EP3260524B1 - 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 partial amounts of an automatic cleaning agent are dosed into the interior of the dishwasher from a storage container located in the interior of the dishwasher in the course of several successive cleaning processes will.

When evaluating modern machine dishwashing detergents, both the performance aspects of these detergents, in particular their cleaning and rinsing performance, and their manageability are the focus of interest for the consumer.

One of the main goals of the manufacturers of machine cleaning agents is to improve the cleaning and rinsing performance of these agents, with more recent attention being paid to the cleaning and rinsing performance in low-temperature cleaning cycles or in cleaning cycles with reduced water consumption.

Typical forms of supply for dishwashing detergents include, in addition to traditional liquid hand dishwashing detergents, in particular machine dishwashing detergents which are mainly marketed in solid form and which are available, for example, as powders or tablets. However, these well-known types of clothing and offerings are subject to constant changes. For some time now, a main focus has been on the simplified dosage of automatic dishwashing detergents.

In this context, devices for multiple dosing of detergents and cleaning agents have recently come to the attention of product developers. In the case of these devices, a distinction can be made between dosing containers integrated in the dishwasher or textile washing machine on the one hand and independent devices independent of the dishwasher or textile washing machine on the other. By means of these devices, which contain a multiple of the amount of cleaning agent required to carry out a cleaning process, detergent or cleaning agent portions are automatically or semi-automatically dosed into the interior of the cleaning machine in the course of several consecutive cleaning processes. For the consumer there is no need for repeated manual dosing of detergents and cleaning agents. Examples of such devices are given in 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 design of the dosing devices used in the interior of dishwashers or textile washing machines, the detergents or cleaning agents contained in these devices for multiple dosing are particularly exposed to changing temperatures over a longer period of time, these temperatures being the first approximation of those used to carry out the washing or cleaning process Same water temperatures. These temperatures can be up to 95 ° C, with temperatures between 50 and 75 ° C usually only being reached in the area of machine dishwashing. A washing or cleaning agent contained in a device provided for multiple dosing is accordingly repeatedly heated to temperatures well above the normal temperatures for transport and storage in the course of several washing or cleaning processes, with temperature-sensitive active substances being affected in particular. The group of these temperature-sensitive washing and cleaning-active substances includes primarily the washing and cleaning-active enzymes.

A number of different protective measures have been proposed to increase the stability of such enzyme-containing liquid washing or cleaning agents. For example, the German patent application teaches DE 2 038 103 (Henkel ) the stabilization of enzyme-containing dishwashing detergents by saccharides, while in the European patent EP 646 170 B1 (Procter & Gamble) Propylene glycol for enzyme stabilization in liquid detergents is disclosed. Further combinations of enzyme-containing and non-enzyme-containing compositions in dishwashing are disclosed in US Pat EP 1 026 230 , EP 0 561 446 , DE 10 2007 042857 and DE 10 2007 039655 disclosed.

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

This object was achieved by means of a cleaning agent combination which comprises two surfactant-containing preparations, one of which also contains an enzyme in addition to the surfactant.

A first subject of the present application is therefore a cleaning agent combination for automatic dosing in machine dishwashing according to claim 1.

The present application describes and claims a cleaning agent combination for automatic dosing in machine dishwashing. As stated above, the cleaning agent combinations according to the invention are intended for automatic dosing and for storage in a dosing device in the interior of the automatic dishwasher and necessarily comprise more than the amount of cleaning agent required to carry out a cleaning cycle. In other words, a subject matter is one

• eine flüssige Reinigungsmittelzubereitung B, enthaltend
  • b1) wenigstens ein nichtionisches Tensid und
  • b2) wenigstens ein reinigungsaktives Enzym;
• eine flüssige Klarspülzusammensetzung C, enthaltend c1) wenigstens ein nichtionisches Tensid, wobei die Zubereitungen weniger als 2 Gew.-% Phosphat umfassen, dadurch gekennzeichnet, dass Reinigungsmittelzubereitungen B und C weniger als 10 Gew.-% Gerüststoffe enthalten,

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.Detergent combination for automatic dosing in automatic dishwashing, comprising

• a liquid detergent preparation B containing
  • b1) at least one nonionic surfactant and
  • b2) at least one cleaning enzyme;
• a liquid rinse aid composition C containing c1) at least one nonionic surfactant, the preparations comprising less than 2% by weight of phosphate, characterized in that detergent preparations B and C contain less than 10% by weight of builders,

wherein the cleaning agent combination comprises the quantities of cleaning agents B and C sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times.

In addition to water, the organic solvents known to the person skilled in the art, in particular the monohydric or polyhydric alcohols, are also suitable solvents for these liquid cleaning agent preparations.

Both the detergent preparation B and the detergent preparation C contain nonionic surfactant. Each of the cleaning agent preparations B and C can contain one, two or more nonionic surfactant (s). The nonionic surfactants in cleaning agent preparations B and C can be identical or different chemical ones Have structures. The detergent preparations B and C have compositions that differ from one another and are therefore not identical.

For the cleaning and rinsing action, it has proven to be advantageous if the proportion by weight of the nonionic surfactant in the total weight of the cleaning agent preparation B is between 0.1 and 30% by weight, preferably between 1.0 and 25% by weight, in particular is 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 cleaning agent combinations according to the invention have particularly advantageous cleaning and rinsing effects in which at least 20% by weight, preferably between 20 and 80% by weight, particularly preferably between 30 and 75% by weight and in particular between 40 and 70 % By weight of the total amount of surfactant in the detergent combination is contained in the detergent preparation B.

The composition of some exemplary liquid cleaning agent combinations according to the invention, in which at least 20 wt .-%, preferably between 20 and 80 wt .-%, particularly preferably between 30 and 75 wt .-% and in particular between 40 and 70 wt .-% of the total amount of surfactant Detergent combination is contained in detergent preparation B, can be found in 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 an abbreviation for "detergent preparation B", as in all the following tables
** "C" is an abbreviation for "detergent preparation C", as in all the following tables
*** "-" means in this, as in all of the following tables: the formulation is free from this component

• 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 component 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 the

• R ^{1 represents} 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 of one another for 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 stand for values between 0.5 and 120, whereby x, y and / or z can also be 0,

are preferred. These surfactants have proven to be superior to other known nonionic surfactants of the prior art with regard to the desired improvement in the cleaning and rinsing performance in the automatic dishwashing agents according to the invention for automatic dosing.

By adding 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 , hereinafter also referred to as "hydroxy mixed ether", surprisingly, the rinse result of enzyme-containing preparations according to the invention can be significantly improved, both in comparison to surfactant-free systems and in comparison to systems that use alternative nonionic surfactants, for example from the group of polyalkoxylated Fatty alcohols.

If the aforementioned hydroxy mixed ethers are used both in detergent preparation B and in detergent preparation C, in addition to the rinse aid result, the formation of deposits on surfaces such as glass, plastic or stainless steel can also be improved. This improvement can be determined compared to an automatic dishwashing agent which contains the same amount of the hydroxy mixed ether alone in one of the two cleaning agent preparations B or C.

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

In particular, those end group-capped poly (oxyalkylated) nonionic surfactants which, according to 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 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² with 1 to 30 carbon atoms, where x for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

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 represents} a linear or branched aliphatic hydrocarbon radical with 4, are particularly preferred up to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15.
, Especially the C (EO) -2-hydroxyalkyl ether _{15-40 8-10} fatty alcohol (PO) ₁ - - to the group of these nonionic surfactants include the C, for example _2-26 Fettatkohot- (PO) ₁ (EO) ₂₂ -2 hydroxydecyl ether.

Also particularly preferred are those end group-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 2} independently of one another represents 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 represents -CH ₃ , and x and y independently of one another represent values between 1 and 32, nonionic surfactants with R ³ = —CH ₃ and values for x from 15 to 32 and y of 0.5 and 1.5 are particularly preferred.

Further preferred nonionic surfactants are the end group-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 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2- Butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5. If 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 can 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, 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 can be different if x 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if 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 can be joined together 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 chosen as an example and can be larger, with the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula becomes R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH ) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Surfactants in which the radicals R ¹ and R ^{2 have} 9 to 14 carbon atoms, R ^{3 represents} 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 have} proven to be particularly effective

• R ^{1 represents} 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 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.

The group of these nonionic surfactants includes, 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 ethers.

Cleaning _{agent 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 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 cleaning agent preparations B of the cleaning agent combinations according to the invention contain at least one washing or cleaning enzyme as a further essential component. The proportion by weight of the washing- or cleaning-active enzyme in the total weight of the cleaning agent preparation B is preferably between 5 and 80% by weight, preferably between 5 and 60% by weight, particularly preferably between 10 and 50% by weight and in particular between 10 and 30 Wt%.

The composition of some exemplary liquid cleaning agent combinations according to the invention, in which at least 20 wt .-%, preferably between 20 and 80 wt .-%, particularly preferably between 30 and 75 wt .-% and in particular between 40 and 70 wt .-% of the total amount of surfactant Detergent combination is contained in detergent preparation B, can be found in 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.In a further preferred embodiment, the cleaning agent 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 for automatic dosing in automatic dishwashing

• 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 of one another for values between 1 and 70; and
• M for 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 represent a branched or unbranched, saturated or unsaturated alkyl radical with 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 the
   • R, R ¹ and R ² independently of one another represent an alkyl radical or alkenyl radical having 6 to 22 carbon atoms and
   • x and y are independently of one another for 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 the
   • R ¹ and R ² independently of one another 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 can be part of detergent preparation B and / or detergent preparation C. One or more Y surfactants are preferably used in combination with one or more hydroxy mixed ethers. The combination of hydroxy mixed ether and Y-surfactant has proven to be advantageous in particular with regard to the rinsing performance. The best rinse aid results were obtained by adding the Y surfactants to detergent composition C, it being possible in turn to increase these results by adding hydroxy mixed ethers to detergent preparations B and C.

• eine Reinigungsmittelzubereitung B, enthaltend
  • b1) wenigstens ein nichtionisches Tensid und
  • b2) wenigstens ein reinigungsaktives Enzym;
• eine Klarspülzusammensetzung C, enthaltend
  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.

A preferred subject of the present application is therefore a cleaning agent combination for automatic dosing in automatic dishwashing according to claim 1, further comprising

• a cleaning agent preparation B containing
  • b1) at least one nonionic surfactant and
  • b2) at least one cleaning enzyme;
• a rinse aid composition C containing
  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 represents a branched or unbranched alkyl radical having 2 to 4 carbon atoms;
  • x and y are independently of one another for values between 1 and 70; and
  • M represents 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 represent a branched or unbranched, saturated or unsaturated alkyl radical with 1 to 18 carbon atoms.

• eine Reinigungsmittelzubereitung B, enthaltend
  • b1) wenigstens ein nichtionisches Tensid der allgemeine 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;
  • b2) wenigstens ein reinigungsaktives Enzym;
• eine Klarspülzusammensetzung C, enthaltend
  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.

Cleaning agent combinations for automatic dosing in automatic dishwashing according to claim 1, further comprising, are particularly preferred

• a cleaning agent 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 represents} 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 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;
  • b2) at least one cleaning enzyme;
• a rinse aid composition C containing
  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 represents a branched or unbranched alkyl radical having 2 to 4 carbon atoms;
  • x and y are independently of one another for values between 1 and 70; and
  • M represents 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 represent a branched or unbranched, saturated or unsaturated alkyl radical with 1 to 18 carbon atoms.

• eine Reinigungsmittelzubereitung B, enthaltend
  • b1) wenigstens ein nichtionisches Tensid der allgemeine 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;
  • b2) wenigstens ein reinigungsaktives Enzym;
• eine Klarspülzusammensetzung C, enthaltend
  • c1) wenigstens ein nichtionisches Tensid der allgemeine 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.

Cleaning agent combinations for automatic dosing in automatic dishwashing according to claim 1, further comprising, are very particularly preferred

• a cleaning agent 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 represents} 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 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;
  • b2) at least one cleaning 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 represents} 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 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;
  • 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 represents a branched or unbranched alkyl radical having 2 to 4 carbon atoms;
    • x and y are independently of one another for values between 1 and 70; and
    • M represents 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 represent a branched or unbranched, saturated or unsaturated alkyl radical with 1 to 18 carbon atoms.

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

The Y-surfactant-containing automatic dishwashing agents according to the invention preferably have a softener system, for example at least one polymer containing sulfonic acid groups.

The enzymes used with particular preference according to the invention include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; Based on the natural molecules, improved variants are available for use in detergents or cleaning agents, and these are accordingly preferred. Washing or cleaning agents preferably contain enzymes in total amounts of 1 × 10 ⁻⁶ to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

The stabilizing effect according to the invention was observed in particular with the amylases and the proteases, which is why cleaning agent preparations B according to the invention, characterized in that they contain a washing or cleaning enzyme from the group of amylases and / or proteases, are preferred.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg as well as their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the subtilase enzymes, but no longer the subtilisins in the narrower sense of the term, thermitase, Proteinase K and the proteases TW3 and TW7.

According to the invention, preferred cleaning agent preparations B contain, based on the total weight of the washing or cleaning agent preparation B, 5 to 50% by weight, preferably 7 to 40% by weight and in particular 10 to 30% by weight protease preparations.
Cleaning agent preparations B which, based on their total weight, contain 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, and the improved further developments of the aforementioned amylases for use in detergents and cleaning agents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) should be emphasized.

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

Cleansing-active proteases and amylases are generally not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations. These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or with stabilizers or other auxiliaries.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example due to the application of polymeric film formers, and due to the coating are stable in storage.

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

As can be seen from the previous statements, 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% by weight of the enzyme protein.

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

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

To increase the bleaching effect, 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. Advantageously, preferably organic, particularly preferably aromatic, compounds interacting with the enzymes are added in order to increase the activity of the oxidoreductases concerned (enhancers) or to ensure the flow of electrons (mediators) in the event of greatly differing redox potentials between the oxidizing enzymes and the soiling.

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

The composition of some exemplary liquid cleaning agent combinations according to the invention, in which at least 20 wt .-%, preferably between 20 and 80 wt .-%, particularly preferably between 30 and 75 wt .-% and in particular between 40 and 70% by weight of the total amount of surfactant in the detergent combination is contained in detergent preparation B, can be found in Table 3 below: 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 stated above, preferred cleaning agent combinations according to the invention comprise at least one liquid cleaning agent preparation, the organic solvents known to the person skilled in the art, in particular the monohydric or polyhydric alcohols, also being used as solvents in addition to water.

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

The term "water content" comprises the total amount of water contained in the agents according to the invention, which is composed of the free water contained in the agents and the water introduced into the detergent or cleaning agent preparations in bound form via the washing and cleaning agents. The water content can be determined, for example, as drying loss or according to Karl Fischer.

Another preferred component of the washing or cleaning agent preparations B or C according to the invention is an organic solvent. Preferred organic solvents come from the group consisting 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 butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether 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 weight proportion of these organic solvents in the total weight of cleaning agent preparations according to the invention is preferably 5 to 80% by weight, more preferably 10 to 70% by weight and in particular 12 to 60 Wt%.

A cleaning agent combination preferred according to the invention is characterized in that the composition B and / or C, based on its total weight, is between 5.0 and 80% by weight, preferably between 10 and 70% by weight and in particular between 12 and 60% by weight. -% organic solvent (s).

A particularly preferred organic solvent, which is particularly effective with regard to the stabilization of the enzyme-containing cleaning agent preparation B, is 1,2 propylene glycol. The proportion by weight of the 1,2 propylene glycol in the total weight of the cleaning agent preparation B according to the invention can vary within wide limits, but such preparations have proven to be particularly stable which contain an organic solvent, preferably 1,2 propylene glycol, the proportion by weight of the 1,2 propylene glycol , in each case based on the total weight of the cleaning agent preparation B, is preferably 15 to 80% by weight, more preferably 30 to 70% by weight and in particular 40 to 60% by weight.

The use of liquid cleaning agent preparations or liquid cleaning agent combinations facilitates repeated automatic dosing of these active substance mixtures.

The composition of some exemplary liquid cleaning agent combinations according to the invention, in which at least 20 wt .-%, preferably between 20 and 80 wt .-%, particularly preferably between 30 and 75 wt .-% and in particular between 40 and 70 wt .-% of the total amount of surfactant Detergent combination is contained in detergent preparation B, can be found in 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 ingredients described above, such as enzymes, solvents and nonionic surfactants from the group of hydroxy mixed ethers, the inventive washing or cleaning agent preparations B and C can contain further ingredients, for example Contain active ingredients from the group of builders, bleaching agents, polymers with active washing and cleaning properties, corrosion inhibitors, fragrances or dyes. In contrast to conventional washing or cleaning agents, preferred washing or cleaning agent preparations B and C according to the invention contain these further ingredients only to a minor extent.

According to the invention, detergent preparations B and C contain less than 10% by weight and in particular less than 5% by weight of builders. Cleaning agent preparations B and C which are free from builders are particularly preferred.

Preference is also given to cleaning agent preparations 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 bleach. Cleaning agent preparations B and C which are free from bleaching agents are particularly preferred.

The composition of some exemplary liquid cleaning agent combinations according to the invention, in which at least 20 wt .-%, preferably between 20 and 80 wt .-%, particularly preferably between 30 and 75 wt .-% and in particular between 40 and 70 wt .-% of the total amount of surfactant Detergent combination is contained in detergent preparation B, can be found in the following table 5: 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 - Builders <10 <10 <5 <5 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 Recipe 3 Recipe 4 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 - Bleach <10 - - - 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 Recipe 5 Recipe 6 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 - Builders <10 <10 <5 <5 Bleach <10 - - - 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 Recipe 7 Recipe 8 B [% by weight] C [% by weight] B [% by weight] C [% by weight] Nonionic surfactant 1 * 2.0 to 20 Yes 5.0 to 15 Yes Nonionic surfactant 2 ** optional Yes optional Yes Protease preparation 5.0 to 50 - 10 to 30 - Amylase preparation 0.1 to 30 - 2.0 to 20 - Builders <10 <10 <5 <5 Bleach <10 - - - 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 * nonionic surfactant from the group of hydroxy mixed ethers
** nonionic surfactant from the group of Y surfactants

Even if the aforementioned other active washing or cleaning ingredients are preferably only contained to a minor extent in the cleaning agent combinations according to the invention, i.e. are directly mixed with them, it is nevertheless desirable to convert these additional ingredients together with the cleaning agent preparations B and C according to the invention to form a cleaning agent assemble. For this purpose, the person skilled in the art can use all of the ready-to-use forms known to him for combination products with a liquid component, with combination products in particular which have proven to be suitable which share the common Allow packaging of three, four or more separate liquid preparations.

Cleaning agent combinations according to the invention, comprising the cleaning agent preparations B and C, contain less than 2% by weight of phosphate. Phosphate-free cleaning agent combinations are very particularly preferred according to the invention. Also preferred are those cleaning agent combinations according to the invention, comprising the cleaning agent preparations 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 cleaning agent combinations according to the invention are free of silicate. Both the lowering of the phosphate content and the lowering of the silicate content have proven to be advantageous for the stability of the cleaning agent combinations according to the invention.

In spite of their high physical and chemical stability, the cleaning agent combinations according to the invention are distinguished by a low level of formulation complexity. This low degree of complexity simplifies the production of the cleaning agents and thus reduces the costs involved in providing these cleaning agents.

In a further embodiment, the cleaning agent combinations according to the invention are combined with one or more further cleaning agents.

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.

A detergent combination comprising

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

The further cleaning agent preparation A combined with the cleaning agent combination according to the invention is preferably a cleaning agent containing builder.

The further cleaning agent preparation A combined with the cleaning agent combination according to the invention is preferably a liquid cleaning agent.

The further cleaning agent preparation A combined with the cleaning agent combination according to the invention is preferably a bleach-free and / or phosphate-free cleaning agent.

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

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

The further cleaning agent preparation A combined with the cleaning agent combination according to the invention is particularly preferably a liquid cleaning agent that contains builders, is free of phosphates, bleaches, surfactants and enzymes.

The composition of some exemplary liquid cleaning agent combinations according to the invention, in which at least 20 wt .-%, preferably between 20 and 80 wt .-%, particularly preferably between 30 and 75 wt .-% and in particular between 40 and 70 wt .-% of the total amount of surfactant Detergent combination is contained in detergent preparation B, can be found in the following table 6: Recipe 1 Recipe 2 A [% by weight] B [% by weight] C [% by weight] A [% by weight] B [% by weight] C [% by weight] Nonionic surfactant optional 2.0 to 20 Yes optional 5.0 to 15 Yes Protease preparation - 5.0 to 50 - - 10 to 30 - Amylase preparation - 0.1 to 30 - - 2.0 to 20 - Builders 5.0 to 60 <10 <10 15 to 40 <5 <5 phosphate - - - - - - Org. Solvent optional 5.0 to 80 5.0 to 60 optional 12 to 60 12 to 60 water 5.0 to 50 10 to 70 20 to 80 5.0 to 50 10 to 40 40 to 70 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Recipe 3 Recipe 4 A [% by weight] B [% by weight] C [% by weight] A [% by weight] B [% by weight] C [% by weight] Nonionic optional 2.0 to 20 Yes optional 5.0 to 15 Yes Surfactant Protease preparation - 5.0 to 50 - - 10 to 30 - Amylase preparation - 0.1 to 30 - - 2.0 to 20 - Builders 5.0 to 60 <10 <10 15 to 40 <5 <5 Bleach - - - - - - Org. Solvent optional 5.0 to 80 5.0 to 60 optional 12 to 60 12 to 60 water 5.0 to 50 10 to 70 20 to 80 5.0 to 50 10 to 40 40 to 70 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Recipe 5 Recipe 6 A [% by weight] B [% by weight] C [% by weight] A [% by weight] B [% by weight] C [% by weight] Nonionic surfactant optional 2.0 to 20 Yes optional 5.0 to 15 Yes Protease preparation - 5.0 to 50 - - 10 to 30 - Amylase preparation - 0.1 to 30 - - 2.0 to 20 - Builders 5.0 to 60 <10 <10 15 to 40 <5 <5 phosphate - - - - - - Bleach - - - - - - Org. Solvent optional 5.0 to 80 5.0 to 60 optional 12 to 60 12 to 60 water 5.0 to 50 10 to 70 20 to 80 5.0 to 50 10 to 40 40 to 70 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Recipe 5 Recipe 6 A [% by weight] B [% by weight] C [% by weight] A [% by weight] B [% by weight] C [% by weight] Nonionic surfactant optional 2.0 to 20 Yes optional 5.0 to 15 Yes Protease preparation - 5.0 to 50 - - 10 to 30 - Amylase preparation - 0.1 to 30 - - 2.0 to 20 - Builders 5.0 to 60 <10 <10 15 to 40 <5 <5 silicate - - - - - - Bleach - - - --- - - Org. Solvent optional 5.0 to 80 5.0 to 60 optional 12 to 60 12 to 60 water 5.0 to 50 10 to 70 20 to 80 5.0 to 50 10 to 40 40 to 70 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Recipe 9 Recipe 10 A [% by weight] B [% by weight] C [% by weight] A [% by weight] B [% by weight] C [% by weight] Nonionic surfactant optional 2.0 to 20 Yes optional 5.0 to 15 Yes Protease preparation - 5.0 to 50 - - 10 to 30 - Amylase preparation - 0.1 to 30 - - 2.0 to 20 - Builders 5.0 to 60 <10 <10 15 to 40 <5 <5 phosphate - - - - - - silicate - - - - - - Bleach - - - - - - Org. Solvent optional 5.0 to 80 5.0 to 60 optional 12 to 60 12 to 60 water 5.0 to 50 10 to 70 20 to 80 5.0 to 50 10 to 40 40 to 70 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Recipe 11 Recipe 12 A [% by weight] B [% by weight] C [% by weight] A [% by weight] B [% by weight] C [% by weight] Nonionic surfactant 1 * optional 2.0 to 20 Yes optional 5.0 to 15 Yes Nonionic surfactant 2 ** optional optional Yes optional optional Yes Protease preparation - 5.0 to 50 - - 10 to 30 - Amylase preparation - 0.1 to 30 - - 2.0 to 20 - Builders 5.0 to 60 <10 <10 15 to 40 <5 <5 phosphate - - - - - - Bleach - - - - - - Org. Solvent optional 5.0 to 80 5.0 to 60 optional 12 to 60 12 to 60 water 5.0 to 50 10 to 70 20 to 80 5.0 to 50 10 to 40 40 to 70 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Recipe 13 Recipe 14 A [% by weight] B [% by weight] C [% by weight] A [% by weight] B [% by weight] C [% by weight] Nonionic surfactant 1 * optional 2.0 to 20 Yes optional 5.0 to 15 Yes Nonionic surfactant 2 ** optional optional Yes optional optional Yes Protease preparation - 5.0 to 50 - - 10 to 30 - Amylase preparation - 0.1 to 30 - - 2.0 to 20 - Builders 5.0 to 60 <10 <10 15 to 40 <5 <5 silicate - - - - - - Bleach - - - - - - Org. Solvent optional 5.0 to 80 5.0 to 60 optional 12 to 60 12 to 60 water 5.0 to 50 10 to 70 20 to 80 5.0 to 50 10 to 40 40 to 70 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Recipe 15 Recipe 16 A [% by weight] B [% by weight] C [% by weight] A [% by weight] B [% by weight] C [% by weight] Nonionic surfactant 1 * optional 2.0 to 20 Yes optional 5.0 to 15 Yes Nonionic surfactant 2 ** optional optional Yes optional optional Yes Protease preparation - 5.0 to 50 - - 10 to 30 - Amylase preparation - 0.1 to 30 - - 2.0 to 20 - Builders 5.0 to 60 <10 <10 15 to 40 <5 <5 phosphate - - - - - - silicate - - - - - - Bleach - - - - - - Org. Solvent optional 5.0 to 80 5.0 to 60 optional 12 to 60 12 to 60 water 5.0 to 50 10 to 70 20 to 80 5.0 to 50 10 to 40 40 to 70 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 * nonionic surfactant from the group of hydroxy mixed ethers
** nonionic surfactant from the group of Y surfactants

Cleaning agent combinations according to the invention, comprising the cleaning agent preparations A, B and C, contain less than 2% by weight of phosphate. Phosphate-free cleaning agent combinations comprising the cleaning agent preparations A, B and C are very particularly preferred according to the invention. Also preferred are those cleaning agent combinations according to the invention, comprising the cleaning agent preparations 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 cleaning agent combinations according to the invention are silicate-free. Both the lowering of the phosphate content and the lowering of the silicate content have proven to be advantageous for the stability of the cleaning agent combinations according to the invention.

The further detergent preparation A can 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 group of organic complexing agents includes, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and other organic cobuilders such as the phosphonates. These substance classes are described below.

Organic complexing agents which can be used are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or its sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, ethylenediamine disuccinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, as well as mixtures of these. In addition to their builder effect, the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value in detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular.
Polymeric aminodicarboxylic acids, their salts or their precursor substances are also to be mentioned as further preferred builder substances. Polyaspartic acids and their salts are particularly preferred.

Further suitable organic complexing agents are polyacetals, which can be obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 carbon 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.

Other 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. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30,000 g / mol can be used.

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

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are also further suitable cobuilders. Ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Farther In this context, glycerol disuccinates and glycerol trisuccinates are also preferred. Suitable amounts used are from 3 to 15% by weight.

The automatic dishwashing agents according to the invention particularly preferably contain methylglycinediacetic acid or a salt of methylglycinediacetic acid.

Other useful organic complexing agents are, for example, acetylated hydroxycarboxylic acids or their salts, which can optionally also be 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 cleaning agent combinations according to the invention are characterized in that the cleaning agent preparation A, based on its 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. Contents of organic complexing agents are preferably above 25% by weight, particularly preferably above 30% by weight and in particular above 35% by weight. The upper limit of the content of organic complexing agents is preferably 85% by weight and in particular 75% by weight.

Particularly preferred automatic dishwashing agents according to the invention contain citrate as one of their essential organic complexing agents. Cleaning agent combinations according to the invention, characterized in that the cleaning agent preparation A contains 2.0 to 50 wt.%, Preferably 4.0 to 40 wt.% And in particular 5.0 to 30 wt.% Citrate, are preferred according to the invention.

A second important organic complexing agent is ethylenediamine disuccinic acid (EDDS), preferred cleaning agent preparations A being characterized in that these, based on their total weight, are 3.0 to 65% by weight, preferably 5.0 to 60% by weight and in particular Contain 10 to 50% by weight of ethylenediamine disuccinic acid. Ethylenediamine disuccinic acid contents above 12% by weight, particularly preferably above 15% by weight and in particular above 20% by weight, are preferably achieved. The upper limit of the content of ethylenediamine disuccinic acid is preferably 55% by weight, and particularly 45% by weight.

Ethylenediamine disuccinic acid has proven to be particularly effective, particularly in phosphate-free detergent preparations, with regard to cleaning tar 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. Regarding the in the The weight proportion of the ethylenediamine disuccinic acid used in agents according to the invention is to be based on the weight proportion of the free acid when the acid salt is used, that is, the weight proportion of the salt is converted to the weight proportion of the acid.

The complex-forming phosphonates form a group of further organic complexing agents used with preference in the cleaning agent preparations A according to the invention, this group including 1-hydroxyethane-1,1-diphosphonic acid and a number of different compounds such as diethylenetriaminepenta (methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt reacting alkaline (pH 9). Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferred as aminoalkanephosphonates. They are preferably in the form of the neutrally reacting sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP. From the class of the phosphonates, HEDP is preferably used as the builder. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, it can be preferred to use aminoalkanephosphonates, in particular DTPMP, or mixtures of the phosphonates mentioned.

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

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

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

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

The cleaning agent preparations according to the invention can of course contain two or more different phosphonates.

The proportion by weight of the phosphonates in the total weight of cleaning agent preparations A according to the invention is preferably 1 to 8% by weight, preferably 1.2 to 6% by weight and in particular 1.5 to 4% by weight.

The alkali carriers form a second group of builders. The group of alkali carriers includes the carbonates and / or hydrogen carbonates as well as the alkali metal hydroxides. The group of carbonates and hydrogen carbonates is summarized in the context of this application by the term (hydrogen) carbonate.

Preferred cleaning agent combinations according to the invention are characterized in that the cleaning agent preparation A, based on its total weight, is 1.0 to 30% by weight, preferably 2.0 to 25% by weight and in particular 5.0 to 20% by weight of builder ( e) from the group of alkali carriers

It is particularly preferred to use (hydrogen) carbonate (s), preferably alkali (hydrogen) carbonate (s), particularly preferably sodium (hydrogen) carbonate or potassium (hydrogen) carbonate in amounts from 1.0 to 40% by weight, preferably 2 , 0 to 30% by weight and in particular 4.0 to 15% by weight based on the total weight of the cleaning agent preparation A.

To increase or adjust the alkalinity, preferred cleaning agent preparations according to the invention contain alkali metal hydroxide (s). The alkali metal hydroxides are preferably used in the detergents 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 the Detergent, used. The cleaning agent preparations A according to the invention particularly preferably contain potassium hydroxide. Cleaning agent preparations according to the invention preferably contain less than 10% by weight, particularly preferably less than 5% by weight and in particular less than 2% by weight phosphate. Phosphate-free cleaning agent preparations A are very particularly preferred according to the invention. Furthermore, those cleaning agent preparations 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 are preferred. Machine dishwashing agents according to the invention which are particularly preferred are free of silicate. By doing without silicate, the physical stability of the automatic dishwashing detergents according to the invention is surprisingly improved.

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

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

The proportion by weight of cleaning-active anionic polymers in the total weight of the cleaning agent preparation A is preferably 1.0 to 30% by weight, preferably 2.0 to 25% by weight and in particular 5.0 to 20% by weight.

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

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

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and 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 particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70,000 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 (co) polymeric polycarboxylates in preferred automatic dishwashing agents is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight, based in each case on the total weight of the automatic dishwashing agent.

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

The unsaturated carboxylic acid (s) used is / are with particular preference unsaturated carboxylic acids of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH ₂ , -OH or -COOH such as defined above or represents —COOH or —COOR ⁴ , where 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. The unsaturated dicarboxylic acids can of course also be used.

The monomers containing sulfonic acid groups are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

preferred, in which R ⁵ to R ⁷ independently of one another for -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, with - NH ₂ , -OH or -COOH-substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present 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 represents an optionally present 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-propen1-sulfonic acid, Styrene sulfonic acid, vinyl sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.

In the polymers, the sulfonic acid groups can be wholly or partially in neutralized form, i.e. the acidic hydrogen atom 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 copolymers containing sulfonic acid groups is preferred according to the invention.

The monomer distribution of the copolymers used with preference according to the invention is, in the case of copolymers which only contain monomers from groups i) and ii), preferably in each case from 5 to 95% by weight of i) or ii), particularly preferably from 50 to 90% by weight of monomer from group ii) and 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 application. Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses 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 furthermore comprise, in addition to carboxyl-containing monomer and sulfonic acid-containing monomer, at least one nonionic, preferably hydrophobic, monomer. The use of these hydrophobically modified polymers made it possible, in particular, to improve the rinse aid performance of automatic dishwashing agents 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 agent, characterized in that the automatic dishwashing agent comprises a copolymer as an anionic copolymer

1. i) Carboxylic acid group-containing monomer (s)
2. ii) Monomer (s) containing sulfonic acid groups
3. iii) nonionic monomer (s).

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 stand for -H, -CH ₃ or -C2H5, and X stands for 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 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, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, α-olefins with 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-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, methyl acrylate, methyl acrylate, butyl acrylate, acrylate - (Methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N - (2-ethylhexyl) acrylamide, octyl acrylate, methacr ylsäureoctylester, 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 cleaning agent combinations according to the invention are characterized in that the cleaning agent combination contains a further, preferably liquid, cleaning agent A

• 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 combination of cleaning agents described above is made up, for example, by means of a packaging material 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 receiving chambers that are separate from one another, each of these receiving chambers containing one of the cleaning agents combined with one another. Examples of such packaging forms are cartridges with two, three, four or more separate receiving chambers, for example two-, three-, four- or multi-chamber bottles. By separating the cleaning agents of different compositions, undesired 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.

Another subject matter of the present application is a cleaning agent supply form for automatic dosing in automatic dishwashing, comprising

1. a) a cleaning agent combination according to the invention in an amount sufficient to carry out at least two, preferably at least four and in particular at least eight times a machine dishwashing process;
2. b) a cartridge for the cleaning agent combination, in which the preferably liquid cleaning agents B and C are present separately from one another.

The recipes disclosed in Tables 1 to 5 are particularly suitable for this purpose.

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;
     • b2) wenigstens ein reinigungsaktives Enzym
   • eine Klarspülzusammensetzung C, enthaltend
     c1) wenigstens ein nichtionisches Tensid
   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.

Another preferred subject matter of the present application is a cleaning agent supply form for automatic dosing in automatic dishwashing, comprising

1. a) a cleaning agent combination comprising
   • a cleaning agent preparation A containing
     a1) at least one builder from the group of organic complexing agents
   • a cleaning agent preparation B containing
     • b1) at least one nonionic surfactant;
     • b2) at least one active cleaning enzyme
   • a rinse aid composition C containing
     c1) at least one nonionic surfactant
   in an amount sufficient for at least two, preferably at least four and in particular at least eight times an automatic dishwashing process;
2. b) a cartridge for the cleaning agent combination, in which the preferably liquid cleaning agents A, B and C are present separately from one another.

The recipes disclosed in Tables 1 to 6 are particularly suitable for this purpose.

In a preferred embodiment, the previously described cartridges of the cleaning agent supply forms are provided with a dispensing device that can be detached 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. By separating the cartridge and the dispenser, for example, filling the cartridge is simplified. Alternatively, the detachable connection between the cartridge and the dispenser enables the cartridges to be exchanged on the dispenser. Such an exchange can be indicated, for example, when the cleaning program is changed 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.

Another subject matter of the present application is a detergent metering system for automatic metering in automatic dishwashing, comprising

1. a) a cleaning agent combination according to the invention in an amount sufficient to carry out at least two, preferably at least four and in particular at least eight times a machine dishwashing process;
2. b) a cartridge for the cleaning agent combination, in which the preferably liquid cleaning agents B and C are present separately from one another;
3. c) a dispensing device detachably connected to the cartridge.

The recipes disclosed in Tables 1 to 5 are particularly suitable for this purpose.

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;
     • b2) wenigstens ein reinigungsaktives Enzym
   • eine Klarspülzusammensetzung C, enthaltend
     c1) wenigstens ein nichtionisches Tensid
   
   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.

An additional preferred subject of the present application is a detergent metering system for automatic metering in automatic dishwashing, comprising

1. a) a cleaning agent combination comprising
   • a cleaning agent preparation A containing
     a1) at least one builder from the group of organic complexing agents
   • a cleaning agent preparation B containing
     • b1) at least one nonionic surfactant;
     • b2) at least one active cleaning enzyme
   • a rinse aid composition C containing
     c1) at least one nonionic surfactant
   
   in an amount sufficient for at least two, preferably at least four and in particular at least eight times an automatic dishwashing process;
2. b) a cartridge for the cleaning agent combination, in which the preferably liquid cleaning agents A, B and C are present separately from one another.
3. c) a dispensing device detachably connected to the cartridge.

The recipes disclosed in Tables 1 to 6 are particularly suitable for this purpose.

Of course, detergent dosing systems are also conceivable in which the cartridge and the dosing device are permanently connected to one another. However, the detachable connection between the cartridge and the dispensing device has the advantage that the dispensing device can be used several times, that is, in combination with several cartridges (reusable dispensing 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.

The present application also relates to a detergent metering system, comprising

1. a) a cleaning agent combination according to the invention in an amount sufficient to carry out at least two, preferably at least four and in particular at least eight times a machine dishwashing process;
2. b) a cartridge for the cleaning agent combination in which the liquid cleaning agents B and C are present separately from one another;
3. c) a dosing device permanently connected to the cartridge.

The recipes disclosed in Tables 1 to 5 are particularly suitable for this purpose.

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;
     • b2) wenigstens ein reinigungsaktives Enzym
   • eine Klarspülzusammensetzung C, enthaltend
     c1) wenigstens ein nichtionisches Tensid
   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.

An additional preferred subject of the present application is a detergent metering system for automatic metering in automatic dishwashing, comprising

1. a) a cleaning agent combination comprising
   • a cleaning agent preparation A containing
     a1) at least one builder from the group of organic complexing agents
   • a cleaning agent preparation B containing
     • b1) at least one nonionic surfactant;
     • b2) at least one active cleaning enzyme
   • a rinse aid composition C containing
     c1) at least one nonionic surfactant
   in an amount sufficient for at least two, preferably at least four and in particular at least eight times an automatic dishwashing process;
2. b) a cartridge for the cleaning agent combination, in which the preferably liquid cleaning agents A, B and C are present separately from one another.
3. c) a dosing device permanently connected to the cartridge.

The recipes disclosed in Tables 1 to 6 are particularly suitable for this purpose.

The aforementioned detergent dosing systems, comprising the detergent supply form according to the invention (and optionally one or two further cleaning agents different from the detergent preparations B and C according to the invention), a cartridge and a dosing device detachably connected to the cartridge are present in a common outer packaging in a preferred embodiment, the filled cartridge and the dispensing device are particularly preferably contained separately from one another in the outer packaging. The outer packaging is used for storage, transport and presentation of the cleaning agent supply form according to the invention and protects it from soiling, impact and shock. In particular, for the purpose of presentation, the outer packaging should be at least partially transparent.

As an alternative or in addition to an outer packaging, there is of course the possibility of marketing the cleaning agent supply form according to the invention in connection with a dishwasher. Such a combination is particularly in the cases advantageous, in which the course of the automatic dishwashing process (for example duration, temperature course, water supply) and the detergent recipe or the control electronics of the dispenser are coordinated with one another.

The dosing system according to the invention consists of the basic components of a cartridge filled with the cleaning agent according to the invention and a dosing device that can be coupled to the cartridge, which in turn is formed from further assemblies, such as component carriers, actuators, closure elements, sensors, energy sources and / or control units.

It is preferred that the dosing system according to the invention is movable. Movable in the sense of this application means that the dosing system is not inextricably linked to a water-carrying device such as a dishwasher, washing machine, tumble dryer or the like, but can be removed by the user from a dishwasher or positioned in a dishwasher, i.e. can be handled independently

According to an alternative embodiment of the invention, it is also conceivable that the dosing device is not detachably connected for the user 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 can have a pH value between 2 and 12 depending on the intended use, all components of the dosing system that come into contact with the preparations should have a corresponding acid and / or alkali resistance. Furthermore, through a suitable choice of material, these components should be largely chemically inert, for example to nonionic surfactants, enzymes and / or fragrances.

cartridge

A cartridge in the context of this application is understood to mean a packaging material which is suitable for enveloping or holding together flowable or scatterable preparations and which can be coupled to a dispensing device for dispensing the preparation.

In particular, a cartridge can also comprise several chambers which can be filled with compositions that differ from one another. 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 in such a way that a release of the preparation from the container under the force of gravity in the Use position of the dispenser can be effected. As a result, no further conveying means are required to release the preparation from the container, which means that the construction of the dispensing device can be kept simple and the manufacturing costs can be kept low.

In a preferred embodiment of the invention, at least one second chamber is provided for receiving at least one second flowable or sprinkleable preparation, the second chamber having at least one outlet opening which is arranged such that a gravity-induced product release from the second chamber in the use position of the dispensing device is effected. The arrangement of a second chamber is particularly advantageous when preparations are stored in the separate containers which are usually not mutually stable, 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 to release volatile preparations such as a fragrance into the environment.

In a further embodiment of the invention, the cartridge is designed in one piece. In this way, the cartridges can be formed cost-effectively in one production step, in particular by suitable blow molding processes. The chambers of a cartridge can be separated from one another by bars or material bridges.

The cartridge can also be formed in several pieces by components manufactured by injection molding and then joined together.

Furthermore, it is conceivable that the cartridge is formed in several pieces in such a way that at least one chamber, preferably all chambers, can be individually removed from the dosing device or inserted into the dosing device. This makes it possible to replace an already emptied chamber when a preparation is consumed differently from one chamber, while the remaining chambers, which can still be filled with preparation, remain in the dispensing device. A targeted and needs-based refilling of the individual chambers or their preparations can thus 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 to one another in a detachable or non-detachable manner by means of a suitable form-fitting, force-fitting or material connection. In particular, the fixation can be achieved by one or more of the connection types from the group of snap-in connections, Velcro connections, press connections, fusion connections, adhesive connections, welded connections, soldered connections, screw connections, wedge connections, clamp connections or Bounce connections take place. In particular, the fixation can also be formed by a shrink tube (so-called sleeve) which, in a heated state, is drawn over the entire or sections of the cartridge and tightly encloses the chambers or the cartridge in the cooled state.

In order to provide the chambers with advantageous residual emptying properties, the bottom of the chambers can be inclined in the shape of a funnel towards the dispensing opening. Furthermore, through a suitable choice of material and / or surface design, the inner wall of a chamber can be designed in such a way that there is little material adhesion of the preparation to the inner chamber wall. This measure also enables the remaining emptying capacity of a chamber to be further optimized.

The chambers of a cartridge can have the same or different filling volumes. In the case of a configuration with two chambers, the ratio of the container volumes is preferably 5: 1, in a configuration with three chambers it is preferably 4: 1: 1, these configurations being 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, the volume ratio of the chambers being approximately 4: 1: 1.

A metering chamber can be formed in or on a chamber in front of the outlet opening in the direction of flow of the preparation. The dosage chamber determines the amount of preparation that is to be released into the environment when the preparation is released from the chamber. This is particularly advantageous if the closure element of the dispensing device, which effects the release of the preparation from a chamber to the environment, can only be put into a release and a closed state without checking the amount to be released. The dosing chamber then ensures that a predefined amount of preparation is released without direct feedback of the dispensed amount of preparation. The metering chambers can be formed in one piece or in several pieces.

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

To ventilate the cartridge chambers, ventilation options can be provided, in particular in the head area of the cartridge, in order to ensure pressure equalization between the interior of the cartridge chambers and the environment when the filling level of the chambers falls. These ventilation options can be designed, for example, as a valve, in particular a silicone valve, micro-openings in the cartridge wall or the like.

If, according to a further embodiment, the cartridge chambers are not ventilated directly, but rather via the dosing device or no ventilation, e.g. when using flexible containers such as bags, this has the advantage that at elevated temperatures in the course of a dishwasher wash cycle As a result of the heating of the chamber contents, a pressure is built up which pushes the preparations to be dosed in the direction of the outlet openings, so that the cartridge can be easily emptied. Furthermore, with such an air-free packaging there is no risk of oxidation of substances in the preparation, which makes pouch packaging or also bag-in-bottle packaging appear appropriate, in particular for preparations sensitive to oxidation.

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

The cartridge can take any shape. It can, for example, be cube-like, spherical or plate-like.

The cartridge and the dosing device can in particular be designed in terms of their spatial shape in such a way that they ensure the lowest possible loss of useful volume, especially in a dishwasher.

To use the dispensing device in dishwashers, it is particularly advantageous to shape the device based on dishes to be cleaned in dishwashers. For example, it can be plate-shaped, roughly the size of a plate. This allows the dispenser to be positioned in a space-saving manner, for example in the lower basket of the dishwasher. Furthermore, the correct positioning of the dosing unit is immediately and intuitively revealed to the user thanks to the plate-like shape. The cartridge preferably has a height: width: depth ratio of between 5: 5: 1 and 50: 50: 1, particularly preferably about 10: 10: 1. The "slim" design of the dispensing device and the cartridge make it possible, in particular, to position the device in the lower cutlery basket of a dishwasher in the receptacles provided for plates. This has the advantage that the preparations dispensed from the dispenser reach the washing liquor directly and cannot adhere to other items to be washed.

Commercially available household dishwashers are usually designed in such a way that larger items, such as pans or large plates, are arranged in the lower basket of the dishwasher. In order to avoid a non-optimal positioning of the dosing system by the user in the upper basket, in an advantageous embodiment of the invention the dosing system is dimensioned in such a way that the dosing system can only be positioned in the receptacles provided in 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 design the dosing unit in the form of a cup with an essentially circular or square base area.

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

Another possibility for reducing the influence of heat on a preparation in a chamber of the cartridge is to isolate the chamber by suitable measures, e.g. by using thermal insulation materials such as styrofoam, which completely or partially enclose the chamber or the cartridge in a suitable manner.

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

This information can be used to select a dosing program stored in the control unit. This ensures that a dosing program that is optimal for a particular preparation is always used. It can also be provided that if there is no RFID label or if there is an RFID label with an incorrect or faulty identifier, no dosing is carried out by the dosing device and instead an optical or acoustic signal is generated that the user is on the present Errors.

In order to rule out incorrect use of the cartridge, the cartridges can also have structural elements that interact with corresponding elements of the dispenser according to the key-lock principle, so that, for example, only cartridges of a certain type can be coupled to the dispenser. This configuration also makes it possible for information about the cartridge coupled to the dispensing device to be sent to the Control unit are transmitted, whereby a matched to the content of the corresponding container control of the dosing device can take place.

The cartridge is designed in particular to hold free-flowing detergents or cleaning agents. Such a cartridge particularly preferably has a plurality of chambers for the spatially separated reception of preparations of a washing or cleaning agent that are different from one another.

The cartridge can be designed such that it can be arranged in or on the dishwasher in a detachable or fixed manner.

Dosing device

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

The dosing device preferably consists of a splash-proof housing that prevents splash water from penetrating into the interior of the dosing device, as can occur, for example, when used in a dishwasher.

It is particularly preferred that the dosing device comprises at least one first interface which interacts in or on a water-carrying device such as in particular a water-carrying household appliance, preferably a dishwasher or washing machine, in such a way that a transfer of electrical energy from the water-carrying device to the dosing device is realized.

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

In an advantageous further development of the invention, a second interface is in each case on the dosing device and the water-carrying device, such as a dishwasher, for the transmission of electromagnetic signals, which in particular contain operating status, measurement and / or control information of the dosing device and / or the water-carrying device such as a Represent dishwasher, trained.

adapter

An adapter can be used to easily couple the dosing system to a water-bearing household appliance. The adapter is used to mechanically and / or electrically connect the dosing system to the water-bearing household appliance.

The adapter is preferably firmly connected to a water-carrying line 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 captured by the water flow and / or spray jet of the household appliance.

The adapter makes it possible to run a dosing system for both an independent and a "buildin" version. It is also possible to design the adapter as a type 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.

In a dishwasher, the adapter can be arranged 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 as such is positioned inaccessible to the user in the water-bearing household appliance, so that the dosing device is inserted into the adapter, for example, during assembly with the household appliance, the adapter, the dosing device and the household appliance in such a way are designed so that a cartridge can be coupled to the dispenser by the user.

As stated at the outset, the cleaning agents according to the invention are distinguished by a particular physical and chemical stability, in particular to temperature fluctuations. The cleaning agents according to the invention are therefore exceptionally suitable for metering by means of a metering system located in the interior of a washing machine or dishwasher. 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 can also be introduced into the interior as a movable device (self-sufficient dosing device), contains the multiple amount of cleaning agent required to carry out an automatic cleaning process .

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

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 cleaning agent 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 movable cartridge of a dosing system provided for positioning in the interior of a dishwasher

with an amount of this cleaning agent combination sufficient for at least two, preferably at least four and in particular at least eight times an automatic dishwashing process to be carried out, is a further subject matter of the present application. As stated above, the cleaning agent combination can include two cleaning agent preparations B and C or, alternatively, three cleaning agent preparations A, B and C. The formulations disclosed in Tables 1 to 6 are particularly suitable for the aforementioned use.

As an alternative to the cleaning agent combination according to the invention, a cleaning agent supply form according to the invention, comprising the cleaning agent combination and a cartridge containing the cleaning agent preparations B and C, can of course also be used to fill a dispensing 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 detergent supply form as a detergent reservoir for

1. i) a dispenser integrated immovably in the interior of a dishwasher or
2. ii) a movable dosing device provided for positioning in the interior of a dishwasher is therefore a further subject matter 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.In particular, the use of a cleaning agent supply form according to the invention for filling is claimed

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

with a sufficient amount of this cleaning agent supply form for at least two, preferably at least four and in particular at least eight times an automatic dishwashing process are also subjects of this application. The cleaning agent supply form can, as stated above, comprise two cleaning agent preparations B and C or, alternatively, three cleaning agent preparations A, B and C. The formulations disclosed in Tables 1 to 6 are particularly suitable for the aforementioned use.

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

An example of a movable cartridge is a container that is brought into the interior of the dishwasher by the consumer 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, which can be integrated into the interior, can also be removed from the interior of the dishwasher by the consumer.

The detergent or detergent combination is metered from the cartridge into the interior of the dishwasher, as described above, preferably by means of a metering device that can be detached from the cartridge. Such a dosing device can be connected to the cartridge by means of an adhesive, latching, snap or plug connection. Cartridges with an undetachably 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.

The use of a detergent supply form according to the invention as a detergent reservoir for

1. i) a dispenser integrated immovably in the interior of a dishwasher or
2. ii) a movable dosing device provided for positioning in the interior of a dishwasher.

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

The use of a detergent metering 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.

Two further subjects of this application are the use of a cleaning agent supply form according to the invention, comprising

1. a) a cleaning agent preparation B according to the invention in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times;
2. b) at least one further cleaning agent preparation C different from B in an amount sufficient for at least two, preferably at least four and in particular at least eight times an automatic dishwashing process;
3. c) a cartridge for the detergent preparations B and C, in which the detergent preparations B and C are present in separate receiving chambers as a detergent reservoir for
   1. i) a dispenser integrated immovably in the interior of a dishwasher or
   2. ii) a movable dosing device provided for positioning in the interior of a dishwasher.

The formulations disclosed in Tables 1 to 5 are particularly suitable for the aforementioned use.

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.

What is further claimed is the use of a cleaning agent supply form according to the invention, comprising

1. a) a detergent preparation A in an amount sufficient for at least two, preferably at least four and in particular at least eight times an automatic dishwashing process;
2. b) a further cleaning agent preparation B according to the invention different from A in an amount sufficient for at least two, preferably at least four, and in particular at least eight, automatic dishwashing processes;
3. c) at least one further cleaning agent preparation C different from A and B in an amount sufficient for at least two, preferably at least four and in particular at least eight times an automatic dishwashing process;
4. d) a cartridge for the detergent preparations A, B and C, in which the detergent preparations A, B and C are in separate receiving chambers

as a detergent reservoir for

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

The formulations disclosed in Tables 1 to 6 are particularly suitable for the aforementioned use.

In summary, both the cleaning agent combinations according to the invention and the cleaning agent supply forms according to the invention are suitable as refill packs for dosing devices that are immovably integrated into the interior of a dishwasher and for movable dosing devices provided for positioning in the interior of a dishwasher.

As stated above, the cleaning agents and cleaning agent combinations according to the invention are used as automatic dishwashing agents. In the dishwashing process according to the invention, it is of course possible to use not only the cleaning agent supply forms according to the invention but also the cleaning agent metering systems according to the invention.

• 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.Automatic dishwashing processes using a cleaning agent combination according to the invention or a cleaning agent supply form according to the invention or of a detergent dosing system according to the invention, characterized in that in its course from a cartridge located in the interior of the dishwasher

• a partial amount b of the detergent preparation B in the cartridge is dosed into the interior of the dishwasher, with a residual amount of the detergent preparation B in the cartridge remaining in the cartridge until the end of the dishwashing process and this residual amount at least twice, preferably at least four times, and in particular corresponds to at least eight times the amount of subset b; and
• a partial amount c of the detergent preparation C in the cartridge is dosed into the interior of the dishwasher, with a residual amount of the detergent preparation C in the cartridge remaining in the cartridge until the end of the dishwashing process and this residual amount at least twice, preferably at least four times, and in particular corresponds to 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 aforementioned 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.

Preferred automatic dishwashing methods using a cleaning agent combination according to the invention or a cleaning agent supply form according to the invention or a cleaning agent metering system according to the invention are characterized in that in their course from a cartridge located in the interior of the dishwasher

• a partial amount a of the cleaning agent preparation A in the cartridge is dosed into the interior of the dishwasher, with a residual amount of the cleaning agent preparation A in the cartridge remaining in the cartridge until the end of the dishwashing process and this residual amount at least twice, preferably at least four times, and in particular corresponds to at least eight times the amount of the subset a; and
• a partial amount b of the detergent preparation B in the cartridge is dosed into the interior of the dishwasher, with a residual amount of the detergent preparation B in the cartridge remaining in the cartridge until the end of the dishwashing process and this residual amount at least twice, preferably at least four times, and in particular corresponds to at least eight times the amount of subset b; and
• a partial amount c of the detergent preparation C in the cartridge is dosed into the interior of the dishwasher, a residual amount of the detergent preparation C in the cartridge remaining in the cartridge until the end of the dishwashing process and this remaining amount at least twice, preferably at least four times and in particular at least eight times the amount of the subset c.

The recipes disclosed in Tables 1 to 6 are particularly suitable for the aforementioned process.

In a preferred embodiment, the detergent preparation B and the detergent preparation C are metered in at different times of the cleaning cycle. Automatic dishwashing methods, characterized in that detergents B and C are dosed with a time delay, detergent preparation B preferably being dosed in the course of the main cleaning cycle, while rinse aid composition C is preferably dosed during 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.

Another preferred subject of this application is therefore an automatic dishwashing process using a cleaning agent combination according to the invention, a cleaning agent supply form according to the invention or a cleaning agent metering system according to the invention, in the course of this

1. a) at a point in time t1, a partial amount b of the cleaning agent preparation B according to the invention located in the cartridge is dosed into the interior of the dishwasher from a cartridge located in the interior of the dishwasher, with a remaining amount of the cleaning agent preparation in the cartridge in the cartridge until the end of the dishwasher process remains, which corresponds to at least double, preferably at least four times and in particular at least eight times the amount of subset b;
2. b) at least one further point in time t2 ≠ t1 from a cartridge located in the interior of the dishwasher, a subset c of the detergent preparation C located in the second cartridge, which differs from the detergent preparation B according to the invention, is dosed into the interior of the dishwasher, with a residual amount of the in this cartridge remaining cleaning agent remains in the cartridge until the end of the dishwashing process, which corresponds to at least twice, preferably at least four times, and in particular at least eight times the amount of subset c.

In preferred embodiments of the above-described automatic dishwashing processes with staggered dosing of the detergent or cleaning agent preparations B and C or A, B and C, the time t2 is at least 1 minute, preferably at least 2 minutes and in particular between 3 and 20 minutes before or after Time t1 is. The time t2 is preferably at least 1 minute, preferably at least 2 minutes and in particular between 3 and 20 minutes after time t1. The recipes disclosed in Tables 1 to 6 are particularly 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 an automatic dishwashing method using a cleaning agent according to the invention or a cleaning agent combination according to the invention or a cleaning agent supply form according to the invention or a cleaning agent metering system according to the invention in the course of this

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

The use of a cleaning agent combination according to the invention, a cleaning agent supply form according to the invention or a cleaning agent metering system according to the invention for washing dishes in a machine dishwashing process is a final subject of the present application.

Claims (15)

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

   - a liquid cleaning agent preparation B containing

   b1) at least one non-ionic surfactant and

   b2) at least one cleaning-active enzyme;

   - a liquid rinse aid composition C containing
   c1) at least one non-ionic surfactant,

   the preparations comprising less than 2 wt.% phosphate, characterized in that cleaning agent preparations B and C contain less than 10 wt.% builders.
2. The cleaning agent combination according to claim 1, characterized in that at least 20 wt.%, preferably between 20 and 80 wt.%, particularly preferably between 30 and 75 wt.% and in particular between 40 and 70 wt.% of the total amount of surfactant in the cleaning agent combination is contained in cleaning agent preparation B.
3. The cleaning agent combination according to one of the preceding claims, characterized in that a surfactant of the 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 independently of one another represent a linear or branched aliphatic hydrocarbon group having 2 to 20 carbon atoms.
4. The cleaning agent combination according to one of the preceding claims, characterized in that the proportion by weight of the non-ionic surfactant relative to 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 0.1 to 30 wt.%, preferably 1.0 to 25 wt.% and in particular 2.0 to 20 wt.% amylase preparation and/or 5 to 50 wt.%, preferably 7 to 40 wt.% and in particular 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 claim 7, characterized in that the cleaning agent preparation A, based on its total weight, contains 5.0 to 60 wt.%, preferably 10 to 50 wt.% and in particular 15 to 40 wt.% builder(s) from the group of organic complexing agents.
9. The use of a cleaning agent combination according to one of claims 1 to 8 for filling

   i) a cartridge of a dosing system integrated immovably in the interior of a dishwasher, or

   ii) a movable cartridge of a dosing system provided for positioning in the interior of a dishwasher

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

    a) a cleaning agent combination according to one of claims 1 to 8 in an amount that is sufficient for carrying out an automatic dishwashing process 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 provided separately from one another.
11. The use of a cleaning agent product format according to claim 10 as a cleaning agent reservoir for

    i) a dosing device integrated immovably in the interior of a dishwasher, or

    ii) a movable dosing device provided for positioning in the interior 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 that is sufficient for carrying out an automatic dishwashing process 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 provided separately from one another;

    c) a dosing device detachably connected to the cartridge.
13. Use of a cleaning agent combination according to one of claims 1 to 8, a cleaning agent product format according to claim 10 or a cleaning agent dosing system according to claim 12 for dishwashing in an automatic dishwashing process.
14. An automatic dishwashing process using a cleaning agent combination according to one of claims 1 to 8 or a cleaning agent product format according to claim 10 or a cleaning agent dosing system according to claim 12, characterized in that in its course from a cartridge located in the interior of the dishwasher

    - a partial amount b of the cleaning agent preparation B located in the cartridge is dosed into the interior of the dishwasher, a residual amount of the cleaning agent preparation B located in the cartridge remaining in the cartridge until the end of the dishwashing process and this residual amount corresponding to at least double, preferably four times and in particular eight times the amount of the partial amount b; and

    - a partial amount c of the cleaning agent preparation C located in the cartridge is dosed into the interior of the dishwasher, a residual amount of the cleaning agent preparation C located in the cartridge remaining in the cartridge until the end of the dishwashing process and this residual amount corresponding to at least double, preferably four times and in particular eight times the amount of the partial amount c.
15. An automatic dishwashing process according to claim 14, characterized in that the dosing of cleaning agents B and C is staggered, the cleaning agent preparation B preferably being dosed during the main cleaning cycle, while the rinse aid composition C is preferably dosed during the rinse cycle.