EP2129762B2 - Complexes métalliques sidérophores utilisés comme catalyseurs de blanchiment - Google Patents

Complexes métalliques sidérophores utilisés comme catalyseurs de blanchiment Download PDF

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EP2129762B2
EP2129762B2 EP08716923.1A EP08716923A EP2129762B2 EP 2129762 B2 EP2129762 B2 EP 2129762B2 EP 08716923 A EP08716923 A EP 08716923A EP 2129762 B2 EP2129762 B2 EP 2129762B2
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Prior art keywords
siderophore
siderophores
complexes
metal
groups
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EP2129762B1 (fr
EP2129762A1 (fr
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Thomas Weber
Ralf Weidenhaupt
Karl-Heinz Maurer
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/39—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 siderophore-metal complexes 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.
  • 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.
  • Siderophores are complex ligands that are secreted by organisms (especially microbes) to firmly bind iron (III) ions and then transport the loaded complex into the cell with the aim of accessing the important iron.
  • the complexation of the iron serve different functional groups such as catecholate groups, salicylate groups, hydroxamate groups, oxazole rings, thiazole rings, citrate hydroxamate groups, alpha-keto-carboxylate groups, alpha-hydroxy carboxylate groups or carboxylic acid amide groups, of which at least two, usually at least three, are usually present in the molecule.
  • siderophores are natural products, they can be easily and inexpensively produced from renewable raw materials, for example, by culturing suitable microorganisms in appropriate media and separating the siderophores they have extracted.
  • the fact that siderophores can be eagerly imported and recycled by countless microorganisms proves that they have good biodegradability, which is a particular advantage for bleach catalysts of this type, especially for detergents and cleaners which ultimately end up in the environment.
  • siderophores can be used to bleach pulp in papermaking or are involved in the natural bleaching process of pulp.
  • hydroxamate siderophores desferrioxamine B, desferritriacetyl fusigen and nocardamine are mentioned in particular.
  • a mediator function with respect to the degradation of lignin by laccases is discussed in the first place ( Niku-Paavola et al. (2003) American Chemical Society Symp Ser 855, 176-190 ; Milagres et al. (2002) Enzymes and Microbial Technology 30, 562-565 ).
  • the iron siderophores could catalyze redox reactions and activate oxygen.
  • the use of siderophores in detergents and cleaners is not described here.
  • EP0325559 discloses a process for preparing different metal complexes of desferrioxamines B and E and desferrithiocin in purer form.
  • Yoder et al. (2006, Journal of Environmental Science and Health, Part A: Toxic / Hazardous Substances & Environmental Engineering 41 (3), 369-380 ) disclose complexes of a pyoverdine with aluminum, calcium, copper, iron, manganese, magnesium and zinc ions as well as studies on their fluorescence.
  • siderophore metal complexes as bleaching agents in detergents and / or their use for the cleaning of textiles or dishes is not yet described in the prior art and thus new. Furthermore, it was surprising that siderophore-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 containing at least one siderophore, preferably at least one siderophore-metal complex. Due to their low fiber and color damage, this is preferably a particularly fiber and / or color-protecting detergent and / or cleaning agent.
  • the siderophore as well as the siderophore-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 siderophores, in particular of siderophore-metal complexes, in detergents and cleaners, in particular in detergents and cleaners for cleaning hard surfaces and textile fabrics.
  • Another object of the present invention is therefore also the use of siderophores, in particular of siderophore 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 siderophores, in particular of siderophore-metal complexes, for the cleaning and / or removal of stains, 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, peanut oil, and mixtures thereof.
  • Another object of the present invention is in particular the use of siderophores, in particular siderophore metal complexes, for bleaching pulp and / or raw cotton.
  • a further subject matter of the present invention is the use of siderophore-metal complexes, in particular in detergents and cleaning agents, for killing germs, in particular for killing bacteria and / or fungi.
  • the present invention further provides a process for the cleaning of textile fabrics or hard surfaces, characterized in that the cleaning is carried out using a siderophore-metal complex, wherein it is due to the particularly fiber and color-preserving properties of the siderophore metal complexes preferably is a fiber and / or color gentle process.
  • the siderophores are used in a preferred embodiment according to the invention directly in the form of a catalytically active siderophore-metal complex.
  • siderophore and metal ion - optionally in the form of any salt - can be presented spatially separated from each other and / or applied sequentially in time.
  • the combination of siderophore and metal ion and thus the formation of the bleach catalyst can then take place directly during the application.
  • the spatial separation of siderophore and metal ion can take place, for example, by using a multi-chamber system, the siderophore and the metal ion being contained in different chambers.
  • the siderophore-metal complex By mixing the components of the various chambers of the multi-chamber system, the siderophore-metal complex can then be generated in situ.
  • the siderophore 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 application, the siderophore and 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 siderophore-metal complex, wherein the siderophore-metal complex is generated in situ.
  • the siderophore and siderophore metal complexes are used in conjunction with an oxygen source, such as a bleach (or bleach activator), which will be discussed further below.
  • an oxygen source such as a bleach (or bleach activator)
  • the siderophore metal complexes cause a relatively strong cleaning and bleaching effect even without the addition of an oxygen source.
  • a particular object 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 siderophore-metal complex, wherein no bleaching agent and / or bleach activator is added, so preferably Atmospheric oxygen is used as the sole source of oxygen.
  • siderophores are compounds that are produced by an organism only under conditions of iron deficiency.
  • this limitation does not apply to the present invention, as even complex ligands produced with sufficient iron present can fulfill the purpose of the present invention. Therefore, in the context of the present invention under the designation o naturally occurring siderophore "any naturally occurring complex ligand, the similar complex-forming properties, as well as a similar Sruktur and function as a siderophore having to understand.
  • siderophore “according to the invention as so-called Chalkophore
  • the naturally occurring siderophore is a siderophore in the strict sense as defined above.
  • a siderophore is furthermore to be understood in a broader sense as meaning in general any compound which contains at least two, preferably at least three, more preferably two or three, especially exactly three, radicals selected from the group consisting of hydroxamate, catecholate, and alpha-hydroxy.
  • Carboxylate, alpha-keto-carboxylate, carboxamide, Citrathydroxamat and, optionally partially or fully hydrogenated, oxazole or thiazole, with those compounds are preferably at least three, more preferably exactly three, selected from catecholate, hydroxamate and, optionally partially or fully hydrogenated, oxazole or thiazole.
  • catecholate is to be understood as meaning the twice-deprotonated form of catechol.
  • the catecholate residues may also be fully or partially protonated, especially in the presence of the uncomplexed free form of the corresponding siderophores.
  • These protonated forms of the catecholate are encompassed according to the invention by the term “catecholate”.
  • the other radicals mentioned in particular in the uncomplexed form of the siderophores, can likewise be present in the protonated or deprotonated state.
  • hydroxamic acid radicals are included in particular by the term “hydroxamate” and by the term “carboxylate” carboxylic acid radicals with.
  • the radicals mentioned are preferably present in deprotonated form.
  • the siderophore is a compound which has at least two, preferably exactly two, hydroxamate groups and at least one further, preferably exactly one further, complexing group, in particular selected from catecholate, carboxylate, alpha-hydroxy Carboxylate, alpha-keto-carboxylate, phenolate, carboxylic acid amide and, optionally partially or fully hydrogenated, imidazole, oxazole or thiazole contains, wherein the further complexing group is preferably selected from catecholate and, optionally partially or fully hydrogenated, oxazole or thiazole.
  • the siderophore is a compound which contains at least three, preferably exactly three, hydroxamate groups.
  • the siderophore is a compound which is at least two, preferably exactly two; Catecholate groups and at least one further, preferably exactly one further, complexing group, in particular selected from hydroxamate, carboxylate, alpha-hydroxy-carboxylate, alpha-keto-carboxylate, phenolate, carboxylic acid amide and optionally partially or fully hydrogenated, imidazole, oxazole or Thiazole, wherein the further complexing group is preferably selected from hydroxamate and, optionally partially or fully hydrogenated, oxazole or thiazole.
  • the siderophore is a compound containing at least three, preferably exactly three, catecholate groups.
  • the siderophore is a compound which has at least two, preferably exactly two, optionally partially or fully hydrogenated, oxazole groups and at least one further, preferably exactly one further, complexing group, in particular selected from hydroxamate , Catecholate, carboxylate, alpha-hydroxy-carboxylate, alpha-keto-carboxylate, phenolate, carboxamide and, optionally partially or fully hydrogenated, imidazole or thiazole, wherein the further complexing group is preferably selected from hydroxamate, catecholate and optionally partially or fully hydrogenated, thiazole.
  • the siderophore is a compound which contains at least three, preferably exactly three, optionally partially or completely hydrogenated, oxazd groups.
  • the siderophore is a compound which has at least two, preferably exactly two, optionally partially or fully hydrogenated, thiazole groups and at least one further, preferably exactly one further, complexing group, in particular selected from hydroxamate , Catecholate, carboxylate, alpha-hydroxy-carboxylate, alpha-keto-carboxylate, phenolate, carboxamide and, optionally partially or completely hydrogenated, imidazole or oxazole, wherein the further complexing group is preferably selected from hydroxamate, catecholate and optionally partially or fully hydrogenated, oxazole.
  • the siderophore is a compound which contains at least three, preferably exactly three, optionally partially or completely hydrogenated, thiazole groups.
  • the siderophore is a compound which has at least two, preferably exactly two, alpha-hydroxy carboxylate groups and at least one further, preferably exactly one further, complexing group, in particular selected from hydroxamate, Catecholate, carboxylate, alpha-keto-carboxylate, phenolate, carboxylic acid amide and, optionally partially or fully hydrogenated, imidazole, oxazole or thiazole, wherein the further complexing group is preferably selected from hydroxamate, catecholate and, optionally partially or fully hydrogenated, oxazole or thiazole.
  • the siderophore is a compound which contains at least three, preferably exactly three, alpha-hydroxy carboxylate groups.
  • a “siderophore” is therefore to be understood as meaning any naturally occurring or naturally occurring compound which has the abovementioned combination of functional groups, regardless of how it was obtained.
  • the siderophore is a naturally occurring siderophore or a derivative thereof, with a derivative of a naturally occurring siderophore
  • Siderophors is understood in particular to be a compound obtainable starting from a naturally occurring siderophore, for example by halogenation, alkylation, acylation, sulfonation, nitration, hydroxylation, decarboxylation or similar modifying reactions, preferably without destroying the backbone of the naturally occurring siderophore.
  • the modification can be carried out, for example, biotechnologically, ie during production in a microorganism, or else chemically in vitro.
  • the modification can serve, in particular, to further improve the properties of the siderophore for use as bleach catalyst ligands, for example in terms of oxidation stability, solubility or color.
  • the siderophore according to the invention is an optionally modified oligopeptide, which preferably comprises 2 to 8 optionally modified peptide bonds, in particular a cyclic oligopeptide, in particular a cyclic pentapeptide or a cyclic hexapeptide can.
  • the abovementioned functional groups may in this case be part of the amino acid residues, but they may instead, in particular the hydroxamate groups, also be part of the optionally cyclic peptide chain and have arisen here in particular by modification of the peptide bonds.
  • the siderophore is a naturally occurring siderophore.
  • siderophores may according to the invention in particular be sideromycins, siderochromes or sideramines.
  • chalcophores such as methanobactin, which are not actually referred to as siderophores, according to the invention are attributable to the siderophores.
  • the naturally non-occurring siderophores in a preferred embodiment are the abovementioned derivatives of naturally occurring siderophores.
  • it may be any other compound, provided that the above combination is found in functional groups.
  • it may in particular also be an oligopeptide, in particular a cyclic oligopeptide such as a cyclic hexapeptide.
  • Naturally occurring siderophores with three hydroxamate groups can be used according to the invention in particular desferrichromes, in particular desferrichrome, desferrichrome A or desferrichrome C, tetraglycyldesferrichromes, desferricrocin, desferrichrysin, desferrirhodin, hexahydrodesferrirhodin, desferrirubin, desferricoprogen, desferrineocoprogen I, desferrineocoprogen II, exochelin MS, fusigen ( Fusarinine C), nocardamine, desferrisalmycin, desferrialbomycins, in particular desferrialbomycin ⁇ 1 , ⁇ 2 or ⁇ , desferrioxamine, in particular desferrioxamine A, A1, A2, B, C, D1, D2, E, Et1, Et2, Et3, Fm, G, H, I, X1, X2, X3, X4, Te1, Te2 or Te3, and desferrimycins
  • pyoverdins in particular the pyoverdines C, D, E or Pa.
  • mycobactins can be used according to the invention, in particular mycobactin J, P, S or T.
  • aerobactin As a naturally occurring siderophore with two hydroxamate groups and one alpha-hydroxy carboxylate group, according to the invention, in particular aerobactin, arthrobactin, acinetoferrin, an aquaquinine, in particular aquaquinin A, B, C or D, an omibactin, in particular ornibactin C4, C6 or C8 , a nannochelin, especially nannochelin B or C, or schizokines.
  • aerobactin in particular aeroquinin A, B, C or D
  • an omibactin in particular ornibactin C4, C6 or C8
  • a nannochelin especially nannochelin B or C, or schizokines.
  • exochelin MN As a naturally occurring siderophore with two hydroxamate groups and one imidazole group, it is possible according to the invention in particular to use exochelin MN.
  • a catecholate group and an alpha-keto-carboxylate group in particular azotobactin D can be used according to the invention.
  • a pseudobactin can be used according to the invention, in particular pseudobactin, pseudobactin 7NSK2, 7SR1, A, A214, M114 or St3.
  • a catecholate group and a partially hydrogenated oxazole ring in particular aceticobactin can be used according to the invention.
  • pseudobactin As a naturally occurring siderophore with a hydroxamate group, an alhpa-hydroxy carboxylate group and several carboxamide groups, pseudobactin can be used according to the invention in particular.
  • putrebactin As a naturally occurring siderophore with a hydroxamate group and several carboxylic acid amide groups, in particular, putrebactin can be used according to the invention.
  • achromobactin As a naturally occurring siderophore with three alpha-hydroxy carboxylate groups, in particular achromobactin can be used according to the invention.
  • rhizoferrin As a naturally occurring siderophore with two alpha-hydroxy carboxylate groups, two carboxylic acid amide groups and two further carboxylate groups, rhizoferrin can be used according to the invention in particular.
  • agrobactin As a naturally occurring siderophore with three catecholate groups, it is possible according to the invention in particular to use agrobactin, enterobactin (enterochelin), fluvibactin, homofluvibactin or bacillibactin (corynebactin).
  • petrobactin As a naturally occurring siderophore with two catecholate groups and one alpha-hydroxy-carboxylate group, in particular, petrobactin can be used according to the invention.
  • chrysobactin As a naturally occurring siderophore with a catecholate group and two carboxylic acid amide groups, in particular chrysobactin can be used according to the invention.
  • Yersiniabactin As a naturally occurring siderophore with three partially hydrogenated thiazole rings, Yersiniabactin can be used according to the invention in particular.
  • ferrrithiocin or pyochelin A can be used according to the invention.
  • the vulnibactin As a naturally occurring siderophore with two partially hydrogenated oxazole groups and one catecholate group, in particular the vulnibactin can be used according to the invention.
  • siderophores which can be used according to the invention are daunorubicin, succinimycin, rifamycin, trencam, pseudomonin, corugatin, gallichrom, fusigen, desferristaphyloferrin, in particular desferristaphyloferrin A or B, desferrivibrioferrin, desferrimaduraferrin, a fusarin, in particular fusarin C, PM, X or Z or triacetylfusarinine C, dimerumic acid, mugineic acid, coelichelin, WCS, methanobactin, gonobactin, amonabactin, in particular amonabactin P or T, an amphibactin, in particular amphibactin G, a rhizobactin, in particular rhizobactin 1021 or DM4, rutuckactin, anguibactin, brucebactin, carboxymycobactin,
  • the siderophore which can be used according to the invention preferably has a complexing constant with respect to iron (III) of less than 10 -3 M -1 , particularly preferably less than 10 -7 , especially less than 10 -20 M -1 .
  • Naturally occurring siderophores are mainly produced by microorganisms, especially bacteria.
  • siderophores are also produced by other organisms, in particular by certain plants that form a community with Thambionten.
  • all naturally occurring siderophores are suitable for the formation of siderophore-metal complexes according to the invention.
  • the naturally occurring siderophores to be used according to the invention are preferably derived from microorganisms, more preferably from bacteria, in particular from Acinetobacter, Actinomyces, Alcaligenes, Bordetella, Alteromonas, Agrobacterium, Aeromonas, Arthrobacter, Azotobacter, Bacillus, Corynebacterium, Brucella, Burkholderia, Erwinia, Penicillium, Aspergillus , Neurospora, Ustillago, Escherichia, Klebsiella, Aerobacter, Saccharopolyspora, Mycobacterium, Penicillium, Fusarium, Neisseria, Pseudomonas, Shewanella, Shigella, Rhizobioma, Rhodotorula, Ralstonia, Salmonella, Staphylococcus, Streptomyces, Vibrio or Yersinia.
  • siderophores can be obtained from their natural producers, but alternatively can also be produced heterologously in another organism by genetically modifying these oranges by incorporating the DNA coding for one or more enzymes involved in the siderophore synthesis. Furthermore, the chemical synthesis of siderophores as another alternative into consideration.
  • As production organisms for heterologous production are preferably also microorganisms in question, preferably fungi, yeasts and bacteria, in particular the genera Aspergillus, Bacillus, Brevibacillus, Actinomyces, Escherichia, Streptomyces, Corynebacterium, Pseudomonas, Saccharomyces, Hansenuta, Pichia and Lactobacillus.
  • the genetic modification of the producing organisms is relatively simple, with a variety of genetic engineering changes being possible to produce a siderophore in an adapted structure, purity, yield or process time.
  • a siderophore-based catalyst can be adapted to the requirements in a particularly versatile manner compared to a non-biotechnologically produced catalyst.
  • Naturally occurring siderophores 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 siderophores should also be readily degradable.
  • the central atom of the metal siderophore complex is an element selected from Ag, Al, Au, B, Bi, Ce, Co, Cr, Cu, Eu, Fe, Ga, Hg, Mn, Mo.
  • the central atom of the metal siderophore complex is a transition metal atom, preferably selected from the group consisting of Mn, Fe, W, Co, Cr, Zn, Bi, Mo, V, Ce, and Cu all from the group Co, Mn, Ce, Zn, Bi or Fe, in any oxidation state.
  • the central atom is selected from Fe (III), Co (II), Co (III), Mn (II), Mn (III), Ce (III), Ce (IV), Zn (II) and Bi (III).
  • siderophores with at least three hydroxamate groups, in particular desferrioxamines, desferrichromes and coprogens, in particular desferrioxamine E, with metal ions of Mn, Fe, Co, Ce, Cr, Zn, Cu, Mo, V, W and Bi ;
  • the metal siderophore complex may be in the form of any salt, and optionally also other 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.
  • counterion ions are cationic counterions such as, in particular, alkali metal and alkaline earth metal ions or anionic counterions such as in particular halide ions or the anions of organic acids.
  • the preparation of the metal siderophore complex can generally be carried out in a simple manner by mixing a metal salt of the corresponding metal with the corresponding siderophore or a salt of the corresponding siderophore in an aqueous environment. By setting a suitable redox potential, the formation of a desired oxidation state can be promoted.
  • Another object of the present invention are siderophore metal complexes, 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), Mo (IV), Mo (VI), Ni (II), Pb (II), Pt (II) Ru (II), Ru (III), Ru (IV), U (IV), V (IV), V (V), W (VI) or Zn (II), with the exception of the metal complexes of Desferri
  • the central atom of the metal-siderophore complex is particularly preferably 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 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), Ce (III), Ce (IV), Zn (II) and Bi (III).
  • the metal siderophore complexes are selected from complexes of the coprogen with metal ions of Mn, Co, Ce, Cr, Zn, Cu, Mo, V, W and Bi; Complexes of siderophores having at least two hydroxamate groups and at least one alpha-hydroxy carboxylate group, in particular ornibactin, arthrobactin and schizokinene, with metal ions of Mn, Co, Ce, Cr, Zn, Cu, Mo, V, W and Bi; Complexes of siderophores having at least two hydroxamate groups and at least one carboxylic acid amide group, in particular the rhodotorulic acid, with metal ions of Mn, Co, Ce, Cr, Zn, Cu, Mo, V, W and Bi; Complexes of siderophores having at least three partially hydrogenated thiazole rings, in particular yersinabactin, with metal ions of Mn, Co, Ce, Cr, Zn, Cu,
  • a particular object of the present invention is the use in particular of the abovementioned siderophore 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 of the present invention is the use in particular of the abovementioned siderophore-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 in particular of the aforementioned siderophore 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 siderophore-metal complex according to the invention.
  • 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 laundry detergent is used.
  • laundry detergent includes, 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 comprise the above-described inventive siderophore-metal complexes in an amount of up to 5% by weight, in particular from 0.001% by weight to 1% by weight and more preferably of 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 and / or bleaches and / or bleach activators may optionally additionally be present in the compositions according to the invention.
  • preferably used substances of these classes of substances as well as preferred amounts is disclosed in the publication WO2008 / 101909 directed.
  • 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.
  • a washing or cleaning agent according to the invention optionally contains further ingredients such as further enzymes, enzyme stabilizers, builders, solvents, thickeners and optionally further usual ingredients, which are explained below.
  • the agents according to the invention comprise surfactants, in particular selected from nonionic, anionic, cationic and amphoteric surfactants. According to the invention, nonionic, anionic and / or amphoteric surfactants are preferably used as surfactants.
  • the surfactants are contained in the detergents or detergents according to the invention in an amount of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight, based on the finished composition.
  • the washing and cleaning agent according to the invention may optionally contain sequestering agents, electrolytes and other auxiliaries, such as optical brighteners, grayness inhibitors, glass corrosion inhibitors, corrosion inhibitors, dye transfer inhibitors, foam inhibitors, disintegration aids, abrasives, soil release agents or soil repellents ", Dyes and / or fragrances, as well as antimicrobial agents, UV-absorbents.
  • sequestering agents such as optical brighteners, grayness inhibitors, glass corrosion inhibitors, corrosion inhibitors, dye transfer inhibitors, foam inhibitors, disintegration aids, abrasives, soil release agents or soil repellents ", Dyes and / or fragrances, as well as antimicrobial agents, UV-absorbents.
  • the optionally used further bleach catalyst according to a) here is preferably selected from the further bleach catalysts mentioned above.
  • Suitable support materials b) are in principle all substances or mixtures of substances which can be used in detergents and cleaners and compatible with the other ingredients, in particular the builders enumerated above, especially the carbonates, including the hydrogencarbonates, the sulfates, the chlorides, the silicates and the phosphates .
  • Particularly suitable carrier materials here are alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, alkali metal silicates, alkali metal silicates, alkali metal phosphates and mixtures of these substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, and / or alkali metal phosphates for the purposes of this invention.
  • the carrier used is the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) or the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
  • the proportion by weight of the support material b) in the total weight of the bleach catalyst granules can be varied within the limits given above, with particular weight percentages above 20 wt .-%, preferably above 40 wt. Regarding the processability and the actual bleaching performance after assembly with other washing and cleaning active ingredients .-% and in particular above 60 wt .-% have proven to be advantageous. Consequently, in the context of the present application, bleach catalyst granules are preferred in which the weight fraction of the carrier material b) in the total weight of the granules is from 20 to 99% by weight, preferably between 40 and 95% by weight and in particular between 60 and 90% by weight ,
  • the bleach activator granules of the invention contain a binder c) from the group of organic polymers.
  • the polymers may be nonionic, anionic, cationic or amphoteric in nature. Natural polymers and modified polymers of natural origin are usable as well as synthetic polymers.
  • the group of nonionic polymers used with particular preference as a binder c) include polyvinyl alcohols, acetalated polyvinyl alcohols, polyvinylpyrrolidones and polyalkylene glycols, especially polyethylene oxides.
  • Preferred polyvinyl alcohols and acetalated polyvinyl alcohols have molecular weights in the range from 10,000 to 100,000 gmol -1 , preferably from 11,000 to 90,000 gmol -1 , particularly preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 .
  • Preferred polyethylene oxides have molecular weights in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000.
  • the group of anionic polymers used with particular preference as a binder c) include, in particular, homo- or copolymeric polycarboxylates, polyacrylic acids and polymethacrylic acids, in particular those which have been mentioned previously as organic builders useful for detergents and cleaners, and polymers containing sulfonic acid groups, in particular those which have been previously mentioned as useful softeners.
  • the weight fraction of the binder c) in the total weight of the granulate is between 0.2 and 4.5% by weight, preferably between 0.5 and 4.0% by weight and in particular between 1.0 and 4, 0% by weight.
  • the bleach catalyst granules preferably have an average particle size between 0.1 and 1.0 mm, more preferably between 0.2 and 0.8 mm and in particular between 0.3 and 0.7 mm, wherein the proportion by weight of the particles having a particle size below 0 , 1 mm preferably at least 4% by weight, particularly preferably at least 6% by weight and in particular at least 8% by weight, but at the same time preferably at most 80% by weight, particularly preferably at most 60% by weight and in particular not more than 40% by weight.
  • enzymes or other ingredients, in particular sensitive can also be formulated in the manner described above.
  • a cleaning agent according to the invention in particular a hard surface cleaner according to the invention, may also contain one or more propellants (INCI propellants), usually in an amount of 1 to 80% by weight, preferably 1.5 to 30% by weight, in particular 2 to 10 Wt .-%, particularly preferably 2.5 to 8 wt .-%, most preferably 3 to 6 wt.%, Contain.
  • ICI propellants usually in an amount of 1 to 80% by weight, preferably 1.5 to 30% by weight, in particular 2 to 10 Wt .-%, particularly preferably 2.5 to 8 wt .-%, most preferably 3 to 6 wt.%, Contain.
  • a separate subject of the invention are processes for the cleaning of textiles or of hard surfaces, in which at least in one of the process steps an inventive siderophore-metal complex is used.
  • a separate subject of the invention is the use of siderophore-metal complexes according to the invention for cleaning textiles or hard surfaces.
  • 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 (pressurized gas containers, 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 more detailed in the WO 96/04940 (Procter & Gamble) and the US patents cited therein to Sprühspendern, to which all reference is made in this regard and the contents of which are hereby incorporated into this application described.
  • Trigger spray dispensers and pump sprayers have opposite.
  • Compressed gas containers have 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.
  • compositions 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.
  • 0.025 mmol (based on the metal atom) of the metal salt to be tested is stirred in 25 mL of deionized water with 0.050 mmol desferrioxamine E (DFE) 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 desferrioxamine E is prepared in the same way, but not mixed with metal salt.
  • DFE desferrioxamine E
  • Table 1 Pipetting scheme: null uncatalyzed bleaching Complex-catalyzed tea solution 400 ⁇ L 400 ⁇ L 400 ⁇ L borate buffer 100 ⁇ L 100 ⁇ L 100 ⁇ L deionized water 500 ⁇ L 400 ⁇ L 300 ⁇ L H 2 O 2 solution 0 ⁇ L 100 ⁇ L 100 ⁇ L Siderophore metal complex solution 0 ⁇ L 0 ⁇ L 100 ⁇ L
  • 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.
  • Example 3 Bleaching of tea and blueberry stains on fabrics by Mn-DFE and Mn-schizokines
  • Example 1 With the Mn-desferrioxamine complex according to Example 1, the bleaching effect on tea and blueberry stains on cotton fabric was examined and compared with a Mn-schizokine complex. For this purpose, mini-wash tests were carried out and then performed a quantitative digital optical evaluation.
  • the L * value, minus that of the uncatalyzed bleach, is a measure of the bleaching performance and indicates how much the tested metal complex promotes hydrogen peroxide bleaching.
  • Table 6 Results of the mini-wash test for the blueberry stains sample L * ⁇ E to zero value ⁇ E uncatalyzed bleach null 75.35 0.00 without metal complex (uncatalyzed) 84.73 9.38 0 MnCl 2 with desferrioxamine E 86.57 11.22 1.84 MnCl 2 with schizokines 87.11 11.75 2.37 sample L * ⁇ E to zero value ⁇ E uncatalyzed bleach null 72,99 0.00 without metal complex (uncatalyzed) 78.42 5.43 0.00 MnCl 2 with desferrioxamine E 80.66 80.66 2.24 MnCl 2 with schizokines 80.98 80.98 2.56
  • the schizokinen-manganese complex as well as the desferrioxamine-E-manganese complex significantly improves the bleaching performance of hydrogen peroxide in terms of blueberry soiling as well as tea soiling, although at 30 ° C a rather low washing temperature was chosen.
  • schizokinen is a bis-hydroxamate-alpha-hydroxycarboxylate siderophore.
  • Example 4 Checking the Washing Performance of Mn-DFE Compared to TAED
  • the catalyst was incorporated into a commercially available powdered detergent with soluble builder (sodium percarbonate).
  • soluble builder sodium percarbonate
  • 2.7% by weight of TAED were used as catalyst in comparison with Mn-DFE complexes each containing 5 mg, 10 mg or 20 mg of Mn ions.
  • the washing tests were carried out in a Miele W 918 washing machine at 20 ° C. and 30 ° C., 16 ° dH (German hardness), pH 10.5. It was washed for 60 minutes in the main wash and the washing was repeated five times each.
  • Table 8 Wash results at 30 ° C soiling tissue TAED Mn-DFE (10 mg Mn) Mn-DFE (20 mg Mn) LSD C-02 Olive oil / carbon black Co 31.2 33.3 34.3 1.9 BC-2 coffee Co 63.3 64.5 64.7 0.9 BC-3 tea Co 62.7 66.3 67.2 2.2 CS-12 schw. Johannisb. Co 65.9 70.6 70.5 2.2 CS-13 Apple juice Co 84.4 85.6 85.7 0.7 CS-103 Red wine, not aged Co 70.8 74.2 73.1 2.2 CS-44 chocolate drink Co 48.5 53.4 55.4 3.1 C-10 Pigmen eau nut oil / high milk concentrate.
  • the Mn-DFE has an at least somewhat better cleaning performance on all soilings tested at 20 ° C as well as at 30 ° C, and even a significantly better cleaning performance on some soils than the TAED, which causes similarly low fiber damage the Mn-DFE.
  • the cleaning performance is as expected at 20 ° C lower than at 30 ° C, the decrease in cleaning performance is relatively low.
  • Mn-DFE also causes a significant bleaching effect with atmospheric oxygen as the sole source of oxygen, in contrast to the prior art Mn-containing catalysts used for comparison.
  • a commercial pulverulent detergent formulation containing percarbonate as a bleaching agent and Mn-DFE as a bleach catalyst was tested for bactericidal activity in the quantitative suspension test.
  • 5.88 g of the detergent formulation with 7 mg of Mn-DFE were dissolved in 900 ml of distilled water and 9 mL of the solution thus obtained was used in the test and a test microbial suspension (s.u.) was added. After 40 minutes exposure time at 30 ° C, the remaining bleach was just completely deactivated with sodium thiosulfate solution and then determined the viable count.
  • the suspension test was carried out in accordance with DIN EN 1040 (dilution neutralization method). The efficacy statement regarding the reduction of living bacteria is given as the reduction rate in orders of magnitude.

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Claims (11)

  1. Agent de lavage ou de nettoyage, caractérisé en ce qu'il contient agents tensioactifs et un sidérophore.
  2. Agent de lavage ou de nettoyage selon la revendication 1, caractérisé en ce que le sidérophore est présent sous la forme d'un complexe sidérophore-métal.
  3. Agent de lavage ou de nettoyage selon la revendication 1 ou 2, caractérisé en ce qu'il s'agit, en ce qui concerne le sidérophore, d'un composé qui contient au moins deux résidus choisis parmi le groupe constitué par un hydroxamate, un catécholate, un α-hydroxycarboxylate, un α-céto-carboxylate, un phénolate, un amide d'acide carboxylique, un citrathydroxamate, ainsi qu'un oxazole ou un thiazole facultativement hydrogéné en partie ou complètement.
  4. Agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'il s'agit, en ce qui concerne le sidérophore, d'un sidérophore existant naturellement choisi parmi le groupe constitué par des sidéromycines, des sidérochromes et des sidéramines.
  5. Agent de lavage ou de nettoyage selon la revendication 4, caractérisé en ce que le sidérophore existant naturellement est choisi parmi le groupe constitué par les desferrichromes, les tétraglycyldesferrichromes, la desferricrocine, la desferrichrysine, la desferrirhodine, l'hexahydrodesferrirhodine, la desferrirubine, le desferricoprogène, le desferrinéocoprogène I, le desferrinéocoprogène II, les exochélines, le fusigène (la fusarinine C), la nocardamine, la desferrisalmycine, les desferrialbomycines, les desferrioxamines, les desferrimycines, les pyoverdines, les mycobactines, l'aérobactine, l'arthrobactine, l'acinétoferrine, les aquachélines, les ornibactines, les nannochélines, les schizokines, l'acide rhodotorulique, les marinobactines, l'azotobactine D, les pseudobactines, l'acinétobactine, la pseudobactine, la putrébactine, l'achromobactine, la rhizoferrine, les altérobactines, l'agrobactine, l'entérobactine (l'enterochéline), la fluvibactine, l'homofluvibactine, la bacillibactine (la corynebactine), la pétrobactine, la salmochéline, l'azotochéline, les myxochélines, la chrysobactine, la yersiniabactine, la ferrithiocine, la pyochéline A, la vulnibactine, la daunorubicine, la succinimycine, la rifamycine, le trencam, la pseudomonine, la corrugatine, le gallichrome, le fusigène, les desferristaphyloferrines, la desferrivibrioferrine, la desferrimaduraferrine, les fusarines, l'acide dimérumique, l'acide muginéique, la coelichéline, le WCS, la méthanobactine, la gonobactine, les amonabactines, les amphibactines, les rhizobactines, la ruckerbactine, l'anguibactine, la brucébactine, la carboxymycobactine, l'érythrobactine, la cépabactine, la méningobactine, la chrysobactine, la quinolobactine, la thioquinolobactine, la vibriobactine, la vanchrobactine, la parabactine et la bacillibactine.
  6. Agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il s'agit, en ce qui concerne le métal des complexes sidérophore-métal, d'un élément choisi parmi Ag, Al, Au, B, Bi, Ce, Co, Cr, Cu, Eu, Fe, Ga, Hg, Mn, Mo, Ni, Pb, Pt, Ru, Ti, U, V, W, Zn et Zr dans n'importe quel degré d'oxydation.
  7. Agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le complexe sidérophore-métal est choisi parmi des complexes de sidérophores comprenant au moins trois groupes hydroxamate, en particulier de desferrioxamines, de desferrichromes et de coprogène, de manière spécifique de la desferrioxamine E, avec des ions métalliques du Mn, Fe, Co, Ce, Cr, Zn, Cu, Mo, V, W et Bi ; des complexes de sidérophores comprenant au moins deux groupes hydroxamate et au moins un groupe catécholate, en particulier de la pyoverdine Pa, avec des ions métalliques du Mn, Fe, Co, Ce, Zn, Cu, Mo, V et Bi ; des complexes de sidérophores comprenant au moins deux groupes hydroxamate et au moins un groupe α-hydroxy-carboxylate, en particulier de l'ornibactine, de l'arthrobactine et de la schizokinène, avec des ions métalliques du Mn, Fe, Co, Ce, Cr, Zn, Cu, Mo, V, W et Bi ; des complexes de sidérophores comprenant au moins deux groupes hydroxamate et au moins un groupe d'amide d'acide carboxylique, en particulier de l'acide rhodotorulique, avec des ions métalliques du Mn, Fe, Co, Ce, Cr, Zn, Cu, Mo, V, W et Bi ; des complexes de sidérophores comprenant au moins trois noyaux thiazole partiellement hydrogénés, en particulier de la yersiniabactine, avec des ions métalliques du Mn, Fe, Co, Ce, Cr, Zn, Cu, Mo, V et Bi ; des complexes de sidérophores comprenant au moins deux groupes α-hydroxycarboxylate, au moins deux groupes d'amide d'acide carboxylique et au moins deux groupes carboxylate supplémentaires, en particulier de la rhizoferrine, avec des ions métalliques du Mn, Fe, Co, Ce, Zn, Cu, Mo, V, W et Bi ; des complexes de sidérophores comprenant au moins trois groupes catécholate, en particulier de l'entérobactine, avec des ions métalliques du Mn, Fe, Co, Ce, Cu, V et Bi.
  8. Utilisation d'agents de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 7 pour le nettoyage de produits plats textiles.
  9. Utilisation d'agents de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 7 pour le nettoyage de surfaces dures.
  10. Utilisation de sidérophores dans des agents de lavage ou de nettoyage, qui contiennent agents tensioactifs.
  11. Utilisation selon la revendication 10, caractérisée en ce que le sidérophore est présent sous la forme d'un complexe sidérophore-métal.
EP08716923.1A 2007-02-20 2008-02-19 Complexes métalliques sidérophores utilisés comme catalyseurs de blanchiment Not-in-force EP2129762B2 (fr)

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EP2129762B1 (fr) 2012-06-27
ES2387518T3 (es) 2012-09-25
PL2129762T3 (pl) 2012-11-30
PL2129762T5 (pl) 2016-05-31
EP2129762A1 (fr) 2009-12-09
ES2387518T5 (es) 2015-11-19
DE102007008655A1 (de) 2008-08-21

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