EP2446012B1 - Détergents pour machines - Google Patents

Détergents pour machines Download PDF

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Publication number
EP2446012B1
EP2446012B1 EP10727406.0A EP10727406A EP2446012B1 EP 2446012 B1 EP2446012 B1 EP 2446012B1 EP 10727406 A EP10727406 A EP 10727406A EP 2446012 B1 EP2446012 B1 EP 2446012B1
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EP
European Patent Office
Prior art keywords
cleaning agent
cartridge
detergent
dishwasher
cleaning
Prior art date
Legal status (The legal status 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 status listed.)
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Application number
EP10727406.0A
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German (de)
English (en)
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EP2446012A1 (fr
Inventor
Arnd Kessler
Thorsten Bastigkeit
Christian Nitsch
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL10727406T priority Critical patent/PL2446012T3/pl
Publication of EP2446012A1 publication Critical patent/EP2446012A1/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
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/06—Hydroxides
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/12—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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/36—Organic compounds containing phosphorus
    • C11D2111/14—

Definitions

  • the present application describes mechanical cleaning processes using detergent compositions containing detergents, in particular dishwashing detergents and laundry detergents, as well as the use of these detergents in machine cleaning processes, in which partial quantities of a mechanical cleaning agent from a storage container located in the interior of the dishwasher or textile washing machine in the course of several successive cleaning cycles in the interior of the dishwasher or textile washing machine are dosed.
  • the object of the present application was therefore in the stabilization of a highly concentrated, liquid washing or cleaning active preparation against phase separation / loss of activity with multiple temperature fluctuations (10 to 75 ° C).
  • Corresponding preparations should be storable in a storage device located in the interior of the dishwasher or textile washing machine without significant loss of activity.
  • cleaning preparations for automatic metering for storage are provided, for example, in a metering device in the interior of the dishwasher or textile washing machine and necessarily comprise more than the amount of cleaning agent necessary for carrying out a cleaning cycle.
  • the subject of this application are liquid (20 ° C) detergent formulations.
  • the liquid detergent formulations A are water-containing.
  • Especially preferred Detergent formulations A are characterized in that the detergent formulation A, based on its total weight, contains between 35 and 75% by weight and in particular between 40 and 70% by weight of water. Water contents above 45 wt .-%, particularly preferably above 50 wt .-% and in particular above 55 wt .-% are preferably realized.
  • the upper limit of the water content is preferably 68% by weight, and more preferably 65% by weight.
  • water content encompasses all of the amount of water contained in the compositions of the invention, which is composed of the free water contained in the agents and the water introduced into the detergent preparations via the washing and cleaning activity in bound form.
  • the water content can be determined, for example, as loss on drying or according to Karl Fischer.
  • the detergent formulations according to the invention are alkaline.
  • alkaline detergent compositions are those preparations which have a pH (10% solution in water, 20 ° C) above 8, preferably between 8.5 and 12.5 and in particular between 9.0 and 12.0.
  • the cleaning agent preparations according to the invention are stabilized by lowering the surfactant content of the high builder-containing liquid preparations.
  • Detergent preparations according to the invention are characterized in that the detergent preparation A, based on its total weight, less than 1.0 wt .-% surfactant.
  • Particularly preferred preparations have a surfactant upper limit of 0.5% by weight, in particular 0.2% by weight.
  • Very particularly preferred detergent formulations A according to the invention are free from surfactants.
  • the detergent formulations A according to the invention contain, in addition to the water as a further essential constituent, from 15 to 60% by weight of builder.
  • the group of builders includes the organic complexing agents as well as the alkali carriers and the cleaning-active anionic polymers.
  • the high builder content of inventive detergent formulations of 15 to 60 wt .-% distributed to these three groups of scaffolds.
  • the group of organic complexing agents includes in particular polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and other organic co-builders such as the phosphonates. These classes of substances are described below.
  • Useful organic complexing agents are, for example, those in the form of the free acid and / or. polycarboxylic acids which can be used for their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, ethylenediamine disuccinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • an acidifying component such as citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric aminodicarboxylic acids, their salts or their precursors such as sodium citrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium tartrate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium sulfate, sodium sulfate, sodium sul
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are from 3 to 15 wt .-%.
  • the automatic dishwashing detergents and laundry detergents according to the invention contain methylglycinediacetic acid or a salt of methylglycinediacetic acid.
  • organic complexing agents are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Preferred detergent formulations A according to the invention are characterized in that the detergent composition A, based on its total weight, is from 17 to 50% by weight, preferably from 20 to 45% by weight and in particular from 23 to 40% by weight builder (s) from the group contains the organic complex images.
  • Contents of organic complexing agents are preferably realized above 25 wt .-%, particularly preferably above 30 wt .-%.
  • the upper limit of the content of organic complexing agents is preferably 55% by weight and especially 35% by weight.
  • Particularly preferred machine dishwasher detergents and machine laundry detergents according to the invention contain citrate as one of their essential organic complexing agents.
  • the term "citrate” also includes citric acid as well as its salts, in particular their alkali metal salts.
  • citric acid as well as its salts, in particular their alkali metal salts.
  • the proportion by weight of citrate used in the compositions according to the invention when the free acid is used, the proportion by weight of the sodium salt must be adjusted, that is to say converted from the proportion by weight of the free acid to the proportion by weight of the sodium salt.
  • Detergent preparations according to the invention characterized in that they contain 2.0 to 50 wt .-%, preferably 4.0 to 40 wt .-% and in particular 5.0 to 30 wt .-% citrate, are inventively preferred.
  • a second important organic chelating agent is ethylenediamine disuccinic acid (EDDS), preferred detergent formulations A being characterized by having from 3.0 to 40% by weight, preferably 5.0 to 30% by weight, and especially, based on their total weight Contain 10 to 20 wt .-% Ethylenediamindibernsteinklare.
  • Levels of ethylenediamine disuccinic acid are preferably realized above 12 wt .-%, particularly preferably above 15 wt .-% and in particular above 20 wt .-%.
  • the upper limit of the content of ethylenediamine disuccinic acid is preferably 55% by weight, and more preferably 45% by weight.
  • Ethylenediamine disuccinic acid has been found to be particularly effective in non-phosphate detergent formulations with respect to dough cleaning in automatic dishwashing.
  • ethylenediamine disuccinic acid includes not only the free acids but also their salts, for example their sodium or potassium salts.
  • EDDS ethylenediamine disuccinic acid
  • the automatic dishwashing compositions according to the invention may finally contain metylglycinediacetic acid (MGDA).
  • MGDA metylglycinediacetic acid
  • the methylglycinediacetic acid can be present in the compositions according to the invention in the form of the free acid, as a partial neutralizate or completely neutralized.
  • the methylglycinediacetic acid is in the form of an alkali metal salt.
  • methylglycinediacetic acid is also preferred for reasons of cost.
  • the complex-forming phosphonates form a group of further organic complexing agents used with preference in the detergent formulations A according to the invention, which group comprises, besides the 1-hydroxyethane-1,1-diphosphonic acid, a number of different compounds such as diethylenetriaminepenta (methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • automatic dishwasher detergents which contain, as phosphonates, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylene triamine penta (methylenephosphonic acid) (DTPMP).
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylene triamine penta
  • the detergent formulations according to the invention may contain two or more different phosphonates.
  • the proportion by weight of the phosphonates in the total weight of detergent formulations A according to the invention is preferably from 0.5 to 15% by weight, preferably from 1.0 to 10% by weight and in particular from 1.5 to 6.0% by weight.
  • compositions of some exemplary detergent formulations A according to the invention can be found in the following tables: Recipe 4 Recipe 5 Recipe 9 Recipe 10 water 35 to 75 40 to 70 water 35 to 75 40 to 70 citrate 5.0 to 30 5.0 to 30 EDDS 10 to 20 10 to 20 phosphonate 1.0 to 10 1.5 to 6.0 phosphonate 1.0 to 10 1.5 to 6.0 surfactant ⁇ 1.0 - * surfactant ⁇ 1.0 - Misc Add 100 Add 100 Misc Add 100 Add 100 * "-" means in this, as in all the following tables: the recipe is free from this ingredient Recipe 14 Recipe 15 Recipe 19 Recipe 20 water 35 to 75 40 to 70 water 35 to 75 40 to 70 citrate 5.0 to 30 5.0 to 30 citrate 5.0 to 30 5.0 to 30 EDDS 10 to 20 10 to 20 EDDS 10 to 20 10 to 20 surfactant ⁇ 1.0 - phosphonate 1.0 to 10 1.5 to 6.0 Misc Add 100 Add 100 surfactant ⁇ 1.0 - Misc Add 100 Add 100
  • a second group of builders form the alkali carriers.
  • the group of alkali carriers include the carbonates and / or bicarbonates as well as the alkali metal hydroxides.
  • the group of carbonates and bicarbonates is summarized in the context of this application by the name (hydrogen) carbonate.
  • Preferred detergent formulations according to the invention are characterized in that the detergent composition A, based on its total weight, 1.0 to 30 wt .-%, preferably 2.0 to 25 wt .-% and in particular 5.0 to 20 wt .-% builder ( e) from the group of alkali carriers.
  • compositions of some exemplary detergent formulations A according to the invention can be found in the following tables: Recipe 24 Recipe 25 Recipe 29 Recipe 30 water 35 to 75 40 to 70 water 35 to 75 40 to 70 citrate 5.0 to 30 5.0 to 30 EDDS 10 to 20 10 to 20 (Hydrogen) carbonate 4.0 to 15 4.0 to 15 (Hydrogen) carbonate 3.0 to 15 4.0 to 12 surfactant ⁇ 1.0 - surfactant ⁇ 1.0 - Misc Add 100 Add 100 Misc Add 100 Add 100 Recipe 34 Recipe 35 Recipe 39 Recipe 40 water 35 to 75 40 to 70 water 35 to 75 40 to 70 citrate 5.0 to 30 5.0 to 30 citrate 5.0 to 30 5.0 to 30 EDDS 10 to 20 10 to 20 EDDS 10 to 20 10 to 20 (Hydrogen) carbonate 3.0 to 15 4.0 to 12 (Hydrogen) carbonate 3.0 to 15 4.0 to 12 surfactant ⁇ 1.0 - phosphate - - Misc Add 100 Add 100 surfactant ⁇ 1.0 - Misc Add 100 Add 100
  • preferred detergent formulations according to the invention contain alkali metal hydroxide (s).
  • the alkali metal hydroxides are in the cleaning agents preferably in amounts between 2.0 and 20 wt .-%, preferably between 3.0 and 15 wt .-% and in particular between 4.0 and 12 wt .-%, each based on the total weight of Detergent used.
  • the detergent formulations A according to the invention comprise sodium hydroxide or potassium hydroxide.
  • compositions of some exemplary detergent formulations A according to the invention can be found in the following tables: Recipe 44 Recipe 45 Recipe 49 Recipe 50 water 35 to 75 40 to 70 water 35 to 75 40 to 70 citrate 5.0 to 30 5.0 to 30 EDDS 10 to 20 10 to 20 alkali hydroxide 3.0 to 15 4.0 to 12 alkali hydroxide 3.0 to 15 4.0 to 12 surfactant ⁇ 1.0 - surfactant ⁇ 1.0 - Misc Add 100 Add 100 Misc Add 100 Add 100 Recipe 54 Recipe 55 Recipe 59 Recipe 60 water 35 to 75 40 to 70 water 35 to 75 40 to 70 citrate 5.0 to 30 5.0 to 30 citrate 5.0 to 30 5.0 to 30 5.0 to 30 EDDS 10 to 20 10 to 20 EDDS 10 to 20 10 to 20 alkali hydroxide 3.0 to 15 4.0 to 12 alkali hydroxide 3.0 to 15 4.0 to 12 surfactant ⁇ 1.0 - phosphate - - Misc Add 100 Add 100 Recipe 59a Recipe 60a water 35 to 75
  • Phosphate-free detergent preparations A are suitable according to the invention. Preference is furthermore given to detergent compositions according to the invention which contain less than 2% by weight, preferably less than 1% by weight and in particular less than 0.5% by weight, of silicate. Both the lowering of the phosphate content and the lowering of the silicate content have proved to be advantageous for the stability of the automatic dishwashing detergents and laundry detergents according to the invention.
  • the cleaning-active anionic polymers form a third group of the builders contained in the detergent formulations according to the invention.
  • the cleaning-active anionic polymers may have two, three, four or more different monomer units.
  • the group of these polymers includes, in addition to the homo- and co-polymeric polycarboxylates u.a. also the copolymeric polysulfonates which, in addition to a monomer from the group of unsaturated carboxylic acids, have at least one further monomer from the group of the unsaturated sulfonic acids.
  • the weight fraction of cleaning-active anionic polymers in the total weight of detergent composition according to the invention is 1.0 to 30 wt .-%, preferably 2.0 to 25 wt .-% and in particular 5.0 to 15 wt .-%.
  • the polymeric polycarboxylates form a first group of cleaning-active anionic polymers.
  • examples of such polymers are the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70,000 g / mol.
  • Suitable anionic polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the content of preferred automatic dishwashing agents on (co) polymeric polycarboxylates is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight, in each case based on the total weight of the automatic dishwashing detergent.
  • Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention is in the case of copolymers which contain only monomers from groups i) (monomers containing carboxylic acid gurppene) and ii) (monomers containing sulfonic acid groups), preferably in each case from 5 to 95% by weight i) or ii ), more preferably from 50 to 90% by weight of monomer from group ii) and from 10 to 50% by weight of monomer from group i), in each case based on the polymer.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the copolymers further comprise at least one nonionic, preferably hydrophobic monomer in addition to carboxyl-containing monomer and sulfonic acid-containing monomer.
  • nonionic, preferably hydrophobic monomer in addition to carboxyl-containing monomer and sulfonic acid-containing monomer.
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C
  • compositions of some exemplary detergent formulations A according to the invention can be found in the following tables: Recipe 64 Recipe 65 Recipe 69 Recipe 70 water 35 to 75 40 to 70 water 35 to 75 40 to 70 citrate 5.0 to 30 5.0 to 30 EDDS 10 to 20 10 to 20 Anionic polymer 2.0 to 25 5.0 to 15 Anionic polymer 2.0 to 25 5.0 to 15 surfactant ⁇ 1.0 - surfactant ⁇ 1.0 - Misc Add 100 Add 100 Misc Add 100 Add 100 Recipe 74 Recipe 75 Recipe 79 Recipe 80 water 35 to 75 40 to 70 water 35 to 75 40 to 70 citrate 5.0 to 30 5.0 to 30 citrate 5.0 to 30 5.0 to 30 EDDS 10 to 20 10 to 20 EDDS 10 to 20 10 to 20 Anionic polymer 2.0 to 25 5.0 to 15 alkali hydroxide 3.0 to 15 4.0 to 12 surfactant ⁇ 1.0 - Anionic polymer 2.0 to 25 5.0 to 15 Misc Add 100 Add 100 surfactant ⁇ 1.0 - Misc Add 100 Add 100 Recipe 79a Recipe 80a Recipe 84
  • the detergent formulations A according to the invention may contain further ingredients, for example active ingredients from the group of corrosion inhibitors, as well as the non-washing or cleaning-active fragrances or dyes.
  • active ingredients from the group of corrosion inhibitors, as well as the non-washing or cleaning-active fragrances or dyes.
  • preferred detergent formulations A according to the invention contain these other ingredients only to a minor extent.
  • perfume oils or perfumes within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-Ylang oil.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to those with the dye-containing agents too treating substrates such as textiles, glass, ceramics or plastic crockery so as not to stain them.
  • the detergent formulations A according to the invention are distinguished by a low formulation complexity. This low level of complexity simplifies the preparation of the detergents and thus reduces the costs involved in providing these detergents.
  • preferred cleaning agents according to the invention are characterized in that, in addition to the essential constituents a) and b), they have at most three, preferably the highest two, particularly preferably at most one and in particular no further washing or cleaning-active constituents.
  • the proportion by weight of further washing- or cleaning-active ingredients is preferably less than 10% by weight, preferably less than 5% by weight, more preferably less than 2% by weight and most preferably less than 1.0% by weight.
  • cleaning agent preparations A which contain less than 10% by weight, preferably less than 5% by weight and in particular less than 2% by weight, of bleaching agent.
  • cleaning agent preparations A which are free of bleaching agents.
  • detergent formulations A which contain less than 8% by weight, preferably less than 3% by weight and in particular less than 1% by weight of enzyme preparation. Particular preference is given to those cleaning agent preparations A which are free of enzyme preparations.
  • the further cleaning agent preparations combined with the detergent composition A according to the invention are preferably detergents containing surfactants and / or enzymes and / or bleaches.
  • proteases amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, as well as their mixtures, are among the enzymes used with particular preference in the detergent preparation B.
  • These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.
  • Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein.
  • the protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • cleaning agent preparations A according to the invention characterized in that they contain a washing- or cleaning-active enzyme from the group of amylases and / or proteases, are preferred.
  • the preparation of the above-described combination of cleaning agents takes place in the form of separate receiving chambers, each of these receiving chambers containing one of the combined detergents.
  • Examples of such Kon Stammionsformen are cartridges with two, three, four or more separate receiving chambers, for example, two-, three-, four- or multi-chamber bottles.
  • the previously described cartridges of the detergent product forms are provided with a dispenser detachable from the cartridge.
  • a dispenser detachable from the cartridge can be connected to the cartridge, for example by means of an adhesive, latching, snap or plug connection.
  • the separation of the cartridge and dosing device, for example, the filling of the cartridge is simplified.
  • the detachable connection of cartridge and dispenser allows the replacement of the cartridges on the dispenser. Such an exchange may be indicated, for example, in the event of a change in the cleaning program or after the cartridge has been completely emptied.
  • detergent forms are also conceivable in which the cartridge and the dosing device are permanently connected to each other.
  • the vorgenanten starvedosiersysteme comprising a cleaning agent according to the invention (and optionally one or two further, different from the cleaning agent according to the invention cleaning), a cartridge and a releasably connected to the cartridge dosing device are in a preferred embodiment in a common outer packaging, wherein the filled cartridge and the dosing device are particularly preferably contained separately from one another in the outer packaging.
  • the outer packaging is used for storage, transport and presentation of the invention makesmitte timessform and protect them from dirt, shock and shock. In particular for the purpose of presentation, the outer packaging should at least partially be made 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 metering device which can be coupled to the cartridge, which in turn is formed from further components such as component carrier, actuator, closure element, sensor, energy source and / or control unit.
  • the metering system according to the invention is mobile. Movable in the sense of this application means that the metering system is not inseparably connected to a water-conducting device such as a dishwasher, washing machine, tumble dryer or the like, but for example from a dishwasher by the user removed or positionable in a dishwasher, so is independently handled, is
  • the dosing device for the user is not detachably connected to a water-carrying device such as a dishwasher, washing machine, tumble dryer or the like and only the cartridge is movable.
  • the preparations to be dosed may have a pH between 2 and 12, depending on the intended use, all components of the dosing system which come into contact with the preparations should have a corresponding acid and / or alkali resistance. Furthermore, these components should be largely chemically inert by a suitable choice of material, for example against nonionic surfactants, enzymes and / or fragrances.
  • a cartridge is understood as meaning a packaging material which is suitable for enveloping or holding together flowable or spreadable preparations and which can be coupled to a dosing device for dispensing the preparation.
  • a cartridge can also comprise a plurality of chambers which can be filled with mutually different compositions. It is also conceivable that a plurality of containers is arranged to form a cartridge unit.
  • the cartridge has at least one outlet opening, which is arranged such that a gravity-induced release of preparation from the container in the position of use of the dosing device can be effected.
  • At least one second chamber is provided for receiving at least one second flowable preparation, the second chamber having at least one outlet opening arranged such that a gravity-induced product release from the second chamber in the use position of the dosing is effected.
  • the arrangement of a second chamber is particularly advantageous if in the separate containers preparations are stored, which are usually not stable to each other, such as bleaching agents and enzymes.
  • one of the chambers can be designed for the delivery of volatile preparations, such as a fragrance to the environment.
  • the cartridge is integrally formed.
  • the cartridges in particular by suitable blow molding, cost-effectively trained in a manufacturing step.
  • the chambers of a cartridge can in this case be separated from one another, for example, by webs or material bridges.
  • the cartridge can also be formed in several pieces by injection molded and then assembled components.
  • the cartridge is formed in such a multi-piece, that at least one chamber, preferably all chambers, can be removed individually from the metering device or inserted into the metering device.
  • This makes it possible, with a different consumption of a preparation from a chamber to exchange an already empty chamber, while the rest, which may still be filled with preparation, remain in the metering device.
  • a targeted and needs-based refilling the individual chambers or their preparations can be achieved.
  • the chambers of a cartridge can be fixed to one another by suitable connection methods, so that a container unit is formed.
  • the chambers can be fixed by a suitable form-fitting, non-positive or cohesive connection releasably or permanently against each other.
  • the fixation by one or more of the types of compounds from the group of snap-in compounds, Velcro, Press connections, fusions, adhesive bonds, welded joints, solder joints, screw, wedge, clamp or bounce joints done.
  • the fixation can also be formed by a shrink sleeve (so-called sleeve), which is pulled in a heated state over the entire or sections of the cartridge and firmly encloses the chambers or the cartridge in the cooled state.
  • the bottom of the chambers may be funnel-shaped inclined towards the discharge opening.
  • the inner wall of a chamber can be formed by suitable choice of material and / or surface design in such a way that a low material adhesion of the preparation to the inner chamber wall is realized. Also by this measure, the residual emptiness of a chamber can be further optimized.
  • the chambers of a cartridge may have the same or different filling volumes.
  • the ratio of container volumes is preferably 5: 1, with a three-chamber configuration it is preferably 4: 1: 1, and these configurations are particularly suitable for use in dishwashers.
  • the cartridge preferably has 3 chambers.
  • the first chamber contains an alkaline cleaning preparation
  • the second chamber contains an enzymatic preparation
  • the third chamber contains a rinse aid, wherein the volume ratio of the chambers is approximately 4: 1: 1.
  • a metering chamber may be formed in the flow direction of the preparation in front of the outlet opening.
  • the preparation amount that is to be released in the release of preparation from the chamber to the environment set. This is particularly advantageous if the closure element of the dosing device, which causes the preparation discharge from a chamber to the environment, can only be put into a dispensing and a closure state without controlling the dispensing quantity. It is then ensured by the metering chamber that a predefined amount of preparation is released without an immediate feedback of the delivered preparation amount.
  • the metering chambers can be formed in one piece or in several pieces.
  • one or more chambers in addition to an outlet opening each have a liquid-tight sealable chamber opening. Through this chamber opening, it is possible, for example, to refill stored in this chamber preparation.
  • ventilation possibilities can be provided in particular in the head region of the cartridge in order to ensure a pressure equalization with decreasing filling level of the chambers between the interior of the cartridge chambers and the environment.
  • These ventilation options can be designed, for example, as a valve, in particular silicone valve, micro-openings in the cartridge wall or the like.
  • the cartridge chambers should not be aerated directly, but via the dosing device or no ventilation, e.g. be provided with the use of flexible containers, such as bags, so this has the advantage that at elevated temperatures in the course of a rinse cycle of a dishwasher by the heating of the chamber contents, a pressure is built up, which presses the preparations to be dosed in the direction of the outlet openings, so that a good residual emptying of the cartridge can be achieved. Furthermore, in the case of such an air-free packaging, there is no risk of oxidation of substances of the preparation, which makes bag packaging or else bag-in-bottle packaging appear expedient, in particular for oxidation-sensitive preparations.
  • the cartridge usually has a filling volume of ⁇ 5,000 ml, in particular ⁇ 1,000 ml, preferably ⁇ 500 ml, more preferably ⁇ 250 ml, most preferably ⁇ 50 ml.
  • the cartridge can take on any spatial form. It can for example be cube-shaped, spherical or plate-like.
  • the cartridge and the dosing device can in particular be configured with respect to their spatial form in such a way that they ensure the least possible loss of useful volume, in particular in a dishwashing machine.
  • the dispenser it is particularly advantageous to mold the device based on dishes to be cleaned in dishwashers.
  • plate-shaped be formed in approximately the dimensions of a plate.
  • the dosing device can be positioned to save space eg in the lower basket of the dishwasher.
  • the correct positioning of the dosing unit opens up to the user intuitively through the plate-like shape.
  • the cartridge preferably has a ratio of height: width: depth between 5: 5: 1 and 50: 50: 1, particularly preferably about 10: 10: 1. Due to the "slim" design of the dosing device and the cartridge, it is 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 dispensed from the dosing preparations go directly into the wash liquor and can not adhere to other items to be washed.
  • the metering system is dimensioned in an advantageous embodiment of the invention such that a positioning of the metering system is only possible in the receptacles provided for the lower basket.
  • the width and the height of the metering system can be selected in particular between 150 mm and 300 mm, particularly preferably between 175 mm and 250 mm.
  • the metering unit in cup shape with a substantially circular or square base.
  • Another way to reduce the effect of heat on a preparation in a chamber of the cartridge is to isolate the chamber by suitable means, e.g. by the use of thermal insulation materials such as styrofoam, which enclose the chamber or the cartridge in a suitable manner, in whole or in part.
  • suitable means e.g. by the use of thermal insulation materials such as styrofoam, which enclose the chamber or the cartridge in a suitable manner, in whole or in part.
  • the cartridge has an RFID tag that contains at least information about the contents of the cartridge and that can be read by the sensor unit.
  • This information can be used to select a dosing program stored in the control unit. In this way it can be ensured that an optimal dosing program is always used for a particular preparation. It can also be provided that in the absence of an RFID label or an RFID label with a wrong or faulty identifier, no dosage is done by the dosing and instead an optical or acoustic signal is generated that the user on the present Error indicates.
  • the cartridges may also have structural elements which cooperate with corresponding elements of the metering device according to the key-lock principle, so that, for example, only cartridges of a particular type can be coupled to the metering device. Furthermore, it is possible by this configuration that information about the coupled to the metering cartridge to the Control unit are transmitted, whereby a matched to the contents of the corresponding container control of the dosing device can be done.
  • the cartridge is designed in particular for receiving flowable detergents or cleaning agents. Particularly preferably, such a cartridge has a plurality of chambers for the spatially separated receiving in each case of different preparations of a washing or cleaning agent.
  • the cartridge may be designed so that it can be detachably or firmly arranged in or on the dishwasher.
  • control unit e.g., a Bosch Sensortec metering device
  • sensor unit e.g., a Bosch Sensortec metering device
  • actuator necessary for operation are integrated in the dosing device.
  • an energy source is also arranged in the metering device.
  • the metering device consists of a splash-proof housing, which prevents the penetration of spray water, as may occur, for example, when used in a dishwasher, into the interior of the metering device.
  • the dosing device comprises at least a first interface, which in or on a water-conducting device such as in particular a water-conducting household appliance, preferably a dishwashing or washing machine formed corresponding interface cooperates in such a way that a transfer of electrical energy from the water-bearing device realized for dosing.
  • a water-conducting device such as in particular a water-conducting household appliance, preferably a dishwashing or washing machine formed corresponding interface cooperates in such a way that a transfer of electrical energy from the water-bearing device realized for dosing.
  • the interfaces are formed by connectors.
  • the interface cells can be designed in such a way that a wireless transmission of electrical energy is effected.
  • a second interface on the dosing device and the water-conducting device, such as a dishwasher, for transmitting electromagnetic signals, in particular Radios-, measuring and / or control information of the dosing and / or the water-bearing device such as Dishwasher represent trained.
  • an adapter By means of an adapter, a simple coupling of the dosing system with a water-conducting domestic appliance can be realized.
  • the adapter serves for the mechanical and / or electrical connection of the metering system with the water-conducting household appliance.
  • the adapter is, preferably fixed, connected to a water-carrying pipe of the household appliance.
  • the adapter it is also conceivable to provide the adapter for positioning in or on the household appliance, in which the adapter is detected by the water flow and / or spray of the household appliance.
  • the adapter makes it possible to run a dosing system both for a stand-alone and "buildin" version. It is also possible to form the adapter as a kind of charging station for the metering system in which, for example, the energy source of the metering device is charged or data is exchanged between the metering device and the adapter.
  • the adapter can be arranged in a dishwasher on one of the inner walls of the washing chamber, in particular on the inner side of the dishwasher door.
  • the adapter is positioned as such inaccessible to the user in the water-conducting household appliance, so that the dosing device is used for example during assembly with the household appliance in the adapter, wherein the adapter, the dosing device and the household appliance in such are formed so that a cartridge can be coupled by the user with the dosing device.
  • the detergents, detergent combinations or detergent product forms used according to the invention are suitable for use in dishwashing as well as for textile cleaning, however, the use of a detergent composition A according to the invention, a detergent combination according to the invention or a detergent product form according to the invention for dishwashing in an automatic dishwashing process is preferred.
  • the cleaning agents according to the invention are distinguished by a particular physical and chemical stability, in particular with respect to temperature fluctuations.
  • the cleaning agents according to the invention are thus exceptionally suitable for the metering by means of a metering system located in the interior of a washing or dishwashing machine.
  • a metering system located in the interior of a washing or dishwashing machine.
  • Such a metering system which can be immovably integrated into the interior of the washing machine or dishwasher (machine-integrated metering device) but of course also as a movable device in the interior can be introduced (self-sufficient dosing device), contains the multiple required to carry out a machine cleaning process amount of the detergent.
  • mobile means that the dispensing and metering system is not permanently detachable with a device such as a dishwasher, washing machine, Tumble dryer or the like is connected, but can be removed for example from a dishwasher or positioned in a dishwasher.
  • An example of a stationary cartridge is a container immovably integrated into the interior, for example in the side wall or the inner lining of the door of a dishwasher.
  • a movable cartridge is a container which is introduced by the consumer into the interior of the dishwasher and remains there during the entire course of a cleaning cycle.
  • a cartridge is, for example, by simply setting in the cutlery or crockery basket, integrated into the interior but can be removed from the consumer again from the interior of the dishwasher.
  • the dosage of the cleaning agent or the detergent combination from the cartridge into the interior of the dishwasher is carried out as described above preferably by means of a detachable from the cartridge dosing.
  • a dosing device can be connected to the cartridge by means of an adhesive, latching, snap or plug connection.
  • cartridges with a permanently connected metering device can of course also be used.
  • the detergent formulations of the invention used with particular preference in these processes correspond to the agents described in detail above, preferably the formulations 4 to 115a disclosed in the Tables.
  • Preferred processes for dishwashing or textile cleaning are characterized in that the liquid detergent preparation from a storage container located in the dishwasher or textile washing machine, which contains the multiple, necessary for carrying out a cleaning process amount of the detergent composition, is dosed into the interior of the dishwasher or textile washing machine ,
  • the formulations 4 to 115a disclosed in the tables are suitable for these processes.
  • the dosage of the detergent preparation according to the invention is preferably carried out in the course of the main cleaning cycle of the automatic dishwashing or machine textile washing process.
  • the storage container used for the dosing can be a storage container integrated in the dishwasher or textile washing machine, ie a storage container permanently attached to the dishwashers or a textile washing machine, but also a self-sufficient, ie self-contained, interior act the dishwasher or textile washing machine einbringbaren reservoir.
  • An example of an integrated storage container is a receptacle integrated in the door of the dishwasher or textile washing machine, which is connected via a supply line to the interior of the dishwasher or textile washing machine.
  • An example of a self-sufficient reservoir is a so-called Kopfstehflasche with a bottom-side outlet valve, which can be adjusted for example in the cutlery basket of the dishwasher.
  • the storage container has at least one chamber for receiving the liquid detergent preparations according to the invention.
  • the reservoir has more than one, preferably two, three, four or more separate, separate receiving chambers, of which at least one chamber the contains liquid detergent formulations according to the invention, while at least one, preferably at least two further chambers, preferably liquid preparations containing / containing a composition deviating from the liquid detergent compositions according to the invention.
  • an amount of between 1.0 and 45 ml, preferably between 5.0 and 40 ml, and in particular between 7.0 and 35 ml, of the inventive liquid detergent preparation A is metered into the interior of the dishwasher or textile washing machine.
  • the volume of preferred storage container with one or more receiving chambers is between 10 and 1000 ml, preferably between 20 and 800 ml and in particular between 50 and 500 ml.
  • the detergent formulations according to the invention are distinguished by a particular temperature stability and the processes according to the invention are used in particular for the repeated dosing of these preparations from storage containers located in the interior of the dishwasher or textile washing machine.
  • Preferred processes according to the invention are characterized in that the liquid detergent preparation A prior to its metering into the interior of the dishwasher or textile washing machine for the duration of at least two, preferably at least four, more preferably at least eight and in particular at least twelve separate cleaning processes in the in the the dishwasher or textile washing machine located reservoir remains.
  • the formulations 4 to 115a disclosed in the tables are suitable for these processes.
  • separated cleaning processes which preferably also include a pre-wash cycle and / or a final rinse cycle or rinse cycle and which can be selected and triggered, for example, by means of the program switch of the dishwasher or textile washing machine.
  • the duration of these separate purification processes is preferably at least 15 minutes, preferably between 20 and 360 minutes, preferably between 30 and 240 minutes.
  • the period of time between two separate cleaning processes, within which the liquid detergent preparation is metered into the interior of the dishwasher is preferably at least 20 minutes, especially at least 60 minutes, more preferably at least 120 minutes.
  • the temperature load of the liquid detergent compositions according to the invention can vary within the limits of the process according to the invention, wherein the liquid detergent formulations are particularly suitable for those processes in which the liquid detergent composition A in the reservoir at least twice, preferably at least four times, more preferably at least eight times and in particular at least twelve times to temperatures above 30 ° C preferably, above 40 ° C and particularly preferably above 50 ° C is heated.
  • a heating to temperatures above 60 ° C or above 70 ° C or a twenty- or thirty-fold heating of the liquid detergent composition A according to the invention can of course be realized.
  • the liquid detergent preparation A in the storage container is warmed by the rinsing liquor surrounding this storage container in each of the separate cleaning processes taking place one after the other.
  • the liquid detergent preparation A in the reservoir between the separate cleaning method to temperatures below 30 ° C, preferably below 26 ° C and in particular below 22 ° C from.
  • Automatic dishwashing processes according to the invention using a detergent preparation A according to the invention are characterized in that in the course of these processes a subset a of the cleaning agent preparation A present in the cartridge is metered into the interior of the dishwasher or textile washing machine from a cartridge located in the interior of the dishwasher or textile washing machine, wherein a residual amount of the detergent present in the cartridge remains in the cartridge until the end of the dishwashing or textile washing process, characterized in that this residual amount corresponds to at least twice, preferably at least four times, and in particular at least eight times, the amount of subset a.
  • An object of this application is therefore further a machine dishwashing or machine textile washing process using a detergent according to the invention comprising a cleaning agent A according to the invention and another A different cleaning agent B, in the course of which a cartridge located in the interior of the dishwasher or textile washing machine, a subset a of the detergent present in the cartridge A and also a subset b of the present in the cartridge detergent B is dosed into the interior of the dishwasher or laundry washing machine, with residual amounts of detergent A and B remain in the cartridge until the end of dishwashing or textile washing process and the residual amount of the cleaning agent A at least twice, preferably at least four times and in particular at least eight times the amount of subset a corresponds and the Remaining amount of the cleaning agent B at least twice, preferably at least four times and in particular at least eight times the amount of subset b corresponds.
  • a subject of this application is further a machine dishwashing or machine textile washing process using a detergent combination according to the invention comprising a detergent A according to the invention and another A different cleaning agent B and a third of A and B different detergent C, in the course of one in the interior a portion a of the present in the cartridge detergent A and also a subset b of the present in the cartridge detergent B and additionally a subset c of the present in the cartridge detergent C in the interior of the dishwasher or laundry washing machine dosed is, with residual amounts of the cleaning agents A, B and C remain until the end of dishwashing or textile washing process in the cartridge and the remaining amount of the detergent A min at least twice, preferably at least four times, and in particular at least eight times, the amount of subset b corresponds to the residual amount of the cleaning agent B and the remaining amount of the cleaning agent C at least the double, preferably at least four times and in particular at least eight times the amount of subset c corresponds.
  • the dosage of the different detergents is preferably carried out at different times of the cleaning cycle.
  • the time t2 is at least 1 minute, preferably at least 2 minutes and in particular between 3 and 20 minutes before or after the time Time t1.
  • the detergent formulations are prepared by mixing and mixing the ingredients at 20 ° C. After preparation, the formulations were heated to 75 ° C. After one-time warming, turbidity and sedimentation were observed in composition V1. The composition E1 remained sedimentation stable even after repeated heating to 75 ° C and subsequent cooling to 20 ° C.

Claims (12)

  1. Utilisation d'une préparation nettoyante A liquide sans phosphates comprenant
    a) 15 à 60 % en poids en adjuvant actif,
    b) 30 à 80 % en poids en eau et
    c) moins de 1 % en poids en tensioactif,
    ou d'une combinaison détergente ou nettoyante comprenant
    a) une préparation nettoyante A comme ci-dessus et
    b) une préparation nettoyante B contenant
    b1) au moins un enzyme détergent actif ou enzyme nettoyant actif,
    ou d'une combinaison nettoyante comprenant
    a) une préparation nettoyante A comme ci-dessus et
    b) une préparation détergente ou nettoyante C contenant
    c1 au moins un tensioactif non-ionique,
    c2 de l'eau
    pour le remplissage
    i) d'une cartouche inamovible intégrée dans l'habitacle d'un lave-vaisselle ou d'une machine à laver, appartenant à un système de dosage ou
    ii) d'une cartouche amovible prévue pour être positionnée dans l'habitacle d'un lave-vaisselle ou d'une machine à laver, appartenant à un système de dosage
    avec une quantité suffisante de cette préparation nettoyante liquide ou de cette combinaison d'agents nettoyant pour la réalisation d'un au moins double, de préférence au moins quadruple et notamment au moins octuple procédé mécanique de lave-vaisselle ou procédé mécanique de machine à laver, caractérisé en ce que la préparation nettoyante A contient, rapporté à son poids total, de 1,0 à 30 % en poids en adjuvant(s) actif(s) issu(s) du groupe des polymère anioniques nettoyants actifs.
  2. Utilisation selon la revendication 1, caractérisée en ce que la préparation nettoyante A contient, rapporté à son poids total, de 17 à 50 % en poids, de préférence de 20 à 45 % en poids et notamment de 23 à 40 % en poids en adjuvant(s) actif(s) issu(s) du groupe des agents complexants organiques.
  3. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que la préparation nettoyante A contient, rapporté à son poids total, de 3,0 à 40 % en poids, de préférence de 5,0 à 30 % en poids et notamment de 10 à 20 % en poids en acide éthylènediaminedisuccinique.
  4. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que la préparation nettoyante A contient, rapporté à son poids total, de 1,0 à 30 % en poids, de préférence de 2,0 à 25 % en poids et notamment de 5,0 à 20 % en poids en adjuvant(s) actif(s) issu(s) du groupe des supports alcalins.
  5. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que la préparation nettoyante A contient, rapporté à son poids total, de 2,0 à 25 % et notamment de 5,0 à 15% en poids en adjuvant(s) actif(s) issu(s) du groupe des polymères anioniques nettoyants actifs.
  6. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que la préparation nettoyante A contient, rapporté à son poids total, entre 40 et 70 % en poids et notamment entre 35 et 75 % en poids en eau.
  7. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que la préparation nettoyante A ne contient aucun tensioactif.
  8. Utilisation d'une forme d'agent nettoyant comprenant
    a) une préparation nettoyante A liquide selon l'une quelconque des revendications précédentes dans une quantité suffisante pour la réalisation d'un au moins double, de préférence au moins quadruple et notamment au moins octuple procédé mécanique de lave-vaisselle ou procédé mécanique de machine à laver ;
    b) une cartouche pour la préparation nettoyante A
    faisant office de réservoir d'agent nettoyant pour
    i) un appareil de dosage inamovible intégré dans l'habitacle d'un lave-vaisselle ou d'une machine à laver ou
    ii) un appareil de dosage amovible prévu pour être positionné dans l'habitacle d'un lave-vaisselle ou d'une machine à laver.
  9. Système de dosage d'agent nettoyant comprenant
    a. une préparation nettoyante A liquide selon l'une quelconque des revendications précédentes dans une quantité suffisante pour la réalisation d'un au moins double, de préférence au moins quadruple et notamment au moins octuple procédé mécanique de lave-vaisselle ou procédé mécanique de machine à laver ;
    b. une cartouche pour la préparation nettoyante A ;
    c. un appareil de dosage raccordé ou raccordable à la cartouche.
  10. Système de dosage d'agent nettoyant selon la revendication 9, lequel comprend un appareil de dosage soluble raccordé avec la cartouche.
  11. Système de dosage d'agent nettoyant selon la revendication 9, lequel comprend un appareil de dosage insoluble raccordé avec la cartouche.
  12. Procédé mécanique de lave-vaisselle ou procédé mécanique de machine à laver utilisant une préparation nettoyante A ou une combinaison d'agents nettoyants ou une forme d'agent nettoyant ou un système de dosage d'agent nettoyant selon l'une quelconque des revendications précédentes, au cours duquel une quantité partielle a) de l'agent nettoyant se trouvant dans le réservoir est dosée dans l'habitacle du lave-vaisselle ou de la machine à laver, à partir d'un réservoir se trouvant dans l'habitacle du lave-vaisselle ou de la machine à laver, dans lequel une quantité résiduelle de l'agent nettoyant se trouvant dans le réservoir demeure dans le réservoir jusqu'à la fin du procédé de lave-vaisselle ou de machine à laver, caractérisé en ce que cette quantité résiduelle correspond au moins à la quantité au moins double, de préférence au moins quadruple et notamment au moins octuple de la quantité partielle a).
EP10727406.0A 2009-06-24 2010-06-23 Détergents pour machines Active EP2446012B1 (fr)

Priority Applications (1)

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PL10727406T PL2446012T3 (pl) 2009-06-24 2010-06-23 Środki do czyszczenia maszynowego

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DE102009027162A DE102009027162A1 (de) 2009-06-24 2009-06-24 Maschinelles Geschirrspülmittel
PCT/EP2010/058902 WO2010149697A1 (fr) 2009-06-24 2010-06-23 Détergents pour machines

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EP2446012A1 EP2446012A1 (fr) 2012-05-02
EP2446012B1 true EP2446012B1 (fr) 2017-08-09

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US (1) US20120088709A1 (fr)
EP (1) EP2446012B1 (fr)
DE (1) DE102009027162A1 (fr)
ES (1) ES2642187T3 (fr)
HU (1) HUE034543T2 (fr)
PL (1) PL2446012T3 (fr)
WO (1) WO2010149697A1 (fr)

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ES2373300B1 (es) * 2011-12-14 2012-12-20 Soro Internacional, S.A. Detergente para lavavajillas.
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EP2446012A1 (fr) 2012-05-02
WO2010149697A1 (fr) 2010-12-29
DE102009027162A1 (de) 2010-12-30
PL2446012T3 (pl) 2018-01-31
ES2642187T3 (es) 2017-11-15
US20120088709A1 (en) 2012-04-12
HUE034543T2 (hu) 2018-02-28

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