Cleaning agent which can be automatically metered

Abstract

The invention relates to a phosphate-free cleaning agent combination, which can be automatically metered and which contains, separate from each other in a packaging material, at least one enzyme-containing preparation and at least one builder-containing preparation that contains 3 to 9 wt.% of at least one complexing agent selected from ethylenediamine disuccinic acid and / or the salt thereof and less than 0.1 wt.% phosphonate.

Description

[0001] “Detergent for automatic dosing”

[0002] The invention relates to a phosphate-free cleaning agent combination for automatic dosing, which contains, separately from one another in a packaging means, at least one enzyme-containing preparation and at least one builder-containing preparation which contains 3 to 9 wt.% of at least one complexing agent selected from ethylenediamine disuccinic acid and / or its salts and less than 0.1 wt.% of phosphonate.

[0003] The packaging and distribution of cleaning products are constantly changing. For some time now, a key focus has been on convenient dosing of cleaning products and simplifying the steps required to carry out a cleaning process.

[0004] Consumers particularly desire devices for multiple dosing of detergents. Devices can be divided into dosing containers integrated into the dishwasher on the one hand and standalone devices independent of the dishwasher on the other. These devices, which contain multiples of the amount of detergent required for a cleaning process, automatically or semi-automatically dispense detergent portions into the interior of the dishwasher during several consecutive cleaning processes. This eliminates the need for consumers to dose the detergent before starting each individual cleaning cycle.Examples of such devices are described 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 und Siemens Hausgeräte GmbH).

[0005] In particular, consumers who do not do a lot of washing up want a solution that is uncomplicated and easy to use.

[0006] Regardless of the precise design of the dosing devices used in the interior of dishwashers, the detergents contained in these multiple-dosing devices are also exposed to changing temperatures over extended periods of time, with these temperatures being approximately the same as the water temperatures used to carry out the cleaning processes. These temperatures can be up to 95°C, although in the field of machine dishwashing, temperatures usually only between 50 and 75°C are reached. A detergent contained in a multiple-dosing device is therefore repeatedly heated to temperatures significantly above the temperatures customary for transport and storage over the course of several cleaning processes, which particularly affects temperature-sensitive active substances.In particular, consumers who load the dishwasher with dishes over several days and whose dirty dishes remain uncleaned inside the dishwasher for some time before a wash cycle is run face the problem that the cleaning performance of the products, especially with stubborn, particularly dried-on food residue on the dishes, such as minced meat, leaves much to be desired compared to washing the dishes immediately after use. However, rinsing food residue before loading them into the dishwasher is not advantageous for ecological and time-saving reasons, as well as in terms of additional water costs.

[0007] WO2010 / 069905 A1 describes compositions containing ethylenediaminedisuccinic acid, carbonate, and citrate. EP2446012 B1 discloses cleaning agent formulations suitable for automatic dosing, containing ethylenediaminedisuccinic acid and phosphonates.

[0008] The objective of this application was therefore to provide a cleaning agent that delivers good cleaning performance, particularly on dried-on food residues, especially minced meat, even when several days pass between individual usage cycles. This system should be inexpensive for the consumer and also environmentally friendly.

[0009] A first subject matter of the present application is therefore a phosphate-free cleaning agent formulation comprising a) a liquid cleaning agent preparation A, containing a1) builder; a2) 3.0 to 9.0 wt. % of at least one complexing agent selected from ethylenediaminedisuccinic acid and / or salts thereof, and a3) less than 0.1 wt. % phosphonate and b) a liquid cleaning agent preparation B which is different from the cleaning agent preparation A and contains, in each case based on the total weight of the cleaning agent preparation B, b1) at least one enzyme, in an amount of at least 0.01 wt. % of active enzyme protein, b2) less than 0.1 wt. % phosphonate b3) optionally 2.5 wt.-% or less complexing agent, and c) optionally a liquid cleaning agent preparation C, different from the cleaning agent preparations A and B, containing c1) an acidifying agent, c2) a glass corrosion inhibitor, c3) optionally a non-ionic surfactant, c4) optionally a hydrotrope and c5) optionally a fragrance and / or fragrance scavenger; and d) a packaging means in which the cleaning agent preparations A, B and optionally C are present separately from one another.

[0010] The advantage for consumers of combining such a composition with the cleaning preparations according to the invention is that they don't have to worry too much about renewing or replacing the active ingredient composition and the cleaning preparations. They simply replace the combination as a whole and don't have to worry about replacing individual products separately.

[0011] Surprisingly, it was found that the cleaning agent formulation according to the invention exhibits comparably good cleaning performance, particularly with stubborn, particularly dried-on food residues on the dishes, especially dried-on minced meat, without containing phosphonates. Rinsing off food residues before loading them into the dishwasher can therefore be eliminated, which is particularly advantageous for ecological and time-saving reasons, as well as with regard to additional water costs.

[0012] The subject matter of this application are corresponding phosphate-free cleaning agent formulations obtained by combining two liquid cleaning agent preparations A and B. The liquid cleaning agent preparations A, B, and C differ from each other in their composition.

[0013] Unless explicitly stated otherwise, all percentages given in connection with the compositions described herein refer to wt. %, based on the respective mixture. If states of matter (solid, liquid) are mentioned in this application, these refer, unless otherwise stated, to room temperature (20°C) at atmospheric pressure of 1 bar.

[0014] The cleaning agent supply form is characterized in that the cleaning agent preparations are phosphate-free, ie they contain less than 1% by weight of phosphate, preferably less than 0.5% by weight of phosphate, particularly preferably less than 0.1% by weight of phosphate and in particular no phosphate.

[0015] The cleaning agent formulation according to the invention is characterized in that cleaning agent preparations A and B contain less than 0.1% by weight of phosphonate, preferably less than 0.05% by weight of phosphonate, particularly preferably less than 0.01% by weight of phosphonate, and in particular no phosphonate. It is very particularly preferred if all compositions of the cleaning agent formulation contain less than 0.1% by weight of phosphonate, preferably less than 0.05% by weight of phosphonate, particularly preferably less than 0.01% by weight of phosphonate, and in particular no phosphonate.

[0016] Cleaning composition A contains, as a complexing agent, from 3.0 to 9 wt.% ethylenediaminedisuccinic acid (EDDS) and / or the corresponding alkali metal salt, preferably the trisodium salt. The trisodium salt of ethylenediaminedisuccinic acid (EDDS) is particularly preferably included.

[0017] Preferred cleaning agent preparations A are characterized in that they contain, based on the total weight of the cleaning agent preparations A, preferably 3.5 to 8.0 wt.% and in particular 4.0 to 7.0 wt.%, very particularly preferably 4.5 to 6.0 wt.% of ethylenediaminedisuccinic acid (EDDS) and / or the corresponding alkali metal salt, preferably the trisodium salt. Very particularly preferably, the trisodium salt of ethylenediaminedisuccinic acid contains from 3.0 to 9 wt.%, preferably from 3.5 to 8.0 wt.% and in particular from 4.0 to 7.0 wt.%, very particularly preferably from 4.5 to 6.0 wt.%.

[0018] The cleaning agent preparation A contains, as its first essential ingredient, one or more builders. Builders include, in particular, carbonates, organic cobuilders, and silicates. Cleaning agent formulations according to the invention are preferably characterized in that the builder a1) is selected from the group consisting of carbonates, bicarbonates, citrates, silicates, polymeric carboxylates, and polymers containing sulfonic acid groups, or mixtures thereof.

[0019] The sulfone-containing polymer used is preferably a sulfopolymer, preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate. The copolymers can have two, three, four, or more different monomer units. Preferred copolymeric polysulfonates contain, in addition to sulfonic acid group-containing monomer(s), at least one monomer from the group of unsaturated carboxylic acids.

[0020] As unsaturated carboxylic acid(s), particularly preferred unsaturated carboxylic acids are those of the formula R 1 (R 2 )C=C(R 3 )COOH is used, in the R 1 to R 3 independently of one another represent -H, -CH3, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH2, -OH or -COOH as defined above or -COOH or -COOR 4 where R 4 a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

[0021] Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid, or mixtures thereof. Unsaturated dicarboxylic acids can, of course, also be used.

[0022] The monomers containing sulfonic acid groups are those of the formula R 5 (R 6 )C=C(R 7 )-X-SO3H is preferred, in which R 5 to R 7 independently of one another represent -H, -CH3, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH2, -OH or -COOH or -COOH or -COOR 4 where R 4is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group selected from -(CH2)n- where n = 0 to 4, -COO-(CH2)k- where k = 1 to 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- and -C(O)-NH-CH(CH3)-CH2-.

[0023] Preferred monomers are those of the formulas

[0024] H2C=CH-X-SO3H, H2C=C(CH3)-X-SO3H or HO3S-X-(R 6 )C=C(R 7 )-X-SO3H, in which R 6 and R 7 are independently selected from -H, -CH3, -CH2CH3, - CH2CH2CH3 and -CH(CH3)2 and X represents an optionally present spacer group selected from -(CH2)n- with n = 0 to 4, -COO-(CH2)k- with k = 1 to 6, -C(O)-NH-C(CH3)2-, - C(O)-NH-C(CH3)2-CH2- and -C(O)-NH-CH(CH3)-CH2-.

[0025] According to a particularly preferred embodiment, a cleaning agent preparation, preferably cleaning agent preparation A, contains such a polymer comprising, as sulfonic acid group-containing monomer, acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid.

[0026] 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-propenesulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-soluble salts. In the polymers, the sulfonic acid groups may be present in completely or partially neutralized form, i.e. the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

[0027] The monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95 wt.% in the case of copolymers containing only carboxylic acid group-containing monomers and sulfonic acid group-containing monomers, particularly preferably 50 to 90 wt.% and 10 to 50 wt.% in the case of copolymers containing only carboxylic acid group-containing monomers, and the proportion of carboxylic acid group-containing monomers is particularly preferably 10 to 50 wt.%. The monomers are preferably selected from those mentioned above. 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 cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 g-mol' 1 , preferably from 4000 to 25,000 g-mol' 1and in particular from 5000 to 15,000 g-mol' 1 have.

[0028] In a further preferred embodiment, the copolymers comprise, in addition to the carboxyl-containing monomer and the sulfonic acid-containing monomer, at least one nonionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers has been shown to improve, in particular, the rinse performance of dishwashing detergents according to the invention.

[0029] Particularly preferably, the cleaning agent preparations, in particular cleaning agent preparation A, comprise a copolymer comprising i) monomers containing carboxylic acid groups ii) monomers containing sulfonic acid groups iii) optionally non-ionic monomers, in particular hydrophobic monomers.

[0030] As non-ionic monomers, monomers of the general formula

[0031] R 1 (R 2 )C=C(R 3 )-XR 4 used in the R1 to R 3 independently of one another represents -H, -CH3 or -C2H5, X represents an optionally present spacer group selected from -CH2-, -C(O)O- and -C(O)-NH-, and R 4represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms. Particularly preferred non-ionic 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, ethylcyclohexyne, 1-octene, a-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-Hexadecene, 1-Octadecene and C22- a-olefin, 2-styrene, a-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate,Pentyl acrylate, hexyl acrylate, methyl methacrylate, A / -(methyl)acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, A / -(2-ethylhexyl)acrylamide, octyl acrylate, octyl methacrylate, A / -(octyl)acrylamide, lauryl acrylate, lauryl methacrylate, A / -(lauryl)acrylamide, stearyl acrylate, stearyl methacrylate, A / -(stearyl)acrylamide, behenyl acrylate, behenyl methacrylate and N-(behenyl)acrylamide or mixtures thereof, in particular acrylic acid, ethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and mixtures thereof.

[0032] Preferred cleaning agent formulations comprise a cleaning agent preparation A which, based on its total weight, contains 2 to 50 wt.%, preferably 5 to 45 wt.% and in particular 8 to 40 wt.% builder.

[0033] Particular preference is given to the use of builders a1) from the group of carbonates and / or hydrogen carbonates, preferably alkali metal carbonates, particularly preferably sodium carbonate, in amounts of 2 to 15% by weight, preferably 3 to 12% by weight and in particular 6 to 10% by weight, in each case based on the weight of the cleaning agent preparation A.

[0034] Organic cobuilders include, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, (poly)aspartic acid, polyacetals, dextrins, and organic cobuilders. These substance classes are described below.

[0035] Useful organic builders include, for example, polycarboxylic acids, which can be used in the form of the free acid and / or their sodium salts. Polycarboxylic acids are understood to be carboxylic acids that carry more than one acid function. Examples include citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, provided such use is acceptable on ecological grounds, and mixtures thereof. Polycarboxylic acids are preferably understood to be non-polymeric polycarboxylates. Such polymeric polycarboxylates have a large number, preferably four or more, of carboxylic acid-containing monomers. In addition to their builder effect, the free acids typically also possess the property of an acidifying component and thus also serve to adjust a lower and milder pH value of cleaning agents.In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof should be mentioned.

[0036] Particularly preferred cleaning agent preparations A according to the invention contain citrate as one of their essential builders. Cleaning agent formulations characterized in that the cleaning agent preparation A contains, based on its total weight, 2 to 40 wt.%, preferably 5 to 30 wt.%, and in particular 7 to 20 wt.% citrate are preferred according to the invention. Citrate or citric acid, particularly in combination and / or with the polymers containing sulfonic acid groups, have proven to be the most effective builders with regard to cleaning performance, such as rinse-rinse performance, and in particular, scale inhibition.

[0037] Particularly preferred cleaning agent formulations are those in which the cleaning agent preparation A, based on its total weight, contains citrate in amounts of 3 to 20 wt.%, in particular 4 to 15 wt.%, and carbonate in amounts of 5 to 30 wt.%, in particular 7 to 20 wt.%.

[0038] Dishwashing detergents according to the invention can contain crystalline layered silicates of the general formula NaMSi x O2x+i ■ y H2O, wherein M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values ​​for x being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.

[0039] Amorphous sodium silicates with a modulus Na2O:SiO2 of 1:2 to 1:3.3, preferably of 1:2 to 1:2.8 and in particular of 1:2 to 1:2.6, which are preferably delayed in dissolution and have secondary washing properties, can also be used.

[0040] In preferred automatic dishwashing detergents according to the invention, the silicate content, based on the total weight of the automatic dishwashing detergent, is limited to amounts below 10 wt.%, preferably below 5 wt.%, and in particular below 2 wt.%. Particularly preferred automatic dishwashing detergents according to the invention are silicate-free.

[0041] Of course, the automatic dishwashing detergents according to the invention can contain the aforementioned builders both in the form of individual substances and in the form of mixtures of two, three, four or more builders.

[0042] Particularly preferred liquid automatic dishwashing detergents are characterized in that the dishwashing detergent contains at least two builders from the group of carbonates and citrates, and polymers containing sulfonic acid groups, wherein the weight fraction of these builders, based on the total weight of the automatic dishwashing detergent, is preferably 2 to 50 wt.%, preferably 5 to 45 wt.%, and in particular 10 to 40 wt.%. The combination of two or more builders from the above-mentioned group has proven advantageous for the cleaning and rinsing performance of automatic dishwashing detergents according to the invention.

[0043] According to a preferred embodiment, the cleaning agent preparation B contains, based on its total weight, 2 to 30 wt.%, preferably 5 to 40 wt.% and in particular 10 to 30 wt.% of citrates, preferably trisodium citrate, and / or

[0044] 2 to 15 wt.%, preferably 4 to 12 wt.% and in particular 6 to 10 wt.% (hydrogen)carbonates, preferably sodium carbonate, and / or

[0045] 1 to 15 wt.%, preferably 2 to 12 wt.% and in particular 3 to 10 wt.% of polymers containing sulfonic acid groups.

[0046] Most preferably, the cleaning agent preparation B contains, based on its total weight, 10 to 30 wt.% trisodium citrate and 6 to 10 wt.% sodium carbonate, and 3 to 10 wt.% polymers containing sulfonic acid groups.

[0047] As a second essential component, cleaning agent preparation A contains a complexing agent that differs from the aforementioned builders. The weight fraction of the complexing agent in relation to the total weight of cleaning agent preparation A is preferably 2 to 60 wt.%, more preferably 3 to 55 wt.%, preferably 4 to 55 wt.%, and in particular 8 to 50 wt.%.

[0048] According to a particularly preferred embodiment, the cleaning agent preparation A contains ethylenediamine disuccinic acid and / or its respective salts in combination with the builders citrate and carbonate and / or hydrogen carbonate and optionally at least one polymer containing sulfonic acid groups.

[0049] According to a particularly preferred embodiment of the cleaning agent formulation, the cleaning agent preparation A contains, based on its total weight, ethylenediamine disuccinic acid (EDDS) and / or salts thereof in amounts of 2 to 8 wt.%, as well as

[0050] 2 to 30 wt.%, preferably 5 to 40 wt.% and in particular 10 to 30 wt.% citrates, preferably trisodium citrate, and / or

[0051] 2 to 15 wt.%, preferably 4 to 12 wt.% and in particular 6 to 10 wt.% (hydrogen)carbonates, preferably sodium carbonate, and / or

[0052] 1 to 15 wt.%, preferably 2 to 12 wt.%, and in particular 3 to 10 wt.% of polymers containing sulfonic acid groups. Very particularly preferably, the cleaning agent preparation B contains, based on its total weight, in amounts of 2 to 8 wt.% of the trisodium salt of ethylenediaminedisuccinic acid (EDDS), 10 to 30 wt.% of trisodium citrate, 6 to 10 wt.% of sodium carbonate, and 3 to 10 wt.% of polymers containing sulfonic acid groups.

[0053] In a preferred embodiment of the invention, one of the cleaning agent preparations, preferably cleaning agent preparation C, further contains at least one surfactant, in particular selected from anionic, nonionic, zwitterionic, and amphoteric surfactants. Alternatively, the surfactants can also be present in a cleaning agent preparation different from cleaning agent preparations A and B. Surfactants are present in a cleaning agent preparation C according to the invention, if used, preferably in an amount of up to 40 wt.%, in particular 2 to 40 wt.% or 4 to 40 wt.%, particularly preferably in an amount of 5 to 35 wt.%, in particular 10 to 30 wt.%.

[0054] Cleaning agent preparation A preferably contains less than 2% by weight of surfactant, preferably less than 1% by weight of surfactant, particularly preferably less than 1% by weight of surfactant, in particular no surfactant, in each case based on the total weight of cleaning agent preparation A.

[0055] Nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, especially primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or, preferably, methyl-branched in the 2-position, or can contain linear and methyl-branched radicals in the mixture, as is usually the case in oxo alcohol radicals. However, alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 carbon atoms, for example, from coconut, palm, tallow, or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.Preferred ethoxylated alcohols include, for example, C12-C14 alcohols with 3 EO, 4 EO, or 7 EO, C8-n-alcohols with 7 EO, C13-C15 alcohols with 3 EO, 5 EO, 7 EO, or 8 EO, C8-s-alcohols with 3 EO, 5 EO, or 7 EO, and mixtures thereof, such as mixtures of C12-C14 alcohol with 3 EO and C12-C18 alcohol with 7 EO. The stated degrees of ethoxylation represent statistical averages, which can be a whole or fractional number for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO, or 40 EO. Nonionic surfactants containing EO and PO groups in the molecule can also be used according to the invention. Block copolymers with EO-PO block units orPO-EO block units can be used, as can EO-PO-EO copolymers or PO-EO-PO copolymers. Mixed alkoxylated nonionic surfactants, in which EO and PO units are distributed randomly rather than in blocks, can also be used. Such products are obtainable by the simultaneous action of ethylene oxide and propylene oxide on fatty alcohols.

[0056] In a preferred embodiment, the content of nonionic surfactants in the cleaning preparation C is 5 to 35 wt.%, preferably 7 to 30 wt.% and in particular 10 to 25 wt.%, based on the total amount of the cleaning preparation C.

[0057] A preferred pH value of cleaning preparations A according to the invention is between 9 and 14, in particular 9 and 12. The pH value can be adjusted, if necessary, by means of appropriate pH adjusters, in particular sodium or potassium hydroxide.

[0058] The cleaning agent preparations B according to the invention contain at least one cleaning-active enzyme as their first essential constituent. The weight fraction of the cleaning-active enzyme preparation in the total weight of the cleaning agent preparation B is preferably between 5 and 80 wt.%, preferably between 5 and 60 wt.%, particularly preferably between 10 and 50 wt.%, and in particular between 10 and 30 wt.%. The enzyme preparations thus used each contain from 0.1 to 40 wt.%, preferably from 0.2 to 30 wt.%, particularly preferably from 0.4 to 20 wt.%, and in particular from 0.8 to 10 wt.% of active enzyme protein.

[0059] The cleaning agent preparation B particularly preferably contains a protease in an amount of at least 0.05 wt.%, preferably of at least 0.1 wt.%, in particular of at least 0.4 wt.% of active enzyme protein and / or an amylase in an amount of at least 0.01 wt.%, preferably of at least 0.05 wt.%, in particular of at least 0.1 wt.% of active enzyme protein, in each case based on the total weight of the cleaning agent preparation B.

[0060] The enzymes used with particular preference include proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, or oxidoreductases, and preferably mixtures thereof. These enzymes are essentially of natural origin; based on the natural molecules, improved variants are available for use in cleaning agents and are therefore preferably used. Cleaning agents preferably contain enzymes in total quantities of 1 x 10 -6Up to 5% by weight based on active protein. The protein concentration can be determined using known methods, such as the BCA method or the biuret method.

[0061] The stabilizing effect according to the invention was observed to a particular extent with amylases, proteases, cellulases and mannanases, which is why liquid cleaning agent preparations B according to the invention, characterized in that they contain at least one cleaning-active enzyme from the group of amylases and / or proteases and / or cellulases and / or mannanases, in particular from the group of amylases and / or proteases, are preferred.

[0062] Among the proteases, those of the subtilisin type are preferred. Examples include subtilisins BPN' and Carlsberg, as well as their more advanced forms, protease PB92, subtilisins 147 and 309, alkaline protease from Bacillus lentus, subtilisin DY, and the enzymes thermitase, proteinase K, and proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the narrower sense.

[0063] Preferred liquid cleaning preparations B according to the invention contain, based on the total weight of the cleaning preparation, 5 to 50 wt.%, preferably 7 to 40 wt.%, and in particular 10 to 30 wt.% of protease preparations. Particularly preferred cleaning preparations B contain, based on their total weight, 15 to 25 wt.% of protease preparations.

[0064] Examples of amylases that can be used according to the invention are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens, from β. stearothermophilus, from Aspergillus niger, and A. oryzae, as well as the improved versions of the aforementioned amylases for use in cleaning agents. Also suitable for this purpose are the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from β. agaradherens (DSM 9948).

[0065] Preferred liquid cleaning preparations B according to the invention contain, based on the total weight of the cleaning preparation, 0.1 to 30 wt.%, preferably 1.0 to 25 wt.%, and in particular 2.0 to 20 wt.% amylase preparations. Particularly preferred cleaning preparations B contain, based on their total weight, 4.0 to 16 wt.% amylase preparations.

[0066] Further liquid cleaning preparations B preferred according to the invention contain, based on the total weight of the cleaning preparation, 0.1 to 30 wt.%, preferably 1.0 to 25 wt.% and in particular 2.0 to 20 wt.% cellulase preparations.

[0067] Further liquid cleaning preparations B preferred according to the invention contain, based on the total weight of the cleaning preparation, 0.1 to 30 wt. %, preferably 1.0 to 25 wt. % and in particular 2.0 to 20 wt. % mannanase preparations. Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also to produce peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed lipases, in particular those with the amino acid exchange D96L. Furthermore, the cutinases originally isolated from Fusarium solani pisi and Humicola insolens can be used, for example. Also usable are lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.

[0068] Further liquid cleaning preparations B preferred according to the invention contain, based on the total weight of the cleaning preparation, 0.1 to 30 wt.%, preferably 1.0 to 25 wt.% and in particular 2.0 to 20 wt.% lipase preparations.

[0069] Furthermore, enzymes collectively known as hemicellulases can be used. In addition to the aforementioned mannanase, these include xanthan lyases, pectin lyases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases, and ß-glucanases.

[0070] To increase the bleaching effect, 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. Advantageously, organic compounds, particularly aromatic ones, that interact with the enzymes are also added to enhance the activity of the respective oxidoreductases (enhancers) or to ensure electron flow between the oxidizing enzymes and the soils in the case of significantly different redox potentials (mediators).

[0071] Cleaning enzymes, especially proteases and amylases, are generally not supplied in the form of pure proteins, but rather in the form of stabilized, storable, and transportable preparations. These prefabricated preparations include, for example, solid preparations obtained by granulation, extrusion, or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, preferably as concentrated as possible, with little water content, and / or containing stabilizers or other additives.

[0072] Alternatively, the enzymes can be encapsulated for both solid and liquid dosage forms, 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 if 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. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers. Such capsules are applied using methods known per se, for example by shake or roll granulation or in fluid-bed processes. Such granules, for example by applying polymeric film formers, are advantageously low in dust and, due to the coating, are stable during storage.

[0073] Furthermore, it is possible to package two or more enzymes together so that a single granulate has multiple enzyme activities.

[0074] As can be seen from the above, the enzyme protein constitutes only a fraction of the total weight of conventional enzyme preparations. Enzyme preparations preferably used according to the invention, in particular the protease and amylase preparations, contain from 0.1 to 40 wt.%, preferably from 0.2 to 30 wt.%, particularly preferably from 0.4 to 20 wt.%, and in particular from 0.8 to 10 wt.% of the enzyme protein.

[0075] Liquid cleaning agent preparations B which are particularly preferred according to the invention therefore contain, based on the total weight of the cleaning agent preparation, 7 to 40% by weight, in particular 10 to 30% by weight, of protease preparations and 2 to 20% by weight, in particular 4.0 to 16% by weight, of amylase preparations, which each contain 0.4 to 20% by weight, in particular 0.8 to 10% by weight, of active protein.

[0076] A preferred pH value of cleaning agent preparations B according to the invention is between 6 and 9.

[0077] The cleaning agent preparations B of the cleaning agent formulations according to the invention preferably contain less than 2.5% by weight of complexing agent. They preferably contain less than 2.5% by weight of complexing agent and / or builders. Reducing the complexing agent content below these upper limits has proven beneficial for cleaning performance. By further reducing the complexing agent content significantly below the upper limits, a further increase in the cleaning performance of cleaning agent formulations according to the invention is surprisingly achievable.

[0078] Accordingly, preferred cleaning agent formulations according to the invention are characterized in that cleaning agent preparation B contains less than 2.0% by weight of complexing agent, preferably less than 1.0% by weight of complexing agent, particularly preferably less than 0.5% by weight of complexing agent, and in particular no complexing agent. The total amount of complexing agent and / or builders contained in cleaning agent preparation B is preferably less than 10% by weight, preferably less than 6% by weight, particularly preferably less than 2% by weight, and in particular 0% by weight.

[0079] An optional component of the cleaning agent preparations according to the invention, in particular cleaning agent preparation B, are organic solvents. Preferred organic solvents come from the group of mono- or polyhydric alcohols, alkanolamines, or glycol ethers. The solvents are preferably selected from ethanol, n- or i-propanol, butanol, glycol, propane- or butanediol, glycerol, monoethanolamine, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy-, ethoxy- or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.Preferred solvents are preferably selected from glycerin, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, and polyethylene glycols, in particular those polyethylene glycols having an average molecular weight between 100 and 800, preferably 200 and 600 g / mol. The weight fraction of these organic solvents in the total weight of the respective cleaning agent preparations according to the invention is preferably 5 to 80 wt.%, preferably 10 to 60 wt.%, and in particular 20 to 50 wt.%.

[0080] A particularly preferred organic solvent that is particularly effective with regard to stabilizing the cleaning agent preparation, in particular cleaning agent preparation B, is 1,2-propylene glycol. The weight fraction of 1,2-propylene glycol in the total weight of the cleaning agent preparations B according to the invention can vary within wide limits; however, preparations that contain, based on the total weight of the respective cleaning agent preparation B, 5 to 80 wt.%, preferably 10 to 60 wt.%, and in particular 20 to 50 wt.% of 1,2-propylene glycol have proven particularly stable. Corresponding preparations are therefore preferred according to the invention.

[0081] For enzyme stabilization, cleaning agent preparations B according to the invention may also contain polyols, in particular sorbitol.

[0082] The liquid cleaning preparations B preferably contain sorbitol based on their total weight

[0083] According to a particular embodiment, the cleaning agent preparation B contains sorbitol in an amount of 2 to 20 wt.%, preferably 5 to 15 wt.% and in particular 8 to 12 wt.%, based on the total weight of the cleaning agent preparation B. In a preferred embodiment, the cleaning agent presentation form further comprises a liquid cleaning agent preparation C, wherein the cleaning agent preparation C is different from the cleaning agent preparations A and B.

[0084] In the automatic dishwashing process according to the invention, the cleaning agent preparations A and B are used in combination with at least one further cleaning agent preparation C. When used in a dishwashing process, this cleaning agent preparation C preferably contains surfactant and / or acid, preferably surfactant and acid.

[0085] By using a surfactant- and / or acid-containing detergent preparation C, the final rinse performance achieved in the dishwashing process according to the invention can be improved. This applies in particular to those preferred process variants in which the dosing of detergent preparations A, B and C takes place at different times. Particularly suitable surfactant additives for detergent preparation C are the nonionic surfactants described above. However, nonionic surfactants of the general formula R 1 -CH(OH)CH2O-(AO)w-(A'O)x-(A”O)y-(A'”O)zR 2 , in the

[0086] R 1 represents a straight-chain or branched, saturated or mono- or polyunsaturated Ce-24 alkyl or alkenyl radical;

[0087] R 2 represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

[0088] A, A', A” and A'” independently represent a residue from the group

[0089] -CH2CH2, -CH2CH2-CH2, -CH2-CH(CH3), -CH2-CH2-CH2-CH2, -CH2-CH(CH3)-CH2-, -CH2- CH(CH2-CH3), w, x, y and z stand for values ​​between 0.5 and 120, where x, y and / or z can also be 0. Non-ionic surfactants of the general formula R have proven particularly effective. 1 -CH(OH)CH2O-(AO) W -R 2 proven in the

[0090] R 1 represents a straight-chain or branched, saturated or mono- or polyunsaturated Ce-24 alkyl or alkenyl radical;

[0091] R 2 represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

[0092] A stands for a radical from the group CH2CH2, -CH2CH2-CH2, -CH2-CH(CH3), and w stands for values ​​between 1 and 120, preferably 10 to 80, in particular 20 to 40. The group of these non-ionic surfactants includes, for example, the C4-22 fatty alcohol (EO)io-ao-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO)22-2-hydroxydecyl ethers and the C4-22 fatty alcohols (EO)4o-so-2-hydroxyalkyl ethers.

[0093] The weight proportion of the non-ionic surfactant in the total weight of the cleaning agent preparation C is preferably from 1.0 to 20 wt.%, preferably from 2.0 to 18, particularly preferably from 4.0 to 15 wt.% and in particular from 6.0 to 12 wt.%.

[0094] In a further particularly preferred embodiment, at least one cleaning agent preparation, in particular at least one cleaning agent preparation further comprising a nonionic surfactant, particularly preferably at least cleaning agent preparation B and / or D contains at least one hydrotrope (hereinafter also referred to as solubilizer). Preferred hydrotropes are xylenesulfonate, cumenesulfonate, urea and / or / V-methylacetamide, particularly preferably cumenesulfonate and / or xylenesulfonate, in particular cumenesulfonate. It has been found that the use of hydrotropes, in particular cumenesulfonate, enormously improves phase stability with regard to temperature fluctuations. This is particularly observed for preparations containing at least one nonionic surfactant.It is particularly preferred that at least the cleaning agent preparation C, in particular the cleaning agent preparations C and B, contains at least one hydrotrope, preferably xylenesulfonate, cumenesulfonate, urea and / or / V-methylacetamide, particularly preferably cumenesulfonate and / or xylenesulfonate, in particular cumenesulfonate, preferably in an amount of 2 to 25% by weight, in particular of 4 to 20% by weight and particularly preferably in an amount of 6 to 15, for example of 7 to 12% by weight, based on the total weight of the respective cleaning agent preparation.

[0095] The weight ratio of the at least one nonionic surfactant to the at least one hydrotrope, preferably xylenesulfonate, cumenesulfonate, urea and / or N-methylacetamide, particularly preferably cumenesulfonate and / or xylenesulfonate, in particular cumenesulfonate, is preferably 2:1 to 1:2, in particular 1.6:1 to 1:1.

[0096] In addition to or as an alternative to the nonionic surfactants, the cleaning agent preparations C according to the invention preferably contain at least one acidifying agent when used in a dishwashing process. Acidifying agents can be added to the cleaning agent preparations C according to the invention to lower the pH of the liquor in the final rinse cycle. Both inorganic and organic acids are suitable for this purpose, provided they are compatible with the other ingredients. For reasons of consumer protection and handling safety, solid mono-, oligo-, and polycarboxylic acids are particularly suitable. From this group, preference is given to formic acid, acetic acid, citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid, and polyacrylic acid. Formic acid, acetic acid, and / or citric acid are very particularly preferred.

[0097] Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt.%), glutaric acid (max. 50 wt.%), and adipic acid (max. 33 wt.%), is commercially available and can also be used with preference as an acidifying agent in the context of the present invention. Cleaning agent preparations C which, based on the total weight of the cleaning agent preparation C, contain one or more acidifying agents, preferably mono-, oligo-, and polycarboxylic acids, particularly preferably formic acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid, and polyacrylic acid, and in particular formic acid, acetic acid, and / or citric acid, in amounts of 0.1 to 12 wt.%, preferably 0.2 to 10 wt.%, and in particular 0.3 to 8.0 wt.%, are preferred embodiments of the present invention.

[0098] The use of formic acid is preferred because, in addition to its acid function in improving the final rinse result, it also has a positive influence on the storage stability of cleaning preparation C, which, as explained above, is subject to strong temperature fluctuations due to storage in the interior of the dishwasher. Furthermore, it has a disinfecting effect, so that when formic acid is used in the final rinse cycle, the number of bacteria is reduced. This applies both to bacteria found in the rinse liquor of the final rinse cycle and to those found in the rinse liquor remaining in the sump of the dishwasher during and after the wash cycle, as well as the interior of the dishwasher. This can also reduce the number of residual germs on the washed dishes.

[0099] It is particularly advantageous if an active ingredient, in particular comprising fragrances and / or fragrance scavengers, and simultaneously formic acid as an acidifying agent are used in cleaning agent composition C. Formic acid itself has a slightly pungent odor that is unpleasant to sensitive consumers, especially if it contains one or more fragrances, in particular those preferred above, and / or one or more fragrance scavengers, in particular, for example, zinc ricinoleate. No unpleasant odor is produced inside the dishwasher either during the dishwashing process or in the time between cleaning cycles.

[0100] The previously described cleaning preparations A, B and C differ in their composition and are therefore not identical.

[0101] Furthermore, the cleaning agent preparations A, B and / or C according to the invention preferably contain at least one glass corrosion inhibitor when used in a dishwashing process. Particularly preferably, preparation(s) A and / or preparation(s) C, preferably at least preparation(s) C, contain a corresponding amount of glass corrosion inhibitor(s).

[0102] These glass corrosion inhibitors are preferably selected from water-soluble zinc salts, preferably zinc chloride, zinc sulfate and / or zinc acetate, particularly preferably zinc acetate, polyalkyleneimines, in particular polyethyleneimines.

[0103] The preparations according to the invention, in particular preparations A and / or C, contain, in a preferred embodiment, as a further constituent at least one zinc salt, in particular inorganic or organic, as a glass corrosion inhibitor. The inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate, and zinc sulfate. The organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group consisting of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, and zinc p-toluenesulfonate. In a particularly preferred embodiment according to the invention, zinc acetate is used as the zinc salt.

[0104] The zinc salt is present in cleaning agent preparations according to the invention preferably in an amount of 0.01 wt.% to 5 wt.%, particularly preferably in an amount of 0.05 wt.% to 3 wt.%, in particular in an amount of 0.1 wt.% to 2 wt.%, based on the total weight of the respective cleaning agent preparation, in particular the respective cleaning agent preparation A or C.

[0105] Polyethylenimines, such as those available under the name Lupasol® (BASF), are preferably used as glass corrosion inhibitors in an amount of 0 to 5 wt.%, in particular 0.01 to 2 wt.%, based on the total weight of the respective preparation.

[0106] The composition of some exemplary cleaning agent formulations according to the invention, comprising the cleaning agent preparations A, B and optionally C, can be found in the following tables.

[0107] The combination of cleaning agents described above is packaged using a packaging medium in which the cleaning agent preparations A and B, or A, B, and C, are separated from one another. This separation can be achieved, for example, by separate compartments, each of which contains one of the combined cleaning agents. Examples of such packaging forms are cartridges with two, three, four, or more separate compartments, for example, two-, three-, four-, or multi-chamber bottles. By separating the cleaning agents of different compositions, undesirable reactions due to chemical incompatibility can be excluded.

[0108] The viscosity of all cleaning agent preparations A and B or A, B and C is preferably less than 120 mPas, in particular from 1 to 100 mPas, in particular 10 to 80 mPas, preferably 20 to 60 mPas (measured at 20 °C with a Brookfield Instrument LVDV II+, spindle 31, 100 rpm). This has the advantage that the cleaning agent preparations can be dosed from the packaging material simply by opening a valve on the underside of the packaging material (in particular the cartridge) on the basis of gravity, preferably without the involvement of electrical or electronic means such as pumps etc. At the same time, the chambers are preferably emptied almost completely, i.e. without any large residual amounts of the cleaning agent preparations to be dosed. This is advantageous for the consumer and for the environment because only small amounts of the cleaning agent preparations remain unused in the chambers of the packaging material or the cartridge.

[0109] According to a preferred embodiment, the cleaning agent packaging is characterized in that the cleaning agent composition C contains at least one fragrance, preferably linalyl acetate, dihydromyrcenol, citronellonitrile, menthyl acetate, methylphenylbutanol, eucalyptol, and mixtures thereof, fragrance scavengers, such as zinc ricinoleate, cyclodextrins, 2-menthyl-5-cyclohexylpentanol, and 1-cyclohexylethanol, in particular zinc ricinoleate; and mixtures thereof, preferably mixtures of at least one fragrance scavenger, preferably with one, two, three, or more fragrances and / or at least one dye. Further preferred are mixtures of at least one fragrance, preferably two, three, or more fragrances, and at least one dye.

[0110] Individual fragrance compounds, e.g., synthetic products of the ester, ether, aldehyde, ketone, alcohol, and hydrocarbon type, can be used as perfume oils or fragrances within the scope of the present invention. However, mixtures of different fragrances are preferred, which together create an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as those obtainable from plant sources, e.g., pine, citrus, jasmine, patchouli, rose, or ylang-ylang oil.

[0111] In order to be perceptible, an odorant must be volatile. In addition to the nature of the functional groups and the structure of the chemical compound, the molecular mass also plays an important role. Most odorants have molecular masses of up to around 200 Daltons, while molecular masses of 300 Daltons and above are rather rare. Due to the varying volatility of odorants, the smell of a perfume or fragrance composed of several odorants changes during evaporation. The olfactory impressions are divided into "top note", "middle note or body" and "base note" (end note or dry out). Since the perception of smell is largely based on the intensity of the smell, the top note of a perfume or fragrance is not made up solely of highly volatile compounds, whereas the base note is made up largely of less volatile, i.e., long-lasting odorants.When composing perfumes, more volatile fragrances can be bound to certain fixatives, for example, which prevents them from evaporating too quickly. The following classification of fragrances into "more volatile" and "more persistent" fragrances therefore says nothing about the olfactory impression or whether the corresponding fragrance is perceived as a top or heart note.

[0112] The fragrances can be processed directly, but it can also be advantageous to apply them to carriers that ensure a long-lasting fragrance through slower fragrance release. Cyclodextrins, for example, have proven to be effective carrier materials, although the cyclodextrin-perfume complexes can also be coated with other excipients.

[0113] Particularly preferred fragrances according to the invention are linalyl acetate, dihydromyrcenol, citronellonitrile, menthyl acetate, methylphenylbutanol and / or eucalyptol and mixtures thereof.

[0114] The well-known ricenolates, especially zinc ricenoleates, can be used as fragrance absorbers (or, as synonymously used below, as odor neutralizers or fragrance neutralizers, agents against malodor or unpleasant odors). 2-menthyl-5-cyclohexylpentanol and 1-cyclohexylethanol are also preferred as fragrance absorbers. Activated carbon and / or cyclodextrins and / or zeolites, preferably acid-modified zeolites, can also be used with particular preference. Zinc ricinoleate, alone or in combination with one or more of the above-mentioned preferred fragrances and / or fragrance absorbers, is particularly preferred because it also has a positive effect on inhibiting glass corrosion during the rinsing process.

[0115] To combat microorganisms, antimicrobial agents can be used alternatively or in addition to the aforementioned fragrances and / or scent traps. Depending on their antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups include benzalkonium chlorides, alkylarylsulfonates, halophenols, and phenolmercuriacetate, although these compounds can also be omitted entirely.

[0116] A further subject matter of the present application is a cleaning agent offer form, comprising a) a cleaning agent preparation A according to the invention in an amount sufficient for carrying out a machine dishwashing process at least twice, preferably at least four times and in particular at least eight times; b) at least one further cleaning agent preparation B different from A in an amount sufficient for carrying out a machine dishwashing process at least twice, preferably at least four times and in particular at least eight times; c) optionally a further cleaning agent preparation C different from A and B in an amount sufficient for carrying out a machine dishwashing process at least twice, preferably at least four times and in particular at least eight times; e) a cartridge for the cleaning agent preparations A and B, orA, B and C, in which the cleaning agent preparations A and B, or A, B, C, are present in separate receiving chambers.

[0117] The present application further provides a detergent dosing system comprising a) a detergent preparation A according to the invention in an amount sufficient for carrying out a machine dishwashing process at least twice, preferably at least four times and in particular at least eight times; b) at least one further detergent preparation B different from A in an amount sufficient for carrying out a machine dishwashing process at least twice, preferably at least four times and in particular at least eight times; c) optionally a further detergent preparation C different from A and B in an amount sufficient for carrying out a machine dishwashing process at least twice, preferably at least four times and in particular at least eight times; e) a cartridge for the detergent preparations A and B orA, B and C, in which the cleaning agent preparations A, B and optionally C are present in separate receiving chambers; f) a dosing device detachably connected to the cartridge.

[0118] In a preferred embodiment, the previously described cartridges of the cleaning agent packages are provided with a dosing device that can be detachably connected to the cartridge. Such a dosing device can be connected to the cartridge, for example, by means of an adhesive, locking, snap-in, or plug-in connection. Separating the cartridge and dosing device simplifies, for example, filling the cartridge. Alternatively, the detachable connection between the cartridge and dosing device allows the cartridges to be replaced at the dosing device. Such a replacement may be necessary, for example, when changing the cleaning program or after the cartridge has been completely emptied.

[0119] A particularly preferred subject matter of this application is a detergent dosing system comprising a) a detergent dispenser according to the invention, comprising a quantity of detergent preparations A and B or A, B, and C sufficient for carrying out a machine dishwashing process at least twice, preferably at least four times, and in particular at least eight times; b) a dosing device detachably connected to the detergent dispenser. Of course, detergent dispensers in which the cartridge and the dosing device are permanently connected to one another are also conceivable.

[0120] The present application furthermore relates to a detergent dosing system, comprising a) a detergent dosage form according to the invention, comprising a quantity of detergent preparations A and B, or A, B and C, sufficient for carrying out a machine dishwashing process at least twice, preferably at least four times and in particular at least eight times; b) a dosing device permanently connected to the detergent dosage form

[0121] The aforementioned cleaning agent dosing systems, comprising the cleaning agent packaging according to the invention (and optionally one or two further compositions different from the cleaning agent preparations A and B or A, B and C or A, B, C and D according to the invention, a cartridge and a dosing device detachably connected to the cartridge are, in a preferred embodiment, present in a common outer packaging, wherein the filled cartridge and the dosing device are particularly preferably contained separately from one another in the outer packaging. The outer packaging serves for the storage, transport and presentation of the cleaning agent packaging according to the invention and protects it from soiling, impact and shock. In particular for the purpose of presentation, the outer packaging should be at least partially transparent.

[0122] Alternatively, or in addition to outer packaging, it is of course possible to market the cleaning agent packaging according to the invention in conjunction with a dishwasher. Such a combination is particularly advantageous in cases where the course of the automatic dishwashing process (e.g., duration, temperature profile, water supply) and the cleaning agent formulation or the control electronics of the dosing device are coordinated.

[0123] 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 a dosing device that can be coupled to the cartridge, which in turn is formed from further components, such as a component carrier, actuator, closure element, sensor, energy source and / or control unit.

[0124] It is preferred that the dosing system according to the invention be movable. Movable in the sense of this application means that the dosing system is not permanently connected to a water-conducting device such as a dishwasher or the like, but rather can be removed from a dishwasher by the user or positioned in a dishwasher, i.e., can be handled independently.

[0125] According to an alternative embodiment of the invention, it is also conceivable that the dosing device is not detachably connected to a water-conducting device such as a dishwasher or the like for the user and only the cartridge is movable.

[0126] Since the preparations to be dispensed can have a pH value between 2 and 14, especially between 2 and 12, depending on their intended use, all components of the dispensing system that come into contact with the preparations should exhibit appropriate acid and / or alkali resistance. Furthermore, these components should be largely chemically inert, for example, against non-ionic surfactants, enzymes, and / or fragrances, through appropriate material selection.

[0127] A cartridge, as defined in this application, is understood to be a packaging suitable for enclosing or holding together flowable or spreadable preparations and which can be coupled to a dosing device for dispensing the preparation. In particular, a cartridge can also comprise several chambers that can be filled with different compositions. It is also conceivable for a plurality of containers to be arranged to form a cartridge unit.

[0128] It is advantageous for the cartridge to have at least one outlet opening arranged in such a way that a gravity-induced release of the preparation from the container can be achieved when the dosing device is in the use position. This eliminates the need for additional conveying means to release the preparation from the container, thus keeping the design of the dosing device simple and manufacturing costs low.

[0129] In a preferred embodiment of the invention, at least one second chamber is provided for accommodating at least one second flowable or spreadable preparation, wherein the second chamber has at least one outlet opening arranged such that gravity-induced product release from the second chamber is achieved in the use position of the dosing device. The provision of a second chamber is particularly advantageous when preparations are stored in the separate containers that are not usually stable together, such as bleaching agents and enzymes.

[0130] Furthermore, according to the invention, it is necessary that more than two, in particular three, four, or five chambers are provided in or on a cartridge. In a further embodiment of the invention, the cartridge is formed in one piece. This allows the cartridges to be produced cost-effectively in a single manufacturing step, in particular by suitable blow-molding processes. The chambers of a cartridge can be separated from one another, for example, by webs or material bridges.

[0131] The cartridge can also be formed from multiple pieces made of injection-molded components that are subsequently assembled. Furthermore, it is conceivable for the cartridge to be formed from multiple pieces such 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, if a preparation is consumed at different levels from one chamber, to replace an already empty chamber while the others, which may still be filled with preparation, remain in the dosing device. This allows for targeted and needs-based refilling of the individual chambers or their preparations.

[0132] The chambers of a cartridge can be fixed to one another by suitable connection methods, forming a container unit. The chambers can be fixed to one another releasably or permanently by a suitable positive, non-positive, or material connection.

[0133] In particular, the fixation can be achieved by one or more of the following connection types: snap-in connections, hook-and-loop connections, press connections, melt connections, adhesive connections, welded connections, soldered connections, screw connections, wedge connections, clamp connections, or impact connections. In particular, the fixation can also be achieved by a shrink tube (so-called sleeve), which is pulled over the entire cartridge or sections of it in a heated state and tightly encloses the chambers or cartridge when cooled.

[0134] To ensure advantageous residual emptying properties of the chambers, the bottom of the chambers can be funnel-shaped and inclined toward the dispensing opening. Furthermore, the inner wall of a chamber can be designed, through a suitable choice of material and / or surface configuration, to minimize adhesion of the preparation to the inner chamber wall. This measure can also further optimize the residual emptying properties of a chamber.

[0135] The chambers of a cartridge can have identical or different filling volumes. In a configuration with two chambers, the ratio of the container volumes is preferably 5:1, and in a configuration with three chambers, it is preferably 4:1:1, these configurations being particularly suitable for use in dishwashers. As mentioned above, the cartridge preferably has 3, 4, 5 or 6 chambers. For use of such a cartridge in a dishwasher, it is particularly preferred that the first chamber contains an alkaline cleaning preparation, the second chamber an enzymatic preparation and the third chamber a rinse aid, the volume ratio of the chambers being approximately 4:1:1.

[0136] A dosing chamber can be formed in or on a chamber, upstream of the outlet opening in the direction of flow of the preparation. The dosing chamber determines the amount of preparation to be released from the chamber into the environment. This is particularly advantageous if the closure element of the dosing device, which releases the preparation from a chamber to the environment, can only be set to a release and a closed state without control of the release amount. The dosing chamber then ensures that a predefined amount of preparation is released without direct feedback of the released amount of preparation. The dosing chambers can be formed as a single piece or in multiple pieces.

[0137] According to a further advantageous development of the invention, one or more chambers each have a liquid-tight sealable chamber opening in addition to an outlet opening. This chamber opening makes it possible, for example, to refill the preparation stored in this chamber.

[0138] To ventilate the cartridge chambers, ventilation options can be provided, particularly in the head area of ​​the cartridge, to ensure pressure equalization between the interior of the cartridge chambers and the environment as the fill level drops. These ventilation options can be designed, for example, as a valve, particularly a silicone valve, micro-openings in the cartridge wall, or the like.

[0139] If, according to a further embodiment, the cartridge chambers are not ventilated directly, but rather via the dosing device, or no ventilation is provided, e.g., when using flexible containers such as bags, this has the advantage that, at elevated temperatures during a dishwasher cycle, the heating of the chamber contents builds up pressure, which pushes the preparations to be dispensed toward the outlet openings, thus ensuring good residual emptying of the cartridge. Furthermore, with such air-free packaging, there is no risk of oxidation of the preparation's substances, which makes bag packaging or bag-in-bottle packaging particularly suitable for oxidation-sensitive preparations.

[0140] The cartridge typically has a filling volume of <5,000 ml, in particular <1,000 ml, preferably <500 ml, particularly preferably <250 ml, and most preferably <50 ml. The cartridge can take on any desired spatial shape. For example, it can be cube-shaped, spherical, or plate-shaped.

[0141] The cartridge and the dosing device can in particular be designed with regard to their spatial shape in such a way that they ensure the lowest possible loss of useful volume, in particular in a dishwasher.

[0142] To use the dosing device in dishwashers, it is particularly advantageous to design the device to resemble dishes to be cleaned in dishwashers. For example, these can be plate-shaped, roughly the size of a plate. This allows the dosing device to be positioned in a space-saving manner, for example in the lower basket of the dishwasher. Furthermore, the plate-like shape makes the correct positioning of the dosing unit immediately and intuitively clear to the user. The cartridge preferably has a height:width:depth ratio of between 5:5:1 and 50:50:1, particularly preferably of approximately 10:10:1. The “slim” design of the dosing device and the cartridge makes 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 dosing device go directly into the dishwashing water and cannot adhere to other items being washed.

[0143] Commercially available household dishwashers are typically designed to accommodate larger items, such as pans or large plates, in the lower basket. To prevent the user from positioning the dosing system incorrectly in the upper basket, an advantageous embodiment of the invention allows the dosing system to be positioned only in the designated receptacles of the lower basket. For this purpose, the width and height of the dosing system can be selected, in particular, between 150 mm and 300 mm, and particularly preferably between 175 mm and 250 mm.

[0144] However, it is also conceivable to design the dosing unit in the shape of a cup with an essentially circular or square base.

[0145] In order to protect heat-sensitive components of a preparation contained in a cartridge from the effects of heat, it is advantageous to manufacture the cartridge from a material with low thermal conductivity.

[0146] A further possibility for reducing the influence of heat on a preparation in a chamber of the cartridge is to insulate the chamber by suitable measures, e.g. by using thermal insulation materials such as Styrofoam, which suitably enclose the chamber or the cartridge in whole or in part. To prevent misuse of the cartridge, the cartridges can also have structural elements that interact with corresponding elements of the dispensing device according to the key-lock principle, so that, for example, only cartridges of a certain type can be coupled to the dispensing device. Furthermore, this design makes it possible for information about the cartridge coupled to the dispensing device to be transmitted to the control unit, whereby the dispensing device can be controlled in a way that is tailored to the contents of the corresponding container.

[0147] The cartridge is designed, in particular, to hold free-flowing cleaning agents. Such a cartridge particularly preferably has a plurality of chambers for spatially separating different cleaning agent preparations. The cartridge can be designed so that it can be mounted detachably or permanently in or on the dishwasher.

[0148] The dosing device integrates the control unit, sensor unit, and at least one actuator required for operation. Preferably, a power source is also arranged in the dosing device.

[0149] Preferably, the dosing device consists of a splash-proof housing that prevents splash water from penetrating into the interior of the dosing device, such as can occur when used in a dishwasher.

[0150] It is particularly preferred that the dosing device comprises at least one first interface which interacts with a corresponding interface formed in or on a water-conducting device, in particular a water-conducting household appliance, preferably a dishwasher, in such a way that a transmission of electrical energy from the water-conducting device to the dosing device is realized.

[0151] In one embodiment of the invention, the interfaces are formed by connectors. In a further embodiment, the interfaces can be designed to enable wireless transmission of electrical energy.

[0152] In an advantageous further development of the invention, a second interface is provided on the dosing device and the water-conducting appliance, such as a dishwasher, for transmitting electromagnetic signals, which in particular represent operating status, measurement, and / or control information of the dosing device and / or the water-conducting appliance, such as a dishwasher. An adapter allows for a simple coupling of the dosing system to a water-conducting household appliance. The adapter serves to mechanically and / or electrically connect the dosing system to the water-conducting household appliance.

[0153] The adapter is preferably permanently connected to a water line of the household appliance. However, it is also conceivable to position the adapter in or on the household appliance, where it is exposed to the water flow and / or spray jet of the household appliance.

[0154] The adapter makes it possible to implement a dosing system in both a standalone and a built-in version. It is also possible to configure the adapter as a charging station for the dosing system, where, for example, the dosing device's power source is charged or data is exchanged between the dosing device and the adapter.

[0155] 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. However, it is also conceivable for the adapter as such to be positioned inaccessible to the user in the water-conducting household appliance, so that the dosing device is inserted into the adapter, for example, during assembly of the household appliance. The adapter, the dosing device, and the household appliance are designed such that a cartridge can be coupled to the dosing device by the user.

[0156] The detergent formulations according to the invention are suitable for use in dishwashing, although the use of a detergent formulation according to the invention or a detergent dosing system for dishwashing in a machine dishwashing process is preferred.

[0157] As stated at the outset, the cleaning agents according to the invention are characterized by particular physical and chemical stability, particularly with respect to temperature fluctuations. The cleaning agents according to the invention are therefore exceptionally suitable for dosing using a dosing system located in the interior of a dishwasher. Such a dosing system, which can be integrated immovably into the interior of the dishwasher (machine-integrated dosing device), but can of course also be introduced into the interior as a movable device (self-contained dosing device), contains several times the amount of cleaning agent required to carry out a machine cleaning process.

[0158] Movable within the meaning of this application means that the dispensing and dosing system is not permanently connected to a device such as a dishwasher or the like, but is, for example, removable from a dishwasher or positionable in a dishwasher.

[0159] The use of a detergent packaging form according to the invention for filling i) a cartridge of a dosing system which is immovably integrated into the interior of a dishwasher or ii) a movable cartridge of a dosing system which is intended for positioning in the interior of a dishwasher with a quantity of this detergent packaging form which is sufficient for carrying out a machine dishwashing process at least twice, preferably at least four times and in particular at least eight times are also the subject matter of this application.

[0160] An example of a fixed cartridge is a container that is permanently integrated into the interior of a dishwasher, for example, into the side panel or the interior panel of the door. An example of a movable cartridge is a container that is inserted into the interior of the dishwasher by the consumer and remains there throughout the entire cleaning cycle. Such a cartridge can be integrated into the interior, for example, by simply placing it in the cutlery or dish basket, but can also be removed from the interior of the dishwasher by the consumer.

[0161] As described above, the detergent or detergent combination is preferably dispensed from the cartridge into the dishwasher's interior using a dosing device that can be removed from the cartridge. Such a dosing device can be connected to the cartridge using an adhesive, locking, snap-in, or plug-in connection. However, cartridges with a permanently attached dosing device are also acceptable.

[0162] The use of a detergent formulation according to the invention as a detergent reservoir for i) a dosing device fixedly integrated into the interior of a dishwasher or ii) a movable dosing device intended for positioning in the interior of a dishwasher is preferred.

[0163] The use of a detergent dosing system according to the invention as a detergent reservoir for a dishwasher is a further subject of the present application.

[0164] Two further subjects of this application are the use of a cleaning agent offer form according to the invention, comprising a) a cleaning agent preparation A according to the invention in an amount sufficient for carrying out a machine dishwashing process at least twice, preferably at least four times and in particular at least eight times; b) at least one further cleaning agent preparation B different from A in an amount sufficient for carrying out a machine dishwashing process at least twice, preferably at least four times and in particular at least eight times; c) optionally a further cleaning agent preparation C different from A and B in an amount sufficient for carrying out a machine dishwashing process at least twice, preferably at least four times and in particular at least eight times; e) a cartridge for the cleaning agent preparations A and B, orA, B and C, in which the detergent preparations A, B, C are present in separate receiving chambers as a detergent reservoir for i) a dosing device fixedly integrated into the interior of a dishwasher or ii) a movable dosing device intended for positioning in the interior of a dishwasher.

[0165] The cleaning agents and cleaning agent combinations according to the invention are, as previously stated, preferably used as automatic dishwashing detergents.

[0166] Automatic dishwashing process using a detergent dispenser or a detergent dosing system according to one of the preceding claims, in the course of which a partial amount a of the detergent preparation A located in the cartridge is dosed into the interior of the dishwasher from a cartridge located in the interior of the dishwasher, wherein a residual amount of the detergent preparation located in the cartridge remains in the cartridge until the end of the dishwashing process, characterized in that this residual amount corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of the partial amount a;and a partial amount b of the cleaning agent preparation B contained in the cartridge is dosed into the interior of the dishwasher, wherein a residual amount of the cleaning agent preparation contained in the cartridge remains in the cartridge until the end of the dishwashing process, characterized in that this residual amount corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of partial amount b; and optionally a partial amount c of the cleaning agent preparation C possibly contained in the cartridge is dosed into the interior of the dishwasher, wherein a residual amount of the cleaning agent preparation contained in the cartridge remains in the cartridge until the end of the dishwashing process, characterized in that this residual amount corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of partial amount c.

[0167] In the dishwashing processes according to the invention, it is of course possible to use not only the detergent delivery forms according to the invention, but also the detergent dosing systems according to the invention.

[0168] In a preferred embodiment, the dosage of cleaning agent preparation A and cleaning agent preparation B and optionally cleaning agent preparation C takes place at different times of the cleaning cycle.

[0169] A further preferred subject matter of this application is therefore a machine dishwashing process using a detergent supply form according to the invention or a detergent dosing system according to the invention, in the course of which a) at a time t1, a partial amount a of the detergent preparation A according to the invention located in the cartridge is dosed into the interior of the dishwasher from a cartridge located in the interior of the dishwasher, wherein a residual amount of the detergent located in the cartridge remains in the cartridge until the end of the dishwashing process, which residual amount corresponds to at least twice,preferably at least four times and in particular at least eight times the amount of partial amount a; b) at least one further time t2 11, a partial amount b of the cleaning agent preparation B located in the second cartridge, which is different from the cleaning agent preparation A according to the invention, is dosed into the interior of the dishwasher from a cartridge located in the interior of the dishwasher, wherein a residual amount of the cleaning agent located in this cartridge remains in the cartridge until the end of the dishwashing process, which residual amount corresponds to at least twice,preferably at least four times and in particular at least eight times the amount of partial amount b; c) optionally at at least one further time t3 t2 11, a partial amount d of the detergent preparation C, which is different from the detergent preparations A and B according to the invention and is located in a further cartridge, is dosed into the interior of the dishwasher from a cartridge located in the interior of the dishwasher, wherein a residual amount of the detergent located in this cartridge remains in the cartridge until the end of the dishwashing process, which residual amount corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of partial amount d. In preferred embodiments of the previously described machine dishwashing processes with time-delayed dosing of the detergent preparations A and B or A,B and C, the time t2 is at least 1 minute, preferably at least 2 minutes and in particular between 3 and 30 minutes, in particular between 3 and 20 minutes, before or after, preferably before the time t1. In preferred embodiments of the previously described automatic dishwashing processes with time-delayed dosing, the time t2 is at least 1 minute, preferably at least 2 minutes and in particular between 3 and 30 minutes, in particular between 3 and 20 minutes, before or after, preferably after the time t1.

[0170] In a preferred embodiment, cleaning preparation B is added to the interior at a temperature of 20-35°C, followed by cleaning preparation A at a temperature of 30-60°C and then cleaning preparation C at a temperature below 20°C.

[0171] Example:

[0172] Table 1 :

[0173] Table 2:

[0174] The cleaning performance of a Miele GSL dishwasher was determined using a 45°C program using the IKW method. 20 g of composition A and 3 g of composition B were added to the wash water for each wash cycle. The test was carried out three times. During each wash cycle, three plates each containing crème brûlée and three plates containing minced meat were examined. The water hardness was 21 °dH. At the end of the wash cycle, the dishes were visually inspected on a scale of 1 to 10, and the arithmetic mean of the nine tests was calculated. On the scale, 1 represents the lowest cleaning performance and 10 the highest; i.e., the higher the value, the better the cleaning performance.

[0175] It was demonstrated that comparably good cleaning performance was achieved on crème brûlée and minced meat, despite using no phosphonate and less EDDS compared to Formula V1 with MGDA. Formula E1 thus contains no phosphonate while maintaining equally good performance. At the same time, less glass corrosion was observed with E1 compared to V1.

Claims

Patent claims: 1 . Phosphate-free cleaning agent formulation, comprising a) a liquid cleaning agent preparation A, containing, in each case based on the total weight of the cleaning agent preparation A, a1) builder; a2) 3.0 to 9.0 wt. % of at least one complexing agent selected from ethylenediaminedisuccinic acid and / or salts thereof, and a3) less than 0.1 wt. % phosphonate and b) a liquid cleaning agent preparation different from the cleaning agent preparation A Cleaning agent preparation B containing, in each case based on the total weight of the cleaning agent preparation B, b1) at least one enzyme, in an amount of at least 0.01 wt.% of active enzyme protein, b2) less than 0.1 wt.% phosphonate b3) optionally 2.5 wt.% or less complexing agent, and c) optionally a liquid, different from the cleaning agent preparations A and B Cleaning agent preparation C, comprising c1) an acidifying agent, c2) a glass corrosion inhibitor, c3) optionally a non-ionic surfactant, c4) optionally a hydrotrope, and c5) optionally a fragrance and / or fragrance scavenger; and d) a packaging means in which the cleaning agent preparations A, B, and optionally C are present separately from one another.

2. Cleaning agent packaging according to claim 1, characterized in that the cleaning agent preparations A, based on their total weight, contain 3.5 to 8.0 wt.% and in particular 4.0 to 7.0 wt.%, very particularly preferably 4.5 to 6.0 wt.% of ethylenediaminedisuccinic acid (EDDS) and / or the corresponding alkali metal salt, preferably the trisodium salt.

3. Cleaning agent packaging according to one of the preceding claims, characterized in that the cleaning agent preparation A, based on its total weight, contains 2 to 50 wt.%, preferably 5 to 45 wt.% and in particular 8 to 30 wt.% builder and / or the builder a1) is selected from the group of carbonates, hydrogen carbonates, citrates, silicates, polymeric carboxylates and polymers containing sulfonic acid groups.

4. Cleaning agent packaging according to one of the preceding claims, characterized in that the cleaning agent preparation B, based on its total weight, 2 to 30 wt.%, preferably 5 to 40 wt.% and in particular 10 to 30 wt.% citrates, preferably trisodium citrate, and / or 2 to 15 wt.%, preferably 4 to 12 wt.% and in particular 6 to 10 wt.% (hydrogen)carbonates, preferably sodium carbonate, and / or Contains 1 to 15 wt.%, preferably 2 to 12 wt.% and in particular 3 to 10 wt.% of polymers containing sulfonic acid groups.

5. Cleaning agent packaging according to one of the preceding claims, characterized in that the cleaning agent preparation A and the cleaning agent preparation B and optionally the cleaning agent preparation C, in each case based on their total weight, do not contain any phosphonate.

6. Cleaning agent packaging according to one of the preceding claims, characterized in that the cleaning agent preparation B contains a cleaning-active enzyme from the group of amylases and / or proteases and / or cellulases and / or hemicellulases and / or lipases, in particular amylases and / or proteases.

7. Cleaning agent packaging according to claim 6, characterized in that the cleaning agent preparation B contains a protease in an amount of at least 0.05% by weight, preferably at least 0.1% by weight, in particular at least 0.4% by weight of active enzyme protein and / or an amylase in an amount of at least 0.01% by weight, preferably at least 0.05% by weight, in particular at least 0.1% by weight of active enzyme protein, in each case based on the total weight of the cleaning agent preparation B.

8. Cleaning agent packaging according to one of the preceding claims, characterized in that the cleaning agent preparation B contains sorbitol, preferably in an amount of 2 to 20 wt.%, more preferably 5 to 15 wt.% and in particular 8 to 12 wt.%, based on the total weight of the cleaning agent preparation.

9. Cleaning agent packaging according to one of the preceding claims, characterized in that the cleaning agent preparation C contains the acidifying agent c1) selected from formic acid, acetic acid, citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid and / or oxalic acid and mixtures thereof, in particular formic acid, acetic acid and / or citric acid, and / or the cleaning agent preparation C contains the acidifying agent d) preferably in amounts of 0.1 to 12% by weight, particularly preferably 0.2 to 10% by weight and in particular 0.3 to 8.0% by weight, in each case based on the total weight of the cleaning agent preparation C.

10. Cleaning agent packaging according to one of the preceding claims, characterized in that the cleaning agent preparation C contains surfactants in an amount of 5 to 35% by weight, in particular 10 to 30% by weight, based on the total weight of the respective preparation.

11. Cleaning agent packaging according to one of the preceding claims, characterized in that in the cleaning agent preparation C the glass corrosion inhibitor c2) is selected from polyalkyleneimines, in particular polyethyleneimines, and / or water-soluble zinc salts, preferably zinc chloride, zinc sulfate and / or zinc acetate, particularly preferably zinc acetate, and / or the cleaning agent preparation C contains the glass corrosion inhibitor c2) preferably in amounts of 0.01 wt.% to 5 wt.%, particularly preferably from 0.05 wt.% to 3 wt.%, in particular from 0.1 wt.% to 2 wt.%, based on the total weight of the cleaning agent preparation C, and / or in the cleaning agent preparation C the hydrotrope c3) is selected from xylenesulfonate, cumenesulfonate, urea and / or / V-methylacetamide, particularly preferably cumenesulfonate and / or xylenesulfonate, in particular cumenesulfonate, and / or the cleaning agent preparation C contains the hydrotrope c3) in a Amount from 2 to 25 wt.-%, in particular from 4 to 20 wt.% and particularly preferably in an amount of from 6 to 15, for example from 7 to 12 wt.%, based on the total weight of the cleaning agent preparation C.

12. Use of a detergent packaging according to one of claims 1 to 11 as a detergent reservoir for i) a dosing device fixedly integrated into the interior of a dishwasher or ii) a movable dosing device intended for positioning in the interior of a dishwasher.

13. Use of a detergent packaging form according to one of claims 1 to 11 for filling i) a cartridge of a dosing system which is immovably integrated into the interior of a dishwasher or ii) a movable cartridge of a dosing system which is intended for positioning in the interior of a dishwasher with a quantity of this detergent packaging form which is sufficient for carrying out a machine dishwashing process or a machine textile washing process at least twice, preferably at least four times and in particular at least eight times.

14. Detergent dosing system, comprising a) a detergent packaging according to one of claims 1 to 10, comprising a quantity of detergent preparations A and B or A, B and C sufficient for carrying out a machine dishwashing process at least twice, preferably at least four times and in particular at least eight times; b) a dosing device detachably connected to the detergent packaging.

15. Use of a detergent dosage form according to one of claims 1 to 11 or of a detergent dosing system according to claim 14 for cleaning dishes in a machine dishwashing process.

16. A machine dishwashing process using a detergent dispenser according to any one of claims 1 to 11 or a detergent dosing system according to claim 14, in the course of which a partial amount a of the detergent preparation A contained in the cartridge is dosed into the interior of the dishwasher from a cartridge located in the interior of the dishwasher, a residual amount of the detergent preparation A contained in the cartridge remaining in the cartridge until the end of the dishwashing process, characterized in that this residual amount corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of the partial amount a;and a partial amount b of the cleaning agent preparation B contained in the cartridge is dosed into the interior of the dishwasher, wherein a residual amount of the cleaning agent preparation contained in the cartridge remains in the cartridge until the end of the dishwashing process, characterized in that this residual amount corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of partial amount b; and optionally a partial amount c of the cleaning agent preparation C which may be present in the cartridge is dosed into the interior of the dishwasher, wherein a residual amount of the cleaning agent preparation contained in the cartridge remains in the cartridge until the end of the dishwashing process, characterized in that this residual amount corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of partial amount c.;

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