EP2220205B1 - Cleaning agent - Google Patents

Description

The present patent application describes detergents or cleaning agents, in particular detergents for the machine cleaning of dishes. This application relates in particular to two-phase or multiphase machine dishwashing detergents which contain bleach catalysts.

Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. Thus, a tableware that has been completely cleaned at first glance of food waste is then rated as not having any flaw if, after machine dishwashing, it still has discolorations which are based, for example, on the attachment of vegetable dyes to the dish surface.

In order to obtain spotless dishes, bleaching agents are used in automatic dishwashing detergents. In order to activate these bleaching agents and to achieve an improved bleaching effect during cleaning at temperatures of 60 ° C. and below, automatic dishwashing detergents generally also contain bleach activators or bleach catalysts, with the bleach catalysts in particular having proven to be particularly effective.

In the European patent application EP 481 793 A1 (Unilever) detergent tablets are disclosed which contain sodium percarbonate, which according to the teaching of this application, preferably from other components detrimental to its stability, for example, in a separate layer, assembled.

Bleach catalysts are used in automatic dishwasher detergents, preferably in the form of prefabricated granules. This is how the European patents describe EP 458 397 B1 (Unilever) EP 458 398 B1 (Unilever) and EP 530 870 B1 (Unilever) bleach catalysts based on various manganese-containing transition metal complexes.

Processes for the preparation of bleach catalyst granules are disclosed in the disclosures EP 544 440 A2 (Unilever) and WO 95/06710 A1 (Unilever) revealed. Characteristic of the methods described therein is the use of large amounts of binders, which are optionally used as melts, this method includes cooling and / or drying stages, which requires the use of additional equipment such as fluidized bed plants.

However, despite their undisputed bleaching performance, the use of bleach catalysts may not yet be considered satisfactory to one skilled in the art. Thus, despite the use of bleach catalysts in particular in low-alkaline, for example, phosphate-free, automatic dishwashing detergents often unexpectedly poor bleaching effects observed. Furthermore, the storage stability of bleach catalyst-containing detergents often leaves something to be desired.

In view of this initial situation, it was therefore the object of the present application to provide a dishwasher detergent which has an improved cleaning performance, in particular on bleachable soiling.

Surprisingly, it has been found that the bleaching action of automatic dishwashing detergents can be increased by the formulation of bleach / bleach activator / bleach catalyst combinations in two or more phase metered units with optimized phase split and the use of specific bleach activator granules having high bleach activator content.

1. a) ein Bleichmittel
2. b) einen Bleichaktivator
3. c) einen Bleichkatalysator ausgewählt aus der Gruppe der bleichverstärkenden Übergangsmetallsalze und Übergangsmetallkomplexe,

wobei das Bleichmittel a) getrennt von den Bestandeilen b) und c) in einer separaten Phase des Wasch- oder Reinigungsmittels vorliegt dadurch gekennzeichnet, dass der Bleichaktivator b) in partikulärer Form eingesetzt wird und die Bleichaktivatorpartikel, bezogen auf ihr Gesamtgewicht, einen Gehalt an Bleichaktivator oberhalb 80 Gew.-% aufweisen.A first subject of this application is therefore a two- or multi-phase washing or cleaning agent comprising

1. a) a bleaching agent
2. b) a bleach activator
3. c) a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes,

wherein the bleaching agent a) is present separately from the components b) and c) in a separate phase of the washing or cleaning agent, characterized in that the bleach activator b) is used in particulate form and the Blleichaktivatorpartikel, based on their total weight, a content of bleach activator have above 80 wt .-%.

Characteristic of the two- or multi-phase detergents or cleaning agents according to the invention is the fact that the bleaching agent a) is present separately from the components b) and c) in a separate phase of the washing or cleaning agent. The object of the claim thus comprises two-phase or multi-phase detergents or cleaners in which the total amount of bleach a) is separate from the total amount of components b) and c) in a separate phase.

• Zweiphasige- Wasch- oder Reinigungsmittel, umfassend
  1. a) ein Bleichmittel
  2. b) einen Bleichaktivator
  3. c) einen Bleichkatalysator ausgewählt aus der Gruppe der bleichverstärkenden Übergangsmetallsalze und Übergangsmetallkomplexe,
  wobei das Bleichmittel a) getrennt von den Bestandeilen b) und c) in einer separaten Phase des Wasch- oder Reinigungsmittels vorliegt dadurch gekennzeichnet, dass der Bleichaktivator b) in partikulärer Form eingesetzt wird und die Bleichaktivatorpartikel, bezogen auf ihr Gesamtgewicht, einen Gehalt an Bleichaktivator oberhalb 80 Gew.-% aufweisen.
• Dreiphasige Wasch- oder Reinigungsmittel, umfassend
  • a) ein Bleichmittel
  • b) einen Bleichaktivator
  • c) einen Bleichkatalysator ausgewählt aus der Gruppe der bleichverstärkenden Übergangsmetallsalze und Übergangsmetallkomplexe,
  wobei das Bleichmittel a) getrennt von den Bestandeilen b) und c) in einer separaten Phase des Wasch- oder Reinigungsmittels vorliegt dadurch gekennzeichnet, dass der Bleichaktivator b) in partikulärer Form eingesetzt wird und die Bleichaktivatorpartikel, bezogen auf ihr Gesamtgewicht, einen Gehalt an Bleichaktivator oberhalb 80 Gew.-% aufweisen.
• Vierphasige Wasch- oder Reinigungsmittel, umfassend
  • a) ein Bleichmittel
  • b) einen Bleichaktivator
  • c) einen Bleichkatalysator ausgewählt aus der Gruppe der bleichverstärkenden Übergangsmetallsalze und Übergangsmetallkomplexe,

wobei das Bleichmittel a) getrennt von den Bestandeilen b) und c) in einer separaten Phase des Wasch- oder Reinigungsmittels vorliegt dadurch gekennzeichnet, dass der Bleichaktivator b) in partikulärer Form eingesetzt wird und die Bleichaktivatorpartikel, bezogen auf ihr Gesamtgewicht, einen Gehalt an Bleichaktivator oberhalb 80 Gew.-% aufweisen.Preferred claims are thus:

• Two-phase washing or cleaning agents, comprising
  1. a) a bleaching agent
  2. b) a bleach activator
  3. c) a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes,
  wherein the bleaching agent a) is present separately from the components b) and c) in a separate phase of the washing or cleaning agent, characterized in that the bleach activator b) used in particulate form and the bleach activator particles, based on their total weight, have a content of bleach activator above 80% by weight.
• Three-phase detergents or cleaners, comprising
  • a) a bleaching agent
  • b) a bleach activator
  • c) a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes,
  wherein the bleaching agent a) is present separately from the components b) and c) in a separate phase of the washing or cleaning agent, characterized in that the bleach activator b) is used in particulate form and the Blleichaktivatorpartikel, based on their total weight, a content of bleach activator have above 80 wt .-%.
• Four-phase detergents or cleaners, comprising
  • a) a bleaching agent
  • b) a bleach activator
  • c) a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes,

wherein the bleaching agent a) is present separately from the components b) and c) in a separate phase of the washing or cleaning agent, characterized in that the bleach activator b) is used in particulate form and the Blleichaktivatorpartikel, based on their total weight, a content of bleach activator have above 80 wt .-%.

Multi-phase detergents or cleaners according to the invention contain as the first essential constituent a bleaching agent, oxygen bleaching agents being preferred. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.

Preferred two-phase or multi-phase detergents or cleaners are characterized in that the bleach a) is an oxygen bleach, preferably sodium percarbonate, more preferably a coated sodium percarbonate.

The proportion by weight of the bleaching agent a), based on the total weight of the washing or cleaning agent, in preferred embodiments is between 2 and 30% by weight, preferably between 4 and 20% by weight and in particular between 6 and 15% by weight.

As a second essential ingredient, two- or more-phase detergents or cleaners according to the invention contain bleach activators. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.

Two-phase or multi-phase detergents or cleaners, characterized in that the bleach activator b) is a bleach activator from the group of the acetylated amines, preferably tetraacetylenediamine (TAED), are preferred according to the invention.

These bleach activators, in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 10% by weight, especially 0.5 to 8% by weight and more preferably 1.0 to 6 Wt .-%, used.

Two-phase or multi-phase detergents or cleaners, characterized in that the proportion by weight of the bleach activator b), based on the total weight of the washing or cleaning agent, is between 0.1 and 10% by weight, preferably between 0.5 and 8% by weight. % and in particular between 1.0 and 6 wt .-%, are preferred according to the invention.

The bleach activator granules used according to the invention are characterized in that, based on their total weight, they have a content of bleach activator above 80% by weight. For the bleaching action described above, it has proven to be advantageous to realize the highest possible Blleichaktivatorgehalt in the granules.

Preferred two-phase or multi-phase detergents or cleaners according to the invention are characterized in that the bleach activator b) is present as bleach activator granules which, based on their total weight, contain more than 85% by weight, preferably more than 90% by weight, of bleach activator preferably above 95 wt .-% and in particular above 97 wt .-%.

With regard to the other active ingredients and auxiliaries in addition to the bleach activator in the bleach activator granules b), it has proven to be particularly advantageous to limit the content of polymeric granulation aids and stabilizers.

The group of polymeric granulation aids includes the natural, but especially the synthetic organic polymers, for example the polymeric polycarboxylates or the polymeric polysulfonates. The group of stabilizers includes in particular the phosphonates described below.

Preferred two- or multi-phase detergents or cleaners according to the invention are characterized in that the bleach activator b) is present as bleach activator granules which, based on its total weight, is less than 20% by weight, preferably less than 15% by weight, particularly preferred less than 10 wt .-% and in particular less than 5 wt .-% of a polymeric Granulationshilfsmittels.

Preferred two- or multi-phase detergents or cleaners according to the invention are furthermore characterized in that the bleach activator b) is present as bleach activator granulate which, based on its total weight, is less than 20% by weight, preferably less than 15% by weight, particularly preferred contains less than 10 wt .-% and in particular less than 5 wt .-% stabilizing additives.

In addition to the bleach activator granules used according to the invention with a bleach activator content above 80% by weight, the two-phase or multi-phase detergents or cleaners may of course also contain bleach activator granules which contain less than 80% by weight bleach activator, but it is preferred to reduce the proportion thereof Limit bleach activator granules with less than 80 wt .-% bleach activator on the total weight of the two- or multi-phase detergents or cleaning agents. Preference is given to two-phase or multi-phase detergents or cleaners which, based on their total weight, contain less than 4% by weight, preferably less than 2% by weight, preferably less than 1% by weight and in particular no bleach activator is present in particulate form and, based on its total weight, a content of bleach activator below 80 wt .-% has.

In addition to the conventional bleach activators, the detergents or cleaners according to the invention contain as third essential constituent at least one bleach catalyst c). These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the inventive compositions, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-Triazacyclononan (TACN), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN ) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are, for example, [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₂ (μ-OAc) ₁ (TACN ) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV ₄ (μ-O) ₆ (TACN) ₄ ] (ClO ₄ ) ₄ , [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (Me-TACN ) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₃ , [Mn ^IV ₂ (μ-O) ₃ ( Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (μ-O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (O) CH ₃ ).

Machine dishwashing detergent, characterized in that it further comprises a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me ₄ -TACN), are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.

Two-phase or multi-phase detergents or cleaners, characterized in that the bleach catalyst c) is a complex of manganese, preferably from the group of the complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ -TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me ₄ -TACN) are preferred according to the invention.

The aforementioned bleach-enhancing transition metal complexes, in particular with the central atoms Mn and Co, are used in customary amounts, preferably in an amount of up to 5% by weight, in particular of 0.0025% by weight to 1% by weight and more preferably of 0, 01 wt .-% to 0.30 wt .-%, each based on the total weight of the bleach catalyst-containing agents used. In special cases, however, more bleach catalyst can be used.

Two- or multi-phase detergents or cleaners, characterized in that the weight fraction of the bleach catalyst c), based on the total weight of the washing or cleaning agent is between 0.001 to 3.0 wt .-%, preferably between 0.01 to 2.0 wt .-% and in particular between 0.01 to 1.0 wt .-%, are inventively preferred.

• (Soweit nicht anders angegeben bezeichnen die aufgeführten Gewichtsanteile in dieser wie in allen folgenden Tabellen die Gesamtmengen der in dem zwei- oder mehrphasigen Wasch- oder Reinigungsmittel enthaltenen Bestandteile.)

Inhaltsstoff Rezeptur 1 [Gew.-%] Rezeptur 2 [Gew.-%] Rezeptur 3 [Gew.-%] Rezeptur 4 [Gew.-%] Sauerstoffbleichmittel [1]* 2 bis 30 4 bis 20 4 bis 20 6 bis 15 Bleichaktivator ^a [≠1] ** 0,1 bis 10 0,5 bis 8 0,5 bis 8 1 bis 6 Bleichkatalysator [≠1] 0,001 bis 3 0,001 bis 3 0,01 bis 2 0,01 bis 1,0 ^a soweit nicht anders angegeben, bezeichnet der Ausdruck "Bleichaktivator" in dieser wie in allen folgenden Tabellen erfindungsgemäße Bleichaktivatoren in partikulärer Form, die, bezogen auf ihr Gesamtgewicht, einen Gehalt an Bleichaktivator oberhalb 80 Gew.-% aufweist
* [1] = Phase 1 (in dieser wie in allen nachfolgenden Tabellen)
** [≠1] = Phase, bei der es nicht um Phase 1 handelt (in dieser wie in allen nachfolgenden Tabellen) Inhaltsstoff Rezeptur 5 [Gew.-%] Rezeptur 6 [Gew.-%] Rezeptur 7 [Gew.-%] Rezeptur 8 [Gew.-%] Natriumpercarbonat [1] 2 bis 30 4 bis 20 4 bis 20 6 bis 15 Bleichaktivator [≠1] 0,1 bis 10 0,5 bis 8 0,5 bis 8 1 bis 6 Bleichkatalysator [#1] 0,001 bis 3 0,001 bis 3 0,01 bis 2 0,01 bis 1,0 Inhaltsstoff Rezeptur 9 [Gew.-%] Rezeptur 10 [Gew.-%] Rezeptur 11 [Gew.-%] Rezeptur 12 [Gew.-%] Natriumpercarbonat [1] 2 bis 30 4 bis 20 4 bis 20 6 bis 15 TAED [#1] 0,1 bis 10 0,5 bis 8 0,5 bis 8 1 bis 6 Bleichkatalysator [≠1] 0,001 bis 3 0,001 bis 3 0,01 bis 2 0,01 bis 1,0 Inhaltsstoff Rezeptur 13 [Gew.-%] Rezeptur 14 [Gew.-%] Rezeptur 15 [Gew.-%] Rezeptur 16 [Gew.-%] Natriumpercarbonat [1] 2 bis 30 4 bis 20 4 bis 20 6 bis 15 TAED [≠1] 0,1 bis 10 0,5 bis 8 0,5 bis 8 1 bis 6 Mn-Me₃-TACN Komplex [≠1] 0,001 bis 3 0,001 bis 3 0,01 bis 2 0,01 bis 1,0 Some exemplary formulations for preferred two- or more-phase detergents or cleaners can be found in the following tables:

• (Unless indicated otherwise, the parts by weight given in this table as well as in all the following tables indicate the total amounts of the constituents contained in the two-phase or multiphase washing or cleaning agent.)

ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] Oxygen bleaching agent [1] * 2 to 30 4 to 20 4 to 20 6 to 15 Bleach activator ^a [≠ 1] ** 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 Bleach catalyst [≠ 1] 0.001 to 3 0.001 to 3 0.01 to 2 0.01 to 1.0 ^a, unless otherwise indicated, the term "bleach activator" in the following tables as in all inventive bleach activators in particulate form which comprises, based on its total weight, a content of bleach activator above 80 wt .-%
* [1] = phase 1 (in this as in all subsequent tables)
** [≠ 1] = phase that is not Phase 1 (in this table as well as in all subsequent tables) ingredient Recipe 5 [% by weight] Recipe 6 [% by weight] Recipe 7 [% by weight] Recipe 8 [% by weight] Sodium percarbonate [1] 2 to 30 4 to 20 4 to 20 6 to 15 Bleach activator [≠ 1] 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 Bleach catalyst [# 1] 0.001 to 3 0.001 to 3 0.01 to 2 0.01 to 1.0 ingredient Recipe 9 [% by weight] Recipe 10 [% by weight] Recipe 11 [% by weight] Recipe 12 [% by weight] Sodium percarbonate [1] 2 to 30 4 to 20 4 to 20 6 to 15 TAED [# 1] 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 Bleach catalyst [≠ 1] 0.001 to 3 0.001 to 3 0.01 to 2 0.01 to 1.0 ingredient Recipe 13 [% by weight] Formulation 14 [% by weight] Recipe 15 [% by weight] Recipe 16 [% by weight] Sodium percarbonate [1] 2 to 30 4 to 20 4 to 20 6 to 15 TAED [≠ 1] 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 Mn-Me ₃ -TACN complex [≠ 1] 0.001 to 3 0.001 to 3 0.01 to 2 0.01 to 1.0

In addition to the ingredients described above, the compositions according to the invention may contain further washing- or cleaning-active substances, preferably from the group of builders, surfactants, polymers, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.

The builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.

Preference is given to using crystalline layer-form silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred Values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.

Detergents or cleaning agents preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} .yH ₂ O of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular of 0.4 to 10 wt .-%, each based on the total weight of these agents.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.

Preferred washing or cleaning agents are free of water-insoluble aluminum silicates, such as the natural or synthetic zeolites used for water softening.

In the context of the present invention, it is preferred that these silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali metal disilicates, be present in detergents or cleaners in amounts of from 3 to 60% by weight, preferably from 8 to 50 Wt .-% and in particular from 20 to 40 wt.%, Each based on the weight of the washing or cleaning agent, are included.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

If phosphates are used as detergents or cleaning agents in the context of the present application, preferred agents comprise these phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (sodium or pentasodium) Potassium tripolyphosphate), in amounts of 5 to 80 wt .-%, preferably from 15 to 75 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the detergent or cleaning agent.

As a further preferred constituent, the washing or cleaning compositions according to the invention comprise at least one acid group-containing polymer which acts as a softener. The acid group-containing polymer comprises at least one acid group-containing monomer and optionally further nonionic (s), preferably hydrophobic monomer (s).

The proportion by weight of this polymer or these polymers in the total weight of the automatic dishwashing agent is preferably 0.1 to 30 wt .-%, preferably 0.5 to 25 wt .-% and in particular 1.0 to 20 wt .-%.

• i) mindestens ein Säuregruppen-haltiges Monomer
• ii) gegebenenfalls weitere(s) nichtionische, vorzugsweise hydrophobe Monomer(e)

enthalten, werden erfindungsgemäß bevorzugt.Detergents or cleaners which, based on their total weight, comprise 0.1 to 30% by weight, preferably 0.5 to 25% by weight and in particular 1.0 to 20% by weight of copolymer (s)

• i) at least one acid group-containing monomer
• ii) optionally further nonionic, preferably hydrophobic monomer (s)

contained are preferred according to the invention.

With regard to the improvement of the bleaching performance, in particular those copolymers have proved to be particularly effective, in which the acid group-containing monomer i) has a carboxylic acid group and / or a sulfonic acid group.

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

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.

In a preferred embodiment, the copolymers further comprise at least one additional ionic monomer in addition to at least one carboxylic acid group-containing monomer.

• i) Monomeren aus der Gruppe der ein- oder mehrfach ungesättigten Carbonsäuren
• ii) gegebenenfalls weitere(s) nichtionische, vorzugsweise hydrophobe Monomer(e)

enthalten.A first group of preferred detergents or cleaners is therefore characterized by comprising copolymer (e)

• i) monomers from the group of mono- or polyunsaturated carboxylic acids
• ii) optionally further nonionic, preferably hydrophobic monomer (s)

contain.

• i) Monomeren aus der Gruppe der ein- oder mehrfach ungesättigten Sulfonsäuren
• ii) gegebenenfalls weitere(s) nichtionische, vorzugsweise hydrophobe Monomer(e)

enthalten.A second group of preferred detergents or cleaners is therefore characterized by comprising copolymer (e)

• i) monomers from the group of mono- or polyunsaturated sulfonic acids
• ii) optionally further nonionic, preferably hydrophobic monomer (s)

contain.

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

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H,

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.

In the polymers, the sulfonic acid groups may be wholly or partly in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.

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

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

In a first preferred embodiment, the copolymers further comprise at least one additional ionic monomer in addition to at least one sulfonic acid group-containing monomer.

As further nonionic, preferably hydrophobic monomer (s), the acid group-containing polymers preferably contain monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ^{3 are} independently of one another H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ⁴ represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred unsaturated hydrocarbon radicals are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, α Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N - (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N - (2-ethylhexyl) acrylamide, acr ylsäureoctylester, Methacrylsäureoctylester, N - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N - (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N - (stearyl) acrylamide, behenyl acrylate, and Methacrylsäurebehenylester N- (Behenyl) acrylamide or mixtures thereof.

Some example formulations for preferred two- or more-phase polymer-containing detergents or cleaners can be found in the following tables: Ingredient [phase] Recipe 17 [% by weight] Recipe 18 [% by weight] Recipe 19 [% by weight] Recipe 20 [% by weight] Oxygen bleaching agent [1] 2 to 30 4 to 20 4 to 20 6 to 15 Bleach activator [≠ 1] 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 Bleach catalyst [≠ 1] 0.001 to 3 0.001 to 3 0.01 to 2 0.01 to 1.0 Acid group-containing polymer * 0.1 to 30 0.5 to 25 1 to 20 1 to 20 * Copolymer (s) comprising
i) at least one acid group-containing monomer
ii) optionally further nonionic, preferably hydrophobic monomer (s) as a constituent of the phase [1] and / or one or more further phases

Further builders are the alkali carriers. Suitable alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention. Particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. Because of their low chemical compatibility with the other ingredients of detergents or cleaners compared with other builders, the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the detergent or cleaning agent used. Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 2 to 50 wt .-%, preferably from 5 to 40 wt .-% and in particular from 7.5 to 30 wt .-%, each based on the weight of the washing or cleaning agent. Particularly preferred are agents which, based on the weight of the washing or cleaning agent less than 20 wt .-%, preferably less than 17 wt .-%, preferably less than 13 wt .-% and in particular less than 9 wt .-% carbonate (e) and / or bicarbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

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

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of detergents or cleaning agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,

Further preferred copolymers are those which have as their monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference. Corresponding polymers have already been described above as constituents of bleach activator granules according to the invention, for which reason reference is made to the statements there to avoid repetitions at this point.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.

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

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are from 3 to 15 wt .-%.

In addition to 1-hydroxyethane-1,1-diphosphonic acid, the complex-forming phosphonates comprise a number of different compounds such as, for example, diethylenetriaminepenta (methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance Meaning as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

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

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

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

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

Of course, the automatic dishwashing compositions of the invention may contain two or more different phosphonates.

Two-phase or multi-phase washing or cleaning agent, characterized in that the two- or multi-phase detergent or cleaning agent further contains at least one phosphonate, preferably 1-hydroxyethane-1,1-diphosphonic acid (HEDP), which together with the bleaching agent a) is present in a phase of the washing or cleaning agent, are preferred according to the invention.

The proportion by weight of the phosphonates is preferably 0.5 to 14 wt .-%, preferably 1 to 12 wt .-% and in particular 2 to 8 wt .-%.

Some exemplary formulations for preferred two- or more-phase phosphonate-containing detergents or cleaners can be found in the following tables: Ingredient [phase] Recipe 21 [% by weight] Recipe 22 [% by weight] Recipe 23 [% by weight] Recipe 24 [% by weight] Oxygen bleaching agent [1] 2 to 30 4 to 20 4 to 20 6 to 15 Bleach activator [≠ 1] 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 Bleach catalyst [≠ 1] 0.001 to 3 0.001 to 3 0.01 to 2 0.01 to 1.0 Phosphonate * 0.5 to 14 1 to 12 1 to 12 2 to 8 * as part of phase [1] and / or one or more additional phases

With particular preference, the inventive machine dishwashing detergents contain methylglycinediacetic acid or a salt of methylglycinediacetic acid, wherein the weight fraction of methylglycinediacetic acid or of the salt of methylglycinediacetic acid is preferably between 0.5 and 15% by weight, preferably between 0.5 and 10% by weight and in particular between 0.5 and 6 wt .-% is.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as builders.

The group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.

Nonionic surfactants which can be used are the nonionic surfactants known to the person skilled in the art. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, washing or cleaning agents, in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

With particular preference, therefore, ethoxylated nonionic surfactant selected from C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole Alcohol was used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide. Of these, the so-called "narrow range ethoxylates" are particularly preferred.

With particular preference further combinations of one or more tallow fatty alcohols with 20 to 30 EO and silicone defoamers are used.

Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred ,

Preferably used surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently stand for integers from 1 to 6.

Particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² , in which R ¹ and R ² independently of one another represents a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 -alkyl or -alkenyl radical; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.

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

Particularly preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.

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

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

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

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

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.

Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,

If anionic surfactants are used as constituents of automatic dishwasher detergents, their content, based on the total weight of the compositions, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight. Machine dishwashing detergents which do not contain anionic surfactants are particularly preferred.

Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants.

In automatic dishwashing detergents, the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. %. Automatic dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.

Some exemplary formulations for preferred two- or more-phase surfactant-containing detergents or cleaners can be found in the following tables: Ingredient [phase] Recipe 25 [% by weight] Recipe 26 [% by weight] Recipe 27 [% by weight] Recipe 28 [% by weight] Oxygen bleaching agent [1] 2 to 30 4 to 20 4 to 20 6 to 15 Bleach activator [≠ 1] 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 Bleach catalyst [≠ 1] 0.001 to 3 0.001 to 3 0.01 to 2 0.01 to 1.0 Nonionic surfactant * 01, to 15 0.2 to 10 0.5 to 8 1 to 6 * as part of phase [1] and / or one or more additional phases

The group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.

"Cationic polymers" in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

For the purposes of the present invention, "amphoteric polymers" furthermore have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.

Preferred washing or cleaning agents, in particular preferred automatic dishwasher detergents, are characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C =CR ³ R, in which each R ¹ , R ² , R ³ , R ⁴ is independently selected from hydrogen, derivatized hydroxy, C _1-30 linear or branched alkyl, aryl, aryl substituted C _1-30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least one quaternized nitrogen atom or at least one amino group having a positive charge in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least one radical R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one Aminogru ppe with a positive charge.

bei der R¹ und R⁴ unabhängig voneinander für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen steht; R² und R³ unabhängig voneinander für eine Alkyl-, Hydroxyalkyl-, oder Aminoalkylgruppe stehen, in denen der Alkylrest linear oder verzweigt ist und zwischen 1 und 6 Kohlenstoffatomen aufweist, wobei es sich vorzugsweise um eine Methylgruppe handelt; x und y unabhängig voneinander für ganze Zahlen zwischen 1 und 3 stehen. X repräsentiert ein Gegenion, vorzugsweise ein Gegenion aus der Gruppe Chlorid, Bromid, Iodid, Sulfat, Hydrogensulfat, Methosulfat, Laurylsulfat, Dodecylbenzolsulfonat, p-Toluolsulfonat (Tosylat), Cumolsulfonat, Xylolsulfonat, Phosphat, Citrat, Formiat, Acetat oder deren Mischungen.In the context of the present application, particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X represents a counterion, preferably a counterion from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula are selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH , -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , - CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H.

werden im Falle von X^-= Chlorid auch als DADMAC (Diallyldimethylammonium-Chlorid) bezeichnet.Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer unit of the formula

in the case of X ^- = chloride, they are also referred to as DADMAC (diallyldimethylammonium chloride).

in der R¹, R², R³, R⁴ und R⁵ unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ungesättigten Alkyl-, oder Hydroxyalkylrest mit 1 bis 6 Kohlenstoffatomen, vorzugsweise für einen linearen oder verzweigten Alkylrest ausgewählt aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, und -(CH₂CH₂-O)_nH steht und x für eine ganze Zahl zwischen 1 und 6 steht.Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another represent a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear one or branched alkyl radical selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH , -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H and x is an integer between 1 and 6.

werden im Falle von X^-= Chlorid auch als MAPTAC (Methyacrylamidopropyl-trimethylammonium-Chlorid) bezeichnet.For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

in the case of X ^- = chloride, also referred to as MAPTAC (methylacrylamidopropyltrimethylammonium chloride).

According to the invention, preference is given to using polymers which contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.

The aforementioned amphoteric polymers have not only cationic groups but also anionic groups or monomer units. Such anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.

Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / -alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionogenic monomers ,

Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.

Also preferred are amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyl trialkyl ammonium chloride and dimethyl (diallyl) ammonium chloride.

Particularly preferred amphoteric polymers are selected from the group consisting of the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl ( meth) acrylic acid copolymers and their alkali metal and ammonium salts.

Particular preference is given to amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth ) acrylic acid copolymers and their alkali metal and ammonium salts.

Detergents or cleaning agents contain the aforementioned cationic and / or amphoteric polymers preferably in amounts of between 0.01 and 10 wt .-%, each based on the total weight of the detergent or cleaning agent. In the context of the present application, however, preference is given to those detergents or cleaners in which the weight fraction of the cationic and / or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing agent is.

To increase the washing or cleaning performance of detergents or cleaners enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 × 10 ^-6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples include the subtilisins BPN 'and Carlsberg and their advanced forms, the protease PB92, the subtilisins 147 and 309, the Alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which are assigned to the subtilases, but no longer to the subtilisins in the narrower sense.

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 improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Preferred are one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, in amounts of 0.1 to 5 wt .-%, preferably from 0.2 to 4.5 wt .-% and in particular from 0.4 to 4 wt .-%, each based on the total enzyme-containing agent used.

Some exemplary formulations for preferred two- or more-phase enzyme-containing detergents or cleaners can be found in the following tables: Ingredient [phase] Recipe 29 [% by weight] Recipe 30 [% by weight] Recipe 31 [% by weight] Recipe 32 [% by weight] Oxygen bleaching agent [1] 2 to 30 4 to 20 4 to 20 6 to 15 Bleach activator [≠ 1] 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 Bleach catalyst [# 1] 0.001 to 3 0.001 to 3 0.01 to 2 0.01 to 1.0 Enzyme preparation [≠ 1] 0.1 to 12 0.2 to 10 0.5 to 8 0.5 to 8 * as part of phase [1] and / or one or more additional phases

Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes.

The spectrum of the invention preferred zinc salts, preferably organic acids, particularly preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 have mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ° C. water temperature). The first group of zinc salts includes, for example, zinc citrate, Zinc oleate and the zinc stearate, the group of soluble zinc salts include, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

With particular preference is used as a glass corrosion inhibitor at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

In the context of the present invention, the content of zinc salt in detergents or cleaners is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight. , or the content of zinc in oxidized form (calculated as Zn ²⁺ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt .-% and in particular between 0.04 to 0, 2 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.

Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylamnotriazole.

In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds used. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

The metal salts and / or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, each based on the total agent.

Two- or multi-phase detergent or cleaning agent, characterized in that the two- or multi-phase detergent or cleaning agent further contains a silver protection agent which is present together with the bleaching agent a) in a phase of the detergent or cleaning agent, are preferred according to the invention.

Some exemplary formulations for preferred two- or more-phase silver protectant-containing detergents or cleaners can be found in the following tables: Ingredient [phase] Recipe 33 [% by weight] Recipe 34 [% by weight] Recipe 35 [% by weight] Recipe 36 [% by weight] Oxygen bleaching agent [1] 2 to 30 4 to 20 4 to 20 6 to 15 Bleach activator [≠ 1] 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 Bleach catalyst [≠ 1] 0.001 to 3 0.001 to 3 0.01 to 2 0.01 to 1.0 Silver protection agent [1] 0.05 to 6 0.05 to 6 0.2 to 2.5 0.2 to 2.5 Ingredient [phase] Recipe 37 [% by weight] Recipe 38 [% by weight] Formulation 39 [% by weight] Recipe 40 [% by weight] Oxygen bleaching agent [1] 2 to 30 4 to 20 4 to 20 6 to 15 Bleach activator ^b [1] 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 Bleach activator [≠ 1] 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 Bleach catalyst [≠ 1] 0.001 to 3 0.001 to 3 0.01 to 2 0.01 to 1.0 Silver protection agent [1] 0.05 to 6 0.05 to 6 0.2 to 2.5 0.2 to 2.5 ^b bleach activator in particulate form, which, based on their total weight, a content of bleach activator below 80 wt .-%

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-Ylang oil.

Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic dishes do not stain them.

In order to facilitate the disintegration of preformed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration times. By tablet disintegrants or disintegrants are meant excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients.

These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.

Preferred disintegration aids, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrating agent-containing agent.

Furthermore, according to the invention, gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries. The gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water. Usually, however, the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas. While a variety of systems are conceivable and executable here, which release, for example, nitrogen, oxygen or hydrogen, the bubble system used in detergents and cleaners can be selected both on the basis of economic and environmental considerations. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.

As Acidifizierungsmittel which release carbon dioxide from the alkali metal salts in aqueous solution, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.

The detergents or cleaners according to the invention are in the form of two- or multiphase offer forms, preferably in the form of two-, three- or four-phase offer forms.

These forms of offer themselves are preferably made up in the form of a dosing unit. The term "detergent or Reinigungsmitteldosiereinheit" referred to in the present application in particular such forms of supply, which contain sufficient to carry out individual cleaning cycles amount of washing and cleaning-active substances. Such forms of supply preferably have, for example, a weight between 8 and 35 g, preferably between 10 and 30 g and in particular between 12 and 25 g. The volume of the shaped bodies is usually in the range between 5 and 40 ml, preferably between 8 and 30 ml and in particular between 12 and 20 ml.

Particularly preferred washing or cleaning agent dosing units have dimensions in the range 5 cm × 3 cm × 3 cm, preferably in the range 4.5 cm × 2.5 cm × 2.5 cm, particularly preferably in the range 4 cm × 2 cm, 2 cm ,

As a "phase" of these two- or multi-phase detergent or Reinigungsmitteldosiereinheiten macroscopically visible areas of these dosing units are referred to in the context of this application. In the case of tableted detergent or detergent dosing units, these are, for example, layers or cores. In the case of metering units in the form of Spritzgußkörpem or foil bags in the Aufnahmekammem these metering units separately present washing or cleaning active preparations are referred to as "phases".

The two- or multi-phase detergents or cleaners according to the invention can have solid or liquid phases or combinations of solid and liquid phases.

Examples of the above-described two- or more-phase detergent or dosing unit are, as stated above, two- or multi-layer tablets, injection molded body with two or more separate receiving chambers or foil pouches with two or more separate receiving chambers.

In a particularly preferred embodiment, the two- or multi-phase detergents or cleaners according to the invention are in the form of a two-phase or multi-phase, preferably one two-layered or multi-layered tablet.

The individual phases of the two- or multi-phase base tablet or Kemtablette are preferably arranged in layers. The proportion by weight of the smallest phase, based on the total tablet, is preferably at least 5% by weight, preferably at least 10% by weight and in particular at least 20% by weight. The proportion by weight of the phase with the highest proportion by weight of the tablet in the case of biphasic tablets is preferably not more than 90% by weight, preferably not more than 80% by weight and in particular between 55 and 70% by weight. For three-phase tablets, the weight fraction of the phase with the highest proportion by weight of the tablet is preferably not more than 80% by weight, preferably not more than 70% by weight and in particular between 35 and 60% by weight.

The manufacture of the dishwasher tablets preferably takes place in a manner known to the person skilled in the art by compressing particulate premixes. In this case, it is preferred according to the invention that the particulate premix has an average particle size between 0.4 and 3.0 mm, preferably between 0.6 and 2.5 mm and in particular between 0.8 and 2.0 mm.

Preferred processes in the context of the present invention are characterized in that the pressing takes place at pressing pressures of 0.01 to 50 kNcm ^-2 , preferably of 0.1 to 40 kNcm ^-2 and in particular of 1 to 25 kNcm ^-2 .

The density of dishwasher tablets preferred according to the invention is between 1.1 and 1.8 g / cm ³ , preferably between 1.2 and 1.7 cm ³ and in particular between 1.3 and 1.6 g / cm ³ .

• a) ein Bleichmittel
• b) einen Bleichaktivator
• c) einen Bleichkatalysator ausgewählt aus der Gruppe der bleichverstärkenden Übergangsmetallsalze und Übergangsmetallkomplexe,

hergestellt und derart zu einer Tablette verpresst wird, dass das Bleichmittel a) getrennt von den Bestandteilen b) und c) in einer separaten Phase des Wasch- oder Reinigungsmittels vorliegt dadurch gekennzeichnet, dass der Bleichaktivator b) in partikulärer Form eingesetzt wird und die Bleichaktivatorpartikel, bezogen auf ihr Gesamtgewicht, einen Gehalt an Bleichaktivator oberhalb 80 Gew.-% aufweisen.A further subject of the present application is therefore a process for the preparation of a two- or multi-phase detergent or cleaner tablet, characterized in that a particulate premix comprising

• a) a bleaching agent
• b) a bleach activator
• c) a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes,

and blended into a tablet in such a way that the bleaching agent a) is present in a separate phase of the washing or cleaning agent, separated from components b) and c), in that the bleach activator b) is used in particulate form and the bleach activator particles, based on their total weight, have a content of bleach activator above 80 wt .-%.

Some example formulations for preferred two or more phase detergent or cleaner tablets can be found in the following tables: Ingredient [phase] Recipe 41 [% by weight] Recipe 42 [% by weight] Recipe 43 [% by weight] Formulation 44 [% by weight] Oxygen bleaching agent [1] 2 to 30 4 to 20 4 to 20 6 to 15 Bleach activator [≠ 1] 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 Bleach catalyst [# 1] 0.001 to 3 0.001 to 3 0.01 to 2 0.01 to 1.0 Builder * 1 to 60 2 to 50 5 to 50 10 to 50 Acid group-containing polymer * 0.1 to 30 0.5 to 25 1 to 20 1 to 20 Nonionic surfactant * 01, to 15 0.2 to 10 0.5 to 8 1 to 6 Enzyme preparation [# 1] 0.1 to 12 0.2 to 10 0.5 to 8 0.5 to 8 * Part of phases [1] and / or [2] and / or one or more additional phases Ingredient [phase] Recipe 45 [% by weight] Recipe 46 [% by weight] Recipe 47 [% by weight] Recipe 48 [% by weight] Oxygen bleaching agent [1] 2 to 30 4 to 20 4 to 20 6 to 15 Bleach activator ^b [1] 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 Bleach activator [# 1] 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 Bleach catalyst [≠ 1] 0.001 to 3 0.001 to 3 0.01 to 2 0.01 to 1.0 Builder * 1 to 60 2 to 50 5 to 50 10 to 50 Acid group-containing polymer * 0.1 to 30 0.5 to 25 1 to 20 1 to 20 Nonionic surfactant * 01, to 15 0.2 to 10 0.5 to 8 1 to 6 Enzyme preparation [# 1] 0.1 to 12 0.2 to 10 0.5 to 8 0.5 to 8 Silver protection agent [1] 0.05 to 6 0.05 to 6 0.2 to 2.5 0.2 to 2.5 ^b bleach activator in particulate form, which, based on their total weight, a content of bleach activator below 80 wt .-%
* Part of phases [1] and / or [2] and / or one or more additional phases

Concentric presses can be provided to increase the throughput with two filling shoes, which only a semicircle must be run through to produce a tablet.

As mentioned above, the tablets in the context of the present invention can also be multi-phase, in particular multi-layered. The moldings can be made in a predetermined spatial form and predetermined size. As a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last embodiment detects the form of presentation from the tablet to compact cylinder pieces with a height to diameter ratio above 1.

To produce two-layered and multi-layered shaped bodies, several filling shoes are arranged one after the other without the slightly pressed-on first layer being ejected before further filling. By suitable process control coat and point tablets can be produced in this way, which have a zwiebelschalenartigen structure, in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible. Producible are further mortar tablets, which have on their upper side a trough (a one-sided opened by webs and a base limited cavity).

Particularly preferred two- or multi-phase detergents or cleaners according to the invention have the form of a well tablet with a core inserted into the well, preferably compressed.

1. a) ein Bleichmittel
2. b) einen Bleichaktivator
3. c) einen Bleichkatalysator ausgewählt aus der Gruppe der bleichverstärkenden Übergangsmetallsalze und Übergangsmetallkomplexe,

hergestellt und derart zu einer Muldentablette verpresst wird, dass das Bleichmittel a) getrennt von den Bestandeilen b) und c) in einer separaten Phase des Wasch- oder Reinigungsmittels vorliegt dadurch gekennzeichnet, dass der Bleichaktivator b) in partikulärer Form eingesetzt wird und die Bleichaktivatorpartikel, bezogen auf ihr Gesamtgewicht, einen Gehalt an Bleichaktivator oberhalb 80 Gew.-% aufweisen.Corresponding processes for producing a dishwashing detergent tablet, characterized in that a particulate premix comprising

1. a) a bleaching agent
2. b) a bleach activator
3. c) a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes,

and is compressed in such a way to a well tablet that the bleaching agent a) is present separately from the components b) and c) in a separate phase of the washing or cleaning agent, characterized in that the bleach activator b) is used in particulate form and the Blleichaktivatorpartikel, based on their total weight, have a content of bleach activator above 80 wt .-%.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be detected by the measurand of the diametric breaking load. This is determinable $$\mathrm{\sigma }=\frac{2P}{\mathrm{\pi }\mathit{dt}}$$

Herein, σ is the diametrical fracture stress (DFS) in Pa, P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article, D is the molded article diameter in meters and t the height of the moldings.

In a further preferred embodiment, the two- or multi-phase detergents or cleaners according to the invention are in the form of injection-molded metering units with two or more separate receiving chambers.

Injection molding refers to the forming of a molding material such that the mass contained in a mass cylinder for more than one injection molding plastically softens under heat and flows under pressure through a nozzle into the cavity of a previously closed tool. The method is mainly applied to non-hardenable molding compounds which solidify in the tool by cooling. Injection molding is a very economical modern process for producing non-cutting shaped articles and is particularly suitable for automated mass production. In practical operation, the thermoplastic molding compounds (powders, granules, cubes, pastes, etc.) are heated to liquefaction (up to 180 ° C) and injected under high pressure (up to 140 MPa) in closed, two-piece, that is from Gesenk (earlier Die) and core (formerly male) existing, preferably water-cooled molds, where they cool and solidify. Can be used piston and screw injection molding machines. Suitable molding compositions (injection molding compositions) are water-soluble polymers such as, for example, cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.

In a third preferred embodiment, the two- or multi-phase detergents or cleaners according to the invention are in the form of film bags with two or more separate receiving chambers.

The film bags are preferably obtained by deep drawing a film-like wrapping material. The deep drawing is preferably carried out by bringing the wrapping material over a receiving trough located in a die forming the deep-drawing tray and shaping the wrapping material into this receiving trough by the action of pressure and / or vacuum. The shell material may be pre-treated before or during the molding by the action of heat and / or solvent and / or conditioning by relative to ambient conditions changed relative humidity and / or temperatures. The pressure action can be carried out by two parts of a tool, which behave as positive and negative to each other and deform a spent between these tools film when squeezed. However, the action of compressed air and / or the weight of the film and / or the weight of an active substance applied to the upper side of the film is also suitable as pressure forces.

Suitable film materials are water-soluble polymers such as, for example, cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.

1. a) ein erfindungsgemäßes maschinelles Geschirrspülmittel;
2. b) eine Anleitung, die den Verbraucher darauf hinweist, das maschinelle Geschirrspülmittel ohne Zusatz eines Klarspülers und/oder eines Enthärtersalzes zu verwenden ist, ist ein weiterer Gegenstand dieser Anmeldung.

The subject matter of the present application is furthermore a process for cleaning dishes in a dishwashing machine, using automatic dishwashing agents according to the invention, wherein the machine dishwashing detergent are preferably metered into the interior of a dishwasher during the passage of a dishwashing program before the main wash cycle or during the main wash cycle. The metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered into the interior of the dishwasher by means of the metering chamber of the dishwasher. In the course of the cleaning process preferably no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher. A kit for a dishwasher, comprising

1. a) a machine dishwashing detergent according to the invention;
2. (b) instructions instructing the consumer to use the automatic dishwashing detergent without the addition of a rinse aid and / or a softening salt are another subject of this application.

The automatic dishwasher detergents according to the invention show their advantageous cleaning properties, in particular also low-temperature cleaning processes. Preferred dishwashing processes using agents according to the invention are therefore characterized in that these processes are carried out at temperatures up to a maximum of 55 ° C., preferably up to a maximum of 50 ° C.

As described above, compositions according to the invention are distinguished from conventional automatic dishwasher detergents by an improved cleaning performance on bleachable soiling. An object of the present application is therefore also the use of a machine dishwashing detergent according to the invention for improving the bleaching performance in automatic dishwashing, in particular for removing tea stains.

Examples

In a dishwashing machine (Miele G 698), dishes soiled at a water hardness of 21 ° dH and a temperature of 50 ° C were subjected to machine cleaning, in each case 21 g of the automatic dishwashing detergents listed in the table below being used in the form of biphasic tablets. ingredient V1 [% by weight] E1 [% by weight] Phase [1] sodium 15 15 Phase [2] TAED 3.9 * 3 ** Mn-Me ₃ -TACN complex 0.05 0.05 Phase [1] potassium 30 30 and / or [2] sodium 12 12 HEDP 2 2 Anionic copolymer 20 20 Nonionic surfactant 5 5 Protease preparation 1.5 1.5 Amylase preparation 1.5 1.5 Misc Add 100 Add 100 Teereinigung 5.0 6.5 Bleach activator granules with a TAED content of 78% by weight
** particulate bleach activator with a TAED content above 97% by weight

The dough cleaning of the automatic dishwashing detergents was evaluated by the IKW method (evaluation scale of tea cleaning: 10 = no contamination to 0 = heavy contamination).

The values given are the mean values of purification tests which were carried out immediately after preparation of the dishwasher tablets and after storage for 4 weeks.

Claims (15)

1. A bi- or multiphasic washing or cleaning agent comprising

   a) a bleaching agent

   b) a bleach activator

   c) a bleach catalyst selected from the group of bleach-boosting transition metal salts and transition metal complexes,

   in which the bleaching agent a) is present, separately from components b) and c), in a separate phase of the washing or cleaning agent, characterised in that the bleach activator b) is used in particulate form and the bleach activator particles have, relative to their total weight, a content of bleach activator of above 80 wt.%.
2. The bi- or multiphasic washing or cleaning agent according to claim 1, characterised in that the bleaching agent a) is an oxygen bleaching agent, preferably sodium percarbonate, particularly preferably a coated sodium percarbonate.
3. The bi- or multiphasic washing or cleaning agent according to any one of the preceding claims, characterised in that the proportion by weight of the bleaching agent a), relative to the total weight of the washing or cleaning agent, amounts to between 2 and 30 wt.%, preferably between 4 and 20 wt.% and in particular between 6 and 15 wt.%.
4. The bi- or multiphasic washing or cleaning agent according to any one of the preceding claims, characterised in that the bleach activator b) is a bleach activator from the group of acetylated amines, preferably tetraacetylethylenediamine (TAED).
5. The bi- or multiphasic washing or cleaning agent according to any one of the preceding claims, characterised in that the proportion by weight of the bleach activator b), relative to the total weight of the washing or cleaning agent, amounts to between 0.1 and 10 wt.%, preferably between 0.5 and 8 wt.% and in particular between 1.0 and 6 wt.%.
6. The bi- or multiphasic washing or cleaning agent according to any one of the preceding claims, characterised in that the bleach activator b) assumes the form of bleach activator granules which, relative to the total weight thereof, have a content of bleach activator of above 85 wt.%, preferably of above 90 wt.%, particularly preferably of above 95 wt.% and in particular of above 97 wt.%.
7. The bi- or multiphasic washing or cleaning agent according to any one of the preceding claims, characterised in that the bleach activator b) assumes the form of bleach activator granules which, relative to the total weight thereof, contain less than 20 wt.%, preferably less than 15 wt.%, particularly preferably less than 10 wt.% and in particular less than 5 wt.% of a polymeric granulation auxiliary.
8. The bi- or multiphasic washing or cleaning agent according to any one of the preceding claims, characterised in that the bleach activator b) assumes the form of bleach activator granules which, relative to the total weight thereof, contain less than 20 wt.%, preferably less than 15 wt.%, particularly preferably less than 10 wt.% and in particular less than 5 wt.% of stabilizing additives.
9. The bi- or multiphasic washing or cleaning agent according to any one of the preceding claims, characterised in that the bleach catalyst c) is a complex of manganese, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me₃-TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me₄-TACN).
10. The bi- or multiphasic washing or cleaning agent according to any one of the preceding claims, characterised in that the proportion by weight of the bleach catalyst c), relative to the total weight of the washing or cleaning agent, amounts to between 0.001 and 3.0 wt.%, preferably between 0.01 and 2.0 wt.% and in particular between 0.01 and 1.0 wt.%.
11. The bi- or multiphasic washing or cleaning agent according to any one of the preceding claims, characterised in that the bi- or multiphasic washing or cleaning agent furthermore contains a phosphonate, preferably 1-hydroxyethane-1,1-diphosphonic acid (HEDP), which is present together with the bleaching agent a) in one phase of the washing or cleaning agent.
12. The bi- or multiphasic washing or cleaning agent according to any one of the preceding claims, characterised in that the washing or cleaning agent assumes the form of a bi- or multiphasic, preferably a bi- or multilayer, tablet.
13. The bi- or multiphasic washing or cleaning agent according to any one of the preceding claims, characterised in that the washing or cleaning agent assumes the form of an injection-molded dispensing unit with two or more compartments which are separate from one another.
14. A method of cleaning dishes in a dishwashing machine using automatic dishwashing agents according to any one of claims 1 to 13.
15. The method according to claim 14, characterised in that no additional water softener and no additional rinse aid is dispensed into the interior of the dishwashing machine in the course of the cleaning method.