Bleaching-active metal complexes

Details Bleaching-active metal complexes Bleaching-active metal complexes

2000-07-10

2003-08-05

Anthony, Joseph D. (Department: 1714)

Compositions

Oxidative bleachant, oxidant containing, or generative

Contains activator admixed with inorganic peroxide

C252S186330, C510S311000, C546S006000, C556S032000, C556S045000

Reexamination Certificate

active

06602441

ABSTRACT:

It is known that the bleaching power of peroxidic bleaches in laundry detergents and cleaning products, such as hydrogen peroxide, perborates, percarbonates, persilicates and perphosphates, and thus the full efficiency of these bleaches for removing tea, coffee, fruit or red wine stains is only attained at relatively high temperatures of significantly above 60° C. To improve the severely reduced bleaching effect at lower temperatures, especially below 60° C., it is possible to use compounds to activate the peroxide bleaches. A number of transition metal salts and corresponding complexes with mostly chelating compounds have been proposed for this purpose, although the effectiveness of a metal or a specific combination of transition metal and complex ligand is not predictable.
Such metal complexes for activating peroxy compounds are described in U.S. Pat. No. 4,728,455, U.S. Pat. No. 5,314,635, U.S. Pat. No. 5,244,594, U.S. Pat. No. 5,114,611, U.S. Pat. No. 5,114,606, EP 549272, EP 544519, EP 544490, EP 544440, EP 509787, EP 458398, WO 9615136.
Neutral metal complexes containing bis(2-hydroxybenzylidene)-2,6-pyridinediamine as ligand are also known, from J. Inorg. Nucl. Chem. 1975, Vol. 37, pp. 2005-2006.
The present invention relates to previously unknown compounds of the formula 1
[L
n
M
m
X
p
]
z
Y
q
  (1)
in which
M is manganese in oxidation stage II, III, IV, V and/or VI or cobalt in oxidation stage II and or III,
X is a coordination group or bridging group,
Y is a counterion in the corresponding stoichiometric amount to balance a charge z present, where
z as the metal complex charge, can be positive, zero or negative,
n and m, independently of one another, are integers of from 1 to 4,
p is an integer from 0 to 15,
q z/charge of Y
L is a ligand of the formula (2)
 in which
R
1
, R
2
independently of one another are hydrogen, C
1
- to C
10
-alkyl, cycloalkyl or aryl,
R
3
, R
4
, R
5
, R
6
, R
7
, R
8
, independently of one another, are hydrogen, C
1
- to C
30
-alkyl, cycloalkyl or aryl, C
1
- to C
4
-alkoxy groups, substituted or unsubstituted amino or ammonium groups, halogen atoms, sulfo groups, carboxyl groups, or groups of the formulae —(CH
2
)
r
—COOH, —(CH
2
)
r
—SO
3
H, —(CH
2
)
r
—PO
3
H
2
, —(CH
2
)
l
—OH, in which r is an integer from 0 to 4 and l is an integer from 1 to 4, and the specified acid groups may also be in salt form, with the exception of compounds of the formula 1 in which M=Mn, x=H
2
O, z=zero and R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, R
7
and R
8
are hydrogen.
X is preferably one of the following groups:
F
−
, Cl
−
, Br
−
, SCN
−
, OH
−
, O
2
2−
, O
2−
, O
2
−
, HOO
−
, R
9
OO
−
, H
2
O, SH
−
, CN
−
, OCN
−
, S
2−
, N
3
−
, NH
3
, NR
9
3
, NR
9
2
−
, R
9
O
−
, R
9
COO
−
, R
9
SO
3
−
and R
9
SO
4
−
, in which R
9
is in each case hydrogen, C
1
- to C
8
-alkyl, cycloalkyl or C
6
- to C
18
-aryl. The counterion Y is preferably an ion of the following formulae:
when z is positive: F
−
, Cl
−
, Br
−
, NO
3
−
, ClO
4
−
, SCN
−
, PF
6
−
, R
9
SO
4
−
, R
9
COO
−
, R
9
SO
3
−
, BF
4
−
, BPh
4
−
, SO
4
2−
and SO
4
2−
;
when z is negative: Li
+
, Na
+
, K
+
, Mg
2+
, Ca
2+
, Al
3+
, NH
4
+
, R
9
NH
3
+
, R
9
2
NH
2
+
, R
9
3
NH
+
and R
9
4
N
+
, in which R
9
is as defined above.
M is preferably manganese, R
1
, R
2
, R
3
, R
4
, R
5
and R
6
are preferably one of the aforementioned groups, with the exception of hydrogen, and R
7
and R
8
are preferably hydrogen.
The ligands of the formula 2 are prepared by reacting salicylaldehyde and 2,6-diaminopyridine or correspondingly substituted derivatives thereof according to the details in J. Inorg. Nucl. Chem. 1975, Vol. 37, pp. 2005-2006. The metal complexes according to the invention are prepared by reacting Mn salts or Co salts with these ligands again according to the details at this literature reference.
The novel mono- or polycyclic complexes of the formula 1 are highly suitable as bleach and oxidation catalysts, in particular in laundry detergents and cleaning products and in textile and paper bleaching. Particular emphasis is to be placed here on textile detergents in the form of pulverulent detergents or as liquid formulations and dishwashing detergents. One advantage of the novel bleach catalysts is their stability to hydrolysis and oxidation and their catalystic effect even at low temperatures. They improve not only the bleaching effect of hydrogen peroxide in such formulations, but also that of organic and inorganic peroxy compounds.
Accordingly, the present invention also provides a process for bleaching soiled substrates, which comprises bringing the soiled substrate in an aqueous bleach liquor into contact with peroxy compounds and an effective amount of one or more of the novel metal complexes as bleach catalysts.
The aqueous bleach liquor preferably comprises these metal complexes, based on the weight of the bleach liquor, in an amount of from 0.001 to 100 ppm of metal, in particular from 0.01 to 50 ppm of metal, especially from 0.03 to 20 ppm of metal (ppm means parts per million, based on the weight). Higher contents of metal complexes, for example up to 500 ppm, can be advantageous in industrial bleaching processes, for example in the textile or paper sector. The low metal contents specified at the beginning refer principally to household textile detergents.
The invention also provides for the use of these bleach catalysts in bleaching laundry detergents and cleaning compositions. In addition to a peroxide compound or a peroxide-releasing compound and the bleach catalyst, these laundry detergents and cleaning compositions also customarily comprise surface-active compounds and other known ingredients.
Suitable peroxides and peroxide-releasing compounds are alkali metal peroxides, organic peroxides, such as urea-hydrogen peroxide adducts, and inorganic per salts, such as alkali metal perborates, percarbonates, perphosphates, persilicates and persulfates. Particular preference is given to sodium perborate tetrahydrate and, in particular, sodium perborate monohydrate. Sodium perborate monohydrate is preferred because of its good shelf life and its good solubility in water. Sodium percarbonate may be preferred for environmental protection reasons. Alkyl hydroperoxides are another suitable group of peroxide compounds. Examples of these substances are cumene hydroperoxide and t-butyl hydroperoxide. Aliphatic or aromatic mono- or dipercarboxylic acids and the corresponding salts are also suitable as peroxy compounds. Examples thereof are peroxy-&agr;-naphthoic acid, peroxylauric acid, peroxystearic acid, N,N-phthaloylaminoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-dioic acid and 4,4′-sulfonylbisperoxybenzoic acid. Other suitable peroxy compounds are inorganic peroxy acid salts, e.g. potassium monopersulfate. Mixtures of two or more of these compounds are also suitable.
The novel laundry detergent and cleaning composition formulations usually comprise from 1 to 30% by weight, in particular from 2 to 25% by weight, of peroxy compounds.
In addition to the peroxy compounds, the laundry detergents and cleaning compositions may additionally comprise bleach activators in customary amounts (from about 1 to 10% by weight).
Examples of such bleach activators are compounds having quaternary ammonium structures, such as, for example, 2-(N,N,N-triethylammonio)ethyl 4-sulfophenyl carbonate, N-octyl-N,N-dimethyl-N-10-carbophenoxydecylammonium chloride, sodium 3-(N,N,N-trimethylammonio)-propyl 4-sulfobenzoate and N,N,N-trimethylammonium tolyl-oxybenzenesulfonate.
In addition to the aforementioned quaternary ammonium salts, esters such as, for example, acylphenolsulfonates and acylalkylphenolsulfonates

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