EP1520910B1 - Utilisation de complexes de métaux de transition comprenant des ligands lactames comme catalysateurs de blanchiment - Google Patents

Utilisation de complexes de métaux de transition comprenant des ligands lactames comme catalysateurs de blanchiment Download PDF

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EP1520910B1
EP1520910B1 EP04020725A EP04020725A EP1520910B1 EP 1520910 B1 EP1520910 B1 EP 1520910B1 EP 04020725 A EP04020725 A EP 04020725A EP 04020725 A EP04020725 A EP 04020725A EP 1520910 B1 EP1520910 B1 EP 1520910B1
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weight
acid
transition metal
bleaching
compound
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EP1520910A1 (fr
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Ekaterina Dr. Jonas
Gerd Dr. Reinhardt
Daniel Kewitz
Aylin Ince
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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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 the use of certain transition metal complex compounds for enhancing the bleaching effect of peroxygen compounds in bleaching colored stains on textiles as well as on hard surfaces, as well as 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.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators.
  • bleach activators For this purpose, numerous proposals have been worked out in the past, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles.
  • NOBS sodium nonanoyloxy-benzenesulphonate
  • ISONOBS sodium isononanoyloxy-benzenesulphonate
  • acylated sugar derivatives such as pentaacetylglucose.
  • manganese complexes are known from EP 0 630 964 which, although they have no pronounced effect on bleach reinforcement of peroxygen compounds, do not discolor dyed textile fibers, they can cause the bleaching of soil or dye removed from the fiber in wash liquors.
  • copper and cobalt complexes are known which can carry ligands from a variety of groups of substances and are to be used as bleaching and oxidation catalysts.
  • WO 97/07191 proposes complexes of manganese, iron, cobalt, ruthenium and malenbdenum with salen-type ligands as activators for peroxygen compounds in hard surface cleaning solutions.
  • the present invention has the object of improving the oxidation and bleaching action of peroxygen compounds, especially inorganic peroxygen compounds, at low temperatures below 80 ° C. especially in the temperature range of about 10 ° C to 45 ° C, the goal.
  • the required metal complexes should be easily accessible and easy to prepare.
  • transition metal complexes with nitrogen-containing ligands contribute significantly to the cleaning performance against colored stains that are on textiles or on hard surfaces.
  • transition metal complexes are used in detergents and cleaners, in particular in textile washing and in hard-surface cleaners, in particular for crockery, and in solutions for bleaching colored stains.
  • L examples of L are aliphatic lactams such as optionally substituted azetidinones, butyrolactams (2-pyrrolidinone), gamma and delta-valerolactams, epsilon-caprolactam, dodecane lactams, pyrrolones, 3-morpholones.
  • Another important group of lactams are aromatic lactams. Examples for this are Hydrocarbostyril, isohydrocarbostyril, benzopiperidone, naphthostyril, phenanthridone.
  • the halides chloride, bromide and iodide are used, but also nitrate, citrate, perchlorate and the complex anions tetrafluoroborate and hexafluorophosphate or anions of organic C 1 -C 22 carboxylic acids such as acetates, propionates, butyrates, hexanoates, octanoates , Nonanoate and Laurate.
  • the anion ligands provide charge balance between the transition metal central atom and the ligand system.
  • the peroxygen compound used are primarily alkali metal perborate mono- or tetrahydrate and / or alkali metal percarbonate, with sodium being the preferred alkali metal. But in addition also alkali metal or ammonium peroxosulfates such as potassium peroxymonosulfate can (technically: Caroat® ® or Oxone ®) can be used.
  • the concentration of the inorganic oxidizing agents on the total formulation of detergents and cleaners is 5 - 90%, preferably 10 - 70%.
  • the amounts of peroxygen compounds are generally chosen 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.
  • the amount of bleach-enhancing complex compound used also depends on the intended use. Depending on the desired degree of activation, it is used in amounts such that 0.01 mmol to 25 mmol, preferably 0.1 mmol to 2 mmol complex per mole of peroxygen compound are used, but in special cases, these limits can also be exceeded or fallen below.
  • 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.
  • the detergents and cleaning agents may contain organic-based oxidizers in the concentration range of 1 to 20%.
  • organic-based oxidizers include all known peroxycarboxylic acids, e.g. Monoperoxyphthalic acid, dodecanediperoxyacid, phthalimidoperoxycarboxylic acids such as PAP and related systems or the amido peracids mentioned in EP-A 170 386.
  • bleaching here 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. The same applies analogously to the bleaching of soiling on hard surfaces. Other potential applications are in personal care, e.g. in the bleaching of hair and to improve the effectiveness of denture cleaners. Furthermore, 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, and washing and cleaning agents for hard surfaces, in particular Dishwashing detergents, such being preferred for use in machine processes containing such complex compounds.
  • the use according to the invention consists essentially in creating conditions for hard surfaces contaminated with colored soiling or, in the case of soiled textiles, conditions under which a peroxidic oxidizing agent and the complex compound can react with one another, with the aim of obtaining more strongly 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 method according to the invention is particularly advantageous using a hard surface cleaner containing the complex compound and optionally a peroxygen-containing oxidizer.
  • 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, pulverulent or tablet-like solids, other shaped bodies, homogeneous solutions or suspensions, may in principle also contain all known bleach-enhancing metal complexes of all known ingredients customary in such agents.
  • 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 have abrasive constituents, in particular quartz flours; Wood flour, 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, that is to say amounts of up to 20% by weight. , 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.
  • Suitable anionic surfactants 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 of this chain length are 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 which are prepared, for example, according to US Pat. Nos. 3,234,158 and 5,075,041, are suitable anionic surfactants.
  • the Schwefelcher-monoester of linear or branched alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C 9 -C II are suitable alcohols containing on average 3.5 mol 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 fatty alcohols and especially ethoxylated fatty alcohols represent.
  • Preferred sulfosuccinates contain C 8 -C 18 fatty alcohol residues or mixtures of these.
  • Suitable further anionic surfactants 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 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, advantageously 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 can be linear or preferably methyl-branched in the 2-position , or may contain 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 represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrowed 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 a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (I) in the radical R 1 -CO for an aliphatic acyl radical having 6 to 22 carbon atoms
  • R 2 for hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] for 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 (II) in the 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
  • R 5 is a linear, branched or a cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to C 1 -C 4 -alkyl or phenyl radicals
  • [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-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides according to WO 95/07331, 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 from 1 to 4 carbon atoms in the alkyl chain, especially 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 the fatty acid alkanolamides may also be suitable.
  • hydroxyalkyl quats of the general structures (III) and (IV) 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, as described in WO 95/19953, WO 95/19954 and WO 95/19955. 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 present 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. Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, are used in particular as water-insoluble, water-dispersible inorganic builder materials.
  • the detergent grade crystalline sodium aluminosilicates particularly 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 which can be determined according to the specifications of the German patent DE 24 12 837, is generally 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 silicates useful as builders preferably have one 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. Those with a molar ratio of Na 2 O: SiO 2 of 1: 1.9 to 1: 2.8 can be prepared by the process of European Patent Application EP 0 425 427.
  • the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si are used x O 2x + 1 ⁇ yH 2 O, in which x, the so-called module, a number from 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 European Patent Application EP 0 164 514.
  • 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 international patent application WO 91/08171.
  • ⁇ -Sodium silicates with a modulus between 1.9 and 3.2 can be prepared according to Japanese patent applications JP 04/238 809 or JP 04/260 6 10.
  • 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, preparable as in the European patent applications EP 0 548 599, EP 0 502 325 and EP 0 425 428 described, can be used.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared by the process of European patent application EP 0 436 835 from sand and soda.
  • Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
  • a granular compound of alkali metal silicate and alkali metal carbonate is used, as described, for example, in International Patent Application WO 95/22592 or as it is commercially available, for example, under the name Nabion®.
  • alkali metal aluminosilicate especially zeolite
  • the weight ratio aluminosilicate to silicate in each case based on anhydrous active substances, preferably 1: 10 to 10: 1.
  • the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
  • Such builder substances are preferably contained in agents according to the invention in amounts of up to 60% by weight, in particular from 5 to 40% by weight.
  • 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 obtainable by oxidation of polysaccharides or dextrins of international patent application WO 93/161 10 or international patent application WO 92/18542 or European patent EP 0 232 202, polymeric acrylic acids, methacrylic acids, Maleic acids and copolymers of these, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality.
  • the 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 50,000 to 120,000, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • Also suitable are 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.
  • Terpolymers may also be used as the water-soluble organic builder substances, the monomers being two unsaturated acids and / or salts thereof, and the third monomer being vinyl alcohol and / or an esterified one Containing ethanol or a carbohydrate.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) -acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Such polymers can be prepared in particular by processes which are described in German patents DE 42 21 381 and DE 43 00 772, and generally have a molecular weight between 1000 and 200,000. Further preferred copolymers are those which are described in the German patent applications DE 43 03 320 and DE 44 17 734 and preferably have as monomers 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 are, in addition to polyphosphonates and Phosphonatalkylcarboxylaten for example organic polymers of native or synthetic origin of the above-mentioned type of polycarboxylates, which act in particular in hard water regions as a co-builder, 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 tri-sodium citrate and preferably trisodium citrate dihydrate are suitable. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • the acids corresponding to the said co-builder salts may also be present.
  • bleach activators that is to say compounds which release peroxocarboxylic acids under perhydrolysis conditions.
  • Suitable are the usual bleach activators which have O- and / or N-acyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (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 or Isononanoyloxybenzolsulfonat (NOBS or ISONOBS) or their amido derivatives as described for example in EP 170 386, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and also acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacet
  • the enzymes optionally contained in the agents according to the invention 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 such as Termamy®, amylase-LT, Maxamyl®, Duramyl®, Purafectel OxAm, cellulases such as Celluzyme®, Carezyme®, K-AC® and / or the cellulases known from International Patent Applications WO 96/34108 and WO 96/34092 and / or Lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®.
  • proteases such as BLAP®, Optimase®, Opticlean®, Maxa
  • the enzymes used can be adsorbed on carriers and / or embedded in encapsulants, as described, for example, in International Patent Applications WO 92/131347 or WO 94/23005, in order to protect them 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, particularly preferably enzymes which are stabilized against oxidative degradation, as described, for example, in International Patent Applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350.
  • 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 from 3 to 30% by weight, based on the total agent.
  • the alkali carrier system preferably used 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 machine for machine dishwashing containing 15 to 65 wt .-%, in particular 20 to 60 wt .-% of water-soluble builder component, 5 to 25 wt .-%, in particular 8 to 17 wt .-%.
  • Oxygen-based bleaching agents respectively; 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 low alkaline, that is its weight percent 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 preferably present in the detergents according to the invention not more than 20% by weight, in particular from 1 to 15% by weight.
  • the compositions of the invention system and environmentally acceptable acids especially 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.
  • Such pH regulators are preferably not more than 10% by weight, in particular from 0.5 to 6% by weight, in the compositions according to the invention.
  • compositions according to the invention are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roller compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleach catalyst are to be expected, can be prepared.
  • 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 of 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.
  • compositions according to the invention in tablet form, the procedure is preferably such that all ingredients are mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric or rotary presses with pressing pressures in the range of 200 ⁇ 10 5 Pa to 1500 ⁇ 10 5 Pa pressed.
  • a tablet thus produced has a weight of 1-5 g to 40 g, in particular from 20 g to 30 g, with a diameter from 3-5 mm to 40 mm.
  • the bleaching performance of the compounds of the invention Cat 1 and Cat 2 was tested in comparison to the bleach activator TAED.
  • 10 mg / l of the catalyst were dissolved in a wash liquor prepared by dissolving 2 g / l of a bleach-free basic detergent (WMP, WFK, Krefeld).
  • WMP bleach-free basic detergent
  • 1 g / l of sodium percarbonate (Degussa) the washing experiments were carried out in a Linitest apparatus (Heraeus) at 20 or 40 ° C. The washing time was 30 min, water hardness 18 ° dH.
  • connection Remission difference (ddR%) 20 ° C 40 ° C BC-1 BC-4 BC-1 BC-4 Cat 1 4.6 1.5 8.8 3.5
  • Cat 2 3.4 1.2 7.6 3.3 TAED (V1) 2.5 1.1 4.0 2.4

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

Claims (7)

  1. Utilisation de complexes d'un métal de transition avec des ligands de type lactame en tant que catalyseurs de blanchiment, caractérisée en ce que les complexes d'un métal de transition ont la formule (1)

            M(L)nXm     (1)

    dans laquelle
    M est un atome d'un métal du groupe Mn, Fe, Co, Ni, Mo , W,
    L est un ligand du groupe des carboxamides cycliques (lactames),
    X est un chlorure, bromure, iodure, nitrate, perchlorate, citrate, tétrafluoroborate, hexafluorophosphate, ou représente des anions d'acides organiques ayant 1 à 22 atomes de carbone,
    n est un nombre de 2 à 4, et m est un nombre de 0 à 4.
  2. Utilisation selon la revendication 1, caractérisée en ce qu'on prend en tant que composé peroxygéné des peracides organiques, du peroxyde d'hydrogène, un perborate et un percarbonate, ainsi que leurs mélanges.
  3. Utilisation selon la revendication 1 dans des solutions aqueuses pour le lavage des textiles, dans des solutions aqueuses de nettoyage destinées à des surfaces dures, et pour le blanchiment de salissures colorées.
  4. Utilisation selon la revendication 1, caractérisée en ce qu'on utilise en même temps que le composé complexe de formule 1 un composé qui dans les conditions d'une perhydrolyse va céder un acide peroxocarboxylique.
  5. Produit de lavage, de blanchiment et de nettoyage, contenant un complexe d'un métal de transition selon la revendication 1.
  6. Produit selon la revendication 5, caractérisé en ce qu'il contient de 0,0025 à 1 % en poids, en particulier de 0,01 à 0,1 % en poids du composé complexe.
  7. Produit selon la revendication 5, caractérisé en ce qu'il contient en plus du composé complexe 1 à 10 % en poids, en particulier 2 à 6 % en poids d'un composé qui, dans les conditions d'une perhydrolyse, va céder un acide peroxycarboxylique.
EP04020725A 2003-09-30 2004-09-01 Utilisation de complexes de métaux de transition comprenant des ligands lactames comme catalysateurs de blanchiment Expired - Lifetime EP1520910B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10345273A DE10345273A1 (de) 2003-09-30 2003-09-30 Verwendung von Übergangsmetallkomplexen mit Lactamliganden als Bleichkatalysatoren
DE10345273 2003-09-30

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EP1520910B1 true EP1520910B1 (fr) 2006-11-29

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WO2009124855A1 (fr) 2008-04-09 2009-10-15 Basf Se Utilisation de composés complexes d'hydrazides métalliques comme catalyseurs d'oxydation
DE102008038376A1 (de) 2008-08-19 2010-02-25 Clariant International Ltd. Verfahren zur Herstellung von 3,7-Diaza-bicyclo[3.3.1]nonan-Verbindungen
DE102008045215A1 (de) 2008-08-30 2010-03-04 Clariant International Ltd. Verwendung von Mangan-Oxalatenn als Bleichkatalysatoren
DE102008045207A1 (de) * 2008-08-30 2010-03-04 Clariant International Limited Bleichkatalysatormischungen bestehend aus Mangansalzen und Oxalsäure oder deren Salze
DE102008064009A1 (de) 2008-12-19 2010-06-24 Clariant International Ltd. Verfahren zur Herstellung von 3,7-Diaza-bicyclo[3.3.1]nonan-Metall-Komplexen
EP2228429A1 (fr) 2009-03-13 2010-09-15 Unilever PLC Combinaison de colorant d'ombrage et de catalyseur
DE102009017722A1 (de) 2009-04-11 2010-10-14 Clariant International Limited Bleichmittelgranulate mit Aktivcoating
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US9657435B2 (en) 2010-06-28 2017-05-23 Basf Se Metal free bleaching composition
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EP2771446A1 (fr) 2011-10-25 2014-09-03 Basf Se Utilisation de copolymères d'acrylate comme agents anti-redéposition de la saleté et agents de libération de la saleté dans des processus de blanchisserie
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EP2857485A1 (fr) 2013-10-07 2015-04-08 WeylChem Switzerland AG Poche à compartiments multiples comprenant des compositions de nettoyage sans alkanolamine, processus de lavage et utilisation de produits de lavage et de nettoyage de textiles et plats
DE102013019269A1 (de) 2013-11-15 2015-06-03 Weylchem Switzerland Ag Geschirrspülmittel sowie dessen Verwendung
PL3074438T3 (pl) 2013-11-27 2018-02-28 Basf Se Bezładne kopolimery jako środki uwalniające brud w procesach prania
WO2017186480A1 (fr) 2016-04-26 2017-11-02 Basf Se Composition de blanchiment sans métal
DE102017004742A1 (de) 2017-05-17 2018-11-22 Weylchem Wiesbaden Gmbh Beschichtete Granulate, deren Verwendung und Wasch- und Reinigungsmittel enthaltend diese
EP3967742A1 (fr) 2020-09-15 2022-03-16 WeylChem Performance Products GmbH Compositions comprenant un catalyseur de blanchiment, procédé de fabrication associé et agent de blanchiment et de nettoyage comprenant ces compositions

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US20050181964A1 (en) 2005-08-18
JP2005105275A (ja) 2005-04-21
EP1520910A1 (fr) 2005-04-06
ES2274364T3 (es) 2007-05-16
DE10345273A1 (de) 2005-04-21
US7094745B2 (en) 2006-08-22

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