EP0814153A2 - Compositon détergente solide ayant une dispersibilité améliorée - Google Patents

Compositon détergente solide ayant une dispersibilité améliorée Download PDF

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Publication number
EP0814153A2
EP0814153A2 EP97116694A EP97116694A EP0814153A2 EP 0814153 A2 EP0814153 A2 EP 0814153A2 EP 97116694 A EP97116694 A EP 97116694A EP 97116694 A EP97116694 A EP 97116694A EP 0814153 A2 EP0814153 A2 EP 0814153A2
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Prior art keywords
weight
detergent
water
solid
treatment agent
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EP97116694A
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German (de)
English (en)
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EP0814153A3 (fr
Inventor
Bernd Dipl.-Chem. Dr. Larson
Kathrin Dipl.-Chem. Dr. Schnepp
Jochen Dipl.-Chem. Dr. Jacobs
Norbert Kühne
Hubert Dipl.-Chem. Dr. Pawelczyk
Volker Runge
Wolfgang Dipl.-Chem. Dr. Seiter
Rene-Andres Dipl.-Chem. Dr. Artiga Gonzalez
Monika Dipl.-Chem. Dr. Böcker
Günther Dipl.-Chem. Dr. Vogt
Eduard Dipl.-Chem. Dr. Smulders
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00Compositions of detergents, not provided for by one single preceding group
    • C11D10/04Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00Special methods for preparing compositions containing mixtures of detergents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065High-density particulate detergent compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/18Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2006Monohydric alcohols
    • C11D3/201Monohydric alcohols linear
    • C11D3/2013Monohydric alcohols linear fatty or with at least 8 carbon atoms in the alkyl chain
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2079Monocarboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds

Definitions

  • the invention relates to a process for the treatment of wash-active solid preparations with a high bulk density, which are in granular form and are produced by extrusion molding of a homogeneous premix with certain liquid or solid, hydrophobic or sparingly water-soluble substances, and the thus produced, Improved products in their induction behavior in household washing machines.
  • washing-active preparations are generally understood to mean detergents, dishwashing detergents and cleaning agents, and also their surfactant-containing preliminary products or premixes. Particularly when such preparations contain higher amounts of nonionic surfactants, when water is added they tend to form a gel-like phase on the surface during the dissolving or dispersing process, which phase can lead to the powder grains sticking together. Under unfavorable conditions, such as exist in some household washing machines with special design features, deposits of lumpy residues can occur in the case of detergents, which are then not available for the actual use of the product. This behavior often has a particularly disruptive effect in the case of solid powdery agents with a high bulk density, which as a rule contain little or no inorganic filler salts which increase the dissolution rate.
  • a mixture of tallow fatty acid partial glyceride and tallow fatty acid amide of hydroxylethylenediamine is proposed as such a hydrophobic compound.
  • detergents with good washing-in behavior can be produced according to the teaching of this application, a clear disadvantage can be seen in the fact that the teaching described there is specific to the formulation. It therefore does not allow other formulations of wash-active preparations, which are favorable for other reasons, to be improved by a post-treatment step without substantial intervention in the formulation structure.
  • detergent additives with improved washing-in behavior, which are described in German Offenlegungsschrift DE 38 22 479.
  • the subject of this published patent application is granular detergent additives, consisting of a granular, porous, water-soluble or water-dispersible carrier material and water-soluble or water-dispersible nonionic surfactants adsorbed thereon, in which the adsorbed nonionic surfactant is present in a homogeneous mixture with a hydrophobic substance having polar groups , wherein the weight ratio of nonionic surfactant to hydrophobic substance is 99: 1 to 60:40.
  • the hydrophobic substance preferably consists of fatty acids with 12 to 22 carbon atoms.
  • the unpublished German patent application DE 41 23 195 describes a process for the production of wash-active preparations in powder or granule form by treating a prefabricated powder or granulate with a liquid, reactive polysiloxane component in certain weight ratios. This will speed up the dissolution the active detergent preparation is reduced and this measure improves their washability.
  • the powdering of the powder product preferably produced by granulation, with finely divided zeolite, in particular zeolite Na-A, is not uncommon, as proposed, for example, in international patent application WO 91/02047.
  • This measure essentially serves to avoid the sticking of the powder products, which have not yet completely dried out or been warmed, and thus contain certain ingredients in a liquid and thus sticky state, directly after production. This powdering has no influence on the induction behavior of the finished products.
  • Another object of the invention is to provide laundry detergents produced by an extrusion process with a high bulk density and improved washing-in behavior in washing machines.
  • the invention thus relates to a process for the production of a detergent-active preparation in granular form with a high bulk density and improved flushing behavior, which is characterized in that a prefabricated detergent-active granulate with a bulk density above 500 g / l, produced by extrusion molding a homogeneous premix, the optionally with the addition of a plasticizer, via hole shapes, which preferably have an opening width of 0.5 mm to 5 mm, then comminuting the extrudate using a Cutting device and subsequent treatment in a rounding device, with mixing with a liquid or solid, hydrophobic and / or water-insoluble component, which is not a zeolite, in contact, the weight ratio of prefabricated granules to liquid or solid, hydrophobic and / or water-insoluble treatment agent between 20: 1 and 2000: 1 is set, and the treatment agent from the group comprising paraffins, inert siloxanes, fatty acid salts, alcohols with 10 to 22 carbon atoms, which can
  • the inventive method can be carried out with comparatively little technical effort.
  • the respective wash-active preparation serves as the starting product and its wash-in behavior is to be improved.
  • a detergent, a detergent precursor or a dishwashing or cleaning agent or other solid surfactant-containing preparations that have been produced by extrusion.
  • the largely water-insoluble inorganic solids among the suitable treatment agents are used in the form of commercially available finely divided powders. It is largely irrelevant whether these materials are present as crystalline substances or amorphous.
  • the silicas, phyllosilicates and hydrotalcites mentioned can in particular also be used in hydrophobicized form. It must be surprising that such inorganic materials are suitable for improving the washing-in behavior of the detergent-active preparations according to the invention, while the desired effect does not occur, or at least does not occur to a sufficient extent, with the same use of finely divided zeolite.
  • a further advantage of the process according to the invention is that some of the treatment agents usable according to the invention, in particular siloxanes and paraffins, have additional benefits in detergents, in particular foam-regulating action.
  • paraffins in question are generally a complex mixture of substances without a sharp melting point.
  • Paraffins which are completely liquid at room temperature that is to say those having a solidification point below 25 ° C., and paraffins which are solid at room temperature can be used.
  • the paraffin wax mixtures known from European patent application EP 309 931 can be used, for example from 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C to 90 ° C, 20% by weight to 49%.
  • paraffins or paraffin mixtures which solidify in the range from 30 ° C. to 90 ° C. are preferably used. It should be noted that even paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin.
  • Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular 40% by weight % to 55% by weight, at 80 ° C a liquid content of 80% by weight to 100% by weight, and at 90 ° C a liquid content of 100% by weight.
  • the temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C. in particularly preferred paraffin wax mixtures, in particular at 75 ° C. to 82 ° C.
  • Inert siloxanes in the context of the invention are liquid organopolysiloxanes, in particular alkyl and aryl polysiloxanes, their copolymers and block polymers with polyalkylene oxides and their acylation products with long-chain fatty acids. They can be present as such or, if desired, in mixtures with other compounds which are customary as defoaming agents, in particular paraffins, long-chain fatty acid esters and finely divided silica, which also silane or otherwise hydrophobize can be belong.
  • organopolysiloxanes containing silica, in particular dimethylpolysiloxanes are used.
  • the content of finely divided silica is preferably from 5% by weight to 10% by weight, based on organopolysiloxane. If liquid organopolysiloxanes are to be used, their viscosity at room temperature is preferably 15,000 mPa.s to 38,000 mPa.s. It can be measured using conventional methods, for example a Brookfield viscometer model RVT using spindle No. 5 at 10 revolutions per minute. It is also possible to use finely divided solid or solid organopolysiloxanes.
  • the solid formulations possible in this connection include the Silkones on organic porous carrier material with protective coating described in the international patent application WO 93/01269, the similarly composed, glycerin-containing foam regulation granules of the international patent application WO 92/13056 and in particular those from the European patent application EP 496 510 known fine-particle foam regulators based on silicone starch.
  • the fatty acid salts which can be used as treatment agents according to the invention are preferably selected from those of the saturated or mono- to polyunsaturated C 8 -C 22 -carboxylic acids.
  • these include pelargonic, capric acid, lauric acid, lauroleic, myristic, Myristolein Textre acid, palmitic acid, stearic acid, Petroselin acid petroselaidic, oleic acid, elaidic acid, linoleic acid, Linolaidin Textre, linolenic acid, eleostearic acid, arachidonic acid, Gadoleinklare, arachidonic acid, behenic acid, erucic acid, Brassidic acid and clupanodonic acid.
  • the C 16 to C 20 carboxylic acids are preferred.
  • the fatty acid salts include those with a mono-, di- or trivalent countercation, in particular the sodium, potassium, lithium, magnesium, calcium and aluminum salts. Among them, calcium stearate is particularly preferred.
  • the long-chain alcohols within the meaning of the invention are selected from the linear or branched-chain, primary or secondary alcohols having 10 to 22 carbon atoms.
  • the descendants of the abovementioned fatty acids are preferred, So-called fatty alcohols, although their branched-chain analogs, so-called oxo alcohols, are also suitable.
  • the alcohols can also be alkoxylated or sulfated.
  • the alkoxylates in question include in particular the ethoxylates and / or propoxylates of linear or branched-chain alcohols with 12 to 18 carbon atoms.
  • the degree of alkoxylation of the alcohols is in particular between 1 and 20, preferably between 3 and 10.
  • the alkoxylates can be prepared in a known manner by reacting the corresponding saturated or unsaturated alcohols with the corresponding alkylene oxides, the degree of alkoxylation used in connection with the present invention being the molar Corresponds to the ratio of alcohol to alkylene oxide.
  • the sulfation products in question include, in particular, primary alkyl sulfates with preferably linear alkyl radicals having 10 to 20 carbon atoms, which have an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as countercation.
  • the derivatives of linear alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are particularly suitable.
  • the sulfation products of primary fatty alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful.
  • Particularly preferred alkyl sulfates contain a tallow alkyl radical, that is to say mixtures with essentially hexadecyl and octadecyl radicals.
  • the alkyl 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.
  • a conventional sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
  • silicas In the case of silicas, a distinction is made between precipitated silicas, which are separated from aqueous silicate solution, and fumed silicas, which are usually obtained from silicon halides by a combustion process, the latter in particular often being referred to as silicon dioxide because of their low or completely absent water content.
  • finely divided pyrogens are preferred Silicas are used, as are commercially available, for example, under the name Aerosil (R) .
  • the contacting of the detergent preparation with the treatment agent is advantageously carried out with mixing.
  • the mixing ratios for the ratio of active detergent preparation to treatment agent are preferably between 25: 1 and 1000: 1, in particular between 100: 1 and 500: 1.
  • the treatment according to the invention can be carried out in conventional granulators, universal mixers or rounding devices, for example spheronizers, and can be carried out by Powdering the prefabricated wash-active preparation with a solid treatment agent, which is expediently in the form of a fine powder, or by spraying a liquid treatment agent.
  • the treatment agent is preferably applied to the wash-active preparation in such amounts that the weight ratio of surfactant to treatment agent contained therein is from 10: 1 to 200: 1, in particular 30: 1 to 120: 1, in particular if the surfactant contains a relatively large amount of nonionic surfactant Preparations are more at the treatment-richer end of the said Range ratio of preferably 10: 1 to 50: 1 (surfactant to treatment agent) is selected.
  • the intention is to improve the flushability of an extruded heavy powder which has been powdered off before the treatment according to the invention with a substance which cannot be used according to the invention, for example zeolite Na-A
  • this can also be done by mixing a mixture of those which cannot be used according to the invention Applies material with treatment agent usable according to the invention simultaneously and thus saves one processing step.
  • the washable preparation to be improved in terms of its rinsability is therefore brought into contact with a mixture, the finely divided zeolite Na-A in detergent quality and a particularly solid treatment agent according to the invention in proportions of 99: 1 to 25:75 , preferably 95: 5 to 20:80 and in particular 80:20 to 50:50.
  • the process according to the invention shows particularly clear effects in wash-active preparations in extruded granulate form which have a bulk density of between 700 and 1200 g per liter.
  • the corresponding wash-active preparations with a liter weight of 700 g / l to 1200 g / l, in particular 800 g / l to 1000 g / l, are assumed.
  • the resulting products which improve their induction behavior, also have bulk densities in the areas mentioned.
  • another advantage is the To evaluate the invention that, in addition to the improvement of the induction behavior by the method according to the invention, an increase in the bulk density of the detergent preparation can also take place.
  • the detergent-active preparations which are suitable according to the invention as starting materials in the context of the invention are, for example, a detergent precursor produced by spray drying and subsequent extrusion-like molding which, when mixed with other detergent components which cannot be spray-dried, gives a detergent.
  • a detergent precursor produced by spray drying and subsequent extrusion-like molding which, when mixed with other detergent components which cannot be spray-dried, gives a detergent.
  • the production of such wash-active preparations with increased density, which are particularly suitable as starting products for the process according to the invention, is described in international patent application WO 91/02047.
  • the treatment with the liquid or solid, hydrophobic and / or water-insoluble component is preferably carried out in the rounding device, in which a Spheronizer® is preferably used.
  • wash-active preparations which contain the hydrophobic and / or water-insoluble component on their surface and in particular on the parts of their surface which are accessible from the outside.
  • An additional advantage of the invention is that the dissolution rate of the preparation treated according to the invention does not change significantly, although its washability is significantly improved.
  • the process according to the invention can also be used successfully if it is not the finished formulation of the detergent that is treated, but only the portion containing surfactants.
  • the detergent precursors, so-called compounds, produced by spray drying can be used directly after the compacting extrusion step.
  • Such preliminary products usually contain all the formulation components of a detergent that are insensitive to heat. They are therefore free from bleaching agents or enzymes, for example, but contain builders and the surfactant components.
  • Corresponding detergent precursors can contain, for example, 40% by weight to 85% by weight of anionic surfactant and 15% by weight to 60% by weight of alkali metal carbonate or, for example, from 20% by weight to 50% by weight of zeolite, 5% by weight % to 15% by weight of layered silicate and / or alkali silicate and up to 35% by weight, in particular 15% by weight to 25% by weight of nonionic surfactant.
  • high-surfactant detergent preparations are treated. These are products which can contain the ingredients mentioned in the framework formulations listed, at least 12% by weight, preferably at least 20% by weight and in particular 40% by weight to 85% by weight of anionic surfactant being present .
  • nonionic surfactant can be present, preferably in amounts from 1% by weight to 40% by weight and in particular in amounts such that the weight ratio of anionic surfactant to nonionic surfactant is 10: 1 to 1: 3.
  • Such high-surfactant wash-active preparations are preferably treated with the treatment agent in mixing ratios (ratio of wash-active preparation to treatment agent) from 20: 1 to 1500: 1, in particular from 100: 1 to 1000: 1.
  • Addition products of 2 to 20, preferably 3 to 15 moles of ethylene oxide with 1 mole of a compound having essentially 10 to 20 carbon atoms from the group of alcohols and alkylphenols can be used as nonionic surfactants.
  • the addition products of 7 to 15 mol of ethylene oxide with primary alcohols, for example with coconut oil or tallow fatty alcohols, with oleyl alcohol, with oxo alcohols, or with secondary alcohols with 8 to 18, preferably 12 to 18, carbon atoms and with mono are particularly important - Or dialkylphenols with 6 to 14 carbon atoms in the alkyl radicals.
  • polyglycol ethers with 2 to 6 ethylene glycol ether residues in the molecule which are not or not completely water-soluble are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
  • suitable nonionic surfactants are alkyl glycosides or alkyl polyglycosides, the alkyl group of which has 8 to 18, preferably 10 to 16, carbon atoms.
  • Builders are generally understood to mean alkali metal carbonates, in particular sodium carbonate, synthetic zeolites and polycarboxylic acids. Preference is given to fine-crystalline, synthetic water-containing zeolites of the NaA type which have a calcium binding capacity (according to the information in German patent DE 22 24 837) in the range from 100 to 200 mg CaO / g. Their particle size is usually in the range from 1 to 10 ⁇ m.
  • Suitable (co) polymeric polycarboxylic acids are polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those made from 50% to 90% acrylic acid and 10% to 50% maleic acid.
  • the molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • the acids mentioned are usually used in the form of their water-soluble salts, in particular the sodium salts.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, in which the proportion of acid is at least 50%.
  • polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, which are obtained by polymerizing esters of glycolic acid, introducing stable terminal end groups and saponifying to give the sodium or potassium salts.
  • polymeric acids which are obtained by polymerizing acrolein and disproportionating the polymer according to Canizzaro using strong alkalis. They are essentially made up of acrylic acid units and vinyl alcohol units or acrolein units.
  • Alkali carbonates and hydroxides, in particular the sodium compounds, are also suitable as alkali components.
  • the detergents according to the invention may contain phosphonic acids, for example aminoalkanephosphonic acids, as cobuilders.
  • Suitable aminoalkanephosphonic acids are preferably ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetrimainpentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably used in the form of the neutral sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP.
  • Their proportion in the compositions, calculated on free acid is preferably up to 1% by weight, in particular 0.1 to 0.5% by weight.
  • Another suitable phosphonic acid is 1-hydroxyethane-1,1-diphosphonic acid or the disodium salt or the tetrasodium salt of this acid.
  • the detergents according to the invention furthermore preferably contain bleaches.
  • the compounds used as bleaching agents in water H 2 O 2 compounds, the sodium perborate tetrahydrate have (NaBO 2 .H 2 O 2 • 3 H 2 O) and the monohydrate (NaBO 2 .H 2 O 2) are particularly important.
  • other borates which produce H 2 O 2 can also be used, for example the perborax Na 2 B 4 O 7 .4H 2 O 2 .
  • peroxy hydrates such as peroxycarbonates (Na 2 CO 3 .1.5 H 2 O 2 ), peroxypyrophosphates, citrate perhydrates, urea-H 2 O 2 - or melamine-H 2 O 2 - Compounds as well as peracidic salts or peracids, such as perbenzoates, peroxyphthalates, diperazelaic acid or diperdodecanedioic acid.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetyl-ethylenediamine, and also carboxylic anhydrides, such as benzoic anhydride and phthalic anhydride and esters of polyols such as glucose pentaacetate.
  • the detergents can contain, as optical brighteners for cotton, in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of similar structure which, instead of the morpholino group, contain a diethanolamino group, carry a methylamino group or a 2-methoxyethylamino group.
  • Possible brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type, for example 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline.
  • Brighteners of the substituted 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl type can also be used. Mixtures of the aforementioned brighteners can also be used.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases and their mixture. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. The enzymes can be adsorbed on carriers and / or embedded in the coating substance in order to protect them against premature decomposition.
  • Suitable foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica.
  • Bis-acylamides derived from C 12-20 fatty acids and C 2-6 diamines or from C 12-20 alkyl amines and C 2-6 dicarboxylic acids can also be used.
  • Mixtures of various foam additives are also advantageously used, for example those made from silicones and paraffins or waxes or from bis-acylamides and paraffins or waxes.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • Layered silicates from the classes of bentonites and smectites are suitable as textile softening additives, for example those according to DE 23 34 899 or EP 026 529. Also suitable are synthetic fine-particle layered silicates with a smectite-like crystal phase, as described in more detail in DE 35 26 405.
  • the layered silicate content can be, for example, 5% by weight to 20% by weight.
  • a granular agent S1 with a bulk density of 813 g / l and the composition given below was produced.
  • strands with a diameter of 1.4 mm were extruded in the kneader-extruder / granulation, a continuously operated fluidized-bed dryer was used for drying the granules, and the final granulate was sieved using a sieve with a mesh size of 2 mm.
  • wash-active preparation S2 from Example 5 was run in a rounding device (Spheronizer® RM 400, manufacturer Schlüter, Neustadt) as described in Examples 1 to 4 with 1.0% by weight calcium stearate (treatment agent B5 ) or 3% by weight. % of a mixture of calcium stearate and zeolite Na-A (weight ratio 1: 2; treatment agent B6 ), each based on the amount of S2 , treated (resulting agents M5 and M6 ). The dissolution rate was not significantly affected by this treatment.

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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Detergent Compositions (AREA)
EP97116694A 1992-07-02 1993-06-24 Compositon détergente solide ayant une dispersibilité améliorée Withdrawn EP0814153A3 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4221736 1992-07-02
DE4221736A DE4221736A1 (de) 1992-07-02 1992-07-02 Feste waschaktive Zubereitung mit verbessertem Einspülverhalten
EP93914715A EP0648259B1 (fr) 1992-07-02 1993-06-24 Preparation detergente solide ayant un meilleur comportement au rin age

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EP93914715.3 Division 1994-01-20

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EP0814153A3 EP0814153A3 (fr) 1999-05-06

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EP93914715A Revoked EP0648259B1 (fr) 1992-07-02 1993-06-24 Preparation detergente solide ayant un meilleur comportement au rin age

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AT (1) ATE170918T1 (fr)
DE (2) DE4221736A1 (fr)
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WO (1) WO1994001526A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998055568A1 (fr) * 1997-06-02 1998-12-10 Henkel Kommanditgesellschaft Auf Aktien Agents de lavage ou de nettoyage a pouvoir nettoyant eleve
WO2001019950A1 (fr) * 1999-09-10 2001-03-22 Henkel Kommanditgesellschaft Auf Aktien Composantes de detergent comprenant des matieres solides a fines particules
WO2001053447A1 (fr) * 2000-01-19 2001-07-26 Cognis Deutschland Gmbh & Co. Kg Granulats tensioactifs
US9228157B2 (en) 2009-04-24 2016-01-05 Conopco, Inc. Manufacture of high active detergent particles

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GB9313878D0 (en) * 1993-07-05 1993-08-18 Unilever Plc Detergent composition or component containing anionic surfactant and process for its preparation
JPH09502743A (ja) * 1993-07-14 1997-03-18 ザ、プロクター、エンド、ギャンブル、カンパニー ペルカーボネートを含有する洗剤組成物およびその製法
DE69535736T2 (de) 1994-02-24 2009-04-30 Henkel Ag & Co. Kgaa Verbesserte enzyme und diese enthaltene detergentien
ES2364776T3 (es) * 1994-02-24 2011-09-14 HENKEL AG & CO. KGAA Enzimas mejoradas y detergentes que las contienen.
CA2189752A1 (fr) * 1994-05-16 1995-11-23 Charles Louis Stearns Composition detergente granulaire contenant des alcools gras ajoutes aux fins de solubilite amelioree dans l'eau froide
DE4434500A1 (de) * 1994-09-27 1996-03-28 Henkel Kgaa Verbessertes Extrusionsverfahren zur Herstellung von Waschmitteln
DE4435742A1 (de) * 1994-10-06 1996-04-11 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate
DE19524287A1 (de) * 1995-07-06 1997-01-09 Henkel Kgaa Von Staub- und Feinanteilen freie granulare Wasch- und Reinigungsmittel hoher Schüttdichte
JPH11513074A (ja) * 1996-07-08 1999-11-09 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン 洗剤またはクリーナー用添加剤およびその製法
DE19627427A1 (de) * 1996-07-08 1998-01-15 Henkel Kgaa Wasch- oder Reinigungsmitteladditiv sowie ein Verfahren zu seiner Herstellung
GB0111863D0 (en) 2001-05-15 2001-07-04 Unilever Plc Granular composition
GB0111862D0 (en) 2001-05-15 2001-07-04 Unilever Plc Granular composition
KR20030091474A (ko) * 2002-05-28 2003-12-03 주식회사 세종파마텍 청소가 용이한 정제 코팅장치
WO2018049029A1 (fr) 2016-09-07 2018-03-15 Ecolab Usa Inc. Compositions détergentes solides et procédés de réglage de la vitesse de distribution de détergents solides utilisant des tensioactifs anioniques

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EP0337330A2 (fr) * 1988-04-15 1989-10-18 Henkel Kommanditgesellschaft auf Aktien Procédé pour augmenter la densité des détergents séchés par pulvérisation et contenant peu de phosphate
EP0360330A2 (fr) * 1988-09-23 1990-03-28 Unilever N.V. Procédé pour préparer les poudres de détergence ayant des propriétés de distribution
DE4123195A1 (de) * 1991-07-12 1993-01-14 Henkel Kgaa Waschaktive zubereitung mit verzoegertem aufloeseverhalten und verfahren zu ihrer herstellung

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NZ188469A (en) * 1977-10-06 1980-12-19 Colgate Palmolive Co Detergent composition comprising a univalent cation-exchanging zeolite a nonionic detergent and builder salts
ES2020949B3 (es) * 1986-01-17 1991-10-16 Kao Corp Composicion detergente granular de alta densidad.
GB8810193D0 (en) * 1988-04-29 1988-06-02 Unilever Plc Detergent compositions & process for preparing them

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EP0337330A2 (fr) * 1988-04-15 1989-10-18 Henkel Kommanditgesellschaft auf Aktien Procédé pour augmenter la densité des détergents séchés par pulvérisation et contenant peu de phosphate
EP0360330A2 (fr) * 1988-09-23 1990-03-28 Unilever N.V. Procédé pour préparer les poudres de détergence ayant des propriétés de distribution
DE4123195A1 (de) * 1991-07-12 1993-01-14 Henkel Kgaa Waschaktive zubereitung mit verzoegertem aufloeseverhalten und verfahren zu ihrer herstellung

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998055568A1 (fr) * 1997-06-02 1998-12-10 Henkel Kommanditgesellschaft Auf Aktien Agents de lavage ou de nettoyage a pouvoir nettoyant eleve
WO2001019950A1 (fr) * 1999-09-10 2001-03-22 Henkel Kommanditgesellschaft Auf Aktien Composantes de detergent comprenant des matieres solides a fines particules
WO2001053447A1 (fr) * 2000-01-19 2001-07-26 Cognis Deutschland Gmbh & Co. Kg Granulats tensioactifs
US9228157B2 (en) 2009-04-24 2016-01-05 Conopco, Inc. Manufacture of high active detergent particles

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Publication number Publication date
WO1994001526A1 (fr) 1994-01-20
ATE170918T1 (de) 1998-09-15
DE59308975D1 (de) 1998-10-15
EP0814153A3 (fr) 1999-05-06
ES2122028T3 (es) 1998-12-16
EP0648259A1 (fr) 1995-04-19
DE4221736A1 (de) 1994-01-05
EP0648259B1 (fr) 1998-09-09

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