Inorganic peroxy compounds, in particular hydrogen peroxide and compounds which liberate hydrogen peroxide, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate, have been employed for a long times as oxidizing agents in bleaching, washing and cleaning processes. Sufficiently rapid bleaching of soiled textiles requires a temperature of at least 80°C.

The oxidizing action of inorganic peroxygen compounds at reduced temperature can be improved by co-using so-called bleaching activators. Bleaching activators are, in particular, N-and 0-acyl compounds, for example polyacylated alkylenediamines, such as tetraacetylethylenediamine (TAED), acetylated glycolurils, N-acetylated hydantoins, diketopiperazines, carboxylic acid anhydrides, carboxylic acid esters, such as, in particular, sodium nonanoyloxy-benzenesulfonate (NOBS), and acylated sugar derivatives.

By using a combination of a peroxy compound and an activator, bleaching can be carried out at about 609C instead of above 80°C without a loss in activity.

In efforts to be able to carry out washing and bleaching below 60°C, the use of transition metal complexes, in particular complexes of manganese, iron, cobalt and copper with at least one polydentate organic ligand, in particular nitrogen-containing ligands, has been described in many documents.

Reference is made by way of example to the complexes described in the following documents: EP 0 544 490, WO 98/54282, WO 00/12808, WO 00/60043, WO 00/52124, EP 0 392 592, WO 99/64156 and WO 00/12667.

Although numerous different transition metal complexes are thus known for the use aimed for, they only partly meet some of the expectations imposed on them.

Thus, if the reactivity is too high there is the risk of a change in colour of dyed textiles, and in the extreme case oxidative damage to the fibres. Furthermore, some complexes decompose the peroxygen compound without a bleaching action, are insufficiently stable to hydrolysis or are susceptible to oxidation.

The doctrine of EP Patent Application no. 0392592 is that the bleaching action of peroxy compounds can be activated in the presence of a catalytic amount of a complex of a transition metal from the series consisting of manganese, cobalt, iron and copper with a non-macrocyclic ligand of the general formula (I) The bridge member B is O, S, CRSR6, NR7 or C=O. The groupings Rl-C=N-R3 and R2-C=N-R4 can form a five-or six- membered optionally substituted heterocyclic ring. As the examples show, 2, 2'-dipyridylamine is always to be used as

the ligand L. However, with this bleaching catalyst there is the risk of a change in colour of dyed textiles, and in some cases also oxidative damage.

Bleaching catalysts with a similar structure of the organic nitrogen-containing ligand are the doctrine of WO 00/32731: The ligand is di (2-pyridyl) methylamine, which can also be N-substituted. This catalyst is suitable for increasing the oxidizing and bleaching action of hydrogen peroxide. A further increase is achieved by combination of such a bleaching catalyst with a so-called activator which can form a peroxycarboxylic acid in the presence of a source of hydrogen peroxide. As has been shown in practice, different property profiles of bleaching catalysts which the products known to date do not achieve in all points are required in washing, bleaching and cleaning compositions.

The object of the present invention is accordingly to provide further transition metal complexes with at least one nitrogen-containing polydentate ligand which are also suitable as a bleaching catalyst for activation of a peroxy compound and preferably also oxygen.

It has been found that transition metal complexes with a transition metal from the series consisting of manganese, iron, cobalt or copper are very active and gentle bleaching catalysts if these have at least one nitrogen-containing polydentate ligand of the general formula (I) wherein the bridge member B and the radicals R1 to R4 have, at least in one feature, a different meaning to the ligands in the last two documents acknowledged.

The invention thus provides the use of a transition metal complex with at least one nitrogen-containing polydentate ligand as a bleaching catalyst for activation of a peroxy compound or of oxygen, wherein the complex is mono-or polynuclear, the transition metal (M) is manganese, iron, cobalt or copper and the nitrogen- containing polydentate ligand (L), at least one of which is present, has the general formula (I)

wherein B represents a bridge member from the series consisting of-O-,-S- RI and R2 independently of one another represent a radical from the series consisting of H, linear, cyclic or branched alkyl, heteroalkyl, aryl, heteroaryl, arylalkyl and heteroarylalkyl, R3 and R4 independently of one another represent a radical from the series consisting of aryl, heteroaryl, alkoxy, arylalkoxy, heteroarylalkyl and arylalkyl, wherein the organic radicals of R1 to R4 can be substituted, the group R1-C=N-R3 and/or R-C=N-R4 independently of one another represent a five-to seven-membered N-

heterocyclic or N-heteroaromatic rings, which additionally can contain one or two further heteroatoms from the series consisting of 0, N and S and can be substituted, the bridge member represents a five-or six-membered optionally substituted cycloalkyl or heterocycloalkyl group with one to 3 heteroatoms from the series consisting of N, O and S and the bridge member represents a five-to seven-membered optionally substituted cycloaliphatic, aromatic, heterocyclic or heteroaromatic radical, wherein Z is chosen from the series consisting of 0,-N (R)-,-N= or-C (OH) 2-and the group G2 can contain one or two heteroatoms from the series consisting of O, N and S and/or substituents, R5 and R6 are independent of one another and can have a meaning according to the definition for R1, and wherein substituents in R1 to R6 and G1 and G2 can be chosen from the series consisting of functional and non-functional substituents, such as, in particular, OH, COOH, SO3H, NH2, N+ (alkyl) 4, S03-, COs', Cl, F, (Cl-C4)-alkoxy, (C1- C4) alkyl, phenyl, benzyl, pyridyl and 2-pyridylmethyl,

and wherein ligands in which the bridge member B represents are excluded if at the same time the ring system formed from R1-C=N-R3 and/or R2-C=N-R4 denotes other than an optionally substituted 1, 3-oxazolin-2-yl ring or if at the same time R3 and R4 denote other than heteroaryl, heteroarylmethyl, alkoxy or aryloxy.

The subclaims relate to preferred embodiments of the use according to the invention.

The present invention also provides the bleaching agent composition defined in the claims, which comprises a peroxy compound, in particular a source of hydrogen peroxide, and a transition metal complex to be used according to the invention in an amount effective for activation. The subclaims of the bleaching agent composition relate to preferred embodiments thereof.

The transition metal complex to be used according to the invention can be mono-or polynuclear and contains as the transition metal one from the series consisting of manganese in the valency level II to IV, iron in the valency level II or III, cobalt in the valency level II or III and copper in the valency level I or II. Depending on the number of heteroatoms capable of ligand formation and their steric alignment in the ligand L, the complex can contain one or more transition metal atoms, preferably one

or two metal atoms of the same type. In general the complex has the general formula [LmMnXo] Yp In this formula, L denotes the ligand to be used according to the invention, M denotes a transition metal atom from the abovementioned series, X denotes a coordinating neutral or mono-or polyvalent ligand for saturation of the ligand sphere and Y denotes a non-coordinating counter-ion, which can be anionic or, if the sum of anionic ligands X and ionic substituents in the ligand L exceeds the sum of the valency of the metal atoms M, can also be cationic. The index m represents an integer in the range from 1 to 4, in particular 1 or 2, the index n represents an integer, preferably 1 or 2, the index o represents zero or an integer in the range from 1 to 8 and the index p represents zero or an integer in order to achieve a complete charge compensation. Y can also be a substituent, such as carboxylate or sulfonate, in the ligand.

The polydentate ligand L to be used according to the invention has the structure according to the general formula (I) already shown. According to a preferred embodiment, the two radicals bonded to the bridge member B are identical, so that in these cases also R1 = R2 and R3 = R According to a preferred embodiment, the bridge member B corresponds to a five-to seven-membered, in particular five-or six-membered ring system according to the general formula

The ring system can be a cycloalkyl group in which Z represents the ketone hydrate structural element-C (OH) 2-.

In preferred ligands, however, B represents a heterocyclic radical where Z =-N (R6)-or a heteroaromatic radical wherein Z can represent-N (R6),-0-or-N=.

Examples of heterocyclic and heteroaromatic bridge members are: pyridine-2,6-diyl, pyrrole-2,5-diyl, imidazole-2, 5- diyl, piperidine-2,6-diyl, morpholino-3,5-diyl, pyrrolidine-2,5-diyl, 1, 3,5-triazine-2, 6-diyl.

The cyclic bridge members B can also have functional or non-functional substituents, for example OH, NH2, COOH, S03H, COOMe, S03Me, wherein Me represents an alkali metal, N+ (C1-C4-alkyl) 4, F, Cl, alkoxy, in particular (C1-C4) alkoxy, alkyl, in particular (C1-C4) alkyl, phenyl, benzyl, pyridyl, 2-pyridylmethyl.

The radicals R1 and R2 in the ligand L can be identical or different and represent H, linear, cyclic or branched alkyl or heteroalkyl, aryl, heteroaryl, arylalkyl and heteroarylalkyl. Examples are methyl, ethyl, i-propyl, tert-butyl, benzyl, phenyl, pyridyl, in particular 2- pyridyl, 1, 3-oxazolin-2-yl, 1, 3-oxazolin-2-methyl and 2- pyridylmethyl.

The radicals R3 and R4 in the ligand L can be, independently of one another, aryl, heteroaryl, alkoxy, aryloxy, heteroaryl, alkyl and arylalkyl. The examples mentioned above for R1 and R2 also apply here. If R3 and/or R4 represents alkoxy or aryloxy, they are preferably

methoxy, ethoxy, 2-hydroxyethoxy, 2-aminoethoxy, 2-N, N- di (C1-C4) alkylaminoethoxy and phenoxy.

According to a preferred embodiment, the groupings R1-C=N- R3 and/or R2-C=N-R4 form a five-or six-membered N- heterocyclic or N-heteroaromatic ring, which additionally can contain one or two heteroatoms, in particular oxygen or nitrogen, and can also be substituted.

Both the radicals R1 to R4 and the abovementioned cyclic groupings which are bonded to the bridge member B can have one or more functional or non-functional substituents.

These are those substituents such as have already been disclosed in connection with the description of the bridge member B. According to particularly preferred embodiments, the heterocyclic or heteroaromatic ring systems bonded to the bridge member B contain one or more linear or branched (C1-to C4) alkyl groups, in particular methyl, isopropyl and tert-butyl, and furthermore phenyl, benzyl, 2- pyridylmethyl or-ethyl or 4-imidazolylmethyl or-ethyl.

According to a further preferred embodiment, the radicals R1 to R4 or the nitrogen-containing ring systems formed therefrom contain hydrophilic substituents in order to increase the solubility of the complex. Examples of these are salt-forming functional substituents and hydroxyalkoxy groupings, which additionally can also contain one or more ether bridges.

According to a particularly preferred embodiment, 1,3- oxazolin-2-yl radicals are bonded to the bridge member B.

These heterocyclic radicals expediently contain a substituent from the series already described above in the 4-position, in particular isopropyl, tert-butyl, benzyl and 2-pyridylmethyl.

According to a further alternative embodiment, R1 and R2 and/or R3 and R4 represent the 1, 3-oxazolin-2-yl ring, which analogously contains a substituent from the abovementioned series.

The chemical name for some examples of suitable ligands and the formulae of some complexes containing them follow below: 2,6-bis [l- (2, 4,6-trimethylphenylimino) ethyl] pyridine (=TMAP) 2,6-bis [l- (2, 6-dimethylphenylimino) ethyl] pyridine (=DMAP) 2,6-bis [l- (2, 6-diisopropylphenylimino) ethyl] pyridine (=DiPAP) 0, 0'-bis (dimethylaminoethyl) pyridine 2,6-dialdoxime 0, 0'-bis (ethyl) pyridine 2,6-dialdoxime

2,6-bis [N-1, 3-oxazolin-2-ylimino)-1, 3-oxazolin-2- ylmethyl] pyridine 2,6-bis [4-(2-pyridyl) methyl)-1, 3-oxazolin-2-yl] pyridine (BiPOP) 2,6-bis [4- (4-imidazolylmethyl)-1, 3-oxazolin-2-yl] pyridine 2,6-bis (4-isopropyl-1, 3-oxazolin-2-yl) pyridine (=BiPOP) 2, 6-bis- (4-benzyl-1, 3-oxazolin-2-yl) pyridine (=Pybox)

2,2-bis (4-tert-butyl-1, 3-oxazolin-2-yl) propane bis [4-tert-butyl-1, 3-oxazolin-2-yl] methylamine 2, 6-bis- (2-pyridyl)-ketone hydrate (DPKH) The ligands can be prepared by generally conventional processes-reference is made by way of example to J. Amer.

Chem. Soc. (1998) 120,4049 ; Chem. Commun. (1989) 489; J.

Organo. Lett. (1996), 507,85 ; Tetrahedron (1994), 50 (47), 13493; Org. Letters 2000,2 (14), 2045 and J. Amer. Chem.

Soc. (1999,121, 669 and 686).

The complexes to be used according to the invention can be produced in a manner known per se. Reference is made by way of example to WO 99/46302 and WO 99/12981. The WO specifications mentioned relate to polymerization catalysts which contain a nitrogen-containing transition metal complex, wherein the polydentate ligand corresponds to the general formula (I) wherein B represents pyridine-2,6-diyl.

However, these documents do not disclose the use of such complexes as a bleaching catalyst.

Apart from the ligand, the catalyst can additionally contain coordinating co-ligands X. X here can be a mono-, di-or trivalent anion or a neutral molecule, which can be coordinated with the transition metal in a mono-, bi-or tridentate manner. The co-ligand is preferably the following groupings: OH-, 0, N03 P04, CN SCN, HS04 SO42, Cl-, Br, F, C104, OCN, HC03, RS, C03z, Sp3z-, RS03, S206, RCOz, H20, ROH, CH3CN, NRR R.

The counter-ion Y of the complex to be used can be anionic or cationic, wherein the number p is chosen such that complete charge compensation is achieved. The counter-ion can preferably have the following meaning: F-, Cl-, Br-, I-, NO3, RS03 (R e. g. preferably CF3), Cl04, RCO2-, P043, HP042 H2PO4-, S04 HS04-, C03, HC03 BF4 PF6, S03, Li+, Na+ K+ Mg2+ ca2+ Ba2+ The bleaching catalysts to be used according to the invention activate elemental oxygen and peroxy compounds.

Peroxy compounds are to be understood as meaning, in particular, hydrogen peroxide, compounds which liberate hydrogen peroxide, such as, in particular, sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate, perphosphates and persulfates, peroxycarboxylic acids and salts thereof and peroxycarboxylic acid bleaching precursors, so-called activators, and mixtures of such substances. Suitable peroxycarboxylic acids can be aliphatic or aromatic in nature and contain one or more peroxycarboxylic acid groups. Aliphatic peroxycarboxylic acids usually contain 1 to 20 C atoms, preferably 1 to 12 C atoms, and the particularly preferred peroxycarboxylic acid is peroxyacetic acid. Among the peroxycarboxylic acids with 2 peroxycarboxylic acid groups, those having 4 to 18 C atoms

are preferred; examples are diperoxyadipic acid, diperoxyazelaic acid, diperoxylauric acid and diperoxydodecanedioic acid, as well as salts of the acids mentioned, for example magnesium salts. Among the aromatic peroxycarboxylic acids there are, in particular, peroxybenzoic acid, m-chlorobenzoic acid, p- sulfonatoperoxybenzoic acid, diperoxyisophthalic acid, phthalimidopercaproic acid, 4,4'-sulfonyl-diperoxybenzoic acid and magnesium salts of these acids.

The peroxycarboxylic acids can also be formed in situ under the use conditions, and in particular from so-called activators, which are in general 0-acyl compounds and N- acyl compounds. Such compounds form the corresponding peroxycarboxylic acid under perhydrolysis conditions in the presence of hydrogen peroxide or a source of hydrogen peroxide. Activators which are particularly preferably to be used are: N, N, N'N'-tetraacetylethylenediamine (TAED), Na 1-methyl-2-benzoyloxybenzene-4-sulfonate, Na nonanoyloxybenzenesulfonate (NOBS), 2- (N, N, N- trimethylammonium) ethyl-sodium 4-sulfophenylcarbonate chloride (SPCC), pentaacetylglucose, phthalic anhydride.

For activation of peroxy compounds, the transition metal complexes to be used according to the invention are in general employed in an amount of 0.001 to 50 wt. %, in particular 0.01 to 20 wt. %, based on the peroxy compounds.

Bleaching agent compositions according to the invention comprise at least one peroxy compound and a transition metal complex to be used according to the invention in an active amount. Such compositions expediently comprise 0.001 to 50 wt. %, in particular 0.01 to 20 wt. % and particularly

preferably 0.01 to 1 wt. % of a transition metal complex with a ligand according to the invention, based on the content of peroxy compounds or precursor of one.

Bleaching agent compositions according to the invention expediently additionally comprise one or more surfactants from the series consisting of anionic, cationic, zwitter- ionic and nonionic surfactants, in particular surfactants such as are used in conventional washing, bleaching and cleaning compositions. Bleaching agent compositions according to the invention can furthermore also comprise organic and/or inorganic builders, such as zeolites.

Further constituents can be those such as are used in conventional washing, bleaching and cleaning compositions, including enzymes, pH regulators and conventional alkali metal carriers, such as alkali metal silicate and alkali metal carbonates.

Examples Example 1: Preparation of the ligand 2,2-bis (tert-butyl-1, 3-oxazolin- 2-yl) propane (Bubox) 50 ml of a 0.5 N methanolic sodium hydroxide solution were added to a solution of 2.52 g (6.90 mmol) N, N-bis [3,3- dimethyl-1-chlorobutyl]-2, 2-dimethyl-1, 3-propanediamide, which was prepared in accordance with J. Am. Chem. Soc.

1991,726-728 (Supplementary Material) l), and the mixture was heated under reflux for 2 hours after the addition. It was then allowed to cool to room temperature and the reaction solution was concentrated to dryness in vacuo.

30 ml saturated NaCl solution were added to the crude product, the mixture was then extracted with 3 x 30 ml

methylene chloride and the combined organic phases were dried over magnesium sulfate. After distillation of the solvent, a pale yellow oil was obtained, which rapidly crystallized. (Yield: 48%) Example 2: Cu complex with the ligand of example 1 A solution of 640 mg (2.17 mmol) bis (oxazolinyl) pyridine in 10 ml methylene chloride was added to a suspension of 291 mg (2.17 mmol) anhydrous copper chloride in methylene chloride. After stirring for 1 hour at room temperature, the solution was filtered and the filtrate was concentrated in vacuo. A pale green powder was obtained in a quantitative yield.

Example 3: a) Fe complex of BiPOP : 420 mg (3.31 mmol) anhydrous FeCl2 were added to 1.00 g (3.31 mmol) of the ligand 2,6-bis (4-isopropyl-1, 3-oxazolin- 2-yl) pyridine (synthesis in accordance with Chem. Comm.

1998,849) in 10 ml methylene chloride. After the addition the blue reaction solution was heated to 80°C and stirred at this temperature for 10 minutes. After slow evaporation of the solvent, the residue was dried in vacuo at 50°C. The complex was obtained as a dark red crystalline powder.

(Yield: 96%)

b) Co complex of BiPOP : 238 mg (1.00 mmol) cobalt (II) chloride hexahydrate were added to a solution of 301 mg (1.00 mmol) 2, 6-bis (4- isopropyl-1, 3-oxazolin-2-yl) pyridine in 10 ml tetrahydrofuran at 40gC and the mixture was stirred for 1 hour at 552C. The solvent was then distilled off and the residue was dried in vacuo at 50°C. (Yield: 98%, blue-green powder) Examples 4 to 9 The complexes of examples 2,3a and 3b and complexes prepared in an analogous manner or a manner known from the literature were investigated for their catalytic action by means of the Morin test and in some cases by means of a washing test.

Morin test: A sodium perborate monohydrate solution, a methanolic solution of tetraacetylethylenediamine and a dilute solution of the combination to be investigated are added to an aqueous Morin solution.

After intensive mixing, the extinction/transmission is measured at 400 nm after 30 minutes at 30°C. The blank value is measured in the absence of the combination to be investigated.

Washing test: Laboratory washing apparatus type ATLAS LAUNDER-0-METER Temperature: 30 °C Washing time: 30 minutes Water hardness: 14°d Staining: tea, in some cases also grass on cotton

Detergent recipe: 12. 2% anionic surfactant 7. 7% nonionic surfactant 2. 0% soap 34. 8% zeolite A 4. 2% polycarboxylate 0. 5% phosphonic acid 4. 1% corrosion inhibitor 1. 1% magnesium silicate 1. 1% greying inhibitor (CMC) 2. 2% sodium sulfate 4. 1% sodium citrate Bleaching component: 17% sodium percarbonate 5% activator TAED Metal complex: 2,400 ppm Detergent concentration: 5 g/1 As a comparison, the base recipe plus percarbonate/TAED, but without a metal complex (= catalyst) was always run (CE1). This change in reflection compared with the starting fabrics is subtracted from the change in reflection achieved with percarbonate/TAED/bleaching catalyst.

The results follow from the table: Table: Complex Morin test Washing test transmission (A R) No. M L X % % 4 Cu Bubox (Cl) 2 90 n. d. 5 Fe BiPOP (Cl) 2 n. d. 0. 3 6 Co BiPOP Cl2 94. 6 5. 3 7 Co TMAP Cl2 94. 4 4. 0 8. Co DMAP C12 94. 4 3. 8 9 Co DiPAP Cl2 93. 0 4. 4 The test results show that the catalysts according to the invention, in particular cobalt complexes, lead to a high increase in the activity of the peroxyacetic acid formed in situ from an activator (TAED) and perborate.