DE102009046222A1 - Machine dishwashing or machine textile washing, comprises dosing a partial quantity of liquid cleaning agent preparation from a cartridge into the inner space of the dishwasher or textile washing machine - Google Patents

Abstract

Machine dishwashing or machine textile washing using a supplied form of a cleaning agent comprising (a) a liquid cleaning agent preparation A containing at least one bleach activator and at least one builder, and (b) a liquid cleaning agent preparation D containing at least one oxygen bleaching agent, comprises dosing a partial quantity of (a), and (d) of the cleaning agent preparations A and D, respectively from a cartridge located preferably in the inner space of the dishwasher or the textile washing machine into the inner space of the dishwasher or textile washing machine. Machine dishwashing or machine textile washing using a supplied form of a cleaning agent comprising (a) a liquid cleaning agent preparation A, containing at least one bleach activator and at least one builder, and (b) a liquid cleaning agent preparation D, containing at least one oxygen bleaching agent, comprises dosing a partial quantity (a), and (d) of the cleaning agent preparations A and D, respectively from a cartridge located preferably in the inner space of the dishwasher or the textile washing machine into the inner space of the dishwasher or the textile washing machine. A residual quantity of the cleaning agent preparations A and D present in the cartridge remains in the cartridge until the end of the dishwashing or the textile washing method, and the residual quantity corresponds to at least double, preferably at least four times or at least eight times the partial quantity (a) and (d), respectively. An independent claim is also included for the supplied form of cleaning agent for use in the method mentioned above liquid, comprising (a) the liquid cleaning agent preparation A, containing at least one builder, and (b) the liquid cleaning agent preparation D, containing at least one oxygen bleaching agent. The cleaning agent preparations A and D are present separately in a common cartridge.

Description

The present application describes automatic dishwashing processes, in particular automatic dishwashing processes using bleach-containing detergents.

The make-up and supply forms of detergents and cleaners are subject to continuously changing requirements. For some time now, the main focus has been on the convenient dosing of detergents and cleaners by the consumer and the simplification of the work steps necessary to carry out a washing or cleaning process.

In this context, dosing systems for the multiple dosing of detergents and cleaners in particular have come into the focus of attention of the product developers in recent times. In these devices, it is possible to distinguish between dosing systems integrated in the dishwasher or textile washing machine on the one hand and independent and mobile dosing systems independent of the dishwasher or textile washing machine on the other hand. By means of these metering systems, which contain the multiple of the amount of detergent necessary for carrying out a single cleaning process, detergent or cleaning agent portions are metered into the interior of the cleaning machine by means of a metering device from a cartridge in an automatic or semi-automatic manner in the course of several successive cleaning processes. For the consumer eliminates the need for repeated manual dosing of detergents and cleaners. Examples of such devices are disclosed in the European patent applications EP 1 759 624 A2 (Reckitt Benckiser) and EP 1 976 970 A1 (Reckitt Benckiser) or in the German patent application DE 10 2005 062 479 A1 (BSH Bosch and Siemens Hausgeräte GmbH).

Regardless of the exact type of dosing used in the interior of dishwashers or textile washing machines contained in these devices for multi-dosing detergents or cleaning agents are exposed over a longer period of time in particular changing temperatures, these temperatures in about the water temperatures used to carry out the washing or cleaning process same. These temperatures can reach up to 95 ° C, whereby in the range of machine dishwashing usually only temperatures between 50 and 75 ° C are reached. Accordingly, a washing or cleaning agent contained in a dosing system provided for multiple dosing is repeatedly heated to temperatures well above the temperatures customary for transport and storage in the course of several washing or cleaning processes, temperature-sensitive active substances in particular being able to be affected. The group of these temperature-sensitive washing and cleaning substances include u. a. the bleaches.

The use of bleaching agents to increase the washing and cleaning performance of detergents and cleaners has been established in the art for decades, with oxygen bleaching agents such as perborates and percarbonates in particular being used in the field of machine textile and dishwashing.

The decisive for the end user cleaning effect of bleach used in detergents and cleaners is determined except by the bleach itself to a considerable extent by the nature of the preparation of these bleaches and their stabilization against environmental influences. Bleaching agents are formulated both in solid and in liquid, for example dispersed, form.

The object of the present application was to provide a machine dishwashing process in which a chemically and physically stable bleach-containing detergent preparation is metered by means of a preferably located in the interior of a dishwasher storage device over several rinses. The bleach-containing detergent preparation should be storable without significant loss of activity in the storage device for the duration of several purification processes.

• a) eine vorzugsweise flüssige Reinigungsmittelzubereitung A, enthaltend mindestens einen Bleichaktivator sowie mindestens einen Gerüststoff;
• b) eine vorzugsweise flüssige Reinigungsmittelzubereitung D, enthaltend mindestens ein Sauerstoffbleichmittel;

wobei die Reinigungsmittelzubereitungen A und D im Verlauf des Geschirrspülverfahrens aus einer vorzugsweise im Innenraum der Geschirrspülmaschine befindlichen Kartusche in den Innenraum der Geschirrspülmaschine dosiert werden, dadurch gekennzeichnet, dass

• – eine Teilmenge a der in der Kartusche befindlichen Reinigungsmittelzubereitung A in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in der Kartusche befindlichen Reinigungsmittelzubereitung A bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt und diese Restmenge mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge a entspricht; und
• – eine Teilmenge d der in der Kartusche befindlichen Reinigungsmittelzubereitung D in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in der Kartusche befindlichen Reinigungsmittelzubereitung D bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt und diese Restmenge mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge d entspricht.

A first subject of the present application is a machine dishwashing process using a detergent offer form

• a) a preferably liquid detergent preparation A containing at least one bleach activator and at least one builder;
• b) a preferably liquid detergent composition D containing at least one oxygen bleach;

wherein the detergent preparations A and D in the course of the dishwashing process are metered from a preferably located in the interior of the dishwasher cartridge into the interior of the dishwasher, characterized in that

• A subset a of the cleaning agent preparation A present in the cartridge is metered into the interior of the dishwasher, a residual amount of the cleaning agent preparation A present in the cartridge remaining in the cartridge until the end of the dishwashing process, and this residual amount of at least twice, preferably at least four times and in particular at least eight times the amount of subset a; and
• A subset d of the cleaning agent preparation D present in the cartridge is metered into the interior of the dishwasher, a residual amount of the cleaning agent preparation D present in the cartridge remaining in the cartridge until the end of the dishwashing process and this residual quantity of at least twice, preferably at least four times and in particular at least eight times the amount of subset d.

In addition to the two detergent formulations A and D, the inventive detergent dosage form may comprise one, two or more further detergent preparations, for example a further detergent preparation B. Such a detergent formulation may contain, for example, at least one enzyme preparation. These two, three or more detergent preparations are preferably present in a common cartridge and are separated from one another. Automatic dishwashing processes according to the invention, characterized in that the detergent preparations A and D or A, B and D are present separately from one another in a common cartridge, are preferred. The joint preparation of the detergent preparations in a common cartridge simplifies the preparation and handling of the detergent preparation. If the detergent preparations in the common cartridge are made up in such a way that the separate detergent preparations A and D or A, B and D are adjacent to one another, ie the receiving chamber used for the preparation of the detergent preparations A, B and D has at least one common wall, then this is the case the preparation of the detergent preparations in a common cartridge also suitable to increase the chemical and physical stability of these detergent formulations and to reduce the adverse effect of necessarily occurring temperature fluctuations.

The inventive methods are used in particular for the repeated dosing of detergent preparations from storage containers located in the interior of the dishwasher. Preferred processes according to the invention are characterized in that a subset of the preferably liquid detergent preparations A, D and optionally B before their metering into the interior of the dishwasher for a period of at least two, preferably at least four, more preferably at least eight and in particular at least twelve separate cleaning process in which remains in the storage container located in the dishwasher.

In the context of the present application, completed cleaning processes are referred to as "separate cleaning processes", which furthermore preferably also comprise a pre-wash cycle and / or a final rinse cycle in addition to the main cleaning cycle and which can be selected and triggered, for example, by means of the program switch of the dishwasher. 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 time period between two separate cleaning processes, within which the liquid detergent preparation is metered into the interior of the dishwasher, is at least 20 minutes, preferably at least 60 minutes, more preferably at least 120 minutes.

The detergent dosage form according to the invention and the detergent formulations according to the invention are distinguished by a particular temperature stability. The temperature load of the 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 preferably liquid detergent compositions A and D, or A, B and D 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 detergent composition A according to the invention can of course be realized.

In other words, the preferably liquid detergent preparations A, D and, if appropriate, B in the storage container are heated by the rinsing liquor surrounding this storage container in each of the successive separate cleaning processes. In preferred processes, the preferably liquid detergent preparation A, D and optionally B in the reservoir between the separate cleaning method to temperatures below 30 ° C, preferably below 26 ° C and in particular below 22 ° C from.

With regard to the cleaning action of inventive methods, the metering of the two, three or more detergent preparations at different times in the course of the dishwashing process has proved to be advantageous. In this case, it is particularly preferred to meter the detergent preparation A into the interior (that is to say the interior space) of the dishwasher before the detergent preparation D. Automatic dishwashing processes according to the invention, characterized in that the detergent preparations A and D or A, B and D are metered into the interior of the dishwasher at different times in the course of the dishwashing process, are preferred according to the invention.

• a) eine vorzugsweise flüssige Reinigungsmittelzubereitung A, enthaltend mindestens einen Bleichaktivator sowie mindestens einen Gerüststoff;
• b) optional eine vorzugsweise flüssige Reinigungsmittelzubereitung B, enthaltend mindestens eine Enzym-Zubereitung;
• c) eine vorzugsweise flüssige Reinigungsmittelzubereitung D, enthaltend mindestens ein Sauerstoffbleichmittel;

wobei die Reinigungsmittelzubereitungen A und D sowie optional B im Verlauf des Geschirrspülverfahrens aus einer im Innenraum der Geschirrspülmaschine befindlichen Kartusche in den Innenraum der Geschirrspülmaschine dosiert werden, dadurch gekennzeichnet, dass

• a) zu einem Zeitpunkt t1 eine Teilmenge a der in der Kartusche befindlichen Reinigungsmittelzubereitung A in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in der Kartusche befindlichen Reinigungsmittelzubereitung A bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt und diese Restmenge mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge a entspricht;
• b) optional zu mindestens einem weiteren Zeitpunkt t2 ≠ t1 eine Teilmenge b der in der Kartusche befindlichen Reinigungsmittelzubereitung B in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in der Kartusche befindlichen Reinigungsmittelzubereitung B bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt und diese Restmenge mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge b entspricht;
• c) zu mindestens einem weiteren Zeitpunkt t3 ≠ t2 ≠ t1 eine Teilmenge d der in der Kartusche befindlichen Reinigungsmittelzubereitung D in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in der Kartusche befindlichen Reinigungsmittelzubereitung D bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt und diese Restmenge mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge d entspricht.

This application further claims a machine dishwashing process using a detergent offer form

• a) a preferably liquid detergent preparation A containing at least one bleach activator and at least one builder;
• b) optionally a preferably liquid detergent preparation B containing at least one enzyme preparation;
• c) a preferably liquid detergent composition D containing at least one oxygen bleach;

wherein the detergent preparations A and D and optionally B in the course of the dishwashing process from a cartridge located in the interior of the dishwasher are metered into the interior of the dishwasher, characterized in that

• a) at a time t1, a subset a of the cleaning agent preparation A present in the cartridge is metered into the interior of the dishwasher, leaving a residual amount of the cleaning agent preparation A present in the cartridge in the cartridge until the end of the dishwashing process, and leaving this residual quantity of at least twice, preferably at least four times and in particular at least eight times the amount of subset a;
• b) optionally at least one further time t2 ≠ t1 a subset b of the present in the cartridge detergent formulation B is dosed into the interior of the dishwasher, with a residual amount of detergent contained in the cartridge B remains in the cartridge until the end of the dishwashing process and this Residual amount of at least twice, preferably at least four times and in particular at least eight times the amount of subset b corresponds;
• c) at least one further time t3 ≠ t2 ≠ t1 a portion d of the present in the cartridge detergent composition D is dosed into the interior of the dishwasher, with a residual amount of detergent present in the cartridge D remains in the cartridge until the end of the dishwashing process and this residual amount corresponds to at least twice, preferably at least four times, and in particular at least eight times, the amount of subset d.

In preferred embodiments of the above-described automatic dishwashing processes with time-delayed metering of the detergent preparations A and D or A, B and D, the time t3 is at least 1 minute, preferably at least 2 minutes and in particular between 3 and 20 minutes after the time t2.

The detergent formulations used in the automatic dishwashing process according to the invention are preferably liquid. As an essential solvent, these preparations preferably contain water. The water content of the detergent preparation B, based on its total weight, preferably between 2 and 50 wt .-%, preferably between 4 and 40 wt .-% and in particular between 5 and 35 wt .-%. The water content of the detergent preparation D is preferably higher and, based on its total weight, is preferably 50 to 99.9% by weight, preferably between 70 and 99% by weight and in particular between 80 and 98% by weight.

The addition of water to the detergent preparations A, B and D not only facilitates their dosage, the water content also accelerates the release of cleaning-active ingredients in the cleaning liquor.

The term "water content" includes the total amount of water contained in the compositions of the invention, which is composed of the free water contained in the agents and the above the washing and cleaning active ingredients in bound form in the detergent formulations registered water. The water content can be determined, for example, as loss on drying or according to Karl Fischer.

Detergent preparation A contains at least one bleach activator as an essential ingredient. The bleach activators preferably used can be assigned to different groups of substances. A first group includes the bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline 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.

It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (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 ] (ClO ₄ ) 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 ).

Detergent formulations A, which comprises a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably 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 particularly preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.

in der R¹⁰ und R¹¹ unabhängig voneinander für Wasserstoff, eine C_1-18-Alkylgruppe, eine Gruppe -NR¹³R¹⁴, eine Gruppe -N⁺R¹³R¹⁴R¹⁵ oder eine Gruppe

In a further preferred embodiment, the bleach-enhancing transition metal complex compound corresponds to the general formula (II),

in R ¹⁰ and R ¹¹ independently of one another represent hydrogen, a C _1-18 -alkyl group, a group -NR ¹³ R ¹⁴ , a group -N ⁺ R ¹³ R ¹⁴ R ¹⁵ or a group

R ^{12 is} hydrogen, -OH, or a C _1-18 alkyl group, R ¹³ , R ¹⁴ and R ^{15 are} independently hydrogen, a C _1-4 alkyl or hydroxyalkyl group and X is halogen and A is a charge-balancing anion ligands, which depending on its charge and the type and number of other charges, in particular the charge of the manganese central atom, also missing or may be present several times. Manganese can have the oxidation state II, III, IV or V therein as well as in the complexes according to formula (I). If desired, though less preferred, other transition metals such as Fe, Co, Ni, V, Ru, Ti, Mo, W, Cu and / or Cr may be present in such complex compounds instead of the Mn central atom.

Preferred automatic dishwashing processes according to the invention are characterized in that the detergent preparation A contains at least one bleach activator from the group of transition metal catalysts, wherein the weight fraction of the bleach activator in the total weight of the detergent composition A is preferably 0.001 to 2.0 wt .-%, preferably 0.001 to 1.0 Wt .-% and in particular 0.001 to 0.5 wt .-% is.

As a second essential component, the detergent preparation A contains at least one builder. The proportion by weight of the builder in the total weight of the detergent preparation A is preferably 15 to 60 wt .-%, particularly preferably 20 to 50 wt .-%.

According to the present application, 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 detergent formulations A according to the invention of from 15 to 60% by weight is distributed over 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. Automatic dishwashing process, characterized in that the detergent preparation A contains a complexing agent, preferably a complexing agent from the group of ethylenediamine disuccinic acid and its salts, the phosphonates and the polycarboxylates, are preferred according to the invention.

Useful organic complexing agents are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or 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. In addition to their builder effect, 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. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here. Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates.

With particular preference, the detergent formulations A according to the invention contain methylglycinediacetic acid or a salt of methylglycinediacetic acid.

Other useful 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.

A second important organic chelating agent is ethylenediamine disuccinic acid (EDDS), preferred detergent formulations A being characterized by having from 2.0 to 20% by weight, preferably 2.0 to 10% by weight, based on their total weight, and in particular Contain 2.0 to 8.0 wt .-% Ethylenediamindibernsteinsäure. Ethylenediamine disuccinic acid has been found to be particularly effective in non-phosphate detergent formulations as being particularly effective in terms of dough cleaning in automatic dishwashing.

The term "ethylenediamine disuccinic acid" (EDDS) includes not only the free acids but also their salts, for example their sodium or potassium salts. With regard to the weight fraction of ethylenediamine disuccinic acid used in the compositions according to the invention, it is necessary, when using the acid salt, to adjust to the proportion by weight of the free acid, that is to say to convert it from the proportion by weight of the salt to the proportion by weight of the acid.

Alternatively or in addition to EDDS, the detergent formulations A according to the invention may finally contain metyhglycinediacetic acid (MGDA). 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. In a particularly preferred embodiment, the methylglycinediacetic acid is in the form of an alkali metal salt.

The methylglycinediacetic acid can be replaced in the machine dishwashing detergents according to the invention by other alkylglycinediacetic acids of the general formula MOOC-CHR-N (CH ₂ COOM) ₂ (R =H or C _2-12 alkyl; M independently of one another H or alkali metal); However, methylglycinediacetic acid is also preferred for reasons of cost.

The complex-forming phosphonates form a group of other organic complexing agents used with preference in the detergent compositions A according to the invention, this group comprising a number of different compounds such as diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) in addition to 1-hydroxyethane-1,1-diphosphonic acid. 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.

Particular preference is given to using 1-hydroxyethane-1,1-diphosphonic acid (HEDP). The proportion by weight of the phosphonates, preferably of the HEDP, in the total weight of detergent formulations A according to the invention is preferably from 0.5 to 20% by weight, preferably from 2.0 to 18% by weight and in particular from 4.0 to 14% by weight.

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 inventive detergent compositions A contain, based on their total weight, 1.0 to 30 wt .-%, preferably 2.0 to 25 wt .-% and in particular 5.0 to 20 wt .-% builder (s) from the group of alkali carriers.

Particularly preferred is the use of (hydrogen) carbonate (s), preferably alkali (hydrogen) carbonate (s), particularly preferably sodium (hydrogen) carbonate or potassium (hydrogen) carbonate in amounts of 1.0 to 40 wt .-%, preferably 2 , 0 to 30 wt .-% and in particular 4.0 to 15 wt .-% based on the total weight of the detergent composition A.

To increase or adjust the alkalinity, preferred detergent formulations A of the invention comprise alkali metal hydroxide (s). The alkali metal hydroxides are in the cleaning agents preferably in amounts between 2.0 and 22 wt .-%, preferably between 4.0 and 20 wt .-% and in particular between 8.0 and 18 wt .-%, each based on the total weight of Detergent used. With particular preference, the detergent compositions A according to the invention comprise potassium hydroxide.

The detergent formulations A, B and D according to the invention, in particular the detergent composition A, may contain further builders in addition to the builders described above. An example of suitable builders are the phosphates, which can be used in the detergent compositions, in particular the detergent composition A, preferably in the form of alkali metal phosphates with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate).

Particularly preferred phosphates according to the invention are the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate).

Detergent formulations A, B and D which are preferred according to the invention contain less than 10% by weight, more preferably less than 5% by weight and in particular less than 2% by weight, of phosphate. Phosphate-free detergent preparations A, B and D are very particularly preferred according to the invention. Preference is furthermore given to detergent compositions A, B and D 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 dishwasher 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 in addition to the homo- and copolymeric 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 formulations A according to the invention is preferably 1.0 to 30% by weight, preferably 2.0 to 25% by weight and in particular 5.0 to 20% by weight.

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.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 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, besides sulfonic acid group-containing monomer (s), at least one monomer selected from the group consisting of unsaturated carboxylic acids.

Unsaturated carboxylic acid (s) used are, with particular preference, unsaturated carboxylic acids of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.

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

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

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 salts.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, d. H. 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. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.

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

• i) Carbonsäuregruppen-haltige Monomer(e)
• ii) Sulfonsäuregruppen-haltige Monomer(e)
• iii) nichtionische Monomer(e).

enthält, werden erfindungsgemäß bevorzugt.A machine detergent composition A containing, as an anionic copolymer, a copolymer

• i) carboxylic acid group-containing monomer (s)
• ii) sulfonic acid group-containing monomer (s)
• iii) nonionic monomer (s).

contains are preferred according to the invention.

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

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1, 3,5-dimethylhexene-1, 4,4-dimehtylhexane-1, ethylcyclohexyn, 1-octene, α-olefins having 10 or more carbon atoms, such as 1- Decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, α-methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4- Benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N- (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, octyl acrylate, octyl acrylate, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, methacrylic acid stearyl ester, N- (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate and N- (behenyl) acrylamide or mixtures thereof.

The weight fraction of cleaning-active anionic sulfonic acid group-containing polymers in the total weight of detergent compositions A according to the invention is preferably 1.0 to 30% by weight, preferably 2.0 to 25% by weight and in particular 5.0 to 20% by weight.

The composition of some preferred liquid detergent formulations according to the invention can be found in the following Table 1. These detergent combinations are particularly suitable for use in a method according to the invention. 1 2 3 4 Detergent preparation A: wt .-% based on the detergent composition A bleach catalyst 0.001 to 2.0 0.001 to 2.0 0.001 to 1.0 0.001 to 0.5 EDDS 2.0 to 20 2.0 to 20 2.0 to 10 2.0 to 8.0 phosphonate 0.5 to 20 2.0 to 18 2.0 to 18 4.0 to 14 (Hydrogen) carbonate 0 to 20 1.0 to 40 2.0 to 30 4.0 to 15 alkali hydroxide 0 to 22 1.0 to 22 4.0 to 20 8.0 to 18 Anionic polymer 0 to 30 1.0 to 30 2.0 to 25 5.0 to 20 water 30 to 80 35 to 75 35 to 75 40 to 70 Misc add 100 add 100 add 100 add 100 Detergent preparation D:% by weight, based on the detergent preparation D Oxygen bleaches Yes Yes Yes Yes Misc add 100 add 100 add 100 add 100

The detergent composition D contains as an essential ingredient at least one oxygen bleach. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.

It is particularly preferable to use hydrogen peroxide as the oxygen bleaching agent. Machine dishwashing process, characterized in that the cleaning agent preparation D contains oxygen peroxide as hydrogen peroxide, wherein the weight fraction of the hydrogen peroxide in the total weight of the detergent composition D preferably between 0.1 and 50 wt .-%, preferably between 0.2 and 35 wt .-%, especially is preferably between 0.5 and 20% by weight and in particular between 1.0 and 10% by weight, are preferred according to the invention. Very particularly preferred is the use of an aqueous hydrogen peroxide solution as detergent preparation D.

In a preferred embodiment, the oxygen bleach-containing detergent composition D is stabilized by the addition of tin compounds, phosphates, di- or triphosphates, phosphonates or radical scavengers.

Preferred detergent compositions D contain, based on their total weight, 10 ppm to 1.0 wt .-%, preferably 20 ppm to 1000 ppm (0.1 wt .-%) and in particular 50 ppm to 500 ppm of a stabilizer from the group of stannates , The preparation of this stannate can be carried out, for example, in situ by hydrolysis of a tin compound, for example tin sulfate, sodium stannate (Na ₂ SnO ₃ .3H ₂ O), tin dichloride or tin tetrachloride. Although it is believed that the stannate stabilizer is colloidal tin oxide, it is still referred to as colloidal sodium stannate or sodium stannate.

In addition to or as an alternative to the stannates, preferred detergent formulations D contain at least one stabilizer from the group of phosphonates. Particularly suitable here are the complex-forming phosphonates mentioned below, preference being given to 1-hydroxyethane-1,1-diphosphonate (HEDP), aminotrimethylenephosphonic acid (ATMP) and diethylenetriaminepentamethylenephosphonate (DTPMP).

In addition to or as an alternative to the stannates and phosphonates, preferred detergent formulations D comprise at least one stabilizer from the group of phosphates, preferably pyrophosphates such as Na ₄ P ₂ O ₇ , Na ₃ HP ₂ O ₇ , HA ₂ H ₂ P ₂ O ₇ and K ₂ H ₂ P ₂ O. ₇

• a) eine vorzugsweise flüssige Reinigungsmittelzubereitung A, enthaltend mindestens einen Gerüststoff sowie mindestens einen Bleichaktivator, vorzugsweise einen Bleichaktivator aus der Gruppe der Übergangsmetallkatalysatoren, wobei der Gewichtsanteil des Bleichaktivators am Gesamtgewicht der Reinigungsmittelzubereitung a vorzugsweise 0,001 bis 2,0 Gew.-%, bevorzugt 0,001 bis 1,0 Gew.-% und insbesondere 0,001 bis 0,5 Gew.-% beträgt;
• b) eine vorzugsweise flüssige Reinigungsmittelzubereitung D, enthaltend mindestens ein Sauerstoffbleichmittel, vorzugsweise Wasserstoffperoxid, wobei der Gewichtsanteil des Wasserstoffperoxids am Gesamtgewicht der Reinigungsmittelzubereitung D vorzugsweise zwischen 0,1 und 50 Gew.-%, bevorzugt zwischen 0,2 und 35 Gew.-%, besonders bevorzugt zwischen 0,5 und 20 Gew.-% und insbesondere zwischen 1,0 und 10 Gew.-% beträgt,

dadurch gekennzeichnet, dass die Reinigungsmittelzubereitungen B und D voneinander getrennt in einer gemeinsamen Kartusche vorliegen.A further subject matter of the present application is thus a detergent dosage form for use in a method according to the invention, comprising

• a) a preferably liquid detergent formulation A comprising at least one builder and at least one bleach activator, preferably a bleach activator from the group of transition metal catalysts, wherein the weight fraction of the bleach activator in the total weight of the detergent composition a preferably 0.001 to 2.0 wt .-%, preferably 0.001 to 1.0 wt .-% and in particular 0.001 to 0.5 wt .-% is;
• b) a preferably liquid detergent preparation D containing at least one oxygen bleach, preferably hydrogen peroxide, wherein the weight fraction of the hydrogen peroxide in the total weight of the detergent composition D is preferably between 0.1 and 50 wt .-%, preferably between 0.2 and 35 wt .-%, more preferably between 0.5 and 20% by weight and in particular between 1.0 and 10% by weight,

characterized in that the detergent formulations B and D are present separately from each other in a common cartridge.

• * 1,2 Propylenglycol

The composition of some preferred liquid detergent formulations according to the invention can be found in the following Table 2. These detergent combinations are particularly suitable for use in a method according to the invention. 1 2 3 4 Detergent preparation A: wt .-% based on the detergent composition A bleach catalyst 0.001 to 2.0 0.001 to 2.0 0.001 to 1.0 0.001 to 0.5 EDDS 2.0 to 20 2.0 to 20 2.0 to 10 2.0 to 8.0 phosphonate 0.5 to 20 2.0 to 18 2.0 to 18 4.0 to 14 (Hydrogen) carbonate 0 to 20 1.0 to 40 2.0 to 30 4.0 to 15 alkali hydroxide 0 to 22 1.0 to 22 4.0 to 20 8.0 to 18 Anionic polymer 0 to 30 1.0 to 30 2.0 to 25 5.0 to 20 water 30 to 80 35 to 75 35 to 75 40 to 70 Misc add 100 add 100 add 100 add 100 Detergent preparation D:% by weight, based on the detergent preparation D hydrogen peroxide 0.1 to 50 0.2 to 35 0.5 to 20 1.0 to 10 phosphonate 0 to 10 0 to 10 0 to 10 0 to 5.0 water 50 to 99 50 to 99 50 to 99 50 to 99 Misc add 100 add 100 add 100 add 100

• * 1,2 propylene glycol

• – eine Teilmenge b der in der Kartusche befindlichen Reinigungsmittelzubereitung B in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in der Kartusche befindlichen Reinigungsmittelzubereitung B bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt und diese Restmenge mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge b entspricht; und

werden erfindungsgemäß bevorzugt.In preferred automatic dishwashing processes according to the invention, the detergent preparations A and D are used in combination with at least one further detergent preparation B. This detergent composition B is preferably enzyme-containing. Corresponding automatic dishwashing process according to the invention, characterized in that the detergent product form comprises, in addition to the detergent compositions A and D, a further, preferably liquid detergent composition B containing at least one enzyme preparation, wherein the detergent composition B during the dishwashing process consists of a cartridge located in the interior of the dishwasher be metered into the interior of the dishwasher, characterized in that

• A subset b of the cleaning agent preparation B present in the cartridge is metered into the interior of the dishwasher, a residual amount of the cleaning agent preparation B present in the cartridge remaining in the cartridge until the end of the dishwashing process and this residual amount of at least twice, preferably at least four times and in particular at least eight times the amount of subset b; and

are preferred according to the invention.

By using an enzyme-containing detergent preparation B, the cleaning performance achieved in the process according to the invention can be further improved. This applies in particular to those preferred process variants in which the dosing of the detergent preparations A and D, or A, B and D, as described above, takes place with a time delay.

As an essential ingredient, preferably used detergent compositions B contain at least one cleaning-active enzyme preparation. The proportion by weight of the cleaning-active enzyme preparation (s) in the total weight of the detergent preparation B is preferably from 10 to 60% by weight, preferably from 20 to 55% by weight and in particular from 30 to 55% by weight. As cleaning-active enzyme preparations in particular cleaning-active enzyme preparation from the group amylase, protease and lipase preparations are used.

The enzymes used with particular preference include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. 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.

According to the invention preferred liquid detergent formulations B contain, based on their total weight, 0.1 to 30 wt .-%, preferably 1.0 to 25 wt .-% and in particular 2.0 to 20 wt .-% cellulase preparations.

Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease P892, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.

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

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

According to the invention preferred liquid detergent formulations B contain, based on their total weight, 0.1 to 30 wt .-%, preferably 1.0 to 25 wt .-% and in particular 2.0 to 20 wt .-% Amylase preparations. Detergent preparations A which, based on their total weight, contain 4.0 to 16% by weight of amylase preparations are particularly preferred.

Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations. Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.

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

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

Furthermore, enzymes can be used, which are summarized by 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 be used according to the invention to increase the bleaching effect. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

Preferably, a plurality of enzymes and / or enzyme preparations, preferably liquid protease preparations and / or amylase preparations and / or lipase preparations are used.

A second preferred constituent of the detergent composition B used according to the invention is the cumene sulfonate. For the cumene sulfonates, the para-isopropylbenzenesulfonate is the preferred compound.

Surprisingly, the cumene sulfonate has been found to be superior not only to solvents such as glycerol, triacetin or diethylene glycol but also to hydrotropes such as xylenesulfonate in terms of its stabilizing properties.

Preferred detergent formulations B according to the invention are characterized in that these detergent preparations contain the cumene sulphonate in amounts of from 0.5 to 60% by weight, preferably in amounts of from 1.0 to 50% by weight, preferably in amounts of from 2.0 to 40% by weight .-% and in particular in quantities between 5.0 and 30 Gew. -%, in each case related to the total weight of the cleaning agent preparations, contained. Particularly preferred are proportions by weight of the cumene sulfonate in the total weight of the detergent composition B between 2.0 and 20 wt .-%, preferably between 3.0 and 18 wt .-% and in particular between 4.0 and 15 wt .-%.

Another preferred constituent of the detergent formulations B used according to the invention is an organic solvent. Preferred organic solvents are selected from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers. The solvents are preferably selected from ethanol, n- or i-propanol, butanol, glycol, propane- or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, di -ethylenglykolethylether, Propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures this solvent. The proportion by weight of these organic solvents in the total weight of detergent formulations B according to the invention is preferably from 5 to 80% by weight, preferably from 8 to 60% by weight and in particular from 10 to 50% by weight.

A particularly preferred organic solvent which is particularly effective in stabilizing the detergent formulation is 1,2-propylene glycol. The proportion by weight of 1,2 propylene glycol in the total weight of the detergent compositions B according to the invention can vary within wide limits, however, such preparations have proven to be particularly stable, containing an organic solvent, preferably 1,2 propylene glycol, wherein the proportion by weight of 1,2 propylene glycol , in each case based on the total weight of the detergent formulations, preferably 5 to 80 wt .-%, preferably 8 to 60 wt .-% and in particular 10 to 50 wt .-% is.

Another preferred constituent of the detergent formulations B according to the invention is the boric acid or a boric acid derivative. In addition to the boric acid are preferably used in particular the boronic acids or their salts or esters, including especially derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic, in particular 4-formylphenyl-boronic acid (4-FPBA), or the Salts or esters of the compounds mentioned. The proportion by weight of boric acid or of boric acid derivatives in the total weight of detergent formulations B according to the invention is preferably between 0.001 to 10% by weight, preferably 0.002 to 6% by weight and in particular 0.05 to 3% by weight.

A particularly preferred boric acid derivative which is particularly effective with respect to the stabilization of the detergent preparation B is 4-formylphenylboronic acid. The proportion by weight of 4-formylphenylboronic acid in the total weight of the detergent compositions B according to the invention can vary within wide limits, but such preparations have proved to be particularly stable, which, based on the total weight of the detergent composition B, 0.001 to 10 wt .-%, preferably 0.002 to 6 wt .-% and in particular 0.05 to 3 wt .-%. Corresponding preparations are therefore preferred according to the invention.

A further preferred constituent of the detergent composition B according to the invention is Ca or Mg ion source. The proportion by weight of the Ca or Mg ion source in the total weight of detergent formulations B according to the invention is preferably between 0.01 to 10% by weight, preferably 0.2 to 8% by weight and in particular 0.5 to 5% by weight.

As particularly preferred and with respect to the stabilization of the detergent preparation B particularly effective Ca ion sources, the organic calcium salts have been found. The proportion by weight of the organic calcium salts in the total weight of the detergent compositions B according to the invention can vary within wide limits, but such preparations have proven to be particularly stable, based on the total weight of the detergent preparation, 0.01 to 10 wt .-%, preferably 0.2 to 8 wt .-% and in particular 0.5 to 5 wt .-%. Corresponding preparations are therefore preferred according to the invention. Detergent formulations B most preferably contain calcium lactate.

• * 1,2 Propylenglycol

1 2 3 4 Reinigungsmittelzubereitung A: Gew.-% bezogen auf die Reinigungsmittelzubereitung A Bleichkatalysator 0,001 bis 2,0 0,001 bis 2,0 0,001 bis 1,0 0,001 bis 0,5 EDDS 2,0 bis 20 2,0 bis 20 2,0 bis 10 2,0 bis 8,0 Phosphonat 0,5 bis 20 2,0 bis 18 2,0 bis 18 4,0 bis 14 (Hydrogen)carbonat 0 bis 20 1,0 bis 40 2,0 bis 30 4,0 bis 15 Alkalihydroxid 0 bis 22 1,0 bis 22 4,0 bis 20 8,0 bis 18 Anionisches Polymer 0 bis 30 1,0 bis 30 2,0 bis 25 5,0 bis 20 Wasser 30 bis 80 35 bis 75 35 bis 75 40 bis 70 Misc add 100 add 100 add 100 add 100 Reinigungsmittelzubereitung B: Gew.-% bezogen auf die Reinigungsmittelzubereitung B Enzymzubereitung 10 bis 60 10 bis 60 30 bis 55 30 bis 55 Org. Lösungsmittel 0 bis 80 5,0 bis 80 8,0 bis 60 10 bis 50* Cumolsulfonat 0 bis 20 2,0 bis 20 3,0 bis 18 4,0 bis 15 Misc add 100 add 100 add 100 add 100 Reinigungsmittelzubereitung D: Gew.-% bezogen auf die Reinigungsmittelzubereitung D Wasserstoffperoxid 0,1 bis 50 0,2 bis 35 0,5 bis 20 1,0 bis 10 Phosphonat 0 bis 10 0 bis 10 0 bis 10 0 bis 5,0 Wasser 50 bis 99 50 bis 99 50 bis 99 50 bis 99 Misc add 100 add 100 add 100 add 100

• * 1,2 Propylenglycol

The composition of some preferred liquid detergent formulations according to the invention can be seen in the following Tables 3 and 4. These detergent combinations are particularly suitable for use in a method according to the invention. 1 2 3 4 Detergent preparation A: wt .-% based on the detergent composition A bleach catalyst 0.001 to 2.0 0.001 to 2.0 0.001 to 1.0 0.001 to 0.5 EDDS 2.0 to 20 2.0 to 20 2.0 to 10 2.0 to 8.0 phosphonate 0.5 to 20 2.0 to 18 2.0 to 18 4.0 to 14 (Hydrogen) carbonate 0 to 20 1.0 to 40 2.0 to 30 4.0 to 15 alkali hydroxide 0 to 22 1.0 to 22 4.0 to 20 8.0 to 18 Anionic polymer 0 to 30 1.0 to 30 2.0 to 25 5.0 to 20 water 30 to 80 35 to 75 35 to 75 40 to 70 Misc add 100 add 100 add 100 add 100 Detergent preparation B:% by weight, based on the detergent preparation B enzyme preparation 10 to 60 10 to 60 30 to 55 30 to 55 Org. Solvent 0 to 80 5.0 to 80 8.0 to 60 10 to 50 * Misc add 100 add 100 add 100 add 100 Detergent preparation D:% by weight, based on the detergent preparation D Oxygen bleaches Yes Yes Yes Yes Misc add 100 add 100 add 100 add 100

• * 1,2 propylene glycol

1 2 3 4 Detergent preparation A: wt .-% based on the detergent composition A bleach catalyst 0.001 to 2.0 0.001 to 2.0 0.001 to 1.0 0.001 to 0.5 EDDS 2.0 to 20 2.0 to 20 2.0 to 10 2.0 to 8.0 phosphonate 0.5 to 20 2.0 to 18 2.0 to 18 4.0 to 14 (Hydrogen) carbonate 0 to 20 1.0 to 40 2.0 to 30 4.0 to 15 alkali hydroxide 0 to 22 1.0 to 22 4.0 to 20 8.0 to 18 Anionic polymer 0 to 30 1.0 to 30 2.0 to 25 5.0 to 20 water 30 to 80 35 to 75 35 to 75 40 to 70 Misc add 100 add 100 add 100 add 100 Detergent preparation B:% by weight, based on the detergent preparation B enzyme preparation 10 to 60 10 to 60 30 to 55 30 to 55 Org. Solvent 0 to 80 5.0 to 80 8.0 to 60 10 to 50 * cumene 0 to 20 2.0 to 20 3.0 to 18 4.0 to 15 Misc add 100 add 100 add 100 add 100 Detergent preparation D:% by weight, based on the detergent preparation D hydrogen peroxide 0.1 to 50 0.2 to 35 0.5 to 20 1.0 to 10 phosphonate 0 to 10 0 to 10 0 to 10 0 to 5.0 water 50 to 99 50 to 99 50 to 99 50 to 99 Misc add 100 add 100 add 100 add 100

• * 1,2 propylene glycol

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

bevorzugt sind.Finally, another preferred constituent of the detergent compositions B according to the invention are the nonionic surfactants, nonionic surfactants of the general formula R ^{1 is} -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A''O) _y - (A '''O) _z -R ² , in the

• R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• - A, A ', A''andA''' are independently a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ),
• - w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0

are preferred.

The weight fraction of these nonionic surfactants in preferred liquid detergent formulations B, based on the total weight of the detergent composition B, is 0.5 to 30% by weight, preferably 2.0 to 25% by weight and in particular 5.0 to 20% by weight. %.

By the addition of the abovementioned nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A''O) _y - (A '''O) _z - R ² , hereinafter also referred to as "hydroxymix ether", surprisingly, the cleaning performance of enzyme-containing preparations according to the invention can be significantly improved both in comparison to surfactant-free system and in comparison to systems containing alternative nonionic surfactants, for example from the group polyalkoxylated fatty alcohols.

By using these nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals, the stability of the enzymes contained in the detergent or cleaning agent preparations according to the invention can be markedly improved.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Particularly preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15. The group of these nonionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ - (EO) _15-40 -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ - (EO) ₂₂ -2 -hydroxydecylether.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value x ≥ 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1 such that the above formula is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH ) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

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

Finally, the nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ^{2 have} proved to be particularly effective, in which

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

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

• * 1,2 Propylenglycol

1 2 3 4 Reinigungsmittelzubereitung A: Gew.-% bezogen auf die Reinigungsmittelzubereitung A Bleichkatalysator 0,001 bis 2,0 0,001 bis 2,0 0,001 bis 1,0 0,001 bis 0,5 EDDS 2,0 bis 20 2,0 bis 20 2,0 bis 10 2,0 bis 8,0 Phosphonat 0,5 bis 20 2,0 bis 18 2,0 bis 18 4,0 bis 14 (Hydrogen)carbonat 0 bis 20 1,0 bis 40 2,0 bis 30 4,0 bis 15 Alkalihydroxid 0 bis 22 1,0 bis 22 4,0 bis 20 8,0 bis 18 Anionisches Polymer 0 bis 30 1,0 bis 30 2,0 bis 25 5,0 bis 20 Wasser 30 bis 80 35 bis 75 35 bis 75 40 bis 70 Misc add 100 add 100 add 100 add 100 Reinigungsmittelzubereitung B: Gew.-% bezogen auf die Reinigungsmittelzubereitung B Enzymzubereitung 10 bis 60 10 bis 60 30 bis 55 30 bis 55 Nichtionisches Tensid 0 bis 30 0,5 bis 30 2,0 bis 25 5,0 bis 20 Org. Lösungsmittel 0 bis 80 5,0 bis 80 8,0 bis 60 10 bis 50 Cumolsulfonat 0 bis 20 2,0 bis 20 3,0 bis 18 4,0 bis 15 Misc add 100 add 100 add 100 add 100 Reinigungsmittelzubereitung D: Gew.-% bezogen auf die Reinigungsmittelzubereitung D Sauerstoffbleichmittel ja ja ja ja Misc add 100 add 100 add 100 add 100

• * 1,2 Propylenglycol

1 2 3 4 Reinigungsmittelzubereitung A: Gew.-% bezogen auf die Reinigungsmittelzubereitung A Bleichkatalysator 0,001 bis 2,0 0,001 bis 2,0 0,001 bis 1,0 0,001 bis 0,5 EDDS 2,0 bis 20 2,0 bis 20 2,0 bis 10 2,0 bis 8,0 Phosphonat 0,5 bis 20 2,0 bis 18 2,0 bis 18 4,0 bis 14 (Hydrogen)carbonat 0 bis 20 1,0 bis 40 2,0 bis 30 4,0 bis 15 Alkalihydroxid 0 bis 22 1,0 bis 22 4,0 bis 20 8,0 bis 18 Anionisches Polymer 0 bis 30 1,0 bis 30 2,0 bis 25 5,0 bis 20 Wasser 30 bis 80 35 bis 75 35 bis 75 40 bis 70 Misc add 100 add 100 add 100 add 100 Reinigungsmittelzubereitung B: Gew.-% bezogen auf die Reinigungsmittelzubereitung B Enzymzubereitung 10 bis 60 10 bis 60 30 bis 55 30 bis 55 Nichtionisches Tensid 0 bis 30 0,5 bis 30 2,0 bis 25 5,0 bis 20 Org. Lösungsmittel 0 bis 80 5,0 bis 80 8,0 bis 60 10 bis 50* Cumolsulfonat 0 bis 20 2,0 bis 20 3,0 bis 18 4,0 bis 15 Misc add 100 add 100 add 100 add 100 Reinigungsmittelzubereitung D: Gew.-% bezogen auf die Reinigungsmittelzubereitung D Wasserstoffperoxid 0,1 bis 50 0,2 bis 35 0,5 bis 20 1,0 bis 10 Phosphonat 0 bis 10 0 bis 10 0 bis 10 0 bis 5,0 Wasser 50 bis 99 50 bis 99 50 bis 99 50 bis 99 Misc add 100 add 100 add 100 add 100

• * 1,2 Propylenglycol

The composition of some preferred liquid detergent formulations according to the invention can be found in the following Table 5 to 7. These detergent combinations are particularly suitable for use in a method according to the invention. 1 2 3 4 Detergent preparation A: wt .-% based on the detergent composition A bleach catalyst 0.001 to 2.0 0.001 to 2.0 0.001 to 1.0 0.001 to 0.5 builder 15 to 60 15 to 60 15 to 55 15 to 55 water 30 to 80 35 to 75 35 to 75 40 to 70 Misc add 100 add 100 add 100 add 100 Detergent preparation B:% by weight, based on the detergent preparation B enzyme preparation Yes Yes Yes Yes Nonionic surfactant 0 to 30 0.5 to 30 2.0 to 25 5.0 to 20 Org. Solvent 0 to 80 5.0 to 80 8.0 to 60 10 to 50 * cumene 0 to 20 2.0 to 20 3.0 to 18 4.0 to 15 Misc add 100 add 100 add 100 add 100 Detergent preparation D:% by weight, based on the detergent preparation D Oxygen bleaches Yes Yes Yes Yes Misc add 100 add 100 add 100 add 100

• * 1,2 propylene glycol

1 2 3 4 Detergent preparation A: wt .-% based on the detergent composition A bleach catalyst 0.001 to 2.0 0.001 to 2.0 0.001 to 1.0 0.001 to 0.5 EDDS 2.0 to 20 2.0 to 20 2.0 to 10 2.0 to 8.0 phosphonate 0.5 to 20 2.0 to 18 2.0 to 18 4.0 to 14 (Hydrogen) carbonate 0 to 20 1.0 to 40 2.0 to 30 4.0 to 15 alkali hydroxide 0 to 22 1.0 to 22 4.0 to 20 8.0 to 18 Anionic polymer 0 to 30 1.0 to 30 2.0 to 25 5.0 to 20 water 30 to 80 35 to 75 35 to 75 40 to 70 Misc add 100 add 100 add 100 add 100 Detergent preparation B:% by weight, based on the detergent preparation B enzyme preparation 10 to 60 10 to 60 30 to 55 30 to 55 Nonionic surfactant 0 to 30 0.5 to 30 2.0 to 25 5.0 to 20 Org. Solvent 0 to 80 5.0 to 80 8.0 to 60 10 to 50 cumene 0 to 20 2.0 to 20 3.0 to 18 4.0 to 15 Misc add 100 add 100 add 100 add 100 Detergent preparation D:% by weight, based on the detergent preparation D Oxygen bleaches Yes Yes Yes Yes Misc add 100 add 100 add 100 add 100

• * 1,2 propylene glycol

1 2 3 4 Detergent preparation A: wt .-% based on the detergent composition A bleach catalyst 0.001 to 2.0 0.001 to 2.0 0.001 to 1.0 0.001 to 0.5 EDDS 2.0 to 20 2.0 to 20 2.0 to 10 2.0 to 8.0 phosphonate 0.5 to 20 2.0 to 18 2.0 to 18 4.0 to 14 (Hydrogen) carbonate 0 to 20 1.0 to 40 2.0 to 30 4.0 to 15 alkali hydroxide 0 to 22 1.0 to 22 4.0 to 20 8.0 to 18 Anionic polymer 0 to 30 1.0 to 30 2.0 to 25 5.0 to 20 water 30 to 80 35 to 75 35 to 75 40 to 70 Misc add 100 add 100 add 100 add 100 Detergent preparation B:% by weight, based on the detergent preparation B enzyme preparation 10 to 60 10 to 60 30 to 55 30 to 55 Nonionic surfactant 0 to 30 0.5 to 30 2.0 to 25 5.0 to 20 Org. Solvent 0 to 80 5.0 to 80 8.0 to 60 10 to 50 * cumene 0 to 20 2.0 to 20 3.0 to 18 4.0 to 15 Misc add 100 add 100 add 100 add 100 Detergent preparation D:% by weight, based on the detergent preparation D hydrogen peroxide 0.1 to 50 0.2 to 35 0.5 to 20 1.0 to 10 phosphonate 0 to 10 0 to 10 0 to 10 0 to 5.0 water 50 to 99 50 to 99 50 to 99 50 to 99 Misc add 100 add 100 add 100 add 100

• * 1,2 propylene glycol

In addition to the above-described ingredients such as enzymes, solvents and nonionic surfactants from the group of hydroxy mixed ethers, detergent compositions B according to the invention can contain further ingredients, for example active ingredients from the group of builders, bleaches, detergents and cleaners, corrosion inhibitors, scent agents. or dyes. In contrast to customary detergents or cleaners, however, preferred detergent formulations B according to the invention contain these other ingredients only to a minor extent.

Particular preference is given according to the invention to those cleaning agent preparations B which contain less than 20% by weight, preferably less than 10% by weight and in particular less than 5% by weight. Contain builders. Particularly preferred are those detergent formulations B which are free of builders.

Preference is furthermore given to detergent formulations B which comprise less than 10% by weight, preferably less than 5% by weight and in particular less than 2% by weight, of bleaching agent. Particularly preferred are those detergent formulations B which are free of bleaching agents.

The automatic dishwashing formulations B used in the process according to the invention are preferably of low alkalinity, their pH (20 ° C.) is preferably between 6.5 and 8.5, and in particular between 7 and 8. The pH (20 ° C.) of the Machine detergent D is preferably between 4.0 and 7.0, preferably between 5.0 and 6.0. The pH values (20 ° C.) of the dishwashing formulations B and D preferably differ by no more than 3.0 units, preferably not more than 2.0 units.

Despite the low alkalinity of the detergent formulations used, the compositions of the invention are characterized by a very good cleaning performance. This is all the more surprising since an alkaline cleaning liquor is considered to be an essential basis for the cleaning result in automatic dishwashing processes.

The detergent formulations A, B and D differ in their composition, so they are not identical.

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 Konfektionsformen are cartridges with two, three, four or more separate receiving chambers, for example, two-, three-, four- or multi-chamber bottles. By separating the detergent of different composition unwanted reactions due to chemical incompatibility can be excluded.

The dosage of the detergent compositions according to the invention is preferably carried out by means of a special metering system. In a preferred embodiment, the previously described cartridges of the detergent product forms are provided with a dispenser detachable from the cartridge. Such a dosing device 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.

Alternatively, 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.

• a) optional eine vorzugsweise flüssige Reinigungsmittelzubereitung A, enthaltend mindestens einen Gerüststoff, in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
• b) eine vorzugsweise flüssige Reinigungsmittelzubereitung B, enthaltend mindestens einen Bleichaktivator; in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
• c) eine vorzugsweise flüssige Reinigungsmittelzubereitung D, enthaltend mindestens ein Sauerstoffbleichmittel; in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;

b) eine Kartusche für die Reinigungsmittelzubereitungen, in welcher die Reinigungsmittelzubereitungen in voneinander getrennten Aufnahmekammern vorliegen;
c) ein mit der Kartusche verbundenes oder verbindbares Dosiergerät.A further subject of the present application is a detergent dosing system comprising

• a) optionally a preferably liquid detergent composition A containing at least one builder, in an amount sufficient for at least twice, preferably at least four times, and in particular at least eight times, to carry out a machine dishwashing process;
• b) a preferably liquid detergent preparation B containing at least one bleach activator; in an amount sufficient for the at least twice, preferably at least four and in particular at least eight times, carrying out a machine dishwashing process;
• c) a preferably liquid detergent composition D containing at least one oxygen bleach; in an amount sufficient for the at least twice, preferably at least four and in particular at least eight times, carrying out a machine dishwashing process;

b) a cartridge for the detergent preparations, in which the detergent formulations are present in separate receiving chambers;
c) a metering device connected or connectable to the cartridge.

The cartridge and the dosing device are preferably releasably connected to each other, however, can also be connected to each other inseparable.

The vorgenanten Reinigungsmitteldosiersysteme comprising detergent compositions according to the invention, a cartridge and a releasably or permanently connected to the cartridge dosing device are in a preferred embodiment in a common outer packaging, the filled cartridge and the dosing are particularly preferably separated from each other contained in the outer packaging. The outer packaging is used for storage, transport and presentation of the invention Reinigungsmitteangebotsform 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.

As an alternative or in addition to an outer packaging, it is of course possible to market the detergent dispensing forms according to the invention in conjunction with a dishwasher. Such a combination is particularly advantageous in cases in which the course of the automatic dishwashing process (eg duration, temperature profile, water supply) and the detergent formulation or the control electronics of the dosing device are matched to one another.

The metering system according to the invention consists of the basic components of a Reinigungsmittelangebotsform invention and a kuppelbarem with the cartridge metering device, which in turn is formed of other components, such as component carrier, actuator, closure element, sensor, power source and / or control unit.

It is preferred that 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, laundry dryer or the like, but can be removed, for example, from a dishwasher by the user or positioned in a dishwasher, ie independently handled, is an alternative embodiment of the invention, it is also conceivable that the metering device for the user is not detachably connected to a water-bearing device such as a dishwasher, washing machine, dryer or the like and only the cartridge is movable.

For the purposes of this application, 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.

In particular, 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.

In a further embodiment of the invention, the cartridge is integrally formed. In this way, 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.

Further, it is conceivable that 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. Thus, 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. In particular, the fixation by one or more of the types of compounds from the group of snap-in compounds, Velcro, press joints, fusions, glued joints, welded joints, solder joints, screw, wedge, clamp or bounce joints can be done. In particular, 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.

To provide advantageous residual emptying characteristics of the chambers, the bottom of the chambers may be funnel-shaped inclined towards the discharge opening. Furthermore, 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. In a two-chamber configuration, the ratio of container volumes is preferably 5: 1, preferably 5: 1: 1 for a three-chamber configuration, these configurations being particularly suitable for use in dishwashers.

The cartridge usually has a filling volume of <5,000 ml, in particular <2,000 ml, preferably between 10 and 1,500 ml, preferably between 50 and 900 ml, and in particular between 250 and 800 ml.

The cartridge can take on any spatial form. It can for example be cube-shaped, spherical or plate-like.

Usually, commercial household dishwashers are designed in such a way that the arrangement of larger items to be washed, such as pans or large plates, is provided in the lower basket of the dishwasher. In order to avoid a non-optimal positioning of the metering by the user in the upper basket, 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. For this purpose, 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.

However, it is also conceivable to form the metering unit in cup shape with a substantially circular or square base.

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

Preferably, 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.

It is particularly preferred that 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.

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

In an advantageous further development of the invention, in each case a second interface on the dosing device and the water-conducting device, such as a dishwasher, for transmitting electromagnetic signals, in particular Betriebszustandands-, measuring and / or control information of the dosing and / or the water-bearing device such as Dishwasher represent trained.

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. However, 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 "build-in" 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. However, it is also conceivable that 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.

As stated at the outset, the detergent product forms according to the invention are distinguished by a particular physical and chemical stability, in particular with respect to temperature fluctuations. The detergent supply forms according to the invention are thus exceptionally suitable for the metering by means of a metering system located in the interior of a dishwasher. Such a metering system, which can be immovably integrated into the interior of the dishwasher (machine-integrated dosing) but of course as a movable device in the interior can be introduced (self-sufficient dosing), contains the multiple required to carry out a machine cleaning process amount of detergent.

Movable in the sense of this application means that the dispensing and dosing system is not permanently connected to a device such as a dishwasher, washing machine, laundry dryer or the like, but can be removed, for example, from a dishwasher or positioned in a dishwasher.

In summary, both the detergent combinations according to the invention and the detergent dosage forms according to the invention are suitable as refill packs for dosing devices that are immovably integrated into the interior of a dishwashing machine and for movable dosing devices provided for positioning in the interior of a dishwashing machine.

• i) ein unbeweglich in den Innenraum einer Geschirrspülmaschine integriertes Dosiergerät oder
• ii) ein für die Positionierung im Innenraum einer Geschirrspülmaschine vorgesehenes bewegliches Dosiergerät.

ist ebenfalls Gegenstand dieser Anmeldung.The use of a Reinigungsmittelangebotsform invention as a cleaning agent reservoir for

• i) a metering device that is immovably integrated into the interior of a dishwasher or
• ii) a provided for positioning in the interior of a dishwasher movable metering device.

is also the subject of this application.

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

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been 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.

Cited patent literature

• EP 1759624 A2 [0003]
• EP 1976970 A1 [0003]
• DE 102005062479 A1 [0003]

Claims (10)

A machine dishwashing process using a detergent dosage form comprising a) a preferably liquid detergent preparation A comprising at least one bleach activator and at least one builder; b) a preferably liquid detergent composition D containing at least one oxygen bleach; wherein the detergent preparations A and D in the course of the dishwashing process are metered from a preferably located in the interior of the dishwasher cartridge in the interior of the dishwasher, characterized in that - a portion a of the present in the cartridge detergent formulation A is dosed into the interior of the dishwasher, wherein a residual amount of the cleaning agent preparation A present in the cartridge remains in the cartridge until the end of the dishwashing process and this residual amount corresponds to at least twice, preferably at least four times, and in particular at least eight times, the quantity of the subset a; and - a subset d of the present in the cartridge detergent formulation D is dosed into the interior of the dishwasher, with a residual amount of detergent contained in the cartridge D remains until the end of dishwashing in the cartridge and this residual amount of at least twice, preferably at least four times and in particular at least eight times the amount of subset d. A machine dishwashing process according to claim 1, characterized in that the detergent preparation A contains at least one bleach activator from the group of transition metal catalysts, wherein the weight fraction of the bleach activator in the total weight of the detergent composition A preferably 0.001 to 2.0 wt .-%, preferably 0.001 to 1.0 Wt .-% and in particular 0.001 to 0.5 wt .-% is. Machine dishwashing process according to one of the preceding claims, characterized in that the detergent preparation A contains a complexing agent, preferably a complexing agent from the group of ethylenediamine disuccinic acid and its salts, the phosphonates and the polycarboxylates. Machine dishwashing process according to one of the preceding claims, characterized in that the detergent composition D contains oxygen peroxide as hydrogen peroxide, wherein the weight fraction of the hydrogen peroxide in the total weight of the detergent composition D preferably between 0.1 and 50 wt .-%, preferably between 0.2 and 35 wt .-%, more preferably between 0.5 and 20 wt .-% and in particular between 1.0 and 10 wt .-% is. Machine dishwashing process according to one of the preceding claims, characterized in that the detergent supply form comprises a further, preferably liquid detergent preparation B containing at least one enzyme preparation, wherein the detergent preparation B in the course of the dishwashing process from a cartridge located in the interior of the dishwasher in the interior the dishwasher be dosed, characterized in that A subset b of the cleaning agent preparation B present in the cartridge is metered into the interior of the dishwasher, a residual amount of the cleaning agent preparation B present in the cartridge remaining in the cartridge until the end of the dishwashing process and this residual amount of at least twice, preferably at least four times and in particular at least eight times the amount of subset b; and Machine dishwashing process according to one of the preceding claims, characterized in that the cleaning agent preparation B contains at least one cleaning-active enzyme preparation from the group of amylase, protease and lipase preparations, wherein the weight fraction of the enzyme preparation (s) in the total weight of the detergent composition B is preferably 10 to 60 wt .-%, preferably 20 to 55 wt .-% and in particular 30 to 55 wt .-% is; A machine dishwashing process according to one of the preceding claims, characterized in that the detergent preparations A and D or A, B and D are present separately from one another in a common cartridge. A machine dishwashing process according to one of the preceding claims, characterized in that the detergent preparations A and D or A, B and D are metered into the interior of the dishwasher at different times in the course of the dishwashing process. A detergent dosage form for use in a method according to any one of claims 1 to 8, comprising a) a preferably liquid detergent preparation A comprising at least one builder and at least one bleach activator, preferably a bleach activator from the group of transition metal catalysts, wherein the weight fraction of the bleach activator on the total weight of the detergent composition A is preferably from 0.001 to 2.0% by weight, preferably from 0.001 to 1.0% by weight and in particular from 0.001 to 0.5% by weight; b) a preferably liquid detergent preparation D containing at least one oxygen bleach, preferably hydrogen peroxide, wherein the weight fraction of the hydrogen peroxide in the total weight of the detergent composition D is preferably between 0.1 and 50 wt .-%, preferably between 0.2 and 35 wt .-%, particularly preferably between 0.5 and 20 wt .-% and in particular between 1.0 and 10 wt .-%, characterized in that the detergent compositions A and D are present separately from each other in a common cartridge. Use of a detergent product form according to claim 9 as a detergent reservoir for i) a metering device that is immovably integrated into the interior of a dishwasher or ii) a provided for positioning in the interior of a dishwasher movable metering device.