EP2294172A1 - Bacitracin-metall-komplexe als bleichkatalysatoren - Google Patents
Bacitracin-metall-komplexe als bleichkatalysatorenInfo
- Publication number
- EP2294172A1 EP2294172A1 EP09761572A EP09761572A EP2294172A1 EP 2294172 A1 EP2294172 A1 EP 2294172A1 EP 09761572 A EP09761572 A EP 09761572A EP 09761572 A EP09761572 A EP 09761572A EP 2294172 A1 EP2294172 A1 EP 2294172A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oligopeptide
- washing
- cleaning
- cleaning agent
- bacitracin
- 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- Withdrawn
Links
Classifications
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- 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
- C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
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- 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
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3719—Polyamides or polyimides
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- 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
-
- 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
- C11D3/3932—Inorganic compounds or complexes
Definitions
- the present invention relates to bacitracin-metal complexes and metal complexes of similar compounds and their use as bleach catalysts, especially in detergents and cleaners.
- bleach activators such as, for example, TAED, which are converted by perhydrolysis into the active species.
- Another possibility for generating activated species is the enzymatically catalyzed perhydrolysis of carboxylic acid esters or nitrile compounds using perhydrolases.
- bleach catalysts to produce activated species, wherein a bleach catalyst is to be understood as meaning a substance which can improve the bleaching performance of hydrogen peroxide on a bleachable substance without itself being involved stoichiometrically in the reaction.
- bleach catalysts has the advantage over the other methods of bleach activation that sub-stoichiometric amounts of the compound are sufficient to achieve space and weight savings in the formulation of the bleach-containing product. Furthermore, the reduction in weight, in particular in washing and cleaning applications, also has the advantage that there is less introduction of substances into the environment, which is particularly advantageous for ecological reasons. In addition, this also transport and packaging costs can be saved.
- bleach activators such as nitriles or TAED in the presence of water
- this problem can be largely avoided when using bleach catalysts.
- the production of acids from non-catalytic bleach activation from the peracids causes a pH shift which may adversely affect bleaching performance.
- the bleaching performance of most bleach activators is often insufficient at low temperatures.
- bleach catalysts are of particular interest over the other techniques of bleach activation, so that there is a general need for new bleach catalysts.
- metal complexes of organic ligands such as salenes, sodimines, tris [salicylideneaminoethyl] amines, monocyclic polyazaalkanes, cross-bridged polycyclic polyazaalkanes, terpyridines and tetraamido ligands are described in particular.
- a disadvantage of the metal complexes described, however, is that they either do not have sufficient bleaching performance, especially at low temperature, or that, with sufficient bleaching performance, undesired damage to paints and possibly also the textile fibers occurs.
- complex ligands of an organic nature is conventionally based on non-renewable raw materials such as crude oil and coal.
- These production methods have the disadvantage of reducing irretrievable resources, so that they are no longer available for subsequent generations.
- complex ligands predominantly or preferably completely from renewable raw materials. This is e.g. carried out on a large scale for citric acid, which is produced biotechnologically by means of fungal cultures.
- Citric acid can chelate metal ions as a chelator, but such citric acid complexes are not particularly important for bleach catalysis, especially for washing and cleaning applications.
- the ligands are natural products or are readily derivable from these derivatives.
- the new bleach catalysts should allow effective cleaning of hard surfaces and fabrics, preferably without unduly damaging the latter and / or the latter.
- the new bleach catalysts should, if possible, have sufficient storage stability in order to be used in detergents and cleaners.
- Bacitracin is a drug and polypeptide antibiotic that inhibits the cell wall synthesis of some bacterial species.
- Bacitracin A consists of the dodecapeptide L-IIe (I) -L-Cys (2) -L-Leu (3) -D-Glu (4) -L-Ile (5) -Lys (6) -D-Orn (7) -L-Ile (8) -D-Phe (9) -L-His (10) -D-Asp (11) -L-Asn (12), wherein the side chain of the S-Cys (2) the L-IIe (I) is bound so that L-IIe (I) and L-Cys (2) form a thiazoline ring, and wherein the C-terminal carboxyl group of the L-Asn (12) is linked to the amino acid side chain of the L-Lys (6) forms an intra-achenic amide bond such that residues 6-12 form a cyclic heptapeptide
- bacitracin A Variants of this main component (bacitracin A) are also described which have the following substitutions with respect to the bacitracin A: bacitracin B 1 (Ne ⁇ Val), bacitracin B 2 (Ne 5Val), bacitracin C 1 (Ne 5Val, Ne ⁇ Val), bacitracin C 2 (NeWaI, Ne ⁇ Val), bacitracin C 3 (NeWaI, Ne5Val), bacitracin D 1b (Leu3Val, Ne5Val, Ne ⁇ Val), bacitracin e (NeWaI, Ne5Val, Ne ⁇ Val) (Pittnauer et al. (2006) J. Mass Spectrom. 41, 421-447 ).
- Bacitracin is used as a zinc salt in aqueous tinctures, ointments, pastes or as a powder. It is used for large or severely soiled wounds such as bite, sting, scrapes and lacerations, as well as superficial skin infections, inflammation of the outer ear and infection-prone burns.
- bacitracin-metal complexes as bleaching agents in detergents and / or their use for cleaning textiles or dishes has not yet been described in the prior art and is therefore new. Furthermore, it was surprising that bacitracin-metal complexes enable effective cleaning of fabrics without unduly damaging the fabrics and at the same time behaving very gently with respect to the colors of the textile fabrics.
- a first subject of the present invention are therefore detergents and cleaners which contain an oligopeptide which has at least one optionally completely or partially hydrogenated thiazole radical, preferably at least one thiazoline radical, and at least one optionally partially or completely hydrogenated imidazole radical, preferably at least one imidazole residue includes.
- Oligopeptides according to the invention preferably comprise 5 to 30 amino acids, more preferably ⁇ to 20, in particular 10 to 15, especially 10, 11, 12, 13, 14 or 15 amino acids.
- Polypeptides of the invention preferably further comprise at least one intra-covalent covalent linkage of two amino acids that are not alpha-peptidically linked to one another.
- the intracellular linkage preferably consists of an epsilon-peptide linkage of the C-terminal carboxyl group of the oligopeptide with an amino group of a lysine side chain.
- the intracellular covalent linkage results in a cyclic peptide structure.
- a cyclic hexa, hepta or octapeptide preferably a cyclic heptapeptide is formed by the intra-covalent covalent linkage.
- the optionally partially or completely hydrogenated thiazole radical and in particular the thiazoline radical is inventively preferably formed by covalent linking of the sulfur of the thiol group of a cysteine side chain with the alpha carbon atom of an adjacent alpha-peptidisch bound amino acid.
- the optionally partially or completely hydrogenated imidazole radical is preferably located in an amino acid side chain, preferably an imidazole radical of a histidine.
- Polypeptides of the invention preferably further comprise at least one amino acid carrying in its side chain a carboxyl group or carboxylic acid amide group. This may in particular be glutamine, glutamic acid, asparagine or aspartic acid.
- the oligopeptide according to the invention comprises 10 to 20, preferably 12, 13, 14 or 15 amino acids, wherein the 7 C-terminal amino acids form a cyclic heptapeptide due to an epsilon-peptidic binding of the C-terminal amino acid and two sequential Amino acids in the N-terminal region outside the cyclic heptapeptide form a thiazoline residue, preferably by covalent linking of the sulfur of the thiol group of a cysteine side chain with the alpha carbon atom of an adjacent alpha-peptidic bound amino acid.
- the oligopeptide according to the invention is bacitracin, in particular bacitracin A, bacitracin B 1 , bacitracin B 2 , bacitracin C 1 , bacitracin C 2 , bacitracin C 3 , bacitracin D 1b or bacitracin E, or to a derivative thereof, wherein a derivative is to be understood as an oligopeptide, which in relation to bacitracin in up to five, preferably up to four, three or two amino acid positions, particularly preferably in exactly one amino acid position, is substituted and / or to Bacitracin N-terminal by up to five, preferably up to four, three or two amino acids, more preferably exactly one amino acid, additionally and / or an oligopeptide is to be understood, starting from bacitracin can be obtained by chemical modification, wherein by chemical modification in particular the alkylation, acylation or glycosylation by appropriate alky
- cyclic peptide of the invention as well as its metal complex can be used in free form as well as in the form of any salt.
- Another object of the present invention is therefore also the use of oligopeptides according to the invention, preferably the bacitracin or a derivative thereof, in particular in the form of metal complexes, in detergents and cleaners, in particular in detergents and cleaners for cleaning hard surfaces and / or textile sheet.
- Another object of the present invention is therefore also the use of inventive oligopeptides, preferably the bacitracin or a derivative thereof, in particular in the form of metal complexes, as an aid for cleaning hard surfaces and as an aid for cleaning textile fabrics.
- the present invention also relates in particular to the use of oligopeptides according to the invention, preferably of the bacitracin or a derivative thereof, in particular in the form of metal complexes, for the purification and / or removal of soils, in particular selected from soiling of tea, coffee, blood, soot, Egg, milk, butter, ink, makeup, lipstick, chocolate, chocolate cream, olive oil, blackcurrant, blueberry, apple juice, red wine, beetroot, curry, peanut oil, and mixtures thereof.
- soils in particular selected from soiling of tea, coffee, blood, soot, Egg, milk, butter, ink, makeup, lipstick, chocolate, chocolate cream, olive oil, blackcurrant, blueberry, apple juice, red wine, beetroot, curry, peanut oil, and mixtures thereof.
- Another object of the present invention is in particular the use of inventive oligopeptides, preferably the bacitracin or a derivative thereof, in particular in the form of metal complexes, for bleaching of pulp and / or raw cotton.
- the present invention further provides a process for the cleaning of textile fabrics or hard surfaces, characterized in that the purification using a metal complex of an oligopeptide according to the invention, in particular Use of a bacitracin-metal complex is carried out, which is preferably a fiber and / or color gentle process due to the particularly fiber and color-preserving properties of these metal complexes.
- oligopeptides according to the invention are used in a preferred embodiment according to the invention directly in the form of a catalytically active metal complex.
- oligopeptide and metal ion according to the invention - optionally in the form of any salt - may be presented spatially separated from each other and / or applied sequentially in time.
- the combination of oligopeptide and metal ion and thus the formation of the bleach catalyst can then take place directly during the application.
- the spatial separation of oligopeptide and metal ion can take place, for example, by using a multi-chamber system, wherein oligopeptide and metal ion are contained in different chambers.
- the metal complex of the oligopeptide can then be generated in situ.
- the oligopeptide and the metal ion may also be contained in different compartments of a powdered detergent, such as in different granules or in different layers of a multilayered granule. Upon dissolution of the granules during the application, the oligopeptide and the metal ion can then combine to form the catalytically active complex.
- a special subject of the present invention is therefore also a process for the cleaning of textile fabrics or hard surfaces, characterized in that the cleaning is carried out using a metal complex of an oligopeptide according to the invention, in particular using a bacitracin-metal complex, wherein the metal Complex is generated in situ.
- the oligopeptides of the invention and / or their metal complexes are used in conjunction with an oxygen source such as a bleach (or bleach activator), which will be further discussed below.
- an oxygen source such as a bleach (or bleach activator)
- the metal complexes cause a relatively strong cleaning and bleaching effect even without the addition of an oxygen source.
- a special subject of the present invention is therefore also a process for the cleaning of fabrics or hard surfaces, characterized in that the cleaning is carried out using a metal complex of an oligopeptide according to the invention, in particular a metal complex of bacitracin or a derivative thereof, wherein no bleach and / or bleach activator is added so that preferably atmospheric oxygen is used as the sole oxygen source.
- the cyclic peptide which can be used according to the invention preferably has a complexing constant with respect to manganese (III) of less than 10 3 M -1 , particularly preferably less than 10 -7 , especially less than 10 -20 M -1 .
- Naturally occurring oligopeptides according to the invention are mainly produced by microorganisms, in particular by bacteria. They are preferably synthesized by so-called nonribosomal peptide synthetases (NRPS). Polypeptides according to the invention are therefore preferably those whose synthesis is naturally carried out by NRPS. In a further embodiment preferred according to the invention, the oligopeptide according to the invention is a naturally occurring antibiotic.
- NRPS nonribosomal peptide synthetases
- NRPS consists of several modules, usually one module per amino acid present in the synthesized oligopeptide. Each module consists of several domains that have specific tasks regarding the incorporation of the respective amino acid. Apart from the start module, where the C domain may be missing, one module comprises at least domains C (condensation, selective binding), A (recognition and activation of the amino acid to be incorporated) and T (temporary fixation of the activated amino acid as thioester). Further optional domains are in particular the domains E (racemization of the amino acid for incorporation as D-amino acid), Z (cyclization of side chains) and Te (thioesterase, cleavage of the finished peptide from the last module).
- C condensation, selective binding
- A recognition and activation of the amino acid to be incorporated
- T temporary fixation of the activated amino acid as thioester
- Further optional domains are in particular the domains E (racemization of the amino acid for incorporation as D-amino acid
- polypeptides to be used according to the invention are naturally derived from microorganisms, in particular from bacteria and fungi, in particular those which naturally contain non-ribosomal peptide synthetases (see in particular Donadio et al. (2007) Natural Product Reports 24 (5), 1073-1079).
- Examples include Aspergillus, in particular Aspergillus aculeatus, nidulans, niger, flavipes, fumigatus, ochraceus, rugulosus, sclerotiorum, sydowii and versicolor, Alternaria, in particular Alternaria alternata, mali and tenuis, Aureobasidium, in particular Aureobasidium pullulans, Bacillus, especially Bacillus brevis, licheniformis , megaterium, pumilus and subtilis, Beauveria, in particular Beauveria bassiana, Cochliobolus, in particular Cochliobolus carbonum, Coleophoma, in particular Coleophoma empetri, Cryptosporiopsis, in particular Cryptosporiopsis quercina, Cylindrocladium, in particular Cylindrocladium scoparium, Diaporthe, in particular Diaporthe toxica, Diheterospora, in particular Diheterospora ch
- NK374186 Phoma, in particular Phoma Hungary, Pithomyces, in particular Pithomyces chartarum, cynodontis and sacchari, Pseudallescheria, in particular Pseudallescheria boydii, Streptomyces, in particular Streptomyces orientalis and clavuligerus, Tolypocladium, in particular Tolypocladium niveum and terricola, Ustillago, in particular Ustillago maydis, Ustilaginoidea, in particular Ustilaginoidea virens, Verticillium, in particular Verticillium lamellicola and lecanii, Trichothecium, in particular Trichothecium roseum , and Zalerion, in particular Zalerion arboricola.
- the naturally occurring polypeptides may be obtained from their natural producers, but may alternatively be heterologously produced in another organism by genetically engineering these oranges by incorporating the DNA encoding one or more enzymes involved in the oligopeptide synthesis. Furthermore, the chemical synthesis of cyclic peptides to be used in accordance with the invention also comes into consideration as a further alternative.
- oligopeptides according to the invention As production organisms for the heterologous production of oligopeptides according to the invention, besides the abovementioned microorganisms which naturally synthesize oligopeptides according to the invention and / or contain NRPS, other fungi, yeasts or bacteria are also contemplated, in particular those whose genus contains representatives which naturally produce NRPS.
- microorganisms which can be used according to the invention include, in particular, Acinetobacter, Actinomyces, Aerobacter, Alcaligenes, Aspergillus, Alteromonas, Agrobacterium, Aeromonas, Arthrobacter, Aspergillus, Azotobacter, Bacillus, Bordetella, Brevibacillus, Brucella, Burkholderia, Corynebacterium, Erwinia, Escherichia, Fusarium, Hansenula, Klebsiella, Lactobacillus, Mycobacterium, Neisseria, Neurospora, Penicillium, Pichia, Pseudomonas, Ralstonia, Rhizobioma, Rhodotorula, Saccharomyces, Saccharopolyspora, Salmonella, Shewanella, Shigella, Staphylococcus, Streptomyces, Ustillago, Vibrio and Yersinia.
- the genetic modification of the producing organisms is relatively easy to carry out, wherein a variety of genetic engineering changes are possible to produce an oligopeptide according to the invention in an adapted structure, purity, yield or process duration.
- a biotechnically produced ligand can be adapted to the requirements in a particularly versatile manner compared with a non-biotechnologically produced one.
- oligopeptides such as bacitracin
- biotechnical producibility of the complex ligands from renewable raw materials is particularly sustainable and enables particularly cost-effective process paths which are not accessible with conventional chemical synthesis.
- Naturally occurring oligopeptides are readily biodegradable, since they are absorbed by numerous microorganisms and are natural substances. This is of particular advantage when the complexes enter the environment as intended or through unwanted processes. Derivatives of naturally occurring oligopeptides should also be readily degradable.
- the central atom for the metal complex basically any metal atom in any oxidation state comes into question.
- the central atom of the metal complex is an element selected from Ag, Al, Au, B, Bi, Ce, Co, Cr, Cu, Eu, Fe, Ga, Hg, Mn, Mo, Ni , Pb, Pt, Ru, Ti, U, V, W, Zn and Zr in any oxidation states, in particular Ag (I), Al (III), Au (III), B (III), Bi (III), Ce (III), Ce (IV), Co (II), Co (III), Cr (III), Cu (I), Cu (II), Eu (II), Eu (III), Fe (II), Fe (III), Ga (III), Hg (II), Mn (II), Mn (III), Mn (IV), Mo (IV), Mo (VI), Ni (II), Pb (II), Pt (II), Ru (II), Ru (III), Ru (IV), U (IV), V (IV), V (V), W (VI)
- the central atom of the metal complex is a transition metal atom, which is preferably selected from the group consisting of Mn, Fe, W, Co, Cr, Zn, Bi, Mo, V, Ce and Cu, especially from the group Co, Mn, Ce, Zn, Bi and Fe, in any oxidation state.
- the central atom is selected from Fe (III), Co (II), Co (III), Mn (II), Mn (III), Mn (IV), Ce (III), Ce (IV), Zn (II) and Bi (III).
- the metal complex can be in the form of any salt and optionally also comprise further ligands and / or coligands.
- Suitable ligands and / or coligands are in particular any desired salt anions, phosphonates, amines, polymers, polyols and co-builders and surfactants, in particular the cobuilders and surfactants listed below by way of example.
- counterions depending on the charge of the metal-oligopeptide complex cationic counterions such as in particular alkali and alkaline earth metal ions or anionic counterions such as in particular halide ions or the anions of organic acids into consideration.
- the preparation of the metal complex can generally be carried out in a simple manner by mixing a metal salt of the corresponding metal with the corresponding oligopeptide or a salt of the corresponding oligopeptide in an aqueous environment. By setting a suitable redox potential, the formation of a desired oxidation state can be promoted.
- a further subject of the present invention are metal complexes of oligopeptides according to the invention, in particular of bacitracin or a derivative thereof, characterized in that the central atom is selected from Ag, Al, Au, B, Bi, Ce, Co, Cr, Cu, Eu, Ga, Hg, Mn, Mo, Ni, Pb, Pt, Ru, Ti, U, V, W, Zn and Zr in any oxidation states, in particular of Ag (I), Al (III), Au (III), B ( III), Bi (III), Ce (III), Ce (IV), Co (II), Co (III), Cr (III), Cu (I), Cu (II), Eu (II), Eu ( III), Fe (II), Fe (III), Ga (III), Hg (II), Mn (II), Mn (III), Mn (IV), Mo (IV), Mo (VI), Ni ( II), Pb (II), Pt (II), Ru (II), Ru (III), Ru (IV), U (IV), V (IV), V (V
- the central atom of the metal complex is a transition metal atom which is selected from the group consisting of Mn, W, Co, Cr, Zn, Bi, Mo, V, Ce and Cu, especially from the group Co , Mn, Ce, Zn or Bi, in any oxidation state.
- the central atom is selected from Co (II), Co (III), Mn (II), Mn (III), Mn (IV), Ce (III), Ce (IV), Zn (II) and Bi (III).
- a particular subject of the present invention is the use of the abovementioned oligopeptide-metal complexes having the stated central atoms in detergents or cleaners, in particular for cleaning textile fabrics or for cleaning hard surfaces.
- Another particular subject matter of the present invention is the use of the abovementioned oligopeptide-metal complexes having the stated central atoms as aids for the cleaning of textile fabrics and as aids for the cleaning of hard surfaces.
- Another particular object of the present invention is also the use of the aforementioned oligopeptide metal complexes having the indicated central atoms for bleaching pulp and / or raw cotton.
- Another object of the present invention are detergents and cleaning agents, in particular surfactant-containing, containing a metal complex according to the invention of an oligopeptide according to the invention, in particular the bacitracin or a derivative thereof.
- the detergents and cleaning agents according to the invention may be any conceivable type of cleaning agent, both concentrates and agents to be used undiluted, for use on a commercial scale, in the washing machine or in hand washing or cleaning.
- These include, for example, detergents for textiles, carpets, or Natural fibers, for which according to the present invention the term detergent is used.
- These include, for example, dishwashing detergents for dishwashers or manual dishwashing detergents or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather; for such according to the present invention, the term cleaning agent is used.
- sterilizing and disinfecting agents are to be regarded as detergents and cleaners in the sense of the invention.
- Embodiments of the present invention include all of the prior art and / or all suitable administration forms of the washing or cleaning agents according to the invention. These include, for example, solid, powdery, liquid, gelatinous or pasty agents, optionally also of several phases, compressed or uncompressed; further include, for example: extrudates, granules, tablets or pouches, packed both in large containers and in portions.
- the detergents or cleaners according to the invention contain the above-described inventive metal complexes of the oligopeptides according to the invention, in particular of the bacitracin or a derivative thereof, in an amount of up to 5% by weight, in particular from 0.001% by weight 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.5 wt .-%, especially from 0.01 to 0.25 wt .-%, each based on the total weight of the detergent or cleaning agent ,
- bleach catalysts may additionally be present in the agents according to the invention.
- These substances may generally be any bleach-enhancing transition metal salt or transition metal complex. Suitable transition metals here are in particular Mn, Fe, Co, Ru, Mo, Ti, V or Cu in different oxidation states.
- complexing ligands are, in particular, as described in the literature, guanidines, aminophenols, amine oxides, salene, Saldimine, lactams, monocyclic and cross-bridged polycyclic polyazaalkanes, terpyridines, dendrimers, tetraamido ligands, bis- and tetrakis (pyridylmethyl) alkylamines, secondary amines and polyoxometalates.
- a complex of manganese in the oxidation state II, III, IV or V which preferably contains one or more macrocyclic ligands having the donor functions N, NR, PR, O and / or S.
- ligands are used which have nitrogen donor functions.
- a bleach catalyst in the compositions according to the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN) , 1, 5,9-Trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1, 4,7-triazacyclononane (Me / TACN).
- macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN) , 1, 5,9-Trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me
- the additional bleach catalyst if used, in the inventive compositions preferably in an amount of up to 5 wt .-%, in particular from 0.0025 wt .-% to 1 wt .-% and particularly preferably of 0.01 wt. % to 0.25% by weight, in each case based on the total weight of the washing or cleaning agent.
- bleaches are preferably present in the detergents and cleaners of the invention in a preferred embodiment, which are preferably the substrate for the bleach catalysts according to the invention and / or supply, although, as already mentioned, the catalysis can also be carried out without the addition of bleaching agents.
- a bleach according to the invention on the one hand, hydrogen peroxide itself and, on the other hand, any compound which produces hydrogen peroxide in an aqueous medium.
- sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as persulfates or persulfuric acid.
- peracidic salts or peracids such as persulfates or persulfuric acid.
- urea peroxohydrate percarbamide which can be described by the formula H 2 N-CO-NH 2 H 2 O 2 .
- they may, if desired, also contain bleaching agents from the group of organic bleaches, although their use is also possible in principle for laundry detergents.
- Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
- peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
- Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid (phthalimidoperoxyhexanoic acid , PAP), o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonylamidoperoperuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxy
- chlorine or bromine releasing substances can be used.
- suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as Potassium and sodium are considered.
- Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
- washing or cleaning agents in particular automatic dishwashing agents, are preferred which contain up to 45% by weight, in particular 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 20% by weight .-% and in particular 5 to 15 wt .-% bleach, preferably sodium percarbonate.
- the active oxygen content of the washing or cleaning agents, in particular the automatic dishwashing agents in each case based on the total weight of the composition, preferably between 0.4 and 10 wt .-%, particularly preferably between 0.5 and 8 wt .-% and in particular between 0.6 and 5 wt .-%.
- Particularly preferred compositions have an active oxygen content above 0.3 wt .-%, preferably above 0.7 wt .-%, more preferably above 0.8 wt .-% and in particular above 1, 0 wt .-% to.
- oxidoreductases which can transfer electrons from - as a rule - an organic substrate, such as glucose, to oxygen as an electron acceptor and thus allow the formation of the desired hydrogen peroxide in situ.
- the oxidoreductase can be used here together with the corresponding organic substrate.
- the use of the oxidoreductases can optionally also be carried out without addition of the corresponding substrate.
- the hydrogen peroxide-producing oxidoreductase is preferably an oxidoreductase which produces hydrogen peroxide by using oxygen as the electron acceptor.
- oxidoreductases of EC classes EC 1.1.3 CH-OH as electron donor
- EC 1.2.3 aldehyde or oxo group as electron donor
- EC 1.4.3 CH-NH 2 as donor
- EC 1.7 are used.
- 3 N-containing group as donor
- EC 1.8.3 S-containing group as donor
- Preferred enzymes are in particular selected from the group consisting of malate oxidase (EC 1.1.3.3), glucose oxidase (EC 1.1.3.4), hexose oxidase (EC 1.1.3.5), cholesterol oxidase (EC 1.1.3.6), Galactose oxidase (EC 1.1.3.9), pyranose oxidase (EC 1.1.3.10), alcohol oxidase (EC 1.1.3.13), choline oxidase (EC 1.1.3.17, see in particular WO 04/58955), oxidases for long chain alcohols (EC 1.1.3.20), glycerol-3-phosphate oxidase (EC 1.1.3.21), cellobiose oxidase (EC 1.1.3.25), nucleoside oxidase (EC 1.1.3.39), D-mannitol oxidase (EC 1.1.3.40), xylitol oxidase (EC 1.1.3.41), aldehyde
- L-glutamate oxidase (EC 1.4.3.1 1), L-lysine oxidase (EC 1.4.3.14), L-aspartate oxidase (EC 1.4.3.16), tryptophan-alpha, beta-oxidase (EC 1.4 .3.17), glycine oxidase EC 1.4.3.19), urea oxidase (EC 1.7.3.3), thiol oxidase (EC 1.8.3.2), glutathione oxidase (EC 1.8.3.3), sorbitol oxidase and enzymes such as described for example in DE102005053529.
- Other preferred enzymes are those derived from the foregoing, for example, by single or multiple mutations in the coding gene, by evolutionary methods, by gene shuffling or by similar methods, and thereby have obtained a new substrate spectrum.
- the hydrogen peroxide-producing oxidoreductase in a preferred embodiment, is one which uses a sugar as an electron donor.
- the hydrogen peroxide-producing and sugar oxidizing oxidoreductase according to the invention is preferably selected from glucose oxidase (EC 1.1.3.4), hexose oxidase (EC 1.1.3.5), galactose oxidase (EC 1.1.3.9) and pyranose oxidase (EC 1.1.3.10 ).
- Particularly preferred according to the invention is the glucose oxidase (EC 1.1.3.4).
- a hydrogen peroxide-producing oxidoreductase additionally preferably organic, more preferably aromatic, interacting with the enzymes compounds added to enhance the activity of the respective oxidoreductases (enhancer) or to the electron flow at greatly different redox potentials between the oxidizing enzymes and the stains ensure (mediators).
- the hydrogen peroxide-producing oxidoreductase is preferably used in the detergents and cleaning agents according to the invention, if used, in an amount such that the total composition has an oxidoreductase-related enzyme activity of from 30 U / g to 20,000 U / g, in particular of 60 U / g to 15,000 U / g.
- the unit 1 U corresponds to the activity of that amount of enzyme which converts 1 ⁇ mol of its substrate at pH 7 and 25 0 C in one minute.
- the substrate optionally to be used when using such a hydrogen peroxide-producing oxidoreductase is generally obtained directly from the name of the particular oxidoreductase.
- the means may optionally also contain bleach activators as additional bleaching aid in addition to the metal complexes according to the invention and the optional further bleach catalysts present.
- bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are the O- and / or N-acyl groups of said C atom number and / or optionally substituted benzoyl groups bear.
- polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morph
- bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula
- R 1 is -H, -CH 3, a C 2 - 24 alkyl or alkenyl group, a substituted C 2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or Alkenylarylrest with a C- ⁇ _ 24 alkyl group, or represents a substituted alkyl or Alkenylarylrest with a C- ⁇ _ 24 alkyl group and at least one further substituent on the aromatic ring
- R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 - OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2
- Bleach activators according to the invention preferably in amounts of up to 15 wt .-%, preferably up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, especially 2 to 8 wt .-% and particularly preferably 2 to 6 % By weight, based in each case on the total weight of the bleach activator-containing agents.
- a washing or cleaning agent according to the invention optionally contains further ingredients such as further enzymes, enzyme stabilizers, surfactants, in particular nonionic , anionic, cationic and / or amphoteric surfactants, builders, polymers, solvents, thickeners, sequestering agents, electrolytes, optical brighteners, grayness inhibitors, color transfer inhibitors, glass corrosion inhibitors, corrosion inhibitors, disintegrants, foam inhibitors, abrasives, dyes, fragrances, antimicrobial agents, UV absorbers , Anti-wrinkling agents, antistatic agents, "soil release” active ingredients or “soil repellents", blowing agents and / or perfume carriers and optionally further customary contents sweeteners.
- further ingredients such as further enzymes, enzyme stabilizers, surfactants, in particular nonionic , anionic, cationic and / or amphoteric surfactants, builders, polymers, solvents, thickeners, sequestering agents, electrolytes, optical brighteners, grayness inhibitors
- inventively preferably usable builders (builders), surfactants, other enzymes, enzyme stabilizers, polymers, solvents, thickeners, optical brighteners, grayness inhibitors, wrinkle inhibitors, antistatic agents, glass corrosion inhibitors, corrosion inhibitors, "soil repellents", dye transfer inhibitors, foam inhibitors, abrasives, disintegration (auxiliary ), Acidisersstoffn, dyes, fragrances, antimicrobial agents, UV-absorbents and blowing agents and their preferred amounts used reference is made to the publication WO2008 / 107346.
- a separate subject of the invention are processes for the automated cleaning of textiles or of hard surfaces, in which at least in one of the process steps an inventive metal complex of a cyclic peptide according to the invention is used.
- Methods for cleaning textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned in a plurality of method steps and washed off after the exposure time, or that the cleaning material is treated in any other way with a detergent or a solution of this agent.
- a separate subject of the invention is the use of metal complexes according to the invention cyclic peptides according to the invention for the purification of textiles or hard surfaces.
- metal complexes according to the invention can, in particular according to the properties described above and the methods described above, be used to oxidatively remove impurities from textiles or from hard surfaces.
- Embodiments include, for example, hand washing, manual removal of stains from fabrics or hard surfaces, or use in conjunction with a machine process.
- the metal complexes according to the invention are in this case provided in the context of one of the above formulations for agents according to the invention, preferably detergents or cleaners.
- a powdery heavy duty detergent according to the invention may preferably be e.g. Contain components that are selected from the following:
- Anionic surfactants e.g. Alkylbenzenesulfonate, alkyl sulfate, in amounts of advantageously 5-30 wt .-%, preferably 8-15 wt .-%, in particular 15-20 wt .-%,
- Nonionic surfactants e.g. Fatty alcohol polyglycol ethers, alkyl polyglucoside, fatty acid glucamide, advantageously 0.1-20% by weight, preferably 2-15% by weight, in particular 6-11% by weight,
- Builders e.g. Zeolite, polycarboxylate, sodium citrate, 5-60% by weight, preferably 10-55% by weight, in particular 15-40% by weight,
- Alkalis e.g. Sodium carbonate, advantageously 1-30% by weight, preferably 2-25% by weight, in particular 5-20% by weight,
- Bleaching agents e.g. Sodium perborate, sodium percarbonate, advantageously 5-25% by weight, preferably 10-20% by weight,
- - corrosion inhibitors e.g. Sodium silicate, advantageously 1-6% by weight, preferably 2-5% by weight, in particular 3-4% by weight,
- Stabilizers eg phosphonates, advantageously 0-1% by weight
- Foam inhibitor for example soap, silicone oils, paraffins, advantageously 0.1-4% by weight, preferably 0.2-2% by weight, in particular 1-3% by weight,
- Enzymes e.g. Proteases, amylases, cellulases, lipases, advantageously 0.1-2% by weight, preferably 0.2-1% by weight, in particular 0.3-0.8% by weight,
- - grayness inhibitor e.g. Carboxymethylcellulose, advantageously 0-1% by weight
- Discoloration inhibitor e.g. Polyvinylpyrrolidone derivatives, advantageously 0-2% by weight,
- Optical brighteners e.g. Stilbene derivative, biphenyl derivative, advantageously 0.1-0.3 wt .-%, in particular 0.1-0.4 wt .-%,
- cyclic peptides according to the invention 0.01 to 5% by weight, preferably 0.02 to 4% by weight and in particular 0.05 to 3% by weight, of cyclic peptides according to the invention and / or metal complexes of these cyclic peptides as bleaching catalysts.
- a liquid heavy duty detergent according to the invention may preferably be e.g. contain the following components that are selected from the following:
- Anionic surfactants e.g. Alkylbenzenesulfonate, alkyl sulfate, in amounts of advantageously 5-40 wt .-%, preferably 8-30 wt .-%, in particular 15-25 wt .-%,
- Nonionic surfactants e.g. Fatty alcohol polyglycol ethers, alkyl polyglucoside, fatty acid glucamide, advantageously 0.1-25% by weight, preferably 5-20% by weight, in particular 10-15% by weight,
- Builders e.g. Zeolite, polycarboxylate, sodium citrate, advantageously 0-15% by weight, preferably 0.01-10% by weight, in particular 0.1-5% by weight,
- Foam inhibitor e.g. Soap, silicone oils, paraffins, advantageously 0.1-4% by weight, preferably 0.2-2% by weight, in particular 1-3% by weight,
- Enzymes e.g. Proteases, amylases, cellulases, lipases, advantageously 0.1-2% by weight, preferably 0.2-1% by weight, in particular 0.3-0.8% by weight,
- Optical brighteners e.g. Stilbene derivative, biphenyl derivative, advantageously 0.1-0.3 wt .-%, in particular 0.1-0.4 wt .-%,
- Soap advantageously 1-20% by weight, preferably 2-15% by weight, in particular 5-10% by weight,
- Alcohols / solvents advantageously 0-25% by weight, preferably 1-20% by weight, in particular 2-15% by weight, From 2 to 20% by weight, preferably from 4 to 15% by weight and in particular from 6 to 12% by weight of bleaching agent; such as
- cyclic peptides according to the invention 0.01 to 5% by weight, preferably 0.02 to 4% by weight and in particular 0.05 to 3% by weight, of cyclic peptides according to the invention and / or metal complexes of these cyclic peptides as bleaching catalysts.
- Another object of the present invention is also a product comprising a composition according to the invention or a detergent or cleaning agent according to the invention, in particular a hard surface cleaner according to the invention, and a spray dispenser.
- the product may be both a single-chamber and a multi-chamber container, in particular a two-chamber container.
- the spray dispenser is preferably a manually activated spray dispenser, in particular selected from the group consisting of aerosol spray dispensers (also known as spray can), pressure-building spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump spray dispensers and trigger spray dispensers with a transparent polyethylene or polyethylene terephthalate container.
- Spray dispensers are described in more detail in WO 96/04940 (Procter & Gamble) and the US patents cited therein about spray dispensers, to which reference is made in this regard and the contents of which are hereby incorporated by reference.
- Triggersprühspender and pump sprayer have over compressed gas tanks the advantage that no propellant must be used.
- suitable particles-passing attachments, nozzles, etc. so-called “nozzle valves”
- enzyme in this embodiment can optionally also be added to the composition in a form immobilized on particles and thus metered in as a cleaning foam.
- Machine dishwashing agents which are particularly preferred according to the invention comprise
- surfactant preferably nonionic (s) and / or amphoteric (s) surfactant (s);
- bleaching agent From 2 to 20% by weight, preferably from 4 to 15% by weight and in particular from 6 to 12% by weight of bleaching agent; such as
- inventive cyclic peptides and / or metal complexes of these cyclic peptides as
- Bleach catalysts The preparation of automatic dishwashing agents according to the invention can take place in different ways.
- the compositions according to the invention can be present in solid or liquid form as well as a combination of solid and liquid forms.
- Powder, granules, extrudates or compactates, in particular tablets, are particularly suitable as firm supply forms.
- the liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels.
- Inventive agents can be formulated in the form of single-phase or multi-phase products.
- automatic dishwashing detergents with one, two, three or four phases are preferred.
- Machine dishwashing detergent characterized in that it is in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.
- the individual phases of multiphase agents may have the same or different states of aggregation.
- Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one solid phase are preferred.
- Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g.
- the volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher.
- the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.
- the automatic dishwasher detergents according to the invention in particular the prefabricated metering units, have a water-soluble coating, with particular preference.
- 0.025 mmol (based on the metal atom) of the metal salt to be investigated is stirred in 25 ml of deionized water with 0.050 mmol of bacitracin for up to 24 hours at room temperature in an open vessel. Subsequently, the pH is adjusted to 10 and allowed to stand for 48 hours at room temperature and then freed of insoluble matter by sterile filtration through a syringe attachment filter. A metal-free solution of bacitracin is used the same way, but not mixed with metal salt.
- the hydrogen peroxide solution is added last before the batches are capped and incubated at 40 ° C. for one hour. Subsequently, the Extinktiosunk takes place at 400 nm in the spectrophotometer against water.
- the decrease in absorbance ⁇ E minus that of the uncatalyzed bleach is a measure of the bleaching performance and indicates how much the tested metal complex can favor hydrogen peroxide bleaching.
- the bleaching performance of the solution with hydrogen peroxide without catalyst was set to 100%, meaning that values above 100 indicate better bleaching performance and values below 100 indicate poorer bleaching performance than the detergent with hydrogen peroxide without catalyst.
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102008027375A DE102008027375A1 (de) | 2008-06-09 | 2008-06-09 | Bacitracin-Metall-Komplexe als Bleichkatalysatoren |
PCT/EP2009/055996 WO2009150009A1 (de) | 2008-06-09 | 2009-05-18 | Bacitracin-metall-komplexe als bleichkatalysatoren |
Publications (1)
Publication Number | Publication Date |
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EP2294172A1 true EP2294172A1 (de) | 2011-03-16 |
Family
ID=40810761
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP09761572A Withdrawn EP2294172A1 (de) | 2008-06-09 | 2009-05-18 | Bacitracin-metall-komplexe als bleichkatalysatoren |
Country Status (4)
Country | Link |
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US (1) | US20110070214A1 (de) |
EP (1) | EP2294172A1 (de) |
DE (1) | DE102008027375A1 (de) |
WO (1) | WO2009150009A1 (de) |
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WO2019113926A1 (en) * | 2017-12-15 | 2019-06-20 | Rhodia Operations | Composition containing lanthanide metal complex |
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WO2009150009A1 (de) | 2009-12-17 |
US20110070214A1 (en) | 2011-03-24 |
WO2009150009A9 (de) | 2010-02-18 |
DE102008027375A1 (de) | 2009-12-10 |
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