Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – For cleaning a specific substrate or removing a specific...
Reexamination Certificate
2001-02-15
2001-10-23
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, C510S372000, C510S376000, C510S378000, C252S186290, C252S186330, C134S025200
Reexamination Certificate
active
06306808
ABSTRACT:
The present invention relates to the use of certain manganese complexes as catalysts for reactions with peroxy compounds for bleaching coloured stains on hard surfaces. The invention relates also to cleaning agents for hard surfaces comprising such catalysts.
Inorganic peroxy compounds, especially hydrogen peroxide and solid peroxy compounds that dissolve in water with the release of hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidising agents for disinfection and bleaching purposes. The oxidising action of such substances in dilute solutions is highly dependent upon temperature. For example, using H
2
O
2
or perborate in alkaline bleaching liquors it is only at temperatures above about 80° C. that sufficiently rapid bleaching of soiled textiles is achieved. At lower temperatures, the oxidising action of the inorganic peroxy compounds can be improved by the addition of so-called bleach activators, for which numerous proposals have been disclosed in the literature. They are especially compounds from the substance classes of the N- and O-acyl compounds, for example polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, and in addition carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxybenzenesulfonate, sodium isononanoyloxybenzenesulfonate, and acylated sugar derivatives, such as pentaacetylglucose. By the addition of such substances, the bleaching action of aqueous peroxide liquors can be increased to such an extent that even at temperatures of around 60° C. their action is substantially the same as that of the peroxide liquor alone at 95° C.
Those temperatures are still too high for cleaning hard surfaces, for example table- and kitchen-ware, by hand and are normally not always achieved even in machine dishwashing methods. In the search for energy-saving methods of cleaning table- and kitchen-ware by machine, in recent years temperatures of less than 60° C., especially less than 50° C. down to cold water temperature, have been gaining importance.
At such low temperatures the action of the previously known activator compounds usually declines noticeably, especially in the case of stains that are difficult to bleach, such as tea residues on porcelain or glass. There has therefore been no lack of efforts to develop activators that are more effective in that temperature range, but without there having been any convincing success to date.
A starting point might be provided by the use of transition metal salts and complexes as so-called bleach catalysts. DE-A-195 29 904 and WO 97/07191 already disclose cleaning agents for table- and kitchen-ware that comprise transition metal complexes of the salen type as activators for peroxy compounds, but those compounds too are still unable to meet all requirements.
It has now been found, surprisingly, that manganese complexes of the formulae given below exhibit a markedly improved bleach-catalysing action on coloured stains on hard surfaces. The addition of such complexes in catalytic amounts to a dishwashing agent that comprises a peroxy compound and optionally TAED (N,N,N′,N′-tetraacetylethylenediamine) results in the substantial removal of tea stains from porcelain at 45° C. in a dishwasher. This is the case even when hard water is used, it being known that tea deposits are more difficult to remove in hard water than in soft water.
The invention accordingly relates to the use of manganese complexes of formula (1) or (2)
wherein
Y is linear or branched alkylene of formula —[C(R
1
)
2
]
m
, wherein m is an integer from 2 to 8 and each R
1
independently of the other(s) is hydrogen or C
1
-C
4
alkyl; —CX═CX—, wherein X is cyano, linear or branched C
1
-C
8
alkyl or di(linear or branched C
1
-C
8
alkyl)amino; —(CH
2
)
q
—NR
1
—(CH
2
)
q
—, wherein R
1
is as defined and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene or 1,2-phenylene radical of formula
wherein R
8
is hydrogen, CH
2
OH, CH
2
NH
2
or SO
3
M, wherein M is hydrogen, an alkali metal atom, ammonium or the cation of an organic amine,
R
5
and R
6
are each independently of the other hydrogen; linear or branched C
1
-C
4
alkyl; linear or branched C
1
-C
8
alkylene-R
2
, wherein R
2
is OR
1
, COOR
1
or NR
3
R
4
; unsubstituted aryl or aryl substituted by cyano, halogen, OR
1
, COOR
1
, nitro, linear or branched C
1
-C
8
alkyl, NR
3
R
4
, wherein R
3
and R
4
are each independently of the other hydrogen or linear or branched C
1
-C
12
alkyl, or by —N
⊕
R
1
R
3
R
4
, wherein R
1
, R
3
and R
4
are as defined,
each R
7
independently of the others is hydrogen or C
1
-C
4
alkyl,
Z
1
and Z
2
are each independently of the other hydrogen, hydroxy, C
1
-C
4
alkoxy or di(C
1
-C
4
-alkyl)amino, and
A is a charge-balancing anionic ligand, as catalysts for reactions with peroxy compounds in cleaning solutions for hard surfaces, especially for table- and kitchen-ware, with the proviso that, in the compounds of formula (1), when Y is 1,2-phenylene the substituents Z
1
, Z
2
, R
5
and R
6
may not all simultaneously be hydrogen.
The preferred compounds according to formula (1) include those wherein Z
1
and/or Z
2
each independently of the other is/are hydrogen, hydroxy, methoxy, ethoxy, dimethylamino or diethylamino.
The preferred compounds according to formulae (1) and (2) also include those wherein Y is ethylene, 1,2- or 1,3-propylene, 1-methyl-1,2-propylene, 2-methyl-1,2-propylene, 1,2-cyclohexylene or 1,2-phenylene. Especially preferred meanings of Y are ethylene, 1,3-propylene, 2-methyl-1,2-propylene, 1,2-cyclohexylene and 1,2-phenylene.
When Y is a 1,2-cyclohexylene radical, it may be in either of its stereoisomeric cis/trans forms.
R
5
and R
6
are each independently of the other preferably hydrogen, methyl, ethyl or unsubstituted phenyl, especially hydrogen.
Alkyl radicals containing from 1 to 4 carbon atoms include especially the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl group.
R
1
is preferably methyl or especially hydrogen.
R
7
is preferably hydrogen, methyl or ethyl, especially methyl.
R
8
is preferably hydrogen.
The charge-balancing anionic ligand A in the compounds of formulae (1) and (2) can be mono- or poly-valent, it being possible in the latter case for a correspondingly greater number of manganese atoms to be neutralised with the said organic ligands. It is preferably a halide, especially a chloride, a hydroxide, hexafluorophosphate, perchlorate or the anion of a carboxylic acid, such as formate, acetate, benzoate or citrate.
The compounds according to formulae (1) and (2) used according to the invention are known or can be prepared by procedures known in principle by the reaction of salicylaldehyde, which may carry the above-defined substituents Z
1
or Z
2
or has two fused rings as in the case of the compounds of formula (2), with diamines H
2
N—Y—NH
2
and reaction of the salen ligands so obtainable with manganese salts, as described, for example, in European Patent Application EP-A-630 964.
The compounds of formula (1) or (2) can be used on their own or in admixtures of two or more compounds of formula (1) or (2). In addition, they can also be used together with one or more uncomplexed salen ligands, for example with those ligands present in the compounds of formula (1) or (2).
The invention relates also to cleaning agents for hard surfaces, especially cleaning agents for table- and kitchen-ware and, among such agents, preferably those for use in cleaning processes carried out by machine, which agents comprise one of the above-described compounds of formula (1) or (2) as bleach catalyst, and to a method of cleaning hard surfaces, especially table- and kitchen-ware, using such a bleach catalyst.
The use according to the invention lies essentially in providing, in the presence of a hard surfac
Allemann Rachel
Bachmann Frank
Dannacher Josef
Dubs Marie-Josée
Hazenkamp Menno
Ciba Specialty Chemicals Corporation
Delcotto Gregory
Mansfield Kevin T.
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