EP2446013B1 - Détergent pour lave-vaisselle - Google Patents

Détergent pour lave-vaisselle Download PDF

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Publication number
EP2446013B1
EP2446013B1 EP10722376.0A EP10722376A EP2446013B1 EP 2446013 B1 EP2446013 B1 EP 2446013B1 EP 10722376 A EP10722376 A EP 10722376A EP 2446013 B1 EP2446013 B1 EP 2446013B1
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EP
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Prior art keywords
cleaning agent
detergent
cartridge
der
cleaning
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EP10722376.0A
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German (de)
English (en)
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EP2446013A1 (fr
Inventor
Arnd Kessler
Christian Nitsch
Thorsten Bastigkeit
Johannes Zipfel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL10722376T priority Critical patent/PL2446013T3/pl
Priority to EP17181064.1A priority patent/EP3260524B1/fr
Priority to PL17181064T priority patent/PL3260524T3/pl
Publication of EP2446013A1 publication Critical patent/EP2446013A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present application describes surfactant-containing automatic dishwashing detergents, automatic dishwashing processes using these dishwashing detergents, and the use of these dishwashing detergents in automatic dishwashing processes, in which portions of a machine detergent from a storage container located in the interior of the dishwasher pass into the interior of the dishwasher over several successive cleaning cycles be dosed.
  • One of the major objectives of the machine cleaners manufacturers is to improve the cleaning and rinse performance of these compositions, with more emphasis being placed recently on the cleaning and rinse performance in low temperature or reduced water consumption cleaning cycles.
  • Typical types of dishwashing detergent in addition to the traditional liquid dishwashing detergents, include, in particular, the automatic dishwashing detergents marketed predominantly in solid form, which are obtainable, for example, as powders or as tablets.
  • automatic dishwashing detergents marketed predominantly in solid form, which are obtainable, for example, as powders or as tablets.
  • these known clothing and supply forms are subject to new changes. For some time now, the main focus has been on the simplified dosing of automatic dishwashing detergents.
  • devices for the multiple dosing of detergents and cleaning agents have recently come into the field of vision of product developers.
  • these devices it is possible to distinguish between dispensing containers integrated in the dishwasher or textile washing machine on the one hand and independent devices which are independent of the dishwasher or textile washing machine on the other hand.
  • portions of washing or cleaning agents are metered into the interior of the cleaning machine in an automatic or semi-automatic manner in the course of several successive cleaning processes.
  • For the consumer eliminates the need for repeated manual dosing of detergents and cleaners.
  • Examples of such devices are disclosed in the European patent application EP 1 759 624 A2 (Reckitt Benckiser) or in the German patent application DE 10 2005 062 479 A1 (BSH Bosch and Siemens Hausmaschine GmbH).
  • these temperatures used in a first approximation to those used to carry out the washing or cleaning process Same water temperatures. These temperatures can reach up to 95 ° C, whereby in the range of machine dishwashing usually only temperatures between 50 and 75 ° 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.
  • This application was based on the object to provide a machine dishwashing detergent, which is stabilized against phase separation / loss of activity with multiple temperature fluctuations (10 to 75 ° C) and stored in a storage device located in the interior of a dishwasher without significant loss of activity, compared to conventional automatic dishwashing detergent however characterized by an improved performance profile.
  • At least one of the detergent preparations B and C is liquid.
  • suitable solvents for these liquid detergent formulations are the organic solvents known to the person skilled in the art, in particular the monohydric or polyhydric alcohols.
  • Both detergent formulation B and detergent formulation C contain nonionic surfactant.
  • Each of detergent formulations B and C may contain one, two or more nonionic surfactant (s).
  • the nonionic surfactants in detergent formulations B and C may be identical or have different chemical structures.
  • the detergent formulations B and C have different compositions from each other, so are not identical.
  • the weight fraction of the nonionic surfactant in the total weight of the detergent composition B between 0.1 and 30 wt .-%, preferably between 1.0 and 25 wt .-%, especially preferably between 2.0 and 20% by weight and in particular between 5.0 and 15% by weight.
  • Such detergent combinations according to the invention have particularly advantageous cleaning and rinsing effects, in which between 30 and 75 wt .-% and in particular between 40 and 70 wt .-% of the total amount of the detergent combination in the detergent composition B is included.
  • composition of some exemplary liquid detergent combinations according to the invention in which between 30 and 75% by weight and in particular between 40 and 70% by weight of the total amount of surfactant of the detergent combination is contained in the detergent composition B, can be taken from the following Table 1: Recipe 1 Recipe 2 B * [% by weight] C ** [% by weight] B * [% by weight] C ** [% by weight] Nonionic surfactant 0.1 to 30 Yes 2.0 to 20 Yes enzyme Yes - *** Yes - *** Misc Add 100 Add 100 Add 100 * "B” is in this, as in all following tables as an abbreviation for "detergent preparation B” ** "C” stands in this, as in all following tables as an abbreviation for "detergent preparation C” *** "-” in this, as in all the following tables, means: the recipe is free of this ingredient
  • the rinse aid result of inventive enzyme-containing preparations are significantly improved both in comparison to surfactant-free systems as well as in comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
  • hydroxy mixed ethers are used both in the detergent formulation B and in the detergent preparation C, in addition to the rinse aid result, it is additionally possible to improve the formation of deposits on surfaces such as glass, plastic or stainless steel. This improvement is detectable over a machine dishwashing detergent containing the same amount of hydroxy mixed ether alone in one of the two detergent formulations B or C.
  • nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals can markedly improve the stability of the enzymes contained in the detergent or cleaning agent preparations according to the invention.
  • 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 O] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4 R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.
  • the group of these nonionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 -EO) 15-40 -2-hydroxyalkyl ethers, in particular also the C 8-10 fatty alcohol (PO) 1 - (EO) 22 -2- hydroxydecylether.
  • nonionic surfactants are the end-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 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.
  • 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 may 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, with 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 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 surfactants include, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular also the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ether.
  • Detergent combination according to the invention characterized in that a surfactant of the general formula R 1 CH (OH) CH 2 O- (CH 2 CH 2 O) 10-120 -R 2 is used as the nonionic surfactant in the composition B and / or C, in R 1 and R 2 independently of one another represent a linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms, are preferred according to the invention.
  • a surfactant of the general formula R 1 CH (OH) CH 2 O- (CH 2 CH 2 O) 10-120 -R 2 is used as the nonionic surfactant in the composition B and / or C, in R 1 and R 2 independently of one another represent a linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms, are preferred according to the invention.
  • the detergent formulations B of the detergent combinations according to the invention contain as a further essential ingredient at least one washing or cleaning-active enzyme.
  • the weight fraction of the washing or cleaning-active enzyme in the total weight of the detergent preparation B 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 wt .-%.
  • composition of some exemplary liquid detergent combinations according to the invention in which between 30 and 75% by weight and in particular between 40 and 70% by weight of the total amount of surfactant of the detergent combination is contained in the detergent composition B can be taken from the following Table 2: Recipe 1 Recipe 2 B [% by weight] C [% by weight] B [% by weight] C [% by weight] Nonionic surfactant 0.1 to 30 Yes 2.0 to 20 Yes Enzyme preparation 5 to 80 - 10 to 30 - Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100
  • the Y-surfactants may be part of the detergent preparation B and / or the detergent preparation C.
  • the use of one or more Y-surfactants in combination with one or more Hydroxymischethern has been found to be particularly advantageous in terms of rinse performance. The best rinse results were obtained by adding the Y-surfactants to the detergent composition C, which results could again be increased by addition of hydroxy mixed ethers to the detergent formulation B and C.
  • the proportion by weight of Y-surfactants in the total weight of the detergent combination according to the invention is preferably 0.2 and 15 wt .-%, preferably between 0.5 and 12 wt .-%, particularly preferably between 1.0 and 8.0 wt .-% and in particular between 2.0 and 6.0% by weight.
  • the Y-surfactant-containing automatic dishwashing compositions according to the invention preferably have via a softening system, for example at least one sulfonic acid group-containing polymer.
  • Proteases amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, as well as their mixtures, are among the enzymes used with particular preference in accordance with the invention. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly. 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 with the amylases and the proteases, which is why detergent formulations B according to the invention, which contain a washing- or cleaning-active enzyme from the group of amylases and / or proteases, are preferred.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carisberg 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.
  • Detergent formulations B preferred according to the invention contain, based on the total weight of the detergent or cleaning preparation B, 5 to 50% by weight, preferably 7 to 40% by weight and in particular 10 to 30% by weight protease preparations. Detergent formulations B which contain, based on their total weight, 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 as well as the further developments of the abovementioned amylases which are improved for use in detergents and cleaners. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • Detergent formulations B preferred according to the invention contain, based on the total weight of the detergent preparation B, from 0.1 to 30% by weight, preferably from 1.0 to 25% by weight and in particular from 2.0 to 20% by weight, of amylase preparations. Especially preferred Detergent formulations B, based on their total weight, contain from 4.0 to 16% by weight of amylase preparations.
  • Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage 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.
  • 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.
  • composition of some exemplary liquid detergent combinations according to the invention in which between 30 and 75% by weight and in particular between 40 and 70% by weight of the total amount of surfactant of the detergent combination is contained in the detergent composition B can be found in the following Table 3: Recipe 1 Recipe 2 B [% by weight] C [% by weight] B [% by weight] C [% by weight] Nonionic surfactant 0.1 to 30 Yes 2.0 to 20 Yes Protease preparation 5.0 to 50 - 10 to 30 - Amylase preparation 0.1 to 30 - 2.0 to 20 - Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100
  • preferred cleaning agent combinations according to the invention comprise at least one liquid cleaning agent preparation, the solvents used, in addition to water, being the organic solvents known to the person skilled in the art, in particular the monohydric or polyhydric alcohols.
  • the water content of the detergent formulations can be between 10 and 90% by weight, based on their total weight.
  • the detergent preparation C based on its total weight, contains water in amounts of between 20 to 90 wt .-%, preferably between 30 and 80 wt .-% and in particular between 40 and 70 wt .-%.
  • water content includes the total amount of water contained in the compositions of the invention, which is composed of the free water contained in the agents and the above the washing and cleaning active in bound form in the washing or cleaning agent formulations registered water.
  • the water content can be determined, for example, as loss on drying or according to Karl Fischer.
  • organic solvent is selected 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 butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, di ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxy
  • composition B and / or C based on their total weight, between 5.0 and 80 wt .-%, preferably between 10 and 70 wt .-% and in particular between 12 and 60 wt. - contains% organic solvent (s).
  • a particularly preferred organic solvent which is particularly effective in stabilizing the enzyme-containing detergent composition B is 1,2-propylene glycol.
  • the proportion by weight of 1,2 propylene glycol in the total weight of the detergent composition B according to the invention can vary within wide limits, however, such preparations have proven to be particularly stable containing an organic solvent, preferably 1,2-propylene glycol, wherein the proportion by weight of 1,2 propylene glycol , in each case based on the total weight of the detergent composition B, preferably 15 to 80 wt .-%, preferably 30 to 70 wt .-% and in particular 40 to 60 wt .-% is.
  • liquid detergent preparations or liquid detergent combinations facilitates the repeated automatic dosing of these mixtures of active substances.
  • composition of some exemplary liquid detergent combinations according to the invention in which between 30 and 75% by weight and in particular between 40 and 70% by weight of the total amount of surfactant of the detergent combination is contained in the detergent composition B, can be taken from the following Table 4: Recipe 1 Recipe 2 B [% by weight] C [% by weight] B [% by weight] C [% by weight] Nonionic surfactant 2.0 to 20 Yes 5.0 to 15 Yes Protease preparation 5.0 to 50 - 10 to 30 - Amylase preparation 0.1 to 30 - 2.0 to 20 - Org. Solvent 5.0 to 80 5.0 to 60 12 to 60 12 to 60 water 10 to 70 20 to 80 10 to 40 40 to 70 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100
  • ingredients such as enzymes, solvents and nonionic surfactants from the group of hydroxy mixed ethers washing or cleaning compositions B and C according to the invention further ingredients, such as active ingredients from the group of builders, bleach, the washing and cleaning active polymers, the Corrosion inhibitors containing fragrances or dyes.
  • active ingredients from the group of builders, bleach, the washing and cleaning active polymers, the Corrosion inhibitors containing fragrances or dyes.
  • preferred detergent or cleaner formulations B and C according to the invention contain these other ingredients only to a minor extent.
  • Particularly preferred according to the invention are those detergent preparations B and C 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 are those detergent preparations B and C which are free of builders.
  • detergent formulations B and C which contain less than 10% by weight, preferably less than 5% by weight and in particular less than 2% by weight, of bleaching agent. Particularly preferred are those detergent formulations B and C which are free of bleaching agents.
  • composition of some exemplary liquid detergent combinations according to the invention in which between 30 and 75% by weight and in particular between 40 and 70% by weight of the total amount of surfactant of the detergent combination is contained in the detergent composition B, can be taken from the following Table 5:
  • Detergent combinations according to the invention comprising detergent formulations B and C preferably contain less than 10% by weight, more preferably less than 5% by weight and in particular less than 2% by weight of phosphate.
  • Phosphate-free detergent combinations are very particularly preferred according to the invention.
  • those detergent combinations according to the invention comprising detergent formulations B and C which contain less than 5% by weight, preferably less than 3% by weight and in particular less than 1% by weight, of silicate.
  • Very particularly preferred machine detergent combinations according to the invention are silicate-free. Both the lowering of the phosphate content and the lowering of the silicate content have proved to be advantageous for the stability of the detergent combinations according to the invention.
  • the detergent combinations according to the invention are characterized by a low formulation complexity despite their high physical and chemical stability. This low level of complexity simplifies the preparation of the detergents and thus reduces the costs involved in providing these detergents.
  • detergent composition A is preferably a builder-containing detergent.
  • the combined with the detergent combination according to the invention further detergent composition A is preferably a liquid detergent.
  • detergent composition A is preferably a bleach and / or phosphate-free detergent.
  • the combined with the detergent combination according to the invention further detergent composition A is preferably a surfactant-free detergent.
  • the further cleaning agent preparation A combined with the cleaning agent combination according to the invention is preferably an enzyme-free cleaning agent.
  • the combined with the detergent combination according to the invention further detergent composition A is particularly preferably a builder-containing, phosphate, bleach, surfactant and enzyme-free, liquid detergent.
  • composition of some exemplary liquid detergent combinations according to the invention in which between 30 and 75% by weight and in particular between 40 and 70% by weight of the total amount of surfactant of the detergent combination is contained in the detergent composition B can be found in the following Table 6:
  • Detergent combinations according to the invention comprising the detergent compositions A, B and C, preferably contain less than 10% by weight, more preferably less than 5 Wt .-% and in particular less than 2 wt .-% phosphate.
  • Phosphate-free detergent combinations comprising the detergent preparations A, B and C are very particularly preferred according to the invention.
  • Very particularly preferred detergent combinations according to the invention are silicate-free. Both the lowering of the phosphate content and the lowering of the silicate content have proved to be advantageous for the stability of the detergent combinations according to the invention.
  • the further detergent composition A may contain, for example, washing or cleaning-active substances from the group of builders, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers.
  • the group of builders includes the organic complexing agents as well as the alkali carriers and the cleaning-active anionic polymers.
  • the high builder content of inventive detergent formulations of 30 to 90 wt .-% distributed to these three groups of scaffolds.
  • the group of organic complexing agents includes in particular polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and other organic co-builders such as the phosphonates. These classes of substances are described below.
  • Useful organic complexing agents 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, ethylenediamine disuccinic 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.
  • NTA nitrilotriacetic acid
  • 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.
  • an acidifying component such as citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric aminodicarboxylic acids, their salts or their precursors such as sodium citrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium sulfate, sodium sulfate, sodium sul
  • 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
  • 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.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. 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 complexing agents are, for example, acetylated hydroxycarboxylic acids or salts thereof, 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.
  • Preferred detergent combinations according to the invention are characterized in that the detergent preparation A, based on their total weight, 5.0 to 60 wt .-%, preferably 10 to 50 wt .-% and in particular 15 to 40 wt .-% builder (s) from the Contains group of organic complex images. Preference is given to contents of organic Complexing agents realized above 25 wt .-%, more preferably above 30 wt .-% and in particular above 35 wt .-%. The upper limit of the content of organic complexing agents is preferably 85% by weight, and more preferably 75% by weight.
  • Particularly preferred automatic dishwasher detergents according to the invention contain citrate as one of their essential organic complexing agents.
  • Detergent combinations according to the invention characterized in that the detergent preparation A contains 2.0 to 50 wt .-%, preferably 4.0 to 40 wt .-% and in particular 5.0 to 30 wt .-% citrate, are inventively preferred.
  • a second important organic chelating agent is ethylenediamine disuccinic acid (EDDS), preferred detergent formulations A being characterized by having from 3.0 to 65% by weight, preferably 5.0 to 60% by weight, based on their total weight, and in particular Contain 10 to 50 wt .-% Ethylenediamindibernsteinklare.
  • Levels of ethylenediamine disuccinic acid are preferably realized above 12 wt .-%, particularly preferably above 15 wt .-% and in particular above 20 wt .-%.
  • the upper limit of the content of ethylenediamine disuccinic acid is preferably 55% by weight, and more preferably 45% by weight.
  • Ethylenediamine disuccinic acid has been found to be particularly effective in non-phosphate detergent formulations as being particularly effective in terms of dough cleaning in automatic dishwashing.
  • ethylenediamine disuccinic acid includes not only the free acids but also their salts, for example their sodium or potassium salts.
  • EDDS ethylenediamine disuccinic acid
  • the complex-forming phosphonates form a group of other organic complexing agents used with preference in the detergent compositions A according to the invention, this group comprising a number of different compounds such as diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) in addition to 1-hydroxyethane-1,1-diphosphonic acid.
  • DTPMP diethylenetriaminepenta
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral reacting Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • automatic dishwashing detergents which contain as phosphonates 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • the detergent formulations according to the invention may contain two or more different phosphonates.
  • the proportion by weight of the phosphonates in the total weight of detergent formulations A according to the invention is preferably from 1 to 8% by weight, preferably from 1.2 to 6% by weight and in particular from 1.5 to 4% by weight.
  • a second group of builders form the alkali carriers.
  • the group of alkali carriers include the carbonates and / or bicarbonates as well as the alkali metal hydroxides.
  • the group of carbonates and bicarbonates is summarized in the context of this application by the name (hydrogen) carbonate.
  • Preferred detergent combinations according to the invention are characterized in that the detergent preparation A, based on its total weight, 1.0 to 30 wt .-%, preferably 2.0 to 25 wt .-% and in particular 5.0 to 20 wt .-% builder ( e) from the group of alkali carriers
  • preferred detergent formulations according to the invention contain alkali metal hydroxide (s).
  • the alkali metal hydroxides are in the cleaning agents preferably in amounts between 2.0 and 20 wt .-%, preferably between 3.0 and 15 wt .-% and in particular between 4.0 and 12 wt .-%, each based on the total weight of Detergent used.
  • the detergent compositions A according to the invention comprise potassium hydroxide.
  • Detergent formulations according to the invention preferably contain less than 10% by weight, more preferably less than 5% by weight and in particular less than 2% by weight of phosphate. Phosphate-free detergent preparations A are very particularly preferred according to the invention.
  • detergent compositions according to the invention which contain less than 2% by weight, preferably less than 1% by weight and in particular less than 0.5% by weight, of silicate.
  • Very particularly preferred automatic dishwasher detergents according to the invention are silicate-free. By dispensing with silicate, the physical stability of the automatic dishwashing detergent according to the invention to be metered is surprisingly improved.
  • the cleaning-active anionic polymers form a third group of the builders contained in the detergent formulations according to the invention.
  • the cleaning-active anionic polymers may have two, three, four or more different monomer units.
  • the group of these polymers includes, in addition to the homo- and co-polymeric polycarboxylates u.a. also the copolymeric polysulfonates which, in addition to a monomer from the group of unsaturated carboxylic acids, have at least one further monomer from the group of the unsaturated sulfonic acids.
  • the weight fraction of cleaning-active anionic polymers in the total weight of the detergent composition A is preferably 1.0 to 30 wt .-%, preferably 2.0 to 25 wt .-% and in particular 5.0 to 20 wt .-%.
  • the polymeric polycarboxylates form a first group of cleaning-active anionic polymers.
  • examples of such polymers are the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70,000 g / mol.
  • Suitable anionic 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 content of preferred automatic dishwashing agents on (co) polymeric polycarboxylates is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight, in each case based on the total weight of the automatic dishwashing detergent.
  • Preferred copolymeric polysulfonates C contain, in addition to sulfonic acid-containing (s) monomer (s) at least one monomer from the group of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are 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. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.
  • 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-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salt
  • 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 ii) and from 10 to 50% by weight of monomer from group i), in each case based on the polymer.
  • 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 automatic dishwashing agents are characterized in that the copolymers have molar masses of 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 .
  • the copolymers further comprise at least one nonionic, preferably hydrophobic monomer in addition to carboxyl-containing monomer and sulfonic acid-containing monomer.
  • nonionic, preferably hydrophobic monomer in addition to carboxyl-containing monomer and sulfonic acid-containing monomer.
  • nonionic 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-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C
  • the preparation of the above-described combination of cleaning agents takes place, for example, by means of a packaging means in which the washing or cleaning agent preparations B and C are present separately from one another.
  • This separation can be achieved for example by separate receiving chambers, each of these receiving chambers containing one of the combined detergent.
  • Kon Stammionsformen 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 detergent product forms are provided with a dispenser detachable from the cartridge.
  • a dispenser detachable from the cartridge can be connected to the cartridge, for example by means of an adhesive, latching, snap or plug connection.
  • the separation of the cartridge and dosing device, for example, the filling of the cartridge is simplified.
  • the detachable connection of cartridge and dispenser allows the replacement of the cartridges on the dispenser. Such an exchange may be indicated, for example, in the event of a change in the cleaning program or after the cartridge has been completely emptied.
  • the vorgenanten starverdosiersysteme comprising the invention starsffen finesform (and optionally one or two further, different from the detergent compositions of the invention B and C cleaning center), a cartridge and a releasably connected to the cartridge dosing device are in a preferred embodiment in a common outer packaging, wherein the filled cartridge and the metering device are particularly preferably contained separately from each other in the outer packaging.
  • the detergent product form according to the invention in conjunction with a dishwasher.
  • Such a combination is particularly advantageous in cases in which the course of the automatic dishwashing process (for example duration, temperature profile, water supply) and the detergent formulation or the control electronics of the dosing device are matched to one another.
  • the dosing system according to the invention consists of the basic components of a cartridge filled with the detergent according to the invention and a metering device which can be coupled to the cartridge, which in turn is formed from further components such as component carrier, actuator, closure element, sensor, energy source and / or control unit.
  • the metering system according to the invention is mobile. Movable in the sense of this application means that the metering system is not inseparably connected to a water-conducting device such as a dishwasher, washing machine, tumble dryer or the like, but for example from a dishwasher by the user removed or positionable in a dishwasher, so is independently handled, is
  • the dosing device for the user is not detachably connected 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 may have a pH between 2 and 12, depending on the intended use, all components of the dosing system which come into contact with the preparations should have a corresponding acid and / or alkali resistance. Furthermore, these components should be largely chemically inert by a suitable choice of material, for example against nonionic surfactants, enzymes and / or fragrances.
  • a cartridge is understood as meaning a packaging material which is suitable for enveloping or holding together flowable or spreadable preparations and which can be coupled to a dosing device for dispensing the preparation.
  • a cartridge can also comprise a plurality of chambers which can be filled with mutually different compositions. 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 such that a gravity-induced release of preparation from the container in the position of use of the dosing device can be effected.
  • At least one second chamber is provided for receiving at least one second flowable preparation, the second chamber having at least one outlet opening arranged such that a gravity-induced product release from the second chamber in the use position of the dosing is effected.
  • the arrangement of a second chamber is particularly advantageous if in the separate containers preparations are stored, which are usually not stable to each other, such as bleaching agents and enzymes.
  • one of the chambers can be designed for the delivery of volatile preparations, such as a fragrance to the environment.
  • the cartridge is integrally formed.
  • the cartridges in particular by suitable blow molding, cost-effectively trained in a manufacturing step.
  • the chambers of a cartridge can in this case be separated from one another, for example, by webs or material bridges.
  • the cartridge can also be formed in several pieces by injection molded and then assembled components.
  • the cartridge is formed in such a multi-piece, that at least one chamber, preferably all chambers, can be removed individually from the metering device or inserted into the metering device.
  • This makes it possible, with a different consumption of a preparation from a chamber to exchange an already empty chamber, while the rest, which may still be filled with preparation, remain in the metering device.
  • a targeted and needs-based refilling the individual chambers or their preparations can 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 by a suitable form-fitting, non-positive or cohesive connection releasably or permanently against each other.
  • the fixation by one or more of Types of connections from the group of snap-in connections, Velcro connections, compression joints, fusible links, adhesive bonds, welded joints, solder joints, screw, wedge, clamp or bounce connections done.
  • the fixation can also be formed by a shrink sleeve (so-called sleeve), which is pulled in a heated state over the entire or sections of the cartridge and firmly encloses the chambers or the cartridge in the cooled state.
  • the bottom of the chambers may be funnel-shaped inclined towards the discharge opening.
  • the inner wall of a chamber can be formed by suitable choice of material and / or surface design in such a way that a low material adhesion of the preparation to the inner chamber wall is realized. Also by this measure, the residual emptiness of a chamber can be further optimized.
  • the chambers of a cartridge may have the same or different filling volumes.
  • the ratio of container volumes is preferably 5: 1, with a three-chamber configuration it is preferably 4: 1: 1, and these configurations are 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, wherein the volume ratio of the chambers is approximately 4: 1: 1.
  • a metering chamber may be formed in the flow direction of the preparation in front of the outlet opening.
  • the preparation amount that is to be released in the release of preparation from the chamber to the environment set. This is particularly advantageous if the closure element of the dosing device, which causes the preparation discharge from a chamber to the environment, can only be put into a dispensing and a closure state without controlling the dispensing quantity. It is then ensured by the metering chamber that a predefined amount of preparation is released without an immediate feedback of the delivered preparation amount.
  • 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 sealable Chamber opening on. Through this chamber opening, it is possible, for example, to refill stored in this chamber preparation.
  • ventilation possibilities can be provided in particular in the head region of the cartridge in order to ensure a pressure equalization with decreasing filling level of the chambers between the interior of the cartridge chambers and the environment.
  • These ventilation options can be designed, for example, as a valve, in particular silicone valve, micro-openings in the cartridge wall or the like.
  • the cartridge chambers should not be aerated directly, but via the dosing device or no ventilation, e.g. be provided with the use of flexible containers, such as bags, so this has the advantage that at elevated temperatures in the course of a rinse cycle of a dishwasher by the heating of the chamber contents, a pressure is built up, which presses the preparations to be dosed in the direction of the outlet openings, so that a good residual emptying of the cartridge can be achieved. Furthermore, in the case of such an air-free packaging, there is no risk of oxidation of substances of the preparation, which makes bag packaging or else bag-in-bottle packaging appear expedient, in particular for oxidation-sensitive preparations.
  • the cartridge usually has a filling volume of ⁇ 5,000 ml, in particular ⁇ 1,000 ml, preferably ⁇ 500 ml, more preferably ⁇ 250 ml, most preferably ⁇ 50 ml.
  • the cartridge can take on any spatial form. It can for example be cube-shaped, spherical or plate-like.
  • the cartridge and the dosing device can in particular be configured with respect to their spatial form in such a way that they ensure the least possible loss of useful volume, in particular in a dishwashing machine.
  • the dispenser it is particularly advantageous to mold the device based on dishes to be cleaned in dishwashers.
  • plate-shaped be formed in approximately the dimensions of a plate.
  • the dosing device can be positioned to save space eg in the lower basket of the dishwasher.
  • the correct positioning of the dosing unit opens up to the user intuitively through the plate-like shape.
  • the cartridge preferably has a ratio of height: width: depth between 5: 5: 1 and 50: 50: 1, particularly preferably about 10: 10: 1. Due to the "slim" design of the dosing device and the cartridge, it is particularly possible, the device in the lower cutlery basket of a dishwasher in the provided for plates Position recordings. This has the advantage that the dispensed from the dosing preparations go directly into the wash liquor and can not adhere to other items to be washed.
  • the metering system is dimensioned in an advantageous embodiment of the invention such that a positioning of the metering system is only possible in the receptacles provided for 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 metering unit in cup shape with a substantially circular or square base.
  • Another way to reduce the effect of heat on a preparation in a chamber of the cartridge is to isolate the chamber by suitable means, e.g. by the use of thermal insulation materials such as styrofoam, which enclose the chamber or the cartridge in a suitable manner, in whole or in part.
  • suitable means e.g. by the use of thermal insulation materials such as styrofoam, which enclose the chamber or the cartridge in a suitable manner, in whole or in part.
  • the cartridge has an RFID tag that contains at least information about the contents of the cartridge and that can be read by the sensor unit.
  • This information can be used to select a dosing program stored in the control unit. In this way it can be ensured that an optimal dosing program is always used for a particular preparation. It can also be provided that in the absence of an RFID label or an RFID label with a wrong or faulty identifier, no dosage is done by the dosing and instead an optical or acoustic signal is generated that the user on the present Error indicates.
  • the cartridges may also have structural elements which cooperate with corresponding elements of the metering device according to the key-lock principle, so that for example only cartridges of a certain type can be coupled to the dosing device. Furthermore, this configuration makes it possible for information about the cartridge coupled to the dosing device to be transmitted to the control unit, as a result of which control of the dosing device coordinated with the contents of the corresponding container can take place.
  • the cartridge is designed in particular for receiving flowable detergents or cleaning agents. Particularly preferably, such a cartridge has a plurality of chambers for the spatially separated receiving in each case of different preparations of a washing or cleaning agent.
  • the cartridge may be designed so that it can be detachably or firmly arranged in or on the dishwasher.
  • control unit e.g., a Bosch Sensortec metering device
  • sensor unit e.g., a Bosch Sensortec metering device
  • actuator necessary for operation are integrated in the dosing device.
  • an energy source is also arranged in the metering device.
  • the metering device consists of a splash-proof housing, which prevents the penetration of spray water, as may occur, for example, when used in a dishwasher, into the interior of the metering device.
  • the dosing device comprises at least a first interface, which in or on a water-conducting device such as in particular a water-conducting household appliance, preferably a dishwashing or washing machine formed corresponding interface cooperates in such a way that a transfer of electrical energy from the water-bearing device realized for dosing.
  • a water-conducting device such as in particular a water-conducting household appliance, preferably a dishwashing or washing machine formed corresponding interface cooperates in such a way that a transfer of electrical energy from the water-bearing device realized for dosing.
  • the interfaces are formed by connectors.
  • the interface cells can be designed in such a way that a wireless transmission of electrical energy is effected.
  • a second interface on the dosing device and the water-conducting device, such as a dishwasher, for transmitting electromagnetic signals, in particular Radios-, measuring and / or control information of the dosing and / or the water-bearing device such as Dishwasher represent trained.
  • an adapter By means of an adapter, a simple coupling of the dosing system with a water-conducting domestic appliance can be realized.
  • the adapter serves for the mechanical and / or electrical connection of the metering system with the water-conducting household appliance.
  • the adapter is, preferably fixed, connected to a water-carrying pipe 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 detected by the water flow and / or spray of the household appliance.
  • the adapter makes it possible to run a dosing system both for a stand-alone and "buildin" version. It is also possible to form the adapter as a kind 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 in a dishwasher on one of the inner walls of the washing chamber, in particular on the inner side of the dishwasher door.
  • the adapter is positioned as such inaccessible to the user in the water-conducting household appliance, so that the dosing device is used for example during assembly with the household appliance in the adapter, wherein the adapter, the dosing device and the household appliance in such are formed so that a cartridge can be coupled by the user with the dosing device.
  • the cleaning agents according to the invention are distinguished by a particular physical and chemical stability, in particular with respect to temperature fluctuations.
  • the cleaning agents according to the invention are thus exceptionally suitable for the metering by means of a metering system located in the interior of a washing or dishwashing machine.
  • a dosing system which can be immovably integrated into the interior of the washing machine or dishwasher (machine-integrated dosing device) but of course as a movable device in the interior can be introduced (self-sufficient dosing), contains the multiple required to carry out a machine cleaning process amount of detergent ,
  • Movable in the sense of this application means that the dispensing and dosing is not permanently connected to a device such as a dishwasher, washing machine, dryer or the like, but can be removed, for example, from a dishwasher or positioned in a dishwasher.
  • a detergent dosage form according to the invention comprising the detergent combination and a cartridge containing the detergent preparations B and C for filling a dosing device.
  • An example of a stationary cartridge is a container immovably integrated into the interior, for example in the side wall or the inner lining of the door of a dishwasher.
  • a movable cartridge is a container which is introduced by the consumer into the interior of the dishwasher and remains there during the entire course of a cleaning cycle.
  • a cartridge is, for example, by simply setting in the cutlery or crockery basket, integrated into the interior but can be removed from the consumer again from the interior of the dishwasher.
  • the dosage of the cleaning agent or the detergent combination from the cartridge into the interior of the dishwasher is carried out as described above preferably by means of a detachable from the cartridge dosing.
  • a dosing device can be connected to the cartridge by means of an adhesive, latching, snap or plug connection.
  • cartridges with a permanently connected metering device can of course also be used.
  • both the detergent combinations according to the invention and the detergent dosage forms according to the invention are suitable as refill packs for dosing devices that are immovably integrated into the interior of a dishwashing machine and for movable dosing devices provided for positioning in the interior of a dishwashing machine.
  • the cleaning agents and detergent combinations according to the invention are, as stated above, used as automatic dishwashing detergents.
  • inventive compositions can be used in the dishwashing processes according to the invention
  • Detergent offer forms but also the starch
  • the dosage of the detergent preparation B and the detergent preparation C takes place at different times of the cleaning cycle.
  • Automatic dishwashing process characterized in that the dosage of the cleaning agents B and C takes place with a time delay, wherein the dosage of the detergent composition B preferably takes place in the course of the main cleaning cycle, while the rinse aid composition C is preferably metered in the course of the rinse cycle, are preferred according to the invention.
  • B and C is the time t2 temporally at least 1 minute, preferably at least 2 minutes and in particular between 3 and 20 minutes before or after the time t1.
  • the time t2 is at least 1 minute in time, preferably at least 2 minutes and in particular between 3 and 20 minutes after the time t1.
  • the formulations disclosed in Tables 1 to 6 are suitable for these processes.

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Claims (15)

  1. Combinaison d'agents nettoyants pour le dosage automatique lors de lavage de vaisselle au moyen d'une machine, comprenant
    - une préparation d'agent nettoyant B contenant
    (b1) au moins un tensioactif non-ionique de la formule générale R1-CH(OH)CH2O-(AO)w-R2, dans laquelle
    - R1 représente un résidu alkényle ou alkyle en C6-24 à chaîne droite ou ramifié, saturé ou mono- ou polyinsaturé ;
    - R2 représente un résidu hydrocarbure linéaire ou ramifié doté de 2 à 20 atomes de carbone, et
    - A représente un résidu issu du groupe CH2CH2, -CH2CH2-CH2, -CH2-CH(CH3), et
    - w représente des valeurs comprises entre 10 et 120, de préférence 10 à 80, notamment 20 à 40 ; et
    (b2) au moins un enzyme à action nettoyante ;
    - une composition de rinçage C contenant
    (c1) au moins un tensioactif non-ionique de la formule générale R1-CH(OH)CH2O-(AO)w-R2, dans laquelle
    - R1 représente un résidu alkényle ou alkyle en C6-24 à chaîne droite ou ramifié, saturé ou mono- ou polyinsaturé ;
    - R2 représente un résidu hydrocarbure linéaire ou ramifié doté de 2 à 20 atomes de carbone, et
    - A représente un résidu issu du groupe CH2CH2, -CH2CH2-CH2, -CH2-CH(CH3), et
    - w représente des valeurs comprises entre 10 et 120, de préférence 10 à 80, notamment 20 à 40 ;
    dans laquelle entre 30 et 75 % en poids de la quantité totale en tensioactif de la combinaison d'agents nettoyants sont contenus dans la préparation d'agent nettoyant B.
  2. Combinaison d'agents nettoyants selon la revendication 1, caractérisée en ce qu'entre 40 et 70 % en poids de la quantité totale de tensioactif de la combinaison d'agents nettoyants est contenu dans la préparation d'agent nettoyant B.
  3. Combinaison d'agents nettoyants selon l'une quelconque des revendications précédentes, caractérisée en ce qu'un tensioactif de la formule générale R1CH(OH)CH2O-(CH2CH2O)10-120-R2 est utilisé en tant que tensioactif non-ionique dans la composition B et/ou C, dans laquelle R1 et R2 représentent indépendamment l'un de l'autre un résidu hydrocarbure aliphatique linéaire ou ramifié doté de 2 à 20 atomes de carbone.
  4. Combinaison d'agents nettoyants selon l'une quelconque des revendications précédentes, caractérisée en ce que la proportion en poids du tensioactif non-ionique dans le poids total de la préparation d'agent nettoyant B s'élève entre 0,1 et 30 % en poids, de préférence entre 1,0 et 25 % en poids, très préférablement entre 2,0 et 20 % en poids et notamment entre 5,0 et 15 % en poids.
  5. Combinaison d'agents nettoyants selon l'une quelconque des revendications précédentes, caractérisée en ce que la composition B et/ou C contient, rapporté à son poids total, entre 5,0 et 80 % en poids, de préférence entre 10 et 70 % en poids et notamment entre 12 et 60 % en poids de solvant(s) organique(s).
  6. Combinaison d'agents nettoyants selon l'une quelconque des revendications précédentes, caractérisée en ce que la composition d'agent nettoyant B contient, rapporté à son poids total, 0,1 à 30 % en poids, de préférence 1,0 à 25 % en poids et notamment 2,0 à 20 % en poids de préparation d'amylase et/ou 5 à 50 % en poids, préférablement 7 à 40 % en poids et notamment 10 à 30 % en poids de préparation de protéase.
  7. Combinaison d'agents nettoyants selon l'une quelconque des revendications précédentes, caractérisée en ce que la combinaison d'agents nettoyants comprend un autre agent nettoyant B de préférence liquide contenant
    (a1) au moins un adjuvant issu du groupe des complexants organiques et
    (a2) au moins un adjuvant issu du groupe des polymères à action nettoyante.
  8. Combinaison d'agents nettoyants selon l'une quelconque des revendications précédentes, caractérisée en ce que la préparation d'agent nettoyant A contient, rapporté à son poids total, 5,0 à 60 % en poids, de préférence 10 à 50 % en poids et notamment 15 à 40 % en poids d'adjuvant(s) issus du groupe des complexants organiques.
  9. Utilisation d'une combinaison d'agents nettoyants selon l'une quelconque des revendications 1 à 8 pour le remplissage
    i) d'une cartouche d'un système de dosage, intégrée de manière inamovible dans l'habitacle d'un lave-vaisselle, ou
    ii) d'une cartouche amovible d'un système de dosage, prévue pour le positionnement dans l'habitacle d'un lave-vaisselle
    avec une quantité suffisante de cette combinaison d'agents nettoyants pour la réalisation d'au moins deux, de préférence d'au moins quatre et notamment d'au moins huit procédés de lavage de vaisselle au moyen d'une machine.
  10. Mode de présentation d'agent nettoyant, comprenant
    a) une combinaison d'agents nettoyants selon l'une quelconque des revendications 1 à 8 dans une quantité suffisante de cette combinaison d'agents nettoyants pour la réalisation d'au moins deux, de préférence d'au moins quatre et notamment d'au moins huit procédés de lavage de vaisselle au moyen d'une machine ;
    b) une cartouche pour la combinaison d'agent nettoyant, dans laquelle les agents nettoyants préférablement liquides B et C se présentent séparément l'un de l'autre.
  11. Utilisation d'un mode de présentation d'agent nettoyant selon la revendication 10 en tant que réservoir d'agent nettoyant pour
    i) un appareil de dosage intégré de manière inamovible dans l'habitacle d'un lave-vaisselle ou
    ii) un appareil de dosage amovible prévu pour le positionnement dans l'habitacle d'un lave-vaisselle.
  12. Système de dosage d'agent nettoyant comprenant
    a) une combinaison d'agents nettoyants selon l'une quelconque des revendications 1 à 8 dans une quantité suffisante de cette combinaison d'agents nettoyants pour la réalisation d'au moins deux, de préférence d'au moins quatre et notamment d'au moins huit procédés de lavage de vaisselle au moyen d'une machine ;
    b) une cartouche pour la combinaison d'agent nettoyant, dans laquelle les agents nettoyants préférablement liquides B et C se présentent séparément l'un de l'autre.
    c) un appareil de dosage lié de manière soluble à la cartouche.
  13. Utilisation d'une combinaison d'agents nettoyants selon l'une quelconque des revendications 1 à 8, d'un mode de présentation d'agent nettoyant selon la revendication 10 ou d'un système de dosage d'agent nettoyant selon la revendication 12 pour le nettoyage de la vaisselle dans un procédé de lavage de la vaisselle au moyen d'une machine.
  14. Procédé de lavage de la vaisselle au moyen d'une machine utilisant une combinaison d'agents nettoyants selon l'une quelconque des revendications 1 à 8 ou d'un mode de présentation d'agent nettoyant selon la revendication 10 ou d'un système de dosage d'agent nettoyant selon la revendication 12, caractérisé en ce qu'au cours de celui-ci, à partir d'une cartouche se trouvant dans l'habitacle du lave-vaisselle,
    - une quantité partielle b de la préparation d'agent nettoyant B se trouvant dans la cartouche est dosée dans l'habitacle du lave-vaisselle, dans laquelle une quantité résiduelle de la préparation d'agent nettoyant B se trouvant dans la cartouche demeure dans la cartouche jusqu'à la fin du procédé du lavage de la vaisselle et cette quantité résiduelle correspond au moins au double, de préférence au quadruple et notamment l'octuple de la quantité partielle b ; et
    - une quantité partielle c de la préparation d'agent nettoyant C se trouvant dans la cartouche est dosée dans l'habitacle du lave-vaisselle, dans laquelle une quantité résiduelle de la préparation d'agent nettoyant C se trouvant dans la cartouche demeure dans la cartouche jusqu'à la fin du procédé du lavage de la vaisselle et cette quantité résiduelle correspond au moins au double, de préférence au quadruple et notamment l'octuple de la quantité partielle c.
  15. Procédé de lavage de vaisselle au moyen d'une machine selon la revendication 14, caractérisé en ce que le dosage des agents nettoyants B et C s'effectue de manière décalée dans le temps, dans lequel le dosage de la préparation d'agent nettoyant B s'effectue de préférence au cours de l'étape principale de nettoyage, tandis que la composition de rinçage C sera de préférence dosée au cours de l'étape de rinçage.
EP10722376.0A 2009-06-24 2010-06-17 Détergent pour lave-vaisselle Active EP2446013B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PL10722376T PL2446013T3 (pl) 2009-06-24 2010-06-17 Środek do maszynowego zmywania naczyń
EP17181064.1A EP3260524B1 (fr) 2009-06-24 2010-06-17 Composition detergente pour lave-vaisselle
PL17181064T PL3260524T3 (pl) 2009-06-24 2010-06-17 Środek do maszynowego zmywania naczyń

Applications Claiming Priority (2)

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DE102009027158A DE102009027158A1 (de) 2009-06-24 2009-06-24 Maschinelles Geschirrspülmittel
PCT/EP2010/058537 WO2010149564A1 (fr) 2009-06-24 2010-06-17 Détergent pour lave-vaisselle

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EP2446013B1 true EP2446013B1 (fr) 2017-08-09

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EP (2) EP3260524B1 (fr)
DE (1) DE102009027158A1 (fr)
ES (2) ES2641943T3 (fr)
HU (1) HUE034494T2 (fr)
PL (2) PL2446013T3 (fr)
WO (1) WO2010149564A1 (fr)

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US20110173536A1 (en) * 2010-01-12 2011-07-14 Mark Allan Payne System and method for facilitating on-site stain removal
DE102011014893A1 (de) 2011-03-23 2012-09-27 i-clean Technologies GmbH Vorrichtung zur Mehrfachdosierung von Reinigern
DE102014100234A1 (de) * 2014-01-10 2015-07-16 Budich International Gmbh Phosphatersatzstoffe für alkalische Maschinenreiniger
DE102014212622A1 (de) 2014-06-30 2015-12-31 Henkel Ag & Co. Kgaa Reinigungsmittel umfassend Hydroxamsäure und/oder deren Salze
CN108884413B (zh) 2016-03-18 2022-04-01 赢创运营有限公司 包含在其上含有至少一种生物表面活性剂的无机固体载体的颗粒
CN106854507A (zh) * 2017-01-05 2017-06-16 长沙协浩吉生物工程有限公司 一种玻璃清洗剂的配制方法
CN106854584A (zh) * 2017-01-05 2017-06-16 长沙协浩吉生物工程有限公司 一种生物餐具洗涤剂的配制方法
CN106854576A (zh) * 2017-01-05 2017-06-16 长沙协浩吉生物工程有限公司 一种生物洗碗机专用洗涤剂的配制方法
CN106854577A (zh) * 2017-01-05 2017-06-16 长沙协浩吉生物工程有限公司 一种沙发皮具清洗剂的配制方法
CN106939255A (zh) * 2017-03-17 2017-07-11 长沙协浩吉生物工程有限公司 一种酵素灶具清洗剂的配制方法
CN106987370A (zh) * 2017-03-18 2017-07-28 长沙协浩吉生物工程有限公司 一种酵素洗车液的配制方法
CA3197110A1 (fr) * 2020-11-17 2022-05-27 Patrick Firmin August Delplancke Procede de lavage automatique de la vaisselle presentant un rincage alcalin

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US20120090644A1 (en) 2012-04-19
EP3260524A1 (fr) 2017-12-27
ES2856868T3 (es) 2021-09-28
EP2446013A1 (fr) 2012-05-02
PL2446013T3 (pl) 2018-01-31
DE102009027158A1 (de) 2010-12-30
PL3260524T3 (pl) 2021-06-28
ES2641943T3 (es) 2017-11-14
US8349785B2 (en) 2013-01-08
HUE034494T2 (en) 2018-02-28
US20120199165A1 (en) 2012-08-09
WO2010149564A1 (fr) 2010-12-29
EP3260524B1 (fr) 2021-01-27

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