EP3080237A1

EP3080237A1 - Machine-type dishwasher detergent containing n-based complexing agents

Info

Publication number: EP3080237A1
Application number: EP14808626.7A
Authority: EP
Inventors: Thomas Eiting; Christian Kropf; Mareile Job; Christian Umbreit; Nina Mussmann; Konstantin Benda; Thorsten Bastigkeit
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2013-12-11
Filing date: 2014-12-05
Publication date: 2016-10-19
Also published as: DE102013225591A1; WO2015086475A1

Abstract

The invention relates to a machine-type dishwasher detergent containing at least one bleaching agent, at least one bleach catalyst and at least one nitrogen-based complexing agent; also to the use of same in a machine-type dishwashing process, and to a corresponding process for machine-type dishwashing.

Description

Machine dishwashing detergent containing N-based complexing agents

The present invention relates to a machine dishwashing detergent which exhibits improved cleaning performance, in particular of bleach-sensitive soiling, the use of this dishwashing detergent and a machine dishwashing method

Use of this dishwashing detergent.

The most important criterion in automatic dishwashing is the cleaning performance of a variety of stains, which in the form of food leftovers in the

Dishwasher be introduced. Insofar, there is a general need for

Dishwashing detergents with increased cleaning performance. In addition, a general trend for reasons of environmental protection in machine dishwashing to dispense with phosphates is observed. The problem thus arises of providing phosphate-free automatic dishwashing detergents without impairing the cleaning performance.

The object of the present invention was therefore to provide a, preferably phosphate-free, machine dishwashing agent which has an increased cleaning performance.

It has now been found that the use of certain N-based chelating agents that can be used as phosphate replacers in automatic dishwashing detergents containing a bleaching agent and a bleach catalyst surprisingly without changing the bleach catalyst amount results in increased bleaching performance and therefore improved bleaching performance

Cleaning performance leads to bleach-sensitive soiling.

A first subject of the present invention is therefore a machine dishwashing detergent containing at least one bleaching agent, at least one bleach catalyst and at least one N-based complex image of the formula

XOOC- (CH ₂ ) n -CH (R 1) -N (R ₂ ) -CH (R 3) -C (R 4) (R 5) -COOX where

X is H, an alkali metal or ammonium;

R1 is H, Ci-Cio-alkyl or C (R6) (R7) -COOX;

R 2 is H, C 1 -C 10 -alkyl or CH 2 COOX;

R 3 is H, C 1 -C 10 -alkyl or COOX;

R4, R5, R6 and R7 are independently H, OH or Ci-Cio-alkyl; and

n is 0 or 1. "At least one" as used herein includes, but is not limited to, 1, 2, 3, 4, 5, 6 and more.

Likewise provided by the present invention is the use of a machine dishwashing detergent according to the invention in a machine dishwashing process, in particular the use for improving the cleaning performance on bleach-sensitive soiling on dishes during its cleaning in an automatic dishwashing machine.

Finally, the present invention is also directed to a machine dishwashing process in which a machine dishwashing agent according to the invention is used, in particular for the purpose of improving the cleaning performance of bleach-sensitive soiling.

These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Further, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular that the invention is not limited to these examples. All percentages are by weight unless otherwise specified. Numeric ranges specified in the format "from x to y" include the above values.If multiple preferred numeric ranges are specified in this format, it is understood that all ranges resulting from the combination of the various endpoints, also be recorded.

In the context of the present invention are fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms. In particular, the oxo alcohols or their derivatives, which are obtainable, for example, by the RoELEN's oxo synthesis, can also be used correspondingly.

Whenever alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.

Substances which also serve as ingredients of cosmetic products are referred to below, where appropriate, according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds carry an INCI name in English, plant ingredients are listed only after Linne in Latin, so-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI names are the International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997), published by The Cosmetic, Toiletry, and Fragrance Association (CTFA), 101 101st Street, NW, Suite 300, Washington, DC, 20036, USA, and more than 9,000 INCI names and references includes more than 37,000 trade names and technical names including related distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook assigns to the ingredients one or more chemical classes, such as polymer ethers, and one or more functions, such as surfactants-cleansing agents, which are further explained and discussed below possibly also referred to.

The indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service.

The N-based complexing agents used according to the invention are compounds of the formula

XOOC- (CH ₂ ) n -CH (R 1) -N (R ₂ ) -CH (R 3) -C (R 4) (R 5) COOX

Where X is H, an alkali metal or ammonium; R 1 is H, C 1 -C 10 -alkyl or C (R 6) (R 7) -COOX; R 2 is H, C 1 -C 10 -alkyl or CH 2 COOX; R 3 is H, C 1 -C 10 -alkyl or COOX; R4, R5, R6 and R7 independently of one another are H, OH or Ci-Cio-alkyl; and n is 0 or 1.

"Alkyl" as used herein refers to saturated straight or branched chain

Hydrocarbons having 1-10, preferably 1-4 carbon atoms include, but are not limited to, methyl, ethyl, n -propyl, iso -propyl, n -butyl, sec -butyl, iso -butyl and tert -butyl.

In preferred embodiments of the invention, R 1 is H or C 1 -C 10 -alkyl, in particular H or methyl. In further preferred embodiments, R 2 is H or C 1 -C 10 -alkyl, R 3 COOX, R 4 OH, R 5 H and n = 0. In still other preferred embodiments, R 2 is CH 2 COOX, R 3 is H or COOX, R 4 is H or OH, R 5 is H and n = 0.

In certain embodiments of the invention R1 is H or Ci-Cio-alkyl, R2 is H, R3 is COOX, R4 is OH, R5 is H and n = 0. In further particular embodiments of the invention R1 is H or Ci-Cio-alkyl, R2 is Ci-Cio-alkyl, R3 is COOX, R4 is OH, R5 is H and n = 0. In still further specific embodiments R1 is H or Ci-Cio-alkyl, R2 is CH2COOX, R3 is H, R4 is H, R5 is H and n = 0. In still further embodiments R1 is H or Ci-Cio-alkyl, R2 is CH2COOX, R3 is COOX, R4 is H, R5 is H and n = 0. In further embodiments R1 is H or C1-C10 alkyl, R2 is CH2COOX, R3 is H, R4 is OH, R5 is H and n = 0. In further embodiments R1 is H or Ci-Cio-alkyl, R2 is CH2COOX, R3 is COOX, R4 is OH, R5 is H and n = 0.

Specific examples of N-based chelating agents useful in the present invention include, but are not limited to, N- (1,2-dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-) hydroxyethyl) alanine, N, N-biscarboxymethyl-.beta.-alanine, N- (1,2-dicarboxy-2-hydroxyethyl) -sarcosine, and N- (1,2-dicarboxy-2-hydroxyethyl) -iminodiacetic acid. In all the above

Embodiments may be used both the free acids and the corresponding salts, in particular the alkali metal salts, preferably the Na salts.

Surprisingly, the N-based chelating agents used according to the invention, which are as defined above, exhibit the property of improving the performance of bleach catalysts contained in the dishwashing detergent and therefore lead to an improved cleaning performance on bleach-sensitive soiling.

In this case, the improvement in bleach catalyst performance or improvement in the cleaning or bleaching performance is generally to be understood as meaning that the removal of stains, in particular bleach-sensitive, when using the dishwashing agent according to the invention

Stains, on dishes when cleaning in an automatic

Dishwasher is significantly improved compared to the use of dishwashing detergents which do not contain the complexing agents according to the invention.

The complexing agents are usually used in amounts of 0, 1 to 40 wt .-%, based on the total formulation of the agent used. Preferred amounts are 2 to 35% by weight and in particular 10 to 30% by weight.

The automatic dishwashing detergents described herein containing at least one bleach, at least one bleach catalyst, and the at least one N-based chelant may be solid or liquid in nature and, in particular, as powdered solids, in densified particulate form, as homogeneous solutions or suspensions. In a further preferred embodiment of the invention, the automatic dishwashing detergent is present in a pre-portioned form. In a further preferred embodiment of the invention, the automatic dishwashing detergent has several spatially separated

Compositions, whereby it is possible to separate incompatible ingredients from each other, or to offer compositions in combination, which are used at different times in the dishwasher. This is particularly advantageous if the automatic dishwashing detergents are present in pre-portioned form. At least one of the compositions is solid and / or at least one of the

Liquid compositions, wherein the complexing agents, the bleaching agents and the

Bleach catalysts are present in at least one of the compositions, but may also be present in several compositions.

The bleach catalysts useful in this invention include, but are not limited to, the group of bleach-enhancing transition metal salts and transition metal complexes, preferably Mn, Fe, Co, Ru or Mo complexes, most preferably from the group the manganese and / or cobalt salts and / or complexes, in particular the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, the manganese sulfate and the complexes of Manganese with 1, 4,7-trimethyl-1, 4,7-triazacyclononane (Mm-TACN) or 1, 2,4,7-tetramethyl-1, 4,7-tri-azacyclononane (Mn4-TACN).

According to the invention, automatic dishwashing agents are preferred which contain 0.001 to 1% by weight, preferably 0.01 to 0.1% by weight of bleach catalyst, preferably a Mn complex, in particular a complex of manganese with 1, 4,7-trimethyl-1 , 4,7-triazacyclononane (Mm-TACN) or 1, 2,4,7-tetramethyl-1, 4,7-triaciazacyclononane (Mm-TACN).

The bleaching agents which can be used according to the invention are washing or cleaning-active substances. Among the compounds which serve as bleaching agents in water H2O2, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaches which can be used are, for example, peroxypyrophosphates, citrate perhydrates and peroxygenic salts or peracids yielding H2O2, such as perbenzoates.

Peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. In addition, all other known to the expert from the prior art can be used

inorganic or organic peroxy bleach.

As a bleaching agent and chlorine or bromine releasing substances can be used. Examples of suitable chlorine or bromine releasing materials

heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid,

Tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

According to the invention, automatic dishwashing agents are preferred which contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight of bleaching agent, preferably sodium percarbonate , contain.

In various embodiments of the invention, the automatic dishwashing agents additionally contain at least one bleach activator. 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. Of all those skilled in the art known from the prior art

Bleach activators are polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferred used. Combinations of conventional bleach activators can also be used. These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight, based in each case on the total weight of bleach activator-containing agents.

The agents according to the invention preferably contain at least one further constituent, in particular at least two further constituents, selected from the group consisting of builders, surfactants, polymers, enzymes, corrosion inhibitors and

Glass corrosion inhibitors, disintegration aids, fragrances and perfume carriers.

The following describes possible ingredients which can be advantageously used in the machine dishwashing detergents according to the invention.

Advantageously, additional builders can be used. The additional builders that can be used include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates. Preferably, however, the agents are phosphate-free.

Preferably, crystalline layered silicates of the general formula

NaMSix02x + i ^■ y H2O are used, wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, wherein particularly preferred values for x being 2, 3 or 4, and y a number from 0 to 33, preferably from 0 to 20 stands. The crystalline layered silicates of the formula NaMSix02x + i ^■ y H2O, for example, by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂ 2045 ^· x H ₂ O, kenyaite), Na-SKS-2 (Na ₂ Si ₄ O ^{29 ·} x H ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ 0i7 ^■ x H2O) or Na-SKS-4 (Na ₂ Si ₄ 09 ^■ x H2O, makatite). Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula

NaMSix02x + i ^■ y H2O, where x is 2. In particular, both ß- and

δ-sodium Na2Si20s ^■ y H2O and further especially Na-SKS-5 (a-Na2Si20s), Na-SKS-7 _(.beta.-Na2 _Si2 05, natrosilite), Na-SKS-9 (NaHSi ₂ 0 ₅ ^■ H2O), Na-SKS-10 (NaHSi ₂ 0 ₅ ^■ 3 H2O, kanemite), Na-SKS-1 (1 t-Na ₂ Si ₂ 05) and Na-SKS-13 (NaHSi ₂ 0 _5), but especially Na-SKS-6 (5-Na ₂ Si ₂ 05) is preferred.

Machine dishwashing detergents preferably contain a weight proportion of crystalline layered silicate of the formula NaMSi _x 02x + y i ^■ H2O of 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-% and in particular from 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 modulus Na 2 O: SiO 2 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 are preferably Delayed and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates can in various ways, for example by surface treatment, compounding, compaction / compaction or by

Overdrying caused. In the context of this invention, the term "amorphous" is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle , cause.

In the context of the present invention, it is preferred that these silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous Alkalidisilikate, in the compositions in amounts of from 3 to 60 wt .-%, preferably from 8 to 50 wt. % and in particular from 20 to 40 wt .-%, each based on the weight of the automatic dishwashing detergent 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 particular preference of pentasodium or Pentakaliumtriphosphat (sodium or

Potassium tripolyphosphate) in the detergent or cleaning industry the greatest importance.

Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids in which one

Metaphosphoric acids (HP03) n and orthophosphoric acid H3PO4 can distinguish in addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Technically important phosphates are the pentasodium triphosphate, NasPsO-io

(Sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K5P3O10 (potassium tripolyphosphate) and corresponding mixed salts (sodium potassium tripolyphosphates).

Preferably, however, the agents are phosphate-free.

If phosphates are used as washing or cleaning substances in machine dishwashing detergent in the present application, preferred agents comprise this phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or 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 automatic dishwashing detergent. Further builders are the alkali carriers. Examples of alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates,

Alkali metal sesquicarbonates, the said alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, preference being given within the meaning of this invention to the use of the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate. 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 dishwasher detergents in comparison with other builders, the optional alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 % By weight and in particular below 2% by weight, in each case based on the total weight of the automatic dishwashing detergent. 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 automatic dishwashing detergent. Particular preference is given to compositions which, based on the weight of the automatic dishwashing agent, are less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and

in particular less than 9% by weight of carbonate (s) and / or hydrogencarbonate (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, nitrilotriacetic acid (NTA), provided such use is not objectionable for environmental reasons, and mixtures thereof. In addition to their builder effect, the free acids typically also have the property of a

Acidification and thus also serve to set a lower and milder pH of the automatic dishwashing detergent. In particular, here are citric acid,

Succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof. The use of citric acid and / or citrates in these compositions has proved to be particularly advantageous for the cleaning and rinsing performance of agents according to the invention. Therefore, according to the invention, preference is given to automatic dishwasher detergents, characterized in that the automatic dishwashing agent contains citric acid or a salt of citric acid and the weight proportion of citric acid or of the salt of citric acid is preferably more than 10% by weight, preferably more than 15% by weight and in particular between 20 and 40 wt .-% is.

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.

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 automatic dishwashing detergents on (co) polymers

Polycarboxylates is preferably 0.5 to 20 wt .-% and in particular 3 to 10 wt .-%.

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

Further preferred copolymers are those which are used as monomers acrolein and

Acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

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

The compositions of the invention may contain surfactants, wherein the nonionic, the anionic, the cationic and the amphoteric surfactants are counted among the group of surfactants. As nonionic surfactants, it is possible to use all 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 determines the distribution of

Specifying monoglycosides and oligoglycosides is any number between 1 and 10;

preferably x is 1, 2 to 1, 4.

Another class of preferred nonionic surfactants which can be 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 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

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

Low-foaming nonionic surfactants can be used as preferred surfactants. With particular preference, the 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. Preferred ethoxylated alcohols include, for example Ci2-i4-alcohols with 3 EO or 4 EO, C9-n-alcohol with 7 EO, C13 15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C ₂ -i8 Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-i4-alcohol with 3 EO and Ci2-is-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 rank 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. Particular preference is given to nonionic surfactants which have a melting point above

Have 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.

Anionic surfactants can also be used as a component of automatic dishwashing detergents. These include in particular alkylbenzenesulfonates, (fatty) alkyl sulfates, (fatty) alkyl ether sulfates and alkanesulfonates. The content of the anionic surfactant is usually 0 to 10% by weight.

Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants. As cationic active substances, for example, cationic compounds of the following formulas can be used:

Ri

U

Ri-N- (CH ₂ ) _n -T-R2

(CH ₂ ) _n -T-R2

wherein each R group is independently selected from C 1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from Cs-28 alkyl or alkenyl groups; R ³ = R or (CH ₂ ) _n -TR ² ; R ⁴ = R or R ² or (CH ₂ ) nTR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

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. %. Machinery

Dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred. 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 automatic dishwashing detergents in addition to nonionic polymers.

"Cationic polymers" for the purposes of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain 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 methacrylate, the vinylpyrrolidone-methoimidazolinium chloride Copolymers, the quaternized polyvinyl alcohols or the INCI names

Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 indicated polymers.

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

Preferred usable amphoteric polymers are from the group of

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, which

Alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated

Carboxylic acids and optionally other ionic or nonionic monomers.

Preferably usable zwitterionic polymers are selected from the group of

Acrylamidoalkyltrialkylammoniumchlorid / 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 Methacroylethylbetain / methacrylate copolymers.

In a particularly preferred embodiment of the present invention, the polymers are present in prefabricated form. For the preparation of the polymers is suitable inter alia the encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;

the encapsulation of the polymers by means of water-insoluble, fusible

Coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;

the co-granulation of the polymers with inert support materials, preferably with

Support materials from the group of washing or cleaning-active substances, particularly preferably from the group of builders (builders) or cobuilders.

Machine dishwashing detergents preferably contain the abovementioned cationic and / or amphoteric polymers in amounts of from 0.01 to 10% by weight, based in each case on the total weight of the automatic dishwashing detergent. In the context of the present application, however, preference is given to those automatic dishwashing detergents in which the

Weight fraction of the cationic and / or amphoteric polymers between 0.01 and 8 wt .-%, preferably between 0.01 and 6 wt .-%, 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 detergent, is.

Preferably, the agents of the present invention contain at least one enzyme preparation or enzyme composition containing one or more enzymes. Suitable enzymes include, but are not limited to, 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, which are preferably used accordingly. Detergents according to the invention 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.

Proteases are among the most technically important enzymes of all. For detergents and cleaners, they are the longest established and contained in virtually all modern, powerful detergents and cleaners enzymes. They cause the degradation of protein-containing stains on the items to be cleaned. Of these, in turn, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are due to the catalytically active amino acids serine proteases. They act as nonspecific endopeptidases and hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range. For an overview of this family, for example, the article "Subtilases: Subtilisin-like Proteases" by R. Siezen, page 75-95 in "Subtilisin enzymes", edited by R. Bott and C. Betzel, New York, 1996. Subtilases are naturally produced by microorganisms. Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.

Examples of the proteases preferably used in detergents and cleaners from

Subtilisin type are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483,

Subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7 attributable to the subtilases, but no longer to the subtilisins in the narrower sense, as well as variants of said proteases which have an altered amino acid sequence compared to the starting protease. Proteases are selectively or randomly modified by methods known from the prior art and thus optimized, for example, for use in detergents and cleaners. These include point mutagenesis, deletion or

Insertional mutagenesis or fusion with other proteins or protein parts. Thus, correspondingly optimized variants are known for most proteases known from the prior art.

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

(DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, those originally from Humicola lanuginosa

(Thermomyces lanuginosus) available, or further developed lipases, especially those with the amino acid exchange D96L.

Furthermore, enzymes can be used which are termed hemicellulases

be summarized. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, in addition, preferably, organic, particularly preferably aromatic, interacting with the enzymes compounds are added to the Activity of the relevant oxidoreductases to enhance (enhancer) or to strong

different redox potentials between the oxidizing enzymes and the

Stains to ensure the flow of electrons (mediators).

A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

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

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core with a water, air and / or

Chemical-impermeable protective layer is coated. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

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

As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Preferably used according to the invention

Protease and amylase preparations contain between 0.1 and 40 wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20 wt .-% and

in particular between 0.8 and 10% by weight of the enzyme protein. Preference is given in particular to those detergents which, in each case based on their

Total weight, 0, 1 to 12 wt .-%, preferably 0.2 to 10 wt .-% and in particular 0.5 to 8 wt .-% enzyme preparations.

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

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. Desintegration aids may preferably be 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.

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, patchouli, rose or ylang-ylang oil.

The preparation of automatic dishwashing compositions described herein can be described in

done in different ways. The agents may be in solid or liquid form as well as in a combination of solid and liquid forms. As fixed offer forms are suitable

in particular powders, granules, extrudates, compactates, in particular tablets. The liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels. The agents can be formulated in the form of single-phase or multi-phase products. In particular, automatic dishwashing detergents with one, two, three or four phases are preferred. Machine dishwashing detergent, characterized in that it is in the form of a prefabricated dosing unit with two or more phases, are particularly preferred. The individual phases of multiphase agents may have the same or different states of matter. In particular, automatic dishwashing detergents are preferred have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one solid phase.

The automatic dishwashing agents described herein are preferably prefabricated into dosage units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g. In order to achieve an optimum cleaning and rinse-aid result, preference is given to those automatic dishwashing agents which are present in the form of a prefabricated dosing unit and between 0.001 and 1 g, preferably between 0.01 and 0.1 g, particularly preferably between 0.01 and 0, 07 g and in particular between 0.01 and 0.05 g of the polymer a) or between 0.1 and 2.5 g, preferably between 0.2 and 2.2 g, particularly preferably between 0.3 and 1, 9 g and in particular between 0.4 and 1.5 g of nonionic surfactant (s) b). The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

The automatic dishwashing agents, in particular the prefabricated metering units, have a water-soluble coating, with particular preference.

The water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.

It is preferred that the water-soluble coating be polyvinyl alcohol or a

Contains polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.

Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose

Molecular weight in the range of 10,000 to 1,000,000 gmor, preferably from 20,000 to 500,000 gmol ¹ , more preferably from 30,000 to 100,000 gmol ^-1 and in particular from 40,000 to 80,000 gmol. The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

In addition, a polymer selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath

(Meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added. A preferred additional polymer is polylactic acids.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and

Mixtures thereof, with itaconic acid being preferred.

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

It may be preferred that the film material contains further additives. The film material may include, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol,

Propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Further

Additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, detackifiers, or mixtures thereof.

Suitable water-soluble films for use in the water-soluble sheaths of

water-soluble packaging according to the invention are films marketed by MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.

The corresponding use of the automatic dishwasher detergents according to the invention is likewise an object of the invention. The invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a dishwashing detergent according to the invention is used. The subject matter of the present application is therefore furthermore a process for the cleaning of dishes in a dishwashing machine, in which the

inventive means during the passage of a dishwashing program before the start of Hauptpülgangs or in the course of the main wash cycle is metered into the interior of a dishwasher. 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 by means of the metering chamber into the interior of the dishwasher.

A typical framework formulation for a machine dishwashing detergent preferably used, for example in tablet form, comprises the following substances:

Citrate 10-50% by weight

Sodium carbonate 10-30% by weight

Sodium percarbonate 5-18% by weight

Bleach activator 0.5-5% by weight

Bleach catalyst 0.01-1% by weight

Sulfopolymer 2.5-15% by weight

Polycarboxylate 0, 1-10% by weight

Nonionic surfactant 0.5-10% by weight

Phosphonate 0.5-5% by weight

Protease 0.1-5% by weight

Amylase 0.1-5% by weight, the data in% by weight being based on the total agent. Instead of or some of the citrate, the N-based chelating agents described herein or mixtures of two or three of these substances may be employed.

Examples

Example 1: Synthesis of N- (1,2-dicarboxy-2-hydroxyethyl) glycine and its Na salt

0.1 mol of NaOH are dissolved in 50 ml of water and then 0.1 mol of glycine is added. To the resulting solution is added 0.1 mol of epoxy succinic acid (or the disodium salt thereof) and refluxed for 8 hours. The resulting solution is concentrated and the corresponding product is isolated.

Example 2: Improvement of the cleaning performance in automatic dishwashing

In a Miele 698 dishwasher at 50 ° C (program "Normal") and 21 ° dH various materials (glass, porcelain (black), stainless steel, plastic) with a

Tea soiling from black tea with a solid dishwashing tablet (20 g;

Composition see Table 1) with bleach catalyst and without N-based complexing agent (V1), with N-based complexing agent and without bleach catalyst (V2) and with bleach catalyst and various N-based complexing agents (M1, M2, M3, M4) and after each Rinsing cycle visually determines the cleaning performance according to IKW (evaluation of 1 -10, the higher the value, the better the performance, differences of at least 1 are significant). The results for the tested formulations are listed in Table 2 as arithmetic mean values. Higher values mean better cleaning performance.

Table 1: Composition of the automatic dishwashing detergent

V1 V2 M1 M2 M3 M4

Citrate 31, 5 15.5 15.5 15.5 15.5 15.5

N- (1,2-dicarboxy-2-hydroxyethyl) glycine, Na-16.0

salt

Ν, Ν-biscarboxymethyl-beta-alanine, Na salt - - - 16.0

N- (1,2-dicarboxy-2-hydroxyethyl) sarcosine, 16.0 Na salt

N- (1,2-dicarboxy-2-hydroxyethyl) -16.0-iminodiacetic acid, Na salt

Tetrasodium iminodisuccinate - 16.0 - - - -

Sodium carbonate 15.6 15.6 15.6 15.6 15.6

15.6

Sodium sulfate 5.7 5.7 5.7 5.7 5.7 5.7

Phosphonate 2.1 2.7 2.7 2.1 2.1

2.7

Sulfonic acid group-containing polymer 13.9 13.9 13.9 13.9 13.9 13.9 Acrylate polymer, Na salt 0.4 0.4 0.4 0.4 0.4 0.4

Nonionic surfactants 6.5 6.5 6.5 6.5 6.5 6.5

Percarbonate 14.4 14.4 14.4 14.4 14.4 14.4

TAED 0.4 0.4 0.4 0.4 0.4 0.4

Bleaching catalyst (Mn-TACN) 1, 1 - 1, 1 1, 1 1, 1 1, 1

Amylase-containing enzyme composition 0.7 0.7 0.7 0.7 0.7 0.7

Protease-containing enzyme composition 2.2 2.2 2.2 2.2 2.2 2.2

Zinc acetate (wt%) 0.2 0.2 0.2 0.2 0.2 0.2

Remains (perfume, dyes, ad ad ad ad ad

Preservatives, water) (% by weight) 100 100 100 100 100 100

Table 2: Cleaning performance on tea soiling

It can be clearly seen from the table that the use of N-based complexing agents, as defined herein, in combination with bleach catalysts leads to a significant improvement in the cleaning performance.

Claims

claims

1. Machine dishwashing detergent, characterized in that the machine

Dishwashing liquid

(i) at least one bleaching agent;

(ii) at least one bleach catalyst; and

(iii) at least one N-based complex of the formula

XOOC- (CH ₂ ) n -CH (R 1) -N (R ₂ ) -CH (R 3) -C (R 4) (R 5) COOX, wherein

X is H, an alkali metal or ammonium;

R1 is H, Ci-Cio-alkyl or C (R6) (R7) -COOX;

R 2 is H, C 1 -C 10 -alkyl or CH 2 COOX;

R 3 is H, C 1 -C 10 -alkyl or COOX;

R4, R5, R6 and R7 are independently H, OH or Ci-Cio-alkyl; and n is 0 or 1.

2. Machine dishwashing detergent according to claim 1, characterized in that R1 is H or Ci-Cio-alkyl.

3. Machine dishwashing detergent according to claim 1 or 2, characterized in that

(i) R2 is H or Ci-Cio-alkyl, R3 COOX, R4 OH, R5 H and n = 0; or

(ii) R2 is CH2COOX, R3 is H or COOX, R4 is H or OH, R5 is H and n = 0.

4. Machine dishwashing detergent according to one of claims 1 to 3, characterized

characterized in that the N-based complexing agent is selected from the group consisting of N- (1, 2-dicarboxy-2-hydroxyethyl) glycine, N- (1, 2-dicarboxy-2-hydroxyethyl) alanine, Ν, Ν Biscarboxymethyl-alanine, N- (1,2-dicarboxy-2-hydroxyethyl) -sarcosine, N- (1,2-dicarboxy-2-hydroxyethyl) -iminodiacetic acid and the alkali metal salts, especially the sodium salts, thereof.

5. Machine dishwashing detergent according to one of claims 1 to 4, characterized

characterized in that the N-based complexing agent in an amount of 0.1 to 40, preferably 2 to 35, more preferably 10 to 30 wt .-% based on the

Total weight of the machine dishwashing agent is included.

6. Machine dishwashing detergent according to one of claims 1 to 5, characterized

in that the bleach catalyst is selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably the Mn, Fe, Co, Ru or Mo complexes, more preferably from the group of manganese and / or cobalt salts and / or complexes, in particular the cobalt (ammine) complexes, the cobalt (acetate) complexes , the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, the manganese sulfate and the 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).

7. Machine dishwashing detergent according to one of claims 1 to 6, characterized

in that the bleach catalyst is present in an amount of 0.001 to 1% by weight, preferably 0.01 to 0.1% by weight, based on the total weight of the automatic dishwashing detergent.

8. Machine dishwashing detergent according to one of claims 1 to 7, characterized

marked that

(1) the machine dishwashing detergent is in solid form; and or

(2) the automatic dishwashing detergent is in pre-portioned form; and or

(3) the automatic dishwashing detergent several spatially separated

Compositions, of which at least one composition is solid and / or a composition is liquid, wherein the at least one N-based complexing agent is contained in at least one of the compositions; and or

(4) the automatic dishwashing detergent contains at least one bleach activator; and or

(5) the automatic dishwashing detergent at least one further ingredient,

preferably at least two further constituents selected from the group consisting of builders, surfactants, polymers, enzymes, corrosion inhibitors, glass corrosion inhibitors, Disintegrationshilfsmitteln, fragrances and perfume carriers.

Use of a machine dishwashing composition according to any one of claims 1-8 in a machine dishwashing process.

10. Machine dishwashing method, characterized in that a machine dishwashing agent according to any one of claims 1-8 is used.