DE102019117742A1 - Pre-portioned detergent system containing percarbonate for automatic dishwashing - Google Patents

Abstract

The present invention relates to a multi-component cleaning agent which is contained in a container with two to eight chambers, comprising at least two components, a liquid component K1 with a viscosity of more than 10,000 mPas being present in a first chamber; and a liquid or solid second component, which is different from K1, is present in a second chamber, the first component K1 comprising at least one percarbonate; the container wall of the first chamber consists of a water-soluble film and has micro-perforations; and the container wall of the second chamber consists of a water-soluble film which optionally has micro-perforations. The invention also relates to the use of the multi-component cleaning agent for removing soiling on objects to be cleaned when cleaning in automatic dishwashers and a method for cleaning objects in automatic dishwashers.

Description

The present invention relates to a multi-component cleaning agent, which is contained in a container with two to eight chambers, comprising at least two components, a liquid component K1 with a viscosity of more than 10,000 mPas in a first chamber and in a second chamber a liquid or solid second component which is different from K1 is present, the first component K1 comprising at least one percarbonate; the container wall of the first chamber consists of a water-soluble film and has micro-perforations; and the container wall of the second chamber consists of a water-soluble film which optionally has micro-perforations. The invention also relates to the use of the multi-component cleaning agent for removing soiling on objects to be cleaned when cleaning in automatic dishwashers and a method for cleaning objects in automatic dishwashers.

Cleaning agents, in particular for automatic dishwashing, which contain percarbonate are particularly preferred for removing stubborn soiling. However, it has hitherto been difficult to produce pre-portioned cleaning agents which are desired by the consumer with the desired properties. The wrapping of powder formulations with water-soluble film is technically demanding. If small amounts of powder get onto the area of the later sealing seam between the upper and lower film of the chamber, a leak will result at this point. Solid components are therefore generally not desirable for pre-portioned detergent systems. Another difficulty is the possible evolution of gas from the solid percarbonate in closed containers, especially after prolonged storage, which should be avoided. Accordingly, there is a need for percarbonate-containing pre-portioned detergents which are storage-stable.

The inventors of the present invention have surprisingly found that the object is achieved by a multi-component cleaning agent, which is present in a container with two to eight chambers, comprising at least two components, with a liquid component K1 with a viscosity of more than 10,000 in a first chamber mPas and a liquid or solid component K2, which is different from K1, is present in a second chamber, the first component K1 comprising at least one percarbonate, the container wall of the first chamber consists of a water-soluble film and has micro-perforations and the container wall of the second chamber consists of a water-soluble film, which optionally has micro-perforations, can be released. To achieve the object, it is therefore necessary that the component containing percarbonate is a liquid component with a specific viscosity, and the chamber of this component has micro-perforations (also referred to as “breathing holes”), since oxygen can be released during storage and the Otherwise the chamber will be inflated. The specific viscosity is necessary so that the liquid component does not escape from the micro-perforations. The multicomponent cleaning agents according to the invention are therefore easy to process, have good storage stability, an attractive appearance and good cleaning and rinsing performance.

In a first aspect, the invention therefore relates to a multi-component cleaning agent, in particular for automatic dishwashing, which is contained in a container with two to eight chambers, comprising at least two components, wherein

a liquid component K1 with a viscosity of more than 10,000 mPas is present in a first chamber;
and in a second chamber a liquid or solid second component, which is different from K1, is present, wherein
the first component K1 comprises at least one percarbonate;
the container wall of the first chamber consists of a water-soluble film and has micro-perforations; and
the container wall of the second chamber consists of a water-soluble film, which optionally has micro-perforations.

In a second aspect, the invention relates to the use of the multi-component cleaning agent according to the present invention for removing soiling from objects to be cleaned when cleaning in automatic dishwashers.

• - Bereitstellen eines Mehrkomponenten-Reinigungsmittels gemäß der vorliegenden Erfindung in einer automatischen Geschirrspülmaschine;
• - Auflösen der Folie durch in Kontakt bringen mit Wasser;
• - In Kontakt bringen der zu reinigenden Gegenstände, insbesondere des Geschirrs, mit der ersten und zweiten Komponente und gegebenenfalls mit der dritten und vierten Komponente.

Finally, in a third aspect, the invention relates to a method for cleaning objects, in particular dishes, in automatic dishwashers, which method comprises the following steps:

• - Providing a multicomponent detergent according to the present invention in an automatic dishwasher;
• - Dissolve the film by bringing it into contact with water;
• Bringing the objects to be cleaned, in particular the dishes, into contact with the first and second components and optionally with the third and fourth components.

According to the invention, the second component is preferably essentially free of bleach, where “essentially free of bleach” means that more preferably below 0.1% by weight, in particular below 0.01% by weight, and most preferably none at all Bleach is included in the second component.

Furthermore, component K1 is preferably essentially free of enzyme, where “essentially free of enzyme” means that more preferably below 0.05% by weight, in particular below 0.001% by weight, and most preferably no enzyme at all in component K1 is included.

“At least one” as used herein refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with constituents of the compound described herein, this indication does not relate to the absolute amount of molecules but to the type of constituent. “At least one enzyme” therefore means, for example, one or more different enzymes, i.e. one or more different types of enzymes.

Unless otherwise stated, all the quantitative data given in connection with the compositions described herein relate to% by weight, in each case based on the total weight of the respective component. Furthermore, quantities of this type which relate to at least one component always relate to the total amount of this type of component contained in the cleaning agent, unless explicitly stated otherwise. This means that such quantitative data, for example in connection with “at least one enzyme”, relates to the total amount of enzymes which are contained in the respective component.

Numerical values given herein without decimal places refer to the full value given with one decimal place. For example, “99%” stands for “99.0%”.

The expressions “approximately” or “approximately” in connection with a numerical value relates to a variance of ± 10% based on the specified numerical value, preferably ± 5%, particularly preferably ± 1%.

If molecular weights or relative molecular weights or molecular weights are described in the present invention, this is, unless explicitly stated otherwise, the number average molecular weight M _N , which can be determined by means of gel permeation chromatography using polystyrene standards.

If a “substituted” compound is described, for example a substituted alkyl, then suitable substituents are known to the person skilled in the art; it is preferably a radical selected from -F, -Cl, -Br, -I, -OH, - NH ₂ , -NHR ¹ , -N (R ¹ ) ₂ , -COOH, -CF ₃ , -SH, -SR ¹ , = O, -OR ¹ , where R ^{1 is} an aliphatic hydrocarbon radical with 1 to 10 carbon atoms which preferably one or more hydrogen atoms, depending on its bond, replaced on the respective compound.

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it goes without saying that the examples contained herein are intended to describe and illustrate the invention, but not to restrict it, and in particular the invention is not limited to these examples.

In the present invention, the terms multi-component cleaning agent, cleaning agent and agent are used synonymously.

In particular, the multi-component cleaning agent is used as a cleaning agent for automatic dishwashing.

The present invention relates to a multi-component cleaning agent, in particular for automatic dishwashing, which is contained in a container with two to eight, preferably two to four, chambers, comprising at least two components, wherein

a liquid component K1 with a viscosity of more than 10,000 mPas, preferably measured by means of a Brookfield LVDV II + viscometer, with spindle 4-25 and 30 rpm at 25 ° C., is present in a first chamber;
and in a second chamber a liquid or solid second component, which is different from K1, is present, wherein
the first component K1 comprises at least one percarbonate;
the container wall of the first chamber consists of a water-soluble film and has micro-perforations; and
the container wall of the second chamber consists of a water-soluble film, which optionally has micro-perforations.

The present invention includes at least two different components. The first component K1 contains at least one percarbonate and has a viscosity of more than 10,000 mPas. The second component is a component different from K1, which is suitable for use in multi-component cleaning agents. Further components that are also suitable for use in multi-component cleaning agents can be contained in further chambers. These are each identical to the first and second component or are different therefrom.

Specific exemplary components K2 to K4 are described below, each of which can preferably be used as a further second component. For the sake of simplicity, these components have been named K2 to K4. In the context of the present invention, however, this does not mean that, for example, component K4 can only be present when K2 and K3 are present. According to the invention, all permutations of the possibilities of K1 and at least one of the further components described are possible. For example, the specific component described as K4 can be present as the second component and thus an embodiment which claims the component K1 with the specific component K4 is a preferred embodiment. The combinations K1 + K3, K1 + K3 + K4, K1 + K2 + K4, for example, are also possible.

“Liquid” generally means that the components are in liquid form and especially flowable at room temperature, i.e. around 20 ° C, and can thus be poured out of a container, for example. For the purposes of the present invention, liquid includes gels which are flowable at 20 ° C.

The liquid components based on water and / or organic solvents can preferably be thickened, in the form of gels.

According to the invention, however, it is very particularly preferred if the multicomponent cleaning agent comprises exclusively liquid and / or gel-like components.

Cleaning agents which consist of the four components K1 to K4 are preferred.

The components of the multi-component cleaning agent are spatially separated from one another.

The term “spatially separated” in relation to the compositions, as used herein, means that the components of the cleaning agent cannot come into contact with one another prior to use. For this purpose, the cleaning agent is provided in a multi-chamber packaging, the respective component being located separately from the other component (s) in a separate chamber.

This makes it possible to avoid contact with incompatible ingredients.

The multi-component cleaning agent, in particular for automatic dishwashing, is contained in a container with two to eight, preferably two to four, chambers. The container of the multicomponent cleaning agent is more preferably a disposable portion, in particular a pouch.

A single portion is preferably to be understood as meaning that the amount of multicomponent cleaning agent required for a wash cycle is contained in the pre-portioned container and should be used in full for a wash cycle. The container should preferably be of a size that can be used to store a portion of a multi-component cleaning agent which is suitable for a wash cycle is. The total weight of the single serving is therefore preferably between 3 and 40 g, in particular between 5 and 10 g. The container is particularly preferably a pouch with two to eight, in particular two to three chambers, which are formed by water-soluble films.

The water-soluble film material is selected from the group consisting of polymers or polymer mixtures. The envelope can be formed from one or from two or more layers of the water-soluble film material. The water-soluble film material of the first layer and of the further layers, if any, can be the same or different. Particularly preferred are foils which, for example, can be glued and / or sealed to form packagings such as tubes or pillows, after they have been filled with the respective component of the multi-component cleaning agent.

In the context of the invention, the films are preferably in the form of multi-chamber pouches, the components K1 and the second component and, if appropriate, the third to eighth components being spatially separated in different chambers of a pouch made of water-soluble films.

According to the invention, the container wall of the first chamber has a water-soluble film with micro-perforations. The production of microperforations is known to the person skilled in the art and is usually carried out by perforation with fine needles, for example needle rollers.

The microperforations in the context of the present invention preferably have a diameter of 0.1 to 1 mm.

It is preferred according to the invention that the respective film has more than one micro-perforation.

The microperforations can already be present in the water-soluble film before the manufacture of the container or, after the film (s) have been sealed in order to manufacture the container, they can be introduced into the respective film. A preferred type of sealing is water sealing.

It is preferred that the respective film is perforated after the film (s) have been sealed in order to create the container. This has the advantage that the micro-perforations cannot accidentally become clogged again by the application of water during water sealing. Furthermore, the micro-perforations are then only on the surface of the container.

In a preferred embodiment, only the first chamber of the container is perforated after sealing, so the microperforations are only located on the surface of the first chamber of the container.

Using the specific first component K1 with a viscosity of more than 10,000 mPas instead of a powdery composition used in the prior art prevents the powder from sticking to the needles, which can be problematic for the manufacturing process of the container.

The multicomponent cleaning agent can preferably be packaged both in large containers and in portions.

The container according to the invention is preferably completely soluble in water.

The water-soluble or water-dispersible film can comprise a homopolymer, a copolymer or mixtures thereof. Water-soluble homopolymers and copolymers are preferably those polymers which are more than 2.5% by weight, more preferably more than 50% by weight, soluble in water at room temperature.

Preferred water-soluble materials are preferably based at least in part on at least one substance from the group consisting of (acetalized) polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, sulphate, carbonate and / or citrate-substituted polyvinyl alcohols, polyalkylene oxides, acrylamides, cellulose esters, cellulose ethers, cellulose amides, cellulose, Polyvinyl acetates, polycarboxylic acids and their salts, polyamino acids or peptides, polyamides, polyacrylamides, copolymers of maleic acid and acrylic acid, copolymers of acrylamides and (meth) acrylic acid, polysaccharides such as starch or guar derivatives, gelatin and, under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27. A water-soluble material is particularly preferred Polyvinyl alcohol base. On the one hand, this is easy to process and inexpensive to obtain. In addition, it is particularly well soluble in water and thus enables the container produced to be used in a variety of ways.

The water-soluble film is preferably based on at least one polymer. More preferably, the polymer has a number average molecular weight from 10,000 to 1,000,000 g / mol, in particular from 40,000 to 80,000 g / mol. It is particularly preferred that the at least one polymer is derived from polyvinyl alcohol, in particular a polyvinyl alcohol polymer, particularly preferably with a number average molecular weight from 10,000 to 1,000,000 g / mol, in particular from 40,000 to 80,000 g / mol.

The water-soluble material can contain mixtures of different substances. Such mixtures enable the mechanical properties of the container to be adjusted and can influence the degree of water solubility.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten.The water-soluble material preferably contains at least one polyvinyl alcohol and / or at least one polyvinyl alcohol homopolymer or polyvinyl alcohol copolymer. "Polyvinyl alcohol" (abbreviation PVAL or PVA sometimes also PVOH) is the name for polymers with a general structure

which in small proportions (approx. 2%) also have structural units of the type

contain.

Commercially available polyvinyl alcohols, which are available as white-yellowish powders or granules with degrees of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol), have degrees of hydrolysis of 98 to 99 mol% or 87 to 89 mol -%, so still contain a residual content of acetyl groups. The manufacturers characterize the polyvinyl alcohols by specifying the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

The polyvinyl alcohols described above are commercially available, for example under the trademark Mowiol® (Clariant), for example Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88, Mowiol® 8-88 and L648, L734, Mowiflex LPTC 221 ex KSE as well as the compounds from Texas Polymers such as Vinex 2034.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically harmless and are at least partially biodegradable.

Preferred polyvinyl alcohol copolymers can comprise dicarboxylic acids as further monomers in addition to vinyl alcohol. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

Likewise preferred polyvinyl alcohol copolymers can comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof in addition to vinyl alcohol.

The water solubility of polyvinyl alcohol polymer can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols have proven to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water highlighted, which are acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof.

Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax and thus set to the desired values in a targeted manner. These are preferably not included. Films made of PVAL are largely impervious to gases such as oxygen, nitrogen, helium, hydrogen and carbon dioxide, but allow water vapor to pass through.

In addition to polyvinyl alcohol, polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyether, polylactic acid, and / or mixtures of the above polymers can be added to the film material suitable as water-soluble material.

Particularly preferred films which can be used for the film according to the invention are the films sold under the name Monosol M8630, C8400 and M8900 from MonoSol LLC, and the films sold under the name Soluble EF from Aicello Chemical Europe GmbH .

The water-soluble material can have further additives. These are, for example, plasticizers such as dipropylene glycol, ethylene glycol or diethylene glycol, water or disintegrating agents.

The water-soluble films can be manufactured using various manufacturing processes. Blowing, extrusion and casting processes should be mentioned here in principle. In a preferred method, starting from a melt, the films are blown with air via a blow pin to form a tube. In the extrusion process, which is also one of the preferred manufacturing processes, the raw materials plasticized by suitable additives are atomized to shape the films. In particular, it may be necessary here to follow the atomization with drying. In the casting process, which is also one of the preferred manufacturing processes, an aqueous polymer preparation is placed on a heatable drying roller, after the water has evaporated it is optionally cooled and the film is removed as a film. If necessary, this film is additionally powdered before or during the removal.

In a preferred embodiment, all foils have micro-perforations.

Components

Component K1

Component K1 is a liquid component with a viscosity of more than 10,000 mPas and contains at least one percarbonate.

The at least one percarbonate is in component K1 preferably in 0.1 to 15.0% by weight, more preferably in 2.5 to 10.0% by weight, in particular in 3.0 to 7.5% by weight , based on the total weight of component K1.

The component K1 can furthermore comprise at least one organic solvent. Suitable organic solvents include mono- or polyhydric alcohols, alkanolamines or glycol ethers. They are preferably miscible with water in the specified concentration range. The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, glycerin, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, diethylene glycol ether, diethylene glycol ether, diethylene glycol mono-ethylene glycol Propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diisopropylene glycol monomethyl ether, diisopropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, ethoxytriglycol, propylene-2-propylene glycol, propylene-2-butyl-2-propylether, propylene-2-butyl-butoxy-ethanol, 3-butoxy-butyl-butoxyethanol, 3-butoxy-butoxy-glycol, propylene-butoxy-2-octanol, n-butoxy-2-butyl-butoxy-ethanol, 3-butoxy-butoxy-butanol, 3-butoxy-butoxy-butanol, 3-butoxy-2-butoxy-butanol, 3-butoxy-butyl-butoxy-ethanol, 3-propylene Mono-, di-, triethanol- and -propanolamine and mixtures of these solvents. However, it is preferred that glycerol and / or 1,2-propanediol are included in component K1.

The component K1 preferably contains less than 10% by weight, more preferably 5% by weight, most preferably less than 1% by weight of water. In a particularly preferred embodiment, component K1 is essentially free of water, where “essentially free of water” means that preferably below 0.1% by weight, in particular below 0.01% by weight, and most preferably no water at all is contained in the first component.

The at least one organic solvent is preferably contained in 10 to 85% by weight, more preferably in 40 to 70% by weight, based on the total weight of component K1.

The component K1 can also contain at least one thickener, preferably selected from organic thickeners. The at least one thickener is more preferably selected from polyacrylate thickeners, xanthan, gellan, guar, alginate, carrageenan, carboxymethyl cellulose, bentonites, welan gum, locust bean gum, agar agar, tragacanth, gum arabic, pectins, polysaccharides, starch, modified starch, dextrins , Gelatins and casein, modified celluloses, hydroxyethyl ether and hydroxypropyl ether, more preferably selected from xanthan, gellan, guar, alginate, carrageenan, carboxymethyl cellulose, locust bean gum, agar agar, tragacanth, gum arabic, pectins, starch, modified starch, dextrins, gelatins and Casein, and modified celluloses, most preferably xanthan gum.

The thickener can preferably be used in amounts of 0.01 to 10% by weight, in particular from 0.1 to 5% by weight, more preferably from 0.2 to 2.5% by weight, based on the total weight of the component K1 can be used.

The component K1 can also contain at least one citrate, in particular sodium citrate. The at least one citrate is preferably contained in amounts of 0.1 to 20% by weight, preferably 1 to 15.0% by weight, in particular 5 to 12.5% by weight, based on the total weight of component K1 .

The component K1 can also contain at least one bleach catalyst, in particular an Mn-based bleach catalyst. The at least one bleach catalyst is preferred in amounts of 0.01 to 2% by weight, preferably 0.1 to 1.5% by weight, in particular 0.5 to 1.0% by weight, based on the total weight of the Component K1 included.

Bleach catalysts are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Manganese complexes in the II, III, IV or IV oxidation state, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S, are used with particular preference. Ligands are preferably used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the agents according to the invention which have 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are for example [Mn ^III ₂ (µ-O) ₁ (µ-OAc) ₂ (TACN) ₂ ] (ClO4) ₂ , [Mn ^III Mn ^IV (µ-O) ₂ (µ-OAc) ₁ (TACN) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV ₄ (µ-O) ₆ (TACN) ₄ ] (ClO ₄ ) ₄ , [Mn ^III ₂ (µ-O) ₁ (µ-OAC) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (µ-O) ₁ (µ-OAC) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₃ , [Mn ^IV ₂ (µ-O) ₃ (Me -TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (µ-O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (O) CH ₃ ).

The at least one bleach catalyst is preferably selected from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ -TACN) or 1,2,4,7-tetramethyl-1,4 , 7-triazacyclononane (Me ₄ -TACN) are preferred according to the invention, since the aforementioned bleach catalysts in particular can significantly improve the cleaning result.

Furthermore, component K1 can contain at least one bleach activator. Under perhydrolysis conditions, these compounds give aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances which carry O- and / or N-acyl groups with the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Multiple acylated alkylenediamines are preferred, tetraacetylethylenediamine (TAED) having proven particularly suitable.

These bleach activators, in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 10% by weight, particularly 0.5 to 8% by weight and particularly preferably 1.0 to 3% by weight Wt .-%, used.

The component K1 can also contain at least one phosphonate. In addition to 1-hydroxyethane-1,1-diphosphonic acid, suitable phosphonates include a number of different compounds such as, for example, 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 preferred. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt reacting alkaline (pH 9). Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferred as aminoalkanephosphonates. They are preferably in the form of the neutrally reacting sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, it can be preferred to use aminoalkanephosphonates, in particular DTPMP, or mixtures of the phosphonates mentioned.

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

Component K1 preferably contains one or more phosphonate (s) from the group

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

1-Hydroxyethane-1,1-diphosphonic acid (HEDP) is particularly preferred.

The proportion by weight of the phosphonates in the total weight of component K1 is preferably 1 to 10% by weight, preferably 1.2 to 8% by weight and in particular 1.5 to 6% by weight.

In addition, component K1 can contain customary additives selected from corrosion inhibitors, foam inhibitors, enzyme stabilizers, protease inhibitors, dyes, fragrances or antimicrobial active ingredients or mixtures thereof. Suitable compounds are described below.

In a preferred embodiment, component K1 is also present
at least one organic solvent; and or
at least one thickener, preferably selected from organic thickeners, in particular xanthan; and or
at least one citrate, especially sodium citrate; and or
at least one bleach catalyst, in particular an Mn-based bleach catalyst; and or
at least one bleach activator, preferably TAED; and or
at least one phosphonate, preferably HEDP; and or
contain at least one further additive selected from corrosion inhibitors, foam inhibitors, enzyme stabilizers, protease inhibitors, dyes, fragrances, or antimicrobial agents.

In a particularly preferred embodiment, component K1 is also present
at least one organic solvent; and
at least one thickener, preferably selected from organic thickeners, in particular xanthan; and
at least one citrate, especially sodium citrate; and
at least one bleach catalyst, in particular an Mn-based bleach catalyst; and
at least one bleach activator, preferably TAED; and
at least one phosphonate, preferably HEDP; and if necessary
contain at least one further additive selected from corrosion inhibitors, foam inhibitors, enzyme stabilizers, protease inhibitors, dyes, fragrances or antimicrobial agents.

The multicomponent cleaning agent according to the invention contains at least one further component which is different from component K1. These are common components for cleaning agents. In the following, exemplary components K2 to K4 are described, each of which is special are suitable as a further component. Several of these components can also be present together with K1. It is particularly preferred that K1 to K4 are present together.

Component K2

Component K2 contains at least one enzyme, the at least one enzyme in component K2 more preferably comprising amylases and proteases or a mixture thereof.

The component K2 is preferably a gel. In particular, the gel preferably has a viscosity of 100 to 5000 mPas, measured by means of a Brookfield LVDV II + viscometer, with spindle 31 and 6 rpm at 25 ° C.

In preferred embodiments, the at least one enzyme is contained in component K2 in 0.05 to 2.5% by weight, preferably 0.25 to 1.5% by weight, based on the total weight of component K2.

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

• • (1) M9L/M202I,
• • (2) M9L/M202I/M323T,
• • (3) M9L/M202I/M323T/M382Y,
• • (4) M9L/M202I/Y295F/A339S,
• • (5) M9L/M202I/Y295F,
• • (6) M9L/M202I/A339S,
• • (7) M9L/M202I/Y295F/A339S,
• • (8) M9L/M202I/Y295F/A339S/E345R,
• • (9) M9L/G149A/M202I/Y295F/A339S/E345R,
• • (10) M9L/M202L,
• • (11) M9L/M202L/M323T,
• • (12) M9L/M202L/M323T/M382Y,
• • (13) M9L/M202L/Y295F/A339S,
• • (14) M9L/M202L/Y295F,
• • (15) M9L/M202L/A339S,
• • (16) M9L/M202L/Y295F/A339S,
• • (17) M9L/M202L/Y295F/A339S,E345R,
• • (18) M9L/G149A/M202L/Y295F/A339S/E345R,
• • (19) M9L/M202T,
• • (20) M9L/M202T/M323T,
• • (21) M9L/M202T/M323T/M382Y,
• • (22) M9L/M202T/Y295F/A339S,
• • (23) M9L/M202T/Y295F,
• • (24) M9L/M202T/A339S,
• • (25) M9L/M202T/Y295F/A339S,
• • (26) M9L/M202T/Y295F/A339S/E345R,
• • (27) M9L/G149A/M202T/Y295F/A339S/E345R,
• • (28) M9L/G149A/M202I/V214T/Y295F/N299Y/M323T/A339S/E345R,
• • (29) M9L/G149A/M202L/V214I/Y295F/M323T/A339S/E345R/M382Y,
• • (30) M9L/G149A/G182T/G186A/M202I/V214I/Y295F/N299Y/M323T/A339S,
• • (31) M9L/G149A/G182T/G186A/M202L/T257I/Y295F/N299Y/M323T/A339S
• • /E345R,
• • (32) M9L/G149A/M202L/V214T/Y295F/N299Y/M323T/A339S/E345R,
• • (33) M9L/G149A/M202I/V214I/Y295F/M323T/A339S/E345R/M382Y,
• • (34) M9L/G149A/G182T/G186A/M202L/V214I/Y295F/N299Y/M323T/A339S,
• • (35) M9L/G149A/G182T/G186A/M202I/T257I/Y295F/N299Y/M323T/A339S/
• • E345R,
• • (36) M9L/G149A/M202I/V214T/Y295F/N299Y/M323T/A339S/E345R/N471 E,
• • (37) M9L/G149A/M202L/V214I/Y295F/M323T/A339S/E345R/M382Y/N471 E,
• • (38) M9L/G149A/G182T/G186A/M202I/V214I/Y295F/N299Y/M323T/A339S/
• • N471E,
• • (39) M9L/G149A/G182T/G186A/M202L/T257I/Y295F/N299Y/M323T/A339S
• • /E345R/N471 E,
• • (40) M202L/M105F/M208F,
• • (41) G133E/M202L/Q361E,
• • (42) G133E/M202L/R444E,
• • (43) M202L/Y295F,
• • (44) M202L/A339S,
• • (45) M202L/M323T,
• • (46) M202L/M323T/M309L,
• • (47) M202L/M323T/M430I,
• • (48) M202L/V214T/R444Y,
• • (49) M202L/N283D/Q361 E,
• • (50) M202L/M382Y/K383R,
• • (51) M202L/K446R/N484Q,
• • (52) M202I/Y295F,
• • (53) M202I/A339S,
• • (54) M202I/M105F/M208F,
• • (55) G133E/M202I/Q361 E,
• • (56) G133E/M202I/R444E,
• • (57) M202I/M323T,
• • (58) M202I/M323T/M309L,
• • (59) M202I/M323T/M430I,
• • (60) M202I/V214T/R444Y,
• • (61) M202I/N283D/Q361E,
• • (62) M202I/M382Y/K383R,
• • (63) M202I/K446R/N484Q,
• • (64) M202V/M105F/M208F,
• • (65) G133E/M202V/Q361 E,
• • (66) G133E/M202V/R444E,
• • (67) M202V/M323T,
• • (68) M202V/M323T/M309L,
• • (69) M202V/M323T/M430I,
• • (70) M202V/M323T/M9L,
• • (71) M202V/V214T/R444Y,
• • (72) M202V/N283D/Q361 E,
• • (73) M202V/M382Y/K383R,
• • (74) M202V/K446R/N484Q,
• • (75) M202T/M105F/M208F,
• • (76) G133E/M202T/Q361 E,
• • (77) G133E/M202T/R444E,
• • (78) M202T/Y295F,
• • (79) M202T/A339S,
• • (80) M202T/M323T,
• • (81) M202T/M323T/M309L,
• • (82) M202T/M323T/M430I,
• • (83) M202T/M323T/M9L,
• • (84) M202TA/214T/R444Y,
• • (85) M202T/N283D/Q361E,
• • (86) M202T/A339S,
• • (87) M202T/Y295F
• • (88) M202T/N299F, Y,
• • (89) M202T/M382Y/K383R oder
• • (90) M202T/K446R/N484Q

An α-amylase variant has proven to be particularly suitable for the use according to the invention, which can either be obtained from a starting α-amylase homologizable with α-amylase AA560 via amino acid changes in the following positions: 9, 149, 182, 186, 202, 257, 295, 299, 323, 339, 345 and optionally others (in the count according to the α-amylase AA560) or which can be obtained from the α-amylase AA560 via the following amino acid changes:

• • (1) M9L / M202I,
• • (2) M9L / M202I / M323T,
• • (3) M9L / M202I / M323T / M382Y,
• • (4) M9L / M202I / Y295F / A339S,
• • (5) M9L / M202I / Y295F,
• • (6) M9L / M202I / A339S,
• • (7) M9L / M202I / Y295F / A339S,
• • (8) M9L / M202I / Y295F / A339S / E345R,
• • (9) M9L / G149A / M202I / Y295F / A339S / E345R,
• • (10) M9L / M202L,
• • (11) M9L / M202L / M323T,
• • (12) M9L / M202L / M323T / M382Y,
• • (13) M9L / M202L / Y295F / A339S,
• • (14) M9L / M202L / Y295F,
• • (15) M9L / M202L / A339S,
• • (16) M9L / M202L / Y295F / A339S,
• • (17) M9L / M202L / Y295F / A339S, E345R,
• • (18) M9L / G149A / M202L / Y295F / A339S / E345R,
• • (19) M9L / M202T,
• • (20) M9L / M202T / M323T,
• • (21) M9L / M202T / M323T / M382Y,
• • (22) M9L / M202T / Y295F / A339S,
• • (23) M9L / M202T / Y295F,
• • (24) M9L / M202T / A339S,
• • (25) M9L / M202T / Y295F / A339S,
• • (26) M9L / M202T / Y295F / A339S / E345R,
• • (27) M9L / G149A / M202T / Y295F / A339S / E345R,
• • (28) M9L / G149A / M202I / V214T / Y295F / N299Y / M323T / A339S / E345R,
• • (29) M9L / G149A / M202L / V214I / Y295F / M323T / A339S / E345R / M382Y,
• • (30) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / A339S,
• • (31) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S
• • / E345R,
• • (32) M9L / G149A / M202L / V214T / Y295F / N299Y / M323T / A339S / E345R,
• • (33) M9L / G149A / M202I / V214I / Y295F / M323T / A339S / E345R / M382Y,
• • (34) M9L / G149A / G182T / G186A / M202L / V214I / Y295F / N299Y / M323T / A339S,
• • (35) M9L / G149A / G182T / G186A / M202I / T257I / Y295F / N299Y / M323T / A339S /
• • E345R,
• • (36) M9L / G149A / M202I / V214T / Y295F / N299Y / M323T / A339S / E345R / N471 E,
• • (37) M9L / G149A / M202L / V214I / Y295F / M323T / A339S / E345R / M382Y / N471 E,
• • (38) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / A339S /
• • N471E,
• • (39) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S
• • / E345R / N471 E,
• • (40) M202L / M105F / M208F,
• • (41) G133E / M202L / Q361E,
• • (42) G133E / M202L / R444E,
• • (43) M202L / Y295F,
• • (44) M202L / A339S,
• • (45) M202L / M323T,
• • (46) M202L / M323T / M309L,
• • (47) M202L / M323T / M430I,
• • (48) M202L / V214T / R444Y,
• • (49) M202L / N283D / Q361 E,
• • (50) M202L / M382Y / K383R,
• • (51) M202L / K446R / N484Q,
• • (52) M202I / Y295F,
• • (53) M202I / A339S,
• • (54) M202I / M105F / M208F,
• • (55) G133E / M202I / Q361 E,
• • (56) G133E / M202I / R444E,
• • (57) M202I / M323T,
• • (58) M202I / M323T / M309L,
• • (59) M202I / M323T / M430I,
• • (60) M202I / V214T / R444Y,
• • (61) M202I / N283D / Q361E,
• • (62) M202I / M382Y / K383R,
• • (63) M202I / K446R / N484Q,
• • (64) M202V / M105F / M208F,
• • (65) G133E / M202V / Q361 E,
• • (66) G133E / M202V / R444E,
• • (67) M202V / M323T,
• • (68) M202V / M323T / M309L,
• • (69) M202V / M323T / M430I,
• • (70) M202V / M323T / M9L,
• • (71) M202V / V214T / R444Y,
• • (72) M202V / N283D / Q361 E,
• • (73) M202V / M382Y / K383R,
• • (74) M202V / K446R / N484Q,
• • (75) M202T / M105F / M208F,
• • (76) G133E / M202T / Q361 E,
• • (77) G133E / M202T / R444E,
• • (78) M202T / Y295F,
• • (79) M202T / A339S,
• • (80) M202T / M323T,
• • (81) M202T / M323T / M309L,
• • (82) M202T / M323T / M430I,
• • (83) M202T / M323T / M9L,
• • (84) M202TA / 214T / R444Y,
• • (85) M202T / N283D / Q361E,
• • (86) M202T / A339S,
• • (87) M202T / Y295F
• • (88) M202T / N299F, Y,
• • (89) M202T / M382Y / K383R or
• • (90) M202T / K446R / N484Q

The α-amylase variant is particularly preferably characterized by one or more amino acid changes in the following positions compared to a starting α-amylase which can be homologated with α-amylase AA560: 118, 183, 184, 195, 320 and 458 (counted according to FIG α-amylase AA560), the α-amylase variant preferably having the following amino acid position assignments in particular: 118K, 183- (deletion), 184- (deletion), 195F, 320K and / or 458K (counting according to α-amylase AA560) .

• • (10) M9L/M202L,
• • (28) M9L/G149A/M202I/V214T/Y295F/N299Y/M323T/A339S/E345R,
• • (31) M9L/G149A/G182T/G186A/M202L/T257I/Y295F/N299Y/M323T/A339S/E345R,
• • (35) M9L/G149A/G182T/G186A/M202I/T257I/Y295F/N299Y/M323T/A339S/E345R,
• • (38) M9L/G149A/G182T/G186A/M202I/V214I/Y295F/N299Y/M323T/A339S/N471E,
• • (39) M9L/G149A/G182T/G186A/M202L/T257I/Y295F/N299Y/M323T/A339S/E345R/N471E,
• • (45) M202L/M323T,
• • (46) M202L/M323T/M309L,
• • (62) M202I/M382Y/K383R,
• • (68) M202V/M323T/M309L,
• • (73) M202V/M382Y/K383R
• • (82) M202T/M323T/M430I
• • (84) M202T/V214T/R444Y.

An α-amylase variant which can be derived from the α-amylase AA560 or a derivative thereof and is preferably derived from this itself is particularly preferred. Particularly preferred are those compositions according to the invention which contain an α-amylase variant which has one of the following amino acid changes compared to α-amylase AA560:

• • (10) M9L / M202L,
• • (28) M9L / G149A / M202I / V214T / Y295F / N299Y / M323T / A339S / E345R,
• • (31) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R,
• • (35) M9L / G149A / G182T / G186A / M202I / T257I / Y295F / N299Y / M323T / A339S / E345R,
• • (38) M9L / G149A / G182T / G186A / M202I / V214I / Y295F / N299Y / M323T / A339S / N471E,
• • (39) M9L / G149A / G182T / G186A / M202L / T257I / Y295F / N299Y / M323T / A339S / E345R / N471E,
• • (45) M202L / M323T,
• • (46) M202L / M323T / M309L,
• • (62) M202I / M382Y / K383R,
• • (68) M202V / M323T / M309L,
• • (73) M202V / M382Y / K383R
• • (82) M202T / M323T / M430I
• • (84) M202T / V214T / R444Y.

Proteases break down protein-containing soiling on the items to be cleaned. Proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62), which are serine proteases due to the catalytically active amino acids, are particularly important. They act as non-specific endopeptidases and hydrolyze any acid amide bonds that are inside peptides or proteins. Their pH optimum is usually in the clearly alkaline range. For example, the article " Subtilases: Subtilisin-like Proteases ”by R. Siezen, pages 75-95 in“ Subtilisin enzymes ”, edited by R. Bott and C. Betzel, New York, 199 6. Subtilases are naturally produced by microorganisms. Among these, the subtilisins formed and secreted by Bacillus species should be mentioned as the most important group within the subtilases.

Examples of the proteases of the subtilisin type preferably used in compositions are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, subtilisin DY and the subtilases, however, no longer the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which can be assigned to the subtilisins in the narrower sense, as well as variants of the proteases mentioned, which have an amino acid sequence that is different from the original protease. Proteases are modified in a targeted or random manner by methods known from the prior art and thus optimized for use in cleaning agents, for example. These include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. For most of the proteases known from the prior art, correspondingly optimized variants are known.

Other suitable enzymes that can also be contained in the cleaning agent, preferably in component K2, include, without being limited to, cellulases, hemicellulases, mannanases, tannases, xylanases, xanthanases, xyloglucanases, β-glucosidases, pectinases, cutinases, carrageenases, Perhydrolases, oxidases, oxidoreductases or lipases, as well as their mixtures.

These enzymes are in principle of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are accordingly preferred. The protein concentration can generally be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) or the biuret method ( AG Gornall, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 ) can be determined. In this regard, the active protein concentration can be determined by titrating the active centers using a suitable irreversible inhibitor and determining the residual activity (cf. M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913 ) respectively.

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

Furthermore, enzymes can be used which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose, or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can also be used. Advantageously, preferably organic, particularly preferably aromatic, compounds interacting with the enzymes are added in order to increase the activity of the oxidoreductases concerned (enhancers) or to ensure the flow of electrons (mediators) in the event of greatly differing redox potentials between the oxidizing enzymes and the soiling.

It is possible to formulate two or more enzymes together so that a single composition has multiple enzyme activities.

The component K2 can also have at least one organic solvent. Suitable organic solvents include mono- or polyhydric alcohols, alkanolamines or glycol ethers. They are preferably miscible with water in the specified concentration range. The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, glycerin, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, diethylene glycol ether, diethylene glycol ether, diethylene glycol mono-ethylene glycol Propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diisopropylene glycol monomethyl ether, diisopropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, ethoxytriglycol, propylene-2-propylene glycol, propylene-2-butyl-2-propylether, propylene-2-butyl-butoxy-ethanol, 3-butoxy-butyl-butoxyethanol, 3-butoxy-butoxy-glycol, propylene-butoxy-2-octanol, n-butoxy-2-butyl-butoxy-ethanol, 3-butoxy-butoxy-butanol, 3-butoxy-butoxy-butanol, 3-butoxy-2-butoxy-butanol, 3-butoxy-butyl-butoxy-ethanol, 3-propylene Mono-, di-, triethanol- and -propanolamine and mixtures of these solvents. However, it is preferred that the cleaning agent comprises glycerine and / or 1,2-propanediol in component K2.

The at least one organic solvent is contained preferably in 10 to 85% by weight, more preferably in 35 to 80% by weight, based on the total weight of component K2.

The component K2 can also contain at least one (poly) saccharide. Saccharides, in particular sorbitol, are preferred. The (poly) saccharide is preferably contained in 0.1 to 10% by weight, more preferably 5.0 to 8.0% by weight, based on the total weight of component K2.

The component K2 can also contain at least one further additive selected from buffer substances, corrosion inhibitors, foam inhibitors, enzyme stabilizers, protease inhibitors, dyes, fragrances, antimicrobial agents, or acids and bases for pH adjustment. An antimicrobial active ingredient is also particularly preferably contained.

Suitable additives are described below.

In a preferred embodiment, component K2 also comprises
at least one enzyme; and or
at least one organic solvent, in particular 1,2-propylene glycol, glycerol or a mixture thereof; and or
at least one (poly) saccharide, preferably sorbitol; and or
at least one further additive selected from buffer substances, corrosion inhibitors, foam inhibitors, enzyme stabilizers, colorants, fragrances, antimicrobial active ingredients, or acids and bases for pH adjustment.

The component K2 particularly preferably also comprises
at least one enzyme comprising at least one protease and at least one amylase; and
at least one organic solvent, in particular 1,2-propylene glycol, glycerol or a mixture thereof; and
at least one (poly) saccharide, preferably sorbitol; and
at least one antimicrobial agent.

Component K3

The component K3 contains at least one builder.

The builders that can be used include aminocarboxylic acids and their salts, carbonates and silicates.

Aminocarboxylic acids and / or their salts represent a further important class of builders. Particularly preferred representatives of this class are methylglycine diacetic acid (MGDA) or its salts and glutamine diacetic acid (GLDA) or its salts or ethylenediamine diacetic acid or its salts (EDDS). Iminodisuccinic acid (IDS) and iminodiacetic acid (IDA) are also suitable.

Polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals and dextrins are to be mentioned in particular as organic co-builders.

Methylglycinediacetic acid (MGDA) or its salts and / or glutaminediacetic acid (GLDA) are preferably used, in particular N, N-bis (carboxymethyl) -L-glutamic acid or its salts, particularly preferably tetrasodium-N, N-bis (carboxymethyl) -L- glutamate. This substance can be purchased from AkzoNobel under the trade name Dissolvine GL 47S, for example.

Suitable organic builder substances are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or its sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, as well as mixtures of these.

The use of carbonate (s) and / or hydrogen carbonate (s), preferably alkali metal carbonate (s), is also possible, but not preferred.

MGDA and / or GLDA are particularly preferably used in amounts of 10 to 90% by weight, more preferably 40 to 80% by weight, based on the total weight of component K3.

Cleaning agents according to the invention can furthermore contain crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} · y H ₂ O as builders, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, where particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. Amorphous sodium silicates with a Na ₂ O: SiO ₂ module of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6 can also be used.

Component K3 can also contain co-builders. Polymeric polycarboxylates are suitable as co-builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a weight-average molecular weight of 500 to 70,000 g / mol.

Suitable polymers are in particular polyacrylates, which preferably have a weight-average molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates from this group, which have a weight-average molecular weight of 2,000 to 10,000 g / mol, and particularly preferably 3,000 to 5,000 g / mol, are preferred.

According to the present invention, the weight-average molecular weight is preferably determined by means of gel permeation chromatography using polystyrene standards.

Examples of particularly preferred substances are Acusol 587D (polyacrylic sulfonate; Rohm & Haas / Dow Chemical company), Acusol 445N (polycarboxylate sodium salt; Rohm & Haas / Dow Chemical company), Acusol 590 (polyacrylate copolymer; Rohm & Haas / Dow Chemical company), Acusol 916 (polyacrylate sodium salt; company Rohm & Haas / Dow Chemical), Sokalan CP42 (modified polycarboxylate sodium salt; company BASF), Sokalan PA 30CL (polycarboxylate sodium salt; company BASF), Dequest P 9000 (polymaleic acid; company Thermphos), alginic acid, poly -2-acrylamido-2-methyl-1-propanesulfonic acid, poly-4-styrene-sulfonic acid-co-maleic acid sodium salt, poly-acrylamido-co-acrylic acid sodium salt, poly-methacrylic acid sodium salt, poly-methyl vinyl ether-old maleic acid or polyvinylsulfonic acid sodium salt, and Noverite AD 810G, an acrylic terpolymer from Lubrizol.

Acusol 590 (polyacrylate copolymer; Rohm & Haas / Dow Chemical company) and / or Noverite AD 810G can particularly preferably be contained in component K3 of the invention. Quantities of 0.1 to 30% by weight, in particular 5 to 20% by weight, based on the total weight of component K3, are preferably used.

Sodium polyacrylate can more preferably be used in component K3, preferably in amounts from 0.1 to 30% by weight, in particular from 5.0 to 20% by weight, based on the total weight of component K3.

In addition, component K3 can contain at least one additive selected from buffer substances, corrosion inhibitors, foam inhibitors, enzyme stabilizers, protease inhibitors, dyes, fragrances, organic solvents, antimicrobial agents, or dispersants. Suitable additives are described below.

In a preferred embodiment, the component contains K3
at least one builder; and or
at least one co-builder, preferably a polyacrylate; and if necessary
at least one further additive selected from corrosion inhibitors, foam inhibitors, enzyme stabilizers, protease inhibitors, colorants, fragrances, organic solvents, antimicrobial agents or dispersants.

In a particularly preferred embodiment, the component contains K3
at least one builder, in particular MGDA and / or GLDA; and
at least one co-builder, in particular at least one polyacrylate.

Component K4

Component K4 contains at least one surfactant, in particular at least one nonionic surfactant or one anionic surfactant or mixtures thereof.

Suitable anionic surfactants are alkyl sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, olefin sulfonates, alkyl sulfonates, alkylbenzenesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates. Fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid esters), in particular sulfosuccinic acid mono- and di-alkyl esters with 8 to 18 carbon atoms, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkane sulfonates (ether carboxylic acids), fatty acids, and fatty acids phosphates and α-sulfofatty acid salts, acyl glutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.

The anionic surfactants are preferably used as sodium salts, but can also be present as other alkali or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts.

All non-ionic surfactants known to the person skilled in the art can be used as further non-ionic surfactants.

Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x , in which R corresponds to a primary linear or methyl-branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18 carbon atoms, and G is the symbol which stands for a glucose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Fatty alcohol alkoxylates of the formula (I) are also suitable as nonionic surfactants, R ¹ -O- (AlkO) _m -H (I), in which
R ^{1 is} a linear or branched, substituted or unsubstituted alkyl group having 6 to 25, preferably 10 to 20, more preferably 12 to 20, most preferably 16 to 18 carbon atoms;
AlkO is an alkylene oxide unit, each of which is selected independently of one another, is preferably an ethylene oxide unit or propylene oxide unit, more preferably is an ethylene oxide unit, most preferably all alkylene oxide units are ethylene oxide units; and
m is 10 to 50, preferably 15 to 35, more preferably 20 to 30, most preferably 25.

The fatty alcohol alkoxylate of the formula (I) is preferably a fatty alcohol alkoxylate which is solid under standard conditions (temperature 25 ° C., pressure 1013 mbar) and can preferably be used in the form of a powder or granules.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.

Further suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

Finally, other low-foaming nonionic surfactants from the group of alkoxylated alcohols can also be used.

A nonionic surfactant that can preferably be used according to the invention is, for example, the ethoxylated fatty alcohol Dehypon E127 or Dehypon Wet from BASF.

Nonionic and / or anionic surfactants can preferably be used in amounts of 10 to 100% by weight, in particular 40 to 90% by weight, based on the total weight of component K4.

The component K4 can also contain at least one organic solvent. Suitable organic solvents include mono- or polyhydric alcohols, alkanolamines or glycol ethers. They are preferably miscible with water in the specified concentration range. The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, glycerin, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, diethylene glycol ether, diethylene glycol ether, diethylene glycol mono-ethylene glycol Propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diisopropylene glycol monomethyl ether, diisopropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, ethoxytriglycol, propylene-2-propylene glycol, propylene-2-butyl-2-propylether, propylene-2-butyl-butoxy-ethanol, 3-butoxy-butyl-butoxyethanol, 3-butoxy-butoxy-glycol, propylene-butoxy-2-octanol, n-butoxy-2-butyl-butoxy-ethanol, 3-butoxy-butoxy-butanol, 3-butoxy-butoxy-butanol, 3-butoxy-2-butoxy-butanol, 3-butoxy-butyl-butoxy-ethanol, 3-propylene Mono-, di-, triethanol- and -propanolamine and mixtures of these solvents. However, it is preferred that the cleaning agent comprises 1,2-propanediol in component K4.

The organic solvent can preferably be present in up to 50% by weight of the component, particularly preferably in 5 to 50% by weight, based on the total weight of component K4.

Furthermore, component K4 can optionally contain at least one further additive selected from buffer substances, corrosion inhibitors, foam inhibitors, enzyme stabilizers, protease inhibitors, dyes, fragrances, antimicrobial active ingredients, or acids and bases for pH adjustment. Suitable additives are described below.

Component K4 can also contain water.

In a preferred embodiment, the component contains K4
at least one surfactant, in particular at least one nonionic surfactant or one anionic surfactant or mixtures thereof; and or
at least one organic solvent; and or
Water; and or
optionally at least one further additive selected from buffer substances, corrosion inhibitors, foam inhibitors, enzyme stabilizers, protease inhibitors, dyes, fragrances, antimicrobial agents or acids and bases for pH adjustment.

In a particularly preferred embodiment, the component contains K4
at least one surfactant, in particular at least one nonionic surfactant or one anionic surfactant or mixtures thereof; and
at least one organic solvent, in particular 1,2-propanediol; and
Water.

In various embodiments, components K1, K3 and K4 are essentially free of protease inhibitors.

Suitable additives which are described in the above embodiments for K1 to K4 are preferably the following.

Further enzyme stabilizers and / or protease inhibitors known to the person skilled in the art can additionally be used in the cleaning agent.

Monoethanolamine can preferably be used in amounts from 0.1 to 10% by weight, in particular from 0.5 to 7% by weight, more preferably from 2 to 6% by weight, based on the total weight of the respective component.

The composition and / or the film can preferably contain bitter substances. Bitter substances are known to the person skilled in the art and all common bitter substances can be used, e.g. denatonium benzoate, glycosides, isoprenoids, alkaloids, amino acids and mixtures thereof. Denatonium benzoate is particularly preferred.

Preferred bitter agents have a bitter value of at least 1,000, preferably at least 10,000, particularly preferably at least 200,000. The standardized method described in the European Pharmacopoeia (5th edition, Grundwerk, Stuttgart 2005, Volume 1, General Part of Monograph Groups, 2.8.15 Bitter Value, p. 278) is used to determine the bitter value. An aqueous solution of quinine hydrochloride with a bitter value of 200,000 serves as a comparison. This means that 1 gram of quinine hydrochloride makes 200 liters of water bitter. The inter-individual taste differences in the organoleptic test of bitterness are compensated for by a correction factor in this procedure.

To adjust and / or stabilize the pH, the agent according to the invention can contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight, based on the total weight of the respective composition. Buffer substances that are also complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate 2H ₂ O and tripotassium citrate H ₂ O. The citrates are particularly preferably used in component K1.

Suitable acids for pH adjustment are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid, citric acid is most preferred. In addition, however, the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used.

Suitable bases come from the group of the alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal carbonates, of which sodium carbonate is preferred.

In the context of the present invention, individual odoriferous compounds, e.g. synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type can be used as perfume oils or fragrances. However, it is preferred to use mixtures of different fragrances which together produce an appealing fragrance note. Such perfume oils can also contain natural odorant mixtures, such as those obtainable from vegetable sources, e.g. pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

The detergent composition can also contain corrosion inhibitors. (Glass) corrosion inhibitors prevent the appearance of cloudiness, streaks and scratches but also the iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of the magnesium and / or zinc salts and / or magnesium and / or zinc complexes. Carboxylic acids containing phosphonic groups also have an effect as corrosion protection agents. In particular, 2-phosphonobutane-1,2,4-tricarboxylic acids are suitable as additives.

The compositions can preferably also contain dyes. Dyes are known to the person skilled in the art and all customary dyes can be used as long as they do not have a negative interaction with the other constituents of the composition.

It is also useful if active ingredients with an antimicrobial effect are used before and / or after the detergent components of the main wash cycle. The use of active ingredients with an antimicrobial effect in the pre-wash cycle has the advantage that the spread and multiplication of microbes in the main wash cycle is prevented or at least reduced. However, the active ingredient is then washed away with the rinsing solution.

For their antimicrobial effectiveness, e.g., cationic surfactants, in particular with a sulfonium, phosphonium, iodonium or arsonium group, are known.

The products of the Acticide® family from Thor GmbH can preferably be used as suitable antimicrobial active ingredients, preferably in amounts of 0.1 to 3% by weight, in particular 0.1 to 1% by weight, based on the total weight of the respective component.

The components K2 and K4 can also contain at least one thickener, preferably selected from organic thickeners. The at least one thickener is preferably selected from polyacrylate thickeners, xanthan, gellan, guar, alginate, carrageenan, carboxymethyl cellulose, bentonites, welan gum, locust bean gum, agar-agar, tragacanth, gum arabic, pectins, polysaccharides, starch, modified starch, dextrins, Gelatins and casein, modified celluloses, hydroxyethyl ether and hydroxypropyl ether, more preferably selected from xanthan, gellan, guar, alginate, carrageenan, carboxymethyl cellulose, locust bean gum, agar agar, tragacanth, gum arabic, pectins, starch, modified starch, dextrins, gelatins and casein , and modified celluloses, most preferably xanthan gum.

The invention also relates to the use of the multi-component cleaning agent according to the invention for removing soiling, especially tea, creme brulee and minced meat, most preferably tea, on objects to be cleaned, especially dishes, when cleaning in automatic dishwashers.

• - Bereitstellen eines Mehrkomponenten-Reinigungsmittels gemäß einem der Ansprüche 1 bis 12 in einer automatischen Geschirrspülmaschine;
• - Auflösen der Folie durch in Kontakt bringen mit Wasser;
• - In Kontakt bringen der zu reinigenden Gegenstände, insbesondere des Geschirrs, mit den Komponenten K1, K2 und gegebenenfalls K3 und K4.

The invention also relates to a method for cleaning objects, in particular dishes, in automatic dishwashers, which comprises the following steps:

• - Providing a multi-component cleaning agent according to one of claims 1 to 12 in an automatic dishwasher;
• - Dissolve the film by bringing it into contact with water;
• Bringing the objects to be cleaned, in particular the dishes, into contact with components K1, K2 and possibly K3 and K4.

All aspects described herein in the context of the components as such are also applicable to the uses and methods described.

Examples

Several components K1 to K4 were produced and their cleaning performance was determined as part of a multi-component cleaning agent (pouch). Component K1: suspension with percarbonate and citrate (dosage 26g) A1 A2 A3 A4 Wt% Wt% Wt% Wt% Glycerine (99.5%) 65.3 65.3 67.3 63.5 Xanthan gum 2.0 2.0 2.0 2.0 Percarbonate (Oxyper SCM (Solvay)) 5.6 - 3.1 7.3 Percarbonate (Ecox C (Kemira)) - 5.6 - - soda 7.3 7.3 8.3 7.5 Sodium citrate 11.5 11.5 11.5 11.0 TAED 2.2 2.2 2.0 2.5 HEDP (Cublen 8514GR) 5.2 5.2 5.2 5.2 Bleach catalyst (Mn-based) 0.8 0.8 0.5 0.9 dye 0.1 0.1 0.1 0.1 Component K2: Enzyme-containing gel (dosage 3.5g) B1 B2 B3 Wt% Wt% Wt% 1,2 propylene glycol 77.3 - 38.6 Glycerin - 77.3 38.7 water 14.5 14.5 14.5 Sorbitol (70%) 7.0 7.0 7.0 Preservative (Acticide SR 1500) 0.1 0.1 0.1 Protease (% by weight of active enzyme) 1.0 1.0 1.0 Amylase (% by weight of active enzyme) 0.1 0.1 0.1 Component K3: Builder phase (dosage 7.6g) C1 C2 C3 C4 Wt% Wt% Wt% Wt% Noverite AD 810G (88% polyacrylate-39) - 20th 10 20th MGDA (40%, Trilon M Max, BASF) 80 - 40 80 GLDA (47%, Dissolvine GL 47S, Akzo) - 80 40 - Acusol 590 (DOW) 20th - 10 - Component K4: rinse aid phase (dosage 3.0g) D1 D2 D3 Wt% Wt% Wt% Nonionic surfactant, ethoxylated and buthoxylated - 40 30th Dehypon Wet (BASF) 100 - 10 1,2 propylene glycol - 50 50 water - 10 10

Cleaning performance in automatic dishwashing

The formulation A1, B1, C1 and D1 were used in the indicated dosages per wash cycle. The cleaning performance on dishes with various types of soiling (IKW) was tested in a Miele GSL 2 with the KL55 program at a water hardness of 8 ° dH. The evaluation was carried out visually according to IKW (scale 1-10, the higher the value, the better the performance). Tea Assam Tee Bob creme brulee Minced meat egg yolk Strength Recipe A1 + B 1 + C1 + D1 10.0 10.0 7.8 7.7 6.0 7.3

The table shows that the formulation according to the invention shows a particular performance, particularly with stubborn tea stains.

QUOTES INCLUDED IN THE DESCRIPTION

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

Non-patent literature cited

• Subtilases: Subtilisin-like Proteases ”by R. Siezen, pages 75-95 in“ Subtilisin enzymes ”, edited by R. Bott and C. Betzel, New York, 199 [0087]
• A. G. Gornall, C. S. Bardawill and M.M. David, J. Biol. Chem., 177 (1948), pp. 751-766 [0090]
• M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913 [0090]

Claims (14)

Multi-component cleaning agent, which is contained in a container with two to eight chambers, comprising at least two components, wherein a liquid component K1 with a viscosity of more than 10,000 mPas is present in a first chamber; and in a second chamber a liquid or solid second component, which is different from K1, is present, wherein the first component K1 comprises at least one percarbonate; the container wall of the first chamber consists of a water-soluble film and has micro-perforations; and the container wall of the second chamber consists of a water-soluble film, which optionally has micro-perforations. Multi-component cleaning agent according to Claim 1 , wherein the container is a single serving. Multi-component cleaning agent according to one of the preceding claims, wherein the water-soluble film is based on at least one polymer which is derived from polyvinyl alcohol. Multi-component cleaning agent according to one of the preceding claims, wherein the second component contains at least one enzyme. Multi-component cleaning agent according to one of the preceding claims, wherein the at least one enzyme is contained in the second component in 0.05 to 2.5% by weight based on the total weight of the second component. A multicomponent cleaning agent according to any preceding claim, further comprising a third component in a third chamber which at least one builder; and or at least one co-builder; and or at least one further additive selected from corrosion inhibitors, foam inhibitors, enzyme stabilizers, protease inhibitors, dyes, fragrances, organic solvents, antimicrobial agents or dispersants; includes or consists of, and the container wall of the third chamber consists of a water-soluble film, which optionally has micro-perforations. A multicomponent cleaning agent according to any preceding claim, further comprising a fourth component in a fourth chamber which at least one surfactant; and or at least one organic solvent; and or at least one further additive selected from buffer substances, corrosion inhibitors, foam inhibitors, enzyme stabilizers, protease inhibitors, dyes, fragrances, antimicrobial agents, or acids and bases for pH adjustment; and or Comprises or consists of water; and the container wall of the fourth chamber consists of a water-soluble film, which optionally has micro-perforations. A multicomponent detergent according to any preceding claim, wherein the second component is a gel. Multi-component cleaning agent according to one of the preceding claims, wherein the at least one percarbonate in component K1 is contained in 0.1 to 15.0% by weight, based on the total weight of component K1. Multi-component cleaning agent according to one of the preceding claims, wherein component K1 further comprises at least one organic solvent; and / or at least one thickener; and / or at least one citrate; and / or at least one bleach catalyst; and / or at least one bleach activator; and or at least one phosphonate; and / or at least one further additive selected from corrosion inhibitors, foam inhibitors, enzyme stabilizers, protease inhibitors, colorants, fragrances or antimicrobial agents. Multi-component cleaning agent according to one of the preceding claims, characterized in that the multi-component cleaning agent contains a bitter substance, the bitter substance is preferably contained in one of the first to fourth components, if present, and / or in the respective film. A multicomponent detergent according to any preceding claim, wherein the second component further comprises at least one organic solvent; and or at least one (polysaccharide; and / or at least one further additive selected from buffer substances, corrosion inhibitors, foam inhibitors, enzyme stabilizers, colorants, fragrances, antimicrobial active ingredients, or acids and bases for pH adjustment. Use of the multi-component cleaning agent according to one of the Claims 1 to 12th for removing dirt from objects to be cleaned when cleaning in automatic dishwashers. A method for cleaning objects in automatic dishwashers, comprising the following steps: providing a multi-component cleaning agent according to one of the Claims 1 to 12th in an automatic dishwasher; - Dissolve the film by bringing it into contact with water; - Bringing the objects to be cleaned into contact with the first and second components and optionally the third and fourth components.