Liquid hand dishwashing detergent composition

Abstract

To provide a liquid hand dishwashing detergent further improved in the drying speed of dishware after hand dishwashing.SOLUTION: A liquid hand dishwashing detergent composition contains: a quaternized acrylic copolymer; and a surfactant system of about 5.0 wt.% to about 50 wt.% of the composition. The surfactant system contains: an anionic surfactant of at least about 40 wt.% of the surfactant system; and an alkoxylated alcohol nonionic surfactant of more than about 3.0 wt.% of the liquid hand dishwashing detergent composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid hand dish detergent composition. [Background technology]

[0002] Hand-washing dishes is a time-consuming task, and many who do it consider it complete when they are able to put the dishes away. Therefore, rapid drying of dishes after washing and rinsing is highly desirable. Drying is particularly affected by water hardness, with water having lower hardness reducing water sheeting from dishes. As household water softeners become more popular, there is an ever-growing need to improve sheeting, and therefore drying speed.

[0003] It is known to use quaternized acrylic copolymers to improve drying speed, such copolymers increasing the drying rate by improving sheeting and beading of water from the dishware.

[0004] However, even if such copolymer is added, there is still a need to further improve the drying time after hand washing of dishware, especially in soft water.It has also been found that the performance of such copolymer in the liquid detergent composition that does not contain alkoxylated alcohol nonionic surfactant is relatively poor, especially in soft water conditions.Therefore, there is still a need to further improve the drying time after hand washing of dishware, without having to use high levels of alkoxylated alcohol nonionic surfactant in the formulation.

[0005] WO 201836864(A) relates to a hard surface treatment composition comprising a quaternized acrylic copolymer and an amphoterically modified polysaccharide, wherein the weight ratio of the quaternized acrylic copolymer to the amphoterically modified polysaccharide is 0.75:1 to 3:1, and the quaternized acrylic copolymer is different from the amphoterically modified polysaccharide. EP 3835399(A1) relates to a hard surface cleaning composition comprising a surfactant system, a first polymer, and a second polymer, wherein the first polymer is polyethyleneimine, as well as the use of the composition for cleaning glass surfaces. U.S. Patent Application Publication No. 2003 / 0134770(A) relates to a liquid detergent composition comprising a polymeric material that is a foam booster and a foam volume enhancer, the composition having increased effectiveness for preventing redeposition of grease during hand washing, the polymeric material being suitable as a foam volume enhancer and a foam durability enhancer, and comprising an effective amount of a polymeric foam booster containing quaternary nitrogen-containing monomer units and / or zwitterionic monomer units. EP 3835399(A1) relates to a hard surface cleaning composition comprising a surfactant system, a first polymer, and a second polymer, the first polymer being polyethyleneimine. U.S. Patent Application Publication No. 2010 / 0197553(A) relates to a liquid hand dishwashing detergent composition comprising a cationic polymer and a wetting agent, and a method of cleaning dishware using such a composition. The cationic polymers disclosed in U.S. Patent Application Publication No. 2010 / 0197553(A) include alternative cationic polymers such as Polyquaternium 16, a copolymer of vinylpyrrolidone and quaternized vinylmethylimidazolium. Unlike quaternized acrylic copolymers, such polymers are not produced by polymerizing ethylenically unsaturated acids and / or salts of such acids. U.S. Patent Application Publication No. 2012 / 028872(A) relates to methods of washing dishes with liquid detergent compositions having a hydrophobic emollient and a crystalline structurant to provide improved hand skin care benefits and excellent grease removal and / or foam persistence. U.S. Patent Application Publication No. 2012 / 028872(A) discloses compositions containing low levels of surfactants and Polyquaternium 11.Polyquaternium 11 is a polymeric quaternary ammonium salt formed by the reaction of diethyl sulfate with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 201836864(A) [Patent Document 2] European Patent No. 3835399(A1) [Patent Document 3] U.S. Patent Application Publication No. 2003 / 0134770(A) [Patent Document 4] U.S. Patent Application Publication No. 2010 / 0197553(A) [Patent Document 5] U.S. Patent Application Publication No. 2012 / 028872(A) Summary of the Invention [Means for solving the problem]

[0007] The present invention relates to a liquid hand dish detergent composition comprising a quaternized acrylic copolymer and from 5.0% to 50% by weight of the liquid hand dish detergent composition of a surfactant system, wherein the surfactant system comprises at least 40% by weight of the surfactant system of an anionic surfactant and greater than 3.0% by weight of the composition of an alkoxylated alcohol nonionic surfactant. DETAILED DESCRIPTION OF THE INVENTION

[0008] In addition to the quaternized acrylic copolymer, the incorporation of a surfactant system as described herein into the liquid composition has been found to further improve the drying rate of dishware after hand dishwashing.

[0009] 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 include, consist of, or consist essentially of the essential elements and limitations of the present 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 example, cookware and tableware made from ceramic, china, metal, glass, plastic (e.g., polyethylene, polypropylene, polystyrene, etc.), and wood.

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

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

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

[0018] Liquid hand dishwashing detergent composition The present composition is a liquid composition for hand dishwashing, and therefore is in liquid form. The liquid hand dishwashing composition is preferably an aqueous composition. Thus, the present composition can contain 50% to 85% by weight, preferably 50% to 75% by weight, of water based on the total weight of the composition.

[0019] The liquid composition has a pH of greater than 6.0, or a pH of 6.0 to 12.0, preferably 7.0 to 11.0, more preferably 7.5 to 10.0, measured as a 10% aqueous solution in demineralised water at 20°C.

[0020] The compositions of the present invention typically contain 0.1 s -1 ~100s -1 The composition may be Newtonian or non-Newtonian, preferably Newtonian, over a range of shear rates of use, where mPa·s is 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, over a typical range of shear rates of use.

[0021] Quaternized Acrylic Copolymer The liquid hand dish detergent comprises a quaternized acrylic copolymer. As used herein, "copolymer" refers to a polymer containing at least two different monomer compositions. The quaternized polymer has the structure NR4 + where R is an alkyl or aryl group. + ) and primary, secondary, or tertiary ammonium cations, quaternary ammonium cations are permanently charged regardless of the pH of their solution.

[0022] The composition preferably comprises from 0.01% to 3.0%, preferably from 0.05% to 2.0%, more preferably from 0.1% to 1.0% by weight of the composition of the quaternized acrylic copolymer.

[0023] The quaternized acrylic copolymer may have a weight average molecular weight (Mw) as measured by aqueous gel permeation chromatography (GPC) with light scattering detection (SEC-MALLS) in the range of 5,000 to 500,000 Da, preferably 15,000 to 300,000 Da, and even more preferably 25,000 to 75,000 Da.

[0024] The quaternized acrylic copolymer can be characterized by its cationic charge density, typically expressed as milliequivalents of charge per gram of compound (mEq / g). The quaternized acrylic copolymer can have an average cationic charge density of 0.01 to 2.8, preferably 0.1 to 2.75, and more preferably 0.75 to 2.25 mEq / g.

[0025] Preferably, the different types of monomer units are randomly distributed throughout the quaternized acrylic copolymer.

[0026] The quaternized acrylic copolymer is preferably derived from cationic and ethylenically unsaturated monomer units.

[0027] The cationic monomer units may be selected from: CH2=CR 1 -Y-(CH2) n -N + R 2 R 3 R 4 X - (a) During the ceremony, Each R 1 are independently selected from hydrogen or methyl, preferably methyl; Each R 2 are independently selected from C1-C4 alkyl(ene), preferably CH2CH=CH2 or methyl, more preferably methyl; Each R 3 , R 4 are independently selected from C1-C4 alkyl, preferably C1-C3 alkyl, more preferably methyl; Each Y is independently CO-NR 5 -(CH2) n , CO-O-(CH2) n , or (CH2) n , preferably CO-NR 5 -(CH2) n or (CH2) n , more preferably CO-NR 5 -(CH2) n is a linking group selected from During the ceremony, Each R 5 are independently selected from hydrogen or methyl, preferably hydrogen; n is an average of 1 to 4, preferably 1 or 3, more preferably 3; X - is a suitable counterion, preferably X - are independently a halide counterion, more preferably Cl - is selected from.

[0028] The choice of linking group Y depends on the reaction scheme used to make the quaternized acrylic copolymer. Preferably, all Y are the same. Preferably, all R 5 is the same.

[0029] The cationic monomer unit can be selected from the group consisting of acrylamidopropyltrimethylammonium chloride (APTAC), methacrylamidopropyltrimethylammonium chloride (MAPTAC), diallyldimethylammonium chloride (DADMAC), acryloyloxyethyltrimethylammonium chloride (AETAC), methyloyloxyethyltrimethylammonium chloride (METAC), and mixtures thereof. Particularly preferred cationic monomers are (meth)acrylamidopropyltrimethylammonium chloride (APTAC or MAPTAC) or diallyldimethylammonium chloride (DADMAC), with methacrylamidopropyltrimethylammonium chloride (MAPTAC) being the most preferred. When DADMAC is polymerized, two polymer structures are possible: an N-substituted piperidine structure or an N-substituted pyrrolidine structure. The pyrrolidine structure is preferred (see John, Wilson; et al. (2002), Synthesis and Use of PolyDADMAC for Water Purification).

[0030] The ethylenically unsaturated monomer may be selected from the group consisting of C3-C8 ethylenically unsaturated acids and / or salts thereof, C3-C8 hydroxyalkyl acrylates, and mixtures thereof, where C3-C8 means that the ethylenically unsaturated acids and / or salts thereof, or C3-C8 hydroxyalkyl acrylates contain 3 to 8 carbon atoms.

[0031] Suitable C3 to C8 ethylenically unsaturated acids and / or salts thereof include (meth)acrylic acid and mixtures thereof, with acrylic acid being preferred. Suitable salts include alkali metal and ammonium salts.

[0032] Suitable C3-C8 hydroxyalkyl acrylates can be selected from the group consisting of ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-2-methylethyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, and mixtures thereof, preferably ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and mixtures thereof, more preferably ethyl (meth)acrylate, with ethyl acrylate being most preferred.

[0033] The quaternized acrylic copolymer may further comprise, as a polymerized monomer, an additional monomer selected from the group consisting of ethyl acrylate, 2-acrylamido-2-methylpropane-sulfonic acid, N-isopropylamide, vinylpyrrolidone, and mixtures thereof, with ethyl acrylate and / or vinylpyrrolidone being preferred, and ethyl acrylate being particularly preferred.

[0034] The additional monomers are preferably present at levels of less than 20 mole %, preferably less than 15 mole %, more preferably less than 10% of the total monomers present in the quaternized acrylic.

[0035] The quaternized acrylic copolymer can include diallyldimethylammonium chloride (DADMAC) as a cationic monomer together with hydroxyethyl acrylate as an ethylenically unsaturated monomer. Such quaternized acrylic copolymer can include vinylpyrrolidone as an additional monomer. Such quaternized acrylic copolymers include those sold by Solvay under the trade name Mirapol® SURF-S FAST DRY.

[0036] More preferably, the quaternized acrylic copolymer can include (meth)acrylamidopropyltrimethylammonium chloride (APTAC or MAPTAC) as a cationic monomer together with acrylate and / or ethyl acrylate as an ethylenically unsaturated monomer. Such quaternized acrylic copolymer can include ethyl acrylate as an additional monomer. Such quaternized acrylic copolymers include those sold by BASF under the trade name Polyquart®, with Polyquart 149A® being particularly preferred.

[0037] surfactant system The liquid composition comprises from 5.0% to 50% by weight, preferably from 6.0% to 40% by weight, most preferably from 15% to 35% by weight of the surfactant system, based on the weight of the total composition.

[0038] Anionic surfactants The surfactant system includes an anionic surfactant. The surfactant system includes at least 40% by weight of the anionic surfactant, preferably 50% to 80% by weight, more preferably 55% to 70% by weight of the surfactant system. The surfactant system preferably does not include fatty acids or salts thereof, since such fatty acids inhibit foam generation.

[0039] Suitable anionic surfactants may be selected from the group consisting of alkyl sulfated surfactants, alkyl sulfonate surfactants, alkyl sulfosuccinate and dialkyl sulfosuccinate ester surfactants, and mixtures thereof.

[0040] The anionic surfactant may comprise at least 70%, preferably at least 85%, more preferably 100% alkyl sulfated anionic surfactant by weight of the anionic surfactant.

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

[0042] The alkyl chains of the alkyl sulfated anionic surfactant may have a molar fraction of C12 and C13 chains of at least 50%, preferably at least 65%, more preferably at least 80%, and most preferably at least 90%. When the C13 / C12 molar ratio of the alkyl chains is at least 57 / 43, preferably 60 / 40 to 90 / 10, more preferably 60 / 40 to 80 / 20, and most preferably 60 / 40 to 70 / 30, foam persistence is particularly improved, especially in the presence of greasy soils, without impairing foam persistence in the presence of particulate soils.

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

[0044] The alkyl sulfated anionic surfactant may be alkoxylated or non-alkoxylated. If alkoxylated, the alkyl sulfated anionic surfactant may have an average alkoxylation degree of less than 3.5, preferably 0.3 to 2.0, more preferably 0.5 to 0.9, to improve the physical stability and foam persistence of the composition of the present invention at low temperatures. If alkoxylated, ethoxylation is preferred.

[0045] The average degree of alkoxylation is the molar average of the alkoxylation degrees of all alkyl sulfated anionic surfactants (i.e., the molar average degree of alkoxylation). Thus, when calculating the molar average degree of alkoxylation, the moles of non-alkoxylated alkyl sulfate anionic surfactants 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 sulfated anionic surfactant.

[0046] The preferred alkyl alkoxy sulfates are alkyl ethoxy sulfates.

[0047] The alkyl sulfated anionic surfactant may have a weight average degree of branching of at least 10%, preferably from 20% to 60%, more preferably from 25% to 45%.

[0048] The alkyl sulfated anionic surfactant may contain at least 5%, preferably at least 10%, and most preferably at least 25% by weight of branching at the C2 position (as measured by counting carbon atoms from the sulfate group for non-alkoxylated alkyl sulfate anionic surfactants and counting from the alkoxy group furthest from the sulfate group for alkoxylated alkyl sulfate anionic surfactants). More preferably, greater than 75%, and even more preferably greater than 90%, by weight of the total branched alkyls are C1-C5 alkyl moieties, preferably C1-C2 alkyl moieties. Formulating compositions of the present invention using alkyl sulfated anionic surfactants with the aforementioned branching levels has been found to result in improved stability at low temperatures. Such compositions require less solvent to achieve good physical stability at low temperatures. Thus, the compositions may contain lower levels of organic solvent, less than 5.0% by weight of the liquid composition, while still possessing improved low-temperature stability. Higher surfactant branching also results in faster initial foam generation, but typically results in lower foam persistence. The weight average branching described herein has been found to provide improved low temperature stability, initial foam generation, and foam persistence.

[0049] The weight average degree of branching of an anionic surfactant mixture can be calculated using the following formula: Weight average branching degree (%) = [(x1 * Wt% of branched chain 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 a starting material before (alkoxylation and) sulfation to produce the alkyl(alkoxy) sulfate anionic surfactant. The weight average branching calculation includes the weight of the alkyl alcohol used to form the unbranched alkyl sulfate anionic surfactant.

[0050] The weight average degree of branching and branching distribution can usually be obtained from the technical data sheet of the surfactant or its constituent alkyl alcohol. Alternatively, branching can be determined through analytical methods known in the art, including capillary gas chromatography with a flame ionization detector on a medium polarity capillary column using hexane as the solvent. The weight average degree of branching and branching distribution are based on the starting alcohol used to produce the alkyl sulfated anionic surfactant.

[0051] Suitable counterions include alkali metal cations, alkaline earth metal cations, alkanolammonium, or ammonium or substituted ammonium, preferably sodium.

[0052] Suitable examples of commercially available alkyl sulfated anionic surfactants include those derived from alcohols sold by Shell under the trade name Neodol® or by Sasol under the trade names Lial®, Isalchem®, and Safol®, or some of the natural alcohols produced by Procter & Gamble Chemicals. Based on the relative fractions of C13 and C12 in the starting alcohol, obtained from the technical data sheet from the supplier or by analysis using methods known in the art, alcohols can be blended to achieve the desired mole fractions of C12 and C13 chains and the desired C13 / C12 ratio.

[0053] The performance of the final product, including grease cleaning, foaming, low temperature stability, and viscosity, can be affected by the breadth of the alkoxylation distribution of the alkoxylated alkyl sulfate anionic surfactant. Through the selection of catalysts and process conditions when making the alkoxylated alkyl sulfate anionic surfactant, the alkoxylation distribution, including its breadth, can be varied.

[0054] Without wishing to be bound by theory, when ethoxylated alkyl sulfates are present, the amount of 1,4-dioxane by-product in the alkoxylated, especially ethoxylated alkyl sulfates, can be reduced by strictly controlling the process conditions and the composition of the raw materials during both the alkoxylation, especially ethoxylation, and sulfation steps. Based on recent technological advances, further reduction of 1,4-dioxane by-products can be achieved by subsequent stripping, distillation, solvent evaporation, centrifugation, microwave irradiation, molecular sieving, or catalytic or enzymatic decomposition steps. Processes for controlling the 1,4-dioxane content in alkoxylated / ethoxylated alkyl sulfates have been widely described in the art. Alternatively, the control of 1,4-dioxane levels in detergent formulations by adding 1,4-dioxane inhibitors such as 5,6-dihydro-3-(4-morpholinyl)-1-[4-(2-oxo-1-piperidinyl)-phenyl]-2-(1-H)-pyridone, the 3-alpha-hydroxy-7-oxo stereoisomeric mixture of cholanic acid, 3-(N-methylamino)-L-alanine and mixtures thereof to formulations containing 1,4-dioxane has also been described in the art.

[0055] Anionic alkyl sulfonate or sulfonic acid surfactants suitable for use herein include alkyl benzene sulfonates, alkyl ester sulfonates, primary and secondary alkane sulfonates (such as paraffin sulfonates), alpha or internal olefin sulfonates, alkyl sulfonated (poly)carboxylic acids, and mixtures thereof, in acid and salt form. Suitable anionic sulfonate or sulfonic acid surfactants include C5-C20 alkyl benzene sulfonates, more preferably C10-C16 alkyl benzene sulfonates, more preferably C11-C13 alkyl benzene sulfonates, C5-C20 alkyl ester sulfonates, especially C5-C20 methyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C5-C20 sulfonated (poly)carboxylic acids, and any mixtures thereof, but preferably C11-C13 alkyl benzene sulfonates. The surfactants can vary widely in their 2-phenyl isomer content. Compared to the sulfonation of alpha olefins, the sulfonation of internal olefins can occur at any position due to randomly positioned double bonds, resulting in a variety of twin-tail branched structures due to the hydrophilic sulfonate and hydroxyl groups of IOS being located in the middle of the alkyl chain. Alkanesulfonates include paraffin sulfonates and other secondary alkanesulfonates (such as Hostapur SAS60 from Clariant).

[0056] Alkyl sulfosuccinate and dialkyl sulfosuccinate esters are organic compounds having the formula MO3SCH(CO2R')CH2CO2R, where R and R' can be H or alkyl groups, and M is a counterion such as sodium (Na). The alkyl sulfosuccinate and dialkyl sulfosuccinate ester surfactants can be alkoxylated or non-alkoxylated, preferably non-alkoxylated. The surfactant system can contain additional anionic surfactants. However, the composition preferably contains less than 30% by weight, preferably less than 15% by weight, and more preferably less than 10% by weight of the surfactant system of additional anionic surfactants. Most preferably, the surfactant system does not contain additional anionic surfactants, preferably no anionic surfactants other than the alkyl sulfated anionic surfactant.

[0057] Co-surfactant To improve surfactant loading after dilution and thus improve foam persistence, the surfactant system may include a co-surfactant, which may be selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.

[0058] The weight ratio of anionic surfactant to co-surfactant may be from 1:1 to 8:1, preferably from 2:1 to 5:1, more preferably from 2.5:1 to 4:1.

[0059] The composition preferably comprises from 0.1% to 20%, more preferably from 0.5% to 15%, especially from 2% to 10% by weight of the composition of co-surfactant. The surfactant system of the composition of the invention preferably comprises up to 50%, preferably from 5% to 40%, more preferably from 10% to 30% by weight of the surfactant system of co-surfactant.

[0060] The co-surfactant is preferably an amphoteric surfactant, more preferably an amine oxide surfactant.

[0061] Amine oxide surfactants may be linear or branched, with linear being preferred. Suitable linear amine oxides are typically water-soluble and characterized by the formula R1-N(R2)(R3)O, 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 can be selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl, and mixtures thereof, with one or both of R2 and R3 preferably being methyl. Linear amine oxide surfactants can include, among others, linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxyethyl dihydroxyethyl amine oxides.

[0062] Preferably, the amine oxide surfactant is selected from the group consisting of alkyl dimethyl amine oxide, alkyl amidopropyl dimethyl amine oxide, and mixtures thereof. Alkyl dimethyl amine oxides such as C8-18 alkyl dimethyl amine oxide or C10-16 alkyl dimethyl amine oxide (e.g., cocodimethyl amine oxide) are particularly preferred. Suitable alkyl dimethyl amine oxides include C10 alkyl dimethyl amine oxide surfactants, C10-12 alkyl dimethyl amine oxide surfactants, C12-C14 alkyl dimethyl amine oxide surfactants, and mixtures thereof. C12-C14 alkyl dimethyl amine oxides are particularly preferred.

[0063] Alternative suitable amine oxide surfactants include mid-branched amine oxide surfactants. As used herein, "mid-branched" means that the amine oxide has one alkyl moiety with n1 carbon atoms, and one alkyl branch in the alkyl moiety has n2 carbon atoms. The alkyl branch is located on the alpha carbon from the nitrogen on the alkyl moiety. This type of branching of amine oxides is also known in the art as internal amine oxides. The sum of n1 and n2 may be 10 to 24, preferably 12 to 20, and more preferably 10 to 16 carbon atoms. The number of carbon atoms in one alkyl moiety (n1) is preferably the same as or similar to the number of carbon atoms in one alkyl branch (n2), thereby providing symmetry between the one alkyl moiety and the one alkyl branch. As used herein, "symmetric" means that in at least 50% by weight, more preferably at least 75% to 100% by weight, of the medium-branched amine oxides used herein, |n1-n2| is 5 or less, preferably 4, and most preferably 0 to 4 carbon atoms. The amine oxide further comprises two moieties independently selected from a C1-3 alkyl, a C1-3 hydroxyalkyl group, or a polyethylene oxide group containing an average of about 1 to about 3 ethylene oxide groups. Preferably, the two moieties are selected from a C1-3 alkyl, more preferably both are selected as a C1 alkyl.

[0064] 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 of the amine oxide is a mid-cut amine oxide of the formula R4R5R6AO, where R4 and R5 are independently selected from hydrogen, C1 to C4 alkyl, or a mixture thereof, and R6 is selected from C12 to C16 alkyl, or a mixture thereof.

[0065] In preferred low-cut amine oxides for use herein, R3 is n-decyl, and preferably both R1 and R2 are methyl. In mid-cut amine oxides of formula R4R5R6AO, preferably both R4 and R5 are methyl.

[0066] Preferably, the amine oxide comprises less than about 5% by weight, more preferably less than 3% by weight, of an 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, based on the weight of the amine oxide. By limiting the amount of amine oxide of the formula R7R8R9AO, both physical stability and suds persistence are improved.

[0067] Suitable zwitterionic surfactants include betaine surfactants, including alkyl betaines, alkylamido betaines, amidoazolinium betaines, sulfobetaines (INCI sultaines), and phosphobetaines, 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, 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.

[0068] Preferred betaines are alkylbetaines of formula (Ia), alkylamidopropylbetaines of formula (Ib), sulfobetaines of formula (Ic) and amidosulfobetaines of formula (Id), R 1 -N + (CH3)2-CH2COO - (IIa) R 1 -CO-NH-(CH2)3-N + (CH3)2-CH2COO - (IIb) R 1 -N + (CH3)2-CH2CH(OH)CH2SO3 - (IIc) R 1 -CO-NH-(CH2)3-N + (CH3)2-CH2CH(OH)CH2SO3 - (IId) In the formula, R1 has the same meaning as in formula (I). Particularly preferred are carbobetaines of formula (Ia) and (Ib) [i.e., in formula (I), Y- is COO-], and more preferred are alkylamidobetaines of formula (Ib).

[0069] Suitable betaines may be selected from the group consisting of capryl / capramidopropyl betaine, cetyl betaine, cetylamidopropyl betaine, cocamidoethyl betaine, cocamidopropyl betaine, coco betaine, decyl betaine, decylamidopropyl betaine, hydrogenated tallow betaine / amidopropyl betaine, isostearamidopropyl betaine, lauramidopropyl betaine, lauryl betaine, myristylamidopropyl betaine, myristyl betaine, oleadopropyl betaine, oleyl betaine, palmamidopropyl betaine, palmitamidopropyl betaine, palm kernelamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, tallowamidopropyl betaine, tallow betaine, undecylenamidopropyl betaine, undecyl betaine, and mixtures thereof [or named according to INCI]. Preferred betaines are selected from the group consisting of cocamidopropyl betaine, cocobetaine, lauramidopropyl betaine, lauryl betaine, myristylamidopropyl betaine, myristyl betaine, and mixtures thereof, with cocamidopropyl betaine being particularly preferred.

[0070] Nonionic surfactants: The surfactant system further comprises greater than 3.0% by weight of the composition of an alkoxylated alcohol nonionic surfactant. Preferably, the surfactant system comprises from 3.5% to 10%, more preferably from 4.0% to 7.5%, by weight of the composition of an alkoxylated alcohol nonionic surfactant.

[0071] The surfactant system may comprise an anionic surfactant and an alkoxylated alcohol nonionic surfactant in a weight ratio of less than 9:1, preferably from 7:1 to 1:1, more preferably from 5:1 to 2:1.

[0072] The surfactant system of the liquid hand dish detergent composition may comprise at least 5%, preferably 5% to 35%, more preferably 10% to 30% by weight of an alkoxylated alcohol nonionic surfactant, based on the weight of the surfactant system.

[0073] Preferably, the alkoxylated alcohol nonionic surfactant is a linear or branched, preferably linear, primary or secondary alkyl alkoxylated nonionic surfactant, preferably an alkyl ethoxylated nonionic surfactant, preferably containing an average of 9 to 15, preferably 10 to 14 carbon atoms in the alkyl chain and an average of 5 to 12, preferably 6 to 10, most preferably 7 to 8 alkylene oxide units per mole of alcohol. The alkoxylated alcohol nonionic surfactant is preferably ethoxylated and / or propoxylated, more preferably ethoxylated.

[0074] The surfactant system may include an additional non-ionic surfactant, such as an alkyl polyglucoside non-ionic surfactant.

[0075] The combination of alkyl polyglucosides with anionic surfactants, particularly alkyl sulfate anionic surfactants, has been found to improve polymeric oil removal, foam persistence, reduced viscosity change with surfactant and / or system changes, and more persistent Newtonian rheology.

[0076] The alkyl polyglucoside surfactant can be selected from C6 to C18 alkyl polyglucoside surfactants. The alkyl polyglucoside surfactant can have a number average degree of polymerization of 0.1 to 3.0, preferably 1.0 to 2.0, more preferably 1.2 to 1.6. The alkyl polyglucoside surfactant can include a blend of short-chain alkyl polyglucoside surfactants having alkyl chains containing 10 or fewer carbon atoms and medium- to long-chain alkyl polyglucoside surfactants having alkyl chains containing more than 10 carbon atoms to 18 carbon atoms, preferably 12 to 14 carbon atoms.

[0077] Short-chain alkyl polyglucoside surfactants have a unimodal chain length distribution of C8 to C10, medium- to long-chain alkyl polyglucoside surfactants have a unimodal chain length distribution of C10 to C18, while medium-chain alkyl polyglucoside surfactants have a unimodal chain length distribution of C12 to C14. In contrast, C8 to C18 alkyl polyglucoside surfactants typically have a unimodal distribution of C8 to C18 alkyl chains, such as C8 to C16. Thus, a combination of a short-chain alkyl polyglucoside surfactant with a medium- to long-chain or medium-chain alkyl polyglucoside surfactant will have a broader chain length distribution, or even a bimodal distribution, than the unblended C8 to C18 alkyl polyglucoside surfactant. Preferably, the weight ratio of the short-chain alkyl polyglucoside surfactant to the long-chain alkyl polyglucoside surfactant is from 1:1 to 10:1, preferably from 1.5:1 to 5:1, more preferably from 2:1 to 4:1. Such a blend of short-chain alkyl polyglucoside surfactant and long-chain alkyl polyglucoside surfactant results in faster dissolution of the detergent solution in water and improved initial foaming combined with improved foam stability.

[0078] C8-C16 alkyl polyglucosides are commercially available from several sources (e.g., Simusol® surfactants from Seppic Corporation, and Glucopon® 600 CSUP, Glucopon® 650 EC, Glucopon® 600 CSUP / MB, and Glucopon® 650 EC / MB from BASF Corporation). Glucopon® 215UP is a preferred short-chain APG surfactant. Glucopon® 600CSUP is a preferred medium- to long-chain APG surfactant.

[0079] When present, the alkyl polyglucosides may be present in the surfactant system at a concentration of 0.5% to 20%, preferably 0.75% to 15%, more preferably 1% to 10%, and most preferably 1% to 5% by weight of the surfactant composition. Alkyl polyglucoside nonionic surfactants typically have higher foaming properties than other nonionic surfactants, such as alkyl ethoxylated alcohols.

[0080] In other preferred compositions, the alkyl polyglucosides are present at a level of less than 2.0%, preferably less than 1.0%, more preferably less than 0.5% by weight of the composition.

[0081] In even more preferred compositions, the composition does not contain any additional nonionic surfactants.

[0082] Further ingredients: The composition can include additional ingredients such as those selected from amphiphilic alkoxylated polyalkyleneimines, cyclic polyamines, triblock copolymers, hydrotropes, organic solvents, other adjunct ingredients such as those described herein, and mixtures thereof.

[0083] Amphiphilic alkoxylated polyalkyleneimines: The compositions of the present invention may further comprise 0.05% to 2%, preferably 0.07% to 1% by weight of the total composition, of an amphiphilic polymer. Suitable amphiphilic polymers may be selected from the group consisting of amphiphilic alkoxylated polyalkyleneimines and mixtures thereof. Amphiphilic alkoxylated polyalkyleneimine polymers have been found to reduce gel formation on hard surfaces being cleaned when the liquid composition is added directly to a cleaning implement (such as a sponge) prior to cleaning and then comes into contact with a heavily oily surface, particularly when the cleaning implement contains little to no water, such as a lightly pre-moistened sponge.

[0084] Preferred amphiphilic alkoxylated polyethyleneimine polymers have the general structure of formula (I):

[0085] [ka] wherein the polyethyleneimine backbone has a weight-average molecular weight of 600, n in formula (I) is an average of 10, m in formula (I) is an average of 7, and R in formula (I) is selected from hydrogen, C1-C4 alkyl, and mixtures thereof, preferably hydrogen. The degree of permanent quaternization in formula (I) may be 0% to 22% of the nitrogen atoms in the polyethyleneimine backbone. The molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer is preferably 10,000 to 15,000 Da.

[0086] More preferably, the amphiphilic alkoxylated polyethyleneimine polymer has the general structure of formula (I), except that the polyethyleneimine backbone has a weight-average molecular weight of 600 Da, n in formula (I) averages 24, m in formula (I) averages 16, and R in formula (I) is selected from hydrogen, C1-C4 alkyl, and mixtures thereof, preferably hydrogen. The degree of permanent quaternization of formula (I) may be 0% to 22% of the nitrogen atoms of the polyethyleneimine backbone, preferably 0%. The molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer is preferably 25,000 to 30,000, most preferably 28,000 Da.

[0087] Amphiphilic alkoxylated polyethyleneimine polymers can be made by the methods described in more detail in WO 2007 / 135645.

[0088] Alternatively, the composition may not include an amphiphilic polymer.

[0089] cyclic polyamines The present compositions can include a cyclic polyamine having an amine functionality to aid in cleaning. The compositions of the present invention preferably contain 0.1% to 3%, more preferably 0.2% to 2%, especially 0.5% to 1% by weight of the total composition of cyclic polyamine.

[0090] Cyclic polyamines have at least two primary amine functional groups. The primary amine may be located at any position within the cyclic amine, but it has been found that better performance is obtained from the viewpoint of grease cleaning when the primary amine is located at the 1- and 3-positions. It has also been found that cyclic amines in which one of the substituents is -CH3 and the remaining is H provide improved grease cleaning performance.

[0091] Thus, the most preferred cyclic polyamines for use in the compositions of the present invention are those selected from the group consisting of 2-methylcyclohexane-1,3-diamine, 4-methylcyclohexane-1,3-diamine, and mixtures thereof. These particular cyclic polyamines, when combined with the surfactant system of the compositions of the present invention, function to improve the suds and grease cleaning profile throughout the dishwashing process.

[0092] Suitable cyclic polyamines may be supplied by BASF under the trade name Baxxodur, with Baxxodur ECX-210 being particularly preferred.

[0093] A combination of cyclic polyamine and magnesium sulfate is particularly preferred. Thus, the present composition may further comprise magnesium sulfate at a level of from 0.001% to 2.0%, preferably from 0.005% to 1.0%, more preferably from 0.01% to 0.5% by weight of the composition.

[0094] triblock copolymer The compositions of the present invention can include a triblock copolymer. The triblock copolymer can be present at a level of 1% to 20%, preferably 3% to 15%, and more preferably 5% to 12% by weight of the total composition. Suitable triblock copolymers include alkylene oxide triblock copolymers, defined as triblock copolymers having alkylene oxide moieties according to formula (I): (EO)x(PO)y(EO)x, where EO represents ethylene oxide and each x represents the number of EO units in the EO block. Each x can independently average 5 to 50, preferably 10 to 40, and more preferably 10 to 30. Preferably, x is the same for both EO blocks, and "same" means that the difference in x between the two EO blocks is within a maximum of 2 units, preferably within a maximum of 1 unit, and more preferably both x's are the same number of units. PO represents propylene oxide and y represents the number of PO units in the PO block. The y's can be set to 28 to 60, preferably 30 to 55, and more preferably 30 to 48 on average.

[0095] Preferably, the ratio of y to each x in the triblock copolymer is 3:1 to 2:1. The ratio of y to the average x of the two EO blocks in the triblock copolymer is preferably 3:1 to 2:1. Preferably, the triblock copolymer has an average weight percentage of total EO that is 30% to 50% by weight of the triblock copolymer. Preferably, the triblock copolymer has an average weight percentage of total PO that is 50% to 70% by weight of the triblock copolymer. It is understood that the average total weight percentages of EO and PO for a triblock copolymer add up to 100%. The triblock copolymer can have an average molecular weight of 2060 to 7880, preferably 2620 to 6710, more preferably 2620 to 5430, and most preferably 2800 to 4700. The average molecular weight is determined using 1H NMR spectroscopy (see Thermo Scientific Application Note No. AN52907).

[0096] Triblock copolymers have the basic structure ABA, where A and B are different homopolymer and / or monomer units. In this case, A is ethylene oxide (EO) and B is propylene oxide (PO). Those skilled in the art will recognize that the term "block copolymer" is synonymous with this definition of "block polymer."

[0097] Triblock copolymers according to formula (I) having specific EO / PO / EO configurations and respective homopolymer lengths have been found to enhance the suds retention performance of liquid hand dish detergent compositions in the presence of greasy soils and / or the suds consistency throughout dilution in the cleaning process.

[0098] Suitable EO-PO-EO triblock copolymers are commercially available from BASF, e.g., under the Pluronic® PE series, and from Dow Chemical Company, e.g., under the Tergitol® L series. Particularly preferred triblock copolymers from BASF are sold under the trade names Pluronic® PE6400 (MW about 2900, about 40 wt. % EO) and Pluronic® PE9400 (MW about 4600, 40 wt. % EO). Particularly preferred triblock copolymers from Dow Chemical Company are sold under the trade name Tergitol® L64 (MW about 2700, about 40 wt. % EO).

[0099] Preferred triblock copolymers are readily biodegradable under aerobic conditions.

[0100] Salts, hydrotropes, organic solvents The compositions of the present invention may further comprise at least one active agent selected from the group consisting of i) salts, ii) hydrotropes, iii) organic solvents, and mixtures thereof.

[0101] The compositions of the present invention may contain from about 0.05% to about 2% by weight of the total composition, preferably from about 0.1% to about 1.5% by weight, or more preferably from about 0.5% to about 1% by weight of a salt, preferably a monovalent or divalent inorganic salt, or a mixture thereof, more preferably a salt selected from sodium chloride, sodium sulfate, and a mixture thereof. Sodium chloride is most preferred.

[0102] The compositions of the present invention may comprise from about 0.1% to about 10%, or preferably from about 0.5% to about 10%, or more preferably from about 1% to about 10% by weight of the total composition of a hydrotrope or mixture thereof, preferably sodium cumene sulfonate.

[0103] The composition may contain about 0.1% to about 10% by weight of an organic solvent, based on the weight of the total composition, or preferably about 0.5% to about 10% by weight, or more preferably about 1% to about 10% by weight. Suitable organic solvents include those selected from the group consisting of alcohols, glycols, glycol ethers, and mixtures thereof, preferably alcohols, glycols, and mixtures thereof. Ethanol is a preferred alcohol. Polyalkylene glycols, particularly polypropylene glycols, are preferred glycols, with polypropylene glycols having a weight-average molecular weight of 750 Da to 1,400 Da being particularly preferred.

[0104] Supplementary ingredients The compositions may optionally contain many other adjunct ingredients such as builders (preferably citrate salts), chelating agents, conditioning polymers, other cleansing polymers, surface modifying polymers, structuring agents, emollients, humectants, skin rejuvenating actives, enzymes, carboxylic acids, scrubbing particles, fragrances, malodor control agents, pigments, dyes, opacifiers, pearlescent particles, inorganic cations such as alkaline earth metals such as Ca / Mg ions, antimicrobial agents, preservatives, viscosity modifiers (e.g., salts such as NaCl and other mono-, di-, and trivalent salts), and pH adjusters and buffering means (e.g., carboxylic acids such as citric acid, HCl, NaOH, KOH, alkanolamines, and carbonates such as sodium carbonate, bicarbonate, sesquicarbonate).

[0105] Packaged Products The hand dishwashing detergent composition can be packaged in a container, typically a plastic container. A suitable container includes an orifice. Typically, the container has a cap, and the orifice is typically provided on the cap. The cap can have an injection port, and the orifice is located at the outlet of the injection port. The injection port can have a length of 0.5 mm to 10 mm.

[0106] The orifice is 3mm at the outlet. 2 ~20mm 2 , preferably 3.8 mm 2 ~12mm 2 , more preferably 5 mm 2 ~10mm 2 and the container further comprises a composition according to the present invention, the cross-sectional area being measured perpendicular to the liquid outlet from the container (i.e. perpendicular to the liquid flow during dispensing).

[0107] The container can typically contain 200 mL to 5,000 mL, preferably 350 mL to 2,000 mL, and more preferably 400 mL to 1,000 mL of the liquid hand dish detergent composition.

[0108] Cleaning method The present invention is further directed to a method of manually washing dishware with the composition of the present invention, comprising the steps of dispensing the composition of the present invention into a volume of water to form a wash solution and immersing dishware in the solution, wherein the dishware is washed with the composition in the presence of water.

[0109] Optionally, the dishware may be rinsed. As used herein, "rinsing" refers to contacting the dishware washed in the process of the present invention with a substantial amount of a suitable solvent, typically water. "Substantial amount" typically refers to about 1 to about 20 liters or under running water.

[0110] The compositions herein can be applied in their diluted form. Soiled dishes are contacted with an effective amount of the present composition, preferably in liquid form, diluted with water, typically about 0.5 mL to about 20 mL (per about 25 dishes to be treated), preferably about 3 mL to about 10 mL. The actual amount of composition used is at the discretion of the user and typically depends on factors such as the specific product formulation of the composition, including the concentration of active ingredients in the 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 present composition 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 diluted composition, the soiled surface of the dishes is contacted with a cloth, sponge, or similar cleaning implement. A cloth, sponge, or similar cleaning implement may be immersed in the composition and water mixture before contacting the dishware, typically for a period 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.

[0111] Alternatively, the composition herein can be applied in its undiluted form to the utensils to be treated. "In its undiluted form" means herein that the composition is applied directly to the surface to be treated or to a cleaning device or implement, such as a brush, sponge, nonwoven material, or woven material, without being significantly diluted by the user immediately prior to application. "In its undiluted form" also includes slight dilution, for example, due to the presence of water on the cleaning device or the addition of water by the consumer to remove residual amounts of the composition from the bottle. Thus, the composition in undiluted form includes a mixture having the composition and water in a ratio ranging from 50:50 to 100:0, preferably 70:30 to 100:0, more preferably 80:20 to 100:0, and even more preferably 90:10 to 100:0, depending on the user's habits and cleaning tasks.

[0112] method A) Molecular weight measurement by gel permeation chromatography Gel permeation chromatography (GPC) with multi-angle light scattering (MALS) and refractive index (RI) detection (GPC-MALS / RI) allows the determination of the weight-average molecular weight, M, of a polymer without the need for comparison to a known reference standard. w , and number average molecular weight M n is a well-known system for directly measuring

[0113] The true number average molecular weight M of the polymer n can be obtained by GPC coupled with light scattering and refractive index detection, provided that the slices taken are sufficiently monodisperse with respect to molecular weight and composition, even though the composition, and therefore the refractive index increment, varies with elution volume.

[0114] For example, the molecular weight distribution of a polymer can be measured using a liquid chromatography system such as an Agilent 1260 Infinity pump system equipped with OpenLab Chemstation software (from Agilent Technology, Santa Clara, CA, USA), which is equipped with two Ultrahydrogel linear columns 7.8 mm ID x 300 mm length (S / N 002C180181 VE077 and 005C180181 VE084, provided by Waters Corporation of Milford, Mass., USA) used in series, and an Ultrahydrogel guard column (6 mm ID x 40 mm length, S / N 2016260401BE105, provided by Waters Corporation of Milford, Mass., USA) installed between the injector and the analytical column to prevent any impurities and suspended solids from reaching the analytical column, and operated at 40°C. A multi-angle light scattering (MALS) detector DAWN® and a refractive index (RI) detector (Wyatt Technology of Santa Barbara, Calif., USA) controlled by Wyatt Astra® software can be used for detection.

[0115] Because the analytes are spread over a relatively narrow time window, an isocratic elution method can be used rather than a gradient elution method. Isocratic means that the mixture of the mobile phase is consistent over the complete test time. Using a gradient means that the composition of the elution mixture changes during the measurement, thus affecting the retention of the analytes. When using a gradient method, the separation can be accelerated or decelerated.

[0116] 0.1 M sodium nitrate in water containing 0.02% sodium azide is used as the mobile phase. Samples are prepared by dissolving the polymer in the mobile phase at approximately 1.0 mg / ml and mixing the solution overnight at room temperature to ensure complete hydration of the polymer. The sample is then filtered through a 0.8 μm Versapor membrane filter (AP4189, supplied by PALL, Life Sciences, NY, USA) using a 3 ml syringe into an LC autosampler vial. The sample is then injected into the column at a flow rate of 1.0 mL / min.

[0117] The number average and weight average molecular weights of the polymers are calculated from dn / dc (differential change in refractive index with concentration) measurements provided by the Astra detector software.

[0118] B) Water sheeting Drying rate is related to the degree of water sheeting: the higher the water sheeting, the less water is retained on the wet item.

[0119] Water sheeting behavior is assessed by scoring the amount of water sheeting observed on gray ceramic plates ("Dinera" plates, 26 cm diameter, supplied by IKEA) when the plates are washed with the hand dish detergent test composition and then left standing vertically on a drying rack. More specifically, A sponge (Scotch-Brite® Classic-schuurspons van cellulose supplied by 3M Belgium, dimensions: 7 cm x 10 cm) is wetted evenly with water equivalent to a hardness of 0.36 mmol / l CaCO3 at 25°C by saturating the sponge with water and then squeezing it by hand until no further water is squeezed out.

[0120] 1 ml of the hand dishwashing composition is evenly distributed on a sponge. The sponge is squeezed vigorously with one hand four times on a ceramic plate to create a lather, and then the plate is washed in 10 circular clockwise motions, covering the edge and center of the plate so that the entire plate is treated with lather.

[0121] The plates are then rinsed for 30 seconds under running water (25°C water with the same water hardness as before (0.36 mmol / l CaCO3 equivalent)) at a flow rate sufficient to allow complete removal of bubbles and complete coverage by water, after which the plates are placed vertically on a drying rack under standard room conditions (20 + / - 1°C).

[0122] The water flowing down the plate is then visually assessed and scored from 0 to 100% depending on the amount of water that flows down the plate during the first 30 seconds and thus leaves areas of the plate that have already dried. 0% corresponds to water remaining on the entire plate, 50% indicates that half of the plate is covered with a film of water, and 100% indicates that no film of water is visibly present. [Example]

[0123] The following compositions were prepared and evaluated for their water sheeting behavior using the methods described herein: Rapid water sheeting is an indication of rapid drying after rinsing.

[0124] In the compositions of Table 1, Comparative Examples A and B had the same composition, except that Example B contained 0.5% by weight of the composition of a quaternized acrylic copolymer useful in the present invention. Both compositions are comparative because neither composition contained an alkoxylated alcohol nonionic surfactant. Comparative Example B demonstrates the drying effect (as evidenced by improved sheeting) of the quaternized acrylic copolymer in a comparative hand dishwashing composition.

[0125] Comparative Example C contained the same overall surfactant level as Comparative Example B, but replaced a portion of the anionic surfactant and cosurfactant with 1.7% by weight of the composition of an alkoxylated alcohol nonionic surfactant. The ratio of anionic surfactant to cosurfactant was kept constant at 3:1 between Comparative Examples B and C. Comparative testing shows a reduced water sheeting effect. Comparative Example D contained the same overall surfactant level as Comparative Example C, but reduced the levels of anionic surfactant and cosurfactant, maintaining the same ratio of anionic surfactant to cosurfactant, and increasing the level of nonionic surfactant to 3.0%. Comparing the water sheeting results from Comparative Example D with Comparative Example C shows that increasing the nonionic level to 3.0% by weight of the composition slightly improved water sheeting.

[0126] In contrast, as can be seen from the results of Inventive Examples 1 and 2 compared to Comparative Example D, further increasing the level of alkoxylated alcohol nonionic surfactant to 4.0% and 7.0% of the composition, respectively, resulted in a significant improvement in water sheeting effectiveness.

[0127] [Table 1] * For comparison 1 Supplied by Shell and sold under the trade name Neodol 91-8® 2 Polyethyleneimine supplied by BASF with a weight average molecular weight of 600 g / mol and a PEI backbone with 24 EO units and 16 PO units per alkoxylated chain 3 A quaternized acrylic copolymer useful in the present invention supplied by BASF and sold under the trade name Polyquart® 149A.

[0128] The following compositions were also prepared and evaluated for their water sheeting behavior using the methods described herein.

[0129] Inventive Example 3 differed from Inventive Example 2 by including a different quaternized acrylic copolymer. In contrast, Comparative Example E included a hydroxypropyl acrylate / dimethylaminoethyl methacrylate copolymer (a 2:1 molar ratio of hydroxypropyl acrylate and dimethylaminoethyl methacrylate), a non-quaternized acrylic copolymer not useful in the present invention. The results below show that the sheeting effect is present in both compositions containing the combination of the quaternized acrylic copolymer and the alkoxylated alkyl alcohol at levels greater than 3.0% by weight of the composition, but is absent in the acrylic copolymer containing tertiary amino groups in place of quaternization (permanent positive charge).

[0130] [Table 2] 4 A quaternized acrylic copolymer useful in the present invention supplied by Solvay and sold under the trade name Mirapol® SURF-S FAST DRY 5 Hydroxypropyl acrylate / dimethylaminoethyl methacrylate copolymer (2:1 molar ratio of hydroxypropyl acrylate and dimethylaminoethyl methacrylate), supplied by Solvay

[0131] The following compositions were also prepared and evaluated for their water sheeting behavior using the methods described herein.

[0132] The composition of Example 4 contained 7.0% by weight of the composition of an alkyl alkoxylated nonionic surfactant and a quaternized acrylic copolymer, and was therefore in accordance with the present invention. In contrast, Example F * contained an alkyl polyglucoside nonionic surfactant instead of an alkoxylated alcohol nonionic surfactant.

[0133] As can be seen from the water sheeting results, the effect of the combination of nonionic surfactant and quaternized acrylic copolymer is only present when the nonionic surfactant comprises an alkoxylated alkyl nonionic surfactant.

[0134] [Table 3] 6 Marketed by BASF under the trade name Glucapon® CSUP

[0135] The following compositions were prepared and evaluated for their water sheeting behavior using the methods described herein: Rapid water sheeting is an indication of rapid drying after rinsing.

[0136] In the compositions of Table 4, inventive Example 5 contained, in addition to the quaternized acrylic copolymer, an anionic surfactant and an alkoxylated alcohol nonionic surfactant in a weight ratio of 4.5:1. Comparative Example H contained the same surfactant system but did not contain the quaternized acrylic copolymer. By comparing the water sheeting results of Example 5 with those of Comparative Example H, the improvement in water sheeting due to the addition of the quaternized acrylic copolymer to a composition containing an anionic surfactant and an alkoxylated alcohol nonionic surfactant in the desired ratio can be seen. In contrast, the water sheeting results of Comparative Examples H-I show that the water sheeting effect is significantly reduced when the ratio of anionic surfactant to alkoxylated alcohol nonionic surfactant exceeds the desired range (a ratio of anionic surfactant to alkoxylated alcohol nonionic surfactant of 12.2).

[0137] [Table 4] * For comparison

[0138] 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 "approximately 40 mm." [1] A liquid hand dish detergent composition comprising a quaternized acrylic copolymer and and a surfactant system in an amount of from about 5.0% to about 50% by weight of the liquid hand dish detergent composition, wherein the surfactant system comprises: a. at least about 40% by weight of the surfactant system of an anionic surfactant; b. greater than about 3.0% by weight of the liquid hand dish detergent composition of an alkoxylated alcohol nonionic surfactant. [2] The composition according to [1], wherein the composition comprises the quaternized acrylic copolymer in an amount of 0.01% to 3.0% by weight, preferably 0.05% to 2.0% by weight, and more preferably 0.1% to 1.0% by weight of the composition. [3] The composition according to [1] or [2], wherein the quaternized acrylic copolymer has a weight average molecular weight (Mw) measured by aqueous gel permeation chromatography (GPC) with light scattering detection (SEC-MALLS) in the range of 5,000 to 500,000 Da, preferably 15,000 to 300,000 Da, and even more preferably 25,000 to 75,000 Da. [4] The composition according to [1], wherein the quaternized acrylic copolymer has an average cationic charge density of 0.01 to 2.8, preferably 0.1 to 2.75, and more preferably 0.75 to 2.25 mEq / g. [5] the quaternized acrylic copolymer is a. a cationic monomer unit selected from: i.CH 2 =CR 1 -YN + R 2 R 3 R 4 X - (a) During the ceremony, Each R 1 are independently selected from hydrogen or methyl, preferably methyl; Each R 2 are independently C1 to C4 alkyl (alkylene), preferably CH 2 CH=CH 2 or methyl, more preferably methyl; Each R 3 、R 4 are independently selected from C1 to C4 alkyl, preferably C1 to C3 alkyl, more preferably methyl; each Y independently represents CO-NR 5 -(CH 2 ) n , CO-O-(CH 2 ) n , or (CH 2 ) n , preferably CO-NR 5 -(CH 2 ) n or (CH 2 ) n , more preferably CO-NR 5 -(CH 2 ) n is a linking group selected from During the ceremony, Each R 5 are independently selected from hydrogen or methyl, preferably hydrogen; n is an average of 1 to 4, preferably 1 or 3, more preferably 3; X - but with a suitable counterion, preferably a halide counterion, more preferably Cl - a cationic monomer unit, b. The composition according to [1], which is derived from an ethylenically unsaturated monomer unit. [6] The composition according to [5], wherein the cationic monomer unit is selected from the group consisting of acrylamidopropyltrimethylammonium chloride (APTAC), diallyldimethylammonium chloride (DADMAC), acryloyloxyethyltrimethylammonium chloride (AETAC), methacrylamidopropyltrimethylammonium chloride (MAPTAC), methyloyloxyethyltrimethylammonium chloride (METAC), and mixtures thereof, preferably (meth)acrylamidopropyltrimethylammonium chloride (APTAC or MAPTAC) or diallyldimethylammonium chloride (DADMAC), more preferably methacrylamidopropyltrimethylammonium chloride (MAPTAC). [7] The composition according to [5], wherein the ethylenically unsaturated monomer unit is selected from the group consisting of a C3 to C8 ethylenically unsaturated acid and / or a salt thereof, a C3 to C8 hydroxyalkyl acrylate, and a mixture thereof. [8] The composition according to [7], wherein the ethylenically unsaturated monomer unit comprises a C3 to C8 ethylenically unsaturated acid and / or a salt thereof, and the C3 to C8 ethylenically unsaturated acid and / or a salt thereof is selected from the group consisting of (meth)acrylic acid or a salt thereof, and more preferably selected from acrylic acid or a salt thereof. [9] The composition according to [7], wherein the ethylenically unsaturated monomer unit comprises a C3 to C8 alkyl acrylate selected from the group consisting of ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-2-methylethyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, and mixtures thereof, preferably ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and mixtures thereof, more preferably ethyl (meth)acrylate, and most preferably ethyl acrylate.

[10] [1] The composition according to [1], wherein the anionic surfactant comprises at least 70% by weight, preferably at least 85% by weight, and more preferably 100% by weight of the anionic surfactant, of an alkyl sulfated anionic surfactant.

[11] A liquid hand dish detergent composition comprising a quaternized acrylic copolymer and and a surfactant system in an amount of from 7.0% to 35% by weight of the liquid hand dish detergent composition, wherein the surfactant system comprises: a. anionic surfactant; b. less than 3.0% by weight of the composition of an alkoxylated alcohol nonionic surfactant; The composition wherein the anionic surfactant and the alkoxylated alcohol nonionic surfactant are present in a weight ratio of less than 10:1.

[12]

[11] The composition according to

[11] , wherein the composition comprises the quaternized acrylic copolymer in an amount of 0.01% to 3.0% by weight, preferably 0.05% to 2.0% by weight, and more preferably 0.1% to 1.0% by weight of the composition.

[13] The composition according to

[11] or

[12] , wherein the quaternized acrylic copolymer has a weight average molecular weight (Mw) measured by aqueous gel permeation chromatography (GPC) with light scattering detection (SEC-MALLS) in the range of 5,000 to 500,000 Da, preferably 15,000 to 300,000 Da, and even more preferably 25,000 to 75,000 Da.

[14] The composition according to

[11] , wherein the quaternized acrylic copolymer has an average cationic charge density of 0.01 to 2.8, preferably 0.1 to 2.75, and more preferably 0.75 to 2.25 mEq / g.

[15] the quaternized acrylic copolymer is a. a cationic monomer unit selected from: i.CH 2 =CR 1 -YN + R 2 R 3 R 4 X - (a) During the ceremony, Each R 1 are independently selected from hydrogen or methyl, preferably methyl; Each R 2 are independently C1 to C4 alkyl (alkylene), preferably CH 2 CH=CH 2 or methyl, more preferably methyl; Each R 3 、R 4 are independently selected from C1 to C4 alkyl, preferably C1 to C3 alkyl, more preferably methyl; each Y independently represents CO-NR 5 -(CH 2 ) n , CO-O-(CH 2 ) n , or (CH 2 ) n , preferably CO-NR 5 -(CH 2 ) n or (CH 2 ) n , more preferably CO-NR 5 -(CH 2 ) n is a linking group selected from During the ceremony, Each R5 are independently selected from hydrogen or methyl, preferably hydrogen; n is an average of 1 to 4, preferably 1 or 3, more preferably 3; X - but with a suitable counterion, preferably a halide counterion, more preferably Cl - a cationic monomer unit, b. The composition according to

[11] , which is derived from an ethylenically unsaturated monomer unit.

[16]

[15] The composition according to

[15] , wherein the cationic monomer unit is selected from the group consisting of acrylamidopropyltrimethylammonium chloride (APTAC), diallyldimethylammonium chloride (DADMAC), acryloyloxyethyltrimethylammonium chloride (AETAC), methacrylamidopropyltrimethylammonium chloride (MAPTAC), methyloyloxyethyltrimethylammonium chloride (METAC), and mixtures thereof, preferably (meth)acrylamidopropyltrimethylammonium chloride (APTAC or MAPTAC) or diallyldimethylammonium chloride (DADMAC), more preferably methacrylamidopropyltrimethylammonium chloride (MAPTAC).

[17] The composition according to

[15] , wherein the ethylenically unsaturated monomer unit is selected from the group consisting of a C3 to C8 ethylenically unsaturated acid and / or a salt thereof, a C3 to C8 hydroxyalkyl acrylate, and a mixture thereof.

[18] The composition according to

[17] , wherein the ethylenically unsaturated monomer unit comprises a C3 to C8 ethylenically unsaturated acid and / or a salt thereof, and the C3 to C8 ethylenically unsaturated acid and / or a salt thereof is selected from the group consisting of (meth)acrylic acid and a salt thereof, and more preferably selected from acrylic acid and a salt thereof.

[19] The composition according to

[17] , wherein the ethylenically unsaturated monomer unit comprises a C3 to C8 alkyl acrylate selected from the group consisting of ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-2-methylethyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, and mixtures thereof, preferably ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and mixtures thereof, more preferably ethyl (meth)acrylate, and most preferably ethyl acrylate.

[20] [1] The composition according to [1], wherein the surfactant system comprises at least 0.5%, preferably at least 1.0%, more preferably at least 2.0% by weight of the composition of the alkoxylated alcohol nonionic surfactant.

Claims

1. A liquid hand dish detergent composition comprising a quaternized acrylic copolymer and and 5.0% to 50% by weight of the liquid hand dish detergent composition of a surfactant system, wherein the surfactant system comprises: a. at least 40% by weight of the surfactant system an anionic surfactant; b. greater than 3.0% to 7.5%, by weight of the liquid hand dish detergent composition, of an alkoxylated alcohol nonionic surfactant; the alkoxylated alcohol nonionic surfactant is a linear or branched, primary or secondary alkyl alkoxylated nonionic surfactant containing an average of 9 to 15 carbon atoms in the alkyl chain and an average of 6 to 10 alkylene oxide units per mole of alcohol; A composition wherein the quaternized acrylic copolymer is derived from cationic and ethylenically unsaturated monomer units, and either (i) or (ii) applies. (i) The cationic monomer units are selected from the group consisting of acrylamidopropyltrimethylammonium chloride (APTAC), acryloyloxyethyltrimethylammonium chloride (AETAC), methacrylamidopropyltrimethylammonium chloride (MAPTAC), methyloyloxyethyltrimethylammonium chloride (METAC), and mixtures thereof, and the ethylenically unsaturated monomer units are selected from the group consisting of (meth)acrylic acid or a salt thereof, and / or ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-2-methylethyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, and mixtures thereof. (ii) the cationic monomer unit is diallyldimethylammonium chloride (DADMAC), and the ethylenically unsaturated monomer unit is selected from the group consisting of ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-2-methylethyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, and mixtures thereof.

2. The composition of claim 1, wherein the composition comprises from 0.01% to 3.0% by weight of the composition of the quaternized acrylic copolymer.

3. 3. The composition of claim 1 or 2, wherein the quaternized acrylic copolymer has a weight average molecular weight (Mw) measured by aqueous gel permeation chromatography (GPC) with light scattering detection (SEC-MALLS) in the range of 5,000 to 500,000 Da.

4. The composition of claim 1, wherein the quaternized acrylic copolymer has an average cationic charge density of 0.01 to 2.8 mEq / g.

5. 2. The composition of claim 1, wherein the cationic monomer unit is selected from the group consisting of (meth)acrylamidopropyltrimethylammonium chloride (APTAC or MAPTAC) or diallyldimethylammonium chloride (DADMAC).

6. The composition of claim 1 , wherein the cationic monomer unit comprises methacrylamidopropyltrimethylammonium chloride (MAPTAC).

7. 2. The composition of claim 1, wherein the ethylenically unsaturated monomer units are selected from the group consisting of acrylic acid or its salts, and / or ethyl (meth)acrylate, and mixtures thereof.

8. The composition of claim 7 wherein the ethylenically unsaturated monomer units comprise ethyl (meth)acrylate.

9. The composition of claim 7 wherein the ethylenically unsaturated monomer units comprise ethyl acrylate.

10. 10. The composition of claim 1, wherein the anionic surfactant comprises at least 85% alkyl sulfated anionic surfactant, by weight of the anionic surfactant.

11. A liquid hand dish detergent composition comprising a quaternized acrylic copolymer and and 7.0% to 35% by weight of the liquid hand dish detergent composition of a surfactant system, wherein the surfactant system comprises: a. an anionic surfactant; b. less than 3.0% by weight of the composition of an alkoxylated alcohol nonionic surfactant; the anionic surfactant and the alkoxylated alcohol nonionic surfactant are present in a weight ratio of less than 10:1; the alkoxylated alcohol nonionic surfactant is a linear or branched, primary or secondary alkyl alkoxylated nonionic surfactant containing an average of 9 to 15 carbon atoms in the alkyl chain and an average of 6 to 10 alkylene oxide units per mole of alcohol; A composition wherein the quaternized acrylic copolymer is derived from cationic and ethylenically unsaturated monomer units, and either (i) or (ii) applies. (i) The cationic monomer units are selected from the group consisting of acrylamidopropyltrimethylammonium chloride (APTAC), acryloyloxyethyltrimethylammonium chloride (AETAC), methacrylamidopropyltrimethylammonium chloride (MAPTAC), methyloyloxyethyltrimethylammonium chloride (METAC), and mixtures thereof, and the ethylenically unsaturated monomer units are selected from the group consisting of (meth)acrylic acid or a salt thereof, and / or ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-2-methylethyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, and mixtures thereof. (ii) the cationic monomer unit is diallyldimethylammonium chloride (DADMAC), and the ethylenically unsaturated monomer unit is selected from the group consisting of ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-2-methylethyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, and mixtures thereof.

12. The composition of claim 11, wherein the composition comprises from 0.01% to 3.0% by weight of the composition of the quaternized acrylic copolymer.

13. 12. The composition of claim 11, wherein the quaternized acrylic copolymer has a weight average molecular weight (Mw) measured by aqueous gel permeation chromatography (GPC) with light scattering detection (SEC-MALLS) in the range of 5,000 to 500,000 Da.

14. The composition of claim 11, wherein the quaternized acrylic copolymer has an average cationic charge density of 0.01 to 2.8 mEq / g.

15. 12. The composition of claim 11, wherein the cationic monomer unit is selected from the group consisting of (meth)acrylamidopropyltrimethylammonium chloride (APTAC or MAPTAC) or diallyldimethylammonium chloride (DADMAC).

16. The composition of claim 11 , wherein the cationic monomer unit comprises methacrylamidopropyltrimethylammonium chloride (MAPTAC).

17. 12. The composition of claim 11, wherein the ethylenically unsaturated monomer units are selected from the group consisting of acrylic acid or its salts, and / or ethyl (meth)acrylate, and mixtures thereof.

18. 18. The composition of claim 17, wherein the ethylenically unsaturated monomer units comprise ethyl (meth)acrylate.

19. 18. The composition of claim 17, wherein the ethylenically unsaturated monomer units comprise ethyl acrylate.

20. 12. The composition of claim 11, wherein said surfactant system comprises at least 0.5% by weight of said composition of said alkoxylated alcohol nonionic surfactant.

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