JP2024100713A - Liquid hand dishwashing detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid hand dishwashing detergent further improved in the drying speed of dishware after hand dishwashing.

SOLUTION: A liquid hand dishwashing detergent composition contains: a quaternized acrylic copolymer; and a surfactant system of 5.0 wt.% to 50 wt.% of the composition. The surfactant system contains: a. an anionic surfactant; and b. a co-surfactant selected from the group consisting of an amphoteric surfactant, a zwitterionic surfactant and a mixture thereof. The anionic surfactant and co-surfactant are present in a weight ratio of less than 1.5:1.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a liquid hand dishwashing detergent composition that contains a quaternized acrylic copolymer and provides further improvement in drying time of dishes after rinsing.

Manual dishwashing is a time-consuming task that is considered complete by many who do it when the dishes can be put away. Rapid drying of dishes after washing and rinsing is therefore highly desirable. Drying is particularly affected by water hardness, with water having lower hardness reducing sheeting of water from dishes. With the increasing popularity of household water softeners, there remains a great need to improve sheeting and therefore drying speed.

The use of quaternized acrylic copolymers to improve drying rates is known. Such copolymers increase the drying rate by improving sheeting of water from the dishware and improving beading of water.

However, the performance of such copolymers in liquid detergent compositions that do not contain alkoxylated alcohol nonionic surfactants has been found to be relatively poor, especially under soft water conditions. Thus, there remains a need to further improve drying times after manual washing of dishes without the need to formulate with high levels of alkoxylated alcohol nonionic surfactants.

WO 201836864 (A) relates to a hard surface treatment composition comprising a quaternized acrylic copolymer and an amphoterically modified polysaccharide, the weight ratio of the quaternized acrylic copolymer to the amphoterically modified polysaccharide being 0.75:1 to 3:1, and the quaternized acrylic copolymer being different from the amphoterically modified polysaccharide. EP 3835399 (A1) relates to a hard surface cleaning composition comprising a surfactant system, a first polymer, and a second polymer, the first polymer being polyethyleneimine, as well as the use of the composition for cleaning glass surfaces. US Patent Publication No. 20030134770(A) relates to a liquid detergent composition comprising a polymeric material that is a foam booster and foam volume extender, the composition having increased effectiveness for preventing redeposition of grease during hand washing, the polymeric material being suitable as a foam volume and foam durability enhancer and comprising an effective amount of a polymeric foam booster containing quaternary nitrogen-containing monomer units and/or zwitterionic monomer units. EP Patent No. 3835399(A1) relates to a hard surface cleaning composition comprising a surfactant system, a first polymer, and a second polymer, the first polymer being polyethyleneimine.

International Publication No. WO 201836864 (A) European Patent No. 3835399(A1) U.S. Patent Application Publication No. 20030134770(A)

The present invention relates to a liquid hand dishwashing detergent composition comprising a quaternized acrylic copolymer and 5.0% to 50% by weight of the liquid hand dishwashing detergent composition of a surfactant system, the surfactant system comprising an anionic surfactant and a co-surfactant selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof, the anionic surfactant and the co-surfactant being present in a weight ratio of less than 1.5:1.

In addition to the quaternized acrylic copolymer, formulating the liquid cleaning composition with a surfactant system as described herein can be used to improve the drying speed of dishware after hand dishwashing.

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.

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

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

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

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

As used herein, the term "particulate soil" refers to 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.

As used herein, the term "suds profile" refers to a characteristic of a cleaning composition with respect to the nature of the foam during the dishwashing process. The term "suds profile" of a cleaning composition includes the initial foam volume generated upon dissolution and agitation of the cleaning composition in an aqueous cleaning solution, typically manual agitation, and the retention of foam during the dishwashing process. Preferably, hand dishwashing cleaning compositions characterized as having a "good suds profile" tend to have a high initial foam volume and/or a sustained foam volume, particularly throughout a significant portion or entirety of the hand dishwashing process. This is important because consumers use the size of the foam as an indicator that enough cleaning composition has been dispensed. Furthermore, consumers also use the sustained foam volume, even toward the end of the dishwashing process, as an indicator that enough active cleaning ingredients (e.g., surfactants) are present. Consumers typically refresh the cleaning solution when foam levels are low. Thus, low foaming cleaning compositions tend to be replenished by consumers more frequently than necessary due to the low foam levels.

It is 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.

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.

Liquid cleaning composition The cleaning composition is a liquid cleaning composition, preferably a liquid hand dishwashing cleaning composition, and is therefore in liquid form. The liquid cleaning composition is preferably an aqueous cleaning composition. Thus, the composition may comprise from 50% to 85%, preferably from 50% to 75%, water by weight of the total composition.

The liquid cleaning composition has a pH greater than 6.0, or between 6.0 and 12.0, preferably between 7.0 and 11.0, more preferably between 7.5 and 10.0, measured as a 10% aqueous solution in demineralized water at 20°C.

The liquid cleaning compositions of the present invention may be Newtonian or non-Newtonian, but are preferably Newtonian. Preferably, the compositions have a viscosity of 10 mPa·s to 10,000 mPa·s, preferably 100 mPa·s to 5,000 mPa·s, more preferably 300 mPa·s to 2,000 mPa·s, or most preferably 500 mPa·s to 1,500 mPa·s, or a combination thereof. Viscosity is measured at 20°C using a Brookfield RT viscometer with spindle 31 adjusted to achieve 40% to 60% torque.

Quaternized Acrylic Copolymers The liquid hand dishwashing detergent comprises a quaternized acrylic copolymer. "Copolymer" as used herein refers to a polymer that comprises at least two different monomer compositions. Quaternized polymers contain quaternary ammonium groups, which are positively charged polyatomic ions of the structure NR ₄ ⁺ , where R is an alkyl or aryl group. Unlike the ammonium ion (NH ₄ ⁺ ) and primary, secondary, or tertiary ammonium cations, quaternary ammonium cations are permanently charged, regardless of the pH of their solutions.

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

The quaternized acrylic copolymer can 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.

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

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

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

The cationic monomer units may be selected from:
CH ₂ =CR ¹ -Y-(CH ₂ ) _n -N ⁺ R ² R ³ R ⁴ X (a),
In the formula,
Each ^R1 is independently selected from hydrogen or methyl, preferably methyl;
each ^R2 is independently selected from C1-C4 alkyl(ene), preferably _CH2CH = _CH2 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 a linking group selected from CO-NR ⁵ -(CH ₂ ) _n , CO-O-(CH ₂ ) _n or (CH ₂ ) _n , preferably CO-NR ⁵ -(CH ₂ ) _n or (CH ₂ ) _n , more preferably CO-NR ⁵ -(CH ₂ ) _n ;
In the formula,
Each ^R5 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 1 ^- is a suitable counter ion, preferably X 1 ^- is a halide counter ion, more preferably Cl 2 ^- .

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 ^R5 are the same.

The cationic monomer units may be selected from the group consisting of acrylamidopropyl trimethylammonium chloride (APTAC), methacrylamidopropyl trimethylammonium chloride (MAPTAC), diallyl dimethyl ammonium chloride (DADMAC), acryloyloxyethyl trimethylammonium chloride (AETAC), methyloyloxyethyl trimethylammonium chloride (METAC), and mixtures thereof. Particularly preferred cationic monomers are (meth)acrylamidopropyl trimethylammonium chloride (APTAC or MAPTAC) or diallyl dimethyl ammonium chloride (DADMAC), with methacrylamidepropyl trimethylammonium chloride (MAPTAC) being the most preferred. When polymerizing DADMAC, two polymer structures are possible: N-substituted piperidine structure or N-substituted pyrrolidine structure. The pyrrolidine structure is preferred (see John, Wilson; et al. (2002), Synthesis and Use of PolyDADMAC for Water Purification).

The ethylenically unsaturated monomer may be selected from the group consisting of C3-C8 ethylenically unsaturated acids and/or salts thereof, C3-C8 hydroxyalkyl acrylates, and mixtures thereof. By C3-C8, it is meant that the ethylenically unsaturated acids and/or salts thereof, or the C3-C8 hydroxyalkyl acrylates contain from 3 to 8 carbon atoms.

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

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

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 especially preferred.

The additional monomers are preferably present at levels less than 20 mol %, preferably less than 15 mol %, and more preferably less than 10 mol % of the total monomers present in the quaternized acrylic.

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

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

Surfactant System The liquid cleaning composition comprises from 5.0% to 50%, preferably from 6.0% to 40%, and most preferably from 15% to 35% by weight of a surfactant system, based on the weight of the total composition. The surfactant system comprises an anionic surfactant and a co-surfactant selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.

The anionic surfactant and co-surfactant are present in a weight ratio of less than 1.5:1, preferably from 0.5:1 to 1.5:1, and more preferably from 0.8:1 to 1.2:1.

Anionic Surfactant The surfactant system comprises an anionic surfactant. The surfactant system may comprise at least 35% anionic surfactant, preferably 35% to 65%, more preferably 40% to 60% by weight of the surfactant system. The surfactant system preferably does not comprise fatty acids or salts thereof, as such fatty acids inhibit foam production.

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

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

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.

The alkyl chains of the alkyl sulfated anionic surfactant may have a molar fraction of C12 and C13 chains of at least 50%, preferably at least 65%, more preferably at least 80%, and most preferably at least 90%. When the C13/C12 molar ratio of the alkyl chains is at least 57/43, preferably 60/40 to 90/10, more preferably 60/40 to 80/20, and most preferably 60/40 to 70/30, foam persistence is particularly improved, especially in the presence of greasy soils, while at the same time foam persistence in the presence of particulate soils is not impaired.

The relative molar amounts of C13 and C12 alkyl chains in the alkyl sulfated anionic surfactant can be derived from the carbon chain length distribution of the anionic surfactant. The carbon chain length distribution of the alkyl chains of the alkyl sulfated anionic surfactant can be obtained from the technical data sheet of the supplier of the surfactant or its constituent alkyl alcohol. Alternatively, the chain length distribution and average molecular weight of the aliphatic 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 the alkoxylated alcohol. Therefore, the alkyl sulfated anionic surfactant must be hydrolyzed back to the corresponding alkyl alcohol and alkyl alkoxylated alcohol before analysis, for example using hydrochloric acid.

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

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

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.

The preferred alkyl alkoxy sulfate is alkyl ethoxy sulfate.

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

The alkyl sulfated anionic surfactant may contain at least 5%, preferably at least 10%, and most preferably at least 25% by weight of the alkyl sulfated anionic surfactant branched at the C2 position (as measured by counting the carbon atoms from the sulfate group for non-alkoxylated alkyl sulfated anionic surfactants and counting from the alkoxy group furthest from the sulfate group for alkoxylated alkyl sulfated anionic surfactants). More preferably, greater than 75% by weight, and even more preferably greater than 90% by weight, of the total amount of branched alkyls are C1-C5 alkyl moieties, preferably C1-C2 alkyl moieties. Formulating compositions of the invention using alkyl sulfated anionic surfactants having the aforementioned branching degrees 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 low concentrations of organic solvent, less than 5.0% by weight based on the weight of the liquid cleaning composition, while still having improved low temperature stability. Higher surfactant branching also results in faster initial foam generation, but typically results in poorer foam persistence. The weight average branching described herein has been found to provide improved low temperature stability, initial foam generation, and foam persistence.

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

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

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

Suitable examples of commercially available alkyl sulfated anionic surfactants include those derived from alcohols sold by Shell under the tradename Neodol® or by Sasol under the tradenames 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 technical data sheets from the supplier or from analysis using methods known in the art, the alcohols can be blended to achieve the desired mole fractions of C12 and C13 chains and the desired C13/C12 ratio.

The performance of the final product, including grease cleaning, foaming, low temperature stability, and viscosity, can be influenced 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.

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 closely 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-product 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, management 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, 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.

Suitable anionic alkylsulfonate or sulfonic acid surfactants for use herein include alkylbenzenesulfonates, alkyl ester sulfonates, primary and secondary alkane sulfonates (such as paraffin sulfonates), alpha or internal olefin sulfonates, alkylsulfonated (poly)carboxylic acids, and mixtures thereof, in acid and salt form. Suitable anionic sulfonate or sulfonic acid surfactants include C5-C20 alkylbenzenesulfonates, more preferably C10-C16 alkylbenzenesulfonates, more preferably C11-C13 alkylbenzenesulfonates, 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 alkylbenzenesulfonates. The surfactants may 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 the random positioning of the double bonds, which results in a variety of twin-tail branched structures due to the hydrophilic sulfonate and hydroxyl group position of IOS in the middle of the alkyl chain. Alkanesulfonates include paraffin sulfonates and other secondary alkanesulfonates (such as Hostapur SAS60 from Clariant).

Alkyl sulfosuccinates and dialkyl sulfosuccinate esters are organic compounds having the formula MO3SCH(CO2R')CH2CO2R, where R and R' can be H or alkyl groups and M is a counterion such as sodium (Na). The alkyl sulfosuccinates and dialkyl sulfosuccinate ester surfactants can be alkoxylated or non-alkoxylated, preferably non-alkoxylated. The surfactant system can include additional anionic surfactants. However, the composition preferably includes less than 30%, preferably less than 15%, more preferably less than 10% by weight of the surfactant system of additional anionic surfactants. Most preferably, the surfactant system does not include additional anionic surfactants, preferably anionic surfactants other than the alkyl sulfated anionic surfactant.

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

The composition preferably comprises from 1.0% to 30%, more preferably from 5.0% to 25%, especially from 10% to 20% by weight of the cleaning composition of a co-surfactant.

The surfactant system of the cleaning composition of the present invention preferably comprises up to 65% by weight of the surfactant system of a co-surfactant, preferably from 30% to 65%, more preferably from 40% to 60%.

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

The amine oxide surfactant 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 may be selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl, and mixtures thereof, with one or both of R2 and R3 being preferably methyl. Specific examples of linear amine oxide surfactants include linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxyethyl dihydroxyethyl amine oxides.

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

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

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

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

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

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

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

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, coco betaine, lauramidopropyl betaine, lauryl betaine, myristyl amidopropyl betaine, myristyl betaine, and mixtures thereof. Cocamidopropyl betaine is particularly preferred.

Nonionic surfactants:
The surfactant system may further comprise less than 3.0% by weight of the composition of an alkoxylated alcohol nonionic surfactant. If present, the surfactant system preferably comprises at least 0.5%, preferably at least 1.0%, more preferably at least 2.0%, by weight of the composition of an alkoxylated alcohol nonionic surfactant. Alternatively, the composition may comprise more than 3.0%, preferably from 3.5% to 10%, more preferably from 4.0% to 7.5%, by weight of the liquid hand dish detergent composition of an alkoxylated alcohol nonionic surfactant.

The anionic surfactant and the alkoxylated alcohol nonionic surfactant may be present in a weight ratio of less than 10:1. The anionic surfactant and the alkoxylated alcohol nonionic surfactant are preferably present in a weight ratio of from 0.8:1 to 6.0:1, more preferably from 3.5:1 to 5.5:1.

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

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 its 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.

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

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

The alkyl polyglucoside surfactant may be selected from C6 to C18 alkyl polyglucoside surfactants. The alkyl polyglucoside surfactant may 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 may comprise a blend of short chain alkyl polyglucoside surfactants having alkyl chains containing 10 or less 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.

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

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® 600 CSUP is a preferred medium to long-chain APG surfactant.

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 are typically more foaming than other nonionic surfactants such as alkyl ethoxylated alcohols.

In other preferred compositions, the alkyl polyglucosides are present at levels less than 2.0%, preferably less than 1.0%, and more preferably less than 0.5% by weight of the composition.

In even more preferred compositions, the composition does not contain any additional nonionic surfactant.

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

Amphiphilic alkoxylated polyalkyleneimines:
The compositions of the present invention may further comprise from 0.05% to 2%, preferably from 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, especially when the cleaning implement contains little to no water, e.g., when a lightly pre-moistened sponge is used.

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

（式中、ポリエチレンイミン主鎖は、重量平均分子量６００を有しており、式（Ｉ）のｎは平均１０であり、式（Ｉ）のｍは平均７であり、式（Ｉ）のＲは、水素、Ｃ_１～Ｃ_４アルキル、及びこれらの混合物、好ましくは水素から選択される）。式（Ｉ）の永久的な四級化度は、ポリエチレンイミン骨格の窒素原子の０％～２２％であってもよい。この両親媒性アルコキシル化ポリエチレンイミンポリマーの分子量は、好ましくは、１０，０００～１５，０００Ｄａである。

where the polyethyleneimine backbone has a weight average molecular weight of 600, n in formula (I) averages 10, m in formula (I) averages 7, and R in formula (I) is selected from hydrogen, C ₁ -C ₄ alkyl, and mixtures thereof, preferably hydrogen. The degree of permanent quaternization in formula (I) may be from 0% to 22% of the nitrogen atoms of the polyethyleneimine backbone. The molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer is preferably from 10,000 to 15,000 Da.

More preferably, the amphiphilic alkoxylated polyethyleneimine polymer has the general structure of formula (I), where the polyethyleneimine backbone has a weight average molecular weight of 600 Da, n in formula (I) is an average of 24, m in formula (I) is an average of 16, and R in formula (I) is selected from hydrogen, _C1 - _C4 alkyl, and mixtures thereof, preferably hydrogen. The degree of permanent quaternization of formula (I) may be from 0% to 22% of the nitrogen atoms of the polyethyleneimine backbone, preferably 0%. The molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer is preferably from 25,000 to 30,000, most preferably 28,000 Da.

The amphiphilic alkoxylated polyethyleneimine polymers can be prepared by the methods described in more detail in WO 2007/135645.

Alternatively, the composition may not include an amphiphilic polymer.

Cyclic Polyamines The present compositions may include cyclic polyamines having amine functional groups to aid in cleaning. The compositions of the present invention preferably comprise from 0.1% to 3%, more preferably from 0.2% to 2%, especially from 0.5% to 1% of a cyclic polyamine by weight of the total composition.

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

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

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

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

Triblock Copolymers The compositions of the present invention may include triblock copolymers. The triblock copolymers may be present at levels of 1% to 20%, preferably 3% to 15%, 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 may independently average 5 to 50, preferably 10 to 40, more preferably 10 to 30. Preferably, x is the same for both EO blocks, with "same" meaning that x differs by up to 2 units between the two EO blocks, preferably up to 1 unit, more preferably both x are the same number of units. PO represents propylene oxide and y represents the number of PO units in the PO block. Each y may be, on average, 28-60, preferably 30-55, and more preferably 30-48.

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 the 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).

A triblock copolymer has 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."

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

Suitable EO-PO-EO triblock copolymers are commercially available, for example, from BASF under the Pluronic® PE series and from Dow Chemical Company 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).

The preferred triblock copolymers are readily biodegradable under aerobic conditions.

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.

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

Hydrotropes:
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.

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

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

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

The orifice may have an open cross-sectional area at the outlet of ^{from 3} mm to ²⁰ mm, preferably ^from 3.8 mm to ¹² mm, more preferably from 5 ^mm to ¹⁰ mm, and the container further comprises a composition according to the invention. The cross-sectional area is measured perpendicular to the liquid outlet from the container (i.e. perpendicular to the liquid flow during dispensing).

The container can typically contain from 200ml to 5,000ml, preferably from 350ml to 2000ml, more preferably from 400ml to 1,000ml of the liquid hand dishwashing detergent composition.

The present invention is further directed to a method of manually washing dishware with the composition of the present invention, the method 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, the dishware being washed with the composition in the presence of water.

Optionally, the dishware may be rinsed. As used herein, "rinsing" refers to contacting the dishware that has been cleaned in the process of the present invention with a significant amount of a suitable solvent, typically water. "Significant amount" typically means about 1 to about 20 L or under running water.

The compositions herein may be applied in their diluted form. The soiled dishware is contacted with an effective amount, typically about 0.5 mL to about 20 mL, preferably about 3 mL to about 10 mL (per about 25 dishes to be treated), of the detergent composition of the present invention diluted with water, preferably in liquid form. The actual amount of cleaning composition used is at the discretion of the user and typically depends on factors such as the particular product formulation of the cleaning composition, including the concentration of active ingredients in the cleaning 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 cleaning composition of the present invention is combined with about 2,000 mL to about 20,000 mL, more typically about 5,000 mL to about 15,000 mL of water in a sink. After immersing the soiled dishware in the sink containing the resulting diluted cleaning composition, the soiled surface of the dishware is contacted with a cloth, sponge, or similar cleaning implement. The cloth, sponge, or similar cleaning implement may be immersed in the mixture of cleaning composition and water prior to contacting the dishware, typically for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary for each application and user. Contacting the cloth, sponge, or similar cleaning implement with the dishware involves simultaneously scrubbing the dishware.

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

Method:
A) 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) is a well-known system for directly measuring the weight average molecular weight _Mw and number average molecular weight _Mn of polymers without the need for comparison to known reference standards.

The true number average molecular weight _Mn of a polymer can be obtained by GPC combined with light scattering and refractive index detection, provided that the slices taken are sufficiently monodisperse with respect to molecular weight and composition, even if the composition, and therefore the refractive index increment, varies with elution volume.

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

Because the analytes are diffused over a relatively narrow time window, isocratic elution can be used rather than gradient elution. Isocratic means that the mixture of mobile phase is consistent over the entire test time. Using a gradient implies that the formulation of the eluent mixture changes during the measurement, thus affecting the retention of the analytes. When using a gradient, the separation can be either accelerated or decelerated.

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

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.

B) Water Sheeting:
The drying rate is related to the degree of water sheeting: the higher the water sheeting, the less water is retained on the wet article.

Water sheeting behavior is evaluated by washing a gray ceramic dish ("Dinera" dish, 26 cm diameter, supplied by IKEA) with the hand dishwashing detergent test composition, followed by scoring the amount of water sheeting observed on the dish when the dish is placed vertically on a drying rack. More specifically,
A sponge (Scotch-Brite® Classic-schuurspons van cellulose supplied by 3M Belgium - dimensions: 7 cm x 10 cm) is uniformly wetted with water equivalent to 3 mmol/l CaCO ₃ of hardness at 25°C by saturating the sponge with water and then squeezing it manually until no more water is squeezed out.

1 ml of the hand dishwashing composition is evenly distributed over the sponge. The sponge is manually squeezed 4 times with full force using one hand over a ceramic dish to create a lather, followed by washing the dish with 10 circular clockwise movements covering the edges as well as the center of the dish so that the entire dish is treated with lather.

The dishes are then rinsed for 30 seconds under running water (25°C water with the same water hardness as before (0.36 mmol/l CaCO ₃ equivalent)) at a flow rate sufficient to allow complete removal of bubbles and complete coverage by water, after which the dishes are placed vertically on a drying rack under standard room conditions (20 +/- 1°C).

The water running down the dish is then visually assessed and a score of 0-100% is given depending on the amount of water that has run down the dish in the first 30 seconds and thus left the area of the dish already dry. 0% corresponds to water remaining on the entire dish, 50% indicates that half of the dish is covered with a film of water and 100% indicates that no film of water is visible.

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

In the compositions of Table 1, inventive Example 1 contained both an anionic surfactant and a co-surfactant in a 1:1 weight ratio in addition to the quaternized acrylic copolymer. Comparative Example A contained the same surfactant system but did not contain the quaternized acrylic copolymer. By comparing the water sheeting results of Example 1 with those from Example A, the improvement in water sheeting from the addition of the quaternized acrylic copolymer in a composition containing an anionic surfactant and a co-surfactant in the desired ratio can be seen. In contrast, the water sheeting results of Comparative Examples B-D show that the water sheeting benefit is substantially reduced when the anionic surfactant to co-surfactant ratio is above the desired range.

^＊比較例
^１Ｐｏｌｙｑｕａｒｔ（登録商標）１４９Ａという商標名で販売され、ＢＡＳＦによって供給されている、本発明で有用な四級化アクリルコポリマー

^* Comparative example
¹ A quaternized acrylic copolymer useful in the present invention sold under the trade name Polyquart® 149A and supplied by BASF.

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."

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."
[1]
A liquid hand dishwashing detergent composition comprising a quaternized acrylic copolymer and
5.0% to 50% by weight of the liquid hand dishwashing detergent composition of a surfactant system comprising
a. an anionic surfactant;
b. a co-surfactant selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof;
A composition wherein said anionic surfactant and said co-surfactant are present in a weight ratio of less than 1.5:1.
[2]
The composition according to [1], wherein the composition comprises 0.01% to 3.0%, preferably 0.05% to 2.0%, more preferably 0.1% to 1.0% by weight of the composition of the quaternized acrylic copolymer.
[3]
The composition according to [1] or [2], wherein the quaternized acrylic copolymer has a weight average molecular weight (Mw) measured by aqueous gel permeation chromatography (GPC) with light scattering detection (SEC-MALLS) in the range of 5,000 to 500,000 Da, preferably 15,000 to 300,000 Da, and even more preferably 25,000 to 75,000 Da.
[4]
The composition according to any one of [1] to [3], wherein the quaternized acrylic copolymer has an average cationic charge density of 0.01 to 2.8, preferably 0.1 to 2.75, more preferably 0.75 to 2.25 mEq/g.
[5]
The quaternized acrylic copolymer is
a. a cationic monomer unit selected from:
i. 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 R2 ^is independently selected from C1-C4 alkyl(ene), preferably _CH2CH =CH2 _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 a linking group selected from CO-NR ⁵ -(CH ₂ ) _n , CO-O-(CH ₂ ) _n or (CH ₂ ) _n , preferably CO-NR ⁵ -(CH ₂ ) _n or (CH ₂ ) _n , more preferably CO-NR ⁵ -(CH ₂ ) _n ;
In the formula,
each R5 ^is independently selected from hydrogen or methyl, preferably hydrogen;
n is an average of 1 to 4, preferably 1 or 3, more preferably 3;
cationic monomer units, wherein X- ^is a suitable counterion, preferably a halide counterion, more preferably Cl- ^;
b. The composition according to any one of [1] to [4], which is derived from an ethylenically unsaturated monomer unit.
[6]
The composition according to [5], wherein the cationic monomer unit is selected from the group consisting of acrylamidopropyl trimethyl ammonium chloride (APTAC), diallyl dimethyl ammonium chloride (DADMAC), acryloyloxyethyl trimethyl ammonium chloride (AETAC), methacrylamidopropyl trimethyl ammonium chloride (MAPTAC), methyloyloxyethyl trimethyl ammonium chloride (METAC), and mixtures thereof, preferably (meth)acrylamidopropyl trimethyl ammonium chloride (APTAC or MAPTAC) or diallyl dimethyl ammonium chloride (DADMAC), more preferably methacrylamidopropyl trimethyl ammonium chloride (MAPTAC).
[7]
The composition according to [5] or [6], wherein the ethylenically unsaturated monomer unit is selected from the group consisting of C3 to C8 ethylenically unsaturated acids and/or salts thereof, C3 to C8 hydroxyalkyl acrylates, and mixtures thereof.
[8]
The composition according to [7], wherein the ethylenically unsaturated monomer unit comprises a C3 to C8 ethylenically unsaturated acid and/or a salt thereof, and the C3 to C8 ethylenically unsaturated acid and/or a salt thereof is selected from the group consisting of (meth)acrylic acid or a salt thereof, more preferably acrylic acid or a salt thereof.
[9]
The composition according to [7] or [8], wherein the ethylenically unsaturated monomer unit comprises a C3 to C8 alkyl acrylate selected from the group consisting of ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-2-methylethyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, and mixtures thereof, preferably ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and mixtures thereof, more preferably ethyl (meth)acrylate, and most preferably ethyl acrylate.
[10]
The composition according to any one of [1] to [9], wherein the anionic surfactant and the co-surfactant are present in a weight ratio of 0.5:1 to 1.5:1, preferably 0.8:1 to 1.2:1.
[11]
The composition according to any one of [1] to [10], wherein the composition comprises 6.0% to 40% by weight, preferably 15% to 35% by weight, of the surfactant system of the total composition.
[12]
The composition according to any of the preceding claims, wherein the surfactant system comprises at least 35% by weight of the surfactant system, preferably 35% to 65% by weight, more preferably 40% to 60% by weight of the surfactant system, of an anionic surfactant.
[13]
The composition according to any one of [1] to [12], wherein the anionic surfactant comprises at least 70% by weight, preferably at least 85% by weight, and more preferably 100% by weight of the anionic surfactant, of an alkyl sulfated anionic surfactant.
[14]
The composition according to any one of [1] to [13], wherein the co-surfactant comprises an amphoteric surfactant, preferably an amine oxide surfactant.
[15]
The composition of any of [1] to [14], wherein the surfactant system comprises less than 10.0%, preferably less than 5.0%, by weight of the surfactant system of an alkoxylated alcohol nonionic surfactant, and more preferably is free of an alkoxylated alcohol nonionic surfactant.

Claims (15)

A liquid hand dishwashing detergent composition comprising a quaternized acrylic copolymer and
5.0% to 50% by weight of the liquid hand dishwashing detergent composition of a surfactant system comprising
a. an anionic surfactant;
b. a co-surfactant selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof;
A composition wherein said anionic surfactant and said co-surfactant are present in a weight ratio of less than 1.5:1. The composition of claim 1, wherein the composition comprises 0.01% to 3.0%, preferably 0.05% to 2.0%, more preferably 0.1% to 1.0% by weight of the composition of the quaternized acrylic copolymer. The composition according to claim 1 or 2, wherein the quaternized acrylic copolymer has a weight average molecular weight (Mw) measured by aqueous gel permeation chromatography (GPC) with light scattering detection (SEC-MALLS) in the range of 5,000 to 500,000 Da, preferably 15,000 to 300,000 Da, and even more preferably 25,000 to 75,000 Da. The composition according to any one of claims 1 to 3, wherein the quaternized acrylic copolymer has an average cationic charge density of 0.01 to 2.8, preferably 0.1 to 2.75, more preferably 0.75 to 2.25 mEq/g. The quaternized acrylic copolymer is
a. a cationic monomer unit selected from:
i. 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 ^R2 is independently selected from C1-C4 alkyl(ene), preferably _CH2CH = _CH2 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 a linking group selected from CO-NR ⁵ -(CH ₂ ) _n , CO-O-(CH ₂ ) _n or (CH ₂ ) _n , preferably CO-NR ⁵ -(CH ₂ ) _n or (CH ₂ ) _n , more preferably CO-NR ⁵ -(CH ₂ ) _n ;
In the formula,
each ^R5 is independently selected from hydrogen or methyl, preferably hydrogen;
n is an average of 1 to 4, preferably 1 or 3, more preferably 3;
cationic monomer units, wherein ^X- is a suitable counterion, preferably a halide counterion, more preferably ^Cl- ;
b. an ethylenically unsaturated monomer unit; and The composition according to claim 5, wherein the cationic monomer unit is selected from the group consisting of acrylamidopropyl trimethyl ammonium chloride (APTAC), diallyl dimethyl ammonium chloride (DADMAC), acryloyloxyethyl trimethyl ammonium chloride (AETAC), methacrylamide propyl trimethyl ammonium chloride (MAPTAC), methyloyloxyethyl trimethyl ammonium chloride (METAC), and mixtures thereof, preferably (meth)acrylamidopropyl trimethyl ammonium chloride (APTAC or MAPTAC) or diallyl dimethyl ammonium chloride (DADMAC), more preferably methacrylamide propyl trimethyl ammonium chloride (MAPTAC). The composition according to claim 5 or 6, wherein the ethylenically unsaturated monomer unit is selected from the group consisting of C3-C8 ethylenically unsaturated acids and/or salts thereof, C3-C8 hydroxyalkyl acrylates, and mixtures thereof. The composition according to claim 7, wherein the ethylenically unsaturated monomer unit comprises a C3-C8 ethylenically unsaturated acid and/or a salt thereof, and the C3-C8 ethylenically unsaturated acid and/or a salt thereof is selected from the group consisting of (meth)acrylic acid or a salt thereof, more preferably acrylic acid or a salt thereof. The composition according to claim 7 or 8, wherein the ethylenically unsaturated monomer units comprise a C3 to C8 alkyl acrylate selected from the group consisting of ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-2-methylethyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, and mixtures thereof, preferably ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and mixtures thereof, more preferably ethyl (meth)acrylate, and most preferably ethyl acrylate. A composition according to any one of claims 1 to 9, wherein the anionic surfactant and the co-surfactant are present in a weight ratio of 0.5:1 to 1.5:1, preferably 0.8:1 to 1.2:1. The composition according to any one of claims 1 to 10, wherein the composition comprises 6.0% to 40% by weight, preferably 15% to 35% by weight, of the surfactant system of the total composition. A composition according to any one of claims 1 to 11, wherein the surfactant system comprises at least 35% by weight of the surfactant system, preferably 35% to 65% by weight, more preferably 40% to 60% by weight of the surfactant system, of an anionic surfactant. The composition according to any one of claims 1 to 12, wherein the anionic surfactant comprises at least 70% by weight of the anionic surfactant, preferably at least 85% by weight, more preferably 100% by weight of the anionic surfactant, of an alkyl sulfated anionic surfactant. The composition according to any one of claims 1 to 13, wherein the co-surfactant comprises an amphoteric surfactant, preferably an amine oxide surfactant. A composition according to any one of claims 1 to 14, wherein the surfactant system comprises less than 10.0%, preferably less than 5.0%, by weight of the surfactant system, of an alkoxylated alcohol non-ionic surfactant, and more preferably is free of an alkoxylated alcohol non-ionic surfactant.

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