EP2823028A1 - Détergent pour vaisselle à la main renfermant des enzymes - Google Patents

Détergent pour vaisselle à la main renfermant des enzymes

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Publication number
EP2823028A1
EP2823028A1 EP13708136.0A EP13708136A EP2823028A1 EP 2823028 A1 EP2823028 A1 EP 2823028A1 EP 13708136 A EP13708136 A EP 13708136A EP 2823028 A1 EP2823028 A1 EP 2823028A1
Authority
EP
European Patent Office
Prior art keywords
disodium
acid
alkyl
sodium
oxide
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.)
Ceased
Application number
EP13708136.0A
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German (de)
English (en)
Inventor
Ulrich Pegelow
Detlef Buisker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2823028A1 publication Critical patent/EP2823028A1/fr
Ceased 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663—Stabilised liquid enzyme compositions

Definitions

  • the invention relates to an enzyme-containing hand dishwashing detergent with improved enzyme stability.
  • Common detergents or cleaners on the market contain surfactants to remove dirt and stains.
  • combinations of a plurality of surfactants in particular from the group of anionic, nonionic, cationic and amphoteric surfactants, are used here.
  • These surfactants alone are often unable to remove dirt and stains sufficiently, so that in modern detergents or cleaning agents, other auxiliaries are used.
  • These other excipients include enzymes of various types such as proteases, amylases, cellulases, mannanases, pectate lyases.
  • hydrolytic enzymes such as proteases, amylases or lipases are part of numerous textile or dishwashing detergents because of their direct cleaning action.
  • Detergents or cleaning enzymes are formulated both in solid and in liquid form.
  • the group of solid enzyme preparations includes, in particular, the enzyme granules consisting of several ingredients, which in turn are preferably incorporated into solid washing or cleaning agents.
  • liquid or gel detergents or cleaners frequently contain liquid enzyme preparations, which, unlike the enzyme granules, are much less protected against external influences.
  • German Patent Application DE 20 38 103 (Henkel) teaches the stabilization of enzyme-containing dishwashing detergents by saccharides, while in European Patent EP 646 170 B1 (Procter & Gamble) propylene glycol is disclosed for enzyme stabilization in liquid detergents.
  • a second group of known stabilizers form borax, boric acids, boronic acids or their salts or esters.
  • These include, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid (4-FPBA) or the salts or esters of the compounds mentioned.
  • boric acids and boric acid derivatives often have the disadvantage that they form undesirable by-products with other ingredients of a composition, especially detergents or cleaning ingredients, so that they are no longer available for the desired cleaning purpose in the relevant agents or even as an impurity on the Laundry left behind.
  • boric acids or borates are considered to be disadvantageous from an environmental point of view.
  • liquid cleaning compositions which contain from 20 to 70% by weight of water, at least one amylase preparation, at least one
  • Calcium ion source and lactic acid or a lactic acid salt.
  • the invention therefore relates to the use of calcium lactate in enzyme-containing
  • Another object of the invention are enzyme-containing hand dishwashing detergents which contain a) at least one calcium ion source and b) lactic acid or a lactic acid salt.
  • Agents according to the invention are therefore at least one calcium ion source and lactic acid or a lactic acid salt.
  • Preferred lactic acid salts are the salts of the alkali and alkaline earth metals. The proportion by weight of the lactic acid or of the lactic acid salt in the total weight of the
  • Hand dishwashing detergent is preferably 0, 1 to 8 wt .-%, preferably 0, 15 to 5 wt .-%, particularly preferably 0.2 to 2 wt .-% and in particular 0.5 to 1, 5 wt .-%. It is particularly preferred to use calcium lactate as a common source of calcium ions and lactic acid. Enzyme-containing hand dishwashing detergents which contain 0.1 to 8% by weight, preferably 0.15 to 5% by weight, particularly preferably 0.2 to 2% by weight and in particular 0.5 to 1.5% by weight of calcium lactate , based on the total hand dishwashing detergent, are therefore preferred according to the invention. Hand dishwashing detergents are usually liquid agents.
  • liquid agents are understood as meaning those which are flowable under normal conditions of use and whose viscosities can vary within a wide range.
  • the liquid preparations also include gelatinous or pasty agents, which may optionally have additional thickening agents known from the prior art.
  • the liquid agents are based on water.
  • calcium lactate already contributes in relatively small amounts to the stabilization of enzymes. While other known enzyme stabilizers are frequently used in amounts of up to 10% by weight, calcium lactate leads to significant enzyme stabilization even at significantly lower concentrations.
  • An agent according to the invention contains at least one enzyme from one of the known enzymes commonly used in detergents or cleaners.
  • an agent according to the invention contains an amylase and / or a protease;
  • the content of the agent on an amylase if appropriate in combination with a protease, is particularly preferred.
  • the use of calcium lactate is also preferred for increasing the stability of amylases, in particular in liquid and, above all, aqueous hand dishwashing detergents.
  • amylases synonymous terms may be used, for example, 1,4-alpha-D-glucan glucanohydrolase or glycogenase.
  • Preparable amylases according to the invention are preferably .alpha.-amylases.
  • Crucial for determining whether an enzyme is an ⁇ -amylase according to the invention is its ability to hydrolyze a (1-4) -glycoside bonds in the amylose of the starch.
  • Amylases which can be synthesized according to the invention are, for example, the a-amylases from Bacillus licheniformis, from Bacillus amyloliquefaciens or from Bacillus stearothermophilus and in particular also improved for use in detergents or cleaners
  • the enzyme from Bacillus licheniformis is available from the company Novozymes under the name Termamyl® and from the company Danisco / Genencor under the name Purasta DST. Further development products of this ⁇ -amylase are available from the company Novozymes under the trade name Duramyl® and Termamy Dultra, from the company Danisco / Genencor under the name Purasta DOxAm and from the company Daiwa Seiko Inc., Tokyo, Japan, as Keistase®.
  • the ⁇ -amylase of Bacillus amyloliquefaciens is sold by the company Novozymes under the name BAN®, and derived variants of the Bacillus stearothermophilus ⁇ -amylase under the names BSG® and Novamyl®, also from the company Novozymes. Furthermore, the a-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948). Likewise, fusion products of all the molecules mentioned can be used. In addition, the further developments of the ⁇ -amylase from Aspergillus niger and A.
  • ⁇ -amylase variants of ⁇ -amylase AA560 according to SEQ ID NO. 1 are particularly advantageous:
  • Figure 1 has one, two, three, four, five or six of the following sequence changes in the a-amylase AA560 count: R1 18K, D183 * (deletion), G184 * (deletion), N195F, R320K, R458K.
  • the ⁇ -amylase variant has all six of the mentioned sequence changes.
  • ⁇ -amylase variant which is resistant to the ⁇ -amylase AA560 according to SEQ ID NO. 1 has the following sequence changes (in the count of ⁇ -amylase AA560):
  • Sequence changes including very particularly preferred variant 31 with the six under (a) sequence changes.
  • liquid hand dishwashing detergents contain, based on her
  • Total weight between 0.001 and 5.0 wt .-%, preferably between 0.01 and 4.0 wt .-% and in particular between 0.05 and 3.0 wt .-% amylase preparations.
  • liquid hand dishwashing detergents which, based on their total weight, contain between 0.07 and 2.0% by weight of amylase preparations.
  • liquid hand dishwashing detergents contain, based on her
  • Total weight between 0.002 and 7.0 wt .-%, preferably between 0.02 and 6.0 wt .-% and in particular between 0, 1 and 5.0 wt .-% protease preparations.
  • Particularly preferred are hand dishwashing detergents which, based on their total weight, contain between 0.2 and 4.0% by weight of protease preparations.
  • washing or cleaning-active amylases and proteases are generally not in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations provided.
  • Preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in liquid or gel form, solutions of the enzymes which are advantageously concentrated as possible, low in water and / or added with stabilizers or other adjuvants.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • a preferably natural polymer or in the form of capsules for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and / or amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and in particular between 0.8 and 10 wt .-% of the enzyme protein, each based on the enzyme preparation.
  • the agents according to the invention may also contain one or more further washing- or cleaning-active enzymes.
  • Particularly suitable are those from the class of hydrolases such as (poly) esterases, lipases,
  • the weight fraction of all washing or cleaning-active enzyme preparations in the total weight of the composition according to the invention is preferably between 0.5 and 15 wt .-%, preferably between 0.5 and 12 wt .-%, particularly preferably between 0.6 and 10 wt. -% and in particular between 0.7 and 8 wt .-%.
  • manual dishwashing agents are provided, which contain as enzymes a combination of amylase and protease and optionally other enzymes.
  • the weight fraction of all washing or cleaning-active enzyme preparations in the total weight of the inventive manual dishwashing detergent is preferably between 0.5 and 5 wt .-%, preferably between 0.7 and 3 wt .-%.
  • compositions according to the invention usually contain, as further constituents, surfactants, in particular anionic surfactants, nonionic surfactants, amphoteric surfactants, betaines and optionally cationic surfactants.
  • surfactants in particular anionic surfactants, nonionic surfactants, amphoteric surfactants, betaines and optionally cationic surfactants.
  • the total amount of the surfactants in the compositions according to the invention can vary within a broad range and, for example, be from 5 to 70% by weight, preferably from 10 to 55% by weight and in particular from 15 to 50% by weight.
  • the anionic surfactants are usually in situ 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 neutralizing corresponding acid used.
  • alkali metals potassium and sodium in particular, as alkaline earth metals calcium and magnesium in particular, and as alkanolamines mono-, di- or triethanolamine.
  • alkanolamines mono-, di- or triethanolamine Particularly preferred are the
  • Calcium salts are used according to the invention, the agents additionally contain calcium lactate, preferably in the amounts indicated above.
  • Particularly preferred anionic surfactants used in manual dishwashing detergents include alkyl ether sulfates and alkyl sulfonates.
  • Alkyl ether sulfates are products of sulfation reactions on alkoxylated alcohols.
  • the person skilled in the art generally means, 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 mono- or poly-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.
  • n 1 to 30, preferably 1 to 20, especially 1 to 10, particularly preferably 2 to 4
  • 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 lower ethoxylated
  • EO ethylene oxide
  • the agent according to the invention in particular a manual dishwashing detergent, in one preferred embodiment contains one or more alkyl ether sulfates in an amount of 10 to 40% by weight, preferably 13 to 35% by weight, in particular 15 to 30% by weight.
  • 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 1 1 to 18 and more preferably 14 to 17
  • suitable alkyl sulfonates are the saturated alkanesulfonates, the unsaturated olefin esters 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 sulfonate groups bonded to the polyether chain are used.
  • Terminal ether sulfonates n-ether sulfonates
  • i-ether sulfonates internal 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-Ci 3 _i 7-alkanesulfonate (INCI Sodium C14-17 alkyl lake sulfonates).
  • a preferred manual dishwashing detergent contains one or more secondary alkyl sulfonates in an amount of 1 to 15% by weight, preferably 3 to 10% by weight, especially 4 to 8% by weight.
  • anionic surfactants which can be used are known to the person skilled in the art from the relevant prior art for detergents or cleaners. These include in particular aliphatic sulfates such as fatty alcohol sulfates, monoglyceride sulfates and ester sulfonates (sulfo fatty acid esters), lignosulfonates, alkylbenzenesulfonates, fatty acid cyanamides, anionic sulfates such as fatty alcohol sulfates, monoglyceride sulfates and ester sulfonates (sulfo fatty acid esters), lignosulfonates, alkylbenzenesulfonates, fatty acid cyanamides, anionic sulfates such as fatty alcohol sulfates, monoglyceride sulfates and ester sulfonates (sulfo fatty acid esters), lignosulfonates, alkylbenzenesulfon
  • Sulfosuccinic acid surfactants fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.
  • Suitable further anionic surfactants are also anionic gemini surfactants having a di-phenyloxide 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 ') S0 3 ", in which R is an alkyl radical having, for example, 6, 10, 12 or 16 carbon atoms and R 'is R or H (Dowfax ® Dry
  • anionic surfactants are the anionic sulfosuccinic acid surfactants sulfosuccinates, sulfosuccinamates and sulfosuccinamides, in particular sulfosuccinates and Sulfosuccinamates, most preferably sulfosuccinates.
  • the sulfosuccinates are the salts of the monoesters and diesters of sulfosuccinic acid HOOCCH (S0 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
  • Trialkanolammoniumsalze 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.
  • 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 with a
  • a particularly preferred sulfosuccinate is Sulfobernsteinklarylpolyglykolester-di-sodium salt (EO lauryl sulfosuccinate, disodium salt; INCI Disodium Laureth Sulfosuccinate), for example, as Tego ® sulfosuccinate F 30 (Evonik) with a sulfosuccinate of 30 parts by weight % is commercially available.
  • 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, especially 8 to 18, more preferably 10 to 16, most preferably 12 to 14
  • Carbon atoms 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.
  • sulfosuccinates and sulfosuccinamates designated according to INCI, which are described in more detail in the International Cosmetic Ingredient Dictionary and Handbook: Ammonium Dinonyl Sulfosuccinates, Ammonium Lauryl Sulfosuccinates, Diamonium Dimethicone Copolyol Sulfosuccinates, Diammonium Lauramido-MEA Sulfosuccinates, Diammonium Lauryl Sulfosuccinates, 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 Sul
  • Sulfosuccinates disodium coco-glucosides sulfosuccinates, disodium cocoyl butyl gluceth-10 sulfosuccinates, disodium C12-15 pareth sulfosuccinates, disodium deceth-5 sulfosuccinates, disodium deceth-6 sulfosuccinates, disodium dihydroxyethyl sulfosuccinyl undecylenates, disodium dimethicone copolyol sulfosuccinates, disodium hydrogenated cottonseed glycerides sulfosuccinates, Disodium isodecyl sulfosuccinate, disodium isostearamido MEA sulfosuccinate, disodium isostearamido MIPA sulfosuccinate, disodium isostearyl sulfosuccinate, disodium
  • Sulfosuccinates disodium oleamido MEA sulfosuccinates, disodium oleamido MIPA sulfosuccinates, disodium oleamido PEG-2 sulfosuccinates, disodium oleth-3 sulfosuccinates, disodium oleyl sulfosuccinates, disodium palmitamido PEG-2 sulfosuccinates, disodium
  • Sulfosuccinates disodium tallamido MEA sulfosuccinates, disodium tallowamido MEA sulfosuccinates, disodium tallow sulfosuccinamates, disodium tridecyl sulfosuccinates, disodium undecylenamido MEA sulfosuccinates, disodium undecylenamido PEG-2 sulfosuccinates, disodium wheat germamido MEA sulfosuccinates, disodium wheat germamido PEG-2
  • Sulfosuccinates Di-TEA Oleamido PEG-2 Sulfosuccinates, Ditridecyl Sodium Sulfosuccinate, Sodium Bisglycol Ricinosulfosuccinate, Sodium / MEA Laureth-2 Sulfosuccinate and Tetrasodium Dicarboxyethyl Stearyl Sulfosuccinamate.
  • Another suitable sulfosuccinamate is disodium C 16-18 alkoxypropylene sulfosuccinamate.
  • Preferred anionic sulfosuccinic are imidosuccinate, mono-Na-sulfosuccinic acid diisobutyl ester (Monawet MB ® 45), mono-Na-sulfosuccinic acid di-octyl ester (Monawet MO-84 ® R2W, Rewopol SB ® DO 75), mono- Na-sulfosuccinic acid di-tridecyl (Monawet ® MT 70) Fettalkoholpolyglykolsulfosuccinat-Na-NH 4 salt (sulfosuccinate S-2), di-sodium sulfosuccinic acid mono-C 12 / i4-3EO ester (Texapon ® SB-3), Natriumsulfobernstein Acidiiso- octyl (Texin DOS 75 ®) and di-sodium sulfosuccinic acid mono-C 12 /
  • 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 Sulfosuccinate, in an amount of usually 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 .-%, extremely 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 /
  • 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 betaines are preferred within the scope of the teaching according to the invention.
  • Suitable betaines which are mainly used in manual dishwashing detergents are the alkylbetaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy formula I,
  • R - [CO-X- (CH 2 ) n ] x -N + (R 2 ) (R 3 ) - (CH 2 ) m - [CH (OH) -CH 2 ] y -Y- (I) in the R is a saturated or unsaturated C 6 -22-alkyl radical, preferably C 8 -18 alkyl group, more preferably a saturated Ci 0 -16 alkyl group, for example a saturated C 12 -14-alkyl,
  • X is NH, NR 4 with the d_ 4 alkyl R 4, O or S,
  • n is a number from 1 to 10, preferably 2 to 5, in particular 3,
  • x is 0 or 1, preferably 1,
  • R 2, R 3 independently represent a CI_ 4 alkyl optionally hydroxysubstituted, such as a
  • n is a number from 1 to 4, in particular 1, 2 or 3,
  • y is 0 or 1
  • Y is COO, S0 3 , OPO (OR 5 ) 0 or P (0) (OR 5 ) 0, where R 5 is a hydrogen atom H or
  • alkyl and alkyl amido betaines of the formula I with a carboxylate group are also called carbobetaines.
  • 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),
  • 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).
  • Palmitamidopropyl betaines palmitoyl carnitines, palm kernelamidopropyl betaines, polytetrafluoroethylene acetoxypropyl betaines, ricinoleamidopropyl betaines, sesamidopropyl betaines, soyamidopropyl betaines, stearamidopropyl betaines, stearyl betaines, tallowamidopropyl betaines, tallowamidopropyl hydroxysultaines, tallow betaines, tallow dihydroxyethyl betaines, undecylenamidopropyl betaines and wheats Germamidopropyl Betaine.
  • a preferred betaine is, for example, cocamidopropyl betaine (cocoamidopropylbetaine).
  • the agent according to the invention comprises one or more betaines in an amount of 1 to 15% by weight, preferably 3 to 10% by weight, in particular 4 to 8% by weight.
  • the surfactants a) alkyl ether sulfate, b) secondary alkanesulfonate and c) betaine contained in the agent according to the invention are preferably present in a ratio a): b): c) of 5: 2: 1 to 3: 1: 1.
  • alkylamidoalkylamines are amphoteric surfactants of the formula (III)
  • R ⁇ CO-NR ⁇ -ICHz ⁇ -NiR ⁇ HCHzCHzOHCHz CHiOH ⁇ i-CHz-Z-OM (III) in the R 9 is a saturated or unsaturated C 6 -22-alkyl radical, preferably C 8 -18-alkyl radical, in particular one saturated Ci 0 -16-alkyl radical, for example a saturated
  • R 0 is a hydrogen atom H or a preferably H
  • i is a number from 1 to 10, preferably 2 to 5, in particular 2 or 3,
  • R is a hydrogen atom H or CH 2 COOM (to M su),
  • j is a number from 1 to 4, preferably 1 or 2, in particular 1,
  • k is a number from 0 to 4, preferably 0 or 1
  • Z is CO, SO 2 , OPO (OR 12 ) or P (O) (OR 12 ), where R 2 is a C 1-4 -alkyl radical or M (su), and
  • M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine.
  • Preferred representatives satisfy the formulas IIIa to IIId,
  • alkylamido alkylamines are the following compounds named according to INCI: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Caprylo- amphodiacetates, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhy- droxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate , Disodium Laureth-5 diacetate Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-
  • Preferred alkyl-substituted amino acids are monoalkyl-substituted amino acids according to formula (IV),
  • NH-CH (R l4 HCH 2) u COOM '(IV) a saturated or unsaturated C 6-22 -alkyl radical, preferably C 8 -18 alkyl group, more preferably a saturated Ci 0 -16 alkyl group, for example a saturated
  • R preferably H
  • u is a number from 0 to 4, preferably 0 or 1, in particular 1, and
  • M ' is a hydrogen, an alkali metal, an alkaline earth metal or a protonated one
  • Alkanolamine eg protonated mono-, di- or triethanolamine, alkyl-substituted imino acids according to formula (V),
  • R 5 -N - [(CH 2 ) -COOM "] 2 (V) in the R 5 is a saturated or unsaturated C 6 -22-alkyl radical, preferably C 8 -18-alkyl radical, in particular a saturated Ci 0 -16-alkyl radical , for example, a saturated
  • v is a number from 1 to 5, preferably 2 or 3, in particular 2, and
  • M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated
  • Alkanolamine e.g. protonated mono-, di- or triethanolamine, where M "in the two carboxy groups may have the same or different meanings, for example hydrogen and sodium or may be twice sodium, and mono- or dialkyl-substituted natural amino acids according to formula (VI),
  • R optionally hydroxy- 7 is a hydrogen atom or a CI_ 4 alkyl or amino substituted, for example a methyl, ethyl, hydroxyethyl or Aminpropylrest,
  • R 8 is the residue of one of the 20 natural a-amino acids H 2 NCH (R 8 ) COOH, and
  • M '" is a hydrogen, an alkali metal, an alkaline earth metal or a protonated
  • Alkanolamine e.g. protonated mono-, di- or triethanolamine.
  • alkyl-substituted amino acids are the aminopropionates according to formula (IVa),
  • alkyl-substituted amino acids are the following designated according to INCI.
  • Acylated amino acids are amino acids, in particular the 20 natural oAmino Acid which R 9 CO carry a saturated or unsaturated fatty acid 9 COOH on the amino acyl residue of the R, wherein R 9 is a saturated or unsaturated C 6 -22-alkyl radical, preferably C 8 -18 alkyl , in particular a saturated C 10 -16-alkyl radical, for example a saturated C 12 -14-alkyl radical.
  • the acylated amino acids may also be used as alkali metal salt, alkaline earth metal salt or
  • Alkanolammonium salt e.g. Mono-, di- or Triethanolammoniumsalz be used.
  • acylated amino acids are the acyl derivatives grouped according to INCI under Amino Acids, e.g. Sodium Cocoyl Glutamate, Lauroyl Glutamic Acid, Capryloyl Glycine or Myristoyl Methylalanine.
  • 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 / io amidopropyl betaine (INCI caprylic / Capramidopropyl 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-hydroxypropanesulfonate (INCI sultaines; Rewoteric AM CAS ®) and the Alkylamidoalkylamin N-
  • 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.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • Preferred ethoxylated alcohols include, for example, C 12-14 alcohols containing 3 EO, 7 EO or 4 EO, C. 9 i Alcohol with 7 EO, C 13 . 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 -i8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as
  • Levels of ethoxylation represent statistical averages, which may be an integer or a fractional number for a particular product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention.
  • the content of nonionic surfactants is in the hand dishwashing detergent preferably 1 to 30 wt .-% and preferably 2 to 25 wt .-%, each based on the total
  • nonionic surfactants are good in combination with an amine oxide
  • Nonionic surfactants in the context of the invention are alkoxylates, but also alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and
  • Fatty acid 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.
  • the amine oxides suitable according to the invention include alkylamine oxides, in particular alkyl dimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides.
  • alkylamine oxides in particular alkyl dimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides.
  • Preferred amine oxides satisfy formula II,
  • R 6 R 7 R 8 N + -O " (II) R 6 - [CO-N H- (CH 2 ) w ] z -N + (R 7 ) (R 8 ) -O " in the R 6 is a saturated or unsaturated C 6-22 -alkyl radical, preferably C 8 -18 alkyl group, more preferably a saturated Ci 0 -16 alkyl group, for example a saturated
  • Ci 2 -i 4 -alkyl radical which in the Alkylamidoaminoxiden via a Carbonylamidoalky- len distr -CO-NH- (CH 2 ) z - and in the Alkoxyalkylaminoxiden via an Oxalkalkylenement -0- (CH 2 ) z - to the nitrogen atom N is attached, wherein z are each a number from 1 to 10, preferably 2 to 5, in particular 3, R 7, R 8 independently represent a CI_ 4 alkyl optionally hydroxysubstituted such as a hydroxyethyl group, especially a methyl radical, is.
  • suitable amine oxides are the following compounds named according to INCI:
  • amine oxides are, for example, cocamidopropylamine oxides (cocoamidopropylamine oxide), but also N-cocoalkyl-N, N-dimethylamine oxide, N-tallowalkyl-N, N-dihydroxyethylamine oxide,
  • Myristylcetyldimethylamine oxide or lauryldimethylamine oxide are examples of Myristylcetyldimethylamine oxide or lauryldimethylamine oxide.
  • the content of amine oxide is in the hand dishwashing detergent preferably 1 to 15 wt .-%, and preferably 2 to 10 wt .-%, each based on the total hand dishwashing detergent.
  • 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. 2 2-alcohols or glycols such as ethylene and / or propylene glycol, wherein the sugar hydroxy group and polyethylene glycol and / or
  • Polypropylene glycol can carry.
  • the esters are the reaction products of one or more, preferably one, sugar 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, especially 7 to 15, especially 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 preferably 8 to 14 carbon atoms, a Ci_.
  • Alkyl in particular a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or n-pentyl radical, or hydrogen and Z is a sugar residue, ie a monosaccharide radical.
  • Particularly preferred sugar amides are the amides of glucose, the glucamides, for example lauroyl-methyl-glucamide.
  • alkylpolyglycosides are particularly preferred sugar surfactants within the scope of the teaching according to the invention and preferably satisfy the general formula R'O (AO) a [G] x in which R '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 for the middle one
  • R'O (AO) a [G] x in which R '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,
  • Alkoxyl michingsgrad from 0 to 20 are.
  • the group (AO) a may also contain different alkyleneoxy, for example ethyleneoxy or propyleneoxy, where it is at a to the average Automatalkoxyl michinggrad, ie the sum of ethoxylation and
  • the alkyl radicals R 'of the APG are linear unsaturated radicals having the stated 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 ' 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 are obtained in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelene's oxosynthesis.
  • the alkyl or alkenyl radical R ' is derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol.
  • lauryl alcohol myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol.
  • Farther Elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof are mentioned.
  • alkyl polyglycosides are, for example C 8 -io- and a C12 -14 alkyl polyglucoside with an average degree of 1, 4 or 1, 5, in particular C. 8 10 -alkyl-1, 5-glucoside and C 12 -14-alkyl-1, 4-glucoside.
  • composition according to the invention may additionally contain one or more cationic surfactants (cation surfactants, INCI quaternary ammonium compounds), usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4% by weight, 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 .-%.
  • 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 due to other ingredients already existing antimicrobial effect 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 ") (R 1 ") (R IV ) N + X " , in which R 1 to R IV are identical . or different C-
  • Imidazolinium compound, form, represent and X ⁇ are halide ions, sulfate ions, hydroxide ions or similar anions.
  • 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 QACs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (m, p-dichlorobenzyl-dimethyl-C 12 -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.
  • 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 such 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-benzyldimethylammonium chloride.
  • a particularly preferred QAV is the Kokospentaethoxy- methylammonium methosulfate (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.
  • hand dishwashing detergent according to the invention for reducing the viscosity further contains one or more water-soluble salts. It may be inorganic and / or organic salts, in a preferred embodiment, the agent contains at least one inorganic salt.
  • Inorganic salts which can be used according to the invention are preferably selected from the group consisting of colorless water-soluble halides, sulfates, sulfites, carbonates, hydrogencarbonates, 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.
  • 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 hand dishwashing detergent of the invention contains in a preferred embodiment 0.1 to 10 wt .-%, preferably 0.5 to 7 wt .-%, particularly preferably 0.8 to 5 wt .-% at least one water-soluble salt. In a particularly preferred embodiment, exclusively inorganic salts are used.
  • no builder substances are present which have calcium-precipitating properties.
  • an agent which contains in particular no carbonate-containing salts.
  • Organic builder substances which may be present in hand dishwashing detergents are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids,
  • NTA Nitrilotriacetic acid
  • MGDA methylglycine diacetic acid
  • Preferred salts are the salts of polycarboxylic acids such as
  • Citric acid Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and
  • polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
  • soluble builders such as, for example, citric acid, or acrylic polymers having a molar mass of from 1,000 to 5,000 g / mol in the liquid
  • Hand dishwashing detergents used.
  • the water content of the preferred liquid and aqueous hand dishwashing detergent is usually 15 to 90 wt .-%, preferably 20 to 85 wt .-%, in particular 30 to 80 wt .-%.
  • the agent according to the invention may additionally comprise one or more water-soluble organic solvents, usually in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight, in particular 2 to 15% by weight, more preferably 3 to 12 wt .-%, most preferably 4 to 8 wt .-%.
  • the solvent is used in the context of the teaching of the invention as needed in particular as a hydrotrope, viscosity regulator and / or additional cold stabilizer. It acts solubilizing in particular for surfactants and electrolyte as well as perfume and dye and thus contributes to their incorporation, prevents the formation of liquid-crystalline phases and has a share in 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 be too strong
  • Hand dishwashing detergent particularly effective organic solvent is the glycerol and the 1, 2 propylene glycol.
  • 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, additives for improving the flow 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 (INCI Opacifying Agents, such as glycol distearate, eg Cutina ® AGS Fa. BASF, or mixtures comprising, for example, the Euperlane ® from.
  • Disinfectants, enzymes, pH adjusters and skin feel-improving or nourishing additives eg dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericerin, collagen partial hydrolyzate, various vegetable protein -Partial hydrolysates, protein hydrolyzate-fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as lecithin, soybean oil, etc., plant extracts such as Aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, AHA complexes) which may be contained in amounts of usually not more than 5% by weight.
  • dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericerin, collagen partial hydrolyzate, various vegetable protein -Partial hydrolysates, protein hydrolyzate-fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as lec
  • Composition according to the invention one or more additives from the group of surfactants, polymers and builders (builder), 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 .-%, wherein as described above on calcium-precipitating builders as far as possible is waived.
  • group of surfactants, polymers and builders builder
  • Polymers suitable as additives are especially maleic acid-acrylic acid copolymer, Na salt (Sokalan ® CP 5), modified polyacrylic acid Na salt (Sokalan CP 10 ®), modified
  • Polycarboxylate Na salt (Sokalan ® HP 25) polyalkylene oxide-modified heptamethyltrisiloxane (Silwet ® L-77), polyalkylene oxide-modified heptamethyltrisiloxane (Silwet ® L-7608), and poly-ethersiloxane (copolymers of polydimethylsiloxanes having ethylene oxide / propylene oxide segments (polyether )), preferably water-soluble linear polyether having terminal polyether as Tegopren ® 5840, Tegopren ® 5843, Tegopren ® 5847, Tegopren ® 5851, Tegopren ® 5863 or Tegopren ® 5878th
  • suitable builders are, in particular polyaspartic acid-Na-salt, Ethylendiamintriacetatkokosalkylacetamid (Rewopol ® CHT 12), methylglycine-tri-sodium salt (Trilon ES ® 9964) and acetophosphonic (Turpinal SL ®).
  • Blends with surfactant or polymeric additives show in the case of Monawet MO-84 ® R2W, Tegopren ® 5843 and Tegopren 5863 ® synergism.
  • Tegopren grades 5843 and 5863 is less preferred when applied to hard surfaces of glass, especially glassware, since these
  • the preferred viscosity for the liquid agent according to the invention is 20 ° C and a shear rate of 30 min "1 - measured with a Brookfield LV DV II viscometer and spindle 31 - in the range of 10 to 5,000 mPa-s, preferably 50 to 2,000 mPa-s, in particular 100 to 1, 000 mPa-s, more preferably 200 to 800 mPa-s, most preferably 300 to
  • the viscosity of the composition according to the invention can be increased - in particular with a low surfactant content of the composition - by thickening agents and / or - especially with a high surfactant content of the composition - can be reduced by the water-soluble inorganic salts contained and by solvents.
  • polymeric thickeners are the polycarboxylates which have a thickening effect as polyelectrolytes, preferably homo- and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, as well as other conventional thickening polymers.
  • Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guaran,
  • xanthan e.g. xanthan and their derivatives, e.g. propoxylated guar, as well as their mixtures.
  • Other polysaccharide thickeners such as starches or cellulose derivatives, may 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, hydroxypropylmethyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • 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
  • a preferred polymeric thickener is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15 * 10 6 and for example, by Fa. Kelco under the trade name Keltrol ®, eg as cream-colored powder Keltrol ® T (transparent) or as white granules Keltrol ® RD (Readily Dispersable).
  • Keltrol ® eg as cream-colored powder Keltrol ® T (transparent) or as white granules Keltrol ® RD (Readily Dispersable).
  • 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.
  • polyacrylic acids are i.a. from the Fa.
  • Carbopol ® for example Carbopol ® 940 (molecular weight approximately 4,000,000), Carbopol ® 941 (molecular weight approximately 1,250,000) or Carbopol ® 934
  • but particularly suitable polymeric thickeners 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 formed with CI_ 4 -alkanols, esters (INCI Acrylates Copolymer), to which about copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which are obtainable for example from Messrs.
  • acrylic acid copolymers (i) copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably formed with CI_ 4 -alkanols, esters (INCI Acrylates Copolymer), to which about copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acryl
  • Rohm & Haas under the trade names 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, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of Cio-3o-alkyl acrylates with one or more monomers selected from the group of acrylic acid, methacrylic acid and their simple, preferably with Ci_ 4 alkanols , Esters (INCI acrylates / C 10-30 alkyl acrylate crosspolymer) and the example of the Fa.
  • Aculyn ® and Acusol ® for example the anionic non-associative polymers Aculyn ® 33 (crosslinked), Acusol ® 810 and Acusol ® 830 (CAS 25852-
  • Carbopol ® eg hydrophobic the Carbopor ETD2623 and Carbopor 1382 (INCI Acrylates / C 10-30 Alkyl Acrylate Crosspolymer) and Carbopol AQUA ® 30 (formerly Carbopol ® EX 473).
  • 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 may be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, for example as available under the trade name Sokalan ® DSC is.
  • 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).
  • antibacterial component agents according to the invention may also contain elemental silver and / or a silver compound.
  • Lactic acid also has the advantage that, like benzoic acid or else salicylic acid as pH regulator and / or buffer substance, it can support or enhance the antibacterial action of the silver and / or the silver compound
  • the pH of the liquid agent according to the invention can also 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 skin and hand tolerance - a range of 4 to 9, preferably 5 to 8.5 and in particular 5.5 to 8.0, is preferred.
  • acids such as mineral acids or citric acid and / or alkalis such as sodium or potassium hydroxide
  • the enzyme-containing hand dishwashing detergent which contains calcium lactate as enzyme stabilizer, at pH values above 7 lead to particularly high enzyme activities and thus enzyme stabilities even after storage of the agent at 30 ° C. Agents of the invention having a pH above 7 therefore become very particular prefers.
  • 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 conduction rates, for example trisodium citrate-2 H 2 O and tripotassium citrate H 2 O.
  • a liquid agent may further contain hydrotropes. This is
  • Suitable hydrotropes are, for example, urea, butyl glycol or aliphatic short-chain anionic or amphoteric solubilizers.
  • a manually activated spray dispenser in particular selected from the group comprising aerosol spray dispenser, even pressure-building spray dispenser, pump spray dispenser and
  • Trigger spray dispensers in particular pump foam dispensers, such as those offered by the company Airspray, the company Taplast, the company Keltec or the Daiwa Can Company.
  • pump spray dispensers and trigger spray dispensers with a polyethylene, polypropylene or polyethylene terephthalate container are also suitable.
  • Such trigger bottles are offered for example by the company Afa-Polytec.
  • the spray head is preferably equipped with a foam nozzle.
  • the agent can also be filled with the addition of a suitable propellant (eg n-butane, a propane / butane mixture, carbon dioxide, nitrogen or a C0 2 / N 2 mixture) in a corresponding aerosol spray bottle.
  • a suitable propellant eg n-butane, a propane / butane mixture, carbon dioxide, nitrogen or a C0 2 / N 2 mixture
  • such a spray dispenser is less preferred.
  • agent according to the invention in the form of a product of the agent according to the invention and a spray or foam dispenser, in particular
  • the inventive particular liquid hand dishwashing detergent is applied either directly, that is undiluted, for example by means of a sponge, to the surface to be cleaned and then removed again with water.
  • the hand dishwashing detergent according to the invention can first be applied with water
  • Comparative Example C1 (see Table 1, amounts in% by weight, quantity and type of perfume, dye and salts were identical in all formulations) were stored at 30 ° C. for 4 weeks. The funds were clear immediately after their preparation as well as after storage. The color impression of the dye had not changed. Subsequently, the residual activity of the amylase used was determined by the method described in M. Lever, Carbohydrate Determination with 4-hydroxybenzoic acid hydrazide (PAHBAH): Effect of Bismuth on the Reaction, Anal. Biochem., 1977, 81, pages 21 to 27.
  • PAHBAH 4-hydroxybenzoic acid hydrazide

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Abstract

La stabilisation d'enzymes dans des détergents pour vaisselle à la main est réalisée par l'utilisation de lactate de calcium.
EP13708136.0A 2012-03-06 2013-03-06 Détergent pour vaisselle à la main renfermant des enzymes Ceased EP2823028A1 (fr)

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DE102012203475A DE102012203475A1 (de) 2012-03-06 2012-03-06 Enzymhaltiges Handgeschirrspülmittel
PCT/EP2013/054474 WO2013131941A1 (fr) 2012-03-06 2013-03-06 Détergent pour vaisselle à la main renfermant des enzymes

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DE102017223281A1 (de) * 2017-12-19 2019-06-19 Henkel Ag & Co. Kgaa Reinigugnsmittel enthaltend durch Betain stabilisierte Amylase
DE102019135615A1 (de) * 2019-12-20 2021-06-24 Henkel Ag & Co. Kgaa Handgeschirrspülmittelzusammensetzung mit Amylase

Citations (2)

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Publication number Priority date Publication date Assignee Title
WO2011036198A1 (fr) * 2009-09-28 2011-03-31 Henkel Ag & Co. Kgaa Composition enzymatique stabilisée
WO2011110593A1 (fr) * 2010-03-12 2011-09-15 Purac Biochem Bv Composition de détergent liquide contenant des enzymes stabilisées

Family Cites Families (10)

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Publication number Priority date Publication date Assignee Title
DE2038103A1 (de) 1970-07-31 1972-02-10 Henkel & Cie Gmbh Waessrige Reinigungsmittelkonzentrate mit einem Gehalt an stabilisierten Enzymen
US4318818A (en) 1979-11-09 1982-03-09 The Procter & Gamble Company Stabilized aqueous enzyme composition
EP0636170B1 (fr) 1992-04-13 1997-08-06 The Procter & Gamble Company Composition thixotrope liquide contenant des enzymes, pour le lavage automatique de la vaisselle
JP3895377B2 (ja) 1995-06-13 2007-03-22 ノボザイムス アクティーゼルスカブ 酵素安定剤としての４−置換フェニルボロン酸
CA2365446C (fr) 1999-03-31 2012-07-10 Novozymes A/S Polypeptides presentant une activite alcaline alpha-amylase et acides nucleiques les codant
AU2001277957A1 (en) 2000-07-22 2002-02-05 Genencor International, Inc. Stabilization of enzymes
DE10131441A1 (de) 2001-06-29 2003-01-30 Henkel Kgaa Eine neue Gruppe von alpha-Amylasen sowie ein Verfahren zur Identifizierung und Gewinnung neuer alpha-Amylasen
DE10163748A1 (de) 2001-12-21 2003-07-17 Henkel Kgaa Neue Glykosylhydrolasen
DE102006038448A1 (de) 2005-12-28 2008-02-21 Henkel Kgaa Enzym-haltiges Reinigungsmittel
DE102010029348A1 (de) 2010-05-27 2011-12-08 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011036198A1 (fr) * 2009-09-28 2011-03-31 Henkel Ag & Co. Kgaa Composition enzymatique stabilisée
WO2011110593A1 (fr) * 2010-03-12 2011-09-15 Purac Biochem Bv Composition de détergent liquide contenant des enzymes stabilisées

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2013131941A1 *

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DE102012203475A1 (de) 2013-09-12

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