Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/88—Ampholytes; Electroneutral compounds
  • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
  • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces

Definitions

• the present invention relates to liquid hand dishwashing detergent compositions and methods of cleaning dishes.
• Hand dishwashing compositions should provide good grease cleaning and sudsing.
• dishes and the like are washed at elevated temperatures in order to more effectively clean dishes.
• greasy soils are softened at elevated temperatures.
• dishes and the like are typically cleaned at temperatures of 35°C or higher.
• WO2017110773A1 relates to liquid detergent composition for hard surfaces, including dishware, and its use for cleaning the aforementioned hard surface at low temperatures.
• JP2013100461A discloses a liquid detergent composition hand-washing tableware at a low temperature (10 to 35 ° C.).
• WO201691688A relates to a liquid cleaning agent for hard surfaces, in particular for washing dishes by hand, containing an ⁇ amylase for cleaning starch stains at low temperature ( ⁇ 40 degrees C).
• JP2015010141A relates to a tableware washing detergent which provides detergency, foaming and rinsibility at low temperatures and aroma and reduced aroma variation at low temperatures.
• WO2014117973A relates to relates to anionic sulfonated cyclic surfactants of specific formula with lower cmc, for providing cleaning at low temperatures.
• EP3971270A relates to a liquid hand dishwashing cleaning compositions that comprise alkyl sulfate anionic surfactant having little or no ethoxylation, which provides improved low temperature stability while also achieving the desired product viscosity, suds mileage and overall cleaning.
• EP3971271A relates to a hand-dishwashing composition which is highly effective at removing grease, providing long-lasting suds under soiled conditions, while having a Newtonian viscosity which is less sensitive to changes on surfactant and solvent levels, the liquid hand dishwashing cleaning composition comprising a surfactant system having a combination of alkyl sulphate anionic surfactant having little or no alkoxylation and an alkyl polyglucoside surfactant.
• EP3971273A relates to a hand-dishwashing composition which is highly effective at removing grease, while also having good suds mileage, and avoiding negatives on physical stability, especially at low temperatures, the hand dishwashing composition comprising a surfactant system, the surfactant system comprising an alkyl sulfate anionic surfactant comprising little or no branching and having a low degree of alkoxylation, or no alkoxylation, and a co-surfactant, in combination with polypropylene glycol of a defined molecular weight, as described herein.
• EP3919594A relates to a liquid detergent composition suitable for washing dishes, fitting both in-sink as well as direct application habits, which provides reduced smearing when used in direct application dishwashing methods, while having good suds mileage especially under in-sink application habit, and good viscosity
• the liquid detergent composition comprises a surfactant system, which comprises an alkyl sulfate anionic surfactant comprising C13 alkyl sulfate anionic surfactant, the C13 alkyl sulfate anionic surfactant comprising a specific fraction of 2-branched C13 alkyl sulfate anionic surfactant, with a specific distribution of the 2-branching.
• EP3971275A relates to a hand-dishwashing composition which is highly effective at emulsifying grease, the liquid hand dishwashing cleaning composition comprising a surfactant system having a combination of alkyl sulphate anionic surfactant and a co-surfactant comprising at least 70% by weight of the co-surfactant of a betaine, in combination with a polypropyleneglycol having a weight average molecular weight from 500 g/mol to 1800 g/mol.
• WO201836864A relates to hard surface treatment compositions comprising quaternised acrylic copolymer and amphoteric modified polysaccharide, wherein the weight ratio of the quaternised acrylic copolymer to the amphoteric modified polysaccharide is from 0.75:1 to 3:1 and the quaternised acrylic copolymer is different from the amphoteric modified polysaccharide.
• EP3835399A1 relates to hard surface cleaning composition comprising a surfactant system; a first polymer; and a second polymer, the first polymer being a polyethyleneimine, as well as to the use of the composition to clean a glass surfaces.
• US20030134770A relates to liquid detergent compositions comprising a polymeric material which is a suds enhancer and a suds volume extender, said compositions having increased effectiveness for preventing re-deposition of grease during hand washing, the polymeric material being suitable as suds volume and suds endurance enhancers and comprising an effective amount of a quaternary nitrogen-containing monomeric unit and/or zwitterionic monomeric unit-containing polymeric suds enhancer.
• US7741265B relates to a cleaning composition for a hard surface which provides for initial cleaning of the hard surface and provision of a hydrophilic coating or barrier layer on the surface which provides residual cleaning to the hard surface for an extended number of rinsings.
• the composition includes a hydrophilic polymer, at least one nonionic surfactant, at least one solvent, an acid and water, wherein the acid provides the composition with a pH of about 2 to 3.5 and the composition is provided in the absence of any anionic, cationic or amphoteric surfactant.
• US7741265B teaches the use of hydrophilic cationic polymers, including acrylic based polymers, for providing a residual cleaning benefit through numerous rinsings.
• US20120028872A relates to a method of cleaning dishware with a liquid detergent composition having a hydrophobic emollient and a crystalline structurant to provide improved hand skin care benefits and superior grease cleaning and/or suds mileage.
• US20120028872A discloses cationic polymers, and their use for enhancing skin benefits.
• US20220081649A relates to a hand-dishwashing composition for removing grease, providing long-lasting suds under soiled conditions, while having a Newtonian viscosity which is less sensitive to changes on surfactant and solvent levels.
• US20220081649A teaches the provision of such benefits through the use of a combination of alkyl sulfate surfactant and short-chain alkyl polyglucoside.
• the present invention relates a liquid hand dishwashing cleaning composition
• a liquid hand dishwashing cleaning composition comprising: from 6% to 50% by weight of the total composition of a surfactant system, and a quaternised acrylic copolymer
• the surfactant system comprises: at least 40% by weight of the surfactant system of anionic surfactant, wherein the anionic surfactant comprises at least 50% by weight of the anionic surfactant of alkyl sulfated anionic surfactant, wherein the alkyl sulfated anionic surfactant has an average degree of alkoxylation of less than 0.1.
• the present invention further relates to methods of cleaning dishware, using such compositions, wherein the method comprises the step of: contacting dishware with the liquid hand dishwashing detergent composition and water, wherein the water has a temperature of 30 °C or less.
• liquid hand dishwashing detergent compositions as described herein, and contrary to methods using more traditionally used compositions comprising ethoxylated alkyl sulfate anionic surfactants, provide more effective sudsing, especially in the presence of greasy soil during low temperature dishwashing. As such, the user is more incentivised to wash their dishware at lower temperatures.
• incorporation of a quaternised acrylic copolymer within a liquid hand dishwashing detergent composition as described herein further improves sudsing during low temperature washing of dishware.
• compositions of the present invention can comprise, consist of, and consist essentially of the essential elements and limitations of the invention described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein.
• the term "dishware” as used herein includes cookware and tableware made from, by non-limiting examples, ceramic, china, metal, glass, plastic ( e . g ., polyethylene, polypropylene, polystyrene, etc.) and wood.
• greye or "greasy” as used herein means materials comprising at least in part (i.e., at least 0.5 wt% by weight of the grease) saturated and unsaturated fats and oils, preferably oils and fats derived from animal sources such as beef, pig and/or chicken.
• pill soils as used herein means inorganic and especially organic, solid soil particles, especially food particles, such as for non-limiting examples: finely divided elemental carbon, baked grease particle, and meat particles.
• sudsing profile refers to the properties of a cleaning composition relating to suds character during the dishwashing process.
• the term "sudsing profile" of a cleaning composition includes suds volume generated upon dissolving and agitation, typically manual agitation, of the cleaning composition in the aqueous washing solution, and the retention of the suds during the dishwashing process.
• hand dishwashing cleaning compositions characterized as having "good sudsing profile” tend to have high suds volume and/or sustained suds volume, particularly during a substantial portion of or for the entire manual dishwashing process. This is important as the consumer uses high suds as an indicator that sufficient cleaning composition has been dosed.
• the consumer also uses the sustained suds volume as an indicator that sufficient active cleaning ingredients (e . g ., surfactants) are present, even towards the end of the dishwashing process.
• the consumer usually renews the washing solution when the sudsing subsides.
• a low sudsing cleaning composition will tend to be replaced by the consumer more frequently than is necessary because of the low sudsing level.
• test methods that are disclosed in the Test Methods Section of the present application must be used to determine the respective values of the parameters of Applicants' inventions as described and claimed herein.
• the cleaning composition is a liquid hand dishwashing cleaning composition.
• the cleaning composition is preferably an aqueous cleaning composition.
• the composition can comprise from 50% to 85%, preferably from 50% to 75%, by weight of the total composition of water.
• the pH of the composition is from about 6 to about 14, preferably from about 7 to about 12, or more preferably from about 7.5 to about 10, as measured at 10% dilution in distilled water at 20°C.
• the pH of the composition can be adjusted using pH modifying ingredients known in the art.
• the composition of the present invention can be Newtonian or non-Newtonian, preferably Newtonian in the usage shear rate range of from 0.1 s -1 to 100 s -1 .
• the composition has a viscosity of from 10 mPa ⁇ s to 10,000 mPa ⁇ s, preferably from 100 mPa ⁇ s to 5,000 mPa ⁇ s, more preferably from 300 mPa ⁇ s to 2,000 mPa ⁇ s, or most preferably from 500 mPa ⁇ s to 1,500 mPa ⁇ s, alternatively combinations thereof.
• the viscosity is measured at 20°C with a Brookfield RT Viscometer using spindle 31 with the RPM of the viscometer adjusted to achieve a torque of between 40% and 60%.
• the liquid cleaning composition comprises from 6.0% to 50%, preferably from 6.0% to 40%, most preferably from 15% to 35%, by weight of the total composition of a surfactant system.
• the liquid hand dishwashing detergent composition comprises a surfactant system, wherein the surfactant system comprises an anionic surfactant system comprising alkyl sulfated anionic surfactant, wherein the alkyl sulfated anionic surfactant has an average degree of alkoxylation of less than 0.1 and is more preferably free of any alkoxylation. If alkoxylation is present, the alkyl sulfate anionic surfactant is preferably ethoxylated.
• the average degree of alkoxylation is the mol average degree of alkoxylation (i . e ., mol average alkoxylation degree) of all the alkyl sulfate anionic surfactant.
• x1, x2, ... are the number of moles of each alkyl (or alkoxy) sulfate anionic surfactant of the mixture and alkoxylation degree is the number of alkoxy groups in each alkyl sulfate anionic surfactant.
• the surfactant system comprises at least 40%, preferably from 60% to 90%, more preferably from 70 to 80% by weight of the surfactant system of the anionic surfactant.
• the anionic surfactant comprises at least 50%, preferably at least 70%, more preferably at least 90% by weight of the anionic surfactant of alkyl sulfated anionic surfactant.
• the anionic surfactant consists of alkyl sulfated surfactant, most preferably primary alkyl sulfated anionic surfactant.
• the surfactant system may comprise small amounts of further anionic surfactant, including sulfonates such as HLAS, or sulfosuccinate anionic surfactants, the surfactant system preferably comprises no further anionic surfactant beyond the alkyl sulfated anionic surfactant.
• the alkyl sulfated anionic surfactant has an alkyl chain comprising an average of from 8 to 18 carbon atoms, preferably from 10 to 14 carbon atoms, more preferably from 12 to 13 carbon atoms.
• the alkyl chain of the alkyl sulfated anionic surfactant preferably has a mol fraction of C12 and C13 chains of at least 50%, preferably at least 65%, more preferably at least 80%, most preferably at least 90%. Suds mileage is particularly improved, especially in the presence of greasy soils, when the C13/C12 mol ratio of the alkyl chain is at least 50/50, preferably from 60/40 to 80/20, most preferably from 60/40 to 70/30, while not compromising suds mileage in the presence of particulate soils.
• the alkyl sulfated anionic surfactant can have an average degree of branching of at least 5.0%, preferably from 10% to 50%, more preferably from 15% to 40%.
• the alkyl sulfated anionic surfactant can comprise a mixture of linear and branched alkyl sulfated anionic surfactant.
• the alkyl chains of the alkyl sulphated anionic surfactant can be derived from natural or synthetic origins.
• the linear chains can be natural alkyl chains which are preferably derived from coconut oil, coconut oil being more sustainably derivable while having a preferred chain length.
• the linear alkyl chains can be blended with a highly branched alkyl chain so that less branched alkyl chains need to be added in order to arrive at the desired degree of branching.
• the overall degree of branching affects not just the sustainability of the sourcing material, but also impacts the amount of organic solvent required to physically stabilise the liquid hand dishwashing composition.
• the branching of the alkyl sulfated anionic surfactant also affects the viscosity as well as the viscosity upon dilution, avoiding viscosity thickening upon dilution and ensuring that the composition is readily dispersible in the water.
• the level of branching in the branched alkyl sulfate or alkyl alkoxy sulfate used in the detergent composition is calculated on a molecular basis.
• Commercially available non-alkoxylated alkyl sulfate anionic surfactant blends that are sold as "branched” will typically comprise a blend of linear alkyl sulfate as well as branched alkyl sulphate molecules.
• alkyl alkoxy sulfate anionic surfactant blends that are sold as "branched” will typically comprise a blend of linear alkyl sulfate, branched alkyl sulfate, as well as linear alkyl alkoxy sulfate and branched alkyl alkoxy sulfate molecules.
• Weight average degree of branching % x 1 ⁇ wt % branched alcohol 1 in alcohol 1 + x 2 ⁇ wt % branched alcohol 2 in alcohol 2 + ... . / x 1 + x 2 + ... . ⁇ 100 wherein x1, x2, ...
• the weight in grams of each alcohol in the total alcohol mixture of the alcohols which were used as starting material before (alkoxylation and) sulphation to produce the alkyl (alkoxy) sulfate anionic surfactant are the weight in grams of each alcohol in the total alcohol mixture of the alcohols which were used as starting material before (alkoxylation and) sulphation to produce the alkyl (alkoxy) sulfate anionic surfactant.
• the weight of the alkyl alcohol used to form the alkyl sulfate anionic surfactant which is not branched is included.
• the weight average degree of branching and the distribution of branching can typically be obtained from the technical data sheet for the surfactant or constituent alkyl alcohol.
• the branching can also be determined through analytical methods known in the art, including capillary gas chromatography with flame ionisation detection on medium polar capillary column, using hexane as the solvent.
• the weight average degree of branching and the distribution of branching is based on the starting alcohol used to produce the alkyl sulfated anionic surfactant.
• the branched alkyl sulfated anionic surfactant can comprise C2-branched alkyl sulfated anionic surfactant and optionally non-C2-branched alkyl sulfated anionic surfactant.
• the branched alkyl sulfated anionic surfactant can comprise at least 90%, preferably at least 95%, more preferably at least 98% by weight of the branched alkyl sulfated anionic surfactant of C2-branched alkyl sulfated anionic surfactant and at most 10%, preferably at most 5%, most preferably at most 2% by weight of the branched alkyl sulfated anionic surfactant of non-C2 branched alkyl sulfate anionic surfactant.
• C2-branched means the alkyl branching is a single alkyl branching on the alkyl chain of the alkyl sulfated anionic surfactant and is positioned on the C2 position, as measured counting carbon atoms from the sulfate group for non-alkoxylated alkyl sulfate anionic surfactants, or counting from the alkoxy-group furthest from the sulfate group for alkoxylated alkyl sulfate anionic surfactants.
• Non-C2 branching means the alkyl chain comprises branching at multiple carbon positions along the alkyl chain backbone, or a single branching group present on a branching position on the alkyl chain other than the C2 position.
• the non-C2 branched alkyl sulfated anionic surfactant can comprise less than 30%, preferably less than 20%, more preferably less than 10% by weight of the non-C2 branched alkyl sulfated anionic surfactant of C1-branched alkyl sulfated anionic surfactant, most preferably the non-C2 branched alkyl sulfated anionic surfactant is free of C1-branched alkyl sulfated anionic surfactant.
• the non-C2 branched alkyl sulfated anionic surfactant can comprise at least 50%, preferably from 60 to 90%, more preferably from 70 to 80% by weight of the non-C2 branched alkyl sulfated anionic surfactant of isomers comprising a single branching at a branching position greater than the 2-position. That is, more than 2 carbons atoms away from the hydrophilic headgroup, as defined above.
• the non-C2 branched alkyl sulfated anionic surfactant can comprise from 5% to 30%, preferably from 7% to 20%, more preferably from 10% to 15% by weight of the non-C2 branched alkyl sulfated anionic surfactant of multi-branched isomers.
• the non-C2 branched alkyl sulfated anionic surfactant can comprise from 5% to 30%, preferably from 7% to 20%, more preferably from 10% to 15% by weight of non-C2 branched alkyl sulfated anionic surfactant of cyclic isomers.
• the acyclic branching groups can be selected from C1 to C5 alkyl groups, and mixtures thereof.
• compositions using alkyl sulfated anionic surfactants having the aforementioned branching distribution and reduced to nil ethoxylation results in reduced viscosensitivity to variations in temperature and, as such, a more consistent dosage experience, compared to compositions comprising alkyl sulfated anionic surfactants with a comparative branching distribution.
• the composition maintains a Newtonian viscosity profile for a broader shear rate range, which means less dosage variation and a more consistent user experience, regardless of how hard the container is squeezed.
• Suitable counterions for the anionic surfactant include alkali metal cation earth alkali metal cation, alkanolammonium or ammonium or substituted ammonium, but preferably sodium.
• Suitable examples of commercially available alkyl sulfated anionic surfactants include, those derived from alcohols sold under the Neodol ® brand-name by Shell, or the Lial ® , Isalchem ® , and Safol ® brand-names by Sasol, or some of the natural alcohols produced by The Procter & Gamble Chemicals company.
• the alcohols can be blended in order to achieve the desired average alkyl chain, average degree of branching and type of branching distribution according to the invention.
• the targeted branched alkyl sulfated anionic surfactant according to the invention has a high dominance of C2 branched alkyl sulfated anionic surfactant content
• the alkyl sulfated anionic surfactant comprises an OXO derived alkyl sulfated anionic surfactant, such as commercially available under the lial and isalchem brandname from the Sasol company, and Neodol from the Shell company, OXO derived alkyl sulfated anionic surfactants comprising branched alkyl sulfated anionic surfactant consisting essentially of C2 branched alkyl sulfate anionic surfactant.
• OXO alcohols are alcohols that are prepared by adding carbon monoxide (CO) and hydrogen (usually combined together as synthesis gas) to an olefin to obtain an aldehyde using the hydroformylation reaction and then hydrogenating the aldehyde to obtain the alcohol.
• CO carbon monoxide
• hydrogen usually combined together as synthesis gas
• the alkyl sulfated anionic surfactant comprises from 60% to 85%, preferably from 75% to 85% by weight of the alkyl sulfate anionic surfactant of OXO-derived alkyl sulfated anionic surfactant, wherein OXO alcohols are alcohols that are prepared by adding carbon monoxide (CO) and hydrogen to an olefin to obtain an aldehyde using the hydroformylation reaction and then hydrogenating the aldehyde to obtain the alcohol.
• CO carbon monoxide
• the alkyl sulfated anionic surfactant then comprises at least 30%, preferably from 40% to 95%, more preferably from 50% to 85% by weight of alkyl sulfated anionic surfactant of this alternative process derived alkyl sulfate anionic surfactant, or of a mixture of OXO derived and this alternative process derived alkyl sulfate anionic surfactant.
• ethoxylated alkyl sulfate is present, without wishing to be bound by theory, through tight control of processing conditions and feedstock material compositions, both during alkoxylation especially ethoxylation and sulfation steps, the amount of 1,4-dioxane by-product within alkoxylated especially ethoxylated alkyl sulfates can be reduced. Based on recent advances in technology, a further reduction of 1,4-dioxane by-product can be achieved by subsequent stripping, distillation, evaporation, centrifugation, microwave irradiation, molecular sieving or catalytic or enzymatic degradation steps.
• 1,4-dioxane level control within detergent formulations has also been described in the art through addition of 1,4-dioxane inhibitors to 1,4-dioxane comprising formulations, such as 5,6-dihydro-3-(4-morpholinyl)-1-[4-(2-oxo-1-piperidinyl)-phenyl]-2-(1-H)-pyridone, 3- ⁇ -hydroxy-7-oxo stereoisomer-mixtures of cholinic acid, 3-(N- methyl amino)-L-alanine, and mixtures thereof.
• 1,4-dioxane inhibitors such as 5,6-dihydro-3-(4-morpholinyl)-1-[4-(2-oxo-1-piperidinyl)-phenyl]-2-(1-H)-pyridone, 3- ⁇ -hydroxy-7-oxo stereoisomer-mixtures of cholinic acid, 3-(N- methyl amino)-L-alanine
• the surfactant system can comprise a co-surfactant in addition to the anionic surfactant.
• the co-surfactant can be selected from the group consisting of an amphoteric surfactant, a zwitterionic surfactant, and mixtures thereof.
• the weight ratio of anionic surfactant to the co-surfactant can be from 2.0:1 to 8.0:1, preferably from 2.0:1 to 5.0:1, more preferably from 2.5:1 to 4.0:1, in order to provide improved grease cleaning, sudsing and viscosity build.
• the surfactant system can comprise from 0.1% to 20%, preferably from 0.5% to 15%, more preferably from 2% to 10% by weight of the cleaning composition of the co-surfactant.
• the surfactant system of the cleaning composition of the present invention can comprise from 10% to 40%, preferably from 15% to 35%, more preferably from 20% to 30%, by weight of the surfactant system of the co-surfactant.
• the co-surfactant can be an amphoteric surfactant, such as an amine oxide surfactant.
• the amine oxide surfactant can be linear or branched, though linear are preferred.
• Suitable linear amine oxides are typically water-soluble, and characterized by the formula R1 - N(R2)(R3) O wherein 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.
• R2 and R3 can be selected from the group consisting of: methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl, and mixtures thereof, though methyl is preferred for one or both of R2 and R3.
• the linear amine oxide surfactants in particular may include linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
• the amine oxide surfactant is selected from the group consisting of: alkyl dimethyl amine oxide, alkyl amido propyl dimethyl amine oxide, and mixtures thereof.
• Alkyl dimethyl amine oxides are preferred, such as C8-18 alkyl dimethyl amine oxides, or C10-16 alkyl dimethyl amine oxides (such as coco dimethyl amine oxide).
• Suitable alkyl dimethyl amine oxides include C10 alkyl dimethyl amine oxide surfactant, C10-12 alkyl dimethyl amine oxide surfactant, C12-C14 alkyl dimethyl amine oxide surfactant, and mixtures thereof.
• C12-C14 alkyl dimethyl amine oxide are particularly preferred.
• the alkyl chain of the alkyl dimethyl amine oxide is a linear alkyl chain, preferably a C12-C14 alkyl chain, more preferably a C12-C14 alkyl chain derived from coconut oil or palm kernel oil.
• amine oxide surfactants include mid-branched amine oxide surfactants.
• mid-branched means that the amine oxide has one alkyl moiety having n1 carbon atoms with one alkyl branch on the alkyl moiety having n2 carbon atoms. The alkyl branch is located on the ⁇ carbon from the nitrogen on the alkyl moiety. This type of branching for the amine oxide is also known in the art as an internal amine oxide.
• the total sum of n1 and n2 can be from 10 to 24 carbon atoms, preferably from 12 to 20, and more preferably from 10 to 16.
• the number of carbon atoms for the one alkyl moiety (n1) is preferably the same or similar to the number of carbon atoms as the one alkyl branch (n2) such that the one alkyl moiety and the one alkyl branch are symmetric.
• symmetric means that
• 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 from 1 to 3 ethylene oxide groups.
• the two moieties are selected from a C1-3 alkyl, more preferably both are selected as C1 alkyl.
• the amine oxide surfactant can be a mixture of amine oxides comprising a mixture of low-cut amine oxide and mid-cut amine oxide.
• the amine oxide of the composition of the invention can then comprises:
• R3 is n-decyl, with preferably both R1 and R2 being methyl.
• R4 and R5 are preferably both methyl.
• the amine oxide comprises less than 5%, more preferably less than 3%, by weight of the amine oxide of an amine oxide of formula R7R8R9AO wherein R7 and R8 are selected from hydrogen, C1-C4 alkyls and mixtures thereof and wherein R9 is selected from C8 alkyls and mixtures thereof.
• R7R8R9AO Limiting the amount of amine oxides of formula R7R8R9AO improves both physical stability and suds mileage.
• the co-surfactant can be zwitterionic surfactants such as a betaine surfactant.
• betaine surfactants include alkyl betaines, alkylamidobetaine, amidazoliniumbetaine, sulphobetaine (INCI Sultaines) as well as the Phosphobetaine, and preferably meets formula (I): R 1 -[CO-X(CH 2 ) n ] x -N + (R 2 )(R 3 )-(CH 2 ) m -[CH(OH)-CH 2 ] y -Y - wherein in formula (I),
• Preferred betaines are the alkyl betaines of formula (IIa), the alkyl amido propyl betaine of formula (IIb), the sulphobetaines of formula (IIc) and the amido sulphobetaine of formula (IId): 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 which R1 has the same meaning as in formula (I).
• Suitable betaines can be selected from the group consisting or [designated in accordance with INCI]: capryl/capramidopropyl betaine, cetyl betaine, cetyl amidopropyl betaine, cocamidoethyl betaine, cocamidopropyl betaine, cocobetaines, decyl betaine, decyl amidopropyl betaine, hydrogenated tallow betaine / amidopropyl betaine, isostearamidopropyl betaine, lauramidopropyl betaine, lauryl betaine, myristyl amidopropyl betaine, myristyl betaine, oleamidopropyl betaine, oleyl betaine, palmamidopropyl betaine, palmitamidopropyl betaine, palm-kernelamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, tallowamidopropyl betaine, tallow betaine
• Preferred betaines are selected from the group consisting of: cocamidopropyl betaine, cocobetaines, lauramidopropyl betaine, lauryl betaine, myristyl amidopropyl betaine, myristyl betaine, and mixtures thereof.
• Cocamidopropyl betaine is particularly preferred.
• the surfactant system can further comprise nonionic surfactant, preferably alkoxylated alcohol nonionic surfactant.
• the surfactant system can comprise at least 0.5%, preferably at least 1.0% more preferably at least 2.0% by weight of the composition of the alkoxylated alcohol nonionic surfactant.
• the anionic surfactant and alkoxylated alcohol nonionic surfactant can be present in a weight ratio of less than 10:1.
• the anionic surfactant and 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 composition can comprise greater than 3.0%, preferably from 3.5% to 10%, more preferably from 4.0% to 7.5% by weight of the liquid hand dishwashing detergent composition of an alkoxylated alcohol nonionic surfactant.
• the alkoxylated alcohol non-ionic surfactant is a linear or branched, preferably linear, primary or secondary alkyl alkoxylated non-ionic surfactant, preferably an alkyl ethoxylated non-ionic surfactant, preferably comprising on average from 9 to 15, preferably from 10 to 14 carbon atoms in its alkyl chain and on average from 5 to 12, preferably from 6 to 10, most preferably from 7 to 8, units of alkylene oxide per mole of alcohol.
• the alkoxylated alcohol non-ionic surfactant is preferably ethoxylated and/or propoxylated, more preferably ethoxylated.
• the surfactant system can comprise a further nonionic surfactant such as an alkyl polyglucoside nonionic surfactant:
• a further nonionic surfactant such as an alkyl polyglucoside nonionic surfactant:
• alkylpolyglucoside and anionic surfactant especially alkyl sulfate anionic surfactant, has been found to improve polymerized grease removal, suds mileage performance, reduced viscosity variation with changes in the surfactant and/or system, and a more sustained Newtonian rheology.
• the alkyl polyglucoside surfactant can be selected from C6-C18 alkyl polyglucoside surfactant.
• the alkyl polyglucoside surfactant can have a number average degree of polymerization of from 0.1 to 3.0, preferably from 1.0 to 2.0, more preferably from 1.2 to 1.6.
• the alkyl polyglucoside surfactant can comprise a blend of short chain alkyl polyglucoside surfactant having an alkyl chain comprising 10 carbon atoms or less, and mid to long chain alkyl polyglucoside surfactant having an alkyl chain comprising greater than 10 carbon atoms to 18 carbon atoms, preferably from 12 to 14 carbon atoms.
• Short chain alkyl polyglucoside surfactants have a monomodal chain length distribution between C8-C10, mid to long chain alkyl polyglucoside surfactants have a monomodal chain length distribution between C10-C18, while mid chain alkyl polyglucoside surfactants have a monomodal chain length distribution between C12-C14.
• C8 to C18 alkyl polyglucoside surfactants typically have a monomodal distribution of alkyl chains between C8 and C18, as with C8 to C16 and the like.
• a combination of short chain alkyl polyglucoside surfactants with mid to long chain or mid chain alkyl polyglucoside surfactants have a broader distribution of chain lengths, or even a bimodal distribution, than non-blended C8 to C18 alkyl polyglucoside surfactants.
• 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. It has been found that a blend of such short chain alkyl polyglucoside surfactant and long chain alkyl polyglucoside surfactant results in faster dissolution of the detergent solution in water and improved initial sudsing, in combination with improved suds stability.
• C8-C16 alkyl polyglucosides are commercially available from several suppliers (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 mid to long chain APG surfactant.
• the alkyl polyglucoside can be present in the surfactant system at a level of from 0.5% to 20%, preferably from 0.75% to 15%, more preferably from 1% to 10%, most preferably from 1% to 5% by weight of the surfactant composition.
• Alkyl polyglucoside nonionic surfactants are typically more sudsing than other nonionic surfactants such as alkyl ethoxlated alcohols.
• the alkyl polyglucoside is 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.
• composition is free of any further nonionic surfactant.
• the liquid hand dishwashing detergent comprises a quaternised acrylic copolymer.
• "Copolymer” as used herein refers to a polymer comprising at least two different monomer compositions.
• Quaternised polymers comprise quaternary ammonium groups, which are positively charged polyatomic ions of the structure NR 4 + , R being an alkyl group or an aryl group. Unlike the ammonium ion (NH 4 + ) and the primary, secondary, or tertiary ammonium cations, the quaternary ammonium cations are permanently charged, independent of the pH of their solution.
• 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 quaternised acrylic copolymer.
• the quaternised acrylic copolymer can have a weight average molecular weight (Mw), measured by aqueous gel permeation chromatography (GPC) with light scattering detection (SEC-MALLS), in the range of from 5,000 to 500,000 Da, preferably from 15,000 to 300,000 Da and even more preferably from 25,000 to 75,000 Da.
• Mw weight average molecular weight
• GPC gel permeation chromatography
• SEC-MALLS light scattering detection
• the quaternised acrylic copolymer may be characterized by a cationic charge density.
• Cationic charge density is 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, more preferably from 1.75 mEq/g to 2.75 mEq/g.
• CCD cationic charge density
• the different types of monomer units are randomly distributed over the quaternised acrylic copolymer.
• the quaternised acrylic copolymer is preferably derived from cationic monomer units and ethylenically unsaturated monomer units.
• X - is a suitable counterion, preferably X - is independently selected from a halide counterion, more preferably Cl - .
• linking group Y is dependent on the reaction scheme used to make the quaternised acrylic copolymer.
• all Y are the same.
• all R 5 are the same.
• the cationic monomer units can be selected from the group consisting of: acrylamidopropyl trimethylammonium chloride (APTAC), methacrylamidopropyltrimethylammonium chloride (MAPTAC), diallyl dimethyl ammonium chloride (DADMAC), acryloyloxyethyltrimethylammonium chloride (AETAC), methyloyloxyethyltrimethyl ammonium chloride (METAC), and mixtures thereof.
• ATAC acrylamidopropyl trimethylammonium chloride
• MMAPTAC methacrylamidopropyltrimethylammonium chloride
• DMAC diallyl dimethyl ammonium chloride
• AETAC acryloyloxyethyltrimethylammonium chloride
• METAC methyloyloxyethyltrimethyl ammonium chloride
• Particularly preferred cationic monomers are (meth)acrylamidopropyltrimethylammonium chloride (APTAC or MAPTAC) or diallyldimethylammonium chloride (DADMAC), with methacrylamidopropyltrimethylammonium chloride (MAPTAC) being most preferred.
• ATAC or MAPTAC diallyldimethylammonium chloride
• DADMAC methacrylamidopropyltrimethylammonium chloride
• Two polymeric structures are possible when polymerizing DADMAC: N-substituted piperidine structure or N-substituted pyrrolidine structure. The pyrrolidine structure is favored (see John, Wilson; et al. (2002), Synthesis and Use of PolyDADMAC for Water Purification).
• the ethylenically unsaturated monomers can be selected from the group consisting of: C3-C8 ethylenically unsaturated acids and/or salts thereof, C3-C8 hydroxyalkyl acrylates, and mixtures thereof.
• C3-C8 it is meant that the ethylenically unsaturated acids and/or salts thereof, or C3-C8 hydroxyalkyl acrylate comprises from 3 to 8 carbon atoms.
• Suitable C3-C8 ethylenically unsaturated acids and/or salts thereof include (meth)acrylic acid and mixtures thereof, with acrylic acid being preferred.
• Suitable salts include alkali metal and ammonium salts.
• 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 quaternised acrylic copolymer can further comprise additional monomers selected from the group consisting of: ethyl acrylate, 2-acrylamido-2-methylpropane-sulfonic acid, N-isopropylamide, vinylpyrrolidone, and mixtures thereof, as polymerized monomers, with ethyl acrylate and/or vinylpyrrolidone being preferred, with ethyl acrylate being particularly preferred.
• the additional monomer is preferably present at a level of less than 20 mol%, preferably less than 15 mol%, more preferably less than 10% of the total monomers present in the quaternised acrylic.
• the quaternised acrylic copolymer can comprise diallyldimethylammonium chloride (DADMAC) as the cationic monomer with hydroxyethylacrylate as the ethylenically unsaturated monomer.
• DMDMAC diallyldimethylammonium chloride
• Such quaternised acrylic copolymers can comprise vinylpyrrolidone as an additional monomer.
• Such quaternised acrylic copolymers include those sold under the tradename of Mirapol ® SURF-S FAST DRY by Solvay.
• the quaternised acrylic copolymer can comprise (meth)acrylamidopropyltrimethylammonium chloride (APTAC or MAPTAC) as the cationic monomer, with acrylate and/or ethyl acrylate as the ethylenically unsaturated monomer.
• ATAC or MAPTAC acrylamidopropyltrimethylammonium chloride
• Such quaternised acrylic copolymers can comprise ethyl acrylate as an additional monomer.
• Such quaternised acrylic copolymers include those sold under the tradename of Polyquart ® by BASF, with Polyquart149A ® being particularly preferred.
• composition can comprise further ingredients such as those selected from: amphiphilic alkoxylated polyalkyleneimines, cyclic polyamines, triblock copolymers, salts, hydrotropes, organic solvents, other adjunct ingredients such as those described herein, and mixtures thereof.
• Amphiphilic alkoxylated polyalkyleneimine The composition 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 can be selected from the group consisting of: amphiphilic alkoxylated polyalkyleneimine and mixtures thereof.
• the amphiphilic alkoxylated polyalkyleneimine polymer has been found to reduce gel formation on the hard surfaces to be cleaned when the liquid composition is added directly to a cleaning implement (such as a sponge) before cleaning and consequently brought in contact with heavily greased surfaces, especially when the cleaning implement comprises a low amount to nil water such as when light pre-wetted sponges are used.
• a preferred amphiphilic alkoxylated polyethyleneimine polymer has the general structure of formula (I): wherein the polyethyleneimine backbone has a weight average molecular weight of 600, n of formula (I) has an average of 10, m of formula (I) has an average of 7 and R of formula (I) is selected from hydrogen, a C 1 -C 4 alkyl and mixtures thereof, preferably hydrogen.
• the degree of permanent quaternization of formula (I) may be from 0% to 22% of the polyethyleneimine backbone nitrogen atoms.
• the molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer preferably is between 10,000 and 15,000 Da.
• the amphiphilic alkoxylated polyethyleneimine polymer has the general structure of formula (I) but wherein the polyethyleneimine backbone has a weight average molecular weight of 600 Da, n of Formula (I) has an average of 24, m of Formula (I) has an average of 16 and R of Formula (I) is selected from hydrogen, a C 1 -C 4 alkyl and mixtures thereof, preferably hydrogen.
• the degree of permanent quaternization of Formula (I) may be from 0% to 22% of the polyethyleneimine backbone nitrogen atoms and is preferably 0%.
• the molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer preferably is between 25,000 and 30,000, most preferably 28,000 Da.
• amphiphilic alkoxylated polyethyleneimine polymers can be made by the methods described in more detail in PCT Publication No. WO 2007/135645 .
• the composition can comprise a cyclic polyamine having amine functionalities that helps cleaning.
• the composition of the invention preferably comprises from 0.1% to 3%, more preferably from 0.2% to 2%, and especially from 0.5% to 1%, by weight of the composition, of the cyclic polyamine.
• the cyclic polyamine has at least two primary amine functionalities.
• the primary amines can be in any position in the cyclic amine but it has been found that in terms of grease cleaning, better performance is obtained when the primary amines are in positions 1,3. It has also been found that cyclic amines in which one of the substituents is -CH3 and the rest are H provided for improved grease cleaning performance.
• the most preferred cyclic polyamine for use with the cleaning composition of the present invention are cyclic polyamine selected from the group consisting of: 2-methylcyclohexane-1,3-diamine, 4-methylcyclohexane-1,3-diamine and mixtures thereof. These specific cyclic polyamines work to improve suds and grease cleaning profile through-out the dishwashing process when formulated together with the surfactant system of the composition of the present invention.
• Suitable cyclic polyamines can be supplied by BASF, under the Baxxodur tradename, with Baxxodur ECX-210 being particularly preferred.
• the composition can further comprise magnesium sulphate at a level of from 0.001 % to 2.0 %, preferably from 0.005 % to 1.0 %, more preferably from 0.01 % to 0.5 % by weight of the composition.
• the composition of the invention can comprise a triblock copolymer.
• the triblock co-polymers can be present at a level of from 0.1% to 10%, preferably from 0.5% to 7.5%, more preferably from 1% to 5%, by weight of the total composition.
• Suitable triblock copolymers include alkylene oxide triblock co-polymers, defined as a triblock co-polymer having alkylene oxide moieties according to Formula (I): (EO)x(PO)y(EO)x, wherein EO represents ethylene oxide, and each x represents the number of EO units within the EO block.
• Each x can independently be on average of from 5 to 50, preferably from 10 to 40, more preferably from 10 to 30.
• x is the same for both EO blocks, wherein the "same" means that the x between the two EO blocks varies within a maximum 2 units, preferably within a maximum of 1 unit, more preferably both x's are the same number of units.
• PO represents propylene oxide
• y represents the number of PO units in the PO block. Each y can on average be from between 28 to 60, preferably from 30 to 55, more preferably from 30 to 48.
• the triblock co-polymer has a ratio of y to each x of from 3:1 to 2:1.
• the triblock co-polymer preferably has a ratio of y to the average x of 2 EO blocks of from 3:1 to 2:1.
• the triblock co-polymer has an average weight percentage of total EO of between 30% and 50% by weight of the tri-block co-polymer.
• the triblock co-polymer has an average weight percentage of total PO of between 50% and 70% by weight of the triblock co-polymer. It is understood that the average total weight % of EO and PO for the triblock co-polymer adds up to 100%.
• the triblock co-polymer can have an average molecular weight of between 2060 and 7880, preferably between 2620 and 6710, more preferably between 2620 and 5430, most preferably between 2800 and 4700. Average molecular weight is determined using a 1H NMR spectroscopy ( see Thermo scientific application note No. AN52907).
• Triblock co-polymers have the basic structure ABA, wherein A and B are different homopolymeric and/or monomeric units.
• A is ethylene oxide (EO) and B is propylene oxide (PO).
• EO ethylene oxide
• PO propylene oxide
• block copolymers is synonymous with this definition of "block polymers”.
• Triblock co-polymers according to Formula (I) with the specific EO/PO/EO arrangement and respective homopolymeric lengths have been found to enhances suds mileage performance of the liquid hand dishwashing detergent composition in the presence of greasy soils and/or suds consistency throughout dilution in the wash process.
• Suitable EO-PO-EO triblock co-polymers are commercially available from BASF such as Pluronic ® PE series, and from the Dow Chemical Company such as Tergitol TM L series.
• Particularly preferred triblock co-polymer from BASF are sold under the tradenames Pluronic ® PE6400 (MW ca 2900, ca 40wt% EO) and Pluronic ® PE 9400 (MW ca 4600, 40 wt% EO).
• Particularly preferred triblock co-polymer from the Dow Chemical Company is sold under the tradename Tergitol TM L64 (MW ca 2700, ca 40 wt% EO).
• Preferred triblock co-polymers are readily biodegradable under aerobic conditions.
• composition of the present invention may further comprise at least one active selected from the group consisting of: salt, hydrotrope, organic solvent, and mixtures thereof.
• composition of the present invention may comprise from 0.05% to 2%, preferably from 0.1% to 1.5%, or more preferably from 0.5% to 1%, by weight of the total composition of a salt, preferably a monovalent or divalent inorganic salt, or a mixture thereof, more preferably selected from: sodium chloride, sodium sulfate, and mixtures thereof.
• a salt preferably a monovalent or divalent inorganic salt, or a mixture thereof, more preferably selected from: sodium chloride, sodium sulfate, and mixtures thereof.
• sodium chloride is most preferred.
• composition of the present invention may comprise from 0.1% to 10%, or preferably from 0.5% to 10%, or more preferably from 1% to 10% by weight of the total composition of a hydrotrope or a mixture thereof, preferably sodium cumene sulfonate.
• the composition can comprise from 0.1% to 10%, or preferably from 0.5% to 10%, or more preferably from 1% to 10% by weight of the total composition of an organic solvent.
• 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 the preferred alcohol.
• Polyalkyleneglycols, especially polypropyleneglycol (PPG), are the preferred glycol.
• the polypropyleneglycol can have a molecular weight of from 400 to 3000, preferably from 600 to 1500, more preferably from 700 to 1300.
• the polypropyleneglycol is preferably poly-1,2-propyleneglycol.
• the cleaning composition may optionally comprise a number of other adjunct ingredients such as builders (preferably citrate), chelants, conditioning polymers, other cleaning polymers, surface modifying polymers, structurants, emollients, humectants, skin rejuvenating actives, enzymes, carboxylic acids, scrubbing particles, perfumes, malodor control agents, pigments, dyes, opacifiers, pearlescent particles, inorganic cations such as alkaline earth metals such as Ca/Mg-ions, antibacterial agents, preservatives, viscosity adjusters (e.g., salt such as NaCl, and other mono-, di- and trivalent salts) and pH adjusters and buffering means (e.g. carboxylic acids such as citric acid, HCl, NaOH, KOH, alkanolamines, carbonates such as sodium carbonates, bicarbonates, sesquicarbonates, and alike).
• adjunct ingredients such as builders (preferably citrate), chelants, conditioning polymers, other cleaning polymers, surface
• the hand dishwashing detergent composition can be packaged in a container, typically plastic containers.
• Suitable containers comprise an orifice.
• the container comprises a cap, with the orifice typically comprised on the cap.
• the cap can comprise a spout, with the orifice at the exit of the spout.
• the spout can have a length of from 0.5 mm to 10 mm.
• the orifice can have an open cross-sectional surface area at the exit of from 3 mm 2 to 20 mm 2 , preferably from 3.8 mm 2 to 12 mm 2 , more preferably from 5 mm 2 to 10 mm 2 , wherein the container further comprises the composition according to the invention.
• the cross-sectional surface area is measured perpendicular to the liquid exit from the container (that is, perpendicular to the liquid flow during dispensing).
• the container can typically comprise from 200 ml to 5,000 ml, preferably from 350 ml to 2000 ml, more preferably from 400 ml to 1,000 ml of the liquid hand dishwashing detergent composition.
• compositions of use in the present invention are used in methods of manually washing dishware.
• the method comprises the step of: contacting dishware with a liquid hand dishwashing detergent composition and water, wherein: the liquid hand dishwashing detergent composition comprises a quaternized acrylic copolymer and a surfactant system, wherein the surfactant system comprises an anionic surfactant system comprising alkyl sulfated anionic surfactant, wherein the alkyl sulfated anionic surfactant has an average degree of alkoxylation of less than 0.1, and the water has a temperature of 30 °C or less, preferably wherein the water has a temperature of from 20 °C to 30 °C.
• the water present in usual households can typically have a hardness of up to 3.0 mmol/l CaCO 3 equivalence.
• the method described herein is suitable for use when washing with water having a hardness of up to 3.0 mmol/l, preferably 0.3 mmol/l to 2.7 mmol/l, more preferably from 0.75 mmol/l to 2 mmol/l CaCO 3 equivalence.
• Suitable methods can include the steps of delivering a liquid hand dishwashing composition to a volume of water to form a wash solution and immersing the dishware in the wash solution.
• the dishware is cleaned with the composition in the presence of water.
• the wash solution can comprise the liquid hand dishwashing detergent composition at a level of from 100 ppm to 10,000 ppm, preferably from 200 ppm to 5000 ppm, more preferably from 500 ppm to 2000 ppm.
• 1.0 ml to 25 ml preferably from 1.0 ml to 25 ml, more preferably from 2.5 ml to 10 ml of the liquid hand dishwashing detergent composition is combined with 1.0 1 to 15 l, preferably from 1.5 l to 10 1, more preferably from 2.5 to 7.5 l of water to form the wash solution.
• the actual amount of detergent composition used will be based on the judgment of the user, and will typically depend upon factors such as the particular product formulation of the detergent composition, including the concentration of active ingredients in the detergent composition, the number of soiled dishes to be cleaned, the degree of soiling on the dishes, and the like.
• the soiled dishware is immersed in the wash liquor obtained, before scrubbing the soiled surface of the dishware with a cloth, sponge, or similar cleaning implement.
• the cloth, sponge, or similar cleaning implement is typically contacted with the dishware for a period of time ranged from 1 to 10 seconds, although the actual time will vary with each application and user preferences. Scrubbing can sometimes also take place after a period of soaking, for instance, after about 30 minutes of soaking.
• the liquid hand dishwashing detergent composition and the water are combined on a device, preferably wherein the device is a brush, a sponge, a nonwoven material, or a woven material, more preferably wherein the device is a sponge.
• the liquid hand dishwashing detergent composition and water can be combined on or in the device at ratios of from 25:75 to 1:99, preferably 15:85 to 1:99, more preferably 10:90 to 1:99.
• the cleaning device or implement and consequently the liquid dishwashing composition and the water, is directly contacted to the surface of each of the soiled dishes, to remove the soiling.
• the cleaning device or implement is typically contacted with each dishware surface for a period of time range from 1 to 10 seconds, although the actual time of application will depend upon factors such as the degree of soiling of the dish.
• the contacting of said cleaning device or implement to the dish surface is preferably accompanied by concurrent scrubbing
• the dishware can be subsequently rinsed.
• rinse it is meant herein contacting the dishware cleaned with the process according to the present invention with substantial quantities of water.
• substantial quantities it is meant usually from 1.0 to 20 L, or under running water.
• GPC-MALS/RI Gel Permeation Chromatography
• MALS Multi-Angle Light Scattering
• RI Refractive Index Detection
• the true number-average molecular weight, M n of polymers can be obtained by GPC coupled with light-scattering detection and refractive index detection even if the composition and therefore the refractive index increment varies with elution volume, provided slices taken are sufficiently monodisperse with respect to molecular weight and composition.
• the molecular weight distribution of 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, CA, USA) provided with two ultrahydrogel linear columns, 7.8mm ID x 300 mm length used in series (S/N 002C180181 VE077 and 005C180181 VE084, supplied by Waters Corporation of Milford, Mass., USA) and an ultrahydrogel guard column (6mm ID x 40mm length, S/N2016260401BE105, also supplied 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, operated at 40°C.
• a multiangle light scattering (MALS) detector DAWN ® and a differential refractive index (RI) detector (Wyatt Technology of Santa Barbara, Calif., USA) controlled by Wyatt Astra ® software can be used for the detection.
• an isocratic rather than gradient elution method can be used. Isocratic means that the mixture of your mobile phase is consistent over the complete testing time. Using a gradient implies that the compounding of the eluent mixture is changed during measurement and so influences the retention of analytes. The separation can be either accelerated or decelerated when using a gradient method.
• 0.1M 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 ⁇ 1.0 mg per ml and by mixing the solution overnight at room temperature to ensure full hydration of the polymer.
• the sample is then filtered through a 0.8 ⁇ m Versapor membrane filter (AP4189, supplied by PALL, Life Sciences, NY, USA) into the LC autosampler vial using a 3-ml syringe.
• the sample is then pumped into the columns at a flow rate of 1.0 mL/min.
• the number average and weight average molecular weights of the polymer are calculated from the dn/dc (differential change of refractive index with concentration) measurements, as provided by the Astra detector software.
• the objective of the Suds Mileage Test is to compare the evolution over time of suds volume generated for different test formulations at specified water hardness, solution temperatures and formulation concentrations, while under the influence of periodic soil injections. Data are compared and expressed versus a reference composition or test condition as a suds mileage index (reference composition or test condition has suds mileage index of 100).
• the steps of the method are as follows:
• the greasy soil composition used in the test is produced through standard mixing of the components described in Table 1.
• Table 1 Greasy Soil Ingredient Weight % Crisco Oil 12.730 Crisco shortening 27.752 Lard 7.638 Refined Rendered Edible Beef Tallow 51.684 Oleic Acid, 90% (Techn) 0.139 Palmitic Acid, 99+% 0.036 Stearic Acid, 99+% 0.021
• compositions were prepared and evaluated for suds mileage benefit in the presence of greasy soil, at a water hardness of 1.25 mmol/L equivalence of Ca, and wash water temperatures of 25 °C (inventive wash method) and 40 °C (comparative and reference wash method), as described herein.
• Example 1 comprised both a quaternised acrylic copolymer and unalkoxylated alkyl sulfate anionic surfactant and hence was of the invention.
• Example A was similar to example 1 but did not comprise a quaternised acrylic copolymer.
• Example B was similar to example 1 but comprised ethoxylated alkyl sulfate anionic surfactant instead of unalkoxylated alkyl sulfate anionic surfactant.
• Example C was similar to example 1 but comprised ethoxylated alkyl sulfate anionic surfactant instead of unalkoxylated alkyl sulfate anionic surfactant and did not comprise a quaternised acrylic copolymer.
• examples A, B and C were comparative compositions.

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