JP2002500242A - Use of transition metal complexes with dendrimer ligands to enhance the bleaching effect of peroxygen compounds - Google Patents

Abstract

  (57) [Summary] It is an object of the present invention to improve the oxidation and bleaching effects of peroxygen compounds. This is essentially achieved by using transition metal complexes having one or several polyamidoamine-type dendrimer ligands. Detergents and detergents, especially those used to wash dishes in dishwashers, contain from about 0.0025 to 0.25% by weight of an active substance of the above type in order to enhance the bleaching effect.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to the use of certain transitions in the bleaching of colored soils, both textiles and hard surfaces, in order to enhance the bleaching effect of peroxygen compounds, more particularly inorganic peroxygen compounds. It relates to the use of metal complex compounds and to laundry and dishwashing detergents containing these complex compounds.

BACKGROUND OF THE INVENTION Inorganic peroxygen compounds, more particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water with the release of hydrogen peroxide, such as sodium perborate and sodium carbonate peroxide Japanese products have long been used as oxidizing agents for disinfection and bleaching. The oxidizing effect of these substances in dilute solutions is largely dependent on temperature. For example, when using H ₂ O ₂ or perborate in an alkaline bleaching solution, the soiled fabric is only bleached quickly enough at temperatures above about 80 ° C.
At relatively low temperatures, the oxidizing effect of the inorganic peroxygen compounds can be improved by the addition of so-called bleach activators. With regard to the bleach activator, in particular, N- or O-acyl compounds, such as polyacylated alkylenediamines, more specifically tetraacetylethylenediamine, acylated glycoluril, more specifically tetraacetylglycoluril, N- Acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, and also carboxylic anhydrides, more specifically phthalic anhydride, carboxylic esters, more specifically nonanoyloxy Many proposals from the group of sodium benzenesulfonate, sodium isononanoyloxybenzenesulfonate, and acylated sugar derivatives such as pentaacetylglucose are known in the literature. By adding these substances, the bleaching effect of the aqueous peroxide solution is obtained at a temperature of only about 60 ° C., substantially the same as that obtained with the peroxide solution alone at 95 ° C. Can be increased to a certain extent.

In research to find energy saving cleaning and bleaching methods, 60
Operating temperatures well below 0 ° C, more specifically below 45 ° C to cold water, have become increasingly important in recent years.

[0004] At such low temperatures, there is generally a discernable reduction in the effect of the activating compounds known hitherto. Thus, while there have been numerous attempts to develop more effective activators for this temperature range, there has been no real success so far. A starting point in this connection is described, for example, in European Patent Application EP 0392
592, EP0444351, EP0458397, EP0544490 and EP0549271, which consist in using transition metal salts and complexes as so-called bleaching catalysts. In these cases, the dyed fabric is at risk of a color change, and in extreme cases, probably due to the high reactivity of the oxidizing intermediates formed from the transition metal salts and complexes and the peroxygen compounds. There is a risk of oxidative damage. European Patent Application EP 0 272 030 discloses a cobalt (III) complex containing an ammonia ligand, which is used as an activator for H ₂ O ₂ , for use in textile cleaning or bleaching compositions. , Di, tri and / or tetradentate ligands). International patent applications WO 96/23859, WO 96/23860 and WO 96/23861 relate to the use of the corresponding Co (III) complexes in detergents of automatic dishwashers. European Patent Application EP 0630964 has no significant effect on enhancing the bleaching effect of peroxygen compounds, does not bleach dyed textile fibers, but can bleach stains or dyes separated from the fibers in the washing liquor. Disclosed are manganese complexes. German patent application DE 44 16 438 describes manganese, copper and cobalt complexes which hold ligands from various groups and are said to be used as bleaching and oxidation catalysts. International Patent Application WO 97/07191 describes manganese containing salen-type ligands as activators for peroxygen compounds in solution for cleaning hard surfaces,
It proposes complexes of iron, cobalt, ruthenium and molybdenum.

[0005] The problem addressed by the present invention is also that at a low temperature of 80 ° C or less, more specifically, about 15 ° C.
It was to improve the oxidation and bleaching effect of inorganic peroxygen compounds at temperatures in the range of ~ 45 [deg.] C.

It has now been found that transition metal complex compounds containing certain dendrimer ligands clearly contribute to the cleaning effect on colored stains on textiles and hard surfaces. This contribution can be increased by using these complexes in combination with compounds that release peroxocarbonic acid under perhydrolysis conditions.

SUMMARY OF THE INVENTION [0007] The present invention relates to peroxygen compounds, more particularly to aqueous solutions for washing laundry and to aqueous solutions for cleaning hard surfaces, more particularly dishes. Complexes of transition metals cobalt, manganese, iron, ruthenium, vanadium, molybdenum, tungsten or mixtures thereof carrying one or more polyamidoamine type dendrimer ligands as activators for inorganic peroxygen compounds As well as its use in corresponding solutions for bleaching colored stains.

DETAILED DESCRIPTION OF THE INVENTION A polyamidoamine compound type dendrimer ligand molecule is represented by the following structure I:

Embedded image

A second generation so-called starburst (star explosion) dendrimer is shown here. This can be obtained by the reaction of ammonia (initiation nucleus) with methyl acrylate and ethylenediamine (generation 0), each new generation by repeating the reaction with methyl acrylate and ethylenediamine, Can be obtained from Half the number of generations (1.5, 2.5, 3.5, etc.) of dendrimer (in these cases, the reaction with ethylenediamine was omitted from the last step and thus terminated by carboxylate groups) Can also be used in the complexes used according to the invention. Instead of ammonia, polyethyleneimine (see structure below):

Embedded image Aromatic systems (eg, benzene), alkanes (eg, ethane), or ethylenediamine can also constitute the initiation nucleus. The corresponding dendrimers and their production are
DATomalia, AMNaylor and Goddard (WAGoddard)
In the review paper [Angew. Chem. 102 (1990), 119-157] as well as in the original literature listed therein. The initiation nucleus is preferably ammonia or ethylenediamine. Preferably, transition metal complexes with generation 3.5 and generation 4.0 dendrimer ligands are used.

[0010] Such dendrimers can be loaded with different stoichiometric amounts of transition metal. In the maximum case, all nitrogen atoms or carboxylate groups of the dendrimer are saturated with the transition metal. In a transition metal complex with a dendrimer ligand in which ethylenediamine is the starting nucleus, the molar ratio of the transition metal to the dendrimer ligand is
It is preferably in the range of 1: 1 to 2 ^{n + 1} : 1 (n indicates the generation of dendrimer). That is, in the complex with the generation 2 dendrimer ligand, the molar ratio is preferably in the range of 1: 1 to 8: 1, more preferably in the range of 3: 1 to 7: 1,
For complexes with generation 3 dendrimer ligands, the molar ratio is preferably 1: 1
１６16: 1, more preferably in the range of 6: 1 to 14: 1, and for complexes with generation 4 dendrimer ligands, the molar ratio is preferably in the range of 1: 1 to 3: 1.
In the range of 2: 1, more preferably in the range of 8: 1 to 28: 1, for complexes with generation 5 dendrimer ligands, the molar ratio is preferably in the range of 1: 1 to 64:
1 and so on.

[0011] Relatively large amounts of transition metals can also be complexed. That is, the dendrimer ligand can be "overloaded" with a transition metal atom. This can be attributed to the effect that the internal amino group can act as a donor.

In the complexes used according to the invention, the transition metal can have an oxidation number from + II to + V (depending on the metal). Cobalt and / or molybdenum are particularly preferred transition metals in the complexes used according to the invention, with cobalt being +
Preferably, it is present at an oxidation number of II or + III, and molybdenum is preferably present at an oxidation number of + IV or + V. Dendrimer complexes with several different transition metals and / or metals with mixed oxidation numbers are also possible, with the combination of transition metals cobalt and manganese giving particularly good results. This combination is particularly useful for Co (II)
And Mn (III), a combination of Co (III) and Mn (II), or preferably a combination of Co (III) and Mn (III). When the complexes used according to the invention contain different metals or the same metal with different oxidation numbers, the molar ratio of these metals in the complex is preferably from 1:30 to 30: 1, more preferably from 1: 2 to 30: 1. 2: 1
, Most preferably about 1: 1. As an alternative to using such a complex comprising a dendrimer ligand and several different metals, a corresponding mixture of several complexes comprising a dendrimer ligand and one metal can also be used.

Also, in addition to the dendrimer ligand, the complex compound used according to the present invention is
Other ligands, usually of relatively simple structure, more specifically neutral or monovalent or polyvalent anionic ligands such as water, nitrate, acetate, formate, citrate, perchlorate and halide ( For example, they can contain chlorides, bromides and iodides), and complex anions such as hexafluorophosphate. Anionic ligands provide charge cancellation between the transition metal central atom and the ligand system. Also, oxo, peroxo and imino ligands can be present. These additional ligands can also have a crosslinking effect, such that oligomeric polynuclear complexes containing at least one dendrimer ligand are formed.

To prepare the complexes used according to the invention, the dendrimer ligand can be reacted with a transition metal salt in a customary solvent such as, for example, acetone or methanol. Dendritic transition metal complexes containing mixed metals that are also active as bleaches are obtained by subjecting dendrimers to two or more different transition metals in different weight ratios. The complexes used as bleach catalysts according to the invention are:
It is usually formed at low temperatures, around room temperature, and is usually obtained in crystalline form from ordinary solvents.

In the present invention, the term “bleaching” is understood to include the bleaching of both soils on the textile surface and soils separated from the textile surface in the washing liquor. Correspondingly, the same applies to the bleaching of soils (more specifically tea) on hard surfaces.

The present invention also provides a method for producing a woven fabric and a hard surface by using the above complex compound in an aqueous solution optionally containing other detergent components (more specifically, an oxidizing agent based on peroxygen).
More specifically, a method for cleaning tableware), and a detergent (such as a dishwasher) for cleaning laundry and hard surfaces containing such complex compounds. Detergents, preferably detergents for use in machines).

The use of the present invention essentially contaminates the conditions such that the peroxide oxidizing agent and the complex compound react with each other to give a product with a more powerful oxidizing effect, with colored stains. It consists in creating in the presence of a hard surface or a correspondingly contaminated fabric. Such conditions occur especially when the reactants encounter each other in an aqueous solution. This can be accomplished by separately adding the peroxygen compound and the complex to a solution containing a laundry detergent or dishwasher, if desired. However, in one particularly advantageous embodiment, the process according to the invention is carried out with the inventive laundry or dishwashing detergent containing a complex compound and an optional peroxygen-containing oxidizing agent. The peroxygen compound itself can be independently added to the solution in which the peroxygen-free laundry or dishwashing detergent is used, and it is also possible to add it, preferably as an aqueous solution or suspension. it can.

This condition can vary widely depending on the intended application. That is, in addition to a pure aqueous solution, a mixture of water and a suitable organic solvent can be used as a reaction medium. The amount of peroxygen compound used is usually chosen such that the solution contains 10 ppm to 10% active oxygen, preferably 50 ppm to 5000 ppm active oxygen. Also, the amount of bleach enhancing complex compound used will depend on the intended application. Depending on the desired degree of activation, the compound is used in an amount such that 0.01 to 25 mmol, preferably 0.1 to 2 mmol, of the complex is used per mole of peroxygen compound. In special cases, higher or lower amounts can also be used.

The laundry detergent and the dishwashing detergent of the present invention are preferably 0.0025 to 0.25% by weight.
And more preferably 0.01 to 0.1% by weight of the bleach-enhancing complex compound as defined above.

In addition to the bleach-enhancing ingredients mentioned above, the laundry detergents and dishwashing detergents according to the invention, which are present as solids in the form of granules, powders or tablets, as other shaped articles, homogeneous solutions or suspensions Can basically contain any known ingredients commonly used in such detergents. More specifically, the detergents of the present invention include builders, surfactants, peroxygen compounds, water-miscible organic solvents, sequestering agents, enzymes, electrolytes, pH regulators and other auxiliaries, such as silver corrosion inhibitors. Agents, foam control agents, additional peroxygen activators and dyes and fragrances can be included.

In addition, the dishwashing detergent of the present invention may contain abrasive components, more specifically silica powder, wood powder, polymer powder, chalk and glass microbeads and mixtures thereof. The abrasive is present in the dishwashing detergent of the present invention preferably in an amount of up to 20% by weight, more specifically in an amount of from 5 to 15% by weight.

The detergent comprises one or more surfactants, more specifically, anionic surfactants, nonionic surfactants and mixtures thereof, and cationic surfactants.
It may contain zwitterionic and amphoteric surfactants. Such surfactants are present in the laundry detergents of the present invention preferably in an amount of 5 to 50% by weight, more preferably 8 to 30% by weight. Dishwashing detergents usually contain relatively small amounts, up to 20% by weight, more particularly up to 10% by weight, preferably 0.5-5% by weight. . Very low effervescent compounds are commonly used in dishwashing detergents.

Suitable anionic surfactants are specifically those containing soap and sulfate or sulfonate groups. Suitable surfactants of the sulfonate type are preferably C _9-13 alkylbenzene sulfonates, olefin sulfonates, i.e. mixtures of alkenes and hydroxyalkane sulfonates, and, for example, C _12-18 monoolefins having internal or terminal double bonds, Disulfonates obtained by sulfonation with sulfur trioxide gas and subsequent alkaline or acidic hydrolysis of the sulfonated product. Other suitable sulfonate-type surfactants are the alkane sulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation followed by hydrolysis or neutralization. Esters of α-sulfofatty acids (ester sulfonates), such as hydrogenated coconut oil, palm kernel oil or α-sulfonated methyl esters of tallow fatty acids (these include plants and / or containing 8 to 20 carbon atoms in the fatty acid molecule). Or obtained by α-sulfonation of methyl esters of fatty acids of animal origin and subsequent neutralization to water-soluble monosalts). The ester is preferably an alpha-sulfonated ester of hydrogenated coconut fatty acid, palm oil fatty acid, palm kernel oil fatty acid or tallow fatty acid, but the sulfonated product of unsaturated fatty acid (e.g., oleic acid) It can also be present in small amounts, preferably up to about 2-3% by weight. Particularly preferred are α-sulfofatty acid alkyl esters containing an alkyl chain of up to 4 carbon atoms in the ester group, such as methyl, ethyl, propyl and butyl esters. It is particularly advantageous to use the methyl esters of α-sulfo fatty acids (MES) and their saponified disalts. Other suitable anionic surfactants are the sulfonated fatty acid glycerol esters, i.e., monoesters, diesters, triesters and mixtures thereof, which are obtained by esterification of monoglycerol with 1-3 moles of fatty acids. Alternatively, it is obtained by transesterification of triglyceride with 0.3-2 mol of glycerol.

Preferred alkyl (alkenyl) sulfates are C _12-18 fatty alcohols (eg, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol) or sulfuric acid half esters of C _10-20 oxo alcohols and the same. Alkali metal salts of the corresponding half esters of chain length secondary alcohols, especially the sodium salts. Other preferred alkyl (alkenyl) sulphates are the above mentioned chain length sulphates which comprise a synthetic linear alkyl chain based on petrochemicals and which have a similar decomposition behavior to the corresponding compounds based on petrochemical raw materials. C _{12 -16} alkyl sulfates and C _12-15 alkyl sulfates, more C _14-15 alkyl sulfates, especially preferred from the standpoint of cleaning performance. Other suitable anionic surfactants are 2,3-alkyl sulphates, which can be prepared, for example, according to US Pat. No. 3,234,258 or US Pat.
It is marketed under the name AN ^R as a product of Shell Oil Company. Also, 1-6 moles of C _7-21 alcohol ethylene oxide ethoxylated linear or branched chain, for example, and 2-methyl-branched containing on average 3.5 moles of ethylene oxide Sid (EO) C _9- Also suitable are sulfuric acid monoesters of _C12-18 fatty alcohols containing ₁₁ alcohols or 1-4 EO. In view of their high foaming capacity, they are usually used in laundry and dishwashing detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Another preferred anionic surfactant is a salt of an alkyl sulfosuccinic acid (also known as sulfosuccinates or sulfosuccinates, sulfosuccinates and alcohols, preferably fatty alcohols, more specifically A monoester and / or a diester with an ethoxylated fatty alcohol). Preferred sulfosuccinates contain _C8-18 fatty alcohol molecules or mixtures thereof. Particularly preferred sulfosuccinates contain fatty alcohol molecules derived from ethoxylated fatty alcohols, which, when considered independently, are nonionic surfactants. Of these sulfosuccinates, those in which the fatty alcohol molecules are derived from a narrow range of ethoxylated fatty alcohols are particularly preferred. Further, an alkyl (alkenyl) succinic acid having preferably 8 to 18 carbon atoms in the alkyl (alkenyl) chain or a salt thereof can also be used.

Other suitable anionic surfactants are fatty acid derivatives of amino acids, such as fatty acid derivatives of N-methyltaurine (tauride) and / or N-methylglycine (sarcoside). Sarcosides or rather sarcosinates, especially sarcosinates of higher optionally mono- or polyunsaturated fatty acids, such as oleyl sarcosinate, are particularly preferred.

[0027] Other suitable anionic surfactants are, in particular, soaps, which are preferably used in an amount of 0.2 to 5% by weight. Suitable soaps are, for example, saturated fatty acid soaps.
(E.g., salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid), and especially soaps derived from natural fatty acids (e.g., coconut oil, palm kernel oil or tallow fatty acid). It is a mixture. Known alkenyl succinates can be used with or as a soap substitute.

Anionic surfactants (including soaps) can be present in the form of their sodium, potassium or ammonium salts, and as soluble salts of organic bases (eg, mono, di or triethanolamine). . The anionic surfactant is preferably present in the form of its sodium or potassium salt, more preferably in the form of its sodium salt.

The anionic surfactant is preferably present in the laundry detergent of the present invention in an amount of 1 to 30% by weight.
And more preferably in an amount of from 5 to 25% by weight.

Preferred nonionic surfactants are alkoxylated (advantageously ethoxylated), more particularly primary alcohols, preferably having 8 to 18 carbon atoms and an average per mole of alcohol. 1 to 12 moles of ethylene oxide (EO)
Alcohol. The alcohol group may be straight-chain or preferably 2-methyl-branched, or may contain straight-chain and methyl-branched groups in the form of the mixtures commonly present in oxo alcohol groups. However, 12-1
The linear groups of naturally occurring alcohols containing 8 carbon atoms (e.g., coconut oil fatty alcohol, palm oil fatty alcohol, tallow fatty alcohol or oleyl alcohol) and on average 2 to 8 alcohols per mole of alcohol Alcohol ethoxylates containing EO are particularly preferred. Preferred ethoxylated alcohols include, for example, C _13-15 alcohols containing C _12-14 alcohols containing 3EO or 4 EO, C _{9-1 1} alcohol containing 7EO, 3EO, 5 EO, the 7EO or 8EO,
3EO, include C _12-18 alcohols and mixtures thereof including 5EO or 7EO (eg, a mixture of C _12-18 alcohols containing C _12-14 alcohol with 7EO containing 3EO) is. The above degree of ethoxylation is a statistical average and can be either an integer or a fraction for a particular product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols containing 12 or more EO can also be used. Examples of such fatty alcohols are 14EO, 16EO, 20
(Tallow) fatty alcohols containing EO, 25EO, 30EO or 40EO.

In addition, these nonionic surfactants include a general formula: RO (G) x, wherein R is a group containing 8 to 22 (preferably 12 to 18) carbon atoms. G is a primary linear or methyl-branched (more specifically, 2-methyl-branched) aliphatic group, wherein G is a glucose unit containing 5 or 6 carbon atoms (preferably glucose). Alkyl glycoside represented by the formula: The degree of oligomerization x (which indicates the distribution of mono- and oligoglycosides) is a number from 1 to 10 (this number may be a fraction, as determined by analysis). Preferably, x = 1.2-1.4.

[0032] Other suitable surfactants are polyhydroxy fatty acid amides of the following formula (III):

R ² | R ¹ —CO—N— [Z] (III) wherein R ¹ CO is an aliphatic acyl group containing 6 to 22 carbon atoms, and R ² is hydrogen Is an alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms, and [Z] is a linear or branched polyhydroxyalkyl group containing 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Is]. Preferably, the polyhydroxy fatty acid amide is derived from a reducing sugar containing 5 or 6 carbon atoms (more specifically, glucose).

The group of polyhydroxyfatty acid amides also includes compounds of formula (IV):

R ⁴ —O—R ⁵ | R ³ —CO—N— [Z] (IV) wherein R ³ is a linear or branched alkyl or alkyl having 7 to 12 carbon atoms. An alkenyl group, R ⁴ is a linear, branched or cyclic alkylene or arylene group containing 2 to 8 carbon atoms, and R ⁵ is a straight chain containing 1 to 8 carbon atoms. A chain, branched or cyclic alkyl or aryl or hydroxyalkyl group (preferably a C _1-4 alkyl or phenyl group), and [Z] represents a linear polyhydroxyalkyl group (where the alkyl chain is At least two hydroxyl groups) or alkoxylated (preferably ethoxylated or propoxylated) derivatives of such groups. Again, [Z] is preferably obtained by reductive amination of a sugar (eg, glucose, fructose, maltose, lactose, galactose, mannose or xylose; then N-alkoxy or N-aryloxy substituted). The resulting compound can be converted to the desired polyhydroxy fatty acid amide by reacting it with a fatty acid methyl ester in the presence of an alkoxide as a catalyst, for example, following the teachings of International Patent Application WO-A-95 / 07331.

Another group of preferred nonionics for use as the sole nonionic surfactant or in combination with other nonionic surfactants, especially for use with alkoxylated fatty alcohols and / or alkyl glycosides The nonionic surfactants are described, for example, in Japanese Patent Application JP 58/217598, preferably alkoxylated fatty acid alkyl esters (preferably ethoxyl) prepared by the method described in International Patent Application WO-A-90 / 13533. Or ethoxylated and propoxylated, preferably containing 1 to 4 carbon atoms in the alkyl chain), and more specifically fatty acid methyl esters.

Nonionic surfactants of the amine oxide type, such as N-coconut alkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethyl amine oxide, and nonionic surfactants of the fatty acid alkanolamide type Ionic surfactants are also suitable. The use of these nonionic surfactants preferably does not exceed the use of ethoxylated fatty alcohols, in particular does not exceed half.

Another suitable surfactant is a so-called Gemini surfactant. Normal,
Gemini surfactants are understood to be compounds containing two hydrophilic groups and two hydrophobic groups per molecule. Usually, these groups are separated from one another by so-called "spacers". This spacer is usually a carbon chain,
The carbon chain should be long enough that the hydrophilic groups are well spaced and can act independently of each other. In general, gemini surfactants are distinguished by unusually low critical micelle concentrations and by their ability to significantly lower the surface tension of water. However, in exceptional cases, gemini surfactants are not only understood to be "dimer" surfactants, but also "trimer" surfactants. Suitable gemini surfactants are, for example, the sulfated hydroxy mixed ethers described in German Patent Application DE-A-432 1022, as well as the earlier German Patent Application DE
Dimer alcohol bis- and trimer alcohols described in 19503061 tris-sulfate and -ether sulfate. The end-capped dimer and trimer mixed ethers described in the earlier German Patent Application DE19513391 are distinguished, inter alia, by their difunctional and polyfunctional nature. That is, because the described end-capped surfactants exhibit good wetting properties and are low foaming, they are particularly suitable for use in mechanical cleaning or cleaning processes. However, international patent applications WO-A-95 / 19953, WO-A-95 /
Gemini polyhydroxy fatty amides or poly-polyhydroxy fatty amides described in 1995 and WO-A-95 / 1995 may also be used.

The laundry detergent of the present invention contains at least one water-soluble and / or water-insoluble organic and / or inorganic builder. Suitable water-soluble organic builders include:
Polycarboxylic acids, more specifically citric and sugar acids, monomeric and polymeric aminopolycarboxylic acids, more specifically methylglycine diacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acid,
More specifically, aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, and polymeric (poly) carboxylic acids, more specifically international patent applications WO93 / 161
10 or International Patent Application WO 92/18542 or European Patent EP 023220
2. Polycarboxylates obtained by oxidation of the polysaccharide or dextrin described in 2 above, polymers of acrylic acid, methacrylic acid, maleic acid and copolymers thereof (polymerizable substances containing no carboxylic acid functional groups in copolymerized form). May be contained in small amounts). The relative molecular weight of a homopolymer of an unsaturated carboxylic acid is usually from 5,000 to 200,000, while the relative molecular weight of a copolymer is from 2,000 to 200,000, preferably from 50,000 to 120,000. 000 (based on free acid). Particularly preferred acrylic / maleic acid copolymers have a relative molecular weight of 50,000 to 100,000. Commercial products are, for example, BASF of Sokalan (Sokalan ^R) CP5, which is CP10 and PA 30. Suitable but less preferred compounds of this group are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinyl methyl ether, vinyl esters, ethylene, propylene and styrene (where the acid comprises at least 50% by weight). Constitute).

Other suitable water-soluble organic builders contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or esterified vinyl alcohol or carbohydrates as a third monomer. It is a terpolymer.
The first acid monomer or salt thereof is derived from a monoethylenically unsaturated _C3-8 carboxylic acid, preferably a _C3-4 monocarboxylic acid, more specifically (meth) acrylic acid. The second acid monomer or a salt thereof may be a derivative of C _4-8 dicarboxylic acid (maleic acid is particularly preferred) and / or a derivative of allylsulfonic acid substituted at the 2-position with an alkyl group or an aryl group. Such polymers can be prepared in particular by the processes described in German Patents DE 422 381 and DE 43 00 772 and usually have a relative molecular weight of from 1,000 to 200,000. Other preferred copolymers are described in German Patent Applications DE4303320 and DE4303320.
No. 4,177,734, which preferably contain as monomers acrolein and acrylic acid / acrylate or vinyl acetate. The organic builder can be used advantageously in the form of an aqueous solution, preferably for the production of liquid detergents, preferably in the form of a 30-50% by weight aqueous solution. All of the above-mentioned acids are usually used in the form of their water-soluble salts, more specifically their alkali metal salts.

If desired, such organic builders can be present in an amount of up to 40% by weight, preferably 25% by weight.
It can be present in an amount up to% by weight, more preferably in an amount of 1 to 8% by weight.
It is preferred to use an amount close to the upper limit in paste form or liquid, more particularly in aqueous detergents.

[0040] Suitable water-soluble inorganic builders are, in particular, alkali metal silicates and polymeric alkali metal phosphates, which are present in the form of their alkaline, neutral or acidic sodium or potassium salts. be able to. Examples of such builders are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.

The crystalline or amorphous alkali metal aluminosilicate may be incorporated in an amount of up to 50% by weight, preferably up to 40% by weight, especially in liquid detergents in an amount of from 1 to 5% by weight, Used as an inorganic builder material. Among these inorganic builders, detergent quality crystalline sodium aluminosilicate, more specifically zeolite A
, P and, optionally, X, individually or in the form of a mixture, such as zeolite A
And the form of the X co-crystallizate preferred [Begobondo (Vegobond ^R) AX, products of Condea Augusta, Inc. (Condea Augusta SPA)]. It is preferred to use an amount close to the above-mentioned upper limit in the solid granular detergent. A suitable aluminosilicate is 30
It is preferred that at least 80% by weight consist of particles smaller than 10 μm without particles larger than μm. Their calcium binding capacity (determinable according to German patent DE 2412837) is usually in the range of 100 to 200 mg CaO / g.

A suitable or partial replacement for the alumosilicates mentioned above is a crystalline alkali metal silicate, which may be on its own or in the form of a mixture with an amorphous silicate. Can exist. Alkali metal silicates suitable as builders in the surfactant mixtures of the present invention include alkali metal oxides and SiO _{2 in} the range of less than 0.95: 1, more specifically in the range of 1: 1.1 to 1:12. And can be amorphous or crystalline. Preferred alkali metal silicates, Na ₂ O: SiO ₂ molar ratio is 1: 2 to 1: 2.8 at a silicic acid sodium, more particularly amorphous sodium silicates. Na ₂ O: SiO ₂ molar ratio is 1: 1.9 to 1: 2.8 Sodium silicate is the European patent application EP04
25427. General _{formula: Na 2 S i x O 2x} + 1 · yH 2 O [ wherein, x is the so-called modulus, the number of 1.9 to 4, y is a number from 0 to 20: preferred The value of x is 2, 3 or 4.] It is preferred to use crystalline layered silicates as crystalline silicates, which can be used as such or with amorphous silicates. It can be present in a mixture. The crystalline layered silicate represented by the above general formula is described, for example, in European Patent Application EP
0164514. Preferred crystalline layered silicates are those in which x in the above general formula is a value of 2 or 3. Particularly preferred are β- and δ-sodium disilicate (Na ₂ Si ₂ O ₅ .yH ₂ O). β-Sodium disilicate can be obtained, for example, by the method described in International Patent Application WO 91/08171. Δ-Sodium silicate having a modulus of 1.9 to 3.2 can be produced according to Japanese Patent Application JP04 / 238809 or JP04 / 260610. The substantially water-free, crystalline alkali metal silicates of the above general formula wherein x is a number from 1.9 to 2.1 are described in European Patent Applications EP 0 548 599, EP 0
It can be obtained from the amorphous alkali metal silicates described in EP 502325 and EP 0425428, which can also be used. Another preferred embodiment of the detergent according to the invention is characterized by the use of crystalline layered sodium silicate having a modulus of 2-3, which can be produced from sand and soda by the method described in European Patent Application EP 0 436 835. . European Patent EP 0164552 and / or E
Crystalline sodium silicate having a modulus of 1.9 to 3.5, obtainable by the method described in P0294753, is used in another preferred embodiment of the detergent according to the invention. Another preferred embodiment of the detergent of the invention, for example, or are described in International Patent Application WO95 / 22592, or, for example, Nabion sold under the name (Nabion ^R), alkali metal silicates and alkali metal carbonates Characterized by the use of granular compounds of When an alkali metal aluminosilicate (more specifically, a zeolite) is present as an additional builder, the weight ratio of aluminosilicate to silicate (based on the active substance without water) is preferably 1
: 10 to 10: 1. In detergents containing both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably from 1: 2 to 2: 1. Yes, more preferably 1: 1
２2: 1.

The builder is preferably present in the detergent according to the invention in an amount of up to 60% by weight, more preferably 5 to 40% by weight.

Basically, any builder commonly used in dishwashing detergents, such as the alkali metal phosphates mentioned above, can be used as the water-soluble builder component in the inventive detergents for hard surfaces. . These are approximately 6 based on the total detergent.
It can be present in an amount up to 0% by weight, more specifically in an amount of 5-20% by weight. Other possible water-soluble builder components other than polyphosphonates and phosphonate alkylcarboxylates are, for example, organic polymers of natural or synthetic origin of the polycarboxylate type mentioned above, which act as co-builders, especially in the hard water region. And natural hydroxycarboxylic acids such as mono- and dihydroxysuccinic acid, α-hydroxypropionic acid and gluconic acid. Preferred organic builder components include salts of citric acid, and more specifically, sodium citrate. The sodium citrate used is anhydrous trisodium citrate, preferably trisodium citrate dihydrate. Trisodium citrate dihydrate can be used in the form of a fine or coarse crystalline powder. The acids corresponding to the co-builder salts mentioned above can also be present depending on the pH value which is finally adjusted in the detergent according to the invention.

Suitable oxygen-based bleaches are, in particular, alkali metal perborate monohydrates or tetrahydrates and / or alkali metal percarbonates, sodium being the preferred alkali metal. The use of sodium percarbonate is particularly advantageous for dishwashing detergents, since this material has a particularly favorable effect on the corrosion behavior of glass. Thus, the oxygen-based bleach is preferably an alkali metal percarbonate, more specifically sodium percarbonate. In addition, or in particular, separately, there may be known peroxycarboxylic acids, such as dodecane diperacid or phthalimidopercarboxylic acid, optionally substituted at the aromatic component. Small amounts of known bleach stabilizers, for example phosphonates, borates or metaborates and metasilicates and magnesium salts (e.g. magnesium sulfate)
May also be useful.

In addition to the complex compounds used according to the invention, conventional transition metal complexes known as bleach activators and / or conventional bleach activators, ie optionally substituted under conditions of perhydrolysis Compounds that produce perbenzoic acid and / or peroxocarboxylic acid (containing 1 to 10 carbon atoms, more specifically 2 to 4 carbon atoms) can be used. Suitable bleach activators include the customary bleach activators mentioned at the outset (optionally substituted benzoyl groups and / or O- and / or N-acyl groups containing the stated number of carbon atoms). ). Preferred bleach activators are polyacylated alkylenediamines, more specifically tetraacetylethylenediamine (TAED), acylated glycoluril, more specifically tetraacetylglycoluril (TAGU), acylated triazine derivatives, Specifically, 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonate, more specifically nonanoyl or isononanoyloxybenzenesulfonate , Acylated polyhydric alcohols, more specifically triacetin, ethylene glycol diacetate and 2
, 5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol, and acylated sugar derivatives, more specifically pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose And acetylated, optionally N-alkylated glucamine and gluconolactone. It is also possible to use the customary combinations of bleach activators known from German Patent Application DE 44 43 177. In one preferred embodiment of the use according to the invention, a compound which forms a peroxocarboxylic acid under conditions of perhydrolysis is used simultaneously with the bleach-enhancing complex compound. In one preferred embodiment of the detergent according to the invention, 1 to 10% by weight, preferably 2 to 6% by weight, of a compound which forms peroxocarboxylic acids under such overhydrolysis conditions are present in addition to the complex compound. I do. The weight ratio of the compound producing peroxocarboxylic acid under perhydrolysis conditions to the complex compound used according to the invention is:
Preferably in the range of 100,000: 1 to 100: 1, more preferably 50,000.
00: 1 to 1,000: 1.

Enzymes optionally present in the detergents of the present invention include proteases, amylases,
Pullulanases, cellulases, cutinases and / or lipases are included. These include proteases such as BLAP ^R , Optimase (Optimase ^R ), Opticlean ^R , Maxacal ^R , Maxapem ^R , Durazym ^R , Purafect ^R OxP, Esperase. ^R) and / or Savinase (Savinase ^R), amylases, for example Termamyl (Termamyl ^R)
, Amylase LT (Amylase-LT ^R), Makisamiru (Maxamyl ^R), Duramyl (Duramyl ^R), Purafekuto (Purafect ^R) OxAm, cellulase, e.g. Seruzaimu (Celluzy
me ^R), Karezaimu (Carezyme ^R), KAC ^R, and / or international patent application WO96
/ 34108 and WO96 / thirty-four thousand and ninety-two known from cellulases and lipases, for example Lipolase (Lipolase ^R), lipoic Max (Lipomax ^R), Rumafasuto (
A Lumafast ^R) and / or Ripojimu (Lipozym ^R). The enzyme used may be adsorbed on a support and / or embedded in a shell-forming material in order to protect it from premature inactivation, as described, for example, in International Patent Applications WO 92/11347 or WO 94/23005. Can be. They are present in the detergents according to the invention preferably in amounts of up to 10% by weight, more preferably 0.05 to 5% by weight. For example, International Patent Applications WO94 / 02597, WO94 / 02618, WO94 / 18
Enzymes stabilized against oxidative degradation known from 314, WO 94/23053 or WO 95/07350 are particularly preferred.

The machine dishwashing detergent according to the invention preferably contains customary alkaline systems, for example alkali metal silicates, alkali metal carbonates and / or alkali metal bicarbonates. Commonly used alkaline systems include carbonates, bicarbonates and alkali metal silicates (SiO ₂ : M ₂ O in a molar ratio of 1: 1 to 2.5: 1: M
Is an alkali metal atom). The alkali metal silicate can be present in an amount of up to 40% by weight, more specifically 3-30% by weight, based on the total detergent. A preferred alkaline system for use in the detergents of the present invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and sodium bicarbonate, in an amount up to 50% by weight, preferably 5-40% by weight. Present in the amount.

The invention is also based on 15 to 65% by weight, more specifically 20 to 60% by weight of the water-soluble builder component, 5 to 25% by weight, more specifically 8 to 17% by weight of oxygen. It relates to a dishwashing detergent containing bleach (based on the total detergent) and 0.01 to 1% by weight of one or more complex compounds as defined above. Such detergents
The pH of a low alkaline detergent, i.e. a 1% by weight solution, is 8-11.5, more specifically 9
~ 11 is preferred.

Another embodiment of the automatic dishwashing detergent of the present invention comprises 20 to 60% by weight of a water-soluble organic builder, more specifically an alkali metal citrate, 3 to 20% by weight of an alkali metal carbonate and 3% by weight. Contains ４０40% by weight of alkali metal disilicate.

To protect silver products, the dishwashing detergents of the present invention can contain a silver corrosion inhibitor. Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, dihydric or trihydric phenols, optionally alkyl or aryl substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, molybdenum, vanadium or cerium. Salts and / or complexes (these metals have an oxidation number II, III, IV, V or VI depending on the metal) and complexes suitable according to the invention [separate from the ligands of the formula (I) And a salt and / or complex of a metal present in the above.

If the foaming of the detergent during use is too severe, for example when an anionic surfactant is present, preferably up to 6% by weight, more preferably about 0.5-4% by weight, of a foam inhibiting compound, preferably Adds a foam control compound from the group consisting of silicone oil, paraffin, paraffin / alcohol combinations, hydrophobized silica, bis-fatty acid amides and mixtures thereof and other known commercial defoamers. be able to. The foaming inhibitor, more specifically a foaming inhibitor containing silicone and / or paraffin, is preferably fixed to a granular water-soluble or water-dispersible support. In this case, a mixture of paraffin and bis-stearylethylenediamide is particularly preferred. Another optional ingredient in the detergents of the present invention is, for example, a fragrance oil.

Organic solvents suitable for use in the detergents of the present invention, especially when the detergent is present in a liquid or paste-like form, include alcohols containing 1 to 4 carbon atoms, more specifically methanol, Ethanol, isopropanol and t-butanol, diols containing 2 to 4 carbon atoms, more particularly ethylene glycol and propylene glycol, and mixtures thereof, and ethers derived from the above-mentioned compounds are included. Such water-miscible solvents are present in the detergents according to the invention preferably in amounts of up to 20% by weight, more preferably in amounts of 1 to 15% by weight.

In order to obtain the desired pH value not automatically achieved by the mixture of the other components, the detergents according to the invention are system-compatible and environmentally compatible acids, more particularly citric acid,
Acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or
Or it may contain adipic acid and an inorganic acid, more specifically sulfuric acid or alkali metal hydrogensulfate, or a base, more specifically ammonia or alkali metal hydroxide. Such pH adjusters can be present in the detergents of the present invention preferably in an amount of up to 10% by weight, more preferably in an amount of 0.5 to 6% by weight.

The detergent according to the invention is preferably present as a preparation in powder, granulate or tablet form. These preparations may be prepared by known methods, for example by mixing, granulating, roller compacting and / or spray drying of heat-sensitive components and more sensitive components (especially including enzymes, bleaches and bleach catalysts). Prepared by the addition of The detergents according to the invention in the form of aqueous solutions or solutions containing other customary solvents are particularly conveniently prepared by simply mixing the components (the components are used as is or in solution in an automatic mixer. Can be introduced).

The granular detergents of high bulk density, more specifically in the range of 650 to 950 g / L, are preferably prepared by a method known from EP 0 486 592, which includes an extrusion step. Another preferred production method is described in European patent EP0642.
No. 576. In addition, the detergent of the present invention in the form of a dust-free, storage-stable, free-flowing powder and / or granule having a high bulk density of 800 to 1,000 g / L comprises a builder component in the first step. Is mixed with at least a portion of the liquid component to form a premix (with an increase in bulk density), and optionally drying the premix thus obtained, followed by other components of the detergent (e.g., bleach catalyst). ).

The tablet-form detergent of the present invention is prepared by mixing all the components in a mixer, and mixing the resulting mixture with a conventional tablet press (for example, an eccentric press or a rotary press).
It is preferable to manufacture by tableting under a pressure of 00 · 10 ^{5 to} 1500 · 10 ⁵ Pa. In this way, a tablet that dissolves quickly enough under the conditions of use and has a flexural strength of usually 150 N or more is easily obtained. The tablets thus produced preferably have a weight of 15 to 40 g, more particularly 20 to 30 g for a diameter of 35 to 40 mm.

Example 1 Preparation of Cobalt (II) -Polyamidoamine Complex Third Generation Polyamidoamine Dendrimer (PAMAM Gen. 3: Obtained from Ethylenediamine, Methyl Acrylate and Ethylenediamine as Starting Nuclei) ) In methanol (12.5 g) was added to a solution of CoC in acetone (50 ml).
to _{l 2 · 6H 2 O (1.205g} ) of a clear dark blue solution was added dropwise Slowly with stirring at room temperature. The resulting pale blue coarse flake precipitate was filtered off, washed with acetone,
The size was reduced in a mortar and dried in a desiccator to constant weight of the blue gel. Cobalt (II) -polyamidoamine in the form of a light blue fine particle powder, 2.
Obtained in a yield of 87 g (B1).

Example 2 Preparation of Cobalt (III) -Polyamidoamine Complex 20% by weight of third generation polyamidoamine dendrimer (PAMAM Gen. 3: obtained from ethylenediamine, methyl acrylate and ethylenediamine as starting nucleus) % Methanol solution (12.5 g) was added to methanol (200 ml).
A clear, dark blue solution of oCl ₂ .6H ₂ O (1.012 g) was slowly added dropwise at room temperature with stirring. Then, oxygen was introduced into the reaction mixture for 2 hours. The resulting pink fine crystalline precipitate was filtered off and dried to constant weight in a desiccator, changing its color first to light gray and then to blue-grey. Cobalt (III
) -Polyamidoamine was obtained in a yield of 0.5 g (B2).

Example 3 : Preparation of molybdenum (V) -polyamidoamine complex 10 weight percent of 4th generation polyamidoamine dendrimer (PAMAM Gen. 4: obtained from ethylenediamine, methyl acrylate and ethylenediamine as starting nucleus) A 5% methanol solution (5 g) was slowly added dropwise to a clear green solution of molybdenum (V) chloride (0.153 g) in methanol (50 ml) at room temperature under nitrogen with stirring. The solution was stirred for 15 minutes. The solvent was then removed from the solution on a rotary evaporator. A light brown fine crystalline product was obtained. This product was powdered in a mortar. The molybdenum (V) -polyamideamine complex (B3) was obtained in the form of a light brown solid in a yield of 0.2 g.

Example 4 Preparation of Cobalt (III) -Polyamidoamine Complex 10 Weight of Fourth Generation Polyamidoamine Dendrimer (PAMAM Gen. 4: Obtained from Ethylenediamine, Methyl Acrylate and Ethylenediamine as Starting Nuclei) A 5% methanol solution (5 g) was slowly added dropwise with stirring at room temperature to a clear pink solution of cobalt (II) chloride hexahydrate (0.266 g) in methanol (50 ml). Then, oxygen was introduced into the reaction mixture for 2 hours. The color of the pink microcrystalline precipitate formed turned dark blue. The solvent was then removed from the solution on a rotary evaporator. The color of the compound turned dark green. The product was reduced in size in a mortar and dried in a desiccator to constant weight of the blue gel. The cobalt (III) -polyamidoamine complex (B4) in the form of a dark green fine crystalline product was obtained in a yield of 0.5 g.

Example 5 : Preparation of cobalt (II) -polyamidoamine complex 3.5th generation polyamidoamine dendrimer (PAMAM Gen. 3.5: obtained from ethylenediamine, methyl acrylate and ethylenediamine as initiator nucleus; Since the reaction with ethylenediamine has been eliminated from the last step, this dendrimer contains a 10% by weight solution of 4.75 g of methanol (containing carboxylate groups as terminal functional groups) in methanol (50 ml). To a clear pink-red solution of cobalt (II) hexahydrate (0.305 g) was slowly added dropwise with stirring at room temperature. The solvent was removed from the resulting pale blue coarse flake precipitate in a rotary evaporator. The color of the compound turned dark blue. This product was powdered in a mortar and dried in a desiccator to constant weight of the blue gel. 0.5 g of cobalt (II) -polyamidoamine complex (B5) in the form of dark blue fine particle powder
In the yield.

Example 6 Cobalt (III) / Mn (4th generation polyamidoamine dendrimer, cobalt (II) chloride hexahydrate and Mn (III) chloride were prepared in the same manner as described in Example 4. I
II) -Polyamidoamine complex (B6) [the molar ratio of Co, Mn and dendrimer ligand is 16: 16: 1] was prepared. Cobalt (III) -polyamidoamine complex (B4
) And the corresponding 1: 1 mixture of Mn (III) -polyamidoamine complex (B7) were further prepared. Thus, the molar ratio of Co, Mn and dendrimer ligand in this mixture was again 16: 16: 1.

Example 7 Sodium perborate monohydrate (98 mg) was dissolved in a solution containing morin (2.5 g) in deionized water (99.5 ml). The pH was adjusted to 9.5 and maintained at this value during the following measurement period using a pH stat. The temperature was also maintained at a constant value of 20 ° C. A solution (0.5 ml) containing the bleaching catalyst to be tested at a concentration of 50 ppm based on transition metal was added. The absorbance E of the solution at 400 nm was measured at 1 minute intervals over 30 minutes. The value D (t) of the decolorization rate (%) is shown in the following table at t = 30 minutes {this D (t) is represented by the formula: D (t) = [E (t) -E (0)] / Calculate according to E (0) * 100}.

For comparison, the same conditions were used except that the usual bleach activator N, N, N ′, N′-tetraacetylethylenediamine (TAED) was used at a concentration of 6% by weight. Tested below (V1).

[0066]

[Table 1]

It is evident that significantly better bleaching effects are obtained with the use of the present invention than with the much higher concentrations of the conventional bleach activator TAED itself. Substantially the same results were obtained when sodium perborate was replaced by sodium percarbonate.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), JP, US (72) Inventor Lars Züchner, Federal Republic of Germany D-40591 Düsseldorf, Hohenzandweg 25 (72) Inventor Horst-Dieter Speckmann Federal Republic of Germany, D-40764 Langenfeld, Eichen Feldstraße 24th No. (72) Inventor Dirk Thyssen DE-41352 Korschen Bloich, Hauptstrasse 37 F-term (reference) 4H003 DA01 DA17 DA19 EB26 EE04 EE05 FA43

Claims (14)

[Claims] 1. One or more as activators for peroxygen compounds in aqueous solutions for washing laundry and in aqueous solutions for cleaning hard surfaces, more particularly dishes. Use of complexes of transition metals cobalt, manganese, iron, ruthenium, vanadium, molybdenum, tungsten or mixtures thereof, which retain the polyamidoamine type dendrimer ligands of the above. 2. The method according to claim 1, wherein the molar ratio of the transition metal to the dendrimer ligand in the transition metal complex is in the range of 1: 1 to 2 ^{n + 1} : 1 (n indicates the generation of the dendrimer). The use according to claim 1, wherein 3. The use according to claim 1, wherein the transition metal complex contains cobalt having an oxidation number of + II or + III and / or molybdenum having an oxidation number of + IV or + V. 4. The method according to claim 1, wherein different metals are present in the transition metal complex and the molar ratio of these metals in the complex is from 1:30 to 30: 1, more specifically from 1: 2 to 2: 1. The use according to any one of claims 1 to 3. 5. Use according to claim 4, wherein the metal cobalt and manganese are present in the transition metal complex. 6. A method according to claim 1, wherein the peroxygen compound to be activated is selected from the group consisting of organic peracids, hydrogen peroxide, perborates and percarbonates and mixtures thereof. 5. Use according to any of 5. 7. Transition metal bearing one or more polyamidoamine type dendrimer ligands in an aqueous solution for washing laundry and in a cleaning aqueous solution for hard surfaces for bleaching colored soils Cobalt, manganese, iron,
Use of complexes of ruthenium, vanadium, molybdenum, tungsten or mixtures thereof. 8. The use according to claim 1, wherein a compound that forms peroxocarboxylic acid under the conditions of perhydrolysis is used simultaneously with the complex compound. 9. The weight ratio of the compound that forms peroxocarboxylic acid under the condition of perhydrolysis to the complex compound is in the range of 100,000: 1 to 100: 1, more specifically 50,000: 9. Use according to claim 8, characterized in that it is in the range 1-1000: 1. 10. Complexes of transition metals cobalt, manganese, iron, ruthenium, vanadium, molybdenum, tungsten or mixtures thereof carrying one or more polyamidoamine type dendrimer ligands, optionally in laundry detergents or dishes A method for cleaning laundry or hard surfaces, more particularly dishes, characterized in that it is used in the form of an aqueous solution containing other components of the detergent. 11. A composition comprising a complex compound of a transition metal cobalt, manganese, iron, ruthenium, vanadium, molybdenum, tungsten or a mixture thereof, holding one or more polyamidoamine type dendrimer ligands. Cleaning composition for hard surfaces to be cured. 12. A composition comprising a complex compound of a transition metal cobalt, manganese, iron, ruthenium, vanadium, molybdenum, tungsten or a mixture thereof carrying one or more polyamidoamine type dendrimer ligands. CLEANING COMPOSITIONS for dishwashing, and more particularly for use in dishwashers. 13. The composition according to claim 11, wherein the composition contains 0.0025 to 0.25% by weight, more specifically 0.01 to 0.1% by weight, of the complex compound. . 14. In addition to the complex compound, 1-10% by weight, more specifically 2% by weight.
14. A composition according to any of claims 11 to 13, characterized in that it contains up to 6% by weight of a compound which forms peroxocarboxylic acids under conditions of perhydrolysis.