EP2414498B1 - Détergents - Google Patents

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Publication number
EP2414498B1
EP2414498B1 EP10712421.6A EP10712421A EP2414498B1 EP 2414498 B1 EP2414498 B1 EP 2414498B1 EP 10712421 A EP10712421 A EP 10712421A EP 2414498 B1 EP2414498 B1 EP 2414498B1
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EP
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Prior art keywords
cleaning agent
washing
cartridge
cleaning
preparation
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EP10712421.6A
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German (de)
English (en)
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EP2414498A1 (fr
Inventor
Thorsten Bastigkeit
Arnd Kessler
Christian Nitsch
Johannes Zipfel
Dorota SENDOR-MÜLLER
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL10712421T priority Critical patent/PL2414498T3/pl
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates

Definitions

  • washing and cleaning agents in particular enzyme-containing washing and cleaning agents.
  • the detergents or cleaning agents contained in these devices for multiple dosing are particularly exposed to changing temperatures over a longer period of time, these temperatures being the first approximation of those used to carry out the washing or cleaning processes Same water temperatures. These temperatures can be up to 95 ° C, with temperatures between 50 and 75 ° C usually only being reached in the area of machine dishwashing.
  • a washing or cleaning agent contained in a device provided for multiple dosing is accordingly repeatedly heated to temperatures well above the normal temperatures for transport and storage in the course of several washing or cleaning processes, with temperature-sensitive ones in particular Active ingredients can be affected.
  • the group of these temperature-sensitive washing and cleaning-active substances includes primarily the washing and cleaning-active enzymes.
  • hydrolytic enzymes such as proteases, amylases or lipases are part of numerous textile and dishwashing detergents because of their direct cleaning effect.
  • proteases serve to break down protein-containing soiling on the items to be cleaned.
  • subtilases occupy an outstanding position due to their favorable enzymatic properties such as stability or optimum pH.
  • ⁇ -amylases From the enzyme class of amylases, ⁇ -amylases in particular are widespread.
  • ⁇ -Amylases (E.C. 3.2.1.1) hydrolyze internal ⁇ -1,4-glycosidic bonds of starch and starch-like polymers.
  • the cleaning effect of the enzymes used in detergents and cleaning agents which is decisive for the end user, is determined not only by the enzyme structure but also to a large extent by the way these enzymes are packaged and how they are stabilized against environmental influences.
  • washing and cleaning enzymes are packaged 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 cleaning agents.
  • liquid or gel-form detergents and cleaning agents often contain liquid enzyme preparations, which, unlike enzyme granules, are far less protected against external influences.
  • German patent applications DE 19717 329 A1 as well as the European registrations EP 1717303 A1 and EP 1 081 215 A1 disclose ways of stabilizing liquid enzyme preparations.
  • DE102007039655 A1 describes enzyme-containing liquid cleaning agents with propylene glycol and nonionic surfactants suitable for multiple dosing.
  • the object of the present application was therefore to stabilize a washing or cleaning enzyme preparation against phase separation / loss of activity in the event of multiple temperature fluctuations, in particular in a temperature range from 10 to 75.degree.
  • Corresponding enzyme preparations should be storable in a storage device located in the interior of the dishwasher or textile washing machine without any significant loss of activity.
  • liquid enzyme preparations can be stabilized by adding a specific hydrotrope.
  • the liquid detergent or cleaning agent preparations A are preferably water-containing. Particularly preferred washing or cleaning agent preparations A are characterized in that the weight fraction of the water, based in each case on the total weight of the washing or cleaning agent preparations, is between 2 and 20% by weight, preferably between 4 and 18% by weight and in particular between 5 and 15% by weight.
  • the washing or cleaning agent preparations according to the invention contain as their first essential component at least one washing or cleaning enzyme.
  • the proportion by weight of the washing or cleaning-active enzyme in the total weight of the washing or cleaning agent preparation is preferably between 5 and 80% by weight, preferably between 5 and 60% by weight, particularly preferably between 10 and 50% by weight and in particular between 10 and 30% by weight.
  • the enzymes used with particular preference include, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; outgoing Improved variants of the natural molecules are available for use in detergents or cleaning agents and are accordingly preferred. Washing or cleaning agents preferably contain enzymes in total amounts of 1 ⁇ 10 ⁇ 6 to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.
  • liquid washing or cleaning agent preparations A according to the invention characterized in that they contain a washing or cleaning enzyme from the group of amylases and / or proteases, are preferred.
  • subtilisin type those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg as well as their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the subtilases, but no longer the subtilisins in the narrower sense of the term, thermitase, Proteinase K and the proteases TW3 and TW7.
  • Liquid washing or cleaning agent preparations A preferred according to the invention contain, based on the total weight of washing or cleaning agent preparation A, 5 to 50% by weight, preferably 7 to 40% by weight and in particular 10 to 30% by weight protease preparations. Washing or cleaning agent preparations A which, based on their total weight, contain 15 to 25% by weight of protease preparations are particularly preferred.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, and the improved further developments of the aforementioned amylases for use in detergents and cleaning agents. Furthermore, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) should be emphasized.
  • Liquid detergent or cleaning agent preparations A preferred according to the invention contain, based on the total weight of the washing or cleaning agent preparation A, 0.1 to 30% by weight, preferably 1.0 to 25% by weight and in particular 2.0 to 20% by weight. -% amylase preparations. Washing or cleaning agent preparations A which, based on their total weight, contain 4.0 to 16% by weight of amylase preparations are particularly preferred.
  • Proteases and amylases that are active in washing or cleaning are generally not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations.
  • These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or with stabilizers or other auxiliaries.
  • the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals.
  • Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example due to the application of polymeric film formers, and due to the coating are stable in storage.
  • 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% by weight of the enzyme protein.
  • lipases or cutinases can also be used, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors.
  • suitable precursors include, for example, the lipases originally obtained from Humicola lanuginosa ( Thermomyces lanuginosus ), or further developed lipases, in particular those with the amino acid substitution D96L.
  • the cutinases which were originally isolated from Fusarium solani pisi and Humicola insolens can be used.
  • Lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii can also be used.
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases)
  • peroxidases such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • phenol oxidases polyphenol oxidases
  • organic, particularly preferably aromatic, compounds interacting with the enzymes are added in order to increase the activity of the oxidoreductases concerned (enhancers) or to ensure the flow of electrons (mediators) in the event of greatly differing redox potentials between the oxidizing enzymes and the soiling.
  • a plurality of enzymes and / or enzyme preparations preferably liquid protease preparations and / or amylase preparations, are preferably used.
  • a second essential component of the detergent or cleaning agent preparations according to the invention is cumene sulfonate.
  • the cumene sulfonates represents the para isopropylbenzenesulfonate is the preferred connection.
  • cumene sulfonate has proven to be superior not only to solvents such as glycerol, triacetin or diethylene glycol but also to hydrotropes such as xylene sulfonate.
  • solvents such as glycerol, triacetin or diethylene glycol
  • hydrotropes such as xylene sulfonate.
  • sufficient stabilization of the enzyme-containing washing or cleaning agent preparation A could not be achieved by means of any other substance.
  • E rfindungscleane washing or cleaning agent preparations A are characterized in that the washing or cleaning agent preparations, the cumene sulfonate in amounts of from 5.0 to 60 wt .-%, preferably in amounts from 5.0 to 50 wt .-%, preferably in quantities of between 52.0 and 40 wt .-% and in particular in amounts between 5.0 and 30 wt .-%, each based on the total weight of the detergent or cleaning agent preparations.
  • Particularly preferred proportions by weight of cumene sulfonate in the total weight of the detergent or cleaning agent preparation A are between 2.0 and 20% by weight, preferably between 3.0 and 18% by weight and in particular between 4.0 and 15% by weight.
  • organic solvent comes from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanol, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy
  • a particularly preferred organic solvent that is particularly effective with regard to stabilizing the detergent or cleaning agent preparation is 1,2-propylene glycol.
  • the proportion by weight of 1,2-propylene glycol in the total weight of the laundry detergent or cleaning agent preparations A according to the invention can vary within wide limits, but those preparations which contain an organic solvent, preferably 1,2-propylene glycol, have proven to be particularly stable, with the proportion by weight of 1,2-propylene glycol, based in each case on the total weight of the detergent or cleaning agent preparations, is preferably 5 to 80% by weight, more preferably 10 to 60% by weight and in particular 20 to 50% by weight.
  • a second preferred component of the washing or cleaning agent preparations according to the invention is boric acid or the boric acid derivative c).
  • boric acid boronic acids or their salts or esters are preferably used, including especially derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid (4-FPBA), or the salts or Esters of the compounds mentioned.
  • the proportion by weight of boric acid or boric acid derivatives in the total weight of detergent or cleaning agent preparations according to the invention is preferably between 0.001 to 10% by weight, more preferably 0.002 to 6% by weight and in particular 0.05 to 3% by weight.
  • a particularly preferred boric acid derivative that is particularly effective with regard to the stabilization of the washing or cleaning agent preparation is 4-formylphenyl boronic acid.
  • the proportion by weight of 4-formylphenyl-boronic acid in the total weight of the laundry detergent or cleaning agent preparation A according to the invention can vary within wide limits, but those preparations which, based on the total weight of the laundry detergent or cleaning agent preparation A, have proven to be particularly stable 10% by weight, preferably 0.002 to 6% by weight and in particular 0.05 to 3% by weight. Corresponding preparations are therefore preferred according to the invention.
  • a third preferred component of the washing or cleaning agent preparations according to the invention is a Ca or Mg ion source d).
  • the proportion by weight of the Ca or Mg ion source in the total weight of detergent or cleaning agent preparations according to the invention is preferably between 0.01 to 10% by weight, preferably 0.2 to 8% by weight and in particular 0.5 to 5% by weight .
  • the organic calcium salts have proven to be particularly preferred and particularly effective Ca ion sources with regard to the stabilization of the washing or cleaning agent preparation.
  • the proportion by weight of the organic calcium salts in the total weight of the washing or cleaning agent preparations A 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 washing or cleaning agent preparation, 0.01 to 10 wt. %, preferably 0.2 to 8% by weight and in particular 0.5 to 5% by weight. Corresponding preparations are therefore preferred according to the invention.
  • a very particularly preferred organic calcium salt is calcium lactate.
  • washing or cleaning agent preparations can furthermore also contain polyols, in particular sorbitol.
  • Polyols, in particular sorbitol are preferably used in amounts of 1 to 20% by weight, in particular 2 to 15% by weight, especially 2 to 10% by weight.
  • composition of some exemplary inventive washing or cleaning agent preparations A can be found in the following tables: Table 1 ⁇ u> (recipes 1-4 not according to the invention) ⁇ /u> Recipe 1 Recipe 2 Recipe 3 Recipe 4 Recipe 5 Amylase preparation 5.0 to 30 5.0 to 25 5.0 to 25 5.0 to 20 5.0 to 20 Protease preparation - * - - - - Cumene sulfonate 0.5 to 60 1.0 to 50 2.0 to 40 2.0 to 40 5.0 to 30 Org.
  • Solvent 0 to 80 0 to 80 0 to 60 0 to 60 0 to 50 Boric acid derivative 0 to 10 0 to 10 0 to 6 0 to 6 0 to 3.0
  • Ca ion source 0 to 10 0 to 8 0 to 8 0 to 8 0 to 5 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Recipe 1 Recipe 2 Recipe 3 Recipe 4 Recipe 5
  • Amylase preparation - - - - - - Protease preparation 5.0 to 50 7.0 to 40 7.0 to 40 10 to 30 10 to 30 Cumene sulfonate 0.5 to 60 1.0 to 50 2.0 to 40 2.0 to 40 5.0 to 30 Org.
  • Solvent 0 to 80 0 to 80 0 to 60 0 to 60 0 to 50 Boric acid derivative 0 to 10 0 to 10 0 to 6 0 to 6 0 to 3.0
  • Ca ion source 0 to 10 0 to 8 0 to 8 0 to 8 0 to 5 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Recipe 1 Recipe 2 Recipe 3 Recipe 4 Recipe 5
  • Amylase preparation 5.0 to 30 5.0 to 25 5.0 to 25 5.0 to 20 5.0 to 20
  • Protease preparation 5.0 to 50 7.0 to 40 7.0 to 40 10 to 30 10 to 30
  • Cumene sulfonate 0.5 to 60 1.0 to 50 2.0 to 40 2.0 to 40 5.0 to 30 Org.
  • Preferred washing or cleaning agent preparations A according to the invention are characterized in that they contain a substance from the group of trihydric or polyhydric alcohols as a further ingredient, preferably in amounts from 0.1 to 20% by weight, particularly preferably from 0.5 to 15% by weight and in particular from 1.0 to 10% by weight.
  • the weight fraction of these nonionic surfactants in preferred liquid washing or cleaning agent preparations A is 0.5 to 30% by weight, preferably 2.0 to 25% by weight and in particular 5.0 to 20% by weight.
  • the cleaning performance of enzyme-containing preparations according to the invention can be significantly improved, both in comparison to surfactant-free systems and in comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
  • nonionic surfactants with one or more free hydroxyl groups on one or both terminal alkyl radicals, the stability of the enzymes contained in the washing or cleaning agent preparations according to the invention can be significantly improved.
  • end-capped poly (oxyalkylated) nonionic surfactants which, according to 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 stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 with 1 to 30 carbon atoms, where x for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
  • R 1 which stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 with 1 to 30 carbon atoms, where x for values
  • R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R 1 represents a linear or branched aliphatic hydrocarbon radical with 4, are particularly preferred up to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15.
  • Especially the C (EO) -2-hydroxyalkyl ether 15-40 8-10 fatty alcohol (PO) 1 - - to the group of these nonionic surfactants include the C 2-26 fatty alcohol, for example (PO) 1 (EO) 22 -2 hydroxydecyl ether.
  • nonionic surfactants are the end group-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 , in which R 1 and R 2 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R 3 represents H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2- Butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 can be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, —CH 3 or —CH 2 CH 3 are particularly 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 can be different if x 2.
  • the value 3 for x has been chosen as an example and can be larger, with the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .
  • R 1 , R 2 and R 3 are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • washing or cleaning agent preparations A according to the invention can contain further ingredients, for example active ingredients from the group of builders, bleaching agents, washing and cleaning-active polymers, corrosion inhibitors, contain fragrances or dyes.
  • active ingredients from the group of builders, bleaching agents, washing and cleaning-active polymers, corrosion inhibitors, contain fragrances or dyes.
  • preferred washing or cleaning agent preparations A according to the invention contain these further ingredients only to a minor extent.
  • washing or cleaning agent preparations A which contain less than 20% by weight, preferably less than 10% by weight and in particular less than 5% by weight of builders.
  • Particularly preferred washing or cleaning agent preparations A which are free from builders.
  • washing or cleaning agent preparations A are preferred which contain less than 10% by weight, preferably less than 5% by weight and in particular less than 2% by weight of bleaching agent.
  • those washing or cleaning agent preparations A which are free from bleaching agents are particularly preferred.
  • washing or cleaning agent preparations A according to the invention are distinguished by a low level of formulation complexity. This low degree of complexity simplifies the production of the cleaning agents and thus reduces the costs involved in providing these cleaning agents.
  • preferred cleaning agents according to the invention are characterized in that, in addition to the essential components a), b), c) and d), they have a maximum of three, preferably a maximum of two, particularly preferably a maximum of one and in particular no further components.
  • the proportion by weight of further constituents is preferably less than 10% by weight, preferably less than 5% by weight, particularly preferably less than 2% by weight and very particularly preferably less than 0.1% by weight.
  • the cleaning agents according to the invention are combined with one or more further cleaning agents.
  • the further cleaning agents combined with the cleaning agent according to the invention are preferably cleaning agents containing surfactants and / or detergents.
  • Preferred liquid preparations are characterized in that they are present together with one, preferably two or three further liquid detergent or cleaning agent preparations to form a combination product.
  • the other one, two or three liquid washing or cleaning agent preparations have a composition that differs 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.
  • the other liquid washing or cleaning agent preparations can contain other washing or cleaning-active substances, substances from the group of builders, polymers, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers being preferred.
  • Bleaching agents and bleach activators can also be used. These preferred ingredients are described in more detail below.
  • the builders include in particular the zeolites, silicates, carbonates and organic cobuilders.
  • crystalline sheet silicates of the formula NaMSi x O 2x + 1 ⁇ y H 2 O, in which x is 2, are particularly suitable.
  • both ⁇ - and ⁇ -sodium disitics are Na 2 Si 2 O 5 ⁇ y H 2 Os, as well as above all Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5 ), Na-SKS-7 ( ⁇ -Na 2 Si 2 O 5 , natrosilite), Na-SKS-9 (NaHSi 2 O 5 ⁇ H 2 O), Na-SKS-10 (NaHSi 2 O 5 ⁇ 3 H 2 O, kanemite), Na-SKS-11 (t -Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 ( ⁇ -Na 2 Si 2 O 5 ) is preferred.
  • Laundry detergents or cleaning agents preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi x O 2x + 1 ⁇ y H 2 O of 0.1 to 20% by weight, preferably 0.2 to 15% by weight and in particular of 0.4 to 10% by weight, based in each case on the total weight of these agents.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.
  • the alkali metal hydroxides are preferably only used in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4% by weight and in particular below 2% by weight, based in each case based on the total weight of the detergent or cleaning agent.
  • Agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides are particularly preferred.
  • Organic cobuilders that may be mentioned are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and phosphonates. These substance classes are described below.
  • Organic builder substances which can be used are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or its sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, as well as mixtures of these.
  • the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value in detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molar masses specified for polymeric polycarboxylates in the context of this document are weight-average molar masses M w of the respective acid form, which were basically determined by means of gel permeation chromatography (GPC) using a UV detector.
  • the measurement was carried out against an external polyacrylic acid standard, which, due to its structural similarity to the polymers under investigation, provides realistic molecular weight values. This information deviates significantly from the molecular weight information in which polystyrene sulfonic acids are used as the standard.
  • the molar weights measured against polystyrene sulfonic acids are generally significantly higher than the molar weights given in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates from this group, which have molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can be preferred.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and 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 particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • Biodegradable polymers composed of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives as monomers or salts of acrylic acid and 2-alkylallylsulphonic acid and sugar derivatives as monomers .
  • copolymers are those which have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • Polymers which are effective as softeners are, for example, the polymers containing sulfonic acid groups, which are used with particular preference.
  • Particularly preferred polymers containing sulfonic acid groups are copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers.
  • unsaturated carboxylic acids of the formula are used as monomers
  • 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, 3- Methacrylamido-2-hydroxy-propanesulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulphonic acid, 2-methyl-2-propen1-sulphonic acid, 3-sulphate-sulphonyl methacrylate, 3-sulphate-sulphonic acid, vinylsulpho-propyl, 3-sulphate-sulphonate , Sulfomethacrylamide, sulfomethyl methacrylamide and water-soluble salts of the acids mentioned.
  • Ethylenically unsaturated compounds are particularly suitable as further ionic or non-ionic monomers.
  • the content of these further ionic or non-ionic monomers in the polymers used is preferably less than 20% by weight, based on the polymer.
  • the sulfonic acid groups can be wholly or partly in neutralized form, i.e. that the acidic hydrogen atom 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 copolymers containing sulfonic acid groups is preferred according to the invention.
  • the monomer distribution of the copolymers used with preference according to the invention is, in the case of copolymers which only contain monomers from groups i) and ii), preferably in each case from 5 to 95% by weight of i) or ii), particularly preferably from 50 to 90% by weight of monomer from group i) and 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • terpolymers particularly preferred are those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 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 application.
  • Preferred washing or cleaning agents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • Particularly preferred copolymers d) contain as carboxyl group-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, cinnamon acid or their mixtures.
  • carboxyl group-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, cinnamon acid or their mixtures.
  • Particularly preferred such monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, ⁇ -
  • Polymeric aminodicarboxylic acids, their salts or their precursor substances are also to be mentioned as further preferred builder substances.
  • Polyaspartic acids and their salts are particularly preferred.
  • Ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • EDDS Ethylenediamine-N, N'-disuccinate
  • glycerol disuccinates and glycerol trisuccinates are also preferred. Suitable amounts used are from 3 to 15% by weight.
  • the automatic dishwashing agents according to the invention particularly preferably contain methylglycinediacetic acid or a salt of methylglycinediacetic acid.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which can optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Glass corrosion inhibitors prevent the appearance of cloudiness, streaks and scratches, but also the iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of the magnesium and zinc salts and the magnesium and zinc complexes.
  • the spectrum of zinc salts preferred according to the invention ranges from salts that are sparingly or insoluble in water, i.e. a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 mg / l, up to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ° C Water temperature).
  • the first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate
  • the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
  • At least one zinc salt of an organic carboxylic acid is used with particular preference as the glass corrosion inhibitor.
  • Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • Corrosion inhibitors serve to protect the items to be washed or the machine, silver protectants being particularly important in the field of machine dishwashing.
  • the known substances of the prior art can be used.
  • silver protectants selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes.
  • 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 tolerable salts.
  • Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulfurous acid, organic Carboxylic acids such as acetic, glycolic, citric and succinic acids. 5-pentyl-, 5-heptyl-, 5-nonyl-, 5-undecyl-, 5-isononyl-, 5-Versatic-10-acid-alkyl-3-amino-1,2,4-triazoles and mixtures are particularly effective of these substances.
  • perfume oils or fragrances individual odoriferous compounds, e.g. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. However, it is preferred to use mixtures of different fragrances which together produce an appealing fragrance note.
  • perfume oils can also contain natural odorant mixtures, such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • Preferred dyes the selection of which presents no difficulty to the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the agents and to light, as well as no pronounced substantivity to the substrates to be treated with the dye-containing agents, such as textiles, glass, ceramics or plastic tableware not to stain them.
  • washing or cleaning agent preparations according to the invention used with particular preference in these processes correspond to the agents described in detail above. Reference is made at this point to the statements made there in order to avoid repetition.
  • Preferred methods for washing dishes or textile cleaning are characterized in that the liquid detergent or cleaning agent preparation from a storage container located in the dishwasher or textile washing machine, which contains the multiple amount of the washing or cleaning agent preparation necessary for carrying out a cleaning process, into the interior of the dishwasher is dosed.
  • the storage container used for dosing can be a storage container integrated into the dishwasher or textile washing machine, i.e. a storage container permanently connected to the dishwasher or textile washing machine, but also a self-sufficient, i.e. independent one in the interior act the dishwasher or textile washing machine introducible storage container.
  • An example of an integrated storage container is a receptacle integrated into the door of the dishwasher, which is connected to the interior of the dishwasher via a supply line.
  • An example of a self-sufficient storage container is a so-called upside-down bottle with an outlet valve on the bottom, which can be placed in the cutlery basket of the dishwasher, for example.
  • the storage container has at least one chamber for receiving the liquid washing or cleaning agent preparations according to the invention.
  • the storage container has more than one, preferably two, three, four or more separate receiving chambers, of which at least one chamber contains the liquid washing or cleaning agent preparations according to the invention, while at least one, preferably at least two further chambers , preferably contains / contain liquid preparations with a composition deviating from the liquid washing or cleaning agent preparations 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 metered into the interior of the dishwasher.
  • the volume of preferred storage containers 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.
  • washing or cleaning agent preparations according to the invention are distinguished by a particular temperature stability and the methods according to the invention are used in particular for repeated dosing of these preparations from storage containers located in the interior of the dishwasher or textile washing machine.
  • Preferred methods according to the invention are characterized in that the liquid detergent or cleaning agent preparation A, before being metered into the interior of the dishwasher or textile washing machine, for a period of at least two, preferably at least four, particularly preferably at least eight and in particular at least twelve separate cleaning processes in the Storage container located in the dishwasher remains.
  • complete cleaning processes are referred to as “separate cleaning processes”, which preferably also include a pre-wash cycle and / or a final rinse cycle in addition to the main cleaning cycle and which can be selected and triggered, for example, by means of the dishwasher's program switch.
  • the duration of these separate cleaning processes is preferably at least 15 minutes, preferably between 20 and 360 minutes, preferably between 30 and 240 minutes.
  • the time between two separate cleaning processes, within which the liquid detergent or cleaning agent preparation is dosed 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 fluctuate within wide limits in the course of the method according to the invention, the liquid detergent or cleaning agent preparations being particularly suitable for those processes in which the liquid washing or cleaning agent preparation A is in the storage container at least twice, preferably at least four times, particularly preferably at least eight times and in particular at least twelve times to temperatures above 30.degree. C., preferably above 40.degree. C. and particularly preferred is heated above 50 ° C. Heating to temperatures above 60 ° C. or above 70 ° C. or twenty or thirty times heating of the liquid detergent or cleaning agent preparation A can of course also be implemented according to the invention.
  • the liquid detergent or cleaning agent preparation A in the storage container is heated by the rinsing liquor surrounding this storage container in each of the separate cleaning processes that take place one after the other.
  • the liquid detergent or cleaning agent preparation A cools in the storage container to temperatures below 30 ° C., preferably below 26 ° C. and in particular below 22 ° C. between the separate cleaning processes.
  • the combination of cleaning agents described above is made up in the form of separate receiving chambers, each of these receiving chambers containing one of the cleaning agents combined with one another.
  • Examples of such packaging forms are cartridges with two, three, four or more separate receiving chambers, for example two-, three-, four- or multi-chamber bottles.
  • the previously described cartridges of the cleaning agent supply forms are provided with a dispensing device that can be detached from the cartridge.
  • a dispensing device can be connected to the cartridge, for example, by means of an adhesive, latching, snap or plug connection.
  • the detachable connection between the cartridge and the dispenser enables the cartridges to be exchanged on the dispenser. Such an exchange can be indicated, for example, when the cleaning program is changed or after the cartridge has been completely emptied.
  • cleaning agent supply forms are also conceivable in which the cartridge and the dosing device are permanently connected to one another.
  • the aforementioned cleaning agent dosing systems comprising a cleaning agent according to the invention (and optionally one or two further cleaning agents different from the cleaning agent according to the invention), a cartridge and a dosing device detachably connected to the cartridge are in a preferred embodiment in a common outer packaging, the filled cartridge and the dispensing device are particularly preferably contained separately from one another in the outer packaging.
  • the outer packaging is used for storage, transport and presentation of the cleaning agent supply form according to the invention and protects it from soiling, impact and shock.
  • the outer packaging should be at least partially transparent.
  • the dosing system according to the invention consists of the basic components of a cartridge filled with the cleaning agent according to the invention and one with the cartridge couplable dosing device, which in turn is formed from further assemblies, such as component carriers, actuators, locking elements, sensors, energy sources and / or control units.
  • the dosing system according to the invention is movable. Movable in the sense of this application means that the dosing system is not inextricably linked to a water-carrying device such as a dishwasher, washing machine, tumble dryer or the like, but can be removed by the user from a dishwasher or positioned in a dishwasher, i.e. can be handled independently
  • the dosing device is not detachably connected for the user to a water-carrying device such as a dishwasher, washing machine, tumble dryer or the like and only the cartridge is movable.
  • the preparations to be dosed can have a pH value between 2 and 12 depending on the intended use, all components of the dosing system that come into contact with the preparations should have a corresponding acid and / or alkali resistance. Furthermore, through a suitable choice of material, these components should be largely chemically inert, for example to nonionic surfactants, enzymes and / or fragrances.
  • a cartridge in the context of this application is understood to mean a packaging material which is suitable for enveloping or holding together flowable or scatterable preparations and which can be coupled to a dispensing device for dispensing the preparation.
  • a cartridge can also comprise several chambers which can be filled with compositions that differ from one another. It is also conceivable that a plurality of containers is arranged to form a cartridge unit.
  • the cartridge has at least one outlet opening which is arranged in such a way that a gravity-induced release of preparation from the container can be brought about when the dispensing device is in the use position.
  • no further conveying means are required for releasing the preparation from the container, which means that the construction of the dispensing device can be kept simple and the manufacturing costs can be kept low.
  • At least one second chamber is provided for receiving at least one second flowable or sprinkleable preparation, the second chamber having at least one outlet opening which is arranged such that a gravity-induced product release from the second chamber in the use position of the dispensing device is effected.
  • the arrangement of a second chamber is particularly advantageous when preparations are stored in the separate containers which are usually not mutually stable, such as bleaching agents and enzymes.
  • one of the chambers can be designed to release volatile preparations such as a fragrance into the environment.
  • the cartridge is designed in one piece.
  • the cartridges can be formed cost-effectively in one production step, in particular by suitable blow molding processes.
  • the chambers of a cartridge can be separated from one another by bars or material bridges.
  • the cartridge can also be formed in several pieces by components manufactured by injection molding and then joined together.
  • the cartridge is formed in several pieces in such a way that at least one chamber, preferably all chambers, can be individually removed from the dosing device or inserted into the dosing device.
  • This makes it possible to replace an already emptied chamber when a preparation is consumed differently from one chamber, while the remaining chambers, which can still be filled with preparation, remain in the dispensing device.
  • a targeted and needs-based refilling of the individual chambers or their preparations can thus be achieved.
  • the chambers of a cartridge can be fixed to one another by suitable connection methods, so that a container unit is formed.
  • the chambers can be fixed to one another in a detachable or non-detachable manner by means of a suitable form-fitting, force-fitting or material connection.
  • the fixation can be done by one or more of the connection types from the group of snap-in connections, Velcro connections, press connections, fusion connections, adhesive connections, welded connections, soldered connections, screw connections, wedge connections, clamp connections or bounce connections.
  • the fixation can also be formed by a shrink tube (so-called sleeve), which in a heated state over the entire or sections the cartridge is pulled and tightly encloses the chambers or the cartridge when it has cooled down.
  • the bottom of the chambers can be inclined in a funnel shape towards the dispensing opening.
  • the inner wall of a chamber can be designed in such a way that there is little material adhesion of the preparation to the inner chamber wall. This measure also enables the remaining emptying capacity of a chamber to be further optimized.
  • the chambers of a cartridge can have the same or different filling volumes.
  • the ratio of the container volumes is preferably 5: 1, in a configuration with three chambers it is preferably 4: 1: 1, these configurations being particularly suitable for use in dishwashers.
  • the cartridge preferably has 3 chambers.
  • the first chamber contains an alkaline cleaning preparation
  • the second chamber contains an enzymatic preparation
  • the third chamber contains a rinse aid, the volume ratio of the chambers being approximately 4: 1: 1.
  • a metering chamber can be formed in or on a chamber in front of the outlet opening in the direction of flow of the preparation.
  • the dosage chamber determines the amount of preparation that is to be released into the environment when the preparation is released from the chamber. This is particularly advantageous if the closure element of the dispensing device, which effects the release of the preparation from a chamber to the environment, can only be put into a release and a closed state without checking the amount to be released.
  • the dosing chamber then ensures that a predefined amount of preparation is released without direct feedback of the dispensed amount of preparation.
  • the metering chambers can be formed in one piece or in several pieces.
  • one or more chambers in addition to an outlet opening, each have a liquid-tight closable chamber opening.
  • This chamber opening makes it possible, for example, to refill preparation stored in this chamber.
  • ventilation options can be provided, in particular in the head area of the cartridge, in order to equalize pressure when the fill level of the cartridge falls To ensure chambers between the interior of the cartridge chambers and the environment.
  • These ventilation options can be designed, for example, as a valve, in particular a silicone valve, micro-openings in the cartridge wall or the like.
  • the cartridge chambers should not be ventilated directly, but rather via the dosing device or no ventilation, e.g. be provided when using flexible containers, such as bags, this has the advantage that at elevated temperatures in the course of a washing cycle of a dishwasher a pressure is built up due to the heating of the chamber contents, which presses the preparations to be dosed in the direction of the outlet openings, so that the cartridge can be emptied easily. Furthermore, with such an air-free packaging there is no risk of oxidation of substances in the preparation, which makes pouch packaging or also bag-in-bottle packaging appear appropriate, in particular for preparations sensitive to oxidation.
  • the cartridge usually has a filling volume of ⁇ 5,000 ml, in particular ⁇ 1,000 ml, preferably ⁇ 500 ml, particularly preferably ⁇ 250 ml, very particularly preferably ⁇ 50 ml.
  • the cartridge can take any shape. It can, for example, be cube-like, spherical or plate-like.
  • the cartridge and the dosing device can in particular be designed in terms of their spatial shape in such a way that they ensure the lowest possible loss of usable volume, in particular in a dishwasher.
  • the dispensing device based on dishes to be cleaned in dishwashers.
  • it can be plate-shaped, roughly the size of a plate.
  • the dosing device can save space e.g. be positioned in the lower basket of the dishwasher.
  • the correct positioning of the dosing unit is immediately and intuitively revealed to the user thanks to the plate-like shape.
  • the cartridge preferably has a height: width: depth ratio of between 5: 5: 1 and 50: 50: 1, particularly preferably about 10: 10: 1.
  • the "slim" design of the dispensing device and the cartridge make it possible, in particular, to position the device in the lower cutlery basket of a dishwasher in the receptacles provided for plates. This has the advantage that the preparations dispensed from the dispenser reach the washing liquor directly and cannot adhere to other items to be washed.
  • the dosing system is dimensioned in such a way that the dosing system can only be positioned in the receptacles provided in the lower basket.
  • the width and the height of the metering system can be selected in particular between 150 mm and 300 mm, particularly preferably between 175 mm and 250 mm.
  • the dosing unit in the form of a cup with an essentially circular or square base area.
  • the cartridge In order to protect heat-sensitive components of a preparation in a cartridge from the effects of heat, it is advantageous to manufacture the cartridge from a material with a low thermal conductivity.
  • Another possibility for reducing the influence of heat on a preparation in a chamber of the cartridge is to isolate the chamber by suitable measures, e.g. through the use of thermal insulation materials such as Styrofoam, which completely or partially enclose the chamber or cartridge in a suitable manner.
  • the cartridge has an RFID label that contains at least information about the contents of the cartridge and that can be read out by the sensor unit.
  • This information can be used to select a dosing program stored in the control unit. This ensures that a dosing program that is optimal for a particular preparation is always used. It can also be provided that if there is no RFID label or if there is an RFID label with an incorrect or faulty identifier, no dosing is carried out by the dosing device and instead an optical or acoustic signal is generated that the user is on the present Errors.
  • the cartridges can also have structural elements that interact with corresponding elements of the dispenser according to the key-lock principle, so that, for example, only cartridges of a certain type can be coupled to the dispenser.
  • This configuration also makes it possible for information about the cartridge coupled to the dosing device to be transmitted to the control unit, which means that the dosing device can be controlled in accordance with the content of the corresponding container.
  • the cartridge is designed in particular to hold free-flowing detergents or cleaning agents.
  • a cartridge particularly preferably has a plurality of chambers for the spatially separated reception of preparations of a washing or cleaning agent that are different from one another.
  • the cartridge can be designed such that it can be arranged in or on the dishwasher in a detachable or fixed manner.
  • control unit The control unit, sensor unit and at least one actuator required for operation are integrated in the dosing device.
  • An energy source is also preferably arranged in the metering device.
  • the dosing device preferably consists of a splash-proof housing which prevents splash water from penetrating into the interior of the dosing device, as can occur, for example, when used in a dishwasher.
  • the dispensing device comprises at least one first interface which interacts with a corresponding interface formed in or on a water-carrying device, in particular a water-carrying household appliance, preferably a dishwasher or washing machine, in such a way that electrical energy can be transmitted from the water-carrying device to the dispenser is realized.
  • a water-carrying device in particular a water-carrying household appliance, preferably a dishwasher or washing machine, in such a way that electrical energy can be transmitted from the water-carrying device to the dispenser is realized.
  • the interfaces are formed by plug connectors.
  • the interfaces can be designed in such a way that a wireless transmission of electrical energy is effected.
  • a second interface is in each case on the dosing device and the water-carrying device, such as a dishwasher, for the transmission of electromagnetic signals, which in particular contain operating status, measurement and / or control information of the dosing device and / or the water-carrying device such as a Represent dishwasher, trained.
  • An adapter can be used to easily couple the dosing system to a water-bearing household appliance.
  • the adapter is used to mechanically and / or electrically connect the dosing system to the water-bearing household appliance.
  • the adapter is preferably firmly connected to a water-carrying line of the household appliance.
  • the adapter it is also conceivable to provide the adapter for positioning in or on the household appliance, in which the adapter is captured by the water flow and / or spray jet of the household appliance.
  • the adapter makes it possible to implement a dosing system for both a stand-alone and a "build-in" version. It is also possible to design the adapter as a type of charging station for the metering system, in which, for example, the energy source of the metering device is charged or data is exchanged between the metering device and the adapter.
  • the adapter can be arranged on one of the inner walls of the washing chamber, in particular on the inner side of the dishwasher door.
  • the adapter as such is positioned inaccessible to the user in the water-bearing household appliance, so that the dosing device is inserted into the adapter, for example, during the assembly of the household appliance, the adapter, the dosing device and the household appliance being designed in this way that a cartridge can be coupled to the dispenser by the user.
  • the detergents, detergent combinations or detergent available forms according to the invention are suitable for use in dishwashing as well as for textile cleaning, although the use of a detergent or cleaning agent preparation A according to the invention, a detergent combination according to the invention or a detergent supply form according to the invention for dishwashing in an automatic dishwasher is preferred.
  • the cleaning agents according to the invention are distinguished by a particular physical and chemical stability, in particular to temperature fluctuations.
  • the cleaning agents according to the invention are therefore exceptionally suitable for metering by means of a metering system located in the interior of a washing machine or dishwasher.
  • a dosing system which can be immovably integrated into the interior of the washing machine or dishwasher (machine-integrated dosing device) but of course can also be introduced into the interior as a movable device (self-sufficient dosing device), contains the multiple amount of cleaning agent required to carry out an automatic cleaning process .
  • Movable in the sense of this application means that the dispensing and dosing system cannot be inextricably linked to a device such as a dishwasher, washing machine, Tumble dryer or the like is connected, but can be removed, for example, from a dishwasher or positioned in a dishwasher.
  • An example of an immovable cartridge is a container that is immovably integrated into the interior, for example into the side wall or the inner lining of the door of a dishwasher.
  • a movable cartridge is a container that is brought into the interior of the dishwasher or textile washing machine by the consumer and remains there during the entire course of a cleaning cycle.
  • a cartridge can be integrated into the interior space, for example by simply placing it in the cutlery or crockery basket, but can also be removed again from the interior of the dishwasher by the consumer.
  • the detergent or detergent combination is metered from the cartridge into the interior of the dishwasher or textile washing machine, as described above, preferably by means of a metering device that can be detached from the cartridge.
  • a metering device can be connected to the cartridge by means of an adhesive, latching, snap or plug connection.
  • Cartridges with an undetachably connected metering device can of course also be used.
  • the cleaning agents and cleaning agent combinations according to the invention are, as stated above, preferably used as automatic dishwashing agents or as machine laundry detergents.
  • Automatic dishwashing methods according to the invention and textile washing methods using a washing or cleaning agent preparation A according to the invention are characterized in that, in the course of these methods, a subset a of the washing or cleaning agent preparation A in the cartridge is transferred from a cartridge located in the interior of the dishwasher or textile washing machine into the interior the dishwasher or textile washing machine is dosed, with a residual amount of the cleaning agent in the cartridge remaining in the cartridge until the end of the dishwashing process or textile washing process, characterized in that this residual amount is at least twice, preferably at least four times and in particular at least eight times the amount corresponds to the subset a.
  • This application therefore also relates to an automatic dishwashing process or machine textile washing process using a cleaning agent combination according to the invention, comprising a cleaning agent A according to the invention and a Another cleaning agent B different from A, in the course of which, from a cartridge located in the interior of the dishwasher or textile washing machine, a portion a of the cleaning agent A in the cartridge and also a portion b of the cleaning agent B in the cartridge into the interior of the dishwasher or Textile washing machine is dosed, with residual amounts of detergents A and B remaining in the cartridge until the end of the dishwashing process or textile washing process and the remaining amount of detergent A corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of sub-amount a and the remaining amount of the cleaning agent B corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of partial amount b.
  • a machine dishwashing process or machine textile washing process using a cleaning agent combination according to the invention comprising a cleaning agent A according to the invention and a further cleaning agent B different from A and a third cleaning agent C different from A and B, in the course of which from one in the interior of the Dishwasher or textile washing machine a subset a of the cleaning agent A in the cartridge and also a portion b of the cleaning agent B in the cartridge and additionally a portion c of the cleaning agent C in the cartridge is dosed into the interior of the dishwasher or textile washing machine , with residual amounts of detergents A, B and C remaining in the cartridge until the end of the dishwashing process or textile washing process and the remaining amount of detergent A at least de r corresponds to twice, preferably at least four times and in particular at least eight times the amount of partial amount a, the remaining amount of cleaning agent B corresponds to at least double, preferably at least four times and in particular at least eight times the amount of partial amount b, and the remaining amount of cleaning agent C is at least
  • the different cleaning agents are preferably metered in at different times of the cleaning cycle.
  • time t2 is at least 1 minute, preferably at least 2 minutes and in particular between 3 and 20 minutes or after time t1.

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Claims (6)

  1. Utilisation d'une préparation liquide d'agent détergent ou nettoyant A, comprenant
    a) au moins 5 % en poids d'au moins une préparation d'enzymes à action détergente ou nettoyante ;
    b) du sulfonate de cumène en quantités comprises entre 5,0 et 60 % en poids,
    ou d'une combinaison d'agents nettoyants, comprenant
    a) une préparation liquide d'agent détergent ou nettoyant A ;
    b) au moins une, de préférence au moins deux autres préparations d'agent détergent ou nettoyant différentes de A,
    pour le remplissage
    i) d'une cartouche d'un système de dosage, laquelle est intégrée de manière immobile dans l'espace intérieur d'un lave-vaisselle ou d'un lave-linge, ou
    ii) d'une cartouche mobile d'un système de dosage, laquelle est prévue pour être positionnée dans l'espace intérieur d'un lave-vaisselle ou d'un lave-linge,
    avec une quantité suffisante de ladite préparation liquide d'agent détergent ou nettoyant ou de ladite combinaison d'agents nettoyants afin d'exécuter au moins deux fois, de préférence au moins quatre fois et en particulier au moins huit fois un procédé de lavage de vaisselle en machine ou un procédé de lavage de linge en machine.
  2. Forme de présentation d'agent nettoyant, comprenant
    a) une préparation liquide d'agent détergent ou nettoyant A, comprenant
    a) au moins 5 % en poids d'au moins une préparation d'enzymes à action détergente ou nettoyante ;
    b) du sulfonate de cumène en quantités comprises entre 5,0 et 60 % en poids,
    en une quantité suffisante afin d'exécuter au moins deux fois, de préférence au moins quatre fois et en particulier au moins huit fois un procédé de lavage de vaisselle en machine ou un procédé de lavage de linge en machine ;
    b) une cartouche destinée à la préparation d'agent détergent ou nettoyant A.
  3. Utilisation d'une forme de présentation d'agent nettoyant selon la revendication 2 comme réservoir d'agent nettoyant pour
    i) un appareil de dosage intégré de manière immobile dans l'espace intérieur d'un lave-vaisselle ou d'un lave-linge, ou
    ii) un appareil de dosage mobile prévu pour être positionné dans l'espace intérieur d'un lave-vaisselle ou d'un lave-linge.
  4. Système de dosage d'agent nettoyant, comprenant
    a) une préparation liquide d'agent détergent ou nettoyant A, comprenant
    a) au moins 5 % en poids d'au moins une préparation d'enzymes à action détergente ou nettoyante ;
    b) du sulfonate de cumène en quantités comprises entre 5,0 et 60 % en poids,
    en une quantité suffisante afin d'exécuter au moins deux fois, de préférence au moins quatre fois et en particulier au moins huit fois un procédé de lavage de vaisselle en machine ou un procédé de lavage de linge en machine ;
    b) une cartouche destinée à la préparation d'agent détergent ou nettoyant A ;
    c) un appareil de dosage relié à la cartouche de manière amovible.
  5. Procédé de lavage de vaisselle en machine ou procédé de lavage de linge en machine utilisant une préparation liquide d'agent détergent ou nettoyant A, comprenant
    a) au moins 5 % en poids d'au moins une préparation d'enzymes à action détergente ou nettoyante ;
    b) du sulfonate de cumène en quantités comprises entre 5,0 et 60 % en poids,
    ou une combinaison d'agents nettoyants, comprenant
    a) une préparation liquide d'agent détergent ou nettoyant A ;
    b) au moins une, de préférence au moins deux autres préparations d'agents détergents ou nettoyants différentes de A,
    ou une forme de présentation d'agent nettoyant ou un système de dosage d'agent nettoyant selon l'une des revendications précédentes, au cours duquel une quantité partielle a de l'agent nettoyant situé dans la cartouche est dosée dans l'espace intérieur du lave-vaisselle ou du lave-linge à partir d'une cartouche située dans l'espace intérieur du lave-vaisselle ou du lave-linge, une quantité résiduelle de l'agent nettoyant situé dans la cartouche restant dans la cartouche jusqu'à la fin du procédé de lavage de vaisselle ou du procédé de lavage de linge, caractérisé en ce que cette quantité résiduelle représente au moins deux fois, de préférence au moins quatre fois et en particulier au moins huit fois la quantité de la quantité partielle a.
  6. Utilisation de sulfonate de cumène, en particulier de para-isopropylbenzènesulfonate, pour stabiliser des préparations d'enzymes à action détergente ou nettoyante, en particulier celles qui contiennent des enzymes à action détergente ou nettoyante du groupe des amylases et/ou des protéases, dans des préparations liquides d'agent détergent ou nettoyant.
EP10712421.6A 2009-04-01 2010-03-31 Détergents Active EP2414498B1 (fr)

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DE102009002095A DE102009002095A1 (de) 2009-04-01 2009-04-01 Reinigungsmittel
PCT/EP2010/054305 WO2010112548A1 (fr) 2009-04-01 2010-03-31 Détergents

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DE (1) DE102009002095A1 (fr)
ES (1) ES2844278T3 (fr)
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WO (1) WO2010112548A1 (fr)

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DE102010002196A1 (de) * 2010-02-22 2011-11-17 Henkel Ag & Co. Kgaa Kartusche für ein wasserführendes Haushaltsgerät
DE102011000889A1 (de) * 2011-02-23 2012-08-23 Witty Chemie Gmbh & Co. Kg Reinigungsmittel für Geschirrspülanlagen und Verfahren dafür
KR102463726B1 (ko) * 2012-07-19 2022-11-07 닛산 가가쿠 가부시키가이샤 반도체용 세정액 및 이것을 이용한 세정방법
DE102012107728A1 (de) * 2012-08-22 2014-02-27 Witty-Chemie Gmbh & Co. Kg Phosphorfreies Reinigungsmittel für Geschirrspülanlagen und Verfahren dafür
RU2642077C2 (ru) 2013-11-11 2018-01-24 ЭКОЛАБ ЮЭсЭй ИНК. Многоцелевой ферментный детергент и способы стабилизации применяемого раствора
CN109312523B (zh) 2016-06-09 2021-03-16 荷兰联合利华有限公司 洗衣液混合设备
TR202004710U5 (tr) 2017-10-05 2021-01-21 Unilever Nv Özelleştirilmiş çamaşır yıkama için usuller ve aygıtlar.
GB2571336A (en) 2018-02-26 2019-08-28 Unilever Plc Methods and system for monitoring and replenishing one or more laundry components
EP3693895B1 (fr) * 2019-02-05 2023-05-03 Nxp B.V. Produit consommable et son procédé de production
CN114630934A (zh) 2019-11-01 2022-06-14 联合利华知识产权控股有限公司 可回收自动定量配给容器

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Publication number Publication date
US20120021965A1 (en) 2012-01-26
US8328951B2 (en) 2012-12-11
EP2414498A1 (fr) 2012-02-08
PL2414498T3 (pl) 2021-05-31
ES2844278T3 (es) 2021-07-21
DE102009002095A1 (de) 2010-10-07
WO2010112548A1 (fr) 2010-10-07

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