Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—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 to enhance the bleaching action of Peroxygen compounds both on bleaching colored stains Textiles as well as on hard surfaces, as well as detergents and cleaners, which contain 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 improvement of the oxidation and bleaching action of peroxygen compounds, especially inorganic ones Peroxygen compounds, at low temperatures below 80 ° C, especially in the temperature range of about 10 ° C to 45 ° C, the goal.
• peroxygen compounds especially inorganic ones Peroxygen compounds
• the to required metal complexes should be easily accessible and easy to prepare.
• transition metal complexes are used in detergents and cleaners, especially in textile washing and hard surface cleaners, especially for dishes, and in solutions for bleaching colored Soiling used.
• L examples of L are aliphatic lactams such as optionally substituted Azetidinones, butyrolactams (2-pyrrolidinone), gamma and delta-valerolactams, epsilon-caprolactam, dodecanlactams, pyrrolones, 3-morpholones.
• Another important group of lactams are aromatic lactams. Examples for this are Hydrocarbostyril, isohydrocarbostyril, benzopiperidone, naphthostyril, phenanthridone. Synthesis and properties of the lactams are i.a. described in "Methods for Production and conversion of lactams "in Houben-Weyl, Methoden der Organic Chemistry, 4th Edition, E. Müller (Ed.), Georg Thieme Verlag Stuttgart 1958, pp. 511-585.
• the halides such as chloride, bromide and iodide are used, but also nitrate, citrate, perchlorate and complex anions such as tetrafluoroborate and hexafluorophosphate or anions of organic C 1 -C 22 carboxylic acids such as acetates, propionates, butyrates, hexanoates , Octanoates, nonanoates and laurates.
• 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.
• alkali metal or ammonium peroxosulfates such as, for example, potassium peroxomonosulfate (technical: Caroat® or Oxone®).
• 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 oxidizing agents contained on an organic basis in the concentration range of 1 - 20%.
• oxidizing agents contained on an organic basis in the concentration range of 1 - 20%.
• peroxycarboxylic acids e.g. monoperoxyphthalic, Dodecanediperoxyacid, phthalimidoperoxycarboxylic acids such as PAP and related Systems or mentioned in EP-A 170 386 Amidopertica Acid.
• bleaching here includes both bleaching on the Textile surface befindlichem dirt as well as the bleaching of in the wash liquor located, detached from the textile surface dirt.
• For the bleaching The same applies mutatis mutandis to soiling on hard surfaces. Further potential applications are in the personal care field, e.g. at the bleaching of hair and improve the effectiveness of denture cleaners. Of others find the metal complexes described use in commercial Laundries, in the bleaching of wood and paper, the bleaching of cotton and in Disinfectants.
• the invention relates to a method for cleaning textiles as well hard surfaces, in particular dishes, using said Complex compounds together with peroxygen compounds in aqueous, optionally further detergent or cleaning agent components containing solution, as well as washing and cleaning agents for hard surfaces, especially dishwashing detergents, such being for use in are preferred by mechanical methods, such complex compounds contain.
• the use of the invention consists essentially in, with colored Stains contaminated hard surfaces or at polluted textiles to create conditions under which a peroxidic Oxidizing agent and the complex compound can react with each other Aim to obtain more strongly oxidizing secondary products.
• Such conditions are particularly present when the reactants in aqueous solution meet each other. This can be done by separately adding the peroxygen compound and the complex to the aqueous solution of the washing and cleaning agent happen.
• the method according to the invention is particularly advantageous using a detergent or cleaning agent for hard Surfaces containing the complex compound and optionally one pers oxygen-containing oxidant.
• the Peroxygen compound may also be used separately in substance or as preferred aqueous solution or suspension are added to the solution when a non-oxygen detergent or cleaning agent is used.
• the detergents and cleaners which are in the form of granules, powdered or tablet-shaped Solids, as other shaped bodies, homogeneous solutions or suspensions may also be mentioned bleach-enhancing metal complex contain in principle all known and customary in such agents ingredients.
• the agents may in particular be builders, surface-active surfactants, Peroxygen compounds, additional peroxygen activators or organic Peracids, water-miscible organic solvents, sequestering agents, Enzymes, as well as special additives with color or fiber-sparing effect included.
• Other auxiliaries such as electrolytes, pH regulators, silver corrosion inhibitors, Foam regulators as well as dyes and fragrances are possible.
• a hard surface cleaner according to the present invention may be used abrasive constituents, in particular quartz flours; Wood flour, Plastic flours, chalks and glass microspheres and mixtures thereof.
• Abrasives are preferably not more than 20% by weight in the cleaning agents, in particular from 5 to 15% by weight.
• the detergents and cleaning agents may contain one or more surfactants, wherein in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants come into question.
• 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 Shares, that is amounts up to 20 wt .-%, in particular up to 10 wt .-% and preferably in the range of 0.5 to 5 wt .-% are included.
• detergents for use in automatic dishwashing are usually low-foam connections used.
• 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 in particular ethoxylated fatty alcohols.
• alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• 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 present.
• the anionic Surfactants in the form of their sodium or potassium salts, in particular in the form of Sodium salts.
• Anionic surfactants are in detergents according to the invention preferably in amounts of 0.5 to 10 wt .-% and in particular in amounts of 5 to 25 wt .-% included.
• 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 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 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 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 this rest stands.
• [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 sole nonionic surfactant or in combination with other nonionic surfactants
• Surfactants especially together with alkoxylated fatty alcohols and / or Alkyl glycosides used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 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 the Fatty acid alkanolamides may be suitable.
• hydroxyalkyl quats of the general structures (III) and (IV) are preferred.
• gemini surfactants are so-called gemini surfactants. This includes In general, compounds which are two hydrophilic Own groups per molecule. These groups are usually by one so-called “spacer” separated from each other. This spacer is usually one Carbon chain, which should be long enough that the hydrophilic groups have a have enough distance to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to control the surface tension of the To greatly reduce water out.
• gemini polyhydroxy fatty acid amides can also be used or poly-polyhydroxy fatty acid amides as described in WO 95/19953, WO 95/19954 and WO 95/19955. Further 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 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. 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 in particular zeolite
• the weight ratio of aluminosilicate to silicate 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 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 builders include polycarboxylic acids, especially 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.
• 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 builders can, in particular for the production of liquid Agent, in the form of aqueous solutions, preferably in the form of 30 to 50 wt .-% iger aqueous solutions are used. All the acids mentioned are usually in the form of their water-soluble salts, in particular their alkali metal salts used.
• organic builders may be used in amounts up to 40 wt .-%, in particular up to 25 wt .-% and preferably from 1 to 8 wt .-% be included. Quantities near the upper limit mentioned are preferably used in pasty or liquid, in particular water-containing agents used.
• water-soluble builder components in cleaning agents according to the invention for hard surfaces come in principle all in means for the machine cleaning crockery commonly used builders, for example the above-mentioned alkali metal phosphates. Their amounts can range up to about 60 wt .-%, in particular 5 to 20 wt .-%, based on the total agent.
• water-soluble builder components are in addition Polyphosphonates and Phosphonatalkylcarboxylaten for example, organic Polymers of native or synthetic origin of the type listed above 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.
• To the preferred organic builder components include the salts of Citric acid, especially sodium citrate.
• sodium citrate come anhydrous Triatrium citrate and preferably trisodium citrate dihydrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
• Adjusted pH can also be added to the mentioned co-builder salts corresponding acids are 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 present in the compositions of 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 those 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®, Opticlean®
• the used enzymes such as in the international Patent Applications WO 92/131347 or WO 94/23005 Carriers may be adsorbed and / or embedded in enveloping substances, against them Protect premature inactivation. They are in inventive washing and Detergents preferably in amounts up to 10 wt .-%, in particular of 0.05 to 5 wt .-%, with particular preference against oxidative degradation stabilized enzymes, such as those from the international Patent Applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350 are known to be 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 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.
• Another object of the invention is a means for machine cleaning of Tableware containing 15 to 65% by weight, in particular 20 to 60% by weight water-soluble builder component, 5 to 25 wt .-%, in particular 8 to 17% by weight.
• Oxygen-based bleaching agents respectively; based on the whole Means, and 0.1 to 1% by weight of one or more of those defined above Metal complexes.
• Such agent is preferably lower alkyl, that is its weight percent solution has a pH of 8 to 11.5, in particular 9 to 11 on.
• means for automatic Cleaning of dishes are 20 to 60% by weight of water-soluble organic builders, in particular alkali citrate, 3 to 20% by weight alkali carbonate and 3 to 40% by weight Alkalidisilicate included.
• inventive Detergents for tableware silver corrosion inhibitors are used.
• 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 in the present invention suitable complexes contained metals with other than in formula (I) predetermined ligands.
• the agents foam too much during use, they can still be used up to 6 wt .-%, preferably about 0.5 to 4 wt .-% of a foam-regulating Compound, preferably from the group comprising silicones, paraffins, paraffin-alcohol combinations, hydrophobized silicas, Bisfettklaamide and their mixtures and other other known commercially available Foam inhibitors are added.
• the foam inhibitors especially silicone and / or paraffin-containing foam inhibitors, to a granular, bound in water or dispersible carrier substance.
• mixtures of paraffins and bistearylethylenediamide are prefers.
• Other optional ingredients in the compositions of the invention are for example, perfume oils.
• usable organic solvents include Alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 carbon atoms, in particular ethylene glycol and Propylene glycol, and mixtures thereof and those mentioned Classes of derivable ether.
• Such water-miscible solvents are preferably not present in the cleaning agents according to the invention 20 wt .-%, in particular from 1 to 15 wt .-%, present.
• Non-self-inflicting pH components can be used agents according to the invention system and environmentally friendly 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 metal hydrogensulfates, or bases, in particular Ammonium or alkali hydroxides.
• environmentally friendly 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 metal hydrogensulfates, or bases, in particular Ammonium or alkali hydroxides.
• pH regulators are in the agents according to the invention preferably not more than 10% by weight, in particular of 0.5 to 6 wt .-%, contained.
• the agents according to the invention are preferably in the form of powdered, granular or tablet-shaped preparations which in a conventional manner, for example by Mixing, granulating, roll compacting and / or by spray-drying the thermally stable components and admixing the more sensitive Components, in particular enzymes, bleach and the Bleaching catalyst are expected to be produced.
• invention Composition in the form of aqueous or other conventional solvent-containing solutions be particularly advantageous by simply mixing the ingredients in Substance or as a solution in an automatic mixer, produced.
• inventive agents in the form of not dusty, storage-stable free-flowing powders and / or granules with high Bulk densities in the range of 800 to 1000 g / l can also take place in that in a first process stage, the builder components with at least one Proportion of liquid mixture components increasing the bulk density of this Premix mixed and subsequently - if desired after a Intermediate drying - the other ingredients of the product, including the Bleaching 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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