Liquid hand dishwashing detergent composition

Abstract

To provide a liquid detergent composition for hand-washing dishes, having an improved drying time especially after hand-washing dishes in soft water.SOLUTION: The liquid hand dishwashing detergent composition comprises between 5.0% and 50% by weight of the detergent composition of a surfactant system, and further comprises a) a cationic polymer, wherein the cationic polymer is selected from the group consisting of a quaternized acrylic copolymer, a cationic polyvinyl alcohol, a cationic polysaccharide, and mixtures thereof, and b) a 1, 2-alkanediol, wherein the alkyl chain of the 1, 2-alkanediol comprises from 4 to 14 carbon atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid detergent composition for hand dishwashing. [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. With the increasing popularity of home water softeners, there is a growing need to improve sheeting and therefore drying speed of dishes after washing.

[0003] The use of cationic polymers, including quaternized acrylic copolymers, cationic polyvinyl alcohols, and cationic celluloses, to improve water sheeting from dishware and thus improve drying is known. However, even with the addition of such cationic polymers, there remains a need to further improve drying times, especially after hand washing of dishware in softened water.

[0004] EP 4400565(A), EP 4400566(A), EP 4400567(A), and EP 4400568 relate to liquid hand dishwashing detergents containing quaternized acrylic copolymers that further improve the drying rate of dishes after hand dishwashing, where the compositions are formulated with a surfactant system that increases the effectiveness of the quaternized acrylic copolymer. EP 4400571(A) relates to liquid hand dishwashing detergent compositions containing cationically modified polyvinyl alcohols and methods of using the same that provide improved rinse and solution feel. EP 4400570(A) relates to liquid hand dishwashing detergent compositions containing hydrophobically modified cationic polyvinyl alcohols and methods of using the same that provide improved rinse. EP 23201537.0 relates to liquid hand dish detergent compositions that provide effective cleaning and enhanced foaming and viscosity, which are formulated with an amine oxide amphoteric cosurfactant and a medium-chain 1,2-alkanediol. EP 24179183.9 relates to liquid hand dish detergent compositions containing a medium-chain 1,2-alkanediol and further improved foaming and viscosity, which are satisfied by formulating the composition with an amine oxide amphoteric cosurfactant. EP 23201583.4 relates to liquid hand dish detergent compositions that provide effective cleaning and enhanced foaming, which are formulated with a surfactant system containing an alkyl sulfated anionic surfactant with little or no alkoxylation, an amphoteric and / or zwitterionic cosurfactant, and a nonionic surfactant in combination with a medium-chain 1,2-alkanediol. WO 201836864(A) relates to a hard surface treatment composition comprising a quaternized acrylic copolymer and an amphoteric modified polysaccharide, wherein the weight ratio of the quaternized acrylic copolymer to the amphoteric modified polysaccharide is 0.75:1 to 3:1, and the quaternized acrylic copolymer is different from the amphoteric modified polysaccharide.EP 3835399(A) relates to a hard surface cleaning composition comprising a surfactant system, a first polymer, and a second polymer, wherein the first polymer is polyethyleneimine, and the use of the composition for cleaning glass surfaces. US Patent Application Publication No. 20030134770(A) relates to a liquid detergent composition comprising a polymeric material that is a foam booster and a foam volume enhancer, wherein the composition has 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(A) relates to a hard surface cleaning composition comprising a surfactant system, a first polymer, and a second polymer, wherein the first polymer is polyethyleneimine. WO 2022 / 199790(A) relates to liquid detergent compositions comprising, or consisting of, at least one hydroxyl compound selected from the group consisting of: (a1) 1,2-hexanediol; (a2) 1,2-heptanediol; (a3) ​​1,2-octanediol; (a4) 1,2-decanediol; (a5) 2,3-heptanediol (a6) 2,3-hexanediol; (a7) 2,3-octanediol; (a8) 2,3-nonanediol; (a9) glyceryl caprylate; (a10) 4-hydroxyacetophenone; and optionally (b) tropolone or mixtures thereof. WO 2023 / 122098(A) discloses a cleaning composition, such as a dishwashing composition, containing one or more anionic surfactants including sodium laureth sulfate (SLES), one or more amphoteric surfactants, and an additive selected from caprylyl glycol, ethanol, and combinations thereof.German Patent Application Publication No. 202017007679(U) relates to 1,2-alkanediols that contain no or at least very few undesirable by-products, in particular lactones that cause odor, and have better quality, stability, and odor than products on the market.WO 2022 / 122935(A) relates to cosmetic or pharmaceutical compositions, preferably skin compositions or home care products, and personal, pharmaceutical, or animal care compositions, comprising or consisting of a specific lipophilic active ingredient and an effective amount of 1,2-heptanediol and / or 2,3-heptanediol, or a specific alkanediol, or a mixture of two or more different specific alkanediols. EP 4227392(A) relates to liquid hand dishwashing detergent compositions containing cationically modified inulin compounds that provide improved rinsing, solution feel, and viscosity control of the final product. EP 1221475(A) relates to liquid detergent compositions containing quaternary nitrogen-containing and / or zwitterionic polymeric foam boosters. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] European Patent No. 4400565(A) [Patent Document 2] European Patent No. 4400566(A) [Patent Document 3] European Patent No. 4400567(A) [Patent Document 4] European Patent No. 4400568 [Patent Document 5] European Patent No. 4400571(A) [Patent Document 6] European Patent No. 4400570(A) [Patent Document 7] European Patent Application Publication No. 23201537.0 [Patent Document 8] European Patent Application Publication No. 24179183.9 [Patent Document 9] European Patent Application Publication No. 23201583.4 [Patent Document 10] International Publication No. 201836864(A) [Patent Document 11] European Patent No. 3835399(A) [Patent Document 12] U.S. Patent Application Publication No. 20030134770(A) [Patent Document 13] European Patent No. 3835399(A) [Patent Document 14] International Publication No. 2022 / 199790(A) [Patent Document 15] International Publication No. 2023 / 122098(A) [Patent Document 16] German Patent Application Publication No. 202017007679(U) [Patent Document 17] International Publication No. 2022 / 122935(A) [Patent Document 18] European Patent No. 4227392(A) [Patent Document 19] European Patent No. 1221475(A) Summary of the Invention [Means for solving the problem]

[0006] The present invention relates to a liquid detergent composition for hand dishwashing, comprising from 5.0% to 50% by weight of the liquid detergent composition of a surfactant system, the detergent composition further comprising a cationic polymer selected from the group consisting of a quaternized acrylic copolymer, a cationic polyvinyl alcohol, a cationic polysaccharide, and mixtures thereof, and a 1,2-alkanediol, the alkyl chain of which contains from 4 to 14 carbon atoms. DETAILED DESCRIPTION OF THE INVENTION

[0007] In addition to the cationic polymer, the incorporation of a surfactant system as described herein into the liquid composition has been found to further improve the drying rate of dishes after hand dishwashing.

[0008] 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.

[0009] 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.

[0010] 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.

[0011] 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.

[0012] The term "include / includes / including" is meant to be non-limiting.

[0013] 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.

[0014] As used herein, the term "suds profile" refers to a characteristic of a composition with respect to foam 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 high initial and / or persistent foam volumes, particularly throughout a significant portion or the entire hand dishwashing process. This is important because consumers use a large amount of foam as an indicator that sufficient composition has been dispensed. Furthermore, consumers also use persistent foam volume, even toward the end of the dishwashing process, as an indicator that sufficient active cleaning ingredients (e.g., surfactants) are present. Consumers typically refresh their washing solutions when sudsing becomes low. Thus, low-sudsing compositions tend to be replaced by consumers more frequently than necessary due to their low suds levels.

[0015] 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.

[0016] Unless specifically stated otherwise, as is clear from the context, all percentages are by weight of the total composition. Unless specifically stated otherwise, all ratios are by weight, and all measurements are made at 25°C unless otherwise specified.

[0017] Liquid dishwashing detergent composition The composition is a liquid composition for hand dishwashing and is therefore in liquid form. The liquid composition for hand dishwashing is preferably an aqueous composition. Therefore, the composition can contain 50% to 85% by weight, preferably 50% to 75% by weight, of water based on the total weight of the composition.

[0018] 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.

[0019] 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.

[0020] cationic polymer The liquid hand dishwashing detergent contains a cationic polymer, preferably in an amount of 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.

[0021] The cationic polymer is selected from the group consisting of quaternized acrylic copolymers, cationic polyvinyl alcohols, cationic polysaccharides, and mixtures thereof, preferably quaternized acrylic copolymers, cationic polyvinyl alcohols, and mixtures thereof, more preferably quaternized acrylic copolymers.

[0022] Quaternized Acrylic Copolymer Liquid hand dish detergents may contain quaternized acrylic copolymers. As used herein, "copolymer" refers to a polymer containing at least two different monomer compositions. Quaternized polymers have 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.

[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 (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] As used herein, the "charge density" of a cationic polymer is defined as the number of cationic sites per gram atomic weight (molecular weight) of polymer, and can be expressed in terms of meq / gram of cationic charge. Generally, adjusting the proportion of amine or quaternary ammonium moieties in the polymer, depending on the pH of the liquid dishwashing liquid in the case of amines, will affect the charge density. Any anionic counterion may be used in conjunction with the cationic deposition polymer, as long as the polymer remains soluble in water and the liquid dishwashing liquid matrix, and the counterion is physically and chemically stable with the essential components of the liquid dishwashing liquid or does not unduly impair the performance, stability, or aesthetics of the product. Non-limiting examples of such counterions include halides (e.g., chlorine, fluorine, bromine, iodine), sulfate, and methyl sulfate.

[0026] Preferably, the different types of monomer units are randomly distributed throughout the quaternized acrylic copolymer.

[0027] The quaternized acrylic copolymer is preferably derived from cationic and ethylenically unsaturated monomer units.

[0028] The cationic monomer units may be selected from: CH2=CR 1 -YN + R 2 R 3 R 4 X - (a) (In the formula, Each R 1 is independently selected from hydrogen or methyl, preferably methyl; Each R 2 is 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 to C4 alkyl, preferably C1 to C3 alkyl, more preferably methyl; each Y independently represents CO-NR 5 -(CH2) n , CO-O-(CH2) n , or (CH2) n and preferably CO-NR 5 -(CH2) n or (CH2) n , more preferably CO-NR 5 -(CH2) n is a linking group which is (In the formula, Each R 5 is 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.

[0029] 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.

[0030] 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), acryloyloxyethyltrimethylammonium chloride (AETAC), methyloyloxyethyltrimethylammonium 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).

[0031] The ethylenically unsaturated monomer is selected from the group consisting of C3-C8 ethylenically unsaturated acids and / or salts thereof, C4-C8 alkyl acrylates, C4-C8 hydroxyalkyl acrylates, and mixtures thereof, preferably a combination of a C3-C8 ethylenically unsaturated acid and a C4-C8 alkyl acrylate, and more preferably a combination of acrylic acid and ethyl acrylate. The C3-C8 ethylenically unsaturated acid and / or salts thereof contain 3 to 8 carbon atoms. The C4-C8 alkyl and C4-C8 hydroxyalkyl acrylates contain 4 to 8 carbon atoms.

[0032] 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.

[0033] Suitable C4 to C8 alkyl or hydroxyalkyl acrylates may 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.

[0034] 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.

[0035] The additional monomers are preferably present in a concentration of less than 20 mole percent, preferably less than 15 mole percent, and more preferably less than 10% of the total monomers present in the quaternized acrylic.

[0036] 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.

[0037] 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.

[0038] Cationic polyvinyl alcohol: The cationic polymer can include, and preferably consists of, cationic polyvinyl alcohol.

[0039] The cationic polyvinyl alcohol can have a weight average molecular mass of the starting polyvinyl alcohol of 10 to 300 kDa, preferably 50 to 250 kDa, and more preferably 100 to 220 kDa, as measured by aqueous gel permeation chromatography (GPC) with light scattering detection (SEC-MALLS).

[0040] Cationic polyvinyl alcohols can be characterized by their cationic charge density, typically expressed as milliequivalents of charge per gram (mEq / g). The cationic polyvinyl alcohols of the present disclosure can be characterized by a cationic charge density (or "CCD") ranging from 0.05 mEq / g to 5.0 mEq / g, preferably from 0.1 mEq / g to 2.5 mEq / g, and more preferably from 0.2 mEq / g to 1.0 mEq / g.

[0041] Methods for determining the degree of polymerization (number average (DPn) and weight average (DPw)), degree of substitution, and cationic charge density are known.

[0042] If additional monomers are present, preferably there are less than 5%, more preferably less than 1%, and most preferably there are no anionically charged monomers. The monomers may be present as blocks, randomly distributed, or as a mixture of block units and randomly distributed units. The hydrophilic cationic polyvinyl alcohol may contain other residual subunits, such as from initiators or other end caps.

[0043] Cationic polyvinyl alcohol is a. Formula (I):

[0044] [ka] (In the formula, a is less than 0.5, more preferably less than 0.1, and most preferably 0; b is 0.1 to 20, preferably 0.5 to 15, and more preferably 1.0 to 10.0; c is 40 to 98, preferably 65 to 95, more preferably 75 to 85; d is 1.0 to 25, preferably 3.0 to 20, more preferably 8.0 to 15; a, b, c, and d are the average mole percentages of monomers present such that a+b+c+d sums to at least 90; e is, on a number average, 3.0 to 18, preferably 3.0 to 15, more preferably 5.0 to 12; f is a number average of 2.0 to 5.0, preferably 2.0 to 4.0, and more preferably 3.0; Rx is C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; Ry is C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; Rz is H or C1-C3 alkyl, preferably C1-C3 alkyl, more preferably C1 alkyl, even more preferably methyl; b.Formula (II):

[0045] [ka] (In the formula, n is 0.1 to 10, preferably 0.5 to 5.0, and more preferably 1.0 to 3.0; o is 40 to 98, preferably 65 to 95, more preferably 75 to 92, p is 1.0 to 25, preferably 3.0 to 20, more preferably 5.0 to 15, m, n, o, and p are the average mole percentages of monomers present such that m+n+o+p sums to at least 90; r is a number average of 2.0 to 5.0, preferably 2.0 to 4.0, and more preferably 3.0; R s is C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; R t is C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; R uis H or C1-C3 alkyl, preferably C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; c.Formula (III):

[0046] [ka] (In the formula, a is 0.5 to 5.0, preferably 1.0 to 4.0, and more preferably 2.0 to 3.0; b is 0.5 to 20, preferably 2.0 to 10, more preferably 4.0 to 6.0; c is 40 to 98, preferably 65 to 95, more preferably 75 to 85; d is 1.0 to 25, preferably 3.0 to 20, more preferably 8.0 to 15; a, b, c, and d are the average mole percentages of monomers present such that a+b+c+d sums to at least 90; e is, on a number average, 3.0 to 18, preferably 3.0 to 15, more preferably 5.0 to 12; f is a number average of 2.0 to 5.0, preferably 2.0 to 4.0, and more preferably 3.0; Rx is C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; Ry is C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; Rz is H or C1-C3 alkyl, preferably C1-C3 alkyl, more preferably C1 alkyl, and even more preferably methyl; d.Formula (IV):

[0047] [ka] (In the formula, m is 0.5 to 5.0, preferably 1.0 to 4.0, and more preferably 2.0 to 3.0; n is 0.1 to 10, preferably 0.5 to 5.0, and more preferably 1.0 to 3.0; o is 40 to 98, preferably 65 to 95, more preferably 75 to 92, p is 1.0 to 25, preferably 3.0 to 20, more preferably 5.0 to 15, m, n, o, and p are the average mole percentages of monomers present such that m+n+o+p sums to at least 90; q is, on a number average, 3.0 to 18, preferably 3.0 to 15, more preferably 5.0 to 12; r is a number average of 2.0 to 5.0, preferably 2.0 to 4.0, and more preferably 3.0; R s is C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; R t is C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; R u is H or C1-C3 alkyl, preferably C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; e. and mixtures thereof.

[0048] The cationic polyvinyl alcohol, particularly the cationic polyvinyl alcohol of formula (I) or (II), may contain an average of less than 1.0 mole percent hydrophobic monomers, such as uncharged alkyl side chains having at least 3 carbon atoms. Alternatively, the cationic polyvinyl alcohol may be hydrophobically modified, such as the cationic polyvinyl alcohols of formulas (III) and (IV).

[0049] Hydrophobically modified polymers are water-soluble polymers containing a small amount of hydrophobic repeating units directly linked to the polymer backbone. The hydrophobic repeating units can be introduced into the polymer via polymerization using hydrophobic monomers and / or via post-polymerization modification. In aqueous solutions, the hydrophobic groups of such polymers tend to associate, minimizing their exposure to the aqueous medium, in a manner similar to the formation of micelles in surfactants above their critical micelle concentration. Such association results in an increase in hydrodynamic size, which can affect solution properties such as viscosity and deposition behavior. Suitable hydrophobic monomer groups can include, for example, a mixture of uncharged oligomeric condensates of nonylphenol, the major component of which is a bis-nonylphenyl moiety. A more preferred hydrophobic material is an uncharged alkyl chain. For example, hydrophobically modified cationic polyvinyl alcohol can include monomers containing uncharged alkyl chains with an average of at least 3 carbon atoms, preferably 3 to 18 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 5 to 10 carbon atoms.

[0050] For cationically modified polyvinyl alcohols having formula (I), a is the average mole percent of hydrophobic monomers, b is the average mole percent of substituted ammonium, and therefore cationic, monomers, c is the average mole percent of vinyl alcohol monomers, and d is the average mole percent of vinyl acetate monomers. a+b+c+d, excluding residues such as initiator molecules, totals at least 90, preferably at least 98, and more preferably at least 100. If additional monomers are present, preferably less than 5%, more preferably less than 1%, of anionically charged monomers are present, and most preferably no anionically charged monomers are present. The monomers may be present as blocks, randomly distributed, or as a mixture of block units and randomly distributed units.

[0051] When the hydrophobic monomer a is present, e is 3.0 to 18, preferably 3.0 to 15, and more preferably 5.0 to 12 on a number average.

[0052] The substituted ammonium groups are bonded to the polymer backbone via connecting alkyl chains. Therefore, f is a number average of 2.0 to 5.0, preferably 2.0 to 4.0, and more preferably 3.0. It has been found that by synthesizing a polymer having the above f value, steric hindrance and charge repulsion, which can limit the reaction between the cationic acetal and the polymer, can be avoided.

[0053] Rx and Ry are independently C1-C3 alkyl, preferably C1-C3 alkyl, preferably C1 alkyl, more preferably methyl. Rz is H or C1-C3 alkyl, preferably C1-C3 alkyl, preferably C1 alkyl, more preferably methyl. The substituted ammonium group can be a "tertiary ammonium group" where Rz is H, or a "quaternary ammonium" group where Rz is C1-C3 alkyl.

[0054] Cationic polyvinyl alcohol polymers according to formula (I) can be made by polymerizing vinyl acetate monomers, followed by (partial) substitution of the acetate groups with hydroxyl groups by hydrolysis to give polyvinyl alcohol (PVA), which can then be post-modified by condensation reaction with a cationic acetal and, optionally, a small amount of a hydrophobic aldehyde, such as octanal or decanal, to give the cationic polyvinyl alcohol polymer.

[0055] During this condensation reaction, some of the polymer's hydroxyl groups are converted to acetal groups. Thus, cationic polyvinyl alcohol polymers contain polyvinyl alcohol and cationic polyvinyl acetal subunits, and optionally contain small amounts of hydrophobic polyvinyl acetal subunits, or consist of such subunits in the case of a 100% hydrolyzed polyvinyl alcohol starting polymer before acetalization. When starting from a partially hydrolyzed polyvinyl alcohol polymer (less than 100% hydrolysis), the cationic polyvinyl alcohol polymer further contains polyvinyl acetate subunits. These polyvinyl alcohol, cationic polyvinyl acetal, and optional polyvinyl acetate and / or hydrophobic polyvinyl acetal subunits can be organized in blocks or randomly, or as a mixture of block units and randomly distributed.

[0056] For cationically modified polyvinyl alcohols having formula (II), the substituted ammonium groups are attached to the polymer backbone via connecting alkyl chains. Therefore, r is a number average of 2.0 to 5.0, preferably 2.0 to 4.0, and more preferably 3.0. It has been found that by synthesizing polymers having the above r values, steric hindrance and charge repulsion, which can limit the reaction between the cationic acetal and the polymer, can be avoided.

[0057] Suitable cationic polyvinyl alcohol polymers according to formula (II) include cationically modified Poval® "CM" polyvinyl alcohols, such as Poval® 23-88CM, supplied by Kuraray.

[0058] For the hydrophobically modified cationic polyvinyl alcohol having formula (III), a is the average mole percent of hydrophobic monomers, b is the average mole percent of substituted ammonium, and therefore cationic, monomers, c is the average mole percent of vinyl alcohol monomers, and d is the average mole percent of vinyl acetate monomers. a + b + c + d, excluding residues such as initiator molecules, totals at least 90, preferably at least 98, and more preferably at least 100. If additional monomers are present, preferably less than 5%, more preferably less than 1%, of anionically charged monomers are present, and most preferably no anionically charged monomers are present. The monomers may be present as blocks, randomly distributed, or as a mixture of block units and randomly distributed units.

[0059] e is 3.0 to 18, preferably 3.0 to 15, and more preferably 5.0 to 12 on a number average.

[0060] The substituted ammonium groups are bonded to the polymer backbone via connecting alkyl chains. Therefore, f is a number average of 2.0 to 5.0, preferably 2.0 to 4.0, and more preferably 3.0. It has been found that by synthesizing a polymer having the above f value, steric hindrance and charge repulsion, which can limit the reaction between the cationic acetal and the polymer, can be avoided.

[0061] Rx and Ry are independently C1-C3 alkyl, preferably C1-C3 alkyl, preferably C1 alkyl, more preferably methyl. Rz is H or C1-C3 alkyl, preferably C1-C3 alkyl, preferably C1 alkyl, more preferably methyl. The substituted ammonium group can be a "tertiary ammonium group" where Rz is H, or a "quaternary ammonium" group where Rz is C1-C3 alkyl.

[0062] The hydrophobically modified cationic polyvinyl alcohol polymer according to formula (III) can be made by polymerizing vinyl acetate monomers, followed by (partial) substitution of the acetate groups with hydroxyl groups by hydrolysis to give polyvinyl alcohol (PVA), which can then be post-modified by a condensation reaction with a hydrophobic aldehyde, such as octanal or decanal, and a cationic acetal to give the hydrophobically modified cationic polyvinyl alcohol polymer.

[0063] During this condensation reaction, some of the polymer's hydroxyl groups are converted to acetal groups. Thus, the hydrophobically modified cationic polyvinyl alcohol polymer comprises polyvinyl alcohol and hydrophobic and cationic polyvinyl acetal subunits, or consists of such subunits in the case of a 100% hydrolyzed polyvinyl alcohol starting polymer before acetalization. When starting from a partially hydrolyzed polyvinyl alcohol polymer (less than 100% hydrolysis), the hydrophobically modified cationic polyvinyl alcohol polymer further comprises polyvinyl acetate subunits. These polyvinyl alcohol, hydrophobic polyvinyl acetal, cationic polyvinyl acetal, and optional polyvinyl acetate subunits can be organized in blocks or randomly, or as a mixture of block units and randomly distributed.

[0064] For the hydrophobically modified cationic polyvinyl alcohol having formula (IV), the substituted ammonium groups are attached to the polymer backbone via a connecting alkyl chain. Therefore, r is a number average of 2.0 to 5.0, preferably 2.0 to 4.0, and more preferably 3.0. It has been found that by synthesizing a polymer having the above r value, steric hindrance and charge repulsion, which can limit the reaction between the cationic acetal and the polymer, can be avoided.

[0065] Hydrophobically modified polyvinyl alcohols according to formula (IV) can be formed by hydrophobically modifying commercially available cationic polyvinyl alcohol polymers, such as the cationically modified Poval® "CM" polyvinyl alcohols supplied by Kuraray (e.g., Poval® 23-88CM). Hydrophobically modifying can be accomplished via post-modification by condensation reaction with a hydrophobic aldehyde, such as octanal or decanal.

[0066] Alternatively, suitable hydrophobically modified cationic polyvinyl alcohols can also be prepared as described in Wang and Ye (J. Polym. Int. 2012; 61 pp571-580) and Ma et al. (J. Appl. Polym. Sci. 2016, 133, 43888).

[0067] Cationic polysaccharides: Suitable cationic polysaccharides contain cationic nitrogen-containing moieties, such as quaternary ammonium, or cationic protonated amino moieties. The average molecular weight of the cationic deposition polymer is preferably from about 5,000 to about 10,000,000, preferably at least about 100,000, more preferably at least about 200,000, but preferably not more than about 1,500,000. The polymer may have a cationic charge density in the range of from about 0.2 meq / g to about 5 meq / g, preferably at least about 0.4 meq / g, more preferably at least about 0.6 meq / g, at the pH of intended use of the dishwashing liquid formulation.

[0068] Specific examples of water-soluble cationic polymers include cationic polysaccharides such as cationic cellulose derivatives, cationic starches, and cationic guar gum derivatives.

[0069] Suitable cationic polysaccharides include cationic cellulose polymers and / or cationic guar gum derivatives, such as guar hydroxypropyltrimonium chloride, e.g., the Jaguar series from Rhodia and the N-Hance polymer series available from Aqualon, and / or salts of hydroxyethyl cellulose reacted with trimethylammonium substituted epoxides (referred to in the industry (CTFA) as Polyquaternium-10), e.g., UCARE LR400 from Dow Amerchol.

[0070] 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.

[0071] Anionic surfactants The surfactant system includes an anionic surfactant. The surfactant system may comprise at least 40% by weight of the anionic surfactant, preferably 50% to 80% by weight, more preferably 55% to 75% by weight of the surfactant system. The surfactant system preferably does not contain fatty acids or salts thereof, since such fatty acids inhibit foam generation.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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 soil, while foam persistence in the presence of particulate soil is not impaired.

[0076] 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.

[0077] 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. When alkoxylated, ethoxylation is preferred.

[0078] 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.

[0079] The preferred alkyl alkoxy sulfates are alkyl ethoxy sulfates.

[0080] 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%.

[0081] 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 having improved low-temperature stability. Higher surfactant branching also results in faster initial foam generation, but typically results in lower foam persistence. The weight average branching described herein has been found to provide improved low temperature stability, initial foam generation, and foam persistence.

[0082] The weight average degree of branching of the anionic surfactant mixture is calculated according to the following formula: Weight average branching degree (%) = [(x1 * Wt% of branched chain alcohol 1 in alcohol 1 + x2 * (wt% of branched-chain alcohol 2 in alcohol 2 + ....) / (x1 + x2 + ....)] × 100 can be calculated using where x1, x2, ... are the weights (in grams) of each alcohol in the total alcohol mixture used as a starting material before (alkoxylation and) sulfation to produce the alkyl(alkoxy) sulfate anionic surfactant. The weight average branching calculation includes the weight of the alkyl alcohol used to form the unbranched alkyl sulfate anionic surfactant.

[0083] 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.

[0084] Suitable counterions include alkali metal cations, alkaline earth metal cations, alkanolammonium, or ammonium or substituted ammonium, preferably sodium.

[0085] 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.

[0086] 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.

[0087] 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 cracking 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.

[0088] 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 (e.g., Hostapur SAS60 from Clariant).

[0089] 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.

[0090] 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.

[0091] The weight ratio of the anionic surfactant to the co-surfactant may be from 1:1 to 8:1, preferably from 2:1 to 5:1, more preferably from 2.5:1 to 4:1.

[0092] 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.

[0093] The co-surfactant is preferably an amphoteric surfactant, more preferably an amine oxide surfactant.

[0094] 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.

[0095] 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.

[0096] 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 can be 10 to 24, preferably 12 to 20, and more preferably 10 to 16 carbon atoms. The number of carbon atoms in one alkyl moiety (n1) is preferably the same as or similar to the number of carbon atoms in one alkyl branch (n2), thereby making the one alkyl moiety and the one alkyl branch symmetrical. As used herein, "symmetrical" means that in at least 50% by weight, more preferably at least 75% to 100% by weight of the mid-branched amine oxides used herein, |n1-n2| is 5 or less, preferably 4, and most preferably 0 to 4 carbon atoms. The amine oxide further comprises two moieties independently selected from a C1-3 alkyl, a C1-3 hydroxyalkyl, or a polyethylene oxide group containing an average of about 1 to about 3 ethylene oxide groups. Preferably, these two moieties are selected from a C1-3 alkyl, and more preferably, both are selected as a C1 alkyl.

[0097] Alternatively, the amine oxide surfactant may be a mixture of amine oxides, including a mixture of low-cut and mid-cut amine oxides. Thus, the amine oxide of the composition of the present invention may be: a) about 10% to about 45% by weight of the amine oxide of a low cut amine oxide of the formula R1R2R3AO, wherein R1 and R2 are independently selected from hydrogen, C1-C4 alkyl, or mixtures thereof, and R3 is selected from C10 alkyl and mixtures thereof; b) 55% to 90% by weight of the amine oxide, a mid-cut amine oxide of formula R4R5R6AO, where R4 and R5 are independently selected from hydrogen, C1-C4 alkyl, or a mixture thereof, and R6 is selected from C12-C16 alkyl, or a mixture thereof.

[0098] 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.

[0099] Preferably, the amine oxide comprises less than about 5% by weight of the amine oxide, more preferably less than 3% by weight of the amine oxide of formula R7R8R9AO, where R7 and R8 are selected from hydrogen, C1-C4 alkyl, and mixtures thereof, and R9 is selected from C8 alkyl and mixtures thereof. By limiting the amount of amine oxide of formula R7R8R9AO, both physical stability and foam persistence are improved.

[0100] Suitable zwitterionic surfactants include betaine surfactants, including alkyl betaines, alkylamido betaines, amidoazolinium betaines, sulfobetaines (INCI sultaines), and phosphobetaines, preferably represented by formula (I): R 1 -[CO-X(CH2) n ] x -N + (R 2 )(R3)-(CH2) m -[CH(OH)-CH2] y -Y - Fulfilling In formula (I), R1 is selected from the group consisting of saturated or unsaturated C6-22 alkyl residues, preferably C8-18 alkyl residues, more preferably saturated C10-16 alkyl residues, and most preferably saturated C12-14 alkyl residues; X is selected from the group consisting of NH, NR4 (wherein R4 is a C1-4 alkyl residue), O, and S; n is an integer of 1 to 10, preferably 2 to 5, and more preferably 3; x is 0 or 1, preferably 1; R2 and R3 are independently selected from the group consisting of C1-4 alkyl residues, substituted hydroxy such as hydroxyethyl, and mixtures thereof, preferably both R2 and R3 are methyl; m is an integer from 1 to 4, preferably 1, 2, or 3; y is 0 or 1, Y is selected from the group consisting of COO, SO3, OPO(OR5)O, or P(O)(OR5)O, where R5 is H or a C1-4 alkyl residue.

[0101] Preferred betaines are the alkyl betaines of formula (Ia), the alkylamidopropyl betaines of formula (Ib), the sulfobetaines of formula (Ic) and the amidosulfobetaines of formula (Id): R 1 -N + (CH3)2-CH2COO - (IIa) R 1 -CO-NH-(CH2)3-N + (CH3)2-CH2COO - (IIb) R 1 -N + (CH3)2-CH2CH(OH)CH2SO3 - (IIc) R 1 -CO-NH-(CH2)3-N + (CH3)2-CH2CH(OH)CH2SO3 - (IId) wherein R1 has the same meaning as in formula (I). Particularly preferred are carbobetaines of formula (Ia) and (Ib) [i.e., in formula (I), Y- is COO-], and more preferred are alkylamidobetaines of formula (Ib).

[0102] 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.

[0103] Nonionic surfactants: The surfactant system can further comprise from 0.5% to 10.0% by weight of the composition of an alkoxylated alcohol nonionic surfactant. The surfactant system preferably comprises from 1.0% to 7.5% by weight of the composition of an alkoxylated alcohol nonionic surfactant.

[0104] The surfactant system may comprise an anionic surfactant and an alkoxylated alcohol nonionic surfactant in a weight ratio of less than 25:1, preferably from 20:1 to 1:1, more preferably from 10:1 to 2:1.

[0105] The surfactant system of the liquid hand dishwashing detergent composition may comprise at least 2.5%, preferably from 5% to 35%, more preferably from 10% to 30%, by weight of the surfactant system of an alkoxylated alcohol nonionic surfactant.

[0106] 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.

[0107] The surfactant system may include an additional non-ionic surfactant, such as an alkyl polyglucoside non-ionic surfactant.

[0108] The combination of alkyl polyglucosides with anionic surfactants, particularly alkyl sulfate anionic surfactants, has been found to improve polymeric grease removal, foam persistence, reduced viscosity change with surfactant and / or system changes, and more persistent Newtonian rheology.

[0109] 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.

[0110] 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 short-chain alkyl polyglucoside surfactant to 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 blends of short-chain alkyl polyglucoside surfactant and long-chain alkyl polyglucoside surfactant have been found to result in faster dissolution of the detergent solution in water and improved initial foaming combined with improved foam stability.

[0111] 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.

[0112] 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 lathering properties than other nonionic surfactants, such as alkyl ethoxylated alcohols.

[0113] 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.

[0114] In even more preferred compositions, the composition does not contain any additional nonionic surfactants.

[0115] 1,2-alkanediols The liquid hand dishwashing detergent composition contains a 1,2-alkanediol. The liquid hand dishwashing detergent composition preferably contains 0.1 to 10% by weight, preferably 0.25 to 5% by weight, more preferably 0.5 to 2% by weight of the 1,2-alkanediol. The 1,2-alkanediol useful in the present invention contains 4 to 14, more preferably 6 to 12, and most preferably 8 to 10 carbon atoms.

[0116] The alkyl chain of the 1,2-alkanediol is preferably a linear alkyl chain. Preferably, the 1,2-alkanediol contains an even number of carbon atoms, and more preferably, the alkyl chain is derived from a natural source such as a fatty acid. Suitable 1,2-alkanediols include linear alkyl chain 1,2-hexanediol, 1,2-hexanediol, 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-tetradecanediol, or a mixture thereof, preferably 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, or a mixture thereof, and most preferably 1,2-octanediol, 1,2-decanediol, or a mixture thereof.

[0117] The 1,2-alkanediols used in the compositions of the present invention have been found to improve the water sheeting and therefore drying properties of the cationic polymers of the present invention. When the 1,2-alkanediols are formulated in the absence of the cationic polymer, no improvement in water sheeting is observed. The 1,2-alkanediols have also been found to improve the foaming and detergency of the detergent composition, while, when they contain more than 6 carbon atoms, they also increase the viscosity of the liquid detergent composition.

[0118] In contrast, 1,2-alkanediols containing fewer than 6 carbon atoms, and especially fewer than 4 carbon atoms, have been shown to reduce the viscosity of liquid hand dishwashing compositions, and long-chain 1,2-alkanediols containing more than 14 carbon atoms have been shown to impair the physical stability of the resulting liquid detergent compositions and to be difficult to dissolve.

[0119] At least 50% by weight, preferably at least 80% by weight, more preferably at least 98% by weight of the 1,2-alkanediols present in the composition may be medium chain 1,2-alkanediols, i.e., C8 to C10 1,2-alkanediols. Even more preferably, the liquid composition does not contain any 1,2-alkanediols containing alkyl chains with less than 4 or more than 14 carbon atoms.

[0120] The liquid hand dishwashing composition may comprise a weight ratio of 1,2-alkanediol to surfactant system of from 1:60 to 1:1, preferably from 1:40 to 1:5, more preferably from 1:30 to 1:10.

[0121] Suitable 1,2-alkanediols include the R-isomer, the S-isomer, or a mixture thereof.

[0122] Suitable 1,2-alkanediol products are available from Symrise or Sigma Aldrich.

[0123] 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.

[0124] Amphiphilic alkoxylated polyalkyleneimines: The compositions of the present invention may further comprise 0.05% to 2%, preferably 0.07% to 1% by weight of the total composition, of an amphiphilic polymer. Suitable amphiphilic polymers may be selected from the group consisting of amphiphilic alkoxylated polyalkyleneimines and mixtures thereof. Amphiphilic alkoxylated polyalkyleneimine polymers have been found to reduce gel formation on hard surfaces being cleaned when the liquid composition is added directly to a cleaning implement (such as a sponge) prior to cleaning and then contacted with a heavily oily surface, particularly when the cleaning implement contains little to no water, for example, when a lightly pre-moistened sponge is used.

[0125] Preferred amphiphilic alkoxylated polyethyleneimine polymers have the formula (I):

[0126] [ka] The polyethyleneimine backbone has a weight-average molecular weight of 600, n in formula (I) is 10 on average, m in formula (I) is 7 on average, 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) can be 0% to 22% of the nitrogen atoms of the polyethyleneimine backbone. The molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer is preferably 10,000 to 15,000 Da.

[0127] 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 permanent degree of quaternization of formula (I) can 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.

[0128] Amphiphilic alkoxylated polyethyleneimine polymers can be made by the methods described in more detail in WO 2007 / 135645.

[0129] Alternatively, the composition may be free of amphiphilic polymers.

[0130] cyclic polyamines The composition may include a cyclic polyamine having an amine functionality to aid in cleaning. The composition of the present invention preferably comprises 0.1 to 3% by weight of the total composition of cyclic polyamine, more preferably 0.2 to 2%, especially 0.5 to 1%.

[0131] Cyclic polyamines have at least two primary amine functional groups. The primary amine can be located at any position within the cyclic amine, but it has been found that better performance can be obtained from the viewpoint of grease cleaning when the primary amine is located at the 1st and 3rd positions. It has also been found that cyclic amines in which one of the substituents is -CH3 and the other is H provide improved grease cleaning performance.

[0132] 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 foam and grease cleaning profile throughout the dishwashing process.

[0133] Suitable cyclic polyamines may be supplied by BASF under the trade name Baxxodur, with Baxxodur ECX-210 being particularly preferred.

[0134] A combination of cyclic polyamine and magnesium sulfate is particularly preferred. Thus, the composition may further comprise magnesium sulfate at a concentration of 0.001% to 2.0% by weight of the composition, preferably 0.005% to 1.0% by weight, and more preferably 0.01% to 0.5% by weight.

[0135] triblock copolymer The compositions of the present invention may contain a triblock copolymer. The triblock copolymer may be present at a concentration of 1% to 20% by weight, preferably 3% to 15% by weight, 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.

[0136] 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).

[0137] 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 phrase "block copolymer" is synonymous with this definition of "block polymer."

[0138] Triblock copolymers according to formula (I) having specific EO / PO / EO configurations and respective homopolymer lengths have been found to enhance the foam persistence performance of liquid hand dishwashing detergent compositions in the presence of greasy soils and / or foam consistency throughout dilution in the cleaning process.

[0139] 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).

[0140] Preferred triblock copolymers are readily biodegradable under aerobic conditions.

[0141] 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.

[0142] The composition 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.

[0143] 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.

[0144] 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, with alcohols, glycols, and mixtures thereof being preferred. Ethanol is a preferred alcohol. Polyalkylene glycols, particularly polypropylene glycols, are preferred glycols, with polypropylene glycols having a weight-average molecular weight of 750 Da to 1,400 Da being particularly preferred.

[0145] pH adjusters and buffers The composition can include pH adjusters and buffering means.Suitable acidic pH adjusters include carboxylic acids, such as citric acid, hydrochloric acid, and combinations thereof.Suitable alkaline pH adjusters include hydroxides such as sodium hydroxide or potassium hydroxide, alkanolamines such as monoethanolamine or triethanolamine, carbonates such as sodium carbonate, bicarbonates, sesquicarbonates, and combinations thereof.Suitable buffering means can include any suitable combination of weak acid and its conjugate base.

[0146] pH adjusters and buffering means may be added at levels necessary to achieve the desired pH.

[0147] Supplementary ingredients The compositions may optionally contain numerous other adjunct ingredients such as builders (preferably citrate salts), chelating agents, conditioning polymers, other cleansing polymers, surface modifying polymers, structuring agents, emollients, moisturizers, 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, and viscosity modifiers (e.g., salts such as NaCl, and other mono-, di-, and trivalent salts).

[0148] Packaged Products The hand dishwashing detergent composition can be packaged in a container, typically a plastic container. Suitable containers include an orifice. Typically, the container has a cap, and the orifice is typically provided on the cap. The cap can have an inlet, and the orifice is at the outlet of the inlet. The inlet can have a length of 0.5 mm to 10 mm.

[0149] 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).

[0150] The container can typically contain 200 mL to 5,000 mL, preferably 350 mL to 2,000 mL, and more preferably 400 mL to 1,000 mL of the liquid hand dishwashing detergent composition.

[0151] 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.

[0152] Optionally, the dishware may be rinsed. As used herein, "rinsing" refers to contacting the dishware washed by the method of the present invention with a substantial amount of a suitable solvent, typically water. "Substantial amount" typically refers to about 1 to about 20 L or under running water.

[0153] 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. The 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.

[0154] Alternatively, the composition herein can be applied in its undiluted form to the utensils to be treated. "In its undiluted form," as used herein, means that the composition is applied directly to the surface to be treated or to a cleaning device or implement, such as a brush, sponge, nonwoven material, or woven material, without 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 of the composition and water in a ratio ranging from 50:50 to 100:0, preferably 70:30 to 100:0, more preferably 80:20 to 100:0, and even more preferably 90:10 to 100:0, depending on the user's habits and cleaning tasks.

[0155] method A) Viscosity Viscosity is measured using a controlled stress rheometer (such as Thermo Scientific's HAAKE MARS or equivalent) using a 60 mm 1° cone and a 52 micrometer gap size at 20° C. After 2 minutes of temperature equilibration, the sample is heated for 10 seconds. -1 The reported viscosity of the liquid hand dishwashing detergent composition is determined by shearing the average shear stress from 15 seconds to 30 seconds at 20°C for 10 seconds. -1 is defined as the shear rate at which the shear force is applied.

[0156] B) 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

[0157] The true number average molecular weight M of the polymern 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.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] C)Drying speed: Drying rate is related to the degree of water sheeting: the better the water sheeting, the less water is retained on the wet item.

[0163] Water sheeting is assessed by scoring the amount of water sheeting observed on black glossy plates made of tempered glass (BACKIG 25cm x 25cm, supplied by IKEA) when they are washed with the hand dish detergent test composition and then left standing vertically on a drying rack. More specifically, A sponge (Schuursponsen merk Delhaize-Easy grip, dimensions: 7 cm x 9.5 cm) is wetted evenly with water equivalent to 2.67 mmol / l CaCO3 hardness at 35°C by saturating the sponge with water and then squeezing it by hand until no further water is squeezed out.

[0164] 1 mL of the hand dishwashing composition is distributed evenly on the sponge.

[0165] The sponge is manually squeezed with one hand four times with full force onto the black glossy plate to create bubbles, and then the plate is washed in ten circular clockwise motions covering the edges and central part of the plate so that the entire plate is treated with bubbles.

[0166] The plate is then rinsed for 15 or 30 seconds under running water (35°C water with a water hardness of 2.67 mmol / L CaCO3 equivalent) at a flow rate sufficient to allow complete removal of air bubbles and complete coverage of the plate with water, after which the plate is placed vertically on a drying rack under standard room conditions (20 + / - 1°C). The water running down the plate is then visually graded on a scale of 0 to 100% to indicate the amount of water still visibly covering the plate after the first 60 seconds. 0% corresponds to water remaining on the entire plate, 50% indicates that half of the plate is covered with a water film, and 100% indicates that no water film is visible. [Example]

[0167] The comparative compositions in Table 1 and the inventive compositions in Table 2 were prepared by mixing the individual components in a batch-type process. All percentages are weight percent based on the active level.

[0168] Comparative Example A contained no 1,2-alkanediol or cationic polymer. Comparative Composition B in Table 1 contained a cationic polymer (quaternized acrylic copolymer) but no 1,2-alkanediol. Comparative Compositions C-G in Table 1 contained a 1,2-alkanediol but no cationic polymer. Inventive Compositions 1-4 in Table 2 contained both a 1,2-alkanediol and a cationic polymer. The cationic polymer used was a quaternized acrylic copolymer sold by BASF under the trade name Polyquart® 149A.

[0169] [Table 1] * For comparison 1 Anionic surfactant, alkyl ethoxylated sulfate, 30% branched 2 A non-ionic surfactant supplied by Shell and sold under the trade name Neodol 91-8® 3 Alkoxylated 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. 4 A cationic polymer sold under the trade name Polyquart® 149A supplied by BASF.

[0170] [Table 2]

[0171] In Table 1, the drying advantage of the cationic polymer (quaternized acrylic copolymer) can be seen by comparing the results of Comparative Example B with those of Comparative Example A. It can be seen from the results of Comparative Examples C-G that compositions containing 1,2-alkanediol but no cationic polymer do not have a significant drying advantage.

[0172] From Table 2 it can be seen that the 1,2-alkanediol itself does not show evidence of improving drying when used alone, but the combination of the same cationic polymer with the 1,2-alkanediol results in further improvement in drying rate due to improved sheeting.

[0173] The comparative compositions and compositions of the present invention in Table 3 were prepared by mixing the individual components in a batch-type process. All percentages are weight percent based on the active level.

[0174] Comparative composition H in Table 3 contained hydroxyethyl acrylate / diallyldimethylammonium chloride cationic copolymer (a quaternized acrylic copolymer sold under the trade name Mirapol® Surf S Fast Dry) but no 1,2-alkanediol. Inventive compositions 6 and 7 contained the same cationic polymer in combination with 1,2-octanediol and 1,2-decanediol, respectively.

[0175] [Table 3] 5 Hydroxyethyl acrylate / diallyldimethylammonium chloride cationic copolymer sold under the trade name Mirapol® Surf S Fast Dry, supplied by Solvay

[0176] From Table 3 it can be seen that drying improvements are also present when using alternative quaternized acrylic copolymers in combination with 1,2-alkanediols.

[0177] The comparative compositions in Table 4 and compositions of the present invention were prepared by mixing the individual components in a batch-type process. All percentages are weight percent based on the active level.

[0178] Comparative Composition I in Table 4 contained a cationic polymer (cationic polyvinyl alcohol, Poval® 23-88CM) but no 1,2-alkanediol. Inventive Composition 8 contained 1,2-octanediol in combination with the same cationic polymer.

[0179] [Table 4] 6 A cationic polymer sold under the trade name Poval® 23-88CM supplied by Kuraray.

[0180] From Table 4 it can be seen that there is also an improvement in drying when cationic polyvinyl alcohol is used in combination with a 1,2-alkanediol as the cationic polymer.

[0181] The comparative compositions and compositions of the present invention in Table 5 were prepared by mixing the individual components in a batch-type process. All percentages are weight percent based on the active level.

[0182] Comparative Example J in Table 5 had the same composition as Comparative Composition A above, but without the cationic polymer or 1,2-alkanediol. Comparative Example K in Table 5 contained a cationic polysaccharide (Polyquaternium 10, quaternized hydroxyethyl cellulose) but no 1,2-alkanediol. Inventive Example 9 contained both a cationic polysaccharide and a 1,2-alkanediol (1,2-decanediol).

[0183] [Table 5] 7 A salt of hydroxyethyl cellulose reacted with a trimethylammonium-substituted epoxide (Polyquaternium 10 sold under the trade name UCare® 400, supplied by DOW)

[0184] From Table 5 it can be seen that there is also an improvement in drying when a cationic polysaccharide is used in combination with a 1,2-alkanediol as the cationic polymer.

[0185] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

Claims

1. 1. A liquid hand dishwashing detergent composition comprising from 5.0% to 50%, by weight of the liquid hand dishwashing detergent composition, of a surfactant system, the detergent composition comprising: a) a cationic polymer selected from the group consisting of quaternized acrylic copolymers, cationic polyvinyl alcohols, cationic polysaccharides, and mixtures thereof; b) a 1,2-alkanediol, wherein the alkyl chain of the 1,2-alkanediol contains from 4 to 14 carbon atoms.

2. 2. The composition of claim 1, wherein the composition 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 said cationic polymer.

3. 3. The composition of claim 1, wherein the cationic polymer is selected from the group consisting of quaternized acrylic copolymers, cationic polyvinyl alcohols, and mixtures thereof, preferably quaternized acrylic copolymers.

4. The cationic polymer comprises, preferably consists of, a quaternized acrylic copolymer, preferably the quaternized acrylic copolymer is a) Below: CH ２ =CR １ -Y-N ＋ R ２ R ３ R ４ X － (a) (In the formula, Each R １ is independently selected from hydrogen or methyl, preferably methyl; Each R ２ are independently selected from C1-C4 alkyl(ene), preferably CH ２ CH=CH ２ or methyl, more preferably methyl; Each R ３ , R ４ is independently selected from C1-C4 alkyl, preferably C1-C3 alkyl, more preferably methyl; Each Y is independently CO-NR ５ - (CH ２ ) ｎ , CO—O—(CH ２ ) ｎ , or (CH ２ ) ｎ and preferably CO—NR ５ - (CH ２ ) ｎ or (CH ２ ) ｎ , more preferably CO-NR ５ - (CH ２ ) ｎ is a linking group which is During the ceremony, Each R ５ is 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 － is) and a cationic monomer unit selected from b) an ethylenically unsaturated monomer selected from the group consisting of a C3 to C8 ethylenically unsaturated acid and / or its salt, a C4 to C8 alkyl acrylate, a C4 to C8 hydroxyalkyl acrylate, and mixtures thereof, preferably a combination of a C3 to C8 ethylenically unsaturated acid and a C4 to C8 alkyl acrylate, more preferably a combination of acrylic acid and ethyl acrylate.

5. 5. The composition of claim 4, wherein the cationic monomer units of the quaternized acrylic copolymer are 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).

6. 6. The composition of claim 5, wherein the cationic monomer units of the quaternized acrylic copolymer comprise, and preferably consist of, methacrylamidopropyltrimethylammonium chloride (MAPTAC), and the ethylenically unsaturated monomer is a combination of a C3 to C8 ethylenically unsaturated acid and a C4 to C8 alkyl acrylate, preferably a combination of acrylic acid and ethyl acrylate.

7. The cationic polymer comprises, preferably consists of, cationic polyvinyl alcohol, and preferably the cationic polyvinyl alcohol is a. Formula (I): 【Chemistry 1】 (In the formula, a is less than 0.5, more preferably less than 0.1, and most preferably 0; b is 0.1 to 20, preferably 0.5 to 15, more preferably 1.0 to 10.0; c is 40 to 98, preferably 65 to 95, more preferably 75 to 85; d is 1.0 to 25, preferably 3.0 to 20, more preferably 8.0 to 15; a, b, c, and d are the average mole percentages of monomers present such that a+b+c+d sums to at least 90; e is, on a number average, 3.0 to 18, preferably 3.0 to 15, more preferably 5.0 to 12; f is a number average of 2.0 to 5.0, preferably 2.0 to 4.0, more preferably 3.0; Rx is C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; Ry is C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; Rz is H or C1-C3 alkyl, preferably C1-C3 alkyl, more preferably C1 alkyl, and even more preferably methyl. a cationic polyvinyl alcohol having the formula: b. Formula (II): 【Chemistry 2】 (In the formula, n is 0.1 to 10, preferably 0.5 to 5.0, more preferably 1.0 to 3.0; o is 40 to 98, preferably 65 to 95, more preferably 75 to 92; p is 1.0 to 25, preferably 3.0 to 20, more preferably 5.0 to 15; m, n, o, and p are the average mole percentages of monomers present such that m+n+o+p sums to at least 90; r is a number average of 2.0 to 5.0, preferably 2.0 to 4.0, more preferably 3.0; R ｓ is C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; R ｔ is C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; R ｕ is H or C1-C3 alkyl, preferably C1-C3 alkyl, preferably C1 alkyl, more preferably methyl a cationic polyvinyl alcohol having the formula: c. Formula (III): 【Transformation 3】 (In the formula, a is 0.5 to 5.0, preferably 1.0 to 4.0, more preferably 2.0 to 3.0; b is 0.5 to 20, preferably 2.0 to 10, more preferably 4.0 to 6.0; c is 40 to 98, preferably 65 to 95, more preferably 75 to 85; d is 1.0 to 25, preferably 3.0 to 20, more preferably 8.0 to 15; a, b, c, and d are the average mole percentages of monomers present such that a+b+c+d sums to at least 90; e is, on a number average, 3.0 to 18, preferably 3.0 to 15, more preferably 5.0 to 12; f is a number average of 2.0 to 5.0, preferably 2.0 to 4.0, more preferably 3.0; R Ｘ is C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; Ry is C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; Rz is H or C1-C3 alkyl, preferably C1-C3 alkyl, more preferably C1 alkyl, and even more preferably methyl. a hydrophobically modified cationic polyvinyl alcohol having the formula: d. Formula (IV): 【Chemistry 4】 (In the formula, m is 0.5 to 5.0, preferably 1.0 to 4.0, more preferably 2.0 to 3.0; n is 0.1 to 10, preferably 0.5 to 5.0, more preferably 1.0 to 3.0; o is 40 to 98, preferably 65 to 95, more preferably 75 to 92; p is 1.0 to 25, preferably 3.0 to 20, more preferably 5.0 to 15; m, n, o, and p are the average mole percentages of monomers present such that m+n+o+p sums to at least 90; q is, on a number average, 3.0 to 18, preferably 3.0 to 15, more preferably 5.0 to 12; r is a number average of 2.0 to 5.0, preferably 2.0 to 4.0, more preferably 3.0; R ｓ is C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; R ｔ is C1-C3 alkyl, preferably C1 alkyl, more preferably methyl; R ｕ is H or C1-C3 alkyl, preferably C1-C3 alkyl, preferably C1 alkyl, more preferably methyl a hydrophobically modified cationic polyvinyl alcohol having the formula: The composition of any one of claims 1 to 3, wherein the composition is selected from the group consisting of:

8. 8. A liquid detergent composition for hand dishwashing according to claim 7, wherein the cationic polyvinyl alcohol is characterized by a weight average molecular weight of the starting polyvinyl alcohol of 10 to 300 kDa, preferably 50 to 250 kDa, more preferably 100 to 220 kDa.

9. A composition according to any preceding claim, wherein the composition comprises from 0.25% to 5.0%, more preferably from 0.5% to 2.0% of said 1,2-alkanediol by weight of the liquid hand dishwashing detergent composition.

10. The composition according to any one of claims 1 to 9, wherein the alkyl chain of the 1,2-alkanediol is a linear alkyl chain.

11. 11. The composition of any one of claims 1 to 10, wherein the 1,2-alkanediol is selected from the group consisting of 1,2-butanediol, 1,2-hexanediol, 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-tetradecanediol, or mixtures thereof, preferably 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, and mixtures thereof, most preferably 1,2-octanediol, 1,2-decanediol, and mixtures thereof.

12. A composition according to any one of the preceding claims, wherein the composition comprises from 6.0% to 40% by weight of the total composition, preferably from 15% to 35% by weight of the surfactant system.

13. 13. A composition according to any preceding claim, wherein the surfactant system comprises at least 40%, preferably from 50% to 80%, more preferably from 55% to 75% by weight of the surfactant system of anionic surfactant.

14. 14. A composition according to any preceding claim, wherein the anionic surfactant comprises at least 70%, preferably at least 85%, more preferably 100% alkyl sulfated anionic surfactant by weight of the anionic surfactant.

15. 15. The composition of any one of claims 1 to 14, wherein the surfactant system further comprises a co-surfactant selected from the group consisting of amphoteric co-surfactants, zwitterionic co-surfactants, and mixtures thereof.

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