EP1749084B1 - Bleichverstärkerkombination für den einsatz in wasch- und reinigungsmitteln - Google Patents

Bleichverstärkerkombination für den einsatz in wasch- und reinigungsmitteln Download PDF

Info

Publication number
EP1749084B1
EP1749084B1 EP05743291A EP05743291A EP1749084B1 EP 1749084 B1 EP1749084 B1 EP 1749084B1 EP 05743291 A EP05743291 A EP 05743291A EP 05743291 A EP05743291 A EP 05743291A EP 1749084 B1 EP1749084 B1 EP 1749084B1
Authority
EP
European Patent Office
Prior art keywords
acid
bleach
formula
type
manganese
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP05743291A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1749084A1 (de
Inventor
Heike Schirmer-Ditze
Doris Dahlmann
Birgit Middelhauve
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL05743291T priority Critical patent/PL1749084T3/pl
Publication of EP1749084A1 publication Critical patent/EP1749084A1/de
Application granted granted Critical
Publication of EP1749084B1 publication Critical patent/EP1749084B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3927—Quarternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/168—Organometallic compounds or orgometallic complexes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames

Definitions

  • the present invention relates to the use of a combination of a bleach activator with a terpyridine compound which is capable of complexing with iron and manganese ions, or a suitably preformed iron or manganese complex for activating peroxygen compounds and / or atmospheric oxygen, in particular for bleaching Paint stains when washing textiles, as well as detergents, cleaners and disinfectants containing such Bleach amplifier combinations.
  • Inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by addition of so-called bleach activators which are able to provide peroxycarboxylic under the abovementioned perhydrolysis and for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example from the British patent GB 836 988 known reactive esters, polyacylated alkylenediamines, in particular N, N, N ', N'-tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, in addition Carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate (NOBS
  • transition metal compounds in particular transition metal complexes, to increase the oxidation power of peroxygen compounds or atmospheric oxygen in detergents and cleaners has also been proposed on several occasions Service.
  • the transition metal compounds proposed for this purpose include, for example, those of the German patent application DE 195 29 905 known manganese, iron, cobalt, ruthenium or molybdenum-salene complexes and their from the German patent application DE 196 20 267 known N-analogues known from the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes described in the German patent application DE 196 05 688 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which are known from the German patent application DE 196 20 411 known cobalt, iron, copper and ruthenium-amine complexes described in the German patent application DE 44 16 438
  • WO 96/23860 and WO 96/23861 known cobalt complexes and in the European patent specification EP 0 443 651 or the European patent applications EP 0 458 397 . EP 0 458 398 . EP 0 549 271 . EP 0 549 272 . EP 0 544 490 and EP 0 544 519 described manganese complexes. Also according to the European patent application EP 0 832 969 Available bleach-enhancing active ingredient combination is to be mentioned here.
  • Combinations of bleach activators and transition metal bleach catalysts are, for example, from that of the international patent application WO 95/27775 and the German patent application DE 196 13 103 , which relates to electrochemically in certain potential ranges with the highest possible current density oxidizable transition metal complexes known.
  • the international patent application WO 2004/007657 refers to certain manganese, titanium, iron, cobalt, nickel or copper complexes having a terpyridine ligand substituted with at least one quaternary nitrogen-carrying radical and their use as catalysts for oxidation reactions.
  • This use of the complexes can also be effected by a washing, cleaning, disinfecting or bleaching agent containing them, conventional bleach activators being mentioned among the other customary ingredients of such agents.
  • an object of the invention is the use of a combination of peroxygen-containing bleach, amide-type bleach activator, sulfonylphenyl ester-type and / or quaternary nitrogen-substituted acetonitrile-type bleach catalyst according to formula (II), in which M is manganese or iron, X is an inorganic ligand and Y m- is an anion and the product of integers m and n is 2, for bleaching paint stains when washing textiles, especially in aqueous, surfactant-containing liquor.
  • Another object of the invention is the corresponding use for simultaneous or alternative disinfecting the laundry.
  • inventively intended success also occurs when one does not use the complex of formula II, but only the corresponding terpyridine ligand and the coming fleet used iron and / or manganese ions, wherein the oxidation state of said metals because of in the wash liquor usually rapidly adjusting redox equilibrium among the different oxidation states usually not essential.
  • a further subject of the invention is therefore the use of a combination of peroxygen-containing bleach, amide-type bleach activator, sulfonylphenyl ester-type and / or quaternary nitrogen-substituted acetonitrile-type and compound of formula (I), in which Y m- is an anion and the product (m ⁇ n) is 2, for bleaching color stains and / or disinfecting the laundry when washing textiles, in aqueous, especially surfactant-containing liquor, the manganese and / or iron Contains ions.
  • the anion (Y m- ) is preferably an organic anion, for example citrate, oxalate, tartrate, formate, a C 2-18 -carboxylate, a C 1-18 - Alkyl sulfate, in particular methosulfate, or a corresponding alkanesulfonate.
  • the inorganic ligand (X) is preferably a halide, in particular chloride, perchlorate, tetrafluoroborate, hexafluorophosphate, nitrate, bisulfate, hydroxide or hydroperoxide.
  • the uses according to the invention can be particularly easily by the use of a detergent, cleaning or disinfecting agent, the pers oxygen bleach, bleach activator of the type mentioned and a compound of formula (I) or a bleach catalyst according to formula (II) in addition to conventional with the bleach activator and said Compound or the bleach catalyst compatible ingredients contains realized.
  • the agent additionally Manganese and / or iron salt and / or a manganese and / or iron complex without a ligand which corresponds to the compound according to formula (I) contains.
  • the molar ratio of manganese or iron or the sum of manganese and iron to the compound of the formula (I) is preferably in the range of 0.001: 1 to 2: 1, especially 0.01: 1 to 1: 1.
  • these contain from 0.01% by weight to 1.5% by weight, in particular from 0.05% by weight to 1% by weight, of a bleach catalyst according to formula (II).
  • Suitable peroxygen compounds are, in particular, organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing or cleaning conditions, such as perborate, percarbonate and / or persilicate.
  • Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle.
  • alkali metal percarbonate alkali metal perborate monohydrate, alkali metal perborate tetrahydrate or hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide.
  • peroxygen compounds are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight, while in the disinfectants according to the invention preferably of 0.5% by weight.
  • % to 40 wt .-% in particular from 5 wt .-% to 20 wt .-%, of peroxygen compounds are included.
  • the bleach activator of the amide type as a preferred further component of the combination or agents to be used according to the invention is preferably a derivative of ammonia or of a mono- or bis-alkylamine. It is preferably made of the compounds of formula (III), (R 1 -CO-) n X (III) in the R 1 is an aryl, alkyl, alkenyl or cycloalkyl radical having 1 to 10 C atoms, n is a number from 1 to 4 and X is a nitrogen-containing leaving group with direct bond between nitrogen on the one hand and the acyl group R 1 - CO on the other hand, and their mixtures selected.
  • R 1 phenyl, C 1 - to C 5 -alkyl, 9-decenyl and mixtures thereof, where the alkyl radicals can be linear or branched-chain.
  • R 1 phenyl, C 1 - to C 5 -alkyl, 9-decenyl and mixtures thereof, where the alkyl radicals can be linear or branched-chain.
  • linear radicals R 1 those having 1 to 9 C atoms are particularly preferred.
  • These compounds according to formula (III) can be prepared by N-acylation with reactive R 1 -CO-derivatives, for example acid chlorides, of the corresponding unsubstituted compounds H n X according to known methods.
  • Preferred nitrogen-containing leaving groups X are those in which the nitrogen carries at least one further acyl group in addition to the acyl group R 1 -CO- to be split off.
  • Examples of such compounds according to formula (III) are the triacylation products of ammonia and the diacylation products of primary alkylamino groups, such as those of ethylenediamine. If the abovementioned at least one further acyl group is likewise not an acyl radical R 1 -CO-, it is preferred, if it has such a graded perhydrolysis activity, that under the conditions of use substantially only from the group R 1 -CO- corresponding peroxycarboxylic acid forms.
  • the nitrogen carrying the group R 1 -CO- is also part of a cyclic amide or imide structure.
  • the latter compounds may be referred to as acylamides or acylimides, wherein the name part "acyl” refers to the group R 1 -CO-.
  • the amide portion of such acylamides preferably consists of an optionally substituted capro or valerolactam group and the imide portion of such acylimides preferably consists of a succinimide, maleimide or phthalimide group, which groups optionally C 1 - to C 4 -alkyl-, hydroxyl , COOH and / or SO 3 H substituents, the latter substituent groups may also be present in the form of their salts.
  • acylimides N-nonanoyl and N-isononanoyl succinimide are preferred.
  • the most preferred compounds is N, N, N ', N'-tetraacetylethylenediamine (TAED).
  • Bleach activators of the sulfonylphenyl ester type preferably correspond to the abovementioned compounds of the formula (III), in which case X is a phenoxy radical carrying a sulfonic acid group or its alkali metal salt, and n is, in particular, 1.
  • Particularly preferred compounds of this type include sodium nonanoyloxybenzenesulfonate, sodium isononanoyloxybenzenesulfonate and sodium lauroyloxybenzenesulfonate.
  • Quaternary nitrogen-substituted acetonitrile bleach activators preferably correspond to the formula (IV) in the R 1 is -H, -CH 3 , a C 2-24 alkyl or alkenyl radical, a substituted C 2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 -alkyl group and at least one further substituent on the aromatic ring
  • R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 - OH, -CH 2 -CH 2
  • R 1 is methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n- Octadecyl radical
  • R 2 and R 3 are selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, wherein one or both of these radicals may advantageously also be a Cyanomethylenrest, preferably.
  • an agent according to the invention contains from 0.5% by weight to 10% by weight, in particular from 1% by weight to 8% by weight, of bleach activator of the types mentioned. Particularly preferred is when amide type bleach activator and quaternary nitrogen substituted acetonitrile bleach activator are coexistent.
  • the substances to be used in combination according to the invention are preferably solid at room temperature.
  • the compounds of formula I or formula II are used in combination with the bleaching agents mentioned preferably for bleaching Farbanschmutzungen in the washing of textiles, especially in aqueous, surfactant-containing liquor.
  • bleaching of paint stains is to be understood in its broadest sense and includes both bleaching of debris on the fabric, bleaching of debris found in the wash liquor and debris removed from the fabric, as well as oxidative destruction of itself in the wash liquor Textile dyes that detach under the washing conditions of textiles before they can be applied to different colored textiles.
  • the combination can be used wherever a particular increase in the oxidation effect, in particular of inorganic peroxygen compounds at low temperatures, is required, for example in the bleaching of textiles, hair or hard surfaces, in the oxidation of organic substances or inorganic intermediates and in disinfection.
  • the use of the present invention is to provide conditions under which the peroxygen compound can react with the compounds employed in combination, with the aim of producing more strongly oxidizing secondary products to obtain.
  • Such conditions are especially present when the reactants meet in aqueous solution. This can be done by separately adding the
  • Peroxygen compound the compound of formula (I) and / or formula (II) and the bleach activator in a separate form to an optionally washing or cleaning agent-containing solution.
  • the process according to the invention is particularly advantageously carried out using a washing, cleaning or disinfecting agent according to the invention which contains the stated ingredients.
  • the peroxygen compound may also be added separately, in bulk or as a preferably aqueous solution or suspension, to the washing, cleaning or disinfecting solution when an oxygen-free agent is used.
  • the conditions can be varied widely.
  • the amounts of peroxygen compounds are generally chosen so that in the solutions between 10 ppm and 10% active oxygen, preferably between 50 and 5000 ppm of active oxygen are present.
  • the detergents, cleaners and disinfectants according to the invention may be in the form of homogeneous solutions or suspensions, especially in powdered solids, in densified particle form, may contain, in addition to the combination to be used according to the invention, in principle all known ingredients customary in such compositions.
  • the detergents and cleaners according to the invention may in particular be builders, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, dye transfer inhibitors, grayness inhibitors, wrinkle-reducing active ingredients and shape-retaining active ingredients, and further adjuvants such as optical brighteners, foam regulators, additional peroxygen activators, dyes and fragrances.
  • a disinfectant according to the invention can be used to enhance the disinfecting action against special germs in addition to the previously mentioned Ingredients contain conventional antimicrobial agents.
  • Such antimicrobial additives are contained in the disinfectants according to the invention preferably in amounts of up to 10 wt .-%, in particular from 0.1 wt .-% to 5 wt .-%.
  • customary substances mentioned at the outset which form peroxycarboxylic acids or peroxoimidic acids under perhydrolysis conditions, and / or customary bleach-activating transition metal complexes can be used.
  • compositions of the invention may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof come into question.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups.
  • N-alkyl-amines vicinal diols, fatty acid esters and fatty acid amides, which correspond to said long-chain alcohol derivatives with respect to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form.
  • Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation.
  • Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkanesulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.
  • Such surfactants are present in the cleaning or washing agents according to the invention in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%, while the disinfectant according to the invention as well as inventive cleaning agent preferably 0.1 wt .-% to 20 wt .-%, in particular 0.2 wt .-% to 5 wt .-% surfactants.
  • An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diene diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the accessible by oxidation of polysaccharides or dextrins polycarboxylates of the international patent application WO 93/16110 or the international patent application WO 92/18542 or the European patent specification EP 0 232 202
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 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.
  • Suitable, though less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers such as vinyl methyl 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 methods described in the German patent DE 42 21 381 and the German patent application DE 43 00 772 are generally described, and generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those described in the German patent applications DE 43 03 320 and DE 44 17 734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
  • the organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in paste-form or liquid, in particular water-containing, agents according to the invention.
  • Suitable water-soluble inorganic builder materials are, in particular, polymeric alkali metal phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used.
  • detergent grade crystalline sodium aluminosilicates especially zeolite A, P. and optionally X
  • Amounts near the above upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Their calcium binding capacity is usually in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions according to the invention 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 of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • 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 y are used 2x + 1 H 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 the European patent application EP 0 164 514 described.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 y H 2 O
  • ⁇ -sodium disilicate can be obtained, for example, by the method described in the international patent application WO 91/08171 is described.
  • ⁇ -Sodium silicates with a modulus between 1.9 and 3.2 can according to Japanese Patent Applications JP 04/238 809 or JP 04/260 610 getting produced.
  • Crystalline sodium silicates with a modulus ranging from 1.9 to 3.5, as prepared by the methods of European patents EP 0 164 552 and or EP 0 294 753 are available are used in a further preferred embodiment of the invention means.
  • a granular compound of alkali metal silicate and alkali metal carbonate is used, as described, for example, in the international patent application WO 95/22592 or as it is commercially available, for example, under the name Nabion® 15.
  • the weight ratio of aluminosilicate to silicate is preferably 1:10 to 10: 1.
  • the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
  • the detergents or cleaners according to the invention are preferably present in the detergents or cleaners according to the invention in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight, while the disinfectants according to the invention are preferably free from the complexing only of the components of the water hardness Builder substances are and preferably not more than 20% by weight, in particular from 0.1% by weight to 5% by weight, of heavy metal complexing substances, preferably from the group comprising aminopolycarboxylic acids, aminopolyphosphonic acids and hydroxypolyphosphonic acids and their water-soluble salts and mixtures thereof, contain.
  • the water-soluble builder block contains at least 2 of components b), c), d) and e) in amounts greater than 0% by weight.
  • component a in a preferred embodiment of the composition according to the invention, 15% by weight to 25% by weight of alkali carbonate, which may at least partly be replaced by alkali metal hydrogencarbonate, and up to 5% by weight, in particular 0.5% by weight. % to 2.5% by weight of citric acid and / or alkali citrate.
  • inventive compositions are as component a) 5 wt .-% to 25 wt .-%, in particular 5 wt .-% to 15 wt .-% citric acid and / or alkali citrate and up to 5 wt .-%, in particular 1 wt .-% to 5 wt .-% alkali carbonate, which may be at least partially replaced by alkali metal bicarbonate included. If both alkali carbonate and alkali bicarbonate are present, the Component a) alkali metal carbonate and alkali metal bicarbonate, preferably in a weight ratio of 10: 1 1 to 1: 1.
  • component b) in a preferred embodiment of the composition according to the invention, 1% by weight to 5% by weight of alkali metal silicate with a modulus in the range from 1.8 to 2.5 are contained.
  • agents according to the invention contain from 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate.
  • Phosphonic acids are also understood as meaning optionally substituted alkylphosphonic acids, which may also have a plurality of phosphonic acid groups (so-called polyphosphonic acids).
  • They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali salts, for example dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1-hydroxyethane 1,1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediamine tetrakis (methylenephosphonic acid) and those described in German Auslegeschrift DE 11 07 207 described acylated derivatives of phosphorous acid, which can also be used in any mixtures.
  • dimethylaminomethane diphosphonic acid 3-aminopropane-1-hydroxy-1,1-diphosphonic acid
  • 1-amino-1-phenylmethane diphosphonic acid 1-hydroxyethane 1,1-diphosphonic acid
  • amino-tris methylenephosphonic acid
  • alkali metal phosphate in particular trisodium polyphosphate, are contained.
  • Alkaliphosphat is the summary term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, very soluble in water powder that lose the water of crystallization on heating and at 200 ° C in the weak acid diphosphate (Disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Madrell's salt.
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt of density 2.33 gcm -3 , has a melting point of 253 ° (decomposition to form (KPO 3 ) x , potassium polyphosphate) and is slightly soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt.
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) ,
  • decahydrate density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4. Condensation of NaH 2 PO 4 or KH 2 PO 4 results in higher mol.
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: fused or annealed phosphates, Graham's salt, Kurrolsches and Madrell's salt.
  • All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • n 3.
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • agents according to the invention contain from 1.5% by weight to 5% by weight of polymeric polycarboxylate, in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid.
  • polymeric polycarboxylate in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid.
  • homopolymers of acrylic acid particularly preferred are those having an average molecular weight in the range from 5,000 D to 15,000 D (PA standard).
  • enzymes which can be used in the compositions apart from the abovementioned oxidase, those from the class of the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof are suitable, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Alcalase®, Esperase®, Savinase®, Durazym® and / or Purafect® OxP, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, cellulases such as Celluzyme® and / or Carezyme®.
  • proteases such
  • Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents.
  • the optionally used enzymes can, for example, in the European patent EP 0 564 476 or in the international patent applications WO 94/23005 be adsorbed to carriers and / or embedded in encapsulating substances to protect against premature inactivation.
  • the detergents, cleaners and disinfectants according to the invention preferably in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight, particularly preferably enzymes which are stabilized against oxidative degradation, such as from international patent applications WO 94/02597 . WO 94/02618 . WO 94/18314 . WO 94/23053 or WO 95/07350 , known to be used.
  • the agent contains 5% by weight to 50% by weight, in particular 8-30% by weight of anionic and / or nonionic surfactant, up to 60% by weight, in particular 5-40% by weight.
  • organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms , in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compound ethers.
  • Such water-miscible solvents are preferably present in the detergents, cleaners and disinfectants according to the invention not more than 30% by weight, in particular from 6% by weight to 20% by weight.
  • the compositions according to the invention can contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid. but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight, in the compositions according to the invention.
  • Soil release polymers are, for example, nonionic or cationic cellulose derivatives.
  • the particularly polyester-active soil release polymers include copolyesters of dicarboxylic acids, for example Adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol.
  • Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR 11 -) a OH, also known as polymeric Diol H- (O- (CHR 11 -) a ) b OH may be present.
  • Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R 11 denotes hydrogen
  • a is a number from 2 to 6
  • b is a number from 1 to 300.
  • the molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10.
  • the degree of polymerization b is preferably in the range of 4 to 200, especially 12 to 140.
  • the molecular weight or the average molecular weight or the maximum molecular weight distribution of preferred soil release polyester is in the range of 250 to 100,000, especially 500 to 50,000
  • the acid underlying the remainder Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof.
  • acids having at least two carboxyl groups may be included in the soil release-capable polyester.
  • alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • the preferred diols HO- (CHR 11 -) a OH include those in which R 11 is hydrogen and a is a Number from 2 to 6, and those in which a has the value 2 and R 11 is selected from hydrogen and the alkyl radicals having 1 to 10, in particular 1 to 3 C-atoms.
  • R 11 is hydrogen and a is a Number from 2 to 6
  • R 11 is selected from hydrogen and the alkyl radicals having 1 to 10, in particular 1 to 3 C-atoms.
  • those of the formula HO-CH 2 -CHR 11 -OH in which R 11 has the abovementioned meaning are particularly preferred.
  • diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
  • Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1000 to 6000.
  • these polyesters may also be end developmentver consideration, with alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids in question as end groups.
  • the hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group.
  • the number of hydroxymonocarboxylic acid units per end group is in the range from 1 to 50, in particular from 1 to 10.
  • polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 have and the Molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used alone or in combination with cellulose derivatives.
  • Polyvinylpyrrolidones polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers belong to the color transfer inhibitors which are suitable for use in laundry detergents according to the invention.
  • the inventive compositions for use in the textile laundry may contain anti-crease agents, since textile fabrics, in particular of rayon, wool, cotton and their mixtures, may tend to wrinkle, because the individual fibers are sensitive to bending, buckling, pressing and squeezing transverse to the fiber direction.
  • anti-crease agents since textile fabrics, in particular of rayon, wool, cotton and their mixtures, may tend to wrinkle, because the individual fibers are sensitive to bending, buckling, pressing and squeezing transverse to the fiber direction.
  • These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
  • Graying inhibitors have the task of keeping suspended from the hard surface and in particular from the textile fiber suspended dirt in the fleet.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • starch derivatives can be used, for example aldehyde starches.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions.
  • the agents may contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or their alkali metal salts.
  • Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl).
  • Mixtures of the aforementioned optical brightener can be used.
  • foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
  • silver corrosion inhibitors are organic disulfides, dihydric phenols, trihydric phenols, optionally alkyl- or aminoalkyl-substituted triazoles such as benzotriazole and cobalt, manganese, titanium, zirconium, hafnium, vanadium or cerium salts and / or complexes in which the Metals in one of the oxidation states II, III, IV, V or VI are present.
  • the terpyridine compound which is capable of complexing with iron and manganese ions, and the correspondingly preformed iron or manganese complex may be in the form of powders or as granules, which may optionally also be coated and / or colored, and conventional support materials and / or or granulation aids may be present. In the case of their use as granules, if desired, they may also contain the amide-type, the sulfonylphenyl-ester type bleach activator and / or the quaternary nitrogen-substituted acetonitrile type.
  • compositions according to the invention presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation, with peroxygen compound and bleach activator combination optionally being added later.
  • inventive compositions having an increased bulk density in particular in the range of 650 g / l to 950 g / l, is one of the European patent EP 486 592 known method comprising an extrusion step is preferred.
  • Detergents, cleaners or disinfectants according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • means for the particular machine cleaning of dishes they are tablet-shaped and can be based on those in the European patents EP 0 579 659 and EP 0 591 282 disclosed methods are produced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
EP05743291A 2004-05-17 2005-05-07 Bleichverstärkerkombination für den einsatz in wasch- und reinigungsmitteln Expired - Lifetime EP1749084B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL05743291T PL1749084T3 (pl) 2004-05-17 2005-05-07 Kompozycja aktywatora bielenia do zastosowania w środkach piorących i czyszczących

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004024816A DE102004024816A1 (de) 2004-05-17 2004-05-17 Bleichverstärkerkombination für den Einsatz in Wasch- und Reinigungsmitteln
PCT/EP2005/004973 WO2005116181A1 (de) 2004-05-17 2005-05-07 Bleichverstärkerkombination für den einsatz in wasch- und reinigungsmitteln

Publications (2)

Publication Number Publication Date
EP1749084A1 EP1749084A1 (de) 2007-02-07
EP1749084B1 true EP1749084B1 (de) 2009-02-25

Family

ID=34968071

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05743291A Expired - Lifetime EP1749084B1 (de) 2004-05-17 2005-05-07 Bleichverstärkerkombination für den einsatz in wasch- und reinigungsmitteln

Country Status (8)

Country Link
US (1) US20080261852A1 (enExample)
EP (1) EP1749084B1 (enExample)
JP (1) JP2007538121A (enExample)
AT (1) ATE423837T1 (enExample)
DE (2) DE102004024816A1 (enExample)
ES (1) ES2319444T3 (enExample)
PL (1) PL1749084T3 (enExample)
WO (1) WO2005116181A1 (enExample)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4838350B2 (ja) * 2006-05-08 2011-12-14 イーコラブ インコーポレイティド 金属表面用酸性洗浄剤
WO2010020583A1 (en) * 2008-08-20 2010-02-25 Basf Se Improved bleach process
US20130111675A1 (en) 2011-11-03 2013-05-09 Ecolab Usa Inc. Sustainable laundry sour compositions with iron control
CN102924524B (zh) * 2012-10-29 2015-02-04 安徽大学 一种具有活体细胞显影功能的锰配合物双光子吸收材料及其合成方法
DE102019217851A1 (de) * 2019-11-20 2021-05-20 Henkel Ag & Co. Kgaa Bleichaktivator mit kationischer Gruppe und diesen enthaltendes Wasch- oder Reinigungsmittel III
DE102019217849A1 (de) * 2019-11-20 2021-05-20 Henkel Ag & Co. Kgaa Bleichaktivator mit kationischer Gruppe und diesen enthaltendes Wasch- oder Reinigungsmittel I

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL252116A (enExample) * 1959-06-03
DE3413571A1 (de) * 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
DE3417649A1 (de) * 1984-05-12 1985-11-14 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von kristallinen natriumsilikaten
FR2597473B1 (fr) * 1986-01-30 1988-08-12 Roquette Freres Procede d'oxydation de di-, tri-, oligo- et polysaccharides en acides polyhydroxycarboxyliques, catalyseur mis en oeuvre et produits ainsi obtenus.
US4915863A (en) * 1987-08-14 1990-04-10 Kao Corporation Bleaching composition
DE4010533A1 (de) * 1990-04-02 1991-10-10 Henkel Kgaa Tablettierte wasch- und/oder reinigungsmittel fuer haushalt und gewerbe und verfahren zu ihrer herstellung
US5229095A (en) * 1989-10-25 1993-07-20 Hoechst Aktiengesellschaft Process for producing amorphous sodium silicate
US5236682A (en) * 1989-10-25 1993-08-17 Hoechst Aktiengesellschaft Process for producing crystalline sodium silicates having a layered structure
YU221490A (sh) * 1989-12-02 1993-10-20 Henkel Kg. Postupak za hidrotermalnu izradu kristalnog natrijum disilikata
DE4000705A1 (de) * 1990-01-12 1991-07-18 Hoechst Ag Verfahren zur herstellung von kristallinen natriumsilikaten
DE4107230C2 (de) * 1991-03-07 1995-04-06 Hoechst Ag Verfahren zur Herstellung von Natriumsilikaten
DE4112075A1 (de) * 1991-04-12 1992-10-15 Henkel Kgaa Verfahren zur herstellung stabiler, bifunktioneller, phospat- und metasilikatfreier niederalkalischer reinigungsmitteltabletten fuer das maschinelle geschirrspuelen
DE4142711A1 (de) * 1991-12-21 1993-06-24 Hoechst Ag Verfahren zur herstellung von kristallinen natriumdisilikaten
DE4221381C1 (de) * 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Zuckern, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4203923A1 (de) * 1992-02-11 1993-08-12 Henkel Kgaa Verfahren zur herstellung von polycarboxylaten auf polysaccharid-basis
DE4300772C2 (de) * 1993-01-14 1997-03-27 Stockhausen Chem Fab Gmbh Wasserlösliche, biologisch abbaubare Copolymere auf Basis von ungesättigten Mono- und Dicarbonsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4303320C2 (de) * 1993-02-05 1995-12-21 Degussa Waschmittelzusammensetzung mit verbessertem Schmutztragevermögen, Verfahren zu dessen Herstellung und Verwendung eines geeigneten Polycarboxylats hierfür
DE4405511A1 (de) * 1994-02-22 1995-08-24 Henkel Kgaa Waschmittel mit amorphen silikatischen Buildersubstanzen
DE19605688A1 (de) * 1996-02-16 1997-08-21 Henkel Kgaa Übergangsmetallkomplexe als Aktivatoren für Persauerstoffverbindungen
DE19620411A1 (de) * 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallamminkomplexe als Aktivatoren für Persauerstoffverbindungen
WO2004007657A1 (en) * 2002-07-11 2004-01-22 Ciba Specialty Chemicals Holding Inc. Use of metal complex compounds as oxidation catalysts
CN1708579A (zh) * 2002-10-29 2005-12-14 西巴特殊化学品控股有限公司 金属配位化合物作为用分子氧或空气进行氧化的催化剂的应用
GB2394720A (en) * 2002-10-30 2004-05-05 Reckitt Benckiser Nv Metal complex compounds in dishwasher formulations
KR101004084B1 (ko) * 2002-10-30 2010-12-27 시바 홀딩 인코포레이티드 산화 촉매로서 유용한 금속 착화합물

Also Published As

Publication number Publication date
ES2319444T3 (es) 2009-05-07
WO2005116181A1 (de) 2005-12-08
ATE423837T1 (de) 2009-03-15
JP2007538121A (ja) 2007-12-27
PL1749084T3 (pl) 2009-07-31
EP1749084A1 (de) 2007-02-07
DE102004024816A1 (de) 2005-12-15
US20080261852A1 (en) 2008-10-23
DE502005006698D1 (de) 2009-04-09

Similar Documents

Publication Publication Date Title
EP2440641B1 (de) Nanopartikuläres mangandioxid
EP2802644B1 (de) Acylhydrazone als bleichverstärkende wirkstoffe
WO2010105961A1 (de) Wasch- oder reinigungsmittel mit gegebenenfalls in situ erzeugtem bleichverstärkendem übergangsmetallkomplex
WO2010105962A1 (de) Wasch- oder reinigungsmittel mit gegebenenfalls in situ erzeugtem bleichverstärkendem übergangsmetallkomplex
EP2737042B1 (de) Wasch- oder reinigungsmittel mit elektrochemisch aktivierbarer mediatorverbindung
EP3134500B1 (de) Wasch- oder reinigungsmittel mit elektrochemisch aktivierbarer anionischer mediatorverbindung
EP2504418B1 (de) Wasch- oder reinigungsmittel mit gegebenenfalls in situ erzeugtem bleichverstärkendem übergangsmetallkomplex
EP1749084B1 (de) Bleichverstärkerkombination für den einsatz in wasch- und reinigungsmitteln
EP2504419B1 (de) Wasch- oder reinigungsmittel mit gegebenenfalls in situ erzeugtem bleichverstärkendem übergangsmetallkomplex
EP1747259A1 (de) Waschmittel mit gegebenenfalls in situ erzeugtem bleichverstärkendem übergangsmetallkomplex
EP2440644A1 (de) Schonendes bleichmittel
EP2046934A1 (de) Wasch- oder reinigungsmittel mit grössenoptimierten bleichwirkstoffteilchen
DE102014213311A1 (de) Neuartiges Waschverfahren mit elektrochemisch aktivierbarer Mediatorverbindung
EP2304014A1 (de) Textilschonendes waschmittel
EP2411498A1 (de) Schonendes bleichmittel
EP2411495A1 (de) Schonendes bleichmittel
WO2010108784A1 (de) Schonendes bleichmittel
EP3095845A1 (de) Acylhydrazone als bleichverstärkende wirkstoffe
DE10162646A1 (de) Bleichaktivatorkombination für den Einsatz in Wasch-und Reinigungsmitteln
EP0866116A2 (de) Bisacylacetale als Bleichaktivatoren für Wasch- und Reinigungsmittel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20060901

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20070816

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HENKEL AG & CO. KGAA

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 502005006698

Country of ref document: DE

Date of ref document: 20090409

Kind code of ref document: P

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2319444

Country of ref document: ES

Kind code of ref document: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20090605

Year of fee payment: 5

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E005341

Country of ref document: HU

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090525

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090625

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CZ

Payment date: 20090424

Year of fee payment: 5

Ref country code: DE

Payment date: 20090429

Year of fee payment: 5

Ref country code: FR

Payment date: 20090515

Year of fee payment: 5

Ref country code: IT

Payment date: 20090518

Year of fee payment: 5

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SK

Payment date: 20090505

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090812

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

BERE Be: lapsed

Owner name: HENKEL A.G. & CO. KGAA

Effective date: 20090531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20090506

Year of fee payment: 5

Ref country code: HU

Payment date: 20090507

Year of fee payment: 5

Ref country code: PL

Payment date: 20090408

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090531

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090531

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090525

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090531

26N No opposition filed

Effective date: 20091126

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090526

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20100507

REG Reference to a national code

Ref country code: SK

Ref legal event code: MM4A

Ref document number: E 5393

Country of ref document: SK

Effective date: 20100507

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20110131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100507

Ref country code: CZ

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100507

Ref country code: HU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090507

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100531

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20110711

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110629

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100508

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090225

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100507

REG Reference to a national code

Ref country code: PL

Ref legal event code: LAPE