EP1592768A2 - Utilisation de derives cellulosiques en tant que regulateurs de moussage - Google Patents

Utilisation de derives cellulosiques en tant que regulateurs de moussage

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Publication number
EP1592768A2
EP1592768A2 EP04707149A EP04707149A EP1592768A2 EP 1592768 A2 EP1592768 A2 EP 1592768A2 EP 04707149 A EP04707149 A EP 04707149A EP 04707149 A EP04707149 A EP 04707149A EP 1592768 A2 EP1592768 A2 EP 1592768A2
Authority
EP
European Patent Office
Prior art keywords
weight
cellulose
water
foam
acid
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.)
Withdrawn
Application number
EP04707149A
Other languages
German (de)
English (en)
Inventor
Josef Penninger
Erik BRÜCKNER
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
Priority claimed from DE10351266A external-priority patent/DE10351266A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1592768A2 publication Critical patent/EP1592768A2/fr
Withdrawn legal-status Critical Current

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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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material

Definitions

  • the invention relates to the use of certain cellulose derivatives as foam regulators in detergents or cleaning agents, and to a fuel which can be stoked and poured, in particulate form, comprising a water-soluble or water-dispersible carrier material and a cellulose derivative adsorbed thereon.
  • Polysiloxanes are known to be comparatively complex to produce with a known good defoaming action and have the disadvantage that, particularly in more recent times, they are often perceived as not entirely satisfactory in terms of their biodegradability.
  • Silicone-free foam regulators are also known.
  • European Patent EP 87233 describes a process for producing a low-foaming detergent in which mixtures of an oily or waxy substance and bisamides are applied to a carrier powder, in particular a spray-dried detergent containing surfactants.
  • the oily or waxy substance can consist, for example, of petroleum jelly with a melting point of 20 ° C to 120 ° C.
  • detergents with a foam regulating agent which contain hydrophobic silicon dioxide and a mixture of solid and liquid hydrocarbons, optionally in a mixture with fatty acid esters. Due to the high content of hydrocarbon which is liquid at room temperature, from 22.5% by weight to about 98% by weight, there is a risk of clumping in such foam regulating agents.
  • Foam regulating agents containing perfume wax mixtures and hydrophobized silica, optionally in combination with branched-chain alcohols, are known from German published patent application DE 34 00 008.
  • Powdered defoamers which contain a liquid mixture of higher molecular weight, branched-chain alcohols with hydrophobized silica in combination with a water-insoluble wax on a water-soluble, powdery carrier, are known from German published patent application DE 31 15 644.
  • European patent application EP 0 309 931 describes foam control agents which contain a relatively complex mixture of paraffin wax and microcrystalline paraffin wax.
  • both silicones and paraffins are comparable to oily soiling with regard to the cleaning performance required in the washing process; They should therefore only be present in the detergent or cleaning agent in as small a quantity as possible, so that they do not impair the effect of the detergent or detergent ingredients necessary for the removal of soiling.
  • the task was therefore to provide a foam regulator that can be assembled in the form of a free-flowing foam regulator and is effective in detergents and cleaning agents over a wide temperature range means in the cold wash area, at medium wash temperatures and also in the hot wash area, a disturbing foam development is suppressed. Furthermore, both the foam regulator and the foam regulating agent containing it should remain stable in storage and effect in a mixture with conventional detergent components and should have no adverse effects on the material to be treated and the environment.
  • the invention thus relates to the use of cellulose derivatives which can be obtained by alkylation and hydroxyalkylation of cellulose to reduce the foaming of detergents or cleaning agents when they are used in aqueous washing or cleaning solutions.
  • Preferred cellulose derivatives are those which are alkylated with ci to do groups, in particular d to C 3 groups, and additionally carry C 2 to do-hydroxyalkyl groups, in particular C 2 to C 3 hydroxyalkyl groups.
  • These can be obtained in a known manner by reacting cellulose with appropriate alkylating agents, for example alkyl halides or alkyl sulfates, and then reacting with corresponding alkylene oxides, such as ethylene oxide and / or propylene oxide.
  • the cellulose derivative contains on average 0.5 to 2.5, in particular 1 to 2, alkyl groups and 0.02 to 0.5, in particular 0.05 to 0.3, hydroxyalkyl groups per anhydroglycosomer monomer unit.
  • the average molar mass of the cellulose derivatives used according to the invention is preferably in the range from 10,000 D to 150,000 D, in particular from 40,000 D to 120,000 D and particularly preferably in the range from 80,000 D to 110,000 D.
  • the degree of polymerization or the molecular weight is determined of the dirt-releasing cellulose derivative is based on the determination of the intrinsic viscosity of sufficiently dilute aqueous solutions using an Ubbelohde capillary viscometer (capillary 0c). Using a constant [H Staudinger and F. Reinecke, "About molecular weight determination on Ceüuloseethern", Liebigs Annalen der Chemie 535, 47 (1938)] and a correction factor [F. Rodriguez and L.
  • Such cellulose derivatives have dirt-removing properties, so that they do not impair the performance of detergents or cleaning agents, but on the contrary, in addition to their foam-regulating action, also contribute to the washing or cleaning result.
  • Another object of the invention is therefore the use of cellulose derivatives, which are obtainable by alkylation and hydroxyalkylation of cellulose, for reducing the foam in the rinse cycles when machine washing textiles.
  • the invention furthermore relates to a granular, free-flowing foam regulating agent which adsorbs 0.5% by weight to 30% by weight of a cellulose derivative to be used according to the invention to 70% by weight to 99.5% by weight of a water-soluble or contains water-dispersible, inorganic and / or organic carrier material.
  • the preferably phosphate-free carrier material has a granular structure and consists of water-soluble or water-dispersible compounds, primarily of inorganic and / or organic salts, which are suitable for use in detergents and cleaning agents.
  • the water-soluble inorganic carrier materials include in particular alkali carbonate, alkali borate, alkali alumosilicate and / or alkali sulfate, optionally with additions of alkali silicate, the latter being able to contribute to good grain stabilities of the agents according to the invention.
  • alkali Kat is preferably a compound with a molar ratio of alkali oxide to SiO 2 of 1: 1.5 to 1: 3.5.
  • the use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water.
  • the inorganic materials which can additionally be used include, in particular, zeolites and layered silicates, for example bentonite.
  • the zeolites which can be used in the carrier material for the foam control agents according to the invention include in particular zeolite A, zeolite P and zeolite X.
  • suitable organic carrier materials are the acetates, tartrates, succinates, citrates, carboxymethylsuccinates and the alkali metal salts of aminopolycarboxylic acids, such as EDTA, hydroxyalkanephosphonates and aminoalkane polyphosphonates, such as 1-hydroxyethane-1, l-diphosphonate and ethylenediaminodiaminotetramino-di-aminophonate-tri-ethylenediamine-tri-aminophonate-ethylenediaminophenate.
  • aminopolycarboxylic acids such as EDTA, hydroxyalkanephosphonates and aminoalkane polyphosphonates, such as 1-hydroxyethane-1, l-diphosphonate and ethylenediaminodiaminotetramino-di-aminophonate-tri-ethylenediamine-tri-aminophonate-ethylenediaminophenate.
  • water-soluble salts of polymeric or copolymeric carboxylic acids for example copolymers of acrylic acid and maleic acid
  • polycarboxylic acids known, for example, from international patent application WO 93/08251, which are obtained by oxidation of polysaccharides.
  • the preferred alkali metal in the alkali salts mentioned is sodium in all cases.
  • Organic substances that are not in salt form, such as starch or starch hydrolysates, can also be used as carrier material components. Mixtures of inorganic and organic salts can often be used with advantage.
  • the carrier material can moreover be film-forming polymers, for example polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, polyacrylates and cellulose ethers which do not correspond to the cellulose derivatives which are essential to the invention, in particular alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and mixtures thereof.
  • cellulose ethers which do not correspond to the cellulose derivatives which are essential to the invention, in particular alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and mixtures thereof.
  • Mixtures of sodium carboxymethyl cellulose and methyl cellulose are preferably used, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
  • the mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50.
  • Such cellulose ether mixtures can be used in solid form or as aqueous solutions, which can be pre-swollen in the usual way.
  • Such film-forming polymers are preferably not contained in the carrier material in excess of 5% by weight, in particular from 0.5% by weight to 2% by weight, based on the total carrier material.
  • the carrier material component of the foam regulating agent according to the invention contains up to 99% by weight, in particular 60% by weight to 95% by weight, of alkali carbonate and / or alkali sulfate, in particular sodium carbonate and / or sodium sulfate, up to 35% by weight , in particular from 0.5% by weight to 30% by weight of alkali silicate, in particular sodium silicate and up to 5% by weight, in particular 0.5% by weight to 2% by weight of water-soluble or water-swellable polymer, especially anionic cellulose ethers.
  • foam regulators can also be used in all aspects of the invention, for example long-chain soaps, in particular beef soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover have microfine, optionally silanized or otherwise hydrophobized Silicic acid can include.
  • foam inhibitors are preferably bound to granular, water-soluble carrier substances, as described, for example, in German patent application DE 34 36 194, European patent applications EP 262 588, EP 301 414, EP 309 931 or European patent EP 150386.
  • the cellulose derivative to be used according to the invention can be incorporated into the particles known from the documents mentioned.
  • an additional paraffin-based defoamer mixture which comprises (a) 70% by weight to 95% by weight of a paraffin wax or paraffin wax mixture and (b) 5% by weight to 30% by weight of one of C 2 -7-diamines and saturated C12-22 carboxylic acid derived bisamide.
  • silicone and paraffin foam regulators it has been found that their defoaming action can be further enhanced by the use of the cellulose derivatives mentioned.
  • the paraffin wax (component a) contained in the optionally preferred additional defoamer mixture generally represents a complex mixture of substances without a sharp melting point.
  • paraffin wax mixture For characterization, its melting range is usually determined by differential thermal analysis (DTA), as described in "The Analyst” 87 ( 1962), 420, and / or its freezing point. This is the temperature at which the wax changes from the liquid to the solid state by slow cooling.
  • DTA differential thermal analysis
  • Paraffins with less than 17 carbon atoms are not usable according to the invention, their proportion in the paraffin wax mixture should therefore be as low as possible and is preferably below the limit which is significantly measurable with conventional analytical methods, for example gas chromatography. Waxes which solidify in the range from 20 ° C. to 70 ° C. are preferably used. It should be noted that paraffin wax mixtures which appear solid at room temperature can contain different proportions of liquid paraffin.
  • the liquid fraction is as high as possible at 40 ° C. without already being 100% at this temperature.
  • Preferred paraffin wax mixtures have a liquid fraction of at least 50% by weight, in particular from 55% by weight to 80% by weight, at 40 ° C. and a liquid fraction of at least 90% by weight at 60 ° C. The consequence of this is that the paraffins are flowable and pumpable at temperatures down to at least 70 ° C., preferably down to at least 60 ° C. It is also important to ensure that the paraffins do not contain any volatile components.
  • Preferred paraffin waxes contain less than 1% by weight, in particular less than 0.5% by weight, of parts which can be evaporated at 110 ° C. and normal pressure. Paraffin waxes which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Guer and Deawax® from DEA Mineralöl AG.
  • Component (b) of the optional additional defoamer mixture consists of bisamides which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18 C atoms and from alkylenediamines with 2 to 7 C atoms.
  • Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated oils, such as tallow or hydrogenated palm oil.
  • Suitable diamines are, for example, ethylenediamine 1,3-propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, p-phenylene diamine and tolylene diamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bis-palmitoyl-ethylenediamine, bis-stearoyl-ethylenediamine and mixtures thereof, and the corresponding derivatives of hexamethylenediamine.
  • the bisamides are preferably in finely divided form and in particular have an average grain size of less than 50 ⁇ m.
  • the maximum particle size of the particles is preferably less than 20 ⁇ m, with at least 50%, in particular at least 75%, of the particles being smaller than 10 ⁇ m. This information regarding the particle size relates to the known determination method with the "Coulter Counter".
  • the above-mentioned additional defoamer mixture can be produced by introducing the finely divided bisamide (component b) into a melt of the constituent (a) and homogenizing it by intensive mixing.
  • the melt should have a temperature of at least 90 ° C and at most 200 ° C.
  • the temperature is preferably 100 ° to 150 ° C.
  • a bisamide can be used and dispersed that has the appropriate particle size from the outset, or a more coarse starting material is used and the melt is subjected to intensive stirring treatment or grinding treatment by means of coil mills, tooth mills or ball mills until the desired particle size is reached.
  • a complete melting of the bisamides in the paraffin melt and subsequent rapid cooling to temperatures below the solidification point of the bisamides with simultaneous homogenization of the melt can also result in a correspondingly fine particle size distribution of the bisamides.
  • a foam regulating agent according to the invention can be produced in a simple manner by spray drying an aqueous composition of its ingredients or by applying the liquid or by heating or dissolving Liquefied Ceululose derivative, optionally also the melted additional defoamer mixture described above, on the granular carrier material, for example by successive admixing, in particular as a spray, to the carrier grain.
  • the carrier grain which can be produced in the customary manner by spray drying an aqueous slurry of the carrier salts, is kept in motion by mixing elements or by fluidization in order to ensure a uniform loading of the carrier material.
  • the spray mixers used for this can be operated continuously or discontinuously.
  • a particle-shaped foam regulating agent according to the invention preferably consists of particles with particle sizes not more than 2 mm, in particular from 0.1 mm to 1.6 mm. It preferably contains not more than 20% by weight, in particular not more than 5% by weight, of particles with a grain size of more than 1.6 mm, and not more than 20% by weight, in particular not more than 5% by weight. Particles with a grain size below 0.1 mm.
  • the tissue-shaped foam control agent preferably has a bulk density in the range from 500 grams per liter to 1000 grams per liter. It is preferably used for the production of detergent or cleaning agents in the form of tissues, a further advantage of the foam control agents according to the invention being their low amount of use with good defoamer performance.
  • Detergents which contain a cellulose derivative to be used according to the invention can contain all the usual other constituents of such compositions.
  • the cellulose derivative is preferably incorporated into detergent in amounts of 0.1% by weight to 5% by weight, in particular 0.5% by weight to 2.5% by weight.
  • the cellulose derivative used according to the invention has a positive effect on the action of certain other detergent and cleaning agent ingredients and that, conversely, the action of the cellulose derivative used according to the invention is enhanced by certain other detergent ingredients.
  • these effects occur in particular in the case of enzymatic active substances, in particular proteases and lipases, in water-insoluble inorganic builders, in water-soluble inorganic and organic builders, in particular based on oxidized carbohydrates, in the case of peroxygen-based bleaching agents, in particular in the case of alkali percarbonate, in the case of synthetic anionic surfactants of the sulfate and sulfonate type and in Graying inhibitors, for example other, in particular anionic, cueulose ethers such as carboxymethyl cellulose, which is why the use of at least one of the other ingredients mentioned together with the cueulose derivative to be used according to the invention is preferred.
  • such an agent contains nonionic surfactant, selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or Fatty acid amides and mixtures thereof, in particular in an amount in the range from 2% by weight to 25% by weight.
  • nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or Fatty acid amides and mixtures thereof, in particular in
  • a further embodiment of such agents comprises the presence of synthetic anionic surfactants of the sulfate and / or sulfonate type, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfofatty acid esters and / or sulfofatty acid disalts, in particular in an amount in the range from 2% by weight to 25% by weight.
  • the anionic surfactant is preferably selected from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms.
  • the nonionic surfactants in question include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
  • the degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
  • the derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used.
  • the alkoxylates in particular the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals, and mixtures thereof, can be used.
  • corresponding alkoxylation products of alkylamines, vicinal diols and carboxamides are those mentioned with regard to the alkyl part Correspond to alcohols, usable.
  • alkyl polyglycosides suitable for incorporation into the agents according to the invention are compounds of the general formula (G) n -OR 12 , in which R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean.
  • R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms
  • G is a glycose unit
  • n is a number between 1 and 10 mean.
  • the glycoside component (G) n is an oligomer or polymer from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, AUose, idose, ribose, Include arabinose, xylose and lyxose.
  • the ougomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization.
  • the degree of ougomerization n generally assumes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the glycosides preferably used below 1.5, in particular between 1.2 and 1.4.
  • the preferred monomer building block is glucose because of its good availability.
  • the alkyl or alkenyl part R 12 of the glycosides preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to produce usable glycosides. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful.
  • Nonionic surfactant is contained in agents which contain a Ceululose derivative used according to the invention, preferably in amounts of 1% by weight to 30% by weight, in particular from 1% by weight to 25% by weight, with amounts in the upper part thereof The range is more likely to be found in liquid detergents and detergent-shaped detergents preferably contain smaller amounts of up to 5% by weight.
  • the nonionic surfactant is at least partially an alkoxylate, preferably an ethoxylate, of a branched chain fatty alcohol, such as isotridecanol.
  • the agents can contain further surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as, for example, alkylbenzenesulfonates, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18% by weight. %, each based on the total mean.
  • synthetic anionic surfactants which are particularly suitable for use in agents of this type are the alkyl and / or alkenyl sulfates having 8 to 22 carbon atoms and carrying an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as countercation.
  • the derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are preferred.
  • the alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
  • Such alkyl and / or alkenyl sulfates are in the compositions which contain a urethane-based polymer according to the invention, preferably in amounts from 0.1% by weight to 15% by weight, in particular from 0.5% by weight to Contain 10% by weight.
  • the sulfate-type surfactants that can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.
  • Suitable anionic surfactants of the sulfonate type include the .alpha.-sulfoesters which can be obtained by reacting fatty acid esters with sulfur trioxide and then re-neutering, in particular those derived from fatty acids having 8 to 22 carbon atoms. preferably 12 to 18 carbon atoms, and linear alcohols with 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, sulfonation products, and the sulfofatty acids resulting from these by formal saponification.
  • Soaps can be considered as further optional surfactant ingredients, whereby saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, as well as soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, are suitable.
  • those soap mixtures are preferred which are 50% to 100% saturated by weight
  • Fatty acid soaps and up to 50% by weight are composed of oleic acid soap.
  • Soap is preferably contained in amounts of 0.1% by weight to 5% by weight.
  • higher amounts of soap as a rule up to 20% by weight, can also be present.
  • the agents can also contain betaines and / or cationic surfactants which - if present - are preferably used in amounts of 0.5% by weight to 7% by weight.
  • ester quats that is, quaternized esters of carboxylic acid and amino alcohol, are particularly preferred. These are known substances that can be obtained using the relevant methods of preparative organic chemistry. In this connection, reference is made to international patent application WO 91/01295, according to which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide.
  • German patent DE 43 08 794 also discloses a process for the production of solid ester quats, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols.
  • suitable dispersants preferably fatty alcohols.
  • an agent which contains a cellulose derivative to be used according to the invention contains water-soluble and / or water-insoluble broths, in particular selected from alkali alumosilicate, crystalline alkali silicate Module over 1, monomeric polycarboxylate, polymeric polycarboxylate and their mixtures, in particular in amounts in the range from 2.5% by weight to 60% by weight.
  • An agent which contains a cellulose derivative to be used according to the invention preferably contains 20% by weight to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic broths.
  • the water-soluble organic builder substances include, in particular, those from the class of the polycarbonic acids, in particular citric acid and sugar acids, and also the polymeric (poly) carboxylic acids, in particular the polycarboxylates of the international patent application WO 93/16110, polymer acrylic, which are accessible by oxidation of polysaccharides - Acids, methacrylic acids, maleic acids and copolymers of these, which can also contain small amounts of polymerizable substances in copolymerized form without a carboxylic acid functionality.
  • the relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
  • Suitable, albeit 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 acid content is at least 50% by weight.
  • Terpolymers which contain two carboxylic acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as monomers can also be used as water-soluble organic building 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 can be a derivative of a C -C 8 dicarboxylic acid, maleic acid being particularly preferred.
  • the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol.
  • vinyl alcohol derivatives are preferred which represent an ester of short-chain carboxylic acids, for example of dC-carboxylic acids, with vinyl alcohol.
  • Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleinate and 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight of vinyl alcohol and / or vinyl acetate.
  • Terpolymers in which the weight ratio (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2, are very particularly preferred.
  • the second acidic monomer or its salt can also be a derivative of an allylsulfonic acid, which is substituted in 2-control with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical, which is preferably derived from benzene or benzene derivatives is.
  • Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight.
  • % preferably 15% by weight to 25% by weight of methyl sulfonic acid or methallylsulfonate and as the third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate.
  • This carbohydrate can be, for example, a mono-, di-, ougosaccharide or polysaccharide, mono-, di- or ougosaccharides being preferred, sucrose being particularly preferred.
  • the use of the third monomer presumably means that breakage units are installed in the polymer which are responsible for the good biodegradability of the polymer.
  • terpolymers can be prepared in particular by processes which are described in German patent specification DE 4221 381 and German patent application DE 43 00 772 and generally have a relative molecular weight between 1000 and 200000, preferably between 200 and 50000 and in particular between 3000 and 10,000 on. They can be used, in particular for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • Organic builder substances of this type are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight contain. Amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, agents.
  • Crystalline or amorphous alkali alumosilicates in particular in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid compositions in particular of 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic powder materials.
  • the crystalline detergent-quality aluminum silicates in particular zeolite NaA and optionally NaX, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particle-shaped agents.
  • Suitable aluminum silicates in particular have no tissues with a grain size of more than 30 mm and preferably consist of at least 80% by weight of tissues with a size of less than 10 mm.
  • Suitable substitutes or tea substitutes for the alumosilicate mentioned are crystalline alkali silicates which can be present either in or in a mixture with amorphous suicates.
  • the alkali silicates which can be used as builders in the compositions preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar Na 2 O: SiO 2 ratio of 1: 2 to 1: 2.8.
  • Such amorphous Alkaüsüikate are commercially available for example under the name Portü®.
  • Those with a molar Na 2 O: SiO 2 ratio of 1: 1.9 to 1: 2.8 can be prepared by the process of European patent application EP 0425 427. As part of the production process, they are preferably added as a solid and not in the form of a solution.
  • both 13- and ⁇ -Na- triumdisüikate (Na 2 Si 2 ⁇ 5 -yH 2 O) is preferred, wherein ⁇ -sodium disuicate can be obtained, for example, by the process described in international patent application WO 91/08171.
  • ⁇ -sodium silicates with a modulus between 1.9 and 3.2 can be prepared according to Japanese patent applications JP 04/238 809 or JP 04/260 610.
  • anhydrous crystalline AlkaüsMikate made of amorphous alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1, can be prepared as described in European patent applications EP 0 548 599, EP 0 502 325 and EP 0425 428 , can be used in agents which contain a cellulose derivative used according to the invention.
  • a crystal sodium silicate with a modulus of 2 to 3 is used, as can be made from sand and soda according to the method of European patent application EP 0436 835.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents or cleaning agents , which contain a cellulose derivative used according to the invention.
  • Their alkali silicate content is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on the anhydrous active substance. If alkali alumosilicate, in particular Zeoüth, is also present as an additional builder substance, the alkali silicate content is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance.
  • the weight ratio of aluminum silicate to sweet, based in each case on anhydrous active substances, is then preferably 4: 1 to 10: 1.
  • the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • the alkali carbonates, alkali hydrogen carbonates and alkali sulfates are suitable their mixtures.
  • additional inorganic material can be present in amounts up to 70% by weight.
  • the agents can contain other ingredients that are customary in washing and cleaning agents.
  • These optional Bestandteüen include ren particular enzymes, enzyme stabilizers, bleaching agents, bleach activators, complexing agents for heavy metals, for example aminopolycarboxylic acids, Aminohydroxypolycarbonkla-, polyphosphonic acids and / or aminopolyphosphonic acids, Farbfixierwirkscher, dye transfer inhibitors, for example Polyvinylpyrroüdon or Polyvinylpyrdin- N-oxide, solvents, and optical Aufheüer, for example, pulp disulfonic acid derivatives.
  • Agents containing a combination used according to the invention preferably contain up to 1% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of the substituted 4,4 ' -Bis (2,4,6-triamino-s-triazinyl) -st Wegneck-2,2'-disulfonic acids, up to 5% by weight, in particular 0.1% by weight to 2% by weight, of complexing agent for Heavy metals, in particular aminoalkylenephosphonic acids and their salts, up to 3% by weight, in particular 0.5% by weight to 2% by weight, of graying inhibitors and up to 2% by weight, in particular 0.1% by weight to 1 % By weight of foam inhibitors, the weight percentages based on total mean.
  • optical brighteners in particular compounds from the class of the substituted 4,4 ' -Bis (2,4,6-triamino-s-triazinyl) -st Wegneck
  • complexing agent for Heavy metals in
  • solvents which are used in particular in liquid compositions are preferably those which are water-miscible. These include the lower alcohols, for example ethanol, propanol, iso-propanol, and the isomeric butanols, glycerol, lower glycols, for example ethylene and propylene glycol, and the ethers which can be derived from the classes of compounds mentioned.
  • the cululose derivatives used according to the invention are usually present in solution or in suspended form.
  • Any enzymes present are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures of these.
  • Protease obtained from microorganisms, such as bacteria or puddles, is primarily suitable. It can be obtained in a known manner from suitable microorganisms by fermentation processes, which play in the German patent applications DE 1940 488, DE 20 44 161, DE 21 01 803 and DE 21 21 397, the US patents US 3 623 957 and US 4 264738, the European patent application EP 006 638 and the international patent application WO 91 / 02792.
  • Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®.
  • the lipase that can be used can be obtained from Humicola lanuginosa, as described, for example, in European patent applications EP 258 068, EP 305 216 and EP 341 947, from Bacgus species, as described, for example, in international patent application WO 91/16422 or European patent application EP 384717.
  • Pseudomonas species such as, for example, in European patent applications EP 468 102, EP 385 401, EP 375 102, EP 334462, EP 331 376, EP 330 641, EP 214761, EP 218 272 or EP 204 284 or international patent application WO 90 / 10695, from Fusarium species, as described for example in the European patent application EP 130 064, from Rhizopus species, as described for example in the European patent application EP 117 553, or from Aspergülus species, as for example in the European patent application EP 167 309 described can be obtained.
  • Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano® lipase, Toyo-Jozo® lipase, Meito® lipase and Diosynth® lipase.
  • Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm.
  • the Ceüulase that can be used can be an enzyme that can be obtained from bacteria or peaches and that has a pH optimum, preferably in the weakly acidic to weakly alkaline range from 6 to 9.5.
  • Such cellulases are known, for example, from German patent applications DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22950 or European patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 550 and known from international patent applications WO 95/02675 and WO 97/14804 and commercially available under the names Ceüuzyme®, Carezyme® and Ecostone®.
  • the usual enzyme stabilizers which may be present, in particular in liquid agents include amino alcohols, for example mono-, di-, triethanol- and propanolamine and mixtures thereof, lower carboxylic acids, for example from the European European patent applications EP 376 705 and EP 378 261 known, boric acid or alkali borates, boric acid-carboxylic acid combinations, as known, for example, from European patent application EP 451 921, boric acid esters, such as from international patent application WO 93/11215 or European patent application EP 511 456 known, boronic acid derivatives, such as known from European patent application EP 583 536, calcium salts, for example the Ca-formic acid combination known from European patent EP 28 865, magnesium salts, such as known from European patent application EP 378 262, and / or sulfur-containing reducing agents, as known, for example, from European patent applications EP 080 748 or EP 080 223.
  • amino alcohols for example mono-, di-, triethanol- and propanolamine and mixtures thereof
  • a further embodiment of such an agent which contains a cellulose derivative to be used according to the invention, contains bleaching agents based on peroxygen, in particular in amounts in the range from 5% by weight to 70% by weight, and optionally bleach activator, in particular in amounts in the range of 2% by weight .-% to 10 wt .-%.
  • bleaching agents that can be considered are the per compounds that are generally used in detergents, such as hydrogen peroxide, perborate, which can be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally present as alkali metal salts, in particular as sodium salts.
  • Such bleaching agents are in detergents which contain a cellulose derivative used according to the invention, preferably in amounts of up to 25% by weight, in particular up to 15% by weight and particularly preferably from 5% by weight to 15% by weight on the entire medium, with percarbonate in particular being used.
  • the optional component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tettacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycol uru, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, cyanuryl amides, sulfuryl amides also carboxylic anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium isononanoyl phenol sulfonate, and acylated sugar derivatives, especially pentaacetyl glucose, and cationic nitric acid derivatives such as trimethylammonium acetonitrile salts.
  • N- or O-acyl compounds for example multiply acylated alkylenediamines, in particular tettacetylethylenediamine, acylated
  • the bleach activators can be used to avoid interaction with the per compounds in the Storage has been coated or granulated with known substances in a known manner, granulated tetraacetylethylenediamine with average grain sizes of 0.01 mm to 0.8 mm, as produced for example by the process described in European Patent EP 37 026, using carboxymethyl cellulose can be granulated l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine, as can be prepared by the method described in German Patent DD 255 884, and / or according to the international patent applications WO 00/50553, WO 00/50556, WO 02/12425, WO 02/12426 or WO 02/26927 processes in trial form ready-made trialkylammonium acetonitrile are particularly preferred.
  • Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, in each case based
  • an agent into which the cellulose derivative to be used according to the invention is incorporated is tissue-shaped and contains 20% by weight to 55% by weight of inorganic builder, up to 10% by weight, in particular 2% by weight to 8 %
  • water-soluble organic builder 10% by weight to 25% by weight of synthetic anionic surfactant, 1% by weight to 5% by weight of nonionic surfactant, up to 25% by weight, in particular 5% by weight up to 20% by weight of bleach, in particular alkali percarbonate, up to 15% by weight, in particular 1% by weight to 10% by weight of bleach activator and up to 25% by weight, in particular 0.1% by weight of 25% by weight of inorganic salts, in particular alkali carbonate and / or bicarbonate.
  • an agent into which the cellulose derivative to be used according to the invention is incorporated is liquid and contains 10% by weight to 25% by weight, in particular 12% by weight to 22.5% by weight, of nonionic surfactant, 2% by weight to 10% by weight, in particular 2.5% by weight to 8% by weight of synthetic anionic surfactant, 3% by weight to 15% by weight, in particular 4.5% by weight to 12.5% by weight of soap, 0.5% by weight to 5% by weight, in particular 1% by weight to 4% by weight of organic builder, in particular polycarboxylate such as citrate, up to 1.5% by weight. %, in particular 0.1% by weight to 1% by weight, of complexing agents for heavy metals, such as phosphonate, and optionally enzyme, enzyme stabilizer, coloring and / or fragrance and water and / or water-miscible solvent.

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Abstract

L'invention concerne des dérivés cellulosiques que l'on peut obtenir par alkylation et hydroxyalkylation de cellulose. Ces dérivés cellulosiques contribuent à réduire le moussage de produits de lavage ou de nettoyage lors de leur utilisation dans des solutions aqueuses pour le lavage ou le nettoyage.
EP04707149A 2003-02-10 2004-01-31 Utilisation de derives cellulosiques en tant que regulateurs de moussage Withdrawn EP1592768A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10305306 2003-02-10
DE10305306 2003-02-10
DE10351266A DE10351266A1 (de) 2003-02-10 2003-10-31 Verwendung von Cellulosederivaten als Schaumregulatoren
DE10351266 2003-10-31
PCT/EP2004/000873 WO2004069976A2 (fr) 2003-02-10 2004-01-31 Utilisation de derives cellulosiques en tant que regulateurs de moussage

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EP1592768A2 true EP1592768A2 (fr) 2005-11-09

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US (1) US20060035804A1 (fr)
EP (1) EP1592768A2 (fr)
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WO (1) WO2004069976A2 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6071523A (en) * 1998-06-03 2000-06-06 Taro Pharmaceuticals Industries, Ltd. Spill resistant pharmaceutical compositions in semi-solid form
EP1592765B1 (fr) * 2003-02-10 2007-05-30 Henkel Kommanditgesellschaft auf Aktien Augmentation de la puissance de nettoyage de produits de lavage a l'aide d'un derive cellulosique et d'un polymere hygroscopique
DE502004003835D1 (de) * 2003-02-10 2007-06-28 Henkel Kgaa Bleichmittelhaltige wasch- oder reinigungsmittel mit wasserlöslichem buildersystem und schmutzablösevermögendem cellulosederivat
DE502004002541D1 (de) * 2003-02-10 2007-02-15 Henkel Kgaa Erhöhung der wasseraufnahmefähigkeit von textilien
DE10351325A1 (de) * 2003-02-10 2004-08-26 Henkel Kgaa Wasch- oder Reinigungsmittel mit wasserlöslichem Buildersystem und schmutzablösevermögendem Cellulosederivat
EP1592763B2 (fr) * 2003-02-10 2011-08-31 Henkel AG & Co. KGaA Detergent contenant un agent de blanchiment et un derive de cellulose facilitant l'elimination des salissures sur les textiles en coton
DE10351321A1 (de) * 2003-02-10 2004-08-26 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch eine Kombination von Cellulosderivaten
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles
US8740993B2 (en) 2012-03-23 2014-06-03 Ecolab Usa Inc. Method for reduced encrustation of textiles using a polymer comprising maleic acid, vinyl acetate, and alkyl acrylate
US8623151B2 (en) 2012-03-23 2014-01-07 Ecolab Usa Inc. Terpolymer containing maleic acid, vinyl acetate, and alkyl acrylate monomers for aluminum protection

Family Cites Families (94)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2016962A (en) * 1932-09-27 1935-10-08 Du Pont Process for producing glucamines and related products
US1985424A (en) * 1933-03-23 1934-12-25 Ici Ltd Alkylene-oxide derivatives of polyhydroxyalkyl-alkylamides
US2703798A (en) * 1950-05-25 1955-03-08 Commercial Solvents Corp Detergents from nu-monoalkyl-glucamines
US2886533A (en) * 1956-07-17 1959-05-12 Wyandotte Chemicals Corp Promoted detergent compositions
NL130828C (fr) * 1959-06-03
GB931438A (fr) * 1960-11-01
GB1005507A (en) * 1963-07-04 1965-09-22 Ici Ltd Improvements in the treatment of synthetic polyamide textile materials
US3523088A (en) * 1966-12-13 1970-08-04 Procter & Gamble Novel antiredeposition agent and built detergent compositions containing said antiredeposition agent
US3547828A (en) * 1968-09-03 1970-12-15 Rohm & Haas Alkyl oligosaccharides and their mixtures with alkyl glucosides and alkanols
BE755886A (fr) * 1969-09-08 1971-03-08 Unilever Nv Enzyme
US3623956A (en) * 1970-01-21 1971-11-30 Rapidase Sa Soc Preparation of microbial alkaline protease by fermentation with bacillus subtilis, variety licheniformis
US3623957A (en) * 1970-01-21 1971-11-30 Baxter Laboratories Inc Preparation of microbial alkaline protease by fermentation with bacillus subtilis, variety licheniformis
US3985923A (en) * 1971-10-28 1976-10-12 The Procter & Gamble Company Process for imparting renewable soil release finish to polyester-containing fabrics
CA1037815A (fr) * 1973-06-20 1978-09-05 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Fabrication d'agents solides de lavage ou de nettoyage versables, contenant une certaine quantite de silicate fixateur de calcium
US4174305A (en) * 1975-04-02 1979-11-13 The Procter & Gamble Company Alkyl benzene sulfonate detergent compositions containing cellulose ether soil release agents
US4000093A (en) * 1975-04-02 1976-12-28 The Procter & Gamble Company Alkyl sulfate detergent compositions
US4136038A (en) * 1976-02-02 1979-01-23 The Procter & Gamble Company Fabric conditioning compositions containing methyl cellulose ether
CH644629A5 (de) * 1977-06-23 1984-08-15 Procter & Gamble Detergenskomposition.
US4127423A (en) * 1977-09-13 1978-11-28 Burton, Parsons And Company, Inc. Contact lens cleaning solution
US4116885A (en) * 1977-09-23 1978-09-26 The Procter & Gamble Company Anionic surfactant-containing detergent compositions having soil-release properties
FR2407980A1 (fr) * 1977-11-02 1979-06-01 Rhone Poulenc Ind Nouvelles compositions anti-salissure et anti-redeposition utilisables en detergence
US4264738A (en) * 1979-08-01 1981-04-28 Stepanov Valentin M Process for purification of proteolytic enzymes
DE3011998C2 (de) * 1980-03-28 1982-06-16 Henkel KGaA, 4000 Düsseldorf Verfahren zur Herstellung eines lagerstabilen, leichtlöslichen Granulates mit einem Gehalt an Bleichaktivatoren
DK187280A (da) * 1980-04-30 1981-10-31 Novo Industri As Ruhedsreducerende middel til et fuldvaskemiddel fuldvaskemiddel og fuldvaskemetode
DE3115644A1 (de) * 1981-04-18 1982-11-04 Henkel KGaA, 4000 Düsseldorf "pulverfoermiger entschaeumer fuer waessrige systeme, verfahren zu seiner herstellung und seine verwendung"
JPS58217599A (ja) * 1982-06-10 1983-12-17 花王株式会社 漂白洗浄剤組成物
JPS591598A (ja) * 1982-06-25 1984-01-06 花王株式会社 洗浄剤組成物
DE3400008A1 (de) * 1984-01-02 1985-07-11 Henkel KGaA, 4000 Düsseldorf Zur verwendung in tensidhaltigen mitteln geeignetes schaumregulierungsmittel
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
GB8519046D0 (en) * 1985-07-29 1985-09-04 Unilever Plc Detergent compositions
DE3633519A1 (de) * 1986-10-02 1988-04-14 Henkel Kgaa Verfahren zur herstellung von rieselfaehigen, stabilen schauminhibitor-konzentraten durch kompaktierende granulation
US4770666A (en) * 1986-12-12 1988-09-13 The Procter & Gamble Company Laundry composition containing peroxyacid bleach and soil release agent
DE3723826A1 (de) * 1987-07-18 1989-01-26 Henkel Kgaa Verfahren zur herstellung von alkylglykosiden
DE3725030A1 (de) * 1987-07-29 1989-02-09 Henkel Kgaa Oberflaechenaktive hydroxysulfonate
DE3732947A1 (de) * 1987-09-30 1989-04-13 Henkel Kgaa Zur verwendung in wasch- und reinigungsmitteln geeignetes schaumregulierungsmittel
US5240851A (en) * 1988-02-22 1993-08-31 Fina Research, S.A. Lipase-producing Pseudomonas aeruginosa strain
DE3827534A1 (de) * 1988-08-13 1990-02-22 Henkel Kgaa Verfahren zur herstellung von alkylglucosidverbindungen aus oligo- und/oder polysacchariden
US5576425A (en) * 1988-10-05 1996-11-19 Henkel Kommanditgesellschaft Auf Aktien Process for the direct production of alkyl glycosides
US5049302A (en) * 1988-10-06 1991-09-17 Basf Corporation Stable liquid detergent compositions with enchanced clay soil detergency and anti-redeposition properties
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
WO1991013138A1 (fr) * 1990-03-02 1991-09-05 The Dow Chemical Company Emploi d'ethers cellulosiques de faible viscosite en tant qu'additifs ameliorant la mousse de savon
US5427936A (en) * 1990-04-14 1995-06-27 Kali-Chemie Aktiengesellschaft Alkaline bacillus lipases, coding DNA sequences therefor and bacilli, which produce these lipases
BR9106922A (pt) * 1990-09-28 1993-08-17 Procter & Gamble Tensoativos de amidas de acidos graxos polihidroxi em composicoes de detergente contendo alvejante
GB9021761D0 (en) * 1990-10-06 1990-11-21 Procter & Gamble Detergent compositions
US5443750A (en) * 1991-01-16 1995-08-22 The Procter & Gamble Company Detergent compositions with high activity cellulase and softening clays
US5411673A (en) * 1991-02-06 1995-05-02 The Procter & Gamble Company Peroxyacid bleach precursor compositions
DE4107230C2 (de) * 1991-03-07 1995-04-06 Hoechst Ag Verfahren zur Herstellung von Natriumsilikaten
DE4134914A1 (de) * 1991-10-23 1993-04-29 Henkel Kgaa Wasch- und reinigungsmittel mit ausgewaehlten builder-systemen
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
US5332518A (en) * 1992-04-23 1994-07-26 Kao Corporation Stable slurry-coated sodium percarbonate, process for producing the same and bleach detergent composition containing the same
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
DE4308794C1 (de) * 1993-03-18 1994-04-21 Henkel Kgaa Verfahren zur Herstellung von festen Esterquats mit verbesserter Wasserdispergierbarkeit
US5405412A (en) * 1994-04-13 1995-04-11 The Procter & Gamble Company Bleaching compounds comprising N-acyl caprolactam and alkanoyloxybenzene sulfonate bleach activators
US5902682A (en) * 1993-07-17 1999-05-11 Degussa Aktiengesellschaft Coated sodium percarbonate particles, a process for their preparation and their use
US5705466A (en) * 1993-08-17 1998-01-06 The Procter & Gamble Company High bulk density granular detergents containing a percarbonate bleach and a powdered silicate
US5445755A (en) * 1994-05-31 1995-08-29 The Procter & Gamble Company Detergent compositions containing a peroxidase/accelerator system without linear alkylbenzenesulfonate
US5837666A (en) * 1994-06-30 1998-11-17 The Procter & Gamble Company Detergent compositions comprising methyl cellulose ether
US5460747A (en) * 1994-08-31 1995-10-24 The Procter & Gamble Co. Multiple-substituted bleach activators
IT1270000B (it) * 1994-09-22 1997-04-16 Solvay Interox Procedimento per la fabbricazione di particelle di persali
US5786316A (en) * 1994-10-27 1998-07-28 The Procter & Gamble Company Cleaning compositions comprising xylanases
US5948744A (en) * 1994-12-01 1999-09-07 Baillely; Gerard Marcel Detergent composition containing combination of nonionic polysaccharide ether with synthetic oxyalkylene-containing soil release agent
US5919271A (en) * 1994-12-31 1999-07-06 Procter & Gamble Company Detergent composition comprising cellulase enzyme and nonionic cellulose ether
US5916481A (en) * 1995-07-25 1999-06-29 The Procter & Gamble Company Low hue photobleaches
US5576282A (en) * 1995-09-11 1996-11-19 The Procter & Gamble Company Color-safe bleach boosters, compositions and laundry methods employing same
DE19620249A1 (de) * 1996-05-21 1997-11-27 Henkel Kgaa Teilchenförmiges Schaumregulierungsmittel auf Paraffin-Basis
DE19636035A1 (de) * 1996-09-05 1998-03-12 Henkel Ecolab Gmbh & Co Ohg Pastenförmiges Wasch- und Reinigungsmittel
US6218351B1 (en) * 1998-03-06 2001-04-17 The Procter & Gamble Compnay Bleach compositions
DE19725508A1 (de) * 1997-06-17 1998-12-24 Clariant Gmbh Wasch- und Reinigungsmittel
US6380145B1 (en) * 1997-07-09 2002-04-30 Procter & Gamble Cleaning compositions comprising a specific oxygenase
US6204234B1 (en) * 1997-07-09 2001-03-20 The Proctor & Gamble Company Cleaning compositions comprising a specific oxygenase
US6444634B1 (en) * 1997-09-11 2002-09-03 The Procter & Gamble Company Bleaching compositions
US6242406B1 (en) * 1997-10-10 2001-06-05 The Procter & Gamble Company Mid-chain branched surfactants with cellulose derivatives
EP1004661A1 (fr) * 1998-11-11 2000-05-31 DALLI-WERKE WÄSCHE- und KÖRPERPFLEGE GmbH & Co. KG Granulé de haute densité, procédé pour sa production, son utilisation en tant que désintégrant pour tablettes
GB9826097D0 (en) * 1998-11-27 1999-01-20 Unilever Plc Detergent compositions
DE19908051A1 (de) * 1999-02-25 2000-08-31 Henkel Kgaa Verfahren zur Herstellung compoundierter Acetonitril-Derivate
US6462008B1 (en) * 1999-03-05 2002-10-08 Case Western Reserve University Detergent compositions comprising photobleaching delivery systems
DE19943470A1 (de) * 1999-09-11 2001-03-15 Clariant Gmbh Kristallines Alkalischichtsilikat
DE10003124A1 (de) * 2000-01-26 2001-08-09 Cognis Deutschland Gmbh Verfahren zur Herstellung von Tensidgranulaten
DE10038832A1 (de) * 2000-08-04 2002-03-28 Henkel Kgaa Umhüllte Bleichaktivatoren
DE10038845A1 (de) * 2000-08-04 2002-02-21 Henkel Kgaa Teilchenförmig konfektionierte Acetonitril-Derivate als Bleichaktivatoren in festen Waschmitteln
DE10038978A1 (de) * 2000-08-10 2002-02-21 Wolff Walsrode Ag Verfahren zur Herstellung von Alkylhydroxyalkylcellulose
US20030166484A1 (en) * 2000-09-28 2003-09-04 Kingma Arend Jouke Coated, granular n-alkylammonium acetonitrile salts and use thereof as bleach activators
CA2439512A1 (fr) * 2001-03-07 2002-09-19 The Procter & Gamble Company Composition de conditionnement pour tissus a ajouter au rincage en cas de detergent residuel
DE10351321A1 (de) * 2003-02-10 2004-08-26 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch eine Kombination von Cellulosderivaten
EP1592763B2 (fr) * 2003-02-10 2011-08-31 Henkel AG & Co. KGaA Detergent contenant un agent de blanchiment et un derive de cellulose facilitant l'elimination des salissures sur les textiles en coton
DE502004003835D1 (de) * 2003-02-10 2007-06-28 Henkel Kgaa Bleichmittelhaltige wasch- oder reinigungsmittel mit wasserlöslichem buildersystem und schmutzablösevermögendem cellulosederivat
DE502004002541D1 (de) * 2003-02-10 2007-02-15 Henkel Kgaa Erhöhung der wasseraufnahmefähigkeit von textilien
EP1592765B1 (fr) * 2003-02-10 2007-05-30 Henkel Kommanditgesellschaft auf Aktien Augmentation de la puissance de nettoyage de produits de lavage a l'aide d'un derive cellulosique et d'un polymere hygroscopique
DE10351325A1 (de) * 2003-02-10 2004-08-26 Henkel Kgaa Wasch- oder Reinigungsmittel mit wasserlöslichem Buildersystem und schmutzablösevermögendem Cellulosederivat

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004069976A2 *

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WO2004069976A2 (fr) 2004-08-19
US20060035804A1 (en) 2006-02-16
JP2006517245A (ja) 2006-07-20

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