Cleaning agent with oligoammine activator complexes for...

Details Cleaning agent with oligoammine activator complexes for... Cleaning agent with oligoammine activator complexes for...

1998-10-01

2001-05-22

Delcotto, Gregory (Department: 1751)

Cleaning compositions for solid surfaces, auxiliary compositions

Cleaning compositions or processes of preparing

For cleaning a specific substrate or removing a specific...

C510S221000, C510S224000, C510S372000, C510S376000, C510S378000, C134S025200, C252S186260, C252S186280, C252S186330

Reexamination Certificate

active

06235695

ABSTRACT:

This invention relates to the use of certain oligoammine complexes of transition metals as activators or catalysts for peroxygen compounds, more particularly inorganic peroxygen compounds, for bleaching colored stains on hard surfaces and to cleaning formulations for hard surfaces containing such activators or catalysts.
Inorganic peroxygen compounds, more particularly hydrogen peroxide, and solid peroxygen compounds which dissolve in water with elimination of hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes. In dilute solutions, the oxidizing effect of these substances depends to a large extent on the temperature. For example, with H
2
O
2
or perborate in alkaline bleaching liquors, sufficiently rapid bleaching of soiled textiles is only achieved at temperatures above about 80° C. At lower temperatures, the oxidizing effect of the inorganic peroxygen compounds can be improved by addition of so-called bleach activators for which numerous proposals, above all from the classes of N- or O-acyl compounds, for example polyacylated alkylenediamines, more particularly tetraacetyl ethylenediamine, acylated glycolurils, more particularly tetraacetyl glycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfuryl amides and cyanurates, also carboxylic anhydrides, more particularly phthalic anhydride, carboxylic acid esters, more particularly sodium nonanoyloxybenzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetyl glucose, can be found in the literature. By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased to such an extent that substantially the same effects are obtained at temperatures of only 60° C. as are obtained with the peroxide liquor alone at 95° C.
In the search for energy-saving washing and bleaching processes, operating temperatures well below 60° C. and, more particularly, below 45° C. down to the temperature of cold water have acquired increasing significance in recent years.
At these low temperatures, there is generally a discernible reduction in the effect of known activator compounds. Accordingly, there has been no shortage of attempts to develop more effective activators for this temperature range although the results achieved thus far have not been convincing. A starting point in this connection is the use of the transition metal salts and complexes proposed, for example, in European patent applications EP 392 592, EP 443 651, EP 458 397, EP 544 490 or EP 549 271 as so-called bleach catalysts. In their case, the high reactivity of the oxidizing intermediates formed from them and the peroxygen compound is presumably responsible for the risk of discoloration of colored textiles and, in extreme cases, oxidative textile damage. In European patent application EP 272 030, cobalt(III) complexes with ammonia ligands which may additionally contain other mono-, bi-, tri- and/or tetradentate ligands are described as activators for H
2
O
2
. European patent application EP 630 964 describes certain manganese complexes which do not have a pronounced effect in boosting the bleaching action of peroxygen compounds and which do not decolor dyed textile fibers although they are capable of bleaching soil or dye detached from fibers in wash liquors. German patent application DE 44 16 438 describes manganese, copper and cobalt complexes which can carry ligands from a number of groups of compounds and which are said to be used as bleaching and oxidation catalysts.
The problem addressed by the present invention was to improve the oxidizing and bleaching effect of inorganic peroxygen compounds at low temperatures below 80° C. and, more particularly, in the range from about 15° C. to 45° C.
It has now been found that certain transition metal complexes containing at least one ammonia molecule as ligand have a distinct bleach-catalyzing effect on colored stains on hard surfaces.
The present invention relates to the use of complex compounds corresponding to general formula I:
[Mn(NH
3
)
6−x
(L)
x
]A
n
  (I)
where M is a transition metal selected from cobalt, iron, copper and ruthenium, L is a ligand selected from the group consisting of water, hydroxide, chlorate, perchlorate, (NO
2
)
−
, carbonate, nitrate, acetate and thiocyanate, x is a number of 0 to 5, A is a salt-forming anion and n—which may even be 0—is a number with such a value that the compound of formula (I) has no charge,
as activators for peroxygen compounds, particularly inorganic peroxygen compounds, in aqueous cleaning solutions for hard surfaces, more particularly for crockery.
In the present case, an (NO
2
)
−
group is a nitro ligand which is attached to the transition metal by the nitrogen atom or a nitrito ligand which is attached to the transition metal by an oxygen atom. The (NO
2
)
−
group may also be attached to a transition metal M to form a chelate
It may also bridge two transition metal atoms asymmetrically:
The above-mentioned transition metals in the bleach catalysts to be used in accordance with the invention are preferably present with oxidation numbers of +2, +3 or +4. Complexes with transition metal central atoms having the oxidation number +3 are preferably used. Preferred complexes include those with cobalt as central atom.
Besides the ammonia ligands, of which at least 1 and preferably at least 5 are present per transition metal central atom, the transition metal complexes to be used in accordance with the invention may contain other inorganic ligands of generally simple structure (L in formula I), more particularly mono- or polyvalent anionic ligands, providing at least one ammonia molecule is present as ligand in the complex. Examples of such other ligands are nitrate, acetate, thiocyanate, chlorate and perchlorate and the halides, such as chloride, bromide, iodide and fluoride. The anionic ligands are intended to provide for charge equalization between the transition metal central atom and the ligand system. Oxo ligands, hydroxo ligands, amido ligands, imido ligands, peroxo ligands and imino ligands may also be present in addition to or instead of the ligands L. These ligands may also have a bridging effect so that polynuclear complexes are formed. These complexes contain at least 1 and preferably at least 4 ammonia ligand(s) and preferably at least 1 (NO
2
)
−
group per transition metal atom. In the case of bridged binuclear complexes, the two metal atoms in the complex do not have to be the same. Binuclear complexes in which the two transition metal central atoms have different oxidation numbers may be used.
In the absence of anionic ligands or if the presence of anionic ligands does not lead to charge equalization in the complex, the compounds to be used in accordance with the invention contain anionic counterions (A in formula I) which neutralize the cationic complex. These anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, halides, such as chloride, fluoride, iodide and bromide, or the anions of carboxylic acids, such as formate, acetate, benzoate or citrate. These anionic counterions are present in the compounds of formula I in such a number (n in formula I) that—in terms of size—the sum of the product of their number with their charge and the product of the number of anionic ligands (L in formula I) with their charge is exactly as large, but with a negative sign, as the charge of the transition metal central atom (M in formula I).
In cases where L is a bidentate ligand, for example the carbonato ligand, as mentioned above, optionally the (NO
2
)
−
ligand or the nitrato ligand, which occupies two bond sites of the transition metal central atom in a mononuclear complex compound, formula (I) can only analogously reproduce the structure of the complex. Complex compounds such as these are more clearly represented b

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