and alkyl alkoxylated alcohol, for example, using hydrochloric acid, before analysis.

[0054] Alkyl sulfate surfactants may or may not be alkoxylated. When alkoxylated, the alkyl sulfated anionic surfactant may have an average degree of alkoxylation of less than 1.0, preferably less than 0.5, more preferably less than 0.25, and even more preferably less than 0.1, and it is particularly preferable that they are not alkoxylated. When alkoxylated, ethoxylation is preferred. Therefore, the alkyl sulfated anionic surfactant may contain less than 10% by weight, preferably less than 5% by weight, of the alkoxylated alkyl sulfate surfactant, and more preferably, the alkyl sulfated anionic surfactant does not contain the alkoxylated alkyl sulfate surfactant.

[0055] The average degree of alkoxylation is the molar average degree of alkoxylation (i.e., molar average degree of alkoxylation) of all alkyl sulfate anionic surfactants. Therefore, when calculating the molar average degree of alkoxylation of alkyl sulfate anionic surfactants, the number of moles of non-alkoxylated sulfate anionic surfactants is included. The number of moles of alkyl glycol sulfate anionic surfactants is excluded. Molar average degree of alkoxylation = (x1 * Degree of alkoxylation of surfactant 1 +x2 * Degree of alkoxylation of surfactant 2 + ...) / (x1 + x2 + ...) In the formula, 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.

[0056] A preferred alkylalkoxy sulfate is an alkylethoxysulfate.

[0057] Ethoxylated alkyl sulfated anionic surfactants are typically formed by first ethoxyling an alkyl alcohol, using an epoxide as a starting material, and adding ethylene oxide (C2H4O) to the alkyl alcohol. The resulting alkylethoxylated nonionic surfactant is then sulfated to form alkylethoxylated sulfate anionic surfactants.

[0058] When alkylethoxylated nonionic surfactants are formed, some polymerization of ethylene oxide occurs, resulting in a relatively broad distribution of the degree of ethoxylation of the alkyl alcohol. The ethylene oxide used to produce ethoxylated surfactants can also cause the formation of 1,4-dioxane, especially if the molecule of the alkylethoxylated sulfate anionic surfactant contains at least two EO groups. This is because the ethylene oxide must first dimerize to form 1,4-dioxane. Although we do not wish to be constrained by theory, in the presence of alkylethoxylated sulfate anionic surfactants, the amount of alkoxylation, particularly 1,4-dioxane byproducts in the ethoxylated alkyl sulfate, can be reduced by strictly controlling the processing conditions and the composition of the raw materials during both the ethoxylation and sulfation steps. Based on recent technological advancements, further reduction of 1,4-dioxane byproducts can be achieved by subsequent stripping, distillation, evaporation, centrifugation, microwave irradiation, molecular sieving, or catalytic or enzymatic decomposition steps. Processes for controlling the 1,4-dioxane content in alkoxylated / ethoxylated alkyl sulfates are widely described in the art. Alternatively, the control of 1,4-dioxane concentration 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, a mixture of 3-alpha-hydroxy-7-oxo stereoisomers of cholanaic acid, 3-(N-methylamino)-L-alanine, and mixtures thereof, to formulations containing 1,4-dioxane is also described in the art. However, further reducing the dioxane concentration in alkylethoxylated surfactants remains difficult.

[0059] Non-alkoxylated alkyl sulfate surfactants can be formed using naturally derived alkyl chains, such as those derived from palm oil or coconut oil. It has also been found that non-alkoxylated alkyl sulfate surfactants are more readily biodegradable by microorganisms in soil and natural water.

[0060] Alkyl sulfated anionic surfactants preferably have an average branching degree of less than 60%, more preferably less than 40%, more preferably less than 20%, and most preferably less than 10%. Alkyl sulfated anionic surfactants are particularly preferably linear. Linear alkyl chains are typically derived from renewable sources.

[0061] Alkyl sulfated anionic surfactants and alkyl alkoxy sulfate anionic surfactants can contain at least 5% by weight, preferably at least 10% by weight, and most preferably at least 25% by weight of branching at the C2 position (measured by counting carbon atoms from the sulfate group for non-alkoxylated alkyl sulfated anionic surfactants and from the alkoxy group furthest from the sulfate group for alkoxylated alkyl sulfated anionic surfactants). More preferably, more than 75% by weight, and even more preferably more than 90% by weight of the total branched alkyl content consists of a C1-C5 alkyl moiety, preferably a C1-C2 alkyl moiety. It has been found that low-temperature stability is improved by formulating the composition of the present invention using alkyl sulfate surfactants or alkyl alkoxy sulfate surfactants having the above degree of branching. Such compositions require less solvent to achieve good physical stability at low temperatures. Therefore, the composition can contain lower concentrations of organic solvents, such as less than 5.0% by weight of the organic solvent in the liquid composition, while still having improved low-temperature stability. Also, the more branching of the surfactant, the faster the initial foam formation, but typically the lower the foam persistence. The weight-average branching described herein has been found to result in improved low-temperature stability, initial bubble formation, and foam persistence.

[0062] The weight-average branching degree of alkyl sulfate anionic surfactants can be calculated using the following formula. Alkyl glycol sulfate anionic surfactants are excluded from the calculation. Weight-average branching degree (%) = [(x1 * Weight % of branched-chain alcohol 1 in alcohol 1 + x2 * (Weight of branched-chain alcohol 2 in alcohol 2 % + ....) / (x1 + x2 + ....)] * 100 In the formula, x1, x2, ... are the weights (grams) of each alcohol in the total alcohol mixture of alcohols used as starting materials before (alkoxylation and) sulfated production to produce alkyl (alkoxy) sulfate anionic surfactants. The weight-average degree of branching calculation includes the weight of the alkyl alcohols used to form the unbranched alkyl sulfate anionic surfactants.

[0063] The weight-average degree of branching and branching distribution can usually be obtained from the technical data sheet of the surfactant or the alkyl alcohol constituting it. Alternatively, branching can also be determined through analytical methods known in the art, including capillary gas chromatography with flame ionization detection in 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 sulfated anionic surfactant.

[0064] The performance characteristics, including oil and grease cleaning, foaming, low-temperature stability, and viscosity of the final product, can be influenced by the width of the alkoxylation distribution of the alkoxylated alkyl sulfated anionic surfactant. The alkoxylation distribution, including its width, can be altered through the selection of catalysts and process conditions when preparing alkoxylated alkyl sulfated anionic surfactants.

[0065] Suitable counterions include alkali metal cations, alkaline earth metal cations, alkanolammonium, or ammonium or substituted ammonium; however, sodium is preferred because the use of alkanolammonium, ammonium, or substituted ammonium may cause discoloration of the composition.

[0066] Suitable examples of commercially available alkyl sulfated 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 produced by Procter & Gamble Chemicals. Based on the relative fractions of C13 and C12 in the starting alcohols obtained from technical data sheets from the supplier or from 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.

[0067] Additional anionic surfactants The anionic surfactant may include additional anionic surfactants selected from the group consisting of alkyl(benzene) sulfonate surfactants, alkyl sulfosuccinate and dialkyl sulfosuccinate ester surfactants, and mixtures thereof.

[0068] Suitable anionic alkyl sulfonate or sulfonic acid surfactants for use herein include alkylbenzene sulfonates, alkyl ester sulfonates, primary and secondary alkanesulfonates (such as paraffin sulfonates), alpha or internal olefin sulfonates, alkyl sulfonated (poly)carboxylic acids, and mixtures thereof, in acid and salt forms. Suitable anionic sulfonate or sulfonic acid surfactants include C5-C20 alkylbenzene sulfonates, more preferably C10-C16 alkylbenzene sulfonates, more preferably C11-C13 alkylbenzene sulfonates, C5-C20 alkyl ester sulfonates, particularly C5-C20 methyl ester sulfonates, C6-C22 primary or secondary alkanesulfonates, C5-C20 sulfonated (poly)carboxylic acids, and any mixtures thereof, with C11-C13 alkylbenzene sulfonates being preferred. The above 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 because the double bond is randomly positioned. This allows for various twin-tail branched structures, with the hydrophilic sulfonate and hydroxyl group of IOS located in the center of the alkyl chain. Examples of alkanesulfonates include paraffin sulfonates and other secondary alkanesulfonates (such as Hostapur SAS60 from Clariant).

[0069] Alkyl sulfosuccinates 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). Alkyl sulfosuccinate and dialkyl sulfosuccinate ester surfactants may be alkoxylated or non-alkoxylated, preferably non-alkoxylated. This surfactant system may contain further 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 as further anionic surfactants. Most preferably, the surfactant system does not contain further anionic surfactants, and preferably does not contain anionic surfactants other than alkyl sulfated anionic surfactants and alkyl glycol sulfate anionic surfactants.

[0070] auxiliary surfactants To improve the packing of the surfactant after dilution and thereby improve foam retention, the surfactant system includes an auxiliary surfactant, which is a zwitterionic surfactant, and the zwitterionic surfactant includes a betaine surfactant.

[0071] The anionic surfactant and the auxiliary surfactant can be present in a weight ratio of 1:1 to 5:1, preferably 1.5:1 to 4.5:1, and more preferably 2:1 to 4:1.

[0072] The composition preferably contains 0.1% to 20% by weight, more preferably 0.5% to 15% by weight, and especially 2% to 10% by weight of auxiliary surfactants of the cleaning composition.

[0073] The surfactant system of the cleaning composition of the present invention preferably contains an auxiliary surfactant of up to 50% by weight of the surfactant system, preferably 10% to 40% by weight, and more preferably 15% to 35% by weight.

[0074] Suitable zwitterionic surfactants include betaine surfactants. Examples of such betaine surfactants include alkylbetaine, alkylamidebetaine, amidazolinium betaine, sulfobetaine (INCI sultaine), phosphobetaine, and mixtures thereof, which preferably satisfy the following formula (I). R 1 -[CO-X(CH2) n ] x -N + (R 2 )(R3)-(CH2) m -[CH(OH)-CH2] y -Y - 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. R1 is preferably a linear alkyl chain and preferably derived from a natural renewable source such as coconut or palm kernel, preferably coconut.

[0075] X is selected from the group consisting of NH, NR4 (where R4 is a C1-4 alkyl residue), O, and S. n is an integer between 1 and 10, preferably between 2 and 5, more preferably between 3. x is 0 or 1, preferably 1. R2 and R3 are independently selected from the group consisting of C1-4 alkyl residues, substituted hydroxyls such as hydroxyethyl, and mixtures thereof, preferably both R2 and R3 are methyl. m is an integer between 1 and 4, preferably 1, 2, or 3. y is either 0 or 1. Y is selected from the group consisting of COO, SO3, OPO(OR5)O, or P(O)(OR5)O (wherein R5 is H or C1-4 alkyl residues).

[0076] Preferred betaines are alkylbetaine of formula (Ia), alkylamidopropylbetaine of formula (Ib), sulfobetaine of formula (Ic), and amidesulfobetaine of formula (Id). R 1 -N + (CH3)2-CH2COO - (Ia) R 1 -CO-NH-(CH2)3-N + (CH3)2-CH2COO - (Ib) R 1 -N + (CH3)2-CH2CH(OH)CH2SO3- (Ic) R 1 -CO-NH-(CH2)3-N + (CH3)2-CH2CH(OH)CH2SO3- (Id) In the formula, R1 has the same meaning as in formula (I). Particularly preferred are the carbobetaines of formulas (Ia) and (Ib) [i.e., in formula (I), Y- is COO-], and more preferred is the alkylamide betaine of formula (Ib).

[0077] Preferred betaines can be selected from the group consisting of capryl / capramidopropyl betaine, cetyl betaine, cetylamidopropyl betaine, cocamidoethyl betaine, cocamidopropyl betaine, cocobetaine, decyl betaine, decylamidopropyl betaine, hydrogenated taro betaine / amidopropyl betaine, isostearamidopropyl betaine, lauramidopropyl betaine, lauryl betaine, myristylamidopropyl betaine, myristyl betaine, oleamidopropyl betaine, oleyl betaine, palmamidopropyl betaine, palmitoamidopropyl betaine, palm kernelamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, taroamidopropyl betaine, taro 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, myristylamidopropyl betaine, myristyl betaine, and mixtures thereof. Cocamidopropyl betaine and / or laurylamidopropyl betaine are particularly preferred.

[0078] The composition may further contain amphoteric surfactant auxiliary surfactants such as amine oxide surfactants. However, the composition preferably does not contain amphoteric surfactants such as amine oxide surfactants.

[0079] Amine oxide surfactants may be linear or branched, but linear is preferred. Preferred linear amine oxides are typically water-soluble and characterized by the formula R1-N(R2)(R3)O. R1 is a C8-18 alkyl group, 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 portions 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, but it is preferable that one or both of R2 and R3 are methyl. Examples of linear amine oxide surfactants include linear C10-C18 alkyldimethylamine oxides and linear C8-C12 alkoxyethyl dihydroxyethylamine oxides.

[0080] Amine oxide surfactants can be selected from the group consisting of alkyldimethylamine oxides, alkylamidopropyldimethylamine oxides, and mixtures thereof. Alkyldimethylamine oxides such as C8-18 alkyldimethylamine oxides or C10-16 alkyldimethylamine oxides (such as cocodimethylamine oxide) are particularly preferred. Preferred alkyldimethylamine oxides include C10 alkyldimethylamine oxide surfactants, C10-12 alkyldimethylamine oxide surfactants, C12-C14 alkyldimethylamine oxide surfactants, and mixtures thereof. C12-C14 alkyldimethylamine oxides are particularly preferred.

[0081] A suitable alternative amine oxide surfactant is a moderately branched amine oxide surfactant. As used herein, “moderately branched” means that the amine oxide has one alkyl moiety having n1 carbon atoms, and one alkyl branch in the alkyl moiety has n2 carbon atoms. The alkyl branch is located from the nitrogen to the alpha carbon on the alkyl moiety. This type of branching of amine oxide is also known in the art as internal amine oxide. 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), so that the alkyl moiety and its alkyl branch are symmetrical. As used herein, “symmetrical” means that in at least 50% by weight, more preferably at least 75% to 100% by weight of the moderately branched amine oxide used herein, |n1-n2| has 5 or fewer, preferably 4, and most preferably 0 to 4 carbon atoms. The amine oxide further comprises two portions independently selected from C1-3 alkyl, C1-3 hydroxyalkyl, or polyethylene oxide groups containing, on average, about 1 to about 3 ethylene oxide groups. Preferably, these two portions are selected from C1-3 alkyl, and more preferably, both are selected as C1 alkyl.

[0082] Alternatively, the amine oxide surfactant may be a mixture of amine oxides, including a mixture of low-cut amine oxides and mid-cut amine oxides. Therefore, the amine oxides in the composition of the present invention are a) A low-cut amine oxide of formula R1R2R3AO in an amount of approximately 10% to approximately 45% by weight of amine oxide, where 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) The amine oxide may contain 55% to 90% by weight of a midcut amine oxide of formula R4R5R6AO (wherein R4 and R5 are independently selected from hydrogen, C1-C4 alkyl, or mixtures thereof, and R6 is selected from C12-C16 alkyl, or mixtures thereof).

[0083] In the low-cut amine oxides preferred for use herein, R3 is n-decyl, and preferably both R1 and R2 are methyl. In the mid-cut amine oxide of formula R4R5R6AO, preferably both R4 and R5 are methyl.

[0084] Preferably, the amine oxide comprises less than about 5% by weight, more preferably less than 3% by weight, of an amine oxide of formula R7R8R9AO (wherein R7 and R8 are selected from hydrogen, C1-C4 alkyl, and mixtures thereof, and R9 is selected from C8 alkyl and mixtures thereof). Limiting the amount of amine oxide of formula R7R8R9AO improves both physical stability and foaming persistence.

[0085] Nonionic surfactants This surfactant system may further include a nonionic surfactant. Suitable nonionic surfactants include alkoxylated alcohol nonionic surfactants, alkyl polyglucoside nonionic surfactants, and mixtures thereof. When the nonionic surfactant includes a blend of alkyl polyglucoside and alkoxylated alcohol nonionic surfactant, the nonionic surfactant may contain alkyl polyglucoside and alkoxylated alcohol nonionic surfactant in a mass ratio of 10:90 to 90:10, preferably 30:70 to 70:30, and more preferably 40:60 to 60:40.

[0086] The surfactant system of the composition of the present invention may further contain 1.0% to 50% by weight, preferably 1.25% to 25% by weight, more preferably 1.5% to 15% by weight, and most preferably 1.5% to 5% by weight of a nonionic surfactant.

[0087] Alkoxylated alcohol nonionic surfactant Preferably, the alkoxylated alcohol nonionic surfactant is a linear or branched primary or secondary alkylalkoxylated nonionic surfactant, preferably an alkylethoxylated nonionic surfactant, which preferably contains an average of 9 to 15 carbon atoms, preferably 10 to 14 carbon atoms, in its 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.

[0088] Suitable examples of commercially available alkoxylated alcohol nonionic surfactants include those derived from alcohols sold by Shell under the trademark Neodol®, or by Sasol under the trademarks Lial®, Isalchem®, and Safol®, or some of the natural alcohols produced by Procter & Gamble Chemicals. Their performance may be affected by the width of the alkoxylation distribution of the alkoxylated alcohol nonionic surfactant. The alkoxylation distribution, including its width, may vary depending on the selection of catalysts and process conditions when producing the alkoxylated alcohol nonionic surfactant.

[0089] Alkyl polyglucoside nonionic surfactant Alkyl polyglucoside nonionic surfactants typically produce more foam than other nonionic surfactants such as alkyl ethoxylated alcohols.

[0090] Combinations of alkyl polyglucosides with anionic surfactants, particularly mixtures of alkyl sulfates and alkyl glycol sulfate anionic surfactants, have been found to improve polymerized oil removal, foam retention, viscosity changes due to changes in surfactants and / or systems, and more persistent Newtonian rheology.

[0091] Alkyl polyglucoside surfactants can be selected from C6-C18 alkyl polyglucoside surfactants. Alkyl polyglucoside surfactants can have a number average degree of polymerization of 0.1-3.0, preferably 1.0-2.0, and more preferably 1.2-1.6. Alkyl polyglucoside surfactants can include blends 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 to 18 carbon atoms, preferably 12-14 carbon atoms. The alkyl chains are preferably linear.

[0092] Short-chain alkyl polyglucoside surfactants have a monomodal chain length distribution of C8-C10, medium-to-long-chain alkyl polyglucoside surfactants have a monomodal chain length distribution of C10-C18, while medium-chain alkyl polyglucoside surfactants have a monomodal chain length distribution of C12-C14. In contrast, C8-C18 alkyl polyglucoside surfactants typically have a monomodal distribution of alkyl chains of C8-C18, such as C8-C16. Therefore, combinations of short-chain alkyl polyglucoside surfactants with medium-to-long-chain or medium-chain alkyl polyglucoside surfactants have a broader chain length distribution, or even a bimodal distribution, than unblended C8-C18 alkyl polyglucoside surfactants. Preferably, the weight ratio of short-chain alkyl polyglucoside surfactant to long-chain alkyl polyglucoside surfactant is 1:1 to 10:1, preferably 1.5:1 to 5:1, and more preferably 2:1 to 4:1. Such blends of short-chain alkyl polyglucoside surfactants and long-chain alkyl polyglucoside surfactants have been found to result in faster dissolution and improved initial foaming of the detergent aqueous solution, combined with improved foaming stability.

[0093] C8-C16 alkyl polyglucosides are commercially available from several suppliers (e.g., Simusol® surfactant 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.

[0094] In preferred compositions, the surfactant system may include alkyl sulfate anionic surfactants having an average degree of branching of less than 10%, alkyl glycol sulfate anionic surfactants, and alkyl polyglucoside nonionic surfactants.

[0095] Further ingredients This cleansing composition may optionally contain many other auxiliary components such as builders (preferably citrates), chelating agents, conditioning polymers, other cleansing polymers, surface modifying polymers, structuring agents, emollients, wetting agents, skin rejuvenating active substances, enzymes, carboxylic acids, scrub particles, fragrances, odor suppressants, pigments, dyes, opacifiers, pearlescent particles, inorganic cations such as alkaline earth metals like Ca / Mg ions, antimicrobial agents, preservatives, viscosity modifiers (e.g., salts such as NaCl and other monovalent, divalent, and trivalent salts), and pH adjusters and buffering means (e.g., carboxylic acids such as citric acid, HCl, NaOH, KOH, alkanolamines, sodium carbonate, bicarbonates, sesquicarbonates, and other carbonates).

[0096] Further preferred components include amphiphilic alkoxylated polyalkyleneimines, cyclic polyamines, triblock copolymers, hydroxypropyl cellulose polymers, salts, hydrotropes, organic solvents, and mixtures thereof.

[0097] Amphiphilic alkoxylated polyalkyleneimines: The compositions of the present invention may further contain 0.05% to 2% by weight, preferably 0.07% to 1% by weight, of an amphiphilic polymer in total weight. Suitable amphiphilic polymers can 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 to be cleaned when their liquid composition is added directly to a cleaning tool (such as a sponge) before cleaning and then brought into contact with a heavily soiled surface, especially when the cleaning tool contains little to no water, for example, when a pre-moistened sponge is used.

[0098] A preferred amphiphilic alkoxylated polyethyleneimine polymer is given by formula (I):

[0099] [ka] The general structure is as shown, the polyethyleneimine skeleton has a weight-average molecular weight of 600, n in formula (I) is on average 10, m in formula (I) is on average 7, and R in formula (I) is selected from hydrogen, C1-C4 alkyl, and mixtures thereof, preferably hydrogen. The permanent degree of quaternization of formula (I) can be 0% to 22% of the nitrogen atoms in the polyethyleneimine skeleton. The molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer is preferably 10,000 to 15,000 Da.

[0100] More preferably, the amphiphilic alkoxylated polyethyleneimine polymer has the general structure of formula (I), wherein the polyethyleneimine skeleton has a weight-average molecular weight of 600 Da, n in formula (I) is on average 24, m in formula (I) is on average 16, and R in formula (I) is selected from hydrogen, C1-C4 alkyl, and mixtures thereof, preferably hydrogen. The permanent degree of quaternization of formula (I) can be 0% to 22% of the nitrogen atoms in the polyethyleneimine skeleton, preferably 0%. The molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer is preferably 25,000 to 30,000, most preferably 28,000 Da.

[0101] Amphiphilic alkoxylated polyethyleneimine polymers can be prepared by the method described in detail in International Publication No. 2007 / 135645.

[0102] Alternatively, the composition may be free of amphiphilic polymers.

[0103] Cyclic polyamines The composition may include a cyclic polyamine having an amine functional group that aids in cleaning. The composition of the present invention preferably contains 0.1% to 3% by weight, more preferably 0.2% to 2% by weight, and particularly 0.5% to 1% by weight of a cyclic polyamine in total.

[0104] Cyclic polyamines have at least two primary amine functional groups. While primary amines can be located at any position within the cyclic amine, it has been found that better performance is obtained when the primary amines are located at positions 1 and 3, from the viewpoint of grease and oil cleaning. It has also been found that cyclic amines in which one substituent is -CH3 and the rest are H atoms result in improved grease and oil cleaning performance.

[0105] Therefore, the most preferred cyclic polyamines for use in the cleaning compositions of the present invention are cyclic polyamines selected from the group consisting of 2-methylcyclohexane-1,3-diamine, 4-methylcyclohexane-1,3-diamine, and mixtures thereof. When these particular cyclic polyamines are formulated with the surfactant system of the compositions of the present invention, they function to improve the foaming and grease-cleaning profiles throughout the dishwashing process.

[0106] Suitable cyclic polyamines can be supplied by BASF under the trademark name Baxxodur, with Baxxodur ECX-210 being particularly preferred.

[0107] A combination of cyclic polyamine and magnesium sulfate is particularly preferred. Therefore, the composition may further contain magnesium sulfate at a concentration of 0.001% to 2.0% by weight, preferably 0.005% to 1.0% by weight, and more preferably 0.01% to 0.5% by weight of the composition.

[0108] Triblock copolymer The compositions of the present invention may contain triblock copolymers. The triblock copolymer may be present in a concentration of 1% to 20% by weight, preferably 3% to 15% by weight, and more preferably 5% to 12% by weight of the whole composition. A suitable triblock copolymer is an alkylene oxide triblock copolymer defined as a triblock copolymer having an alkylene oxide moiety according to formula (I): (EO)x(PO)y(EO)x, where EO represents ethylene oxide and x represents the number of EO units in each EO block. Each x can be independently, on average, 5 to 50, preferably 10 to 40, and more preferably 10 to 30. Preferably, x is the same for both EO blocks, where "same" means that the difference in x between the two EO blocks is at most 2 units, preferably at most 1 unit, and more preferably both x have the same number of units. PO represents propylene oxide and y represents the number of PO units in the PO block. Each y can be, on average, 28 to 60, preferably 30 to 55, and more preferably 30 to 48.

[0109] Preferably, the ratio of y to each x in the triblock copolymer is 3:1 to 2:1. Preferably, the ratio of y to the average x of the two EO blocks in the triblock copolymer is 3:1 to 2:1. Preferably, the triblock copolymer has an average weight percentage of all EO that is 30% to 50% by weight of the triblock copolymer. Preferably, the triblock copolymer has an average weight percentage of all PO that is 50% to 70% by weight of the triblock copolymer. It is understood that the average total weight percentage of EO and PO in the triblock copolymer is 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).

[0110] A triblock copolymer has a 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 phrase “block copolymer” is synonymous with this definition of “block polymer.”

[0111] Triblock copolymers according to formula (I), having specific EO / PO / EO configurations and respective homopolymer lengths, have been found to enhance the foaming persistence and / or foam consistency throughout dilution in liquid dishwashing detergent compositions in the presence of oily stains.

[0112] Suitable EO-PO-EO triblock copolymers are commercially available, for example, from BASF as the Pluronic® PE series and from Dow Chemical Company as the Tergitol® L series. Particularly preferred triblock copolymers from BASF are sold under the trademark names Pluronic® PE6400 (approximately 2900 MW, approximately 40% by weight EO) and Pluronic® PE9400 (approximately 4600 MW, approximately 40% by weight EO). Particularly preferred triblock copolymers from Dow Chemical are sold under the trademark name Tergitol® L64 (approximately 2700 MW, approximately 40% by weight EO).

[0113] Preferred triblock copolymers readily biodegrade under aerobic conditions.

[0114] salt: The compositions of the present invention may contain, more preferably, about 0.05% to about 2% by weight, preferably about 0.1% to about 1.5% by weight, or more preferably about 0.5% 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 mixtures thereof. Sodium chloride is most preferred.

[0115] Hydrotrope: The composition of the present invention may contain about 0.1% to about 10% by weight, preferably about 0.5% to about 10% by weight, or more preferably about 1% to about 10% by weight, of hydrotrope or a mixture thereof, preferably sodium cumenesulfonate, in the total composition. .

[0116] Organic solvents: The composition may contain an organic solvent in an amount of about 0.1% to about 10% by weight of the total composition, 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, with alcohols, glycols, and mixtures thereof being preferred. 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.

[0117] Packaged Products Dishwashing detergent compositions can be packaged in containers, typically plastic containers. Suitable containers include an orifice. Typically, the container has a cap, and the orifice is typically located on the cap. The cap may have a spout, and the orifice is located at the outlet of the spout. The spout may have a length of 0.5 mm to 10 mm.

[0118] The orifice is 3mm at the exit. 2 ~20mm 2 Preferably 3.8 mm 2 ~12mm 2 , more preferably 5mm 2 ~10mm 2 The container may have an open cross-sectional area and further comprises the composition according to the present invention. The cross-sectional area is measured perpendicular to the liquid outlet from the container (i.e., perpendicular to the liquid flow during distribution).

[0119] The container can typically contain a liquid dishwashing detergent composition in a volume of 200 mL to 5,000 mL, preferably 350 mL to 2,000 mL, and more preferably 400 mL to 1,000 mL.

[0120] Alternatively, dishwashing detergent compositions can be packaged in reversible containers. Such reversible containers typically have a cap at the bottom of the container, which includes either a lid or a self-sealing valve, or a combination thereof. The cap preferably includes a self-sealing valve. A suitable self-sealing valve is a slit valve. The self-sealing valve defines an orifice that opens in reaction when the pressure inside the valve exceeds the pressure outside the valve. Bottom-shaped dispensing containers may include an impact-resistant system, such as that described in International Publication No. 2019108293(A1).

[0121] Cleaning method The present invention further relates to a method for manually washing tableware with the composition of the present invention. This method includes the steps of supplying the composition of the present invention to a predetermined volume of water to form a washing solution, and immersing the tableware in the solution. The tableware is washed with the composition in the presence of water.

[0122] Optionally, the dishes may be rinsed. In this specification, “rinsing” means bringing the dishes, which have been cleaned by the method according to the present invention, into contact with a considerable amount of a suitable solvent, typically water. “Considerable amount” usually means about 1 to about 20 liters or under running water.

[0123] The compositions described herein may be applied in their diluted form. Soiled dishes are brought into contact with an effective amount, typically about 0.5 mL to about 20 mL, preferably about 3 mL to about 10 mL, of the cleaning composition of the present invention diluted with water (for about 25 dishes to be processed), preferably in liquid form. The actual amount of cleaning composition used is at the user's discretion and typically depends on factors such as the formulation of the specific product of the cleaning composition, including the concentration of the active ingredients in the cleaning composition, the number of 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. After immersing the soiled dishes in the sink containing the thus diluted cleaning composition, the soiled surfaces of the dishes are brought into contact with a cloth, sponge, or similar cleaning tool. The cloth, sponge, or similar cleaning tool may be immersed in a mixture of the cleaning composition and water before contact with the dishes, typically for a period ranging from about 1 to about 10 seconds, although the actual time will vary depending on the application and user. Contacting the cloth, sponge, or similar cleaning tool with the dishes involves simultaneously scrubbing the dishes.

[0124] Alternatively, the undiluted form of the composition as specified herein may be applied to the dishes to be processed. “Undiluted form” means, as used herein, that the composition is applied directly to the surface to be processed, or to a cleaning device or tool such as a brush, sponge, nonwoven or woven material, without any significant dilution by the user immediately before application. “Undiluted form” also includes, for example, slight dilution due to the presence of water on the surface of the cleaning device, or the addition of water by the consumer to remove any remaining amount of the composition from the bottle. Therefore, 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 operations.

[0125] method pH pH is measured as a 10% aqueous solution in desalinated water at 20°C using a pH meter such as the Orion Model 720A equipped with an Ag / AgCl electrode (e.g., Orion Sure Flow electrode Model 9172BN), and calibrated using standardized pH 7 and pH 10 buffers.

[0126] Viscosity measurement (Brookfield) Viscosity is measured at 20°C using a Brookfield RT viscometer with spindle 31, whose RPM is adjusted to achieve 40%–60% torque for viscosities above 100 mPas. For viscosities below 100 mPas, spindle 18 is used.

[0127] Foaming persistence in the presence of oily particulate matter The purpose of the foam persistence test is to compare the time-dependent development of foam volume generated for various test formulations at specified water hardness, solution temperature, and formulation concentration while under the influence of periodic fouling injection. The data are compared and expressed as a foam persistence index relative to a reference composition (the reference composition has a foam persistence index of 100). The procedure is as follows: 1. A specified amount of the test composition, corresponding to the target composition concentration (here, 0.12 wt%), is dispensed through a plastic pipette at a flow rate of 0.67 mL / second into a sink filled with water (here, water hardness: 0.36 mmol CaCO3 (2 dH), water temperature: 46°C) at a constant pressure of 4 bar until the sink reaches 4 L, at a height of 37 cm above the bottom surface of the sink (dimensions: diameter 300 mm and height 288 mm). 2. Initial foam volume generated (measured as average foam height × sink surface area, cm²) 3 The value (represented by ) is recorded immediately after filling is complete. 3. Immediately pour a fixed amount (6 mL) of dirt having the following specified composition into the center of the sink. 4. Mix the resulting solution using a metal blade (10cm x 5cm) that rotates 20 times at 85 RPM and is positioned in the center of the sink at a 45-degree angle at the gas-liquid interface. 5. Record another measurement of the total foaming volume immediately after the blade rotation ends. 6. The measured total foaming volume is 400 cm³. 3 Repeat steps 3-5 until the minimum level is reached. 400cm 3 The amount of dirt required to reach that level is considered to be the foaming persistence of the test composition. 7. Each test composition is tested four times under the same test conditions (i.e., water temperature, composition concentration, water hardness, and type of dirt). 8. The average foaming persistence is calculated by taking the average of four tests performed for each sample under the specified test conditions. 9. The foaming persistence index is calculated by comparing the average persistence of the test composition sample to that of the reference composition sample. The calculation is as follows:

[0128]

number

[0129] The particulate matter composition used in the test was prepared by mixing the components listed in Table 1 in a standard manner.

[0130] [Table 1]

[0131] Low temperature stability The liquid composition is stored in a 30 mL glass vial at 5°C for 1 day, and then the phase stability of the liquid composition is visually evaluated. [Examples]

[0132] Example of synthesis The following blends containing alkyl glycol sulfate and alkyl sulfated anionic surfactants were prepared as follows:

[0133] Synthesis Example 1: Co-synthesis of a blend of C12 alkylethylene glycol sulfate and C12 alkyl sulfate Co-synthesis of branched-chain C12 alkyloxyethanol (mainly 2-[(1-methylundecyl)oxy]ethanol (CAS 5940-87-4)) and dodecane-2-ol (CAS 10203-28-8): 50.18 g (0.298 mol) of 1-dodecene, 74.08 g (1.19 mol) of ethylene glycol, 49.84 g (0.262 mol) of p-toluenesulfonic acid monohydrate, and a magnetic stirring rod were added to a 2-liter round-bottom reaction flask. The reaction flask was heated in a silicone oil bath maintained at 130°C while mixing and aerating with air. After 2 hours, the reaction mixture was sampled for thin-layer chromatography (TLC) analysis. The TLC results showed product formation and the presence of residual starting materials. The reaction flask was removed from the oil bath and cooled to room temperature (21°C). At this point, the reaction product was combined with 1 L of 10 wt% aqueous sodium carbonate solution, and then washed three times with 2 L of ethyl acetate in a separatory funnel. The ethyl acetate layers were combined, anhydrous sodium sulfate was added and dried, the sodium sulfate was removed by filtration, and the mixture was concentrated by evaporating the solvent using a rotary evaporator. The product was purified by silica gel column chromatography (80:20 hexane:ethyl acetate mobile phase), and the fractions containing the desired product were combined and concentrated by evaporating the solvent using a rotary evaporator to obtain 4.012 g of the product. The presence of the desired 2-[(1-methylundecyl)oxy]ethanol and dodecane-2-ol products was confirmed by NMR and MS analysis.

[0134] A second synthesis and purification was completed on a similar scale using the procedure described above, yielding 4.672 g of the desired product. The two separately synthesized / purified blends of 2-[(1-methylundecyl)oxy]ethanol and dodecane-2-ol were combined for subsequent sulfation.

[0135] Cosulfation of a blend of branched-chain C12 alkyloxyethanol and dodecane-2-ol: A 1 L three-necked round-bottom flask was fitted with a magnetic stirring rod and an additive funnel having a pressure equalization arm and a nitrogen gas supply section at the center neck. A thermometer was attached to one side neck, and a vent tube leading to a gas bubbler filled with demineralized water was attached to the other neck to capture the HC1 gas generated from the reaction. A 2 L glass trap was placed between the gas bubbler and the reaction flask to prevent water from being drawn back into the reaction flask. 135.5 g of a blend of 2-[(1-methylundecyl)oxy]ethanol and dodecane-2-ol, and 150 mL of ACS reagent-grade diethyl ether (EMD Millipore product number EX0190) were added to the round-bottom flask. 72.6 g (0.617 mol) of 99.0% chlorosulfonic acid (Sigma-Aldrich product number 571024) was added to the additive funnel. A nitrogen gas stream was directed from the top of the addition funnel, through the flask, out the vent at the side opening, and into the gas bubbler. An ice / NaCl / water bath was placed around the reaction flask. Mixing was initiated, forming a clear, dark orange solution. After the reaction mixture reached 5°C, chlorosulfonic acid was added dropwise at a rate that controlled exothermic heat release and maintained the temperature below 10°C. The addition of chlorosulfonic acid was completed in 60 minutes.

[0136] The ice / NaCl / water bath was replaced with a 22°C water bath. The vent tube attached to the gas bubbler was switched to a vacuum tube attached to a diaphragm vacuum pump. A solvent trap cooled in a dry ice / isopropanol bath was placed along the vacuum tube between the reaction flask and the vacuum pump to capture volatiles drawn from the reaction mixture. A dial pressure gauge (US Gauge, capable of measuring 0-30 inchHg) was placed in the vacuum tube after the solvent trap to measure the vacuum level of the system. The reactants were continued to mix for 14 minutes under nitrogen gas sweep while maintaining the vacuum system.

[0137] While mixing continued, the vacuum pump was started to begin applying vacuum to the reaction mixture. The vacuum level was slowly increased by gradually reducing the nitrogen gas flow rate from the addition funnel. This was done to control foaming of the reaction mixture. Finally, the nitrogen flow was completely stopped, and a full vacuum was applied to the reaction mixture (30 inches Hg [1.02 bar] measured with the vacuum gauge indicates that a full vacuum was applied). A full vacuum was reached 27 minutes after the start of the vacuum process. Mixing continued for an additional 26 minutes under full vacuum, at which point the reaction mixture was a clear, brownish fluid with minimal foaming observed, at which point the vacuum was released with a nitrogen gas flow.

[0138] While maintaining good eddy mixing using a magnetic stirring rod, the reaction mixture was slowly poured into a solution of 144.8 grams (0.676 moles) of 25.2 wt% sodium methoxide in methanol reagent (Sigma-Aldrich product number 156256) diluted to a total volume of 1 liter with ACS reagent-grade methanol (EMD Millipore product number MX0475) contained in a glass beaker, converting the sulfated 2-[(1-methylundecyl)oxy]ethanol and dodecane-2-ol reaction product from acid sulfate to sodium salt. The resulting product was a turbid mixture with a pale brown precipitate, accompanied by good eddy mixing. Approximately 0.2 g of this neutralization reaction product was dissolved in approximately 0.5 g of desalted water, and the pH was measured using pH test paper, resulting in a pH of approximately 10-11. The resulting product was mixed for a further 15 minutes, and the pH was measured again to be 10-11.

[0139] The reaction product was concentrated by evaporating the solvent using a rotary evaporator equipped with a water bath set to 50°C until the mixture began to foam, at which point the mixture was poured into a glass crystallization dish. The crystallization dish was placed in a vacuum oven at 21°C under partial vacuum with a slow flow of nitrogen gas through the oven to further concentrate the product mixture while preventing foaming. The internal pressure of the vacuum oven was approximately 4 inHg [0.14 bar]. After 4 days, the concentrated reaction product was removed from the vacuum oven. The product was solid at this point. The solid was crushed into smaller particles using a spatula and then placed in a vacuum oven at 27°C under complete vacuum. After 7 hours, the product was ground into smaller particles using a mortar and pestle and then placed overnight in a vacuum oven at 21°C under complete vacuum. The following day, the product was again ground into smaller particles using a mortar and pestle and then returned to the vacuum oven at 27°C for 7 hours under complete vacuum, and then overnight at 21°C under complete vacuum. The following day, the product was sampled for NMR analysis (proton, carbon, and DEPT) and placed in a vacuum oven at 21°C under complete vacuum. The next day, the product was pulverized using a mechanical grinder and then placed in a vacuum oven at 27°C for 3 hours under complete vacuum, followed by 21°C for 5 days. After 5 days, the product was sampled for proton NMR and standard cationic SO3 titration analysis, and then transferred to a bottle for storage. 188.2 g of a light brown solid was obtained.

[0140] NMR analysis: 0.0424 g of the product was dissolved in a mixture of 0.6 g of heavy water and 0.3 g of methanol-d4 and subjected to NMR analysis. 1 H, 13 (C, and DEPT). NMR identified the desired target products, 2-[(1-methylundecyl)oxy]ethanol sulfate sodium and 2-dodecanol sulfate sodium.

[0141] The NMR resonance of 2-dodecanol sodium sulfate was verified by synthesizing a reference sample of 2-dodecanol sodium sulfate via the sulfation of 2-dodecanol (Sigma-Aldrich product number D221503) using the standard sulfation procedure described above.

[0142] Quantification of the levels of C12 alkyl ethylene glycol sulfate and C12 alkyl sulfate in the sulfation product is as follows: 1 The concentration was determined using 1H NMR. The concentration of the alkylethylene glycol sulfate anionic surfactant was calculated to be 86.5% by weight of the sulfation product, mainly 2-[(1-methylundecyl)oxy]ethanol sulfate sodium (i.e., when R1 is methyl and R2 is n-decyl, 13 (Determined by 13C NMR). The concentration of the 2-dodecanol sulfate anionic surfactant was calculated to be 13.5% by weight of the sulfation product.

[0143] The final product, based on solids, was determined to be an 89.6% blend of active total sulfated surfactants by standard cationic SO3 titration analysis (ASTM international standard designation: D3049). The remaining 10.4% non-surfactant solids consisted of impurities such as sodium sulfate, sodium chloride, and residual water.

[0144] Synthesis Example 2: Co-synthesis of C14 alkyl glycol sulfate and C14 alkyl sulfate blend Co-synthesis of branched-chain C14 alkyloxyethanol (mainly 2-[(1-methyltridecyl)oxy]ethanol (CAS #19494-32-7)) and tetradecane-2-ol (CAS 4706-81-4): 150 g (0.765 mol) of 1-tetradecene, 142 g (2.28 mol) of ethylene glycol, 138 g (0.726 mol) of p-toluenesulfonic acid monohydrate, and a magnetic stirring rod were added to a 2-liter round-bottom reaction flask. The reaction flask was heated in a silicone oil bath maintained at 100°C while mixing and aerating with air. After 72 hours, the reaction mixture was sampled for TLC analysis. The TLC results showed product formation and the presence of residual starting materials. The reaction flask was removed from the oil bath and cooled to room temperature (21°C). At this point, the reaction product was combined with 2 L of 10 wt% aqueous sodium carbonate solution and then washed three times with 1.5 L of ethyl acetate in a separatory funnel. The ethyl acetate layers were combined, dried by adding anhydrous sodium sulfate, filtered to remove sodium sulfate, and then concentrated by evaporating the solvent using a rotary evaporator. The product was purified by silica gel column chromatography (80:20 hexane:ethyl acetate mobile phase), and the fractions containing the desired product were combined and concentrated by evaporating the solvent using a rotary evaporator to obtain 16 g of the product. The presence of the desired products 2[(1-methyltridecyl)oxy]ethanol and tetradecane-2-ol was confirmed by NMR and MS analysis.

[0145] A second synthesis and purification was completed on a similar scale using the procedure described above, yielding 4 g of product. The two separately synthesized / purified blends of 2[(1-methyltridecyl)oxy]ethanol and tetradecane-2-ol were combined for subsequent sulfation.

[0146] Cosulfation of a blend of branched-chain C14 alkyloxyethanol and tetradecane-2-ol: A 250 mL three-necked round-bottom flask was fitted with a magnetic stirring rod and an additive funnel having a pressure equalizing arm and a nitrogen gas supply section at the center neck. A thermometer was attached to one side neck, and a vent tube leading to a gas bubbler filled with demineralized water was attached to the other neck to capture the HC1 gas generated from the reaction. A 2 L glass trap was placed between the gas bubbler and the reaction flask to prevent water from being drawn back into the reaction flask. 20.702 grams of a blend of 2-[(1-methyltridecyl)oxy]ethanol and tetradecane-2-ol, along with 85 mL of ACS reagent-grade diethyl ether (EMD Millipore product number EX0190), were added to the round-bottom flask. 9.852 grams (0.0842 mol) of 99.6% chlorosulfonic acid (Sigma-Aldrich product number 571024) were added to the additive funnel. A nitrogen gas stream was directed from the top of the addition funnel, through the flask, out the vent at the side opening, and into the gas bubbler. An ice / NaCl / water bath was placed around the reaction flask. Mixing was initiated, forming a clear, pale yellow solution. After the reaction mixture reached 7°C, chlorosulfonic acid was added dropwise at a rate that controlled the exothermic heat release and maintained the temperature below 10°C. The addition of chlorosulfonic acid was completed in 16 minutes.

[0147] The ice / NaCl / water bath was replaced with a 22°C water bath. The vent tube attached to the gas bubbler was switched to a vacuum tube attached to a diaphragm vacuum pump. A solvent trap cooled in a dry ice / isopropanol bath was placed along the vacuum tube between the reaction flask and the vacuum pump to capture volatiles drawn from the reaction mixture. A dial pressure gauge (US Gauge, capable of measuring 0-30 inchHg) was placed in the vacuum tube after the solvent trap to measure the vacuum level of the system. The reactants were continued to mix for 14 minutes under nitrogen gas sweep while maintaining the vacuum system.

[0148] While mixing continued, the vacuum pump was started to begin applying vacuum to the reaction mixture. The vacuum level was slowly increased by gradually reducing the nitrogen gas flow rate from the addition funnel. This was done to control foaming of the reaction mixture. Finally, the nitrogen flow was completely stopped, and a perfect vacuum was applied to the reaction mixture (30 inches Hg [1.02 bar] measured with the vacuum gauge indicates that a perfect vacuum was applied). A perfect vacuum was reached 24 minutes after the start of the vacuum process. Mixing was continued for an additional 11 minutes under perfect vacuum, at which point the reaction mixture was a clear, dark orange fluid with minimal foaming observed, at which point the vacuum was released with a nitrogen gas flow.

[0149] While eddy mixing was maintained using a magnetic stirring rod, the reaction mixture was slowly poured into a 500 mL round-bottom flask containing 85 mL of methanol reagent (Sigma-Aldrich product number 156256) diluted with ACS reagent-grade methanol (EMD Millipore product number MX0475), into a solution of 19.764 g (0.0922 mol) of 25.2 wt% sodium methoxide, converting the sulfated 2-[(1-methyltridecyl)oxy]ethanol and tetradecane-2-ol reaction product from acid sulfate to sodium salt. The resulting product was a turbid mixture with a white precipitate, accompanied by good eddy mixing. Approximately 0.2 g of this neutralization product was dissolved in approximately 0.5 g of desalted water, and the pH was measured using pH test paper, resulting in a pH of approximately 10. The resulting product was mixed for a further 15 minutes, and the pH was measured again to be 10.

[0150] The reaction product was concentrated by evaporating the solvent using a rotary evaporator equipped with a water bath set to 50°C to obtain a soft yellow solid. The product was placed in a vacuum oven at approximately 27°C under complete vacuum for 1 hour, and then left overnight at 21°C under complete vacuum. The next day, the product was crushed into smaller particles using a spatula and then placed in a vacuum oven at 27°C under complete vacuum. After 7 hours, the product was further ground into smaller particles using a mortar and pestle and then left overnight in a vacuum oven at 21°C under complete vacuum. The next day, the product was sampled for NMR analysis and then returned to the vacuum oven at 21°C under complete vacuum for an additional 3 days, after which it was transferred to a bottle for storage. 27.5 g of a light brown solid product was obtained.

[0151] NMR analysis: 0.0360 g of the product was dissolved in a mixture of 0.6 g of heavy water and 0.3 g of methanol-d4 and subjected to NMR analysis. 1 H, 13 (C, and DEPT). NMR identified the desired target products, 2-[(1-methyltridecyl)oxy]ethanol sulfate sodium and 2-tetradecanol sulfate sodium.

[0152] Quantification of the levels of C14 alkyl ethylene glycol sulfate and C14 alkyl sulfate in the sulfation product is as follows: 1 The concentration was determined using 1H NMR. The concentration of the alkyl glycol sulfate anionic surfactant was calculated to be 94.8% by weight of the sulfation product, mainly 2-[(1-methyltridecyl)oxy]ethanol sulfate sodium (i.e., when R1 is methyl and R2 is n-dodecyl, 13 (Determined by 13C NMR). The concentration of the 2-tetradecanol sulfate anionic surfactant was calculated to be 5.2% by weight of the sulfated product.

[0153] The final product, based on solids, was determined to be a 90.33% active total sulfated surfactant blend by standard cationic SO3 titration analysis (ASTM international standard designation: D3049). The remaining 9.67% non-surfactant solids consisted of impurities such as sodium sulfate, sodium chloride, and residual water.

[0154] Synthesis Example 3: Co-synthesis of C16 alkyl glycol sulfate and C16 alkyl sulfate blend Co-synthesis of branched-chain C14 alkyloxyethanol (mainly 2-[(1-methylpentadecyl)oxy]ethanol (CAS #30714-96-6)) and hexadecane-2-ol (CAS 14852-31-4): 100.73 g (0.453 mol) of 1-hexadecene, 112.81 g (1.82 mol) of ethylene glycol, 77.80 g (0.409 mol) of p-toluenesulfonic acid monohydrate, and a magnetic stirring rod were added to a 2-liter round-bottom reaction flask. The reaction flask was heated in a silicone oil bath maintained at 130°C while mixing and aerating with air. After 7 hours, the reaction mixture was sampled for TLC analysis. The TLC results showed product formation and the presence of residual starting materials. The reaction flask was removed from the oil bath and cooled to room temperature (21°C). At this point, the reaction product was combined with 2 L of 10 wt% aqueous sodium carbonate solution and then washed three times with 1.5 L of ethyl acetate in a separatory funnel. The ethyl acetate layers were combined, dried by adding anhydrous sodium sulfate, filtered to remove sodium sulfate, and then concentrated by evaporating the solvent using a rotary evaporator. The product was purified by silica gel column chromatography (80:20 hexane:ethyl acetate mobile phase), and the fractions containing the desired product were combined and concentrated by evaporating the solvent using a rotary evaporator to obtain 3.91 g of the product. The presence of the desired products, 2-[(1-methylpentadecyl)oxy]ethanol and hexadecane-2-ol, was confirmed by NMR and MS analysis.

[0155] A second synthesis and purification was completed on a similar scale using the procedure described above, yielding 4.51 g of product. The two separately synthesized / purified blends of 2-[(1-methylpentadecyl)oxy]ethanol and hexadecane-2-ol were combined for subsequent sulfation.

[0156] Cosulfation of branched-chain C16 alkyloxyethanol and hexadecane-2-ol blend: Sulfation and neutralization were completed using the same procedure as before.

[0157] Quantification of the levels of C16 alkylethylene glycol sulfate and C16 alkyl sulfate in the sulfation product is as follows: 1 The concentration was determined using 1H NMR. The concentration of the alkyl ether sulfate anionic surfactant was calculated to be 83.6% by weight of the sulfation product, mainly 2-[(1-methylpentadecyl)oxy]ethanol sulfate sodium (i.e., when R1 is methyl and R2 is n-tetradecyl, 13 (Determined by 13C NMR). The concentration of the 2-hexadecanol sulfate anionic surfactant was calculated to be 16.4% by weight of the sulfation product.

[0158] The final product was determined to be an 87.5% active total sulfated surfactant blend by titration analysis of standard cationic SO3 (ASTM international standard designation: D3049) on a solid basis. The remaining 12.5% ​​non-surfactant solids consisted of impurities such as sodium sulfate, sodium chloride, and residual water.

[0159] Synthesis Example 4: Co-synthesis of C14 alkyl glycol sulfate and C14 alkyl sulfate blend with isolation of pure C14 alkyl glycol sulfate Co-synthesis of branched-chain C14 alkyloxyethanol (mainly 2-[(1-methyltridecyl)oxy]ethanol (CAS #19494-32-7)) and tetradecane-2-ol (CAS 4706-81-4), accompanied by isolation of pure C14 alkyl glycol sulfate: 250 g (1.27 mol) of 1-tetradecene, 236 g (3.80 mol) of ethylene glycol, 208 g (1.09 mol) of p-toluenesulfonic acid monohydrate, and a magnetic stirring rod were added to a 500 mL round-bottom reaction flask. The reaction flask was heated in a silicone oil bath maintained at 120-130°C while mixing and aerating with air. After 48 hours, the reaction mixture was sampled for TLC analysis. The TLC results showed product formation and the presence of residual starting materials. The reaction flask was removed from the oil bath and cooled to room temperature (21°C). At this point, the reaction product was combined with 2 L of 10 wt% aqueous sodium carbonate solution and then washed three times with 1.5 L of ethyl acetate in a separatory funnel. The ethyl acetate layers were combined, dried by adding anhydrous sodium sulfate, filtered to remove sodium sulfate, and then concentrated by evaporating the solvent using a rotary evaporator. The product was purified by silica gel column chromatography (80:20 hexane:ethyl acetate mobile phase), and the fractions containing the desired products were combined and concentrated by evaporating the solvent using a rotary evaporator to obtain 25.6 g of the product. The presence of the desired products 2[(1-methyltridecyl)oxy]ethanol and tetradecane-2-ol was confirmed by NMR analysis.

[0160] Two additional synthesis and purification processes were completed on a similar scale using the procedure described above, yielding a total of 75.57 g of product. Three separately synthesized / purified 2[(1-methyltridecyl)oxy]ethanol and tetradecane-2-ol blends were combined for subsequent sulfation.

[0161] Cosulfation of a blend of branched-chain C14 alkyloxyethanol and tetradecane-2-ol: A 500 mL three-necked round-bottom flask was fitted with a magnetic stirring rod and an additive funnel having a pressure equalizing arm and a nitrogen gas supply section at the center neck. A thermometer was attached to one side neck, and a vent tube leading to a gas bubbler filled with demineralized water was attached to the other neck to capture the HC1 gas generated from the reaction. A 2-liter glass trap was placed between the gas bubbler and the reaction flask to prevent water from being drawn back into the reaction flask. 74.656 grams of a blend of 2-[(1-methyltridecyl)oxy]ethanol and tetradecane-2-ol, along with 150 mL of ACS reagent-grade diethyl ether (EMD Millipore product number EX0190), were added to the round-bottom flask. 35.5 grams (0.304 mol) of 99.6% chlorosulfonic acid (Sigma-Aldrich product number 571024) were added to the additive funnel. A nitrogen gas stream was directed from the top of the addition funnel, through the flask, out the vent at the side opening, and into the gas bubbler. An ice / NaCl / water bath was placed around the reaction flask. Mixing was initiated, forming a clear, dark orange solution. After the reaction mixture reached 5°C, chlorosulfonic acid was added dropwise at a rate that controlled the exothermic heat release and maintained the temperature below 10°C. The addition of chlorosulfonic acid was completed in 35 minutes.

[0162] The addition funnel was removed and replaced with a nitrogen gas supply. Nitrogen gas was continuously flowed through the flask to the gas bubbler. The ice / NaCl / water bath was replaced with a 22°C water bath. The vent tube attached to the gas bubbler was switched to a vacuum tube attached to a diaphragm vacuum pump. A solvent trap cooled in a dry ice / isopropanol bath was placed along the vacuum tube between the reaction flask and the vacuum pump to capture volatiles drawn from the reaction mixture. A dial pressure gauge (US Gauge, capable of measuring 0-30 inchHg) was placed in the vacuum tube after the solvent trap to measure the vacuum level of the system. The reactants were continuously mixed for 20 minutes under nitrogen gas sweep while maintaining a vacuum system.

[0163] While mixing continued, the vacuum pump was started to begin applying vacuum to the reaction mixture. The vacuum level was slowly increased by gradually reducing the nitrogen gas flow. This was done to control foaming of the reaction mixture. Finally, the nitrogen flow was completely stopped, and a perfect vacuum was applied to the reaction mixture (30 inches Hg [1.02 bar] measured with a vacuum gauge indicates that a perfect vacuum was applied). A perfect vacuum was reached 38 minutes after the start of the vacuum process. Mixing was continued for an additional 10 minutes under perfect vacuum, at which point the reaction mixture was a clear, brownish fluid with minimal foaming observed, at which point the vacuum was released with a nitrogen gas flow.

[0164] While maintaining good vortex mixing using a magnetic stirring rod, the reaction mixture was slowly poured into a 500 mL glass beaker containing 250 mL of ACS reagent-grade methanol (EMD Millipore product number MX0475) diluted methanol reagent (Sigma-Aldrich product number 156256) containing 71.2 g (0.331 mol) of 25.2 wt% sodium methoxide solution, converting the sulfated 2-[(1-methyltridecyl)oxy]ethanol and tetradecane-2-ol reaction product from acid sulfate to sodium salt. The resulting product was a turbid mixture with a white precipitate, accompanied by good vortex mixing. Approximately 0.2 g of this neutralization product was dissolved in approximately 0.5 g of desalted water, and the pH was measured using pH test paper, resulting in a pH of approximately 11. The resulting product was mixed for a further 15 minutes, and the pH was measured again to be 11.

[0165] The reaction product was concentrated by evaporating the solvent using a rotary evaporator equipped with a water bath set to 50°C until the mixture began to foam, at which point the mixture was poured into a glass crystallization dish. The crystallization dish was placed in a vacuum oven at 21°C under partial vacuum with a slow flow of nitrogen gas through the oven to further concentrate the product mixture while preventing foaming. The internal pressure of the vacuum oven was approximately 2 in Hg [0.068 bar]. The following day, the concentrated reaction product was removed from the vacuum oven. The product was now a soft solid. The solid was broken into smaller particles using a spatula and then left at 27°C under complete vacuum for 6 hours, and then overnight in a vacuum oven at 21°C under complete vacuum. The following day, the solid product was broken into smaller particles using a spatula and then left at 27°C under complete vacuum for 7 hours, and then overnight in a vacuum oven at 21°C under complete vacuum. The next day, the product was still a soft solid and was then transferred to a bottle for storage. 101 g of a brown, soft solid product was obtained. The product was sampled for NMR (proton, carbon, and DEPT) and standard cationic SO3 titration analysis.

[0166] NMR analysis: 0.0363 g of the product was dissolved in a mixture of 0.6 g of heavy water and 0.3 g of methanol-d4 and subjected to NMR analysis. 1 H, 13 (C, and DEPT). NMR identified the desired target products, 2-[(1-methyltridecyl)oxy]ethanol sulfate sodium and 2-tetradecanol sulfate sodium.

[0167] The product was determined to be an 81.1% active sulfated surfactant blend by solid content, based on standard cationic SO3 titration analysis (ASTM international standard name: D3049).

[0168] Purification of a blend of 2-[(1-methyltridecyl)oxy]ethanol sulfate sodium and 2-tetradecanol sulfate sodium: 101 g of a blend of 2-[(1-methyltridecyl)oxy]ethanol sulfate sodium and 2-tetradecanol sulfate sodium, along with 271 g of methanol, were added to a 1 L round-bottom flask with a magnetic stirring rod. The flask was stoppered and mixed with good vortex mixing at 21°C for 2.5 hours, at which point the solid product was well dispersed as fine particles. The mixture was vacuum filtered through Grade 4 filter paper, and the solid filtration cake was washed twice with 50 mL of 5°C methanol. The solid filtration cake was transferred to a glass crystallization dish and placed in a vacuum oven at 21°C under complete vacuum. The following day, the solid product was ground into finer particles using a mortar and pestle and placed in a vacuum oven at 21°C under complete vacuum. After 3 days, the product was removed and transferred to a bottle for storage. 46.1 g of off-white solid product was obtained. The product was sampled for NMR (proton, carbon, and DEPT) and standard cationic SO3 titration analysis.

[0169] NMR analysis: 0.04 g of the product was dissolved in a mixture of 0.6 g of heavy water and 0.3 g of methanol-d4 and subjected to NMR analysis. 1 H, 13 (C, and DEPT). By NMR, the target product, 2-[(1-methyltridecyl)oxy]ethanol sulfate sodium, was identified in high purity with all major impurities removed, including the complete removal of 2-tetradecanol sulfate sodium.

[0170] The product was determined to be 89.76% active 2-[(1-methyltridecyl)oxy]ethanol sodium sulfate by titration analysis of standard cationic SO3 (ASTM international standard designation: D3049) on a solid basis. The remaining 10.24% non-surfactant solids consisted of impurities such as sodium sulfate, sodium chloride, and residual water.

[0171] Synthesis Example 5: Synthesis of C16 alkyl glycol sulfate Synthesis of branched-chain C16 alkyloxyethanol (mainly 2-[(1-methylpentadecyl)oxy]ethanol (CAS#30714-96-6)): 101.73 g (0.453 mol) of 1-hexadecene, 112.80 g (1.82 mol) of ethylene glycol, 70.50 g (0.371 mol) of p-toluenesulfonic acid monohydrate, and a magnetic stirring rod were added to a 2-liter round-bottom reaction flask. The reaction flask was heated in a silicone oil bath maintained at 130°C while mixing and aerating with air. After 7 hours, the reaction mixture was sampled for TLC analysis. The TLC results showed product formation and the presence of residual starting materials. The reaction flask was removed from the oil bath and cooled to room temperature (21°C). At this point, the reaction product was combined with 2 L of 10 wt% aqueous sodium carbonate solution and then washed three times with 1.5 L of ethyl acetate in a separatory funnel. The ethyl acetate layers were combined, dried by adding anhydrous sodium sulfate, filtered to remove sodium sulfate, and then concentrated by evaporating the solvent using a rotary evaporator. The product was purified by silica gel column chromatography (80:20 hexane:ethyl acetate mobile phase), and the fractions containing the desired product were combined and concentrated by evaporating the solvent using a rotary evaporator to obtain 4.7 g of the product. The presence of the desired product, 2-[(1-methylpentadecyl)oxy]ethanol, was confirmed by NMR analysis.

[0172] Two further synthesis and purification were completed on a similar scale using the procedure described above to obtain additional products. Three separately synthesized / purified batches of 2-[(1-methylpentadecyl)oxy]ethanol were combined to obtain 12.1 g of product for subsequent sulfation.

[0173] Sulfation of branched-chain C16 alkyloxyethanol: 10.046 grams (0.035065 mol) of 2-[(1-methylpentadecyl)oxy]ethanol and 25 mL of ACS reagent-grade diethyl ether (EMD Millipore product number EX0190) were added to a 100 mL round-bottom flask with a magnetic stirring rod. An addition funnel with a pressure equalizing arm containing 4.335 grams (0.0371 mol) of 99.6% chlorosulfonic acid (Sigma-Aldrich product number 571024) was attached to the flask. A nitrogen gas line from a gas bubbler was attached to the top of the addition funnel. An ice / NaCl / water bath was placed around the reaction flask. Mixing was started, forming a clear, pale yellow solution. Chlorosulfonic acid was added dropwise at a rate of one drop every 1-3 seconds. The addition of chlorosulfonic acid was completed within 12 minutes, at which point the reaction mixture was clear and yellow. Two mL of diethyl ether was added to the addition funnel, rinsed in residual chlorosulfonic acid, and mixing continued for an additional five minutes. The reaction mixture was concentrated by evaporating the solvent and residual HCl using a rotary evaporator equipped with a water bath set to 25°C to form a clear, dark orange liquid.

[0174] While eddy mixing was maintained using a magnetic stirring rod, the concentrated reaction mixture was slowly poured into a 250 mL glass beaker containing 50 mL of ACS reagent-grade methanol (EMD Millipore product number MX0475) diluted methanol reagent (Sigma-Aldrich product number 156256) containing 8.655 g (0.0404 mol) of 25.2 wt% sodium methoxide solution, converting the sulfated 2-[(1-methylpentadecyl)oxy]ethanol reaction product from acid sulfate to sodium salt. The resulting product was a turbid mixture with a white precipitate, accompanied by good eddy mixing. Approximately 0.2 g of this neutralization product was dissolved in approximately 0.5 g of desalted water, and the pH was measured using pH test paper, resulting in a pH of approximately 9-10. The resulting product was mixed for a further 15 minutes, and the pH was measured again to be 9-10.

[0175] The neutralization reaction product was concentrated by evaporating the solvent using a rotary evaporator equipped with a water bath set to 50°C to obtain a soft solid. The solid was placed in a vacuum oven at 21°C under complete vacuum. The following day, the solid product was crushed into smaller particles using a spatula, then placed in a vacuum oven at 21°C under complete vacuum for 7 hours, and then ground into even smaller particles using a mortar and pestle. The ground product was placed in a vacuum oven at 21°C under complete vacuum. After 3 days, a sample was taken for NMR (proton, carbon, and DEPT) analysis, and the product was placed in a vacuum oven at 21°C under complete vacuum. The following day, the product was transferred to a storage bottle. 13.1 g of brown solid product was obtained.

[0176] NMR analysis: 0.0347 g of the product was dissolved in a mixture of 0.6 g of heavy water + 0.3 g of methanol-d4 and subjected to NMR analysis. 1 H, 13 (C, and DEPT). NMR identified the desired target product, 2-[(1-methylpentadecyl)oxy]ethanol sulfate sodium, in high purity.

[0177] The final product was determined to be 89.70% active 2-[(1-methylpentadecyl)oxy]ethanol sulfate sodium by titration analysis of standard cationic SO3 (ASTM international standard designation: D3049) on a solid basis. The remaining 10.30% non-surfactant solids consisted of impurities such as sodium sulfate, sodium chloride, and residual water.

[0178] Performance evaluation The following liquid compositions for hand-washing dishes were prepared by simple mixing. Each example contained the same concentration of anionic surfactants, but differed in the type of auxiliary surfactant.

[0179] The foaming persistence in the presence of oily particulate matter, using the compositions of the present invention and comparative compositions, was evaluated using the test methods described herein.

[0180] [Table 2] * Comparative Example 1 65% by weight of C12 (from Synthesis Example 1), 30% by weight of C14 (from Synthesis Example 2), and 5% by weight of C16 (from Synthesis Example 3) 2 Tensagex® EOC970, supplied by KLK Tensachem. 3 An 86.6% branched-chain C13 AE2.0S was prepared by ethoxyling alcohol 1 to an average of 2.0 moles per mole, as described in the examples of European Patent Application Publication No. 3919594(A), and then sulfurizing the resulting ethoxylated alcohol. 4 Fragrances, dyes, preservatives

[0181] [Table 3] 5 Supplied by Procter & Gamble

[0182] Comparative Example A contained an alkyl sulfate ethoxylated anionic surfactant with an average ethoxylation degree of 1.0 and an amine oxide amphoteric surfactant. Thus, the composition provided good foaming persistence (reference) and low-temperature stability. Comparative Example B also contained an alkyl sulfate ethoxylated anionic surfactant with an average ethoxylation degree of 1.0, but also contained a betaine zwitterionic surfactant as an auxiliary surfactant. Comparing the foaming persistence results from the two examples, it can be seen that when a liquid composition for hand washing dishes contains an alkyl ethoxylated sulfate anionic surfactant, the foaming persistence in the presence of oily particulate matter is similar whether the composition contains an amine oxide or a betaine surfactant as an auxiliary surfactant, and both provide good low-temperature stability. Since both compositions contained an alkyl ethoxylated sulfate anionic surfactant, they both contained a higher concentration of 1,4-dioxane.

[0183] Essentially, all 1,4-dioxanes can be eliminated by formulating compositions using unethoxylated linear alkyl sulfates. However, as shown by comparing the results of Comparative Example C with those of Comparative Example A, replacing the alkylethoxylated sulfate anionic surfactant with an alkyl sulfated anionic surfactant in compositions containing amine oxides as auxiliary surfactants results in a slight reduction in foam persistence in the presence of oily particulate matter, as well as a significant decrease in low-temperature stability. The results of Comparative Example D show that replacing the amine oxide auxiliary surfactant with a betaine auxiliary surfactant results in a further reduction in foam persistence in such compositions containing unethoxylated linear alkyl sulfated anionic surfactants, in addition to insufficient low-temperature stability.

[0184] Essentially all 1,4-dioxanes can also be eliminated by formulating the composition using alkyl glycol sulfate anionic surfactants. However, as can be seen by comparing the results of Comparative Example E with those of Comparative Example A, replacing the alkyl ethoxylated sulfate anionic surfactant with an alkyl glycol sulfate anionic surfactant significantly reduced foam persistence in the presence of oily particulate matter when the composition contained an amine oxide as an auxiliary surfactant. Comparing the foam persistence of Composition 1 of the present invention with that of Comparative Example E, it is shown that when the formulation contains a betaine auxiliary surfactant instead of an amine oxide auxiliary surfactant, the foam persistence in the presence of oily particulate matter is substantially improved. In fact, the foam persistence increases to the level found in compositions containing both alkyl ethoxylated sulfate anionic surfactants and amine oxide auxiliary surfactants. In addition, the composition of Example 1 of the present invention, which includes a combination of alkyl glycol sulfate anionic surfactant and betaine, also provided good low-temperature stability. This combination of advantages is thought to result from the high degree of C1 branching observed in the alkyl glycol sulfate anionic surfactant used in the present invention, in combination with the betaine auxiliary surfactant.

[0185] Comparative Example F contained a branched-chain alkylethoxylated sulfate anionic surfactant (average branching degree 42.8% and average ethoxylation degree 1) in combination with an amine oxide auxiliary surfactant. Comparative Example G contained the same branched-chain alkylethoxylated sulfate anionic surfactant in combination with betaine as an auxiliary surfactant. The results show that for both compositions containing the branched-chain alkylethoxylated sulfate anionic surfactant, both foaming persistence in the presence of oily particulate matter and low-temperature stability were substantially reduced, regardless of whether amine oxide or betaine was used as the auxiliary surfactant.

[0186] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​listed. Instead, unless otherwise specified, each such dimension is intended to mean both the listed value and the functionally equivalent range encompassing that value. For example, a dimension disclosed as "40 mm" is intended to mean "approximately 40 mm."

Claims

1. A liquid detergent composition for hand washing dishes, comprising 5.0% to 50% by weight of a surfactant system, wherein the surfactant system is a. An anionic surfactant, wherein the anionic surfactant comprises an alkyl glycol sulfate anionic surfactant, and the alkyl glycol sulfate anionic surfactant has the formula: R1CH(R2)(OCH ２ CH ２ ) ｎ OSO3 － M ＋ (I) has, During the ceremony, R1 is independently H, alkyl, alkylene, or a mixture thereof. R2 is independently an alkyl, alkylene, or a mixture thereof. The total number of carbon atoms present in R1 and R2 is, on average, 7 to 19. n is 1 to 3, where 90 mol% or more of the surfactant molecules in structure (I) have an n of 1, and 10 mol% or less of the surfactant molecules in structure (I) have an n of 2 or more. M+ is a counterion, an anionic surfactant, b. A liquid dishwashing detergent composition comprising an auxiliary surfactant, wherein the auxiliary surfactant is a zwitterionic surfactant, and the zwitterionic surfactant includes a betaine surfactant.

2. a. The composition comprises 6.0% to 40% by weight, preferably 15% to 35% by weight, of the surfactant system in the total composition. b. The composition according to claim 1, wherein the surfactant system comprises at least 40% by weight, preferably 60% to 90% by weight, and more preferably 65% ​​to 85% by weight of the anionic surfactant of the surfactant system.

3. The composition according to claim 1 or 2, wherein R1 comprises, on average, 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, in the alkyl glycol sulfate anionic surfactant of formula (I).

4. The composition according to claim 3, wherein in at least 80 mol%, more preferably at least 90 mol%, of the alkyl glycol sulfate anionic surfactant of formula (I), R1 comprises one carbon atom, more preferably methyl.

5. The composition according to any one of claims 1 to 4, wherein R2 comprises, on average, 6 to 19 carbon atoms, preferably 8 to 17 carbon atoms, more preferably 9 to 15 carbon atoms, and most preferably 10 to 13 carbon atoms, in the alkyl glycol sulfate anionic surfactant of formula (I).

6. The composition according to any one of claims 1 to 5, wherein R2 is a linear, branched, or combination thereof in the alkyl glycol sulfate anionic surfactant of formula (I), and preferably R2 is a linear.

7. The composition according to any one of claims 1 to 6, wherein the alkyl glycol sulfate anionic surfactant of formula (I) has a total number of carbon atoms present in R1 and R2, on average, 9 to 17, more preferably 11 to 15, and most preferably 11 to 13.

8. The alkyl glycol sulfate anionic surfactant of formula (I), wherein 92 mol% or more of the surfactant molecules of structure (I) have 1 n, 8 mol% or less of the surfactant molecules of structure (I) have 2 or more n, preferably 95 mol% or more of the surfactant molecules of structure (I) have 1 n, and 5 mol% or less of the surfactant molecules of structure (I) have 2 or more n, according to any one of claims 1 to 7.

9. The composition according to any one of claims 1 to 8, wherein the anionic surfactant further comprises an alkyl sulfated anionic surfactant, and more preferably the anionic surfactant comprises at least 70% by weight, more preferably at least 85% by weight, and most preferably 100% by weight of the alkyl sulfated anionic surfactant and the alkyl glycol sulfate anionic surfactant.

10. a. The alkyl sulfated anionic surfactant has a number-average alkyl chain length of 8 to 18 carbon atoms, preferably 10 to 14, more preferably 12 to 14, and most preferably 12 to 13 carbon atoms. b. The alkyl sulfated anionic surfactant has an average degree of alkoxylation of less than 1.0, preferably less than 0.5, more preferably less than 0.25, and even more preferably less than 0.1, and most preferably the alkyl sulfated anionic surfactant does not contain alkoxylation. c. The alkyl sulfated anionic surfactant has an average branching degree of less than 60%, preferably less than 40%, preferably less than 20%, and most preferably less than 10%, and d. The composition according to claim 9, which is a combination of these.

11. The composition according to claim 9 or 10, wherein the alkyl sulfated anionic surfactant and the alkyl glycol sulfate anionic surfactant are 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.

12. The composition according to any one of claims 1 to 11, wherein the anionic surfactant and the auxiliary surfactant are present in a weight ratio of 1:1 to 5:1, preferably 1.5:1 to 4.5:1, and more preferably 2:1 to 4:

1.

13. The composition according to any one of claims 1 to 12, wherein the betaine surfactant is a betaine surfactant selected from the group consisting of alkylbetaine, alkylamidealkylbetaine, amidazolinium betaine, sulfobetaine (INCI sultaine), phosphobetaine, and mixtures thereof, and most preferably cocoamidopropylbetaine.

14. The composition according to any one of claims 1 to 13, wherein the surfactant system further comprises a nonionic surfactant.

15. The composition according to any one of claims 1 to 14, wherein, when measured as a 10% aqueous solution in desalinated water at 20°C, the composition has a pH of 7.0 or higher, preferably 7.0 to 12.0, more preferably 8.0 to 11.0, and most preferably 8.5 to 10.0.

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