Liquid hand dishwashing composition

Abstract

To provide a liquid hand dishwashing composition, and a method of washing dishware at temperature below 30°C where a liquid detergent composition provides improved foaming in the presence of grease stains.SOLUTION: A liquid hand dishwashing cleaning composition contains: a surfactant system of 6 wt.% to 50 wt.% of the total composition; and a quaternized acrylic copolymer. The surfactant system contains an anionic surfactant of at least 40 wt.% of the surfactant system. The anionic surfactant contains an alkyl sulfated anionic surfactant of at least 50 wt.% of the anionic surfactant. The alkyl sulfated anionic surfactant has an average degree of alkoxylation of less than 0.1.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid hand dishwashing detergent composition and a method for cleaning dishes. [Background technology]

[0002] Hand dishwashing compositions should provide good grease removal and foaming. Typically, dishes and the like are washed at high temperatures to more effectively clean the dishes. Specifically, grease stains are softened at high temperatures. Therefore, dishes and the like are typically washed at temperatures above 35°C.

[0003] However, there is a strong desire to wash dishes in a more sustainable and cost-effective manner. Heating the water used when washing dishes is one of the most environmentally undesirable steps in the hand dishwashing process and is also one of the steps that most increase the cost of washing dishes. Therefore, there is a strong desire to wash dishes at lower temperatures. However, there remains a high degree of skepticism from users that hand dishwashing detergents can provide effective grease removal at low temperatures. Because the amount of residual foam (foam persistence) is typically viewed by users as an indicator of cleaning effectiveness, especially for grease stains, improving foaming performance at low dishwashing temperatures is a way to reassure users that washing at lower water temperatures still results in good cleaning of dishes.

[0004] Therefore, there remains a need for a method of cleaning dishes at temperatures below 30° C., where the liquid detergent composition provides improved sudsing in the presence of greasy soils.

[0005] WO 2017110773(A1) relates to a liquid detergent composition for hard surfaces, including dishware, and its use for cleaning the aforementioned hard surfaces at low temperatures. JP 2013100461(A) discloses a liquid detergent composition for hand-washing dishes at low temperatures (10-35°C). WO 201691688(A) relates to a liquid detergent for hard surfaces, specifically for hand-washing dishes, containing alpha-amylase for cleaning starch stains at low temperatures (<40°C). JP 2015010141(A) relates to a dishwashing detergent that provides detergency, foaming and rinsing properties at low temperatures, and fragrance and reduced fragrance drift at low temperatures. WO 2014117973(A) relates to anionic sulfonated cyclic surfactants of specific chemical formulas with lower cmc for providing cleaning at low temperatures. EP 3971270(A) relates to a liquid hand dishwashing cleaning composition comprising an alkyl sulfate anionic surfactant with little or no ethoxylation, which provides improved low temperature stability while also achieving the desired product viscosity, foam persistence, and overall cleaning. EP 3971271(A) relates to a liquid hand dishwashing cleaning composition that is highly effective at removing grease and grease, which provides long-lasting foam under soiled conditions, yet has a Newtonian viscosity that is insensitive to changes in surfactant and solvent levels, the liquid hand dishwashing cleaning composition comprising a surfactant system having a combination of an alkyl sulfate anionic surfactant with little or no alkoxylation and an alkyl polyglucoside surfactant. EP 3971273(A) relates to a hand dishwashing composition that is highly effective at removing grease and grease, also having good foam persistence and avoiding adverse effects on physical stability, particularly at low temperatures, the hand dishwashing composition comprising a surfactant system comprising an alkyl sulfate anionic surfactant with little or no branching and low or no alkoxylation, in combination with a polypropylene glycol of defined molecular weight as described herein, and a co-surfactant.EP 3919594(A) relates to a liquid detergent composition suitable for washing dishes, which is compatible with both in-sink and direct application methods, and which provides reduced smearing when used in direct application dishwashing methods, while having good foam persistence and good viscosity, particularly under in-sink application methods. The liquid detergent composition comprises an alkyl sulfate anionic surfactant, including a C13 alkyl sulfate anionic surfactant, and the C13 alkyl sulfate anionic surfactant contains a specific fraction of 2-branched C13 alkyl sulfate anionic surfactant with a specific distribution of 2-branched. EP 3971275(A) relates to a liquid hand dishwashing composition that is highly effective at emulsifying grease and oils. The liquid hand dishwashing cleaning composition comprises a surfactant system having a combination of an alkyl sulfate anionic surfactant and a co-surfactant comprising at least 70% by weight of the co-surfactant, including betaine, in combination with polypropylene glycol having a weight average molecular weight of 500 g / mol to 1800 g / mol. 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. 20030134770(A) relates to a liquid detergent composition comprising a polymeric material that is a foam booster and foam volume extender, the composition having increased effectiveness for preventing redeposition of grease during hand washing, the polymeric material being suitable as a foam volume and foam durability enhancer and comprising an effective amount of a polymeric foam booster containing quaternary nitrogen-containing monomer units and / or zwitterionic monomer units. U.S. Patent Application Publication No. 7,741,265(B) relates to a cleaning composition for hard surfaces that provides a hydrophilic coating or barrier layer on the surface, providing initial cleaning of the hard surface and providing residual cleaning on the hard surface for an extended number of rinsings.The composition includes a hydrophilic polymer, at least one nonionic surfactant, at least one solvent, an acid, and water, where the acid provides the composition with a pH of about 2 to 3.5, and the composition is provided in the absence of any anionic, cationic, or amphoteric surfactants. U.S. Patent No. 7,741,265 (B) teaches the use of hydrophilic cationic polymers, including acrylic polymers, to provide residual cleaning benefits through multiple rinses. U.S. Patent Application Publication No. 20120028872 (A) relates to a method of washing dishware with a liquid detergent composition having a hydrophobic emollient and a crystalline structurant to provide improved hand skin care benefits and superior grease removal and / or foam persistence. U.S. Patent Application Publication No. 20120028872 (A) discloses cationic polymers and their use to enhance skin benefits. U.S. Patent Application Publication No. 20220081649(A) relates to a hand dishwashing composition for removing grease that provides long-lasting foam under soiled conditions while having a Newtonian viscosity that is insensitive to changes in surfactant and solvent levels. U.S. Patent Application Publication No. 20220081649(A) teaches providing such benefits through the use of a combination of an alkyl sulfate surfactant and a short-chain alkyl polyglucoside. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2017110773(A)1 [Patent Document 2] JP2013100461(A) No. [Patent Document 3] International Publication No. 201691688(A) [Patent Document 4] JP2015010141(A) No. [Patent Document 5] International Publication No. 2014117973(A) [Patent Document 6] European Patent No. 3971270(A) [Patent Document 7] European Patent No. 3971271(A) [Patent Document 8] European Patent No. 3971273(A) [Patent Document 9] European Patent No. 3919594(A) [Patent Document 10] European Patent No. 3971275(A) [Patent Document 11] International Publication No. 201836864(A) [Patent Document 12] European Patent No. 3835399(A1) [Patent Document 13] U.S. Patent Application Publication No. 20030134770(A) [Patent Document 14] U.S. Patent No. 7741265(B) [Patent Document 15] U.S. Patent Application Publication No. 20120028872(A) [Patent Document 16] U.S. Patent Application Publication No. 20220081649(A) Summary of the Invention [Means for solving the problem]

[0007] The present invention relates to a liquid hand dishwashing detergent composition comprising: a surfactant system in an amount of 6% to 50% by weight of the total composition; and a quaternized acrylic copolymer, wherein the surfactant system comprises at least 40% anionic surfactant by weight of the surfactant system, and the anionic surfactant comprises at least 50% alkyl sulfated anionic surfactant by weight of the anionic surfactant, the alkyl sulfated anionic surfactant having an average degree of alkoxylation of less than 0.1.

[0008] The invention further relates to a method of cleaning dishware using such a composition, the method comprising contacting the dishware with a liquid hand dishwashing detergent composition and water, wherein the water has a temperature of 30°C or less. DETAILED DESCRIPTION OF THE INVENTION

[0009] It has been found that the method of using the liquid hand dishwashing detergent composition described herein provides more effective foaming, especially in the presence of grease stains during low-temperature dishwashing, compared to the method of using more traditionally used compositions containing ethoxylated alkyl sulfate anionic surfactants.Therefore, users are more encouraged to wash dishes at lower temperatures.In addition, the incorporation of quaternized acrylic copolymers into the hand dishwashing detergent composition described herein further improves foaming during low-temperature dishwashing.

[0010] 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.

[0011] 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.

[0012] 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.

[0013] As used herein, the terms "oil" or "oleaginous" mean that the substance comprises, at least in part (i.e., at least 0.5% by weight of the oil), saturated and unsaturated fats and oils, preferably oils and fats derived from animal sources such as beef, pork, and / or chicken.

[0014] The term "include / includes / including" is meant to be non-limiting.

[0015] 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.

[0016] As used herein, the term "suds profile" refers to a characteristic of a cleaning composition related to the quality of foam during the dishwashing process. The term "suds profile" of a cleaning composition includes the volume of foam generated during dissolution and agitation of the cleaning composition in an aqueous washing solution, typically manual agitation, and foam retention during the dishwashing process. Preferably, hand dishwashing cleaning compositions characterized as having a "good suds profile" tend to have a high and / or persistent foam volume, particularly throughout a significant portion or the entire hand dishwashing process. This is important because consumers use high foam volume as an indicator that sufficient cleaning composition has been dispensed. Furthermore, consumers also use persistent foam volume as an indication that sufficient active cleaning ingredients (e.g., surfactants) are present, even toward the end of the dishwashing process. Consumers typically refresh their washing solutions when suds levels decrease. Thus, low-sudsing cleaning compositions tend to be replenished by consumers more frequently than necessary due to their low foam levels.

[0017] 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.

[0018] 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, all ratios are by weight unless specifically stated otherwise, and all measurements are made at 25°C unless otherwise specified.

[0019] Cleaning Composition The cleaning composition is a liquid cleaning composition for hand dishwashing. The cleaning composition is preferably an aqueous cleaning composition. Therefore, the composition may contain 50 to 85% by weight, preferably 50 to 75% by weight, of water based on the total weight of the composition.

[0020] Preferably, the pH of the composition, when measured at a 10% dilution in distilled water at 20° C., is from about 6 to about 14, preferably from about 7 to about 12, or more preferably from about 7.5 to about 10. The pH of the composition can be adjusted using pH adjusting ingredients known in the art.

[0021] The composition of the present invention is -1 ~100s -1 The viscosity may be Newtonian or non-Newtonian, preferably Newtonian, within the range of shear rates used. Preferably, the composition has a viscosity of 10 mPa·s to 10,000 mPa·s, preferably 100 mPa·s to 5,000 mPa·s, more preferably 300 mPa·s to 2,000 mPa·s, or most preferably 500 mPa·s to 1,500 mPa·s, or a combination thereof. Viscosity is measured at 20°C using a Brookfield RT viscometer using spindle 31 with the viscometer RPM adjusted to achieve 40% to 60% torque.

[0022] surfactant system The liquid cleaning composition comprises from 6.0% to 50%, preferably from 6.0% to 40%, most preferably from 15% to 35% of a surfactant system by weight of the total composition.

[0023] Anionic surfactants: The liquid hand dish detergent composition comprises a surfactant system, the surfactant system comprising an anionic surfactant system comprising an alkyl sulfated anionic surfactant, the alkyl sulfated anionic surfactant having an average degree of alkoxylation of less than 0.1, and more preferably being free of any alkoxylation. If alkoxylation is present, the alkyl sulfated anionic surfactant is preferably ethoxylated.

[0024] The average degree of alkoxylation is the molar average degree of alkoxylation of all alkyl sulfate anionic surfactants (i.e., the molar average degree of alkoxylation). Thus, when calculating the molar average degree of alkoxylation, the number of moles of non-alkoxylated sulfate anionic surfactants is included.

[0025] 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.

[0026] For improved lathering, the surfactant system comprises at least 40%, preferably 60% to 90%, more preferably 70% to 80% anionic surfactant by weight of the surfactant system.

[0027] The anionic surfactant comprises at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% by weight of the alkyl sulfated anionic surfactant of the anionic surfactant.Most preferably, the anionic surfactant is composed of alkyl sulfated surfactant, most preferably primary alkyl sulfated anionic surfactant.Thus, although the surfactant system can comprise a small amount of additional anionic surfactant, including sulfonate such as HLAS, or sulfosuccinate anionic surfactant, the surfactant system preferably does not comprise any additional anionic surfactant beyond the alkyl sulfated anionic surfactant.

[0028] The alkyl sulfated anionic surfactants have alkyl chains containing an average of 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms, and more preferably 12 to 13 carbon atoms.

[0029] The alkyl chains of the alkyl sulfated anionic surfactant preferably 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 50 / 50, 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, while foam persistence in the presence of particulate soils is not impaired.

[0030] The alkyl sulfated anionic surfactant may have an average degree of branching of at least 5.0%, preferably 10% to 50%, more preferably 15% to 40%, and thus may comprise a mixture of linear and branched alkyl sulfated anionic surfactants.

[0031] The alkyl chain of the alkyl sulfated anionic surfactant can be derived from natural or synthetic origin.The linear alkyl chain can be preferably derived from coconut oil, and coconut oil has a preferred chain length while being more persistently derived.The linear alkyl chain can be blended with highly branched alkyl chain, so that less branched alkyl chain needs to be added to reach the desired branching degree.

[0032] The overall degree of branching (and how branching is achieved) not only affects the sustainability of the feedstock, but also the amount of organic solvent needed to physically stabilize the liquid hand dishwashing composition. Branching of the alkyl sulfated anionic surfactant also affects viscosity and viscosity upon dilution, avoiding viscosity thickening upon dilution and ensuring that the composition is easily dispersible in water.

[0033] The branching level in the branched alkyl sulfate or alkyl alkoxy sulfate used in the detergent composition is calculated on a molecular basis. A commercially available blend of non-alkoxylated alkyl sulfate anionic surfactants sold as "branched" will typically contain a blend of linear alkyl sulfate molecules and branched alkyl sulfate molecules. A commercially available alkyl alkoxy sulfate anionic surfactant blend sold as "branched" will typically contain a blend of linear alkyl sulfate, branched alkyl sulfate, and linear alkyl alkoxy sulfate and branched alkyl alkoxy sulfate molecules. The actual calculation of branching degree is calculated using the following weight average branching degree calculation: 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 prior to (alkoxylation and) sulfation to produce the alkyl(alkoxy) sulfate anionic surfactant. The weight average branching degree calculation includes the weight of the alkyl alcohols used to form the unbranched alkyl sulfate anionic surfactant.

[0034] 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.

[0035] The branched alkyl sulfated anionic surfactant may comprise a C2 branched alkyl sulfated anionic surfactant and, optionally, a non-C2 branched alkyl sulfated anionic surfactant. The branched alkyl sulfated anionic surfactant may comprise at least 90% by weight, preferably at least 95% by weight, more preferably at least 98% by weight of the C2 branched alkyl sulfated anionic surfactant, and at most 10% by weight, preferably at most 5% by weight, most preferably at most 2% by weight of the branched alkyl sulfated anionic surfactant, of the non-C2 branched alkyl sulfate anionic surfactant.

[0036] C2 branched means that the alkyl branch is a single alkyl branch on the alkyl chain of the alkyl sulfated anionic surfactant and is located at the C2 position, counting carbon atoms from the sulfate group in the case of a non-alkoxylated alkyl sulfate anionic surfactant, or from the alkoxy group furthest from the sulfate group in the case of an alkoxylated alkyl sulfate anionic surfactant.

[0037] Non-C2 branched means that the alkyl chain contains branches at multiple carbon positions along the alkyl chain backbone, or a single branch group present at a branch position on the alkyl chain other than the C2 position.

[0038] The non-C2 branched alkyl sulfated anionic surfactant may comprise less than 30%, preferably less than 20%, more preferably less than 10% by weight of C1 branched alkyl sulfated anionic surfactant of the non-C2 branched alkyl sulfated anionic surfactant, and most preferably the non-C2 branched alkyl sulfated anionic surfactant is free of C1 branched alkyl sulfated anionic surfactant.

[0039] The non-C2 branched alkyl sulfated anionic surfactant may comprise at least 50% by weight, preferably 60-90% by weight, and more preferably 70-80% by weight, of the non-C2 branched alkyl sulfated anionic surfactant, of isomers containing single branches at branching positions greater than 2. This means that the branching positions are separated from the hydrophilic head group, as defined above, by more than two carbon atoms. The non-C2 branched alkyl sulfated anionic surfactant may comprise 5% to 30% by weight, preferably 7% to 20% by weight, and more preferably 10% to 15% by weight of the non-C2 branched alkyl sulfated anionic surfactant, of multi-branched isomers. The non-C2 branched alkyl sulfated anionic surfactant may comprise 5% to 30% by weight, preferably 7% to 20% by weight, and more preferably 10% to 15% by weight of the non-C2 branched alkyl sulfated anionic surfactant, of cyclic isomers. The acyclic branched groups, if present, may be selected from C1-C5 alkyl groups and mixtures thereof.

[0040] Formulating compositions using alkyl sulfated anionic surfactants with the above-mentioned branching distribution and reduced to no ethoxylation reduces viscosity sensitivity to temperature fluctuations, thus providing a more consistent dosage experience compared to compositions containing alkyl sulfated anionic surfactants with comparable branching distributions.Furthermore, the compositions maintain a Newtonian viscosity profile over a wider shear rate range, which means less dosage fluctuation and a more consistent user experience, regardless of how hard the container is squeezed.

[0041] Suitable counterions for anionic surfactants include alkali metal cations, alkaline earth metal cations, alkanolammonium, or ammonium or substituted ammonium, preferably sodium.

[0042] 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. Alcohols can be blended to achieve the desired average alkyl chain, average branching degree, and branching distribution type according to the present invention. The target branched alkyl sulfated anionic surfactant according to the present invention is one that has a high C2 branched alkyl sulfated anionic surfactant content, and preferably, the alkyl sulfated anionic surfactant includes OXO-derivatized alkyl sulfated anionic surfactants, such as those sold under the trade names Lial and Isalchem ​​by Sasol and Neodol by Shell, including branched alkyl sulfated anionic surfactants consisting essentially of C2 branched alkyl sulfate anionic surfactants. OXO alcohols are alcohols prepared by adding carbon monoxide (CO) and hydrogen (usually combined as synthesis gas) to an olefin, using a hydroformylation reaction to obtain an aldehyde, and then hydrogenating the aldehyde to obtain an alcohol. More preferably, the alkyl sulfated anionic surfactant comprises 60% to 85%, preferably 75% to 85% by weight of the alkyl sulfated anionic surfactant. The OXO alcohol is an alcohol prepared by adding carbon monoxide (CO) and hydrogen to an olefin, using a hydroformylation reaction to obtain an aldehyde, and then hydrogenating the aldehyde to obtain an alcohol. Alternative processes that result in alkyl sulfated anionic surfactants, including branched alkyl sulfated anionic surfactants, with a high preference for C2 branched alkyl sulfated anionic surfactants, are also considered suitable for the present invention. Examples of such alternative methods are described in U.S. Patent Application Nos. 63 / 035125 and 63 / 035131.Thus, the alkyl sulfated anionic surfactant then comprises at least 30%, preferably 40% to 95%, more preferably 50% to 85%, by weight of the alkyl sulfated anionic surfactant, of an alkyl sulfate anionic surfactant derived from this alternative process, or a mixture of an OXO-derivatized alkyl sulfate anionic surfactant and an alkyl sulfate anionic surfactant derived from this alternative process.

[0043] Without being bound by theory, when ethoxylated alkyl sulfates are present, the amount of 1,4-dioxane by-product in the alkoxylated, especially ethoxylated alkyl sulfates, can be reduced by strictly controlling the process conditions and raw material composition during both the alkoxylation, especially ethoxylation, and sulfation steps. Based on recent technological advances, further reduction of 1,4-dioxane by-products can be achieved by subsequent stripping, distillation, solvent evaporation, centrifugation, microwave irradiation, molecular sieving, or catalytic or enzymatic cracking steps. Methods for controlling the 1,4-dioxane content in alkoxylated / ethoxylated alkyl sulfates are widely known in the art. Alternatively, the control of 1,4-dioxane levels in detergent formulations by adding 1,4-dioxane inhibitors such as 5,6-dihydro-3-(4-morpholinyl)-1-[4-(2-oxo-1-piperidinyl)-phenyl]-2-(1-H)-pyridone, the 3-alpha-hydroxy-7-oxo stereoisomeric mixture of cholanic acid, 3-(N-methylamino)-L-alanine and mixtures thereof to formulations containing 1,4-dioxane has also been described in the art.

[0044] Co-surfactant To improve surfactant loading after dilution and thus improve lather persistence, the surfactant system may include a co-surfactant in addition to the anionic surfactant.

[0045] The co-surfactant may be selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.

[0046] The weight ratio of the anionic surfactant to the co-surfactant may be 2.0:1 to 8.0:1, preferably 2.0:1 to 5.0:1, more preferably 2.5:1 to 4.0:1 to achieve improved grease cleaning, foaming and viscosity building.

[0047] The surfactant system may comprise from 0.1% to 20%, preferably from 0.5% to 15%, more preferably from 2% to 10% by weight of the cleaning composition of co-surfactant. The surfactant system of the cleaning composition of the present invention may comprise from 10% to 40%, preferably from 15% to 35%, more preferably from 20% to 30% by weight of the surfactant system of co-surfactant.

[0048] The co-surfactant can be an amphoteric surfactant such as an amine oxide surfactant. The amine oxide surfactant can 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 a C1-3 alkyl group, a C1-3 hydroxyalkyl group, 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. Specific examples of linear amine oxide surfactants include linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxyethyl dihydroxyethyl amine oxides.

[0049] Preferably, the amine oxide surfactant is selected from the group consisting of alkyl dimethylamine oxide, alkylamidopropyl dimethylamine oxide, and mixtures thereof. Alkyl dimethylamine oxides such as C8-18 alkyl dimethylamine oxide or C10-16 alkyl dimethylamine oxide (e.g., cocodimethylamine oxide) are preferred. 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. C12-C14 alkyl dimethylamine oxides are particularly preferred. Preferably, the alkyl chain of the alkyl dimethylamine oxide is a linear alkyl chain, preferably a C12-C14 alkyl chain, more preferably a C12-C14 alkyl chain derived from coconut oil or palm oil.

[0050] 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 mid-branched amine oxides used herein, |n1-n2| is 5 or less, preferably 4, and most preferably 0 to 4 carbon atoms. The amine oxide further comprises two moieties independently selected from a C1-3 alkyl, a C1-3 hydroxyalkyl group, or a polyethylene oxide group containing an average of 1 to 3 ethylene oxide groups. Preferably, the two moieties are selected from a C1-3 alkyl, and more preferably, both are selected as a C1 alkyl.

[0051] 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) 10% to 45% by weight of the amine oxide of a low cut amine oxide having the formula R1R2R3AO, wherein R1 and R2 are independently selected from hydrogen, C1-C4 alkyl, or mixtures thereof, and R3 is selected from C10 alkyl, or 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.

[0052] 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.

[0053] Preferably, the amine oxide comprises less than 5% by weight of the amine oxide, more preferably less than 3% by weight of the amine oxide of formula R7R8R9AO, where R7 and R8 are selected from hydrogen, C1-C4 alkyl and mixtures thereof, and R9 is selected from C8 alkyl and mixtures thereof. By limiting the amount of amine oxide of formula R7R8R9AO, both physical stability and suds persistence are improved.

[0054] The co-surfactant may be a zwitterionic surfactant such as a betaine surfactant, 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.

[0055] Preferred betaines are alkylbetaines of formula (IIa), alkylamidopropylbetaines of formula (IIb), sulfobetaines of formula (IIc) and amidosulfobetaines of formula (IId), 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 (IIa) and (IIb) [i.e., in formula (I), Y - =COO-], more preferred are alkylamidobetaines of formula (IIb).

[0056] 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.

[0057] Nonionic surfactants: The surfactant system may further comprise a non-ionic surfactant, preferably an alkoxylated alcohol non-ionic surfactant.

[0058] The surfactant system may comprise at least 0.5%, preferably at least 1.0%, and more preferably at least 2.0% by weight of the composition of an alkoxylated alcohol nonionic surfactant. The anionic surfactant and the alkoxylated alcohol nonionic surfactant may be present in a weight ratio of less than 10:1. The anionic surfactant and the alkoxylated alcohol nonionic surfactant are preferably present in a weight ratio of 0.8:1 to 6.0:1, more preferably 3.5:1 to 5.5:1. Alternatively, the composition may comprise more than 3.0%, preferably 3.5% to 10%, more preferably 4.0% to 7.5% by weight of the liquid hand dish detergent composition of an alkoxylated alcohol nonionic surfactant.

[0059] 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.

[0060] The surfactant system may include an additional non-ionic surfactant, such as an alkyl polyglucoside non-ionic surfactant.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] In even more preferred compositions, the composition does not contain any additional nonionic surfactants.

[0068] Quaternized Acrylic Copolymer The liquid hand dish detergent comprises a quaternized acrylic copolymer. As used herein, "copolymer" refers to a polymer comprising at least two different monomer compositions. The quaternized polymer has the structure NR4 + The ammonium ion (NH4 +) and primary, secondary, or tertiary ammonium cations, quaternary ammonium cations are permanently charged, regardless of the pH of their solution.

[0069] 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.

[0070] 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.

[0071] The quaternized acrylic copolymer may be characterized by its cationic charge density, typically expressed as milliequivalents of charge per gram of compound (mEq / g). The hydrophobically modified cationic polyvinyl alcohol of the present disclosure may be characterized by a cationic charge density (or "CCD") ranging from 0.10 mEq / g to 4.0 mEq / g, preferably from 1.0 mEq / g to 3.50 mEq / g, and more preferably from 1.75 mEq / g to 2.75 mEq / g.

[0072] Preferably, the different types of monomer units are randomly distributed throughout the quaternized acrylic copolymer.

[0073] The quaternized acrylic copolymer is preferably derived from cationic and ethylenically unsaturated monomer units.

[0074] 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 - is a halide counterion, more preferably Cl - is.

[0075] 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 are the same.

[0076] The cationic monomer unit can be selected from the group consisting of acrylamidopropyl trimethylammonium chloride (APTAC), methacrylamidopropyl trimethylammonium chloride (MAPTAC), diallyl dimethyl ammonium chloride (DADMAC), acryloyloxyethyl trimethylammonium chloride (AETAC), methyloyloxyethyl trimethylammonium chloride (METAC), and mixtures thereof. Particularly preferred cationic monomers are (meth)acrylamidopropyl trimethylammonium chloride (APTAC or MAPTAC) or diallyl dimethyl ammonium chloride (DADMAC), with methacrylamidopropyl trimethylammonium chloride (MAPTAC) being 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).

[0077] 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.

[0078] Suitable C3-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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] The quaternized acrylic copolymer can include hydroxyethyl acrylate as the ethylenically unsaturated monomer and diallyldimethylammonium chloride (DADMAC) as the cationic 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.

[0083] More preferably, the quaternized acrylic copolymer can contain acrylate and / or ethyl acrylate as the ethylenically unsaturated monomer, together with (meth)acrylamidopropyltrimethylammonium chloride (APTAC or MAPTAC) as the cationic monomer. Such quaternized acrylic copolymer can contain 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.

[0084] Further ingredients: The composition can include additional ingredients such as those selected from amphiphilic alkoxylated polyalkyleneimines, cyclic polyamines, triblock copolymers, salts, hydrotopes, organic solvents, other adjunct ingredients such as those described herein, and mixtures thereof.

[0085] 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.

[0086] Preferred amphiphilic alkoxylated polyethyleneimine polymers have the general structure of formula (I):

[0087] [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.

[0088] 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.

[0089] Amphiphilic alkoxylated polyethyleneimine polymers can be made by the methods described in more detail in WO 2007 / 135645.

[0090] cyclic polyamines The present compositions can include a cyclic polyamine with amine functionality to aid in cleaning. The compositions of the present invention preferably comprise from 0.1% to 3%, more preferably from 0.2% to 2%, especially from 0.5% to 1%, by weight of the composition of the cyclic polyamine.

[0091] 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.

[0092] Thus, the most preferred cyclic polyamines for use in the cleaning compositions of the present invention are those selected from the group consisting of 2-methylcyclohexane-1,3-diamine, 4-methylcyclohexane-1,3-diamine, and mixtures thereof. These particular cyclic polyamines, when combined with the surfactant system of the compositions of the present invention, function to improve the suds and grease cleaning profile throughout the dishwashing process.

[0093] Suitable cyclic polyamines may be supplied by BASF under the trade name Baxxodur, with Baxxodur ECX-210 being particularly preferred.

[0094] 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.

[0095] triblock copolymer The compositions of the present invention may include a triblock copolymer. The triblock copolymer may be present at a level of 0.1% to 10%, preferably 0.5% to 7.5%, and more preferably 1% to 5% 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. Each y can be set to 28 to 60, preferably 30 to 55, and more preferably 30 to 48 on average.

[0096] 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).

[0097] 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."

[0098] 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.

[0099] 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).

[0100] Preferred triblock copolymers are readily biodegradable under aerobic conditions.

[0101] The compositions of the present invention may further comprise at least one active selected from the group consisting of salts, hydrotropes, organic solvents, and mixtures thereof.

[0102] salt: The composition of the present invention may contain 0.05% to 2% by weight of the total composition, preferably 0.1% to 1.5% by weight, or more preferably 0.5% to 1% by weight of a salt, preferably a monovalent or divalent inorganic salt or a mixture thereof, more preferably selected from sodium chloride, sodium sulfate, and a mixture thereof, with sodium chloride being most preferred.

[0103] Hydrotropes: The compositions of the present invention may comprise from 0.1% to 10%, or preferably from 0.5% to 10%, or more preferably from 1% to 10% by weight of the total composition of a hydrotope or mixture thereof, preferably sodium cumene sulfonate.

[0104] Organic solvents: The present composition may contain 0.1% to 10% by weight of the organic solvent, or preferably 0.5% to 10% by weight, or more preferably 1% to 10% by weight of the total 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 (PPG), are preferred glycols. The polypropylene glycol may have a molecular weight of 400 to 3,000, preferably 600 to 1,500, and more preferably 700 to 1,300. The polypropylene glycol is preferably poly-1,2-propylene glycol.

[0105] Supplementary ingredients The present cleaning compositions may optionally contain many other adjunct ingredients such as builders (preferably citrates), chelating agents, conditioning polymers, other cleaning polymers, surface modifying polymers, structuring agents, emollients, humectants, skin rejuvenating actives, enzymes, carboxylic acids, scrubbing particles, fragrances, malodor control agents, pigments, dyes, opacifiers, pearlescent particles, inorganic cations such as alkaline earth metals such as Ca / Mg ions, antimicrobial agents, preservatives, viscosity modifiers (e.g., salts such as NaCl and other mono-, di-, and trivalent salts), and pH adjusters and buffering means (e.g., carboxylic acids such as citric acid, HCl, NaOH, KOH, alkanolamines, carbonates such as sodium carbonate, bicarbonates, sesquicarbonates, etc.).

[0106] 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.

[0107] 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).

[0108] The container can typically contain 200 ml to 5,000 ml, preferably 350 ml to 2,000 ml, more preferably 400 ml to 1,000 ml of the liquid hand dish detergent composition.

[0109] Cleaning method The compositions useful in the present invention are used in a method for manually washing dishware, comprising the step of contacting dishware with a liquid hand dishwashing detergent composition and water, the liquid hand dishwashing detergent composition comprising a quaternized acrylic copolymer and a surfactant system, the surfactant system comprising an anionic surfactant system including an alkyl sulfated anionic surfactant, the alkyl sulfated anionic surfactant having an average degree of alkoxylation of less than 0.1, and the water having a temperature of 30°C or less, preferably between 20°C and 30°C.

[0110] Water present in a typical household may typically have a hardness of up to 3.0 mmol / l CaCO3 equivalents. Accordingly, the methods described herein are suitable for use when washing with water having a hardness of up to 3.0 mmol / l, preferably 0.3 mmol / l to 2.7 mmol / l, and more preferably 0.75 mmol / l to 2 mmol / l CaCO3 equivalents.

[0111] A suitable method includes the steps of dispensing a liquid hand dishwashing composition into a volume of water to form a wash solution and immersing dishware in the wash solution, where the dishware is cleaned with the composition in the presence of water.

[0112] The cleaning solution may contain the liquid hand dishwashing detergent composition at a concentration of from 100 ppm to 10,000 ppm, preferably from 200 ppm to 5000 ppm, more preferably from 500 ppm to 2000 ppm.

[0113] Typically, 0.5 ml to 50 ml, preferably 1.0 ml to 25 ml, more preferably 2.5 ml to 10 ml of liquid hand dish detergent composition is combined with 1.0 L to 15 L, preferably 1.5 L to 10 L, more preferably 2.5 to 7.5 L of water to form a wash solution. The actual amount of detergent composition used is at the discretion of the user and will generally depend on factors such as the particular product formulation of the detergent composition, including the concentration of active ingredients in the detergent composition, the number of soiled dishes to be washed, the degree of soiling of the dishes, etc.

[0114] After the soiled dishware is immersed in the resulting cleaning solution, a cloth, sponge, or similar cleaning implement is used to wipe the soiled surface of the dishware. The cloth, sponge, or similar cleaning implement is typically in contact with the dishware for a period ranging from 1 to 10 seconds, although the actual time will vary depending on the application and user preference. Wiping can sometimes be done after a period of immersion, for example, about 30 minutes.

[0115] Alternatively, before contacting the dishware with the liquid hand dishwashing detergent composition and water, the liquid hand dishwashing detergent composition and water are combined on a device, preferably the device is a brush, sponge, nonwoven material, or woven material, more preferably the device is a sponge. The liquid hand dishwashing detergent composition and water can be combined on or in the device in a ratio of 25:75 to 1:99, preferably 15:85 to 1:99, more preferably 10:90 to 1:99.

[0116] The cleaning device or utensil, and consequently the liquid dishwashing composition and water, are directly contacted with the surface of each soiled dish to remove the soiling. The cleaning device or utensil is typically contacted with each dish surface for a period 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 dish. Preferably, contact of the cleaning device or utensil with the dish surface is accompanied by wiping.

[0117] The dishware may then be rinsed. By "rinsing" in the present invention is meant contacting the dishware washed by the process of the present invention with a large amount of water. "A large amount" typically means about 1.0 to about 20 L or under running water.

[0118] Test Method Molecular weight determination 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

[0119] 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 if the composition, and therefore the refractive index increment, varies with elution volume.

[0120] For example, the molecular weight distribution of a polymer can be measured using a hydrochromatographic 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 7.8 mm i.d. x 300 mm long UltraHydrogel linear columns (S / N 002C180181 VE077 and 005C180181 VE084) supplied by Waters Corporation (Milford, Mass., USA) used in series, and an UltraHydrogel guard column (6 mm i.d. x 40 mm long, S / N 2016260401BE105, also supplied by Waters Corporation (Milford, Mass., USA)) operated at 40°C and placed between the injector and the analytical column to prevent any impurities and suspended solids from reaching the analytical column. A multi-angle light scattering (MALS) detector DAWN® and a refractive index (RI) detector (Wyatt Technology, Santa Barbara, Calif., USA) controlled by Wyatt Astra® software can be used for detection.

[0121] Because the analytes are dispersed over a relatively narrow time window, isocratic elution can be used rather than gradient elution. Isocratic means that the mixture of the mobile phase is consistent over the entire test period. The use of a gradient implies that the composition of the eluent mixture changes during the run, thus affecting the retention of the analytes. When using a gradient, the separation can either be accelerated or decelerated.

[0122] 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 into an LC autosampler vial through a 0.8 μm Versapor membrane filter (AP4189, supplied by PALL, Life Sciences, NY, USA) using a 3 ml syringe. The sample is then pumped into the column at a flow rate of 1.0 mL / min.

[0123] 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.

[0124] Foam durability The purpose of the foam persistence test is to compare the change in foam volume generated over time for test agents with different specified water hardness, solution temperatures, and formulation concentrations while under the influence of intermittent soil injections. The data are compared and expressed as a foam persistence index relative to a reference composition or test condition (the reference composition or test condition has a foam persistence index of 100). The steps of the method are as follows: 1. Dispense 0.12% by weight of the test composition into a stream of water having the desired water hardness and the desired water temperature through a plastic pipette at a flow rate of 0.67 mL / sec at a height 37 cm above the bottom of a sink (dimensions: diameter 300 mm, height 288 mm) and fill the sink to 4 L at a constant pressure of 4 bar. 2. The initial foam volume generated (measured as the average foam volume X above the liquid in the sink (cm 3 (represented by ) is recorded immediately after filling is completed. 3. Immediately pour a fixed volume (6 mL) of soil containing the specified composition below into the center of the sink. 4. Mix the resulting solution using a metal blade (10 cm x 5 cm) positioned at a 45° angle to the air-liquid interface in the center of the sink, rotating 20 times at 85 RPM. 5. Another measurement of total lather volume is recorded immediately after the blade rotation has finished. 6. The measured total foam volume is 400 cm 3 Repeat steps 3-5 until you reach a level of 400cm 3 The amount of soil added required to reach a level of suds is considered the suds persistence of the test composition. 7. Each test composition is tested four times per test condition (i.e., water temperature, composition concentration, water hardness, soil type). 8. Calculate the average foam persistence as the average of four replicates per sample for the stated test conditions. 9. Calculate the Lather Persistence Index by comparing the average persistence of the test composition samples at 25° C. with the same test samples at 40° C. in the same target water hardness. The calculation is as follows:

[0125]

number

[0126] The greasy soil compositions used in the tests are prepared by standard mixing of the ingredients listed in Table 1.

[0127] [Table 1] [Example]

[0128] The following compositions were prepared and evaluated for foam persistence benefits in the presence of greasy soils at a water hardness of 1.25 mmol / L equivalent Ca and wash water temperatures of 25°C (inventive wash method) and 40°C (comparative and reference wash methods), as described herein.

[0129] Example 1 contained both a quaternized acrylic copolymer and a non-alkoxylated alkyl sulfate anionic surfactant and was therefore in accordance with the present invention. Example A was similar to Example 1, but did not contain a quaternized acrylic copolymer. Example B was similar to Example 1, but contained an ethoxylated alkyl sulfate anionic surfactant instead of the non-alkoxylated alkyl sulfate anionic surfactant. Example C was similar to Example 1, but contained an ethoxylated alkyl sulfate anionic surfactant instead of the non-alkoxylated alkyl sulfate anionic surfactant and did not contain a quaternized acrylic copolymer. Thus, Examples A, B, and C were comparative compositions.

[0130] The resulting foam persistence in the presence of greasy soil for all compositions is listed in Table 1.

[0131] [Table 2] * Comparative Example 1 It is produced by sulfating C12-13 alkyl alcohols and is sold under the trade name Neodol 23® and supplied by Shell. 2 It is produced by sulfating ethoxylated C12-13 alkyl alcohols and is sold under the trade name Neodol 23-2® and supplied by Shell. 3Sold under the trade name Neodol® and supplied by Shell 4 Polyethyleneimine containing a PEI backbone with a weight average molecular weight of 600 g / mol and 24 EO and 16 PO units per alkoxylated chain, supplied by BASF 5 A quaternized acrylic copolymer useful in the present invention sold under the trade name Polyquart® 149A and supplied by BASF

[0132] As can be seen from the above results, the presence of the quaternized acrylic copolymer in a composition containing an alkyl ethoxylated sulfate anionic surfactant provides a negligible improvement in foam persistence in the presence of greasy soils when washing dishware using water at cold temperatures compared to when washing dishware using water at warm temperatures (compare results from Comparative Example B with those of Comparative Example C).

[0133] By comparing the results from Comparative Example A with those of Comparative Example C, it can be seen that formulating a composition without the presence of the quaternized acrylic copolymer and using a non-alkoxylated alkyl sulfate surfactant instead of an ethoxylated alkyl sulfate results in a surprising improvement in foam persistence during low temperature washing of dishes, even though the ethoxylated alkyl sulfate surfactant-containing composition is typically more stable at low temperatures than a similar composition formulated using a non-alkoxylated alkyl sulfate anionic surfactant.

[0134] By comparing the results from Example 1 with those from Example A, it can be seen that incorporating a quaternized acrylic copolymer into the composition, in addition to a surfactant system comprising a non-alkoxylated alkyl sulfate anionic surfactant, provides further improvement in low temperature versus high temperature foam persistence.

[0135] 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 dishwashing cleaning composition comprising: 6% to 50% by weight of the total composition of a surfactant system; and a quaternized acrylic copolymer; the surfactant system 1. A composition comprising at least 40% by weight of said surfactant system an anionic surfactant, said anionic surfactant comprising at least 50% by weight of said anionic surfactant alkyl sulfated anionic surfactant, said alkyl sulfated anionic surfactant having an average degree of alkoxylation of less than 0.1. [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 any one of [1] to [3], wherein the quaternized acrylic copolymer has an average cationic charge density of 0.01 to 2.8, preferably 0.1 to 2.75, more preferably 0.75 to 2.25 cationic units per 100 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 is 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, R 5 is 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 any one of [1] to [4], 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] or [6], 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 any one of [1] to [7], wherein the quaternized acrylic copolymer further comprises, as a polymerized monomer, an additional monomer selected from the group consisting of ethyl acrylate, 2-acrylamido-2-methylpropane-sulfonic acid, N-isopropylamide, and mixtures thereof, preferably ethyl acrylate. [9] The composition according to any one of [1] to [8], wherein the surfactant system is contained in an amount of 6.0% by weight to 40% by weight, preferably 15% by weight to 35% by weight, of the total weight of the composition.

[10] The composition according to any one of [1] to [9], wherein the surfactant system comprises an anionic surfactant in an amount of at least 50% by weight of the surfactant system, preferably 50% to 80% by weight, and more preferably 55% to 70% by weight.

[11] The composition according to any one of [1] to

[10] , wherein the anionic surfactant comprises an alkyl sulfated anionic surfactant in an amount of at least 70% by weight, preferably at least 85% by weight, and more preferably 100% by weight of the anionic surfactant.

[12] The composition according to any one of [1] to

[11] , wherein the alkyl sulfated anionic surfactant does not contain alkoxylation.

[13] The composition according to any one of [1] to

[12] , wherein the surfactant system comprises a nonionic surfactant, and the nonionic surfactant comprises an alkoxylated alcohol nonionic surfactant.

[14] The composition according to any one of [1] to

[13] , wherein the surfactant system further comprises a co-surfactant selected from the group consisting of amphoteric co-surfactants, zwitterionic co-surfactants, and mixtures thereof.

[15] A method for washing tableware, comprising the step of contacting tableware with the liquid hand dishwashing detergent composition according to any one of [1] to

[14] and water, wherein the water has a temperature of 30°C or less.

Claims

1. A liquid hand dishwashing cleaning composition comprising: 6% to 50% by weight of the total composition of a surfactant system; and a quaternized acrylic copolymer; the surfactant system 1. A composition comprising at least 40% by weight of said surfactant system an anionic surfactant, said anionic surfactant comprising at least 50% by weight of said anionic surfactant alkyl sulfated anionic surfactant, said alkyl sulfated anionic surfactant having an average degree of alkoxylation of less than 0.

1.

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 or 2, wherein the quaternized acrylic copolymer has an average cationic charge density of 0.01 to 2.8 cationic units per 100 mEq / g.

5. The quaternized acrylic copolymer derived from cationic monomer units and ethylenically unsaturated monomer units, (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; or (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; The composition according to claim 1 or 2, wherein any one of the following is applied.

6. 6. The composition of claim 5, wherein the cationic monomer unit is selected from the group consisting of acrylamidopropyltrimethylammonium chloride (APTAC), methacrylamidopropyltrimethylammonium chloride (MAPTAC), and diallyldimethylammonium chloride (DADMAC).

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

8. The composition of claim 5, wherein the ethylenically unsaturated monomer unit is selected from the group consisting of acrylic acid or a salt thereof, ethyl (meth)acrylate, and mixtures thereof.

9. The composition of claim 8, wherein the ethylenically unsaturated monomer units include ethyl acrylate.

10. The composition described in claim 5, wherein the cationic monomer unit is selected from the group consisting of acrylamidopropyltrimethylammonium chloride (APTAC) and methacrylamidopropyltrimethylammonium chloride (MAPTAC), and the ethylenically unsaturated monomer unit is selected from the group consisting of acrylic acid or a salt thereof, ethyl (meth)acrylate, and mixtures thereof.

11. 3. The composition of claim 1, wherein the composition comprises from 6.0% to 40% by weight of the total composition of the surfactant system.

12. 3. The composition of claim 1, wherein the surfactant system comprises at least 50% anionic surfactant by weight of the surfactant system.

13. 3. The composition of claim 1, wherein the anionic surfactant comprises at least 70% alkyl sulfated anionic surfactant by weight of the anionic surfactant.

14. 3. The composition of claim 1, wherein the alkyl sulfated anionic surfactant is free of alkoxylation.

15. 3. The composition of claim 1 or 2, wherein the surfactant system comprises a nonionic surfactant, the nonionic surfactant comprising an alkoxylated alcohol nonionic surfactant.

16. 3. The composition of claim 1, wherein the surfactant system further comprises a co-surfactant selected from the group consisting of amphoteric co-surfactants, zwitterionic co-surfactants, and mixtures thereof.

17. 10. A method for washing dishes, comprising contacting the dishes with the liquid hand dish detergent composition of claim 1 and water, wherein the water has a temperature of 30°C or less.

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