WO2020152005A1 - Formulations de produit de nettoyage pour lavage de vaisselle automatique avec agent de blanchiment - Google Patents

Formulations de produit de nettoyage pour lavage de vaisselle automatique avec agent de blanchiment Download PDF

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Publication number
WO2020152005A1
WO2020152005A1 PCT/EP2020/050893 EP2020050893W WO2020152005A1 WO 2020152005 A1 WO2020152005 A1 WO 2020152005A1 EP 2020050893 W EP2020050893 W EP 2020050893W WO 2020152005 A1 WO2020152005 A1 WO 2020152005A1
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WIPO (PCT)
Prior art keywords
weight
preparation
acid
detergent
cleaning agent
Prior art date
Application number
PCT/EP2020/050893
Other languages
German (de)
English (en)
Inventor
Thomas Doering
Brigitte Kempen
Arnd Kessler
Original Assignee
Henkel Ag & Co. Kgaa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Priority to ES20700896T priority Critical patent/ES2952573T3/es
Priority to EP20700896.2A priority patent/EP3914686B1/fr
Priority to PL20700896.2T priority patent/PL3914686T3/pl
Publication of WO2020152005A1 publication Critical patent/WO2020152005A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045—Multi-compartment
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/046—Insoluble free body dispenser
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the invention relates to forms of detergent for automatic dishwashing, which contain different detergent preparations and a spatially separated one
  • devices for multiple dosing of cleaning agents are from
  • Devices can now be differentiated into metering containers integrated in the dishwasher on the one hand and independent devices independent of the dishwasher on the other. By means of these devices, the multiple of those necessary for carrying out a cleaning process
  • 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.
  • WO2012126536 A1 describes a dosing system for a dishwasher, which has at least one means for the substantially continuous, water-induced release of at least one additive into the rinse water during a rinse program
  • Dishwasher particularly preferably from the group of bleach catalysts
  • Bleach activators bleaching, glass corrosion inhibitors, surfactants and / or
  • Disinfectant preparations Regardless of the exact design of the dosing devices used in the interior of dishwashers, the devices for multiple dosing are contained in these devices
  • temperatures Exposed to temperatures, 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, in particular temperature-sensitive ones
  • hydrolytic enzymes such as proteases and amylases are components of numerous dishwashing detergents.
  • 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.
  • the object of the present application is therefore to provide a
  • compositions comprising a) containing a liquid (20 ° C.) cleaning agent preparation A.
  • 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.
  • 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 the carbonates, the hydrogen carbonates, the citrates, the silicates, the polymeric carboxylates and the sulfonic acid group-containing polymers or mixtures thereof.
  • Preferred forms of detergent supply comprise a detergent preparation A which, based on its total weight, 2 to 50% by weight, preferably 6 to 45% by weight and
  • builders a1) from the group of the carbonates and / or hydrogen carbonates, preferably alkali carbonates, is particularly preferred
  • Sodium carbonate in amounts of 2 to 30% by weight, preferably 3 to 20% by weight and in particular 4 to 15% by weight, in each case based on the weight of the
  • Organic cobuilders include, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, (poly) aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid,
  • Polycarboxylic acids are preferably understood to mean non-polymeric polycarboxylates. Such polymeric polycarboxylates have a larger number, preferably 4 or more carboxylic acid-containing monomers.
  • 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
  • Citric acid 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 have in particular in combination with phosphonate, in particular 1-hydroxyethane-1, 1-diphosphonic acid, and / or
  • 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.
  • Copolymers of polycarboxylates are furthermore suitable, 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 can use crystalline layered silicates of the general formula NaMSi x 0 2x + i y H2O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values are x 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • Amorphous sodium silicates with a module Na2Ü: S1O2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferred, can also be used
  • 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 contain the aforementioned builders both in the form of individual substances and in the form of
  • 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 above group has proven itself for the The cleaning and rinsing performance of automatic dishwashing agents according to the invention has proven to be advantageous.
  • 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.
  • Preferred copolymers polysulfonates contain, in addition to monomer (s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, a-chloroacrylic acid, a-cyanoacrylic acid, crotonic acid, a-phenyl-acrylic acid, maleic acid,
  • H 2 C CH-X-S0 3 H
  • H 2 C C (CH3) -X-S0 3 H or H0 3
  • SX- (R 6 ) C C (R 7 ) -X-S0 3 H
  • the detergent preparation in particular detergent preparation A, contains a polymer comprising
  • 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-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenlsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl propyl acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.
  • the polymers the
  • All or part of the sulfonic acid groups are present in neutralized form, which means that the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions.
  • metal ions preferably alkali metal ions and in particular by 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 share of
  • Monomers containing carboxylic acid groups from 10 to 50% by weight the monomers here being preferably selected from the abovementioned.
  • 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 of from 2000 to 200,000 g mof 1 , preferably from 4000 to 25,000 g mof 1 and in particular from 5000 to 15,000 g mof 1 .
  • the copolymers additionally comprise
  • Monomer containing carboxyl groups and monomer containing sulfonic acid groups furthermore 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.
  • the detergent preparations particularly preferably comprise, in particular
  • Detergent preparation A comprising a copolymer i) Monomers containing carboxylic acid groups
  • Preferred nonionic monomers are monomers of the general formula
  • 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, ⁇ -olefins with 10 or more
  • Carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-a-olefin, 2-styrene, a-methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2 -Ethyl-4-benzylstyrene, 1 -vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate,
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • 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 3 to 55% 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.
  • the complex-forming phosphonates comprise a number
  • DTPMP diethylenetriaminepenta- (methylenephosphonic acid)
  • hydroxyalkane or aminoalkanephosphonates are of particular importance as a cobuilder. It will preferably used as the sodium salt, the disodium salt being neutral and the
  • Tetrasodium salt reacts alkaline (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.
  • a detergent composition A preferred in the context of this application contains one or more phosphonate (s) from the group
  • ATMP aminotrimethylenephosphonic acid
  • ETMP ethylenediaminetetra (methylenephosphonic acid)
  • DTPMP Diethylenetriaminepenta (methylenephosphonic acid)
  • HDTMP hexamethylenediaminetetra (methylenephosphonic acid)
  • NTMP Nitrilotri (methylenephosphonic acid)
  • Detergent compositions A which contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) as phosphonates are particularly preferred.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • phosphonates are particularly preferred.
  • the automatic dishwashing detergents according to the invention can of course contain two or more different phosphonates.
  • Total weight of cleaning agent compositions A according to the invention is preferably 1 to 8% by weight, preferably 1.2 to 6% by weight, preferably 1.3 to 5% by weight; particularly preferably 1.4 to 4.5% by weight and in particular 1.5 to 4% by weight.
  • 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 A /, A / -diacetic acid, iminodibernic acid, methyl diacetic acid, hydroxynimetic acid, dibglystimic acid, 1, 1-diphosphonic acid or diethylenetriaminepenta (methylenephosphonic acid) and their salts or mixtures thereof, preferably L-glutamic acid A /, A / -diacetic acid and / or
  • Methylglycinediacetic acid and its salts include not only the free acids but also their salts,
  • the cleaning agent preparations A according to the invention can in particular be L-glutamic acid A /, A / -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.
  • L-glutamic acid A /, A / -diacetic acid and / or the corresponding alkali salt (GLDA) preferably the tetrasodium salt
  • MGDA methylglycinediacetic acid
  • MGDA methylglycinediacetic acid
  • preferred cleaning agent preparations A are characterized in that, based on the total weight of the
  • Detergent preparations A 3.0 to 35 wt .-%, preferably 4.0 to 30 wt .-% and in particular 8.0 to 25 wt .-% methylglycinediacetic acid.
  • the cleaning agent preparation A contains the complexing agents selected from phosphonates, if permitted for regulatory reasons, and / or MGDA and their respective salts.
  • the builders then include citrate and carbonate and / or hydrogen carbonate.
  • 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.
  • MGDA and / or its salt 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.
  • 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.
  • preparation A can also be free of MGDA and / or GLDA, i.e.
  • MGDA and / or GLDA have less than 1% by weight of MGDA and / or GLDA, preferably less than 0.5% by weight of MGDA and / or GLDA, particularly preferably less than 0.1% by weight of MGDA and / or GLDA and in particular none Contains MGDA and / or GLDA.
  • 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.
  • the surfactants can also be contained in a cleaning agent preparation different from the cleaning agent preparations A and B.
  • Surfactants are in one Detergent preparation B according to the invention, if used, preferably 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 linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues from 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, C12-14 alcohols with 3 EO, 4 EO or 7 EO, Cg-n alcohol with 7 EO, Ci3-i5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2 -i8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci 2 -i 4 alcohol with 3 EO and Ci2-i8 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).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO,
  • Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention.
  • 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.
  • 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.
  • 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.
  • the cleaning preparation B can also contain anionic surfactants.
  • anionic surfactants are those of the sulfonate and Sulphates used.
  • the surfactants of the sulfonate type are preferably Cg- 13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from Ci2-is monoolefins with an end or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from Ci2-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of a-sulfofatty acids (ester sulfonates), for example the a-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.
  • the content of anionic surfactants in the cleaning preparation B is 0.1 to 30% by weight, preferably 2 to 20% by weight, based on the
  • a preferred pH value of cleaning preparations A according to the invention is between 9 and 14, in particular 9 and 12.
  • the pH can be adjusted, if necessary, by
  • pH adjusting agents in particular sodium hydroxide or potassium hydroxide, are carried out.
  • 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 x 10 -6 to 5 wt .-% 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 in particular in the case of the amylases, proteases, cellulases and mannanases, which is why liquid liquids according to the invention
  • Detergent preparations B characterized in that they contain at least one cleaning-active enzyme from the group of amylases and / or proteases and / or cellulases and / or mannanases, in particular from the group of amylases and / or proteases.
  • subtilisin type 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 which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • 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.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens, from ß. stearothermophilus, from Aspergillus niger and A. oryzae, and the further developments of the aforementioned amylases, which have been improved for use in cleaning agents. Furthermore, the a-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from ß. agaradherens
  • 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, those originally from Humicola lanuginosa
  • Thermomyces lanuginosus available or further developed lipases, especially 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, their
  • 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.
  • enzymes can be used, which are termed hemicellulases
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenoloxidases, polyphenoloxidases)
  • peroxidases such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally preferably added in order to increase the activity of the oxidoreductases in question (enhancers) or in the case of greatly different redox potentials between the oxidizing enzymes and the
  • 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 form agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers or other auxiliaries.
  • 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 in such 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 granular or roll granulation or in fluid-bed processes. Such granules are advantageously more polymeric, for example by application
  • 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 from 0.1 to 40% by weight, preferably from 0.2 to 30% by weight, particularly preferably from 0.4 to 20% by weight and in particular from 0, 8 to 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.
  • 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. The lowering of the
  • Chelating agent content below these upper limits has been shown to be for cleaning performance proven advantageous.
  • a further decrease in the content of complexing agent significantly below the upper limits is surprisingly a further increase in
  • 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.
  • 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
  • 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 each
  • Detergent preparations according to the invention are 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 cleaning agent 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 5 to 80 wt .-%, preferably 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.
  • 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 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 wt .-%, 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 cleaning agent preparations according to the invention can vary within wide limits, but those preparations which, based on the total weight of the cleaning agent preparations according to the invention can vary within wide limits, but those preparations which, based on the total weight of the cleaning agent preparations according to the invention.
  • Detergent preparation 0.01 to 10 wt .-%, preferably 0.2 to 8 wt .-% and in particular 0.5 to 5 wt .-% contain. Appropriate preparations are therefore preferred according to the invention.
  • detergent preparations B according to the invention may also contain polyols, in particular sorbitol.
  • 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.
  • the Detergent preparations B 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.
  • the detergent form further comprises a liquid detergent preparation C, the detergent preparation C being different from the detergent preparations A and B.
  • 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.
  • nonionic surfactants of the general formula R 1 -CH (0H) CH20- (A0) w- (AO) x- (A ”0) y- (A '” 0) zR 2 in which
  • R 1 is a linear or branched, saturated or mono- or polyunsaturated C6 is 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 -CH2CH2, -CH2CH2-CH2, -CH 2 -CH (CH 3 ), -CH2-CH2-CH2-CH2, -CH2-CH (CH 3 ) -CH 2 -, -CH 2 - CH (CH 2 -CH 3 ),
  • w, x, y and z stand for values between 0.5 and 120, where x, y and / or z can also be 0
  • non-ionic surfactants of the general formula R 1 -CH (0H) CH 2 0- (A0) -R 2 , in which the
  • R 1 for a straight-chain or branched, saturated or single or
  • R 2 represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A represents a radical from the group CH2CH2, -CH2CH2-CH2, -CH2-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 C4-22 fatty alcohol (EO) io-8o-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ether and the C4-22 Fetta I ko h 01 - (EO) 4 o-so-2-hyd roxy a I ky I eth e r.
  • 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.
  • Detergent preparation in particular at least one detergent preparation further comprising a nonionic surfactant, particularly preferably at least
  • Detergent preparation B and / or D at least one hydrotrope (hereinafter also referred to as a solubilizer).
  • Preferred hydrotropes are xylene sulfonate, cumene sulfonate, urea and / or / V-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.
  • At least the detergent preparation C in particular the detergent preparations C and B, have at least one hydrotrope, preferably xylene sulfonate, cumene sulfonate, urea and / or N-methylacetamide, particularly preferably cumene sulfonate and / or xylene sulfonate, especially cumene sulfonate, preferably in an amount from 2 to 25% by weight, in particular from 4 to 20% by weight and particularly preferably in an amount of 6 to 15, for example from 7 to 12% by weight, based on the total weight of the respective detergent preparation.
  • hydrotrope preferably xylene sulfonate, cumene sulfonate, urea and / or N-methylacetamide, particularly preferably cumene sulfonate and / or xylene sulfonate, especially cumene sulfonate, preferably in an amount from 2 to 25% by weight, in particular from 4 to 20% by weight and particularly
  • 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.
  • 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.
  • 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 commercially available and as an acidifying agent in the context of the present invention Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight) can also be used with preference.
  • Detergent preparations C based on the total weight of the
  • Detergent preparation C 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 up to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.3 to 8.0% by weight are preferred
  • 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.
  • an active ingredient composition D in particular comprising fragrances and / or scent scavengers
  • 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.
  • 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).
  • Glass corrosion inhibitors selected from water-soluble zinc salts, preferably zinc chloride, Zinc sulfate and / or zinc acetate, particularly preferably zinc acetate, polyalkyleneimines, in particular polyethyleneimines.
  • the preparations according to the invention in particular preparations A and / or C, contain at least one zinc salt as a further constituent,
  • 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 of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
  • 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.
  • 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 proportion by weight 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 .-%.
  • an oxygen bleaching agent selected from hydrogen peroxide, peroxomonosulfate salts, peroxodisulfate salts and PAP
  • the oxidizing agent is preferably selected from chlorine dioxide, calcium hypochlorite, potassium hypochlorite, sodium hypochlorite.
  • the bleaching agent preparation comprises sodium hypochlorite as the oxidizing agent.
  • the bleaching agent composition E contains the at least one oxidizing agent, preferably the alkali metal hypochlorite, in particular that 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
  • the bleach preparation E in particular the bleach preparation E, comprising alkali metal hypochlorite, particularly preferably sodium hypochlorite, further comprises a phosphonate.
  • alkali metal hypochlorite particularly preferably sodium hypochlorite
  • a phosphonate further comprises a phosphonate.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • PBTC 2-phosphonobutane-1, 2,4-tricarboxylic acid
  • 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 .
  • 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 in 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.
  • 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.
  • 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 preferred by the presence of alkalizing agents in the
  • 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, in the sense of this invention the alkali metal hydroxides and alkali carbonates, in particular sodium hydroxide or sodium hydroxide, sodium hydroxide, potassium hydroxide, are preferred Sodium hydroxide, potassium hydroxides can be used. Sodium and / or potassium hydroxide 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.
  • alkali carbonates, especially sodium carbonate can also be used as pH adjusters.
  • 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.
  • 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.
  • the combination of cleaning agents described above is packaged using a packaging material 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.
  • preparations A and / or B preferably A and B
  • 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 one
  • a polymeric carrier material contains at least 10% by weight, preferably at least 30% by weight, particularly preferably at least 70% by weight of ethylene / vinyl acetate copolymer, preferably entirely of ethylene / vinyl acetate copolymer is made.
  • 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 a 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.
  • LDPE low density polyethylene
  • ethylene / vinyl acetate copolymers described above are widely available commercially, for example under the tradename Elvax ® (Dupont).
  • Elvax ® 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.
  • Elvax ® 360 are also suitable.
  • 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.
  • Suitable carrier materials are the cyclodextrins.
  • inorganic carrier materials are preferably also used. Be particularly preferred
  • Forms of cleaning agent 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 and / or
  • 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.
  • the detergent dosage forms can contain such zinc or bismuth-containing glasses, particularly preferably zinc phosphate-containing glasses, in addition to a further active ingredient composition comprising a carrier material, preferably a
  • cleaning agent contain water-insoluble carrier material and at least one active ingredient 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 contain and furthermore at least one, preferably two, three or more
  • Contain active ingredient compositions which comprise one or more fragrances and / or one or more fragrance scavengers as active ingredients.
  • thermoplastic in particular thermoplastic
  • Deformation of the carrier materials in the course of one or more applications will result in a change in the carrier material surface, in particular a change in the size of the
  • 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 method of determination for the
  • Carrier materials also simplify the manufacture of the inventive forms. Preferred forms of offer are therefore characterized in that all used
  • Carrier materials are insoluble in water.
  • the material compositions can in principle assume all physical states and / or spatial shapes that can be achieved depending on the chemical and physical properties of the carrier materials. In a further embodiment, at least one of the
  • At least one of the active substance compositions is in the form of a solid.
  • Material compositions in the form of individual blocks comprising an entire composition of active ingredients are used with particular preference.
  • the material compositions can preferably be in particulate form, the material compositions in which the carrier material comprises at least one of the
  • Material compositions are 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 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.
  • 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 have no pronounced substantivity to the substrates to be treated with the dye-containing compositions, for example glass, ceramic or plastic dishes, and so on stain.
  • the form of cleaning agent 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,
  • 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.
  • Fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type can be used. However, are preferred Mixtures of different fragrances are used, which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • a fragrance 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 odoriferous substances, the smell of a perfume or fragrance composed of several odoriferous substances changes during evaporation, whereby the odor impressions are described in 'top note' (top note), 'heart or middle note' (middle note or body ) and "base note” (end note or dry out).
  • the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note largely consists of less
  • more volatile fragrances can be bound, for example, to certain fixatives, which prevents them from evaporating too quickly.
  • the subsequent classification of the fragrances into more volatile ”or“ adherent ”fragrances is therefore over the smell impression and whether the corresponding odorant is the head ode r heart note is perceived, nothing is said.
  • 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.
  • fragrances are linalyl acetate, dihydromyrcenol,
  • Citronellonitrile menthyl acetate, methylphenylbutanol and / or eucalyptol and their
  • 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 special preferred because it also has a positive effect on the inhibition of glass corrosion during the rinsing process.
  • Fragrances and / or fragrance scavengers antimicrobial agents are used.
  • bacteriostatics and bactericides fungistatics and fungicides etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halophenols and
  • Phenol mercuric acetate although these compounds can also be dispensed with entirely.
  • the active substances can be contained in the active substance preparations in any quantities.
  • dosing devices are particularly preferred in which the proportion by weight of the active substance (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 material composition (s).
  • active ingredient compositions 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.
  • 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).
  • Another object of the present application is a cleaning agent supply form, comprising
  • 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;
  • Another object of the present application is a detergent dosing system comprising
  • 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;
  • At least one further material 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 material D.
  • 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;
  • the cartridges described above are the
  • a dispenser that can be detached from the cartridge.
  • 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.
  • a particularly preferred subject matter of this application is a detergent dosing system comprising
  • a cleaning agent supply form according to any one of the preceding claims, comprising one for the at least twice, preferably at least four times and
  • Dishwashing method sufficient amount of bleaching agent preparation E as well as cleaning agent preparations A and / or B and / or C;
  • detergent dosing systems comprising the detergent supply form according to the invention comprising bleach preparation E (and optionally one or two further detergent preparations A and B or A, B and C or A, B of the detergent preparations according to the invention,
  • a cartridge and a dosing device detachably connected to the cartridge are in a preferred embodiment in a common outer packaging, the filled cartridge and the dosing device being particularly preferably contained separately from one another in the outer packaging.
  • the outer packaging is used for storage, transport and presentation of the form of cleaning agent according to the invention and protects it from dirt, shock and impact.
  • the outer packaging should be designed to be at least partially transparent.
  • the dosing system according to the invention consists of the basic components of a cartridge filled with the cleaning agent according to the invention and a dosing device that 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.
  • 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
  • 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.
  • 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.
  • a cartridge can also comprise a plurality of chambers which are different from one another
  • compositions can be filled. It is also conceivable for a plurality of containers to be arranged to form a cartridge unit.
  • 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 when the metering device is in the use position.
  • 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.
  • 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 caused by gravity from the second chamber in the use position of the metering device is effected.
  • the arrangement of a second chamber is particularly advantageous if if there are preparations in the separate containers which are usually not stable with one another, such as bleaches and enzymes.
  • 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.
  • the cartridge is formed in one piece.
  • 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.
  • connection types from the group of snap-in connections, Velcro connections, press connections, fusion connections, adhesive connections, welded connections, soldered connections, screw connections,
  • 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.
  • a shrink tube so-called sleeve
  • the bottom of the chambers can be inclined in a funnel shape towards the discharge opening.
  • the inner wall of a chamber can be designed in such a way by a suitable choice of material and / or surface design that the material adheres little to the inner one Chamber wall is realized. 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.
  • the ratio of the container volumes is preferably 5: 1, in a configuration with three chambers preferably 4: 1: 1, whereby this
  • Configurations are particularly suitable for use in dishwashers.
  • the cartridge preferably has 3, 4, 5 or 6 chambers.
  • the first chamber contains an alkaline cleaning preparation
  • the second chamber contains an enzymatic preparation
  • the third chamber contains a rinse aid, the volume ratio of the chambers being approximately 4: 1: 1.
  • the fourth chamber contains the at least one
  • Material composition comprising the at least one material 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.
  • 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.
  • 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.
  • the cartridge chambers are not to be directly ventilated, but rather to be provided via the metering device or no ventilation, for example when using flexible containers, such as bags, this has the advantage that in the case of increased Temperatures in the course of a dishwashing cycle of a dishwasher, due to the heating of the chamber contents, a pressure is built up which presses the preparations to be dosed in the direction of the outlet openings, so that 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.
  • the dosing device based on the dishes to be cleaned in dishwashers.
  • 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.
  • the dosing system is dimensioned such that the dosing system can only be positioned in the receptacles provided for the lower basket.
  • the width and the height of the metering system can be chosen in particular between 150 mm and 300 mm, particularly preferably between 175 mm and 250 mm.
  • the dosing unit in a cup shape with an essentially circular or square base area.
  • 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.
  • 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.
  • the cartridges can also have structural elements which correspond to corresponding elements of the metering device
  • Control unit are transmitted, whereby a control of the dosing device can take place which is coordinated with the content of the corresponding container.
  • the cartridge is designed in particular to accommodate flowable cleaning agents.
  • 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 so that it is detachable or fixed in or on the
  • Dishwasher can be arranged.
  • 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 consists of a splash-proof housing that prevents the ingress of splash water, such as when used in a
  • Dishwasher can prevent inside the dosing device.
  • 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.
  • a water-carrying device in particular a water-carrying household appliance, preferably a dishwasher
  • the interfaces are formed by plug connectors.
  • the interfaces can be designed in such a way that wireless transmission of electrical energy is effected.
  • a second interface is provided on the dosing device and the water-carrying device, such as a dishwasher
  • 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 use the adapter for positioning in or on
  • 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 use the adapter as a kind of charging station for the
  • Form dosing system in which, for example, the energy source of the dosing device is charged or data is exchanged between the dosing device and the adapter.
  • the adapter can be arranged in a dishwasher on one of the inner walls of the washing chamber, in particular on the inner side of the dishwasher door.
  • the adapter 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 an inventive one is nevertheless
  • the cleaning agents according to the invention are notable for particular physical and chemical stability
  • 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.
  • a dosing system which can be immovably integrated into the interior of the dishwasher (machine-integrated dosing device), but of course can also be introduced into the interior as a movable device (self-sufficient dosing device), contains several for carrying out a machine
  • 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.
  • a movable cartridge of a dosing system provided for positioning in the interior of a dishwasher
  • 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 dosage 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 dispenser that can be detached from the cartridge.
  • a dispenser that can be detached 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.
  • Detergent reservoir for i) a dosing device immovably integrated into the interior of a dishwasher or ii) one for positioning in the interior of a
  • Movable dosing device provided in the dishwasher is preferred.
  • Detergent reservoir for a dishwasher is a further subject of the present application.
  • a detergent 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;
  • Detergent 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 detergent reservoirs for
  • the cleaning agents and cleaning agent combinations according to the invention are preferably used as automatic dishwashing agents.
  • a partial amount a of the detergent preparation A located in the cartridge is metered into the interior of the dishwasher, a remaining amount of the detergent preparation located in the cartridge remaining in the cartridge until the end of the dishwashing process, characterized in that it
  • Residual amount corresponds to at least twice, preferably at least 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 remaining amount of the detergent preparation located in the cartridge remaining in the cartridge until the end of the dishwashing process, characterized in that it
  • Residual amount corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of subset b; and optionally a portion 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 located in the cartridge remaining in the cartridge until the end of the dishwashing process, thereby
  • this residual amount corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of subset c.
  • 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 located in the cartridge remaining in the cartridge until the end of the dishwashing process, characterized in that it
  • the remaining amount corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of the partial amount d and a partial amount e of the bleaching agent preparation E in the cartridge is metered into the interior of the dishwasher, with a remaining amount of the cleaning agent preparation in the cartridge being used until the end of the dishwashing process 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.
  • the invention also relates to a machine
  • Dishwashing process in which the active ingredient composition is in the cartridge and through which the washing liquor and / or air flows through openings.
  • 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 .
  • 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.
  • 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
  • Dishwashing process remains in the cartridge, which of the at least double,
  • Cartridge located in 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, with a remaining amount of the cleaning agent located in this cartridge until the end of the
  • Dishwashing method remains in the cartridge, which is at least double,
  • Cartridge located inside the dishwasher a subset d of the detergent preparation C located in another cartridge, different from the cleaning agent preparations A and B according to the invention, into the interior of the
  • Dishwasher is metered, with a residual amount of that in this cartridge Detergent 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 c and
  • Residual amount corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of subset e;
  • 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 .
  • FIG. 1 shows a detergent dosing system 101, with a dosing device 102 and a cartridge 103.
  • the cartridge has a chamber 104 for storing
  • a slide 105 with a handle 107 is optionally provided for optionally closing and opening the chamber. By moving the slider 105, the column 106 is closed or opened.
  • a membrane - not shown further here - is additionally attached within the column 106.
  • a membrane 108 is attached to an outer wall of a chamber 109 for storing the preparation, by means of which a membrane is prevented from being suppressed when the chamber 109 is emptied.

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Abstract

L'invention concerne une forme de présentation de produit de nettoyage comprenant a) une préparation de produit de nettoyage liquide A qui contient a1) agent anticalcaire, a2) agent complexant, b) une préparation de produit de nettoyage liquide B qui contient b1) au moins une préparation enzymatique à action nettoyante ainsi que b2) sélectivement au moins un tensioactif non ionique ainsi que c) éventuellement une préparation de produit de nettoyage C qui contient c1) un agent d'acidification et d) un moyen d'emballage qui comprend une préparation d'agent de blanchiment E séparée spatialement des autres préparations de produits de nettoyage. L'invention concerne également l'utilisation de la forme de présentation de produit de nettoyage comme réservoir de produit de nettoyage pour i) un organe de dosage intégré dans l'espace intérieur d'un lave-vaisselle ou ii) un organe de dosage mobile destiné au positionnement dans l'espace intérieur d'un lave-vaisselle. L'invention concerne un système de dosage de produit de nettoyage comprenant a) la forme de présentation de produit de nettoyage, b) un organe de dosage relié de manière détachable à la forme de présentation de produit de nettoyage. L'invention concerne un procédé de lavage de vaisselle en machine.
PCT/EP2020/050893 2019-01-21 2020-01-15 Formulations de produit de nettoyage pour lavage de vaisselle automatique avec agent de blanchiment WO2020152005A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
ES20700896T ES2952573T3 (es) 2019-01-21 2020-01-15 Formulaciones de detergente para el lavado automático de vajilla con lejía
EP20700896.2A EP3914686B1 (fr) 2019-01-21 2020-01-15 Formulations de produit de nettoyage pour lavage de vaisselle automatique avec agent de blanchiment
PL20700896.2T PL3914686T3 (pl) 2019-01-21 2020-01-15 Formulacje czyszczące ze środkiem wybielającym do automatycznego mycia naczyń

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102019200701.5 2019-01-21
DE102019200701.5A DE102019200701A1 (de) 2019-01-21 2019-01-21 Reinigerformulierungen zum automatischen Geschirrspülen mit Bleichmittel

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WO2020152005A1 true WO2020152005A1 (fr) 2020-07-30

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EP (1) EP3914686B1 (fr)
DE (1) DE102019200701A1 (fr)
ES (1) ES2952573T3 (fr)
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WO (1) WO2020152005A1 (fr)

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EP1759624A2 (fr) 2002-03-06 2007-03-07 Reckitt Benckiser N.V. Améliorations d'un récipient ou relative à un récipient
DE102005062479A1 (de) 2005-12-27 2007-07-05 BSH Bosch und Siemens Hausgeräte GmbH Dosiervorrichtung für die Zugabe eines Zuschlagmittels in einen Behandlungsraum und Geschirrspülmaschine mit einer Dosiervorrichtung
DE102010028482A1 (de) * 2010-05-03 2011-11-03 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülverfahren
DE102010030021A1 (de) * 2010-06-14 2011-12-15 Henkel Ag & Co. Kgaa Maschinelles Reinigungsverfahren
WO2012126536A1 (fr) 2011-03-23 2012-09-27 Henkel Ag & Co. Kgaa Système de dosage pour un lave-vaisselle

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WO2011051418A1 (fr) * 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Procédé de lavage en machine

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EP1759624A2 (fr) 2002-03-06 2007-03-07 Reckitt Benckiser N.V. Améliorations d'un récipient ou relative à un récipient
GB2400608A (en) * 2003-03-07 2004-10-20 Reckitt Benckiser Nv Emanator blister for the release of a detergent
DE102005062479A1 (de) 2005-12-27 2007-07-05 BSH Bosch und Siemens Hausgeräte GmbH Dosiervorrichtung für die Zugabe eines Zuschlagmittels in einen Behandlungsraum und Geschirrspülmaschine mit einer Dosiervorrichtung
DE102010028482A1 (de) * 2010-05-03 2011-11-03 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülverfahren
DE102010030021A1 (de) * 2010-06-14 2011-12-15 Henkel Ag & Co. Kgaa Maschinelles Reinigungsverfahren
WO2012126536A1 (fr) 2011-03-23 2012-09-27 Henkel Ag & Co. Kgaa Système de dosage pour un lave-vaisselle

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PL3914686T3 (pl) 2023-10-23
EP3914686B1 (fr) 2023-06-14
ES2952573T3 (es) 2023-11-02
DE102019200701A1 (de) 2020-07-23
EP3914686A1 (fr) 2021-12-01

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