Bleaching and dyeing; fluid treatment and chemical modification – Bleaching – Chemical
Reexamination Certificate
1998-12-11
2002-06-25
Gupta, Yogendra N. (Department: 1751)
Bleaching and dyeing; fluid treatment and chemical modification
Bleaching
Chemical
C008S137000, C008S139000, C435S190000, C510S375000, C510S376000, C510S439000, C510S530000, C510S297000, C510S392000
Reexamination Certificate
active
06409770
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to a bleach or detergent which, besides typical ingredients, contains a bleaching system of an amino alcohol oxidase or D-amino acid oxidase and a substrate for this oxidase.
Modern heavy-duty detergents and bleaching washing aids, so-called bleaches, normally contain an oxygen-based oxidizing agent, more particularly a peracid, a peracid salt, hydrogen peroxide or a substance which yields hydrogen peroxide under aqueous in-use conditions. Since the bleaching effect of hydrogen peroxide on its own is often found to be inadequate, bleaching systems of a per compound which yields hydrogen peroxide in water and a bleach activator which generates a peracid under perhydrolysis conditions are generally used. The most prominent example of such a bleaching system is the widely used combination of alkali metal perborate and N,N,N′,N′-tetraacetyl ethylenediamine. There has been no shortage of attempts to improve this bleaching system by modification. For example, it is proposed in International patent application WO 89/09813 to use a peroxidase enzyme, i.e. an enzyme which catalyzes the reaction of hydrogen peroxide with organic or inorganic substances, as bleach activator.
Besides inorganic hydrogen peroxide precursors such as, for example, perborate, percarbonate, perphosphate and persilicate, it has also occasionally been proposed to use enzymatic systems which are capable of producing hydrogen peroxide from oxygen, for example from atmospheric oxygen. Enzymes such as these are normally referred to as oxidases and are classified according to their substrate. Oxidases are redox enzymes with the classification EC 1 (classification of the Enzyme Commission) which are generally flavine-dependent and of which the oxidized form is capable of oxidizing a substrate. The resulting reduced form of the enzyme is reoxidized by molecular oxygen in aqueous systems, hydrogen peroxide being formed as another product. Examples of such enzymes and their substrates which follow the name of the enzyme are phenol oxidase, amino acid oxidase, xanthine oxidase, urate oxidase, alcohol oxidase, cholesterol oxidase and glucose oxidase.
DE-OS 19 18 729 describes detergents which, besides surfactants, contain 0.5% by weight to 10% by weight of glucose oxidase and 5% by weight to 30% by weight of glucose or starch. In the latter case, 0.5% by weight to 10% by weight of amyloglucosidase is said to be additionally present. DE-OS 20 64 146 discloses detergents containing 1% by weight to 50% by weight of water-soluble surfactant and 0.01% by weight to 2% by weight of lipoxidase. Polyunsaturated fatty acids are preferably present as substrates for the lipoxidase. DE-OS 25 57 623 describes detergents which, in addition to surfactants and builders, contain 0.3% by weight to 10% by weight of urate oxidase, galactose oxidase or C
1-3
alcohol oxidase and 3% by weight to 30% by weight of uric acid, galactose or C
1-3
alcohols and/or corresponding ketoalcohols. European patent EP 0 072 098 relates to liquid bleaches containing a C
1-4
alcohol oxidase and a C
1-4
alcohol. In European patent application EP 0 603 931, it is proposed to stabilize the glucose oxidase/glucose system in liquid detergents by the addition of Cu
2+
and/or Ag
+
ions and to enhance the bleaching effect of the enzymatically produced hydrogen peroxide by the presence of bleaching catalysts, more particularly metal porphines, metal porphyrines, metal phthalocyanines and/or haemine. The same objective is also followed by International patent application WO 95/07972 which describes bleaches containing an enzymatic system to produce hydrogen peroxide and a bleach-catalyzing coordination complex of Mn or Fe. International patent application WO 94/25574 discloses an L-amino acid oxidase of a certain strain of the microorganism
Trichoderma harzianum
and detergents containing this oxidase.
DESCRIPTION OF THE INVENTION
The problem addressed by the present invention was to provide a bleaching formulation with improved effectiveness of the enzymatically produced hydrogen peroxide under washing conditions.
It has now surprisingly been found that the bleaching effect of hydrogen peroxide produced enzymatically in typical washing, bleaching and cleaning liquors can be significantly increased, even in the absence of typical activators, if the hydrogen peroxide is produced in situ through the use of amino alcohol oxidase or D-amino acid oxidase.
Accordingly, the present invention relates to a bleach or detergent containing an enzymatic bleaching system which is capable of producing hydrogen peroxide under in-use conditions and, optionally, synthetic surfactant, organic and/or inorganic builder and other typical ingredients of bleaches or detergents, characterized in that the bleaching system consists of an enzyme having amino alcohol oxidase or D-amino acid oxidase activity and of a substrate for this enzyme.
The present invention also relates to the use of a bleaching system of an enzyme having amino alcohol oxidase or D-amino acid oxidase activity and of a substrate for this enzyme for bleaching fabric stains under washing conditions.
The present invention also relates to the use of a system of an enzyme having amino alcohol oxidase or D-amino acid oxidase activity and of a substrate for this enzyme for reducing dye transfer from dyed fabrics to undyed or differently colored fabrics when they come into contact under washing or rinsing conditions.
Amino alcohol oxidases catalyze the oxidation of primary alcohol functions of amino alcohols by oxygen to the corresponding acid function with formation of hydrogen peroxide. Where they are used, it is essential that an amino alcohol with a primary alcohol function be present as substrate for the amino alcohol oxidase. The preferred amino alcohol oxidase for the purposes of the present invention is choline oxidase (EC 1.1.3.17) which is used together with its substrate choline preferably present as halide. D-amino acid oxidases (EC 1.4.3.3) catalyze the reaction:
D-amino acid+H
2
O+O
2
→alpha-ketoacid+NH
3
+H
2
O
2
According to the invention, preferred substrates for D-amino acid oxidases are—either individually or in the form of mixtures—glycine, D-alanine, D-arginine, D-asparagine, D-aspartic acid, D-cysteine, D-glutamine, D-glutamic acid, D-histidine, D-isoleucine, D-leucine, D-lysine, D-methionine, D-phenyl alanine, D-proline, D-serine, D-threonine, D-tryptophane, D-tyrosine and D-valine, which may be used without enantiomers or in admixture with their L-enantiomers. According to the invention, it is particularly preferred to use D-alanine.
The oxidases suitable for use in the bleaches/detergents according to the invention are enzymes obtainable from microorganisms or organs of higher animals which have an optimum pH preferably in the almost neutral to mildly alkaline range of about pH 6 to pH 9.5. The activity of enzymes is normally expressed in U/g, the unit 1 U corresponding to the activity of that quantity of enzyme which reacts 1 &mgr;mole of its substrate in 1 minute at pH 7/25° C. 1 U thus corresponds to 1/60 &mgr;catal. Choline oxidase as produced, for example, by alcaligenes species or by
Arthrobacter globiformis
is preferably used as the amino alcohol oxidase. D-amino acid oxidase of standardized activity, obtained for example from pig's kidneys, is commercially available and, like choline oxidase, can be obtained for example from the Sigma company. The oxidase is preferably used in the bleach/detergent according to the invention in such quantities that the bleaching composition/detergent as a whole has an oxidase activity of 30 U/g to 20,000 U/g and, more particularly, 60 U/g to 15,000 U/g. Bleaching systems/detergents with oxidase activities in the ranges mentioned release hydrogen peroxide sufficiently quickly for standard European machine washing processes. The enzymes with amino alcohol oxidase or D-amino acid oxidase activity used in accordance with the invention have a far higher activit
Grothus Maria
Richert Achim
Weiss Albrecht
Gupta Yogendra N.
Harper Stephen D.
Henkel Kommanditgesellschaft auf Aktien
Mruk Brian P.
Murphy Glenn E.J.
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