EP4105306A1 - Hochkonzentrierte verdünnbare handgeschirrspülmittelzusammensetzung - Google Patents

Hochkonzentrierte verdünnbare handgeschirrspülmittelzusammensetzung Download PDF

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Publication number
EP4105306A1
EP4105306A1 EP21179560.4A EP21179560A EP4105306A1 EP 4105306 A1 EP4105306 A1 EP 4105306A1 EP 21179560 A EP21179560 A EP 21179560A EP 4105306 A1 EP4105306 A1 EP 4105306A1
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EP
European Patent Office
Prior art keywords
liquid composition
group
alkyl
oil
acid
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.)
Pending
Application number
EP21179560.4A
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English (en)
French (fr)
Inventor
Marwa AMRAOUI
Lisa-Marie Schuetz
Nilgun Esin Aksoy Abaci
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to EP21179560.4A priority Critical patent/EP4105306A1/de
Publication of EP4105306A1 publication Critical patent/EP4105306A1/de
Pending legal-status Critical Current

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • 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
    • C11D1/90—Betaines
    • 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 concentrates to be diluted with water for hard surface cleaning purposes, in particular manual dishwashing purposes, comprising at least one electrolyte salt in an amount of about 0.05 to about 10 wt.-%.
  • the present invention further relates to the use thereof as well as to a method of preparation, which comprises diluting the concentrate with water.
  • concentrates which contain a higher level of washing- and cleaning-active ingredients than conventional products.
  • the concentrates are either used by the consumer directly for washing or cleaning, in which case a lower quantity corresponding to the concentration is required, or they are first diluted with a specified quantity of water and only then applied like a conventional product.
  • concentrates are offered, which, after dilution with water, are used by the consumer in the same way as conventional hand dishwashing detergents. Washing and cleaning compositions provided in the form of concentrates thus constitute an excellent solution for low-income consumers seeking financial leniency, since the production, packaging, transport and storage of concentrates is less costly compared to conventional product forms.
  • a respective product must nonetheless fulfill a complex profile of requirements in order to find acceptance with consumers.
  • consumers in addition to the primary washing and cleaning effect as well as transport and storage stability, consumers expect not only an attractive appearance, a pleasant fragrance and good skin compatibility, but also, in particular, easy handling and dosing.
  • consumers prefer products with an increased viscosity (compared to conventional, i.e. non-concentrated liquid products), which can be dosed more accurately and run more slowly on inclined and, in particular, vertical surfaces, i.e. act longer on the surface to be cleaned.
  • the diluted concentrate is to have a sufficiently increased viscosity, this usually means that the viscosity of the undiluted concentrate is still much higher and, accordingly, that the handling properties and solubility of the concentrate are hardly or no longer acceptable.
  • the present invention relates to a liquid composition, particularly a manual dishwashing detergent composition, said composition being a concentrate to be diluted with water while maintaining or increasing viscosity, characterized in that it comprises at least one electrolyte salt selected from the group consisting of alkali metal salts and/or alkaline earth metal salts of an inorganic acid, preferably an inorganic acid selected from the group consisting of the hydrohalic acids, nitric acid and sulfuric acid, more particularly the chlorides and sulfates in an amount of about 0.05 to about 10 wt.-%, preferably about 0.5 to about 5 wt.-%, based on the total weight of the liquid composition.
  • the present invention further relates to the use of a liquid composition as disclosed herein for the cleaning of hard surfaces, particularly for the manual cleaning of dishes, and to the use of a liquid composition as disclosed herein for the preparation of a dilute aqueous hard surface cleaning composition, particularly for the preparation of a dilute manual dishwashing detergent composition.
  • the present inventio also relates to a method for the preparation of a dilute aqueous hard surface cleaning composition, particularly a dilute manual dishwashing detergent composition, characterized in that a liquid composition as disclosed herein is diluted with about 1 to about 8 parts, preferably about 1.5 to about 7 parts, more preferably about 2 to about 7 parts, particularly about 2 to about 4 parts of water, based on the volume of the liquid composition.
  • liquid refers to compounds or mixtures of compounds that are flowable and pourable at room temperature (about 15 °C to about 25 °C).
  • “One or more”, as used herein, relates to at least one and comprises 1, 2, 3, 4, 5, 6, 7, 8, 9 or more of the referenced species.
  • an ingredient it refers to the type of ingredient and not to the absolute number of molecules.
  • “At least one surfactant” thus means, for example, at least one type of surfactant, meaning that one type of surfactant or a mixture of several different surfactants may be meant. Together with weight indications, the indication refers to all compounds of the indicated type contained in the composition/mixture, i.e. that the composition does not contain any further compounds of this type beyond the indicated amount of the corresponding compounds.
  • molar masses this information always refers to the number-average molar mass M n , unless explicitly stated otherwise.
  • the number average molar mass can be determined, for example, by gel permeation chromatography (GPC) according to DIN 55672-1:2007-08 with THF as eluent.
  • the weight average molecular weight M w can also be determined by GPC as described for M n .
  • alkaline earth metals are mentioned in the following as counterions for monovalent anions, this means that the alkaline earth metal is naturally present only in half the amount of substance-sufficient for charge balance - as the anion.
  • fatty acids or fatty alcohols or derivatives thereof - unless otherwise indicated - are representative of branched or unbranched carboxylic acids or alcohols or derivatives thereof preferably having 6 to 22 carbon atoms.
  • the former are preferred for ecological reasons, in particular because of their vegetable basis as being based on renewable raw materials, without, however, limiting the teaching according to the invention to them.
  • the oxo-alcohols obtainable, for example, according to the ROELEN oxo-synthesis or their derivatives can also be used accordingly.
  • INCI means that the following or preceding name is a name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry, and Fragrance Association (CTFA).
  • CTFA Cosmetic, Toiletry, and Fragrance Association
  • CAS means that the following sequence of numbers is a designation of the Chemical Abstracts Service.
  • the liquid compositions according to the present invention may be referred to as “homecare compositions” or "household cleaners".
  • Household cleaners within the meaning of the present invention are, for example, cleaning agents for cleaning hard surfaces, such as window cleaners, bath cleaners, WC cleaners or dishwashing detergents, including hand dishwashing detergents and dishwashing detergents for machine use.
  • the liquid compositions disclosed herein are manual dishwashing detergent compositions.
  • the liquid compositions are in the form of concentrates to be diluted with water while maintaining or increasing their viscosity.
  • Viscosity maintenance in the sense of the teaching according to the invention also includes a decrease in viscosity which is not significant for the user, i.e. a decrease in the viscosity value determined as described below by not more than 50 %, preferably not more than 30 %, in particular not more than 10 % and particularly preferably not more than 5 %.
  • the liquid compositions of the present invention comprise at least one electrolyte salt.
  • Electrolyte salts in the context of the present invention are salts which break up into their ionic constituents in the water-based composition according to the invention.
  • Preferred salts are the salts, more particularly alkali metal and/or alkaline earth metal salts, of an inorganic acid, preferably an inorganic acid from the group consisting of the hydrohalic acids, nitric acid and sulfuric acid, more particularly the chlorides and sulfates.
  • the at least one electrolyte salt is selected from the group consisting of alkali metal salts, preferably from the group consisting of alkali metal chlorides and sulfates, more preferably from the group consisting of alkali chlorides, particularly from the group consisting of NaCl and KCI, and mixtures thereof.
  • Another suitable electrolyte salt is magnesium sulfate, more particularly the MgSO 4 7H 2 O also known as Epsom salt and occurring as the mineral epsomite.
  • an electrolyte salt may also be used in the form of its corresponding acid/base pair, for example hydrochloric acid and sodium hydroxide instead of sodium chloride.
  • the electrolyte salt is present in an amount of about 0.05 to about 10 wt.-%, preferably about 0.5 to about 5 wt.-%, for instance, but without limitation, in an amount of about 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2, 3, 4 or 5 wt.-%, based on the total weight of the liquid composition.
  • the liquid composition according to the present invention preferably further comprises at least one detersive surfactant.
  • the liquid composition comprises at least one surfactant, preferably at least two surfactants, selected from the group consisting of anionic surfactants, nonionic surfactants and amphoteric surfactants.
  • composition according to the invention preferably contains surfactants in a total quantity of normally 0.5 to 80 wt.-%, preferably 1 to 70 wt.-%, more preferably 5 to 60 wt.-%, most preferably 10 to 50 wt.-% and, in one most particularly preferred embodiment, 10 to 40 wt.-%, for example 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35 or 40 wt.-% or a range created by the combination of two amounts from the aforementioned list.
  • the anionic surfactants which may be used in accordance with the invention, include aliphatic sulfates, such as fatty alcohol sulfates and fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin suffonates.
  • aliphatic sulfates such as fatty alcohol sulfates and fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n-alkyl
  • alkyl benzene sulfonates fatty acid cyanamides, sulfosuccinic acid esters, fatty acid isethionates, acylaminoalkane sulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.
  • Suitable anionic surfactants also include anionic gemini surfactants with a diphenyl oxide basic structure, two sulfonate groups and an alkyl group on one or both benzene rings corresponding to the formula -O 3 S(C 6 H 3 R)O(C 6 H 3 R')SO 3 - in which R is an alkyl group containing, for example, 6, 10, 12 or 16 carbon atoms and R' stands for R or H (Dowfax ® Dry Hydrotrope Powder containing C 16 alkyl group(s); INCI: Sodium Hexyldiphenyl Ether Sulfonate, Disodium Decyl Phenyl Ether Disulfonate, Disodium Lauryl Phenyl Ether Disulfonate, Disodium Cetyl Phenyl Ether Disulfonate) and fluorinated anionic surfactants, more particularly perfluorinated alkyl sulfonates, such as ammonium C 9/10 perfluoroalkyl sul
  • Alkyl ether sulfates are products of sulfation reactions on alkoxylated alcohols.
  • Alkoxylated alcohols are generally understood by the expert to be the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols -in the context of the invention preferably with relatively long-chain alcohols, i.e. with aliphatic straight-chain or single- or multiple-branch, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably straight-chain, acyclic saturated alcohols containing 6 to 22, preferably 8 to 18, more preferably 10 to 16 and most preferably 12 to 14 carbon atoms.
  • Another embodiment of the alkoxylation consists in using mixtures of the alkylene oxides, preferably a mixture of ethylene oxide and propylene oxide.
  • alkyl ether sulfates are normally used in the form of alkali metal, alkaline earth metal and/or mono-, di- or trialkanolammonium salts and/or in the form of the corresponding acids to be neutralized with the corresponding alkali metal hydroxide, alkaline earth metal hydroxide and/or mono-, di or trialkanolamine.
  • Preferred alkali metals are potassium and in particular sodium
  • preferred alkaline earth metals are calcium and in particular magnesium
  • preferred alkanolamines are mono-, di- or triethanolamine.
  • the sodium salts are particularly preferred.
  • the alkyl sulfonates normally contain an aliphatic, straight-chain or single- or multiple-branch, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably branched, acyclic, saturated alkyl group containing 6 to 22, preferably 9 to 20, more preferably 11 to 18 and most preferably 13 to 17 carbon atoms.
  • suitable alkyl sulfonates are the saturated alkane sulfonates, the unsaturated olefin sulfonates and the ether sulfonates (formally derived from the alkoxylated alcohols on which the alkyl ether sulfates are also based) where terminal ester sulfonates (n-ether sulfonates) with the sulfonate function attached to the polyether chain and internal ester sulfonates (i-ester sulfonates) with the sulfonate function attached to the alkyl group.
  • the alkane sulfonates more particularly alkane sulfonates with a branched, preferably secondary, alkyl group, for example the secondary alkanesulfonate sec. Na C 13-17 alkane sulfonate (INCI Sodium C 14-17 Alkyl Sec. Sulfonate), are preferred.
  • alkyl ether sulfates and alkyl sulfonates as well as other anionic surfactants are normally used in the form of alkali metal, alkaline earth metal and/or mono-, di- or trialkanolammonium salts and/or in the form of the corresponding acids to be neutralized with the corresponding alkali metal hydroxide, alkaline earth metal hydroxide and/or mono-, di or trialkanolamine.
  • Preferred alkali metals are potassium and in particular sodium
  • preferred alkaline earth metals are calcium and in particular magnesium and preferred alkanolamines are mono-, di- or triethanolamine.
  • the sodium salts are particularly preferred.
  • anionic surfactants are the anionic sulfosuccinic acid surfactants sulfosuccinates, sulfosuccinamates and sulfosuccinamides, more particularly sulfosuccinates and sulfosuccinamates and most preferably sulfosuccinates.
  • the sulfosuccinates are the salts of the mono- and diesters of sulfosuccinic acid HOOCCH(SO 3 H)CH 2 COOH while the sulfosuccinamates are understood to be the salts of the monoamides of sulfosuccinic acid and the sulfosuccinamides are understood to be the salts of the diamides of sulfosuccinic acid.
  • anionic surfactants is provided by A. Domsch and B. Irrgang in Anionic Surfactants: Organic Chemistry (edited by H. W. Stache; Surfactant Science Series; Volume 56; ISBN 0-8247-9394-2; Marcel Dekker, Inc., New York 1996, pages 501-549 ).
  • the salts are preferably alkali metal salts, ammonium salts and mono-, di- and trialkanolammonium salts, for example mono-, di- and triethanolammonium salts, more particularly lithium, sodium, potassium and ammonium salts, more preferably sodium and ammonium salts and most preferably sodium salts.
  • one or both carboxyl groups of the sulfosuccinic acid is/are preferably esterified with one or two identical or different unbranched, branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alcohols containing 4 to 22, preferably 6 to 20, more preferably 8 to 18, most preferably 10 to 16 and, in one most particularly preferred embodiment, 12 to 14 carbon atoms.
  • esters of unbranched and/or saturated and/or acyclic and/or alkoxylated alcohols more particularly unbranched saturated fatty alcohols and/or unbranched saturated fatty alcohols alkoxylated with ethylene and/or propylene oxide, preferably ethylene oxide, with a degree of alkoxylation of 1 to 20, preferably 1 to 15, more preferably 1 to 10, most preferably 1 to 6 and, in one most particularly preferred embodiment, 1 to 4.
  • the monoesters are preferrably the diesters.
  • a particularly preferred sulfosuccinate is sulfosuccinic acid lauryl polyglycol ester disodium salt (lauryl-EO-sulfosuccinate, disodium salt, INCI Disodium Laureth Sulfosuccinate) which is commercially obtainable, for example, as Tego ® Sulfosuccinat F30 (Goldschmidt) with a sulfosuccinate content of 30% by weight.
  • one or both carboxyl groups of the sulfosuccinic acid preferably form a carboxylic acid amide with a primary or secondary amine which carries one or two identical or different, unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alkyl groups containing 4 to 22, preferably 6 to 20, more preferably 8 to 18, most preferably 10 to 16 and, in one most particularly preferred embodiment, 12 to 14 carbon atoms.
  • sulfosuccinates and sulfosuccinamates referred to by their INCI names which are described in more detail in International Cosmetic Ingredient Dictionary and Handbook: Ammonium Dinonyl Sulfosuccinate, Ammonium Lauryl Sulfosuccinate, Diammonium Dimethicone Copolyol Sulfosuccinate, Diammonium Lauramido-MEA Sulfosuccinate, Diammonium Lauryl Sulfosuccinate, Diammonium Oleamido PEG-2 Sulfosuccinate, Diamyl Sodium Sulfosuccinate, Dicapryl Sodium Sulfosuccinate, Dicyclohexyl Sodium Sulfosuccinate, Diheptyl Sodium Sulfosuccinate, Dihexyl Sodium Sulfosuccinate, Diisobutyl Sodium Sulfosuccinate, Dioctyl Sodium Sulfos
  • Preferred anionic sulfosuccinic acid surfactants are imidosuccinate, mono-Na-sulfosuccinic acid diisobutyl ester (Monawet( MB 45), mono-Na-sulfosuccinic acid dioctyl ester (Monawet ® MO-84 R2W, Rewopol ® SB DO 75), mono-Na-sulfosuccinic acid di-tridecyl ester (Monawet ® MT 70), fatty alcohol polyglycol sulfosuccinate-Na-NH 4 salt (sulfosuccinate, S-2), di-Na-sulfosuccinic acid monO-C 12-14 -3EO ester (Texapon ® SB-3), sodium sulfosuccinic acid diisooctyl ester (Texin ® DOS 75) and di-Na-sulfosuccinic acid mono-C 12/18 este
  • the liquid composition comprises at least one anionic surfactant selected from the group consisting of aliphatic sulfates, preferably from the group consisting of fatty alcohol sulfates and fatty alcohol ether sulfates, more preferably from the group consisting of Na C 12-14 fatty alcohol ether sulfate (1-4 EO), preferably Na C 12-14 fatty alcohol ether sulfate (1-2 EO), as herein described above.
  • anionic surfactant selected from the group consisting of aliphatic sulfates, preferably from the group consisting of fatty alcohol sulfates and fatty alcohol ether sulfates, more preferably from the group consisting of Na C 12-14 fatty alcohol ether sulfate (1-4 EO), preferably Na C 12-14 fatty alcohol ether sulfate (1-2 EO), as herein described above.
  • a liquid composition according to the present invention contains at least one anionic surfactant in an amount of about 1 to about 55 wt.-%, preferably about 2 to about 50 wt.-%, more preferably about 3 to about 45 wt.-%, for instance, but without limitation, in an amount of about 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 2526, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44 or 45 wt.-%, based on the total weight of the composition.
  • the liquid composition comprises least one fatty alcohol ether sulfate, as herein described above, in an amount of about 1 to about 50 wt.-%, preferably about 3 to about 40 wt.-%, more preferably about 5 to about 35 wt.-%, for instance, but without limitation, in an amount of about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35 wt.-%, based on the total weight of the composition
  • amphoteric surfactants which may be used in accordance with the invention include betaines, alkyl amidoalkyl amines, alkyl-substituted amino acids, acylated amino acids and biosurfactants.
  • Betaines suitable for incorporation according to the present invention are the alkyl betaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably correspond to 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) in which R 1 is a saturated or unsaturated C 6-22 alkyl group, preferably a C 8-18 alkyl group and more preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group, X is NH, NR 4 with the C 1-4 alkyl group R 4 , O or S, n is a number of 1 to 10, preferably 2 to 5 and more preferably 3, x is 0 or 1, preferably 1, R 2 and
  • Preferred amphoteric surfactants are the alkyl betaines corresponding to formula (la), the alkylamidobetaines corresponding to formula (lb), the sulfobetaines corresponding to formula (Ic) and the amidosulfobetaines corresponding to 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 R 1 is as defined for formula I.
  • amphoteric surfactants are the carbobetaines and more particularly the carbobetaines corresponding to formulae (la) and (lb), the alkylamidobetaines corresponding to formula (Ib) being most particularly preferred.
  • betaines and sulfobetaines are the following compounds identified by their INCI names: Almondamidopropyl Betaine, Apricotamidopropyl Betaine, Avocadamidopropyl Betaine, Babassuamidopropyl Betaine, Behenamidopropyl Betaine, Behenyl Betaine, Betaine, Canolamidopropyl Betaine, Capryl/Capramidopropyl Betaine, Carnitine, Cetyl Betaine, Cocamidoethyl Betaine, Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Coco-Betaine, Coco-Hydroxysultaine, Coco/Oleamidopropyl Betaine, Coco-Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate
  • alkylamido alkylamines are amphoteric surfactants corresponding to formula (III): R 9 -CO-NR 10 -(CH 2 ) i -(R 11 )-(CH 2 CH 2 O) j -(CH 2 ) k [CH(OH)] l -CH 2 -Z-OM (III) in which R 9 is a saturated or unsaturated C 6-22 alkyl group, preferably a C 8-18 alkyl group and more preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group, R 10 is a hydrogen atom H or a C 1-4 alkyl group, preferably H, i is a number of 1 to 10, preferably 2 to 5, more preferably 2 or 3, R 11 is a hydrogen atom H or CH 2 COOM (for M, see below), j is a number of 1 to 4, preferably 1 or 2, more preferably 1, k is a number of
  • alkylamido alkylamines are the following compounds identified by their INCI names: Cocoamphodipropionic Acid, Cocobetainamido Amphopropionate, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-Isodeceth-7 Carboxyamphodiacetate
  • preferred alkyl-substituted amino acids are monoalkyl-substituted amino acids corresponding to formula (IV): R 13 -NH-CH(R 14 )-(CH 2 ) u -COOM' (IV) in which R 13 is a saturated or unsaturated C 6-22 alkyl group, preferably a C 8-18 alkyl group and more preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group, R 14 is a hydrogen atom H or a C 1-4 alkyl group, preferably H, u is a number of 1 to 4, preferably 0 or 1, more preferably 1, and M' is a hydrogen atom, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine, alkyl-substituted imino acids corresponding to formula (IV): R 13 -NH-CH(R 14 )-(CH 2 ) u
  • alkyl-substituted amino acids are the aminopropionates corresponding to formula (IVa): R 13 -NH-CH 2 CH 2 COOM' (IVa) in which R 13 and M' have the same meanings as in formula (IV).
  • alkyl-substituted amino acids are the following compounds identified by their INCI names: Aminopropyl Laurylglutamine, Cocaminobutyric Acid, Cocaminopropionic Acid, DEA-Lauraminopropionate, Disodium Cocaminopropyl Iminodiacetate, Disodium Dicarboxyethyl Cocopropylenediamine, Disodium Lauriminodipropionate, Disodium Steariminodipropionate, Disodium Tallowiminodipropionate, Lauraminopropionic Acid, Lauryl Aminopropylglycine, Lauryl Diethylenediaminoglycine, Myristaminopropionic Acid, Sodium C12-15 Alkoxypropyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA-Lauraminopropionat
  • Acylated amino acids are amino acids, more particularly the 20 natural ⁇ -amino acids, which carry the acyl group R 19 CO of a saturated or unsaturated fatty acid R 19 COOH at the amino nitrogen atom (R 19 being a saturated or unsaturated C 6-22 alkyl group, preferably a C 8-18 alkyl group and more preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group).
  • the acylated amino acids may also be used in the form of an alkali metal salt, an alkaline earth metal salt or alkanolammonium salt, for example mono-, di- or triethanolamine.
  • acylated amino acids are the acyl derivatives known collectively by the INCI name of Amino Acids, for example Sodium Cocoyl Glutamate, Lauroyl Glutamic Acid, Capryloyl Glycine oder Myristoyl Methylalanine.
  • the liquid composition of the present invention comprises at least one amphoteric surfactant selected from the group consisting of alkyl betaines, alkylamidobetaines, imidazolinium betaines, sulfobetaines, phosphobetaines, alkyl amidoalkyl amines, alkyl-substituted amino acids, acylated amino acids and biosurfactants, preferably from the group consisting of alkylamidobetaines.
  • amphoteric surfactant selected from the group consisting of alkyl betaines, alkylamidobetaines, imidazolinium betaines, sulfobetaines, phosphobetaines, alkyl amidoalkyl amines, alkyl-substituted amino acids, acylated amino acids and biosurfactants, preferably from the group consisting of alkylamidobetaines.
  • a liquid composition according to the present invention contains at least one amphoteric surfactant in an amount of about 1 to about 35 wt.-%, preferably about 2 to about 30 wt.-%, more preferably about 3 to about 25 wt.-%, for instance, but without limitation, in an amount of about 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24 or 25 wt.-%, based on the total weight of the composition.
  • a liquid composition according to the present invention contains at least one betaine in an amount of about 1 to about 30 wt.-%, preferably about 2 to about 25 wt.-%, more preferably about 3 to about 20 wt.-%, for instance, but without limitation, in an amount of about 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 wt.-%, based on the total weight of the composition.
  • Nonionic surfactants in the context of the invention are alkoxylates, such as polyglycol ethers, fatty alcohol polyglycol ethers, alkyl phenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters.
  • Block polymers of ethylene oxide and propylene oxide and fatty acid alkanolamides and fatty acid polyglycol ethers are also suitable.
  • Important classes of nonionic surfactants according to the invention are also the amine oxides and the sugar surfactants, more particularly the alkyl polyglucosides.
  • suitable amine oxides include alkyl amine oxides, more particularly alkyl dimethyl amine oxides, alkylamidoamine oxides and alkoxyalkyl amine oxides.
  • Preferred amine oxides correspond to formula II: R 6 R 7 R 8 N + -O- (II) R 6 -[CO-NH-(CH 2 ) w ] z -N + (R 7 )(R 8 )-O - (II) in which R 6 is a saturated or unsaturated C 6-22 alkyl group, preferably a C 8-18 alkyl group, more preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group which, in the alkylamidoamine oxides, is attached to the nitrogen atom via a carbonylamidoalkylene group -CO-NH-(CH 2 ) z - and, in the alkoxyalkyl amine oxides, via an oxa-alkylene group -O-
  • Suitable amine oxides are the following compounds identified by their INCI names: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, Decyltetradecylamine Oxide, Diaminopyrimidine Oxide, Dihydroxyethyl C 8-10 Alkoxypropylamine Oxide, Dihydroxyethyl C 9-11 Alkoxypropylamine Oxide, Dihydroxyethyl C 12-15 Alkoxypropylamine Oxide, Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallowamine Oxide, Hydroxyethyl Hydroxypropyl C 12-15 Alk
  • the liquid composition comprises at least one amine oxide in an amount of about 0.1 to about 25 wt.-%, preferably in an amount of about 0.5 to about 15 wt.-%, more preferably in an amount of about 1 to about 7 wt.-%, for instance, but without limitation, in an amount of about 1, 2, 3, 4, 5, 6 or 7 wt.-%, based on the total weight of the composition.
  • fatty alcohol polyglycol ethers are unbranched or branched, saturated or unsaturated C 10-22 alcohols alkoxylated with ethylene oxide (EO) and/or propylene oxide (PO) with a degree of alkoxylation of up to 30, preferably ethoxylated C 10-18 fatty alcohols with a degree of ethoxylation of less than 30, preferably with a degree of ethoxylation of 1 to 20, more preferably 1 to 12, most preferably 1 to 8 and, in one most particularly preferred embodiment, 2 to 5, for example C 12-14 fatty alcohol ethoxylates with 2, 3 or 4 EO or a mixture of the C 12-14 fatty alcohol ethoxylates with 3 and 4 EO in a ratio by weight of 1 to 1 or isotridecyl alcohol ethoxylate with 5, 8 or 12 EO.
  • EO ethylene oxide
  • PO propylene oxide
  • Sugar surfactants are known surface-active compounds which include, for example, the sugar surfactant classes of alkyl glucose esters, aldobionamides, gluconamides (sugar acid amides), glycerol amides, glycerol glycolipids, polyhydroxyfatty acid amide sugar surfactants (sugar amides) and alkyl polyglycosides described, for example, in WO 97/00609 A1 (Henkel Corporation) and the publications cited therein (pages 4 to 12) to which reference is explicitly made in this regard and of which the disclosure is hereby included in the present application.
  • sugar surfactant classes include, for example, the sugar surfactant classes of alkyl glucose esters, aldobionamides, gluconamides (sugar acid amides), glycerol amides, glycerol glycolipids, polyhydroxyfatty acid amide sugar surfactants (sugar amides) and alkyl polyglycosides described, for example,
  • preferred sugar surfactants are the alkyl polyglycosides and the sugar amides and their derivatives, more particularly their ethers and esters.
  • the ethers are the products of the reaction of one or more, preferably one, sugar hydroxy group with a compound containing one or more hydroxy groups, for example C 1-22 alcohols or glycols, such as ethylene and/or propylene glycol; the sugar hydroxy group may also carry polyethylene glycol and/or propylene glycol residues.
  • the esters are the reaction products of one or more, preferably one, sugar hydroxy group with a carboxylic acid, more particularly a C 6-22 fatty acid.
  • Particularly preferred sugar amides correspond to the formula R'C(O)N(R")[Z], where R' is a linear or branched, saturated or unsaturated acyl group, preferably a linear unsaturated acyl group, containing 5 to 21, preferably 5 to 17, more preferably 7 to 15 and most preferably 7 to 13 carbon atoms, R" is a linear or branched, saturated or unsaturated alkyl group, preferably a linear unsaturated alkyl group, containing 6 to 22, preferably 6 to 18, more preferably 8 to 16 and most preferably 8 to 14 carbon atoms, a C 1-5 alkyl group, more particularly a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert.butyl or n-pentyl group, or hydrogen and Z is a sugar unit, i.e. a monosaccharide unit.
  • Particularly preferred sugar amides are the amides of glucose, the
  • alkyl polyglycosides are particularly preferred sugar surfactants for the purposes of the present invention and preferably correspond to the general formula R 1 O(AO) a [G] x , where R 1 is a linear or branched, saturated or unsaturated alkyl group containing 6 to 22, preferably 6 to 18 and more preferably 8 to 14 carbon atoms, [G] is a glycosidic sugar unit and x is a number of 1 to 10 and AO stands for an alkyleneoxy group, for example an ethyleneoxy or propyleneoxy group, and a stands for the mean degree of alkoxylation of 0 to 20.
  • the group (AO) a may also contain various alkyleneoxy units, for example ethyleneoxy or propyleneoxy units, in which case a stands for the mean total degree of alkoxylation, i.e. the sum of the degree of ethoxylation and the degree of propoxylation.
  • alkyl groups R 1 of the APGs are linear unsaturated groups with the indicated number of carbon atoms.
  • APGs are nonionic surfactants and represent known substances which may be obtained by the relevant methods of preparative organic chemistry.
  • the index x indicates the degree of oligomerization (DP degree), i.e. distribution of mono- and oligoglycosides, and is a number of 1 to 10. Whereas x in a given compound must always be an integer and, above all, may assume a value of 1 to 6, the value x for a certain alkyl oligoglycoside is an analytically determined calculated quantity which is generally a broken number.
  • Alkyl glycosides having an average degree of oligomerization x of 1.1 to 3.0 are preferably used. Alkyl glycosides having a degree of oligomerization of less than 1.7 and, more particularly, between 1.2 and 1.6 are preferred from the applicational point of view.
  • the glycosidic sugar used is preferably xylose but especially glucose.
  • the alkyl or alkenyl radical R 1 may be derived from primary alcohols containing 8 to 18 and preferably 8 to 14 carbon atoms. Typical examples are caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and the technical mixtures thereof obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 1 is preferably derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol and may also be derived from elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof.
  • preferred alkyl polyglycosides are, for example, C 8-10 and a C 12-14 alkyl polyglucoside with a DP degree of 1.4 or 1.5, more particularly C 8-10 alkyl-1,5-glucoside and C 12 -14 alkyl-1,4-glucoside.
  • the liquid composition comprises at least one nonionic surfactant selected from the group consisting of polyglycol ethers, fatty alcohol polyglycol ethers, alkyl phenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers, hydroxy mixed ethers, fatty acid polyglycol esters, block polymers of ethylene oxide and propylene oxide and fatty acid alkanolamides and fatty acid polyglycol ethers, amine oxides, sugar surfactants, preferably from the group consisting of amine oxides and alkyl polyglucosides.
  • nonionic surfactant selected from the group consisting of polyglycol ethers, fatty alcohol polyglycol ethers, alkyl phenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers, hydroxy mixed ethers, fatty acid polyglycol esters, block polymers of ethylene oxide and propylene oxide and fatty acid alkanolamides and
  • a liquid composition according to the present invention contains at least one nonionic surfactant in an amount of about 1 to about 35 wt.-%, preferably about 2 to about 30 wt.-%, more preferably about 3 to about 25 wt.-%, for instance, but without limitation, in an amount of about 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24 or 25 wt.-%, based on the total weight of the composition.
  • the liquid composition comprises at least one amine oxide, as herein described above, in an amount of about 1 to about 30 wt.-%, preferably about 2 to about 25 wt.-%, more preferably about 3 to about 20 wt.-%, based on the total weight of the composition.
  • the liquid composition comprises at least one fatty alcohol ether sulfate in an amount of about 1 to about 50 wt.-%, preferably about 3 to about 40 wt.-%, more preferably about 5 to about 35 wt.-%, based on the total weight of the composition; and/or at least one amine oxide in an amount of about 1 to about 30 wt.-%, preferably about 2 to about 25 wt.-%, more preferably about 3 to about 20 wt.-%, based on the total weight of the composition; and/or at least one betaine in an amount of about 1 to about 30 wt.-%, preferably about 2 to about 25 wt.-%, more preferably about 3 to about 20 wt.-%, based on the total weight of the composition.
  • the liquid composition comprises, in addition to any of the aforementioned ingredients, at least one further ingredient, which may improve cleaning performance, stability, aesthetics or other attributes and characteristics of the liquid composition.
  • the liquid compositions further comprise at least one additive selected from the group consisting of additional surfactants, additional water-soluble salts, acids, perfumes, solvents, dyes, opacifiers, viscosity regulators, enzymes, corrosion inhibitors, pH-value adjuster, preservatives, UV stabilizers, skin-care substances, or mixtures thereof.
  • composition according to the invention may additionally contain one or more cationic surfactants (cationic surfactants; INCI Quaternary Ammonium Compounds).
  • cationic surfactants cationic surfactants; INCI Quaternary Ammonium Compounds.
  • Preferred cationic surfactants are the quaternary surface-active compounds, more particularly containing an ammonium, sulfonium, phosphonium, iodonium or arsonium group, which are described as antimicrobial agents, for example, in K. H. Wall conferenceußer's "Praxis der Sterilisation, Desinfetechnisch-Konservtechnik: Keimidentifying-Betriebshygiene” (5th Edition, Stuttgart/New York: Thieme, 1995 ).
  • the composition can be given an antimicrobial effect or any antimicrobial activity already present through other ingredients can be improved.
  • Particularly preferred cationic surfactants are quaternary ammonium compounds (QUATS; INCI Quaternary Ammonium Compounds) corresponding to the general formula (R I )(R II )(R III )(R IV )N + X - , in which R I to R IV may be the same or different and represent C 1-22 alkyl groups, C 7-28 aralkyl groups or heterocyclic groups, two or - in the case of an aromatic compound, such as pyridine - even three groups together with the nitrogen atom forming the heterocycle, for example a pyridinium or imidazolinium compound, and X - represents halide ions, sulfate ions, hydroxide ions or similar anions.
  • at least one of the substituents preferably has a chain length of 8 to 18 and, more preferably, 12 to 16 carbon atoms.
  • QUATS can be obtained by reaction of tertiary amines with alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide and also ethylene oxide.
  • alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide and also ethylene oxide.
  • alkylation of tertiary amines with one long alkyl chain and two methyl groups is particularly simple.
  • the quaternization of tertiary amines containing two long chains and one methyl group can also be carried out under mild conditions using methyl chloride.
  • Amines containing three long alkyl chains or hydroxysubstituted alkyl chains lack reactivity and are preferably quaternized with dimethyl sulfate.
  • Suitable QUATS are, for example, benzalkonium chloride (N-alkyl-N,N-dimethylbenzyl ammonium chloride, CAS No. 8001-54-5 ), benzalkon B (m,p-dichlorobenzyl dimethyl-C 12 -alkyl ammonium chloride, CAS No. 58390-78-6 ), benzoxonium chloride (benzyldodecyl-bis-(2-hydroxyethyl)-ammonium chloride), cetrimonium bromide (N-hexadecyl-N,N-trimethyl ammonium bromide, CAS No.
  • benzalkonium chloride N-alkyl-N,N-dimethylbenzyl ammonium chloride, CAS No. 8001-54-5
  • benzalkon B m,p-dichlorobenzyl dimethyl-C 12 -alkyl ammonium chloride, CAS No. 58390-78-6
  • benzetonium chloride N,N-di-methyl-N-[2-[2-[p-(1,1,3,3-tetramethylbutyl)-phenoxy]-ethoxy]-ethyl]-benzyl ammonium chloride, CAS No. 121-54-0
  • dialkyl dimethyl ammonium chlorides such as di-n-decyidimethyl ammonium chloride ( CAS No. 7173-51-5-5 ), didecyldimethyl ammonium bromide ( CAS No. 2390-68-3 ), dioctyl dimethyl ammonium chloride, 1-cetylpyridinium chloride ( CAS No.
  • QUATS are the benzalkonium chlorides containing C 8-18 alkyl groups, more particularly C 12-14 alkyl benzyl dimethyl ammonium chloride.
  • a particularly preferred QUAT is cocopentaethoxy methyl ammonium methosulfate (INCI PEG-5 Cocomonium Methosulfate; Rewoquat ® CPEM).
  • the cationic surfactant used should be compatible with anionic surfactants or should only be used in very small amounts. In one particular embodiment of the invention, no cationic surfactants are used at all.
  • a detergent may further contain at least one water-soluble and/or water-insoluble, organic and/or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and saccharic acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid) and 1-hydroxyethyl-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxylic acids, in particular polycarboxylates obtainable by oxidation of polysaccharides or dextrins, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small proportions of polymerizable substances without carboxylic acid functionality incorporated therein by polymerization.
  • polycarboxylic acids in particular citric acid and saccharic acids
  • the relative molecular mass of the homopolymers of unsaturated carboxylic acids is in general between about 3,000 and about 200,000, that of the copolymers between about 2,000 and about 200,000, preferably about 30,000 to about 120,000, in each case relative to free acid.
  • One particularly preferred acrylic acid/maleic acid copolymer has a relative molecular mass of about 30,000 to about 100,000.
  • Conventional commercial products are for example Sokalan ® CP 5, CP 10 and PA 30 from BASF.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, the acid fraction of which amounts to at least 50 wt. %.
  • vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene
  • the acid fraction of which amounts to at least 50 wt. % Terpolymers containing as monomers two unsaturated acids and/or the salts thereof and, as third monomer, vinyl alcohol and/or a esterified vinyl alcohol or a carbohydrate may also be used as water-soluble organic builder substances.
  • the first acidic monomer or the salt thereof is derived from a monoethylenically unsaturated C3-C8-carboxylic acid and preferably from a C3-C4-monocarboxylic acid, in particular from (meth)acrylic acid.
  • the second acidic monomer or the salt thereof may be a derivative of a C4-C8-dicarboxylic acid, maleic acid being particularly preferred, and/or a derivative of an allylsulfonic acid, which is substituted in position 2 with an alkyl or aryl residue.
  • Such polymers generally have a relative molecular mass of between about 1,000 and about 200,000.
  • copolymers are those, which comprise acrolein and acrylic acid/acrylic acid salts or vinyl acetate as monomers.
  • the organic builder substances may be used, in particular for producing liquid products, in the form of aqueous solutions, preferably in the form of about 30 to about 50 wt. % aqueous solutions. All the stated acids are generally used in the form of the water-soluble salts, in particular the alkali metal salts, thereof.
  • Such organic builder substances may, if desired, be present in quantities of up to 40 wt.-%, in particular of up to 25 wt.-% and preferably of about 1 wt.-% to about 8 wt.-%. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular water-containing detergent formulations as contemplated herein.
  • Water-soluble inorganic builder materials which may in particular be considered, are alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be present in the form of the alkaline, neutral or acidic sodium or potassium salts thereof.
  • alkali metal silicates alkali metal carbonates
  • alkali metal phosphates which may be present in the form of the alkaline, neutral or acidic sodium or potassium salts thereof.
  • these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogendiphosphate, pentasodium triphosphate, "sodium hexametaphosphate", oligomeric trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • Water-insoluble, water-dispersible inorganic builder materials which are used are in particular crystalline or amorphous alkali metal aluminosilicates, in quantities of up to 50 wt. %, preferably of no more than 40 wt. % and, in liquid products, in particular from about 1 wt. % to about 5 wt. %.
  • Preferred such materials are crystalline sodium aluminosilicates of detergent grade, in particular zeolite A, P and optionally X, alone or in mixtures, for example in the form of a co-crystallization product of zeolites A and X (Vegobond ® AX, a commercial product of Condea Augusta S.p.A.).
  • Suitable aluminosilicates in particular comprise no particles with a grain size of above 30 ⁇ m and preferably consist to an extent of at least 80 wt.-% of particles with a size below 10 ⁇ m.
  • Their calcium binding capacity which may be determined as stated in German patent DE 24 12 837 , is generally in the range from 100 to 200 mg of CaO per gram.
  • Suitable substitutes or partial substitutes for the described aluminosilicates are crystalline alkali metal silicates, which may be present alone or mixed with amorphous silicates.
  • the alkali metal silicates usable as builders in the products as contemplated herein preferably have a molar ratio of alkali metal oxide to SiO 2 of below 0.95, in particular of about 1:1.1 to about 1:12 and may be in amorphous or crystalline form.
  • Preferred alkali metal silicates are sodium silicates, in particular amorphous sodium silicates, with an Na 2 O:SiO 2 molar ratio of 1:2 to 1:2.8.
  • crystalline silicates which may be present alone or mixed with amorphous silicates, are crystalline phyllosilicates of the general formula Na 2 Si x O 2x +1 ⁇ y H 2 O, in which x, or "modulus", is a number from about 1.9 to about 22, in particular about 1.9 to about 4 and y is a number from 0 to about 33 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates are those in which x in the stated general formula assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates are preferred.
  • Virtually anhydrous crystalline alkali metal silicates of the above-stated general formula in which x means a number from about 1.9 to about 2.1, which are produced from amorphous alkali metal silicates, may be used in detergents as contemplated herein.
  • Crystalline layered silicates of the above-stated formula (I) are commercially available from Clariant GmbH under the trade name Na-SKS, for example Na-SKS-1 (Na 2 Si 22 O 45 xH 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 xH 2 O, makatite).
  • Na-SKS for example Na-SKS-1 (Na 2 Si 22 O 45 xH 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 xH 2 O, makatite).
  • Suitable representatives of these are primarily Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5 ), Na-SKS-7 ( ⁇ -Na 2 Si 2 O 5 , natrosilite), Na-SKS-9 (NaHSi 2 O 5 ⁇ 3H 2 0), Na-SKS-10 (NaHSi 2 O 5 ⁇ 3H 2 0, kanemite), Na-SKS-11 (t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but in particular Na-SKS-6 ( ⁇ -Na 2 Si 2 O 5 ).
  • a granular compound is used which is prepared from crystalline phyllosilicate and citrate, from crystalline phyllosilicate and above-stated (co)polymeric polycarboxylic acid, or from alkali metal silicate and alkali metal carbonate, as is commercially available for example under the name Nabion ® 15.
  • Builder substances may be present in detergent formulations as contemplated herein in quantities of up to 20 wt.-%, in particular of about 1 wt.-% to about 15 wt.-%, based on the total weight of the composition.
  • the skin care substance may be a compound or mixture of compounds and may preferably be hydrophobic, liquid or solid and must be compatible with the other ingredients of the composition.
  • the skin care compound may be selected, for instance, from:
  • Skin care substances may be present in the compositions according to the present invention in quantities of up to 5 wt.-%, in particular of about 0.1 wt.-% to about 4 wt.-%, based on the total weight of the composition.
  • the composition comprises a perfume.
  • suitable perfume oils may comprise individual fragrant compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol, and hydrocarbon type.
  • Fragrant compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate, benzyl salicylate, cyclohexyl salicylate, floramate, melusate and jasmecyclate.
  • DMBCA dimethylbenzyl carbinyl acetate
  • benzyl acetate ethylmethylphenyl
  • the ethers include, for example, benzyl ethyl ether and ambroxan;
  • the aldehydes include, for example, the linear alkanals containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, lilial and bourgeonal;
  • the ketones include, for example, the ionones, isomethyl ionone and methyl cedryl ketone;
  • the alcohols include anethol, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol and the hydrocarbons include, for example the terpenes, such as limonene and pinene.
  • mixtures of various fragrances which together produce an attractive fragrant note of the resulting perfume oil, are preferably used.
  • the perfume oils may also contain natural mixtures of fragrances, as are obtainable from vegetal sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are e.g. muscatel sage oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetivert oil, olibanum oil, galbanum oil and laudanum oil and orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
  • vegetal sources for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • muscatel sage oil chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetivert oil, olibanum oil, galbanum oil and laudanum oil and orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
  • Exemplary long-lasting fragrances may be selected from essential oils, such as angelica root oil, aniseed oil, arnica flowers oil, basil oil, bay oil, bergamot oil, champax blossom oil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil, ginger grass oil, guaiacum wood oil, Indian wood oil, helichrysum oil, ho oil, ginger oil, iris oil, cajuput oil, sweet flag oil, chamomile oil, camphor oil, Canoga oil, cardamom oil, cassia oil, Scotch fir oil, copaiba balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemon grass oil, limette oil, mandarin oil, melissa oil, amber seed oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil,
  • the higher boiling or solid fragrances of natural or synthetic origin can be advantageously used as long-lasting fragrances or mixtures of fragrances.
  • These compounds include for example the following compounds and their mixtures: ambrettolide, amyl cinnamaldehyde, anethol, anisaldehyde, anis alcohol, anisole, methyl anthranilate, acetophenone, benzyl acetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, borneol, bornyl acetate, bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin,
  • the advantageously utilizable fragrances of higher volatility particularly include the lower boiling fragrances of natural or synthetic origin that can be used alone or in mixtures.
  • Exemplary fragrances of higher volatility are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linalyl acetate and linalyl propionate, menthol, menthone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
  • essential oils may be used as the benefit agent.
  • exemplary essential oils are angelica fine (angelica archangelica), aniseed (pimpinella anisum), benzoe siam (styrax tokinensis), cabreuva (myrocarpus fastigiatus), cajeput (melaleuca leucadendron), cistrose (cistrus ladaniferus), copaiba-balsam (copaifera reticulata), costic root (saussurea discolor), silver fir needle (abies alba), elemi (canarium luzonicum), fennel (foeniculum dulce) pine-needle (picea abies), geranium (pelargonium graveolens), ho-leaves (cinnamonum camphora), immortals (straw flower), helichrysum ang., ginger, perforate St.
  • John's wort hypericum perforatum
  • jojoba German chamomile (matricaria recutita), chamomile oil blue (matricaria chamomilla), Roman chamomile (anthemis nobilis), wild chamomile (ormensis multicaulis), carrot (daucus carota), knee pine (pinus mugho), lavander (lavendula hybrida), litsea cubeba (may chang), manuca (leptospermum scoparium), balm mint (melissa officinalis), pine tree (pinus pinaster), myrrh (commiphora molmol), myrtle (myrtus communis), neem (azadirachta), niaouli (mqv) melaleuca quin.
  • the amount of perfume in the compositions according to the present invention may be up to 5 wt.-%, in particular about 0.01 wt.-% to about 5 wt.-%, more preferably about 0.1 to about 4 wt.-%, based on the total weight of the composition.
  • the water content of the liquid composition according to the invention may be in the range of about 5 to 40 wt.-%, preferably about 7 to 35 wt.-%, more preferably about 10 to 25 wt.-%, based on the total weight of the liquid composition.
  • the composition according to the invention may advantageously contain one or more water-soluble organic solvents in a quantity of typically 0.1 to 15 wt.-%, preferably 1 to 12 wt.-%, more preferably 1 to 10 wt.-%, based on the total weight of the composition.
  • the solvent is used in particular as a hydrotropic agent, a viscosity adjuster and/or low-temperature stabilizer according to requirements. It has a solubilizing effect, particularly on surfactants and electrolytes, perfumes and dyes, and thus contributes to their incorporation, prevents the formation of liquid crystalline phases and contributes to the formation of clear products.
  • the viscosity of the composition according to the invention decreases with increasing solvent content. However, too much solvent can produce a fall in viscosity. Finally, the cold cloud and clear point of the composition according to the invention decreases with increasing solvent content.
  • Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C 1-20 hydrocarbons, preferably C 2-15 hydrocarbons, containing at least one hydroxy group and optionally one or more ether functions C-O-C, i.e. oxygen atoms interrupting the carbon atom chain.
  • Preferred solvents are the C 2-6 alkylene glycols and poly-C 2-3 -alkylene glycol ethers, optionally etherified on one side with a C 1-6 alkanol, containing on average 1 to 9 identical or different, preferably identical, alkylene glycol groups per molecule and the C 1-6 alcohols, preferably ethanol, n-propanol or isopropanol, more particularly ethanol.
  • solvents are the following compounds identified by their INCI names: Alcohol (Ethanol), Buteth-3, Butoxydiglycol, Butoxyethanol, Butoxyisopropanol, Butoxypropanol, n-Butyl Alcohol, t-Butyl Alcohol, Butylene Glycol, Butyloctanol, Diethylene Glycol, Dimethoxydiglycol, Dimethyl Ether, Dipropylene Glycol, Ethoxydiglycol, Ethoxyethanol, Ethyl Hexanediol, Glycol, Hexanediol, 1,2,6-Hexanetriol, Hexyl Alcohol, Hexylene Glycol, Isobutoxypropanol, Isopentyldiol, Isopropyl Alcohol (isoPropanol), 3-Methoxybutanol, Methoxydiglycol, Methoxyethanol, Methoxyisopropanol, Methoxymethylbutanol, Methoxy PEG-10
  • Particularly preferred solvents are the poly-C 2-3 -alkylene glycol ethers etherified on one side with a C 1-6 alkanol and containing on average 1 to 9 and preferably 2 to 3 ethylene or propylene glycol groups, for example PPG-2 Methyl Ether (dipropylene glycol monomethyl ether).
  • Most particularly preferred solvents are the C 2-3 alcohols ethanol, n-propanol and/or isopropanol, more particularly ethanol.
  • suitable solubilizers are, for example, alkanolamines and alkyl benzene sulfonates containing 1 to 3 carbon atoms in the alkyl chain.
  • the viscosity favorable for the composition according to the invention is in the range from about 10 to about 2,000 mPa ⁇ s, preferably about 50 to about 1,000 mPa ⁇ s, in particular about 100 to about 1200 mPa ⁇ s (instead of 1000 mPas), more preferably about 200 to about 1000 mPa ⁇ s.
  • the diluted composition After dilution of the liquid composition with, based on the volume of the liquid composition, about 1 to about 8 parts, preferably about 1.5 to about 7 parts, more preferably about 2 to about 7 parts, particularly about 2 to about 4 parts of water, the diluted composition preferably has a viscosity (at 20° C and at a shear rate of 30 s -1 , as measured with a Brookfield LV DV 11 viscosimeter, spindle 25) of about 30 to about 100,000 mPa ⁇ s, preferably about 50 to about 90,000 mPa ⁇ s, in particular about 100 to about 60,00 mPa ⁇ s, most preferably about 500 to about 55,000 mPa ⁇ s, such as, or instance but without limitation, about 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 2000, 2,500, 3,000
  • Polymeric thickeners in the context of the present invention are the polycarboxylates with a thickening effect as polyelectrolytes, preferably homopolymers and copolymers of acrylic acid, more particularly acrylic acid copolymers, such as acrylic acid/methacrylic acid copolymers, and the polysaccharides, more particularly heteropolysaccharides, and other typical thickening polymers.
  • Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guaran, tragacanth, geilan, ramsan, dextran or xanthan and their derivatives, e.g. propoxylated guar, as well as their mixtures.
  • Other polysaccharide thickeners such as starches or celluose derivatives, can be used alternatively, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g.
  • hydroxyethyl starch starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • a particularly preferred polymeric thickener is the microbial anionic heteropolysaccharide xanthan gum which is produced by Xanthomonas campestris and a few other species under aerobic conditions and which has a molecular weight of 2 to 15 ⁇ 10 6 .
  • This polymer is obtainable from Kelco, for example, under the name of Keltrol ® , for example as the cream-colored powder Keltrol ® T (transparent) or the white granules Keltrol ® RD (readily dispersible).
  • Acrylic acid polymers suitable as polymeric thickeners are, for example, the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, more particularly an allyl ether of sucrose, pentaerythritol or propylene (INCI Carbomer), which are also known as carboxyvinyl polymers.
  • Polyacrylic acids such as these are obtainable inter alia from B.F. Goodrich under the name of Carbopol ® , for example Carbopol ® 940 (molecular weight ca. 4,000,000 g/mol), Carbopol ® 941 (molecular weight ca. 1,250,000 g/mol) or Carbopol ® 934 (molecular weight ca. 3,000,000 g/mol).
  • acrylic acid copolymers are the following acrylic acid copolymers: (i) copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters preferably formed with C 1-4 alkanols (INCI Acrylates Copolymer), which include for example the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate ( CAS 250235-69-2 ) or of butyl acrylate and methyl methacrylate ( CAS 25852-37-3 ) and which are obtainable, for example, from Rohm & Haas under the names of Aculyn ® and Acusol ® , for example the anionic non-associative polymers Aculyn ® 33 (crosslinked), Acusol ® 810 and Acusol ® 830 ( CAS 25852-37-3 ); (ii) crosslinked high molecular weight acrylic acid copolymers which include, for example, the copolymers of C 10-30 alkyl
  • Carbopol ® for example the hydrophobicized Carbopol ® ETD 2623 and Carbopol ® 1382 (INCI Acrylates/C10-30 Alkyl Acrylate Crosspolymer) and Carbopol ® AQUA 30 (formerly Carbopol ® EX 473).
  • the polymeric thickener content is normally not more than 8% by weight, preferably between 0.1 and 7% by weight, more preferably between 0.5 and 6% by weight, most preferably between 1 and 5% by weight and, in one most particularly preferred embodiment, between 1.5 and 4% by weight.
  • the compositions according to the present invention are free from polymeric thickeners, and preferably do not contain any thickeners at all, as the thickening effect is brought about by the presence of the at least one electrolyte salt in the amounts provided herein.
  • the composition is free from polymeric thickeners.
  • one or more dicarboxylic acids and/or salts thereof may be added, advantageously in quantities of 0.1 to 8% by weight, preferably in quantities of 0.5 to 7% by weight, more preferably in quantities of 1.3 to 6% by weight and most preferably in quantities of 2 to 4% by weight.
  • a change in the content of dicarboxylic acid (salt), more particularly in quantities above 2% by weight, can contribute to a clear solution of the ingredients.
  • the viscosity of the mixture can also be influenced within certain limits by this component.
  • this component influences the solubility of the mixture.
  • the component in question is used where the surfactant content is high, more particularly above 30% by weight.
  • the composition according to the invention is preferably free from dicarboxylic acids (salts).
  • auxiliaries and additives particularly in manual dishwashing detergents and cleaners for hard surfaces, more particularly builders, UV stabilizers, pearlizers (INCI Opacifying Agents; for example glycol distearate, for example Cutina ® AGS of Henkel AG & Co.
  • compositions according to the invention may be present in the compositions according to the invention in quantities of normally not more than 5% by weight, preferably 0.1 to 3 wt.-%.
  • the pH-value of the of the compositions according to the invention may be adjusted with typical pH adjusters, for example acids, such as mineral acids or citric acid, and/or alkalis, such as sodium or potassium hydroxide, a pH in the range from 6.0 to 9, preferably in the range from 6.5 to 8.5 and more particularly in the range from 6.8 to 8.5 being preferred.
  • acids such as mineral acids or citric acid
  • alkalis such as sodium or potassium hydroxide
  • the composition according to the invention may contain one or more buffers (INCI Buffering Agents) in quantities of typically 0.001 to 5% by weight, preferably 0.005 to 3% by weight, more preferably 0.01 to 2% by weight, most preferably 0.05 to 1% by weight and, in one most particularly preferred embodiment, 0.1 to 0.5% by weight, for example 0.2% by weight.
  • Buffers which are also complexing agents or even chelators (INCI Chelating Agents) are preferred.
  • Particularly preferred buffers are citric acid or the citrates, more particularly the sodium and potassium citrates, for example trisodium citrate *2 H 2 O and tripotassium citrate *H 2 O.
  • composition according to the invention may be prepared by stirring the individual constituents together in any order.
  • the addition sequence is not crucial to the production of the composition.
  • Water, surfactants and optionally others of the ingredients mentioned above are preferably stirred together. If perfume and/or dye is/are used, they are subsequently added to the solution obtained. The pH value is then adjusted as described above.
  • the present invention relates to the use of a liquid composition, as herein described above, for the cleaning of hard surfaces, as herein defined, particularly for manual dishwashing applications.
  • the present invention also relates to the use of a liquid composition, as herein described above, for the preparation of a dilute aqueous hard surface cleaning composition, particularly for the preparation of a dilute manual dishwashing detergent composition.
  • the present invention furthermore relates to a method for the preparation of a dilute aqueous hard surface cleaning composition, particularly a dilute manual dishwashing detergent composition, characterized in that a liquid composition as herein disclosed and described is diluted with about 1 to about 8 parts, preferably about 1.5 to about 7 parts, more preferably about 2 to about 7 parts, particularly about 2 to about 4 parts of water, based on the volume of the liquid composition.
  • Each of liquid composition Examples 1-4 was prepared by first mixing the electrolyte salt(s), GLDA, potassium acetate, phenoxyethanol, biocide, perfume, and amine oxide with about 30-90 wt.-% of the total water content in the final concentrate composition.
  • the pH of the resultant mixture was adjusted to be in the range of about 7.6-9.7 by adding citric acid, after which the fatty alcohol ether sulfates, the betaine, the dye and ethanol, insofar present, was added.
  • the pH of the resultant mixture was adjusted to be in the range of about 7.8-7.9 by adding citric acid, after which the enzymes were added.
  • the remainder of the water portion was added to obtain the desired amount of concentrate.
  • Viscosities were measured at 20 °C, 3 rpm, Spindle 31, Brookfield DV2T.

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2412837A1 (de) 1973-04-13 1974-10-31 Henkel & Cie Gmbh Verfahren zum waschen und reinigen der oberflaechen von festen werkstoffen, insbesondere von textilien, sowie mittel zur durchfuehrung des verfahrens
EP0425427A2 (de) 1989-10-25 1991-05-02 Hoechst Aktiengesellschaft Verfahren zur Herstellung von Natriumsilikaten
WO1997000609A1 (en) 1995-06-21 1997-01-09 Henkel Corporation Method for increasing the efficacy of an odor masking agent
WO2008074667A1 (en) * 2006-12-20 2008-06-26 Unilever N.V. Dishwashing composition
US20100197553A1 (en) * 2009-02-02 2010-08-05 Freddy Arthur Barnabas Liquid hand dishwashing detergent composition
US20170022458A1 (en) * 2015-07-20 2017-01-26 The Procter & Gamble Company Consumer products having an asepsis connotation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2412837A1 (de) 1973-04-13 1974-10-31 Henkel & Cie Gmbh Verfahren zum waschen und reinigen der oberflaechen von festen werkstoffen, insbesondere von textilien, sowie mittel zur durchfuehrung des verfahrens
EP0425427A2 (de) 1989-10-25 1991-05-02 Hoechst Aktiengesellschaft Verfahren zur Herstellung von Natriumsilikaten
WO1997000609A1 (en) 1995-06-21 1997-01-09 Henkel Corporation Method for increasing the efficacy of an odor masking agent
WO2008074667A1 (en) * 2006-12-20 2008-06-26 Unilever N.V. Dishwashing composition
US20100197553A1 (en) * 2009-02-02 2010-08-05 Freddy Arthur Barnabas Liquid hand dishwashing detergent composition
US20170022458A1 (en) * 2015-07-20 2017-01-26 The Procter & Gamble Company Consumer products having an asepsis connotation

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
A. DOMSCHB. IRRGANG: "Surfactant Science Series", vol. 56, 1996, MARCEL DEKKER, INC., article "Anionic Surfactants: Organic Chemistry", pages: 501 - 549
CAS , no. 58390-78-6
CAS, no. 250235-69-2
K. H. WALLHAUBER: "Praxis der Sterilisation, Desinfektion-Konservierung: Keimidentifizierung-Betriebshygiene", 1995, THIEME

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