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EP3456799B1 - Composition de nettoyage liquide pour laver la vaisselle à la main - Google Patents

Composition de nettoyage liquide pour laver la vaisselle à la main Download PDF

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Publication number
EP3456799B1
EP3456799B1 EP17191347.8A EP17191347A EP3456799B1 EP 3456799 B1 EP3456799 B1 EP 3456799B1 EP 17191347 A EP17191347 A EP 17191347A EP 3456799 B1 EP3456799 B1 EP 3456799B1
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EP
European Patent Office
Prior art keywords
surfactant
alkyl
weight
branched
sulfate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP17191347.8A
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German (de)
English (en)
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EP3456799A1 (fr
Inventor
Jan Julien Marie-Louise Billiauw
Roel Krols
Christopher Stephen Jones
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
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Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to ES17191347T priority Critical patent/ES2871098T3/es
Priority to EP17191347.8A priority patent/EP3456799B1/fr
Priority to PCT/US2018/049431 priority patent/WO2019055249A1/fr
Publication of EP3456799A1 publication Critical patent/EP3456799A1/fr
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Publication of EP3456799B1 publication Critical patent/EP3456799B1/fr
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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
    • C11D1/66—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming 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
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/75—Amino oxides
    • 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

Definitions

  • the present invention relates to a liquid hand dishwashing cleaning composition
  • a liquid hand dishwashing cleaning composition comprising a surfactant system comprising an anionic surfactant and a co-surfactant, wherein the anionic surfactant is selected from a mixture of a linear anionic surfactant and a branched anionic surfactant with a defined degree of branching on branched alkyl sulfate and branched alkyl ethoxy sulfate surfactant.
  • the composition provides good sudsing profile, in particular suds stabilization benefit in the presence of particulate soils.
  • the composition also provides good cleaning of particulate soils.
  • the user relies on the sudsing profile as an indicator of the composition's cleaning ability.
  • the generated foam must produce high suds volume and/or longevity (i.e., mileage) of the suds ( i.e., stable suds), preferably with sustained suds aesthetics throughout dilution during the wash process ( i.e., suds whiteness and consistency), to indicate to the user that sufficient active ingredients (e.g ., surfactants) are present to perform the desired cleaning.
  • branched anionic surfactant comprises a defined branching split between branched alkyl sulfate and branched alkyl ethoxy sulfate anionic surfactant, in particular to improve suds generation and/or suds stabilization in the presence of particulate soils.
  • the need remains for a cleaning composition having a good sudsing profile, in particular increased suds volume and/or increased suds stabilization benefits in the presence of particulate soils, particularly through-out the entire manual dishwashing operation.
  • the need also exists for a cleaning composition, particularly a hand dishwashing cleaning composition, that sustains suds aesthetics throughout the dilution and the wash process, and provides good product dissolution and good cleaning, particularly good cleaning of particulate soils.
  • the Applicant has discovered that some or all of the above-mentioned needs can be at least partially fulfilled through cleaning compositions as described herein below.
  • EP2757144A1 relates to a liquid detergent comprising from about 5% to about 20% by weight thereof of a surfactant system wherein the surfactant system comprises a branched anionic surfactant having a level of branching of from about 5% to about 40% and wherein the detergent at 20°C has a pouring viscosity of from about 2500 mPa s to about 6000 mPa s as measured at 20°C and a ratio of medium to high shear viscosity of from about 2 to about 1.
  • EP2264136A1 relates to a hand dishwashing detergent composition comprising a chelant and branched surfactants to provide superior grease cleaning and shine.
  • WO2006/069211A1 relates to a detergent composition
  • a detergent composition comprising an alkyl ethoxylate sulfate surfactant having an average ethoxylation level of from 1 to 5; from 1% to 8.5%, by weight of said composition, of amine oxide; and a pH from 5.5 to 8.5,
  • the composition comprises a combined level of free fatty alcohols and sulfated alcohols of less than 3% by weight of said composition.
  • WO2017/079960A1 relates to cleaning compositions with improved sudsing profiles which contain the combination of one or more branched, unethoxylated C6-C14 alkyl sulphate surfactants with one or more linear, unalkoxylated C6-C18 alkyl sulfate surfactants, the cleaning compositions being particularly suitable for hand-washing dishes or fabrics.
  • WO2002/044312A relates to a hand dishwashing composition which includes from 0.1 % to 90 % of a sudsing surfactant, an effective amount of a suds suppresser, and the balance adjunct ingredients, as well as a method for reducing the amount of water used during the rinsing step of a hand dishwashing process.
  • the present invention meets one or more of these needs based on the surprising discovery that by formulating a cleaning composition having a surfactant system comprising an anionic surfactant selected from a mixture of a linear anionic surfactant and a branched anionic surfactant, with a defined degree of branching between a branched alkyl sulfate and a branched alkyl ethoxy sulfate surfactant, such a composition exhibits good sudsing profile, particularly desirable suds volume and sustained suds stabilization in the presence of particulate soils.
  • the present invention is directed to a liquid hand dishwashing cleaning composition according to claim 1, comprising from 1% to 60%, preferably from 5% to 50%, more preferably from 8% to 45%, most preferably from 15% to 40%, by weight of the total composition of a surfactant system comprising an anionic surfactant and a co-surfactant.
  • the anionic surfactant has an average alkyl chain length of from 8 to 18, preferably from 10 to 14, more preferably from 12 to 14, most preferably from 12 to 13 carbon atoms.
  • the anionic surfactant has a weight average degree of branching of from 35% to 60%, preferably from 38% to 55%, most preferably from 40% to 50%, and an average degree of ethoxylation of less than 5, preferably less than 3, more preferably less than 2 and more than 0.5, most preferably between 0.5 and 0.9.
  • the anionic surfactant consists of a mixture of an alkyl sulfate and an alkyl alkoxy sulfate preferably an alkyl ethoxy sulfate, preferably the mixture of the alkyl sulfate and the alkyl alkoxy sulfate preferably the alkyl ethoxy sulfate is a mixture of linear anionic surfactant and branched anionic surfactant.
  • the branched anionic surfactant consists of from 5% to 25%, preferably from 10% to 20%, by weight of the total branched anionic surfactant of a branched alkyl ethoxy sulfate surfactant and from 75% to 95%, preferably from 80% to 90%, by weight of the total branched anionic surfactant of a branched alkyl sulfate surfactant, wherein the branching split between branched alkyl sulfate and branched alkyl alkoxy sulfate is defined based on the formulated molecules within the final formulation rather than the added raw materials.
  • the co-surfactant is selected from the group consisting of an amphoteric surfactant, a zwitterionic surfactant and mixtures thereof, preferably an amphoteric surfactant, more preferably an amine oxide surfactant.
  • the weight ratio of the anionic surfactant to the co-surfactant is from 1:1 to 8:1, preferably from 2:1 to 5:1, more preferably from 2.5:1 to 4:1.
  • the present invention includes a liquid hand dishwashing cleaning composition
  • a liquid hand dishwashing cleaning composition comprising from 15% to 40% by weight of the total composition of a surfactant system comprising an anionic surfactant, and an amine oxide co-surfactant.
  • the anionic surfactant has a weight average degree of branching of from 40% to 50%, and an average degree of ethoxylation of between 0.5 and 0.9.
  • the anionic surfactant is selected from a mixture of a linear anionic and a branched anionic surfactant.
  • the linear anionic surfactant is a mixture of a linear alkyl sulfate surfactant and a linear alkyl ethoxy sulfate surfactant.
  • the branched anionic surfactant is a mixture of from 10% to 20% by weight of the total branched anionic surfactant of a branched alkyl ethoxy sulfate surfactant and from 80% to 90% by weight of the total branched anionic surfactant of a branched alkyl sulfate surfactant.
  • the weight ratio of the anionic surfactant to the amine oxide co-surfactant is between 2.5:1 and 4:1.
  • a method of manually washing dishware using the composition of the invention comprises the steps of: delivering a composition of the invention to a volume of water to form a wash solution and immersing the dishware in the solution.
  • composition of the invention for the stabilization of suds in the presence of particulate soils.
  • composition of the present invention it is an object of the composition of the present invention to exhibit good sudsing profile, preferably high suds volume and sustained suds aesthetics (i.e. whiteness and/or consistency) throughout dilution and the wash process.
  • composition of the present invention it is an object of the composition of the present invention to exhibit good sudsing profile, preferably stable suds during a substantial portion of or for the entire manual dishwashing process.
  • good tough food cleaning e.g., cooked-, baked- and burnt-on soils
  • good product dissolution and particulate soil cleaning e.g., cooked-, baked- and burnt-on soils
  • 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.
  • ishware 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 present invention relates to a liquid hand dishwashing cleaning compositions having a good sudsing profile, including high suds volume generation and/or sustained suds stabilization through-out a substantial portion of, or the entire dishwashing process. This signals to the user that there are still sufficient active ingredients present to provide good cleaning performance, as such triggering less re-dosing and overconsumption of the product by the user.
  • the Applicant has surprisingly found that by selecting a surfactant system with the defined degree of branching and branching split sustained suds stabilization and/or high suds volume can be achieved.
  • the results are unexpected since previous attempts to improve sudsing profile have not focused on the use of such branched anionic surfactant systems.
  • compositions of the present invention present good stability due to the compatibility of the surfactant system with the remaining ingredients of the composition.
  • the composition can also be aesthetically pleasant because the presence of the surfactant system does not alter the appearance of the composition, i.e., transparent, translucent, etc.
  • the composition of the present invention can also provide good grease removal, in particular good uncooked grease removal, and particulate soil removal.
  • the cleaning composition is a hand dishwashing cleaning composition in liquid form.
  • the composition contains from 50% to 85%, preferably from 50% to 75%, by weight of the total composition of a liquid carrier in which the other essential and optional components are dissolved, dispersed or suspended.
  • a liquid carrier in which the other essential and optional components are dissolved, dispersed or suspended.
  • One preferred component of the liquid carrier is 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.
  • the composition has an initial 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. Viscosity is measured with a Brookfield RT Viscometer using spindle 21 at 20 RPM at 25°C.
  • the cleaning composition of the invention is especially suitable for use as a hand dishwashing detergent. Due to its desirable sudsing profile, it is extremely suitable for use in diluted form in a full sink of water to wash dishes.
  • the cleaning composition comprises from 1% to 60%, preferably from 5% to 50%, more preferably from 8% to 45%, most preferably from 15% to 40%, by weight of the total composition of a surfactant system comprising an anionic surfactant and a co-surfactant.
  • the surfactant system for the cleaning composition of the present invention comprises from 60% to 90%, preferably from 65% to 85%, more preferably from 70% to 80%, by weight of the surfactant system of an anionic surfactant.
  • the anionic surfactant consists of a mixture of an alkyl sulfate and an alkyl alkoxy sulfate preferably an alkyl ethoxy sulfate, preferably the mixture of an alkyl sulfate and the alkyl alkoxy sulfate preferably the alkyl ethoxy sulfate is a mixture of linear anionic surfactant and branched anionic surfactant.
  • the preferred average alkyl chain length of the linear anionic surfactant is from 12 to 14 carbon atoms.
  • the surfactant system comprises from 35% to 70%, more preferably from 40% to 65%, even more preferably from 45% to 60%, by weight of the anionic surfactant of a linear anionic surfactant.
  • the branched anionic surfactant is selected from 5% to 25%, preferably from 10% to 20%, by weight of the total branched anionic surfactant of a branched alkyl ethoxy sulfate surfactant and from 75% to 95%, preferably from 80% to 90%, by weight of the total branched anionic surfactant of a branched alkyl sulfate surfactant.
  • This degree of branching and branching split contributes to enhanced suds longevity of the composition. It also contributes to the stability of the detergent.
  • the preferred average alkyl chain length of the branched anionic surfactant is from 12 to 15, more preferably from 12 to 13 carbons.
  • the surfactant system comprises from 30% to 65%, more preferably from 35% to 60%, even more preferably from 40% to 55% by weight of the anionic surfactant of a branched anionic surfactant.
  • composition of the present invention wherein no further anionic surfactant, other than the alkyl sulfate, the alkyl alkoxy sulfate preferably the alkyl ethoxy sulfate, or mixtures thereof, is added to the composition.
  • the weight average degree of branching of the anionic surfactant is from 35% to 60%, preferably from 38% to 55%, more preferably from 40% to 50%.
  • the average degree of ethoxylation of the anionic surfactant mixture is less than 5, preferably less than 3, more preferably less than 2 and more than 0.5, most preferably between 0.5 and 0.9.
  • the average alkoxylation degree is the mol average alkoxylation degree of all the components of the mixture (i.e., mol average alkoxylation degree) of the anionic surfactant. In the mol average alkoxylation degree calculation the weight of sulfate anionic surfactant components not having alkoxylate groups should also be included.
  • Mol average alkoxylation degree x 1 ⁇ alkoxylation degree of surfactant 1 + x 2 ⁇ alkoxylation degree of surfactant 2 + .... / x 1 + x 2 + .... wherein x1, x2, ... are the number of moles of each sulfate anionic surfactant of the mixture and alkoxylation degree is the number of alkoxy groups in each sulfate anionic surfactant.
  • a commercially available branched alkyl ethoxy sulfate raw material will comprise a mixture of linear alkyl sulfate, branched alkyl sulfate, linear alkyl ethoxy sulfate and branched alkyl ethoxy sulfate.
  • the branched alkyl sulfate fraction will have to be considered to calculate the degree of branched alkyl sulfate by weight of the total branched anionic surfactant, while the branched alkyl ethoxy sulfate fraction will have to be considered to calculate the degree of branched alkyl ethoxy sulfate by weight of the total branched anionic surfactant in the final formulation.
  • the actual calculation will have to be executed based on the starting alcohol and ethoxylated alcohols, rather than on the final sulfated materials, as explained in the weight average degree of branching calculation above.
  • Suitable counterions include alkali metal cation earth alkali metal cation, alkanolammonium or ammonium or substituted ammonium, but preferably sodium.
  • Suitable examples of commercially available sulfates include, those based on Neodol alcohols ex the Shell company, Lial - Isalchem and Safol® ex the Sasol company, natural alcohols ex The Procter & Gamble Chemicals company.
  • the skilled person in the art can create mixtures of these starting materials to achieve the anionic surfactant composition according to the invention, considering the relative fractions of linear alkyl sulfate, linear alkyl ethoxy sulfate, branched alkyl sulfate and branched alkyl ethoxy sulfate, as obtained from the technical data sheets from the relative suppliers or analytically analyzed.
  • the branched alkyl ethoxy sulfate surfactant of the present invention comprises at least 5%, more preferably at least 10%, by weight of the branched alkyl ethoxy sulfate surfactant of an alkyl ethoxy sulfate surfactant with the branching on the C2 position.
  • the branched alkyl ethoxy sulfate surfactant comprises at least 90%, more preferably 100%, by weight of the branched alkyl ethoxy sulfate surfactant of an alkyl ethoxy sulfate surfactant with the branching on the C2 position.
  • the branched alkyl sulfate surfactant preferably comprises at least 5%, more preferably at least 10%, even more preferably at least 20%, most preferably at least 30%, by weight of the branched alkyl sulfate surfactant of a branched alkyl sulfate surfactant with the branching on the C2 position.
  • the branched alkyl sulfate surfactant comprises at least 90%, more preferably 100% by weight of the branched alkyl sulfate surfactant of a branched alkyl sulfate surfactant with the branching on the C2 position.
  • the branched alkyl group of the branched anionic surfactant is predominantly, preferably greater than 75%, more preferably greater than 90%, of the total branched alkyl content, of a C1-C5 alkyl moiety, preferably a C1-C2 alkyl moiety.
  • the surfactant system of the composition of the present invention comprises a co-surfactant.
  • the composition preferably comprises from 0.1% to 20%, more preferably from 0.5% to 15%, even more preferably from 2% to 10%, by weight of the cleaning composition of the co-surfactant.
  • the surfactant system for the cleaning composition of the present invention comprises from 10% to 40%, preferably from 15% to 35%, more preferably from 20% to 30%, by weight of the surfactant system of a co-surfactant.
  • the co-surfactant is selected from the group consisting of an amphoteric surfactant, a zwitterionic surfactant, and mixtures thereof.
  • the composition of the present invention will preferably comprise an amine oxide as the amphoteric surfactant.
  • the amine oxide surfactant is selected from the group consisting of a linear or branched alkyl amine oxide surfactant, a linear or branched alkyl amidopropyl amine oxide surfactant, and mixtures thereof, more preferably a linear alkyl dimethyl amine oxide surfactant, even more preferably a linear C10 alkyl dimethyl amine oxide surfactant, a linear C12-C14 alkyl dimethyl amine oxide surfactant, and mixtures thereof, most preferably a linear C12-C14 alkyl dimethyl amine oxide surfactant
  • the amine oxide surfactant is alkyl dimethyl amine oxide or alkyl amido propyl dimethyl amine oxide, preferably alkyl dimethyl amine oxide and especially coco dimethyl amino oxide, most preferably C12-C14 alkyl dimethyl amine oxide.
  • Typical linear amine oxides include water-soluble amine oxides containing one R1 C8-18 alkyl moiety and 2 R2 and R3 moieties selected from the group consisting of C1-3 alkyl groups and C1-3 hydroxyalkyl groups.
  • amine oxide is characterized by the formula R1 - N(R2)(R3) O wherein R1 is a C8-18 alkyl and R2 and R3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl.
  • 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.
  • Preferred amine oxides include linear C10, linear C10-C12, and linear C12-C14 alkyl dimethyl amine oxides.
  • 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 is 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) should be approximately the same 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 about 1 to about 3 ethylene oxide groups.
  • the two moieties are selected from a C1-3 alkyl, more preferably both are selected as a C1 alkyl.
  • the amine oxide surfactant is a mixture of amine oxides comprising a low-cut amine oxide and a mid-cut amine oxide.
  • the amine oxide of the composition of the invention then comprises:
  • R3 is n-decyl.
  • R1 and R2 are both methyl.
  • R1 and R2 are both methyl and R3 is n-decyl.
  • the amine oxide comprises less than about 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.
  • Compositions comprising R7R8R9AO tend to be unstable and do not provide very suds mileage.
  • the zwitterionic surfactant is a betaine surfactant.
  • Suitable betaine surfactant includes alkyl betaines, alkylamidobetaine, amidazoliniumbetaine, sulfobetaine (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- (I) wherein
  • Preferred betaines are the alkyl betaines of the Formula (Ia), the alkyl amido propyl betaine of the Formula (Ib), the Sulfo betaines of the Formula (Ic) and the Amido sulfobetaine of the Formula (Id): R 1 -N(CH 3 ) 2 -CH 2 COO - (Ia) R 1 -CO-NH(CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 COO- (Ib) R 1 -N + (CH 3 ) 2 -CH 2 CH(OH)CH 2 SO 3 - (Ic) R 1 -CO-NH-(CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 CH(OH)CH 2 SO 3 - (Id) in which R1 as the same meaning as in Formula (I).
  • betaines and sulfobetaine are the following [designated in accordance with INCI]: Almondamidopropyl of betaines, Apricotam idopropyl betaines, Avocadamidopropyl of betaines, Babassuamidopropyl of betaines, Behenam idopropyl betaines, Behenyl of betaines, betaines, Canolam idopropyl betaines, Capryl/Capram idopropyl betaines, Carnitine, Cetyl of betaines, Cocamidoethyl of betaines, Cocam idopropyl betaines, Cocam idopropyl Hydroxysultaine, Coco betaines, Coco Hydroxysultaine, Coco/Oleam idopropyl betaines, Coco Sultaine, Decyl of betaines, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl
  • a preferred betaine is, for example, cocoamidopropylbetaine.
  • the surfactant system of the composition of the present invention further comprises from 1% to 25%, preferably from 1.25% to 20%, more preferably from 1.5% to 15%, most preferably from 1.5% to 5%, by weight of the surfactant system, of a non-ionic surfactant.
  • the non-ionic surfactant is a linear or branched, 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 ethylene oxide per mole of alcohol.
  • the composition of the present invention further comprises from 0.5% to 20%, more preferably from 0.75% to 15%, more preferably from 1% to 10%, most preferably from 1% to 5% by weight of the surfactant system of alkyl polyglucoside (“APG") surfactant.
  • APG alkyl polyglucoside
  • the alkyl polyglucoside surfactant is a C8-C16 alkyl polyglucoside surfactant, preferably a C8-C14 alkyl polyglucoside surfactant, preferably with an average degree of polymerization of between 0.1 and 3, more preferably between 0.5 and 2.5, even more preferably between 1 and 2.
  • the alkyl polyglucoside surfactant has an average alkyl carbon chain length between 10 and 16, preferably between 10 and 14, most preferably between 12 and 14, with an average degree of polymerization of between 0.5 and 2.5 preferably between 1 and 2, most preferably between 1.2 and 1.6.
  • 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).
  • composition of the present invention wherein composition comprises a surfactant system comprising:
  • composition of the present invention may further comprise from about 0.01% to about 5%, preferably from about 0.05% to about 2%, more preferably from about 0.07% to about 1% by weight of the total composition of an amphiphilic polymer selected from the groups consisting of amphiphilic alkoxylated polyalkyleneimine and mixtures thereof, preferably an amphiphilic alkoxylated polyalkyleneimine.
  • the amphiphilic alkoxylated polyalkyleneimine is an alkoxylated polyethyleneimine polymer comprising a polyethyleneimine backbone having average molecular weight range from 100 to 5,000, preferably from 400 to 2,000, more preferably from 400 to 1,000 Daltons and the alkoxylated polyethyleneimine polymer further comprising:
  • Preferred amphiphilic alkoxylated polyethyleneimine polymers comprise EO and PO groups within their alkoxylation chains, the PO groups preferably being in terminal position of the alkoxy chains, and the alkoxylation chains preferably being hydrogen capped.
  • Hydrophilic alkoxylated polyethyleneimine polymers solely comprising ethoxy (EO) units within the alkoxylation chain could also optionally be formulated within the scope of this invention.
  • R represents an ethylene spacer and E represents a C 1 -C 4 alkyl moiety and X- represents a suitable water soluble counterion.
  • the alkoxylation modification of the polyethyleneimine backbone consists of the replacement of a hydrogen atom by a polyalkoxylene chain having an average of about 1 to about 50 alkoxy moieties, preferably from about 20 to about 45 alkoxy moieties, most preferably from about 30 to about 45 alkoxy moieties.
  • the alkoxy moieties are selected from ethoxy (EO), propoxy (PO),butoxy (BO), and mixtures thereof.
  • Alkoxy moieties solely comprising ethoxy units are outside the scope of the invention though.
  • the polyalkoxylene chain is selected from ethoxy/propoxy block moieties.
  • the polyalkoxylene chain is ethoxy/propoxy block moieties having an average degree of ethoxylation from about 3 to about 30 and an average degree of propoxylation from about 1 to about 20, more preferably ethoxy/propoxy block moieties having an average degree of ethoxylation from about 20 to about 30 and an average degree of propoxylation from about 10 to about 20.
  • the ethoxy/propoxy block moieties have a relative ethoxy to propoxy unit ratio between 3 to 1 and 1 to 1, preferably between 2 to 1 and 1 to 1.
  • the polyalkoxylene chain is the ethoxy/propoxy block moieties wherein the propoxy moiety block is the terminal alkoxy moiety block.
  • the modification may result in permanent quaternization of the polyethyleneimine backbone nitrogen atoms.
  • the degree of permanent quaternization may be from 0% to about 30% of the polyethyleneimine backbone nitrogen atoms. It is preferred to have less than 30% of the polyethyleneimine backbone nitrogen atoms permanently quaternized. Most preferably the degree of quaternization is about 0%.
  • a preferred polyethyleneimine has the general structure of Formula (II): wherein the polyethyleneimine backbone has a weight average molecular weight of about 600, n of formula (II) has an average of about 10, m of formula (II) has an average of about 7 and R of formula (II) is selected from hydrogen, a C 1 -C 4 alkyl and mixtures thereof, preferably hydrogen.
  • the degree of permanent quaternization of formula (II) may be from 0% to about 22% of the polyethyleneimine backbone nitrogen atoms.
  • the molecular weight of this polyethyleneimine preferably is between 10,000 and 15,000.
  • An alternative polyethyleneimine has the general structure of Formula (II) but wherein the polyethyleneimine backbone has a weight average molecular weight of about 600, n of Formula (II) has an average of about 24, m of Formula (II) has an average of about 16 and R of Formula (II) is selected from hydrogen, a C 1 -C 4 alkyl and mixtures thereof, preferably hydrogen.
  • the degree of permanent quaternization of Formula (II) may be from 0% to about 22% of the polyethyleneimine backbone nitrogen atoms.
  • the molecular weight of this polyethyleneimine preferably is between 25,000 and 30,000.
  • polyethyleneimine has the general structure of Formula (II) wherein the polyethyleneimine backbone has a weight average molecular weight of about 600, n of Formula (II) has an average of about 24, m of Formula (II) has an average of about 16 and R of Formula (II) is hydrogen.
  • the degree of permanent quaternization of Formula (II) is 0% of the polyethyleneimine backbone nitrogen atoms.
  • the molecular weight of this polyethyleneimine preferably is about from about 25,000 to 30,000, most preferably about 28,000.
  • polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like, as described in more detail in PCT Publication No. WO 2007/135645 .
  • a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like, as described in more detail in PCT Publication No. WO 2007/135645 .
  • the cyclic polyamine of the invention is a cleaning polyamine.
  • the cleaning polyamine comprises amine functionalities that helps cleaning as part of a cleaning composition.
  • the composition of the invention preferably comprises from about 0.1 % to about 10%, more preferably from about 0.2% to about 5%, and especially from about 0.3% to about 2%, by weight of the composition, of the cyclic polyamine.
  • cyclic amine herein encompasses a single amine and a mixture thereof.
  • the amine can be subjected to protonation depending on the pH of the cleaning medium in which it is used.
  • the cyclic polyamine of the invention conforms to the following Formula (I): wherein R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from the group consisting of NH2, -H, linear or branched alkyl having from 1 to 10 carbon atoms, and linear or branched alkenyl having from 1 to 10 carbon atoms, n is from 0 to 3, preferably n is 1, and wherein at least one of the Rs is NH2 and the remaining “Rs" are independently selected from the group consisting of NH2, -H, linear or branched alkyl having 1 to 10 carbon atoms, and linear or branched alkenyl having from 1 to 10 carbon atoms.
  • the cyclic polyamine is a diamine, wherein n is 1, R 2 is
  • the amine of the invention is a cyclic amine with 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.
  • the inventors have surprisingly found that these specific cyclic polyamine works to improve suds profile through-out the dishwashing process when formulated together with the specific surfactant system according to the present invention.
  • composition of the present invention may comprise at least one active selected from the group consisting of: i) a salt, ii) a hydrotrope, iii) an organic solvent, and mixtures thereof.
  • composition 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, divalent inorganic salt or a mixture thereof, more preferably sodium chloride, sodium sulfate or a mixture thereof, most preferably sodium chloride.
  • a salt preferably a monovalent, divalent inorganic salt or a mixture thereof, more preferably sodium chloride, sodium sulfate or a mixture thereof, most preferably sodium chloride.
  • composition 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 a mixture thereof, preferably sodium cumene sulfonate.
  • the composition of the present invention may comprise an organic solvent.
  • Suitable organic solvents include C4-14 ethers and diethers, polyols, glycols, alkoxylated glycols, C6-C16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic linear or branched alcohols, alkoxylated aliphatic linear or branched alcohols, alkoxylated C1-C5 alcohols, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof.
  • the organic solvents include alcohols, glycols, and glycol ethers, alternatively alcohols and glycols.
  • the composition comprises from 0% to less than about 50%, preferably from about 0.01% to about 25%, more preferably from about 0.1% to about 10%, or most preferably from about 0.5% to about 5%, by weight of the total composition of an organic solvent, preferably an alcohol, more preferably ethanol, a polyalkyleneglycol, more preferably polypropyleneglycol, and mixtures thereof.
  • an organic solvent preferably an alcohol, more preferably ethanol, a polyalkyleneglycol, more preferably polypropyleneglycol, and mixtures thereof.
  • the cleaning composition herein may optionally comprise a number of other adjunct ingredients such as builders (e.g ., preferably citrate), chelants, conditioning polymers, cleaning polymers, surface modifying polymers, soil flocculating polymers, structurants, emollients, humectants, skin rejuvenating actives, enzymes, carboxylic acids, scrubbing particles, bleach and bleach activators, perfumes, malodor control agents, pigments, dyes, opacifiers, beads, pearlescent particles, microcapsules, 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, phosphoric and sulfonic acids, carbonates such as sodium carbonates, bicarbonates, sesquicarbonates, borates, silicates, phosphates, imidazole and alike).
  • the invention is directed to a method of manually washing dishware with the composition of the present invention.
  • the method comprises the steps of delivering a composition of the present invention to a volume of water to form a wash solution and immersing the dishware in the solution.
  • the dishware can be cleaned with the composition in the presence of water.
  • the dishware can be rinsed.
  • rinsed it is meant herein contacting the dishware cleaned with the process according to the present invention with substantial quantities of appropriate solvent, typically water.
  • substantial quantities it is meant usually about 1 L to about 20 L.
  • the composition herein can be applied in its diluted form.
  • Soiled dishware are contacted with an effective amount, typically from about 0.5 mL to about 20 mL (per about 25 dishes being treated), preferably from about 3 mL to about 10 mL, of the cleaning composition, preferably in liquid form, of the present invention diluted in water.
  • the actual amount of cleaning 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 cleaning composition, including the concentration of active ingredients in the cleaning composition, the number of soiled dishes to be cleaned, the degree of soiling on the dishes, and the like.
  • a cleaning composition of the invention is combined with from about 2,000 mL to about 20,000 mL, more typically from about 5,000 mL to about 15,000 mL of water in a sink having a volumetric capacity in the range of from about 1,000 mL to about 20,000 mL, more typically from about 5,000 mL to about 15,000 mL.
  • the soiled dishware are immersed in the sink containing the diluted cleaning compositions then obtained, where contacting the soiled surface of the dishware with a cloth, sponge, or similar cleaning impement cleans them.
  • the cloth, sponge, or similar cleaning implement may be immersed in the cleaning composition and water mixture prior to being contacted with the dishware, and is typically contacted with the dishware for a period of time ranged from about 1 to about 10 seconds, although the actual time will vary with each application and user.
  • the contacting of cloth, sponge, or similar cleaning implement to the dishware is preferably accompanied by a concurrent scrubbing of the dishware.
  • Another aspect of the present invention is directed to use of a hand dishwashing cleaning composition of the present invention for providing good sudsing profile, including suds stabilization in the presence of particulate soils.
  • the objective of the Suds Mileage Index 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 as a suds mileage index (reference composition has suds mileage index of 100).
  • the steps of the method are as follows:
  • Soil composition is produced through standard mixing of the components described in Table 1.
  • Table 1 Particulate Soil Ingredient Weight % Zwan Flemish Carbonades 22.67 Beaten Eggs 4.78 Smash Instant Mash Potato 9.26 McDougall's Sponge Mix 3.30 Milk UHT Full Cream 22.22 Bisto Gravy Granules 1.30 Mazola® Pure Corn Oil 9.29 Demineralized water 26.32 Sodium Benzoate 0.42 Potassium Sorbate 0.42
  • Example 1 Inventive and Comparative Compositions
  • Comparative Composition 1 The ability of a cleaning composition to maintain its suds mileage is assessed for a cleaning composition comprising an average degree of branching (45%) and a branched AES over branched AS ratio (18/82) according to the invention (Inventive Composition 1).
  • Comparative Compositions 1-3 having a branched AES over branched AS ratio (0/100; 40/60; 62/38 - 45% average degree of branching respectively) outside the scope of the present invention are also assessed.
  • Comparative Composition 3 has been made from 2 different alcohol blends (Comparative Compositions 3a and 3b) and suds mileage results were averaged. The foregoing compositions are produced through standard mixing of the components described in Table 2. Table 2 - Inventive and Comparative Compositions Inventive Comp.
  • Example 1a Suds Mileage Index of Inventive and Comparative Compositions
  • the resultant compositions including the Inventive Composition 1 and Comparative Compositions 1-3 are assessed according to the Suds Mileage Index test method as described herein.
  • the Suds Mileage Index results of the test are summarized in Table 3. The higher the Suds Mileage Index value, the better in maintaining suds mileage.
  • the data shows that the inventive composition (Inventive Composition 1) according to the invention has a stronger suds robustness in the presence of greasy soils compared to Comparative Compositions 1-3 outside the scope of the invention.

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Claims (14)

  1. Composition liquide de nettoyage pour le lavage de la vaisselle à la main comprenant :
    A) de 1 % à 60 %, de préférence de 5 % à 50 %, plus préférablement de 8 % à 45 %, le plus préférablement de 15 % à 40 % en poids de la composition totale d'un système tensioactif comprenant un agent tensioactif anionique et un co-tensioactif, dans laquelle :
    (i) la longueur moyenne de chaîne alkyle de l'agent tensioactif anionique va de 8 à 18, de préférence de 10 à 14, plus préférablement de 12 à 14, le plus préférablement de 12 à 13 atomes de carbone ;
    (ii) l'agent tensioactif anionique a un degré moyen de ramification en poids allant de 35 % à 60 %, de préférence de 38 % à 55 %, le plus préférablement de 40 % à 50 %, et un degré moyen d'éthoxylation inférieur à 5, de préférence inférieur à 3, plus préférablement inférieur à 2 et de plus de 0,5, le plus préférablement entre 0,5 et 0,9 ;
    (iii) l'agent tensioactif anionique est constitué d'un mélange d'un sulfate d'alkyle et d'un alcoxysulfate d'alkyle de préférence un éthoxysulfate d'alkyle, le mélange du sulfate d'alkyle et de l'alcoxysulfate d'alkyle de préférence l'éthoxysulfate d'alkyle, est un mélange d'agent tensioactif anionique linéaire et d'agent tensioactif anionique ramifié, dans laquelle :
    a. l'agent tensioactif anionique ramifié est constitué de 5 % à 25 %, de préférence de 10 % à 20 %, en poids de l'agent tensioactif anionique ramifié total d'un alcoxysulfate d'alkyle ramifié de préférence un agent tensioactif éthoxysulfate d'alkyle ramifié et de 75 % à 95 %, de préférence de 80 % à 90 %, en poids de l'agent tensioactif anionique ramifié total d'un agent tensioactif sulfate d'alkyle ramifié, dans laquelle la fraction de ramification entre sulfate d'alkyle ramifié et alcoxysulfate d'alkyle ramifié est définie sur la base des molécules formulées au sein de la formulation finale plutôt que sur les matières premières ajoutées ; et
    (iv) le co-tensioactif est choisi dans le groupe constitué d'un agent tensioactif amphotère, un agent tensioactif zwittérionique et des mélanges de ceux-ci, de préférence un agent tensioactif amphotère, plus préférablement un agent tensioactif oxyde d'amine ;
    dans laquelle le rapport pondéral de l'agent tensioactif anionique au co-tensioactif va de 1:1 à 8:1, de préférence de 2:1 à 5:1, plus préférablement de 2,5:1 à 4:1.
  2. Composition selon la revendication 1, dans laquelle l'alcoxysulfate d'alkyle ramifié est un agent tensioactif éthoxysulfate d'alkyle ramifié, dans laquelle l'agent tensioactif éthoxysulfate d'alkyle ramifié comprend au moins 5 %, de préférence au moins 10 %, en poids de l'agent tensioactif éthoxysulfate d'alkyle ramifié d'un agent tensioactif alkyl-éthoxy-sulfate avec la ramification sur la position C2.
  3. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'agent tensioactif sulfate d'alkyle ramifié comprend au moins 5 %, de préférence au moins 10 %, plus préférablement au moins 20 %, encore plus préférablement au moins 30 %, en poids de l'agent tensioactif sulfate d'alkyle ramifié d'un agent tensioactif sulfate d'alkyle ramifié avec la ramification sur la position C2.
  4. Composition selon l'une quelconque des revendications précédentes, dans laquelle le groupe de ramification sur l'agent tensioactif anionique ramifié représente plus de 75 %, plus préférablement plus de 90 %, en poids de la teneur totale en alkyle ramifié, d'un fragment alkyle en C1 à C5, de préférence un fragment alkyle en C1 à C2.
  5. Composition selon l'une quelconque des revendications précédentes, dans laquelle le co-tensioactif est un agent tensioactif amphotère qui est un agent tensioactif oxyde d'amine, dans laquelle l'agent tensioactif oxyde d'amine est choisi dans le groupe constitué d'un agent tensioactif oxyde d'alkylamine linéaire ou ramifié, un agent tensioactif oxyde d'alkyl-amidopropyl-amine linéaire ou ramifié, et des mélanges de ceux-ci, de préférence un agent tensioactif oxyde d'alkyl-diméthylamine linéaire, plus préférablement un agent tensioactif oxyde d'(alkyl en C10)-diméthylamine linéaire, un agent tensioactif oxyde d'(alkyl en C12 à C14)-diméthylamine linéaire, et des mélanges de ceux-ci, le plus préférablement un agent tensioactif oxyde d'(alkyl en C12 à C14)-diméthylamine linéaire.
  6. Composition selon l'une quelconque des revendications précédentes, comprenant en outre de 1 % à 25 %, de préférence de 1,25 % à 20 %, plus préférablement de 1,5 % à 15 %, le plus préférablement de 1,5 % à 5 % en poids du système tensioactif d'un agent tensioactif non ionique, de préférence un agent tensioactif non ionique éthoxylé d'alkyle, comprenant de préférence en moyenne de 9 à 15, de préférence de 10 à 14 atomes de carbone dans sa chaîne alkyle et en moyenne de 5 à 12, de préférence de 6 à 10, le plus préférablement de 7 à 8, motifs d'oxyde d'éthylène par mole d'alcool.
  7. Composition selon l'une quelconque des revendications précédentes, comprenant en outre de 0,5 % à 20 %, de préférence de 0,75 % à 15 %, plus préférablement de 1 % à 10 %, le plus préférablement de 1 % à 5 % en poids du système tensioactif d'un agent tensioactif alkyl-polyglucoside, dans laquelle l'agent tensioactif alkyl-polyglucoside est un agent tensioactif alkyl-polyglucoside en C8 à C16, de préférence un agent tensioactif alkyl-polyglucoside en C8 à C14, de préférence avec un degré moyen de polymérisation compris entre 0,1 et 3, de préférence entre 0,5 et 2,5, de préférence entre 1 et 2.
  8. Composition selon l'une quelconque des revendications précédentes comprenant en outre de 0,05 % à 2 % en poids de la composition totale d'une polyalkylène-imine alcoxylée amphiphile et des mélanges de celles-ci, dans laquelle la polyalkylène-imine alcoxylée amphiphile est un polymère polyéthylène-imine alcoxylée comprenant un squelette polyéthylène-imine ayant une plage de masse moléculaire moyenne allant de 100 à 5000, de préférence de 400 à 2000, plus préférablement de 400 à 1000 Daltons et le polymère polyéthylène-imine alcoxylée comprenant en outre :
    i) une ou deux modifications de type alcoxylation par atome d'azote par une chaîne polyalcoxylène ayant une moyenne d'environ 1 à environ 50 fragments alcoxy par modification, dans laquelle le fragment alcoxy terminal de la modification de type alcoxylation est coiffé avec un hydrogène, un alkyle en C1 à C4 ou mélanges de ceux-ci ;
    ii) un ajout d'un fragment alkyle en C1 à C4 et une ou deux modifications de type alcoxylation par atome d'azote par une chaîne polyalcoxylène ayant une moyenne d'environ 1 à environ 50 fragments alcoxy par modification, dans laquelle le fragment alcoxy terminal est coiffé avec un hydrogène, un alkyle en C1 à C4 ou mélanges de ceux-ci ; ou
    iii) une de leurs combinaisons ; et
    dans laquelle les fragments alcoxy comprennent éthoxy (EO) et/ou propoxy (PO) et/ou butoxy (BO) et dans laquelle lorsque la modification de type alcoxylation comprend EO elle comprend également PO ou BO.
  9. Composition selon l'une quelconque des revendications précédentes, comprenant en outre une polyamine cyclique de Formule (I) :
    Figure imgb0010
     dans laquelle R1, R2, R3, R4 et R5 sont chacun indépendamment choisis dans le groupe constitué de NH2, -H, un alkyle linéaire ou ramifié ayant de 1 à 10 atomes de carbone, et un alcényle linéaire ou ramifié ayant de 1 à 10 atomes de carbone, n va de 0 à 3, de préférence n vaut 1, et dans laquelle au moins l'un des R est NH2 et les R restants sont indépendamment choisis dans le groupe constitué de NH2, -H, un alkyle linéaire ou ramifié ayant de 1 à 10 atomes de carbone, un alcényle linéaire ou ramifié ayant de 1 à 10 atomes de carbone ; de préférence dans laquelle la polyamine cyclique est une diamine, dans laquelle n vaut 1, R2 est NH2 et au moins l'un parmi R1, R3, R4 et R5 est CH3 et les R restants sont H, le plus préférablement dans laquelle la polyamine cyclique est choisie dans le groupe constitué de la 2-méthylcyclohexane-1,3-diamine, de la 4-méthylcyclohexane-1,3-diamine et de mélanges de celles-ci.
  10. Composition selon l'une quelconque des revendications précédentes, comprenant en outre au moins un agent actif choisi dans le groupe constitué de :
    (i) de 0,05 % à 2 %, de préférence 0,1 % à 1,5 %, plus préférablement 0,5 % à 1 %, en poids de la composition totale d'un sel, de préférence un sel inorganique monovalent, divalent ou un mélange de ceux-ci, plus préférablement du chlorure de sodium, du sulfate de sodium ou un mélange de ceux-ci, le plus préférablement du chlorure de sodium ;
    (ii) de 1 % à 10 % en poids de la composition totale d'un hydrotrope, de préférence du cumène-sulfonate de sodium ;
    (iii) de 0,01 % à 25 % en poids de la composition totale d'un solvant organique, de préférence un alcool, plus préférablement de l'éthanol, un polyalkylène-glycol, plus préférablement du polypropylène glycol ; et
    (iv) leurs mélanges.
  11. Composition selon l'une quelconque des revendications précédentes, dans laquelle la composition a une viscosité initiale allant de 10 mPa·s à 10 000 mPa·s, de préférence allant de 100 mPa·s à 5000 mPa·s, plus préférablement allant de 300 mPa·s à 2000 mPa·s, le plus préférablement allant de 500 mPa·s à 1500 mPa·s, telle que mesurée sur un viscosimètre Brookfield RVT utilisant un mobile cylindrique 21 à 20 tr/min à 25 °C.
  12. Composition liquide de nettoyage pour le lavage de la vaisselle à la main selon la revendication 1, comprenant :
    A) de 15 % à 40 % en poids de la composition totale du système tensioactif dans laquelle le co-tensioactif est un agent tensioactif oxyde d'amine, dans laquelle :
    i) l'agent tensioactif anionique a un degré moyen de ramification en poids allant de 40 % à 50 % et un degré moyen d'éthoxylation compris entre 0,5 et 0,9 ;
    ii) l'agent tensioactif anionique et le co-tensioactif oxyde d'amine sont dans un rapport pondéral compris entre 2,5:1 et 4:1 ; et
    iii) dans laquelle :
    a. l'agent tensioactif anionique linéaire est un mélange d'un agent tensioactif sulfate d'alkyle linéaire et d'un agent tensioactif éthoxysulfate d'alkyle linéaire ; et
    b. l'agent tensioactif anionique ramifié est un mélange de 10 % à 20 % en poids de l'agent tensioactif anionique ramifié total d'un agent tensioactif éthoxysulfate d'alkyle ramifié et de 80 % à 90 % en poids de l'agent tensioactif anionique ramifié total d'un agent tensioactif sulfate d'alkyle ramifié.
  13. Procédé de lavage manuel de la vaisselle comprenant les étapes consistant à : distribuer une composition selon l'une quelconque des revendications 1 à 12 à un volume d'eau pour former une solution de lavage et immerger la vaisselle dans la solution.
  14. Utilisation d'une composition selon l'une quelconque des revendications 1 à 12, pour la stabilisation de mousse en présence de salissures particulaires.
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US20230159855A1 (en) * 2020-04-09 2023-05-25 Conopco, Inc., D/B/A Unilever Laundry detergent composition
EP3919597A1 (fr) 2020-06-05 2021-12-08 The Procter & Gamble Company Composition de détergent liquide pour lavage de la vaisselle à la main
PL3919594T3 (pl) * 2020-06-05 2025-04-28 The Procter & Gamble Company Ciekła kompozycja detergentu do ręcznego zmywania naczyń
DE102023203496A1 (de) 2023-04-18 2024-10-24 Henkel Ag & Co. Kgaa Fettlösende Handgeschirrspülmittel mit verzweigtem Ethersulfat
EP4516887A1 (fr) * 2023-08-29 2025-03-05 The Procter & Gamble Company Composition liquide pour le nettoyage de la vaisselle à la main

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2002230378A1 (en) * 2000-11-29 2002-06-11 The Procter And Gamble Company Hand dishwashing composition containing a suds suppresser and a method of use therefor
EP1674560A1 (fr) * 2004-12-21 2006-06-28 The Procter & Gamble Company Composition pour le lavage de la vaisselle
EP2021452B1 (fr) 2006-05-22 2018-03-21 The Procter and Gamble Company Composition détergente liquide pour nettoyage des graisses amélioré
ES2412684T3 (es) * 2009-06-19 2013-07-12 The Procter & Gamble Company Composición detergente de lavado de vajillas a mano líquida
EP2757144B2 (fr) * 2013-01-21 2023-12-20 The Procter & Gamble Company Détergent
EP3374482B1 (fr) * 2015-11-13 2023-11-01 The Procter & Gamble Company Compositions de nettoyage contenant des tensioactifs de sulfate d'alkyle ramifié et des tensioactifs de sulfate d'alkyle linéaire
EP3243895A1 (fr) * 2016-05-13 2017-11-15 The Procter and Gamble Company Composition de nettoyage

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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ES2871098T3 (es) 2021-10-28
WO2019055249A1 (fr) 2019-03-21
EP3456799A1 (fr) 2019-03-20

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