EP0845026A1 - Systeme multicomposant destine a etre utilise avec des substances detersives - Google Patents

Systeme multicomposant destine a etre utilise avec des substances detersives

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Publication number
EP0845026A1
EP0845026A1 EP96922848A EP96922848A EP0845026A1 EP 0845026 A1 EP0845026 A1 EP 0845026A1 EP 96922848 A EP96922848 A EP 96922848A EP 96922848 A EP96922848 A EP 96922848A EP 0845026 A1 EP0845026 A1 EP 0845026A1
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EP
European Patent Office
Prior art keywords
alkyl
triazolo
carbonyl
hydroxy
salts
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.)
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Application number
EP96922848A
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German (de)
English (en)
Inventor
Hans-Peter Dr. 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 HANS-PETER DR CALL KRIMHILD
CALL Hans-Peter Dr
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Application filed by CALL HANS-PETER DR CALL KRIMHILD, CALL Hans-Peter Dr filed Critical CALL HANS-PETER DR CALL KRIMHILD
Publication of EP0845026A1 publication Critical patent/EP0845026A1/fr
Withdrawn legal-status Critical Current

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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
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/2034—Monohydric alcohols aromatic
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2072—Aldehydes-ketones
    • 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
    • C11D3/38—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

Definitions

  • Multi-component system for use with detergent substances
  • the present invention relates to a new multi-component system for use with detergent substances.
  • the conventional bleaching systems in household detergents are unsatisfactory, particularly in the low temperature range. Below a washing temperature of 60 ° C, the standard bleach H 2 0 2 / sodium perborate / sodium numper carbonate must be activated by adding chemical bleach activators such as TAED and SNOBS. There is also a search for more biodegradable, biocompatible and low-dose bleaching systems for low-temperature washing. While enzymes are already in technical use for protein starch and fat solution as well as for fiber treatment in the washing process, no enzymatic principle has been available for detergent bleaching.
  • WO 1/05839 describes the use of various oxidizing enzymes (oxidases and peroxidases) to prevent “dye transfer”. It is known that peroxidases are able to add different pigments (3-hydroxyflavone and betaine by horseradish peroxidase, carotene by peroxidase) "decolorize”. The patent application mentioned describes the decolorization (also called “bleaching") of textile dyes detached from the laundry and present in the liquor (conversion of a dyed substrate into an undyed, oxidized substance).
  • the enzyme is intended to counteract, for example, 5 hypochlorite, which is also the dye attacks on or in the tissue have the advantage of decolorizing only dye present in solution, hydrogen peroxide or a corresponding precursor or hydrogen peroxide generated in situ being involved in the catalysis of the decolorization.
  • the enzyme reaction can be partially 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.
  • 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 organic chemicals that contain at least two aromatic rings, at least one of which is substituted with defined radicals.
  • mixtures containing peroxidases is also known from WO 92/18687.
  • a special system consisting of oxidases and substrates suitable for this purpose and hydrogen peroxide is described in DE-OS 4231 761.
  • DE-OS 19 18729 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 of inhibition or catalase frequently occurring in GOD serves.
  • GOD glucose oxidase
  • the PCT / EP / 94/01967 finally includes a
  • Multi-component bleaching system for use with wash-active substances consisting of oxidation catalysts and oxidizing agents as well as aliphatic, cycloaliphatic, heterocyclic or aromatic compounds containing NO, NOH or H-NR-OH.
  • a disadvantage of all previously known detergent systems is that the cleaning and bleaching action is still unsatisfactory or the mediator substances, for example in PCT / EP94 / 01087, are added in too large an amount must be and thus environmental and economic problems can arise.
  • the object of the present invention is accordingly to provide an improved multicomponent system for use with detergent substances which does not have the disadvantages of the prior art described and which, above all, the actual mediator substances are enhanced in their action or in situ, i.e. regenerated during the washing process.
  • a multicomponent system comprising a) optionally at least one oxidation catalyst, b) at least one suitable oxidizing agent, c) at least one mediator selects from the group of hydroxylamines, hydroxylamine derivatives, hydroxamic acids, hydroxamic acid derivatives, aliphatic, cycloaliphatic, heterocyclic or aromatic Compounds which contain at least one N-hydroxy, oxime, N-oxi or N, N'-dioxi function, d) at least one comediator selected from the group of aryl-substituted alcohols, carbonyl compounds, aliphatic ethers, phenol ethers and / or oefins (alkenes) and e) if appropriate, a small amount of at least one free amine of a mediator used in each case.
  • one or more of the mediators and comediators mentioned can be used here.
  • the use of a mediator and a comediator is preferred.
  • Working with a mediator and two or more comediators is also conceivable.
  • the substances of the multi-component bleaching system listed under a), b), c), d), e) are preferably used in a ratio of 2: 0.2: 10: 0.2: 0.2, with each component of the system having 2 to 10 can be multiplied.
  • 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.
  • 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 Nomenclature, Acadernic Press, Inc., 1992, pp. 24-154) can be used.
  • Enzymes of the classes mentioned below are preferably used:
  • Class 1.1 enzymes which comprise all dehydrogenases which act on primary, secondary alcohols and Seüiiacetale, and which are accepted as acceptors NAD + or NADP + (subclass. 1.1.1.), Cytochrome (1.1.2), oxygen (O 2 ) (1.1 .3), disulfides (1.1.4), quinones (1.1.5) or other acceptors (1.1.99).
  • the enzymes of class 1.1.5 with quinones as acceptors and the enzymes of class 1.1.3 are particularly preferred. with oxygen as the acceptor, cellobiose: quinone-l-oxidoreductase (1.1.5.1) is particularly preferred in this class.
  • Enzymes of class 1.2 can also be used.
  • This class of enzymes (1.1.5.1) includes those enzymes that oxidize aldehydes to the corresponding acids or oxo groups.
  • the acceptors can be NAD + , NADP + (1.2.1), cytochrome (1.2.2), oxygen (1.2.3), sulfides (1.2.4), iron-sulfur proteins (1.2.5) or other acceptors (1.2 .99).
  • 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.
  • This class includes enzymes that act on CH-CH groups of the donor.
  • the corresponding acceptors are NAD + , NADP + (1.3.1) cytochromes (1.3.2), oxygen (1.3.3), quinones or related compounds (1.3.5), iron-sulfur proteins (1.3.7) or others Acceptors (1.3.99).
  • the enzymes of class (1.3.3) with oxygen as the acceptor and (1.3.5) with quinones etc. as the acceptor are particularly preferred.
  • Enzymes of class 1.4 can also be used which act on CH-NH 2 groups of the donor.
  • the corresponding acceptors are NAD + 'NADP + (1.4.1), cytochrome (1.4.2), oxygen (1.4.3), disulfides (1.4.4), iron-sulfur proteins (1.4.7) or other acceptors ( 1.4.99).
  • Enzymes of class 1.4.3 with oxygen as the acceptor are also particularly preferred here.
  • Enzymes of class 1.5 which act on CH-NH groups of the donor can also be used.
  • the corresponding acceptors are NAD + , NADP + (1.5.1), oxygen (1.5.3), disulfides (1.5.4), quinones (1.5.5) or other acceptors (1.5.99).
  • enzymes with oxygen (O 2 ) (1.5.3) and with quinones (1.5.5) are particularly preferred as acceptors.
  • Enzymes of class 1.6 which act on NADH or NADPH can also be used.
  • the acceptors here are NADP + (1.6.1), heme proteins (1.6.2), disulfides (1.6.4), quinones (1.6.5), NO 2 groups (1.6.6), and a flavin (1.6.8 ) or some other acceptors (1.6.99).
  • Enzymes of class 1.6.5 with quinones as acceptors are particularly preferred here.
  • Enzymes of class 1.7 can also be used, which act as donors on other NO 2 compounds and as acceptors cytochromes (1.7.2), oxygen (O 2 ) (1.7.3), iron-sulfur proteins (1.7.7) or others (1.7.99). Class 1.7.3 with oxygen as the acceptor is particularly preferred here.
  • Enzymes of class 1.8 can also be used, which act as donors on sulfur groups and NAD +, NADP + (1.8.1), cytochromes (1.8.2), oxygen (O 2 ) (1.8.3), disulfides (1.8. 4), quinones (1.8.5), iron-sulfur proteins (1.8.7) or others (1.8.99). Class 1.8.3 with oxygen (O 2 ) and (1.8.5) with quinones as acceptors is particularly preferred.
  • Enzymes of class 1.9 can also be used, which act as donors on heme groups and have oxygen (O 2 ) (1.9.3), NO 2 compounds (1.9.6) and others (1.9.99) as acceptors.
  • Group 1.9.3 with oxygen (O 2 ) as acceptor (cytochrome oxidases) is particularly preferred here.
  • Enzymes of class 1.12 which act on hydrogen as a donor are also suitable.
  • the acceptors are NAD + or NADP + (1.12.1) or others (1.12.99).
  • the enzymes that can be used also include those of classes 1.13 and 1.14 (oxygenases).
  • Enzymes of class 1.15 are also mentioned, 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. NAD + or NADP + (1.16.1) or oxygen (0 2 ) (1.16.3) act as acceptors. Enzymes of class 1.16.3.1 (ferroxidase, eg ceruloplasmin) are particularly preferred here. 97/48786 PC17EP96 / 02658
  • Enzymes belonging to group 1.17 (action on CH 2 groups which are oxidized to -CHOH-), 1.18 (action on reduced ferredoxin as donor), 1.19 (action on reduced flavodoxin as donor) and 1.97 ( other oxidoreductases).
  • the very particularly preferred enzymes include those of class 1.10 that act on biphenols and related compounds. They catalyze the oxidation of biphenols and ascorbates. NAD + , NADP + (1.10.1), cytochrome (1.10.2), oxygen (1.10.3) or others (1.10.99) act as acceptors. Of these in turn, class 1.10.3 enzymes with oxygen (0 2 ) as the acceptor are particularly preferred.
  • enzymes in this class are in particular the enzymes catechol oxidase (tyrosinase) (1.10.3.1), L-ascorbate oxidase (1.10.3.3), O-aminophenol oxidase (1.10.3.4) and laccase (benzene diohoxigen
  • Oxidoreductase (1.10.3.2) is preferred, the laccases (benzenediol oxy oxidoreductase) (1.10.3.2.) Being particularly preferred.
  • the enzymes of group 1.11 are also particularly preferred. which act on a peroxide as an acceptor.
  • This only subclass (1.11.1) contains the peroxidases.
  • the cytochrome C peroxidases (1.11.1.5), catalase (1.11.1.6), the peroxidase (1.11.1.6), the iodide peroxidase (1.11.1.8) and the glutathione peroxidase (1.11.1.9) are very particularly preferred here.
  • the chloride peroxidase (1.11.1.10), the L-ascorbate peroxidase (1.11.1.11), the phospholipid hydroperoxide glutathione peroxidase (1.1.1.1.12), the manganese peroxidase (1.12.1.13), the Diarylpropane 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.
  • White rot fungi such as pleurotus, phlebia and trametes are used in particular for the production of the preferred enzymes from group 1.11.1, but especially from group 1.10.3, in particular for the production of laccases.
  • the multi-component system according to the invention contains at least one
  • Oxidizing agent examples include air, oxygen, ozone, H 2 O 2 , organic peroxides, peracids such as peracetic acid, performic acid, persulfuric acid, persitric acid, metachloroperoxidbenzoic acid, perchloric acid, perborates, peracetates, persulfates, peroxides or acid impulse species and their radicals such as OH; OOH; Singlet oxygen, superoxide (O " 2 ), ozonide, dioxygenyl cation (O 2 + ), dioxirane, dioxitane or fremy radicals can be used.
  • Oxidizing agents are preferably used which can either be generated by the corresponding oxidoreductases, for example dioxiranes from laccases plus carbonyls, or which can chemically regenerate the mediator (for example Caro's acid + benzotriazole gives hydroxybenzotriazole) or can react directly.
  • the multicomponent system according to the invention preferably contains as mediator (component c) at least one compound which has at least one N-hydroxy, oxime, N-oxi or D-dioxi function and / or one of the compounds of the formulas I, II mentioned below , III, IV or V, the compounds of the formulas II, III, IV and V being preferred, the compounds of the formulas III, IV and V being particularly preferred and compounds of the formulas IV and V being particularly preferred.
  • Hydroxylamines open chain or cyclic, aliphatic or aromatic, heterocyclic
  • the substituents R 1 and R 2 which may be the same or different, each independently represent one of the following groups represent hydrogen, Q - C 12 alkyl, carbonyl-Q-Cs alkyl, phenyl, aryl, whose QQ 2 alkyl, carbonyl, QQ alkyl, phenyl, aryl groups are unsubstituted or can furthermore be substituted one or more times with the radical R 3 .
  • the radical R 3 can be one of the following groups: hydrogen, halogen, hydroxy-, formyl-, carboxy- and salts and esters thereof, amino-, nitro-, Cj-Cji-alkyl, C r C 5 -alkyloxy, carbonyl- C r C 6 alkyl, phenyl, sulfono, their esters and salts, sulfamoyl, carbamoyl, phospho-, phosphono-, phosphonooxy and their salts and esters.
  • amino, carbamoyl and sulfamoyl groups of the radical R 3 can be unsubstituted or mono- or disubstituted with hydroxy-, Cj-Q-alkyl-, C r C 3 -alkoxy.
  • the radicals R 1 and R 2 can together form a group -B-.
  • n represents an integer from 1 to 6 and m represents an integer from 1 to 3.
  • R 4 is a substituent defined as R 3 .
  • hydroxylamines which can be used are: N, N-dipropylhydroylamine, N, N-diisopropylhydroxylamine, N-hydroxyipyrrolidine, N-hydroxypiperidine, N-hydroxyhexahydroazepine, N, N-dibenzylhydroxylamine, phenylhydroxylamine, 3-hydroxylamino-3-phenylpropionic acid, 2-hydroxylamine 3-phenylpropionic acid, N-sulfomethylhydroxylamine, N-sulfomethylhydroylamine.
  • the radicals R 9 to R 12 , R 15 and R 16 can be identical or different and, independently of one another, represent one of the following groups: hydrogen, halogen, hydroxyl, formyl, carboxy and salts and esters thereof, amino, nitro, C r C 12 -alkyl, C r C 6 -alkyloxy, carbonyl-C r C 6 -alkyl, phenyl, sulfono esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters.
  • the amino, carbamoyl and sulfamoyl groups of the radicals R 9 to R 12 , R 15 and R 16 can be unsubstituted or substituted once or twice with hydroxy, QQ-alkyl, C j -Q-alkoxy.
  • the radicals R 15 and R 16 can form a common group -G-.
  • the radicals R to R can be identical or different and, independently of one another, represent one of the following groups: hydrogen; Halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, QC ⁇ alkyl, Q-Cs alkoxy, carbonyl-C 1 -C 6 alkyl, phenyl, sulfono esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters.
  • the amino, carbamoyl and sulfamoyl groups of the radicals R 5 to R can be unsubstituted or mono- or disubstituted with hydroxy, C 1 -C 3 alkyl, QC j alkoxy.
  • the C r C 12 alkyl, C j -C 6 alkyloxy, carbonyl-QQ-alkyl, phenyl, aryl groups of the radicals R 5 to R 8 can be unsubstituted or one or more times with the radical R 18 be substituted.
  • the radical R 18 can be one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C r C 12 alkyl, C 1 -C 6 alkoxy, carbonyl-C r C 6- alkyl, phenyl, aryl, and their esters and salts.
  • the carbamoyl, sulfamoyl, amino groups of the radical R 18 can be unsubstituted or substituted once or twice with the radical R 19 .
  • the R 19 radical can be one of the following groups: hydrogen; hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C, -C, 12 - alkyl, Cj-Q-alkyloxy, carbonyl-Cj-C 6 -alkyl, phenyl, aryl.
  • Examples of the aforementioned compounds are 1-hydroxy-l, 2,3-triazole-4,5-dicarboxylic acid, 1-phenyl-1 Hl, 2,3-triazole-3-oxide, 5-chloro-l-phenyl-l H-1,2,3-triazole-3-oxide, 5-methyl-l-phenyl-1 Hl, 2,3-triazole-3-oxide, 4- (2,2 dimethylpropanoyl) -l-hydroxy-1 H - 1,2,3-triazole, 4-hydroxy-2-phenyl-2H-1,2,3-triazole-1-oxide, 2,4,5-triphenyl-2H-1,2,3-triazole-1 -oxide, 1-benzyl-1 Hl, 2,3-triazole-3-oxide, 1-benzyl-4-chloro-1 Hl, 2,3-triazole-3-oxide, 1-benzyl-4-bromo-1H - l, 2,3-triazole-3-oxide, l-benzyl-4-methoxy-l
  • the radicals R 5 to R 12 may be the same or different and independently of one another are one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxyl and salts and esters thereof, amino, nitro, C r C 12 - alkyl, C r C 6 -alkyloxy, carbonyl-C r C 6 -alkyl, phenyl, sulfono esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters.
  • the amino, carbamoyl and sulfamoyl groups of the radicals R 5 to R 12 can be unsubstituted or furthermore mono or disubstituted with hydroxy, C, - be substituted alkoxy -Q-C 3 alkyl, C j.
  • the C r C 12 alkyl, C r C 6 alkyloxy, carbonyl C j - C 6 alkyl, phenyl, aryl, aryl Cj - C 6 alkyl groups of the radicals R 5 to R 12 can be unsubstituted or substituted one or more times with the radical R 13 .
  • the radical R 13 can be one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and also their salts and esters, amino, nitro, Q - C 12 alkyl, Q - C 6 alkyloxy, carbonyl C j - C 6 , - alkyl, phenyl, aryl, sulfono, sulfeno, sulfino and their esters and salts.
  • the carbamoyl, sulfamoyl, amino groups of the radical R can be unsubstituted or can be substituted once or twice with the radical R 14
  • the radical R 14 can be one of the following groups: hydrogen, hydroxyl, formyl, carboxy and their salts and esters, amino, nitro, Q - C 12 alkyl, C x - C 6 -alkyloxy, carbonyl-Q - C 6 .- alkyl, phenyl, aryl.
  • 1-hydroxy-benzimidazole such as 1-hydroxybenzimidazole-2-carboxylic acid
  • 1-hydroxybenzimidazole 2-methyl-l-hydroxy-benzimidazole
  • 2-phenyl-l-hydroxy-benzimidazole 2-phenyl-l-hydroxy-benzimidazole
  • 1-hydrozyindoles such as e.g. 2-phenyl-l-hydroxyindole.
  • R, 1 1 6 0 can be: hydrogen, Q - C 10 - alkyl, Q - C ] 0 - carbonyl, the C, - C 10 alkyl, C, - C 10 - carbonyl of which may be unsubstituted or with a radical R 17 , which is defined as R 3 , can be substituted one or more times.
  • the radicals R 5 to R 8 can be identical or different and independently of one another represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, QC ⁇ - alkyl, QQ-alkyloxy, carbonyl- C r C 6 alkyl, phenyl, sulfono esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters.
  • the amino, carbamoyl and sufamoyl groups of the radicals R 5 to R 8 can be unsubstituted or substituted once or twice with hydroxy, QQ-alkyl, Cj-Q-alkoxy.
  • the C r C 12 alkyl, C r C 6 alkyloxy, carbonyl Ci - C 6 alkyl, phenyl, aryl groups of the radicals R 5 to R 8 can be unsubstituted or one or more with the radical R 18 may be substituted
  • the radical R 18 can be one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and also their salts and esters, amino, nitro, Q - C 12 alkyl, C, - C 6 alkyloxy, carbonyl Q - C 6, .- alkyl, phenyl, aryl, sulfono, sulfeno, sulfino and esters and salts.
  • the radical R 19 can be one of the following groups: hydrogen, hydroxyl, formyl, carboxy and their salts and esters, amino, nitro, Q - C 12 alkyl, Q - C 6 alkyloxy, carbonyl Q - C 6 .- alkyl, phenyl, aryl.
  • 1H-hydroxybenzotriazoles such as: 1-hydroxybenzotriazole, 1-hydroxybenzotriazole-6-sulfonic acid, 1-hydroxybenzotriazole-6-carboxylic acid, 1-hydroxybenzotriazole-6-N-phenylcarboxamide, 5-ethoxy-6-nitro- l-hydroxybenzotriazole, 4-ethyl-7-methyl-6-nitro-1-hydroxybenzotriazole, 2,3-bis (4-ethoxyphenyl) -4,6-dinitro-2,3-dihydro-l-hydroxybenzotriazole , 2,3-bis (2-bromo-4-methylphenyl) -4,6-dinitro-2,3-dihydro-I-hydroxybenzotriazole, 2,3-bis (4-bromo-phenyl) -4 , 6-dinitro-2,3-dihydro-1-hydroxybenzotriazole, 2,3-bis (4-carboxyphenyl) -4,6-dinitro
  • 3H-benzotriazole-1-oxides such as: 3H-benzotriazole-1-oxide, 6-acetyl-3H-benzotriazole-1-oxide, 5-ethoxy-6-nitro- 3H-benzotriazole-l-oxide, 4-ethyl-7-methyl-6-nitro-3H-benzotriazole-l-oxide, 6-amino-3,5-dimethyl-3H-benzotriazole-1-oxide, 6-amino- 3-methyl-3H-benzotriazole-1-oxide, 5-bromo-3H-benzotriazole-1-oxide, 6-bromo-3H-benzotriazole-1-oxide, 4-bromo-7-methyl-3H-benzotriazole-1- oxide, 5-bromo-4-chloro-6-nitro-3H-benzotriazole-l-oxide, 4-bromo-6-nitro-3H-benzotriazole-l
  • examples of compounds of the formulas IV and V are 2H-benzotriazole-1-oxides, such as: 2- (4-acetoxy-phenyl) -2H-benzotriazole-1-oxide, 6-acetylamino-2-phenyl-2H-benzotriazole- 1-oxide, 2- (4-ethylphenyl) -4,6-dinitro-2H-benzotriazole-l-oxide, 2- (3-aminophenyl) -2H-benzotriazole-l-oxide, 2- (4-aminophenyl ) -2H-benzotriazole-1-oxide, 6-amino-2-phenyl-2H-benzotriazole-l-oxide, 5-bromo-4-chloro-6-nitro-2-phenyl-2H-benzotriazole-l-oxide, 2- (4-bromophenyl) -2H-benzotriazole-l-oxide, 5-bromo-2-phenyl-2H-benzo
  • heterocycles which contain at least one N-hydroxyl, oxime, N-oxi, N, N-dioxi function or a further heteroatom, such as O, S, Se, Te, such as:
  • 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-l, 2,3,4-tetrahydro-isoquinoline, ⁇ - (N-oxy-1,2,3,4-tetrahydroisoquinolino ) -propionic acid, l, 3-dihydroxy-2N-benzylimidobenzimidazoline.
  • 1-hydroxy-1H-benzotriazole gives the best results as a bleach additive in a multi-component system for use with detergent substances.
  • HBT 1-hydroxy-1H-benzotriazole
  • BT laccase
  • This compound is relatively poorly degradable and could represent a considerable environmental impact in large quantities. Its reaction speed is also not very high and to some extent leads to damage to the enzymes used. It also reacts (in addition to BT) to colored other degradation products that are undesirable.
  • mediators are particularly preferred (these show this undesired coloring only to a very limited extent) and are those which from the group of cyclic N-hydroxy compounds with at least one optionally substituted five- or six-membered ring containing the structure mentioned in formula A.
  • R 1 is hydrogen, hydroxyl, 1 ⁇ myl, carbamoyl, sulfono, ester or salt of sulfono, sulfamoyl, nitro, amino, phenyl, acrylic Q - C 5 alkyl, Q - C 12 -Alkyl-,
  • carbamoyl, sulfamoyl, amino and phenyl radicals can be unsubstituted or substituted one or more times with a radical R and the aryl-QQ-alkyl, C r C ⁇ 2 alkyl, C 1 -C 5 alkoxy, C r C 10 carbonyl, carbonyl-C r C 6 alkyl radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R 2
  • R 2 is the same or different and hydroxyl, formyl, carboxy radical, ester or salt of the carboxy radical, carbamoyl, sulfono ester or salt of the sulfono radical, sulfamoyl, nitro, amino, pheny, Q ⁇ alkyl -, C r C 5 - alkoxy radical.
  • the multicomponent system according to the invention contains mediators which are available on an industrial scale and are less expensive than HBT. These mediators react under the influence of oxidizing agents to form products without disruptive discoloration. For their part, these products are completely degradable.
  • the multicomponent system according to the invention preferably comprises as mediator (component c) at least one compound of the general formula VI, VII, VIII or IX,
  • R 19 and R 20 are the same or different and have the meaning of R 3 .
  • mediators are compounds of the general formulas VI, VII, VIII or IX in which X and Y are O or S.
  • N-hydroxy-phthalimide and optionally substituted N-hydroxy-phthalimide derivatives examples include N-hydroxymaleimide and optionally substituted N-hydroxymaleimide derivatives, N-hydroxy-naphthalimide and optionally substituted N-hydroxy-naphthalimide Derivatives, N-hydroxysuccinimide and optionally substituted N-hydroxysuccinimide derivatives, preferably those in which the radicals R -R are polycyclically linked.
  • N-hydroxyphthalimide is particularly preferred as mediator (component c of the multicomponent system according to the invention).
  • Compounds of the formula VI which are suitable as mediators are, for example: N-hydroxyphthalimide, N-hydroxybenzene-l, 2,4-tricarboximide, N, N'-dihydroxy-pyromellitic acid diimide,
  • a compound of formula IX suitable as a mediator is, for example:
  • a compound suitable as a mediator with a six-membered ring containing the structure mentioned in formula A is, for example:
  • the compounds mentioned by way of example are also suitable as mediators in the form of their salts or esters.
  • Mediators are also particularly preferred because of the low cost, the good degradability, the substantially lower "damage potential" to enzymes and the very fast reaction rate, characterized in that they are selected from the group of oximes of the general formula X or XI.
  • X is the same or different and O, S, or NR 1 mean where
  • R 1 is hydrogen, hydroxyl, formyl, carbamoyl, sulfono, ester or salt of sulfono, sulfamoyl, nitro, amino, phenyl, acrylic-C, -C 5 -alkyl-, C r C 12 - Alkyl, C r C 5 alkoxy, C 1 -C 10 carbonyl, carbonyl C r C 6 - alkyl, phospho-, phosphono-, phosphonooxy, ester or salt of the phosphonooxy, 3 / where carbomyl, sulfamoyl, amino and phenyl radicals can be unsubstituted or substituted one or more times with a radical R and the aryl-Cj- C 5 -alkyl-, QC ⁇ -alkyl-, C r C 5 -alkoxy- , C r C 10 carbonyl, carbonyl C r C 6 alkyl radicals
  • R 2 is the same or different and is hydroxy, formyl, carboxy, ester or salt of carboxy, carbamoyl, sulfono ester or salt of sulfono, sulfamoyl, nitro, amino, phenyl, C r C 5 alkyl -, C 1 -C 5 alkoxy and
  • radicals R 3 and R 4 are identical or different and are halogen, carboxy, ester or salt of the carboxy radical, or have the meanings given for R 1 , or to form a ring (-CR R) n with n equal to 2, 3 orr 4 are linked and
  • R 5 and R 6 have the meanings given for R 1 and
  • R 7 and R 8 are the same or different and represent halogen, carboxy, ester or salt of the carboxy, or have the meanings given for R 1 .
  • mediators in the multicomponent system according to the invention are compounds of the general formula I in which X is O or S and the other radicals have the meanings given above.
  • An example of such a compound is dimethyl 2-hydroxyiminomalonate.
  • mediators are isonitroso derivatives of cyclic ureides of the general formula II. Examples of such compounds are 1-methylvioluric acid, 1,3-dimethylvioluric acid, thiovioluric acid, alloxane-4,5-dioxime.
  • mediator is alloxan-5-oxime hydrate (violuric acid) and / or its esters or salts.
  • Component (d) can contain, for example, aliphatic ethers, aryl-substituted alcohols, such as 2,3-dimethoxybenzyl alcohol, 3,4-dimethoxybenzyl alcohol, 2,4-dimethoxybenzyl alcohol, 2,6-dimethoxybenzyl alcohol, homovanillyl alcohol, ethylene glycol monophenyl ether, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 4-hydroxy alcohol , 4-hydroxy-3-methoxybenzyl alcohol, 2-methoxybenzyl alcohol, 2,5-dimethoxybenzyl alcohol, 3,4-dimethoxybenzylamine, 2,4-dimethoxybenzylamine hydrochloride, veratryl alcohol, coniferyl alcohol.
  • aliphatic ethers such as 2,3-dimethoxybenzyl alcohol, 3,4-dimethoxybenzyl alcohol, 2,4-dimethoxybenzyl alcohol, 2,6-dimethoxybenzyl alcohol, homovanillyl alcohol,
  • Olefins alkenes
  • B 2-allylphenol, 2-allyl-6-methylphenol, allylbenzene, 3,4-dimethoxypropenylbenzene, p-methoxystyrene, 1-allylimidazole, 1-vinylimidazole, styrene, stilbene, allylphenyl ether, cinnamic acid benzyl ester, cinnamic acid methyl ester, 2,4, 6-triallyloxy-l, 3,5-triazine, 1,2,4-trivinylcyclohexane, 4-allyl-l, 2-dimethoxybenzene, 4-tert- Vinyl butylbenzoic acid ester, squalene, benzoin allyl ether, cyclohexene, dihydropyran, N-benzylcinnamic acid anilide.
  • Phenol ethers are preferably used, e.g. 2,3-dimethoxybenzyl alcohol, 3,4-dimethoxybenzyl alcohol, 2,4-
  • carbonyl compounds such as 4-aminobenzophenone, 4-acetylbiphenyl, benzophenone, benzil, benzophenone hydrazone, 3,4-dimethoxybenzaldehyde, 3,4-dimethoxybenzoic acid, 3,4-dimethoxybenzophenone, 4-dimethylaminobenzaldehyde, 4-acetylbiphenylhydrazone, benzop carboxylic acid, benzoylacetone, bis (4,4'-dimethylamino) benzophenone, benzoin, benzoin oxime, N-benzoyl-N-phenyl-hydroxylamine, 2-amino-5-chloro-benzophenone, 3-hydroxy-4-methoxybenzaldehyde, 4 Methoxybenzaldehyde, anthraquinone-2-sulfonic acid, 4-methylaminobenzaldehyde, benzaldehyde, benzophenone-2-car
  • the reaction is mediated in cascade form or the actual mediator compounds are recycled in situ, i.e. during the reaction and surprisingly leads to a significant improvement in the bleaching reaction.
  • the multi-moment system preferably contains benztriazole as the free amine.
  • the bleaching system can contain phenolic compounds and / or non-phenolic compounds with one or more benzene cores.
  • H 2 0 2 organic peroxides, sodium perborate and / or sodium percarbonate.
  • Oxygen can also be generated by H 2 0 2 + catalase or the like or H 2 0 2 from GOD + glucose or the like "in situ".
  • a multicomponent bleaching system containing cation-forming metal salts is also preferred. Fe Fe, Mn, Mn, Mn 4+ , Cu + , Cu 2+ , Ti 3+ , Cer 4+ , Mg 2+ and Al 3+ should be used as cations.
  • the bleaching system can additionally contain polysaccharides and / or proteins.
  • Suitable polysaccharides are glucans, mannans, dextrans, levans, pectins, alginates or plant gums and / or the polysaccharides produced by the fungi or produced in the mixed culture with yeasts.
  • Gelatin, albumin and others are proteins. applicable.
  • simple sugar, oligomer sugar, amino acids, PEG, polyethylene oxides, polyethyleneimines and polydimethylsiloxyne can be added.
  • the multi-component bleaching system according to the invention can be used in combination with known washing-active detergent additives.
  • the bleaching system works 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.
  • the washing solution is washed with STW (Standard Tap Water) at 14 ° dH. scheduled.
  • STW Standard Tap Water
  • 200,000 IU of Laccase from Coriolus versicolor / 100 ml are used as enzyme dosage and 200 mg of hydroxybenzotriazole / 100 ml are used as mediatose dosage.
  • Table 1 shows the results in comparison with a commercial liquid detergent (without bleaching system) and a full detergent (with bleaching system).
  • 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.
  • STW Standard Tap Water
  • 200,000 IU laccase from Coriolus versicolor / 100 ml are used as enzyme dosage and 200 mg hydroxybenzotriazole / 100 ml are used as mediatose dosage.

Abstract

L'invention a pour objet un système multicomposant destiné à être utilisé avec des substances détersives, renfermant: a) éventuellement au moins un catalyseur d'oxydation, b) au moins un oxydant approprié; c) au moins un médiateur choisi dans le groupe comprenant l'hydroxylamine, les dérivés d'hydroxylamine, les acides hydroxamiques, les dérivés d'acides hydroxamiques, les composés aliphatiques, cycloaliphatiques, hétérocycliques ou aromatiques ayant au moins une fonction N-hydroxy, oxime, N-oxy ou N, N'-dioxy; d) au moins un co-médiateur choisi dans le groupe comprenant les alcools aryle-substitués, les composés carbonyle, les éthers aliphatiques, les éthers du phénol et/ou les oléfines (alcènes); et e) éventuellement une faible quantité d'au moins une amine libre de chacun des médiateurs introduits.
EP96922848A 1996-06-19 1996-06-19 Systeme multicomposant destine a etre utilise avec des substances detersives Withdrawn EP0845026A1 (fr)

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