EP2807242B1 - Enzyme-containing washing or cleaning composition comprising calcium nitrate - Google Patents

Enzyme-containing washing or cleaning composition comprising calcium nitrate Download PDF

Info

Publication number
EP2807242B1
EP2807242B1 EP13700936.1A EP13700936A EP2807242B1 EP 2807242 B1 EP2807242 B1 EP 2807242B1 EP 13700936 A EP13700936 A EP 13700936A EP 2807242 B1 EP2807242 B1 EP 2807242B1
Authority
EP
European Patent Office
Prior art keywords
alkyl
acid
enzyme
weight
amylase
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.)
Not-in-force
Application number
EP13700936.1A
Other languages
German (de)
French (fr)
Other versions
EP2807242A1 (en
Inventor
Ulrich Pegelow
Detlef Buisker
Ines Raschke
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2807242A1 publication Critical patent/EP2807242A1/en
Application granted granted Critical
Publication of EP2807242B1 publication Critical patent/EP2807242B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only
    • 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
    • C11D3/048—Nitrates or nitrites
    • 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
    • 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

Definitions

  • the invention relates to an enzyme-containing washing or cleaning agent, in particular a liquid detergent or cleaning agent 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 10 2007 028 509 A1 discloses a liquid, highly foaming washing or cleaning agent with stable viscosity, in which, inter alia, calcium salts can be used as the electrolyte.
  • 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 abovementioned compounds.
  • 4-FPBA 4-formylphenylboronic acid
  • the latter compounds as enzyme stabilizers are disclosed, for example, in the international patent application WO 96/41859 A1 (Novo Nordisk).
  • boric acids and boric acid derivatives for example, often have the disadvantage that they interact with other ingredients of a composition, in particular detergents or cleaning agent ingredients. form undesirable by-products so that they are no longer available in the agents concerned for the desired cleaning purpose or even remain as an impurity on the laundry.
  • boric acids or borates are considered to be disadvantageous from an environmental point of view.
  • the object of the present application was therefore to provide an improved stabilizing agent for enzymes and an enzyme-containing washing or cleaning agent with increased enzyme stability.
  • the invention therefore relates to the use of calcium nitrate in enzyme-containing detergents or cleaners with fatty alcohol ether sulfate and betaine to increase the stability of amylase.
  • Another object of the invention are enzyme-containing detergents or cleaning agents which contain a fatty alcohol ether sulfate, a betaine, calcium nitrate and amylase and optionally one or more other enzymes.
  • Another object of the invention is a method for manual or automatic cleaning of hard surfaces, in particular of crockery, using an agent according to the invention.
  • calcium nitrate has a stabilizing effect of enzymes.
  • Calcium nitrate is a salt that is anhydrous or hydrate. Particular preference is given to the use of calcium nitrate tetrahydrate or enzyme-containing detergents or cleaning agents which comprise calcium nitrate tetrahydrate. Since calcium nitrate is a hygroscopic salt which dissolves relatively rapidly under the influence of air, the use of calcium nitrate, in particular of calcium nitrate tetrahydrate, in liquid and, above all, aqueous washing or cleaning agents is preferred. Accordingly, preferred are agents of the invention which are in liquid form and especially in aqueous form.
  • 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 an aqueous base, wherein the agents may also have proportions of organic solvents. The person skilled in the corresponding organic solvents, which can be used in liquid, aqueous detergents or cleaning agents, known from the literature.
  • calcium nitrate 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 nitrate leads to significant enzyme stabilization even at significantly lower concentrations.
  • an agent which contains calcium nitrate in amounts of from 0.02% to less than 1% by weight.
  • Liquid, in particular aqueous washing or cleaning agents which contain calcium nitrate, preferably in the above-indicated preferred amounts and are clear, transparent liquids immediately after preparation, have the additional advantage that when stored at low temperatures, preferably at temperatures of maximum 10 ° C and especially at 0 ° C, over a longer storage period, especially when stored for 4 weeks, no turbidity occur.
  • An inventive composition contains at least one enzyme from the group of known, commonly used in detergents or cleaning agents enzymes.
  • the agent according to the invention contains an amylase, optionally in combination with a protease.
  • 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 ⁇ (1-4) -glycoside bonds in the amylose of the starch.
  • Amylases which can be synthesized according to the invention are, for example, the ⁇ -amylases from Bacillus licheniformis, from Bacillus amyloliquefaciens or from Bacillus stearothermophilus and in particular also improved for use in detergents or cleaners Further developments.
  • the enzyme from Bacillus licheniformis is available from the company Novozymes under the name Termamyl® and from the company Danisco / Genencor under the name Purastar®ST.
  • this ⁇ -amylase is available from the company Novozymes under the trade name Duramyl® and Termamyl®ultra, from the company Danisco / Genencor under the name Purastar®OxAm and from the company Daiwa Seiko Inc., Tokyo, Japan, as Keistase®.
  • the Bacillus amyloliquefaciens ⁇ -amylase is sold by the company Novozymes under the name BAN®, and variants derived from the Bacillus stearothermophilus ⁇ -amylase under the names BSG® and Novamyl®, also from the company Novozymes. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp.
  • a 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948).
  • CCTase cyclodextrin glucanotransferase
  • fusion products of all the molecules mentioned can be used.
  • the further developments of the ⁇ -amylase from Aspergillus niger and A. oryzae available under the trade name Fungamyl® from the company Novozymes are suitable.
  • Further advantageously usable commercial products are, for example, the amylase-LT® and Stainzyme® or Stainzyme ultra® or Stainzyme plus®, the latter also from the company Novozymes.
  • variants of these enzymes obtainable by point mutations can be used according to the invention.
  • amylases are disclosed in International Publications WO 00/60060 .
  • WO 03/002711 WO 03/054177 and WO07 / 079938 , whose disclosure is therefore expressly referred to, or whose disclosure in this regard is therefore expressly incorporated into the present patent application.
  • Very particularly preferred according to the invention is the ⁇ -amylase variant mentioned above under (a) and the ⁇ -amylase variant 31 mentioned under (c) with the six sequence changes mentioned under (a).
  • Liquid detergents or cleaners preferred according to the invention contain, based on their total weight, between 0.001 and 5.0% by weight, preferably between 0.01 and 4.0% by weight and in particular between 0.05 and 3.0% by weight. -% amylase preparations. Particular preference is given to liquid washing or cleaning compositions which, based on their total weight, contain between 0.07 and 2.0% by weight of amylase preparations.
  • Liquid detergents preferred according to the invention contain, based on their total weight, between 0.002 and 7.0% by weight, preferably between 0.02 and 6.0% by weight, and in particular between 0.1 and 5.0% by weight of protease preparations. Particular preference is given to 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 provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gelled agents, solutions of the enzymes which advantageously are concentrated, low in water and / or mixed with stabilizers or other auxiliaries.
  • 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.
  • 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 polymeric film-forming agent, low in dust and storage stable due to the coating.
  • 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.
  • compositions according to the invention may also contain one or more further washing- or cleaning-active enzymes.
  • hydrolases such as (poly) esterases, lipases, glycosyl hydrolases, hemicellulases, in particular mannanases, xanthan lyases, pect
  • 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 .-%.
  • the agent according to the invention is a hard surface cleaner, in particular a liquid hard surface cleaner, for example a liquid automatic dishwashing detergent or a liquid manual dishwashing detergent or an all-purpose cleaner.
  • a hard surface cleaner for example a liquid automatic dishwashing detergent or a liquid manual dishwashing detergent or an all-purpose cleaner.
  • an agent which is used for manual dishwashing contains calcium nitrate, advantageously in the amounts indicated above, amylase and optionally one or more further enzymes, in particular protease and / or lipase and / or mannanase and / or pectate lyase and / or cellulase.
  • 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 may contain further surfactants as further constituents, in particular anionic surfactants, nonionic surfactants, amphoteric surfactants, in particular further betaines and also 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.
  • Particularly preferred are the sodium salts.
  • the compositions additionally contain calcium nitrate according to the invention, 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 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.
  • EO ethylene oxide units
  • composition according to the invention in particular a manual dishwashing detergent, contains one or more alkyl ether sulfates, in a preferred embodiment in an amount of from 10 to 40% by weight, preferably from 13 to 35% by weight, in particular from 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 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 ether sulfonates (i-ether sulfonates) with associated with the alkyl radical sulfonate function.
  • 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).
  • composition according to the invention in particular a manual dishwashing detergent, preferably contains one or more secondary alkyl sulfonates in an amount of usually 1 to 15% by weight, preferably 3 to 10% by weight, in particular 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 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, alkylbenzen
  • 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 having, for example, 6, 10, 12 or 16 carbon atoms and R 'is R or H (Dowfax® Dry Hydrotropic Powder with C 16 -alkyl radical (s); INCI Sodium hexyldiphenyl ether sulfonate, disodium decyl Phenyl ether disulfonates, disodium lauryl phenyl ether disulfonates, disodium cetyl phenyl ether disulfonates) and fluorinated anionic surfactants, in particular perfluorinated alkyl sulfonates such as ammonium C 9/10 perfluoroalkylsul
  • 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 monoesters and diesters of sulfosuccinic acid 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 commercially available, for example, as Tego® sulfosuccinate F 30 (Goldschmidt) having a sulfosuccinate content of 30% by weight.
  • 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 (amphoteric surfactants, zwitterionic surfactants) which can be used according to the invention include alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, and in particular the betaines used according to the invention.
  • 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
  • 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 15 wt .-%, preferably 3 to 10 wt .-%, in particular 4 to 8 wt .-%.
  • 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.
  • 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 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, in particular a saturated C 10-16 alkyl radical, for example a saturated C 12-14 alkyl radical.
  • 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.
  • amphoteric surfactant combination contains at least one betaine, preferably at least one alkylamidobetaine, more preferably cocoamidopropylbetaine.
  • amphoteric surfactant combination preferably contains at least one amphoteric surfactant from the group comprising sodium carboxyethyl cocosphoethyl imidazoline (Phosphoteric® TC-6), C 8/10 amidopropyl betaine (INCI Capryl / Capramidopropyl Betaine, Tego® Betaine 810), N-2-hydroxyethyl-N-carboxymethyl fatty acid amido-ethylamine-Na (Rewoteric® AMV) and N-capryl / caprin-amidoethyl-N-ethyl ether-propionate-Na (Rewoteric® AMVSF) and the betaine 3- (3-cocoamido-propyl) -dimethylammonium-2-hydroxypropanesulfonate (INCI Sultaine; Rewoteric® AM CAS) and the alkylamidoalkylamine N- [N '(N "-2-hydroxyethyl)
  • 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.
  • nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 Mol used ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • 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.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO, 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range 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. More preferably, the hard surface cleaner contains a C 12-18 fatty alcohol with 7 EO or a C 13-15 oxo alcohol with 7 EO as the nonionic surfactant.
  • the content of nonionic surfactants in the cleaning agent is preferably 1 to 30% by weight and preferably 2 to 25% by weight, in each case based on the total cleaning agent.
  • nonionic surfactants in combination with an amine oxide have good cleaning performance on grease-soiled hard surfaces such as dishes.
  • 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 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.
  • Preferred amine oxides are, for example, cocamidopropylamine oxides (cocoamidopropylamine oxide), but also N-cocoalkyl-N, N-dimethylamine oxide, N-tallowkyl-N, N-dihydroxyethylamine oxide, myristylcetyldimethylamine oxide or lauryldimethylamine oxide.
  • the content of amine oxide in the cleaning agent is preferably 1 to 15% by weight and preferably 2 to 10% by weight, in each case based on the total cleaning agent.
  • 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 Propylenoxyoli, and a for 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 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 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 according to the invention may additionally contain one or more cationic surfactants (cationic 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 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 are prepared by reacting tertiary amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • the alkylation of tertiary amines with a long alkyl radical and two methyl groups succeeds particularly easily, and the quatern
  • Preferred 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 QAV is cocospentaethoxymethylammonium 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.
  • the preferred liquid cleaning agent according to the invention for reducing the viscosity further comprises 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 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.
  • 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 in a preferred embodiment 0.1 to 10 wt .-%, preferably 0.5 to 7 wt .-%, particularly preferably 0.8 to 5 wt .-% of at least one water-soluble salt. In a particularly preferred embodiment, exclusively inorganic salts are used.
  • the water-soluble salt is used in particular for setting a lower viscosity in hard surface cleaners which have a high surfactant concentration, in particular a high alkyl ether sulfate concentration.
  • a high surfactant concentration in particular a high alkyl ether sulfate concentration.
  • one or more water-soluble salts are accordingly added to the compositions.
  • no builder substances are present which have calcium-precipitating properties. Accordingly, an agent is preferred which contains in particular no carbonate-containing salts. But also the use of soaps is handled restrictively.
  • Organic builder substances which may be present in the washing or cleaning agent are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, where polycarboxylic acids are understood to mean those carboxylic acids which carry more than one acid function.
  • polycarboxylic acids are understood to mean those carboxylic acids which carry more than one acid function.
  • these are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) and derivatives thereof and mixtures thereof.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • 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 detergents or cleaners.
  • the water content of the preferred liquid, aqueous agent is usually 15 to 90 wt .-%, preferably 20 to 85 wt .-%, in particular 30 to 80 wt .-%.
  • the agent according to the invention may advantageously additionally contain 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 cause excessive viscosity drop.
  • Preferred organic solvents are selected from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers.
  • the solvents are selected from ethanol, n- or i-propanol, butanol, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether , Propylenglykolmethyl-, ethyl or propyl ether, Dipropylenglykolmethyl- or ethyl ether, methoxy, ethoxy or Butoxytriglykol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propyl
  • a particularly preferred organic solvent which is particularly effective in stabilizing the enzymatic detergents is glycerin and 1,2-propylene glycol.
  • 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 hydroxyl 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 C 1-6 -alcohols, preferably ethanol, n-propanol or isopropanol, especially ethanol.
  • Exemplary solvents are the following INCI compounds: alcohol (ethanol), buteth-3, butoxy diglycol, butoxyethanol, butoxyisopropanol, butoxypropanol, n-butyl alcohol, t-butyl alcohol, butylene glycol, butyloctanol, diethylene glycol, dimethoxy diglycol, dimethyl ether, Dipropylene glycol, ethoxydiglycol, ethoxyethanol, ethyl hexanediol, glycol, hexanediol, 1,2,6-hexanetriol, hexyl alcohol, hexylene glycol, isobutoxypropanol, isopentyldiol, isopropyl alcohol (isopropanol), 3-methoxybutanol, methoxydiglycol, methoxyethanol, methoxyisopropanol, Methoxymethylbutanol, Methoxy PEG-10, Methylal,
  • 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, for example PPG-2 methyl ether (dipropylene glycol monomethyl ether).
  • 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 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, organic salts, Disinfectants, enzymes, pH adjusters and skin feel-improving 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. %, wherein as described above on calcium-precipitating builders is largely dispensed with.
  • 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. %, wherein as described above on calcium-precipitating builders is largely dispensed with.
  • the viscosity preferred 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 from 10 to 5,000 mPa ⁇ s, preferably 50 to 2,000 mPa ⁇ s, in particular 100 to 1000 mPa ⁇ s, more preferably 200 to 800 mPa ⁇ s, most preferably 300 to 700 mPa ⁇ s, for example 300 to 400 mPa ⁇ s.
  • 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 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, 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.
  • a preferred polymeric thickener is the microbial anionic heteropolysaccharide xanthan gum produced by Xanthomonas campestris and some other species under aerobic conditions having a molecular weight of 2-15 x 10 6 and is available, for example, from 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.
  • polyalkenyl polyether in particular an allyl ether of sucrose, pentaerythritol or propylene
  • carboxyvinyl polymers Such polyacrylic acids are i.a. available from BFGoodrich under the trade name Carbopol®, e.g. Carbopol® 940 (molecular weight about 4,000,000), Carbopol® 941 (molecular weight about 1,250,000) or Carbopol® 934 (molecular weight about 3,000,000).
  • 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) and which are available, for example, from 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
  • 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 their salts may be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, as described e.g. available under the trade name Sokalan® DSC.
  • 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).
  • auxiliary agents and additives customary in hand dishwashing detergents and other cleaners for hard surfaces in particular UV stabilizers, perfume, pearlescing agents (INCI Opacifying Agents, for example glycol distearate, eg Cutina® AGS from Cognis, or US Pat containing mixtures thereof, for example the Euperlane® from Cognis), dyes, corrosion inhibitors, preservatives (for example the technical 2-bromo-2-nitropropane-1,3-diol (CAS 52-51-7), also referred to as Bronopol, which is commercially available, for example, as Myacide® BT or Boots Bronopol BT from Boots), disinfectants, pH stabilizers 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 hydrolyzates, protein hydrolyzate-fatty acid
  • antibacterial component agents according to the invention may also contain elemental silver and / or a silver compound.
  • the pH of the liquid composition 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, where a range from 4 to 9, in particular with the desired skin and hand tolerance , preferably 5 to 8.5, in particular 5.5 to 8.0, 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.
  • a liquid agent may further contain hydrotropes.
  • hydrotropes are solubilizers. Suitable hydrotropes are, for example, urea, butyl glycol or aliphatic short-chain anionic or amphoteric solubilizers.
  • the composition according to the invention for use in the form of a foam should be applied either directly to the surface to be cleaned or to a sponge, a cloth, a brush or another, optionally moistened, cleaning aid.
  • a manually activated spray dispenser in particular selected from the group comprising aerosol spray dispenser, self-pressure spray dispenser, pump spray dispenser and trigger spray dispensers, in particular pump foam dispenser, as for example from 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 CO 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 CO 2 / N 2 mixture
  • a suitable propellant eg n-butane, a propane / butane mixture, carbon dioxide, nitrogen or a CO 2 / N 2 mixture
  • the agent according to the invention in the form of a product from the agent according to the invention and a spray or foam dispenser, in particular pump foam dispenser, be placed on the market.
  • the liquid detergent according to the invention 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 cleaning agent according to the invention can first be diluted with water to concentrations of 1: 1 to 1: 1000, and then the resulting cleaning solution is brought into contact with the surface to be cleaned.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Enzymes And Modification Thereof (AREA)

Description

Die Erfindung betrifft ein enzymhaltiges Wasch- oder Reinigungsmittel, insbesondere ein flüssiges Wasch- oder Reinigungsmittel mit verbesserter Enzymstabilität.The invention relates to an enzyme-containing washing or cleaning agent, in particular a liquid detergent or cleaning agent with improved enzyme stability.

Übliche Wasch- oder Reinigungsmittel des Marktes enthalten Tenside zur Entfernung von Schmutz und Flecken. In der Regel werden hierbei Kombinationen aus mehreren Tensiden, insbesondere aus der Gruppe der anionischen, nichtionischen, kationischen und amphoteren Tenside verwendet. Diese Tenside allein sind häufig nicht in der Lage, Schmutz und Flecken hinreichend zu entfernen, so dass in modernen Wasch- oder Reinigungsmitteln weitere Hilfsstoffe eingesetzt werden. Zu diesen weiteren Hilfsstoffen gehören Enzyme verschiedener Arten wie Proteasen, Amylasen, Cellulasen, Mannanasen, Pektatlyasen. Dem Fachmann sind weitere Enzymklassen bekannt. Insbesondere hydrolytische Enzyme wie Proteasen, Amylasen oder Lipasen sind wegen ihrer unmittelbar reinigenden Wirkung Bestandteil zahlreicher Textil- oder Geschirrreinigungsmittel.Common detergents or cleaners on the market contain surfactants to remove dirt and stains. As a rule, 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. The skilled worker is aware of other classes of enzymes. In particular, hydrolytic enzymes such as proteases, amylases or lipases are part of numerous textile or dishwashing detergents because of their direct cleaning action.

Die für den Endverbraucher entscheidende Reinigungswirkung der in Wasch- oder Reinigungsmitteln eingesetzten Enzyme wird neben der Enzymstruktur in wesentlichem Maße auch durch die Art der Konfektionierung dieser Enzyme und ihrer Stabilisierung gegen Umwelteinflüsse bestimmt.The decisive for the end user cleaning effect of the enzymes used in detergents or cleaning agents is determined in addition to the enzyme structure to a considerable extent by the nature of the preparation of these enzymes and their stabilization against environmental influences.

Wasch- oder reinigungsaktive Enzyme werden sowohl in fester als auch in flüssiger Form konfektioniert. Zur Gruppe der festen Enzymzubereitungen zählen insbesondere die aus mehreren Inhaltsstoffen bestehenden Enzymgranulate, die ihrerseits vorzugsweise in feste Wasch- oder Reinigungsmittel eingearbeitet werden. Flüssige oder gelförmige Wasch- oder Reinigungsmittel enthalten im Gegensatz hierzu häufig flüssige Enzymzubereitungen, wobei diese, anders als die Enzymgranulate gegen äußere Einflüsse weit weniger geschützt sind.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. In contrast, liquid or gel detergents or cleaners frequently contain liquid enzyme preparations, which, unlike the enzyme granules, are much less protected against external influences.

Zur Erhöhung der Stabilität derartiger Enzym-haltiger flüssiger Wasch- oder Reinigungsmittel wurden eine Reihe unterschiedlicher Schutzmaßnahmen vorgeschlagen. So lehrt beispielsweise die deutsche Patentanmeldung DE 20 38 103 (Henkel ) die Stabilisierung von Enzym-haltigen Geschirrspülmitteln durch Sacharide, während in dem europäischen Patent EP 646 170 B1 (Procter & Gamble) Propylenglykol zur Enzymstabilisierung in flüssigen Reinigungsmitteln offenbart wird.To increase the stability of such enzyme-containing liquid detergents or cleaners, a number of different protective measures have been proposed. For example, the German patent application teaches DE 20 38 103 (Henkel ) the stabilization of enzyme-containing dishwashing detergents by sacharides, while in the European patent EP 646 170 B1 (Procter & Gamble) Propylene glycol for enzyme stabilization in liquid detergents is disclosed.

Das US amerikanische Patent 5,510,052 (Colgate-Palmolive) offenbart die Aktivierung von Enzymen durch den Einsatz von Calciumverbindungen in Geschirrvorbehandlungsmitteln.The US American patent 5,510,052 (Colgate-Palmolive) discloses the activation of enzymes by the use of calcium compounds in dishwashing agents.

Die internationale Anmeldung WO 00/42144 (Procter & Gamble) offenbart Waschmittelzusammensetzungen, welche Metallkationen sowie Enzyme enthalten, befasst sich allerdings nicht mit der Stabilisierung der Enzyme.The international application WO 00/42144 (Procter & Gamble) discloses detergent compositions containing metal cations as well as enzymes, but does not address the stabilization of the enzymes.

Die internationale Anmeldung WO 00/43488 (Procter & Gamble) offenbart Geschirrspülmitteltabletten, in welchen neben anderen enzymstabilisierenden Substanzen auch Calciumkationen eingesetzt werden können.The international application WO 00/43488 (Procter & Gamble) discloses dishwasher tablets in which calcium cations can be used in addition to other enzyme-stabilizing substances.

Saboury (Biologica, Bratislava, Bd. 57, Nr. Suppl. 11, 2002, Seiten 221-228 ) beschäftigte sich mit der Stabilität, Aktivität und Bindungseigenschaften von α-Amylase bei Wechselwirkung mit Calcium- und Cobaltkationen. Saboury (Biologica, Bratislava, Vol. 57, No. Suppl. 11, 2002, pages 221-228 ) focused on the stability, activity and binding properties of α-amylase interacting with calcium and cobalt cations.

Rameshkumar (International Journal of Microbiological Research 2 (2): 143-148, 2011 ) beschäftigte sich mit der Produktion von α-Amylasen, unter anderem in Anwesenheit von Calciumsalzen. Rameshkumar (International Journal of Microbiological Research 2 (2): 143-148, 2011 ) dealt with the production of α-amylases, inter alia in the presence of calcium salts.

Die deutsche Patentanmeldung DE 10 2007 028 509 A1 (Henkel) offenbart ein flüssiges, hochschäumendes Wasch- oder Reinigungsmittel mit stabiler Viskosität, in welchem unter anderem Calciumsalze als Elektrolyt eingesetzt werden können.The German patent application DE 10 2007 028 509 A1 (Henkel) discloses a liquid, highly foaming washing or cleaning agent with stable viscosity, in which, inter alia, calcium salts can be used as the electrolyte.

Als reversible Proteaseinhibitoren sind im Stand der Technik Polyole, insbesondere Glycerin und 1,2-Propylenglycol beschrieben. Eine entsprechende technische Offenbarung findet sich beispielsweise in der internationalen Anmeldung WO 02/08398 A2 (Genencor).As reversible protease inhibitors in the prior art polyols, especially glycerol and 1,2-propylene glycol are described. A corresponding technical disclosure can be found, for example, in the international application WO 02/08398 A2 (Genencor).

Die Stabilisierung von Enzymen in wässrigen Reinigungsmitteln durch Calciumsalze wie Calciumformiat, Calciumacetat oder Calciumpropionat beschreibt das US amerikanische Patent 4,318, 818 (Procter & Gamble). Salze mehrwertiger Kationen wie Calciumkationen führen jedoch in wässerigen Systemen, insbesondere in manuellen Geschirrspülmitteln häufig zu Trübungen während der Lagerung. Dieser negative Effekt verstärkt sich bei der Lagerung bei tiefen Temperaturen. Dadurch sind die möglichen Einsatzkonzentrationen limitiert, so dass keine ausreichende enzymstabilisierende Wirkung garantiert werden kann.The stabilization of enzymes in aqueous detergents by calcium salts such as calcium formate, calcium acetate or calcium propionate describes the US American patent 4,318, 818 (Procter & Gamble). However, salts of polyvalent cations, such as calcium cations, often result in clouding during storage in aqueous systems, especially in manual dishwashing detergents. This negative effect intensifies during storage at low temperatures. As a result, the possible use concentrations are limited, so that a sufficient enzyme-stabilizing effect can not be guaranteed.

Eine zweite Gruppe bekannter Stabilisatoren bilden Borax, Borsäuren, Boronsäuren oder deren Salze oder Ester. Darunter sind vor allem Derivate mit aromatischen Gruppen, etwa ortho-, meta- oder para-substituierte Phenylboronsäuren zu erwähnen, insbesondere 4-Formylphenyl-Boronsäure (4-FPBA) beziehungsweise die Salze oder Ester der genannten Verbindungen. Letztgenannte Verbindungen als Enzymstabilisatoren sind beispielsweise offenbart in der internationalen Patentanmeldung WO 96/41859 A1 (Novo Nordisk). Allerdings weisen beispielsweise Borsäuren und Borsäurederivate oftmals den Nachteil auf, dass sie mit anderen Inhaltsstoffen einer Zusammensetzung, insbesondere Wasch- bzw. Reinigungsmittelinhaltsstoffen, unerwünschte Nebenprodukte bilden, so dass diese in den betreffenden Mitteln nicht mehr für den erwünschten Reinigungszweck zur Verfügung stehen oder sogar als Verunreinigung auf dem Waschgut zurückbleiben. Ferner werden Borsäuren bzw. Borate unter Umweltaspekten als nachteilig betrachtet.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 abovementioned compounds. The latter compounds as enzyme stabilizers are disclosed, for example, in the international patent application WO 96/41859 A1 (Novo Nordisk). However, boric acids and boric acid derivatives, for example, often have the disadvantage that they interact with other ingredients of a composition, in particular detergents or cleaning agent ingredients. form undesirable by-products so that they are no longer available in the agents concerned for the desired cleaning purpose or even remain as an impurity on the laundry. Furthermore, boric acids or borates are considered to be disadvantageous from an environmental point of view.

Die bisher aufgefundenen und im Stand der Technik beschriebenen Methoden zur Stabilisierung von Enzymen sind in Abhängigkeit von der chemischen Natur der Stabilisatoren nicht in jeder Reinigungsmittelformulierung einsetzbar und hinsichtlich ihrer stabilisierenden Wirkung nicht immer ausreichend.Depending on the chemical nature of the stabilizers, the methods for the stabilization of enzymes which have hitherto been found and described in the prior art can not be used in every detergent formulation and are not always adequate with regard to their stabilizing action.

Die Aufgabe der vorliegenden Anmeldung bestand daher in der Bereitstellung eines verbesserten Stabilisierungsmittels für Enzyme sowie eines Enzym-haltigen Wasch- oder Reinigungsmittels mit erhöhter Enzymstabilität.The object of the present application was therefore to provide an improved stabilizing agent for enzymes and an enzyme-containing washing or cleaning agent with increased enzyme stability.

Es wurde nun gefunden, dass die Nachteile der oben beschriebenen Art bei der Verwendung einer speziellen Calciumverbindung nicht auftreten.It has now been found that the disadvantages of the type described above do not occur when using a special calcium compound.

Gegenstand der Erfindung ist daher die Verwendung von Calciumnitrat in enzymhaltigen Wasch- oder Reinigungsmitteln mit Fettalkoholethersulfat und Betain zur Erhöhung der Stabilität von Amylase.The invention therefore relates to the use of calcium nitrate in enzyme-containing detergents or cleaners with fatty alcohol ether sulfate and betaine to increase the stability of amylase.

Ein weiterer Gegenstand der Erfindung sind enzymhaltige Wasch- oder Reinigungsmittel, welche ein Fettalkoholethersulfat, ein Betain, Calciumnitrat sowie Amylase und gegebenenfalls ein oder mehrere weitere Enzyme enthalten.Another object of the invention are enzyme-containing detergents or cleaning agents which contain a fatty alcohol ether sulfate, a betaine, calcium nitrate and amylase and optionally one or more other enzymes.

Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur manuellen oder maschinellen Reinigung harter Oberflächen, insbesondere von Geschirr, unter Einsatz eines erfindungsgemäßen Mittels.Another object of the invention is a method for manual or automatic cleaning of hard surfaces, in particular of crockery, using an agent according to the invention.

Überraschenderweise wurde gefunden, dass Calciumnitrat eine stabilisierende Wirkung von Enzymen aufweist. Calciumnitrat ist ein Salz, welches wasserfrei oder als Hydrat vorkommt. Insbesondere bevorzugt ist die Verwendung von Calciumnitrat-Tetrahydrat beziehungsweise sind enzymhaltige Wasch- oder Reinigungsmittel, welche Calciumnitrat-Tetrahydrat aufweisen. Da Calciumnitrat ein hygroskopisches Salz ist, welches unter Lufteinfluss relativ schnell zerfließt, ist die Verwendung von Calciumnitrat, insbesondere von Calciumnitrat-Tetrahydrat, in flüssigen und vor allem wässerigen Wasch- oder Reinigungsmitteln bevorzugt. Dementsprechend bevorzugt sind erfindungsgemäße Mittel, die in flüssiger Form vorliegen und vor allem in wässeriger Form vorliegen In der Beschreibung bezieht sich der Ausdruck "erfindungsgemäss" ausschliesslich auf beanspruchte Gegenstände.Tritt der Ausdruck in Kombination mit Gegenständen auf, die nicht zum beanspruchten Gegenstand gehören, ist der Term lediglich als deskriptiv anzusehen. Im Rahmen der vorliegenden Erfindung werden unter flüssigen Mitteln solche verstanden, die unter normalen Anwendungsbedingungen fließfähig sind und deren Viskositäten in einem breiten Rahmen variieren können. Zu den flüssigen Zubereitungen zählen auch gelförmige oder pastöse Mittel, welche gegebenenfalls zusätzliche aus dem Stand der Technik bekannte Verdickungsmittel aufweisen können. In einer weiter bevorzugten Ausführungsform der Erfindung beruhen die flüssigen Mittel auf wässeriger Basis, wobei die Mittel auch Anteile an organischen Lösungsmitteln aufweisen können. Dem Fachmann sind entsprechende organische Lösungsmittel, welche in flüssigen, wässerigen Wasch- oder Reinigungsmitteln eingesetzt werden können, aus der Literatur bekannt.Surprisingly, it has been found that calcium nitrate has a stabilizing effect of enzymes. Calcium nitrate is a salt that is anhydrous or hydrate. Particular preference is given to the use of calcium nitrate tetrahydrate or enzyme-containing detergents or cleaning agents which comprise calcium nitrate tetrahydrate. Since calcium nitrate is a hygroscopic salt which dissolves relatively rapidly under the influence of air, the use of calcium nitrate, in particular of calcium nitrate tetrahydrate, in liquid and, above all, aqueous washing or cleaning agents is preferred. Accordingly, preferred are agents of the invention which are in liquid form and especially in aqueous form. In the specification, the term "according to the invention" refers exclusively to claimed articles. If the term occurs in combination with articles not belonging to the claimed subject-matter to regard the term merely as descriptive. In the context of the present invention, 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. In a further preferred embodiment of the invention, the liquid agents are based on an aqueous base, wherein the agents may also have proportions of organic solvents. The person skilled in the corresponding organic solvents, which can be used in liquid, aqueous detergents or cleaning agents, known from the literature.

Vorteilhafterweise hat es sich herausgestellt, dass Calciumnitrat bereits in relativ geringen Mengen zur Stabilisierung von Enzymen beiträgt. Während andere bekannte Enzymstabilisatoren häufig in Mengen bis zu 10 Gew.-% eingesetzt werden, führt Calciumnitrat bereits in deutlich geringeren Konzentrationen zu einer signifikanten Enzymstabilisierung.Advantageously, it has been found that calcium nitrate 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 nitrate leads to significant enzyme stabilization even at significantly lower concentrations.

In einer bevorzugten Ausführungsform der Erfindung ist daher ein Mittel vorgesehen, welches Calciumnitrat in Mengen von 0,02 Gew.-% bis weniger als 1 Gew.-% enthält. Insbesondere sind Mittel bevorzugt, welche Calciumnitrat in Mengen von 0,05 Gew.-% bis 0,5 Gew.-% mit weiterer Bevorzugung von 0,1 bis 0,3 Gew.-% aufweisen.In a preferred embodiment of the invention, therefore, an agent is provided which contains calcium nitrate in amounts of from 0.02% to less than 1% by weight. In particular, agents which contain calcium nitrate in amounts of from 0.05% by weight to 0.5% by weight, with further preference from 0.1% to 0.3% by weight, are preferred.

Flüssige, insbesondere wässerige Wasch- oder Reinigungsmittel, welche Calciumnitrat, vorzugsweise in den oben angegebenen bevorzugten Mengen enthalten und direkt nach der Herstellung klare, transparente Flüssigkeiten darstellen, weisen den zusätzlichen Vorteil auf, dass bei Lagerung auch bei tiefen Temperaturen, vorzugsweise bei Temperaturen von maximal 10 °C und insbesondere bei 0°C, über einen längeren Lagerzeitraum, insbesondere bei 4-wöchiger Lagerung, keine Trübungen auftreten.Liquid, in particular aqueous washing or cleaning agents which contain calcium nitrate, preferably in the above-indicated preferred amounts and are clear, transparent liquids immediately after preparation, have the additional advantage that when stored at low temperatures, preferably at temperatures of maximum 10 ° C and especially at 0 ° C, over a longer storage period, especially when stored for 4 weeks, no turbidity occur.

Ein erfindungsgemäßes Mittel enthält mindestens ein Enzym aus der Gruppe der bekannten, in Wasch- oder Reinigungsmitteln üblicherweise eingesetzten Enzyme. Das erfindungsgemäße Mittel enthält eine Amylase, gegebenenfalls in Kombination mit einer Protease.An inventive composition contains at least one enzyme from the group of known, commonly used in detergents or cleaning agents enzymes. The agent according to the invention contains an amylase, optionally in combination with a protease.

Für Amylasen können synonyme Begriffe verwendet werden, beispielsweise 1,4-alpha-D-Glucan-Glucanohydrolase oder Glycogenase. Erfindungsgemäß konfektionierbare Amylasen sind vorzugsweise α-Amylasen. Entscheidend dafür, ob ein Enzym eine α-Amylase im Sinne der Erfindung ist, ist deren Fähigkeit zur Hydrolyse von α(1-4)-Glykosidbindungen in der Amylose der Stärke.For 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 α-amylase according to the invention is its ability to hydrolyze α (1-4) -glycoside bonds in the amylose of the starch.

Erfindungsgemäß konfektionierbare Amylasen sind beispielsweise die α-Amylasen aus Bacillus licheniformis, aus Bacillus amyloliquefaciens oder aus Bacillus stearothermophilus sowie insbesondere auch deren für den Einsatz in Wasch- oder Reinigungsmitteln verbesserte Weiterentwicklungen. Das Enzym aus Bacillus licheniformis ist von dem Unternehmen Novozymes unter dem Namen Termamyl® und von dem Unternehmen Danisco/Genencor unter dem Namen Purastar®ST erhältlich. Weiterentwicklungsprodukte dieser α-Amylase sind von dem Unternehmen Novozymes unter den Handelsnamen Duramyl® und Termamyl®ultra, von dem Unternehmen Danisco/Genencor unter dem Namen Purastar®OxAm und von dem Unternehmen Daiwa Seiko Inc., Tokyo, Japan, als Keistase® erhältlich. Die α-Amylase von Bacillus amyloliquefaciens wird von dem Unternehmen Novozymes unter dem Namen BAN® vertrieben, und abgeleitete Varianten von der α-Amylase aus Bacillus stearothermophilus unter den Namen BSG® und Novamyl®, ebenfalls von dem Unternehmen Novozymes. Des Weiteren sind für diesen Zweck die α-Amylase aus Bacillus sp. A 7-7 (DSM 12368) und die Cyclodextrin-Glucanotransferase (CGTase) aus Bacillus agaradherens (DSM 9948) hervorzuheben. Ebenso sind Fusionsprodukte aller genannten Moleküle einsetzbar. Darüber hinaus sind die unter den Handelsnamen Fungamyl® von dem Unternehmen Novozymes erhältlichen Weiterentwicklungen der α-Amylase aus Aspergillus niger und A. oryzae geeignet. Weitere vorteilhaft einsetzbare Handelsprodukte sind beispielsweise die Amylase-LT® und Stainzyme® oder Stainzyme ultra® bzw. Stainzyme plus®, letztere ebenfalls von dem Unternehmen Novozymes. Auch durch Punktmutationen erhältliche Varianten dieser Enzyme können erfindungsgemäß eingesetzt werden. Besonders bevorzugte Amylasen sind offenbart in den internationalen Offenlegungsschriften WO 00/60060 , WO 03/002711 , WO 03/054177 und WO07/079938 , auf deren Offenbarung daher ausdrücklich verwiesen wird bzw. deren diesbezüglicher Offenbarungsgehalt daher ausdrücklich in die vorliegende Patentanmeldung mit einbezogen wird.Amylases which can be synthesized according to the invention are, for example, the α-amylases from Bacillus licheniformis, from Bacillus amyloliquefaciens or from Bacillus stearothermophilus and in particular also improved for use in detergents or cleaners Further developments. The enzyme from Bacillus licheniformis is available from the company Novozymes under the name Termamyl® and from the company Danisco / Genencor under the name Purastar®ST. Further development products of this α-amylase are available from the company Novozymes under the trade name Duramyl® and Termamyl®ultra, from the company Danisco / Genencor under the name Purastar®OxAm and from the company Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. The Bacillus amyloliquefaciens α-amylase is sold by the company Novozymes under the name BAN®, and variants derived from the Bacillus stearothermophilus α-amylase under the names BSG® and Novamyl®, also from the company Novozymes. Furthermore, for this purpose, the α-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 α-amylase from Aspergillus niger and A. oryzae available under the trade name Fungamyl® from the company Novozymes are suitable. Further advantageously usable commercial products are, for example, the amylase-LT® and Stainzyme® or Stainzyme ultra® or Stainzyme plus®, the latter also from the company Novozymes. Also variants of these enzymes obtainable by point mutations can be used according to the invention. Particularly preferred amylases are disclosed in International Publications WO 00/60060 . WO 03/002711 . WO 03/054177 and WO07 / 079938 , whose disclosure is therefore expressly referred to, or whose disclosure in this regard is therefore expressly incorporated into the present patent application.

Besonders geeignet für den Einsatz in erfindungsgemäßen Mitteln sind α-Amylase-Varianten der α-Amylase AA560 gemäß SEQ ID NO. 1. Folgende Varianten sind besonders vorteilhaft:

  1. (a) α-Amylase-Variante, die gegenüber der α-Amylase AA560 gemäß SEQ ID NO. 1 eine, zwei, drei, vier, fünf oder sechs der folgenden Sequenzveränderungen in der Zählung der α-Amylase AA560 aufweist: R118K, D183* (Deletion), G184* (Deletion), N195F, R320K, R458K. Besonders bevorzugt weist die α-Amylase-Variante alle sechs der genannten Sequenzveränderungen auf.
  2. (b) α-Amylase-Variante, die gegenüber der α-Amylase AA560 gemäß SEQ ID NO. 1 folgende Sequenzveränderungen aufweist (in der Zählung der α-Amylase AA560):
    1. (1) M9L / M202I,
    2. (2) M9L / M202I / M323T,
    3. (3) M9L / M202I / M323T / M382Y,
    4. (4) M9L / M202I / Y295F / A339S,
    5. (5) M9L / M202I / Y295F,
    6. (6) M9L / M202I / A339S,
    7. (7) M9L / M202I / Y295F / A339S,
    8. (8) M9L / M202I / Y295F / A339S / E345R,
    9. (9) M9L / G149A / M202I / Y295F / A339S / E345R,
    10. (10) M9L / M202L,
    11. (11) M9L / M202L / M323T,
    12. (12) M9L / M202L / M323T / M382Y,
    13. (13) M9L / M202L / Y295F / A339S,
    14. (14) M9L / M202L / Y295F,
    15. (15) M9L / M202L / A339S,
    16. (16) M9L / M202L / Y295F / A339S,
    17. (17) M9L / M202L / Y295F / A339S, E345R,
    18. (18) M9L / G149A / M202L / Y295F / A339S / E345R,
    19. (19) M9L / M202T,
    20. (20) M9L / M202T / M323T,
    21. (21) M9L / M202T / M323T / M382Y,
    22. (22) M9L / M202T / Y295F / A339S,
    23. (23) M9L / M202T / Y295F,
    24. (24) M9L / M202T / A339S,
    25. (25) M9L / M202T / Y295F / A339S,
    26. (26) M9L / M202T / Y295F / A339S / E345R,
    27. (27) M9L / G149A / M202T / Y295F / A339S / E345R,
    28. (28) M9L / G149A / M202I / V214T / Y295F / N299Y / M323T / A339S / E345R,
    29. (29) M9L / G149A / M202L / V214I / Y295F / M323T / A339S / E345R / M382Y,
    30. (30) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / A339S,
    31. (31) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R,
    32. (32) M9L / G149A / M202L / V214T / Y295F / N299Y / M323T / A339S / E345R,
    33. (33) M9L / G149A / M202I / V214I / Y295F / M323T / A339S / E345R / M382Y,
    34. (34) M9L / G149A / G182T / G186A / M202L / V214I / Y295F / N299Y / M323T / A339S,
    35. (35) M9L / G149A / G182T / G186A / M202I / T257I / Y295F / N299Y / M323T / A339S / E345R,
    36. (36) M9L / G149A / M202I / V214T / Y295F / N299Y / M323T / A339S / E345R / N471E,
    37. (37) M9L / G149A / M202L / V214I / Y295F / M323T / A339S / E345R / M382Y / N471E,
    38. (38) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / A339S / N471E,
    39. (39) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R / N471E,
    40. (40) M202L / M105F / M208F,
    41. (41) G133E / M202L / Q361E,
    42. (42) G133E / M202L / R444E,
    43. (43) M202L / Y295F,
    44. (44) M202L / A339S,
    45. (45) M202L / M323T,
    46. (46) M202L / M323T / M309L,
    47. (47) M202L / M323T / M430I,
    48. (48) M202L / V214T / R444Y,
    49. (49) M202L / N283D / Q361E,
    50. (50) M202L / M382Y / K383R,
    51. (51) M202L / K446R / N484Q,
    52. (52) M202I / Y295F,
    53. (53) M202I / A339S,
    54. (54) M202I / M105F / M208F,
    55. (55) G133E / M202I / Q361E,
    56. (56) G133E / M202I / R444E,
    57. (57) M202I / M323T,
    58. (58) M202I / M323T / M309L,
    59. (59) M202I / M323T / M430I,
    60. (60) M202I / V214T / R444Y,
    61. (61) M202I / N283D / Q361E,
    62. (62) M202I / M382Y / K383R,
    63. (63) M202I / K446R / N484Q,
    64. (64) M202V / M105F / M208F,
    65. (65) G133E / M202V / Q361E,
    66. (66) G133E / M202V / R444E,
    67. (67) M202V / M323T,
    68. (68) M202V / M323T / M309L,
    69. (69) M202V / M323T / M430I,
    70. (70) M202V / M323T / M9L,
    71. (71) M202V / V214T / R444Y,
    72. (72) M202V / N283D / Q361E,
    73. (73) M202V / M382Y / K383R,
    74. (74) M202V / K446R / N484Q,
    75. (75) M202T / M105F / M208F,
    76. (76) G133E / M202T / Q361E,
    77. (77) G133E / M202T / R444E,
    78. (78) M202T / Y295F,
    79. (79) M202T / A339S,
    80. (80) M202T / M323T,
    81. (81) M202T / M323T / M309L,
    82. (82) M202T / M323T / M430I,
    83. (83) M202T / M323T / M9L,
    84. (84) M202T / V214T / R444Y,
    85. (85) M202T / N283D / Q361E,
    86. (86) M202T / A339S,
    87. (87) M202T / Y295F
    88. (88) M202T / N299F,Y,
    89. (89) M202T / M382Y / K383R oder
    90. (90) M202T / K446R / N484Q

    Hierunter ganz besonders bevorzugt sind folgende α-Amylase-Varianten:
    • (10) M9L / M202L,
    • (28) M9L / G149A / M202I / V214T / Y295F / N299Y / M323T / A339S / E345R,
    • (31) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R,
    • (35) M9L / G149A / G182T / G186A / M202I / T257I / Y295F / N299Y / M323T / (38) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / (39) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R / N471E,
    • (45) M202L / M323T,
    • (46) M202L / M323T / M309L,
    • (62) M202I / M382Y / K383R,
    • (68) M202V / M323T / M309L,
    • (73) M202V / M382Y / K383R
    • (82) M202T / M323T / M430I oder
    • (84) M202T / V214T / R444Y
  3. (c) α-Amylase-Variante gemäß (b), die zusätzlich alle sechs unter (a) genannten Sequenzveränderungen aufweist, hierunter ganz besonders bevorzugt Variante 31 mit den sechs unter (a) genannten Sequenzveränderungen.
Particularly suitable for use in agents according to the invention are α-amylase variants of α-amylase AA560 according to SEQ ID NO. 1. The following variants are particularly advantageous:
  1. (a) α-amylase variant which is resistant to the α-amylase AA560 according to SEQ ID NO. Figure 1 has one, two, three, four, five or six of the following sequence changes in the count of α-amylase AA560: R118K, D183 * (deletion), G184 * (deletion), N195F, R320K, R458K. Most preferably, the α-amylase variant has all six of the mentioned sequence changes.
  2. (b) α-amylase variant which is resistant to the α-amylase AA560 according to SEQ ID NO. 1 has the following sequence changes (in the count of α-amylase AA560):
    1. (1) M9L / M202I,
    2. (2) M9L / M202I / M323T,
    3. (3) M9L / M202I / M323T / M382Y,
    4. (4) M9L / M202I / Y295F / A339S,
    5. (5) M9L / M202I / Y295F,
    6. (6) M9L / M202I / A339S,
    7. (7) M9L / M202I / Y295F / A339S,
    8. (8) M9L / M202I / Y295F / A339S / E345R,
    9. (9) M9L / G149A / M202I / Y295F / A339S / E345R,
    10. (10) M9L / M202L,
    11. (11) M9L / M202L / M323T,
    12. (12) M9L / M202L / M323T / M382Y,
    13. (13) M9L / M202L / Y295F / A339S,
    14. (14) M9L / M202L / Y295F,
    15. (15) M9L / M202L / A339S,
    16. (16) M9L / M202L / Y295F / A339S,
    17. (17) M9L / M202L / Y295F / A339S, E345R,
    18. (18) M9L / G149A / M202L / Y295F / A339S / E345R,
    19. (19) M9L / M202T,
    20. (20) M9L / M202T / M323T,
    21. (21) M9L / M202T / M323T / M382Y,
    22. (22) M9L / M202T / Y295F / A339S,
    23. (23) M9L / M202T / Y295F,
    24. (24) M9L / M202T / A339S,
    25. (25) M9L / M202T / Y295F / A339S,
    26. (26) M9L / M202T / Y295F / A339S / E345R,
    27. (27) M9L / G149A / M202T / Y295F / A339S / E345R,
    28. (28) M9L / G149A / M202I / V214T / Y295F / N299Y / M323T / A339S / E345R,
    29. (29) M9L / G149A / M202L / V214I / Y295F / M323T / A339S / E345R / M382Y,
    30. (30) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / A339S,
    31. (31) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R,
    32. (32) M9L / G149A / M202L / V214T / Y295F / N299Y / M323T / A339S / E345R,
    33. (33) M9L / G149A / M202I / V214I / Y295F / M323T / A339S / E345R / M382Y,
    34. (34) M9L / G149A / G182T / G186A / M202L / V214I / Y295F / N299Y / M323T / A339S,
    35. (35) M9L / G149A / G182T / G186A / M202I / T257I / Y295F / N299Y / M323T / A339S / E345R,
    36. (36) M9L / G149A / M202I / V214T / Y295F / N299Y / M323T / A339S / E345R / N471E,
    37. (37) M9L / G149A / M202L / V214I / Y295F / M323T / A339S / E345R / M382Y / N471E,
    38. (38) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / A339S / N471E,
    39. (39) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R / N471E,
    40. (40) M202L / M105F / M208F,
    41. (41) G133E / M202L / Q361E,
    42. (42) G133E / M202L / R444E,
    43. (43) M202L / Y295F,
    44. (44) M202L / A339S,
    45. (45) M202L / M323T,
    46. (46) M202L / M323T / M309L,
    47. (47) M202L / M323T / M430I,
    48. (48) M202L / V214T / R444Y,
    49. (49) M202L / N283D / Q361E,
    50. (50) M202L / M382Y / K383R,
    51. (51) M202L / K446R / N484Q,
    52. (52) M202I / Y295F,
    53. (53) M202I / A339S,
    54. (54) M202I / M105F / M208F,
    55. (55) G133E / M202I / Q361E,
    56. (56) G133E / M202I / R444E,
    57. (57) M202I / M323T,
    58. (58) M202I / M323T / M309L,
    59. (59) M202I / M323T / M430I,
    60. (60) M202I / V214T / R444Y,
    61. (61) M202I / N283D / Q361E,
    62. (62) M202I / M382Y / K383R,
    63. (63) M202I / K446R / N484Q,
    64. (64) M202V / M105F / M208F,
    65. (65) G133E / M202V / Q361E,
    66. (66) G133E / M202V / R444E,
    67. (67) M202V / M323T,
    68. (68) M202V / M323T / M309L,
    69. (69) M202V / M323T / M430I,
    70. (70) M202V / M323T / M9L,
    71. (71) M202V / V214T / R444Y,
    72. (72) M202V / N283D / Q361E,
    73. (73) M202V / M382Y / K383R,
    74. (74) M202V / K446R / N484Q,
    75. (75) M202T / M105F / M208F,
    76. (76) G133E / M202T / Q361E,
    77. (77) G133E / M202T / R444E,
    78. (78) M202T / Y295F,
    79. (79) M202T / A339S,
    80. (80) M202T / M323T,
    81. (81) M202T / M323T / M309L,
    82. (82) M202T / M323T / M430I,
    83. (83) M202T / M323T / M9L,
    84. (84) M202T / V214T / R444Y,
    85. (85) M202T / N283D / Q361E,
    86. (86) M202T / A339S,
    87. (87) M202T / Y295F
    88. (88) M202T / N299F, Y,
    89. (89) M202T / M382Y / K383R or
    90. (90) M202T / K446R / N484Q

    Of these, very particular preference is given to the following α-amylase variants:
    • (10) M9L / M202L,
    • (28) M9L / G149A / M202I / V214T / Y295F / N299Y / M323T / A339S / E345R,
    • (31) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R,
    • (35) M9L / G149A / G182T / G186A / M202I / T257I / Y295F / N299Y / M323T / (38) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / (39) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R / N471E,
    • (45) M202L / M323T,
    • (46) M202L / M323T / M309L,
    • (62) M202I / M382Y / K383R,
    • (68) M202V / M323T / M309L,
    • (73) M202V / M382Y / K383R
    • (82) M202T / M323T / M430I or
    • (84) M202T / V214T / R444Y
  3. (c) α-amylase variant according to (b), which additionally has all six sequence changes mentioned under (a), among these very particularly preferably variant 31 with the six sequence changes mentioned under (a).

Erfindungsgemäß ganz besonders bevorzugt ist die vorstehend unter (a) genannte α-Amylase-Variante sowie die unter (c) genannte α-Amylase-Variante 31 mit den sechs unter (a) genannten Sequenzveränderungen.Very particularly preferred according to the invention is the α-amylase variant mentioned above under (a) and the α-amylase variant 31 mentioned under (c) with the six sequence changes mentioned under (a).

Erfindungsgemäß bevorzugte flüssige Wasch- oder Reinigungsmittel enthalten, bezogen auf ihr Gesamtgewicht, zwischen 0,001 und 5,0 Gew.-%, vorzugsweise zwischen 0,01 und 4,0 Gew.-% und insbesondere zwischen 0,05 und 3,0 Gew.-% Amylase-Zubereitungen. Besonders bevorzugt werden flüssige Wasch- oder Reinigungsmittel, die bezogen auf ihr Gesamtgewicht zwischen 0,07 und 2,0 Gew.-% Amylase-Zubereitungen enthalten.Liquid detergents or cleaners preferred according to the invention contain, based on their total weight, between 0.001 and 5.0% by weight, preferably between 0.01 and 4.0% by weight and in particular between 0.05 and 3.0% by weight. -% amylase preparations. Particular preference is given to liquid washing or cleaning compositions which, based on their total weight, contain between 0.07 and 2.0% by weight of amylase preparations.

Erfindungsgemäß bevorzugte flüssige Reinigungsmittel enthalten, bezogen auf ihr Gesamtgewicht, zwischen 0,002 und 7,0 Gew.-%, vorzugsweise zwischen 0,02 und 6,0 Gew.-% und insbesondere zwischen 0,1 und 5,0 Gew.-% Protease-Zubereitungen. Besonders bevorzugt werden Reinigungsmittel, die bezogen auf ihr Gesamtgewicht zwischen 0,2 und 4,0 Gew.-% Protease-Zubereitungen enthalten.Liquid detergents preferred according to the invention contain, based on their total weight, between 0.002 and 7.0% by weight, preferably between 0.02 and 6.0% by weight, and in particular between 0.1 and 5.0% by weight of protease preparations. Particular preference is given to detergents which, based on their total weight, contain between 0.2 and 4.0% by weight of protease preparations.

Aus den bereits oben genannten Gründen werden wasch- oder reinigungsaktive Amylasen und Proteasen in der Regel nicht in Form des reinen Proteins, sondern vielmehr in Form stabilisierter, lager- und transportfähiger Zubereitungen bereitgestellt. Zu diesen vorkonfektionierten Zubereitungen zählen beispielsweise die durch Granulation, Extrusion oder Lyophilisierung erhaltenen festen Präparationen oder, insbesondere bei flüssigen oder gelförmigen Mitteln, Lösungen der Enzyme, welche vorteilhafterweise möglichst konzentriert, wasserarm und/oder mit Stabilisatoren oder weiteren Hilfsmitteln versetzt sind.For the reasons already mentioned above, washing or cleaning-active amylases and proteases are generally not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations. Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gelled agents, solutions of the enzymes which advantageously are concentrated, low in water and / or mixed with stabilizers or other auxiliaries.

Alternativ können die Enzyme sowohl für die feste als auch für die flüssige Darreichungsform verkapselt werden, beispielsweise durch Sprühtrocknung oder Extrusion der Enzymlösung zusammen mit einem vorzugsweise natürlichen Polymer oder in Form von Kapseln, beispielsweise solchen, bei denen die Enzyme wie in einem erstarrten Gel eingeschlossen sind oder in solchen vom Kern-Schale-Typ, bei dem ein enzymhaltiger Kern mit einer Wasser-, Luft- und/oder Chemikalien-undurchlässigen Schutzschicht überzogen ist. In aufgelagerten Schichten können zusätzlich weitere Wirkstoffe, beispielsweise Stabilisatoren, Emulgatoren, Pigmente, Bleich- oder Farbstoffe aufgebracht werden. Derartige Kapseln werden nach an sich bekannten Methoden, beispielsweise durch Schüttel- oder Rollgranulation oder in Fluid-bed-Prozessen aufgebracht. Vorteilhafterweise sind derartige Granulate, beispielsweise durch Aufbringen polymerer Filmbildner, staubarm und aufgrund der Beschichtung lagerstabil.Alternatively, 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. In deposited layers, 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. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

Weiterhin ist es möglich, zwei oder mehrere Enzyme zusammen zu konfektionieren, so dass ein einzelnes Granulat mehrere Enzymaktivitäten aufweist.Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.

Wie aus den vorherigen Ausführungen ersichtlich, bildet das Enzym-Protein nur einen Bruchteil des Gesamtgewichts üblicher Enzym-Zubereitungen. Erfindungsgemäß bevorzugt eingesetzte Protease- und/oder Amylase-Zubereitungen enthalten zwischen 0,1 und 40 Gew.-%, bevorzugt zwischen 0,2 und 30 Gew.-%, besonders bevorzugt zwischen 0,4 und 20 Gew.-% und insbesondere zwischen 0,8 und 10 Gew.-% des Enzymproteins, jeweils bezogen auf die Enzym-Zubereitung.As can be seen from the previous statements, 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.

Neben der Amylase und der gegebenenfalls vorhandenen Protease können die erfindungsgemäßen Mittel noch ein oder mehrere weitere wasch- oder reinigungsaktive Enzyme enthalten. Geeignet sind dabei insbesondere solche aus der Klasse der Hydrolasen wie der (Poly)Esterasen, Lipasen, Glykosylhydrolasen, Hemicellulasen, zu denen insbesondere Mannanasen, Xanthanlyasen, Pektinlyasen (=Pektinasen), Pektinesterasen, Pektatlyasen, Xyloglucanasen (=Xylanasen), Pullulanasen und β-Glucanasen gezählt werden, Cutinasen, β-Glucanasen, Oxidasen, Peroxidasen, Mannanasen, Perhydrolasen, Oxireduktasen und/oder Laccasen. Für weitere mögliche Enzyme und Enzym-Zubereitungen wird auf den einschlägigen Stand der Technik zu Wasch- oder Reinigungsmitteln verwiesen. Der Gewichtsanteil aller wasch- oder reinigungsaktiven Enzym-Zubereitungen am Gesamtgewicht des erfindungsgemäßen Mittels beträgt vorzugsweise zwischen 0,5 und 15 Gew.-%, bevorzugt zwischen 0,5 und 12 Gew.-%, besonders bevorzugt zwischen 0,6 und 10 Gew.-% und insbesondere zwischen 0,7 und 8 Gew.-%.In addition to the amylase and the optionally present protease, the compositions 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, glycosyl hydrolases, hemicellulases, in particular mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β- Glucanases, cutinases, β-glucanases, oxidases, peroxidases, mannanases, perhydrolases, Oxireduktasen and / or Laccases. For other possible enzymes and enzyme preparations, reference is made to the relevant state of the art for detergents or cleaning agents. 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 .-%.

In einer bevorzugten Ausführungsform der Erfindung handelt es sich bei dem erfindungsgemäßen Mittel um ein Reinigungsmittel für harte Oberflächen, insbesondere um ein flüssiges Reinigungsmittel für harte Oberflächen, beispielsweise um ein flüssiges maschinelles Geschirrspülmittel oder ein flüssiges manuelles Geschirrspülmittel oder einen Allzweckreiniger. Insbesondere bevorzugt ist ein Mittel, welches zur manuellen Geschirrreinigung eingesetzt wird. Ein derartiges Mittel enthält neben Calciumnitrat, vorteilhafterweise in den oben angegebenen Mengen, Amylase und gegebenenfalls ein oder mehrere weitere Enzyme, insbesondere Protease und/oder Lipase und/oder Mannanase und/oder Pektatlyase und/oder Cellulase. Mit besonderem Vorteil werden manuelle Geschirrspülmittel bereitgestellt, welche als Enzyme eine Kombination aus Amylase und Protease sowie gegebenenfalls weitere Enzyme enthält. Der Gewichtsanteil aller wasch- oder reinigungsaktiven Enzym-Zubereitungen am Gesamtgewicht des erfindungsgemäßen manuellen Geschirrspülmittels beträgt vorzugsweise zwischen 0,5 und 5 Gew.-%, bevorzugt zwischen 0,7 und 3 Gew.-%.In a preferred embodiment of the invention, the agent according to the invention is a hard surface cleaner, in particular a liquid hard surface cleaner, for example a liquid automatic dishwashing detergent or a liquid manual dishwashing detergent or an all-purpose cleaner. Particularly preferred is an agent which is used for manual dishwashing. Such an agent contains calcium nitrate, advantageously in the amounts indicated above, amylase and optionally one or more further enzymes, in particular protease and / or lipase and / or mannanase and / or pectate lyase and / or cellulase. With particular advantage, 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 .-%.

Die erfindungsgemäßen Mittel können als weitere Bestandteile weitere Tenside enthalten, vor allem anionische Tenside, nichtionische Tenside, amphotere Tenside, insbesondere weitere Betaine sowie kationische Tenside. Die Gesamtmenge der Tenside in den erfindungsgemäßen Mitteln kann in einem breiten Rahmen variieren und beispielsweise 5 bis 70 Gew.-%, vorzugsweise 10 bis 55 Gew.-% und insbesondere 15 bis 50 Gew.-% betragen.The compositions according to the invention may contain further surfactants as further constituents, in particular anionic surfactants, nonionic surfactants, amphoteric surfactants, in particular further betaines and also 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.

Die anionischen Tenside werden üblicherweise als Alkalimetall-, Erdalkalimetall- und/oder Mono-, Di- bzw. Trialkanolammoniumsalz und/oder aber auch in Form ihrer mit dem entsprechenden Alkalimetallhydroxid, Erdalkalimetallhydroxid und/oder Mono-, Di- bzw. Trialkanolamin in situ zu neutralisierenden korrespondierenden Säure eingesetzt. Bevorzugt sind hierbei als Alkalimetalle Kalium und insbesondere Natrium, als Erdalkalimetalle Calcium und insbesondere Magnesium, sowie als Alkanolamine Mono-, Di- oder Triethanolamin. Besonders bevorzugt sind die Natriumsalze. Selbst wenn in manuellen Geschirrspülmitteln Aniontenside in Form ihrer Calciumsalze eingesetzt werden, enthalten die Mittel erfindungsgemäß zusätzlich Calciumnitrat, vorzugsweise in den oben angegebenen Mengen.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. Preference is given here as alkali metals potassium and sodium in particular, as alkaline earth metals calcium and magnesium in particular, and as alkanolamines mono-, di- or triethanolamine. Particularly preferred are the sodium salts. Even if anionic surfactants in the form of their calcium salts are used in manual dishwashing detergents, the compositions additionally contain calcium nitrate according to the invention, preferably in the amounts indicated above.

Zu den insbesondere in manuellen Geschirrspülmitteln bevorzugt eingesetzten Aniontensiden zählen vor allem Alkylethersulfate und Alkylsulfonate.Particularly preferred anionic surfactants used in manual dishwashing detergents include alkyl ether sulfates and alkyl sulfonates.

Alkylethersulfate (Fettalkoholethersulfate, INCI Alkyl Ether Sulfates) sind Produkte von Sulfatierreaktionen an alkoxylierten Alkoholen. Dabei versteht der Fachmann allgemein unter alkoxylierten Alkoholen die Reaktionsprodukte von Alkylenoxid, bevorzugt Ethylenoxid, mit Alkoholen, im Sinne der vorliegenden Erfindung bevorzugt mit längerkettigen Alkoholen, d.h. mit aliphatischen geradkettigen oder ein oder mehrfach verzweigten, acyclischen oder cyclischen, gesättigten oder ein oder mehrfach ungesättigten, vorzugsweise geradkettigen, acyclischen, gesättigten, Alkoholen mit 6 bis 22, vorzugsweise 8 bis 18, insbesondere 10 bis 16 und besonders bevorzugt 12 bis 14 Kohlenstoffatomen. In der Regel entsteht aus n Molen Ethylenoxid und einem Mol Alkohol, abhängig von den Reaktionsbedingungen, ein komplexes Gemisch von Additionsprodukten unterschiedlicher Ethoxylierungsgrade (n = 1 bis 30, vorzugsweise 1 bis 20, insbesondere 1 bis 10, besonders bevorzugt 2 bis 4). Eine weitere Ausführungsform der Alkoxylierung besteht im Einsatz von Gemischen der Alkylenoxide, bevorzugt des Gemisches von Ethylenoxid und Propylenoxid. Ganz besonders bevorzugt im Sinne der vorliegenden Erfindung sind niederethoxylierte Fettalkohole mit 1 bis 4 Ethylenoxideinheiten (EO), insbesondere 1 bis 2 EO, beispielsweise 2 EO, wie Na-C12-14-Fettalkohol+2EO-sulfat.Alkyl ether sulfates (fatty alcohol ether sulfates, INCI alkyl ether sulfates) are products of sulfation reactions on alkoxylated alcohols. In this context, 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. In general, from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, a complex mixture of addition products of different degrees of ethoxylation (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 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.

Das erfindungsgemäße Mittel, insbesondere ein manuelles Geschirrspülmittel, enthält ein oder mehrere Alkylethersulfate, in einer bevorzugten Ausführungsform in einer Menge von 10 bis 40 Gew.-%, vorzugsweise 13 bis 35 Gew.-%, insbesondere 15 bis 30 Gew.-%.The composition according to the invention, in particular a manual dishwashing detergent, contains one or more alkyl ether sulfates, in a preferred embodiment in an amount of from 10 to 40% by weight, preferably from 13 to 35% by weight, in particular from 15 to 30% by weight.

Die Alkylsulfonate (INCI Sulfonic Acids) weisen üblicherweise einen aliphatischen geradkettigen oder ein- oder mehrfach verzweigten, acyclischen oder cyclischen, gesättigten oder ein- oder mehrfach ungesättigten, vorzugsweise verzweigten, acyclischen, gesättigten, Alkylrest mit 6 bis 22, vorzugsweise 9 bis 20, insbesondere 11 bis 18 und besonders bevorzugt 14 bis 17 Kohlenstoffatomen auf.The alkyl sulfonates (INCI sulfonic acids) 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.

Geeignete Alkylsulfonate sind dementsprechend die gesättigten Alkansulfonate, die ungesättigten Olefinsulfonate und die - sich formal von den auch den Alkylethersulfaten zugrunde liegenden alkoxylierten Alkoholen ableitenden - Ethersulfonate, bei denen man endständige Ethersulfonate (n-Ethersulfonate) mit an die Polyether-Kette gebundener Sulfonat-Funktion und innenständige Ethersulfonate (i-Ethersulfonate) mit mit dem Alkylrest verknüpfter Sulfonat-Funktion unterscheidet. Erfindungsgemäß bevorzugt sind die Alkansulfonate, insbesondere Alkansulfonate mit einem verzweigten, vorzugsweise sekundären, Alkylrest, beispielsweise das sekundäre Alkansulfonat sek. Na-C13-17-Alkansulfonat (INCI Sodium C14-17 Alkyl Sec Sulfonate).Accordingly, 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 ether sulfonates (i-ether sulfonates) with associated with the alkyl radical sulfonate function. Preference according to the invention is given to the 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).

Das erfindungsgemäße Mittel, insbesondere ein manuelles Geschirrspülmittel, enthält bevorzugt ein oder mehrere sekundäre Alkylsulfonate in einer Menge von üblicherweise 1 bis 15 Gew.-%, vorzugsweise 3 bis 10 Gew.-%, insbesondere 4 bis 8 Gew.-%.The composition according to the invention, in particular a manual dishwashing detergent, preferably contains one or more secondary alkyl sulfonates in an amount of usually 1 to 15% by weight, preferably 3 to 10% by weight, in particular 4 to 8% by weight.

Weitere mögliche einsetzbare Aniontenside sind dem Fachmann aus dem einschlägigen Stand der Technik zu Wasch- oder Reinigungsmitteln bekannt. Hierzu zählen insbesondere aliphatische Sulfate wie Fettalkoholsulfate, Monoglyceridsulfate sowie Estersulfonate (Sulfofettsäureester), Ligninsulfonate, Alkylbenzolsulfonate, Fettsäurecyanamide, anionische Sulfobernsteinsäuretenside, Fettsäureisethionate, Acylaminoalkansulfonate (Fettsäuretauride), Fettsäuresarcosinate, Ethercarbonsäuren und Alkyl(ether)phosphate.Further possible 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 sulfosuccinic acid surfactants, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.

Geeignete weitere anionische Tenside sind auch anionische Gemini-Tenside mit einer Diphenyloxid-Grundstruktur, 2 Sulfonatgruppen und einem Alkylrest an einem oder beiden Benzolringen gemäß der Formel -O3S(C6H3R)O(C6H3R')SO3 -, in der R für einen Alkylrest mit beispielsweise 6, 10, 12 oder 16 Kohlenstoffatomen und R' für R oder H steht (Dowfax® Dry Hydrotrope Powder mit C16-Alkylrest(en); INCI Sodium Hexyldiphenyl Ether Sulfonate, Disodium Decyl Phenyl Ether Disulfonate, Disodium Lauryl Phenyl Ether Disulfonate, Disodium Cetyl Phenyl Ether Disulfonate) und fluorierte anionische Tenside, insbesondere perfluorierte Alkylsulfonate wie Ammonium-C9/10-Perfluoroalkylsulfonat (Fluorad® FC 120) und Perfluoroctansulfonsäure-KaliumSalz (Fluorad® FC 95), wobei ein Gehalt an Fluorverbindungen in den erfindungsgemäßen Wasch-oder Reinigungsmitteln weniger bevorzugt ist.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 having, for example, 6, 10, 12 or 16 carbon atoms and R 'is R or H (Dowfax® Dry Hydrotropic Powder with C 16 -alkyl radical (s); INCI Sodium hexyldiphenyl ether sulfonate, disodium decyl Phenyl ether disulfonates, disodium lauryl phenyl ether disulfonates, disodium cetyl phenyl ether disulfonates) and fluorinated anionic surfactants, in particular perfluorinated alkyl sulfonates such as ammonium C 9/10 perfluoroalkylsulfonate (Fluorad® FC 120) and perfluorooctanesulfonic acid potassium salt (Fluorad® FC 95), wherein a content of fluorine compounds in the washing or cleaning agents according to the invention is less preferred.

Besonders bevorzugte weitere anionische Tenside sind die anionischen Sulfobernsteinsäuretenside Sulfosuccinate, Sulfosuccinamate und Sulfosuccinamide, insbesondere Sulfosuccinate und Sulfosuccinamate, äußerst bevorzugt Sulfosuccinate. Bei den Sulfosuccinaten handelt es sich um die Salze der Mono- und Diester der Sulfobernsteinsäure HOOCCH(SO3H)CH2COOH, während man unter den Sulfosuccinamaten die Salze der Monoamide der Sulfobernsteinsäure und unter den Sulfosuccinamiden die Salze der Diamide der Sulfobernsteinsäure versteht. Bei den Salzen handelt es sich bevorzugt um Alkalimetallsalze, Ammoniumsalze sowie Mono-, Di- bzw. Trialkanolammoniumsalze, beispielsweise Mono-, Di- bzw. Triethanolammoniumsalze, insbesondere um Lithium-, Natrium-, Kalium- oder Ammoniumsalze, besonders bevorzugt Natrium-oder Ammoniumsalze, äußerst bevorzugt Natriumsalze.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 monoesters and diesters of sulfosuccinic acid 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.

In den Sulfosuccinaten ist eine bzw. sind beide Carboxylgruppen der Sulfobernsteinsäure vorzugsweise mit einem bzw. zwei gleichen oder verschiedenen unverzweigten oder verzweigten, gesättigten oder ungesättigten, acyclischen oder cyclischen, optional alkoxylierten Alkoholen mit 4 bis 22, vorzugsweise 6 bis 20, insbesondere 8 bis 18, besonders bevorzugt 10 bis 16, äußerst bevorzugt 12 bis 14 Kohlenstoffatomen verestert. Besonders bevorzugt sind die Ester unverzweigter und/oder gesättigter und/oder acyclischer und/oder alkoxylierter Alkohole, insbesondere unverzweigter, gesättigter Fettalkohole und/oder unverzweigter, gesättigter, mit Ethylen-und/oder Propylenoxid, vorzugsweise Ethylenoxid, alkoxylierter Fettalkohole mit einem Alkoxylierungsgrad von 1 bis 20, vorzugsweise 1 bis 15, insbesondere 1 bis 10, besonders bevorzugt 1 bis 6, äußerst bevorzugt 1 bis 4. Die Monoester werden im Rahmen der vorliegenden Erfindung gegenüber den Diestern bevorzugt. Ein besonders bevorzugtes Sulfosuccinat ist Sulfobernsteinsäurelaurylpolyglykolester-di-Natrium-Salz (Lauryl-EO-sulfosuccinat, Di-Na-Salz; INCI Disodium Laureth Sulfosuccinate), das beispielsweise als Tego® Sulfosuccinat F 30 (Goldschmidt) mit einem Sulfosuccinatgehalt von 30 Gew.-% kommerziell erhältlich ist.
In den Sulfosuccinamaten bzw. Sulfosuccinamiden bildet eine bzw. bilden beide Carboxylgruppen der Sulfobernsteinsäure vorzugsweise mit einem primären oder sekundären Amin, das einen oder zwei gleiche oder verschiedene, unverzweigte oder verzweigte, gesättigte oder ungesättigte, acyclische oder cyclische, optional alkoxylierte Alkylreste mit 4 bis 22, vorzugsweise 6 bis 20, insbesondere 8 bis 18, besonders bevorzugt 10 bis 16, äußerst bevorzugt 12 bis 14 Kohlenstoffatomen trägt, ein Carbonsäureamid. Besonders bevorzugt sind unverzweigte und/oder gesättigte und/oder acyclische Alkylreste, insbesondere unverzweigte, gesättigte Fettalkylreste.In the sulfosuccinates, 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. Particularly preferred are the 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 commercially available, for example, as Tego® sulfosuccinate F 30 (Goldschmidt) having a sulfosuccinate content of 30% by weight.
In the sulfosuccinamates or sulfosuccinamides, 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.

In einer besonderen Ausführungsform enthält das erfindungsgemäße Mittel als anionische Sulfobernsteinsäuretenside ein oder mehrere Sulfosuccinate, Sulfosuccinamate und/oder Sulfosuccinamide, vorzugsweise Sulfosuccinate und/oder Sulfosuccinamate, insbesondere Sulfosuccinate, in einer Menge von üblicherweise 0,001 bis 5 Gew.-%, vorzugsweise 0,01 bis 4 Gew.-%, insbesondere 0,1 bis 3 Gew.-%, besonders bevorzugt 0,2 bis 2 Gew.-%, äußerst bevorzugt 0,5 bis 1,5 Gew.-%, beispielsweise 1 Gew.-%.In a particular embodiment, 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 .-%.

Zu den Amphotensiden (amphoteren Tensiden, zwitterionischen Tensiden), die erfindungsgemäß eingesetzt werden können, zählen Alkylamidoalkylamine, alkylsubstituierte Aminosäuren, acylierte Aminosäuren bzw. Biotenside, und insbesondere die erfindungsgemäß eingesetzten Betaine.The 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, and in particular the betaines used according to the invention.

Geeignete Betaine, welche vor allem in manuellen Geschirrspülmitteln Einsatz finden, sind die Alkylbetaine, die Alkylamidobetaine, die Imidazoliniumbetaine, die Sulfobetaine (INCI Sultaines) sowie die Phosphobetaine und genügen vorzugsweise Formel I,

        R1-[CO-X-(CH2)n]x-N+(R2)(R3)-(CH2)m-[CH(OH)-CH2]y-Y-     (I)

in der

R1
ein gesättigter oder ungesättigter C6-22-Alkylrest, vorzugsweise C8-18-Alkylrest, insbesondere ein gesättigter C10-16-Alkylrest, beispielsweise ein gesättigter C12-14-Alkylrest,
X
NH, NR4 mit dem C1-4-Alkylrest R4, O oder S,
n
eine Zahl von 1 bis 10, vorzugsweise 2 bis 5, insbesondere 3,
x
0 oder 1, vorzugsweise 1,
R2, R3
unabhängig voneinander ein C1-4-Alkylrest, ggf. hydroxysubstituiert wie z.B. ein Hydroxyethylrest, insbesondere aber ein Methylrest,
m
eine Zahl von 1 bis 4, insbesondere 1, 2 oder 3,
y
0 oder 1 und
Y
COO, SO3, OPO(OR5)O oder P(O)(OR5)O, wobei R5 ein Wasserstoffatom H oder ein C1-4-Alkylrest ist.
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 1 - [CO-X- (CH 2 ) n ] x -N + (R 2 ) (R 3 ) - (CH 2 ) m - [CH (OH) -CH 2 ] y -Y- (I)

in the
R 1
a saturated or unsaturated C 6-22 alkyl, preferably C 8-18 alkyl group, preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group,
X
NH, NR 4 with the C 1-4 -alkyl radical R 4 , O or S,
n
a number from 1 to 10, preferably 2 to 5, in particular 3,
x
0 or 1, preferably 1,
R 2 , R 3
independently of one another represent a C 1-4 -alkyl radical, if appropriate hydroxy-substituted, for example a hydroxyethyl radical, but in particular a methyl radical,
m
a number from 1 to 4, in particular 1, 2 or 3,
y
0 or 1 and
Y
COO, SO 3 , OPO (OR 5 ) O or P (O) (OR 5 ) O, wherein R 5 is hydrogen H or C 1-4 alkyl.

Die Alkyl- und Alkylamidobetaine, Betaine der Formel I mit einer Carboxylatgruppe (Y- = COO-), heißen auch Carbobetaine.
Bevorzugte Betaine sind die Alkylbetaine der Formel (la), die Alkylamidobetaine der Formel (Ib), die Sulfobetaine der Formel (Ic) und die Amidosulfobetaine der Formel (Id),

        R1-N+(CH3)2-CH2COO-     (Ia)

        R1-CO-NH-(CH2)3-N+(CH3)2-CH2COO-     (Ib)

        R1-N+(CH3)2-CH2CH(OH)CH2SO3 -     (Ic)

        R1-CO-NH-(CH2)3-N+(C H3)2-CH2CH(OH)CH2SO3 -     (Id)

in denen R1 die gleiche Bedeutung wie in Formel I hat.The alkyl and alkylamido betaines, betaines of the formula I having a carboxylate group (Y = COO-) 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),

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.

Besonders bevorzugte Betaine sind die Carbobetaine, insbesondere die Carbobetaine der Formel (Ia) und (Ib), äußerst bevorzugt die Alkylamidobetaine der Formel (Ib).Particularly preferred 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).

Ein bevorzugtes Betain ist beispielsweise Cocamidopropyl Betaine (Cocoamidopropylbetain).A preferred betaine is, for example, cocamidopropyl betaine (cocoamidopropylbetaine).

Das erfindungsgemäße Mittel enthält ein oder mehrere Betaine in einer Menge von üblicherweise 1 bis 15 Gew.-%, vorzugsweise 3 bis 10 Gew.-%, insbesondere 4 bis 8 Gew.-%.
Die im erfindungsgemäßen Mittel enthaltenen Tenside a) Alkylethersulfat, b) sekundäres Alkansulfonat und c) Betain, sind vorzugsweise in einem Verhältnis a) : b) : c) von 5:2:1 bis 3:1:1 vorhanden.The agent of the invention contains one or more betaines in an amount of usually 1 to 15 wt .-%, preferably 3 to 10 wt .-%, in particular 4 to 8 wt .-%.
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.

Die Alkylamidoalkylamine (INCI Alkylamido Alkylamines) sind Amphotenside der Formel (III),

        R9-CO-NR10-(CH2)i-N(R11)-(CH2CH2O)j-(CH2)k-[CH(OH)]l-CH2-Z-OM     (III)

in der

R9
ein gesättiger oder ungesättigter C6-22-Alkylrest, vorzugsweise C8-18-Alkylrest, insbesondere ein gesättigter C10-16-Alkylrest, beispielsweise ein gesättigter C12-14-Alkylrest,
R10
ein Wasserstoffatom H oder ein C1-4-Alkylrest, vorzugsweise H,
i
eine Zahl von 1 bis 10, vorzugsweise 2 bis 5, insbesondere 2 oder 3,
R11
ein Wasserstoffatom H oder CH2COOM (zu M s.u.),
j
eine Zahl von 1 bis 4, vorzugsweise 1 oder 2, insbesondere 1,
k
eine Zahl von 0 bis 4, vorzugsweise 0 oder 1,
l
0 oder 1, wobei k = 1 ist, wenn l = 1 ist,
Z
CO, SO2, OPO(OR12) oder P(O)(OR12), wobei R12 ein C1-4-Alkylrest oder M (s.u.) ist, und
M
ein Wasserstoff, ein Alkalimetall, ein Erdalkalimetall oder ein protoniertes Alkanolamin, z.B. protoniertes Mono-, Di- oder Triethanolamin, ist.
The alkylamidoalkylamines (INCI alkylamido alkylamines) are amphoteric surfactants of the formula (III)

R 9 -CO-NR 10 - (CH 2 ) i -N (R 11 ) - (CH 2 CH 2 O) j - (CH 2 ) k - [CH (OH)] l -CH 2 -Z-OM ( III)

in the
R 9
a saturated or unsaturated C 6-22 alkyl, preferably C 8-18 alkyl group, preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group,
R 10
a hydrogen atom H or a C 1-4 -alkyl radical, preferably H,
i
a number from 1 to 10, preferably 2 to 5, in particular 2 or 3,
R 11
a hydrogen atom H or CH 2 COOM (to M su),
j
a number from 1 to 4, preferably 1 or 2, in particular 1,
k
a number from 0 to 4, preferably 0 or 1,
l
0 or 1, where k = 1 when l = 1,
Z
CO, SO 2 , OPO (OR 12 ) or P (O) (OR 12 ), wherein R 12 is a C 1-4 alkyl radical or M (su), and
M
a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine.

Bevorzugte Vertreter genügen den Formeln IIIa bis IIId,

        R9-CO-NH-(CH2)2-N(R11)-CH2CH2O-CH2-COOM     (IIIa)

        R9-CO-NH-(CH2)2-N(R11)-CH2CH2O-CH2CH2-COOM     (IIIb)

        R9-CO-NH-(CH2)2-N(R11)-CH2CH2O-CH2CH(OH)CH2-SO3M     (IIIc)

        R9-CO-NH-(CH2)2-N(R11)-CH2CH2O-CH2CH(OH)CH2-OPO3HM     (IIId)

in denen R11 und M die gleiche Bedeutung wie in Formel (III) haben.Preferred representatives satisfy the formulas IIIa to IIId,

R 9 -CO-NH- (CH 2 ) 2 -N (R 11 ) -CH 2 CH 2 O-CH 2 -COOM (IIIa)

R 9 -CO-NH- (CH 2 ) 2 -N (R 11 ) -CH 2 CH 2 O-CH 2 CH 2 -COOM (IIIb)

R 9 -CO-NH- (CH 2 ) 2 -N (R 11 ) -CH 2 CH 2 O-CH 2 CH (OH) CH 2 -SO 3 M (IIIc)

R 9 -CO-NH- (CH 2 ) 2 -N (R 11 ) -CH 2 CH 2 O-CH 2 CH (OH) CH 2 -OPO 3 HM (IIId)

in which R 11 and M have the same meaning as in formula (III).

Erfindungsgemäß bevorzugte alkylsubstituierte Aminosäuren (INCI Alkyl-Substituted Amino Acids) sind monoalkylsubstituierte Aminosäuren gemäß Formel (IV),

        R13-NH-CH(R14)-(CH2)u-COOM'     (IV)

in der

R13
ein gesättiger oder ungesättigter C6-22-Alkylrest, vorzugsweise C8-18-Alkylrest, insbesondere ein gesättigter C10-16-Alkylrest, beispielsweise ein gesättigter C12-14-Alkylrest,
R14
ein Wasserstoffatom H oder ein C1-4-Alkylrest, vorzugsweise H,
u
eine Zahl von 0 bis 4, vorzugsweise 0 oder 1, insbesondere 1, und
M'
ein Wasserstoff, ein Alkalimetall, ein Erdalkalimetall oder ein protoniertes Alkanolamin, z.B. protoniertes Mono-, Di- oder Triethanolamin, ist,
alkylsubstituierte Iminosäuren gemäß Formel (V),

        R15-N-[(CH2)v-COOM"]2     (V)

in der
R15
ein gesättiger oder ungesättigter C6-22-Alkylrest, vorzugsweise C8-18-Alkylrest, insbesondere ein gesättigter C10-16-Alkylrest, beispielsweise ein gesättigter C12-14-Alkylrest,
v
eine Zahl von 1 bis 5, vorzugsweise 2 oder 3, insbesondere 2, und
M"
ein Wasserstoff, ein Alkalimetall, ein Erdalkalimetall oder ein protoniertes Alkanolamin, z.B. protoniertes Mono-, Di- oder Triethanolamin, wobei M" in den beiden Carboxygruppen die gleiche oder zwei verschiedene Bedeutungen haben kann, z.B. Wasserstoff und Natrium oder zweimal Natrium sein kann, ist,
und mono- oder dialkylsubstituierte natürliche Aminosäuren gemäß Formel (VI),

        R16-N(R17)-CH(R18)-COOM'"     (VI)

in der
R16
ein gesättiger oder ungesättigter C6-22-Alkylrest, vorzugsweise C8-18-Alkylrest, insbesondere ein gesättigter C10-16-Alkylrest, beispielsweise ein gesättigter C12-14-Alkylrest,
R17
ein Wasserstoffatom oder ein C1-4-Alkylrest, ggf. hydroxy- oder aminsubstituiert, z.B. ein Methyl-, Ethyl-, Hydroxyethyl- oder Aminpropylrest,
R18
den Rest einer der 20 natürlichen α-Aminosäuren H2NCH(R18)COOH, und
M'"
ein Wasserstoff, ein Alkalimetall, ein Erdalkalimetall oder ein protoniertes Alkanolamin, z.B. protoniertes Mono-, Di- oder Triethanolamin, ist.
Preferred alkyl-substituted amino acids (INCI alkyl-substituted amino acids) according to the invention are monoalkyl-substituted amino acids according to formula (IV),

R 13 -NH-CH (R 14 ) - (CH 2 ) u -COOM '(IV)

in the
R 13
a saturated or unsaturated C 6-22 alkyl, preferably C 8-18 alkyl group, preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group,
R 14
a hydrogen atom H or a C 1-4 -alkyl radical, preferably H,
u
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 alkanolamine, for example protonated mono-, di- or triethanolamine,
alkyl-substituted imino acids according to formula (V),

R 15 -N - [(CH 2 ) v -COOM "] 2 (V)

in the
R 15
a saturated or unsaturated C 6-22 alkyl, preferably C 8-18 alkyl group, preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group,
v
a number from 1 to 5, preferably 2 or 3, in particular 2, and
M "
a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine, where M "may have the same or two different meanings in the two carboxy groups, for example hydrogen and sodium or may be twice sodium .
and mono- or dialkyl-substituted natural amino acids according to formula (VI),

R 16 -N (R 17 ) -CH (R 18 ) -COOM '"(VI)

in the
R 16
a saturated or unsaturated C 6-22 alkyl, preferably C 8-18 alkyl group, preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group,
R 17
is a hydrogen atom or a C 1-4 -alkyl radical, optionally hydroxyl- or amine-substituted, for example a methyl, ethyl, hydroxyethyl or aminopropyl radical,
R 18
the remainder of one of the 20 natural α-amino acids H 2 NCH (R 18 ) COOH, and
M '"
a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine.

Besonders bevorzugte alkylsubstituierte Aminosäuren sind die Aminopropionate gemäß Formel (IVa),

        R13-NH-CH2CH2COOM'     (IVa)

in der R13 und M' die gleiche Bedeutung wie in Formel (IV) haben.Particularly preferred 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).

Acylierte Aminosäuren sind Aminosäuren, insbesondere die 20 natürlichen α-Aminosäuren, die am Aminostickstoffatom den Acylrest R19CO einer gesättigten oder ungesättigen Fettsäure R19COOH tragen, wobei R19 ein gesättiger oder ungesättigter C6-22-Alkylrest, vorzugsweise C8-18-Alkylrest, insbesondere ein gesättigter C10-16-Alkylrest, beispielsweise ein gesättigter C12-14-Alkylrest ist. Die acylierten Aminosäuren können auch als Alkalimetallsalz, Erdalkalimetallsalz oder Alkanolammoniumsalz, z.B. Mono-, Di- oder Triethanolammoniumsalz, eingesetzt werden. Beispielhafte acylierte Aminosäuren sind die gemäß INCI unter Amino Acids zusammengefassten Acylderivate, z.B. Sodium Cocoyl Glutamate, Lauroyl Glutamic Acid, Capryloyl Glycine oder Myristoyl Methylalanine.Acylated amino acids are amino acids, in particular the 20 natural α-amino acids which carry on the amino nitrogen 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, in particular a saturated C 10-16 alkyl radical, for example a saturated C 12-14 alkyl radical. 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. Exemplary 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.

In einer besonderen Ausführungsform der Erfindung wird eine Kombination aus zwei oder mehr verschiedenen Amphotensiden, insbesondere eine binäre Amphotensidkombination eingesetzt. Die Amphotensidkombination enthält mindestens ein Betain, vorzugsweise mindestens ein Alkylamidobetain, besonders bevorzugt Cocoamidopropylbetain.In a particular embodiment of the invention, a combination of two or more different amphoteric surfactants, in particular a binary Amphotensidkombination is used. The amphoteric surfactant combination contains at least one betaine, preferably at least one alkylamidobetaine, more preferably cocoamidopropylbetaine.

Weiterhin enthält die Amphotensidkombination vorzugsweise mindestens ein amphoteres Tensid aus der Gruppe umfassend Natriumcarboxyethylkokosphosphoethylimidazolin (Phosphoteric® TC-6), C8/10-Amidopropylbetain (INCI Capryl/Capramidopropyl Betaine; Tego® Betaine 810), N-2-Hydroxyethyl-N-carboxymethyl-fettsäureamido-ethylamin-Na (Rewoteric® AMV) und N-Capryl/Caprin-amidoethyl-N-ethylether-propionat-Na (Rewoteric® AMVSF) sowie das Betain 3-(3-Cocoamido-propyl)-dimethylammonium-2-hydroxypropansulfonat (INCI Sultaine; Rewoteric® AM CAS) und das Alkylamidoalkylamin N-[N'(N"-2-Hydroxyethyl-N"-carboxyethylaminoethyl)-essigsäureamido]-N,N-dimethyl-N-cocos-ammoniumbetain (Rewoteric® QAM 50), insbesondere zusammen mit Cocoamidopropylbetain.
In einer weiteren besonderen Ausführungsform enthält das erfindungsgemäße Mittel ein oder mehrere Amphotenside in einer Menge von mehr als 8 Gew.-%. In noch einer weiteren besonderen Ausführungsform enthält das erfindungsgemäße Mittel ein oder mehrere Amphotenside in einer Menge von weniger als 2 Gew.-%.Furthermore, the amphoteric surfactant combination preferably contains at least one amphoteric surfactant from the group comprising sodium carboxyethyl cocosphoethyl imidazoline (Phosphoteric® TC-6), C 8/10 amidopropyl betaine (INCI Capryl / Capramidopropyl Betaine, Tego® Betaine 810), N-2-hydroxyethyl-N-carboxymethyl fatty acid amido-ethylamine-Na (Rewoteric® AMV) and N-capryl / caprin-amidoethyl-N-ethyl ether-propionate-Na (Rewoteric® AMVSF) and the betaine 3- (3-cocoamido-propyl) -dimethylammonium-2-hydroxypropanesulfonate (INCI Sultaine; Rewoteric® AM CAS) and the alkylamidoalkylamine N- [N '(N "-2-hydroxyethyl-N" -carboxyethylaminoethyl) -acetic acid amido] -N, N-dimethyl-N-coco-ammoniumbetaine (Rewoteric® QAM 50 ), in particular together with cocoamidopropylbetaine.
In a further particular embodiment, 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.

Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, zum Beispiel aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-14-Alkohole mit 3 EO, 4 EO oder 7 EO, C9-11-Alkohol mit 7 EO, C13-15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-14-Alkohol mit 3 EO und C12-18-Alkohol mit 7 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO. Auch nichtionische Tenside, die EO- und PO-Gruppen zusammen im Molekül enthalten, sind erfindungsgemäß einsetzbar. Insbesondere bevorzugt enthält das Reinigungsmittel für harte Oberflächen einen C12-18-Fettalkohol mit 7 EO oder einen C13-15-Oxoalkohol mit 7 EO als nichtionisches Tensid.
Der Gehalt an nichtionischen Tensiden beträgt in dem Reinigungsmittel bevorzugt 1 bis 30 Gew.-% und vorzugsweise 2 bis 25 Gew.-%, jeweils bezogen auf das gesamte Reinigungsmittel.As nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 Mol used ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, 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. The preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO, 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, 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. More preferably, the hard surface cleaner contains a C 12-18 fatty alcohol with 7 EO or a C 13-15 oxo alcohol with 7 EO as the nonionic surfactant.
The content of nonionic surfactants in the cleaning agent is preferably 1 to 30% by weight and preferably 2 to 25% by weight, in each case based on the total cleaning agent.

Diese nichtionische Tenside weisen in Kombination mit einem Aminoxid eine gute Reinigungsleistung an Fett-verschmutzten harten Oberflächen, wie beispielsweise Geschirr, auf.These nonionic surfactants in combination with an amine oxide have good cleaning performance on grease-soiled hard surfaces such as dishes.

Nichtionische Tenside im Rahmen der Erfindung sind Alkoxylate aber auch Alkylphenolpolyglykolether, endgruppenverschlossene Polyglykolether, Mischether und Hydroxymischether und Fettsäurepolyglykolester. Ebenfalls geeignet sind Blockpolymere aus Ethylenoxid und Propylenoxid sowie Fettsäurealkanolamide und Fettsäurepolyglykolether. Wichtige Klassen erfindungsgemäßer nichtionischer Tenside sind weiterhin die Aminoxide und die Zuckertenside, insbesondere die Alkylpolyglucoside.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 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.

Zu den erfindungsgemäß geeigneten Aminoxiden gehören Alkylaminoxide, insbesondere Alkyldimethylaminoxide, Alkylamidoaminoxide und Alkoxyalkylaminoxide. Bevorzugte Aminoxide genügen Formel II,

        R6R7R8N+-O-     (II)

        R6-[CO-NH-(CH2)w]z-N+(R7)(R8)-O-     (II)

in der

R6
ein gesättiger oder ungesättigter C6-22-Alkylrest, vorzugsweise C8-18-Alkylrest, insbesondere ein gesättigter C10-16-Alkylrest, beispielsweise ein gesättigter C12-14-Alkylrest, der in den Alkylamidoaminoxiden über eine Carbonylamidoalkylengruppe -CO-NH-(CH2)z- und in den Alkoxyalkylaminoxiden über eine Oxaalkylengruppe -O-(CH2)z- an das Stickstoffatom N gebunden ist, wobei z jeweils für eine Zahl von 1 bis 10, vorzugsweise 2 bis 5, insbesondere 3,
R7, R8
unabhängig voneinander ein C1-4-Alkylrest, ggf. hydroxysubstituiert wie z.B. ein Hydroxyethylrest, insbesondere ein Methylrest, ist.
The amine oxides suitable in accordance with the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides. Preferred amine oxides satisfy formula II,

R 6 R 7 R 8 N + -O - (II)

R 6 - [CO-NH- (CH 2 ) w ] z -N + (R 7 ) (R 8 ) -O - (II)

in the
R 6
a saturated or unsaturated C 6-22 alkyl, preferably C 8-18 alkyl group, preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group, in the alkylamidoamine oxides over a carbonylamidoalkylene -CO-NH - (CH 2 ) z - and in the alkoxyalkylamine oxides via an oxaalkylene group -O- (CH 2 ) z - is bonded to the nitrogen atom N, where z is in each case a number from 1 to 10, preferably 2 to 5, in particular 3,
R 7 , R 8
independently of one another a C 1-4 -alkyl radical, if appropriate hydroxy-substituted, for example a hydroxyethyl radical, in particular a methyl radical.

Bevorzugte Aminoxide sind beispielsweise Cocamidopropylamine Oxide (Cocoamidopropylaminoxid), aber auch N-Kokosalkyl-N,N-dimethylaminoxid, N-Talgalkyl-N,N-dihydroxyethylaminoxid, Myristylcetyldimethylaminoxid oder Lauryldimethylaminoxid.Preferred amine oxides are, for example, cocamidopropylamine oxides (cocoamidopropylamine oxide), but also N-cocoalkyl-N, N-dimethylamine oxide, N-tallowkyl-N, N-dihydroxyethylamine oxide, myristylcetyldimethylamine oxide or lauryldimethylamine oxide.

Der Gehalt an Aminoxid beträgt in dem Reinigungsmittel bevorzugt 1 bis 15 Gew.-% und vorzugsweise 2 bis 10 Gew.-%, jeweils bezogen auf das gesamte Reinigungsmittel.The content of amine oxide in the cleaning agent is preferably 1 to 15% by weight and preferably 2 to 10% by weight, in each case based on the total cleaning agent.

Zuckertenside sind bekannte oberflächenaktive Verbindungen, zu denen beispielsweise die Zuckertensidklassen der Alkylglucoseester, Aldobionamide, Gluconamide (Zuckersäureamide), Glycerinamide, Glyceringlykolipide, Polyhydroxyfettsäureamidzuckertenside (Zuckeramide) und Alkylpolyglykoside zählen. Im Rahmen der erfindungsgemäßen Lehre bevorzugte Zuckertenside sind die Alkylpolyglykoside und die Zuckeramide sowie deren Derivate, insbesondere ihre Ether und Ester. Bei den Ethern handelt es sich um die Produkte der Reaktion einer oder mehrerer, vorzugsweise einer, Zuckerhydroxygruppe mit einer eine oder mehrere Hydroxygruppen enthaltenden Verbindung, beispielsweise C1-22-Alkoholen oder Glykolen wie Ethylen- und/oder Propylenglykol, wobei die Zuckerhydroxygruppe auch Polyethylenglykol- und/oder Polypropylenglykolreste tragen kann. Die Ester sind die Reaktionsprodukte einer oder mehrerer, vorzugsweise einer, Zuckerhydroxygruppe mit einer Carbonsäure, insbesondere einer C6-22-Fettsäure.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.

Besonders bevorzugte Zuckeramide genügen der Formel R'C(O)N(R")[Z], in der R' für einen linearen oder verzweigten, gesättigten oder ungesättigten Acylrest, vorzugsweise einen linearen ungesättigten Acylrest, mit 5 bis 21, vorzugsweise 5 bis 17, insbesondere 7 bis 15, besonders bevorzugt 7 bis 13 Kohlenstoffatomen, R" für einen linearen oder verzweigten, gesättigten oder ungesättigten Alkylrest, vorzugsweise einen linearen ungesättigten Alkylrest, mit 6 bis 22, vorzugsweise 6 bis 18, insbesondere 8 bis 16, besonders bevorzugt 8 bis 14 Kohlenstoffatomen, einen C1-5-Alkylrest, insbesondere einen Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, tert-Butyl- oder n-Pentylrest, oder Wasserstoff und Z für einen Zuckerrest, d.h. einen Monosaccharidrest, stehen. Besonders bevorzugte Zuckeramide sind die Amide der Glucose, die Glucamide, beispielsweise Lauroyl-methyl-glucamid.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 example lauroyl-methyl-glucamide.

Die Alkylpolyglykoside (APG) sind im Rahmen der erfindungsgemäßen Lehre besonders bevorzugte Zuckertenside und genügen vorzugsweise der allgemeinen Formel RiO(AO)a[G]x, in der Ri für einen linearen oder verzweigten, gesättigten oder ungesättigten Alkylrest mit 6 bis 22, vorzugsweise 6 bis 18, insbesondere 8 bis 16, besonders bevorzugt 8 bis 14 Kohlenstoffatomen, [G] für einen glykosidisch verknüpften Zuckerrest und x für eine Zahl von 1 bis 10 sowie AO für eine Alkylenoxygruppe, z.B. eine Ethylenoxy- oder Propylenoxygruppe, und a für den mittleren Alkoxylierungsgrad von 0 bis 20 stehen. Hierbei kann die Gruppe (AO)a auch verschiedene Alkylenoxyeinheiten enthalten, z.B. Ethylenoxy- oder Propylenoxyeinheiten, wobei es sich dann bei a um den mittleren Gesamtalkoxylierungsgrad, d.h. die Summe aus Ethoxylierungs- und Propoxylierungsgrad, handelt. Soweit nachfolgend nicht näher bzw. anders ausgeführt, handelt es sich bei den Alkylresten Ri der APG um lineare ungesättigte Reste mit der angegebenen Zahl an Kohlenstoffatomen.The alkylpolyglycosides (APG) 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 Propylenoxygruppe, and a for the average degree of alkoxylation of 0 to 20. In this case, 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. Unless stated below or otherwise, the alkyl radicals R i of the APG are linear unsaturated radicals having the stated number of carbon atoms.

APG sind nichtionische Tenside und stellen bekannte Stoffe dar, die nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden können. Die Indexzahl x gibt den Oligomerisierungsgrad (DP-Grad) an, d.h. die Verteilung von Mono- und Oligoglykosiden, und steht für eine Zahl zwischen 1 und 10. Während x in einer gegebenen Verbindung stets ganzzahlig sein muss und hier vor allem die Werte x = 1 bis 6 annehmen kann, ist der Wert x für ein bestimmtes Alkylglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkylglykoside mit einem mittleren Oligomerisierungsgrad x von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkylglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,6 liegt. Als glykosidischer Zucker wird vorzugsweise Xylose, insbesondere aber Glucose verwendet.APG are nonionic surfactants and are known substances that can be obtained by the relevant methods of preparative organic chemistry. The index number x indicates the degree of oligomerization (DP degree), i. the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While x in a given compound always has to be an integer, and above all can assume the values x = 1 to 6, the value x is for a specific alkyl glycoside an analytically determined arithmetical variable, which usually represents a fractional number. Preferably, 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.

Der Alkyl- bzw. Alkenylrest Ri kann sich von primären Alkoholen mit 8 bis 18, vorzugsweise 8 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Gemische, wie sie beispielsweise im Verlauf der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der ROELENschen Oxosynthese anfallen.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.

Vorzugsweise leitet sich der Alkyl- bzw. Alkenylrest Ri aber von Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol oder Oleylalkohol ab. Weiterhin sind Elaidylalkohol, Petroselinylalkohol, Arachidylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol sowie deren technische Gemische zu nennen.Preferably, however, 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.

Besonders bevorzugte APG sind nicht alkoxyliert (a = 0) und genügen Formel RO[G]x, in der R wie zuvor für einen linearen oder verzweigten, gesättigten oder ungesättigten Alkylrest mit 4 bis 22 Kohlenstoffatomen, [G] für einen glykosidisch verknüpften Zuckerrest, vorzugsweise Glucoserest, und x für eine Zahl von 1 bis 10, bevorzugt 1,1 bis 3, insbesondere 1,2 bis 1,6, stehen. Dementsprechend bevorzugte Alkylpolyglykoside sind beispielsweise C8-10- und ein C12-14-Alkyl-polyglucosid mit einem DP-Grad von 1,4 oder 1,5, insbesondere C8-10- Alkyl-1,5-glucosid und C12-14-Alkyl-1,4-glucosid.Particularly preferred APG are not alkoxylated (a = 0) and satisfy the formula RO [G] x , in which R is as previously described for a linear or branched, saturated or unsaturated alkyl radical having 4 to 22 carbon atoms, [G] for a glycosidically linked sugar radical, preferably glucose residue, and x is a number from 1 to 10, preferably 1.1 to 3, in particular 1.2 to 1.6. Accordingly, 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.

Das erfindungsgemäße Mittel kann zusätzlich ein oder mehrere kationische Tenside (Kationtenside; INCI Quaternary Ammonium Compounds) enthalten, üblicherweise in einer Menge von 0,001 bis 5 Gew.-%, vorzugsweise 0,01 bis 4 Gew.-%, insbesondere 0,1 bis 3 Gew.-%, besonders bevorzugt 0,2 bis 2 Gew.-%, äußerst bevorzugt 0,5 bis 1,5 Gew.-%, beispielsweise 1 Gew.-%. Bevorzugte kationische Tenside sind die quaternären oberflächenaktiven Verbindungen, insbesondere mit einer Ammonium-, Sulfonium-, Phosphonium-, Jodonium- oder Arsoniumgruppe, die auch als antimikrobielle Wirkstoffe bekannt sind. Durch den Einsatz von quaternären oberflächenaktiven Verbindungen mit antimikrobieller Wirkung kann das Mittel mit einer antimikrobiellen Wirkung ausgestaltet werden bzw. dessen gegebenenfalls aufgrund anderer Inhaltsstoffe bereits vorhandene antimikrobielle Wirkung verbessert werden.The composition according to the invention may additionally contain one or more cationic surfactants (cationic 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 .-%. 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. Through the use of quaternary surface-active compounds with antimicrobial action, the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.

Besonders bevorzugte kationische Tenside sind die quaternären Ammoniumverbindungen (QAV; INCI Quaternary Ammonium Compounds) gemäß der allgemeinen Formel (RI)(RII)(RIII)(RIV)N+ X-, in der RI bis RIV gleiche oder verschiedene C1-22-Alkylreste, C7-28-Aralkylreste oder heterozyklische Reste, wobei zwei oder im Falle einer aromatischen Einbindung wie im Pyridin sogar drei Reste gemeinsam mit dem Stickstoffatom den Heterozyklus, z.B. eine Pyridinium- oder Imidazoliniumverbindung, bilden, darstellen und X- Halogenidionen, Sulfationen, Hydroxidionen oder ähnliche Anionen sind. Für eine optimale antimikrobielle Wirkung weist vorzugsweise wenigstens einer der Reste eine Kettenlänge von 8 bis 18, insbesondere 12 bis 16, C-Atomen auf.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 Imidazoliniumverbindung form, and represent X - are halide ions, sulfate ions, hydroxide ions or similar anions. For optimum antimicrobial activity, preferably at least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

QAV sind durch Umsetzung tertiärer Amine mit Alkylierungsmitteln, wie z.B. Methylchlorid, Benzylchlorid, Dimethylsulfat, Dodecylbromid, aber auch Ethylenoxid herstellbar. Die Alkylierung von tertiären Aminen mit einem langen Alkyl-Rest und zwei Methyl-Gruppen gelingt besonders leicht, auch die Quaternierung von tertiären Aminen mit zwei langen Resten und einer Methyl-Gruppe kann mit Hilfe von Methylchlorid unter milden Bedingungen durchgeführt werden. Amine, die über drei lange Alkyl-Reste oder Hydroxy-substituierte Alkyl-Reste verfügen, sind wenig reaktiv und werden bevorzugt mit Dimethylsulfat quaterniert.QACs are prepared by reacting tertiary amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced. The alkylation of tertiary amines with a long alkyl radical and two methyl groups succeeds particularly easily, and the quaternization of tertiary amines with two long radicals and one methyl group can be carried out with the aid of methyl chloride under mild conditions. Amines having three long alkyl radicals or hydroxy-substituted alkyl radicals are less reactive and are preferably quaternized with dimethyl sulfate.

Bevorzugte QAV sind die Benzalkoniumchloride mit C8-C18-Alkylresten, insbesondere C12-C14-Alkyl-benzyl-dimethylammoniumchlorid. Eine besonders bevorzugte QAV ist das Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5 Cocomonium Methosulfate; Rewoquat® CPEM).Preferred 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 QAV is cocospentaethoxymethylammonium methosulfate (INCI PEG-5 Cocomonium Methosulfate; Rewoquat® CPEM).

Zur Vermeidung möglicher Inkompatibilitäten der kationischen Tenside mit den erfindungsgemäß enthaltenen anionischen Tensiden werden möglichst aniontensidverträgliches und/oder möglichst wenig kationisches Tensid eingesetzt oder in einer besonderen Ausführungsform der Erfindung gänzlich auf kationische Tenside verzichtet.In order to avoid possible incompatibilities of the cationic surfactants with the anionic surfactants according to the invention anionic surfactant-compatible and / or cationic surfactant is preferably used or omitted in a particular embodiment of the invention entirely on cationic surfactants.

In einer bevorzugten Ausführungsform enthält das erfindungsgemäße, bevorzugte flüssige Reinigungsmittel zur Absenkung der Viskosität weiterhin ein oder mehrere wasserlösliche Salze. Es kann sich dabei um anorganische und/oder organische Salze handeln, in einer bevorzugten Ausführungsform enthält das Mittel dabei mindestens ein anorganisches Salz.In a preferred embodiment, the preferred liquid cleaning agent according to the invention for reducing the viscosity further comprises 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.

Erfindungsgemäß einsetzbare anorganische Salze sind dabei vorzugsweise ausgewählt aus der Gruppe umfassend farblose wasserlösliche Halogenide, Sulfate, Sulfite, Carbonate, Hydrogencarbonate, Nitrate, Nitrite, Phosphate und/oder Oxide der Alkalimetalle, der Erdalkalimetalle, des Aluminiums und/oder der Übergangsmetalle; weiterhin sind Ammoniumsalze einsetzbar. Besonders bevorzugt sind dabei Halogenide und Sulfate der Alkalimetalle; vorzugsweise ist das anorganische Salz daher ausgewählt aus der Gruppe umfassend Natriumchlorid, Kaliumchlorid, Natriumsulfat, Kaliumsulfat sowie Gemische derselben.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.

Bei den erfindungsgemäß einsetzbaren organischen Salzen handelt es sich insbesondere um farblose wasserlösliche Alkalimetall-, Erdalkalimetall-, Ammonium-, Aluminium- und/oder Übergangsmetallsalze der Carbonsäuren. Vorzugsweise sind die Salze ausgewählt aus der Gruppe umfassend Formiat, Acetat, Propionat, Citrat, Malat, Tartrat, Succinat, Malonat, Oxalat, Lactat sowie Gemische derselben.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. Preferably, the salts are selected from the group comprising formate, acetate, propionate, citrate, malate, tartrate, succinate, malonate, oxalate, lactate and mixtures thereof.

Das erfindungsgemäße Reinigungsmittel enthält in einer bevorzugten Ausführungsform 0,1 bis 10 Gew.-%, vorzugsweise 0,5 bis 7 Gew.-%, besonders bevorzugt 0,8 bis 5 Gew.-% mindestens eines wasserlöslichen Salzes. In einer besonders bevorzugten Ausführungsform werden dabei ausschließlich anorganische Salze eingesetzt.The cleaning agent according to 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 .-% of at least one water-soluble salt. In a particularly preferred embodiment, exclusively inorganic salts are used.

Das wasserlösliche Salz wird insbesondere zur Einstellung einer geringeren Viskosität bei Reinigungsmitteln für harte Oberflächen verwendet, die eine hohe Tensidkonzentration, insbesondere eine hohe Alkylethersulfatkonzentration, aufweisen. In einem Verfahren zur Senkung der Viskosität hoch tensidhaltiger, insbesondere hoch alkylethersulfathaltiger Reinigungsmittel für harte Oberflächen werden den Mitteln dementsprechend ein oder mehrere wasserlösliche Salze zugesetzt.The water-soluble salt is used in particular for setting a lower viscosity in hard surface cleaners which have a high surfactant concentration, in particular a high alkyl ether sulfate concentration. In a process for reducing the viscosity of high-surfactant, especially high alkyl ether sulfate hard surface cleaners, one or more water-soluble salts are accordingly added to the compositions.

Vorteilhafterweise sind in einer Ausführungsform der Erfindung in dem erfindungsgemäßen Mittel keine Buildersubstanzen vorhanden, welche Calcium-fällende Eigenschaften aufweisen. Dementsprechend wird ein Mittel bevorzugt, welches insbesondere keine Carbonat-haltigen Salze enthält. Aber auch der Einsatz von Seifen wird restriktiv gehandhabt.Advantageously, in one embodiment of the invention in the agent according to the invention, no builder substances are present which have calcium-precipitating properties. Accordingly, an agent is preferred which contains in particular no carbonate-containing salts. But also the use of soaps is handled restrictively.

Der Einsatz anderer Buildersubstanzen wie Silikaten, Aluminiumsilikaten (insbesondere Zeolithen), Salze organischer Di- und Polycarbonsäuren sowie Mischungen dieser Stoffe, vorzugsweise wasserlöslicher Buildersubstanzen kann hingegen von Vorteil sein.The use of other builders, such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builders may, however, be of advantage.

Organische Buildersubstanzen, welche in dem Wasch- oder Reinigungsmittel vorhanden sein können, sind beispielsweise die in Form ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wobei unter Polycarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), Methylglycindiessigsäure (MGDA) und deren Abkömmlinge sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren und Mischungen aus diesen.Organic builder substances which may be present in the washing or cleaning agent are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, where polycarboxylic acids are understood to mean those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) and derivatives thereof and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

Als Gerüststoffe sind weiter polymere Polycarboxylate geeignet. Dies sind beispielsweise die Alkalimetallsalze der Polyacrylsäure oder der Polymethacrylsäure, zum Beispiel solche mit einer relativen Molekülmasse von 600 bis 750.000 g / mol.As builders further 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.

Geeignete Polymere sind insbesondere Polyacrylate, die bevorzugt eine Molekülmasse von 1.000 bis 15.000 g / mol aufweisen. Aufgrund ihrer überlegenen Löslichkeit können aus dieser Gruppe wiederum die kurzkettigen Polyacrylate, die Molmassen von 1.000 bis 10.000 g / mol, und besonders bevorzugt von 1.000 bis 5.000 g / mol, aufweisen, bevorzugt sein.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.

Geeignet sind weiterhin copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Zur Verbesserung der Wasserlöslichkeit können die Polymere auch Allylsulfonsäuren, wie Allyloxybenzolsulfonsäure und Methallylsulfonsäure, als Monomer enthalten.Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To improve the water solubility, the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

Bevorzugt werden allerdings lösliche Gerüststoffe, wie beispielsweise Citronensäure, oder Acrylpolymere mit einer Molmasse von 1.000 bis 5.000 g / mol in den flüssigen Wasch- oder Reinigungsmitteln eingesetzt.However, preference is given to using 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 detergents or cleaners.

Der Wassergehalt des bevorzugten flüssigen, wässerigen Mittels beträgt üblicherweise 15 bis 90 Gew.-%, vorzugsweise 20 bis 85 Gew.-%, insbesondere 30 bis 80 Gew.-%. Das erfindungsgemäße Mittel kann vorteilhafterweise zusätzlich ein oder mehrere wasserlösliche organische Lösungsmittel enthalten, üblicherweise in einer Menge von 0,1 bis 30 Gew.-%, vorzugsweise 1 bis 20 Gew.-%, insbesondere 2 bis 15 Gew.-%, besonders bevorzugt 3 bis 12 Gew.-%, äußerst bevorzugt 4 bis 8 Gew.-%.The water content of the preferred liquid, aqueous agent is usually 15 to 90 wt .-%, preferably 20 to 85 wt .-%, in particular 30 to 80 wt .-%. The agent according to the invention may advantageously additionally contain 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 .-%.

Das Lösungsmittel wird im Rahmen der erfindungsgemäßen Lehre nach Bedarf insbesondere als Hydrotropikum, Viskositätsregulator und/oder zusätzlicher Kältestabilisator eingesetzt. Es wirkt lösungsvermittelnd insbesondere für Tenside und Elektrolyt sowie Parfüm und Farbstoff und trägt so zu deren Einarbeitung bei, verhindert die Ausbildung flüssigkristalliner Phasen und hat Anteil an der Bildung klarer Produkte. Die Viskosität des erfindungsgemäßen Mittels verringert sich mit zunehmender Lösungsmittelmenge. Zuviel Lösungsmittel kann jedoch einen zu starken Viskositätsabfall bewirken.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 cause excessive viscosity drop.

Bevorzugte organische Lösungsmittel stammen aus der Gruppe ein- oder mehrwertigen Alkohole, Alkanolamine oder Glykolether. Vorzugsweise werden die Lösungsmittel ausgewählt aus Ethanol, n- oder i-Propanol, Butanol, Glykol, Propan- oder Butandiol, Glycerin, Diglykol, Propyl- oder Butyldiglykol, Hexylenglycol, Ethylenglykolmethylether, Ethylenglykolethylether, Ethylenglykolpropylether, Ethylenglykolmono-n-butylether, Diethylenglykolmethylether, Diethylenglykolethylether, Propylenglykolmethyl-, -ethyl- oder -propylether, Dipropylenglykolmethyl-, oder -ethylether, Methoxy-, Ethoxy- oder Butoxytriglykol, 1-Butoxyethoxy-2-propanol, 3-Methyl-3-methoxybutanol, Propylen-glykol-t-butylether sowie Mischungen dieser Lösungsmittel. Der Gewichtsanteil dieser organischen Lösungsmittel am Gesamtgewicht erfindungsgemäßer Reinigungsmittel beträgt vorzugsweise 0,1 bis 10 Gew.-%, bevorzugt 0,2 bis 8,0 Gew.-% und insbesondere 0,5 bis 5,0 Gew.-%.Preferred organic solvents are selected from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers. Preferably, the solvents are selected from ethanol, n- or i-propanol, butanol, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether , Propylenglykolmethyl-, ethyl or propyl ether, Dipropylenglykolmethyl- or ethyl ether, methoxy, ethoxy or Butoxytriglykol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and Mixtures of these solvents. The proportion by weight of these organic solvents in the total weight of cleaning agents according to the invention is preferably from 0.1 to 10% by weight, preferably from 0.2 to 8.0% by weight and in particular from 0.5 to 5.0% by weight.

Ein besonders bevorzugtes und in Bezug auf die Stabilisierung der enzymatischen Reinigungsmittel besonders wirksames organisches Lösungsmittel ist das Glycerin sowie das 1,2 Propylenglykol.A particularly preferred organic solvent which is particularly effective in stabilizing the enzymatic detergents is glycerin and 1,2-propylene glycol.

Geeignete Lösungsmittel sind beispielsweise auch gesättigte oder ungesättigte, vorzugsweise gesättigte, verzweigte oder unverzweigte C1-20-Kohlenwasserstoffe, bevorzugt C2-15-Kohlenwasserstoffe, mit mindestens einer Hydroxygruppe und gegebenenfalls einer oder mehreren Etherfunktionen C-O-C, d.h. die Kohlenstoffatomkette unterbrechenden Sauerstoffatomen.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 hydroxyl group and optionally one or more ether functions COC, ie the carbon atom chain interrupting oxygen atoms.

Bevorzugte Lösungsmittel sind die - gegebenenfalls einseitig mit einem C1-6-Alkanol veretherten - C2-6-Alkylenglykole und Poly-C2-3-alkylenglykolether mit durchschnittlich 1 bis 9 gleichen oder verschiedenen, vorzugsweise gleichen, Alkylenglykolgruppen pro Molekül wie auch die C1-6-Alkohole, vorzugsweise Ethanol, n-Propanol oder iso-Propanol, insbesondere Ethanol.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 C 1-6 -alcohols, preferably ethanol, n-propanol or isopropanol, especially ethanol.

Beispielhafte Lösungsmittel sind die folgenden gemäß INCI benannten Verbindungen: Alcohol (Ethanol), Buteth-3, Butoxydiglycol, Butoxyethanol, Butoxyisopropanol, Butoxypropanol, n-Butyl Alcohol, t-Butyl Alcohol, Butylene Glycol, Butyloctanol, Diethylene Glycol, Dimethoxydiglycol, Dimethyl Ether, Dipropylene Glycol, Ethoxydiglycol, Ethoxyethanol, Ethyl Hexanediol, Glycol, Hexanediol, 1,2,6-Hexanetriol, Hexyl Alcohol, Hexylene Glycol, Isobutoxypropanol, Isopentyldiol, Isopropyl Alcohol (iso-Propanol), 3-Methoxybutanol, Methoxydiglycol, Methoxyethanol, Methoxyisopropanol, Methoxymethylbutanol, Methoxy PEG-10, Methylal, Methyl Alcohol, Methyl Hexyl Ether, Methylpropanediol, Neopentyl Glycol, PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-6 Methyl Ether, Pentylene Glycol, PPG-7, PPG-2-Buteth-3, PPG-2 Butyl Ether, PPG-3 Butyl Ether, PPG-2 Methyl Ether, PPG-3 Methyl Ether, PPG-2 Propyl Ether, Propanediol, Propyl Alcohol (n-Propanol), Propylene Glycol, Propylene Glycol Butyl Ether, Propylene Glycol Propyl Ether, Tetrahydrofurfuryl Alcohol, Trimethylhexanol.Exemplary solvents are the following INCI compounds: alcohol (ethanol), buteth-3, butoxy diglycol, butoxyethanol, butoxyisopropanol, butoxypropanol, n-butyl alcohol, t-butyl alcohol, butylene glycol, butyloctanol, diethylene glycol, dimethoxy diglycol, dimethyl ether, Dipropylene glycol, ethoxydiglycol, ethoxyethanol, ethyl hexanediol, glycol, hexanediol, 1,2,6-hexanetriol, hexyl alcohol, hexylene glycol, isobutoxypropanol, isopentyldiol, isopropyl alcohol (isopropanol), 3-methoxybutanol, methoxydiglycol, methoxyethanol, methoxyisopropanol, Methoxymethylbutanol, Methoxy PEG-10, Methylal, Methyl Alcohol, Methyl Hexyl Ether, Methylpropanediol, Neopentyl Glycol, PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-6 Methyl Ether, Pentylene Glycol, PPG-7, PPG-2-buteth-3, PPG-2 butyl ether, PPG-3 butyl ether, PPG-2 methyl ether, PPG-3 methyl ether, PPG-2 propyl ether, propanediol, propyl alcohol (n-propanol ), Propylene glycol, propylene glycol butyl ether, propylene glycol Propyl ether, tetrahydrofurfuryl alcohol, trimethylhexanol.

Besonders bevorzugte Lösungsmittel sind die einseitig mit einem C1-6-Alkanol veretherten Poly-C2-3-alkylenglykolether mit durchschnittlich 1 bis 9, vorzugsweise 2 bis 3, Ethylen- oder Propylenglykolgruppen, beispielsweise PPG-2 Methyl Ether (Dipropylenglykolmonomethylether).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, for example PPG-2 methyl ether (dipropylene glycol monomethyl ether).

Als Lösungsvermittler insbesondere für Parfüm und Farbstoffe können außer den zuvor beschriebenen Lösungsmitteln beispielsweise auch Alkanolamine sowie Alkylbenzolsulfonate mit 1 bis 3 Kohlenstoffatomen im Alkylrest eingesetzt werden.As a 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.

Neben den bisher genannten Komponenten können die erfindungsgemäßen Mittel weitere Inhaltsstoffe enthalten. Hierzu zählen beispielsweise weitere Tenside, Additive zur Verbesserung des Ablauf- und Trocknungsverhaltens, zur Einstellung der Viskosität, zur Stabilisierung sowie weitere in Handgeschirrspülmitteln übliche Hilfs- und Zusatzstoffe, etwa UV-Stabilisatoren, Parfüm, Perlglanzmittel, Farbstoffe, Korrosionsinhibitoren, Konservierungsmittel, organische Salze, Desinfektionsmittel, Enzyme, pH-Stellmittel sowie Hautgefühl-verbessernde oder pflegende Additive.In addition to the components mentioned so far, the compositions according to the invention may contain further ingredients. These include, for example, other surfactants, 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, organic salts, Disinfectants, enzymes, pH adjusters and skin feel-improving or nourishing additives.

Zur weiteren Verbesserung des Ablauf- und/oder Trocknungsverhaltens kann das erfindungsgemäße Mittel ein oder mehrere Additive aus der Gruppe der Tenside, der Polymere und der Buildersubstanzen (Builder) enthalten, üblicherweise in einer Menge von 0,001 bis 5 Gew.-%, vorzugsweise 0,01 bis 4 Gew.-%, insbesondere 0,1 bis 3 Gew.-%, besonders bevorzugt 0,2 bis 2 Gew.-%, äußerst bevorzugt 0,5 bis 1,5 Gew.-%, beispielsweise 1 Gew.-%, wobei wie oben beschrieben auf Calcium-fällende Buildersubstanzen weitestgehend verzichtet wird.To further improve the running and / or drying behavior, 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. %, wherein as described above on calcium-precipitating builders is largely dispensed with.

Für weitere Inhaltsstoffe maschineller Geschirrspülmittel, insbesondere flüssiger maschineller Geschirrspülmittel wird auf die Offenbarung der WO 2011/147665 verwiesen.For further ingredients of automatic dishwashing detergent, in particular liquid automatic dishwashing detergent, reference is made to the disclosure of US Pat WO 2011/147665 directed.

Die für das erfindungsgemäße flüssige Mittel bevorzugte Viskosität liegt bei 20 °C und einer Scherrate von 30 min-1 - gemessen mit einem Viskosimeter vom Typ Brookfield LV DV II und Spindel 31 - im Bereich von 10 bis 5.000 mPa·s, vorzugsweise 50 bis 2.000 mPa·s, insbesondere 100 bis 1.000 mPa·s, besonders bevorzugt 200 bis 800 mPa·s, äußerst bevorzugt 300 bis 700 mPa·s, beispielsweise 300 bis 400 mPa·s. Die Viskosität des erfindungsgemäßen Mittels kann - insbesondere bei einem geringen Tensidgehalt des Mittels - durch Verdickungsmittel erhöht und/oder - insbesondere bei einem hohen Tensidgehalt des Mittels - durch die enthaltenen wasserlöslichen anorganischen Salze sowie durch Lösungsmittel verringert werden.The viscosity preferred 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 from 10 to 5,000 mPa · s, preferably 50 to 2,000 mPa · s, in particular 100 to 1000 mPa · s, more preferably 200 to 800 mPa · s, most preferably 300 to 700 mPa · s, for example 300 to 400 mPa · s. 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.

Polymere Verdickungsmittel im Sinne der vorliegenden Erfindung sind die als Polyelektrolyte verdickend wirkenden Polycarboxylate, vorzugsweise Homo- und Copolymerisate der Acrylsäure, insbesondere Acrylsäure-Copolymere wie Acrylsäure-Methacrylsäure-Copolymere, und die Polysaccharide, insbesondere Heteropolysaccharide, sowie andere übliche verdickende Polymere.For the purposes of the present invention, 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.

Geeignete Polysaccharide bzw. Heteropolysaccharide sind die Polysaccharidgummen, beispielsweise Gummi arabicum, Agar, Alginate, Carrageene und ihre Salze, Guar, Guaran, Tragacant, Gellan, Ramsan, Dextran oder Xanthan und ihre Derivate, z.B. propoxyliertes Guar, sowie ihre Mischungen. Andere Polysaccharidverdicker, wie Stärken oder Cellulosederivate, können alternativ, vorzugsweise aber zusätzlich zu einem Polysaccharidgummi eingesetzt werden, beispielsweise Stärken verschiedensten Ursprungs und Stärkederivate, z.B. Hydroxyethylstärke, Stärkephosphatester oder Stärkeacetate, oder Carboxymethylcellulose bzw. ihr Natriumsalz, Methyl-, Ethyl-, Hydroxyethyl-, Hydroxypropyl-, Hydroxypropyl-methyl- oder Hydroxyethyl-methylcellulose oder Celluloseacetat.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, 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, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.

Ein bevorzugtes polymeres Verdickungsmittel ist das mikrobielle anionische Heteropolysaccharid Xanthan Gum, das von Xanthomonas campestris und einigen anderen Species unter aeroben Bedingungen mit einem Molekulargewicht von 2-15×106 produziert wird und beispielsweise von der Fa. Kelco unter dem Handelsnamen Keltrol® erhältlich ist, z.B. als cremefarbenes Pulver Keltrol® T (Transparent) oder als weißes Granulat Keltrol® RD (Readily Dispersable).A preferred polymeric thickener is the microbial anionic heteropolysaccharide xanthan gum produced by Xanthomonas campestris and some other species under aerobic conditions having a molecular weight of 2-15 x 10 6 and is available, for example, from Kelco under the trade name Keltrol®, eg as cream-colored powder Keltrol® T (transparent) or as white granules Keltrol® RD (Readily Dispersable).

Als polymere Verdickungsmittel geeignete Acrylsäure-Polymere sind beispielsweise hochmolekulare mit einem Polyalkenylpolyether, insbesondere einem Allylether von Saccharose, Pentaerythrit oder Propylen, vernetzte Homopolymere der Acrylsäure (INCI Carbomer), die auch als Carboxyvinylpolymere bezeichnet werden. Solche Polyacrylsäuren sind u.a. von der Fa. BFGoodrich unter dem Handelsnamen Carbopol® erhältlich, z.B. Carbopol® 940 (Molekulargewicht ca. 4.000.000), Carbopol® 941 (Molekulargewicht ca. 1.250.000) oder Carbopol® 934 (Molekulargewicht ca. 3.000.000).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. Such polyacrylic acids are i.a. available from BFGoodrich under the trade name Carbopol®, e.g. Carbopol® 940 (molecular weight about 4,000,000), Carbopol® 941 (molecular weight about 1,250,000) or Carbopol® 934 (molecular weight about 3,000,000).

Besonders geeignete polymere Verdickungsmittel sind aber folgende Acrylsäure-Copolymere: (i) Copolymere von zwei oder mehr Monomeren aus der Gruppe der Acrylsäure, Methacrylsäure und ihrer einfachen, vorzugsweise mit C1-4-Alkanolen gebildeten, Ester (INCI Acrylates Copolymer), zu denen etwa die Copolymere von Methacrylsäure, Butylacrylat und Methylmethacrylat (CAS 25035-69-2) oder von Butylacrylat und Methylmethacrylat (CAS 25852-37-3) gehören und die beispielsweise von der Fa. Rohm & Haas unter den Handelsnamen Aculyn® und Acusol® erhältlich sind, z.B. die anionischen nicht-assoziativen Polymere Aculyn® 33 (vernetzt), Acusol® 810 und Acusol® 830 (CAS 25852-37-3); (ii) vernetzte hochmolekulare Acrylsäurecopolymere, zu denen etwa die mit einem Allylether der Saccharose oder des Pentaerythrits vernetzten Copolymere von C10-30-Alkylacrylaten mit einem oder mehreren Monomeren aus der Gruppe der Acrylsäure, Methacrylsäure und ihrer einfachen, vorzugsweise mit C1-4-Alkanolen gebildeten, Ester (INCI Acrylates/C10-30 Alkyl Acrylate Crosspolymer) gehören und die beispielsweise von der Fa. BFGoodrich unter dem Handelsnamen Carbopol® erhältlich sind, z.B. das hydrophobierte Carbopol® ETD2623 und Carbopol® 1382 (INCI Acrylates/C10-30 Alkyl Acrylate Crosspolymer) sowie Carbopol® AQUA 30 (früher Carbopol® EX 473).However, 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 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) and which are available, for example, from 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 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, esters (INCI acrylates / C10-30 alkyl acrylate crosspolymer) and which are available, for example, from BFGoodrich under the trade name Carbopol®, for example the hydrophobized Carbopol® ETD2623 and Carbopol® 1382 (INCI Acrylates / C10-30 Alkyl acrylate crosspolymer) and Carbopol® AQUA 30 (formerly Carbopol® EX 473).

Der Gehalt an polymerem Verdickungsmittel beträgt üblicherweise nicht mehr als 8 Gew.-%, vorzugsweise zwischen 0,1 und 7 Gew.-%, besonders bevorzugt zwischen 0,5 und 6 Gew.-%, insbesondere zwischen 1 und 5 Gew.-% und äußerst bevorzugt zwischen 1,5 und 4 Gew.-%, beispielsweise zwischen 2 und 2,5 Gew.-%.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.

In einer bevorzugten Ausführungsform der Erfindung ist das Mittel jedoch frei von polymeren Verdickungsmitteln.In a preferred embodiment of the invention, however, the agent is free of polymeric thickeners.

Zur Stabilisierung des erfindungsgemäßen Mittels, insbesondere bei hohem Tensidgehalt, können ein oder mehrere Dicarbonsäuren und/oder deren Salze zugesetzt werden, insbesondere eine Zusammensetzung aus Na-Salzen der Adipin-, Bernstein- und Glutarsäure, wie sie z.B. unter dem Handelsnamen Sokalan® DSC erhältlich ist. Der Einsatz erfolgt hierbei vorteilhafterweise in Mengen von 0,1 bis 8 Gew.-%, vorzugsweise 0,5 bis 7 Gew.-%, insbesondere 1,3 bis 6 Gew.-% und besonders bevorzugt 2 bis 4 Gew.-%.To stabilize the agent according to the invention, in particular at high surfactant content, one or more dicarboxylic acids and / or their salts may be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, as described e.g. available under the trade name Sokalan® DSC. 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 .-%.

Eine Veränderung des Dicarbonsäure(salz)-Gehaltes kann - insbesondere in Mengen oberhalb 2 Gew.-% - zu einer klaren Lösung der Inhaltsstoffe beitragen. Ebenfalls ist innerhalb gewisser Grenzen eine Beeinflussung der Viskosität der Mischung durch dieses Mittel möglich. Weiterhin beeinflusst diese Komponente die Löslichkeit der Mischung. Diese Komponente wird besonders bevorzugt bei hohen Tensidgehalten eingesetzt, insbesondere bei Tensidgehalten oberhalb 30 Gew.-%.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 .-%.

Kann jedoch auf deren Einsatz verzichtet werden, so ist das erfindungsgemäße Mittel vorzugsweise frei von Dicarbonsäure(salze)n.However, if it is possible to dispense with their use, the agent according to the invention is preferably free from dicarboxylic acid (salts).

Daneben können noch ein oder mehrere weitere - insbesondere in Handgeschirrspülmitteln und weiteren Reinigungsmitteln für harte Oberflächen - übliche Hilfs- und Zusatzstoffe, insbesondere UV-Stabilisatoren, Parfüm, Perlglanzmittel (INCI Opacifying Agents; beispielsweise Glykoldistearat, z.B. Cutina® AGS der Fa. Cognis, bzw. dieses enthaltende Mischungen, z.B. die Euperlane® der Fa. Cognis), Farbstoffe, Korrosionsinhibitoren, Konservierungsmittel (z.B. das technische auch als Bronopol bezeichnete 2-Brom-2-nitropropan-1,3-diol (CAS 52-51-7), das beispielsweise als Myacide® BT oder als Boots Bronopol BT von der Firma Boots gewerblich erhältlich ist), Desinfektionsmittel, pH-Stellmittel sowie Hautgefühl-verbessernde oder pflegende Additive (z.B. dermatologisch wirksame Substanzen wie Vitamin A, Vitamin B2, Vitamin B12, Vitamin C, Vitamin E, D-Panthenol, Sericerin, Collagen-Partial-Hydrolysat, verschiedene pflanzliche Protein-Partial-Hydrolysate, Proteinhydrolysat-Fettsäure-Kondensate, Liposome, Cholesterin, pflanzliche und tierische Öle wie z.B. Lecithin, Sojaöl, usw., Pflanzenextrakte wie z.B. Aloe Vera, Azulen, Hamamelisextrakte, Algenextrakte, usw., Allantoin, A.H.A.-Komplexe), in Mengen von üblicherweise nicht mehr als 5 Gew.-% enthalten sein.In addition, one or more further auxiliary agents and additives customary in hand dishwashing detergents and other cleaners for hard surfaces, in particular UV stabilizers, perfume, pearlescing agents (INCI Opacifying Agents, for example glycol distearate, eg Cutina® AGS from Cognis, or US Pat containing mixtures thereof, for example the Euperlane® from Cognis), dyes, corrosion inhibitors, preservatives (for example the technical 2-bromo-2-nitropropane-1,3-diol (CAS 52-51-7), also referred to as Bronopol, which is commercially available, for example, as Myacide® BT or Boots Bronopol BT from Boots), disinfectants, pH stabilizers 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 hydrolyzates, 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), in amounts of usually not more than 5% by weight. % be included.

Als antibakterielle Komponente können erfindungsgemäße Mittel auch elementares Silber und/oder eine Silberverbindung enthalten.As antibacterial component agents according to the invention may also contain elemental silver and / or a silver compound.

Beim Einsatz von Benzoesäure, Salicylsäure oder Milchsäure als pH-Regulatoren und/oder Puffer-Substanzen können diese Verbindungen die antibakterielle Wirkung des Silbers und/oder der Silberverbindung unterstützen bzw. verstärken.When using benzoic acid, salicylic acid or lactic acid as pH regulators and / or buffer substances, these compounds can support or enhance the antibacterial action of the silver and / or the silver compound.

Der pH-Wert des erfindungsgemäßen flüssigen Mittels kann mittels üblicher pH-Regulatoren, beispielsweise Säuren wie Mineralsäuren oder Citronensäure und/oder Alkalien wie Natrium- oder Kaliumhydroxid, eingestellt werden, wobei - insbesondere bei gewünschter Haut- und Handverträglichkeit - ein Bereich von 4 bis 9, vorzugsweise 5 bis 8,5, insbesondere 5,5 bis 8,0, bevorzugt ist. Zur Einstellung und/oder Stabilisierung des pH-Werts kann das erfindungsgemäße Mittel ein oder mehrere Puffer-Substanzen (INCI Buffering Agents) enthalten, üblicherweise in Mengen von 0,001 bis 5 Gew.-%, vorzugsweise 0,005 bis 3 Gew.-%, insbesondere 0,01 bis 2 Gew.-%, besonders bevorzugt 0,05 bis 1 Gew.-%, äußerst bevorzugt 0,1 bis 0,5 Gew.-%, beispielsweise 0,2 Gew.-%. Bevorzugt sind Puffer-Substanzen, die zugleich Komplexbildner oder sogar Chelatbildner (Chelatoren, INCI Chelating Agents) sind. Besonders bevorzugte Puffer-Substanzen sind die Citronensäure bzw. die Citrate, insbesondere die Natrium- und Kaliumcitrate, beispielsweise Trinatriumcitrat·2H2O und Trikaliumcitrat·H2O.The pH of the liquid composition 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, where a range from 4 to 9, in particular with the desired skin and hand tolerance , preferably 5 to 8.5, in particular 5.5 to 8.0, is preferred. For adjusting and / or stabilizing the pH, 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 .-%. Preference is given to 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.

Ein flüssiges Mittel kann weiterhin Hydrotrope enthalten. Hierbei handelt es sich um Löslichkeitsvermittler. Geeignete Hydrotrope sind beispielsweise Harnstoff, Butylglycol, oder aliphatische kurzkettige anionische oder amphotere Lösungsvermittler.A liquid agent may further contain hydrotropes. These are solubilizers. Suitable hydrotropes are, for example, urea, butyl glycol or aliphatic short-chain anionic or amphoteric solubilizers.

In einer Ausführungsform soll das erfindungsgemäße Mittel zur Anwendung in Form eines Schaums entweder direkt auf die zu reinigende Oberfläche oder auf einen Schwamm, ein Tuch, eine Bürste oder ein anderes, gegebenenfalls angefeuchtetes, Reinigungshilfsmittel aufgetragen werden. Zur Schaumerzeugung eignet sich in besonderer Weise ein manuell aktivierter Sprühspender, insbesondere ausgewählt aus der Gruppe umfassend Aerosolsprühspender, selbst Druck aufbauende Sprühspender, Pumpsprühspender und Triggersprühspender, insbesondere Pumpschaumspender, wie sie beispielsweise von der Firma Airspray, der Firma Taplast, der Firma Keltec oder auch der Daiwa Can Company angeboten werden. Neben Triggerflaschen eignen sich auch Pumpsprühspender und Triggersprühspender mit einem Behälter aus Polyethylen, Polypropylen oder Polyethylenterephthalat. Solche Triggerflaschen werden beispielsweise von der Firma Afa-Polytec angeboten. Der Sprühkopf ist vorzugsweise mit einer Schaumdüse ausgestattet. Daneben kann das Mittel auch unter Zusatz eines geeigneten Treibmittels (z.B. n-Butan, ein Propan/Butan-Gemisch, Kohlendioxid, Stickstoff oder ein CO2/N2-Gemisch) in eine entsprechende Aerosolsprühflasche gefüllt werden. Ein solcher Sprühspender ist jedoch weniger bevorzugt.In one embodiment, the composition according to the invention for use in the form of a foam should be applied either directly to the surface to be cleaned or to a sponge, a cloth, a brush or another, optionally moistened, cleaning aid. For generating foam in a special way, a manually activated spray dispenser, in particular selected from the group comprising aerosol spray dispenser, self-pressure spray dispenser, pump spray dispenser and trigger spray dispensers, in particular pump foam dispenser, as for example from the company Airspray, the company Taplast, the company Keltec or the Daiwa Can Company. In addition to trigger bottles, 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. In addition, 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 CO 2 / N 2 mixture) in a corresponding aerosol spray bottle. However, such a spray dispenser is less preferred.

Dementsprechend kann das erfindungsgemäße Mittel in Form eines Erzeugnisses aus dem erfindungsgemäßen Mittel und einem Sprüh- oder Schaumspender, insbesondere Pumpschaumspender, in Verkehr gebracht werden.Accordingly, the agent according to the invention in the form of a product from the agent according to the invention and a spray or foam dispenser, in particular pump foam dispenser, be placed on the market.

Zur manuellen Reinigung einer harten Oberfläche wird das erfindungsgemäße insbesondere flüssige Reinigungsmittel entweder direkt, das heißt unverdünnt, beispielsweise mittels eines Schwamms, auf die zu reinigende Oberfläche aufgebracht und anschließend mit Wasser wieder entfernt.For manual cleaning of a hard surface, the liquid detergent according to the invention 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.

Alternativ kann das erfindungsgemäße Reinigungsmittel zunächst mit Wasser auf Konzentrationen von 1 : 1 bis 1 : 1000 verdünnt werden und anschließend wird die erhaltene Reinigungslösung mit der zu reinigenden Oberfläche in Kontakt gebracht.Alternatively, the cleaning agent according to the invention can first be diluted with water to concentrations of 1: 1 to 1: 1000, and then the resulting cleaning solution is brought into contact with the surface to be cleaned.

Beispielexample 1. Restaktivität nach Lagerung bei_30 °C:1. Residual activity after storage at 30 ° C:

Die folgenden manuellen Geschirrspülmittel M1 (erfindungsgemäß), V1 und V2 (Vergleichsbeispiele) (siehe Tabelle 1; Mengenangaben in Gew.-%; Menge und Art an Parfüm, Farbstoff und Salzen waren in allen Rezepturen identisch) wurden 4 Wochen bei 30°C gelagert. Die Mittel waren direkt nach ihrer Herstellung wie auch nach der Lagerung klar. Der Farbeindruck des Farbstoffs hatte sich nicht verändert. Anschließend wurde die Restaktivität der eingesetzten Amylase mittels der Methode bestimmt, die in M. Lever, Carbohydrate Determination with 4-hydroxybenzoic acid hydrazide (PAHBAH): Effect of Bismuth on the Reaction, Anal. Biochem., 1977, 81, Seiten 21 bis 27 beschrieben ist.The following manual dishwashing detergents M1 (Inventive), V1 and V2 (Comparative Examples) (see Table 1, amounts in% by weight, amount 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, pp. 21-27 is described.

Die Ergebnisse belegen die enzymstabilisierende Wirkung von Calciumnitrat gegenüber nichtstabilisierten manuellen Geschirrspülmitteln (V2), aber auch gegenüber Mitteln, welche mit herkömmlichen bekannten Calcium-Stabilisatoren (V1) versetzt waren. Tabelle 1: Inhaltsstoff M1 V1 V2 C14-C16-Fettalkoholethersulfat mit 2 EO 8,8 8,8 8,8 Cocoamidopropylbetain 1,2 1,2 1,2 Stainzyme® 12L (Amylase) 0,8 0,8 0,8 Calciumnitrat-Tetrahydrat 0,2 --- --- Calciumchlorid --- 0,2 --- Parfüm 0,2 0,2 0,2 Farbstoff 0,01 0,01 0,01 Salze 2,0 2,0 2,0 Wasser Auf 100 Auf 100 Auf 100 pH* 8,0 8,0 8,0 Restaktivität 45 % Nur Spuren Nicht nachweisbar * Messbedingungen: unverdünnt, gemessen bei 20 °C; die Einstellung erfolgte mit Natriumhydroxid beziehungsweise Citronensäure The results demonstrate the enzyme-stabilizing effect of calcium nitrate over non-stabilized manual dishwashing detergents (V2), but also against agents added with conventional known calcium stabilizers (V1). Table 1: ingredient M1 V1 V2 C14-C16 fatty alcohol ether sulfate with 2 EO 8.8 8.8 8.8 cocoamidopropyl 1.2 1.2 1.2 Stainzyme® 12L (amylase) 0.8 0.8 0.8 Calcium nitrate tetrahydrate 0.2 --- --- calcium chloride --- 0.2 --- Perfume 0.2 0.2 0.2 dye 0.01 0.01 0.01 salts 2.0 2.0 2.0 water At 100 At 100 At 100 pH * 8.0 8.0 8.0 residual activity 45% Only traces Not detectable * Measurement conditions: undiluted, measured at 20 ° C; the adjustment was carried out with sodium hydroxide or citric acid

2. Laqestabilität bei niedrigen Temperaturen2. Storage stability at low temperatures

Die Lagerversuche wurden bei 0 °C wiederholt und das Trübungsverhalten nach 4wöchiger Lagerung der nach ihrer Herstellung klaren Produkte M1 und V1 visuell überprüft. Es wurden folgende Ergebnisse gefunden (siehe Tabelle 2): Tabelle 2: Mittel Aussehen vor Lagerung bei 0 °C Aussehen nach 4 wöchiger Lagerung bei 0 °C M1 Klar Keine Trübung, keine Ausflockung V1 Klar Ausflockungen The storage experiments were repeated at 0 ° C and the turbidity behavior after 4 weeks of storage of clear after their preparation products M1 and V1 visually checked. The following results were found (see Table 2): Table 2: medium Appearance before storage at 0 ° C Appearance after 4 weeks storage at 0 ° C M1 Clear No haze, no flocculation V1 Clear flocculation

SEQUENCE LISTINGSEQUENCE LISTING

  • <110> Henkel AG & Co. KGaA<110> Henkel AG & Co. KGaA
  • <120> Enzymhaltiges Wasch- oder Reinigungsmittel<120> Enzyme-containing detergent or cleaner
  • <130> PT019528 PCT<130> PT019528 PCT
  • <160> 1<160> 1
  • <170> PatentIn version 3.3<170> PatentIn version 3.3
  • <210> 1
    <211> 485
    <212> PRT
    <213> Bacillus sp.    <210> 1
    <211> 485
    <212> PRT
    <213> Bacillus sp.
  • <400> 1
    Figure imgb0001
    Figure imgb0002
    Figure imgb0003
    <400> 1
    Figure imgb0001
    Figure imgb0002
    Figure imgb0003

Claims (7)

  1. The use of calcium nitrate in enzyme-containing washing or cleaning agents, comprising fatty alcohol ether sulfate and betaine, for improving the stability of amylase.
  2. The use according to claim 1 in liquid, aqueous washing or cleaning agents.
  3. An enzyme-containing, in particular liquid washing or cleaning agent, characterized in that it contains a fatty alcohol ether sulfate, a betaine, calcium nitrate, preferably in the form of calcium nitrate tetrahydrate, as well as amylase and optionally one or more further enzymes.
  4. The agent according to claim 3, characterized in that it contains calcium nitrate in amounts of from 0.02 to less than 1 wt.%, preferably from 0.05 to 0.5 wt.%, in particular from 0.1 to 0.3 wt.%.
  5. The agent according to one of claims 3 and 4, characterized in that it is a liquid agent for cleaning hard surfaces.
  6. The agent according to one of claims 3 to 5, characterized in that it does not comprise any builders that precipitate calcium.
  7. A method for manually or automatically cleaning hard surfaces, in particular dishes, by using an agent according to one of claims 4 to 6.
EP13700936.1A 2012-01-24 2013-01-24 Enzyme-containing washing or cleaning composition comprising calcium nitrate Not-in-force EP2807242B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012200959A DE102012200959A1 (en) 2012-01-24 2012-01-24 Enzyme-containing detergent or cleaner
PCT/EP2013/051340 WO2013110705A1 (en) 2012-01-24 2013-01-24 Enzyme-containing washing or cleaning composition comprising calcium nitrate

Publications (2)

Publication Number Publication Date
EP2807242A1 EP2807242A1 (en) 2014-12-03
EP2807242B1 true EP2807242B1 (en) 2018-06-20

Family

ID=47598868

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13700936.1A Not-in-force EP2807242B1 (en) 2012-01-24 2013-01-24 Enzyme-containing washing or cleaning composition comprising calcium nitrate

Country Status (7)

Country Link
US (1) US10005987B2 (en)
EP (1) EP2807242B1 (en)
KR (1) KR20140119131A (en)
DE (1) DE102012200959A1 (en)
RU (1) RU2640421C2 (en)
WO (1) WO2013110705A1 (en)
ZA (1) ZA201406200B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9920219B2 (en) 2015-06-22 2018-03-20 Awi Licensing Llc Soil and dirt repellent powder coatings
US10752785B2 (en) * 2016-09-09 2020-08-25 IndusCo, Ltd. Anti-slip botanical antimicrobial microemulsions
JP7162595B2 (en) 2017-01-19 2022-10-28 ノバルティス アーゲー Enzyme reaction medium containing surfactant
DE102017223281A1 (en) * 2017-12-19 2019-06-19 Henkel Ag & Co. Kgaa Purifying agent containing betaine stabilized amylase

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5510052A (en) * 1994-08-25 1996-04-23 Colgate-Palmolive Co. Enzymatic aqueous pretreatment composition for dishware

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2038103A1 (en) 1970-07-31 1972-02-10 Henkel & Cie Gmbh Dish-washing concentrates - contg enzymes, stabilised with sugar alcohols, monosaccharides or disaccharides
US4318818A (en) 1979-11-09 1982-03-09 The Procter & Gamble Company Stabilized aqueous enzyme composition
US4483781A (en) * 1983-09-02 1984-11-20 The Procter & Gamble Company Magnesium salts of peroxycarboxylic acids
BR9306243A (en) 1992-04-13 1998-06-23 Procter & Gamble Composition for automatic washing of thixotropic liquid dishes with enzyme
EP0646170A4 (en) 1992-06-19 1997-02-26 Joslin Diabetes Center Inc DIABETOGENE -i(rad): A TYPE II DIABETES SPECIFIC GENE.
DE69621131T2 (en) 1995-06-13 2002-11-28 Novozymes A/S, Bagsvaerd 4-SUBSTITUTED-PHENYLBORONIC ACIDS AS ENZYME STABILIZERS
US5880076A (en) * 1997-08-04 1999-03-09 Lever Brothers Company, Division Of Conopco, Inc. Compositions comprising glycacarbamate and glycaurea compounds
DE69937841T2 (en) * 1999-01-13 2008-12-11 The Procter & Gamble Company, Cincinnati CELLULOSEPOLYMER-CONTAINING DETERGENT
JP4132678B2 (en) * 1999-01-23 2008-08-13 ザ プロクター アンド ギャンブル カンパニー Detergent tablet
CN1234854C (en) 1999-03-31 2006-01-04 诺维信公司 Polypeptides having alkaline alpha-amylase activity and uncleic acids encoding same
ES2329874T3 (en) 2000-07-22 2009-12-02 Genencor International, Inc. STABILIZATION OF ENZYMES.
DE10131441A1 (en) 2001-06-29 2003-01-30 Henkel Kgaa A new group of alpha amylases and a method for identifying and obtaining new alpha amylases
DE10163748A1 (en) 2001-12-21 2003-07-17 Henkel Kgaa New glycosyl hydrolases
US7645720B2 (en) * 2005-12-13 2010-01-12 Momentive Performance Materials Inc. Extreme environment surfactant compositions comprising hydrolysis resistant organomodified disiloxane surfactants
DE102006038448A1 (en) 2005-12-28 2008-02-21 Henkel Kgaa Enzyme-containing cleaning agent
DE102007028509A1 (en) * 2007-06-18 2008-12-24 Henkel Ag & Co. Kgaa Liquid, highly foaming washing or cleaning agent with stable viscosity
DE102010029348A1 (en) 2010-05-27 2011-12-08 Henkel Ag & Co. Kgaa Machine dishwashing detergent

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5510052A (en) * 1994-08-25 1996-04-23 Colgate-Palmolive Co. Enzymatic aqueous pretreatment composition for dishware

Also Published As

Publication number Publication date
DE102012200959A1 (en) 2013-07-25
ZA201406200B (en) 2016-01-27
US10005987B2 (en) 2018-06-26
EP2807242A1 (en) 2014-12-03
KR20140119131A (en) 2014-10-08
RU2640421C2 (en) 2018-01-09
RU2014134323A (en) 2016-03-20
US20140329734A1 (en) 2014-11-06
WO2013110705A1 (en) 2013-08-01

Similar Documents

Publication Publication Date Title
EP3230428B1 (en) Hand dishwashing detergent having an improved effect against starch
EP2185677B1 (en) Detergents
WO2013037609A2 (en) Method for adapting a hydrolytic enzyme to a component that stabilizes the hydrolytic enzyme
EP2807242B1 (en) Enzyme-containing washing or cleaning composition comprising calcium nitrate
EP3074494B1 (en) Lipase stabilization in dishwashing detergents
EP2956533B1 (en) Liquid washing or cleaning product having improved enzyme stability
EP3114198B1 (en) Pre-portioned cleaning agent comprising at least two separate liquid preparations
EP3538633A1 (en) Amlyase for detergent and cleaning agent applications
DE102017223275A1 (en) Amine oxide-containing cleaning agents with synergistic proteases and amylases
DE102012203475A1 (en) Enzyme-containing hand dishwashing detergent
DE102020134229A1 (en) Soaked cleaning cloth
EP3194552B1 (en) Cleaning composition
DE102013224454A1 (en) Hand dishwashing detergent with improved range
DE102019133382A1 (en) Hand dishwashing detergent composition with lipase
DE102019135615A1 (en) Hand dishwashing detergent composition with amylase
DE102019219832A1 (en) Self-degreasing hand dishwashing detergent
DE102017223280A1 (en) LAS-containing detergents with synergistic proteases and amylases
WO2017144623A1 (en) Stabilization of protease in cleaning agents containing alkylbenzene sulphonate
DE102014204352A1 (en) Foam stabilization of LAS formulations in hard water
EP2732017A1 (en) Rinsing and cleaning agent

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140212

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20160309

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20180214

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1010612

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180715

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502013010423

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180620

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180920

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180920

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180921

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181020

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502013010423

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20190321

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502013010423

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20190124

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190124

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190131

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190131

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190131

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190131

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190124

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190124

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1010612

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190124

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190124

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181022

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20130124

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180620