Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – With oxygen or halogen containing chemical bleach or oxidant...
Reexamination Certificate
1998-06-04
2001-05-01
Del Cotto, Gregory R. (Department: 1751)
Cleaning compositions for solid surfaces, auxiliary compositions
Cleaning compositions or processes of preparing
With oxygen or halogen containing chemical bleach or oxidant...
C510S320000, C510S321000, C510S392000, C510S530000, C510S226000
Reexamination Certificate
active
06225275
ABSTRACT:
TECHNICAL FIELD
The present invention generally relates to the activation of enzymes by means of enhancing agents. More in particular, the invention is concerned with the activation of oxido-reductases, especially the activation of peroxidase in a process for bleaching fabrics during washing.
BACKGROUND AND PRIOR ART
Oxidoreductases are enzymes concerned with biological oxidation and reduction, and therefore with respiration and fermentation processes. The class of oxidoreductases includes oxidases, laccases (1.10.3), peroxidases (1.11.1.7) and oxygenases. The use of peroxidase and laccase enzymes in a process for the oxidation of a wide variety of substrates is already known. For example, the use of peroxidases for bleaching fabrics during washing has been suggested in EP-A-424 398 (Novo Nordisk). WO-A-91/05839 (Novo Nordisk) describes the inhibition of dye transfer during the wash by means of peroxidase or an enzyme exhibiting oxidase activity on phenolic compounds. The compositions are said to bleach any dissolved textile dye so that no dye can redeposit upon the fabric. U.S. Pat. No. 4,690,895 (Repligen Corporation) discloses the use of a specific peroxidase, namely ligninase, to bleach or decolorize kraft pulp for the production of paper.
It is also known that the activity of oxidoreductases, especially peroxidases, may be increased by the addition of certain organic compounds. The use of such activated enzyme systems for various purposes has also been described, for instance for inhibiting dye transfer in a washing process. The above mentioned WO-A-91/05839 (Novo Nordisk) also describes that the addition of another oxidisable substrate may enhance the enzyme activity. Examples of such oxidisable substrates or “enhancers” are certain phenolic compounds, e.g. 2,4-dichlorophenol.
In three subsequent patent applications (WO-A-94/12619, WO-A-94/12620 and WO-A-94/12621, all Novo Nordisk) it is disclosed that the action of peroxidase in such anti dye-transfer compositions may be enhanced by the addition of a number of aromatic compounds, of which 2,2′-azo-bis-(3-ethylbenzo-thiazoline-6-sulphonate) or ABTS appears to be the preferred compound. However, some of these aromatic compounds may not be attractive as ingredients of detergent compositions for economical or environmental reasons. Furthermore, some of these enhancers like ABTS are, in their oxidised form, dyestuffs themselves. This has the disadvantage that the washed fabrics may be coloured by residual amounts of oxidised ABTS.
WO-A-97/06244 (Ciba) discloses various other compounds as enhancers for peroxidase and laccase systems, such as substituted naphtols, barbituric acids, and substituted coumarins.
Thus, although some of these approaches have been successful to a certain extent, there is still a need for alternative or improved enhancers for the activity of an oxidoreductases. In particular, there is a need for effective enzymatic bleach compositions. It is therefor an object of the present invention to provide such effective alternative or improved oxidoreductase enhancers and enzymatic bleach compositions containing them.
We have now surprisingly found that these and other objects can be achieved by new enzyme enhancers of the invention.
DEFINITION OF THE INVENTION
According to a first aspect of the invention, there is provided a process for enhancing the activity of an oxidoreductase, comprising adding to the enzyme, as an enhancer for the activity of said enzyme, a compound having the formula:
wherein R
1
-R
4
may each independently represent hydrogen, hydroxy, halogen, nitroso, formyl, carboxyl, and esters and salts thereof, carbamoyl, sulfo, and esters and salts hereof, sulfamoyl, nitro, amino, phenyl, C
1
-C
20
alkyl, C
1
-C
8
alkoxy, carbonyl-C
1
-C
6
-alkoxy, aryl-C
1
-C
6
-alkyl, whereby:
the carbamoyl, sulfamoyl and amino groups may be unsubstituted or substituted once or twice with hydroxy, C
1
-C
6
-alkyl, C
1
-C
6
-alkoxy, in which C
1
-C
6
-group may be saturated or unsaturated, branched or unbranched and may be substituted once or twice with halogen, nitroso, hydroxy, formyl, carboxy, and esters and salts thereof, carbamoyl, sulfo, and esters and salts hereof, sulfamoyl; and
the phenyl group may be substituted with once or twice with halogen, nitroso, hydroxy, formyl, carboxy, and esters and salts thereof, carbamoyl, sulfo, and esters and salts hereof, sulfamoyl; and
the C
1
-C
20
alkyl, C
1
-C
8
alkoxy, carbonyl-C
1
-C
6
-alkoxy, and aryl-C
1
-C
6
-alkyl groups may be saturated or unsaturated, branched or unbranched, and may be substituted with halogen, hydroxy, nitroso, formyl, carboxy, and esters and salts thereof, carbamoyl, sulfo, and esters and salts thereof, sulfamoyl, nitro, amino, phenyl, aminoalkyl, piperidino, piperazinyl, pyrrolidin-2-yl, C
1
-C
6
-alkyl, C
1
-C
6
-alkoxy;
whereby two of the groups R
1
-R
4
may linked together by any group, and
A is a five or six membered heterocyclic ring which may be optionally substituted with any of the radicals as defined for R
1
-R
4
.
According to a second aspect, there is provided an enzymatic bleach composition comprising an oxidoreductase and an enhancer as shown above. According to a third aspect, there is provided a detergent composition comprising the enzymatic bleach composition and which additionally comprises one or more surfactants. According to a fourth aspect, there is provided a process for inhibiting the transfer of a textile dye from one dyed fabric onto the same or another fabric when said fabrics are washed together using the above bleaching composition or a bleaching detergent composition.
DESCRIPTION OF THE INVENTION
A first aspect of the invention is a process for enhancing the activity of an oxidoreductase by adding to the enzyme, certain specific compounds which are capable of enhancing the activity of said oxidoreductase enzyme, the so-called “enhancers”. A second aspect of the invention is formed by enzymatic bleach compositions comprising an oxidoreductase and said enhancers.
(a) The oxidoreductase
The enzymatic bleach compositions according to the invention comprise, as a first constituent, an oxidoreductase. The enzyme may either be an enzyme exhibiting peroxidase activity (which is then used together with a source of hydrogen peroxide), or a phenol oxidizing enzyme. A “phenol oxidizing enzyme” is defined for the purpose of the present invention as an enzyme or a system in which an enzyme, by using hydrogen peroxide or molecular oxygen, is capable of oxidizing organic compounds containing phenolic groups. Examples of such enzymes are peroxidases and oxidases. Suitable enzymes are disclosed in EP-A-495 835 (Novo Nordisk). For instance, suitable peroxidases may be isolated from and are producible by plants or microorganisms such as bacteria or fungi. Preferred fungi are strains belonging to the class of the Basidiomycetes, in particular Coprinus, or to the class of Hyphomycetes, in particular Arthromyces, especially
Arthromyces ramosus
. Other preferred sources are Hormographiella sp. or Soybean peroxidase. Other relevant peroxidases are haloperoxidases (U.S. Pat. No. 4,397,192) such as chloride peroxidases, bromide peroxidases and iodide peroxidases. Other potential sources of useful peroxidases are listed in B.C. Saunders et al., Peroxidases, London, 1964, pp 41-43. Also of interest are synthetic or semi-synthetic derivatives and models of such enzymes, such as those comprising iron- or manganese-porphyrin systems, microperoxidases, and iron- or manganese-phthalocyanine compounds, e.g. as described in U.S. Pat. No. 4,077,768, WO-A-91/05858 and WO-A-92/16634. Examples of suitable enzymes exhibiting oxidase activity on phenolic compounds are catechol oxidase and laccase and bilirubin oxidase.
In the context of this invention, laccase and laccase related enzymes contemplate any laccase enzyme comprised by the enzyme classification (EC 1.10.3.2), any catechol oxidase enzyme comprised by the enzyme classification (EC 1.10.3.1), any bilirubin oxidase enzyme comprised by the enzyme classification (EC 1.3.3.5) or an
Hage Ronald
Hora Jiri
Swarthoff Ton
Twisker Robin Stefan
Del Cotto Gregory R.
Lever Brothers Company Division of Conopco, Inc.
Mitelman Rimma
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