Liquid detergent composition for hand dishwashing

Abstract

To provide a liquid detergent composition suitable for washing dishes, fitting both in-sink soaking and direct application methods, which provides reduced smearing when used in direct application dishwashing methods.SOLUTION: The liquid detergent composition is formulated to contain a surfactant system, which comprises alkyl sulfate anionic surfactants including C13 alkyl sulfate anionic surfactants, where the C13 alkyl sulfate anionic surfactants include a specific fraction of 2-branched C13 alkyl sulfate anionic surfactants, where the 2-branched C13 alkyl sulfate anionic surfactants include respective specific fractions of 2-pentyl octyl and 2-methyl dodecyl.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to liquid detergent compositions, in particular liquid detergents for hand dishwashing. [Background technology]

[0002] Some consumers prefer to wash dishes by immersing them in a diluted liquid detergent composition in the sink, while others prefer to apply the liquid detergent composition directly to the dish or via a tool such as a sponge. This "direct application" method improves grease cleaning because a higher concentration of surfactants is applied directly to the stain. With the direct application method, consumers want long-lasting grease cleaning performance and fast and long-lasting foaming. Traditionally, the application method of immersing in a diluted detergent composition in the sink was the predominant practice in most geographical regions. Today, although some regional differences still exist, both practices are regionally balanced, presenting detergent formulators with the challenge of delivering products to consumers that meet the needs of both consumer groups. A recurring problem with this "direct application" method of washing dishes is smearing. Smearing causes stains on the dish to come into contact with undiluted or only slightly diluted detergent composition, resulting in the stains on the dish being smeared over a large area of ​​the dish rather than being absorbed by the sponge. Such smearing not only leaves the dishes feeling unclean, but also results in the dishes requiring more effort to rinse, and is particularly prevalent when formulating linear or lightly branched surfactant materials.

[0003] Therefore, there is a need for a detergent composition suitable for washing dishes, suitable for both the sink soaking method and the direct application method, which can reduce smearing when used for washing dishes by the direct application method.

[0004] EP 2606111A, WO 9533025A, US 5968888A and US 2005 / 0170990A disclose a method for hand washing dishes, comprising contacting dishes with a liquid detergent composition in undiluted form. US 2007 / 0123447A1, WO 2006 / 041740A1 and US 6,008,181 disclose dishwashing compositions comprising branched surfactants. US 9,493,725B2 relates to detergent compositions, more particularly to detergent compositions containing branched surfactants. EP 3633016A relates to a liquid hand dishwashing composition which improves the amount of foam and foam persistence while still providing the desired cleaning power when using a diluted liquid hand dishwashing composition to wash dishes, especially in the presence of greasy and particulate soils. The composition is formulated with a surfactant system comprising an alkyl sulfate anionic surfactant and a co-surfactant, the alkyl chains of which have a molar fraction of at least 50% C12 and C13 chains, and a C13 / C12 molar ratio of at least 57 / 43. No. 9,828,565B relates to compositions containing mixtures of different tridecanols and their derivatives and their use as laundry detergents, cleaning products, or agricultural aids, emulsifiers, lubricant additives, pour point depressants, or personal care ingredients, in which at least about 60% by weight of the mixture is a linear tridecanol and at least about 10% by weight of the mixture is a branched tridecanol having a branch on the second carbon atom. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] European Patent Application Publication No. 2606111A [Patent Document 2] International Patent Application Publication No. 9533025A [Patent Document 3] U.S. Patent No. 5,968,888A [Patent Document 4] US Patent Application Publication No. 2005 / 0170990A [Patent Document 5] US Patent Application Publication No. 2007 / 0123447A1 [Patent Document 6] International Patent Application Publication No. 2006 / 041740A1 [Patent Document 7] U.S. Patent No. 6,008,181 [Patent Document 8] U.S. Patent No. 9,493,725B2 [Patent Document 9] European Patent Application Publication No. 3633016A [Patent Document 10] U.S. Patent No. 9,828,565B Summary of the Invention [Means for solving the problem]

[0006] The present invention relates to an alkyl sulfate anionic surfactant for use in a liquid detergent composition selected from the group consisting of hair shampoos, hair conditioners, shaving foams or gels, laundry detergents, hard surface cleaners, personal cleaners, bar soaps, hand soaps, shower gels, automatic dishwashing compositions, hand dishwashing compositions, and mixtures thereof, the alkyl sulfate anionic surfactant comprising at least 90%, preferably at least 95%, and most preferably at least 98% by weight of C13 alkyl sulfate anionic surfactant based on the weight of the total alkyl sulfate anionic surfactant, the C13 alkyl sulfate anionic surfactant comprising: a) at least 75% by weight of the C13 alkyl sulfate anionic surfactant based on the weight of the C13 alkyl sulfate anionic surfactant; % by weight of linear C13 alkyl sulfate, b) more than 25% by weight of 2-branched C13 alkyl sulfate anionic surfactants, based on the weight of the C13 alkyl sulfate anionic surfactant, comprising no more than 10% by weight of 2-pentyloctyl, based on the weight of the 2-branched alkyl chain, and more than 70% by weight of 2-methyldodecyl, based on the weight of the 2-branched alkyl chain, and c) less than 5% by weight of other branched C13 alkyl sulfate anionic surfactants, based on the weight of the C13 alkyl sulfate anionic surfactant, the sum of a), b), and c) above adding up to 100% by weight, based on the weight of the C13 alkyl sulfate anionic surfactant.

[0007] The present invention further relates to a liquid detergent composition comprising from 5.0% to 60% by weight of a surfactant system, based on the weight of the total composition, the surfactant system comprising at least one alkyl sulfate anionic surfactant, the alkyl sulfate anionic surfactant having a weight average degree of branching of less than 40%, the alkyl sulfate anionic surfactant comprising at least 10% by weight, based on the weight of the alkyl sulfate anionic surfactant, of a C13 alkyl sulfate anionic surfactant, the C13 alkyl sulfate anionic surfactant having a weight average degree of branching of less than 40%, and The active agent comprises less than 80% by weight of a linear C13 alkyl sulfate, based on the weight of the C13 alkyl sulfate anionic surfactant, and greater than 5% by weight of a 2-branched C13 alkyl sulfate anionic surfactant, based on the weight of the C13 alkyl sulfate anionic surfactant, the 2-branched C13 alkyl sulfate anionic surfactant comprising no more than 7.0% by weight of 2-pentyloctyl, based on the weight of the 2-branched alkyl chain, and greater than 70% by weight of 2-methyldodecyl, based on the weight of the 2-branched alkyl chain. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] It has been found that by formulating liquid detergent compositions with branched anionic surfactants, the size and location of the branches are tightly controlled, resulting in reduced smearing of greasy soils when washing dishes using direct application methods.

[0009] definition As used herein, articles such as "a" and "an" used in the claims are understood to mean one or more of what is claimed or described.

[0010] As used herein, the term "comprising" means that steps and ingredients other than those specifically mentioned can be added. This term encompasses the terms "consisting of" and "consisting essentially of." The compositions of the present invention can comprise, consist of, or consist essentially of the essential elements and limitations of the invention described herein, as well as any additional or optional ingredients, components, steps, or limitations described herein.

[0011] As used herein, the term "dishware" includes, by way of non-limiting examples, cookware and tableware made from ceramic, china, metal, glass, plastic (e.g., polyethylene, polypropylene, polystyrene, etc.), and wood.

[0012] As used herein, the terms "fat" or "oleaginous" mean that the substance comprises, at least in part (i.e., at least 0.5% by weight of the fat), saturated and unsaturated fats and oils, preferably oils and fats derived from animal sources such as beef, pork, and / or chicken.

[0013] The terms "include / includes / including" are meant to be non-limiting.

[0014] As used herein, the term "particulate soil" means inorganic and especially organic solid soil particles, especially food particles, non-limiting examples of which include ultrafine particulate elemental carbon, baked grease particles, and meat particles.

[0015] As used herein, the term "suds profile" refers to a property of a liquid detergent composition with respect to the characteristics of the foam during the dishwashing process. The term "suds profile" of a detergent composition includes the foam volume generated when the liquid detergent composition is dissolved in the washing water solution and stirred, typically by hand, and the maintenance of the foam during the dishwashing process. Preferably, liquid hand dishwashing detergent compositions characterized as having a "good suds profile" tend to have a high foam volume and / or a sustained foam volume, especially throughout a significant portion or the entire hand dishwashing process. This is important since consumers use a high amount of foam as an indication that enough liquid detergent composition has been dispensed. In addition, consumers also use a sustained foam volume as an indication that enough active cleaning ingredients (e.g., surfactants) are present, even toward the end of the dishwashing process. Consumers typically refresh the washing solution when sudsing becomes low. Thus, low foaming detergent compositions tend to cause consumers to replace the washing solution more frequently than necessary due to the low suds level.

[0016] It will be understood that the test methods disclosed in the Test Methods section of this application must be used to determine the values ​​of each of the parameters of Applicants' inventions described and claimed herein.

[0017] In all embodiments of the present invention, unless specifically stated otherwise, as is clear from the context, all percentages are by weight of the total composition, unless specifically stated otherwise, all ratios are by weight, and all measurements are made at 25° C. unless otherwise specified.

[0018] Alkyl Sulfate Anionic Surfactants The alkyl sulfate anionic surfactants described herein can be used in liquid detergent compositions selected from the group consisting of hair shampoos, hair conditioners, shaving foams or gels, laundry detergents, hard surface cleaners, personal cleaners, bar soaps, hand soaps, shower gels, automatic dishwashing compositions, hand dishwashing compositions, and mixtures thereof, and are particularly preferred for use in laundry detergents, hard surface cleaners, automatic dishwashing compositions, hand dishwashing compositions, and mixtures thereof, especially hand dishwashing compositions.

[0019] The alkyl sulfate anionic surfactant comprises at least 90% by weight, preferably at least 95% by weight, and most preferably at least 98% by weight, of a C13 alkyl sulfate anionic surfactant, based on the weight of the total alkyl sulfate anionic surfactant, the C13 alkyl sulfate anionic surfactant comprising: a) less than 75% by weight, based on the weight of the C13 alkyl sulfate anionic surfactant, of linear C13 alkyl sulfate; and b) greater than 25% by weight, based on the weight of the C13 alkyl sulfate anionic surfactant, of 2-branched C13 alkyl sulfate. a) a 2-branched C13 alkyl sulfate anionic surfactant comprising not more than 10% by weight of 2-pentyloctyl, based on the weight of the 2-branched alkyl chains, and more than 70% by weight of 2-methyldodecyl, based on the weight of the 2-branched alkyl chains; and b) less than 5% by weight of other branched C13 alkyl sulfate anionic surfactants, based on the weight of the C13 alkyl sulfate anionic surfactant, the sum of a), b), and c) above being 100% by weight, based on the weight of the C13 alkyl sulfate anionic surfactant.

[0020] The term C13 alkyl sulfate anionic surfactant means that the alkyl sulfate anionic surfactant comprises an alkyl chain of 13 carbon atoms. Thus, in the case of a blend of alkyl sulfate anionic surfactants with an average chain length of 13 carbon atoms, only the alkyl sulfate anionic surfactants comprising a C13 alkyl chain fall under the definition of C13 alkyl sulfate anionic surfactant. Independent of the average alkyl chain length, for blends comprising multiple alkyl chains including a C13 alkyl subfraction, only the C13 subfraction falls under the definition of C13 alkyl sulfate anionic surfactant.

[0021] With regard to the specific degree and type of C2-branching, the C13 alkyl sulfate anionic surfactant may be comprised of less than 70% by weight, preferably 60% to 70% by weight, of linear C13 alkyl sulfate, based on the weight of the C13 alkyl sulfate anionic surfactant, more than 30% by weight, preferably 30% to 40% by weight, of 2-branched C13 alkyl sulfate anionic surfactant, based on the weight of the C13 alkyl sulfate anionic surfactant, and less than 3.0% by weight, preferably 0.1% to 2.0% by weight, based on the weight of the C13 alkyl sulfate anionic surfactant, of other branched C13 alkyl sulfate anionic surfactants.

[0022] The 2-branched C13 alkyl sulfate anionic surfactant may contain less than 7.0% by weight, preferably less than 5.0% by weight, of 2-pentyloctyl, based on the weight of the 2-branched alkyl chains, and more than 75% by weight, preferably 80% to 95% by weight, of 2-methyldodecyl, based on the weight of the 2-branched alkyl chains.

[0023] The remaining fraction of the 2-branched C13 alkyl sulfate may include 2-ethyl-1-undecyl sulfate anionic surfactant (preferably 20% by weight or less, more preferably 15% by weight or less, and most preferably 5% to 15% by weight, based on the weight of the 2-branched C13 alkyl sulfate), 2-propyl-1-decyl sulfate anionic surfactant (preferably 10% by weight or less, more preferably 5% by weight or less, and most preferably 2% by weight or less, based on the weight of the 2-branched C13 alkyl sulfate), and 2-butyl-1-nonyl sulfate anionic surfactant (preferably 10% by weight or less, more preferably 5% by weight or less, and most preferably 2% by weight or less, based on the weight of the 2-branched C13 alkyl sulfate).

[0024] Thus, the alkyl chains of the C13 alkyl sulfate anionic surfactants according to the invention are low branched and have an increased methyl to pentyl branching ratio compared to other low branched chain alcohols, such as those produced according to the Oxo process, which have a branching degree of about 18%, but an increased pentyl to methyl branching ratio (e.g., sold under the trademark Neodol®), and also compared to more highly branched materials, which have an even higher pentyl to methyl branching ratio (e.g., sold under the trademark Isalchem®).

[0025] The alkyl sulfate anionic surfactant may be selected from non-alkoxylated alkyl sulfate anionic surfactants, or alkoxylated alkyl sulfate anionic surfactants, or mixtures thereof.

[0026] When the C13 alkyl sulfate anionic surfactant is an alkoxylated anionic sulfate surfactant, the alkoxylated C13 anionic sulfate surfactant is preferably an ethoxylated C13 alkyl sulfate anionic surfactant. Preferably, the C13 alkyl sulfate anionic surfactant has an average degree of alkoxylation of less than 5, preferably less than 3, more preferably less than 2 and greater than 0.5, most preferably 0.5-0.9, in order to improve the physical stability of the composition of the present invention at low temperatures and improve the foam persistence. The average degree of alkoxylation is the molar average degree of alkoxylation of all the alkyl sulfate anionic surfactants (i.e., the molar average degree of alkoxylation). Therefore, when calculating the molar average degree of alkoxylation, the number of moles of the C13 non-alkoxylated sulfate anionic surfactant will be included as follows: Molar average degree of alkoxylation = (x1 * Alkoxylation degree of surfactant 1 + x2 * Alkoxylation degree of surfactant 2 +....) / (x1+x2+....) where x1, x2, ... are the 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.

[0027] Suitable alkyl sulfate anionic surfactants can be made using the following process. A two-step process can be used to produce branched aldehyde products from linear alpha olefin feedstocks, from which the alkyl sulfate anionic surfactants described herein can be derived.The two-step process uses rhodium organophosphorus catalysts in both the first and second process steps.The first process step is an isomerization reaction step, and the second process step is a hydroformylation reaction step.The branched aldehyde can undergo a further hydrogenation step to produce branched alcohols.

[0028] The isomerization and hydroformylation reactions disclosed herein may be catalyzed by a rhodium organophosphorus catalyst, which may be at least one of: (1) an organometallic complex of rhodium and one organophosphorus ligand, or (2) an organometallic complex of rhodium and two or more organophosphorus ligands.

[0029] The organophosphorus ligand may be a phosphine. In a non-limiting example of a phosphine ligand, the phosphine ligand may be triphenylphosphine. The organophosphorus ligand may be a phosphite. In a non-limiting example of a phosphite ligand, the phosphite ligand may be tris(2,4-di-t-butylphenyl) phosphite. Mixtures of different types of organophosphorus ligands may also be used, such as mixtures of phosphines and phosphites. In a non-limiting example of a mixture of organophosphorus ligands, the organophosphorus ligand may be a mixture of triphenylphosphine and tris(2,4-di-t-butylphenyl) phosphite. The reaction system may contain an inert high boiling solvent, such as a polyalphaolefin. The first catalyst may be formed when the molar ratio of phosphorus to rhodium is in the range of 1:1 to 1000:1, or 5:1 to 50:1, or 15:1 to 25:1. The concentration of rhodium may range from 1 ppm to 1000 ppm, or from 10 ppm to 200 ppm, or from 25 ppm to 75 ppm. The molar ratio of CO to H2 may range from 10:1 to 1:10, or from 2:1 to 1:2, or from 1.3:1 to 1:1.3.

[0030] In the isomerization reaction, the first step can be a reaction of isomerizing linear alpha olefins in the presence of carbon monoxide (CO) and hydrogen (H2) at a first pressure. The isomerization can be catalyzed by a rhodium organophosphorus catalyst, which can be at least one of: (1) an organometallic complex of rhodium with one type of organophosphorus ligand, or (2) an organometallic complex of rhodium with two or more types of organophosphorus ligands. The isomerization reaction can produce isomerized olefins, including the same or different types of linear internal olefins.

[0031] The isomerization step can be carried out at a temperature ranging from 30° C. to 500° C., or from 50° C. to 150° C., or from 70° C. to 100° C. The isomerization step can be carried out at a gauge pressure ranging from 0.1 bar (0.01 MPa above atmospheric pressure) to 10 bar (1 MPa above atmospheric pressure), or from 0.5 bar (0.05 MPa above atmospheric pressure) to 5 bar (0.5 MPa above atmospheric pressure), or from 1 bar (0.1 MPa above atmospheric pressure) to 2 bar (0.2 MPa above atmospheric pressure).

[0032] The isomerization step may produce a reaction product comprising 20% ​​by weight or more isomerized olefins, or 40% by weight or more isomerized olefins, or 60% by weight or more isomerized olefins, or 90% by weight or more isomerized olefins.

[0033] In the hydroformylation reaction step, the isomerized olefin is hydroformylated in the presence of CO and H2 at a second pressure higher than the first pressure to produce a branched aldehyde. The hydroformylation reaction can be catalyzed by a rhodium organophosphorus catalyst, which can be at least one of: (1) an organometallic complex of rhodium with one organophosphorus ligand, or (2) an organometallic complex of rhodium with two or more organophosphorus ligands. The resulting branched aldehyde is a 2-alkyl branched aldehyde. The linear alpha olefin is 1-dodecene, and the branched aldehyde is a branched C13 aldehyde.

[0034] The hydroformylation step may be carried out at a temperature in the range of 30° C. to 500° C., or 50° C. to 150° C., or 70° C. to 100° C. The hydroformylation step may be carried out at a gauge pressure in the range of 5 bar (0.5 MPa above atmospheric pressure) to 400 bar (40 MPa above atmospheric pressure), or 10 bar (1.0 MPa above atmospheric pressure) to 100 bar (10 MPa above atmospheric pressure), or 15 bar (1.5 MPa above atmospheric pressure) to 20 bar (2 MPa above atmospheric pressure).

[0035] The hydroformylation process may produce a reaction product containing 25% by weight or more branched chain aldehydes, or 40% by weight or more branched chain aldehydes, or 60% by weight or more branched chain aldehydes, or 90% by weight or more branched chain aldehydes.

[0036] The product of the hydroformylation reaction can be distilled. The process can include separating the branched aldehyde product from the hydroformylation as an overhead from the first catalyst stream via a distillation process. The distillation step can be carried out at a temperature ranging from 100° C. to 200° C., or from 125° C. to 175° C. The distillation step can be carried out under vacuum, at a pressure of less than 500 mbar absolute (0.05 MPa), or less than 100 mbar absolute (0.01 MPa), or less than 30 mbar absolute (0.003 MPa).

[0037] The above process may also include a step of hydrogenating the branched aldehyde product in the presence of a hydrogenation catalyst to produce a branched alcohol product composition. The hydrogenation catalyst may be a base metal catalyst, a nickel-supported catalyst, a cobalt-supported catalyst, a Raney® (WR Grace & Co., 7500 Grace Drive, Columbia, Md. 21044) nickel catalyst, or a precious metal catalyst. The hydrogenation step may be carried out at a temperature ranging from 30° C. to 500° C., or from 50° C. to 200° C., or from 100° C. to 150° C. The hydrogenation step may be carried out at a gauge pressure ranging from 5 bar (0.5 MPa above atmospheric pressure) to 400 bar (40 MPa above atmospheric pressure), or from 10 bar (1 MPa above atmospheric pressure) to 100 bar (10 MPa above atmospheric pressure), or from 30 bar (3 MPa above atmospheric pressure) to 50 bar (5 MPa above atmospheric pressure).

[0038] The hydrogenation step may produce a reaction product containing 25% by weight or more branched chain alcohols, or 40% by weight or more branched chain alcohols, or 60% by weight or more branched chain alcohols, or 90% by weight or more branched chain alcohols.

[0039] The C12 olefin source used in the hydroformylation to produce the starting C13 aldehyde and subsequent alcohol used in the present invention can have low levels of impurities in the starting C13 alcohol and therefore in the C13 alkyl sulfate. Without being bound by theory, such impurities present in the C12 olefin feedstock can include vinylidene olefins, branched olefins, paraffins, aromatic components, and low levels of olefins with chain lengths other than 12. Branched and vinylidene olefins are typically 5% or less in the C12 alpha olefin source. Impurities in the resulting C13 alcohol may include low levels of linear and branched alcohols in the C10-C16 range, particularly C11 and C15 alcohols, typically less than 2% by weight, preferably less than 1% by weight based on the weight of the mixture, low levels of branching other than the 2-alkyl position resulting from branched and vinylidene olefins, typically less than about 5% by weight, preferably less than 2% by weight based on the weight of the alcohol mixture, paraffins and olefins, typically less than 1% by weight, preferably less than about 0.5% by weight based on the weight of the alcohol mixture, and low levels of aldehydes, typically having a carbonyl number of less than 500 mg / kg, preferably less than about 200 mg / kg. These impurities in the alcohol may result in low levels of paraffins, linear and branched alkyls with total carbon numbers other than C13, and alkyl sulfates with branches at positions other than the 2-alkyl position, which may vary in length but are typically linear alkyl chains having 1 to 6 carbons. The hydroformylation step may also produce impurities such as linear and branched paraffins, residual olefins from incomplete hydroformylation, as well as esters, formates, and heavy ends (dimers, trimers). Impurities that are not reduced to alcohol in the hydrogenation step may be removed during final purification of the alcohol by distillation.

[0040] Alkyl sulfates are typically prepared by the reaction of fatty alcohols with sulfur trioxide (SO3) or its derivatives, or by the reaction of unsaturated compounds with sulfuric acid. The process using sulfur trioxide is widely used, especially in the manufacture of alkyl sulfate anionic surfactants for use in detergent compositions.

[0041] Suitable derivatives of sulfur trioxide include sulfur trioxide complexes such as, for example, chlorosulfonic acid, sulfuric acid, or sulfamic acid. Sulfur trioxide is preferred because it tends to result in a purer product. The sulfation reaction is typically carried out in a continuous process using a cascaded falling film reactor or tube bundle reactor, with sulfur trioxide being applied in equimolar or slight excess amounts, typically at a temperature range of 20°C to 60°C. The reaction temperature is determined, at least in part, by the freezing point of the aliphatic alcohol in the reaction. The above reaction typically results in the acid form of the alkyl sulfate anionic surfactant, which is typically neutralized in a subsequent step using an alkali such as, for example, sodium hydroxide, potassium hydroxide, magnesium hydroxide, lithium hydroxide, calcium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diamines, polyamines, primary amines, secondary amines, tertiary amines, amine-containing surfactants, and mixtures thereof.

[0042] It is also well known that the process of sulfating fatty alcohol to obtain alkyl sulfate anionic surfactants also results in various impurities. The exact nature of these impurities depends on the conditions of sulfation and neutralization. However, in general, the impurities of the sulfation process include one or more inorganic salts, unreacted fatty alcohol, and olefins ("The Effect of Reaction By-Products on the Viscosities of Sodium Lauryl Sulfate Solutions," Journal of the American Oil Chemists' Society, Vol. 55, No. 12, p. 909-913 (1978), CFP Putnik and SEMcGuire). The concentration of non-alkyl sulfate impurities in the alkyl sulfate anionic surfactant of the present invention can be less than 6 wt%, preferably less than 4 wt%, and most preferably less than 2 wt%, based on the weight of alkyl sulfate anionic surfactant.

[0043] In the case of alkyl alkoxy sulfates, the fatty alcohol is first alkoxylated prior to sulfation. Alkoxylation is a process in which lower molecular weight epoxides (oxiranes), such as ethylene oxide, propylene oxide, and butylene oxide, are reacted with fatty alcohols. These epoxides can be reacted with fatty alcohols using various base or acid catalysts. In base-catalyzed alkoxylation, the alcoholate anion that is first formed by reaction with the catalyst (alkali metal, alkali metal oxide, carbonate, hydroxide, or alkoxide) nucleophilically attacks the epoxide.

[0044] Traditional alkaline catalysts for alkoxylation include potassium hydroxide and sodium hydroxide, which produce a somewhat broad distribution of alkoxylates. Other catalysts for alkoxylation have been developed that produce narrower alkoxylate oligomer distributions. Suitable examples of narrow range alkoxylation catalysts include many alkaline earth (Mg, Ca, Ba, Sr, etc.) derived catalysts, Lewis acid catalysts, such as zirconium dodecane oxide sulfate, and certain boron halide catalysts. A specific average degree of alkoxylation can be achieved by selecting the starting amount of fatty acid alcohol and ethylene oxide, or by blending together various amounts of alkoxylated surfactants with different average degrees of alkoxylation.

[0045] Alkoxylated impurities may include dialkyl ethers, polyalkylene glycol dialkyl ethers, olefins, and polyalkylene glycols. Impurities may also include catalysts or components of catalysts used in the various processes.

[0046] Liquid detergent composition The liquid detergent composition may be provided by a process comprising combining the aforementioned alkyl sulfate anionic surfactants, as described herein, with additional surfactants and, optionally, with additional ingredients.

[0047] The liquid detergent composition is preferably a liquid detergent composition for hand dishwashing. The liquid detergent composition is preferably an aqueous liquid detergent composition. Thus, the composition may contain 50% to 85% by weight, preferably 50% to 75% by weight, of water based on the weight of the total composition.

[0048] Preferably, the pH of the composition is from about 6 to about 14, preferably from about 7 to about 12, or more preferably from about 7.5 to about 10, when measured at a 10% dilution in distilled water at 20° C. The pH of the composition can be adjusted using pH adjusting ingredients known in the art.

[0049] The compositions of the present invention can be Newtonian or non-Newtonian, but are preferably Newtonian, and preferably have a viscosity of from 10 mPa·s to 10,000 mPa·s, preferably from 100 mPa·s to 5,000 mPa·s, more preferably from 300 mPa·s to 2,000 mPa·s, or most preferably from 500 mPa·s to 1,500 mPa·s, or a combination thereof, as measured using the viscosity measurement method described herein.

[0050] Surfactant Systems The liquid detergent composition may comprise from 5.0% to 60% by weight, preferably from 8.0% to 45% by weight, most preferably from 15% to 40% by weight of a surfactant system, based on the weight of the total composition.

[0051] The surfactant system comprises at least one alkyl sulfate anionic surfactant having a weight average degree of branching less than 40%, preferably greater than 10%, more preferably greater than 20%, even more preferably greater than 30%, and most preferably between 30% and 40%. The surfactant system may comprise from 60% to 90% by weight, preferably from 65% to 85% by weight, more preferably from 70% to 80% by weight of alkyl sulfate anionic surfactant, based on the weight of the surfactant system.

[0052] The C13 alkyl sulfate anionic surfactant comprises less than 80% by weight of a linear C13 alkyl sulfate, based on the weight of the C13 alkyl sulfate anionic surfactant, and greater than 5% by weight of a 2-branched C13 alkyl sulfate anionic surfactant, based on the weight of the C13 alkyl sulfate anionic surfactant, of which the 2-branched C13 alkyl sulfate anionic surfactant comprises less than 7.0% by weight of 2-pentyl octyl, based on the weight of the 2-branched alkyl chain, and greater than 70% by weight of 2-methyl dodecyl, based on the weight of the 2-branched alkyl chain.

[0053] The surfactant system includes at least one alkyl sulfate anionic surfactant, the alkyl sulfate anionic surfactant including at least 10% by weight of a C13 alkyl sulfate anionic surfactant, based on the weight of the alkyl sulfate anionic surfactant.

[0054] The alkyl sulfate anionic surfactant may include other alkyl sulfate anionic surfactants in addition to the C13 alkyl sulfate anionic surfactant as defined herein. Such alkyl sulfate anionic surfactant blends may have an average alkyl chain length of C12 to C14, but preferably the average chain length is C13.

[0055] The surfactant system may comprise from 60% to 90%, preferably from 65% to 85%, more preferably from 70% to 80% by weight of an alkyl sulfate anionic surfactant, based on the weight of the surfactant system.

[0056] The alkyl sulfate anionic surfactant may comprise from 15% to 80% by weight, preferably from 30% to 70% by weight, of an alkyl sulfate consisting of a C13 alkyl sulfate anionic surfactant, based on the weight of the alkyl sulfate anionic surfactant.

[0057] The C13 alkyl sulfate anionic surfactant may comprise less than 75% by weight, preferably 50% to 70% by weight, of a linear C13 alkyl sulfate, based on the weight of the C13 alkyl sulfate anionic surfactant, and more than 10% by weight, preferably 15% to 30% by weight, of a 2-branched C13 alkyl sulfate anionic surfactant, based on the weight of the C13 alkyl sulfate anionic surfactant.

[0058] The 2-branched C13 alkyl sulfate anionic surfactant may contain 5.0% by weight or less, preferably 3.0% by weight or less, of a 2-pentyloctyl sulfate anionic surfactant, based on the weight of the 2-branched C13 alkyl sulfate, and more than 80% by weight, preferably 85% to 95% by weight, of a 2-methyldodecyl sulfate anionic surfactant, based on the weight of the 2-branched C13 alkyl sulfate anionic surfactant.

[0059] To provide a combination of improved grease removal and increased cleaning speed, the molar average alkyl chain length of the alkyl sulfate anionic surfactant can be from 8 to 18, preferably from 10 to 14, more preferably from 12 to 14, and most preferably from 12 to 13 carbon atoms.

[0060] The molar average alkyl chain length of the alkyl sulfate anionic surfactant can be derived from the carbon chain length distribution of the anionic surfactant. The carbon chain length distribution of the alkyl chain of the alkyl sulfate anionic surfactant can be obtained from the technical data sheet of the surfactant or the alkyl alcohol that constitutes it. Alternatively, the chain length distribution and average molecular weight of the aliphatic alcohol used to make the alkyl sulfate anionic surfactant can 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, the alkyl sulfate anionic surfactant must be hydrolyzed back to the corresponding alkyl alcohol and alkyl alkoxylated alcohol before analysis, for example using hydrochloric acid.

[0061] It has been found that the weight average branching in combination with the specific type of branching formulation described herein improves stability at low temperatures, prevents smearing, improves initial foam generation, improves foam persistence, and allows for increased viscosity of the product. The alkyl sulfate anionic surfactant may have a weight average degree of branching of more than 10%, preferably more than 20%, more preferably more than 30%, and even more preferably 30% to 40%. The alkyl sulfate anionic surfactant may 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, based on the weight of the alkyl sulfate anionic surfactant (measured by counting carbon atoms from the sulfate group in the case of non-alkoxylated alkyl sulfate anionic surfactants, and from the alkoxy group furthest from the sulfate group in the case of alkoxylated alkyl sulfate anionic surfactants). Formulating the compositions of the present invention with alkyl sulfate anionic surfactants having the aforementioned degrees of branching has been found to result in improved stability at low temperatures. Such compositions require less solvent to achieve good physical stability at low temperatures, and therefore may contain low concentrations of organic solvent, less than 5.0% by weight, based on the weight of the liquid detergent composition, while still having improved low temperature stability.

[0062] The weight average degree of branching of an anionic surfactant mixture can be calculated using the following formula: Weight average branching degree (%) = [(x1 * Weight % of branched alcohol 1 in alcohol 1 + x2 * (wt% of branched alcohol 2 in alcohol 2 + ....) / (x1 + x2 + ....)] * 100 (where x1, x2, ... are the weights (in grams) of each alcohol in the total alcohol mixture used as starting material prior to (alkoxylation and) sulfation to produce the alkyl(alkoxy)sulfate anionic surfactant.) The weight average degree of branching calculation includes the weight of the alkyl alcohol used to form the unbranched alkyl sulfate anionic surfactant.

[0063] The weight average degree of branching and branching distribution can typically be obtained from the technical data sheet of the surfactant or its constituent alkyl alcohol. Alternatively, branching can be determined through analytical methods known in the art, including capillary gas chromatography with 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 sulfate anionic surfactant.

[0064] Suitable counterions include alkali metal cations, alkaline earth metal cations, alkanolammonium, or ammonium or substituted ammonium, preferably sodium.

[0065] The alkyl sulfate anionic surfactant may be selected from non-alkoxylated alkyl sulfate anionic surfactants, or alkoxylated alkyl sulfate anionic surfactants, or mixtures thereof. Blends of non-alkoxylated and alkoxylated alkyl sulfate anionic surfactants are preferred.

[0066] Thus, the alkyl sulfate anionic surfactant can, and preferably does, comprise, in addition to the C13 alkyl sulfate anionic surfactant, a further alkyl sulfate anionic surfactant, which may be a non-alkoxylated or alkoxylated alkyl sulfate anionic surfactant or a mixture thereof, but preferably comprises an alkoxylated alkyl sulfate anionic surfactant, more preferably an ethoxylated alkyl sulfate anionic surfactant.

[0067] Said further alkyl sulphate anionic surfactant may have an average alkyl chain length of from 8 to 18, preferably from 10 to 14, more preferably from 12 to 14, most preferably from 12 to 13 carbon atoms. Said further alkyl sulphate anionic surfactant may have an average degree of alkoxylation such that the alkyl sulphate anionic surfactant has an average degree of alkoxylation of less than 5, preferably less than 3, more preferably from 0.5 to 2.0, most preferably from 0.5 to 0.9.

[0068] The above further alkyl sulfate anionic surfactants may have a weight average degree of branching such that the alkyl sulfate anionic surfactant has a weight average degree of branching of more than 10%, preferably more than 20%, more preferably more than 30%, even more preferably from 30% to 60%, and most preferably from 30% to 50%.

[0069] When the alkyl sulfate anionic surfactant is an alkoxylated anionic sulfate surfactant, the alkoxylated anionic sulfate surfactant is preferably an ethoxylated alkyl sulfate anionic surfactant. Preferably, the alkyl sulfate anionic surfactant has an average degree of alkoxylation of less than 5, preferably less than 3, more preferably less than 2 and greater than 0.5, most preferably between 0.5 and 0.9, in order to improve the physical stability of the composition of the present invention at low temperatures and improve the foam persistence. The average degree of alkoxylation is the molar average degree of alkoxylation of all the alkyl sulfate anionic surfactants (i.e., the molar average degree of alkoxylation). Thus, when calculating the molar average degree of alkoxylation, the moles of non-alkoxylated sulfate anionic surfactant are included. Molar average degree of alkoxylation = (x1 * Alkoxylation degree of surfactant 1 + x2 * Alkoxylation degree of surfactant 2 +....) / (x1+x2+....) where x1, x2, ... are the 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.

[0070] The preferred alkyl alkoxy sulfates are the alkyl ethoxy sulfates. Suitable examples of commercially available alkyl sulfate anionic surfactants that may be added to the C13 alkyl sulfate anionic surfactant include those derived from alcohols sold by Shell under the brand name Neodol® or by Sasol under the brand names Lial®, Isalchem®, Alfol®, Nacol®, Nafol®, Isofol®, Marlipal®, and Safol®, or some of the natural alcohols manufactured by Procter & Gamble Chemicals. Such alkyl sulfate anionic surfactants may be non-alkoxylated alkyl sulfate anionic surfactants or alkoxylated alkyl sulfate anionic surfactants, or combinations thereof. When the alkyl sulfate anionic surfactant is an alkoxylated alkyl sulfate anionic surfactant, it is preferably an ethoxylated alkyl sulfate anionic surfactant.

[0071] Multiple starting alkyl alcohols may be blended together and sulfated to provide the alkyl sulfate anionic surfactant, or multiple alkyl sulfate anionic surfactants may be blended together individually or mixtures of multiple alkyl sulfate anionic surfactants to provide the alkyl sulfate anionic surfactant.

[0072] Based on the relative fractions of different alkyl chain lengths in the starting alcohols, obtained from technical data sheets from the supplier or from analysis using methods known in the art, the alcohols can be blended to achieve the desired molar distribution of alkyl chain lengths.

[0073] Performance including grease cleaning, foaming, low temperature stability, and end product viscosity can be influenced by the breadth of the alkoxylation distribution of the alkoxylated alkyl sulfate anionic surfactant. The alkoxylation distribution, including its breadth, can be varied through the selection of catalysts and process conditions when making the alkoxylated alkyl sulfate anionic surfactant.

[0074] Without being bound by theory, the amount of 1,4-dioxane by-product in alkoxylated, especially ethoxylated, alkyl sulfates can be minimized through strict control of process conditions and raw material composition during the alkoxylation, especially ethoxylation and sulfation steps. The 1,4-dioxane by-product can be further reduced by stripping, distillation, evaporation, centrifugation, microwave irradiation, molecular sieving, or catalytic or enzymatic degradation steps of the resulting 1,4-dioxane. Processes for controlling the 1,4-dioxane content in alkoxylated / ethoxylated alkyl sulfates are widely known in the art. Alternatively, it is also known in the art to control the 1,4-dioxane concentration in detergent formulations through the addition of 1,4-dioxane inhibitors to formulations containing 1,4-dioxane, such as 5,6-dihydro-3-(4-morpholinyl)-1-[4-(2-oxo-1-piperidinyl)phenyl]-2(1H)-pyridone, 3a-hydroxy-7-oxo-mixture of cholanic acid, 3-(N-methylamino)-L-alanine, and mixtures thereof. By strictly controlling 1,4-dioxane throughout the raw materials and detergent manufacturing process, the residual 1,4-dioxane content of the product formulation can be less than 10 ppm, preferably less than 5 ppm, and even more preferably less than 1 ppm.

[0075] The surfactant system may include additional anionic surfactants. If such additional anionic surfactants are present, they may be present at a level of less than 30%, preferably less than 10%, based on the weight of the anionic surfactant. More preferably, the surfactant system does not include additional anionic surfactants. If such anionic surfactants are present, examples thereof include sulfonate surfactants such as alkylbenzenesulfonates, sulfosuccinates, alkylcarboxylates (soaps), alkylethoxycarboxylates, acylsarcosinates, acylglycinates, acylglutamates, rhamnolipids, sophorolipid anionic surfactants.

[0076] The surfactant system may further comprise a co-surfactant selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof, preferably selected from the group consisting of amine oxides, betaines, and mixtures thereof, more preferably selected from amine oxide surfactants.

[0077] The liquid detergent composition may comprise from 0.1% to 20% by weight, more preferably from 0.5% to 15% by weight, especially from 2% to 10% by weight, of a co-surfactant, based on the weight of the liquid detergent composition, to improve surfactant loading and therefore grease cleaning performance and foam persistence.

[0078] The surfactant system of the liquid detergent composition of the present invention preferably comprises from 10% to 40% by weight, preferably from 15% to 35% by weight, more preferably from 20% to 30% by weight of co-surfactant, based on the weight of the surfactant system.

[0079] To improve surfactant loading after dilution and therefore improve foam persistence, the surfactant system may include a co-surfactant in addition to the alkyl sulfate anionic surfactant such that the weight ratio of alkyl sulfate anionic surfactant to co-surfactant is from 1:1 to 8:1, preferably from 2:1 to 5:1, more preferably from 2.5:1 to 4:1.

[0080] Suitable amine oxide surfactants may be linear or branched, with linear being preferred. Suitable linear amine oxides are typically water-soluble and are characterized by the formula R1-N(R2)(R3)O, where R1 is a C8-18 alkyl and the R2 and R3 moieties are selected from the group consisting of C1-3 alkyl groups, C1-3 hydroxyalkyl groups, and mixtures thereof. For example, R2 and R3 may be selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl, and mixtures thereof, with one or both of R2 and R3 being preferably methyl. Linear amine oxide surfactants may include, inter alia, linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxyethyl dihydroxyethyl amine oxides.

[0081] Preferably, the amine oxide surfactant is selected from the group consisting of alkyl dimethylamine oxide, alkyl amidopropyl dimethylamine oxide, and mixtures thereof. Preferred are alkyl dimethylamine oxides such as C8-18 alkyl dimethylamine oxide or C10-16 alkyl dimethylamine oxide (such as cocodimethylamine oxide). Suitable alkyl dimethylamine oxides include C10 alkyl dimethylamine oxide surfactants, C10-12 alkyl dimethylamine oxide surfactants, C12-C14 alkyl dimethylamine oxide surfactants, and mixtures thereof. Particularly preferred are C12-C14 alkyl dimethylamine oxides.

[0082] Another suitable amine oxide surfactant includes mid-branched amine oxide surfactants. As used herein, "mid-branched" means that the amine oxide has one alkyl moiety with n1 carbon atoms, and one alkyl branch in the alkyl moiety has n2 carbon atoms. The alkyl branch is located on the alpha carbon from the nitrogen on the alkyl moiety. This type of branching of the amine oxide is also known in the art as an internal amine oxide. The sum of n1 and n2 may be 10-24, preferably 12-20, more preferably 10-16 carbon atoms. The number of carbon atoms in one alkyl moiety (n1) is preferably the same or similar to the number of carbon atoms in one alkyl branch (n2), so that the one alkyl moiety and the one alkyl branch are symmetric. As used herein, "symmetric" means that in at least 50% by weight, more preferably at least 75% to 100% by weight of the mid-branched amine oxides used herein, |n1-n2| is 5 or less, preferably 4, most preferably 0-4 carbon atoms. The amine oxide further comprises two moieties independently selected from a C1-3 alkyl group, a C1-3 hydroxyalkyl group, or a polyethylene oxide group containing an average of about 1 to about 3 ethylene oxide groups. Preferably, the two moieties are selected from a C1-3 alkyl group, and more preferably, both are selected as a C1 alkyl group.

[0083] Alternatively, the amine oxide surfactant may be a mixture of amine oxides, including a mixture of low cut and mid cut amine oxides. Thus, the amine oxide of the composition of the present invention may be: a) about 10% to about 45% by weight, based on the weight of the amine oxide, of a low cut amine oxide of the formula R1R2R3AO, 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) 55% to 90% by weight, based on the weight of the amine oxide, of a mid-cut amine oxide of formula R4R5R6AO, where R4 and R5 are independently selected from hydrogen, C1 to C4 alkyl, or mixtures thereof, and R6 is selected from C12 to C16 alkyl, or mixtures thereof.

[0084] In the preferred low cut amine oxides for use herein, R3 is n-decyl, and preferably R1 and R2 are both methyl. In the mid cut amine oxides of formula R4R5R6AO, preferably R4 and R5 are both methyl.

[0085] Preferably, the amine oxide comprises less than about 5% by weight, more preferably less than 3% by weight, based on the weight of the amine oxide, of the formula R7R8R9AO, where R7 and R8 are selected from hydrogen, C1-C4 alkyl, and mixtures thereof, and R9 is selected from C8 alkyl, and mixtures thereof. By limiting the amount of amine oxide of the formula R7R8R9AO, both physical stability and lather persistence are improved.

[0086] Suitable zwitterionic surfactants include betaine surfactants, including alkyl betaines, alkyl amido betaines, amido azolinium betaines, sulfo betaines (INCI sultaines), and phospho betaines, preferably satisfying 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; X is selected from the group consisting of NH, NR4 (wherein R4 is a C1-4 alkyl residue), O, and S; n is an integer of 1 to 10, preferably 2 to 5, and more preferably 3; x is 0 or 1, preferably 1; R2 and R3 are independently selected from the group consisting of C1-4 alkyl residues, substituted hydroxy such as hydroxyethyl, and mixtures thereof, preferably both R2 and R3 are methyl; m is an integer from 1 to 4, preferably an integer of 1, 2, or 3; y is 0 or 1, and Y is selected from the group consisting of COO, SO3, OPO(OR5)O, or P(O)(OR5)O, where R5 is H or a C1-4 alkyl residue.

[0087] Preferred betaines are the alkyl betaines of formula (Ia), the alkyl amidopropyl betaines of formula (Ib), the sulfo betaines of formula (Ic) and the amido sulfo betaines of formula (Id): R 1 -N(CH3)2-CH2COO - (IIa) R 1 -CO-NH-(CH2)3-N + (CH3)2-CH2COO - (IIb) R 1 -N + (CH3)2-CH2CH(OH)CH2SO3 - (IIc) R 1 -CO-NH-(CH2)3-N + (CH3)2-CH2CH(OH)CH2SO3 - (IId) (wherein R1 has the same meaning as in formula (I).) Particularly preferred are carbobetaines of formula (Ia) and (Ib) [i.e., in formula (I), Y- is COO-], and more preferred are alkylamidobetaines of formula (Ib).

[0088] Suitable betaines may be selected from the group consisting of capryl / capramidopropyl betaine, cetyl betaine, cetylamidopropyl betaine, cocamidoethyl betaine, cocamidopropyl betaine, coco betaine, decyl betaine, decylamidopropyl betaine, hydrogenated tallow betaine / amidopropyl betaine, isostearamidopropyl betaine, lauramidopropyl betaine, lauryl betaine, myristyl amidopropyl betaine, myristyl betaine, oleadopropyl betaine, oleyl betaine, palmamidopropyl betaine, palmitamidopropyl betaine, palm kernelamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, tallowamidopropyl betaine, tallow betaine, undecylenamidopropyl betaine, undecyl betaine, and mixtures thereof, or [named according to INCI]. Preferred betaines are selected from the group consisting of cocamidopropyl betaine, coco betaine, lauramidopropyl betaine, lauryl betaine, myristyl amidopropyl betaine, myristyl betaine, and mixtures thereof. Cocamidopropyl betaine is particularly preferred.

[0089] Nonionic surfactants: The surfactant system may further comprise a nonionic surfactant, preferably at a level of from 1.0% to 25%, more preferably from 1.25% to 15%, and most preferably from 1.5% to 5.0% by weight based on the weight of the surfactant system. Suitable nonionic surfactants include alkoxylated nonionic surfactants, and mixtures thereof.

[0090] Preferred alkoxylated nonionic surfactants are linear or branched primary or secondary alkyl alkoxylated nonionic surfactants, preferably alkyl ethoxylated nonionic surfactants, preferably containing an average of 9 to 15, preferably 10 to 14 carbon atoms in the alkyl chain and containing an average of 5 to 12, preferably 6 to 10, most preferably 7 to 8 ethylene oxide units per mole of alcohol.

[0091] Additional Ingredients: The composition may further comprise at least one active agent selected from the group consisting of amphiphilic alkoxylated polyalkyleneimines, cyclic polyamines or oligoamines, salts, hydrotropes, organic solvents, and mixtures thereof.

[0092] Amphiphilic alkoxylated polyalkyleneimines: The composition of the present invention may further comprise about 0.05% to about 2% by weight, preferably about 0.07% to about 1% by weight, of an amphiphilic polymer based on the weight of the entire composition. Suitable amphiphilic polymers may be selected from the group consisting of amphiphilic alkoxylated polyalkyleneimines and mixtures thereof. Amphiphilic alkoxylated polyalkyleneimine polymers have been found to reduce gel formation on hard surfaces being cleaned when the liquid composition is added directly to a cleaning implement (such as a sponge) prior to cleaning and then contacted with a heavily oily surface, particularly when the cleaning implement contains little to no water, e.g., when a lightly pre-moistened sponge is used.

[0093] Preferably, the amphiphilic alkoxylated polyalkyleneimine is an alkoxylated polyethyleneimine polymer comprising a polyethyleneimine backbone having a weight average molecular weight range of 100 to 5,000, preferably 400 to 2,000, more preferably 400 to 1,000 Daltons. The polyethyleneimine backbone comprises the following modifications: (i) an alkoxylation modification, depending on whether the modification is present on an internal or terminal nitrogen atom in the polyethyleneimine backbone, of one or two alkoxylation modifications per nitrogen atom, the alkoxylation modification consisting of replacement of a hydrogen atom with a polyalkoxylene chain having an average of about 1 to about 50 alkoxy moieties per modification, the terminal alkoxy moieties of the alkoxylation modification being capped with hydrogen, C1-C4 alkyl, or mixtures thereof; (ii) substitution and alkoxylation modification of one C1-C4 alkyl moiety and one or two alkoxylation modifications per nitrogen atom, depending on whether the substitution is on an internal or terminal nitrogen atom in the polyethyleneimine backbone, the alkoxylation modification consisting of replacement of hydrogen atoms with polyalkoxylene chains having an average of about 1 to about 50 alkoxy moieties per modification, and the terminal alkoxy moieties are capped with hydrogen, C1-C4 alkyl, or mixtures thereof; or (iii) Combinations of these.

[0094] For example, possible modifications to the terminal nitrogen atom in the polyethyleneimine backbone are shown below, but are not limited to these, where R represents an ethylene spacer, E represents a C1-C4 alkyl moiety, and X- represents a suitable water-soluble counterion.

[0095] [ka]

[0096] Also, for example, possible modifications to internal nitrogen atoms in the polyethyleneimine backbone are shown below, but are not limited to these (wherein R represents an ethylene spacer, E represents a C1-C4 alkyl moiety, and X- represents a suitable water-soluble counterion):

[0097] [ka]

[0098] The alkoxylation modification of the polyethyleneimine backbone consists of the replacement of hydrogen atoms with polyalkoxylene chains having an average of about 1 to about 50 alkoxy moieties, preferably about 20 to about 45 alkoxy moieties, and most preferably about 30 to about 45 alkoxy moieties. The alkoxy moieties are selected from ethoxy (EO), propoxy (PO), butoxy (BO), and mixtures thereof. However, alkoxy moieties containing only ethoxy units are outside the scope of use of the present invention. Preferably, the polyalkoxylene chains are selected from ethoxy / propoxy block moieties. More preferably, the polyalkoxylene chains are ethoxy / propoxy block moieties having an average degree of ethoxylation of about 3 to about 30 and an average degree of propoxylation of about 1 to about 20, more preferably an ethoxy / propoxy block moiety having an average degree of ethoxylation of about 20 to about 30 and an average degree of propoxylation of about 10 to about 20.

[0099] More preferably, the ethoxy / propoxy block moiety has a relative ratio of ethoxy units to propoxy units of from 3:1 to 1:1, preferably from 2:1 to 1:1.Most preferably, the polyalkoxylene chain is an ethoxy / propoxy block moiety, with the propoxy moiety being the terminal alkoxy moiety block.

[0100] As a result of this modification, the nitrogen atoms of the polyethyleneimine backbone may be permanently quaternized. The degree of permanent quaternization may be between 0% and about 30% of the nitrogen atoms of the polyethyleneimine backbone. It is preferred that less than 30% of the nitrogen atoms of the polyethyleneimine backbone are permanently quaternized. Most preferably, the degree of quaternization is about 0%.

[0101] Preferred amphiphilic alkoxylated polyethyleneimine polymers have the general structure of formula (II):

[0102] [ka] wherein the weight average molecular weight of the polyethyleneimine backbone is about 600, the average of n in formula (II) is about 10, the average of m in formula (II) is about 7, and R in formula (II) is selected from hydrogen, C1-C4 alkyl, and mixtures thereof, preferably hydrogen. The degree of permanent quaternization in formula (II) can be from 0% to about 22% of the nitrogen atoms of the polyethyleneimine backbone. The molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer is preferably from 10,000 to 15,000 Da.

[0103] More preferably, the amphiphilic alkoxylated polyethyleneimine polymer has the general structure of formula (II), where the weight average molecular weight of the polyethyleneimine backbone is about 600 Da, the average of n in formula (II) is about 24, the average of m in formula (II) is about 16, and R in formula (II) is selected from hydrogen, C1-C4 alkyl, and mixtures thereof, preferably hydrogen. The permanent degree of quaternization of formula (II) may be 0% to about 22% of the polyethyleneimine backbone nitrogen atoms, preferably 0%. The molecular weight of the amphiphilic alkoxylated polyethyleneimine polymer is preferably 25,000 to 30,000 Da, most preferably 28,000 Da.

[0104] Amphiphilic alkoxylated polyethyleneimine polymers can be made by the methods described in more detail in WO 2007 / 135645.

[0105] Cyclic polyamines or oligoamines: The compositions may include cyclic polyamines or oligoamines having amine functional groups to aid in cleaning. The compositions of the present invention preferably include from about 0.1% to about 3% by weight, more preferably from about 0.2% to about 2% by weight, and especially from about 0.5% to about 1% by weight, of a cyclic polyamine or oligoamine, based on the weight of the composition.

[0106] The amine may be protonated depending on the pH of the cleaning medium in which it is used. A preferred cyclic polyamine or oligoamine has the following formula (III):

[0107] [ka] (wherein R1, R2, R3, R4, and R5 are independently selected from the group consisting of NH2, -H, linear or branched alkyl having about 1 to about 10 carbon atoms, and linear or branched alkenyl having about 1 to about 10 carbon atoms; n is about 1 to about 3, preferably n is 1, at least one of R is NH2, and the remaining "R"s are independently selected from the group consisting of NH2, -H, linear or branched alkyl having about 1 to about 10 carbon atoms, and linear or branched alkenyl having about 1 to about 10 carbon atoms). Preferably, the cyclic polyamine or oligoamine is a diamine where n is 1, R2 is NH2, at least one of R1, R3, R4, and R5 is CH3, and the remaining R is H.

[0108] Cyclic polyamines or oligoamines have at least two primary amine functional groups. The primary amine may be present at any position in the cyclic amine, but it has been found that, from the viewpoint of grease cleaning, better performance is obtained when the primary amine is present at the 1,3 positions. It has also been found that cyclic amines in which one of the substituents is -CH3 and the remaining is H provide improved grease cleaning performance.

[0109] Thus, the most preferred cyclic polyamines or oligoamines for use in the liquid detergent compositions of the present invention are those selected from the group consisting of 2-methylcyclohexane-1,3-diamine, 4-methylcyclohexane-1,3-diamine, and mixtures thereof. These particular cyclic polyamines or oligoamines function to improve the suds and grease cleaning profile throughout the dishwashing process when formulated with the surfactant system of the compositions of the present invention.

[0110] salt: The composition of the present invention may contain, based on the weight of the entire composition, about 0.05% by weight to about 2% by weight, preferably about 0.1% by weight to about 1.5% by weight, or more preferably about 0.5% by weight to about 1% by weight of a salt, preferably a monovalent or divalent inorganic salt, or a mixture thereof, more preferably a salt selected from sodium chloride, sodium sulfate, and mixtures thereof. Sodium chloride is most preferred.

[0111] Hydrotropes: The compositions of the present invention may contain from about 0.1% to about 10% by weight, or preferably from about 0.5% to about 10% by weight, or more preferably from about 1% to about 10% by weight, of a hydrotope or mixture thereof, preferably sodium cumene sulfonate, based on the weight of the total composition.

[0112] Organic solvents: The composition may contain about 0.1% to about 10% by weight, or preferably about 0.5% to about 10% by weight, or more preferably about 1% to about 10% by weight, of an organic solvent based on the weight of the entire composition. Suitable organic solvents include organic solvents selected from the group consisting of alcohols, glycols, glycol ethers, and mixtures thereof, preferably alcohols, glycols, and mixtures thereof. Ethanol is a preferred alcohol. Polyalkylene glycols, particularly polypropylene glycol, are preferred glycols.

[0113] Supplementary ingredients The liquid detergent compositions may optionally contain many other adjunct ingredients, examples of which include builders (preferably citrates), chelating agents, conditioning polymers, other cleaning polymers, surface modifying polymers, structurants, emollients, humectants, skin rejuvenation actives, enzymes, carboxylic acids, scrubbing particles, fragrances, malodor control agents, pigments, dyes, opacifiers, pearlescent particles, inorganic cations such as alkaline earth metals such as Ca / Mg ions, antimicrobial agents, preservatives, viscosity modifiers (e.g., salts such as NaCl and other mono-, di-, and trivalent salts), and pH adjusters and buffers (e.g., carboxylic acids such as citric acid, HCl, NaOH, KOH, alkanolamines, carbonates such as sodium carbonate, bicarbonates, sesquicarbonates, and the like).

[0114] Cleaning Method The compositions of the present invention can be used to clean dishes in a variety of ways depending on the level and type of soil or grease, and consumer preference.

[0115] For example, the composition can be used in a method for hand washing dishware, diluting the composition before applying the composition to the soiled dishware. The method includes the steps of providing a composition of the present invention to a volume of water to form a cleaning solution, and immersing the dishware in the solution. The dishware is washed with the composition in the presence of water. Optionally, the dishware may be rinsed. As used herein, "rinsing" refers to contacting the dishware washed in the process according to the present invention with a substantial amount of a suitable solvent, typically water. "Substantial amount" typically refers to about 1 to about 20 L or under running water.

[0116] The compositions herein may be applied in their diluted form. The soiled dishes are contacted with an effective amount, typically about 0.5 mL to about 20 mL, preferably about 3 mL to about 10 mL (per about 25 dishes to be treated), of the liquid detergent composition of the present invention (preferably in liquid form) diluted with water. The actual amount of liquid detergent composition used is at the discretion of the user and typically depends on factors such as the specific product formulation of the liquid cleaning composition, including the concentration of active ingredients in the liquid detergent composition, the number of soiled dishes to be cleaned, and the degree of soiling of the dishes. Generally, about 0.01 mL to about 150 mL, preferably about 3 mL to about 40 mL, of the liquid detergent 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 resulting diluted liquid detergent composition, the soiled surface of the dishes is contacted with a cloth, sponge, or similar cleaning implement. Prior to contacting the dishware, a cloth, sponge, or similar cleaning implement may be immersed in the mixture of liquid detergent composition and water, and is typically contacted with the dishware for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user. Contacting the cloth, sponge, or similar cleaning implement with the dishware involves simultaneously scrubbing the dishware.

[0117] The present invention may also be used in a method of directly applying the liquid detergent composition. Such a method includes contacting the composition in its undiluted form with the dishes. The composition may be poured directly onto the dishes from its container. Alternatively, the composition may first be applied to a cleaning device or implement, such as a brush, sponge, nonwoven material, or woven material. The cleaning device or implement, and thus the liquid dishwashing composition in its undiluted form, is then directly contacted with the respective surfaces of the soiled dishes to remove the soiling. The cleaning device or implement is typically contacted with the respective dish surfaces for a period of time ranging from about 1 to about 10 seconds, although the actual application time will depend on factors such as the degree of soiling of the dishes. Contacting the cleaning device or implement with the dish surfaces is preferably accompanied by simultaneous scrubbing. Alternatively, the device or implement may be immersed in the undiluted liquid hand dishwashing detergent composition in a small container capable of housing the cleaning device. Prior to application of the composition, the soiled dishes may be immersed in a water bath or held under running water to wet the surfaces of the dishes. The method may include an optional rinsing step after the step of contacting the dishware with the liquid detergent composition.

[0118] The compositions of the present invention are particularly useful for grease cleaning and foam persistence improvement during direct application dishwashing processes and in dishwashing processes where the detergent composition is diluted (e.g., in a sink).In addition, they are useful for preventing early foam formation and smearing during direct application dishwashing processes, and are also useful for improving stability at low temperatures and providing a highly viscous formulation.

[0119] Test Method Smear test: 1 g of lard (Saindoux raffine from Olma) is applied evenly with a brush onto a black ceramic plate (28 cm diameter). 2 g of each of the different test compositions is distributed evenly over the polishing surface (width x length side) of a pre-moistened Scotch Brite 3M sponge (dimensions: width 7 cm x length 10 cm x height 1.5 cm) evenly loaded with 30 g of soft tap water (7 dH) at 42°C. New sponges are used for all tests. Before use, these sponges are preconditioned by washing three times in a Miele Softtronic W3205 machine on the "Quick" program (40C) in the absence of cleaning products. The sponge with detergent is squeezed by hand twice with constant force. The sponge with detergent side is then placed in contact with the soiled plate and wiped with circular movements with consistent hand pressure, covering the entire surface area of ​​the plate as would be done during a normal hand dishwashing action. After the sponge has been moved in 40 circular movements over the plate, a photograph is taken and the plate is visually assessed for the presence or absence of detergent / soil smears.

[0120] viscosity: Viscosity is measured on a Brookfield RT viscometer using spindle 21 at 20° C. and 12 RPM. EXAMPLES

[0121] Examples of suitable alkyl sulfate anionic surfactants and their synthesis: Below are representative, non-limiting examples of suitable alkyl sulfate anionic surfactants, and non-limiting methods of synthesis are included below.

[0122] Using the process already described, the alcohol compositions described in the following alcohol examples 1 and 2 are obtained and analyzed by gas chromatography using flame ionization detection (GC / FID). Samples are prepared as 1% (w / v) dichloromethane solutions and injected into a capillary GC column: DB-1 (height 15 m x inner diameter 0.25 mm, membrane thickness 0.1 μm) using an oven temperature program [initial temperature 80°C hold (1 min), ramp to 220°C at 10°C / min, ramp to 350°C at 30°C / min and hold (1 min)] for a total run time of 19 min. Further GC parameters include column flow rate: 1.4 mL / min (H2), injection temperature: 300°C, sample volume: 1 μL, split ratio: 1 / 400, FID temperature: 350°C, H2 flow rate: 40 mL / min, air flow: 400 mL / min, and make-up gas flow rate: 25 mL / min.

[0123] Alcohol Example 1 Synthesis of narrowly branched tridecanol (alcohol 1) C12 linear alpha olefin feedstock (1-dodecene) was obtained from Chevron Phillips Chemical Company LP, P.O. Box 4910, The Woodlands, Texas 77387-4910, and is identified by the trade name AlphaPlus® 1-dodecene (Chevron Phillips Chemical Company LP). The homogeneous rhodium organophosphorus catalyst used in this example is an organometallic complex of Rh(CO)2ACAC ((acetylacetonato)dicarbonylrhodium(I)) and triphenylphosphine ligands. The 1-dodecene linear alpha olefin was added to a rhodium catalyst solution in a stainless steel autoclave to obtain a starting reaction mixture with a rhodium concentration of 50 ppm and a P to Rh molar ratio of 20. The alpha olefin feed was then directly hydroformylated (without isomerization step) in the presence of a CO / H2 atmosphere and 14 bar gauge pressure at 90°C for 5 hours. The molar ratio of CO to H2 was 1:1.20. The resulting hydroformylation reaction product was distilled to recover a branched C13 aldehyde overhead, the composition of which included: 1-Tridecanal 68.6% by weight 2-Methyl-dodecanal 25.1% by weight 2-Ethyl undecanal 2.1% by weight 2-Propyl-decanal 0.6% by weight Others 3.6% by weight

[0124] The weight percent of branches in the branched chain C13 aldehyde product was 28.8%.

[0125] The tridecanal mixture was hydrogenated as follows: 64 wt% nickel on silica (BASF Ni5249-P, 5.0 g) was placed in a 300 mL Parr reactor, followed by hexane (20 mL) to wet the catalyst. After wetting, tridecanal (101 g) was added, followed by hexane (75 mL). The reactor was placed on a reactor stand, purged with nitrogen (5 x 20 psig), then hydrogen (3 x 400 psig), and filled with hydrogen (420 psig). The reactor was rapidly heated to 95°C with stirring. After hydrogen consumption ceased (approximately 1 hour), the reactor was cooled to room temperature. The reaction mixture was filtered through a glass microfiber filter and the hexane was removed under reduced pressure to give the branched tridecanol (alcohol 1 in Table 1) product as a clear oil (93 g). Its composition included: 1-Tridecanol 67.65% by weight 2-Methyl-dodecanol 28.6% by weight 2-Ethyl-undecanol 2.95% by weight Others 0.8% by weight

[0126] Alkyl Sulfate Example 1: Synthesis of Narrowly Branched Tridecanol Sulfate Using Chlorosulfonic Acid A 500 mL 3-neck round bottom flask was fitted with a magnetic stir bar for mixing, an addition funnel with a nitrogen gas supply in the center neck, a thermometer in one side neck, and a tube vent in the other neck leading to a gas bubbler filled with 1N sodium hydroxide to capture HCl gas evolved from the reaction. 104.948 g of C13 rich 2-alkyl and linear primary alcohol mixture composition from alcohol example 1 and 110 mL of ACS reagent grade diethyl ether were added to the round bottom flask. 64.092 g of 98.5% chlorosulfonic acid was added to the addition funnel. A stream of nitrogen gas flows from the top of the addition funnel through the flask and out the side neck vent to the sodium hydroxide bubbler. An 18°C ​​water bath was placed around the reaction flask. Mixing was started and once the reaction mixture reached 19°C, chlorosulfonic acid was added dropwise at a rate to maintain the temperature at or below 25°C. Ice was added to the water bath as needed to control the exothermic reaction temperature. The addition of chlorosulfonic acid was completed in 47 minutes.

[0127] The water bath was warmed to 22°C. The tubing vent attached to the sodium hydroxide bubbler was switched to a vacuum tube attached to a water aspirator. A solvent trap cooled with a dry ice / isopropanol bath was placed in line with the vacuum tube between the reaction flask and the aspirator to capture volatiles pulled from the reaction mixture. A dial pressure gauge (US Gauge, capable of measuring 0-30 in. Hg) was placed in the vacuum tube after the solvent trap to measure the vacuum in the system. The reactants were allowed to continue mixing under a nitrogen gas sweep for 29 minutes while the vacuum system was achieved.

[0128] While mixing continued, the aspirator was turned on and vacuum was applied to the reaction mixture. The vacuum level was slowly increased by gradually decreasing the nitrogen gas flow rate from the addition funnel. This was done to control foaming of the reaction mixture. Finally, the nitrogen flow was stopped completely and full vacuum was applied to the reaction mixture (30 inches Hg measured on the vacuum gauge indicates full vacuum was applied). Full vacuum was achieved 66 minutes after the start of the vacuum process, at which point the reaction mixture had a temperature of 20° C. Mixing continued under full vacuum for an additional 46 minutes, at which point the reaction mixture had a temperature of 20° C. and was a slightly hazy, pale orange fluid with minimal bubbling. The vacuum was broken by injecting in nitrogen gas.

[0129] The reaction mixture was slowly poured over a period of about 2-3 minutes into a mixture of 133.908 g of a 25 wt. % sodium methoxide solution in methanol and 508 g of ACS reagent grade methanol contained in a stainless steel beaker to convert the C13 rich 2-alkyl and linear primary alcohol mixture composition reaction product from the acid sulfate form to the sodium sulfate salt form while providing good vortex mixing using an overhead mixer with stainless steel mixing blades. The resulting product was a creamy white mixture that was fluid and mixed very well. About 0.2 g of the reaction product was dissolved in about 0.5 g of deionized water and measured with pH paper to be about pH 12. The resulting product was mixed for an additional 20 minutes.

[0130] The reaction product was poured into a flat glass dish in a fume hood. The product was left overnight to yield a soft, white solid. Residual solvent was dried by placing the product in a vacuum oven under full vacuum at 22° C. After 24 hours, the product was removed from the vacuum oven and ground into a powder using a mortar and pestle before being placed back into the vacuum oven under full vacuum at 22° C. After drying for an additional 4 days, the product was removed from the vacuum oven and 161.0 g of white solid product was recovered.

[0131] The final product was determined to be 88.8% active by standard cationic SO3 titration analysis.

[0132] Alkyl Sulfate Example 2 Synthesis of Narrowly Branched Tridecanol Ethoxylates The pressure reactor was placed under vacuum and the narrow branched tridecanol from Alcohol Example 1 (85 g) was added, followed by a 25 wt % solution of sodium methoxide in methanol (3.0 g, 0.025 eq.). The reactor was kept under vacuum and the reaction mixture was heated to 75° C. and maintained at that temperature for approximately 2 hours while nitrogen was slowly bubbled through the reaction mixture. The nitrogen purging was stopped and the reaction mixture was heated to 95° C. and ethylene oxide (37 g, 2.0 eq.) was added in small increments while maintaining the reaction temperature below 100° C. After the ethylene oxide addition was complete, the reactor was stirred until the pressure in the reactor was equalized. The reactor was cooled to 75° C., the stirring speed was reduced, and vacuum was applied for 30 minutes while nitrogen was slowly bubbled through the reaction mixture over 30 minutes. The product was neutralized with acetic acid to give narrow branched tridecanol ethoxylate (2 moles) or C13AE2 (116.2 g) as a slightly yellow liquid.

[0133] Alkyl Sulfate Example 3 Synthesis of Narrowly Branched Tridecanol Ethoxy Sulfate Using Chlorosulfonic Acid A 500 mL 3-neck round bottom flask was fitted with a magnetic stir bar for mixing, an addition funnel with a nitrogen gas supply in the center neck, a thermometer in one side neck, and a tube vent in the other neck leading to a gas bubbler filled with 1-normal sodium hydroxide to capture HCl gas evolved from the reaction. 112.863 g of narrow branched C13 rich 2-alkyl and linear primary alcohol 2-molar average ethoxylate composition from alkyl sulfate example 2 and 100 mL of ACS reagent grade diethyl ether were added to the round bottom flask. 47.896 g of 98.5% chlorosulfonic acid was added to the addition funnel. A stream of nitrogen gas was allowed to flow from the top of the addition funnel through the flask, out the side neck vent, and into the sodium hydroxide bubbler. The reaction flask was cooled in an ice / NaCl / water bath. Mixing was started and once the reaction mixture reached 10° C., chlorosulfonic acid was added dropwise at a rate sufficient to maintain the temperature below 10° C. Addition of the chlorosulfonic acid was completed in 20 minutes.

[0134] The ice / NaCl / water bath was replaced with a 22-25°C water bath. The tubing vent attached to the sodium hydroxide bubbler was switched to a vacuum tube attached to a water aspirator. A solvent trap cooled with a dry ice / isopropanol bath was placed in line with the vacuum tube between the reaction flask and the aspirator to capture volatiles being pulled from the reaction mixture. A dial pressure gauge (US Gauge, capable of measuring 0-30 in. Hg) was placed in the vacuum tube after the solvent trap to measure the vacuum in the system. The reaction was allowed to continue mixing under a nitrogen gas sweep for 25 minutes while the water bath was replaced and a vacuum system was established.

[0135] While mixing continued, the aspirator was turned on and vacuum was initiated on the reaction mixture. The vacuum level was slowly increased by gradually decreasing the nitrogen gas flow rate from the addition funnel. This was done to control foaming of the reaction mixture. After 40 minutes from the start of the vacuum process, near full vacuum was achieved, but the reaction mixture was foaming excessively, so the nitrogen gas flow was turned off completely and full vacuum was applied. The temperature of the reaction mixture was 18°C. Mixing continued under near full vacuum conditions for an additional 21 minutes, at which point the reaction mixture had a temperature of 20°C and was a clear, orange fluid. The vacuum was completely broken by injecting in nitrogen gas.

[0136] The reaction mixture was slowly poured over a period of about 2-3 minutes into a mixture of 100.406 g of a 25 wt. % sodium methoxide solution in methanol and 416 g of ACS reagent grade methanol contained in a stainless steel beaker to convert the C13 rich 2-alkyl and linear primary alcohol 2-molar average ethoxylate composition reaction product from the acidic sulfate salt form to the sodium sulfate salt form while providing good vortex mixing using an overhead mixer with stainless steel mixing blades. The resulting product was a milky white mixture that was fluid and mixed very well. About 0.2 g of the reaction product was dissolved in about 0.5 g of deionized water and measured with pH paper to have a pH of about 12. The resulting product was mixed for an additional 15 minutes.

[0137] The reaction product was poured into a flat glass dish in a fume hood. The product was left to stand overnight to give a semi-solid mixture. The product was thoroughly mixed with a spatula and placed in a vacuum oven under vacuum with a slow argon flow at 22° C. to prevent foaming of the product, and residual solvent was dried. After 24 hours, the argon flow was turned off and the product was left under full vacuum at 22° C. for 3 days to give a soft, sticky solid. The solid was broken into smaller pieces with a spatula and drying continued in the vacuum oven. After an additional day, the product was removed from the vacuum oven and 156.38 g of a white, soft, sticky solid product was recovered.

[0138] The final product was determined to be 88.4% active by standard cationic SO3 titration analysis.

[0139] Smear resistance The effect of the type of branching in the alkyl chain of alkyl sulfate anionic surfactants was evaluated on smear resistance in liquid hand dishwashing formulations according to the test method described herein.

[0140] Test materials: Relative smearing was determined for alkyl sulfate anionic surfactants based on the starting alcohols summarized in Table 1. All starting alcohols consisted essentially of C13 alkyl chains. Alcohol 1 used to make the alkyl sulfate anionic surfactants in the composition(s) of the present invention has the branching type as claimed and was made according to the manufacturing process described herein. Alcohols A and B have higher pentyl-type branching than required for the C13 alkyl sulfates used in the present invention and lower methyl-type branching than required for the C13 alkyl sulfates used in the present invention.

[0141] [Table 1] + Percentage based on weight of starting C13 alcohol ++ Percentage of branched C13 alcohol by weight +++ For example, isomers with branches at positions other than C2, paraffins, alcohols with chain lengths other than 13, etc.

[0142] The starting C13 alcohols of Table 1 and the further (non-ethoxylated and ethoxylated) alcohols listed in Table 2b were sulfated separately in a pilot plant and then mixed to obtain alkyl sulfate blends having the desired average branching and average ethoxylation degree as described in Tables 2a and 2b, but with a branching distribution either used in the present invention (Example 1 by using alcohol 1) or used in the comparative compositions (Examples A and C by using C13 alcohols A and B), or used in Comparative Example B, which has an average branching degree outside the range of the present invention, even if alcohol 1 is used. The alkyl sulfate distribution in the different AES compositions obtained is summarized in Table 2c.

[0143] [Table 2] * comparison

[0144] [Table 3] * comparison

[0145] The alkyl sulfate blends of Tables 2a-b have the following distribution of weight percent of alkyl sulfate chains (Table 2c):

[0146] [Table 4]

[0147] Table 3 summarizes liquid hand dishwashing detergent compositions prepared using the resulting alkyl ethoxy sulfate blends as described in Tables 2a-2c. The AES levels are presented in Table 3 as the sodium salt. The liquid detergent formulations were prepared using a batch process by mixing the individual raw materials together at room temperature.

[0148] [Table 5]

[0149] The data in Table 4 summarizes the smear performance of the detergent compositions.

[0150] As can be seen from Comparative Examples A and C, when a detergent composition was formulated to contain a C13 alkyl sulfate anionic surfactant comprising more than 7.0% by weight of 2-pentyl-octyl sulfate anionic surfactant based on the weight of the 2-branched C13 alkyl sulfate anionic surfactant and less than 70% by weight of 2-methyl-dodecyl sulfate anionic surfactant based on the weight of the 2-branched C13 alkyl sulfate anionic surfactant, the composition failed the smear test.

[0151] Comparative Example B contains 2-methyl-dodecyl sulfate anionic surfactant and 2-pentyl-octyl sulfate anionic surfactant at the concentrations required by the present invention, but the average AES branching degree was too high and Comparative Example B also failed the smearing test.

[0152] As can be seen from Example 1, compositions containing 2-methyl-dodecyl sulfate anionic surfactant and 2-pentyl-octyl sulfate anionic surfactant in the concentrations required by the present invention, while having a weight average branching degree of alkyl(ethoxy) sulfate of less than 40%, passed the smearing test.

[0153] [Table 6] * Comparative Example

[0154] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

[0155] All documents cited herein, including any cross-referenced or related patents or patent applications, and any patent applications or patents to which this application claims priority or benefit, are incorporated herein by reference in their entirety, unless expressly stated to the contrary. The citation of any document shall not be deemed to be prior art to any invention disclosed or claimed herein, or to teach, suggest or disclose such invention, either alone or in combination with any other reference(s). Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall apply.

[0156] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

1. A C13 alkyl sulfate anionic surfactant for use in a liquid detergent composition that is a hand dishwashing composition, comprising: The C13 alkyl sulfate anionic surfactant is a) less than 75% by weight of a linear C13 alkyl sulfate, based on the weight of the C13 alkyl sulfate anionic surfactant; b) greater than 25% by weight, based on the weight of the C13 alkyl sulfate anionic surfactant, of a 2-branched C13 alkyl sulfate anionic surfactant, 10% by weight or less of 2-pentyloctyl, based on the weight of the 2-branched alkyl chains; and greater than 70% by weight, based on the weight of the 2-branched chains, of 2-methyldodecyl; a 2-branched C13 alkyl sulfate anionic surfactant comprising c) less than 5% by weight of other branched C13 alkyl sulfate anionic surfactants; It consists of: a), b) and c) together add up to 100% by weight, based on the weight of the C13 alkyl sulfate anionic surfactant; Alkyl sulfate anionic surfactant.

2. a. 60% to 70% by weight of a linear C13 alkyl sulfate, based on the weight of the C13 alkyl sulfate anionic surfactant; b. 30% to 40% by weight of a 2-branched C13 alkyl sulfate anionic surfactant, based on the weight of the C13 alkyl sulfate anionic surfactant; c. 0.1% to 2.0% by weight, based on the weight of the C13 alkyl sulfate anionic surfactant, of another branched chain C13 alkyl sulfate anionic surfactant; The C13 alkyl sulfate anionic surfactant of claim 1, comprising:

3. The 2-branched C13 alkyl sulfate anionic surfactant is a. less than 5.0 weight percent 2-pentyloctyl, based on the weight of the 2-branched alkyl chains; b. 80% to 95% by weight of 2-methyldodecyl, based on the weight of the 2-branched alkyl chain; 3. The C13 alkyl sulfate anionic surfactant of claim 1, comprising:

4. A non-alkoxylated, alkoxylated, or a mixture thereof. The C13 alkyl sulfate anionic surfactant according to any one of claims 1 to 3.

5. A liquid detergent composition for hand dishwashing, comprising: 5.0% to 60% by weight of a surfactant system, based on the weight of the total composition; The surfactant system comprises: a) at least one alkyl sulfate anionic surfactant, said alkyl sulfate anionic surfactant having a weight average degree of branching of less than 40%, said alkyl sulfate anionic surfactant comprising at least 10% by weight of a C13 alkyl sulfate anionic surfactant, based on the weight of said alkyl sulfate anionic surfactant, said C13 alkyl sulfate anionic surfactant comprising: (i) less than 80% by weight of a linear C13 alkyl sulfate, based on the weight of the C13 alkyl sulfate anionic surfactant; (ii) greater than 5% by weight, based on the weight of the C13 alkyl sulfate anionic surfactant, of a 2-branched C13 alkyl sulfate anionic surfactant, 7.0% by weight or less of 2-pentyloctyl, based on the weight of the 2-branched alkyl chains, and greater than 70% by weight of 2-methyldodecyl, based on the weight of the 2-branched alkyl chains. A liquid detergent composition for hand dishwashing comprising a 2-branched C13 alkyl sulfate anionic surfactant comprising:

6. The composition of claim 5, wherein the liquid detergent composition comprises from 8.0% to 45% by weight of the surfactant system, based on the weight of the total composition.

7. 7. The composition of claim 5 or 6, wherein the surfactant system comprises from 60% to 90% by weight of the alkyl sulfate anionic surfactant, based on the weight of the surfactant system.

8. A composition according to any one of claims 5 to 7, wherein the average alkyl chain length of the alkyl sulfate anionic surfactant is from 12 to 13 carbon atoms.

9. A composition according to any one of claims 5 to 8, wherein the alkyl sulphate anionic surfactant has a weight average degree of branching of greater than 30%.

10. 10. The composition of any one of claims 5 to 9, wherein the alkyl sulfate anionic surfactant comprises from 30% to 70% by weight, based on the weight of the alkyl sulfate anionic surfactant, of an alkyl sulfate consisting of a C13 alkyl sulfate anionic surfactant.

11. The C13 alkyl sulfate anionic surfactant is a. 50% to 70% by weight of a linear C13 alkyl sulfate, based on the weight of the C13 alkyl sulfate anionic surfactant; b. 15% to 30% by weight of a 2-branched C13 alkyl sulfate anionic surfactant, based on the weight of the C13 alkyl sulfate anionic surfactant; The composition according to any one of claims 5 to 10, comprising:

12. The 2-branched C13 alkyl sulfate anionic surfactant is a. 3.0% or less of a 2-pentyloctyl sulfate anionic surfactant, based on the weight of the 2-branched C13 alkyl sulfate; b. 85% to 95% by weight of a 2-methyldodecyl sulfate anionic surfactant, based on the weight of the 2-branched C13 alkyl sulfate anionic surfactant; The composition according to any one of claims 5 to 11, comprising:

13. the alkyl sulfate anionic surfactant is selected from a non-alkoxylated alkyl sulfate anionic surfactant, or an alkoxylated alkyl sulfate anionic surfactant, or a mixture thereof; The composition according to any one of claims 5 to 12.

14. A composition according to any one of claims 5 to 13, wherein the surfactant system does not comprise any further anionic surfactant.

15. 15. The composition of any one of claims 5 to 14, wherein the surfactant system further comprises a co-surfactant selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.

16. A composition according to claim 15, wherein the surfactant system comprises the co-surfactant at a level of from 0.1% to 20% by weight based on the weight of the liquid detergent composition.

17. 17. A composition according to claim 15 or 16, wherein the surfactant system comprises the co-surfactant at a concentration of from 10% to 40% by weight, based on the weight of the surfactant system.

18. A composition according to any one of claims 15 to 17, wherein the surfactant system comprises the alkyl sulphate anionic surfactant and the co-surfactant in a weight ratio of from 1:1 to 8:

1.

19. The composition of claims 5 to 18, wherein the surfactant system further comprises a non-ionic surfactant.

20. A process for making a liquid detergent composition according to any one of claims 5 to 19, comprising the step of combining the C13 alkyl sulphate anionic surfactant according to claim 1 with a further surfactant.

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