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EP2401351B1 - Liquide vaisselle - Google Patents

Liquide vaisselle Download PDF

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Publication number
EP2401351B1
EP2401351B1 EP10703660.0A EP10703660A EP2401351B1 EP 2401351 B1 EP2401351 B1 EP 2401351B1 EP 10703660 A EP10703660 A EP 10703660A EP 2401351 B1 EP2401351 B1 EP 2401351B1
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EP
European Patent Office
Prior art keywords
cleaning agent
agent according
aqueous cleaning
alkyl
surfactant
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Active
Application number
EP10703660.0A
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German (de)
English (en)
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EP2401351A1 (fr
Inventor
Detlef Buisker
Heinz-Dieter Soldanski
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL10703660T priority Critical patent/PL2401351T3/pl
Publication of EP2401351A1 publication Critical patent/EP2401351A1/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
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • 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
    • C11D1/143—Sulfonic 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

Definitions

  • the invention relates to an aqueous cleaning agent for hard surfaces, which contains a surfactant combination of fatty alcohol ether sulfate and at least one other surfactant and 10 to 40 wt .-% of a water-soluble salt.
  • This cleaning agent is preferably used for manual dishwashing.
  • Liquid aqueous hand dishwashing detergents are used in countless households. However, in particular in the case of stubborn, encrusted or burnt soiling, they are reaching the limits of their applicability, since longer soaking times and greater mechanical action of force are required in order to achieve a satisfactory cleaning result. If a quick cleaning is desired, therefore, more detergents are used, such as more alkaline cleaning sprays or abrasives. However, this is desirable neither from an economic nor ecological point of view. Another problem is the limited skin compatibility of many conventional hand dishwashing detergents as well as the additional detergents used.
  • an aqueous cleaning agent which contains a special surfactant mixture and additionally has a high concentration of common salt, beyond its saturation point, on the one hand by the abrasive action of the undissolved salt crystals has a particularly good cleaning performance especially on stubborn stains and on the other hand has very good skin compatibility even at low dilution.
  • Water-soluble salts have been used for some time in hard surface cleaners, for example, for viscosity adjustment or as components of buffer systems. But also suspended salt particles already served as abrasives. This is how it works WO 2007/085410 A1 a detergent composition in which salt particles may be suspended thanks to an internal structure. However, the surfactant combination of fatty alcohol ether sulfate and at least one other surfactant is not claimed here. A skin-friendly effect was not found for this agent; the cleaning performance of encrusted stains is called "satisfactory".
  • EP 958340 B1 claims a surfactant-containing antibacterial cleaning composition having abrasive particles, which are preferably salts. However, this agent should be free of anionic surfactants. Neither a good cleaning performance on baked fat soil nor a skin-friendly effect was found.
  • DE 100 23438 discloses concentrates, in particular hand dishwashing detergents containing surfactants and electrolyte salts.
  • EP 334 566 discloses liquid hard surface cleaners containing surfactants and water soluble salts.
  • the subject of the present invention is an aqueous hard surface cleaner comprising a surfactant combination of fatty alcohol ether sulfate and betaine surfactant and 15 to 40% by weight of a water-soluble salt, wherein it is fatty alcohol ether sulfate, secondary alkanesulfonate and betaine surfactant in the ratio 2: 0: 1 to 5: 1: 1 and the salt concentration must be so high that the salt does not dissolve completely.
  • This detergent is particularly suitable as a hand dishwashing detergent, with the stubborn, burnt or dried dirt can be removed well.
  • a further subject of the present application is accordingly the use of the cleaning agent according to the invention for the manual rinsing of dishes.
  • the cleaning agent according to the invention also has the advantage that it is washed out more slowly from a sponge than a comparable formulation with a smaller amount of salt.
  • the long shelf life in the sponge is particularly advantageous if the items to be washed are cleaned under running water, as it leads to lower losses and thus to a higher efficiency.
  • fatty acids or fatty alcohols or their derivatives are representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms.
  • the former are particularly preferred for their vegetable base as based on renewable raw materials for environmental reasons, but without limiting the teaching of the invention to them.
  • the oxo alcohols or their derivatives which are obtainable, for example, by the ROELEN's oxo synthesis can also be used correspondingly.
  • alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.
  • the International Cosmetic Ingredient Dictionary and Handbook assigns to the ingredients one or more chemical classes, for example, polymeric ethers, and one or more functions, For example, Surfactants - Cleansing Agents, which in turn explains it in more detail and which may also be referred to below.
  • the indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service.
  • composition of the invention contains surfactants in a total amount of usually 7 to 40 wt .-%, preferably 12 to 35 wt .-%, in particular 16 to 25 wt .-%.
  • the surfactants are a surfactant combination of fatty alcohol ether sulfate and at least one other surfactant comprising secondary alkanesulfonate and betaine surfactant.
  • composition according to the invention may additionally comprise one or more further anionic surfactants, amphoteric surfactants, nonionic surfactants and / or cationic surfactants, in particular for improving cleaning action, run-off behavior and / or drying behavior.
  • alkyl ether sulfates and alkyl sulfonates and the other anionic surfactants are usually used as alkali metal, alkaline earth metal and / or mono-, di- or Trialkanolammoniumsalz and / or in the form of their with the corresponding alkali metal hydroxide, alkaline earth metal hydroxide and / or mono-, di- or trialkanolamine used in situ to be neutralized corresponding acid.
  • Particularly preferred are the sodium salts.
  • Alkyl ether sulfates are products of sulfation reactions on alkoxylated alcohols.
  • the person skilled in the art generally understands, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the context of the present invention preferably with longer-chain alcohols, ie with aliphatic straight-chain or one or more branched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably straight-chain, acyclic, saturated, alcohols having 6 to 22, preferably 8 to 18, in particular 10 to 16 and particularly preferably 12 to 14 carbon atoms.
  • Another embodiment of the alkoxylation is the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • Very particularly preferred for the purposes of the present invention are low-ethoxylated fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 2 EO, such as Na-C 12-14 fatty alcohol + 2EO sulfate.
  • the composition according to the invention contains one or more alkyl ether sulfates in an amount of 5 to 20% by weight, preferably 8 to 16% by weight.
  • Preferred betaines are the alkylbetaines of the formula (Ia), the alkylamidobetaines of the formula (Ib), the sulfobetaines of the formula (Ic) and the amidosulfobetaines 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 is -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 has the same meaning as in formula I.
  • betaines are the carbo-betaines, in particular the carbo-betaines of the formula (Ia) and (Ib), most preferably the alkylamido-betaines of the formula (Ib).
  • a preferred betaine is, for example, cocamidopropyl betaine (cocoamidopropylbetaine).
  • the agent of the invention contains one or more betaines in an amount of usually 1 to 10 wt .-%, preferably 2 to 8 wt .-%.
  • the agents according to the invention preferably also contain one or more alkylsulfonates.
  • the alkyl sulfonates usually have an aliphatic straight-chain or mono- or poly-branched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably branched, acyclic, saturated, alkyl radical having 6 to 22, preferably 9 to 20, in particular 11 to 18 and particularly preferably 14 to 17 carbon atoms.
  • suitable alkyl sulfonates are the saturated alkanesulfonates, the unsaturated olefin sulfonates and the ether sulfonates which are derived formally from the alkoxylated alcohols on which the alkyl ether sulfates are based, in which terminal ether sulfonates (n-ether sulfonates) having a sulfonate function bound to the polyether chain and internal radicals Ethersulfonate (i-ether sulfonates) with the alkyl-linked sulfonate function distinguishes.
  • alkanesulfonates in particular alkanesulfonates having a branched, preferably secondary, alkyl radical, for example the secondary alkanesulfonate sec. Na C 13-17 alkanesulfonate (INCI Sodium C14-17 Alkyl Sec Sulfonate).
  • the agent according to the invention preferably contains one or more secondary alkanesulfonates in an amount of usually 1 to 10% by weight, preferably 2 to 8% by weight.
  • the agent according to the invention may additionally contain one or more nonionic surfactants, usually in an amount of 0.001 to 10 wt .-%, preferably 0.01 to 6 wt .-%, in particular 0.1 to 4 wt .-%, particularly preferably 0 , 2 to 2 wt .-%.
  • Nonionic surfactants in the context of the invention are alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, endgroup-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also suitable are block polymers of ethylene oxide and propylene oxide as well as fatty acid alkanolamides and fatty acid polyglycol ethers. Important classes of nonionic surfactants according to the invention are furthermore the amine oxides and the sugar surfactants, in particular the alkyl polyglucosides.
  • a preferred amine oxide is, for example, cocamidopropylamine oxides (cocoamidopropylamine oxide).
  • Sugar surfactants are known surface-active compounds, which include, for example, the sugar surfactant classes of the alkyl glucose esters, aldobionamides, gluconamides (sugar acid amides), glycerolamides, glycerol glycolipids, polyhydroxy fatty acid amide sugar surfactants (sugar amides) and alkyl polyglycosides.
  • Preferred sugar surfactants within the scope of the teaching according to the invention are the alkyl polyglycosides and the sugar amides and their derivatives, in particular 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 also being polyethylene glycol - And / or polypropylene glycol can carry.
  • the esters are the reaction products of one or more, preferably one, sugar hydroxy group with a carboxylic acid, in particular a C 6-22 fatty acid.
  • Particularly preferred sugar amides satisfy the formula R'C (O) N (R ") [Z], in which R 'is a linear or branched, saturated or unsaturated acyl radical, preferably a linear unsaturated acyl radical, having 5 to 21, preferably 5 to 17, in particular 7 to 15, particularly preferably 7 to 13 carbon atoms, R "is a linear or branched, saturated or unsaturated alkyl radical, preferably a linear unsaturated alkyl radical, having 6 to 22, preferably 6 to 18, in particular 8 to 16, particularly preferred 8 to 14 carbon atoms, a C 1-5 alkyl radical, in particular a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or n-pentyl radical, or hydrogen and Z for a Sugar residue, ie a Monosaccharidrest stand.
  • Particularly preferred sugar amides are the amides of glucose, the glucamides, for
  • alkylpolyglycosides are particularly preferred sugar surfactants within the scope of the teaching according to the invention and preferably satisfy the general formula R i O (AO) a [G] x in which R i is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 , preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms, [G] for a glycosidically linked sugar residue and x for a number from 1 to 10 and AO for an alkyleneoxy group, for example an ethyleneoxy or propyleneoxy group, and a represent the average degree of alkoxylation of 0 to 20.
  • R i is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 , preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms
  • [G] for a glycosidically linked sugar residue and x for a number from 1 to 10
  • AO for an alkyleneoxy group,
  • the group (AO) a may also contain different alkyleneoxy units, for example ethyleneoxy or propyleneoxy units, in which case a is the average total degree of alkoxylation, ie the sum of degree of ethoxylation and degree of propoxylation.
  • alkyl radicals R i of the APG are linear unsaturated radicals having the specified number of carbon atoms.
  • APG are nonionic surfactants and are known substances that can be obtained by the relevant methods of preparative organic chemistry.
  • alkyl glycosides having a mean degree of oligomerization x of 1.1 to 3.0 are used. From an application point of view, those alkyl glycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6 are preferred.
  • the glycosidic sugar used is preferably xylose, but especially glucose.
  • the alkyl or alkenyl radical R i can be derived from primary alcohols having 8 to 18, preferably 8 to 14 carbon atoms. Typical examples are caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and technical mixtures thereof, such as those obtained during the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from ROELEN's oxosynthesis.
  • the alkyl or alkenyl radical R i is derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Also to be mentioned are elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof.
  • preferred alkyl polyglycosides are, for example, C 8-10 and C 12-14 alkyl polyglucoside having a DP degree of 1.4 or 1.5, especially C 8-10 alkyl-1,5-glucoside and C 12-14 alkyl-1,4-glucoside.
  • composition of the invention may additionally comprise one or more other anionic surfactants, usually in an amount of 0.001 to 5 wt .-%, preferably 0.01 to 4 wt .-%, in particular 0.1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1.5 wt .-%, for example, 1 wt .-%.
  • anionic surfactants usually in an amount of 0.001 to 5 wt .-%, preferably 0.01 to 4 wt .-%, in particular 0.1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1.5 wt .-%, for example, 1 wt .-%.
  • Suitable further anionic surfactants are, in particular, aliphatic sulfates such as fatty alcohol sulfates, monoglyceride sulfates and ester sulfonates (sulfo fatty acid esters), lignosulfonates, alkylbenzenesulfonates, fatty acid cyanamides, anionic sulfosuccinic acid surfactants, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.
  • aliphatic sulfates such as fatty alcohol sulfates, monoglyceride sulfates and ester sulfonates (sulfo fatty acid esters), lignosulfonates, alkylbenzenesulfonates, fatty acid cyanamides, anionic sulfos
  • Suitable further anionic surfactants are also anionic gemini surfactants having a diphenyl oxide basic structure, 2 sulfonate groups and an alkyl radical on one or both benzene rings according 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 radical with, for example, 6, 10, 12 or 16 carbon atoms and R 'is R or H (Dowfax ® Dry hydrotropes Powder with C 16 alkyl radical (s); INCI Sodium Hexyldiphenyl ether sulfonates, Disodium decyl Phenyl ether disulfonates, disodium lauryl phenyl ether disulfonates, disodium cetyl phenyl ether disulfonates).
  • Particularly preferred further anionic surfactants are the anionic sulfosuccinic acid surfactants sulfosuccinates, sulfosuccinamates and sulfosuccinamides, especially sulfosuccinates and sulfosuccinamates, most preferably sulfosuccinates.
  • the sulfosuccinates are the salts of the mono- and diesters of sulfosuccinic HOOCCH (SO 3 H) CH 2 COOH, while the sulfosuccinamates are the salts of the monoamides of sulfosuccinic acid and the sulfosuccinamides are the salts of the diamides of sulfosuccinic acid.
  • the salts are preferably alkali metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular lithium, sodium, potassium or ammonium salts, more preferably sodium or ammonium salts , most preferably sodium salts.
  • one or both carboxyl groups of the sulfosuccinic acid is preferably with one or two identical or different unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alcohols having 4 to 22, preferably 6 to 20, in particular 8 to 18 , more preferably 10 to 16, most preferably 12 to 14 carbon atoms esterified.
  • esters of unbranched and / or saturated and / or acyclic and / or alkoxylated alcohols in particular unbranched, saturated fatty alcohols and / or unbranched, saturated, with ethylene and / or propylene oxide, preferably ethylene oxide, alkoxylated fatty alcohols having a degree of alkoxylation of 1 to 20, preferably 1 to 15, in particular 1 to 10, more preferably 1 to 6, most preferably 1 to 4.
  • the monoesters are preferred in the context of the present invention over the diesters.
  • a particularly preferred sulfosuccinate is sulfosuccinic acid lauryl polyglycol ester di-sodium salt (lauryl EO sulfosuccinate, di-Na salt, INCI disodium laureth sulfosuccinate), which is described, for example, as Tego ® sulfosuccinate F 30 (Goldschmidt) is commercially available with a sulfosuccinate of 30 wt .-%.
  • one or both form carboxyl groups of the sulfosuccinic acid preferably with a primary or secondary amine having one or two identical or different, unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alkyl radicals having 4 to 22 , preferably 6 to 20, in particular 8 to 18, more preferably 10 to 16, most preferably 12 to 14 carbon atoms carries, a carboxylic acid amide.
  • Particular preference is given to unbranched and / or saturated and / or acyclic alkyl radicals, in particular unbranched, saturated fatty alkyl radicals.
  • the agent according to the invention contains as anionic sulfosuccinic acid surfactants one or more sulfosuccinates, sulfosuccinamates and / or sulfosuccinamides, preferably sulfosuccinates and / or sulfosuccinamates, in particular sulfosuccinates, in an amount of usually 0.001 to 5% by weight, preferably 0.01 to 4 wt .-%, in particular 0.1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1.5 wt .-%, for example 1 wt .-%.
  • anionic sulfosuccinic acid surfactants one or more sulfosuccinates, sulfosuccinamates and / or sulfosuccinamides, preferably sulfosuccinates and / or s
  • amphoteric surfactants are amphoteric surfactants.
  • amphoteric surfactants (amphoteric surfactants, zwitterionic surfactants) which can be used according to the invention include alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, of which the alkylamidoalkylamines are preferred within the scope of the teaching according to the invention.
  • alkyl-substituted amino acids are the aminopropionates according to formula (IVa), R 13 -NH-CH 2 CH 2 COOM '(IVa) in which R 13 and M 'have the same meaning as in formula (IV).
  • Acylated amino acids are amino acids, in particular the 20 natural ⁇ -amino acids which carry on the amino nitrogen atom the acyl radical R 19 CO of a saturated or unsaturated fatty acid R 19 COOH, where R 19 is a saturated or unsaturated C 6-22 alkyl radical. preferably C 8-18 alkyl group, preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group.
  • the acylated amino acids can also be used as the alkali metal salt, alkaline earth metal salt or alkanolammonium salt, for example mono-, di- or triethanolammonium salt.
  • acylated amino acids are the acyl derivatives summarized in accordance with INCI under Amino Acids, for example sodium cocoyl glutamate, lauroyl glutamic acid, capryloyl glycine or myristoyl methylalanine.
  • a combination of two or more different amphoteric surfactants in particular a binary Amphotensidkombination is used.
  • the amphoteric surfactant combination preferably contains at least one betaine, in particular at least one alkylamidobetaine, more preferably cocoamidopropylbetaine.
  • amphoteric surfactants preferably contains at least one amphoteric surfactant is selected from the group comprising Natriumcarboxyethylkokosphosphoethylimidazolin (Phosphoteric ® TC-6), C 8/10 -Amidopropylbetain (INCI CapryUCapramidopropyl Betaine, Betaine Tego ® 810), N-2-hydroxyethyl-N-carboxymethyl-fettklamido ethylamine Na (Rewoteric ® AMV) and N-caprylic / capric amidoethyl-N-ethyl-propionate-Na (Rewoteric AMVSF ®) and the betaine 3- (3-cocoamido-propyl) dimethylammonium-2-hydroxypropane (INCI sultaines; Rewoteric AM CAS ®) and the Alkylamidoalkylamin N- [N '(N "-2-
  • the agent according to the invention contains one or more amphoteric surfactants in an amount of more than 8% by weight. In yet another particular embodiment, the agent according to the invention contains one or more amphoteric surfactants in an amount of less than 2% by weight.
  • composition according to the invention may additionally comprise one or more cationic surfactants (cationic surfactants), usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4% by weight, in particular 0.1 to 3% by weight, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1.5 wt .-%, for example 1 wt .-%.
  • cationic surfactants usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4% by weight, in particular 0.1 to 3% by weight, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1.5 wt .-%, for example 1 wt .-%.
  • Preferred cationic surfactants are the quaternary surface-active compounds, in particular with an ammonium, sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • Particularly preferred cationic surfactants are the quaternary ammonium compounds (QAV, INCI quaternary ammonium compounds) according to the general formula (R I ) (R II ) (R III ) (R IV ) N + X - , in which R I to R IV are the same or various C 1-22 -alkyl radicals, C 7-28 -Aralkylreste or heterocyclic radicals, wherein two or in the case of an aromatic inclusion as in pyridine even three radicals together with the nitrogen atom, the heterocycle, for example a pyridinium or Imidazoliniumtress form, and represent X - are halide ions, sulfate ions, hydroxide ions or similar anions.
  • at least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QACs can be prepared by reacting tertiary amines with alkylating agents, such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • the alkylation of tertiary amines with a long alkyl radical and two methyl groups succeeds particularly easily, and the quaternization of tertiary
  • Suitable QAVs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (m, p-dichlorobenzyl-dimethyl-C 1-2 -alkylammonium chloride, CAS No. 58390 -78-6), benzoxonium chloride (benzyl-dodecyl-bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No.
  • benzalkonium chloride N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5
  • benzalkone B m, p-dichlorobenzyl-dimethyl-C 1-2 -alkylammonium chloride, CAS No. 583
  • benzetonium chloride N, N-dimethyl-N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzyl ammonium chloride, CAS No. 121-54-0
  • dialkyldimethylammonium chlorides as Di-n-decyl-dimethyl-ammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyl-dimethyl-ammonium chloride, 1-cetylpyridinium chloride (CAS No.
  • QACs are the benzalkonium chlorides having C 8 -C 18 -alkyl radicals, in particular C 12 -C 14 -alkyl-benzyl-dimethylammonium chloride.
  • a particularly preferred QAC is the Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5 Cocomonium Methosulfate; Rewoquat CPEM ®).
  • anionic surfactant-compatible and / or cationic surfactant is preferably used or omitted in a particular embodiment of the invention entirely on cationic surfactants.
  • the cleaning agent according to the invention also contains one or more water-soluble salts. These may be inorganic and / or organic salts, in a preferred embodiment it is at least one inorganic salt.
  • Inorganic salts which can be used according to the invention are preferably selected from the group comprising colorless water-soluble halides, sulfates, sulfites, carbonates, bicarbonates, nitrates, nitrites, phosphates and / or oxides of the alkali metals, alkaline earth metals, aluminum and / or transition metals; Furthermore, ammonium salts can be used. Particularly preferred are halides and sulfates of the alkali metals; Preferably, therefore, the inorganic salt is selected from the group comprising sodium chloride, potassium chloride, sodium sulfate, potassium sulfate and mixtures thereof. In a preferred embodiment, sodium chloride is used.
  • the organic salts which can be used according to the invention are, in particular, colorless water-soluble alkali metal, alkaline earth metal, ammonium, aluminum and / or transition metal salts of the carboxylic acids.
  • the salts are selected from the group comprising formate, acetate, propionate, citrate, malate, tartrate, succinate, malonate, oxalate, lactate and mixtures thereof.
  • the cleaning agent according to the invention contains 15 to 40% by weight, more preferably 15 to 30% by weight, of at least one water-soluble salt. It should be noted that the salt concentration in the cleaning agent according to the invention must be so high that the salt is not completely dissolved, so the saturation point is exceeded. Furthermore, a salt is preferable whose water solubility changes only slightly over a wide temperature range.
  • exclusively inorganic salts are used, most preferably sodium chloride.
  • the water content of the aqueous composition according to the invention is usually 15 to 60 wt .-%, preferably 20 to 50 wt .-%.
  • the agent according to the invention may advantageously additionally comprise one or more water-soluble organic solvents, usually in an amount of from 0.1 to 10% by weight, preferably from 1 to 8% by weight.
  • the solvent is used in the context of the teaching of the invention as needed in particular as a hydrotrope, viscosity regulator and / or cold stabilizer. It acts solubilizing, prevents the formation of liquid-crystalline phases and contributes to the formation of clear products.
  • the viscosity of the agent according to the invention decreases with increasing amount of solvent. However, too much solvent can cause excessive viscosity drop. Finally, as the amount of solvent increases, the clouding and clearing point of the composition according to the invention decreases.
  • Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C 1-20 -hydrocarbons, preferably C 2-15 -hydrocarbons, having at least one hydroxy group and optionally one or more ether functions COC, ie the carbon atom chain interrupting oxygen atoms.
  • Preferred solvents are the - optionally unilaterally etherified with a C 1-6 alkanol - C 2-6 alkylene glycols and poly-C 2-3 alkylene glycol having an average of 1 to 9 identical or different, preferably the same, alkylene glycol groups per molecule as well as the C 1-6 -alcohols, preferably ethanol, n-propanol or iso-propanol, in particular ethanol.
  • Particularly preferred solvents are the unilaterally etherified with a C 1-6 alkanol poly-C 2-3 alkylene glycol having an average of 1 to 9, preferably 2 to 3, ethylene or propylene glycol groups, for example PPG-2 methyl ether (dipropylene glycol monomethyl ether).
  • the solvent is selected from the group comprising methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol and mixtures thereof.
  • Most preferred solvents are the C 2-3 alcohols ethanol, n-propanol and / or iso-propanol, especially ethanol.
  • solubilizer in particular for perfume and dyes, for example, alkanolamines and alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical can be used in addition to the solvents described above.
  • compositions according to the invention may contain further ingredients.
  • these include, for example, other surfactants, water-insoluble organic and / or inorganic abrasives, additives for improving the drainage and drying behavior, for adjusting the viscosity, for stabilization and other customary in manual dishwashing detergents and additives, such as UV stabilizers, perfume, pearlescing agents, dyes , Corrosion inhibitors, preservatives, bitter substances, organic salts, disinfectants, enzymes, structuring polymers, defoamers, encapsulated ingredients (eg encapsulated perfume, enzymes), pH adjusters and skin feel enhancing or nourishing additives.
  • other surfactants such as UV stabilizers, perfume, pearlescing agents, dyes , Corrosion inhibitors, preservatives, bitter substances, organic salts, disinfectants, enzymes, structuring polymers, defoamers, encapsulated ingredients (eg encapsulated perfume, enzymes), pH adjusters and skin feel enhancing or nourishing additives
  • the agent according to the invention may contain one or more additives from the group of surfactants, polymers and builders (builders), usually in an amount of 0.001 to 5% by weight, preferably 0, 01 to 4 wt .-%, in particular 0.1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1.5 wt .-%, for example 1 part by weight. %.
  • the additives mentioned are dispensed with.
  • composition according to the invention may additionally contain one or more polymeric thickeners.
  • polymeric thickeners are the polycarboxylates which have a thickening effect as polyelectrolytes, preferably homopolymers and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, and other customary thickening polymers.
  • Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, for example propoxylated guar, and also their mixtures.
  • polysaccharide thickeners such as starches or cellulose derivatives
  • starches or cellulose derivatives may alternatively or preferably be used in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • starches of various origins and starch derivatives for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI Carbomer), which are also referred to as carboxyvinyl polymers.
  • a polyalkenyl polyether in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI Carbomer), which are also referred to as carboxyvinyl polymers.
  • 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, preferably with C 1-4 alkanols formed esters (INCI acrylates copolymer), to which such as the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of C 10-30 alkyl acrylates with one or more monomers selected from the group of acrylic acid, methacrylic acid and their simple, preferably with C 1-4 Alkanols formed esters (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer).
  • the content of polymeric thickener is usually not more than 8 wt .-%, preferably between 0.1 and 7 wt .-%, particularly preferably between 0.5 and 6 wt .-%, in particular between 1 and 5 wt .-% and most preferably between 1.5 and 4% by weight, for example between 2 and 2.5% by weight.
  • the agent is free of polymeric thickeners.
  • one or more dicarboxylic acids and / or salts thereof can be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, as described, for example, in US Pat Trade name Sokalan ® DSC is available.
  • the use is advantageously carried out in amounts of 0.1 to 8 wt .-%, preferably 0.5 to 7 wt .-%, in particular 1.3 to 6 wt .-% and particularly preferably 2 to 4 wt .-%.
  • a change in the dicarboxylic acid (salt) content can - especially in amounts above 2 wt .-% - contribute to a clear solution of the ingredients. Also, within certain limits, influencing the viscosity of the mixture by this means is possible. Furthermore, this component influences the solubility of the mixture. This component is particularly preferably used at high surfactant contents, in particular at surfactant contents above 30 wt .-%.
  • the agent according to the invention is preferably free from dicarboxylic acid (salts).
  • one or more further - especially in hand dishwashing detergents and cleaning agents for hard surfaces - conventional auxiliaries and additives, in particular UV stabilizers, perfumes, pearlescent agents (INCI opacifying agents, for example glycol distearate, for example Cutina ® AGS from Cognis, respectively. this containing mixtures, for example the Euperlane Fa.
  • conventional auxiliaries and additives in particular UV stabilizers, perfumes, pearlescent agents (INCI opacifying agents, for example glycol distearate, for example Cutina ® AGS from Cognis, respectively. this containing mixtures, for example the Euperlane Fa.
  • the pH of the agent according to the invention can be adjusted by means of customary pH regulators, for example acids such as mineral acids or citric acid and / or alkalis such as sodium or potassium hydroxide, wherein - in particular with the desired hand tolerance - a range from 4 to 9, preferably 5 to 8, in particular 5.5 to 7.5, is preferred.
  • acids such as mineral acids or citric acid
  • alkalis such as sodium or potassium hydroxide
  • the agent according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%, preferably 0.005 to 3 wt .-%, in particular 0 , 01 to 2 wt .-%, particularly preferably 0.05 to 1 wt .-%, most preferably 0.1 to 0.5 wt .-%, for example, 0.2 wt .-%.
  • buffer substances which are at the same time complexing agents or even chelating agents (INCI chelating agents).
  • Particularly preferred buffer substances are the citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate.2H 2 O and tripotassium citrate H 2 O.
  • composition according to the invention can be used for cleaning hard surfaces, in particular for manual cleaning of dishes. Due to the contained surfactant combination, it is characterized by a good drainage and drying behavior, thanks to the abrasive action of the salts it contains, it also has a very good cleaning performance, even on stubborn and baked stains, and finally, it also has a high skin friendliness.
  • compositions of the invention showed improved skin compatibility compared to the comparison means V1.
  • an elbow flexion test was performed.
  • the formulations E7 and V1 were each used in 25% dilution.
  • the application in the elbow was made by the subjects themselves 2x daily for a total of 6 minutes.
  • the skin reactions were assessed before the next application.
  • the skin at the elbow was examined by measuring skin moisture and barrier function (TEWL). During the entire test period, the application site was not creamed.
  • TEWL skin moisture and barrier function
  • the comparator V1 induced slight to very severe scaling, mild to very strong erythema (redness) and a slight fissure. In addition, subjects often reported itching, burning and tightness during and after washing.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Detergent Compositions (AREA)
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Claims (10)

  1. Détergent aqueux pour surfaces dures, contenant une combinaison d'agents tensioactifs comportant un éther sulfate d'alcool gras et au moins un autre agent tensio-actif choisi dans le groupe comprenant un sulfonate d'alcane secondaire et un agent tensioactif bétaïnique ainsi que 15 à 40% en poids d'un sel hydrosoluble, caractérisé en ce qu'il contient l'éther sulfate d'alcool gras, le sulfonate d'alcane secondaire et l'agent tensioactif bétaïnique dans le rapport 2:0:1 à 5:1:1 et en ce que la concentration en sel doit être telle que le sel ne se dissout pas complètement.
  2. Détergent aqueux selon la revendication 1, caractérisé en ce que l'éther sulfate d'alcool gras est contenu dans des quantités allant de 5 à 20% en poids, de façon particulièrement préférée de 8 à 16% en poids.
  3. Détergent aqueux selon l'une quelconque des revendications 1 à 2, caractérisé en ce que le sulfonate d'alcane secondaire est contenu dans des quantités allant de 1 à 10% en poids, de façon particulièrement préférée de 2 à 8% en poids.
  4. Détergent aqueux selon l'une des revendications précédentes, caractérisé en ce que l'agent tensioactif bétaïnique est contenu dans des quantités allant de 1 à 10% en poids, de façon particulièrement préférée de 2 à 8% en poids.
  5. Détergent aqueux selon l'une des revendications précédentes, caractérisé en ce que l'autre agent tensioactif est un agent tensioactif non ionique, de préférence un polyglycol éther d'alcool gras, de préférence dans des quantités allant de 0,001 à 10% en poids, de façon particulièrement préférée de 0,01 à 6% en poids, plus préférablement de 0,1 à 4% en poids, en particulier de 0,2 à 2% en poids.
  6. Détergent aqueux selon l'une des revendications précédentes, caractérisé en ce que le sel hydrosoluble est contenu dans des quantités allant de 15 à 30% en poids.
  7. Détergent aqueux selon l'une des revendications précédentes, caractérisé en ce que le sel hydrosoluble est un sel minéral et est de préférence choisi dans le groupe comprenant les halogénures, sulfates, sulfites, carbonates, hydrogénocarbonates, nitrates, nitrites, phosphates, et/ou oxydes de métaux alcalins, de métaux alcalino-terreux, d'aluminium et/ou de métaux de transition hydrosolubles incolores et leurs mélanges, de façon particulièrement préférée dans le groupe des halogénures et des sulfates de métaux alcalins et leurs mélanges, en particulier dans le groupe comprenant le chlorure de sodium, le chlorure de potassium, le sulfate de sodium, le sulfate de potassium et leurs mélanges, et de manière très préférée le chlorure de sodium.
  8. Détergent aqueux selon l'une des revendications précédentes, caractérisé en ce qu'il comprend des solvants organiques, de préférence choisis dans le groupe comprenant le méthanol, l'éthanol, l'isopropanol, le n-propanol, l'éthylène glycol, le propylène glycol et leurs mélanges, de façon particulièrement préférée l'éthanol, dans des quantités allant de 0,1 à 10% en poids, de préférence de 1 à 8% en poids.
  9. Détergent aqueux selon l'une des revendications précédentes, caractérisé en ce qu'il contient d'autres substances actives utilisée habituellement dans des détergents pour surfaces dures, de préférence choisis dans le groupe comprenant d'autres agents tensioactifs, des substances abrasives organiques et/ou minérales non hydrosolubles, des bases, des acides, des modificateurs de viscosité, des acides gras, des solvants, d'autres polymères, des agents antibactériens, des agents de conservation, des substances amères, des solubilisants, des agents complexants, des enzymes, des colorants, des parfums, des agents nacrants, des stabilisants, des agents d'ajustement du pH, des additifs de soin de la peau ou d'amélioration de sensation cutanée, et leurs mélanges.
  10. Utilisation d'un détergent aqueux selon l'une des revendications précédentes pour le lavage de la vaisselle à la main.
EP10703660.0A 2009-02-26 2010-02-17 Liquide vaisselle Active EP2401351B1 (fr)

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DE102009001186A DE102009001186A1 (de) 2009-02-26 2009-02-26 Handgeschirrspülmittel
PCT/EP2010/051948 WO2010097316A1 (fr) 2009-02-26 2010-02-17 Liquide vaisselle

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EP2401351B1 true EP2401351B1 (fr) 2015-10-07

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KR (1) KR101730190B1 (fr)
DE (1) DE102009001186A1 (fr)
ES (1) ES2558437T3 (fr)
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WO (1) WO2010097316A1 (fr)

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JP5864584B2 (ja) * 2010-09-21 2016-02-17 ザ プロクター アンド ギャンブルカンパニー 液体洗浄組成物
GB201108912D0 (en) * 2011-05-27 2011-07-13 Reckitt Benckiser Nv Composition
DE102012222186A1 (de) * 2012-12-04 2014-06-05 Henkel Ag & Co. Kgaa Strukturiertes Reinigungsmittel mit Fließgrenze
WO2014200657A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase provenant destreptomyces xiamenensis
WO2014200658A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase issue de promicromonospora vindobonensis
WO2014200656A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase provenant de streptomyces umbrinus
US20160130571A1 (en) 2013-06-17 2016-05-12 Danisco Us Inc. Alpha-Amylase from Bacillaceae Family Member
KR102154005B1 (ko) * 2013-07-19 2020-09-09 라이온 가부시키가이샤 와이프 오프용의 액체 세정제
WO2015050723A1 (fr) 2013-10-03 2015-04-09 Danisco Us Inc. Alpha-amylases provenant de exiguobacterium, méthodes d'utilisation de celles-ci
EP3052622B1 (fr) 2013-10-03 2018-09-19 Danisco US Inc. Alpha-amylases faisant partie d'un sous-ensemble d'exiguobacterium, et procédés d'utilisation correspondants
EP3071691B1 (fr) 2013-11-20 2019-10-23 Danisco US Inc. Variants d'alpha-amylases ayant une sensibilité réduite au clivage protéasique, et leurs procédés d'utilisation
KR102166027B1 (ko) * 2013-11-22 2020-10-15 주식회사 엘지생활건강 액체 세제 조성물
DE102013224454A1 (de) 2013-11-28 2015-05-28 Henkel Ag & Co. Kgaa Handgeschirrspülmittel mit verbesserter Reichweite
DE102014204352A1 (de) 2014-03-10 2015-09-10 Henkel Ag & Co. Kgaa Schaumstabilisierung von LAS-Formulierungen in hartem Wasser
WO2017173324A2 (fr) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions et procédés
WO2017173190A2 (fr) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions et procédés
EP3456807A1 (fr) * 2017-09-13 2019-03-20 The Procter & Gamble Company Composition de nettoyage
KR102066686B1 (ko) * 2019-08-29 2020-01-15 주식회사 엘지생활건강 과량의 전해질을 포함하는 액체 세정제 조성물

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EP0334566B1 (fr) * 1988-03-21 1994-08-31 Unilever Plc Composition détergente liquide
US6037316A (en) * 1996-09-17 2000-03-14 The Clorox Company Water soluble abrasive composition containing borax pentahydrate
AU734049B2 (en) 1996-12-31 2001-05-31 Reckitt Benckiser (Uk) Limited Abrasive cleaning compositions
DE10023438A1 (de) * 2000-05-12 2001-11-22 Henkel Kgaa Konzentrat zur Verdünnung unter Viskositätserhalt oder -erhöhung
US20050176614A1 (en) * 2002-10-16 2005-08-11 Heinz-Dieter Soldanski Transparent abrasive cleaning product, especially manual dishwashing liquid
DE102005031193A1 (de) * 2005-07-01 2007-01-04 Henkel Kgaa Viskositätseinstellung bei Handgeschirrspülmittel
GB2434586A (en) 2006-01-24 2007-08-01 Henkel Uk Structured liquid abrasive composition

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DE102009001186A1 (de) 2010-09-02
EP2401351A1 (fr) 2012-01-04
US8329631B2 (en) 2012-12-11
KR20110124247A (ko) 2011-11-16
US20110312868A1 (en) 2011-12-22
PL2401351T3 (pl) 2016-03-31
KR101730190B1 (ko) 2017-04-25
ES2558437T3 (es) 2016-02-04
WO2010097316A1 (fr) 2010-09-02

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