DE102019200701A1 - Detergent formulations for automatic dishwashing with bleach - Google Patents

Abstract

The invention relates to forms of detergent for automatic dishwashing, which contain different detergent preparations and a spatially separated bleach preparation.

Description

The invention relates to forms of detergent for automatic dishwashing, which contain different detergent preparations and a spatially separated bleach preparation.

The form and form of supply of cleaning agents are always subject to new changes. For some time now, the main focus has been on the convenient dosing of cleaning agents and the simplification of the work steps required to carry out a cleaning process.

In particular, devices for multiple dosing of cleaning agents are desired by the consumer. Devices can be differentiated between metering containers integrated in the dishwasher on the one hand and independent devices independent of the dishwasher on the other. Using these devices, which contain several times the amount of detergent required to carry out a cleaning process, detergent portions are metered into the interior of the cleaning machine in an automatic or semi-automatic manner in the course of several successive cleaning processes. For the consumer, this eliminates the need to dose the detergent before the start of each cleaning cycle. Examples of such devices are found in the European patent application EP 1 759 624 A2 (Reckitt Benckiser) or in the German patent application DE 10 2005 062 479 A1 (BSH Bosch and Siemens Hausgeräte GmbH).

In particular, consumers with a low flushing / washing volume want a solution that is uncomplicated and easy to use. In particular, dishwashers that are loaded with dishes for several days and in which the soiled items remain uncleaned for some time inside the dishwasher before a washing cycle is carried out have the problem that unpleasant smells, e.g. develop through acidifying milk, etc.

The WO2012126536 A1 describes a dosing system for a dishwasher, which at least one means for the substantially continuous, water-induced release of at least one additive into the rinse water during a dishwasher rinse program, particularly preferably from the group of bleaching catalysts, bleach activators, bleaching, glass corrosion inhibitors, surfactants and / or disinfection additives preparations.

Regardless of the exact design of the dosing devices used in the interior of dishwashers, the detergents contained in these devices for multiple dosing are also exposed to changing temperatures over a longer period of time, 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, with usually only temperatures between 50 and 75 ° C being achieved in the area of machine dishwashing. A cleaning agent contained in a device provided for multiple dosing is accordingly repeatedly heated in the course of several cleaning processes to temperatures significantly above the temperatures customary for transport and storage, with temperature-sensitive active substances in particular being affected.

In order to increase the cleaning performance in machine dishwashing, enzymes have been added to the cleaning agents for a long time. In particular, hydrolytic enzymes such as proteases and amylases are components of numerous dishwashing detergents. However, it is also known that detergents based only on enzyme-containing compositions, e.g. Insufficiently remove coffee and tea stains from the objects to be cleaned.

Bleach-containing cleaning compositions can remove this type of soiling very well. However, these compositions have weaknesses in removing stains such as minced meat, egg yolk or spaghetti. A combination of enzymes and bleach-containing cleaning compositions in cleaning agents is therefore desirable in order to remove these soiling with different requirements in a single rinse cycle of an automatic dishwasher.

However, enzymes are unstable in the presence of oxidizing agents and lose their activity. This is especially true for liquid cleaning compositions. Therefore, the cleaning performance of conventional cleaning compositions that combine enzymes and bleaches in one composition is greatly reduced.

Therefore, possibilities are sought to apply both enzymes and strong oxidizing agents, in particular chlorine-containing oxidizing agents, to the items to be cleaned in a rinse cycle of an automatic dishwasher without reducing the cleaning performance, in particular that of the enzymes.

The object of the present application is accordingly to provide a form of cleaning agent which provides good cleaning performance even with regard to bleachable soiling and in this case contains compositions which are stable with respect to temperature changes.

1. a) eine flüssige (20°C) Reinigungsmittelzubereitung A, enthaltend a1) Gerüststoff; a2) Komplexbildner und/oder
2. b) eine flüssige (20°C) von der Reinigungsmittelzubereitung A verschiedene Reinigungsmittelzubereitung B, enthaltend b1) mindestens eine reinigungsaktiven Enzymzubereitung sowie b2) optional mindestens ein nichtionisches Tensid sowie
3. c) gegebenenfalls eine flüssige (20°C) von der Reinigungsmittelzubereitung A und B verschiedene Reinigungsmittelzubereitung C, enthaltend
   • c1) ein Acidifizierungsmittel, sowie optional weniger als 1 Gew.-%, bevorzugt weniger als 0,5 Gew.-%, insbesondere weniger als 0,1 Gew.-% Enzymzubereitung, und
4. d) ein Verpackungsmittel, in welchem die Reinigungsmittelzubereitungen A und/oder B sowie ggf. C getrennt voneinander vorliegen, dadurch gekennzeichnet, dass es eine von den anderen Reinigungsmittelzubereitungen räumlich getrennte Bleichmittelzubereitung E umfasst.

The object is achieved by a form of cleaning agent, comprising

1. a) a liquid (20 ° C.) detergent preparation A, containing a1) builders; a2) complexing agents and / or
2. b) a liquid (20 ° C.) detergent preparation B different from detergent preparation A, containing b1) at least one detergent-active enzyme preparation and b2) optionally at least one nonionic surfactant and
3. c) optionally containing a liquid (20 ° C.) detergent preparation C different from detergent preparation A and B.
   • c1) an acidifying agent, and optionally less than 1% by weight, preferably less than 0.5% by weight, in particular less than 0.1% by weight of enzyme preparation, and
4. d) a packaging material in which the cleaning agent preparations A and / or B and optionally C are present separately from one another, characterized in that it comprises a bleaching agent preparation E spatially separated from the other cleaning agent preparations.

Unless explicitly stated otherwise, all percentages given in connection with the compositions described herein relate to% by weight, in each case based on the mixture in question. If physical states (solid, liquid) are mentioned in the present application, unless otherwise stated, these relate to room temperature (20 ° C.) at normal pressure of 1 bar.

The form of the detergent is characterized in that the detergent preparations are phosphate-free, i.e. that 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.

The cleaning agent preparation A contains one or more builders as the first essential component. The builders in particular include carbonates, organic cobuilders and silicates. Forms of cleaning agent according to the invention are preferably characterized in that the builder a1) is selected from the group of carbonates, bicarbonates, citrates, silicates, polymeric carboxylates and polymers containing sulfonic acid groups.

Preferred forms of detergent supply comprise a detergent preparation A which, based on its total weight, contains 2 to 50% by weight, preferably 6 to 45% by weight and in particular 10 to 40% by weight of builder.

It is particularly preferred to use builders a1) from the group of carbonates and / or hydrogen carbonates, preferably alkali carbonates, particularly preferably sodium carbonate, in amounts of 2 to 30% by weight, preferably 3 to 20% by weight and in particular 4 up to 15% by weight, each based on the weight of the detergent preparation A.

Organic cobuilders include, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances are described below.

Usable organic builder substances are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, such carboxylic acids being among polycarboxylic acids can be understood that carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, provided that such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Particularly preferred cleaning agent preparations A according to the invention contain citrate as one of their essential builders. Forms of cleaning agent, characterized in that the cleaning agent preparation A, based on their total weight, contains 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight of citrate, are preferred according to the invention. Citrate or citric acid, in particular in combination with phosphonate, in particular 1-hydroxyethane-1,1-diphosphonic acid, and / or the polymers containing sulfonic acid groups have proven to be the most effective builders in terms of cleaning performance, such as rinse aid performance and in particular scale inhibition.

Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The amount of (co) polymeric polycarboxylates in the automatic dishwashing detergents is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.

Automatic dishwashing agents according to the invention can contain crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .y H ₂ O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, where are particularly preferred values for x 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are preferably delayed release and have secondary washing properties.

In preferred automatic dishwashing agents according to the invention, the silicate content, based on the total weight of the automatic dishwashing agent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight. Particularly preferred automatic dishwashing agents according to the invention are silicate-free.

The automatic dishwashing agents according to the invention can of course contain the aforementioned builders both in the form of individual substances and in the form of substance mixtures of two, three, four or more builders.

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

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

Unsaturated carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH, in which R ¹ to R ³ independently of one another for -H, -CH ₃ , are used as unsaturated carboxylic acid (s) 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 for -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylene malonic acid, sorbic acid, cinnamic acid or mixtures thereof. Of course, the unsaturated dicarboxylic acids can also be used.

In the case of the monomers containing sulfonic acid groups, those of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H are preferred, in which R ⁵ to R ⁷ independently of one another are —H, —CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with - NH ₂ , -OH or -COOH or for -COOH or -COOR ⁴ R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical with 1 to 12 carbon atoms, and X stands for an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO - (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, - C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and - C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Preferred among these monomers are those of the formulas H ₂ C = CH-X-SO ₃ H, H ₂ C = C (CH ₃ ) -X-SO ₃ H or HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H, in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , - CH ₂ CH ₂ CH ₃ and -CH (CH ₃ ) ₂ and X stands for an optionally available spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, - C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

According to a particularly preferred embodiment, the gel phase contains a polymer comprising, as the monomer containing sulfonic acid groups, acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts. The sulfonic acid groups in the polymers can be wholly or partly in neutralized form, that is to say that the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can 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.

The monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95% by weight in each case in copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are preferably selected from the aforementioned. 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 intended use. Preferred cleaning agents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

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

1. i) Carbonsäuregruppen-haltige Monomere
2. ii) Sulfonsäuregruppen-haltige Monomere
3. iii) optional nichtionische Monomere, insbesondere hydrophobe Monomere eingesetzt wird.

The at least one gel phase particularly preferably further comprises an anionic copolymer, a copolymer comprising as the anionic copolymer

1. i) Monomers containing carboxylic acid groups
2. ii) Monomers containing sulfonic acid groups
3. iii) optionally nonionic monomers, in particular hydrophobic monomers, are used.

Monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or - C ₂ H ₅ , are preferably used as nonionic monomers , X stands for an optionally available spacer group, which is selected from -CH ₂ -, - C (O) O- and -C (O) -NH-, and R ⁴ for a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or represents an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, α-olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C ₂₂ -α-otefin, 2-styrene α-methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid propyl ester, acrylic acid butyl ester, acrylate, acrylate, acrylate, acrylate N- (methyl) acrylamide, 2-ethylhexyl acrylic acid, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, octyl acrylate, methacrylic acid ylic acid octyl ester, N- (octyl) acrylamide, acrylic acid lauryl ester, methacrylic acid lauryl ester, N- (lauryl) acrylamide, acrylic acid stearyl ester, methacrylic acid stearyl ester, N- (stearyl) acrylamide, acrylic acid beyl ester, methacrylic acid behenyl ester and N- (behenyl) acrylate, especially their mixtures, acrylate or acrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and mixtures thereof.

As a second essential component, the cleaning agent preparation A contains a complexing agent which is different from the builders mentioned above. The weight fraction of the complexing agent in the total weight of the cleaning agent preparation A is preferably 2 to 60% by weight, preferably 4 to 55% by weight and in particular 8 to 50% by weight.

The phosphonates form a first group of preferred complexing agents. In addition to 1-hydroxyethane-1,1-diphosphonic acid, the complex-forming phosphonates comprise a number of different compounds such as, for example, diethylenetriaminepenta- (methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkanephosphonates are particularly preferred in this application. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

1. a) Aminotrimethylenphosphonsäure (ATMP) und/oder deren Salze;
2. b) Ethylendiamintetra(methylenphosphonsäure) (EDTMP) und/oder deren Salze;
3. c) Diethylentriaminpenta(methylenphosphonsäure) (DTPMP) und/oder deren Salze;
4. d) 1-Hydroxyethan-1,1-diphosphonsäure (HEDP) und/oder deren Salze;
5. e) 2-Phosphonobutan-1,2,4-tricarbonsäure (PBTC) und/oder deren Salze;
6. f) Hexamethylendiamintetra(methylenphosphonsäure) (HDTMP) und/oder deren Salze;
7. g) Nitrilotri(methylenphosphonsäure) (NTMP) und/oder deren Salze.

A detergent composition A preferred in the context of this application contains one or more phosphonate (s) from the group

1. a) aminotrimethylenephosphonic acid (ATMP) and / or its salts;
2. b) ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and / or their salts;
3. c) Diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) and / or their salts;
4. d) 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or its salts;
5. e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or its salts;
6. f) hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and / or their salts;
7. g) Nitrilotri (methylenephosphonic acid) (NTMP) and / or their salts.

Detergent compositions A which contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) as phosphonates are particularly preferred.

The automatic dishwashing detergents according to the invention can of course contain two or more different phosphonates. The proportion by weight of the phosphonates in the total weight of detergent compositions A according to the invention is preferably 1 to 8% by weight, preferably 1.2 to 6% by weight and in particular 1.5 to 4% by weight.

Particularly preferred forms of cleaning agent are characterized in that the complexing agent a2) is selected from the group of hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glutamic acid diacetic acid, in particular L-glutamic acid-N, N-diacetic acid, iminodisuccinic acid, hydroxynimic acid diacid, hydroxynimic acid dehydroacetic acid, hydroxynimic acid dibasic, 1-diphosphonic acid or diethylenetriaminepenta (methylenephosphonic acid) and their salts or mixtures thereof, preferably L-glutamic acid-N, N-diacetic acid and / or methylglycinediacetic acid and their salts. The term methylglycinediacetic acid or L-glutamic acid-N, N-diacetic acid includes not only the free acids but also their salts, for example their sodium or potassium salts.

The detergent preparations A according to the invention can contain, in particular, L-glutamic acid-N, N-diacetic acid and / or the corresponding alkali salt (GLDA), preferably the tetrasodium salt, and / or methylglycinediacetic acid and / or the corresponding alkali salt, preferably the trisodium salt, as particularly preferred complexing agents. The trisodium salt of methylglycinediacetic acid (MGDA) or the corresponding sodium salts are very particularly preferably present, preferred cleaning agent preparations A being characterized in that, based on the total weight of the cleaning agent preparations A, they are 3.0 to 35% by weight, preferably 4 , 0 to 30 wt .-% and in particular 8.0 to 25 wt .-% methylglycinediacetic acid.

According to a particularly preferred embodiment, the cleaning agent preparation A contains the complexing agents selected from phosphonates, if permitted for regulatory reasons, and / or MGDA and their respective salts. In particular, the builders then include citrate and carbonate and / or hydrogen carbonate.

According to a particularly preferred embodiment of the form of detergent, the detergent preparation A contains, based on its total weight, MGDA and / or its salts in amounts of 5 to 30% by weight, in particular 8 to 25% by weight, for example 10 to 15% by weight .-%, citrate in amounts of 3 to 20% by weight, in particular 4 to 15% by weight, and carbonate in amounts of 5 to 30% by weight, in particular 7 to 20% by weight. In addition to these active substances mentioned, if this is permissible for regulatory reasons, phosphonate and / or its salt is also preferred in amounts of 1.2 to 6% by weight, in particular 1.5 to 4% by weight.

In a preferred embodiment of the invention, one of the cleaning agent preparation, preferably cleaning agent preparation B, furthermore contains at least one surfactant, in particular selected from anionic, nonionic, zwitterionic and amphoteric surfactants. Alternatively, the surfactants can also be contained in a cleaning agent preparation different from the cleaning agent preparations A and B. If used in a cleaning agent preparation B according to the invention, surfactants are preferably used in an amount of up to 40% by weight, in particular 2 to 40% by weight or 4 to 40% by weight, particularly preferably in an amount of 5 to 35% by weight .-%, in particular 10 to 30 wt .-%, contain.

Detergent 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 detergent preparation A.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linearly or preferably 2-branched methyl or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO, 4 EO or 7 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction 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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated nonionic surfactants can also be used, in which the EO and PO units are not distributed in blocks, but are statistically distributed. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

In a preferred embodiment, the content of nonionic surfactants in the cleaning preparation B is 5 to 30% by weight, preferably 7 to 20% by weight and in particular 9 to 15% by weight, based on the total amount of the cleaning preparation B.

In addition to the nonionic surfactants, the cleaning preparation B can also contain anionic surfactants. Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable. The anionic surfactants including the soaps can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

In a preferred embodiment, the content of anionic surfactants in cleaning preparation B is 0.1 to 30% by weight, preferably 2 to 20% by weight, based on the total amount of cleaning preparation A.

A preferred pH of cleaning preparations A according to the invention is between 9 and 14, in particular 9 and 12. The pH can, if necessary, be adjusted by means of appropriate pH adjusting agents, in particular sodium hydroxide.

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% by weight, preferably between 5 and 60% by weight, particularly preferably between 10 and 50% by weight and in particular between 10 and 30% by weight. %. The enzyme preparations used in this way each contain from 0.1 to 40% by weight, preferably from 0.2 to 30% by weight and particularly preferably from 0.4 to 20% by weight and in particular from 0.8 up to 10% by weight of active enzyme protein.

The enzymes used with particular preference include proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are accordingly preferred. Detergents preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5 % By weight based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

The stabilizing effect according to the invention was observed to a particular degree in the case of the amylases, proteases, cellulases and mannanases, which is why liquid cleaning agent preparations B according to the invention, characterized in that they have at least one cleaning-active enzyme from the group of the amylases and / or proteases and / or cellulases and / or Mannanases, in particular from the group of amylases and / or proteases, are included.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309 , the alkaline protease from Bacillus lentus, Subtilisin DY and the enzymes Thermitase, Proteinase K and the proteases TW3 and TW7, which can no longer be assigned to the Subtilisins in the narrower sense.

Liquid detergent preparations B preferred according to the invention contain, based on the total weight of the detergent preparation, 5 to 50% by weight, preferably 7 to 40% by weight and in particular 10 to 30% by weight of protease preparations. Detergent preparations A which contain 15 to 25% by weight of protease preparations, based on their total weight, are particularly preferred.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Liquid detergent preparations B preferred according to the invention contain, based on the total weight of the detergent preparation, 0.1 to 30% by weight, preferably 1.0 to 25% by weight and in particular 2.0 to 20% by weight of amylase preparations. Detergent preparations B are particularly preferred which, based on their total weight, contain 4.0 to 16% by weight of amylase preparations.

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

Further liquid cleaning preparations B preferred according to the invention contain, based on the total weight of the cleaning agent preparation, 0.1 to 30% by weight, preferably 1.0 to 25% by weight and in particular 2.0 to 20% by weight of mannanase preparations.

Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or developed further, in particular those with the amino acid exchange D96L. Furthermore, the cutinases can be used, for example, which were originally isolated from Fusarium solani pisi and Humicola insolens. Lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii can also be used.

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

Furthermore, enzymes can be used, which are summarized under the term hemicellulases. In addition to the mannanase already mentioned, these include, for example, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

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 (phenoloxidases, polyphenol oxidases) can be used according to the invention. Advantageously, organic, particularly preferably aromatic, compounds which interact with the enzymes are additionally preferably added in order to increase the activity of the oxidoreductases in question amplify (Enhancer) or to ensure the flow of electrons (mediators) in the case of very different redox potentials between the oxidizing enzymes and the soiling.

Cleaning-active enzymes, in particular proteases and amylases, are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations. These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or mixed with stabilizers or other auxiliaries.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or those of the core-shell type in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.

Furthermore, it is possible to assemble two or more enzymes together, so that a single granulate has several enzyme activities.

As can be seen from the previous explanations, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10% by weight of the enzyme protein.

Liquid detergent preparations B which are particularly preferred according to the invention therefore contain, based on the total weight of the detergent 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 are used, each containing 0.4 to 20% by weight, in particular 0.8 to 10% by weight, of active protein.

According to a preferred embodiment, the liquid detergent preparations B comprise amylases and / or proteases and / or cellulases and / or hemicellulases and / or lipases, in particular amylases and / or proteases, preferably in an amount of 0.01 to 5% by weight, preferably 0.05 to 2.5 wt .-%, in particular 0.1 to 1.5 wt .-% of active enzyme protein based on the total weight of detergent preparation B contains.

A plurality of enzymes and / or enzyme preparations, preferably liquid protease preparations and / or amylase preparations, and optionally cellulase preparations and / or mannanase preparations are preferably used.

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

The cleaning agent preparations B of the cleaning agent dosage forms 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 agents and / or builders. Lowering the complexing agent content below these upper limits has proven to be advantageous for the cleaning performance. A further reduction in the content of complexing agent clearly below the upper limits surprisingly enables a further increase in the cleaning performance of the forms of cleaning agent according to the invention.

Accordingly, preferred forms of detergent according to the invention are characterized in that the detergent 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 none Contains complexing agents.

The total amount of complexing agent and / or builders contained in the detergent 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.

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 butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene 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 glycerol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol and polyethylene glycols, in particular those polyethylene glycols which have an average molecular weight between 100 and 800, preferably 200 and 600 g / mol. The proportion by weight of these organic solvents in the total weight of the respective cleaning agent preparations according to the invention is preferably 5 to 80% by weight, preferably 10 to 60% by weight and in particular 20 to 50% by weight.

A particularly preferred organic solvent which is particularly effective in terms of stabilizing the cleaning agent preparation, in particular cleaning agent preparation B, is 1,2-propylene glycol. The proportion by weight of 1,2-propylene glycol in the total weight of the detergent preparations B according to the invention can vary within wide limits, but those preparations which, based on the total weight of the respective detergent preparation B, are preferably 5 to 80% by weight have proven to be particularly stable Contain 10 to 60 wt .-% and in particular 20 to 50 wt .-% 1,2-propylene glycol. Appropriate preparations are therefore preferred according to the invention.

Another optional component of the cleaning agent preparations B according to the invention is a boric acid or a boric acid derivative. In addition to the boric acid, the boronic acids or their salts or esters are preferably used, including above all derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenyl-boronic acid (4-FPBA), or the Salts or esters of the compounds mentioned. The proportion by weight of boric acid or the boric acid derivatives in the total weight of cleaning agent preparations B according to the invention is preferably between 0.001 to 10% by weight, preferably 0.002 to 6% by weight and in particular 0.05 to 3% by weight.

A particularly preferred boric acid derivative which is particularly effective in terms of stabilizing the cleaning agent preparation is 4-formylphenyl-boronic acid. The proportion by weight of 4-formylphenyl-boronic acid in the total weight of the detergent preparations according to the invention can vary within wide limits, but such preparations have proven to be particularly stable which, based on the total weight of the detergent preparation B, 0.001 to 10% by weight, preferably 0.002 to 6% by weight and in particular 0.05 to 3% by weight. Appropriate preparations are therefore preferred according to the invention.

Another optional component of the cleaning agent preparations according to the invention is a Ca or Mg ion source. The weight fraction of the Ca or Mg ion source in the total weight of cleaning agent preparations B according to the invention is preferably between 0.01 and 10% by weight, preferably 0.2 to 8% by weight and in particular 0.5 to 5% by weight.

The organic calcium salts have proven to be particularly preferred and particularly effective in terms of stabilizing the cleaning agent preparation B.

The proportion by weight of the organic calcium salts in the total weight of the detergent preparations according to the invention can vary within wide limits, but such preparations have proven to be particularly stable which, based on the total weight of the detergent preparation, 0.01 to 10 wt .-%, preferably 0.2 to Contain 8 wt .-% and in particular 0.5 to 5 wt .-%. Appropriate preparations are therefore preferred according to the invention.

To stabilize the enzyme, detergent preparations B according to the invention may also contain polyols, in particular sorbitol.

Based on their total weight, the liquid detergent preparations B preferably contain 30% by weight and less, preferably 25% by weight and less, in particular 15% by weight and less. In a further preferred embodiment, the detergent preparations B contain, based on their total weight, 0.5 to 30% by weight, preferably 1.0 to 25% by weight and in particular 1.5 to 30% by weight of water.

In a preferred embodiment, the detergent form further comprises a liquid detergent preparation C, the detergent preparation C being different from the detergent preparations A and B.

In the automatic dishwashing method according to the invention, the detergent preparations A and B and the active compound composition D are used in a preferred embodiment in combination with at least one further detergent preparation C. When used in a dishwashing process, this detergent preparation C is preferably surfactant and / or acidic, preferably surfactant and acidic.

• - R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• - R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• - A, A', A" und A'" unabhängig voneinander für einen Rest aus der Gruppe -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, -CH₂-CH(CH2-CH3) stehen,
  • - w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können

eingesetzt. Als besonders wirkungsvoll haben sich hierbei die nichtionischen Tenside der allgemeine Formel R¹-CH(OH)CH₂O-(AO)_w-R² erwiesen, in der

• - R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• - R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• - A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
• - w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht.

By using a detergent preparation C containing surfactant and / or acid, the rinse aid achieved in the dishwashing method according to the invention can be improved. This applies in particular to those preferred process variants in which the dosage of the cleaning agent preparations A, B and C is carried out with a time delay. The nonionic surfactants described above are particularly suitable as surfactant additives for the cleaning agent preparation C. However, nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² , are preferably used of the

• - R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• - R ^{2 represents} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• - A, A ', A "and A'" independently of one another for a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (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

used. The non-ionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ² , in which the

• - R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• - R ^{2 represents} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• - A represents a radical from the group CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), and
• - w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40.

The group of these nonionic surfactants includes, for example, the C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular also the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ether and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether.

The weight fraction of the nonionic surfactant in the total weight of the detergent preparation C is preferably from 1.0 to 20% by weight, preferably from 2.0 to 18, particularly preferably from 4.0 to 15% by weight and in particular from 6.0 to 12% by weight.

In a further particularly preferred embodiment, at least one detergent preparation, in particular at least one detergent preparation further comprising a nonionic surfactant, particularly preferably at least detergent preparation B and / or D contains at least one hydrotrope (hereinafter also referred to as a solubilizer). Preferred hydrotropes are xylene sulfonate, cumene sulfonate, urea and / or N-methylacetamide, particularly preferably cumene sulfonate and / or xylene sulfonate, especially cumene sulfonate. It was found that the use of hydrotropes, in particular cumene sulfonate, enormously improves the phase stability with regard to the temperature fluctuations. This can be observed in particular for preparations which contain 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 at least one hydrotrope, preferably xylene sulfonate, cumene sulfonate, urea and / or N-methylacetamide, particularly preferably cumene sulfonate and / or xylene sulfonate, in particular Cumene sulfonate, preferably in an amount of 2 to 25% by weight, in particular 4 to 20% by weight and particularly preferably in an amount of 6 to 15, for example 7 to 12% by weight, based on the total weight of the respective detergent preparation. The weight ratio of the at least one nonionic surfactant to the at least one hydrotrope, preferably xylene sulfonate, cumene sulfonate, urea and / or N-methylacetamide, particularly preferably cumene sulfonate and / or xylene sulfonate, in particular cumene sulfonate, is preferred. 2: 1 to 1: 2, in particular 1.6: 1 to 1: 1.

In addition or as an alternative to the nonionic surfactants, the cleaning agent preparations C according to the invention preferably contain at least one acidifying agent c1) when used in a dishwashing process. Acidifying agents can be added to the cleaning agent preparations C according to the invention in order to lower the pH of the liquor in the rinse cycle. Both inorganic acids and organic acids are suitable here, provided they are compatible with the other ingredients. For reasons of consumer protection and handling safety, the solid mono-, oligo- and polycarboxylic acids in particular can be used. Preferred from this group are formic acid, citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight). Detergent preparations C which, based on the total weight of the detergent 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% by weight, preferably 0.2 to 10% by weight and in particular 0.3 to 8.0% by weight are preferred embodiments of the present invention.

The use of formic acid is preferred since, in addition to the acid function to improve the rinse aid result, it also has a positive influence on the storage stability of the cleaning preparation C, which, as explained above, is subject to severe temperature fluctuations due to storage in the interior of the dishwasher. Furthermore, it has a disinfectant effect, so that when using formic acid in the rinse cycle, both the number of bacteria is reduced. This applies both to those bacteria that are in the rinse liquor of the rinse cycle and to those that remain in the sump of the dishwasher during and after the rinse cycle as well as the interior of the dishwasher. The number of residual germs on the washed dishes can also be reduced as a result.

It is particularly advantageous if an active ingredient composition D, in particular comprising fragrances and / or scent scavengers, and at the same time formic acid is used as an acidifying agent in preparation C. The formic acid itself has a slightly pungent smell, which is noticeable to sensitive consumers. Due to the separate storage of the active ingredient composition and the release of the at least one active ingredient D, in particular if it is one or more fragrances, in particular those preferred above, and / or one or more fragrance scavengers, in particular e.g. Zinc ricinoleate, does not produce an unpleasant smell inside the dishwasher, neither during the dishwashing process nor between cleaning cycles.

The cleaning agent preparations A, B and C described above differ in their composition and are therefore not identical.

Furthermore, the detergent preparations A, B and / or C according to the invention preferably contain at least one glass corrosion inhibitor when used in a dishwashing process. Preparation (s) A and / or preparation (s) C particularly preferably contain a corresponding amount of glass corrosion inhibitor (s). 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.

In a preferred embodiment, the preparations according to the invention, in particular preparations A and / or C, contain at least one zinc salt as a further constituent, 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 zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, Zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate. In an embodiment which is particularly preferred according to the invention, zinc acetate is used as the zinc salt.

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

Polyethyleneimines, such as those available under the name Lupasol® (BASF), are preferably used in an amount of 0 to 5% by weight, in particular 0.01 to 2% by weight, based on the total weight of the preparation Glass corrosion inhibitors are used.

According to a particularly preferred embodiment, the bleaching agent preparation E contains at least one oxidizing agent.

Suitable cleaning agent preparations E contain an oxygen bleaching agent selected from hydrogen peroxide, peroxomonosulfate salts, peroxodisulfate salts and PAP, the weight fraction of the oxygen bleaching agent in the total weight of the bleaching agent preparation E preferably being between 0.1 and 50% by weight, preferably between 0.2 and 35% by weight. -%, particularly preferably between 0.5 and 20 wt .-% and in particular between 1.0 and 10 wt .-%.

According to a preferred embodiment, the oxidizing agent is preferably selected from chlorine dioxide, calcium hypochlorite, potassium hypochlorite, sodium hypochlorite. According to a particularly preferred embodiment, the bleaching agent preparation comprises sodium hypochlorite as the oxidizing agent.

According to a further preferred embodiment, the bleaching agent composition E contains the at least one oxidizing agent, preferably the alkali metal hypochlorite, in particular sodium hypochlorite, in amounts of 0.1 to 8.0% by weight, preferably in 0.15 to 3.0% by weight , and more preferably in 0.2 to 1.0% by weight based on the total weight of bleach preparation.

According to a particularly preferred embodiment, the bleach preparation E, in particular the bleach preparation E, comprising alkali metal hypochlorite, particularly preferably sodium hypochlorite, further comprises a phosphonate. The (preferably organic) phosphonates already described above, in particular the complex-forming phosphonates described above, are suitable for this.

The 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or its salts or the 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or its salts are particularly preferably used in bleaching agent preparation E. The proportion by weight of the phosphonates, preferably the HEDP or the PBTC, in the total weight of bleaching agent preparations E according to the invention is preferably 0.01 to 15% by weight, preferably 0.05 to 12% by weight and in particular 1.0 to 10% by weight .

According to a further particularly preferred embodiment, at least one of the cleaning agent preparation A and / or B comprises at least one bleach activator from the group of transition metal catalysts.

The proportion by weight of the bleach activator to the total weight of the detergent preparation B is preferably 0.001 to 2.0% by weight, preferably 0.001 to 1.0% by weight and in particular 0.001 to 0.5% by weight.

Preferably the bleach composition is aqueous, i.e. it has a water content of 10 to 98% by weight, in particular 15 to 96% by weight, particularly preferably 20 to 95% by weight, in each case based on the total amount of bleaching agent composition E.

Preferably the pH of bleach composition E is alkaline, i.e. it has a pH at 20 ° C. (undiluted) of pH 8 and higher, preferably pH 9 and higher, in particular pH 10 and higher. This is preferably achieved by the presence of alkalizing agents in the bleaching agent composition E.

Particularly suitable alkalizing agents are the hydroxides, preferably alkali metal hydroxides, the carbonates, bicarbonates or sesquicarbonates, preferably alkali metal carbonates or alkali metal bicarbonates or alkali metal sesquicarbonates, for the purposes of this invention preferably those Alkali metal hydroxides and alkali carbonates, in particular sodium hydroxide, potassium hydroxides, sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, more preferably sodium hydroxide, potassium hydroxides, can be used. Sodium and / or potassium hydroxide are preferably used in amounts of 0.1 to 25% by weight, in particular 0.15 to 20% by weight, based on the total weight of the bleaching agent composition E.

It is also possible, but not preferred, to use carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonate (s), particularly preferably sodium carbonate. Alkali carbonates, especially sodium carbonate, can also be used as pH adjusters.

According to the invention, the cleaning agent preparations A and / or B and optionally C are preferably essentially free of bleach, where “essentially free of bleach” means that preferably less than 0.1% by weight, in particular less than 0.01% by weight , and most preferably there is no bleach at all in the particular detergent preparation. It is particularly preferred if none of the cleaning agent preparations A, B and C contain bleach.

The composition of some exemplary cleaning agent forms according to the invention, comprising the cleaning agent preparations A, B, C and E can be found in the following tables. Recipe 1 Recipe 2 Recipe 3 Recipe 4 Ingredients W.-uR preparation A [% By weight] [% By weight] [% By weight] [% By weight] Builders 2 to 50 2 to 50 2 to 30 4 to 30 MGDA 2 to 60 8 to 30 10 to 20 12 to 15 Phosphonates, if permitted by regulation 0 to 10 1 to 8 1.2 to 6 1.5 to 4 Surfactants 2 to 40 4 to 40 5 to 35 5 to 35 Misc ad 100 ad 100 ad 100 ad 100 Ingredients W.-uR preparation B Enzyme preparation, preferably protease and / or amylase preparation at least 5 at least 5 at least 5 at least 5 Complexing agent <2.5 <2.5 <2.5 <2.5 Misc ad 100 ad 100 ad 100 ad 100 Ingredients W.-uR preparation C Surfactants, preferably non-ionic surfactants 0-40 2.0-35 5.0-30 6.0-12.0 Acid, preferably formic acid 0.1-12 0.2-10 0.3-8.0 0.3-8.0 Zinc salt 0.01-5.0 0.05-3.0 0.05-3.0 0.1-2.0 Hydrotrope, especially cumene sulfonate 2-25 4-20 6-15 6-15 Misc ad 100 ad 100 ad 100 ad 100 Ingredients bleach preparation E KOH NaOH Hypochlorite 0.1-8 0.15-3.0 0.15-3.0 0.2-1.0 Water glass 0-10 0-5 0-4 0-4 Polyacrylate, sodium salt, homopolymer 0-10 0-5 1-4 1.5-3.5 Phosphonates (if permitted by regulation) 0-15 0.01-15 0.05-12.0 0.1-10.0 Water / misc. ad 100 ad 100 ad 100 ad 100

The combination of cleaning agents described above is packaged using a packaging agent in which the cleaning agent preparations A and / or B and E or A and B and E or A, B and C and E are present separately. This separation can be achieved, for example, by separate receiving chambers, each of these receiving chambers containing one of the cleaning agents combined with one another. Examples of such assembly forms are cartridges with two, three, four or more separate receiving chambers, 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.

In addition to preparations A and / or B, preferably A and B, according to a preferred embodiment there is additionally at least one active substance composition in the packaging means, preferably at least one, separate from the cleaning agent preparations, in particular from the cleaning agent preparations A and B Contains fragrance D.

In a particularly preferred embodiment of the present invention, the polymeric carrier material of the particles consists at least partially of ethylene / vinyl acetate copolymer. Another preferred subject of the present application is therefore a cleaning agent supply form as described above, characterized in that a polymeric carrier material has at least 10% by weight, preferably at least 30% by weight, particularly preferably at least 70% by weight, of ethylene / vinyl acetate copolymer contains, preferably is made entirely of ethylene / vinyl acetate copolymer.

Ethylene / vinyl acetate copolymers is the name for copolymers of ethylene and vinyl acetate. This polymer is generally produced in a process comparable to the production of low density polyethylene (LDPE). With an increasing proportion of vinyl acetate, the crystallinity of the polyethylene is interrupted and in this way the melting and softening points or the hardness of the resulting products are reduced. The vinyl acetate also makes the copolymer more polar and thus improves its adhesion to polar substrates.

The ethylene / vinyl acetate copolymers described above are widely available commercially, for example under the tradename Elvax ^® (Dupont). Particularly suitable in the context of the present invention, polyvinyl alcohols are, for example Elvax ^® 265, Elvax ^® 240, Elvax ^® 205W, Elvax ^® 200W, as well as Elvax ^® 360. Also suitable are, for example, products available under the trade Evatane® (Arkema).

In the context of the present invention, in particular in the area of scenting the interior of automatic dishwashers, active substance compositions are particularly preferred in which ethylene / vinyl acetate copolymer is used as the polymeric carrier material and this copolymer contains 5 to 50% by weight of vinyl acetate, preferably 10 to 40% by weight .-% vinyl acetate and in particular 20 to 30 wt .-% vinyl acetate, each based on the total weight of the copolymer contains.
Other suitable carrier materials are the cyclodextrins.

Alternatively or in addition to the aforementioned carrier materials, inorganic carrier materials are preferably also used. Forms of cleaning agents are particularly preferred, characterized in that at least one of the carrier materials is an inorganic carrier material, preferably a silicate, phosphate or borate.

The silicates, phosphates or borates are preferably in the form of a glass, particularly preferably in the form of a water-soluble glass. Particularly preferred glasses are glasses containing zinc and / or bismuth, in particular glasses containing bismuth phosphate and / or glasses containing zinc phosphate. In one In such a case, the carrier material is water-soluble and already contains in its substance the active ingredient, in particular the glass corrosion inhibitors (zinc and / or bismuth) in the carrier material.

In a preferred embodiment, the cleaning agent dosage forms can contain such glasses containing zinc or bismuth, particularly preferably glass containing zinc phosphate, in addition to a further active substance composition comprising a carrier material, preferably a water-insoluble carrier material and at least one active substance D. These can then be contained in a common chamber or in separate chambers, in particular in one or more chambers which have openings, in particular openings such that the washing liquor and / or the air can flow through them. Preferred forms of cleaning agent are those which contain a glass containing zinc phosphate or bismuth phosphate and furthermore contain at least one, preferably two, three or more active substance compositions which comprise one or more fragrances and / or one or more fragrance scavengers as active substances.

In the context of the present application, thermoplastic carrier materials or carrier materials which deform plastically under the influence of the ambient temperatures occurring during use are particularly preferred. The plastic deformation of the carrier materials in the course of one or more applications results in a change in the carrier material surface, in particular a change in the size of the carrier material surface, which in turn has an advantageous effect on the release profile and the release kinetics of the active cleaning compositions contained in the active substance compositions. Dosing devices, characterized in that at least one polymeric carrier material has a melting or softening point between 40 and 125 ° C, preferably between 60 and 100 ° C, particularly preferably a melting point of 70 to 90 ° C and in particular between 73 and 80 ° C ( preferred determination method for the melting point according to ISO 11357-3) are preferred according to the invention.

The forms of detergent according to the invention are particularly suitable for multiple dosing of the active substances contained in them. In order to ensure such multiple dosing via a large number of cleaning processes, it has proven to be advantageous to use only water-insoluble carrier materials. These water-insoluble carrier materials also simplify the production of the forms according to the invention. Preferred forms of offer are therefore characterized in that all the carrier materials used are water-insoluble.

The active substance compositions can in principle assume all physical states and / or spatial forms that can be achieved depending on the chemical and physical properties of the carrier materials. In a further embodiment, at least one of the active substance compositions is in the form of a gel.

In a further embodiment, at least one of the active substance compositions is in the form of a solid. Active ingredient compositions in the form of individual blocks comprising an entire active ingredient composition are used with particular preference. The active substance compositions can preferably be in particulate form, the active substance compositions in which the carrier material of at least one of the active substance compositions is in particle form, these particles preferably having an average diameter of 0.5 to 20 mm, preferably 1 to 10 mm and in particular 3 have up to 6 mm, are particularly preferred.

Active ingredient compositions which comprise at least one colored active ingredient composition are particularly preferably used. The coloring of at least one of the active ingredient compositions enables an optical differentiation of these compositions to be achieved and the multiple use of these different compositions can be clarified in a simple manner. Furthermore, the dyes are also suitable as an indicator, in particular as a consumption indicator for the colored active ingredient compositions.

Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to the substrates to be treated with the dye-containing compositions, such as glass, ceramics or plastic tableware, not to mention stain.

When choosing the colorant, it must be noted that the colorants have a high storage stability and insensitivity to light and do not have too strong an affinity for glass, ceramics or plastic dishes. At the same time, when choosing suitable colorants, it should also be borne in mind that Colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the cleaning agents varies. In the case of readily water-soluble colorants, colorant concentrations in the range from a few 10 ^-2 to 10 ^-3 % by weight are typically chosen. In contrast, in the case of the pigment dyes which are particularly preferred on account of their brilliance but are less readily water-soluble, the suitable concentration of the colorant in cleaning agents is typically a few 10 ^-3 to 10 ^-4 % by weight.

According to a preferred embodiment, the cleaning agent supply form is characterized in that the at least one active ingredient D is selected from the group of fragrances, preferably linalyl acetate, dihydromyrcenol, citronellonitrile, menthyl acetate, methylphenylbutanol, eucalyptol and their mixtures, fragrance scavengers, e.g. Zinc ricinoleate, cyclodextrins, 2-menthyl-5-cyclohexylpentanol and 1-cyclohexylethanol, in particular zinc ricinoleate; Dyes, glass corrosion inhibitors, antimicrobial agents, germicides or fungicides 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. Mixtures of at least one fragrance, preferably two, three or more fragrances and at least one dye, are further preferred.

In the context of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. However, mixtures of different fragrances are preferably used, which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.

In order to be perceptible, a fragrance must be volatile, whereby in addition to the nature of the functional groups and the structure of the chemical compound, the molar mass also plays an important role. Most odoriferous substances have molecular weights of up to about 200 daltons, while molecular weights of 300 daltons and more are an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions are described in "top note", "heart or middle note" (middle note or body ) and "base note" (end note or dry out). Since the smell is largely based on the intensity of the smell, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note largely consists of less volatile, i.e. non-stick fragrances. When composing perfumes, more volatile fragrances can be bound to certain fixatives, for example, which prevents them from evaporating too quickly. In the subsequent classification of the fragrances into “more volatile” or “adhesive” fragrances, nothing is said about the odor impression and whether the corresponding fragrance is perceived as a top or heart note.

The fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers which ensure a long-lasting fragrance due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

According to the invention, particularly preferred fragrances are linalyl acetate, dihydromyrcenol, citronellonitrile, menthyl acetate, methylphenylbutanol and / or eucalyptol and mixtures thereof.

The known ricenolates, in particular the zinc ricenoleates, can be used, for example, as scent catchers (or, as is also used synonymously below, odor neutralizers or fragrance neutralizers, agents against malodour or bad odors). Also preferred are 2-menthyl-5-cyclohexylpentanol and 1-cyclohexylethanol. 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 fragrances and / or scent scavengers is particularly preferred, since it also has a positive effect on the inhibition of glass corrosion during the rinsing process.

To combat microorganisms, antimicrobial agents can be used as an alternative or in addition to the above-mentioned fragrances and / or fragrance scavengers. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistats and Fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlyl sulfonates, halophenols and phenol mercuric acetate, although these compounds can also be dispensed with entirely.

In principle, the active substances can be contained in the active substance preparations in any amounts. However, dosing devices are particularly preferred in which the proportion by weight of the active ingredient (s) is 1 to 70% by weight, preferably 10 to 60% by weight, particularly preferably 20 to 50% by weight, in particular 30 to 40% by weight, is based in each case on the total weight of the active ingredient composition (s).

If more than one active ingredient composition is present in the detergent form, these can be present separately from one another or next to one another in the packaging means of the detergent form. The different active substance compositions can preferably be present next to one another, that is to say in direct contact with one another, in the packaging means of the detergent form.

According to a particularly preferred embodiment of the present invention, the viscosity of all cleaning agent preparations A and B or A, B and C, the viscosity of cleaning agent preparations A and B or A, B and C is less than 120 mPas (measured at 20 ° C. with a Brookfield Instrument LVDV II +, spindle 31, 100 rpm). The viscosity of all cleaning agent preparations is particularly preferably 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).

1. a) eine erfindungsgemäße Reinigungsmittelzubereitung A in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
2. b) mindestens eine weitere von A verschiedene Reinigungsmittelzubereitung B in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
3. c) gegebenenfalls eine weitere von A und B verschiedene Reinigungsmittelzubereitung C in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
4. d) gegebenenfalls mindestens eine weitere von A und B verschiedene Wirkstoffzusammensetzung in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge, die mindestens ein Trägermaterial, bevorzugt ein wasserunlösliches Trägermaterial, und mindestens einen Wirkstoff D enthält;
5. e) eine Kartusche für die Reinigungsmittelzubereitungen A und B, bzw. A, B und C bzw. A, B, C und D, in welcher die Reinigungsmittelzubereitungen A und B, bzw. A, B, C bzw. A, B, C und D in voneinander getrennten Aufnahmekammern vorliegen.

Another object of the present application is a cleaning agent supply form, comprising

1. a) a cleaning agent preparation A according to the invention in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times;
2. b) at least one further cleaning agent preparation B different from A in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times;
3. c) optionally a further cleaning agent preparation C different from A and B in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times;
4. d) if appropriate, at least one further active ingredient composition different from A and B in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times, the contains at least one carrier material, preferably a water-insoluble carrier material, and at least one active ingredient D;
5. e) a cartridge for the cleaning agent preparations A and B, or A, B and C or A, B, C and D, in which the cleaning agent preparations A and B, or A, B, C or A, B, C and D are present in separate receiving chambers.

1. a) eine erfindungsgemäße Reinigungsmittelzubereitung A in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
2. b) mindestens eine weitere von A verschiedene Reinigungsmittelzubereitung B in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
3. c) gegebenenfalls eine weitere von A und B und E verschiedene Reinigungsmittelzubereitung C in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
4. d) gegebenenfalls mindestens eine weitere von A und B verschiedene Wirkstoffzusammensetzung in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge, die mindestens ein Trägermaterial, bevorzugt ein wasserunlösliches Trägermaterial, und mindestens einen Wirkstoff D enthält
5. e) mindestens eine weitere von A und B verschiedene Bleichmittelzubereitung E in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
6. f) eine Kartusche für die Zubereitungen A und E bzw. B und E, bzw. A, B und E bzw. A, B, E, und C bzw. A, B, E und D bzw. A, B, C, E und D, in welcher die Zubereitungen A und E, bzw. B und E, bzw. A, B und E, bzw. A, B, E und C, bzw. A, B, E und D, bzw. A, B, E, C und D in voneinander getrennten Aufnahmekammern vorliegen;
7. g) ein mit der Kartusche lösbar verbundenes Dosiergerät.

Another object of the present application is a detergent dosing system comprising

1. a) a cleaning agent preparation A according to the invention in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times;
2. b) at least one further cleaning agent preparation B different from A in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times;
3. c) if appropriate, a further cleaning agent preparation C different from A and B and E in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times;
4. d) optionally at least one further active ingredient composition different from A and B in an amount sufficient for at least twice, preferably at least four times and in particular at least eight times to carry out an automatic dishwashing process which contains at least one carrier material, preferably a water-insoluble carrier material, and at least one active substance D.
5. e) at least one further bleaching agent preparation E different from A and B in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times;
6. f) a cartridge for the preparations A and E or B and E, or A, B and E or A, B, E, and C or A, B, E and D or A, B, C, E and D, in which the preparations A and E, or B and E, or A, B and E, or A, B, E and C, or A, B, E and D, or A, B, E, C and D exist in separate receiving chambers;
7. g) a dispenser detachably connected to the cartridge.

In a preferred embodiment, the cartridges of the detergent forms described above are provided with a metering device that can be detached from the cartridge. Such a metering device can be connected to the cartridge, for example, by means of an adhesive, snap-in, snap or plug connection. The cartridge and dosing device are separated, for example, simplifying the filling of the cartridge. Alternatively, the detachable connection of the cartridge and metering device enables the cartridges on the metering device to be replaced. Such an exchange can be indicated, for example, when the cleaning program is changed or after the cartridge has been completely emptied.

1. a) eine erfindungsgemäße Reinigungsmittelangebotsform, umfassend eine für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichende Menge an Reinigungsmittelzubereitungen A und B bzw. A, B und C bzw. A, B, C und D;
2. b) ein mit der Reinigungsmittelangebotsform lösbar verbundenes Dosiergerät.

A particularly preferred subject matter of this application is a detergent dosing system comprising

1. a) a cleaning agent supply form according to the invention, comprising a sufficient amount of cleaning agent preparations A and B or A, B and C or A, B, C and D for carrying out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times;
2. b) a dosing device detachably connected to the form of detergent supply.

Of course, forms of cleaning agent are also conceivable in which the cartridge and the dosing device are connected to one another in an inseparable manner.

1. a) eine erfindungsgemäße Reinigungsmittelangebotsform, umfassend eine für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichende Menge an Reinigungsmittelzubereitungen A und B, bzw. A, B und C bzw. A, B, C und D;
2. b) ein mit der Reinigungsmittelangebotsform unlösbar verbundenes Dosiergerät

The present application furthermore relates to a detergent dosing system comprising

1. a) a cleaning agent supply form according to the invention, comprising a sufficient amount of cleaning agent preparations A and B, or A, B and C or A, B, C and D for carrying out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times;
2. b) a dosing device that is permanently connected to the form of the detergent

The above-mentioned detergent dosing systems, comprising the detergent supply form according to the invention (and optionally one or two further compositions different from the detergent preparations A and B or A, B and C or A, B, C and D according to the invention, a cartridge and a detachable with the cartridge In a preferred embodiment, the connected dosing device is present in a common outer packaging, the filled cartridge and the dosing device being particularly preferably contained separately from one another in the outer packaging. The outer packaging serves for storage, transport and presentation of the form of cleaning agent according to the invention and protects it from soiling. Strike and shock, especially for the purpose of presentation, the outer packaging should at least partially be made transparent.

Alternatively or in addition to an outer packaging, there is of course the possibility of marketing the form of cleaning agent according to the invention in connection with a dishwasher. Such a combination is particularly advantageous in cases where the course of the automatic dishwashing process (e.g. duration, temperature course, water supply) and the cleaning agent formulation or the control electronics of the dosing device are coordinated.

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 which can be coupled to the cartridge, which in turn is formed from further assemblies, such as, for example, component carrier, actuator, closure element, sensor, energy source and / or control unit.

It is preferred that the metering system according to the invention is movable. Movable in the sense of this application means that the metering system is not permanently connected to a water-carrying device such as a dishwasher or the like, but rather can be removed from a dishwasher by the user or can be positioned in a dishwasher, that is to say it can be handled independently

According to an alternative embodiment of the invention, it is also conceivable that the metering device is not releasably connected to a water-carrying device such as a dishwasher or the like for the user and only the cartridge is movable.

Since the preparations to be dosed may have a pH between 2 and 14, in particular 2 and 12, depending on the intended use, all components of the dosing system which come into contact with the preparations should have an appropriate acid and / or alkali resistance. Furthermore, these components should be largely chemically inert, for example, against nonionic surfactants, enzymes and / or fragrances, through a suitable choice of material.

A cartridge in the sense of this application is understood to mean a packaging material which is suitable for enveloping or holding together flowable or scatterable preparations and which can be coupled to a metering device for dispensing the preparation. In particular, a cartridge can also comprise a plurality of chambers which can be filled with compositions which differ from one another. It is also conceivable for a plurality of containers to be arranged to form a cartridge unit.

It is advantageous that the cartridge has at least one outlet opening, which is arranged in such a way that the preparation can be released from the container under the force of gravity in the use position of the metering device. As a result, no further funding is required to release preparation from the container, which means that the construction of the metering device can be simple and the production costs can be kept low.

In a preferred embodiment of the invention, at least one second chamber is provided for receiving at least one second flowable or scatterable preparation, the second chamber having at least one outlet opening which is arranged in such a way that product release from the second chamber caused by gravity is in the use position of the metering device is effected. The arrangement of a second chamber is particularly advantageous when preparations are stored in the separate containers, which are usually not stable with one another, such as bleaching agents and enzymes.

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 particular, at least one of the chambers for dispensing active substances) D, such as a glass corrosion inhibitor, a fragrance or in particular an odor neutralizer to the environment, is designed such that it has openings through which the washing liquor and / or the air can flow.

In a further embodiment of the invention, the cartridge is formed in one piece. As a result, the cartridges can be formed inexpensively in one production step, in particular by means of suitable blow molding processes. The chambers of a cartridge can be separated from one another, for example, by webs or material bridges.

The cartridge can also be formed in several pieces by components that are injection molded and then joined together. Furthermore, it is conceivable for the cartridge to be formed in such a way that at least one chamber, preferably all chambers, can be removed individually from the metering device or inserted into the metering device. This makes it possible to replace a chamber that has already been emptied if the consumption of a preparation from one chamber varies, while the others, which may still be filled with preparation, remain in the metering device. In this way, a targeted and needs-based refilling of the individual chambers or their preparations can be achieved.

The chambers of a cartridge can be fixed to one another by suitable connection methods, so that a container unit is formed. The chambers can be releasably or non-releasably fixed to one another by a suitable positive, non-positive or material connection.

In particular, the fixation can be carried out by one or more of the connection types from the group of snap-in connections, Velcro connections, press connections, fusion connections, adhesive connections, welded connections, soldered connections, screw connections, wedge connections, clamp connections or bump connections. In particular, the fixation can also be formed by a shrink tube (so-called sleeve), which is pulled over the entire or sections of the cartridge in a heated state and firmly encloses the chambers or the cartridge in the cooled state.

In order to provide advantageous residual emptying properties of the chambers, the bottom of the chambers can be inclined in a funnel shape towards the discharge opening. Furthermore, the interior wall of a chamber can be designed in such a way by a suitable choice of material and / or surface design that the preparation has little material adherence to the interior chamber wall. This measure can also further optimize the residual emptiness of a chamber.

The chambers of a cartridge can have the same or different filling volumes. In a configuration with two chambers, the ratio of the container volumes is preferably 5: 1, in a configuration with three chambers 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 the use of such a cartridge in a dishwasher, it is particularly preferred that the first chamber contains an alkaline cleaning preparation, the second chamber contains an enzymatic preparation and the third chamber contains a rinse aid, the volume ratio of the chambers being approximately 4: 1: 1. The fourth chamber contains the at least one active substance composition, comprising the at least one active substance D and a carrier material, preferably a water-insoluble carrier material.

A dosing chamber can be formed in or on a chamber in the direction of flow of the preparation in front of the outlet opening. The metering chamber determines the amount of preparation that is to be released to the environment when preparation is released from the chamber. This is particularly advantageous if the closure element of the metering device, which causes the preparation to be dispensed from a chamber into the environment, can only be put into a dispensing and a closed state without checking the dispensing quantity. The dosing chamber then ensures that a predefined amount of preparation is released without an immediate feedback of the dispensed preparation quantity. The metering chambers can be formed in one piece or in several pieces.

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

For ventilation of the cartridge chambers, ventilation options can be provided in particular in the head region of the cartridge, in order to ensure pressure compensation when the filling level of the chambers falls between the interior of the cartridge chambers and the surroundings. These ventilation options can be designed, for example, as a valve, in particular a silicone valve, micro-openings in the cartridge wall or the like.

According to a further embodiment, if the cartridge chambers are not to be ventilated directly, but rather via the metering device or no ventilation, e.g. when using flexible containers, such as bags, this has the advantage that at elevated temperatures in the course of a dishwashing cycle of a dishwasher, heating the chamber contents builds up a pressure which pushes the preparations to be metered in the direction of the outlet openings, so that the cartridge can be easily emptied. Furthermore, with such air-free packaging, there is no risk of oxidation of substances in the preparation, which makes bag packaging or bag-in-bottle packaging appear expedient, in particular for preparations sensitive to oxidation.

The cartridge usually has a filling volume of <5,000 ml, in particular <1,000 ml, preferably <500 ml, particularly preferably <250 ml, very particularly preferably <50 ml.

The cartridge can take any shape. For example, it can be cube-shaped, spherical or plate-like.

The shape of the cartridge and the metering device can in particular be designed in such a way that they ensure the smallest possible usable volume loss, in particular in a dishwasher.

To use the dosing device in dishwashers, it is particularly advantageous to shape the device based on the dishes to be cleaned in dishwashers. For example, it can be plate-shaped, approximately in the dimensions of a plate. This allows the dosing device to be space-saving, e.g. be positioned in the lower basket of the dishwasher. Furthermore, the correct positioning of the dosing unit is immediately intuitive for the user due to the plate-like shape. The cartridge preferably has a ratio of height: width: depth between 5: 5: 1 and 50: 50: 1, particularly preferably of about 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 washing liquor and cannot adhere to other items to be washed.

Commercial household dishwashers are usually designed in such a way that the arrangement of larger items to be washed, such as pans or large plates, is provided in the lower basket of the dishwasher. In order to avoid a non-optimal positioning of the dosing system by the user in the upper basket, in an advantageous embodiment of the invention the dosing system is dimensioned such that the dosing system can only be positioned in the receptacles provided for the lower basket. For this purpose, the width and the height of the metering system can be chosen in particular between 150mm and 300mm, particularly preferably between 175mm and 250mm. However, it is also conceivable to design the dosing unit in a cup shape with an essentially circular or square base area.

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

A further possibility for reducing the influence of heat on a preparation in a chamber of the cartridge is to isolate the chamber by means of suitable measures, e.g. through the use of thermal insulation materials such as styrofoam, which completely or partially enclose the chamber or the cartridge in a suitable manner.

In a preferred embodiment of the invention, the cartridge has an RFID label that at least contains information about the content of the cartridge and that can be read out by the sensor unit.

This information can be used to select a dosing program stored in the control unit. This can ensure that an optimal dosing program is always used for a specific preparation. It can also be provided that, in the absence of an RFID label or an RFID label with an incorrect or incorrect identifier, the metering device does not dose and instead an optical or acoustic signal is generated that the user is aware of the existing error indicates.

In order to prevent the cartridge from being misused, the cartridges can also have structural elements which interact with corresponding elements of the metering device according to the key-lock principle, so that, for example, only cartridges of a certain type can be coupled to the metering device. Furthermore, this configuration makes it possible for information about the cartridge coupled to the dosing device to be transmitted to the control unit, as a result of which the dosing device can be controlled in a manner which is coordinated with the content of the corresponding container.

The cartridge is designed in particular to accommodate flowable cleaning agents. Such a cartridge particularly preferably has a plurality of chambers for spatially separated accommodation of preparations of a cleaning agent which are in each case different from one another. The cartridge can be designed such that it can be detachably or firmly arranged in or on the dishwasher.

The control unit, sensor unit and at least one actuator necessary for operation are integrated in the dosing device. An energy source is preferably also arranged in the metering device.

The metering device preferably consists of a splash-proof housing that prevents the penetration of splashing water, as can occur, for example, when used in a dishwasher, into the interior of the metering device.

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

In one embodiment of the invention, the interfaces are formed by plug connectors. In a further embodiment, the interfaces can be designed in such a way that wireless transmission of electrical energy is effected.

In an advantageous further development of the invention, there is a second interface on the metering device and the water-carrying device, such as a dishwasher, for the transmission of electromagnetic signals, which include, in particular, operating status, measurement and / or control information of the metering device and / or the water-carrying device, such as one Represent dishwasher, trained.

An adapter can be used to easily couple the dosing system to a water-bearing household appliance. The adapter is used for the mechanical and / or electrical connection of the dosing system to the water-bearing household appliance.
The adapter is, preferably fixed, connected to a water-carrying line of the household appliance. However, it is also conceivable to provide the adapter for positioning in or on the household appliance, in which the adapter is captured by the water flow and / or spray jet of the household appliance.

The adapter makes it possible to design a dosing system for both a self-sufficient and a "build-in" version. It is also possible to design the adapter as a kind of charging station for the metering system, in which, for example, the energy source of the metering device is charged or data is exchanged between the metering device and the adapter.

The adapter can be arranged in a dishwasher on one of the inner walls of the washing chamber, in particular on the inner side of the dishwasher door. However, it is also conceivable that the adapter as such is positioned inaccessible to the user in the water-bearing household appliance, so that the metering device is inserted into the adapter, for example during assembly of the household device, the adapter, the metering device and the household device being designed in this way that a cartridge can be coupled to the dosing device by the user.

The forms of detergent according to the invention are suitable for use in dishwashing, but the use of a form of detergent according to the invention or a detergent dosing system for washing dishes in a machine dishwashing process is preferred.

As stated at the beginning, the cleaning agents according to the invention are notable for special physical and chemical stability, in particular with respect to temperature fluctuations. The cleaning agents according to the invention are therefore particularly suitable for metering by means of a metering system located in the interior of a dishwasher. Such a dosing system, which can be immovably integrated into the interior of the dishwasher (machine-integrated dosing device), but can of course also be introduced into the interior as a mobile device (self-sufficient dosing device), contains the multiple amount of detergent required to carry out a mechanical cleaning process .

Moving in the sense of this application means that the dispensing and metering system is not inextricably linked to a device such as a dishwasher or the like, but is, for example, removable from a dishwasher or positionable in a dishwasher.

1. i) einer unbeweglich in den Innenraum einer Geschirrspülmaschine integrierten Kartusche eines Dosiersystems oder
2. ii) einer für die Positionierung im Innenraum einer Geschirrspülmaschine vorgesehenen beweglichen Kartusche eines Dosiersystems

mit einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge dieser Reinigungsmittelangebotsform sind ebenfalls Gegenstände dieser Anmeldung.The use of a form of cleaning agent according to the invention for filling

1. i) a cartridge of a metering system immovably integrated into the interior of a dishwasher or
2. ii) a movable cartridge of a dosing system provided for positioning in the interior of a dishwasher

With this application form sufficient for at least twice, preferably at least four times and in particular at least eight times to carry out an automatic dishwashing process are also objects of this application.

An example of an immovable cartridge is a container integrated immovably into the interior, for example into the side wall or the interior lining of the door of a dishwasher. An example of a movable cartridge is a container that the consumer places in the interior of the dishwasher and remains there throughout the course of a cleaning cycle. Such a cartridge can be integrated into the interior, for example by simply placing it in the cutlery or crockery basket, but can also be removed from the interior of the dishwasher by the consumer.

The dosing of the cleaning agent or the cleaning agent combination from the cartridge into the interior of the dishwasher is preferably carried out as described above by means of a dosing device detachable from the cartridge. Such a metering device can be connected to the cartridge by means of an adhesive, latching, snap or plug connection. Cartridges with an inseparably connected dosing device can of course also be used.

The use of a form of detergent according to the invention as a detergent reservoir for i) a metering device immovably integrated into the interior of a dishwasher or ii) a movable metering device provided for positioning in the interior of a dishwasher is preferred.

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.

1. a) eine Reinigungsmittelzubereitung A in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge; und/oder
2. b) mindestens eine weitere von A verschiedene Reinigungsmittelzubereitung B in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge; sowie
3. c) gegebenenfalls eine weitere von A und B verschiedene Reinigungsmittelzubereitung C in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
4. d) gegebenenfalls mindestens eine weitere von A und B verschiedene Wirkstoffzusammensetzung in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge, die mindestens ein Trägermaterial, bevorzugt wasserunlösliches Trägermaterial, und mindestens einen Wirkstoff D enthält;sowie
5. e) mindestens eine weitere von A und/oder B verschiedene Bleichmittelzubereitung E in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
6. f) eine Kartusche für die Reinigungsmittelzubereitungen A und/oder B und E, bzw. A und/oder B und E sowie C bzw. A und/oder B und E sowie ggf. C und ggf. D, in welcher die Reinigungsmittelzubereitungen A und/oder B und E, bzw. A und/oder B und E sowie ggf. C bzw. A und/oder B und E, sowie ggf. C und D in voneinander getrennten Aufnahmekammern vorliegen als Reinigungsmittelreservoir für
   1. i) ein unbeweglich in den Innenraum einer Geschirrspülmaschine integriertes Dosiergerät oder
   2. ii) ein für die Positionierung im Innenraum einer Geschirrspülmaschine vorgesehenes bewegliches Dosiergerät.

Two further subjects of this application are the use of a cleaning agent supply form according to the invention, comprising

1. a) a cleaning agent preparation A in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times; and or
2. b) at least one further cleaning agent preparation B different from A in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times; such as
3. c) optionally a further cleaning agent preparation C different from A and B in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times;
4. d) optionally at least one further active ingredient composition different from A and B in an amount sufficient for at least twice, preferably at least four times and in particular at least eight times to carry out an automatic dishwashing process which contains at least one carrier material, preferably water-insoluble carrier material, and at least one active substance D; and
5. e) at least one further bleaching agent preparation E different from A and / or B in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times;
6. f) a cartridge for the cleaning agent preparations A and / or B and E, or A and / or B and E as well as C or A and / or B and E and possibly C and possibly D, in which the cleaning agent preparations A and / or B and E, or A and / or B and E as well as possibly C or A and / or B and E as well as possibly C and D in separate receiving chambers are available as a detergent reservoir for
   1. i) a dosing device immovably integrated into the interior of a dishwasher or
   2. ii) a movable metering device provided for positioning in the interior of a dishwasher.

As stated above, the cleaning agents and cleaning agent combinations according to the invention are preferably used as automatic dishwashing agents.

• - eine Teilmenge a der in der Kartusche befindlichen Reinigungsmittelzubereitung A in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in der Kartusche befindlichen Reinigungsmittelzubereitung bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt, dadurch gekennzeichnet, dass diese Restmenge mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge a entspricht; und
• - eine Teilmenge b der in der Kartusche befindlichen Reinigungsmittelzubereitung B in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in der Kartusche befindlichen Reinigungsmittelzubereitung bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt, dadurch gekennzeichnet, dass diese Restmenge mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge b entspricht; und
• - gegebenenfalls eine Teilmenge c der in der Kartusche gegebenenfalls befindlichen Reinigungsmittelzubereitung C in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in der Kartusche befindlichen Reinigungsmittelzubereitung bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt, dadurch gekennzeichnet, dass diese Restmenge mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge c entspricht.
• - gegebenenfalls eine Teilmenge d der in der Kartusche gegebenenfalls befindlichen Wirkstoffe D in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge des in der Kartusche befindlichen Wirkstoffes bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt, dadurch gekennzeichnet, dass diese Restmenge mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge d entspricht sowie
• - eine Teilmenge e der in der Kartusche befindlichen Bleichmittelzubereitung E in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in der Kartusche befindlichen Reinigungsmittelzubereitung bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt, dadurch gekennzeichnet, dass diese Restmenge mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge e entspricht.

Automatic dishwashing process using a form of detergent or a detergent dosing system according to one of the preceding claims, in the course of which from a cartridge located in the interior of the dishwasher

• - A portion of the detergent preparation A located in the cartridge is metered into the interior of the dishwasher, a residual amount of the detergent preparation located in the cartridge remaining in the cartridge until the end of the dishwashing process, characterized in that this residual amount is at least twice, preferably at least corresponds to four times and in particular at least eight times the amount of subset a; and
• - A portion b of the detergent preparation B located in the cartridge is metered into the interior of the dishwasher, a residual amount of the detergent preparation located in the cartridge remaining in the cartridge until the end of the dishwashing process, characterized in that this residual amount is at least twice, preferably at least corresponds to four times and in particular at least eight times the amount of subset b; and
• - If necessary, a portion c of the detergent preparation C, if any, in the cartridge is metered into the interior of the dishwasher, a remaining amount of the detergent preparation in the cartridge remaining in the cartridge until the end of the dishwashing process, characterized in that this residual amount is at least twice as much, preferably corresponds to at least four times and in particular at least eight times the amount of subset c.
• - if necessary, a partial amount d of the active ingredients D which may be present in the cartridge is metered into the interior of the dishwasher, a residual amount of the active ingredient present in the cartridge remaining in the cartridge until the end of the dishwashing process, characterized in that this residual amount is at least twice as much, preferably corresponds to at least four times and in particular at least eight times the amount of subset d and
• - A partial amount e of the bleaching agent preparation E located in the cartridge is metered into the interior of the dishwasher, a remaining amount of the cleaning agent preparation located in the cartridge remaining in the cartridge until the end of the dishwashing process, characterized in that this remaining amount is at least twice, preferably at least corresponds to four times and in particular at least eight times the amount of subset e.

According to a preferred embodiment, the invention also relates to an automatic dishwashing process in which the active substance composition is in the cartridge and the washing liquor and / or air flows through openings. When air flows through it, fragrance (s) are released into the air in the interior of the dishwasher and, in addition to scenting the washing liquor during the dishwashing process, also leads to an odor situation that is pleasant for the consumer when opening and loading the dishwasher .

In the dishwashing method according to the invention it is of course not only possible to use the cleaning agent dosage forms according to the invention but also the cleaning agent metering systems according to the invention.

In a preferred embodiment, the dosage of the cleaning agent preparation A and the cleaning agent preparation B and optionally the cleaning agent preparation C is carried out at different times in the cleaning cycle.

1. a) zu einem Zeitpunkt t1 aus einer im Innenraum der Geschirrspülmaschine befindlichen Kartusche eine Teilmenge a der in der Kartusche befindlichen erfindungsgemäßen Reinigungsmittelzubereitung A in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge des in der Kartusche befindlichen Reinigungsmittels bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt, welche der mindestens doppelten, vorzugsweise der mindestens vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge a entspricht;
2. b) zu mindestens einem weiteren Zeitpunkt t2 ≠ t1 aus einer im Innenraum der Geschirrspülmaschine befindlichen Kartusche eine Teilmenge b der in der zweiten Kartusche befindlichen von der erfindungsgemäßen Reinigungsmittelzubereitung A unterschiedlichen Reinigungsmittelzubereitung B in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge des in dieser Kartusche befindlichen Reinigungsmittels bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt, welche mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge b entspricht;
3. c) gegebenenfalls zu mindestens einem weiteren Zeitpunkt t3 ≠ t2 ≠ t1 aus einer im Innenraum der Geschirrspülmaschine befindlichen Kartusche eine Teilmenge d der in einer weiteren Kartusche befindlichen von den erfindungsgemäßen Reinigungsmittelzubereitungen A und B unterschiedlichen Reinigungsmittelzubereitung C in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge des in dieser Kartusche befindlichen Reinigungsmittels bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt, welche mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge c entspricht sowie
4. d) zu mindestens einem weiteren Zeitpunkt t4 ≠ t2 und/oder t4 ≠ t1 bzw. zu mindestens einem weiteren Zeitpunkt t4 ≠ t3 ≠ t2 ≠ t1 eine Teilmenge e der in der Kartusche befindlichen Bleichmittelzubereitung E in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in der Kartusche befindlichen Reinigungsmittelzubereitung bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt, dadurch gekennzeichnet, dass diese Restmenge mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge e entspricht;

Another preferred subject of this application is therefore a machine dishwashing process using a cleaning agent supply form according to the invention or a cleaning agent metering system according to the invention, in the course thereof

1. a) at a time t1 from a cartridge located in the interior of the dishwasher, a subset a of the cleaning agent preparation A according to the invention located in the cartridge is metered into the interior of the dishwasher, with a remaining amount of the cleaning agent located in the cartridge until the end of the dishwashing process in the cartridge remains which corresponds to the at least double, preferably at least four times and in particular at least eight times the amount of subset a;
2. b) at least one further point in time t2 ≠ t1 from a cartridge located in the interior of the dishwasher, a portion b of the detergent preparation B located in the second cartridge, which is different from the cleaning agent preparation A according to the invention, is metered into the interior of the dishwasher, a residual amount of the in this cartridge cleaning agent present remains in the cartridge until the end of the dishwashing process, which corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of subset b;
3. c) if necessary at least one further time t3 ≠ t2 ≠ t1 from a cartridge located in the interior of the dishwasher, a portion d of the detergent preparation C located in another cartridge, which is different from the cleaning agent preparations A and B according to the invention, is metered into the interior of the dishwasher, one The remaining amount of the cleaning agent contained in this cartridge remains in the cartridge until the end of the dishwashing process, which corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of partial amount c and
4. d) at least one further time t4 ≠ t2 and / or t4 ≠ t1 or at least one further time t4 ≠ t3 ≠ t2 ≠ t1, a subset e of the bleaching agent preparation E located in the cartridge is metered into the interior of the dishwasher, one Remaining amount of the detergent preparation in the cartridge remains in the cartridge until the end of the dishwashing process, characterized in that this remaining amount corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of subset e;

In preferred embodiments of the machine dishwashing methods described above with time-shifted dosing of the cleaning agent preparations A and B or A, B and C, the time t2 is at least 1 minute in time, 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. The metering t4 is preferably carried out at least 1 minute, preferably at least 2 minutes and in particular between 5 and 40 minutes, in particular between 7 and 35 minutes, before or after, preferably after the time t2 .

The 1 shows a detergent dosing system 101 , with a dosing device 102 and a cartridge 103 . The cartridge has a chamber 104 for storing active ingredient composition. A slide can be used to optionally close and open the chamber 105 with one handle 107 intended. By moving the slider 105 becomes the column 106 locked or opened. Inside the column 106 In addition, a membrane - not shown here - is attached.

There is also an outer wall of a chamber 109 a membrane for storing the preparation 108 attached, by which when emptying the chamber 109 a negative pressure in this chamber 109 is prevented.

QUOTES INCLUDE IN THE DESCRIPTION

This list of documents listed by the applicant has been generated automatically and is only included for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• EP 1759624 A2 [0003]
• DE 102005062479 A1 [0003]
• WO 2012126536 A1 [0005]

Claims (17)

Detergent supply form, comprising a) a liquid (20 ° C.) detergent preparation A, containing a1) builders; a2) complexing agent b) a liquid (20 ° C) different from the cleaning agent preparation A, containing b1) at least one cleaning-active enzyme preparation and b2) optionally at least one non-ionic surfactant and c) optionally a liquid (20 ° C) from the cleaning agent preparation A and B various cleaning agent preparations C, containing c1) an acidifying agent, and optionally less than 1% by weight, preferably less than 0.5% by weight, in particular less than 0.1% by weight, of enzyme preparation, and d) a packaging material , in which the cleaning agent preparations A and / or B and optionally C are present separately from one another, characterized in that it comprises a bleaching agent preparation E spatially separated from the other cleaning agent preparations. Form of detergent according to Claim 1 , characterized in that the bleaching agent preparation E is at least one oxidizing agent, preferably an oxidizing agent based on chlorine, the oxidizing agent preferably being selected from chlorine dioxide, calcium hypochlorite, potassium hypochlorite, sodium hypochlorite, in particular the bleaching agent preparation comprises as an oxidizing agent sodium hypochlorite. Detergent supply form according to one of the preceding claims, characterized in that the at least one oxidizing agent in the bleach preparation E, preferably the alkali metal hypochlorite, in 0.1 to 8.0% by weight, preferably in 0.15 to 3.0% by weight , and more preferably in 0.2 to 1.0 wt .-%, based on the total weight of bleach preparation. Detergent form according to one of the preceding claims, characterized in that the bleaching preparation E, preferably comprising alkali metal hypochlorite, furthermore a phosphonate, preferably in an amount of 0.01 to 15.0% by weight, preferably 0.05 to 12.0%. -% and in particular 0.1 to 10.0 wt .-%. Form of cleaning agent according to one of the preceding claims, characterized in that the cleaning agent preparation A, based on its total weight, contains 2 to 50% by weight, preferably 6 to 45% by weight and in particular 10 to 40% by weight of builder and / or the builder a1) is selected from the group of the carbonates, the hydrogen carbonates, the citrates, the silicates, the polymeric carboxylates and the polymers containing sulfonic acid groups. Cleaning agent form according to one of the preceding claims, characterized in that the complexing agent a2) is selected from the group of hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glutamic acid diacetic acid, in particular L-glutamic acid-N, N-diesiacetic acid, hydroxynacetic acid, dibylacetic acid, dihydroxy acid -1,1-diphosphonic acid or diethylenetriaminepenta (methylenephosphonic acid) and their salts or their mixtures, preferably L-glutamic acid N, N-diacetic acid and / or methylglycinediacetic acid and their salts and / or the detergent preparation A 2 to 60% by weight, preferably Contains 4 to 55 wt .-% and in particular 8 to 50 wt .-% complexing agents. Form of cleaning agent according to one of the preceding claims, characterized in that the cleaning agent preparation B is 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, preferably in an amount from 0.01 to 5% by weight, preferably 0.05 to 2.5% by weight, in particular 0.1 to 1.5% by weight, of active enzyme protein, based on the total weight of detergent preparation B, contains. Form of detergent according to one of the preceding claims, characterized in that the detergent preparation B, based on its total weight, contains 30% by weight and less, preferably 25% by weight and less, in particular 15% by weight and less, and / or the Detergent preparation B contains organic solvent, preferably selected from glycerol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol and polyethylene glycols, in particular 1,2-propylene glycol, the proportion by weight of 1,2-propylene glycol based on the total weight of the detergent preparation , preferably 5 to 80 wt .-%, preferably 10 to 60 wt .-% and in particular 20 to 50 wt .-%. Form of detergent according to one of the preceding claims, characterized in that the detergent preparation B and / or C each 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 . Cleaning agent form according to one of the preceding claims, characterized in that the cleaning agent preparation C, the acidifying agent c1) selected from formic acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and / or polyacrylic acid, in particular formic acid, acetic acid and / or citric acid, and / or the cleaning agent preparation C the acidifying agent c1) 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 detergent preparation C contains. Form of cleaning agent according to one of the preceding claims, characterized in that the cleaning agent preparation C contains a glass corrosion inhibitor c2) which is preferably 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 the glass corrosion inhibitor c2) preferably in amounts of 0.01% by weight to 5% by weight, particularly preferably 0.05% by weight to 3% by weight, in particular 0.1% by weight .-% to 2 wt .-%, based on the total weight of the detergent preparation C contains. Cleaning agent supply form according to one of the preceding claims, characterized in that the cleaning agent preparation C contains a hydrotrope c3) which is preferably selected from xylene sulfonate, cumene sulfonate, and / or N-methylacetamide, particularly preferably cumene sulfonate and / or xylene sulfonate, in particular cumene sulfonate, and / or the cleaning agent preparation C the hydrotrope c3) in an amount of 2 to 25% by weight, in particular 4 to 20% by weight and particularly preferably in an amount of 6 to 15, for example 7 to 12% by weight on the total weight of the detergent preparation C contains. Use of a cleaning agent supply form according to one of the preceding claims as a cleaning agent reservoir for i) a dosing device immovably integrated into the interior of a dishwasher or ii) a movable metering device provided for positioning in the interior. Use of a cleaning agent supply form according to one of the preceding claims for filling i) a cartridge of a metering system immovably integrated into the interior of a dishwasher or ii) a movable cartridge of a dosing system provided for positioning in the interior of a dishwasher with an amount of this detergent supply form which is sufficient for at least twice, preferably at least four times and in particular at least eight times to carry out an automatic dishwashing method or automatic textile washing method. Detergent dosing system, comprehensive a) a cleaning agent supply form according to any one of the preceding claims, comprising an amount of bleaching agent preparation E as well as of cleaning agent preparations A and / or B and / or C sufficient for carrying out an automatic 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 form of detergent supply. Use of a form of detergent or a detergent dosing system according to one of the preceding claims for washing dishes in an automatic dishwashing process. Automatic dishwashing process using a form of detergent or a detergent dosing system according to one of the preceding claims, in the course of which a cartridge located in the interior of the dishwasher - a partial amount a of the detergent preparation A in the cartridge is metered into the interior of the dishwasher, a remaining amount of the detergent preparation in the cartridge remaining in the cartridge until the end of the dishwashing process, characterized in that this residual amount is at least twice, preferably at least corresponds to four times and in particular at least eight times the amount of subset a; and / or - a portion b of the detergent preparation B located in the cartridge is metered into the interior of the dishwasher, a residual amount of the detergent preparation located in the cartridge remaining in the cartridge until the end of the dishwashing process, characterized in that this residual amount is at least twice as much , preferably corresponds to at least four times and in particular at least eight times the amount of subset b; and - if necessary, a partial amount c of the detergent preparation C which may be present in the cartridge is metered into the interior of the dishwasher, a residual amount of the detergent preparation present in the cartridge remaining in the cartridge until the end of the dishwashing process, characterized in that this residual amount is at least the corresponds to twice, preferably at least four times and in particular at least eight times the amount of the partial amount c, and - a partial amount e of the bleaching agent preparation E located in the cartridge is metered into the interior of the dishwasher, with a remaining amount of the cleaning agent preparation located in the cartridge by the end of the Dishwashing method remains in the cartridge, 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 subset e;

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