EP2446013B1 - Automatic dishwashing detergent composition - Google Patents

Description

The present application describes surfactant-containing automatic dishwashing detergents, automatic dishwashing processes using these dishwashing detergents, and the use of these dishwashing detergents in automatic dishwashing processes, in which portions of a machine detergent from a storage container located in the interior of the dishwasher pass into the interior of the dishwasher over several successive cleaning cycles be dosed.

In the evaluation of modern automatic dishwashing detergents, the consumer is not only concerned with the performance aspects of these agents, in particular their cleaning and rinsing performance, but also with their handling properties.

One of the major objectives of the machine cleaners manufacturers is to improve the cleaning and rinse performance of these compositions, with more emphasis being placed recently on the cleaning and rinse performance in low temperature or reduced water consumption cleaning cycles.

Typical types of dishwashing detergent, in addition to the traditional liquid dishwashing detergents, include, in particular, the automatic dishwashing detergents marketed predominantly in solid form, which are obtainable, for example, as powders or as tablets. However, these known clothing and supply forms are subject to new changes. For some time now, the main focus has been on the simplified dosing of automatic dishwashing detergents.

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

Regardless of the exact type of dosing used in the interior of dishwashers or textile washing machines contained in these devices for multidose washing or cleaning agents are exposed over a longer period of time, in particular changing temperatures, these temperatures used in a first approximation to those used to carry out the washing or cleaning process Same water temperatures. 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 device provided for multiple dosing is repeatedly heated in the course of several washing or cleaning processes to temperatures well above the temperatures customary for transport and storage, with temperature-sensitive active substances in particular being affected. The group of these temperature-sensitive washing and cleaning-active substances primarily include the washing and cleaning-active enzymes.

To increase the stability of such enzyme-containing liquid detergents or cleaners, a number of different protective measures have been proposed. For example, the German patent application teaches DE 2 038 103 (Henkel ) the stabilization of enzyme-containing dishwashing detergents by sacharides, while in the European patent EP 646 170 B1 (Procter & Gamble) Propylene glycol for enzyme stabilization in liquid detergents is disclosed. Propylene glycol together with hydroxy mixed ethers as nonionic surfactants for the stabilization of enzyme-containing detergents or cleaners is also in DE 10 2007 039 655 A1 (Henkel ) disclosed.

This application was based on the object to provide a machine dishwashing detergent, which is stabilized against phase separation / loss of activity with multiple temperature fluctuations (10 to 75 ° C) and stored in a storage device located in the interior of a dishwasher without significant loss of activity, compared to conventional automatic dishwashing detergent however characterized by an improved performance profile.

This object has been achieved by means of a detergent combination comprising two surfactant-containing preparations, one of which further contains an enzyme in addition to the surfactant.

• eine Reinigungsmittelzubereitung B, enthaltend
  • b1) wenigstens ein nichtionisches Tensid der allgemeinen Formel R¹-CH(OH)CH₂O-(AO)_w-R², in der
    • R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder Alkenylrest steht;
    • R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen steht;
    • A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
    w für Werte zwischen 10 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht; und
  • b2) wenigstens ein reinigungsaktives Enzym;
• eine Klarspülzusammensetzung C, enthaltend
  • c1) wenigstens ein nichtionisches Tensid, der allgemeinen Formel R¹-CH(OH)CH₂O-(AO)_w-R², in der
    • R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder Alkenylrest steht;
    • R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen steht;
    • A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
      w für Werte zwischen 10 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht;

wobei zwischen 30 und 75 Gew.-% der Gesamttensidmenge der Reinigungsmittelkombination in der Reinigungsmittelzubereitung B enthalten sind.A first subject of the present application is therefore a detergent combination for automatic dosing in automatic dishwashing comprising

• a detergent preparation B containing
  • b1) at least one nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ² , in which
    • R ^{1 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 from 2 to 20 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 10 and 120, preferably 10 to 80, in particular 20 to 40; and
  • b2) at least one cleaning-active enzyme;
• a rinse aid composition C containing
  • c1) at least one nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ² in which
    • R ^{1 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 from 2 to 20 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 10 and 120, preferably 10 to 80, in particular 20 to 40;

wherein between 30 and 75 wt .-% of the total amount of surfactant of the detergent combination in the detergent formulation B are included.

• eine Reinigungsmittelzubereitung B, enthaltend
  • b1) wenigstens ein nichtionisches Tensid der allgemeinen Formel R¹-CH(OH)CH₂O-(AO)_w-R², in der
    • R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder Alkenylrest steht;
    • R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen steht;
    • A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
    w für Werte zwischen 10 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht; und
  • b2) wenigstens ein reinigungsaktives Enzym;
• eine Klarspülzusammensetzung C, enthaltend
  • c1) wenigstens ein nichtionisches Tensid, der allgemeinen Formel R¹-CH(OH)CH₂O-(AO)_w-R², in der
    • R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder Alkenylrest steht;
    • R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen steht;
    • A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
      w für Werte zwischen 10 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht;

wobei zwischen 30 und 75 Gew.-% der Gesamttensidmenge der Reinigungsmittelkombination in der Reinigungsmittelzubereitung B enthalten sind und wobei die Reinigungsmittelkombination die zur mindestens zweimaligen, vorzugsweise mindestens viermaligen und insbesondere mindestens achtmaligen Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Mengen der Reinigungsmittel B und C umfasst.The present application describes and claims a detergent combination for automatic dosing in automatic dishwashing. As stated above, the detergent combinations according to the invention for the automatic dosing and for the storage in a metering device in the interior of the automatic dishwasher are provided and necessarily include more than the amount necessary for performing a cleaning cycle amount of the detergent. An object of the claim is therefore in other words one
Detergent combination for automatic dosing in automatic dishwashing, comprising

• a detergent preparation B containing
  • b1) at least one nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ² , in which
    • R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
    • R ² represents a linear or branched hydrocarbon radical having 2 to 20 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 10 and 120, preferably 10 to 80, in particular 20 to 40; and
  • b2) at least one cleaning-active enzyme;
• a rinse aid composition C containing
  • c1) at least one nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ² in which
    • R ^{1 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 from 2 to 20 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 10 and 120, preferably 10 to 80, in particular 20 to 40;

wherein between 30 and 75 wt .-% of the total amount of surfactant of the detergent combination in the detergent composition B are included and wherein the detergent combination comprises at least twice, preferably at least four times and in particular at least eight times performing an automatic dishwashing sufficient amounts of detergent B and C.

In preferred detergent combinations according to the invention, at least one of the detergent preparations B and C, preferably both, is liquid. In addition to water, suitable solvents for these liquid detergent formulations are the organic solvents known to the person skilled in the art, in particular the monohydric or polyhydric alcohols.

• eine flüssige Reinigungsmittelzubereitung B, enthaltend
  • b1) wenigstens ein nichtionisches Tensid der allgemeinen Formel R¹-CH(OH)CH₂O-(AO)_w-R², in der
    • R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder Alkenylrest steht;
    • R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen steht;
    • A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
    w für Werte zwischen 10 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht; und
  • b2) wenigstens ein reinigungsaktives Enzym;
• eine flüssige Klarspülzusammensetzung C, enthaltend
  • c1) wenigstens ein nichtionisches Tensid, der allgemeinen Formel R¹-CH(OH)CH₂O-(AO)_w-R², in der
    • R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder Alkenylrest steht;
    • R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen steht;
    • A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
      w für Werte zwischen 10 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht;

wobei zwischen 30 und 75 Gew.-% der Gesamttensidmenge der Reinigungsmittelkombination in der Reinigungsmittelzubereitung B enthalten sind und wobei die Reinigungsmittelkombination die zur mindestens zweimaligen, vorzugsweise mindestens viermaligen und insbesondere mindestens achtmaligen Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Mengen der Reinigungsmittel B und C umfasst.In other words, a preferred object of the invention is a detergent combination for automatic dosing in automated dishwashing

• a liquid detergent composition B containing
  • b1) at least one nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ² , in which
    • R ^{1 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 from 2 to 20 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 10 and 120, preferably 10 to 80, in particular 20 to 40; and
  • b2) at least one cleaning-active enzyme;
• a liquid rinse aid C containing
  • c1) at least one nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ² in which
    • R ^{1 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 from 2 to 20 carbon atoms;
    • A represents a radical from the group CH ₂ CH _2, -CH ₂ CH ₂ -CH _2, -CH ₂ -CH (CH _3), and
      w stands for values between 10 and 120, preferably 10 to 80, in particular 20 to 40;

wherein between 30 and 75 wt .-% of the total amount of surfactant of the detergent combination in the detergent composition B are included and wherein the detergent combination comprises at least twice, preferably at least four times and in particular at least eight times performing an automatic dishwashing sufficient amounts of detergent B and C.

Both detergent formulation B and detergent formulation C contain nonionic surfactant. Each of detergent formulations B and C may contain one, two or more nonionic surfactant (s). The nonionic surfactants in detergent formulations B and C may be identical or have different chemical structures. The detergent formulations B and C have different compositions from each other, so are not identical.

For the cleaning as for the rinse effect, it has proven to be advantageous if the weight fraction of the nonionic surfactant in the total weight of the detergent composition B between 0.1 and 30 wt .-%, preferably between 1.0 and 25 wt .-%, especially preferably between 2.0 and 20% by weight and in particular between 5.0 and 15% by weight.

With a constant amount of surfactant, such detergent combinations according to the invention have particularly advantageous cleaning and rinsing effects, in which between 30 and 75 wt .-% and in particular between 40 and 70 wt .-% of the total amount of the detergent combination in the detergent composition B is included.

The composition of some exemplary liquid detergent combinations according to the invention, in which between 30 and 75% by weight and in particular between 40 and 70% by weight of the total amount of surfactant of the detergent combination is contained in the detergent composition B, can be taken from the following Table 1: Recipe 1 Recipe 2 B * [% by weight] C ** [% by weight] B * [% by weight] C ** [% by weight] Nonionic surfactant 0.1 to 30 Yes 2.0 to 20 Yes enzyme Yes - *** Yes - *** Misc Add 100 Add 100 Add 100 Add 100 * "B" is in this, as in all following tables as an abbreviation for "detergent preparation B"
** "C" stands in this, as in all following tables as an abbreviation for "detergent preparation C"
*** "-" in this, as in all the following tables, means: the recipe is free of this ingredient

• 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. Diese Tenside haben sich hinsichtlich der angestrebten Verbesserung der Reinigungs- und Klarspülleistung in den erfindungsgemäßen maschinellen Geschirrspülmitteln zur automatischen Dosierung weiteren bekannten nichtionischen Tensiden des Standes der Technik als überlegen erwiesen.An essential constituent of the washing or cleaning agent preparations B and C according to the invention are the nonionic surfactants, 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 in which

• R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ² represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A, A ', A "and A'" independently represent 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. With regard to the desired improvement in the cleaning and rinsing performance in the automatic dishwashing detergents according to the invention, these surfactants have proven to be superior to other known nonionic surfactants of the prior art.

Thus, by the addition of the aforementioned 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 , also referred to as "Hydroxymix ethers", surprisingly, the rinse aid result of inventive enzyme-containing preparations are significantly improved both in comparison to surfactant-free systems as well as in comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

If the abovementioned hydroxy mixed ethers are used both in the detergent formulation B and in the detergent preparation C, in addition to the rinse aid result, it is additionally possible to improve the formation of deposits on surfaces such as glass, plastic or stainless steel. This improvement is detectable over a machine dishwashing detergent containing the same amount of hydroxy mixed ether alone in one of the two detergent formulations B or C.

The use of these nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals can markedly improve the stability of the enzymes contained in the detergent or cleaning agent preparations according to the invention.

Particularly preferred are 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 of one another values between 1 and 32, wherein Nonionic surfactants with R ³ = -CH ₃ and values for x of 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.

• 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 20 Kohlenstoffatomen steht;
• A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
• w für Werte zwischen 10 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 , which according to the invention are contained in the detergent composition B and in the rinse aid composition C, in which

• R ^{1 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 from 2 to 20 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 10 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.

Detergent combination according to the invention, characterized in that a surfactant of the general formula R ¹ CH (OH) CH ₂ O- (CH ₂ CH ₂ O) _10-120 -R ^{2 is} used as the nonionic surfactant in the composition B and / or C, in R ¹ and R ² independently of one another represent a linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms, are preferred according to the invention.

The detergent formulations B of the detergent combinations according to the invention contain as a further essential ingredient at least one washing or cleaning-active enzyme. The weight fraction of the washing or cleaning-active enzyme in the total weight of the detergent preparation B is preferably between 5 and 80% by weight, preferably between 5 and 60% by weight, particularly preferably between 10 and 50% by weight and in particular between 10 and 30 wt .-%.

The composition of some exemplary liquid detergent combinations according to the invention in which between 30 and 75% by weight and in particular between 40 and 70% by weight of the total amount of surfactant of the detergent combination is contained in the detergent composition B can be taken from the following Table 2: Recipe 1 Recipe 2 B [% by weight] C [% by weight] B [% by weight] C [% by weight] Nonionic surfactant 0.1 to 30 Yes 2.0 to 20 Yes Enzyme preparation 5 to 80 - 10 to 30 - Misc Add 100 Add 100 Add 100 Add 100

• R¹ und R² unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, gegebenenfalls hydroxylierten Alkylrest mit 4 bis 22 Kohlenstoffatomen;
• Alk für eine verzweigten oder unverzweigten Alkylrest mit 2 bis 4 Kohlenstoffatomen;
• x und y unabhängig voneinander für Werte zwischen 1 und 70; und
• M für einen Alkylrest aus der Gruppe CH₂, CHR³, CR³R⁴, CH₂CHR³ und CHR³CHR⁴, wobei R³ und R⁴ unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten Alkylrest mit 1 bis 18 Kohlenstoffatomen

steht.
Diese speziellen nichtionischen Tenside werden nachfolgend als Y-Tenside bezeichnet.In a further preferred embodiment, the automatic dishwashing detergent combination according to the invention contains a nonionic surfactant of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ² , in which

• R ¹ and R ² independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms;
• Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms;
• x and y independently represent values between 1 and 70; and
• M is an alkyl radical from the group CH ₂ , CHR ³ , CR ³ R ⁴ , CH ₂ CHR ³ and CHR ³ CHR ⁴ , where R ³ and R ⁴ independently of one another are a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms

stands.
These special nonionic surfactants are referred to below as Y-surfactants.

1. a) das nichtionische Tensid der allgemeinen Formel R¹-CH(OH)CH₂-O(CH₂CH₂O)_xCH₂CHR(OCH₂CH₂)_yO-CH₂CH(OH)-R², in der
   • R, R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen und
   • x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen;
2. b) das nichtionische Tensid der allgemeinen Formel R¹-O(CH₂CH₂O)_xCH₂(OCH₂CH₂)_yO-R², in der
   • R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen und
   • x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen.

Two particularly preferred nonionic surfactants from the group of Y-surfactants are

1. a) the nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₂ CH (OH) -R ² , in of the
   • R, R ¹ and R ² independently represent an alkyl radical or alkenyl radical having 6 to 22 carbon atoms and
   • x and y independently represent values between 1 and 40;
2. b) the nonionic surfactant of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CH ₂ (OCH ₂ CH ₂ ) _y OR ² in which
   • R ¹ and R ² independently represent an alkyl radical or alkenyl radical having 4 to 22 carbon atoms and
   • x and y independently represent values between 1 and 40.

The Y-surfactants may be part of the detergent preparation B and / or the detergent preparation C. Preferably, the use of one or more Y-surfactants in combination with one or more Hydroxymischethern. The combination of hydroxy mixed ether and Y-surfactant has been found to be particularly advantageous in terms of rinse performance. The best rinse results were obtained by adding the Y-surfactants to the detergent composition C, which results could again be increased by addition of hydroxy mixed ethers to the detergent formulation B and C.

• - eine Reinigungsmittelzubereitung B, enthaltend
  • b1) wenigstens ein nichtionisches Tensid der allgemeinen Formel R¹-CH(OH)CH₂O-(AO)_w-R², in der
    • R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder Alkenylrest steht;
    • R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen steht;
    • A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
    w für Werte zwischen 10 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht; und
  • b2) wenigstens ein reinigungsaktives Enzym;
• eine Klarspülzusammensetzung C, enthaltend
  • c1) wenigstens ein nichtionisches Tensid, der allgemeinen Formel R¹-CH(OH)CH₂O-(AO)_w-R², in der
    • R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder Alkenylrest steht;
    • R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen steht;
    • A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
      w für Werte zwischen 10 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht;
  • c2) wenigstens ein nichtionisches Tensid der allgemeinen Formel R¹O(AlkO)_xM(OAlk)_yOR², in der
    • R¹ und R² unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, gegebenenfalls hydroxylierten Alkylrest mit 4 bis 22 Kohlenstoffatomen stehen;
    • Alk für eine verzweigten oder unverzweigten Alkylrest mit 2 bis 4 Kohlenstoffatomen steht;
    • x und y unabhängig voneinander für Werte zwischen 1 und 70 stehen; und
    • M für einen Alkylrest aus der Gruppe CH₂, CHR³, CR³R⁴, CH₂CHR³ und CHR³CHR⁴ steht, wobei R³ und R⁴ unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten Alkylrest mit 1 bis 18 Kohlenstoffatomen stehen,

wobei zwischen 30 und 75 Gew.-% der Gesamttensidmenge der Reinigungsmittelkombination in der Reinigungsmittelzubereitung B enthalten sind. A preferred subject of the present application is therefore a detergent combination for automatic dosing in automatic dishwashing comprising

• a detergent preparation B containing
  • b1) at least one nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ² , in which
    • R ^{1 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 from 2 to 20 carbon atoms;
    • A represents a radical from the group CH ₂ CH _2, -CH ₂ CH ₂ -CH _2, -CH ₂ -CH (CH _3), and
    w stands for values between 10 and 120, preferably 10 to 80, in particular 20 to 40; and
  • b2) at least one cleaning-active enzyme;
• a rinse aid composition C containing
  • c1) at least one nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ² in which
    • R ^{1 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 from 2 to 20 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 10 and 120, preferably 10 to 80, in particular 20 to 40;
  • c2) at least one nonionic surfactant of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ² , in which
    • R ¹ and R ² independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms;
    • Alk is a branched or unbranched alkyl radical having from 2 to 4 carbon atoms;
    • x and y independently represent values between 1 and 70; and
    • M is an alkyl radical selected from the group consisting of CH ₂ , CHR ³ , CR ³ R ⁴ , CH ₂ CHR ³ and CHR ³ CHR ⁴ , where R ³ and R ⁴ independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms,

wherein between 30 and 75 wt .-% of the total amount of surfactant of the detergent combination in the detergent formulation B are included.

The proportion by weight of Y-surfactants in the total weight of the detergent combination according to the invention is preferably 0.2 and 15 wt .-%, preferably between 0.5 and 12 wt .-%, particularly preferably between 1.0 and 8.0 wt .-% and in particular between 2.0 and 6.0% by weight.

The Y-surfactant-containing automatic dishwashing compositions according to the invention preferably have via a softening system, for example at least one sulfonic acid group-containing polymer.

Proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, as well as their mixtures, are among the enzymes used with particular preference in accordance with the invention. 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.

The stabilizing effect according to the invention has been observed to a particular extent with the amylases and the proteases, which is why detergent formulations B according to the invention, which contain a washing- or cleaning-active enzyme from the group of amylases and / or proteases, are preferred.

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

Detergent formulations B preferred according to the invention contain, based on the total weight of the detergent or cleaning preparation B, 5 to 50% by weight, preferably 7 to 40% by weight and in particular 10 to 30% by weight 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, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the abovementioned 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).

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

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.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

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

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. Also usable are 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, several enzymes and / or enzyme preparations, preferably liquid protease preparations and / or amylase preparations are used.

The composition of some exemplary liquid detergent combinations according to the invention in which between 30 and 75% by weight and in particular between 40 and 70% by weight of the total amount of surfactant of the detergent combination is contained in the detergent composition B can be found in the following Table 3: Recipe 1 Recipe 2 B [% by weight] C [% by weight] B [% by weight] C [% by weight] Nonionic surfactant 0.1 to 30 Yes 2.0 to 20 Yes Protease preparation 5.0 to 50 - 10 to 30 - Amylase preparation 0.1 to 30 - 2.0 to 20 - Misc Add 100 Add 100 Add 100 Add 100

As mentioned at the outset, preferred cleaning agent combinations according to the invention comprise at least one liquid cleaning agent preparation, the solvents used, in addition to water, being the organic solvents known to the person skilled in the art, in particular the monohydric or polyhydric alcohols.

The water content of the detergent formulations can be between 10 and 90% by weight, based on their total weight. In a preferred embodiment, in particular the detergent preparation C, based on its total weight, contains water in amounts of between 20 to 90 wt .-%, preferably between 30 and 80 wt .-% and in particular between 40 and 70 wt .-%.

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 in bound form in the washing or cleaning agent formulations registered water. The water content can be determined, for example, as loss on drying or according to Karl Fischer.

Another preferred constituent of the washing or cleaning agent preparations B or C 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 ethylene glycol ethyl ether, 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 of these solvents. The proportion by weight of these organic solvents in the total weight of detergent formulations according to the invention is preferably from 5 to 80% by weight, preferably from 10 to 70% by weight and in particular from 12 to 60% by weight.

An inventively preferred detergent combination is characterized in that the composition B and / or C, based on their total weight, between 5.0 and 80 wt .-%, preferably between 10 and 70 wt .-% and in particular between 12 and 60 wt. - contains% organic solvent (s).

A particularly preferred organic solvent which is particularly effective in stabilizing the enzyme-containing detergent composition B is 1,2-propylene glycol. The proportion by weight of 1,2 propylene glycol in the total weight of the detergent composition 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 composition B, preferably 15 to 80 wt .-%, preferably 30 to 70 wt .-% and in particular 40 to 60 wt .-% is.

The use of liquid detergent preparations or liquid detergent combinations facilitates the repeated automatic dosing of these mixtures of active substances.

The composition of some exemplary liquid detergent combinations according to the invention, in which between 30 and 75% by weight and in particular between 40 and 70% by weight of the total amount of surfactant of the detergent combination is contained in the detergent composition B, can be taken from the following Table 4: Recipe 1 Recipe 2 B [% by weight] C [% by weight] B [% by weight] C [% by weight] Nonionic surfactant 2.0 to 20 Yes 5.0 to 15 Yes Protease preparation 5.0 to 50 - 10 to 30 - Amylase preparation 0.1 to 30 - 2.0 to 20 - Org. Solvent 5.0 to 80 5.0 to 60 12 to 60 12 to 60 water 10 to 70 20 to 80 10 to 40 40 to 70 Misc Add 100 Add 100 Add 100 Add 100

In addition to the above-described ingredients such as enzymes, solvents and nonionic surfactants from the group of hydroxy mixed ethers washing or cleaning compositions B and C according to the invention further ingredients, such as active ingredients from the group of builders, bleach, the washing and cleaning active polymers, the Corrosion inhibitors containing fragrances or dyes. In contrast to customary detergents or cleaners, however, preferred detergent or cleaner formulations B and C according to the invention contain these other ingredients only to a minor extent.

Particularly preferred according to the invention are those detergent preparations B and C which contain less than 20% by weight, preferably less than 10% by weight and in particular less than 5% by weight of builders. Particularly preferred are those detergent preparations B and C which are free of builders.

Preference is furthermore given to detergent formulations B and C which contain 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 and C which are free of bleaching agents.

The composition of some exemplary liquid detergent combinations according to the invention, in which between 30 and 75% by weight and in particular between 40 and 70% by weight of the total amount of surfactant of the detergent combination is contained in the detergent composition B, can be taken from the following Table 5:

Even though the abovementioned further washing- or cleaning-active ingredients are preferably contained only to a minor extent in the detergent combinations according to the invention, ie are directly mixed with these, it is nevertheless desirable to add these further ingredients together with the detergent compositions B and C according to the invention to a detergent assemble. For this purpose, the person skilled in all known to him confection forms for combination products with liquid content, in particular those combination products have been found to be suitable, which allow the joint confection of three, four or more separate liquid preparations.

Detergent combinations according to the invention comprising detergent formulations B and C preferably 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 combinations are very particularly preferred according to the invention. Also preferred are those detergent combinations according to the invention comprising detergent formulations B and C which contain less than 5% by weight, preferably less than 3% by weight and in particular less than 1% by weight, of silicate. Very particularly preferred machine detergent combinations according to the invention are silicate-free. Both the lowering of the phosphate content and the lowering of the silicate content have proved to be advantageous for the stability of the detergent combinations according to the invention.

The detergent combinations according to the invention are characterized by a low formulation complexity despite their high physical and chemical stability. This low level of complexity simplifies the preparation of the detergents and thus reduces the costs involved in providing these detergents.

1. a) eine erfindungsgemäße Reinigungsmittelkombination, umfassend die Reinigungsmittelzubereitungen B und C;
2. b) mindestens eine weitere von B und C verschiedene Reinigungsmittelzubereitung A ist ein weiterer Gegenstand der vorliegenden Anmeldung.

The detergent combinations according to the invention are combined in another embodiment with one or more other cleaning agents.
A detergent combination comprising

1. a) a detergent combination according to the invention, comprising the detergent compositions B and C;
2. b) at least one further cleaning agent preparation A other than B and C is a further subject of the present application.

When combined with the detergent combination according to the invention further detergent composition A is preferably a builder-containing detergent.

The combined with the detergent combination according to the invention further detergent composition A is preferably a liquid detergent.

In the combined with the detergent combination according to the invention further detergent composition A is preferably a bleach and / or phosphate-free detergent.

The combined with the detergent combination according to the invention further detergent composition A is preferably a surfactant-free detergent.

The further cleaning agent preparation A combined with the cleaning agent combination according to the invention is preferably an enzyme-free cleaning agent.

The combined with the detergent combination according to the invention further detergent composition A is particularly preferably a builder-containing, phosphate, bleach, surfactant and enzyme-free, liquid detergent.

The composition of some exemplary liquid detergent combinations according to the invention in which between 30 and 75% by weight and in particular between 40 and 70% by weight of the total amount of surfactant of the detergent combination is contained in the detergent composition B can be found in the following Table 6:

Detergent combinations according to the invention, comprising the detergent compositions A, B and C, preferably contain less than 10% by weight, more preferably less than 5 Wt .-% and in particular less than 2 wt .-% phosphate. Phosphate-free detergent combinations comprising the detergent preparations A, B and C are very particularly preferred according to the invention. Preference is furthermore given to those detergent combinations according to the invention comprising the detergent compositions A, B and C which contain less than 5% by weight, preferably less than 3% by weight and in particular less than 1% by weight, of silicate. Very particularly preferred detergent combinations according to the invention are silicate-free. Both the lowering of the phosphate content and the lowering of the silicate content have proved to be advantageous for the stability of the detergent combinations according to the invention.

The further detergent composition A may contain, for example, washing or cleaning-active substances from the group of builders, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers.

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 inventive detergent formulations of 30 to 90 wt .-% distributed to these three groups of scaffolds.
The group of organic complexing agents includes in particular polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and other organic co-builders such as the phosphonates. These classes of substances are described below.

Useful organic complexing agents are, for example, 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.

Further suitable organic complexing agents are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic complexing agents are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.

Oxydisuccinates and other derivatives of disuccinates, 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. Suitable amounts are from 3 to 15 wt .-%.

With particular preference, the automatic dishwasher detergents 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.

Preferred detergent combinations according to the invention are characterized in that the detergent preparation A, based on their total weight, 5.0 to 60 wt .-%, preferably 10 to 50 wt .-% and in particular 15 to 40 wt .-% builder (s) from the Contains group of organic complex images. Preference is given to contents of organic Complexing agents realized above 25 wt .-%, more preferably above 30 wt .-% and in particular above 35 wt .-%. The upper limit of the content of organic complexing agents is preferably 85% by weight, and more preferably 75% by weight.

Particularly preferred automatic dishwasher detergents according to the invention contain citrate as one of their essential organic complexing agents. Detergent combinations according to the invention, characterized in that the detergent preparation A contains 2.0 to 50 wt .-%, preferably 4.0 to 40 wt .-% and in particular 5.0 to 30 wt .-% citrate, are inventively preferred.

A second important organic chelating agent is ethylenediamine disuccinic acid (EDDS), preferred detergent formulations A being characterized by having from 3.0 to 65% by weight, preferably 5.0 to 60% by weight, based on their total weight, and in particular Contain 10 to 50 wt .-% Ethylenediamindibernsteinsäure. Levels of ethylenediamine disuccinic acid are preferably realized above 12 wt .-%, particularly preferably above 15 wt .-% and in particular above 20 wt .-%. The upper limit of the content of ethylenediamine disuccinic acid is preferably 55% by weight, and more preferably 45% by weight.

Ethylenediamine disuccinic acid has been found to be particularly effective in non-phosphate detergent formulations 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.

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 reacting Sodium salts, e.g. 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.

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

An automatic dishwashing agent preferred in the context of this application contains one or more phosphonate (s) from the group

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

Particularly preferred are automatic dishwashing detergents which contain as phosphonates 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).

Of course, the detergent formulations according to the invention may contain two or more different phosphonates.

The proportion by weight of the phosphonates in the total weight of detergent formulations A according to the invention is preferably from 1 to 8% by weight, preferably from 1.2 to 6% by weight and in particular from 1.5 to 4% 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 detergent combinations according to the invention are characterized in that the detergent preparation A, based on its total weight, 1.0 to 30 wt .-%, preferably 2.0 to 25 wt .-% and in particular 5.0 to 20 wt .-% builder ( e) from the group of alkali carriers

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 according to the invention contain alkali metal hydroxide (s). The alkali metal hydroxides are in the cleaning agents preferably in amounts between 2.0 and 20 wt .-%, preferably between 3.0 and 15 wt .-% and in particular between 4.0 and 12 wt .-%, each based on the total weight of Detergent used. With particular preference, the detergent compositions A according to the invention comprise potassium hydroxide.
Detergent formulations according to the invention preferably 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 are very particularly preferred according to the invention. Preference is furthermore given to detergent compositions according to the invention which contain less than 2% by weight, preferably less than 1% by weight and in particular less than 0.5% by weight, of silicate. Very particularly preferred automatic dishwasher detergents according to the invention are silicate-free. By dispensing with silicate, the physical stability of the automatic dishwashing detergent according to the invention to be metered is surprisingly improved.

The cleaning-active anionic polymers form a third group of the builders contained in the detergent formulations according to the invention.

The cleaning-active anionic polymers may have two, three, four or more different monomer units. The group of these polymers includes, in addition to the homo- and co-polymeric polycarboxylates u.a. also the copolymeric polysulfonates which, in addition to a monomer from the group of unsaturated carboxylic acids, have at least one further monomer from the group of the unsaturated sulfonic acids.

The weight fraction of cleaning-active anionic polymers in the total weight of the detergent composition A is preferably 1.0 to 30 wt .-%, preferably 2.0 to 25 wt .-% and in particular 5.0 to 20 wt .-%.

The polymeric polycarboxylates form a first group of cleaning-active anionic polymers. Examples of such polymers are the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70,000 g / mol.

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

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 C contain, in addition to sulfonic acid-containing (s) monomer (s) at least one monomer from the group of unsaturated carboxylic acids.

As unsaturated carboxylic acid (s) is / are used 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 each other is -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 - 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 ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) 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-propenylsulfonic 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, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group ii) and from 10 to 50% by weight of monomer from group i), in each case based on the polymer.

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

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.

1. i) Carbonsäuregruppen-haltige Monomer(e)
2. ii) Sulfonsäuregruppen-haltige Monomer(e)
3. iii) nichtionische Monomer(e).

enthält, werden erfindungsgemäß bevorzugt.Automatic dishwashing detergent, characterized in that the automatic dishwashing detergent comprises as anionic copolymer a copolymer comprising

1. i) carboxylic acid group-containing monomer (s)
2. ii) sulfonic acid group-containing monomer (s)
3. 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 is an optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or is 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-dimethylhexane-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, Acrylsäurectctyle ster, Methacrylsäureoctylester, N - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, Stearyl acrylate, stearyl methacrylate, N - (stearyl) acrylamide, behenyl acrylate, Methacrylsäurebehenylester and N - (behenyl) acrylamide or mixtures thereof.

• a1) mindestens einen Gerüststoff aus der Gruppe der organischen Komplexbildner
• a2) mindestens einen Gerüststoff aus der Gruppe der reinigungsaktiven Polymere umfasst.

Preferred detergent combination according to the invention are characterized in that the detergent combination contains a further, preferably liquid, cleaning agent A comprising

• a1) at least one builder from the group of organic complexing agents
• a2) comprises at least one builder from the group of cleaning-active polymers.

The preparation of the above-described combination of cleaning agents takes place, for example, by means of a packaging means in which the washing or cleaning agent preparations B and C are present separately from one another. This separation can be achieved for example by separate receiving chambers, each of these receiving chambers containing one of the combined detergent. 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.

1. a) eine erfindungsgemäße Reinigungsmittelkombination in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
2. b) eine Kartusche für die Reinigungsmittelkombination, in der die vorzugsweise flüssigen Reinigungsmittel B und C getrennt voneinander vorliegen. Hierfür eignen sich insbesondere die in den Tabellen 1 bis 5 offenbarten Rezepturen.

A further subject of the present application is a detergent dosage form for automatic dosing in automatic dishwashing comprising

1. a) a combination of detergents according to the invention in an amount sufficient for at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process;
2. b) a cartridge for the detergent combination, in which the preferably liquid detergent B and C are present separately. Particularly suitable for this purpose are the formulations disclosed in Tables 1 to 5.

1. a) eine Reinigungsmittelkombination, umfassend
   • eine Reinigungsmittelzubereitung A, enthaltend
     • a1) wenigstens einen Gerüststoff aus der Gruppe der organischen Komplexbildner
   • eine Reinigungsmittelzubereitung B, enthaltend
     • b1) wenigstens ein nichtionisches Tensid der allgemeinen Formel R¹ -CH(OH)CH₂O-(AO)_w-R², in der
   • R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder Alkenylrest steht;
   • R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen steht;
   • A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
   • w für Werte zwischen 10 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht; und
     • b2) wenigstens ein reinigungsaktives Enzym;
   • eine Klarspülzusammensetzung C, enthaltend
     • c1) wenigstens ein nichtionisches Tensid, der allgemeinen Formel R1-CH(OH)CH2O-(AO)w-R2, in der
   • R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C₆-₂₄-Alkyl- oder -Alkenylrest steht;
   • R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen steht;
   • A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
   • w für Werte zwischen 10 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht;
   wobei zwischen 30 und 75 Gew.-% der Gesamttensidmenge der Reinigungsmittelkombination in der Reinigungsmittelzubereitung B enthalten sind
   in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
2. b) eine Kartusche für die Reinigungsmittelkombination, in der die vorzugsweise flüssigen Reinigungsmittel A, B und C getrennt voneinander vorliegen.

Hierfür eignen sich insbesondere die in den Tabellen 1 bis 6 offenbarten Rezepturen.Another preferred subject of the present application is a detergent dosage form for automatic dosing in automatic dishwashing comprising

1. a) a detergent combination comprising
   • a detergent preparation A containing
     • a1) at least one builder from the group of organic complexing agents
   • a detergent preparation B containing
     • b1) at least one nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ² in which
   • R ^{1 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 from 2 to 20 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 10 and 120, preferably 10 to 80, in particular 20 to 40; and
     • b2) at least one cleaning-active enzyme;
   • a rinse aid composition C containing
     • c1) at least one nonionic surfactant of the general formula R1-CH (OH) CH2O- (AO) w-R2, in the
   • R ¹ is a linear or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;
   • R ^{2 is} a linear or branched hydrocarbon radical having from 2 to 20 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 10 and 120, preferably 10 to 80, in particular 20 to 40;
   wherein between 30 and 75 wt .-% of the total amount of surfactant of the detergent combination in the detergent formulation B are included
   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;
2. b) a cartridge for the detergent combination in which the preferably liquid detergents A, B and C are present separately.

Particularly suitable for this purpose are the formulations disclosed in Tables 1 to 6.

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.

1. a) eine erfindungsgemäße Reinigungsmittelkombination in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
2. b) eine Kartusche für die Reinigungsmittelkombination, in der die vorzugsweise flüssigen Reinigungsmittel B und C getrennt voneinander vorliegen;
3. c) ein mit der Kartusche lösbar verbundenes Dosiergerät.

Hierfür eignen sich insbesondere die in den Tabellen 1 bis 5 offenbarten Rezepturen.A further subject of the present application is a detergent dosing system for automatic dosing in automatic dishwashing, comprising

1. a) a combination of detergents according to the invention in an amount sufficient for at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process;
2. b) a cartridge for the detergent combination, in which the preferably liquid detergent B and C are present separately from each other;
3. c) a dispenser detachably connected to the cartridge.

Particularly suitable for this purpose are the formulations disclosed in Tables 1 to 5.

1. a) eine Reinigungsmittelkombination, umfassend
   • eine Reinigungsmittelzubereitung A, enthaltend
     • a1) wenigstens einen Gerüststoff aus der Gruppe der organischen Komplexbildner
   • eine Reinigungsmittelzubereitung B, enthaltend
     • b1) wenigstens ein nichtionisches Tensid der allgemeinen Formel R¹ -CH(OH)CH₂O-(AO)_w-R², in der
   • R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder Alkenylrest steht;
   • R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen steht;
   • A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
   • w für Werte zwischen 10 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht; und
     • b2) wenigstens ein reinigungsaktives Enzym;
   • eine Klarspülzusammensetzung C, enthaltend
     • c1) wenigstens ein nichtionisches Tensid, der allgemeinen Formel R1-CH(OH)CH₂O-(AO)w-R2, in der
   • R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C₆-₂₄-Alkyl- oder -Alkenylrest steht;
   • R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen steht;
   • A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
   • w für Werte zwischen 10 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht;
   wobei zwischen 30 und 75 Gew.-% der Gesamttensidmenge der Reinigungsmittelkombination in der Reinigungsmittelzubereitung B enthalten sind
   in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
2. b) eine Kartusche für die Reinigungsmittelkombination, in der die vorzugsweise flüssigen Reinigungsmittel A, B und C getrennt voneinander vorliegen.
3. c) ein mit der Kartusche lösbar verbundenes Dosiergerät.

Hierfür eignen sich insbesondere die in den Tabellen 1 bis 6 offenbarten Rezepturen.An additional preferred subject matter of the present application is a detergent dosing system for automatic dosing in automatic dishwashing comprising

1. a) a detergent combination comprising
   • a detergent preparation A containing
     • a1) at least one builder from the group of organic complexing agents
   • a detergent preparation B containing
     • b1) at least one nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ² in which
   • R ^{1 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 from 2 to 20 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 10 and 120, preferably 10 to 80, in particular 20 to 40; and
     • b2) at least one cleaning-active enzyme;
   • a rinse aid composition C containing
     • c1) at least one nonionic surfactant of the general formula R ₁ -CH (OH) CH ₂ O- (AO) w-R ₂ , in the
   • R ¹ is a linear or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;
   • R ^{2 is} a linear or branched hydrocarbon radical having from 2 to 20 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 10 and 120, preferably 10 to 80, in particular 20 to 40;
   wherein between 30 and 75 wt .-% of the total amount of surfactant of the detergent combination in the detergent formulation B are included
   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;
2. b) a cartridge for the detergent combination in which the preferably liquid detergents A, B and C are present separately.
3. c) a dispenser detachably connected to the cartridge.

Particularly suitable for this purpose are the formulations disclosed in Tables 1 to 6.

Of course, Reinigungsmitteldosiersysteme are conceivable in which the cartridge and the metering device are permanently connected to each other. However, the detachable connection between the cartridge and the dosing device has the advantage that the dosing device can be used several times, that is, in combination with several cartridges (reusable dosing device).

1. a) eine erfindungsgemäße Reinigungsmittelkombination in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
2. b) eine Kartusche für die Reinigungsmittelkombination, in der die flüssigen Reinigungsmittel B und C getrennt voneinander vorliegen;
3. c) ein mit der Kartusche unlösbar verbundenes Dosiergerät.

Hierfür eignen sich insbesondere die in den Tabellen 1 bis 5 offenbarten Rezepturen.An object of the present application is further a Reinigungsmitteldosiersystem comprising

1. a) a combination of detergents according to the invention in an amount sufficient for at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process;
2. b) a cartridge for the detergent combination in which the liquid detergents B and C are present separately;
3. c) a metering device undetachably connected to the cartridge.

Particularly suitable for this purpose are the formulations disclosed in Tables 1 to 5.

1. a) eine Reinigungsmittelkombination, umfassend
   • eine Reinigungsmittelzubereitung A, enthaltend
     • a1) wenigstens einen Gerüststoff aus der Gruppe der organischen Komplexbildner
   • eine Reinigungsmittelzubereitung B, enthaltend
     • b1) wenigstens ein nichtionisches Tensid der allgemeinen Formel R¹ -CH(OH)CH₂O-(AO)_w-R², in der
   • R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder Alkenylrest steht;
   • R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen steht;
   • A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
   • w für Werte zwischen 10 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht; und
     • b2) wenigstens ein reinigungsaktives Enzym;
   • eine Klarspülzusammensetzung C, enthaltend
     • c1) wenigstens ein nichtionisches Tensid, der allgemeinen Formel R1-CH(OH)CH2O-(AO)w-R2, in der
   • R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C₆-₂₄-Alkyl- oder -Alkenylrest steht;
   • R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen steht;
   • A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
   • w für Werte zwischen 10 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht;
   wobei zwischen 30 und 75 Gew.-% der Gesamttensidmenge der Reinigungsmittelkombination in der Reinigungsmittelzubereitung B enthalten sind
   in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
2. b) eine Kartusche für die Reinigungsmittelkombination, in der die vorzugsweise flüssigen Reinigungsmittel A, B und C getrennt voneinander vorliegen.
3. c) ein mit der Kartusche unlösbar verbundenes Dosiergerät.

Hierfür eignen sich insbesondere die in den Tabellen 1 bis 6 offenbarten Rezepturen.An additional preferred subject matter of the present application is a detergent dosing system for automatic dosing in automatic dishwashing comprising

1. a) a detergent combination comprising
   • a detergent preparation A containing
     • a1) at least one builder from the group of organic complexing agents
   • a detergent preparation B containing
     • b1) at least one nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ² in which
   • R ^{1 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 from 2 to 20 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 10 and 120, preferably 10 to 80, in particular 20 to 40; and
     • b2) at least one cleaning-active enzyme;
   • a rinse aid composition C containing
     • c1) at least one nonionic surfactant of the general formula R1-CH (OH) CH2O- (AO) w-R2, in the
   • R ¹ is a linear or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;
   • R ^{2 is} a linear or branched hydrocarbon radical having from 2 to 20 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 10 and 120, preferably 10 to 80, in particular 20 to 40;
   wherein between 30 and 75 wt .-% of the total amount of surfactant of the detergent combination in the detergent formulation B are included
   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;
2. b) a cartridge for the detergent combination in which the preferably liquid detergents A, B and C are present separately.
3. c) a metering device undetachably connected to the cartridge.

Particularly suitable for this purpose are the formulations disclosed in Tables 1 to 6.

The vorgenanten Reinigungsmitteldosiersysteme, comprising the invention Reinigungsmittelangebotsform (and optionally one or two further, different from the detergent compositions of the invention B and C cleaning center), a cartridge and a releasably connected to the cartridge dosing device are in a preferred embodiment in a common outer packaging, wherein the filled cartridge and the metering device are particularly preferably contained separately from each other 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 product form 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 (for example duration, temperature profile, water supply) and the detergent formulation or the control electronics of the dosing device are matched to one another.

The dosing system according to the invention consists of the basic components of a cartridge filled with the detergent according to the invention and a metering device which can be coupled to the cartridge, which in turn is formed from further components such as component carrier, actuator, closure element, sensor, energy source and / or control unit.

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, tumble dryer or the like, but for example from a dishwasher by the user removed or positionable in a dishwasher, so is independently handled, is

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

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

cartridge

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.

It is advantageous that the cartridge has at least one outlet opening, which is arranged such that a gravity-induced release of preparation from the container in the position of use of the dosing device can be effected. As a result, no further funding for the release of preparation from the container is required, whereby the structure of the metering device can be kept simple and the production costs low.

In a preferred embodiment of the invention, at least one second chamber is provided for receiving at least one second flowable preparation, the second chamber having at least one outlet opening arranged such that a gravity-induced product release from the second chamber in the use position of the dosing is effected. The arrangement of a second chamber is particularly advantageous if in the separate containers preparations are stored, which are usually not stable to each other, such as bleaching agents and enzymes.

Furthermore, it is conceivable that more than two, in particular three to four chambers are provided in or on a cartridge. In particular, one of the chambers can be designed for the delivery of volatile preparations, such as a fragrance to the environment.

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 Types of connections from the group of snap-in connections, Velcro connections, compression joints, fusible links, adhesive bonds, welded joints, solder joints, screw, wedge, clamp or bounce connections 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, with a three-chamber configuration it is preferably 4: 1: 1, and these configurations are particularly suitable for use in dishwashers.

As mentioned above, the cartridge preferably has 3 chambers. For the use of such a cartridge in a dishwasher, it is particularly preferred that the first chamber contains an alkaline cleaning preparation, the second chamber contains an enzymatic preparation and the third chamber contains a rinse aid, wherein the volume ratio of the chambers is approximately 4: 1: 1.

In or on a chamber, a metering chamber may be formed in the flow direction of the preparation in front of the outlet opening. Through the metering chamber, the preparation amount that is to be released in the release of preparation from the chamber to the environment, set. This is particularly advantageous if the closure element of the dosing device, which causes the preparation discharge from a chamber to the environment, can only be put into a dispensing and a closure state without controlling the dispensing quantity. It is then ensured by the metering chamber that a predefined amount of preparation is released without an immediate feedback of the delivered preparation amount. The metering chambers can be formed in one piece or in several pieces.

According to a further advantageous development of the invention, one or more chambers in addition to an outlet opening each have a liquid-tight sealable Chamber opening on. Through this chamber opening, it is possible, for example, to refill stored in this chamber preparation.

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

According to another embodiment, the cartridge chambers should not be aerated directly, but via the dosing device or no ventilation, e.g. be provided with the use of flexible containers, such as bags, so this has the advantage that at elevated temperatures in the course of a rinse cycle of a dishwasher by the heating of the chamber contents, a pressure is built up, which presses the preparations to be dosed in the direction of the outlet openings, so that a good residual emptying of the cartridge can be achieved. Furthermore, in the case of such an air-free packaging, there is no risk of oxidation of substances of the preparation, which makes bag packaging or else bag-in-bottle packaging appear expedient, in particular for oxidation-sensitive preparations.

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

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

The cartridge and the dosing device can in particular be configured with respect to their spatial form in such a way that they ensure the least possible loss of useful volume, in particular in a dishwashing machine.

To use the dispenser in dishwashers, it is particularly advantageous to mold the device based on dishes to be cleaned in dishwashers. So this example, plate-shaped, be formed in approximately the dimensions of a plate. As a result, the dosing device can be positioned to save space eg in the lower basket of the dishwasher. Furthermore, the correct positioning of the dosing unit opens up to the user intuitively through the plate-like shape. The cartridge preferably has a ratio of height: width: depth between 5: 5: 1 and 50: 50: 1, particularly preferably about 10: 10: 1. Due to the "slim" design of the dosing device and the cartridge, it is particularly possible, the device in the lower cutlery basket of a dishwasher in the provided for plates Position recordings. This has the advantage that the dispensed from the dosing preparations go directly into the wash liquor and can not adhere to other items to be washed.

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.

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

Another way to reduce the effect of heat on a preparation in a chamber of the cartridge is to isolate the chamber by suitable means, e.g. by the use of thermal insulation materials such as styrofoam, which enclose the chamber or the cartridge in a suitable manner, in whole or in part.

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

This information can be used to select a dosing program stored in the control unit. In this way it can be ensured that an optimal dosing program is always used for a particular preparation. It can also be provided that in the absence of an RFID label or an RFID label with a wrong or faulty identifier, no dosage is done by the dosing and instead an optical or acoustic signal is generated that the user on the present Error indicates.

To preclude misuse of the cartridge, the cartridges may also have structural elements which cooperate with corresponding elements of the metering device according to the key-lock principle, so that for example only cartridges of a certain type can be coupled to the dosing device. Furthermore, this configuration makes it possible for information about the cartridge coupled to the dosing device to be transmitted to the control unit, as a result of which control of the dosing device coordinated with the contents of the corresponding container can take place.

The cartridge is designed in particular for receiving flowable detergents or cleaning agents. Particularly preferably, such a cartridge has a plurality of chambers for the spatially separated receiving in each case of different preparations of a washing or cleaning agent.
The cartridge may be designed so that it can be detachably or firmly arranged in or on the dishwasher.

dosing

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.

adapter

By means of an adapter, a simple coupling of the dosing system with a water-conducting domestic appliance can be realized. The adapter serves for the mechanical and / or electrical connection of the metering system with the water-conducting household appliance.

The adapter is, preferably fixed, connected to a water-carrying pipe of the household appliance. 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 "buildin" version. It is also possible to form the adapter as a kind of charging station for the metering system in which, for example, the energy source of the metering device is charged or data is exchanged between the metering device and the adapter.

The adapter can be arranged in a dishwasher on one of the inner walls of the washing chamber, in particular on the inner side of the dishwasher door. 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 cleaning agents according to the invention are distinguished by a particular physical and chemical stability, in particular with respect to temperature fluctuations. The cleaning agents according to the invention are thus exceptionally suitable for the metering by means of a metering system located in the interior of a washing or dishwashing machine. Such a dosing system, which can be immovably integrated into the interior of the washing machine or dishwasher (machine-integrated dosing device) 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 is not permanently connected to a device such as a dishwasher, washing machine, dryer or the like, but can be removed, for example, from a dishwasher or positioned in a dishwasher.

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

mit einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge dieser Reinigungsmittelkombination, ist ein weiterer Gegenstand der vorliegenden Anmeldung. Die Reinigungsmittelkombination kann dabei, wie weiter oben ausgeführt, zwei Reinigungsmittelzubereitungen B und C oder alternativ drei Reinigungsmittelzubereitungen A, B und C umfassen. Für die vorgenannte Verwendung eignen sich insbesondere die in den Tabellen 1 bis 6 offenbarten Rezepturen.The use of a detergent combination according to the invention for filling

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

with a sufficient for the at least twice, preferably at least four times and in particular at least eight times performing a machine dishwashing sufficient amount of this combination of detergents, is a further subject of the present application. The detergent combination may, as stated above, comprise two detergent formulations B and C or alternatively three detergent formulations A, B and C. For the aforementioned use, in particular the formulations disclosed in Tables 1 to 6 are suitable.

As an alternative to the detergent combination according to the invention, it is of course also possible to use a detergent dosage form according to the invention comprising the detergent combination and a cartridge containing the detergent preparations B and C for filling a dosing device.

1. i) ein unbeweglich in den Innenraum einer Geschirrspülmaschine integriertes Dosiergerät oder
2. ii) ein für die Positionierung im Innenraum einer Geschirrspülmaschine vorgesehenes bewegliches Dosiergerät, ist daher ein weiterer Gegenstand der vorliegenden Anmeldung.

The use of a Reinigungsmittelangebotsform as a cleaning agent reservoir for

1. i) a metering device that is immovably integrated into the interior of a dishwasher or
2. ii) a provided for positioning in the interior of a dishwasher mobile dosing device, is therefore a further subject of the present application.

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

mit einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge dieser Reinigungsmittelangebotsform sind ebenfalls Gegenstände dieser Anmeldung. Die Reinigungsmittelangebotsform kann dabei, wie weiter oben ausgeführt, zwei Reinigungsmittelzubereitungen B und C oder alternativ drei Reinigungsmittelzubereitungen A, B und C umfassen. Für die vorgenannte Verwendung eignen sich insbesondere die in den Tabellen 1 bis 6 offenbarten Rezepturen.Claimed is in particular the use of a detergent dosage form according to the invention for filling

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

With an at least twice, preferably at least four times and in particular at least eight times carrying out a machine dishwashing sufficient amount of Reinigungsmittelangebotsform are also subjects of this application. The detergent supply form can, as stated above, comprise two detergent preparations B and C or alternatively three detergent preparations A, B and C. For the aforementioned use, in particular the formulations disclosed in Tables 1 to 6 are suitable.

An example of a stationary cartridge is a container immovably integrated into the interior, for example in the side wall or the inner lining of the door of a dishwasher.

An example of a movable cartridge is a container which is introduced by the consumer into the interior of the dishwasher and remains there during the entire course of a cleaning cycle. Such a cartridge is, for example, by simply setting in the cutlery or crockery basket, integrated into the interior but can be removed from the consumer again from the interior of the dishwasher.

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

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

Die Reinigungsmittelangebotsform kann dabei, wie weiter oben ausgeführt, zwei Reinigungsmittelzubereitungen B und C oder alternativ drei Reinigungsmittelzubereitungen A, B und C umfassen. Für die vorgenannte Verwendung eignen sich insbesondere die in den Tabellen 1 bis 6 offenbarten Rezepturen.The use of a Reinigungsmittelangebotsform invention as a cleaning agent reservoir for

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

The detergent supply form can, as stated above, comprise two detergent preparations B and C or alternatively three detergent preparations A, B and C. For the aforementioned use, in particular the formulations disclosed in Tables 1 to 6 are suitable.

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

1. a) eine erfindungsgemäße Reinigungsmittelzubereitung B in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
2. b) mindestens eine weitere von B verschiedene Reinigungsmittelzubereitung C in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
3. c) eine Kartusche für die Reinigungsmittelzubereitungen B und C, in welcher die Reinigungsmittelzubereitungen B und C in voneinander getrennten Aufnahmekammern vorliegen als Reinigungsmittelreservoir für
   1. i) ein unbeweglich in den Innenraum einer Geschirrspülmaschine integriertes Dosiergerät oder
   2. ii) ein für die Positionierung im Innenraum einer Geschirrspülmaschine vorgesehenes bewegliches Dosiergerät.

Für die vorgenannte Verwendung eignen sich insbesondere die in den Tabellen 1 bis 5 offenbarten Rezepturen.Two further objects of this application are the use of a detergent dosage form according to the invention, comprising

1. a) a detergent formulation B according to the invention in an amount sufficient for at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process;
2. b) at least one further detergent preparation C other than B in an amount sufficient for at least twice, preferably at least four times, and in particular at least eight times, carrying out a machine dishwashing process;
3. c) a cartridge for the detergent preparations B and C, in which the detergent formulations B and C in separate receiving chambers are present as a detergent reservoir for
   1. i) a metering device that is immovably integrated into the interior of a dishwasher or
   2. ii) a provided for positioning in the interior of a dishwasher movable metering device.

For the aforementioned use, in particular the formulations disclosed in Tables 1 to 5 are suitable.

1. a) eine Reinigungsmittelzubereitung A in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
2. b) eine weitere von A verschiedene erfindungsgemäße Reinigungsmittelzubereitung B in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
3. c) mindestens eine weitere von A und B verschiedene Reinigungsmittelzubereitung C in einer für die mindestens zweimalige, vorzugsweise mindestens viermalige und insbesondere mindestens achtmalige Durchführung eines maschinellen Geschirrspülverfahrens ausreichenden Menge;
4. d) eine Kartusche für die Reinigungsmittelzubereitungen A, B und C, in welcher die Reinigungsmittelzubereitungen A, B und C in voneinander getrennten Aufnahmekammern

vorliegen
als Reinigungsmittelreservoir für

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

Für die vorgenannte Verwendung eignen sich insbesondere die in den Tabellen 1 bis 6 offenbarten Rezepturen.Claimed is also the use of a Reinigungsmittelangebotsform invention, comprising

1. a) a detergent preparation A 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;
2. b) another detergent composition B according to the invention which is different from A 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;
3. c) at least one further cleaning agent preparation C which differs from A and B in an amount sufficient for at least twice, preferably at least four times, and in particular at least eight times, carrying out a machine dishwashing process;
4. d) a cartridge for the detergent preparations A, B and C, in which the detergent compositions A, B and C in separate receiving chambers

be present
as a cleaning agent reservoir for

• iii) a metering device immovably integrated into the interior of a dishwashing machine or
• iv) a provided for positioning in the interior of a dishwasher movable dosing device.

For the aforementioned use, in particular the formulations disclosed in Tables 1 to 6 are suitable.

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.

The cleaning agents and detergent combinations according to the invention are, as stated above, used as automatic dishwashing detergents. Of course, not only the inventive compositions can be used in the dishwashing processes according to the invention Detergent offer forms but also the Reinigungsmitteldosiersysteme invention are used.

• 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
• eine Teilmenge c der in der Kartusche befindlichen Reinigungsmittelzubereitung C in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in der Kartusche befindlichen Reinigungsmittelzubereitung C 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 c entspricht,

sind ein weiterer Gegenstand der vorliegenden Anmeldung.
Für das vorgenannte Verfahren eignen sich insbesondere die in den Tabellen 1 bis 5 offenbarten Rezepturen.Automatic dishwashing process using a detergent combination according to the invention or a detergent dosage form according to the invention or a detergent dosing system according to the invention characterized in that in its course from a located in the interior of the dishwasher cartridge

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

are another subject of the present application.
The recipes disclosed in Tables 1 to 5 are particularly suitable for the abovementioned process.

• 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 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
• eine Teilmenge c der in der Kartusche befindlichen Reinigungsmittelzubereitung C in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in der Kartusche befindlichen Reinigungsmittelzubereitung C 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 c entspricht.

Für das vorgenannte Verfahren eignen sich insbesondere die in den Tabellen 1 bis 6 offenbarten Rezepturen.Preferred automatic dishwashing processes using a detergent combination according to the invention or a detergent dosage form according to the invention or a detergent dosing system according to the invention are characterized in that in their course from a cartridge located in the interior of the dishwasher

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

In particular, the formulations disclosed in Tables 1 to 6 are suitable for the abovementioned process.

In a preferred embodiment, the dosage of the detergent preparation B and the detergent preparation C takes place at different times of the cleaning cycle. Automatic dishwashing process, characterized in that the dosage of the cleaning agents B and C takes place with a time delay, wherein the dosage of the detergent composition B preferably takes place in the course of the main cleaning cycle, while the rinse aid composition C is preferably metered in the course of the rinse cycle, are preferred according to the invention.

1. a) zu einem Zeitpunkt t1 aus einer im Innenraum der Geschirrspülmaschine befindlichen Kartusche eine Teilmenge b der in der Kartusche befindlichen erfindungsgemäßen Reinigungsmittelzubereitung B in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in der Kartusche befindlichen Reinigungsmittelzubereitung bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt, welche der mindestens doppelten, vorzugsweise der mindestens vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge b entspricht;
2. b) zu mindestens einem weiteren Zeitpunkt t2 # t1 aus einer im Innenraum der Geschirrspülmaschine befindlichen Kartusche eine Teilmenge c des in der zweiten Kartusche befindlichen von der erfindungsgemäßen Reinigungsmittelzubereitung B unterschiedliche Reinigungsmittelzubereitung C in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge des in dieser Kartusche befindlichen Reinigungsmittels bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt, welche mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge c entspricht.

A further preferred subject matter of this application is therefore a machine dishwashing process using a detergent combination according to the invention, a detergent product form according to the invention or a detergent dosing system according to the invention, in the course of which

1. a) at a time t1 from a cartridge located in the interior of the dishwasher, a portion b of the present invention in the detergent detergent composition B is dosed into the interior of the dishwasher, wherein a residual amount of detergent contained in the cartridge until the end of dishwashing in the cartridge which corresponds to at least twice, preferably at least four times, and in particular at least eight times, the amount of subset b;
2. b) at least one further time t2 # t1 from a cartridge located in the interior of the dishwasher is dosed a subset c of the present in the second cartridge of the detergent composition B different detergent composition C in the interior of the dishwasher, wherein a residual amount of in this cartridge remaining cleaning agent remains in the cartridge until the end of dishwashing, which corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of subset c.

In preferred embodiments of the above-described automatic dishwashing processes with time-staggered dosing of the detergent preparations B and C or A, B and C is the time t2 temporally at least 1 minute, preferably at least 2 minutes and in particular between 3 and 20 minutes before or after the time t1. Preferably, the time t2 is at least 1 minute in time, preferably at least 2 minutes and in particular between 3 and 20 minutes after the time t1. In particular, the formulations disclosed in Tables 1 to 6 are suitable for these processes.

1. a) zu einem Zeitpunkt t1 aus einer im Innenraum der Geschirrspülmaschine befindlichen Kartusche eine Teilmenge a der in der Kartusche befindlichen erfindungsgemäßen Reinigungsmittelzubereitung A in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in der Kartusche befindlichen Reinigungsmittelzubereitung A bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt, welche der mindestens doppelten, vorzugsweise der mindestens vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge a entspricht;
2. b) zu mindestens einem weiteren Zeitpunkt t2 ≠ t1 aus einer im Innenraum der Geschirrspülmaschine befindlichen Kartusche eine Teilmenge b der in der zweiten Kartusche befindlichen von der erfindungsgemäßen Reinigungsmittelzubereitung A unterschiedlichen Reinigungsmittelzubereitung B in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in dieser Kartusche befindlichen Reinigungsmittelzubereitung B bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt, welche mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge b entspricht;
3. c) zu mindestens einem weiteren Zeitpunkt t3 ≠ t2 ≠ t1 aus einer im Innenraum der Geschirrspülmaschine befindlichen Kartusche eine Teilmenge c der in der dritten Kartusche befindlichen von der erfindungsgemäßen Reinigungsmittelzubereitung A und der Reinigungsmittelzubereitung B unterschiedlichen Reinigungsmittelzubereitung C in den Innenraum der Geschirrspülmaschine dosiert wird, wobei eine Restmenge der in dieser Kartusche befindlichen Reinigungsmittelzubereitung C bis zum Ende des Geschirrspülverfahrens in der Kartusche verbleibt, welche mindestens der doppelten, vorzugsweise mindestens der vierfachen und insbesondere mindestens der achtfachen Menge der Teilmenge c entspricht.

This application further claims a machine dishwashing process using a cleaning agent according to the invention or a detergent combination according to the invention or a detergent dosage form or a detergent dosage system according to the invention, in the course of which

1. a) at a time t1 from a cartridge located in the interior of the dishwasher a subset a of the present invention in the cartridge detergent composition A is dosed into the interior of the dishwasher, wherein a residual amount of the present in the cartridge detergent composition A until the end of dishwashing in the Cartridge remains, which corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of subset a;
2. b) at least one further time t2 ≠ t1 from a cartridge located in the interior of the dishwasher is dosed a subset b of located in the second cartridge of the detergent composition A different detergent composition B in the interior of the dishwasher, wherein a residual amount of in this cartridge remaining detergent composition B remains in the cartridge until the end of the dishwashing process, which corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of subset b;
3. c) at least one further time t3 ≠ t2 ≠ t1 from a cartridge located in the interior of the dishwasher is dosed a subset c of the present in the third cartridge of the detergent composition A and the detergent composition B different detergent preparation C in the interior of the dishwasher, wherein a residual amount of the cleaning agent preparation C present in this cartridge remains in the cartridge until the end of the dishwashing process, which corresponds to at least twice, preferably at least four times, and in particular at least eight times, the quantity of the subset c.

The use of a detergent combination according to the invention, a detergent dosage form according to the invention or a detergent dosage system according to the invention for dishwashing in a dishwasher automatic machine is a final subject matter of the present application.

Claims (15)

1. A cleaning agent combination for automatic dosing during automatic dishwashing, comprising

   - a cleaning agent preparation B, containing

   (b1) at least one non-ionic surfactant of general formula R¹-CH(OH)CH₂O-(AO)_w-R², in which

   - R¹ represents a straight-chain or branched, saturated or monounsaturated or polyunsaturated C₆-₂₄ alkyl or alkenyl functional group;

   - R² represents a linear or branched hydrocarbon functional group having 2 to 20 carbon atoms;

   - A represents a functional group from the group comprising CH₂CH₂,-CH₂CH₂-CH₂ and -CH₂-CH(CH₃), and

   - w represents values between 10 and 120, preferably from 10 to 80, in particular from 20 to 40; and

   (b2) at least one cleaning-active enzyme;

   - a rinsing composition C, containing

   (c1) at least one non-ionic surfactant of general formula R¹-CH(OH)CH₂O-(AO)_w-R₂, in which

   - R¹ represents a straight-chain or branched, saturated or monounsaturated or polyunsaturated C₆-₂₄ alkyl or alkenyl functional group;

   - R² represents a linear or branched hydrocarbon functional group having 2 to 20 carbon atoms;

   - A represents a functional group from the group comprising CH₂CH₂, - CH₂CH₂-CH₂ and -CH₂-CH(CH₃), and

   - w represents values between 10 and 120, preferably from 10 to 80, in particular from 20 to 40;

   wherein between 30 and 75 wt.% of the total surfactant amount in the cleaning agent combination is contained in the cleaning agent preparation B.
2. The cleaning agent combination according to claim 1, characterized in that between 40 and 70 wt.% of the total surfactant amount in the cleaning agent combination is contained in the cleaning agent preparation B.
3. The cleaning agent combination according to one of the preceding claims, characterized in that a surfactant of general formula R¹CH(OH)CH₂O-(CH₂CH₂O)_10-120-R² is used as the non-ionic surfactant in the composition B and/or C, in which R¹ and R² represent, independently of one another, a linear or branched aliphatic hydrocarbon functional group having 2 to 20 carbon atoms.
4. The cleaning agent combination according to one of the preceding claims, characterized in that the percentage by weight of the non-ionic surfactant in the total weight of the cleaning agent preparation B is between 0.1 and 30 wt.%, preferably between 1.0 and 25 wt.%, particularly preferably between 2.0 and 20 wt.%, and in particular between 5.0 and 15 wt.%.
5. The cleaning agent combination according to one of the preceding claims, characterized in that the composition B and/or C, based on its total weight, contains between 5.0 and 80 wt.%, preferably between 10 and 70 wt.%, and in particular between 12 and 60 wt.% organic solvent(s).
6. The cleaning agent combination according to one of the preceding claims, characterized in that the cleaning agent preparation B, based on its total weight, contains from 0.1 to 30 wt.%, preferably from 1.0 to 25 wt.%, and in particular from 2.0 to 20 wt.% amylase preparation and/or from 5 to 50 wt.%, preferably from 7 to 40 wt.%, and in particular from 10 to 30 wt.% protease preparation.
7. The cleaning agent combination according to one of the preceding claims, characterized in that the cleaning agent combination comprises a further preferably liquid cleaning agent A, containing

   (a1) at least one builder from the group of organic complexing agents, and

   (a2) at least one builder from the group of cleaning-active polymers.
8. The cleaning agent combination according to one of the preceding claims, characterized in that the cleaning agent preparation A, based on its total weight, contains from 5.0 to 60 wt.%, preferably from 10 to 50 wt.%, and in particular from 15 to 40 wt.% builder(s) from the group of organic complexing agents.
9. The use of the cleaning agent combination according to one of claims 1 to 8 for filling

   i) a cartridge of a dosing system that is immovably integrated in the internal space of a dishwasher, or

   ii) a movable cartridge of a dosing system for being positioned in the internal space of a dishwasher,

   comprising an amount of said cleaning agent combination sufficient for carrying out an automatic dishwashing method at least twice, preferably at least four times, and in particular at least eight times.
10. A cleaning agent product, comprising

    a) a cleaning agent combination according to one of claims 1 to 8 in an amount sufficient for carrying out an automatic dishwashing method at least twice, preferably at least four times, and in particular at least eight times;

    b) a cartridge for the cleaning agent combination, in which the preferably liquid cleaning agents B and C are present in a manner separated from one another.
11. The use of a cleaning agent product according to claim 10 as a cleaning agent reservoir for

    i) a dosing device that is immovably integrated in the internal space of a dishwasher, or

    ii) a movable dosing device for being positioned in the internal space of a dishwasher.
12. A cleaning agent dosing system, comprising

    a) a cleaning agent combination according to one of claims 1 to 8 in an amount sufficient for carrying out an automatic dishwashing method at least twice, preferably at least four times, and in particular at least eight times;

    b) a cartridge for the cleaning agent combination, in which the preferably liquid cleaning agents B and C are present in a manner separate from one another.

    c) a dosing device detachably connected to the cartridge.
13. The use of a cleaning agent combination according to one of claims 1 to 8, of a cleaning agent product according to claim 10, or of a cleaning agent dosing system according to claim 12 for dishwashing in an automatic dishwashing method.
14. An automatic dishwashing method using a cleaning agent combination according to one of claims 1 to 8 or using a cleaning agent product according to claim 10 or using a cleaning agent dosing system according to claim 12, characterized in that, in the course thereof, from a cartridge in the internal space of the dishwasher,

    - a portion b of the cleaning agent preparation B in the cartridge is dosed into the internal space of the dishwasher, a residual amount of the cleaning agent preparation B in the cartridge remaining in the cartridge until the end of the dishwashing method, and said residual amount corresponding to at least double, preferably at least four times, and in particular at least eight times the portion b; and

    - a portion c of the cleaning agent preparation C in the cartridge is dosed into the internal space of the dishwasher, a residual amount of the cleaning agent preparation C in the cartridge remaining in the cartridge until the end of the dishwashing method, and said residual amount corresponding to at least double, preferably at least four times, and in particular at least eight times the portion c.
15. The automatic dishwashing method according to claim 14, characterized in that cleaning agents B and C are dosed in a delayed manner, the cleaning agent preparation B being dosed preferably in the course of the main cleaning cycle, whilst the rinsing composition C is preferably dosed in the course of the rinsing cycle.