EP1557457A1 - Use of transition metal complexes as bleach catalysts in washing and cleaning agents - Google Patents
Use of transition metal complexes as bleach catalysts in washing and cleaning agents Download PDFInfo
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- EP1557457A1 EP1557457A1 EP05000385A EP05000385A EP1557457A1 EP 1557457 A1 EP1557457 A1 EP 1557457A1 EP 05000385 A EP05000385 A EP 05000385A EP 05000385 A EP05000385 A EP 05000385A EP 1557457 A1 EP1557457 A1 EP 1557457A1
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- transition metal
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- bleaching
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/168—Organometallic compounds or orgometallic complexes
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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 macrocyclic, N-containing ligands, in particular unbound cycles or cyclam ligands and their transition metal complexes in bleaching colored Soiling on textiles as well as on hard surfaces, and washing Detergents 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 multiply acylated alkylenediamines, in particular tetraacetylglycoluril, N-acylated Caprolactams such as benzoylcaprolactam, acetylcaprolactam or Nonanoyl-caprolactam, hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, Diketopiperazines, sulfurylamides and cyanurates, as well as carboxylic acid anhydrides, in particular phthalic anhydride and substituted maleic anhydrides, Carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate (NOBS), Sodium isononanoyloxy-benzenesulfonate
- transition metal salts and their complex compounds as described, for example, in EP 0 237 111, EP 0 272 030, EP 0 306 089, EP 0 392 592 or EP 0 443 651.
- transition metal salts and their complex compounds as described, for example, in EP 0 237 111, EP 0 272 030, EP 0 306 089, EP 0 392 592 or EP 0 443 651.
- EP 0 439 387 claims binuclear metal complexes with ligands obtained by reacting a dialdehyde with primary polyamines as an oxygen carrier.
- EP 0 458 397 and '398 describe the use of manganese complexes of the general formula [L n Mn m X p ] z Y q , wherein L comprises macrocyclic, N-containing ligands.
- ligands based on 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 TACN) and their derivatives are described.
- ligands examples include 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 2001/048 298 describes corresponding bridged ligands for bleaching with atmospheric oxygen. The problem with these ligands, however, is their complicated production, which results in particular from the introduction of the bridge into the molecule. As a result, the overall yields of the syntheses are not very high.
- the present invention has the improvement of the oxidation and bleaching action of detergents and cleaners at low temperatures below 80 ° C, especially in the temperature range of about 20 ° C to 45 ° C, to the destination.
- the alkylaryl radicals contain 6 to 16 carbon atoms in the Alkyl part, as aryl phenyl is preferred.
- transition metal complexes of the formula (I) are used in washing and Detergents, in particular in textile washing and in cleaning preparations for Hard surfaces, especially for dishes, and in solutions for bleaching used colored stains. This happens on the one hand in the presence of Hydrogen peroxide, hydrogen peroxide-releasing compounds or a Peroxygen compound. On the other hand, the complexes can also by the Oxygen in the air can be activated without the addition of a peroxo compound necessary is.
- Fe (tcm) (OTf) 2 is used in Science, 2003, 299, 1037-1039 as a precursor to [FeO (tmc) (NCCH 3 )] (OTf) 2 .
- the synthesis of cyclam is described inter alia in WO 1997/049691. None of these references gives hints on the use of these compounds as bleaching agents in detergents and cleaners.
- the ligands (IV) and (V) 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.
- peroxygen compounds or Atmospheric oxygen in question come peroxygen compounds or Atmospheric oxygen in question.
- peroxygen compound come in the first place Hydrogen peroxide, alkali perborate mono or tetrahydrate and / or Alkali percarbonates, with sodium being the preferred alkali metal, into consideration.
- alkali metal or ammonium peroxosulphates such as e.g. Potassium peroxomonosulfate (technically: Caroat® or Oxone®) can be used.
- the Concentration of the inorganic oxidizing agent on the overall formulation of the Washing and cleaning agent is 2 - 90%, preferably 5 - 60%.
- peroxycarboxylic acids e.g. Monoperoxyphthalic acid, peracetic acid, dodecanediperoxyacid, phthalimidoperoxycarboxylic acids like PAP and related systems or amido peracids.
- the amounts of peroxygen compounds are generally so chosen that in the solutions of detergents and cleaners between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm Active oxygen are present.
- the amount of bleach-enhancing Complex connection depends on the purpose of use. Depending on the desired Activation level is in an amount of 0.01 mmol to 25 mmol, preferably 0.1 mmol to 2 mmol complex per mole of peroxygen compound used, however In special cases, these limits may also be exceeded or fallen short of.
- 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 included.
- bleach catalysts or bleach activators can be used in order to widen the spectrum of action of the bleaching systems according to the invention and to increase the efficiency, in particular with regard to the germicidal effect (disinfection).
- conventional bleach activators that is to say compounds which release peroxycarboxylic acids under perhydrolysis conditions, can be used. 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 or Isononanoyloxybenzolsulfonat (NOBS or ISONOBS) or their amido derivatives, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetylglucose (PAG ), Pentaacety
- open-chain or cyclic nitrile quats are suitable for this purpose.
- the combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used.
- benzoylcaprolactam or acetylcaprolactam can be used.
- combinations of the complexes according to the invention with other metal complexes can also be used.
- bleaching here includes both the bleaching of on the textile surface dirt as well as the bleaching of the wash liquor, dirt removed from the textile surface.
- For the bleaching of Soiling on hard surfaces applies mutatis mutandis to the same.
- Further potential applications are in the personal care field, e.g. at the bleaching of hair and improve the effectiveness of denture cleaners.
- 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 detergents and cleaners 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 be present except the said 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.
- 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 flours, 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 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 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 from 0.5 to 10% by weight and in particular in amounts of 5 contain up to 25 wt .-%.
- 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 is a Glykoseiki with 5 or 6 C-atoms, preferably for 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 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 (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-alyloxy-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 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.
- 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. 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.
- 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 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 metal silicates are the sodium silicates, in particular the amorphous sodium silicates with a molar ratio Na 2 O: SiO 2, of 1: 2 to 1: 2.8.
- Such silicates 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 x O 2x + 1 ⁇ YH be used 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 ß-sodium are preferred, with .beta.-sodium disilicate being obtainable, for example, by the process described in 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.
- 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 granular compound of alkali silicate and alkali carbonate is used, as it is commercially available, for example, under the name Nabion®.
- 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 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 mean.
- Other possible 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.
- 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 92/111347 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 are 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 Builderkompenente, 5 to 25 wt .-%, in particular 8 to 17 wt .-% Oxygen-based bleach, based in each case on the total agent, and 0.1 to 1 wt .-% of one or more of the metal complexes defined above.
- Such a thing Agent is preferably lower alkyl, i. its solution has a pH of 8 to 11.5, especially 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, bis-fatty acid amides and their Mixtures and other known commercially available foam inhibitors added become.
- the foam inhibitors in particular silicone and / or paraffinic foam inhibitors, to a granular, water-soluble or dispersible carrier substance bound.
- there are Blends of paraffins and bistearylethylenediamide are preferred.
- Ingredients in the compositions according to 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.
- compositions according to the invention are in the form of powdery, 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 invention Complexes preferably as an aqueous solution or in microencapsulated form for Commitment. Are they used for the purpose of using atmospheric oxygen (aerial bleaching) can be dispensed with the use of peroxo compounds. Should however, in combination with a peroxo compound, e.g. Hydrogen peroxide for Use, we recommend the use of a multi-chamber container.
- a peroxo compound e.g. Hydrogen peroxide for Use
- 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 Cat 1, Cat 2 or Cat 3 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) After addition of 1 g / l of sodium percarbonate (Degussa), the washing experiments were carried out in a Linitest apparatus (Fa.
- the washing time was 30 min, water hardness 18 ° dH.
- As a bleaching test fabric served two tea stains on cotton BC-1 and BC3, WFK, Krefeld).
- Cat 1 shows significant advantages over the conventional bleach activator TAED, which was used in much higher concentrations (V1). Substantially similar results were obtained when replacing sodium percarbonate with sodium perborate.
- the bleaching performance of the compound of the invention Cat 1 was tested in combination with the bleach activator TAED.
- 10 mg / l Cat 1 and 200 mg / l TAED 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) After addition of 1 g / l of sodium percarbonate (Degussa), the washing experiments were carried out in a Linitest apparatus (Fa. The washing time was 30 min, water hardness 18 ° dH.
- As a bleaching test fabric served two tea stains on cotton BC-1 and BC3, WFK, Krefeld).
- the bleaching performance of the compounds of the invention Cat 1 and Cat 2 was tested without the addition of peroxides.
- the washing tests were in a Linitest device (Heraeus) at 20 and 40 ° C performed. The washing time was 30 min, water hardness 18 ° dH. After washing, the fabric was dried and ironed.
- As a bleaching test fabric served two self-made oily Stains on cotton (ketchup / oil and curry / oil, made by boil ketchup or curry powder with sunflower oil).
- As a bleaching result the remission difference, measured with an Elrepho device, after the Laundry compared to unwashed fabric.
- V1 the detergent without complex addition was used.
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Abstract
Description
Die vorliegende Erfindung betrifft die Verwendung bestimmter macrocyclischer, N-haltiger Liganden, insbesondere nicht überbrückter Cyclen- oder Cyclam-Liganden sowie deren Übergangsmetallkomplexe beim Bleichen von farbigen Anschmutzungen sowohl an Textilien wie auch an harten Oberflächen, sowie Waschund Reinigungsmittel, welche derartige Komplexverbindungen enthalten.The present invention relates to the use of certain macrocyclic, N-containing ligands, in particular unbound cycles or cyclam ligands and their transition metal complexes in bleaching colored Soiling on textiles as well as on hard surfaces, and washing Detergents containing such complex compounds.
Anorganische Persauerstoffverbindungen, insbesondere Wasserstoffperoxid und feste Persauerstoffverbindungen, die sich in Wasser unter Freisetzung von Wasserstoffperoxid lösen, wie Natriumperborat und Natriumcarbonat-Perhydrat, werden seit langem als Oxidationsmittel zu Desinfektions- und Bleichzwecken verwendet. Die Oxidationswirkung dieser Substanzen hängt in verdünnten Lösungen stark von der Temperatur ab; so erzielt man beispielsweise mit H2O2 oder Perborat in alkalischen Bleichflotten erst bei Temperaturen oberhalb von etwa 80°C eine ausreichend schnelle Bleiche verschmutzter Textilien.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.
Bei niedrigeren Temperaturen kann die Oxidationswirkung der anorganischen Persauerstoffverbindungen durch Zusatz sogenannter Bleichaktivatoren verbessert werden. Hierfür wurden in der Vergangenheit zahlreiche Vorschläge erarbeitet, vor allem aus den Stoffklassen der N- oder O-Acylverbindungen, beispielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylglykoluril, N-acylierte Caprolactame wie Benzoylcaprolactam, Acetylcaprolactam oder Nonanoylcaprolactam, Hydantoine, Hydrazide, Triazole, Hydrotriazine, Urazole, Diketopiperazine, Sulfurylamide und Cyanurate, außerdem Carbonsäureanhydride, insbesondere Phthalsäureanhydrid und substituierte Maleinsäureanhydride, Carbonsäureester, insbesondere Natrium-nonanoyloxy-benzolsulfonat (NOBS), Natrium-isononanoyloxy-benzolsulfonat (ISONOBS) und acylierte Zuckerderivate, wie Pentaacetylglukose. Durch Zusatz dieser Substanzen kann die Bleichwirkung wässriger Peroxidlösungen so weit gesteigert werden, dass bereits bei Temperaturen um 60°C im wesentlichen die gleichen Wirkungen wie mit der Peroxidlösung allein bei 95°C eintreten.At lower temperatures, the oxidation effect of the inorganic Peroxygen compounds improved by the addition of so-called bleach activators become. For this purpose, numerous proposals have been worked out in the past all from the classes of N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylglycoluril, N-acylated Caprolactams such as benzoylcaprolactam, acetylcaprolactam or Nonanoyl-caprolactam, hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, Diketopiperazines, sulfurylamides and cyanurates, as well as carboxylic acid anhydrides, in particular phthalic anhydride and substituted maleic anhydrides, Carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate (NOBS), Sodium isononanoyloxy-benzenesulfonate (ISONOBS) and acylated sugar derivatives, like pentaacetylglucose. By adding these substances, the bleaching effect aqueous peroxide solutions are increased so much that even at temperatures at 60 ° C, substantially the same effects as with the peroxide solution alone at 95 ° C.
Im Bemühen um energiesparende Wasch- und Bleichverfahren gewinnen in den
letzten Jahren Anwendungstemperaturen deutlich unterhalb 60°C, insbesondere
unterhalb 45°C bis herunter zur Kaltwassertemperatur an Bedeutung.
Bei diesen niedrigen Temperaturen lässt die Wirkung der bisher bekannten
Aktivatorverbindungen in der Regel erkennbar nach. Es hat deshalb nicht an
Bestrebungen gefehlt, für diesen Temperaturbereich wirksamere Bleichsysteme zu
entwickeln, ohne dass bis heute ein überzeugender Erfolg zu verzeichnen gewesen
wäre.In the search for energy-saving washing and bleaching processes in recent years application temperatures well below 60 ° C, especially below 45 ° C down to the cold water temperature in importance.
At these low temperatures, the effect of the previously known activator compounds usually decreases noticeably. There has therefore been no lack of efforts to develop for this temperature range more effective bleaching systems, without that to date a convincing success would have been recorded.
Ein Ansatzpunkt dazu ergibt sich durch den Einsatz von Übergangsmetallsalzen und deren Komplexverbindungen, wie sie zum Beispiel in EP 0 237 111, EP 0 272 030, EP 0 306 089, EP 0 392 592 oder EP 0 443 651 beschrieben sind. Weiterhin werden in WO 97/07191 Komplexe des Mangans, Eisens, Kobalts, Rutheniums und des Molybdäns mit Liganden vom Salen-Typ als Katalysatoren für Persauerstoffverbindungen in Reinigungslösungen für harte Oberflächen vorgeschlagen.One starting point for this is the use of transition metal salts and their complex compounds, as described, for example, in EP 0 237 111, EP 0 272 030, EP 0 306 089, EP 0 392 592 or EP 0 443 651. Continue to be in WO 97/07191 complexes of manganese, iron, cobalt, ruthenium and the Molybdenum with salen-type ligands as catalysts for Peroxygen compounds in cleaning solutions for hard surfaces proposed.
Eine Vielzahl von Komplexen mit macrocyclischen N-haltigen Liganden sind in den
letzten Jahren in der Literatur als Bleichkatalysatoren beschrieben worden. So
werden in EP 0 439 387 binucleare Metallkomplexe mit Liganden, erhalten durch
Umsetzung eines Dialdehyds mit primären Polyaminen, als Sauerstoffcarrier
beansprucht.
EP 0 458 397 und '398 beschreiben die Verwendung von Mangankomplexen der
allgemeinen Form [LnMnmXp]z Yq, wobei L macrocyclische, N-haltige Liganden
umfasst. Beschrieben werden insbesondere Liganden auf Basis 1,4,7-Trimethyl-1,4,7-triazacyclononan
(Me3TACN) und deren Derivate. Verbindungen des Typs
[LMn(OR)3] Y werden in EP 0 544 519 beschrieben, wobei als Liganden
insbesondere TACN, Me3TACN, 1,5,9-Trimethyl-1,5,9-triazacyclodecan in Betracht
kommen. Übergangsmetallkomplexe mit starren Liganden, insbesondere starr
überbrückte
N-haltige Macrocyclen mit mindestens 3 Donoratomen, von denen 2 einen
Brückenkopf bilden, werden ausführlich in WO 1998/039 098 als
Oxidationskatalysatoren beschrieben. Beispiele für die Liganden sind 5,12-Dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecan
(Bcyclam) und 5-N-Octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecan.
In WO 2001/048 298 werden
entsprechende überbrückte Liganden für die Bleiche mit Luftsauerstoff beschrieben.
Problematisch bei diesen Liganden ist jedoch deren aufwendige Herstellung, die
insbesondere von der Einführung der Brücke in das Molekül herrührt. Infolgedessen
sind die Gesamtausbeuten der Synthesen nicht sehr hoch.A variety of macrocyclic N-containing ligand complexes have been reported in the literature as bleach catalysts in recent years. For example, EP 0 439 387 claims binuclear metal complexes with ligands obtained by reacting a dialdehyde with primary polyamines as an oxygen carrier.
EP 0 458 397 and '398 describe the use of manganese complexes of the general formula [L n Mn m X p ] z Y q , wherein L comprises macrocyclic, N-containing ligands. In particular, ligands based on 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 TACN) and their derivatives are described. Compounds of the type [LMn (OR) 3 ] Y are described in EP 0 544 519, suitable ligands being, in particular, TACN, Me 3 TACN, 1,5,9-trimethyl-1,5,9-triazacyclodecane. 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 WO 1998/039 098 as oxidation catalysts. Examples of 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 2001/048 298 describes corresponding bridged ligands for bleaching with atmospheric oxygen. The problem with these ligands, however, is their complicated production, which results in particular from the introduction of the bridge into the molecule. As a result, the overall yields of the syntheses are not very high.
Ähnliche Metallkomplexe basierend auf unverbrückten macrocyclische Liganden werden in WO 2000/012 808 als "aerial bleaching systems" zum Einsatz in Waschund Reinigungsmitteln beansprucht. In der Vielzahl der aufgezählten potentiellen Liganden finden sich auch Cyclam-Liganden und Cyclen-Liganden der allgemeinen Formeln (I) und (II): wobei die Gruppen R1-R4 Wasserstoff, Alkyl-, Aryl- oder Heteroarylgruppen bzw. über- bzw. verbrückende Gruppen darstellen können. Näher wird auf diese Verbindungsklasse weder in der Beschreibung noch in den Beispielen eingegangen.Similar metal complexes based on unbridged macrocyclic ligands are claimed in WO 2000/012 808 as "aerial bleaching systems" for use in detergents and cleaners. The multitude of listed potential ligands also includes cyclam ligands and cyclic ligands of the general formulas (I) and (II): where the groups R 1 -R 4 can represent hydrogen, alkyl, aryl or heteroaryl groups or bridging or bridging groups. This class of compounds is not discussed in detail in the description or in the examples.
Entsprechend den dortigen Angaben werden diese Verbindungen ausdrücklich nur in solchen Wasch- und Reinigungsmitteln eingesetzt, die frei sind von Wasserstoffperoxid und anderen Peroxyverbindungen.According to the information there these connections are expressly only in such detergents and cleaners used, which are free of Hydrogen peroxide and other peroxy compounds.
Überraschenderweise wurde nun gefunden, dass bestimmte Verbindungen innerhalb der Gruppen der Cyclame und Cyclene (I) und (II) auch in Wasserstoffperoxid und andere Peroxyverbindungen enthaltende Wasch- und Reinigungsmitteln eingesetzt werden können und deutliche Vorteile hinsichtlich des Bleichvermögens aufweisen. Surprisingly, it has now been found that certain compounds are within the groups of Cyclame and Cyclene (I) and (II) also in hydrogen peroxide and used other washing and cleaning agents containing peroxy compounds can be and have significant advantages in terms of bleaching ability.
Die vorliegende Erfindung hat die Verbesserung der Oxidations- und Bleichwirkung von Wasch- und Reinigungsmitteln bei niedrigen Temperaturen unterhalb von 80°C, insbesondere im Temperaturbereich von ca. 20°C bis 45°C, zum Ziel.The present invention has the improvement of the oxidation and bleaching action of detergents and cleaners at low temperatures below 80 ° C, especially in the temperature range of about 20 ° C to 45 ° C, to the destination.
Gegenstand der Erfindung ist die Verwendung von Übergangsmetallkomplexen der
Formel (I)
- M
- ein Metallatom aus der Gruppe Mn und Fe,
- L
- ein Ligand der allgemeinen Formel (II) oder (III)
X und Y ein Neutral- oder Anionligand aus der Gruppe CH3CN, Chlorid, Bromid, Nitrat, Perchlorat, Sulfat, Citrat, Hexafluorophosphat, Trifluormethansulfonat, Tetrafluoroborat, Tetraphenylborat, oder Anionen organischer Säuren mit C1-C22 Kohlenstoffatomen,
n und m eine Zahl von 0 bis 4 bedeuten, als Bleichkatalysator in Wasch- und Reinigungsmitteln.The invention relates to the use of transition metal complexes of the formula (I)
- M
- a metal atom from the group Mn and Fe,
- L
- a ligand of the general formula (II) or (III)
X and Y are a neutral or anion ligand from the group CH 3 CN, chloride, bromide, nitrate, perchlorate, sulfate, citrate, hexafluorophosphate, trifluoromethanesulfonate, tetrafluoroborate, tetraphenylborate, or anions of organic acids with C 1 -C 22 carbon atoms,
n and m represent a number from 0 to 4, as a bleach catalyst in detergents and cleaners.
Bevorzugt werden Komplexe mit Übergangsmetallzentralatomen in den Oxidationsstufen +2, +3 oder +4 verwendet, wobei Komplexe mit Mangan oder Eisen als Zentralatom bevorzugt sind. Die Alkylarylreste enthalten 6 bis 16 C-Atome im Alkylteil, als Aryl ist Phenyl bevorzugt.Preference is given to complexes with transition metal central atoms in the Oxidation levels +2, +3 or +4 are used, with complexes containing manganese or iron are preferred as the central atom. The alkylaryl radicals contain 6 to 16 carbon atoms in the Alkyl part, as aryl phenyl is preferred.
Diese Übergangsmetallkomplexe der Formel (I) werden in Wasch- und Reinigungsmitteln, insbesondere in der Textilwäsche und in Reinigungsmitteln für harte Oberflächen, insbesondere für Geschirr, und in Lösungen zum Bleichen von farbigen Anschmutzungen eingesetzt. Dies geschieht zum einen in Gegenwart von Wasserstoffperoxid, Wasserstoffperoxid-freisetzenden Verbindungen oder einer Persauerstoffverbindung. Zum anderen können die Komplexe aber auch durch den Sauerstoff der Luft aktiviert werden, ohne dass der Zusatz einer Peroxoverbindung notwendig ist.These transition metal complexes of the formula (I) are used in washing and Detergents, in particular in textile washing and in cleaning preparations for Hard surfaces, especially for dishes, and in solutions for bleaching used colored stains. This happens on the one hand in the presence of Hydrogen peroxide, hydrogen peroxide-releasing compounds or a Peroxygen compound. On the other hand, the complexes can also by the Oxygen in the air can be activated without the addition of a peroxo compound necessary is.
Erfindungsgemäße Eisen- oder Mangankomplexe von Cyclam oder Tetraalkylcyclam sind bereits in der Literatur beschrieben. So sind cis-(1,4,8,11-Tetraazacyclotetradecan)dichloro-eisen (III) chlorid und trans-(1,4,8,11-Tetraazacyclotetradecan)dichloro-eisen (III) chlorid in J.Chem. Soc. Dalton Trans., 1997, 3459-3463 charakterisiert. Mangan-Derivate des Tetramethylcyclams (tmc) werden z.B. in Inorg. Chem. 2001, 40, 5722-5726 beschrieben. Fe(tcm)(OTf)2 wird in Science, 2003, 299, 1037-1039 als Vorstufe zu [FeO(tmc)(NCCH3)] (OTf)2 verwendet. Die Synthese von Cyclam wird u.a. in WO 1997/049691 beschrieben. Keine dieser Literaturstellen gibt Hinweise zum Einsatz dieser Verbindungen als Bleichmittel in Wasch- und Reinigungsmitteln.Iron or manganese complexes of cyclam or tetraalkylcyclam according to the invention have already been described in the literature. Thus, cis- (1,4,8,11-tetraazacyclotetradecane) dichloro-iron (III) chloride and trans- (1,4,8,11-tetraazacyclotetradecane) dichloro-iron (III) chloride are disclosed in J. Chem. Soc. Dalton Trans., 1997, 3459-3463. Manganese derivatives of tetramethylcyclam (tmc) are described, for example, in Inorg. Chem. 2001, 40, 5722-5726. Fe (tcm) (OTf) 2 is used in Science, 2003, 299, 1037-1039 as a precursor to [FeO (tmc) (NCCH 3 )] (OTf) 2 . The synthesis of cyclam is described inter alia in WO 1997/049691. None of these references gives hints on the use of these compounds as bleaching agents in detergents and cleaners.
Neben den erfindungsgemäßen Komplexen der unsubstituierten oder tetrasubstituierten Cyclame oder Cyclene der Formel (I) sind insbesondere Komplexe mit 2 Alkyl- oder Alkarylresten am Tetraazacyclus mit den allgemeinen Strukturen (IV) und (V) besonders bevorzugt: wobei R1 und R3 eine Methyl-, Ethyl-, Propyl-, Butyl- oder Benzylgruppe darstellen.In addition to the inventive complexes 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 (IV) and (V): wherein R1 and R3 represent a methyl, ethyl, propyl, butyl or benzyl group.
Besonders bevorzugt sind Komplexe mit folgenden Liganden: 1,8-Dimethylcyclam, 1,7-Dimethylcyclen, 1,8-Diethylcyclam, 1,7-Diethylcyclen, 1,8-Dibenzylcyclam und 1,7-Dibenzylcyclen. Particular preference is given to complexes with the following ligands: 1,8-dimethylcyclam, 1,7-dimethylcycles, 1,8-diethylcyclam, 1,7-diethylcycles, 1,8-dibenzylcyclam and 1.7 Dibenzylcyclen.
Die Liganden (IV) und (V) können hergestellt werden nach J. Kotter et.al., Collect. Czech. Chem. Commun., 2000, 65, 243-266, oder R. Tripier et.al., Chem. Commun., 2001, 2728-2729.The ligands (IV) and (V) 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.
Zur Aktivierung der Komplexe kommen Persauerstoffverbindungen oder Luftsauerstoff in Frage. Als Persauerstoffverbindung kommen in erster Linie Wasserstoffperoxid, Alkaliperborat-mono beziehungsweise -tetrahydrate und/oder Alkalipercarbonate, wobei Natrium das bevorzugte Alkalimetall ist, in Betracht. Daneben können aber auch Alkalimetall- oder Ammoniumperoxosulfate, wie z.B. Kaliumperoxomonosulfat (technisch: Caroat® oder Oxone®) verwendet werden. Die Konzentration der anorganischen Oxidationsmittel an der Gesamtformulierung der Wasch- und Reinigungsmittel beträgt 2 - 90 %, vorzugsweise 5 - 60 %.To activate the complexes come peroxygen compounds or Atmospheric oxygen in question. As peroxygen compound come in the first place Hydrogen peroxide, alkali perborate mono or tetrahydrate and / or Alkali percarbonates, with sodium being the preferred alkali metal, into consideration. In addition, however, alkali metal or ammonium peroxosulphates, such as e.g. Potassium peroxomonosulfate (technically: Caroat® or Oxone®) can be used. The Concentration of the inorganic oxidizing agent on the overall formulation of the Washing and cleaning agent is 2 - 90%, preferably 5 - 60%.
Als Persauerstoffverbindungen kommen auch Oxidationsmittel auf organischer Basis in Frage. Hierzu zählen alle bekannten Peroxycarbonsäuren, z.B. Monoperoxyphthalsäure, Peressigsäure, Dodecandiperoxysäure, Phthalimidoperoxycarbonsäuren wie PAP und verwandte Systeme oder Amidopersäuren.As peroxygen compounds also come oxidizing agents on an organic basis in question. These include all known peroxycarboxylic acids, e.g. Monoperoxyphthalic acid, peracetic acid, dodecanediperoxyacid, phthalimidoperoxycarboxylic acids like PAP and related systems or amido peracids.
Die Einsatzmengen an Persauerstoffverbindungen werden im allgemeinen so gewählt, dass in den Lösungen der Wasch- und Reinigungsmittel zwischen 10 ppm und 10 % Aktivsauerstoff, vorzugsweise zwischen 50 ppm und 5000 ppm Aktivsauerstoff vorhanden sind. Auch die verwendete Menge an bleichverstärkender Komplexverbindung hängt vom Anwendungszweck ab. Je nach gewünschtem Aktivierungsgrad wird sie in einer Menge von 0,01 mmol bis 25 mmol, vorzugsweise 0,1 mmol bis 2 mmol Komplex pro Mol Persauerstoffverbindung verwendet, doch können in besonderen Fällen diese Grenzen auch über- oder unterschritten werden. In Wasch- und Reinigungsmitteln sind vorzugsweise 0,0025 bis 1 Gew.-%, insbesondere 0,01 bis 0,5 Gew.-% an der oben definierten bleichverstärkenden Komplexverbindung enthalten.The amounts of peroxygen compounds are generally so chosen that in the solutions of detergents and cleaners between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm Active oxygen are present. Also the amount of bleach-enhancing Complex connection depends on the purpose of use. Depending on the desired Activation level is in an amount of 0.01 mmol to 25 mmol, preferably 0.1 mmol to 2 mmol complex per mole of peroxygen compound used, however In special cases, these limits may also be exceeded or fallen short of. In 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 included.
Neben den erfindungsgemäßen Eisen- oder Mangankomplexen, Wasserstoffperoxid
und Persalzen können weitere Bleichkatalysatoren oder Bleichaktivatoren eingesetzt
werden, um das Wirkspektrum der erfindungsgemäßen Bleichsysteme zu verbreitern
und die Effizienz insbesondere hinsichtlich der keimabtötenden Wirkung
(Desinfektion) zu steigern.
Zusätzlich zu den erfindungsgemäß eingesetzten Komplexverbindungen können
konventionelle Bleichaktivatoren, das heißt Verbindungen, die unter
Perhydrolysebedingungen Peroxocarbonsäuren freisetzen, eingesetzt werden.
Geeignet sind die üblichen Bleichaktivatoren, die O- und/oder N-Acylgruppen
enthalten. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere
Tetraacetylethylendianim (TAED), acylierte Glykolurile, insbesondere
Tetraacetylglykoluril (TAGU), acylierte Triazinderivate- insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin
(DADHT), acylierte Phenylsulfonate, insbesondere
Nonanoyl- oder Isononanoyloxybenzolsulfonat (NOBS bzw. ISONOBS) oder deren
Amidoderivate, acylierte mehrwertige Alkohole, insbesondere Triacetin,
Ethylenglykoldiacetat und 2,5-Diacetoxy-2,5-dihydrofuran sowie acetyliertes Sorbit
und Mannit, und acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG),
Pentaacetylfructose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes,
gegebenenfalls N-alkyliertes Glucamin und Gluconolacton. Weiterhin sind
offenkettige oder cyclische Nitrilquats für diesen Einsatzzweck geeignet. Auch die
aus der deutschen Patentanmeldung DE 44 43 177 bekannten Kombinationen
konventioneller Bleichaktivatoren können eingesetzt werden. Weiterhin können
Benzoylcaprolactam oder Acetylcaprolactam zur Anwendung kommen. Zusätzlich
sind auch Kombinationen der erfindungsgemäßen Komplexe mit anderen
Metallkomplexen einsetzbar.In addition to the iron or manganese complexes, hydrogen peroxide and persalts according to the invention, further bleach catalysts or bleach activators can be used in order to widen the spectrum of action of the bleaching systems according to the invention and to increase the efficiency, in particular with regard to the germicidal effect (disinfection).
In addition to the complex compounds used according to the invention, conventional bleach activators, that is to say compounds which release peroxycarboxylic acids under perhydrolysis conditions, can be used. Suitable are the usual bleach activators containing O- and / or N-acyl groups. Preference is given to 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 or Isononanoyloxybenzolsulfonat (NOBS or ISONOBS) or their amido derivatives, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetylglucose (PAG ), Pentaacetyl-fructose, tetraacetyl-xylose and octa-acetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone. Furthermore, open-chain or cyclic nitrile quats are suitable for this purpose. The combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used. Furthermore, benzoylcaprolactam or acetylcaprolactam can be used. In addition, combinations of the complexes according to the invention with other metal complexes can also be used.
Der Begriff der Bleiche umfasst hier sowohl das Bleichen von auf der Textiloberfläche befindendem Schmutz als auch das Bleichen von in der Waschflotte befindlichem, von der textilen Oberfläche abgelöstem Schmutz. Für das Bleichen von Anschmutzungen auf harten Oberflächen gilt sinngemäß das gleiche. Weitere potentielle Anwendungen finden sich im Personal Care Bereich z.B. bei der Bleiche von Haaren und zur Verbesserung der Wirksamkeit von Gebissreinigern. Des weiteren finden die beschriebenen Metallkomplexe Verwendung in gewerblichen Wäschereien, bei der Holz- und Papierbleiche, der Bleiche von Baumwolle und in Desinfektionsmitteln. The term bleaching here includes both the bleaching of on the textile surface dirt as well as the bleaching of the wash liquor, dirt removed from the textile surface. For the bleaching of Soiling on hard surfaces applies mutatis mutandis to the same. 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.
Weiterhin betrifft die Erfindung ein Verfahren zur Reinigung von Textilien wie auch von harten Oberflächen, insbesondere von Geschirr, unter Einsatz der genannten Komplexverbindungen zusammen mit Persauerstoffverbindungen in wässriger, gegebenenfalls weitere Wasch- beziehungsweise Reinigungsmittelbestandteile enthaltender Lösung, sowie Waschmittel und Reinigungsmittel für harte Oberflächen, insbesondere Reinigungsmittel für Geschirr, wobei solche für den Einsatz in maschinellen Verfahren bevorzugt sind, die derartige Komplexverbindungen enthalten.Furthermore, 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 detergents and cleaners for hard surfaces, especially dishwashing detergents, such being for use in are preferred by mechanical methods, such complex compounds contain.
Die erfindungsgemäße Verwendung besteht im wesentlichen darin, bei mit farbigen Anschmutzungen verunreinigten harten Oberflächen beziehungsweise bei verschmutzten Textilien Bedingungen zu schaffen, unter denen ein peroxidisches Oxidationsmittel und die Komplexverbindung miteinander reagieren können, mit dem Ziel, stärker oxidierend wirkende Folgeprodukte zu erhalten. Solche Bedingungen liegen insbesondere dann vor, wenn die Reaktionspartner in wässriger Lösung aufeinander treffen. Dies kann durch separate Zugabe der Persauerstoffverbindung und des Komplexes zu der wässrigen Lösung des Wasch- und Reinigungsmittels geschehen. Besonders vorteilhaft wird das erfindungsgemäße Verfahren jedoch unter Verwendung eines Waschmittels beziehungsweise Reinigungsmittels für harte Oberflächen, das die Komplexverbindung und gegebenenfalls ein persauerstoffhaltiges Oxidationsmittel enthält, durchgeführt. Die Persauerstoffverbindung kann auch separat in Substanz oder als vorzugsweise wässrige Lösung oder Suspension zur Lösung zugegeben werden, wenn ein persauerstofffreies Wasch- oder Reinigungsmittel verwendet wird.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. However, 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.
Die Wasch- und Reinigungsmittel, die als Granulate, pulver- oder tablettenförmige Feststoffe, als sonstige Formkörper, homogene Lösungen oder Suspensionen vorliegen können, können außer dem genannten bleichverstärkenden Metallkomplex im Prinzip alle bekannten und in derartigen Mitteln üblichen Inhaltsstoffe enthalten. Die Mittel können insbesondere Buildersubstanzen, oberflächenaktive Tenside, Persauerstoffverbindungen, zusätzliche Persauerstoff-Aktivatoren oder organische Persäuren, wassermischbare organische Lösungsmittel, Sequestrierungsmittel, Enzyme, sowie spezielle Additive mit farb- oder faserschonender Wirkung enthalten. 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 be present except the said 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.
Weitere Hilfsstoffe wie Elektrolyte, pH-Regulatoren, Silberkorrosionsinhibitoren, Schaumregulatoren sowie Farb- und Duftstoffe sind möglich.Other auxiliaries such as electrolytes, pH regulators, silver corrosion inhibitors, Foam regulators as well as dyes and fragrances are possible.
Ein erfindungsgemäßes Reinigungsmittel für harte Oberflächen kann darüber hinaus abrasiv wirkende Bestandteile, insbesondere Quarzmehle, Holzmehle, Kunststoffmehle, Kreiden und Mikroglaskugeln sowie deren Gemische enthalten. Abrasivstoffe sind in den Reinigungsmitteln vorzugsweise nicht über 20 Gew.-%, insbesondere von 5 bis 15 Gew.-%, enthalten.In addition, a hard surface cleaner according to the present invention may be used Abrasive constituents, in particular quartz flours, wood flours, 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.
Die Wasch- und Reinigungsmittel können ein oder mehrere Tenside enthalten, wobei insbesondere anionische Tenside, nichtionische Tenside und deren Gemische, aber auch kationische, zwitterionische und amphotere Tenside in Frage kommen. Derartige Tenside sind in erfindungsgemäßen Waschmitteln in Mengenanteilen von vorzugsweise 1 bis 50 Gew.-%, insbesondere von 3 bis 30 Gew.-%, enthalten, wohingegen in Reinigungsmitteln für harte Oberflächen normalerweise geringere Anteile, das heißt Mengen bis zu 20 Gew.-%, insbesondere bis zu 10 Gew.-% und vorzugsweise im Bereich von 0,5 bis 5 Gew.-% enthalten sind. In Reinigungsmitteln für den Einsatz in maschinellen Geschirrspülverfahren werden normalerweise schaumarme Verbindungen eingesetzt.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. Such 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. In detergents for use in automatic dishwashing are usually low-foam connections used.
Geeignete anionische Tenside sind insbesondere Seifen und solche, die Sulfat- oder Sulfonatgruppen enthalten. Als Tenside vom Sulfonat-Typ kommen vorzugsweise C9-C13-Alkylbenzolsulfonate, Olefinsulfonate, das heißt Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus C12-C18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse beziehungsweise Neutralisation gewonnen werden. Geeignet sind auch die Ester von alpha-Sulfofettsäuren (Estersulfonate), zum Beispiel die alpha-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren, die durch Sulfonierung der Methylester von Fettsäuren pflanzlichen und/oder tierischen Ursprungs mit 8 bis 20 C-Atomen im Fettsäuremolekül und nachfolgende Neutralisation zu wasserlöslichen Mono-Salzen hergestellt werden. Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups. As 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. Also suitable are alkanesulfonates which are obtained from C 12 -C 18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of alpha-sulfo fatty acids (ester sulfonates), 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.
Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester, welche Mono-, Di- und Triester sowie deren Gemische darstellen. Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C8-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlänge bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten. Auch 2,3-Alkylsulfate, sind geeignete Anionentenside. Geeignet sind auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten Alkohole, wie 2-Methylverzweigte C9-C11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-C18-Fettalkohole mit 1 bis 4 EO.Other suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof. Examples of 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. Also preferred are 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. Also suitable are the 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.
Zu den bevorzugten Aniontensiden gehören auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden, und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise mit Fettalkoholen und insbesondere mit ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten-C8-C18-Fettalkoholreste oder Mischungen aus diesen. Als weitere anionische Tenside kommen Fettsäurederivate von Aminosäuren, beispielsweise von N-Methyltaurin (Tauride) und/oder von N-Methylglycin (Sarkosinate) in Betracht. Als weitere anionische Tenside kommen insbesondere Seifen, beispielsweise in Mengen von 0,2 bis 5 Gew.-%, in Betracht. Geeignet sind insbesondere gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierten Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, zum Beispiel Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische.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 are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosinate). As further 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.
Die anionischen Tenside, einschließlich der Seifen, können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor. Anionische Tenside sind in erfindungsgemäßen Waschmitteln vorzugsweise in Mengen von 0,5 bis 10 Gew.-% und insbesondere in Mengen von 5 bis 25 Gew.-% enthalten.The anionic surfactants, including soaps, 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. Preferably, 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 from 0.5 to 10% by weight and in particular in amounts of 5 contain up to 25 wt .-%.
Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann, beziehungsweise lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z. B. aus Kokos-, Palm, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-C14-Alkohole mit 3 EO oder 4 EO, C9-C11-Alkohole mit 7 EO, C13-C15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-C18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-C14-Alkohol mit 3 EO und C12-C18-Alkohol mit 7 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind (Talg-) Fettalkohole mit 14 EO, 16 EO, 20 EO, 25 EO, 30 EO oder 40 EO.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. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for. From coconut, palm, tallow fat or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. 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). In addition to these nonionic surfactants, 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.
Zu den nichtionischen Tensiden zählen auch Alkylglykoside der allgemeinen Formel
RO(G)x, in der R einen primären geradkettigen oder methylverzweigten,
insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22,
vorzugsweise 12 bis 18 C-Atomen bedeutet und G für eine Glykoseeinheit mit 5 oder
6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die
Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl -
die als analytisch zu bestimmende Größe auch gebrochene Werte annehmen kann -
zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4. Ebenfalls geeignet sind
Polyhydroxyfettsäureamide der Formel (I),
in der Rest R1 CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R2
für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und
[Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10
Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Vorzugsweise leiten sich die
Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6
Kohlenstoffatomen, insbesondere von der Glucose ab.
Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der
Formel (II)
in der R3 einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 21
Kohlenstoffatomen, R4 einen linearen, verzweigten oder cyclischen Alkylenrest oder
einen Arylenrest mit 6 bis 8 Kohlenstoffatomen und R5 einen linearen, verzweigten
oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8
Kohlenstoffatomen bedeutet, wobei C1-C4-Alkyl- oder Phenylreste bevorzugt sind,
und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens
zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte
oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise
durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose,
Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Alyloxysubstituierten
Verbindungen können dann beispielsweise durch Umsetzung mit
Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die
gewünschten Polyhydroxyfettsäureamide überführt werden. 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 is a Glykoseeinheit with 5 or 6 C-atoms, preferably for 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. Also suitable are polyhydroxy fatty acid amides of the formula (I) 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 and [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 (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. The N-alkoxy- or N-alyloxy-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.
Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen und/oder Alkylglykosiden, eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester.Another class of preferred 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.
Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid und der Fettsäurealkanolamide können geeignet sein.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.
Aus der großen Gruppe der kationische Tenside sind insbesondere Hydroxyalkylquats der allgemeinen Strukturen (III) und (IV) bevorzugt. mit den Resten R1, R2, R3 = C1-C22 Alkyl, und n = 1 bis 5.Of the large group of cationic surfactants, in particular hydroxyalkyl quats of the general structures (III) and (IV) are preferred. with the radicals R 1, R 2, R 3 = C 1 -C 22 alkyl, and n = 1 to 5.
Als weitere Tenside kommen sogenannte Gemini-Tenside in Betracht. Hierunter werden im allgemeinen solche Verbindungen verstanden, die zwei hydrophile Gruppen pro Molekül besitzen. Diese Gruppen sind in der Regel durch einen sogenannten "Spacer" voneinander getrennt. Dieser Spacer ist in der Regel eine Kohlenstoffkette, die lang genug sein sollte, dass die hydrophilen Gruppen einen ausreichenden Abstand haben, damit sie unabhängig voneinander agieren können. Derartige Tenside zeichnen sich allgemeinen durch eine ungewöhnlich geringe kritische Micellkonzentration und die Fähigkeit, die Oberflächenspannung des Wassers stark zu reduzieren, aus. Eingesetzt werden können aber auch Gemini-Polyhydroxyfettsäureamide oder Poly-Polyhydroxyfettsäureamide. Weitere Tensidtypen können dendrimere Strukturen aufweisen. Other suitable 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. However, gemini polyhydroxy fatty acid amides can also be used or poly-polyhydroxy fatty acid amides. Further Surfactant types may have dendrimeric structures.
Ein erfindungsgemäßes Waschmittel enthält vorzugsweise mindestens einen wasserlöslichen und/oder wasserunlöslichen, organischen und/oder anorganischen Builder.A detergent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic Builder.
Als wasserlösliche anorganische Buildermaterialien kommen insbesondere
Alkalisilikate und polymere Alkaliphosphate, die in Form ihrer alkalischen, neutralen
oder sauren Natrium- oder Kaliumsalze vorliegen können, in Betracht. Beispiele
hierfür sind Trinatriumphosphat, Tetranatriumdiphosphat, Dinatriumdihydrogendiphosphat,
Pentanatriumtriphosphat, sogenanntes Natriumhexametaphosphat sowie
die entsprechenden Kaliumsalze beziehungsweise Gemische aus Natrium- und
Kaliumsalzen. Als wasserunlösliche, wasserdispergierbare anorganische
Buildermaterialien werden insbesondere kristalline oder amorphe Alkalialumosilikate,
in Mengen von bis zu 50 Gew.-% eingesetzt. Unter diesen sind die kristallinen
Natriumalumosilikate in Waschmittelqualität, insbesondere Zeolith A, P und
gegebenenfalls X, allein oder in Mischungen, beispielsweise in Form eines Co-Kristallisats
aus den Zeolithen A und X bevorzugt. Ihr Calciumbindevermögen, das
nach den Angaben der deutschen Patentschrift DE 24 12 837 bestimmt werden
kann, liegt in der Regel im Bereich von 100 bis 200 mg CaO pro Gramm. Geeignete
Buildersubstanzen sind weiterhin kristalline Alkalisilikate, die allein oder im Gemisch
mit amorphen Silikaten vorliegen können. Die als Gerüststoffe brauchbaren
Alkalisilikate weisen vorzugsweise ein molares Verhältnis von Alkalioxid zu SiO2
unter 0,95, insbesondere von 1 : 1,1 bis 1 : 12 auf und können amorph oder kristallin
vorliegen. Bevorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die
amorphen Natriumsilikate mit einem molaren Verhältnis Na20 : SiO, von 1 : 2 bis 1 :
2.8. Solche Silikate können nach dem Verfahren der europäischen Patentanmeldung
EP 0 425 427 hergestellt werden. Als kristalline Silikate, die allein oder im Gemisch
mit amorphen Silikaten vorliegen können, werden vorzugsweise kristalline
Schichtsilikate der allgemeinen Formel Na2SixO2x+1 · Y H2O eingesetzt, in der x,
das so genannte Modul, eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und
bevorzugte Werte für x 2, 3 oder 4 sind. Kristalline Schichtsilikate, die unter diese
allgemeine Formel fallen, werden beispielsweise in der europäischen
Patentanmeldung EP 0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate
sind solche, bei denen x in der genannten allgemeinen Formel die Werte 2
oder 3 annimmt. Insbesondere sind sowohl α- als auch ß-Natriumdisilikate
(Na2Si2O5 · y H2O) bevorzugt, wobei ß-Natriumdisilikat beispielsweise nach dem
Verfahren erhalten werden kann, das in WO 91/08171 beschrieben ist.
ß-Natriumsilikate mit einem Modul zwischen 1,9 und 3,2 können gemäß den
japanischen Patentanmeldungen JP 04/238 809 oder
JP 04/260 6 10 hergestellt werden. Auch aus amorphen Silikaten hergestellte,
praktisch wasserfreie kristalline Alkalisilikate der obengenannten allgemeinen
Formel, in der x eine Zahl von 1,9 bis 2,1 bedeutet, können eingesetzt werden. In
einer weiteren bevorzugten Ausführungsform derartiger Mittel wird ein kristallines
Natriumschichtsilikat mit einem Modul von 2 bis 3 eingesetzt. Kristalline
Natriumsilikate mit einem Modul im Bereich von 1,9 bis 3,5, werden in einer weiteren
bevorzugten Ausführungsform eingesetzt. In einer bevorzugten Ausgestaltung setzt
man ein granulares Compound aus Alkalisilikat und Alkalicarbonat ein, wie es
beispielsweise unter dem Namen Nabion® im Handel erhältlich ist. Falls als
zusätzliche Buildersubstanz auch Alkalialumosilikat, insbesondere Zeolith, vorhanden
ist, beträgt das Gewichtsverhältnis Alumosilikat zu Silikat, jeweils bezogen auf
wasserfreie Aktivsubstanzen, vorzugsweise 1 : 10 bis 10 : 1. In Mitteln, die sowohl
amorphe als auch kristalline Alkalisilikate enthalten, beträgt das Gewichtsverhältnis
von amorphem Alkalisilikat zu kristallinem Alkalisilikat vorzugsweise 1 : 2 bis 2 : 1
und insbesondere 1 : 1 bis 2 : 1.
Derartige Buildersubstanzen sind in erfindungsgemäßen Mitteln vorzugsweise in
Mengen bis zu 60 Gew.-%, insbesondere von 5 bis 40 Gew.-%, enthalten.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. 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. Among these, preferred are 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 metal silicates are the sodium silicates, in particular the amorphous sodium silicates with a molar ratio Na 2 O: SiO 2, of 1: 2 to 1: 2.8. Such silicates 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 x O 2x + 1 · YH be used 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. In particular, both α- and ß-sodium (Na 2 Si 2 O 5 · yH 2 O) are preferred, with .beta.-sodium disilicate being obtainable, for example, by the process described in WO 91/08171. β-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. 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. In a further preferred embodiment of such agents, 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. In a preferred embodiment, a granular compound of alkali silicate and alkali carbonate is used, as it is commercially available, for example, under the name Nabion®. 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. In compositions containing both amorphous and crystalline alkali silicates, 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.
Zu den wasserlöslichen organischen Buildersubstanzen gehören Polycarbonsäuren, insbesondere Zitronensäure und Zuckersäuren, Aminopolycarbonsäuren, insbesondere Methylglycindiessigsäure, Nitrilotriessigsäure und Ethylendiamintetraessigsäure sowie Polyasparaginsäure.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.
Polyphosphonsäuren, insbesondere Aminotris(methylenphosphonsäure),
Ethylendiamintetrakis(methylenphosphonsäure) und 1 -Hydroxyethan-1,1-diphosphonsäure
können ebenfalls eingesetzt werden. Bevorzugt sind auch
polymere (Poly-)carbonsäuren, insbesondere die durch Oxidation von
Polysacchariden beziehungsweise Dextrinen zugänglichen Polycarboxylate der
internationalen Patentanmeldung WO 93/161 10 beziehungsweise der
internationalen Patentanmeldung WO 92/18542 oder der europäischen Patentschrift
EP 0 232 202, polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und
Mischpolymere aus diesen, die auch geringe Anteile polymerisierbarer Substanzen
ohne Carbonsäurefunktionalität einpolymerisiert enthalten können. Die relative
Molekülmasse der Homopolymeren ungesättigter Carbonsäuren liegt im allgemeinen
zwischen 5000 und 200 000, die der Copolymeren zwischen 2000 und 200 000,
vorzugsweise 50 000 bis 120 000, jeweils bezogen auf freie Säure. Ein besonders
bevorzugtes Acrylsäure-Maleinsäure-Copolymer weist eine relative Molekülmasse
von 50 000 bis 100 000 auf. Handelsübliche Produkte sind zum Beispiel Sokalan®
CP 5, CP 10 und PA 30 der Firma BASF. Geeignet sind weiterhin Copolymere der
Acrylsäure oder Methacrylsäure mit Vinylethern, wie Vinylmethylethern, Vinylester,
Ethylen, Propylen und Styrol, in denen der Anteil der Säure mindestens 50 Gew.-%
beträgt. Als wasserlösliche organische Buildersubstanzen können auch Terpolymere
eingesetzt werden, die als Monomere zwei ungesättigte Säuren und/oder deren
Salze sowie als drittes Monomer Vinylalkohol und/oder einem veresterten
Vinylalkohol oder ein Kohlenhydrat enthalten. Das erste saure Monomer
beziehungsweise dessen Salz leitet sich von einer monoethylenisch ungesättigten
C3-C8-Carbonsäure und vorzugsweise von einer C3-C4-Monocarbonsäure,
insbesondere von (Meth)-acrylsäure ab.
Das zweite saure Monomer beziehungsweise-dessen Salz kann ein Derivat einer
C4-C8-Dicarbonsäure, wobei Maleinsäure besonders bevorzugt ist, und/oder ein
Derivat einer Allylsulfonsäure, die in 2-Stellung mit einem Alkyl- oder Arylrest
substituiert ist, sein. Derartige Polymere lassen sich insbesondere nach Verfahren
herstellen, die in den deutschen Patentschriften DE 42 21 381 und DE 43 00 772
beschrieben sind, und weisen im allgemeinen eine relative Molekülmasse zwischen
1000 und 200 000 auf. Weitere bevorzugte Copolymere sind solche, die in den
deutschen Patentanmeldungen DE 43 03 320 und DE 44 17 734 beschrieben
werden und als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäuresalze
beziehungsweise Vinylacetat aufweisen.Polyphosphonic acids, especially aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid can also be used. Also preferred are 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. It is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer as water-soluble organic builder substances. 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.
Die organischen Buildersubstanzen können, insbesondere zur Herstellung flüssiger Mittel, in Form wässriger Lösungen, vorzugsweise in Form 30 bis 50 gew.-%iger wässriger Lösungen eingesetzt werden. Alle genannten Säuren werden in der Regel in Form ihrer wasserlöslichen Salze, insbesondere ihre Alkalisalze, eingesetzt. 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.
Derartige organische Buildersubstanzen können gewünschtenfalls in Mengen bis zu 40 Gew.-%, insbesondere bis zu 25 Gew.-% und vorzugsweise von 1 bis 8 Gew.-% enthalten sein. Mengen nahe der genannten Obergrenze werden vorzugsweise in pastenförmigen oder flüssigen, insbesondere wasserhaltigen Mitteln eingesetzt.If desired, such 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.
Als wasserlösliche Builderkomponenten in erfindungsgemäßen Reinigungsmitteln für harte Oberflächen kommen prinzipiell alle in Mitteln für die maschinelle Reinigung von Geschirr üblicherweise eingesetzten Builder in Frage, zum Beispiel die obengenannten Alkaliphosphate. Ihre Mengen können im Bereich von bis zu etwa 60 Gew.-%, insbesondere 5 bis 20 Gew.-%, bezogen auf das gesamte Mittel liegen. Weitere mögliche wasserlösliche Builder-Komponenten sind neben Polyphosphonaten und Phosphonatalkylcarboxylaten zum Beispiel organische Polymere nativen oder synthetischen Ursprungs vom oben aufgeführten Typ der Polycarboxylate, die insbesondere in Hartwasserregionen als Co-Builder wirken, und natürlich vorkommende Hvdroxycarbonsäuren wie zum Beispiel Mono-, Dihydroxybernsteinsäure, alpha-Hydroxypropionsäure und Gluconsäure. Zu den bevorzugten organischen Builder-Komponenten gehören die Salze der Zitronensäure, insbesondere Natriumcitrat. Als Natriumcitrat kommen wasserfreies Triatriumcitrat und vorzugsweise Trinatriumcitratdihydrat in Betracht. Trinatriumcitratdihydrat kann als fein- oder grobkristallines Pulver eingesetzt werden. In Abhängigkeit vom letztlich in den erfindungsgemäßen Reinigungsmitteln eingestellten pH-Wert können auch die zu den genannten Co-Builder-Salzen korrespondierenden Säuren vorliegen.As 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 mean. Other possible 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. As sodium citrate come anhydrous Triatrium citrate and preferably trisodium citrate dihydrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. Depending on the final cleaning agents in the invention Adjusted pH can also be added to the mentioned co-builder salts corresponding acids are present.
Zu den in erfindungsgemäßen Mitteln gegebenenfalls enthaltenen Enzymen gehören Proteasen, Amylasen, Pullulanasen, Cellulasen, Cutinasen und/oder Lipasen, beispielsweise Proteasen wie BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® und/oder Savinase®, Amylasen wie Termamy®, Amylase-LT, Maxamyl®, Duramyl®, Purafectel OxAm, Cellulasen wie Celluzyme®, Carezyme®, K-AC® und/oder die aus den internationalen Patentanmeldungen WO 96/34108 und WO 96/34092 bekannten Cellulasen und/oder Lipasen wie Lipolase®, Lipomax®, Lumafast® und/oder Lipozym®. Die verwendeten Enzyme können, wie zum Beispiel in den internationalen Patentanmeldungen WO 92/111347 oder WO 94/23005 beschrieben, an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Inaktivierung zu schützen. Sie sind in erfindungsgemäßen Wasch- und Reinigungsmitteln vorzugsweise in Mengen bis zu 10 Gew.-%, insbesondere von 0,05 bis 5 Gew.-%, enthalten, wobei besonders bevorzugt gegen oxidativen Abbau stabilisierte Enzyme, eingesetzt werden.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®. The used enzymes, such as in the international Patent Applications WO 92/111347 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 are used.
Vorzugsweise enthalten erfindungsgemäße maschinelle Geschirrreinigungsmittel die üblichen Alkaliträger wie zum Beispiel Alkalisilikate, Alkalicarbonate und/oder Alkalihydrogencarbonate. Zu den üblicherweise eingesetzten Alkaliträgern zählen Carbonate, Hydrogencarbonate und Alkalisilikate mit einem Molverhältnis SiO2/M20 (M = Alkaliatom) von 1 : 1 bis 2,5 : 1. Alkalisilikate können dabei in Mengen von bis zu 40 Gew.-%, insbesondere 3 bis 30 Gew.-%, bezogen auf das gesamte Mittel, enthalten sein. Das in erfindungsgemäßen Reinigungsmitteln bevorzugt eingesetzte Alkaliträgersystem ist ein Gemisch aus Carbonat und Hydrogencarbonat, vorzugsweise Natriumcarbonat und -hydrogencarbonat, das in einer Menge von bis zu 50 Gew.-%, vorzugsweise 5 bis 40 Gew.-%, enthalten sein kann.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. The alkali carriers used conventionally include carbonates, bicarbonates and alkali silicates having a molar ratio of SiO 2 / M 2 O (M = alkali metal) of 1: 1 to 2.5: 1. 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.
Ein weiterer Erfindungsgegenstand ist ein Mittel zum maschinellen Reinigen von Geschirr, enthaltend 15 bis 65 Gew:-%, insbesondere 20 bis 60 Gew.-% wasserlösliche Builderkompenente, 5 bis 25 Gew.-%, insbesondere 8 bis 17 Gew.-% Bleichmittel auf Sauerstoffbasis, jeweils bezogen auf das gesamte Mittel, und 0,1 bis 1 Gew.-% einer oder mehrerer der oben definierten Metallkomplexe. Ein derartiges Mittel ist vorzugsweise niederalkalisch, d.h. seine Lösung weist einen pH-Wert von 8 bis 11,5, insbesondere 9 bis 11 auf.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 Builderkompenente, 5 to 25 wt .-%, in particular 8 to 17 wt .-% Oxygen-based bleach, based in each case on the total agent, and 0.1 to 1 wt .-% of one or more of the metal complexes defined above. Such a thing Agent is preferably lower alkyl, i. its solution has a pH of 8 to 11.5, especially 9 to 11 on.
In einer weiteren Ausführungsform erfindungsgemäßer Mittel zur automatischen Reinigung von Geschirr sind 20 bis 60 Gew.-% wasserlöslicher organischer Builder, insbesondere Alkalicitrat, 3 bis 20 Gew.-% Alkalicarbonat und 3 bis 40 Gew.-% Alkalidisilikat enthalten.In a further embodiment of the invention 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.
Um einen Silberkorrosionsschutz zu bewirken, können in erfindungsgemäßen Reinigungsmitteln für Geschirr Silberkorrosionsinhibitoren eingesetzt werden. Bevorzugte Silberkorrosionsschutzmittel sind organische Sulfide wie Cystin und Cystein, zwei- oder dreiwertige Phenole, gegebenenfalls alkyl- oder arylsubstituierte Triazole wie Benzotriazol, Isocyanursäure, Titan-, Zirkonium-, Hafnium-, Molybdän-, Vanadium- oder Cersalze und/oder -komplexe, sowie Salze und/oder Komplexe der in den erfindungsgemäß geeigneten Komplexen enthaltenen Metalle mit anderen als in Formel (I) vorgegebenen Liganden.In order to effect silver corrosion protection, in 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.
Sofern die Mittel bei der Anwendung zu stark schäumen, können ihnen noch bis zu 6 Gew.-%, vorzugsweise etwa 0,5 bis 4 Gew.-% einer schaumregulierenden Verbindung, vorzugsweise aus der Gruppe umfassend Silikone, Paraffine, Paraffin-Alkohol-Kombinationen, hydrophobierte Kieselsäuren, Bisfettsäureamide sowie deren Gemische und sonstige bekannte im Handel erhältliche Schauminhibitoren zugesetzt werden. Vorzugsweise sind die Schauminhibitoren, insbesondere Silikon- und/oder paraffinhaltige Schauminhibitoren, an eine granulare, in Wasser lösliche beziehungsweise dispergierbare Trägersubstanz gebunden. Insbesondere sind dabei Mischungen aus Paraffinen und Bistearylethylendiamid bevorzugt. Weitere fakultative Inhaltsstoffe in den erfindungsgemäßen Mitteln sind zum Beispiel Parfümöle.If 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, bis-fatty acid amides and their Mixtures and other known commercially available foam inhibitors added become. Preferably, the foam inhibitors, in particular silicone and / or paraffinic foam inhibitors, to a granular, water-soluble or dispersible carrier substance bound. In particular, there are Blends of paraffins and bistearylethylenediamide are preferred. Further optional Ingredients in the compositions according to the invention are, for example, perfume oils.
Zu den in den erfindungsgemäßen Mitteln, insbesondere wenn sie in flüssiger oder pastöser Form vorliegen, verwendbaren organischen Lösungsmitteln gehören Alkohole mit 1 bis 4 C-Atomen, insbesondere-Methanol, Ethanol, Isopropanol und tert-Butanol, Diole mit 2 bis 4 C-Atomen, insbesondere Ethylenglykol und Propylenglykol, sowie deren Gemische und die aus den genannten Verbindungsklassen ableitbaren Ether. Derartige wassermischbare Lösungsmittel sind in den erfindungsgemäßen Reinigungsmitteln vorzugsweise nicht über 20 Gew.-%, insbesondere von 1 bis 15 Gew.-%, vorhanden.To those in the inventive compositions, especially when in liquid or pasty form, 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.
Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH-Werts können die erfindungsgemäßen Mittel System- und umweltverträgliche Säuren, insbesondere Zitronensäure, Essigsäure, Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure oder Alkalihydrogensulfate, oder Basen, insbesondere Ammonium- oder Alkalihydroxide, enthalten. Derartige pH-Regulatoren sind in den erfindungsgemäßen Mitteln vorzugsweise nicht über 10 Gew.-%, insbesondere von 0,5 bis 6 Gew.-%, enthalten.To set a desired one, by mixing the rest 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. Such 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.
Die erfindungsgemäßen Mittel liegen als pulverförmige, granulare oder tablettenförmige Präparate vor, die in an sich bekannter Weise, beispielsweise durch Mischen, Granulieren, Walzenkompaktieren und/oder durch Sprühtrocknung der thermisch belastbaren Komponenten und Zumischen der empfindlicheren Komponenten, zu denen insbesondere Enzyme, Bleichmittel und der Bleichkatalysator zu rechnen sind, hergestellt werden können. Erfindungsgemäße Mittel in Form wässriger oder sonstige übliche Lösungsmittel enthaltender Lösungen werden besonders vorteilhaft durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automatischen Mischer gegeben werden können, hergestellt.The compositions according to the invention are in the form of powdery, 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.
Zur Herstellung von teilchenförmigen Mitteln mit erhöhtem Schüttgewicht, insbesondere im Bereich von 650 g/l bis 950 g/l, ist ein aus der europäischen Patentschrift EP 0 486 592 bekanntes, einen Extrusionsschritt aufweisendes Verfahren bevorzugt. Eine weitere bevorzugte Herstellung mit Hilfe eines Granulationsverfahrens ist in der europäischen Patentschrift EP 0 642 576 beschrieben. Die Herstellung erfindungsgemäßer Mittel in Form von nicht staubenden, lagerstabil rieselfähigen Pulvern und/oder Granulaten mit hohen Schüttdichten im Bereich von 800 bis 1000 g/l kann auch dadurch erfolgen, dass man in einer ersten Verfahrensstufe die Builder-Komponenten mit wenigstens einem Anteil flüssiger Mischungskomponenten unter Erhöhung der Schüttdichte dieses Vorgemisches vermischt und nachfolgend - gewünschtenfalls nach einer Zwischentrocknung - die weiteren Bestandteile des Mittels, darunter den Bleichkatalysator, mit dem so gewonnenen Vorgemisch vereinigt.For the production of particulate agents with increased bulk density, in particular in the range of 650 g / l to 950 g / l, is one from the European Patent EP 0 486 592 known, having an extrusion step Preferred method. Another preferred preparation using a Granulation process is described in European Patent EP 0 642 576 described. The preparation of 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.
Zur Herstellung von erfindungsgemäßen Mitteln in Tablettenform geht man vorzugsweise derart vor, dass man alle Bestandteile in einem Mischer miteinander vermischt und das Gemisch mittels herkömmlicher Tablettenpressen, beispielsweise Exzenterpressen oder Rundläuferpressen, mit Pressdrucken im Bereich von 200 . 105 Pa bis 1500 105 Pa verpresst. Man erhält so problemlos bruchfeste und dennoch unter Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Biegefestigkeiten von normalerweise über 150 N. Vorzugsweise weist eine derart hergestellte Tablette ein Gewicht von 1-5 g bis 40 g, insbesondere von 20 g bis 30 g auf, bei einem Durchmesser von 3-5 mm bis 40 mm.For the preparation of 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. This gives unbreakable, yet sufficiently rapidly soluble tablets under application conditions with flexural strengths of normally over 150 N. Preferably, 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.
In flüssigen oder pastösen Anwendungen kommen die erfindungsgemäßen Komplexe vorzugsweise als wässrige Lösung oder in mikroverkapselter Form zum Einsatz. Werden sie zum Zwecke der Nutzung von Luftsauerstoff eingesetzt (aerial bleaching) kann auf den Einsatz von Peroxoverbindungen verzichtet werden. Sollen sie jedoch in Kombination mit einer Peroxoverbindung, z.B. Wasserstoffperoxid zum Einsatz kommen, empfiehlt sich die Verwendung eines Mehrkammerbehälters.In liquid or pasty applications, the invention Complexes preferably as an aqueous solution or in microencapsulated form for Commitment. Are they used for the purpose of using atmospheric oxygen (aerial bleaching) can be dispensed with the use of peroxo compounds. Should however, in combination with a peroxo compound, e.g. Hydrogen peroxide for Use, we recommend the use of a multi-chamber container.
12,6 g (0,1 mol) Mangan(II)chlorid wurden in 100 ml DMAC gelöst. Die Lösung wurde
mit 25,6 g (0,1 mol) 1,8-Diethyl-1,4,8,11-Tetraazacyclotetradecan versetzt. Das
Reaktionsgemisch wurde 5 Stunden auf 100°C erwärmt. Die erhaltene Suspension
wurde auf Raumtemperatur abgekühlt, der entstandene Feststoff abfiltriert, mit 50 ml
DMAC gewaschen und anschließend bei 80°C im Vakuum getrocknet. Es wurden
37,1 g des hellgrauen Komplexes erhalten, was einer Ausbeute von 97,0 %
entspricht.
12,7 g (0,1 mol) Eisen(II)chlorid wurden in 100 ml DMAC vorgelegt und anschließend
mit 25,6 g (0,1 mol) 1,8-Diethyl-1,4,8,11-Tetraazacyclotetradecan versetzt. Das
Reaktionsgemisch wurde 5 Stunden auf 100°C erwärmt. Die erhaltene Suspension
wurde auf Raumtemperatur abgekühlt, der entstandene Feststoff abfiltriert, mit 50ml
DMAC gewaschen und anschließend bei 80°C im Vakuum getrocknet. Es wurden
34,9 g des beige-hellbraunen Komplexes erhalten, was einer Ausbeute von 91,0 %
entspricht.
Unter Stickstoff wurden 9,0 g (0,072mol) Mangan(II)chlorid in 100ml DMAC gelöst.
Die Lösung wurde mit 14,4 g (0,072mol) 1,4,8,11-Tetraaza-cyclotetradecan versetzt.
Das Reaktionsgemisch wurde 5 Stunden auf 100°C erwärmt, anschließend auf
Raumtemperatur abgekühlt. Der entstandene Niederschlag wurde abfiltriert, mit
50 ml DMAC gewaschen und anschließend bei 80°C im Vakuum getrocknet. Es
wurden 22,9 g des hellgrauen Komplexes erhalten, was einer Ausbeute von 97,5 %
entspricht.
Unter Stickstoff wurden 2,5 g (0,02 mol) Mangan(II)chlorid in 100 ml Methanol gelöst. Die Lösung wurde mit 4,5 g (0,02 mol) 1,8-Dimethyl-1,4,8,11-Tetraazacyclotetradecan versetzt. Das Reaktionsgemisch wurde 2 Stunden bei Raumtemperatur gerührt und danach mit 16,4 g (0,048 mol) Natriumtetraphenylborat versetzt. Nachdem die Reaktion weitere 30 min bei Raumtemperatur gerührt wurde, wurde der entstandene Niederschlag abfiltriert, mehrmals mit Methanol gewaschen und getrocknet. Es wurden 11,3 g des hellgrauen Komplexes erhalten, was einer Ausbeute von 88,6 % entspricht.Under nitrogen, 2.5 g (0.02 mol) of manganese (II) chloride were dissolved in 100 ml of methanol. The solution was treated with 4.5 g (0.02 mol) of 1,8-dimethyl-1,4,8,11-tetraazacyclotetradecane added. The reaction mixture was allowed to stand at room temperature for 2 hours stirred and then mixed with 16.4 g (0.048 mol) of sodium tetraphenylborate. After the reaction was stirred for a further 30 minutes at room temperature, the filtered precipitate, washed several times with methanol and dried. There were obtained 11.3 g of the light gray complex, which was a Yield of 88.6% corresponds.
Unter Stickstoff wurden 2,5 g (0,02mol) Mangan(II)chlorid in 100 ml Methanol gelöst. Die Lösung wurde mit 5,1 g (0,02mol) 1,8-Diethyl-1,4,8,11-Tetraazacyclotetradecan versetzt. Das Reaktionsgemisch wurde 2 Stunden bei Raumtemperatur gerührt und danach mit 16,4 g (0,048mol) Natriumtetraphenylborat versetzt. Nachdem die Reaktion weitere 30 min bei Raumtemperatur gerührt wurde, wurde der entstandene Niederschlag abfiltriert, mehrmals mit Methanol gewaschen und getrocknet. Es wurden 6,4 g des hellbeigen Komplexes erhalten, was einer Ausbeute von 48,0% entspricht.Under nitrogen, 2.5 g (0.02 mol) of manganese (II) chloride were dissolved in 100 ml of methanol. The solution was treated with 5.1 g (0.02 mol) of 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane added. The reaction mixture was stirred for 2 hours at room temperature and then mixed with 16.4 g (0.048 mol) of sodium tetraphenylborate. after the Reaction was stirred for a further 30 min at room temperature, the resulting Precipitate filtered off, washed several times with methanol and dried. It 6.4 g of the light beige complex were obtained, resulting in a yield of 48.0%. equivalent.
Die Bleichleistung der erfindungsgemäßen Verbindungen Cat 1 und Cat 2 wurde im
Vergleich zum Bleichaktivator TAED ausgeprüft. Hierzu wurden 10 mg/l Cat 1, Cat 2
bzw. Cat 3 in einer Waschlauge, hergestellt durch Auflösen von 2 g/l eines
bleichmittelfreien Grundwaschmittels (WMP, WFK, Krefeld), gelöst. Nach Zugabe
von 1 g/l Natriumpercarbonat (Fa. Degussa) wurden die Waschversuche in einem
Linitest-Gerät (Fa. Heraus) bei 40°C durchgeführt. Die Waschzeit betrug 30 min,
Wasserhärte 18°dH. Als Bleichtestgewebe dienten zwei Teeanschmutzungen auf
Baumwolle (BC-1 und BC3, WFK, Krefeld). Als Bleichergebnis wurde die
Remissionsdifferenz, gemessen mit einem Elrepho-Gerät, nach der Wäsche im
Vergleich zum ungewaschenen Gewebe gewertet. Als Vergleichsversuch (V1)
wurden statt der erfindungsgemäßen 10 mg/l der Verbindungen (Cat 1 bis Cat 3)
250 mg/l TAED eingesetzt.
Man erkennt, dass durch die erfindungsgemäßen Verbindungen (Cat 1 bis Cat 3)
eine signifikante Bleichwirkung erreicht werden kann. Insbesondere Cat 1 zeigt auch
deutliche Vorteile gegenüber dem konventionellen Bleichaktivator TAED, der in
wesentlich höherer Konzentration eingesetzt wurde (V1).
Im wesentlichen gleiche Ergebnisse wurden erhalten, wenn man das
Natriumpercarbonat durch Natriumperborat ersetzte.It can be seen that a significant bleaching effect can be achieved by the compounds according to the invention (Cat 1 to Cat 3). In particular, Cat 1 also shows significant advantages over the conventional bleach activator TAED, which was used in much higher concentrations (V1).
Substantially similar results were obtained when replacing sodium percarbonate with sodium perborate.
Die Bleichleistung der erfindungsgemäßen Verbindung Cat 1 wurde in Kombination
mit dem Bleichaktivator TAED ausgeprüft. Hierzu wurden 10 mg/l Cat 1 und 200 mg/l
TAED in einer Waschlauge, hergestellt durch Auflösen von 2 g/l eines
bleichmittelfreien Grundwaschmittels (WMP, WFK, Krefeld), gelöst. Nach Zugabe
von 1 g/l Natriumpercarbonat (Fa. Degussa) wurden die Waschversuche in einem
Linitest-Gerät (Fa. Heraus) bei 40°C durchgeführt. Die Waschzeit betrug 30 min,
Wasserhärte 18°dH. Als Bleichtestgewebe dienten zwei Teeanschmutzungen auf
Baumwolle (BC-1 und BC3, WFK, Krefeld). Als Bleichergebnis wurde die
Remissionsdifferenz, gemessen mit einem Elrepho-Gerät, nach der Wäsche im
Vergleich zum ungewaschenen Gewebe gewertet. Als Vergleichsversuch (V2)
wurden 250 mg/l TAED eingesetzt.
Man erkennt, dass durch die erfindungsgemäße Verbindung Cat 1 eine signifikante Bleichwirkung erreicht werden kann. Im wesentlichen gleiche Ergebnisse wurden erhalten, wenn man das Natriumpercarbonat durch Natriumperborat ersetzte.It can be seen that by means of the compound Cat 1 according to the invention a significant Bleaching effect can be achieved. Substantially similar results were obtained obtained by replacing the sodium percarbonate with sodium perborate.
Die Bleichleistung der erfindungsgemäßen Verbindungen Cat 1 und Cat 2 wurde ohne Zugabe von Peroxiden ausgeprüft. Hierzu wurden 10 mg/l Cat 1 bzw. Cat 2 in einer Waschlauge, hergestellt durch Auflösen von 2 g/l eines bleichmittelfreien Grundwaschmittels (WMP, WFK, Krefeld), gelöst. Die Waschversuche wurden in einem Linitest-Gerät (Fa. Heräus) bei 20 und 40°C durchgeführt. Die Waschzeit betrug 30 min, Wasserhärte 18°dH. Nach der Wäsche wurde das Gewebe getrocknet und gebügelt. Als Bleichtestgewebe dienten zwei selbst hergestellte ölhaltige Anschmutzungen auf Baumwolle (Ketchup/Öl und Curry/Öl, hergestellt durch auskochen von Ketchup bzw. Curry-Pulver mit Sonnenblumenöl). Als Bleichergebnis wurde die Remissionsdifferenz, gemessen mit einem Elrepho-Gerät, nach der Wäsche im Vergleich zum ungewaschenen Gewebe gewertet. Als Vergleichsversuch (V1) wurde das Waschmittel ohne Komplexzusatz verwendet.The bleaching performance of the compounds of the invention Cat 1 and Cat 2 was tested without the addition of peroxides. For this purpose, 10 mg / l Cat 1 or Cat 2 in a wash liquor prepared by dissolving 2 g / L of a bleach-free Basic detergent (WMP, WFK, Krefeld), solved. The washing tests were in a Linitest device (Heraeus) at 20 and 40 ° C performed. The washing time was 30 min, water hardness 18 ° dH. After washing, the fabric was dried and ironed. As a bleaching test fabric served two self-made oily Stains on cotton (ketchup / oil and curry / oil, made by boil ketchup or curry powder with sunflower oil). As a bleaching result the remission difference, measured with an Elrepho device, after the Laundry compared to unwashed fabric. As a comparative experiment (V1) the detergent without complex addition was used.
Man erkennt, dass die erfindungsgemäßen Verbindungen, insbesondere Cat 1 und 2, die eine signifikante Bleichwirkung bewirken.It can be seen that the compounds according to the invention, in particular Cat 1 and 2, which cause a significant bleaching effect.
Die Versuche wurden analog Beispiel 6 durchgeführt. Als Waschtemperaturen
wurden 20 und 40°C gewählt.
Die Versuche wurden analog Beispiel 8 bei 20°C an Curry/Ölanschmutzung durchgeführt. The experiments were carried out analogously to Example 8 at 20 ° C to curry / Ölanschmutzung carried out.
Claims (7)
- M
- ein Metallatom aus der Gruppe Mn und Fe,
- L
- ein Ligand der allgemeinen Formel (II) oder (III)
X und Y ein Neutral- oder Anionligand aus der Gruppe CH3CN, Chlorid, Bromid, Nitrat, Perchlorat, Sulfat, Citrat, Hexafluorophosphat, Trifluormethansulfonat, Tetrafluoroborat, Tetraphenylborat oder ein Anion organischer Säuren mit C1-C22 Kohlenstoffatomen,
n und m eine Zahl von 0 bis 4 bedeuten, als Bleichkatalysator in Wasch- und Reinigungsmitteln.Use of transition metal complexes of the formula (I)
- M
- a metal atom from the group Mn and Fe,
- L
- a ligand of the general formula (II) or (III)
X and Y are a neutral or anion ligand selected from the group consisting of CH 3 CN, chloride, bromide, nitrate, perchlorate, sulfate, citrate, hexafluorophosphate, trifluoromethanesulfonate, tetrafluoroborate, tetraphenylborate or an organic acid anion having C 1 -C 22 carbon atoms,
n and m represent a number from 0 to 4, as a bleach catalyst in detergents and cleaners.
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DE102004003710 | 2004-01-24 | ||
DE102004003710A DE102004003710A1 (en) | 2004-01-24 | 2004-01-24 | Use of transition metal complexes as bleaching catalysts in detergents and cleaners |
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EP1557457B1 EP1557457B1 (en) | 2007-11-14 |
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US (1) | US7205267B2 (en) |
EP (1) | EP1557457B1 (en) |
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Also Published As
Publication number | Publication date |
---|---|
JP2005232450A (en) | 2005-09-02 |
US20050209120A1 (en) | 2005-09-22 |
US7205267B2 (en) | 2007-04-17 |
EP1557457B1 (en) | 2007-11-14 |
JP5041665B2 (en) | 2012-10-03 |
ES2295983T3 (en) | 2008-04-16 |
DE502005001918D1 (en) | 2007-12-27 |
DE102004003710A1 (en) | 2005-08-11 |
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