EP2673349B1 - Utilisation de complexes de métaux de transition en tant que catalyseurs de blanchiment dans des produits détergents et nettoyants - Google Patents

Utilisation de complexes de métaux de transition en tant que catalyseurs de blanchiment dans des produits détergents et nettoyants Download PDF

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Publication number
EP2673349B1
EP2673349B1 EP20120702767 EP12702767A EP2673349B1 EP 2673349 B1 EP2673349 B1 EP 2673349B1 EP 20120702767 EP20120702767 EP 20120702767 EP 12702767 A EP12702767 A EP 12702767A EP 2673349 B1 EP2673349 B1 EP 2673349B1
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Prior art keywords
washing
cleaning composition
complexes
acid
weight
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EP2673349A1 (fr
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Gerd Reinhardt
Werner Janitschek
Miriam Ladwig
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Weylchem Switzerland AG
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Weylchem Switzerland AG
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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
    • C11D3/395—Bleaching agents
    • C11D3/3951—Bleaching agents combined with specific additives
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/391—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—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
    • 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
    • C11D3/43—Solvents
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen

Definitions

  • the present invention relates to the use of transition metal complexes which, in addition to a tetraoxylene unit, contain two macrocyclic, N-containing ligands, in particular cyclic or cyclam ligands, for bleaching colored stains on textiles as well as on hard surfaces.
  • the invention also relates to detergents and cleaners containing such complex compounds.
  • Inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles.
  • N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacetylglycoluril, N-acylated caprolactams such as benzoylcaprolactam, acetylcaprolactam or Nonanoylcaprolactam, hydantoins, hydrazides, triazoles, hydrotriazines, urazoles , Diketopiperazines, sulfururamides and cyanurates, as well as carboxylic anhydrides, in particular phthalic anhydride and substituted maleic anhydrides, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate (NOBS), sodium isononanoyloxy-benzenesulfonate (ISONOBS), sodium nonanoyloxy-benzenesulfonate (NOBS), sodium isononanoyloxy-benzenesulfonate (ISONOBS)
  • transition metal salts and their complex compounds as described, for example, in US Pat EP 0 237 111 .
  • EP 0 392 592 or EP 0 443 651 are described.
  • WO 97/07191 Complexes of manganese, iron, cobalt, ruthenium and malenbdenum with salen-type ligands have been proposed as catalysts for peroxygen compounds in hard surface cleaning solutions.
  • Transition-metal complexes with rigid ligands in particular rigidly bridged N-containing macrocycles having at least 3 donor atoms, 2 of which form a bridgehead, are described in detail in US Pat WO 1998/039335 and WO 1998/039098 described as oxidation catalysts.
  • the ligands are 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane (Bcyclam) and 5-N-octyl-12-methyl-1,5,8,12- tetraaza-bicyclo [6.6.2] hexadecane.
  • WO 2001/048298 corresponding bridged ligands for bleaching with atmospheric oxygen are described.
  • Similar metal complexes based on unbridged macrocyclic ligands are proposed in WO 2000/012808 claimed as "aerial whitening systems" for use in detergents and cleaners.
  • Metal complexes containing one or more dioxolene or tetraoxolene units are interesting systems because the ligands are "non-innocent” ligands that can change their oxidation state in redox reactions.
  • dioxole unit usually (substituted) catecholates or semichinones are used.
  • Bioinorganic aspects of "non-innocent” ligands are e.g. In W. Kaim and B. Schwerderski, "Non-innocent ligands in bioinorganic chemistry", Coordination Chemistry Reviews, 254 (2010), 1580-1588 described.
  • Tetraoxolene complexes with a tetraoxolate unit between two transition metals and their redox chemistry are z.
  • JS Miller and KS Min “Oxidation Leads to Reduction - Redox-Induced Electron Transfer (RIET),” Angew. Chem. 121 (2009), 268-278 or Ch. Carbonera et al., "Thermally and Light-Induced Valence-Tautomeric Transition in Dinuclear Cobalt-Tetraoxolene Complex", Angew. Chem. Int. Ed., 43 (2004), 3136-3138 described.
  • transition metal complexes containing catecholate, semiquinone or tetraoxolene ligands can be used in detergents and cleaning agents and have clear advantages in terms of bleaching ability on colored stains. They can be used either in detergents and cleaners which contain hydrogen peroxide and other peroxy compounds (eg peroxycarboxylic acids), but also in those which are free of oxidizing agents.
  • Object of the present invention was to improve the oxidation and bleaching action of detergents and cleaners at particularly low temperatures below 60 ° C, in particular in the temperature range of 20 ° C to 45 ° C to achieve.
  • radicals R and R 1 to R 4 are preferably hydrogen or methyl groups, alkylaryl radicals containing 6 to 16 C atoms in the alkyl part, phenyl being preferred as aryl.
  • radicals R5 are preferably hydrogen or chlorine.
  • complexes according to the invention of the unsubstituted or tetrasubstituted cyclams or cyclenes of the formula (I) particular preference is given to complexes having 2 alkyl or alkaryl radicals on the tetraazacycle having the general structures (V), (VI) and the bridged cyclams (VII): wherein R4 and R4 independently represent a methyl, ethyl, propyl, butyl or benzyl group.
  • Especially preferred according to the invention are complexes with the following ligands: 1,8-dimethylcyclam, 1,7-dimethylcycles, 1,8-diethylcyclam, 1,7-diethylcycles, 1,8-dibenzylcyclam and 1,7-dibenzylcycles.
  • the ligands (V) and (VI) can be prepared according to J. Kotter et al., Collect. Czech. Chem. Commun., 2000, 65, 243-266 , or R. Tripier et al., Chem. Commun., 2001, 2728-2729 , Syntheses of ligands of formula (VII) are z. In WO 1998/039335 and WO 1998/039098 described.
  • transition metal complexes of the formula (I) are used in detergents and cleaners, in particular in textile washing and in hard-surface cleaners, then especially for dishes, and in solutions for bleaching colored stains. This is done firstly in the presence of hydrogen peroxide, hydrogen peroxide-releasing compounds or a peroxygen compound. It was surprising that the complexes can also be used without a peroxo compound or z. B. be activated by the oxygen in the air.
  • peroxygen compounds or atmospheric oxygen come into question.
  • the peroxygen compounds used are primarily hydrogen peroxide, alkali perborate mono- or tetrahydrate and / or alkali metal percarbonate, with sodium being the preferred alkali metal.
  • alkali metal or ammonium peroxosulphates such as.
  • potassium peroxomonosulfate technically: Caroat ® or Oxone ®
  • concentration of the inorganic oxidizing agents on the total formulation of detergents and cleaners is 2 to 90%, preferably 3 to 60%, particularly preferably 5 to 25%.
  • peroxygen compounds are organic-based oxidants. These include all known peroxycarboxylic acids, eg. Monoperoxyphthalic acid, peracetic acid, dodecanediperoxyacid, phthalimidoperoxycarboxylic acids such as PAP and related systems or amido peracids.
  • peroxycarboxylic acids eg. Monoperoxyphthalic acid, peracetic acid, dodecanediperoxyacid, phthalimidoperoxycarboxylic acids such as PAP and related systems or amido peracids.
  • the amounts of peroxygen compounds used are generally selected so that between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen, are present in the solutions of the detergents and cleaners. Also the amount used Bleach-enhancing complex compound depends on the application. Depending on the desired degree of activation, it is used in an amount of 0.01 mmol to 25 mmol, preferably 0.1 mmol to 2 mmol complex per mole of peroxygen compound. However, these limits can also be exceeded or fallen short of in special cases.
  • detergents and cleaners are preferably 0.0025 to 1 wt .-%, in particular 0.01 to 0.5 wt .-%, of the above-defined bleach-enhancing complex compound.
  • bleach catalysts or bleach activators can advantageously be used in combination in order to widen the spectrum of action of the bleaching systems used according to the invention and to increase the efficiency, in particular with regard to the germicidal effect (disinfection).
  • bleach activators that is to say compounds which release peroxycarboxylic acids under perhydrolysis conditions.
  • Suitable are the usual bleach activators containing O- and / or N-acyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenedianim (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives-in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates , in particular nonanoyl, isononanoyl or lauroylbenzenesulfonate (NOBS, ISONOBS or LOBS) or their amido derivatives (eg NACAOBS), acylated hydroxycarboxylic acids such as acetylsalicylic acid or nonanoyloxybenzoic acid (NOBA) and decanoyloxybenzoic acid (DOBA), acylated polyhydric alcohols, in particular triacetin, Ethylene glycol, te
  • bleach activators in the overall formulation of detergents and cleaners is 0.1 to 20 wt .-%, preferably 0.5 to 10 wt .-%, particularly preferably 1 to 6 wt .-%, each based on the total weight.
  • the term bleaching encompasses both the bleaching of dirt located on the textile surface and the bleaching of dirt located in the wash liquor and detached from the textile surface.
  • Further potential applications can be found in the personal care field z.
  • the described metal complexes find use in commercial laundries, in wood and paper bleaching, bleaching of cotton and in disinfectants.
  • the invention relates to a process for the purification of textiles as well as hard surfaces, in particular crockery, using said complex compounds together with peroxygen compounds in aqueous, optionally further detergent or cleaning agent components containing solution.
  • the invention also relates to detergents and hard surface cleaners, in particular to dishwashing detergents, such being preferred for use in machine processes containing such complex compounds.
  • the use according to the invention essentially consists of providing conditions for colored surfaces contaminated with colored soiling or, in the case of soiled textiles, among them peroxidic oxidizing agent and the complex compound can react with each other, with the aim of obtaining more oxidizing secondary products. Such conditions are especially present when the reactants meet in aqueous solution.
  • This can be done by separately adding the peroxygen compound and the complex to the aqueous solution of the detergent and cleaner.
  • the process according to the invention is particularly advantageously carried out using a detergent or hard surface cleaning agent which contains the complex compound and optionally a peroxygen-containing oxidizing agent.
  • the peroxygen compound may also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, when a non-oxygen detergent or cleaner is used.
  • the washing and cleaning agents which may be in the form of granules, powdery or tablet-like solids, other shaped bodies, homogeneous solutions or suspensions, may contain, in principle, all known ingredients customary in such agents, as well as the said bleach-enhancing metal complex.
  • the compositions may contain, in particular, builder substances, surface-active surfactants, peroxygen compounds, additional peroxygen activators or organic peracids, water-miscible organic solvents, sequestering agents, enzymes, and special additives with color- or fiber-sparing action.
  • Other auxiliaries such as electrolytes, pH regulators, silver corrosion inhibitors, foam regulators, as well as dyes and fragrances are possible.
  • a hard surface cleaning agent according to the invention may contain abrasive constituents, in particular quartz flours, wood flours, plastic flours, chalks and glass microspheres, and mixtures thereof.
  • Abrasives are preferably not more than 20 wt .-%, in particular from 5 to 15 wt .-%, contained in the cleaning agents.
  • the detergents and cleaners may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • surfactants are present in detergent compositions according to the invention in proportions of preferably from 1 to 50% by weight, in particular from 3 to 30% by weight, whereas in hard-surface cleaners normally lower proportions, ie. H. Amounts up to 20 wt .-%, in particular up to 10 wt .-% and preferably in the range of 0.5 to 5 wt .-%, are included.
  • Dishwashing detergents typically use low-foam compounds.
  • Anionic surfactants which are suitable according to the invention are in particular soaps and those which contain sulfate or sulfonate groups.
  • surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, olefinsulfonates, that is mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those of monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12 -C 18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of alpha-sulfo fatty acids for example the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by sulfonating the methyl esters of fatty acids of vegetable and / or animal origin having 8 to 20 carbon atoms be prepared in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts.
  • alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 8 -C 20 -oxo alcohols and those half esters of secondary alcohols this chain length is preferred.
  • alk (en) ylsulfates of said chain length which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis.
  • 2,3-alkyl sulfates are also suitable anionic surfactants.
  • sulfuric acid monoesters of straight-chain or branched alcohols ethoxylated with from 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 -alcohols containing on average 3.5 mol of ethylene oxide (EO) or C 12 -C 18 -fatty alcohols with 1 up to 4 EO.
  • the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably with fatty alcohols and in particular with ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 -C 18 fatty alcohol residues or mixtures of these.
  • Suitable further anionic surfactants according to the invention are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosinate).
  • anionic surfactants are in particular soaps, for example in amounts of 0.2 to 5 wt .-%, into consideration.
  • Particularly suitable in the context are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Anionic surfactants are preferably present in detergents according to the invention in amounts of from 0.5 to 10% by weight and in particular in amounts of from 5 to 25% by weight.
  • the nonionic surfactants used are preferably alkoxylated, preferably ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohols with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7 EO.
  • the degrees of ethoxylation given above represent statistical averages which may be an integer or a fractional number for a particular product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms, and G represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number which, as the size to be determined analytically, can also be fractions, between 1 and 10; preferably x is 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (VIII) in the radical R 1 CO is an aliphatic acyl radical having 6 to 22 carbon atoms
  • R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 Hydroxyl groups.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (IX) in R 3 is a linear or branched alkyl or alkenyl radical having 7 to 21 carbon atoms, R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 6 to 8 carbon atoms and R 5 is a linear, branched or cyclic alkyl radical or an aryl radical or a Oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1 -C 4 alkyl or phenyl radicals are preferred, and Z is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.
  • R 3 is a linear or branched alkyl or alkenyl radical having 7 to 21 carbon atoms
  • R 4 is a linear, branched or cyclic alkylene radical or an
  • Z is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-allyloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide and of the fatty acid alkanolamide type may also be suitable according to the invention.
  • hydroxyalkyl quats of the general structures (X) and (XI) are preferred.
  • surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called “spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides. Other surfactant types may have dendrimeric structures.
  • a detergent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates and polymeric alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • the water-insoluble, water-dispersible inorganic builder materials used are, in particular, crystalline or amorphous alkali aluminosilicates, in amounts of up to 50% by weight.
  • the detergent grade crystalline sodium aluminosilicates especially zeolite A, P and optionally X, alone or in mixtures, for example in the form of a cocrystal of zeolites A and X.
  • Their calcium binding capacity is usually in the range of 100 to 200 mg CaO per gram.
  • Suitable builder substances are also crystalline alkali metal silicates, which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates with a molar ratio of Na 2 O: SiO, of 1: 2 to 1: 2.8.
  • Such silicates can be prepared by the process of European patent application EP 0 425 427 getting produced.
  • the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na 2 Si x O used 2x + 1 ⁇ y H 2 O in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Crystalline layered silicates which fall under this general formula are described, for example, in the European patent application EP 0 164 514 described.
  • preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates are preferred, whereby ⁇ -sodium disilicate can be obtained, for example, by the process described in US Pat WO 91/08171 is described.
  • ⁇ -Sodium silicates with a modulus between 1.9 and 3.2 can according to Japanese Patent Applications JP 04/238 809 or JP 04/260 610 getting produced.
  • Also prepared from amorphous silicates practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used.
  • Crystalline sodium silicates with a modulus in the range 1.9 to 3.5 are used in another preferred embodiment.
  • a preferred embodiment is a granular compound of alkali metal silicate and alkali metal as it is available, for example under the name Nabion ® commercially. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1.
  • the weight ratio is from amorphous alkali metal silicate to crystalline alkali metal silicate, preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • Such builder substances are preferably present in detergents and cleaners according to the invention in amounts of up to a maximum of 60% by weight, preferably in the range of from 5 to 40% by weight, based on the total weight of the washing and cleaning agent.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid.
  • Polyphosphonic acids especially aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid can also be used.
  • polymeric (poly) carboxylic acids in particular the polycarboxylates of the international patent application which are obtainable by oxidation of polysaccharides or dextrins WO 93/16110 or the international patent application WO 92/18542 or the European patent specification EP 0 232 202 , polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small amounts of polymerizable substances copolymerized without carboxylic acid functionality.
  • the average molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200 000, that of the copolymers between 2000 and 200 000, preferably between 50 000 to 120 000, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has an average molecular weight of 50,000 to 100,000.
  • Commercial products are, for example Sokalan ® CP 5, CP 10 and PA 30 from BASF.
  • copolymers of acrylic acid or methacrylic acid with vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid, preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) acrylic acid, wherein the second acidic monomer or its salt Derivative of a C 4 -C 8 dicarboxylic acid, maleic acid is particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position with an alkyl or aryl radical.
  • Such polymers can be prepared in particular by methods described in the German patents DE 42 21 381 and DE 43 00 772 are generally described, and generally have a molecular weight between 1000 and 200,000. Further preferred Copolymers are those described in German patent applications DE 43 03 320 and DE 44 17 734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
  • the organic builder substances can, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 wt .-% aqueous solutions are used. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1 to 8% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular water-containing agents.
  • Suitable water-soluble builder components in hard surface cleaners according to the invention are in principle all builders customarily used in detergents for dishwashing, for example the abovementioned alkali metal phosphates. Their amounts may be in the range of up to about 60 wt .-%, in particular 5 to 20 wt .-%, based on the total mean.
  • water-soluble builder components in addition to polyphosphonates and phosphonate alkyl carboxylates, are, for example, organic polymers of the above-mentioned type of polycarboxylates, which act as co-builders, especially in hard water regions, and naturally occurring hydroxycarboxylic acids, such as mono-, dihydroxysuccinic acid, alpha- Hydroxypropionic acid and gluconic acid.
  • Preferred organic builder components include the salts of citric acid, especially sodium citrate.
  • sodium citrate anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • Detergents adjusted pH value can also be present corresponding to the said co-builder salts acids.
  • enzymes include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example proteases such as BLAP ®, Optimase ®, Opticlean ®, Maxacal ®, Maxapem ®, Durazym ®, Purafect ® OxP, Esperase ® and / or Savinase ®, amylases as Termamy ®, amylase LT, Maxamyl ®, Duramyl ®, Purafectel OxAm, cellulases as Celluzyme ®, Carezyme ®, K-AC ® and / or from the international patent applications WO 96/34108 and WO 96/34092 known cellulases and / or lipases such as Lipolase ®, Lipomax ®, Lumafast ® and / or Lipozym ®.
  • proteases such as BLAP ®, Optimase ®
  • the enzymes used can, for example, in the international patent applications WO 92/111347 or WO 94/23005 be adsorbed to carriers and / or embedded in encapsulating substances to protect against premature inactivation. They are preferably present in detergents and cleaners according to the invention in amounts of up to 10% by weight, in particular from 0.05 to 5% by weight, enzymes which are particularly preferably stabilized against oxidative degradation being used.
  • Machine dishwashing detergents according to the invention preferably comprise the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates may be present in amounts of up to 40% by weight, in particular 3 to 30 wt .-%, based on the total agent to be included.
  • the alkali carrier system used most preferably in cleaning agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which may be present in an amount of up to 50% by weight, preferably 5 to 40% by weight.
  • a further subject of the invention is a means for mechanically cleaning dishes containing 15 to 65% by weight, in particular 20 to 60% by weight.
  • water-soluble Builderkompenente 5 to 25 wt .-%, in particular 8 to 17 wt .-%.
  • Oxygen-based bleaching agent in each case based on the total agent, and 0.1 to 1 wt .-% of one or more of the metal complexes defined above.
  • Such an agent is preferably lower alkyl, ie its solution has a pH of 8 to 11.5, especially 9 to 11.
  • inventive means for the automatic cleaning of dishes are 20 to 60 wt .-% of water-soluble organic builder, in particular alkali citrate, 3 to 20 wt .-% alkali carbonate and 3 to 40 wt .-% Alkalidisilikat included.
  • silver corrosion inhibitors can be used in dishwashing detergents according to the invention.
  • Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, molybdenum, vanadium or cerium salts and / or complexes, as well as Salts and / or complexes of the metals present in the complexes suitable according to the invention with other than in formula (I) predetermined ligands.
  • the agents foam too much during use, they may still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-regulating compound, preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettklareamide and mixtures thereof and other other known commercially available foam inhibitors are added.
  • a foam-regulating compound preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettklareamide and mixtures thereof and other other known commercially available foam inhibitors are added.
  • the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
  • Further optional ingredients in the compositions according to the invention are, for example, perfume oils.
  • organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compounds ethers.
  • Such water-miscible solvents are present in the cleaning agents according to the invention in amounts of preferably not more than 20% by weight, in particular from 1 to 15% by weight.
  • the compositions according to the invention may contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides.
  • system- and environmentally compatible acids in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid
  • mineral acids in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides.
  • pH regulators are present in the compositions according to the invention in amounts of preferably not more than 10% by weight, in particular from 0.5 to 6% by weight.
  • compositions according to the invention are present as pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the like Bleaching catalyst are expected to be produced.
  • Solutions according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / l can also be achieved by using the builder components with at least a proportion of liquid mixture components in a first process stage while increasing the bulk density of this premix and subsequently - if desired after an intermediate drying - the other constituents of the agent, including the bleach catalyst, combined with the thus obtained premix.
  • a tablet thus produced has a weight of 1 to 40 g, in particular from 5 to 30 g, with a diameter of 3 to 40 mm, preferably from 5 to 35 mm.
  • the complexes according to the invention are preferably used as aqueous solution or in microencapsulated form. If they are used for the purpose of using atmospheric oxygen (aerial bleaching), the use of peroxo compounds can be dispensed with. become. However, if they are to be used in combination with a peroxo compound, e.g. B. hydrogen peroxide are used, the use of a multi-chamber container is recommended.
  • a peroxo compound e.g. B. hydrogen peroxide are used, the use of a multi-chamber container is recommended.
  • Catalyst 1 (diethyl-cyclam) 2 Mn 2 (DHBQ) (PF 6 ) 2
  • Example 2 The procedure is analogous to Example 1 and initially prepared from 1,8-dimethyl-1,4,8,11-tetraazacyclotetradecane and manganese dichloride 1,8-dimethyl-1,4,8,11-tetraazacyclotetradecan manganese (II) dichloride. This is then mixed with 2,5-dihydroxy-1,4-benzoquinone (DHBQ) and sodium hydroxide solution and precipitated with KPF 6 . It is taken up in methyl chloride, filtered off formed brownstone and the concentrate recrystallized from methanol. Yield: 62% blue-violet fine crystals.
  • DVBQ 2,5-dihydroxy-1,4-benzoquinone
  • Catalyst 3 was analog A.
  • the et al. "Tetraoxylenes Radical Stabilization by Interaction with Transition Metal Ion", Inorg. Chem., 30 (1991), 2590 from d, l-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (CHT), manganese dichloride, 2,5-dihydroxy-1,4-benzoquinone (DHBQ) and KPF 6 produced. Yield after primary crystallization 65%.
  • Catalyst 4 (diethyl-Bcyclam) 2 Mn 2 (DHBQ) (PF 6 ) 2
  • diethyl-Bcyclam For the preparation of 5,12-diethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane (diethyl-Bcyclam) was prepared according to WO 1998/039 098 method, however, carried out the quaternization with diethyl sulfate instead of methyl iodide. The ligand was then reacted with managandichloride in dimethylactetamide to (diethyl-Bcyclam) MnCl 2 .
  • the bleach-increasing performance of the compounds of the invention Cat 1 and Cat 4 was tested in comparison to sodium percarbonate.
  • 10 mg / l Cat 1 or Cat 4 were dissolved in a wash liquor prepared by dissolving 2 g / l of a bleach-free basic detergent (IEC-A, WFK, Krefeld).
  • a bleach-free basic detergent IEC-A, WFK, Krefeld.
  • the washing tests were carried out in a Linitest apparatus (Heraeus) at a temperature of 40.degree. The washing time was 30 min, water hardness 18 ° dH.
  • the bleaching performance of the compounds of the invention Cat 1 and Cat 4 was tested without the addition of peroxides.
  • 10 mg / l Cat 1 or Cat 4 were dissolved in a wash liquor prepared by dissolving 2 g / l of a bleach-free basic detergent (IEC-A, WFK, Krefeld).
  • the washing tests were carried out in a Linitest apparatus (Heraeus) at a temperature of 40 ° C. The washing time was 30 min, water hardness 18 ° dH. After washing, the fabric was dried and ironed.
  • Curry on cotton (BC-34, CFT) ketchup on cotton (10-T, WFK, Krefeld), tomato on cotton (CS-20, CFT) served as bleaching test cloth.

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Claims (15)

  1. Utilisation de complexes de métaux de transition, qui contiennent, outre une unité tétraoxalène, deux ligands contenant de l'azote macrocycliques, en particulier des ligands cyclènes ou cyclams, en tant que catalyseurs de blanchiment dans des produits nettoyants et détergents destinés à des matières textiles ou à des surfaces solides, caractérisée en ce que les complexes de métaux de transition employés présentent la formule chimique générale (I)

            [(L)M(Y)M(L)] Xm      (I)

    où
    M représente un atome métallique parmi le groupe constitué de Mn et Fe,
    L représente un ligand présentant la formule générale (II) ou (III)
    Figure imgb0015
     où
    R représente un hydrogène ou un alcoyle contenant de 1 à 8 atomes de carbone,
    R1, R2, R3 et R4 sont identiques ou différents et représentent un hydrogène, un alcoyle contenant de 1 à 8 atomes de carbone, une unité alcoyle contenant de 2 à 4 atomes de carbone avec un pont azote ou un alcaryle contenant de 6 à 16 atomes de carbone,
    n est un entier compris entre 0 et 6,
    Y est un groupement présentant la formule (IV)
    Figure imgb0016
     où
    R5 sont des groupements identiques ou différents et représentent un hydrogène, un alcoyle contenant de 1 à 4 atomes de carbone, Cl ou Br,
    X représente un ligand neutre ou anionique sélectionné parmi le groupe constitué de CH3CN, de chlorure, de bromure, de nitrate, de perchlorate, de sulfate, de citrate, d'hexafluorophosphate, de trifluorométhanesulfonate, de tétrafluoroborate, de tétraphénylborate, ou des acides organiques anioniques contenant de 1 à 22 atomes de carbone, ou H2O, et
    m est un entier compris entre 0 et 4.
  2. Utilisation selon la revendication 1, caractérisée en ce que les complexes avec des atomes centraux de métaux de transition avec des degrés d'oxydation de +2, +3 ou +4 sont employés, où les complexes avec du manganèse en tant qu'atome central sont préférés, et en ce que les groupements R et R1 à R4 sont de préférence un hydrogène ou un groupement méthyle ou un groupement alcoylaryle contenant de 6 à 16 atomes de carbone dans la partie alcoyle, où en tant qu'aryle, le phényle est préféré.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que, dans le groupement à pont métallique de la formule (IV), les groupements R5 représentent un hydrogène ou un chlore.
  4. Utilisation selon une des revendications 1 à 3, caractérisée en ce que les ligands L sont sélectionnés parmi le groupe constitué : du 1,4,7,10-tétraazacyclododécane (cyclène) ; du 1,7-diméthyl-1,4,7,10-tétraazacyclododécane ; du 1,4,8,11-tétraazacyclotétradécane (cyclam) ; du 1,4,8,11-tétraméthyl-1,4,8,11-tétraazacyclotétradécane ; du 5,7,7,12,14,14-hexaméthyl-1,4,8,11-tétraazacyclotétradécane ; du 1,8-diméthyl-1,4,8,11-tétraazacyclotétradécane ; du 1,8-diéthyl-1,4,8,11-tétraazacyclotétradécane (diéthylcyclam) ; du 5,12-diméthyl-1,5,8,12-tétraaza-bicyclo[6.6.2]hexadécane (diméthyl-Bcyclam), du 5,12-diéthyl-1,5,8,12-tétraaza-bicyclo[6.6.2]hexadécane (diéthyl-Bcyclam) et du 5-N-octyl-12-méthyl-1,5,8,12-tétraazabicyclo[6.6.2]hexadécane.
  5. Utilisation selon une des revendications 1 à 4, caractérisée en ce que, outre les complexes du cyclam ou du cyclène non substitué ou tétrasubstitué de la formule (I), des complexes contenant 2 groupements alcoyles ou alcaryles sur le cycle tétraaza présentant les structures générales (V), (VI) ainsi que le cyclam ponté (VII) présentant les formules chimiques générales suivantes sont utilisés :
    Figure imgb0017
     où R4 et R4 représentent indépendamment l'un de l'autre un groupement méthyle, éthyle, propyle, butyle ou benzyle.
  6. Utilisation selon une des revendications 1 à 5, caractérisée en ce que des complexes sont utilisés avec un ou plusieurs ligands sélectionnés parmi le groupe constitué : du 1,8-diméthylcyclam, du 1,7-diméthylcyclène, du 1,8-diéthylcyclam, du 1,7-diéthylcyclène, du 1,8-dibenzylcyclam et du 1,7-dibenzylcyclène.
  7. Produit nettoyant et détergent, destiné au lavage de matières textiles ou à des surfaces solides, de préférence destiné à de la vaisselle, et destiné à des solutions de blanchiment de salissures colorées, caractérisé en ce qu'il contient en tant que catalyseurs de blanchiment des complexes de métaux de transition selon une des revendications 1 à 6.
  8. Produit nettoyant et détergent selon la revendication 7, caractérisé en ce qu'il contient les complexes de métaux de transition selon une proportion allant de 0,0025 à 1 % en poids, de préférence allant de 0,01 à 0,5 % en poids.
  9. Produit nettoyant et détergent selon la revendication 7 ou 8, caractérisé en ce qu'il contient en plus d'autres agents d'activation de blanchiment, qui libèrent dans des conditions de perhydrolyse des acides peroxocarboniques, de préférence des agents d'activation de blanchiment, qui contiennent des groupements O-acyle et/ou N-acyle et qui sont sélectionnés parmi le groupe constitué : d'alcoylènediamines multi-acylées, en particulier la tétraacétyléthylènediamine (TAED), de glycoluriles acylés, en particulier le tétraacétylglycolurile (TAGU), de dérivés de triazine acylés, en particulier la 1,5-diacétyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), de phénylsulfonates acylés, en particulier le nonanoyloxybenzolsulfonate, l'isononanoyloxybenzolsulfonate ou le lauroyloxybenzolsulfonate (respectivement, NOBS, ISONOBS ou LOBS) ou leurs dérivés amido, d'acides hydroxycarboxyliques acylés tels que l'acide acétylsalicylique ou l'acide nonanoyloxybenzoïque (NOBA) et l'acide décanoyloxybenzoïque (DOBA), d'alcools multivalents acylés, en particulier la triacétine, l'éthylèneglycoldiacétate et le 2,5-diacétoxy-2,5-dihydrofurane ainsi que le sorbitol et le mannitol acétylés, et de dérivés d'oses acylés, en particulier le pentaacétylglucose (PAG), le pentaacétylfructose, le tétraacétylxylose et l'octaacétyllactose ainsi que la glucamine et la gluconolactone éventuellement N-alcoylées acétylées.
  10. Produit nettoyant et détergent selon la revendication 9, caractérisé en ce qu'il contient en plus d'autres agents d'activation de blanchiment selon une proportion allant de 0,1 à 20 % en poids, de préférence allant de 0,5 à 10 % en poids, de manière particulièrement préférée allant de 1 à 6 % en poids, par rapport à la masse totale du produit nettoyant et détergent.
  11. Produit nettoyant et détergent selon une des revendications 7 à 10, caractérisé en ce qu'il contient en plus d'autres ammoniumnitriles acycliques ou cyclique ou un benzoylcaprolactame ou un acétylcaprolactame.
  12. Produit nettoyant et détergent selon une des revendications 7 à 11, caractérisé en ce qu'il se présente sous la forme de granules ou sous la forme de matières solides sous forme de poudre ou de tablette ou sous la forme d'une solution homogène ou sous la forme d'une suspension.
  13. Produit nettoyant et détergent selon une des revendications 7 à 12, caractérisé en ce qu'il contient en plus des adjuvants de lavage, des agents tensio-actifs, des composés peroxygénés, des agents d'activation peroxygénés supplémentaires ou des peracides organiques, des solvants organiques miscibles dans l'eau, des agents séquestrants, des enzymes, ou des additifs spéciaux ayant une action respectueuse vis-à-vis des couleurs ou des fibres et/ou d'autres produits consommables secondaires comme des électrolytes, des régulateurs de pH, des inhibiteurs de ternissement, des régulateurs de mousse ainsi que des matières colorantes et odoriférantes ou des combinaisons de ces adjuvants.
  14. Produit nettoyant et détergent selon la revendication 13, caractérisé en ce qu'il contient des composés peroxygénés, de préférence un peroxyde inorganique ou un peroxyde d'hydrogène selon une proportion préférée allant de 5 à 25 % en poids, par rapport à la masse totale du produit nettoyant et détergent.
  15. Utilisation d'un produit nettoyant et détergent selon une des revendications 7 à 14, en tant que lessive pour des matières textiles ou en tant que détergent pour des surfaces solides, en particulier en tant que détergent pour la vaisselle, où ceux-ci sont préférés pour une introduction dans un procédé mécanique, ou dans le domaine des soins personnels, de manière préférée pour un éclaircissement des cheveux et pour une amélioration de l'efficacité de prothèses dentaires, en particulier à de faibles températures, ou dans des blanchisseries professionnelles, pour le blanchiment du bois et du papier, le blanchiment du coton ou dans les agents de désinfection.
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US20140005091A1 (en) 2014-01-02
EP2673349A1 (fr) 2013-12-18
JP2014511404A (ja) 2014-05-15
US9102903B2 (en) 2015-08-11
DE102011010818A1 (de) 2012-08-16

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