EP0983334A1 - Systeme de blanchiment aux enzymes a nouveaux composes renfor ant l'action enzymatique - Google Patents

Systeme de blanchiment aux enzymes a nouveaux composes renfor ant l'action enzymatique

Info

Publication number
EP0983334A1
EP0983334A1 EP98933507A EP98933507A EP0983334A1 EP 0983334 A1 EP0983334 A1 EP 0983334A1 EP 98933507 A EP98933507 A EP 98933507A EP 98933507 A EP98933507 A EP 98933507A EP 0983334 A1 EP0983334 A1 EP 0983334A1
Authority
EP
European Patent Office
Prior art keywords
acid
compounds
hydroxy
group
bleaching system
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98933507A
Other languages
German (de)
English (en)
Inventor
Hans Peter Call
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Call Krimhild
Original Assignee
Call Krimhild
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Call Krimhild filed Critical Call Krimhild
Publication of EP0983334A1 publication Critical patent/EP0983334A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • C11D3/323—Amides; Substituted amides urea or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38654—Preparations containing enzymes, e.g. protease or amylase containing oxidase or reductase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3481—Organic compounds containing sulfur containing sulfur in a heterocyclic ring, e.g. sultones or sulfolanes

Definitions

  • the present invention relates to an enzymatic bleaching system with new enzyme-terminating compounds for use with washing-active substances.
  • the conventional bleaching systems in household detergents are unsatisfactory, particularly in the low temperature range.
  • the standard bleach H 2 O 2 / sodium perborate / sodium percarbonate must be activated below 60 ° C by adding chemical bleach activators such as TAED and SNOBS.
  • chemical bleach activators such as TAED and SNOBS.
  • TAED and SNOBS chemical bleach activators
  • WO 91/05839 describes the use of various oxidatively acting enzymes (oxidases and peroxidases) to prevent “dye transfer”. It is known that peroxidases are able to remove various pigments (3-hydroxyflavone and betaine from horseradish peroxidase and carotene) "Decolorize” peroxidase)
  • the patent application mentioned describes the decolorization (also called “bleaching”) of textile dyes detached from the wash and present in the liquor (conversion of a dyed substrate into an undyed, oxidized substance).
  • the enzyme is intended to counteract, for example, hypochlorite, which also contains the dye or attack in the tissue have the advantage of decolorizing only dye present in dissolved form, hydrogen peroxide or a corresponding precursor or hydrogen peroxide generated in situ being involved in the catalysis of the decolorization.
  • the enzyme reaction can in part be carried out by adding additional oxidizable enzyme substrate, for example metal ions such as Mn ⁇ + , halide ions such as Cl * or Br " or organic phenols such as p-hydroxycinnamic acid and 2,4-dichlorophenol can be increased.
  • additional oxidizable enzyme substrate for example metal ions such as Mn ⁇ + , halide ions such as Cl * or Br " or organic phenols such as p-hydroxycinnamic acid and 2,4-dichlorophenol can be increased.
  • metal ions such as Mn ⁇ +
  • halide ions such as Cl * or Br
  • organic phenols such as p-hydroxycinnamic acid and 2,4-dichlorophenol
  • Enhancer substances are characterized in WO 94/12620 on the basis of their half-life.
  • enhancer substances are organic chemicals which contain at least two aromatic rings, at least one of which is substituted with defined radicals. All three applications relate to "dye transfer inhibition" and the use of the respective enhancer substances together with peroxidases as a detergent additive or detergent composition in the detergent sector. The combination of these enhancer substances is limited to peroxidases.
  • WO 92/18687 is also limited the use of mixtures containing peroxidases is known, a special system of oxidases and suitable substrates and hydrogen peroxide is disclosed in the
  • DE-OS 19 18 729 relates to another special detergent system which consists of glucose and glucose oxidase or starch, amyloglucosidase and glucose oxidase (GOD), and an additive of hydroxylamine or hydroxylamine compounds, the hydroxylamine or its derivatives frequently being used to inhibit GOD Occurring catalase is used and has in no way been described as a mediator additive.
  • EP 0267 046 B1, US 4,863,636; WO 92/18687 and EP 0 704 523 A1 these systems mostly having hydrolases + bleach activators which have an activating action on added peroxide or per compounds or, for example by complexing metal salts, prevent the decomposition of the peroxides or, in particular, have a positive effect on dye transfer inhibition .
  • they pure mediator compounds that directly and specifically enhance the enzyme action and, moreover, the chemicals used do not belong to the group that is preferred in the present invention.
  • WO 94/29425 and DE 44 45088 AI and WO 97/48786 contain a multi-component bleaching system or a multi-component bleaching system made of oxidoreductases,
  • WO 97/06244 describes systems for bleaching cellulose, dye transfer inhibition and bleaching stains when using detergents, which work with enzymes (peroxidases, laccases) and enzyme-enhancing (hetero) aromatic compounds such as nitroso compounds, etc. described.
  • relatively aggressive chemicals NO - / NOH compounds
  • generated radicals for example NO radicals
  • the object of the present invention is accordingly to provide an improved bleaching system for use with detergent substances which does not have the disadvantages of the prior art described and which, above all, in the form of the actual mediator substances for use in detergent bleaching, also with regard to chemical aggressiveness (possible mutagenicity potential, possible
  • Fiber damage and better performance compared to the known systems that use the above-mentioned NO- / NOH compounds or classes of compounds (phenothiazines, Phenoxazines, see WO 94/12619; WO 94/12620 and WO 94 126121) contain, is more suitable.
  • mediators from the group of amides such as e.g. Hydrazides or 1,2,4-triazolidine-3,5-diones (urazoles) from the group of the imides such as e.g. Hydantoins and from the group of oxocarbons are used, which, surprisingly with peroxidases and / or laccases or other oxidases, exhibit a bleaching performance that is better than that of the known systems mentioned above when used in detergent bleaching.
  • mediators from the group of amides such as e.g. Hydrazides or 1,2,4-triazolidine-3,5-diones (urazoles) from the group of the imides such as e.g. Hydantoins and from the group of oxocarbons
  • mediator-enhancing compounds media enhancers
  • Red / Ox mediation e.g. through regeneration of the entire system through regeneration of the main mediator, through an increase in the oxidation potential, through extension of the radical lifetime or through various simultaneous properties
  • mediator enhancers can be of the NO- / NOH-HRN-OH type or the amide type such as e.g. hydrazides, urazoles or the imide type e.g. Hydantoins belong to or
  • Nonphenols or special cationic radical-forming phenolic compounds or like radical cations according to "Wurster” or radical anions or combinations of several mediation enhancers mentioned. * (Where N -> means nitrogen and R -> means residues)
  • an enzymatic bleaching system with new enzyme-strengthening compounds comprising: a) at least one oxidation catalyst, b) at least one suitable oxidizing agent, c) at least one mediator from the group of amides such as hydrazides or 1,2,4-triazolidine-3,5-diones (urazoles) and / or from the group of imides such as hydantoins and / or from the group of oxocarbons
  • ABTS aryl-substituted alcohols
  • nonphenols such as Veratryl alcohol
  • phenol derivatives such as p-hydroxycinnamic acid, 2,4-dichlorophenol, p-hydroxybenzene sulfonate, vanillin (4-hydroxy-3-methoxy-benzaldehyde), p-hydroxybenzoic acid, 5-amino-2-hydroxybenzoic acid (5 -Amino-silicic acid) or radical cation compounds according to "Wurster"
  • both one and more of the mediators and mediation amplifiers mentioned can be used here.
  • the use of a mediator and a mediation amplifier is preferred.
  • Working with a mediator and two or more mediation enhancers is also conceivable.
  • it is also possible to use two or more mediators with a mediation amplifier but it is an essential requirement for improved performance of the bleaching system according to the invention that the mediator / mediation amplifier ratio 5000-1 to 1: 1 is particularly preferably 500: 1 to 1 1, while the ratio when using several mediators and mediation enhancers within these mediator or mediation enhancer concentrations depends on the respective combinations
  • the individual components of the extended multi-component system according to the invention are described in more detail below: Oxidation catalysts
  • the multicomponent system according to the invention preferably contains at least one oxidation catalyst.
  • Enzymes are preferably used as oxidation catalysts.
  • the term enzyme also encompasses enzymatically active proteins or peptides or prosthetic groups of enzymes.
  • the enzymes can likewise come from wild-type strains or from genetically modified host strains.
  • the particularly preferred enzymes include laccases and peroxidases, with the peroxidases partly because of their pH active optimums which extend far further into the alkaline environment have considerable advantages when used for bleaching in detergents.
  • oxidoreductases of classes 1.1.1. to 1.97 according to the International Enzyme Nomenclature: Committee of the International Union of Biochemistry and Molecular Biology (Enzyme
  • Class 1.1 enzymes particularly preferably the class 1.1.5 enzymes with quinones as acceptors and the class 1.1.3 enzymes. with oxygen as the acceptor, cellobiose: quinone-1-oxidoreductase (1.1.5.1) is particularly preferred in this class.
  • Enzymes of class 1.2 can also be used.
  • the enzymes of group (1.2.3) with oxygen as the acceptor are particularly preferred here.
  • Enzymes of class 1.3 can also be used.
  • the enzymes of class (1.3.3) with oxygen as acceptor and (1.3.5) with quinones etc. as acceptor are also particularly preferred here.
  • Bilirubin oxidase (1.3.3.5) is particularly preferred.
  • Class 1.4 enzymes can also be used. Enzymes of class 1.4.3 with oxygen as the acceptor are also particularly preferred here. Enzymes of class 1.5 can also be used. Here, too, are particularly preferred
  • Enzymes with oxygen (1.5.3) and with quinones (1.5.5) as acceptors Enzymes of class 1.6 can also be used. Enzymes of class 1.6.5 with quinones as acceptors are particularly preferred. Enzymes of class 1.7 can also be used. Class 1.7.3 with oxygen as the acceptor is particularly preferred here.
  • Enzymes of class 1.8 can also be used.
  • Enzymes of class 1.15 can also be used, which act as acceptors on superoxide radicals.
  • Superoxide dismutase (1.15.1 1) is particularly preferred here.
  • Enzymes of class 1.16 can also be used. Enzymes of class 1.16.3.1 (ferroxidase, e.g. ceruloplasmin) are particularly preferred here. Enzymes belonging to groups 1.17 and 1.18 (action on reduced ferredoxin as donor) and 1.19 (action on reduced flavodoxin as
  • the very particularly preferred enzymes include those of class 1.10.
  • the enzymes in this class are catechol oxidase (tyrosinase) (1.10.3.1), L-ascorbate oxidase (1.10.3.3), O-aminophenol oxidase
  • laccase benzene dioxoxid oxidoreductase
  • the enzymes of group 1.11 are also particularly preferred.
  • cytochrome-C peroxidases (1.11.1.5), catalase (1.11.1.6), the peroxidase (1.11.1.6) and the iodide peroxidase (1.11.1.8) are particularly preferred.
  • L-ascorbate peroxidase (1.11.1.11), the phospholipid hydroperoxide glutathione peroxidase (1.11.1.12), the manganese peroxidase (1.12.1.13), the diaryl propane peroxidase (ligninase, lignin peroxidase).
  • the enzymes mentioned are commercially available or can be obtained by standard methods. Plants, animal cells, bacteria and fungi, for example, come into consideration as organisms for the production of the enzymes. Basically, both naturally occurring and genetically modified organisms can be enzyme producers. Parts of unicellular or multicellular organisms are also conceivable as enzyme producers, especially cell cultures
  • the multicomponent system according to the invention contains at least one oxidizing agent.
  • the oxidizing agents that can be used are, for example, air, oxygen, ozone, peroxide compounds such as H 2 O 2 , organic peroxides, persic acids such as peracetic acid, performic acid, persulfuric acid, perspaltic acid, metachloroperoxibenzoic acid, perchloric acid, percarbons such as perborates, perborates Oxygen species and their radicals such as OH radical, OOH radical, OFT radical, superoxide (O " 2 ), dioxygenyl cation (O 2 + ), singlet oxygen, ozonide (O 3 " ), dioxiranes, dioxitanes or fremy radicals are used .
  • the bleaching system according to the invention contains, as mediators, compounds selected from the group of amides such as e.g. the hydrazides or urazoles, which surprisingly do not have the disadvantages of the mediators known from the prior art
  • Preferred mediators in the bleaching system according to the invention are compounds of the general formulas I (amides) and II (hydrazides) '
  • radicals R 1 to R 3 may be the same or different and may independently represent hydrogen, alkyl, aryl or acyl radicals.
  • R 4 can be hydrogen, alkyl, alkoxy, carboxy, nitro or amino.
  • the radicals R can be the same or different and independently of one another are hydrogen, alkyl, aryl or.
  • the following compounds are particularly preferred: Maleic hydrazide, 2-nitrobenzhydrazide, p-toluenesulphonylhydrazide, Nicotinic hydrazide, Isonicotinic acid hydrazide, 4,4'-Oxydibenzenesulfonylhydrazide, Bencoic hydrazide, Phthalhydrazide, 3-Aminophthal hydrazide, 1-Naphthoic-Hydroxy 2-naphthoic hydrazide, hydroxybenzhydrazide, oxamic hydrazide, oxalyl dihydrazide, terephthalic dihydrazide, isophthalic dihydrazide, L-tyrosine hydrazide, Oxalic bis (benzylidene hydrazide), salicylidene salicyl hydrazide, thiophenes-2-carbonic acid hydrazide, fur
  • Preferred mediators in the bleaching system according to the invention are compounds of the general formula VI (imides):
  • radicals R can be the same or different and independently represent hydrogen, alkyl, aryl, acyl or amino groups.
  • radicals R can be the same or different and independently of one another are hydrogen
  • mediators in the bleaching system according to the invention are compounds of the general formula X, such as ⁇ -hydroxycarbonyl compounds of the general formula X a, ⁇ -dicarbonyl compounds of the general formula X b, ⁇ -hydroxycarbonyl compounds of the general formula X c, and ⁇ -dicarbonyl compounds of the general formula Formula X d, X a X b X c X d
  • radicals R 1 to R 8 can each independently represent one of the following atoms or atom groups: hydrogen, halogen, alkyl, alkyloxy, aryl, aryloxy, hydroxy, oxo, formyl, thioxo, mercapto, alkylthio, sulfeno, sulfino, sulfo, Sulfamoyl, amino, imino, amido, amidino, hydroxycarbamoyl, hydroximino, nitroso, nitro, hydrazono and where the radicals R 1 and R 2 ; R 3 and R 4 ; R 5 and R 6 ; R 7 and R 8 can form a common group and where n> 1.
  • radicals R 9 to R 10 each independently of the other one of the following radicals
  • Atoms or groups of atoms can be: hydrogen, halogen, alkyl, alkyloxy, aryl, aryloxy, hydroxy, oxo, formyl, thioxo, mercapto, alkylthio, sulfeno, sulfino,
  • radicals R 11 to R 12 can each independently represent one of the following atoms or atom groups: hydrogen, halogen, alkyl, alkyloxy, aryl, aryloxy, hydroxy, oxo, formyl, thioxo, mercapto, alkylthio, sulfeno, sulfino, sulfo, Sulfamoyl, amino, imino, amido, amidino, hydroxycarbamoyl, hydroximino, nitroso, nitro, hydrazono and m> 0.
  • Cyclic oxocarbons of the general formula XIII (general empirical formula: H2C x O x , and their dianions of the general formula) are particularly preferred
  • This component of the bleaching system contains at least one compound as a mediation enhancer, selected from the group of the NO, NOH, HRN-OH compounds (as also described in patent applications WO 94/29425, DE 44 45 088
  • AI or in particular in WO 97/48786 (page 11 to page 25) are described in detail) such as e.g. Hydroxylamines, hydroxylamine derivatives, hydroxamic acids, hydroxamic acid derivatives, the aliphatic, cycloaliphatic, heterocyclic or aromatic compounds which contain at least one N-hydroxyl, oxime, N-oxy, or N, N'-dioxy
  • Hydroxylamines (open-chain or cyclic, aliphatic or aromatic, heterocyclic) of the general formula (A):
  • N N-dipropylhydroylamine
  • N N-diisopropylhydroxylamine
  • N-hydroxyipyrrolidine N-hydroxypiperidine
  • N-hydroxyhexahydroazepine N, N-dibenzylhydroxylamine
  • phenylhydroxylamine 3-hydroxylamino-3-phenylpropionic acid
  • 2 -Hydroxylamino-3-phenylpropionic acid N-sulfomethylhydroxylamine.
  • l-hydroxybenzimidazoles such as 1-hydroxybenzimidazole-2-carboxylic acid, 1-hydroxybenzimidazole, 2-methyl-l-hydroxybenzimidazole, 2-phenyl-l-hydroxybenzimidazole and 1-hydroxyindoles, such as 2-phenyl-l-hydroxyindole and in particular derivatives of 1-hydroxybenzotriazole and the tautomeric benzotriazole-1-oxide or of lH-hydroxybenzotriazole, also: aziridines, diaziridines, pyrroles, dihydropyrroles, tetrahydropyrroles, pyrazoles, dihydropyrazole, tetrahydidazole, tetrahydidazole, tetrahydrozole, tetrahydrozole, tetrahydrozole, tetrahydrozole, tetrahydrozole, tetrahydrozole, tetrahydrozole, tetrahydrozole
  • condensed N-heterocycles such as triazolo and tetrazolo compounds which have at least one N-hydroxy, oxime, N-oxi, N, N-dioxi function and, in addition to N, a further heteroatom such as O, S, Se, Te can contain.
  • Quinoline-N-oxide isoquinoline-N-oxide, N-hydroxy-1,2,3, 4-tetrahydroisoquinoline, ß- (N-oxy-1, 2,3, 4-tetrahydro-isoquinolino) propionic acid, 1, 3-Dihydroxy-2-N-benzylimidobenzimidazoline.
  • media enhancers are those belonging to the group of cyclic N-hydroxy compounds with at least one optionally substituted five- or six-membered ring having the following structure (formula B):
  • R 1 is hydrogen, hydroxyl, formyl, carbamoyl, sulfono radical, ester or salt of the sulfono radical, sulfamoyl, nitro, amino, phenyl, aryl-Ci - Cs-alkyl -,
  • Ci - C ⁇ -alkyl, -C-C 5 alkoxy, Ci-Cio-carbonyl, carbonyl-Ci-C ⁇ -alkyl-phospho-, phosphonophosphonooxy radical, ester or salt of the phosphonooxy radical, the carbamoyl, sulfamoyl, amino and phenyl radicals can be unsubstituted or substituted one or more times with a radical R 2 and the aryl-Ci-Cs - alkyl, C ⁇ -C ⁇ 2 alkyl, Ci-Cs alkoxy , Ci-Cio-carbonyl, carbonyl -CC-C 6 alkyl radicals may be saturated or unsaturated, branched or unbranched and may be substituted one or more times with a radical R 2 , where R 2 is the same or different and is hydroxy -, Formyl ⁇ , carboxy radical, ester or salt of the carboxy radical, carbamoyl, sulfon
  • mediation enhancers are compounds of the general formulas C, D, E or F in which X and Y are O or S.
  • N-hydroxy-phthalimides and substituted N-hydroxy-phthalimide derivatives examples of such compounds are N-hydroxy-phthalimides and substituted N-hydroxy-phthalimide derivatives, N-hydroxymaleimides and substituted ones
  • N-hydroxymaleimide derivatives N-hydroxy-naphthalimide and substituted N-hydroxy-naphthalimide derivatives, N-hydroxysuccinimides and substituted N-hydroxysuccinimide derivatives, particularly preferred: N-hydroxyphthalimide, N-hydroxy-benzene-l, 2,4 -tricarboximide, NN-dihydroxy-pyromellitic diimide, N, N'-dihydroxybenzophenone-3,3 ', 4,4'-tetracarbonate diimide, N-hydroxymaleimide, pyridine-2,3-dicarboxylic acid-N-hydroxyimide, Nl-hydroxysuccinimide, N-1-hydroxy tartarimide, N-hydroxy-5-norboraen-2,3-dicarboximide, exo-N-hydroxy-7-oxabicyclo [2.2.1] -hept-5-en-2,3-dicarboximide , N-hydroxy-cis-cyclohexane-1, 2-dicarboximide,
  • mediation enhancers are compounds selected from the group of oximes according to the following general formulas G and H:
  • X is the same or different and is O, S, or NR 1 , where
  • R 1 is hydrogen, hydroxyl, formyl, carbamoyl, sulfono radical, ester or salt of the sulfono radical, sulfamoyl, nitro, amino, phenyl, aryl-Ci - C5- alkyl, C ⁇ -C ⁇ 2 -alkyl-,
  • R 7 and R 8 are identical or different and represent halogen, carboxy radical, ester or salt of the carboxy radical, or have the meanings given for R 1 .
  • mediation enhancers are compounds of the general formula G in which X is O or S and the other radicals have the meanings given above.
  • X is O or S and the other radicals have the meanings given above.
  • An example of such a compound is
  • Isonitroso derivatives of cyclic ureides of the general formula H such as 1-methylvioluric acid, 1,3-dimethylvoluric acid, thiovioluric acid, alloxane-4,5-dioxime, are particularly preferred as meditation enhancers
  • Alloxan-5-oxime hydrate (violet acid) and / or its esters, ethers or salts
  • mediation enhancers are compounds from the class of the N-aryl-N-hydroxy amides of the general formulas I, J, and K:
  • A is monovalent homo- or heteroaromatic mono- or dinuclear residue and D is double-bonded homo- or heteroaromatic mono- or dinuclear residue and these aromatics are represented by one or more, identical or different
  • R 2 can be substituted one or more times, wherein
  • R 2 is the same or different and is hydroxyl, formyl, cyano, carbamoyl, carboxy, ester or salt of carboxy, carbamoyl, sulfono-, sulfamoyl, nitro, nitroso, amino, phenyl, Ci - C 5 alkyl, Ci -Cs alkoxy, Ci -C 5 alkylcarbonyl radical and two radicals R 1 or R 2 in pairs over a bridge [-CR 3 R 4 -] m with m equal 0,1,2,3 or 4 can be linked and
  • A present in amidic form, monovalent acid residue of acids selected from the group carboxylic acid with up to 20 carbon atoms, carbonic acid, half-ester of
  • Sulfonic acids, phosphonic acids, phosphoric acids, monoesters of phosphoric acid means.
  • mediation enhancers are compounds of the general formulas Ki, K 2 , K 3 , K »and Ks:
  • Ar 1 monovalent homo- or heteroaromatic mononuclear aryl radical
  • Ar 2 means double-bonded homo- or heteroaromatic mononuclear aryl radical, which is selected by one or more, identical or different radicals R 7 selected from the group consisting of hydroxyl, cyano, carboxy radical, ester or salt of the carboxy radical, sulfono radical, ester or salt of the sulfono residue, nitro-, nitroso-, amino-, d -C ⁇ -alkyl-,
  • Ci-Cs-alkoxy, Ci-Cio-carbonyl, carbonyl-Ci-C ⁇ -alkyl radical can be substituted, where the amino radicals can be unsubstituted or substituted one or more times with a radical R 8 and the C 1 -C 2 alkyl, Ci -Cs alkoxy, Ci -Cio-carbonyl, carbonyl-Ci -C ⁇ - alkyl radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R 8 , is the same or different and hydroxyl, carboxy radical, ester or salt of carboxy
  • R 3 and R 4 have the meanings already mentioned and one or more non-adjacent groups [-CR J R 4 -] by oxygen, sulfur or an imino residue optionally substituted by a C 1 -C 4 -alkyl radical and two adjacent groups
  • R 5 identical or different monovalent radicals selected from the group phenyl, aryl-Ci-d -alkyl-, Ci -C ⁇ 2 alkyl, Ci -Cs alkoxy, Ci -Cio-carbonyl radical means, wherein phenyl radicals are unsubstituted or substituted one or more times with a radical R 9 can and aryl-Ci-d -alkyl-, -C ⁇ -C ⁇ 2 alkyl, Ci -Cs alkoxy, Ci -Cio carbonyl radicals can be saturated or unsaturated, branched or unbranched and with a radical R 9 one or can be substituted several times, wherein
  • R 9 is the same or different and hydroxyl, formyl, cyano, carboxy radical, ester or salt of the carboxy radical, carbamoyl, sulfono, sulfamoyl, nitro, nitroso, amino, phenyl, Ci -Cs -alkyl-, Ci -d-alkoxy radical means and
  • R 6 denotes divalent radicals selected from the group consisting of ortho-, meta-, para-phenylene, aryl-Ci-d-alkyl, dd 2 -alkylene, Ci-Cs-alkylenedioxi radical, phenylene radicals being unsubstituted or a - Or can be substituted several times with a radical R 9 and the ar ldd -alkyl, C 1 -C 2 -alkyl, Ci-Cs-alkoxy radicals can be saturated or unsaturated, branched or unbranched and with a radical R 9 one or can be substituted several times, where p is 0 or 1 and q is an integer from 1-3.
  • Ar 1 is preferably phenyl radical and Ar 2 is ortho-phenylene radical, where Ar 1 is selected from up to five from Ar 2 by up to four identical or different radicals from the group Ci — C 3 alkyl, Ci — C 3 alkylcarbonyl, carboxy radical, sulfono radical,
  • Ester or salt of the sulfono residue, hydroxy, cyano, nitro, nitroso and amino residue can be substituted, wherein amino residues with two different residues selected from the group hydroxy and
  • Ci -C 3 alkylcarbonyl may be substituted.
  • R 5 is preferably a monovalent radical selected from the group consisting of hydrogen, phenyl, C 1 -C 2 -alkyl, C 1 -C 8 -alkoxy radical, the C 1 -C 2 -alkyl radicals and the C 1 -C 5 -alkoxy radical Residues can be saturated or unsaturated, branched or unbranched.
  • R 6 preferably denotes double-bonded radicals selected from the group consisting of ortho- or para-phenylene, Ci-C 2 alkylene, Ci-d-alkylenedioxy radical, the aryl-d -C 5 alkyl, Ci -C ⁇ _-alkyl, Ci -Cs-alkoxy radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R 9 .
  • R 9 preferably denotes carboxy radical, ester or salt of the carboxy radical, carbamoyl, phenyl, C 1 -C 3 -alkoxy radical.
  • Particularly preferred meditation enhancers in the bleaching system according to the invention are: N-hydroxyacetanilide, N-hydroxypivaloylanilide, N-hydroxyacrylanilide, N-hydroxybenzoyl anilide, N-hydroxy-methyl-sulfonylanilide, N-hydroxy-N-phenylmethylcarbamate, N-hydroxy-3- oxo-butyrylanilide, N-hydroxy-4-cyanoacetanilide, N-
  • N-hydroxyacetanilide N-hydroxyformanilide, N-hydroxy-N-phenylmethylcarbamate, N-hydroxy-2-methylacetanilide, 1-hydroxy-3, 4-dihydroquinolin- (1 H) -2-one, and N-acetoxyacetanilide.
  • mediation enhancers in the bleaching system according to the invention are compounds of the class of the stable nitroxyl radicals (nitroxides) of the general formulas L, M and N:
  • Ar is a monovalent homo- or heteroaromatic mono- or dinuclear radical and these aromatics by one or more, identical or different radicals R 1 , selected from the group halogen, formyl, cyano, carbamoyl, carboxy, ester or salt of the carboxy radical, sulfono radical, ester or salt of the sulfono radical, sulfamoyl, nitro, nitroso, amino, phenyl, aryl-C j -Cs-alkyl, Ci-C ⁇ alkyl,
  • Ci-Cio-carbonyl, carbonyl-Ci-Cg-alkyl, phospho-, phosphono-, phosphonooxy radical, ester or salt of the phosphonooxy radical can be substituted and where phenyl, carbamoyl and sulfamoyl radicals can be unsubstituted or substituted one or more times with a radical R 2 , the amino radical can be substituted once or twice with R 2 and the aryl-C 1 -C 4 -alkyl, C 1 -C 4 -alkyl -, C 1 - Cs-alkoxy, Ci-Cio-carbonyl, carbonyl-C j -C ß -alkyl radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R 2 , where R 2 is a - Can be present several times and is the same or different and hydroxyl,
  • R 4 is the same or different and hydroxyl, formyl, cyano, carboxy radical, ester or salt of the carboxy radical, carbamoyl, sulfono, sulfamoyl, nitro, nitroso, amino, phenyl, C ⁇ - C 5 alkyl, Cj - C 5 alkoxy radical, C ⁇ - C 5 alkylcarbonyl radical and two radicals R 3 or R 4 in pairs over a bridge [-CR 5 R 6 -] m with m being the same
  • R 5 and R 6 are identical or different and halogen, carboxy radical, ester or salt of the carboxy radical, carbamoyl, sulfamoyl, phenyl, benzoyl, Cj-Cs-alkyl, C1-C5-aikoxy- Radical, C Cs-alkylcarbonyl radical and one or more non-adjacent groups [-CR 5 R 6 -] by oxygen, sulfur or an imino radical optionally substituted by Cj-Cs-alkyl and two adjacent ones
  • Particularly preferred mediation enhancers are nitroxyl radicals of the general formulas (N t ) and (N 2 ):
  • R 1 is the same or different and is phenyl-, aryl-Ci-Cs-alkyl-, C j -C ⁇ alkyl-,
  • C Cs-alkoxy, CpC j o-carbonyl, carbonyl-C ⁇ Cg-alkyl means and phenyl radicals can be unsubstituted or substituted one or more times with a radical R 3 and the aryl -CC 5 alkyl -, Ci-C ⁇ alkyl, C j -Cs alkoxy, Cj-Cjo-carbonyl, carbonyl-Ci-Cö-alkyl radicals can be saturated or unsaturated, branched or unbranched and with a radical R 3 - or can be substituted several times, where R 3 can be present one or more times and is the same or different and hydroxyl, formyl, carboxy radical, ester or salt of the carboxy radical, carbamoyl, sulfono, sulfamoyl, nitro, nitroso, amino, phenyl, benzoyl, C Cs-alkyl, C j -Cs-alkoxy
  • Particularly preferred mediation enhancers are:
  • 2,2,6,6-tetramethyl-piperidine-1 -oxy 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1 -oxy, 4-oxo-2,2,6,6 -tetramethyl-piperidine-1 -oxyl, 4-acetamido-2,2,6,6-tetramethyl-piperidine-1 -oxy, 4- (ethoxyfluorophosphinyloxy) -2,2,6,6-tetramethyl-piperidine-1 -oxyl , 4- (isothiocyanato) -2,2,6,6-tetramethyl-piperidine-1 -oxyl, 4-maleimido-2,2,6,6-tetramethyl-piperidine-1 -oxyl, 4- (4-N_trobenzoyloxy) -2,2,6,6-tetra-methyl-piperidine-1 -oxy, 4- (phosphonooxy) -2,2,6,6-tetramethyl-piperidine-1 -oxy, 4-cyano-2,2,6 , 6-
  • 2,2,6,6-tetramethyl-piperidine-1-oxyl 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxy, 4-oxo-2 , 2,6,6-tetramethyl-piperidine-1 -oxyl, 4-acetamido-2,2,6,6-tetramethyl-piperidine-1 -oxyl, 4- (isothiocyanato) -2,2,6,6-tetramethyl -piperidine-1 -oxy, 4-maleimido-2,2,6,6-tetramethyl-piperidine-1 -oxy, 4- (4-nitrobenzoyloxy) -2,2,6,6-tetramethyl-piperidine-1 -oxy , 4- (phosphonooxy) -2,2,6,6-tetramethyl-piperidine-1 -oxyl, 4-cyano-2,2,6,6-tetramethyl-piperidine-1-oxyl, 3-carbamoyl-2,2 , 5,5-tetramethyl-piperidine-1-oxyl, 4-o
  • mediation enhancers are compounds such as:
  • ABTS aryl-substituted alcohols
  • non-phenols such as veratryl alcohol
  • phenol derivatives such as p-hydroxycinnamic acid, 2,4-dichlorophenol, p-hydroxybenzene sulfonate, vanillin (4-hydroxy-3-methoxy-benzaldehyde), p-Hy - Droxybenzoic acid, 5-amino-2-hydroxy-benzoic acid (5-aminosilicate acid).
  • radical cation compounds according to “Wurster” (lit .:
  • Radical anions such as e.g. B semiquinones et al
  • the bleaching system can contain phenolic compounds and / or non-phenolic compounds
  • Contain compounds with one or more benzene cores Contain compounds with one or more benzene cores.
  • the bleaching system can be used as catalysts, modified enzymes, enzyme components, prosthetic groups or mimic substances, preferably compounds or compounds containing ham or ham groups
  • Air oxygen
  • H 2 0 2 organic peroxides, sodium perborate and / or sodium percarbonate.
  • Oxygen can also be obtained from H 2 O 2 + catalase or systems, or H 2 O, from GOD +
  • Glucose or similar Systems can be generated "in situ".
  • a bleaching system containing cation-forming metal salts is also preferred.
  • Fe 2+ , Fe 3+ , Mn 2+ , Mn 3+, Mn 4+ , Cu + , Cu 2+ , Ti 3+ , Cer 4+ , Mg 2+ and Al 3+ are preferably used as cations.
  • the bleaching system can also contain polysaccharides and / or proteins. Suitable polysaccharides are glucans, mannans, dextrans, levans, pectins, alginates or plant gums and / or the polysaccharides formed by the fungi or produced in the mixed culture with yeasts. Gelatin, albumin and others are proteins. applicable.
  • simple sugar, oligomer sugar, amino acids, polyethylene glycols, polyethylene oxides, polyethyleneimines and polydimethylsiloxanes can be added.
  • the bleaching system according to the invention can be used with new compounds which enhance enzyme activity in combination with all detergent ingredients or detergent additives known in the art.
  • the bleaching system is normally used in a pH range from 2 to 12, preferably 4 to 10 and at temperatures between 10 ° C and 60 ° C, preferably 20 ° to 40 ° C.
  • Examples 1 to 3 comparative examples (old systems with NO - / NOH compounds as mediators)
  • Standard cotton rag In 100 ml wash solution (in 300 ml Erlenmeyer flasks) a cloth (5x5 cm) is incubated at 40 ° C for 40 min with reciprocal shaking (120 rpm). The wash solution is subjected to a ten-minute temperature adjustment before the start of the incubation. The washing solution is washed with STW (Standard Tap Water) at 14 ° dH. scheduled. 200 IU Laccase * from Coriolus versicolor / 100 ml are used as enzyme dosage and 20Q mg hydroxybenzotriazole 100 ml is used as mediatose dosage. After the "wash liquor” has been poured off, it is filled with cold, strong water jet 3 times and poured off.
  • STW Standard Tap Water
  • Table 1 shows the results compared to a commercial liquid detergent
  • wash solution in 100 ml Erlenmeyer flask, a cloth (5x5 cm) is incubated at 40 ° C for 40 min with reciprocal shaking (120 rpm). The wash solution is subjected to a ten-minute temperature adjustment before the start of the incubation. The washing solution is washed with STW (Standard Tap Water) at 14 ° dH. scheduled. 200 IU laccase from Coriolus versicolor / 100 ml are used as enzyme dosage and 200 mg hydroxybenzotriazole / 100 ml are used as mediatose dosage. After pouring off the "wash liquor”, apply 3x with a cold, strong water jet. fills and poured.
  • STW Standard Tap Water
  • washing solution in 100 ml of washing solution (in a 300 ml Erlenmeyer flask) a cloth is clothed (5x5 cm) at 40 ° C for 40 min with reciprocal shaking (120 rpm). The wash solution is subjected to a ten-minute temperature adjustment before the start of the incubation.
  • the washing solution is prepared with STW (Standard Tap Water) at 14 ° dH. 20 IU laccase from Coriolus versicolor / 100 ml is used as enzyme dosage and 50 mg phthalhydrazide / 100 ml is used as mediatose dosage. After the “wash liquor” has been poured off, it is filled with cold, strong water jet 3 times and poured off. The results are shown in Table 4.
  • Influence of a laccase + mediator on a tea-soiled standard wool cloth In 100 ml washing solution (in a 300 ml Erlenmeyer flask) a cloth cloth (5x5 cm) is incubated at 40 ° C for 40 min with reciprocal shaking (120 rpm).
  • the wash solution is subjected to a ten-minute temperature adjustment before the start of the incubation.
  • the washing solution is prepared with STW (Standard Tap Water) at 14 ° dH. 20 IU laccase from Coriolus versicolor / 100 ml is used as enzyme dosage and 50 mg urazole / 100 ml is used as mediatose dosage.
  • STW Standard Tap Water
  • the washing solution is prepared with STW (Standard Tap Water) at 14 ° dH. 20 IU Laccase from Coriolus versicolor / 100 ml and 50 mg of 4-tert-butylurazole / 100 ml is used as mediatordose.
  • STW Standard Tap Water
  • Influence of a laccase + mediator on a tea-soiled standard wool cloth In 100 ml washing solution (in a 300 ml Erlenmeyer flask) a cloth cloth (5x5 cm) is incubated at 40 ° C for 40 min with reciprocal shaking (120 rpm).
  • the wash solution is subjected to a ten-minute temperature adjustment before the start of the incubation.
  • the washing solution is prepared with STW (Standard Tap Water) at 14 ° dH. 20 IU laccase from Coriolus versicolor / 100 ml are used as enzyme dosage and 50 mg hydantoyl-5-acetic acid / 100 ml is used as mediatose dosage.
  • STW Standard Tap Water
  • Influence of a laccase + mediator on a tea-soiled standard wool cloth In 100 ml washing solution (in a 300 ml Erlenmeyer flask) a cloth cloth (5x5 cm) is incubated at 40 ° C for 40 min with reciprocal shaking (120 rpm). The wash solution is subjected to a ten-minute temperature adjustment before the start of the incubation.
  • the washing solution is prepared with STW (Standard Tap Water) at 14 ° dH. 20 IU Laccase from Coriolus versicolor / 100 ml are used as enzyme dosage and 50 mg squaric acid / 100 ml is used as mediatose dosage. After the “wash liquor” has been poured off, it is filled with cold, strong water jet 3 times and poured off. The results are shown in Table 4.
  • STW Standard Tap Water
  • Influence of a laccase + mediator on a tea-soiled standard wool cloth In 100 ml washing solution (in a 300 ml Erlenmeyer flask) a cloth cloth (5x5 cm) is incubated at 40 ° C for 40 min with reciprocal shaking (120 rpm).
  • the wash solution is subjected to a ten-minute temperature adjustment before the start of the incubation.
  • the washing solution is prepared with STW (Standard Tap Water) at 14 ° dH. 20 IU laccase from Coriolus versicolor / 100 ml is used as enzyme dosage and 50 mg croconic acid / 100 ml is used as mediatose dosage.
  • STW Standard Tap Water
  • the wash solution is subjected to a ten-minute temperature adjustment before the start of the incubation.
  • the washing solution is prepared with STW (Standard Tap Water) at 14 ° dH. 0.1 mg peroxidase IU (Horseradish / Sigma P 8000) / 100 ml is used as enzyme dosage and 50 mg phthalhydrazide / 100 ml is used as mediatose dosage.
  • STW Standard Tap Water
  • Influence of a peroxidase + mediator on a tea-soiled standard wool cloth In 100 ml wash solution (in 300 ml Erlenmeyer flask) a cloth (5x5 cm) is incubated at 40 ° C for 40 min with reciprocal shaking (120 rpm). The wash solution is subjected to a ten-minute temperature adjustment before the start of the incubation. The washing solution is prepared with STW (Standard Tap Water) at 14 ° dH.
  • STW Standard Tap Water
  • Influence of a peroxidase + mediator on a tea-soiled standard wool rag In 100 ml washing solution (in a 300 ml Erlenmeyer flask) a cloth (5x5 cm) is incubated at 40 ° C for 40 min with reciprocal shaking (120 rpm). The wash solution is subjected to a ten-minute temperature adjustment before the start of the incubation.
  • the washing solution is prepared with STW (Standard Tap Water) at 14 ° dH. 0.5 mg peroxidase IU (Horseradish / Sigma P 8000) / 100 ml is used as enzyme dosage and 50 mg 4-tert-butylurazole / 100 ml is used as mediatose dosage. After the “wash liquor” has been poured off, it is filled with cold, strong water jet 3 times and poured off. The results are shown in Table 4.
  • Influence of a peroxidase + mediator on a tea-soiled standard wool cloth In 100 ml washing solution (in a 300 ml Erlenmeyer flask) a cloth cloth (5x5 cm) is incubated at 40 ° C for 40 min with reciprocal shaking (120 rpm). Before the start of the incubation, the wash solution is subjected to a temperature adjustment of ten minutes.
  • the wash solution is made up with STW (Standard Tap Water) at 14 ° dH. 0 1 mg peroxidase IU (Horseradish / Sigma P 8000) / 100 ml is used as enzyme dosage and 50 mg HydantoyI-5-acetic acid / 100 ml is used as mediatose dosage.
  • STW Standard Tap Water
  • the wash solution is prepared with STW (Standard Tap Water) at 14 ° dH. 0 1 mg peroxidase IU (Horseradish / Sigma P 8000) / 100 ml are used as enzyme dosage and 50 mg squaric acid / 100 ml is used as mediatose dosage. After the “washing liquor” has been poured off, it is filled up with cold, strong water jet 3 times and poured off. The results are shown in Table 4.
  • Influence of a peroxidase + mediator on a tea-soiled standard wool cloth In 100 ml wash solution (in a 300 ml Erlenmeyer flask), a cloth (5x5 cm) is incubated at 40 ° C for 40 min with reciprocal shaking (120 rpm). The wash solution becomes one before starting the incubation subjected to a ten-minute temperature adjustment
  • the wash solution is prepared with STW (Standard Tap Water) at 14 ° dH.
  • the wash solution is subjected to a ten-minute temperature adjustment before the start of the incubation.
  • the washing solution is prepared with STW (Standard Tap Water) at 14 ° dH.
  • Standard wool rags In 100 ml of washing solution (in a 300 ml Erlenmeyer flask), one cloth is used
  • the wash solution is subjected to a ten-minute temperature adjustment before the start of the incubation.
  • the washing solution is prepared with STW (Standard Tap Water) at 14 ° dH. 0.1 mg peroxidase IU (Horseradish / Sigma P 8000) / 100 ml is used as enzyme dosage and 50 mg urazole +0.5 mg N, N-dimethylhydroxylamine / 100 ml is used as mediatose dosage.
  • STW Standard Tap Water
  • Standard wool rag In 100 ml washing solution (in a 300 ml Erlenmeyer flask) a cloth is placed
  • the wash solution is subjected to a ten-minute temperature adjustment before the start of the incubation.
  • the washing solution is prepared with STW (Standard Tap Water) at 14 ° dH. 0.1 mg peroxidase IU (Horseradish / Sigma P 8000) / 100 ml is used as enzyme dosage and 50 mg urazole + 0.5 mg ABTS / 100 ml is used as mediatose dosage.
  • STW Standard Tap Water
  • Standard wool rags In 100 ml of washing solution (in a 300 ml Erlenmeyer flask), one cloth is used
  • the wash solution is subjected to a ten-minute temperature adjustment before the start of the incubation.
  • the washing solution is prepared with STW (Standard Tap Water) at 14 ° dH. 0.1 mg peroxidase IU (Horseradish / Sigma P 8000) / 100 ml is used as enzyme dosage and 50 mg urazole + 0.5 mg N, N-dimethyl-p-phenylene diamine / 100 ml is used as mediatose dosage. After pouring off the "wash liquor", use cold, strong
  • Standard wool rags In 100 ml of washing solution (in a 300 ml Erlenmeyer flask), one cloth is used
  • the wash solution is subjected to a ten-minute temperature adjustment before the start of the incubation.
  • the washing solution is prepared with STW (Standard Tap Water) at 14 ° dH. 0.1 mg peroxidase IU (Horseradish / Sigma P 8000) / 100 ml is used as enzyme dosage and 50 mg urazole + 0.5 mg promazine / 100 ml is used as mediatose dosage.
  • STW Standard Tap Water
  • Standard wool rag In 100 ml washing solution (in a 300 ml Erlenmeyer flask) a cloth is placed
  • the wash solution is subjected to a ten-minute temperature adjustment before the start of the incubation.
  • the washing solution is prepared with STW (Standard Tap Water) at 14 ° dH. 0.1 mg peroxidase IU (Horseradish / Sigma P 8000) / 100 ml is used as enzyme dosage and 50 mg urazole + 0.5 mg hydroquinone sulfonic acid are used as mediatose dosage.
  • STW Standard Tap Water
  • Influence of a peroxidase + mediator + mediation enhancer on a tea-soiled standard wool flap In 100 ml wash solution (in a 300 ml Erlenmeyer flask), a cloth rag (5x5 cm) is incubated at 40 ° C for 40 min with reciprocal shaking (120 rpm). Before the start of the incubation, the wash solution is subjected to a ten-minute temperature adjustment
  • the wash solution is prepared with STW (Standard Tap Water) at 14 ° dH. 0 1 mg peroxidase IU (Horseradish / Sigma P 8000) / 100 ml are used as enzyme dosage and 50 mg urazole + 0.5 mg 5-amino-2-hydroxybenzoic acid / 100 ml are used as mediatose dosage. After the “wash liquor” has been poured off, it is filled with cold, strong water jet 3 and poured off. The results are shown in Table 4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un système de blanchiment aux enzymes à nouveaux composés renforçant l'action enzymatique, destiné à être utilisé avec des substances détersives, renfermant a) au moins un catalyseur d'oxydation, b) au moins un agent d'oxydation, c) au moins un médiateur du groupe amide, tel que par exemple l'hydrazide ou la 1,2,4-triazolidine-3,5-dione (urazole) et/ou du groupe imide, tel que par exemple l'hydantoïne et/ou du groupe oxo-carbone. Pour renforcer la réaction, on peut ajouter au moins un agent renforçant la médiation, choisi dans le groupe des composés NO-, NOH-, HRN-OH, de l'hydrazide, de l'urazole, de l'hydantoïne, de l'oxo-carbone ou des substances génératrices de cations du type phénothiazine, phénoxazine, du type (R=N-N=R) (par exemple, ABTS), des alcools arylsubstitués (non phénols) tels que, par exemple l'alcool vératrylique, des composés phénoliques spéciaux formant des radicaux cationiques, des cations- radicalaires selon 'Wurster' et des anions radicalaires.
EP98933507A 1997-05-12 1998-05-11 Systeme de blanchiment aux enzymes a nouveaux composes renfor ant l'action enzymatique Withdrawn EP0983334A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19719898 1997-05-12
DE19719898 1997-05-12
PCT/DE1998/001313 WO1998051772A1 (fr) 1997-05-12 1998-05-11 Systeme de blanchiment aux enzymes a nouveaux composes renforçant l'action enzymatique

Publications (1)

Publication Number Publication Date
EP0983334A1 true EP0983334A1 (fr) 2000-03-08

Family

ID=7829259

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98933507A Withdrawn EP0983334A1 (fr) 1997-05-12 1998-05-11 Systeme de blanchiment aux enzymes a nouveaux composes renfor ant l'action enzymatique

Country Status (3)

Country Link
EP (1) EP0983334A1 (fr)
AU (1) AU8331698A (fr)
WO (1) WO1998051772A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12168011B2 (en) 2022-02-21 2024-12-17 Verona Pharma Plc Formulation production process
US12251384B1 (en) 2023-06-26 2025-03-18 Verona Pharma Plc Particulate composition

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TR199902957T2 (xx) * 1997-06-10 2004-12-21 Unilever N.V. Bir enzimin etkinli�ini art�rma y�ntemi, a�art�c� bile�imi, deterjan bile�imi ve boya aktar�m�n� �nleme y�ntemi.
WO1999024537A2 (fr) * 1997-11-10 1999-05-20 The Procter & Gamble Company Activateurs de blanchiment n,n-diacylhydroxylamine o-substituee et compositions les utilisant
US6034047A (en) * 1998-09-04 2000-03-07 Au; Van Bleach detergent compositions comprising nitrones and nitroso spin traps
CN1325434A (zh) * 1998-10-30 2001-12-05 西巴特殊化学品控股有限公司 洗涤及干洗方法
US6592867B2 (en) 1998-11-09 2003-07-15 Novozymes A/S Antimicrobial composition containing an oxidoreductase and an enhancer of the N-hydroxyanilide-type
ATE238669T1 (de) * 1998-11-09 2003-05-15 Novozymes As Antimikorbielle zusammensetzung, die eine oxidoreduktase und ein verstärkungsmittel vom n- hydroxyanilid-typ enthält
US6117833A (en) * 1998-12-16 2000-09-12 Lever Brothers Company Bleaching compositions and method for bleaching substrates directly with air
FR2794364B1 (fr) * 1999-06-01 2004-08-20 Oreal Composition de teinture d'oxydation des fibres keratiniques et procede de teinture mettant en oeuvre cette composition
WO2001000768A1 (fr) 1999-06-23 2001-01-04 Unilever N.V. Compositions de detergents de blanchiment
AU1143601A (en) 1999-11-11 2001-06-06 Convents, Daniel Method and composition for enhancing the activity of an enzyme
AU1386501A (en) * 1999-11-11 2001-06-06 Convents, Daniel Method and composition for enhancing the activity of an enzyme
WO2001092454A1 (fr) * 2000-05-31 2001-12-06 Unilever N.V. Composition et procede d'oxydation enzymatique
BR0115039A (pt) 2000-10-31 2004-02-03 Unilever Nv Processo de oxidação, composição para a oxidação de substâncias, e, composição detergente para o branqueamento de manchas e/ou anti transferência de corantes
ES2524922T3 (es) 2005-05-10 2014-12-15 Intermune, Inc. Derivados de piridona para modular el sistema de proteína cinasa activada por estrés
WO2008101810A1 (fr) * 2007-02-20 2008-08-28 Henkel Ag & Co. Kgaa Utilisation de dérivés d'urée dans des agents de lavage et de nettoyage
CA2726588C (fr) 2008-06-03 2019-04-16 Karl Kossen Composes et procedes de traitement des troubles inflammatoires et fibrotiques
DE102009001787A1 (de) * 2009-03-24 2010-09-30 Henkel Ag & Co. Kgaa Schonendes Bleichmittel
AR092742A1 (es) 2012-10-02 2015-04-29 Intermune Inc Piridinonas antifibroticas
MX382781B (es) 2014-04-02 2025-03-13 Intermune Inc Piridinonas anti-fibroticas.
US9383644B2 (en) 2014-09-18 2016-07-05 Heraeus Precious Metals North America Daychem LLC Sulfonic acid derivative compounds as photoacid generators in resist applications
US9477150B2 (en) 2015-03-13 2016-10-25 Heraeus Precious Metals North America Daychem LLC Sulfonic acid derivative compounds as photoacid generators in resist applications

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ273923A (en) * 1993-06-16 1997-06-24 Call Hans Peter Multicomponent bleaching system for detergents comprising oxidation catalysts, oxidising agents and mediator system
DK77393D0 (da) * 1993-06-29 1993-06-29 Novo Nordisk As Aktivering af enzymer
DE4445088A1 (de) * 1994-12-16 1996-06-20 Ibv Ind Bioverfahren Mehrkomponentenbleichsystem aus Oxidoreductasen, Oxidationsmitteln, Mediatoren und Mediator-verstärkenden oder recyclierenden Verbindungen zur Verwendung mit waschaktiven Substanzen
AU6702296A (en) * 1995-08-08 1997-03-05 Ciba Specialty Chemicals Holding Inc. Method for enhancing the activity of an enzyme, compounds showing enzyme activity enhancement, and detergents containing such compounds
WO1997011217A1 (fr) * 1995-09-19 1997-03-27 Novo Nordisk A/S Blanchiment de taches
DE69714594T2 (de) * 1996-05-09 2003-04-24 Novozymes A/S, Bagsvaerd Antimikrobielle peroxidase-zusammensetzungen
AU6357896A (en) * 1996-06-19 1998-01-07 Hans-Peter Call Multicomponent system for use with detergent substances

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9851772A1 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12168011B2 (en) 2022-02-21 2024-12-17 Verona Pharma Plc Formulation production process
US12409180B2 (en) 2022-02-21 2025-09-09 Verona Pharma Plc Formulation production process
US12251384B1 (en) 2023-06-26 2025-03-18 Verona Pharma Plc Particulate composition

Also Published As

Publication number Publication date
WO1998051772A1 (fr) 1998-11-19
AU8331698A (en) 1998-12-08

Similar Documents

Publication Publication Date Title
EP0983334A1 (fr) Systeme de blanchiment aux enzymes a nouveaux composes renfor ant l'action enzymatique
DE19821263A1 (de) Enzymatisches Bleichsystem mit enzymwirkungsverstärkenden Verbindungen zur Behandlung von Textilien
EP0845026A1 (fr) Systeme multicomposant destine a etre utilise avec des substances detersives
EP0745154B1 (fr) Systeme a plusieurs constituants pour modifier, degrader ou blanchir la lignine, les matieres contenant de la lignine ou analogues et procedes d'utilisation
EP0845027B1 (fr) Complexes d'activateurs a action catalytique pour composes peroxygene
DE69405407T2 (de) Iminiumsalze als bleichmittelkatalysatoren
DE69705514T2 (de) Sulfanamine als bleichmittelkatalysatoren
WO1999001607A2 (fr) Systeme d'oxydation enzymatique contenant de nouveaux composes renforcant l'action enzymatique
DE19536082A1 (de) Aktivatorkomplexe für Persauerstoffverbindungen
DE19721886A1 (de) Bleichsystem
DE4445088A1 (de) Mehrkomponentenbleichsystem aus Oxidoreductasen, Oxidationsmitteln, Mediatoren und Mediator-verstärkenden oder recyclierenden Verbindungen zur Verwendung mit waschaktiven Substanzen
DE60104208T2 (de) Waschmittelzusammensetzung sowie verfahren zum geschirrspuelen
EP1483442A2 (fr) Nouvelles activites catalytiques d'oxydo-reductases pour l'oxydation et/ou le blanchiment
DE29823426U1 (de) Detergenzzusammensetzung zum Geschirrspülen
DE19820947B4 (de) Enzymatisches Bleichsystem mit neuen enzymwirkungsverstärkenden Verbindungen zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder Verändern oder Abbau von Kohle sowie Verfahren unter Verwendung des Bleichsystems
EP0882814B1 (fr) Système et procédé pour le fractionnement électrochimique des composés
EP3406698A1 (fr) Composition de blanchiment pour lavage ou nettoyage comprenant un précurseur d'oxaziridine
DE19723912A1 (de) Verfahren zur Bleiche von gefärbten zellulosehaltigen Faserprodukten
DE2240605A1 (de) Bleichmittel
EP0902021B1 (fr) Sels de polyamines cycliques
DE10311766A1 (de) Oxidationssystem enthaltend einen makrocyclischen Metallkomplex, dessen Herstellung und Verwendung
EP3167038A1 (fr) Procédé de lavage d'un nouveau type utilisant un composé médiateur électrochimiquement activable
EP1092762B1 (fr) Compositions stables contenant des médiateurs, des composés péroxyde et des stabilisateurs de pH ainsi que leur utilisation dans des systèmes de blanchiment enzymatique
DE102010028742A1 (de) Waschhilfsmittel mit bleichkatalysierenden Metallkomplexen
EP3024918B1 (fr) Carboxylate de manganèse pour l'activation des peroxygènes

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19991210

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK FR GB IT LI NL

17Q First examination report despatched

Effective date: 20050301

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20091201