EP2181185A1 - Agents nettoyants - Google Patents

Agents nettoyants

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Publication number
EP2181185A1
EP2181185A1 EP08759945A EP08759945A EP2181185A1 EP 2181185 A1 EP2181185 A1 EP 2181185A1 EP 08759945 A EP08759945 A EP 08759945A EP 08759945 A EP08759945 A EP 08759945A EP 2181185 A1 EP2181185 A1 EP 2181185A1
Authority
EP
European Patent Office
Prior art keywords
cleaning
group
cleaning agent
acid
branched
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.)
Withdrawn
Application number
EP08759945A
Other languages
German (de)
English (en)
Inventor
Arnd Kessler
Nina Viola Reichhardt
Nadine Warkotsch
Johannes Zipfel
Christian Nitsch
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 EP2181185A1 publication Critical patent/EP2181185A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols

Definitions

  • the present application describes detergents and cleaners, in particular enzyme-containing detergents and cleaners.
  • the detergents or cleaning agents contained in these multidose dosing devices are exposed to varying temperatures over a relatively long period of time, which temperatures approximates those used to carry out the washing or cleaning Cleaning method used water temperatures same. These temperatures can be up to 95 0 C, wherein in the range of machine dishwashing usually only temperatures between 50 and 75 0 C are reached. Accordingly, a washing or cleaning agent contained in a device provided for multiple dosing is repeatedly heated in the course of several washing or cleaning processes to temperatures well above the temperatures customary for transport and storage, with temperature-sensitive active substances in particular being affected. The group of these temperature-sensitive washing and cleaning-active substances primarily include the washing and cleaning-active enzymes.
  • hydrolytic enzymes such as proteases, amylases or lipases are part of numerous textile or dishwashing detergents because of their direct cleaning action.
  • proteases in particular serine proteases, to which the subtilases according to the invention are also calculated, are used for the degradation of proteinaceous soils on the items to be cleaned.
  • subtilases occupy an outstanding position due to their favorable enzymatic properties such as stability or pH optimum.
  • the ⁇ -amylases are in particular widespread from the enzyme class of the amylases, ⁇ -amylases (E.C. 3.2.1.1) hydrolyze internal ⁇ -1, 4-glycosidic bonds of starch and starch-like polymers.
  • Detergents and cleaning enzymes are formulated in both solid and 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 detergents and cleaners.
  • liquid or gel detergents and cleaners often contain liquid enzyme preparations, which, unlike the enzyme granules, are much less protected against external influences.
  • German patent application DE 2 038 103 (Henkel) teaches the stabilization of enzyme-containing dishwashing detergents by saccharides, while in European patent EP 646 170 B1 (Procter & Gamble) propylene glycol is disclosed for enzyme stabilization in liquid detergents.
  • liquid enzyme preparations can be stabilized by the addition of a mixture of propylene glycol and specific nonionic surfactants from the group of hydroxy mixed ethers in the required manner.
  • a first subject of this application is therefore a liquid, aqueous washing or cleaning agent preparation, comprising a) at least one washing or cleaning-active enzyme; b) 1, 2 propylene glycol c) nonionic surfactant of the general formula R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A"'O) z -R 2 , in the
  • R 1 is a linear or branched, saturated or mono- or polyunsaturated C 6 - 24 represents alkyl or alkenyl;
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A, A ', A "and A'” independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) - CH 2 -, -CH 2 -CH (CH 2 -CH 3 ), w, x, y and z are for values between 0.5 and 120 where x, y and / or z can also be 0.
  • liquid, aqueous detergent or cleaning agent preparations are liquid, aqueous detergent or cleaning agent preparations.
  • those formulations which contain at least 5% by weight, preferably at least 10% by weight, of water are referred to as "aqueous.”
  • Preferred liquid detergent or cleaning agent preparations according to the invention are characterized in that the weight fraction of the water is from 5 to 35% by weight. %, preferably 10 to 25 wt .-% and in particular 12 to 30 wt .-%, each based on the total weight of the detergent or cleaning agent preparation is.
  • the washing or cleaning agent preparations according to the invention contain as their first essential constituent at least one washing or cleaning-active enzyme.
  • the enzymes used with particular preference include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; starting from the Natural molecules are available for use in detergents or cleaning agents improved variants available, which are used according to preferred.
  • Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein.
  • the protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • the stabilizing effect according to the invention has been observed to a particular extent in the case of the amylases and the proteases, for which reason liquid washing or cleaning agent preparations according to the invention, characterized in that they contain a washing- or cleaning-active enzyme from the group of amylases and / or proteases, are preferred.
  • the proteases those of the subtilisin type are preferable.
  • subtilisins BPN 'and Carlsberg and their further developed forms examples of these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • preferred liquid washing or cleaning agent preparations contain 5 to 50% by weight, preferably 7 to 45% by weight and in particular 10 to 40% by weight of protease preparations.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens, from ⁇ . stearothermophilus, from Aspergillus niger and A. oryzae, as well as improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from ⁇ . agaradherens (DSM 9948).
  • preferred liquid detergent or cleaning agent preparation based on the total weight of the detergent or cleaning agent preparation, 0.1 to 20 wt .-%, preferably 0.2 to 15 wt .-% and in particular 1, 0 to 12 wt .-% amylase preparations.
  • Washing or cleaning-active proteases and amylases 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 gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further 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 amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.
  • lipases or cutinases are also usable according to the invention.
  • these include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • enzymes and / or enzyme preparations preferably liquid protease preparations and / or amylase preparations are used.
  • a second essential constituent of the washing or cleaning agent preparations according to the invention is 1,2-propylene glycol.
  • the proportion by weight of 1, 2 propylene glycol in the total weight of the detergent or cleaning compositions according to the invention can vary within wide limits, but such preparations have proven to be particularly stable, which, based on the total weight of the detergent or cleaning agent preparation, 5 to 60 wt .-% , preferably 10 to 50 wt .-% and in particular 15 to 45 wt .-% 1, 2 propylene glycol. Corresponding preparations are therefore preferred according to the invention.
  • a third essential constituent of the detergent or cleaning agent preparations according to the invention are the nonionic surfactants of the general formula R 1 -CH (OH) CH 2 O- (AO) W - (A'O) x - (A "O) y - (A '' O) z -R 2 , in the
  • R 1 is a linear or branched, saturated or mono- or polyunsaturated C 6 - 24 represents alkyl or alkenyl;
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A, A ', A "and A'” independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) - CH 2 -, -CH 2 -CH (CH 2 -CH 3 ), w, x, y and z are for values between 0.5 and 120 where x, y and / or z can also be 0.
  • nonionic surfactants of the general formula R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A '" O) z -R 2 , also referred to below as "hydroxymix ether"
  • inventive enzyme-containing preparations can be significantly improved both in comparison to surfactant-free system and compared to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols contain.
  • liquid washing or cleaning agent preparations comprising a) from 0.1 to 20% by weight of amylase preparation b) from 5 to 50% by weight protease preparation c) from 10 to 50% by weight 1, 2 propylene glycol d) from 2 to 30% by weight nonionic surfactant of the general formula R 1 -CH (OH) CH 2 O- (AO) W - (A'O) x - (A "O) y - (A '" O) z -R 2 in which
  • R 1 represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6 - 24 represents alkyl or alkenyl;
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • - w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
  • nonionic surfactant of the general formula R-CH (OH) CH 2 ⁇ - (AO) w - (AO) x - (A "O) y - (A '" O) z -R in which
  • R 1 is a linear or branched, saturated or mono- or polyunsaturated C 6 - 24 represents alkyl or alkenyl;
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A'” independently represent a group from the group
  • - w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
  • nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals, the stability of the enzymes contained in the detergent or cleaning agent preparations according to the invention can be markedly improved.
  • the proportion by weight of these nonionic surfactants in preferred liquid detergent or cleaning agent preparations based on the total weight of the detergent or cleaning agent preparation, 0.5 to 30 wt .-%, preferably 2.0 to 25 wt .-% and in particular 5.0 to 20% by weight.
  • end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
  • surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 OI y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4 to R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1, 5 and y is at least 15.
  • R 1 is a linear or branched aliphatic hydrocarbon radical with 4 to R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1, 5 and y is at least 15.
  • the group of these nonionic surfactants include, for example, the C 2 .
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 P] x [CH 2 J k CH (OH) [CH 2 ] J OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl - or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated , aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred, for the radical R 3 are H, -CH 3 or - CH 2 CH 3 bes onders preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x> 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • nonionic surfactant of the general formula have proven to be particularly effective
  • R 1 is a linear or branched, saturated or mono- or polyunsaturated C 6 - 24 represents alkyl or alkenyl;
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A is a radical from the group CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), and w is from 1 to 120, preferably from 10 to 80, in particular from 20 to
  • nonionic surfactants include, for example, the C 4 . 22 fatty alcohol (EO) 10 - 8 o-2-hydroxyalkyl ethers, in particular the C 8 - I2 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4 . 22 fatty alcohol (EO) 40 - 8 O-2-hydroxyalkyl ether
  • a preferred subject matter of the present application is therefore liquid detergent or cleaning agent preparation according to one of the preceding claims, characterized in that the nonionic surfactant c) has the general formula R 1 -CH (OH) CH 2 O- (AO) W -R 2 , in the
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6 . 24 alkyl or alkenyl radical;
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A is a radical from the group CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), and w is from 1 to 120, preferably from 10 to 80, in particular from 20 to 40 stands
  • ingredients described above such as enzymes, solvents and nonionic surfactants from the group of hydroxy mixed ethers washing or cleaning compositions according to the invention further ingredients, such as active ingredients from the group of builders, bleaching agents, surfactants, the washing and cleaning active polymers, the Enzymes containing corrosion inhibitors, fragrances or dyes.
  • active ingredients from the group of builders, bleaching agents, surfactants, the washing and cleaning active polymers, the Enzymes containing corrosion inhibitors, fragrances or dyes.
  • preferred detergent or cleaner formulations according to the invention contain these other ingredients only to a minor extent, since a reduction in the proportion by weight of these ingredients has the effect of improving the cleaning performance as well as the meterability of these agents.
  • washing or cleaning agent preparations which are less than 20% by weight, preferably less than 10% by weight and in particular less than 5
  • Wt .-% builders included. Particularly preferred are those washing or cleaning agent preparations which are free of builders.
  • washing or cleaning agent preparations which contain less than 10% by weight, preferably less than 5% by weight and in particular less than 2% by weight, of bleaching agent. Particular preference is given to those washing or cleaning agent preparations which are free of bleaching agents.
  • Preferred liquid preparations are characterized in that they are formulated together with one, preferably two or three further liquid washing or cleaning agent preparations to form a combination product.
  • the further one, two or three liquid washing or cleaning agent preparations have a composition differing from the enzyme-containing washing or cleaning agent preparation according to the invention.
  • the other one, two or three liquid detergent or cleaning agent preparations are preferably bleach-free and / or phosphate-free.
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6 - 24 represents alkyl or alkenyl;
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A'” independently represent a group from the group
  • CH 2 -, -CH 2 -CH (CH 2 -CH 3 ), w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
  • compositions according to the invention described above may contain other substances which are active in washing or cleaning, substances from the group of builders, polymers, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers being preferred. Also usable are bleaching agents and bleach activators. These preferred ingredients will be described in more detail below.
  • the builders include in particular the zeolites, silicates, carbonates and organic cobuilders.
  • preferred crystalline layered silicates of general formula NaMSi x O 2x + I ⁇ y H 2 O are used, wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, wherein particularly preferred Values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • the crystalline layered silicates of the formula NaMSi x O 2x + 1 ⁇ y H 2 O are sold for example by Clariant GmbH (Germany) under the trade name Na-SKS.
  • silicates Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS -3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, Makatite).
  • crystalline layer silicates with the formula NaMSi x O 2x + 1 ⁇ y H 2 O, in which x stands for 2 h.
  • x stands for 2 h.
  • Washing or cleaning composition preferably contain a weight proportion of crystalline layered silicate of the formula NaMSi x O 2x + 1 ⁇ y H 2 O from 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-% and in particular of 0.4 to 10 wt .-%, each based on the total weight of these agents.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
  • the dissolution delay compared to conventional amorphous sodium silicates may be caused in various ways, for example by surface treatment, compounding, grain pakt réelle / compression or by overdrying.
  • amorphous is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle , cause.
  • X-ray amorphous silicates are used whose silicate particles produce fuzzy or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such X-ray amorphous silicates also have a dissolution delay compared to conventional water glasses on.
  • compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are especially preferred.
  • alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the alkali silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
  • alkali metal carbonates in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
  • the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the detergent or cleaning agent used.
  • Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning 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), if such use is not objectionable for ecological reasons, and mixtures of these.
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 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.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
  • copolymers are those which have as their monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.
  • sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.
  • R 1 to R 3 independently of one another are -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, S-methacrylamido-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylannid and water-soluble salts of said acids.
  • Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds.
  • the content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer.
  • the copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii).
  • Particularly preferred polymers have certain structural units, which are described below.
  • copolymers which are structural units of the formula are preferred.
  • polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred.
  • the corresponding copolymers contain the structural units of the formula
  • Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
  • copolymers which contain structural units of the formula - [CH 2 -CHCOOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p -
  • maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol "1 , preferably from 4000 to 25,000 gmol " 1 and in particular from 5000 to 15,000 gmol "1 .
  • the washing or cleaning agent preparations according to the invention comprise a hydrophobically modified copolymer. Surprisingly, the addition of the hydrophobically modified copolymers additionally improved the cleaning performance of the enzymes, in particular of the proteases.
  • a further preferred subject matter of the present application is consequently a liquid, aqueous washing or cleaning agent preparation comprising a) at least one washing or cleaning-active enzyme; b) 1, 2 propylene glycol c) nonionic surfactant of the general formula R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A"'O) z -R 2 , in the
  • R 1 represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6 - 24 represents alkyl or alkenyl;
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • - w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
  • Particularly preferred copolymers d) contain as carboxyl-containing monomers i) acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • carboxyl-containing monomers i) acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • R 1 is a linear or branched, saturated or mono- or polyunsaturated C 6 - 24 represents alkyl or alkenyl;
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A, A ', A "and A'” independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) - CH 2 -, -CH 2 -CH (CH 2 -CH 3 ),
  • - w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
  • polymeric aminodicarboxylic acids their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrups having a DE of between 20 and 37, and so-called yellow dextrins and white dextrins having higher molecular weights in the range of 2000 to 30,000 g / mol.
  • oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred. Suitable amounts are from 3 to 15 wt .-%.
  • the automatic dishwasher detergents according to the invention contain methylglycinediacetic acid or a salt of methylglycinediacetic acid.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • the group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1, 2 to 1, 4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • surfactants are polyhydroxy fatty acid amides of the formula
  • R is an aliphatic acyl radical having 6 to 22 carbon atoms
  • R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms
  • 4- alkyl or phenyl radicals are preferred
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • Low-foaming nonionic surfactants are used as preferred surfactants.
  • washing or cleaning agents in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
  • Preferred ethoxylated alcohols include, for example, C12 - 14 - alcohols with 3 EO or 4 EO, C 9 n-alcohol with 7 EO, C-ms alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 2 - 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci 2 - 14 -alcohol with 3 EO and C-
  • the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • NRE narrow rank ethoxylates
  • fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactants consisting of C 6 - 2 o-monohydroxyalkanols or C 6 - 2 o-alkylphenols or C 16 - 2 o-fatty alcohols and more than 12 moles, preferably more than 15 moles and especially more than 20 moles of ethylene oxide per mole of alcohol were used.
  • a particularly preferred nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C- ⁇ 6 - 2 o alcohol), preferably obtained a d 8 alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide.
  • particularly preferred are the so-called “narrow-range ethoxylates.”
  • combinations of one or more tallow fatty alcohols with 20 to 30 EO and silicone defoamers are used.
  • Nonionic surfactants which have a melting point above room temperature.
  • nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa s, preferably above 35 Pa s and in particular above 40 Pa s. Also, nonionic surfactants having waxy consistency at room temperature are preferred depending on their purpose.
  • Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
  • the nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol content of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight, of the total molecular weight of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25 Wt .-% of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane contains.
  • nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6 - 24 represents alkyl or alkenyl; each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently stand for integers from 1 to 6.
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as usually present in oxo alcohol radicals.
  • nonionic surfactants in which R 1 in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 1 1 carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or -CH (CH 3 ) 2 are suitable.
  • Nonionic surfactants are summary particularly preferred which have a C. 9-i 5 alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned mostly do not consist of an individual representative but of Mixtures, which can result in mean values for both the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation and, consequently, fractional numbers.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,
  • anionic surfactants are used as constituents of automatic dishwasher detergents, their content, based on the total weight of the compositions, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight. Machine dishwashing detergents which do not contain anionic surfactants are particularly preferred.
  • cationic active substances for example, cationic compounds of the following formulas can be used:
  • the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. %.
  • Machine dishwashing detergents which do not contain cationic or amphoteric surfactants are particularly preferred.
  • the group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners.
  • the washing or cleaning-active polymers for example the rinse aid polymers and / or polymers which act as softeners.
  • cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.
  • “Cationic polymers” in the context of the present application are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride Copolymers, the quaternized polyvinyl alcohols or the polymers listed under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • amphoteric polymers further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • R 1 and R 4 are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms;
  • R 2 and R 3 are independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group;
  • x and y independently represent integers between 1 and 3.
  • X " represents a counterion, preferably a counterion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
  • Preferred radicals R 1 and R 4 in the above formula are selected from -CH 3, -CH 2 -CH 3, - CH 2 -CH 2 -CH 3, -CH (CH 3) -CH 3, -CH 2 -OH , -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H.
  • X " in the R 1 , R 2 , R 3 , R 4 and R 5 are independently of one another a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from CH 3 , -CH 2 -CH 3 , -CH 2 - CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 - CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n is H and x is an integer between 1 and 6.
  • H 2 C C (CHS) -C (O) -NH- (CH 2 ) X - N + (C HS) 3
  • MAPTAC Metalacrylamidopropyl trimethylammonium chloride
  • amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
  • anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates.
  • Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and their derivatives, the allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
  • Preferred usable amphoteric polymers are from the group of alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methyl methacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylanninoalkyl (neth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacryl - Amide / Alkymethacrylat / Alkylaminoethylmethacrylat / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or noni
  • Preferred zwitterionic polymers are from the group of acrylamidoalkyltri alkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.
  • amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride.
  • amphoteric polymers are selected from the group of the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethy1-diallyl ammonium chloride / alkyl
  • amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid
  • the polymers are present in prefabricated form.
  • encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions is suitable, preferably by means of water-soluble or water-dispersible natural or synthetic polymers; the encapsulation of the polymers by means of water-insoluble, meltable coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 0 C; the co-granulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing- or cleaning-active substances, more preferably from the group of builders or cobuilders.
  • Detergents or cleaning agents contain the aforementioned cationic and / or amphoteric polymers preferably in amounts between 0.01 and 10 wt .-%, each based on the Total weight of washing or cleaning agent.
  • Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes.
  • preferred zinc salts preferably organic acids, particularly preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 have mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 2O 0 C. water temperature).
  • the first group of zinc salts includes, for example, the zinc nitrate, the zinc oleate and the zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
  • the glass corrosion inhibitor at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and Zinkeitrat used.
  • Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art.
  • silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferred. According to the invention, preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts.
  • Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric and succinic acid.
  • organic carboxylic acids such as acetic, glycolic, citric and succinic acid.
  • perfume oils or perfumes within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-Ylang oil.
  • a fragrance In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note”, “middle note” or “body note” ) and “base note” (end note or dry out).
  • the top note of a perfume does not consist solely of volatile compounds, while the base note is largely made up of less volatile, i. adherent fragrances.
  • more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly.
  • fixatives preventing them from evaporating too quickly.
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the compositions and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic dishes, so as not to stain them.
  • a further subject of this application is a process for the purification of dishes in a dishwasher using a liquid washing or cleaning agent preparation, comprising a) at least one washing or cleaning-active enzyme; b) 1, 2 propylene glycol c) nonionic surfactant of the general formula R 1 -CH (OH) CH 2 O- (AO) W - (A'O) X - (A "O) y - (A"'O) z -R 2 , in the
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6 - 24 represents alkyl or alkenyl;
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A'” independently represent a group from the group
  • - w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
  • washing or cleaning agent preparations according to the invention which are used with particular preference in these processes correspond to the agents described in detail above.
  • Preferred methods for dishwashing are characterized in that the liquid washing or cleaning agent preparation from a storage container located in the dishwasher, which contains the multiple, necessary for carrying out a cleaning process amount of detergent or cleaning agent preparation, is dosed into the interior of the dishwasher.
  • the storage container used for metering can be a storage container integrated into the dishwasher, ie a storage container permanently attached to the dishwashers, but also a self-sufficient storage container which can be introduced into the interior of the dishwasher.
  • An example of an integrated storage container is a receptacle integrated in the door of the dishwasher, which is connected via a feed line to the interior of the dishwasher.
  • the storage container has at least one chamber for receiving the liquid detergent or cleaning agent preparations according to the invention.
  • the storage container has more than one, preferably two, three, four or more separate, separate receiving chambers, of which at least one chamber contains the liquid detergent or cleaning agent according to the invention, while at least one, preferably at least two further chambers , preferably contains liquid preparations with a composition deviating from the liquid detergent or cleaner compositions according to the invention.
  • an amount between 1, 0 and 15 ml, preferably between 2.0 and 12 ml and in particular between 4.0 and 10 ml of the liquid detergent or cleaning agent preparation according to the invention is metered into the interior of the dishwasher per cleaning cycle.
  • the volume of preferred storage container with one or more receiving chambers is between 10 and 1000 ml, preferably between 20 and 800 ml and in particular between 50 and 500 ml.
  • the washing or cleaning agent preparations according to the invention are distinguished by a particular temperature stability and the processes according to the invention are used in particular for the repeated dosing of these preparations from storage containers located in the interior of the dishwasher.
  • Preferred processes according to the invention are characterized in that the liquid detergent or cleaning agent preparation before being metered into the interior of the dishwasher for the duration of at least two, preferably at least four, more preferably at least eight and in particular at least twelve separate cleaning process in the in the Dishwasher located reservoir remains.
  • separated cleaning processes are referred to as "separate cleaning processes", which furthermore preferably also include a pre-wash cycle and / or a final rinse cycle in addition to the main cleaning cycle and which are selected and triggered, for example, by means of the program switch of the dishwasher can.
  • the duration of these separate purification processes is preferably at least 15 minutes, preferably between 20 and 360 minutes, preferably between 30 and 240 minutes.
  • the time period between two separate cleaning processes, within which the liquid detergent or cleaning agent preparation is metered into the interior of the dishwasher, is at least 20 minutes, preferably at least 60 minutes, particularly preferably at least 120 minutes.
  • the temperature load of the liquid detergent or cleaning agent preparations according to the invention can vary within the limits of the process according to the invention, wherein the liquid detergent or cleaning compositions are particularly suitable for those processes in which the liquid detergent or cleaning agent preparation in the reservoir at least twice, preferably at least four times, particularly preferably is heated to temperatures above 3O 0 C, preferably above 4O 0 C, more preferably heated above 5O 0 C for at least eight times and especially at least twelve times.
  • a heating to temperatures above 6O 0 C or above 7O 0 C or a twenty- or thirty-fold heating of the liquid detergent or cleaning agent preparation according to the invention can of course be realized.
  • the liquid washing or cleaning agent preparation in the storage container is heated by the rinsing liquor surrounding this storage container in each of the separate cleaning processes taking place one after the other.
  • the liquid washing or cleaning agent preparation is cooled in the reservoir between the separate purification process to temperatures below 3O 0 C, preferably below 26 0 C and in particular below 22 0 C..
  • nonionic surfactant of the general formula R 1 -CH (OH) CH 2 O- (AO) W -
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6 - 24 represents alkyl or alkenyl;
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A, A ', A "and A'” independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) - CH 2 -, -CH 2 -CH (CH 2 -CH 3 ), w, x, y and z are for values between 0.5 and 120 where x, y and / or z can also be 0. for the stabilization of liquid enzyme preparations, is a further subject of the present invention
  • the nonionic surfactants of the general formula R 1 -CH (OH) CH 2 O- (AO) W - (A'O) x - (A "O) y - (A '" O) z -R 2 for stabilization of liquid preparations containing amylase (s) and / or protease (s).
  • the enzyme-containing agents were V1 (not according to the invention) and E1
  • the enzyme-containing cleaner stabilized by the addition of a hydroxymix ether has significantly better cleaning results both on the stains relevant for the amylase and on the proteases relevant to the protease than the hydroxy mixed ether-free cleaners.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

L'invention se rapporte à une préparation détergente ou nettoyante liquide et aqueuse comprenant d) au moins une enzyme active pour le lavage ou le nettoyage; e) du 1,2-propylèneglycol; f) un tensioactif non ionique de formule générale R1-CH(OH)CH2O-(AO)w-(A'O)x- (A'O)y-(A''O)z-R2, dans laquelle, R1 désigne un radical alcényle ou alkyle en C6-C24 à chaîne linéaire ou ramifiée, saturé ou insaturé une ou plusieurs fois; R2 désigne un radical hydrocarboné linéaire ou ramifié ayant de 2 à 26 atomes de carbone; A, A', A' et A'' représentent, indépendamment les uns des autres un radical issu du groupe -CH2CH2, -CH2CH2-CH2, -CH2-CH(CH3), -CH2-CH2-CH2-CH2, -CH2-CH(CH3)- CH2- et -CH2-CH(CH2-CH3); w, x, y et z désignent des valeurs comprises entre 0,5 et 120; x, y et/ou z désignent des valeurs pouvant être égales à zéro; ces agents se caractérisent par une bonne stabilité de phases et d'enzymes ainsi que par de bonnes performances en termes de nettoyage.
EP08759945A 2007-08-22 2008-05-23 Agents nettoyants Withdrawn EP2181185A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007039655A DE102007039655A1 (de) 2007-08-22 2007-08-22 Reinigungsmittel
PCT/EP2008/056344 WO2009024364A1 (fr) 2007-08-22 2008-05-23 Agents nettoyants

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EP2181185A1 true EP2181185A1 (fr) 2010-05-05

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US (1) US20100216683A1 (fr)
EP (1) EP2181185A1 (fr)
KR (1) KR20100046018A (fr)
CN (1) CN101784649B (fr)
CA (1) CA2697247A1 (fr)
DE (1) DE102007039655A1 (fr)
RU (1) RU2010110434A (fr)
WO (1) WO2009024364A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008060470A1 (de) * 2008-12-05 2010-06-10 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102009002095A1 (de) * 2009-04-01 2010-10-07 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102009002094A1 (de) * 2009-04-01 2010-10-07 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102009027158A1 (de) * 2009-06-24 2010-12-30 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
WO2011051418A1 (fr) * 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Procédé de lavage en machine
DE102009046240A1 (de) * 2009-10-30 2011-05-12 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülverfahren
DE102009046220A1 (de) * 2009-10-30 2011-05-12 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülverfahren
EP2494018A1 (fr) * 2009-10-30 2012-09-05 Henkel AG & Co. KGaA Procédé de lavage en machine
DE102011000889A1 (de) * 2011-02-23 2012-08-23 Witty Chemie Gmbh & Co. Kg Reinigungsmittel für Geschirrspülanlagen und Verfahren dafür
DE102011005695A1 (de) * 2011-03-17 2012-09-20 Henkel Ag & Co. Kgaa Geschirrspülmittel
DE102012107728A1 (de) * 2012-08-22 2014-02-27 Witty-Chemie Gmbh & Co. Kg Phosphorfreies Reinigungsmittel für Geschirrspülanlagen und Verfahren dafür
JP2017503061A (ja) 2013-11-11 2017-01-26 エコラボ ユーエスエー インコーポレイティド 多目的酵素洗剤及び使用溶液を安定化する方法
DE102014202221A1 (de) 2014-02-06 2015-08-06 Henkel Ag & Co. Kgaa Mehrphasiges vorportioniertes Reinigungsmittel

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2038103A1 (de) 1970-07-31 1972-02-10 Henkel & Cie Gmbh Waessrige Reinigungsmittelkonzentrate mit einem Gehalt an stabilisierten Enzymen
EP0636170B1 (fr) * 1992-04-13 1997-08-06 The Procter & Gamble Company Composition thixotrope liquide contenant des enzymes, pour le lavage automatique de la vaisselle
WO1994000558A1 (fr) 1992-06-19 1994-01-06 Joslin Diabetes Center, Inc. Rad diabetogene: un gene specifique au diabete de type ii
US5967157A (en) * 1996-09-11 1999-10-19 The Procter & Gamble Company Automatic dishwashing compositions containing low foaming nonionic surfactants in conjunction with enzymes
US6376450B1 (en) * 1998-10-23 2002-04-23 Chanchal Kumar Ghosh Cleaning compositions containing multiply-substituted protease variants
EP1303582B1 (fr) * 2000-07-22 2009-09-23 Genencor International, Inc. Stabilisation d'enzymes
DE10116020A1 (de) * 2001-03-30 2002-10-02 Cognis Deutschland Gmbh Hydroxymischether mit hohem Ethoxylierungsgrad als Entschäumer
DE10150400A1 (de) * 2001-10-11 2003-04-17 Cognis Deutschland Gmbh Feste Wasch-, Spül- und Reinigungsmittel
US20040127381A1 (en) * 2001-11-30 2004-07-01 The Procter & Gamble Company Dual-compartment laundry composition containing equilbrium peracid solution
GB2386129B (en) 2002-03-06 2004-12-01 Reckitt Benckiser Nv Detergent dosing device
US20050049166A1 (en) * 2003-08-29 2005-03-03 Huang Tsao-Chin Clare Enzyme-based cleaning composition and method of use
DE102004048591A1 (de) * 2004-04-27 2005-11-24 Henkel Kgaa Reinigungsmittel mit Klarspültensid und einer speziellen α-Amylase
DE102004021384A1 (de) * 2004-04-30 2005-11-24 Henkel Kgaa Verfahren zur Herstellung von Granulaten mit verbesserter Lagerstabilität und Abriebfestigkeit
DE102005062479A1 (de) * 2005-12-27 2007-07-05 BSH Bosch und Siemens Hausgeräte GmbH Dosiervorrichtung für die Zugabe eines Zuschlagmittels in einen Behandlungsraum und Geschirrspülmaschine mit einer Dosiervorrichtung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009024364A1 *

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Publication number Publication date
RU2010110434A (ru) 2011-09-27
KR20100046018A (ko) 2010-05-04
CA2697247A1 (fr) 2009-02-26
US20100216683A1 (en) 2010-08-26
WO2009024364A1 (fr) 2009-02-26
DE102007039655A1 (de) 2009-02-26
CN101784649B (zh) 2012-07-18
CN101784649A (zh) 2010-07-21

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