WO1993005133A1 - Procede de lavage et/ou de nettoyage - Google Patents

Procede de lavage et/ou de nettoyage Download PDF

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Publication number
WO1993005133A1
WO1993005133A1 PCT/EP1992/001934 EP9201934W WO9305133A1 WO 1993005133 A1 WO1993005133 A1 WO 1993005133A1 EP 9201934 W EP9201934 W EP 9201934W WO 9305133 A1 WO9305133 A1 WO 9305133A1
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Prior art keywords
alkali carbonate
carbonate
weight
treated
untreated
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PCT/EP1992/001934
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German (de)
English (en)
Inventor
Christian Block
Hans Dolhaine
Johannes Hachgenei
Gerald Schreiber
Jörg Poethkow
Horst Upadek
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Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO1993005133A1 publication Critical patent/WO1993005133A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates

Definitions

  • the invention relates to a method for washing and / or cleaning, new agents 4 which are used in this method, and methods for producing the new agents.
  • a disadvantage of these zeolites is, however, that in washing and / or cleaning processes in which agents are used which contain both zeolite and alkali carbonate, the formation of the sparingly soluble calcium carbonate from alkali carbonate and the hardness-forming agent of the water takes place faster than the cation exchange through the builder substance zeolite. In order to avoid disruptive incrustations, it is therefore necessary to add further compounds, for example polymeric polycarboxylates, to the agents used in the washing and / or cleaning processes, which are intended to prevent the calcium carbonate formed from settling on hard surfaces or textile fabrics ⁇ beats.
  • further compounds for example polymeric polycarboxylates
  • the object of the invention was to provide a washing and / or cleaning process in which washing, rinsing or cleaning agents coexist usual ingredients, and in which the formation of incrustations is counteracted without relying on the use of substances which prevent or delay the deposition of calcium carbonate on hard surfaces or textile fabrics, for example polymeric polycarboxylates .
  • a further task was to provide alkali carbonates in a new form of supply which can be used in the washing and / or cleaning processes according to the invention or in the washing, rinsing or cleaning agents used there.
  • the invention accordingly relates in a first embodiment to a washing and / or cleaning process, the formation of incrustations being reduced when using a washing, rinsing or cleaning agent with conventional ingredients in that the formation of alkali carbonate to water with a hardness above 0 ° d caused formation of calcium carbonate in the amounts that exceed the solubility product of calcium carbonate at temperatures between 15 and 95 ° C, reduced or avoided by the alkali carbonate of washing, rinsing or Cleaning fleet is made available with a time delay.
  • the alkali carbonate is preferably made available to the washing, rinsing or cleaning liquor with a time delay such that in the first minute, in particular in the first 2 minutes and with particular advantage in the first 10 minutes, for example after 3, 4, 5 or 6 minutes, after adding the washing, rinsing or cleaning agent to the liquor, 10 to 100% by weight, preferably 20 to 100% by weight and in particular 30 to 80% by weight, less alkali carbonate, based on the total amount of alkali carbonate is made available when this is the case with the same total amount of alkali carbonate which is introduced via a conventional alkali carbonate-containing agent with a customary composition.
  • the alkali carbonate can be made available with a time delay in that a treated alkali carbonate, which was obtained by modifying an untreated alkali carbonate and has a lower dissolution rate in water at temperatures between 15 and 95 ° C. than the untreated alkali carbonate, has separately with a Washing, rinsing or cleaning agent is introduced into the washing and / or cleaning liquor or as part of a washing, rinsing or cleaning agent in the washing and / or cleaning liquor.
  • the alkali carbonate is made available with a time delay in that the addition of a treated or untreated alkali carbonate to the washing, rinsing or cleaning liquor is 1 to 5 minutes, preferably 2 to 3 minutes, after the addition of a wash -, Flushing or cleaning agent that does not contain alkali carbonate takes place.
  • an “untreated alkali carbonate” is understood to mean a commercially available alkali carbonate which serves as the starting material for the production of the “treated alkali carbonate”.
  • these commercially available alkali carbonates are both light and compacted, powdery or granular alkali carbonates with a bulk density between 300 and 1 200 g / 1 and roller-compacted alkali carbonates in Schülpen-For.
  • These untreated alkali carbonates can be obtained, for example, from Matthes & Weber, Federal Republic of Germany, Sodawerk Bernburg GmbH, Federal Republic of Germany, or Deutsche Solvay-Werke GmbH.
  • a sodium carbonate in particular a water-containing or anhydrous granulated or crystallized sodium carbonate with a bulk density between 500 and 1200 g / 1, with particular advantage between 800 and 1000 g / 1, is preferably used as the untreated alkali carbonate, the latter at least 85% by weight.
  • -% consists of particles with a diameter between 200 and 2,000 microns and a maximum of 5 wt .-% of particles with a diameter smaller than 200 microns.
  • the invention relates to the treated alkali metal carbonate, which has a lower dissolution rate in water than the untreated alkali metal carbonate at temperatures between 15 and 95 ° C.
  • a treated alkali carbonate is preferred, which is obtained by melting the untreated alkali carbonate and then grinding the cooled melt, a maximum of 10% by weight of the ground particles having a diameter of less than 0.8 mm and in particular at least 90% by weight. of the ground particles have a diameter between 0.8 and 2 mm.
  • a treated alkali metal carbonate is preferred which contains untreated or treated alkali metal carbonate or which is obtained by melting the untreated alkali metal carbonate and then grinding the cooled melt and is partially or completely coated.
  • 10 to 100%, preferably 30 to 100% and in particular 50 to 100% of the entire surface of the untreated alkali carbonate are coated.
  • the coating substance can accordingly be used in a very variable weight ratio of coating substance: alkali carbonate.
  • treated, coated alkali carbonate contains 0.5 to 90% by weight, in particular 1 to 50% by weight and particularly advantageously 2 to 25% by weight, based in each case on the untreated alkali carbonate, of coating substance.
  • the treated alkali carbonates contain coating substances which are anionic surfactants in their acid form.
  • Suitable anionic surfactants in their acid form are, for example, those of the organically derivatized sulfonic and sulfuric acid type.
  • sulfonic acid type are preferably alkyl aryl sulfonic acids, especially Cg-Cj j -alkylbenzenesulfonic, Cg-Cis-alkyl sulfonic acids, mono- or polyunsaturated C 8 -C 22 Alky1ensulfonklaren, more particularly sondere monoethylenically unsaturated C8-C22 Alkylensulfonklaren, and sulphonic acids of mono- and / or polycarboxylic acids, especially ⁇ -sulfo fatty acids and sulfosuccinic acid.
  • alkyl aryl sulfonic acids especially Cg-Cj j -alkylbenzenesulfonic, Cg-Cis-alkyl sulfonic acids, mono- or polyunsaturated C 8 -C 22 Alky1ensulfonklaren, more particularly sondere monoethylenically unsaturated C8-C
  • Suitable organic derivatives of the sulfuric acid type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin (alkylsulfuric acids), that is to say from C 16 -C 12 alcohols, in particular from fatty alcohols, for example from coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol , Lauryl, myristyl, palmityl or stearyl alcohol, or the C ⁇ o-C2 ⁇ -0 * oalkoholen, and those of secondary alcohols of this chain length.
  • alkylsulfuric acids alkylsulfuric acids
  • the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched Cg-Cn- Alcohols with an average of 3.5 moles of ethylene oxide per mole of alcohol are suitable.
  • Fatty acid monoglyceride sulfuric acids are also suitable.
  • anionic surfactants in their acid form are fatty acids from natural or synthetic, preferably saturated or ethylenically unsaturated C8-C28 fatty acids or mixtures thereof.
  • Natural fatty acid mixtures are particularly suitable, for example coconut, palm kernel or tallow fatty acids. Preference is given to those which are composed of 50 to 100% of saturated C 12-18 fatty acids and 0 to 50% by weight of oleic acids. Longer-chain fatty acids with 15 to 24 carbon atoms, optionally in a mixture with shorter-chain fatty acids with 8 to 10 carbon atoms, are particularly preferred.
  • Particularly preferred fatty acids are stearic acid and isostearic acid or mixtures thereof.
  • Suitable anionic surfactants in their acid form are the fluorinated or perfluorinated derivatives of the sulfuric acid derivatives, sulfonic acid derivatives and fatty acids mentioned.
  • the treated alkali carbonate preferably contains anionic surfactants in their acid form in an amount of 0.5 to 50% by weight, based on the untreated alkali carbonate.
  • the treated alkali metal carbonates contain organic derivatives of sulfuric acid and sulfonic acid, for example Cs-Ci8-alkylsulfuric acid and Cg-C ⁇ -alkylbenzenesulfonic acid, in amounts of
  • the content of fatty acids or fatty acid mixtures in the treated alkali metal carbonates is preferably 1 to 15% by weight and in particular 2 to 10% by weight, in each case based on the untreated alkali carbonate, it being particularly advantageous if the treated alkali metal carbonates as coating substances are a mixture from fatty acids or a fatty acid mixture and organic derivatives of sulfuric acids or sulfonic acids, for example
  • treated alkali carbonates which contain a mixture of fatty acid or one as coating substances Fatty acid mixture and alkali silicates, for example a mixture of 2 to 15% by weight of fatty acid or fatty acid mixture and 2 to 10% by weight of amorphous alkali silicate.
  • the coating of the untreated alkali carbonate with anionic surfactants in their acid form can be carried out in all customary mixing and / or granulating devices. Temperatures between room temperature and 150 ° C., for example up to 100 ° C. and in particular between 40 and 80 ° C., are preferably used. In the cases in which treated alkali carbonate is produced by coating untreated alkali carbonate with fatty acid or a fatty acid mixture, it is particularly advantageous if the coating of the untreated alkali carbonate is carried out at temperatures above the melting point of the fatty acid or the fatty acid mixture.
  • Non-surfactant-like foam inhibitors for example silicones, preferably organopolysiloxanes, and their mixtures with microfine, optionally silanized silica, paraffins or waxes.
  • silicones preferably organopolysiloxanes, and their mixtures with microfine, optionally silanized silica, paraffins or waxes.
  • linear or branched dimethylpolysiloxanes which advantageously contain a relative molecular mass between 1,000 and 100,000, are preferred.
  • Branched dimethylpolysiloxanes which have carboxylate groups in the side chains have particularly advantageous properties.
  • the silicones are used alone or in a mixture, in particular in a mixture with other coating substances.
  • the content of silicones in the treated alkali carbonates is preferably 0.1 to 5% by weight, based on the sum of untreated alkali carbonate and coating substances.
  • the untreated alkali carbonate is coated with silicones as described above, preferably at temperatures between 40 and 150 °
  • Suitable coating substances are solids from the group calcium stearate, microwaxes, for example a micropowder, which is available under the name Hoechst-Wachs Cv R ) from Hoechst AG, Federal Republic of Germany, amorphous and crystalline alkali silicates, zeolite, in particular zeolite NaA in detergent quality , and natural or synthetic layered silicates, especially sectites and bentonites. Finely divided solids are preferably used as the coating substance, which consist of at least 90% of particles with a diameter below 40 ⁇ m.
  • the alkali silicates are preferably amorphous alkali silicates with a molar ratio M2O to SiO 2 of 1: 2.0 to 1: 4.5 and in particular of 1: 2.3 to 1: 4.0, where M is preferably sodium or potassium.
  • the coating substance preferably consists of one or more of the fine-particle solids mentioned and of mixtures of the fine-particle solids with other coating substances.
  • the content of coating substances of finely divided solids in the treated alkali metal carbonates is preferably 0.5 to 90% by weight, based on the untreated alkali metal carbonate.
  • Calcium stearate is advantageously up to 8% by weight, in particular up to 5% by weight and particularly advantageously between 1 and 2% by weight, and microwaxes in amounts between 1 and 20% by weight, in particular between 2 and 10 % By weight used, in each case based on the untreated alkali carbonate.
  • Alkali silicates preferably sodium silicates, on the other hand, are advantageously used in amounts between 1 and 90% by weight, in particular between 3 and 80% by weight, based in each case on the untreated alkali carbonate.
  • the coating of the untreated alkali carbonate with the above-mentioned, preferably finely divided solids is preferably carried out in conventional mixing, pouring and granulating devices in a dry mixing process. It is particularly preferred that the untreated alkali carbonate with the finely divided, preferably only moderately water-soluble to water-insoluble solids at room temperature to slightly elevated temperatures which are below the melting temperature of the coating substance and preferably do not exceed 60 ° C, in particular 40 ° C, is mixed dry.
  • the temperature for solidifying the core shell with the core to a temperature above the melting point of the coating substance is increased, the temperature preferably being below 150 ° C. and in particular below 100 ° C.
  • Coating substances which consist of dispersions of nonionic surfactants and moderately water-soluble to water-insoluble solids are particularly advantageous.
  • Suitable nonionic surfactants include adducts of 1 to 80 moles of ethylene oxide (E0) with 1 mole of an aliphatic compound having essentially 8 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides or alkanesulfonamides.
  • E0 ethylene oxide
  • the addition products of 2 to 20 moles, in particular of 2 to 8 moles of ethylene oxide, to primary alcohols, such as, for example, to the addition products of 3, 5 or 7 E0 to coconut or tallow fatty alcohols, to oleyl alcohol, to oxo alcohols, or to secondary alcohols are particularly important Alcohols with 8 to 18, preferably 12 to 18 carbon atoms, and mixtures of these.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a restricted homolog distribution (narrow range ethoxylates, nre).
  • Other nonionic surfactants that can be used are alkyl glycosides of the general formula R-0- (G) x , in which R is a primary straight-chain or aliphatic radical which is methyl-branched in the 2-position and has 8 to 22, preferably 12 to 18, carbon atoms, and G is a symbol , which stands for a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10, preferably between 1 and 2 and in particular is significantly less than 1.4, for example in amounts of 1 to 10 wt.
  • the preferred solids include synthetic and natural aluminosilicates, for example zeolite, in particular zeolite NaA in detergent quality. Further preferred aluminosilicates are layered silicates, especially smectites and bentonites.
  • the weight ratio of nonionic surfactant: solid in the dispersions is preferably 10: 1 to 1: 5 and in particular 5: 1 to 1: 1.
  • treated alkali metal carbonates contain coating substances, the mixtures of dispersions from moderately water-soluble to water-insoluble represent solids in nonionic surfactants with anionic surfactants in acid form.
  • the content of the treated alkali carbonates in coating substances from dispersions of moderately water-soluble to water-insoluble solids in nonionic surfactants is preferably 0.5 to 25% by weight and in particular 1 to 15% by weight, in each case based on the untreated Alkali carbonate.
  • the coating of the untreated alkali carbonate with dispersions of moderately water-soluble to water-insoluble solids in nonionic surfactants is preferably carried out like the coating of the untreated alkali carbonate with anionic surfactants in their acid form. Temperatures from 40 to 100 ° C. and in particular from 60 to 80 ° C. are particularly preferred.
  • the invention relates to a method for producing a treated alkali carbonate, the coating being carried out with an aqueous solution or an aqueous dispersion of the coating substances.
  • the coating is preferably carried out with an aqueous solution of an alkali silicate with a molar ratio M2O to SiO 2 of 1: 2.0 to 1: 4.5, where M stands for sodium or potassium.
  • M stands for sodium or potassium.
  • a 10 to 60% strength by weight solution of an alkali silicate is advantageously sprayed onto the untreated alkali carbonate at elevated temperatures, in particular at temperatures between 80 and 140 ° C., in a mixer or granulator, in a warm air stream or in a fluidized bed.
  • the process can be carried out in conventional mixers, for example of the Lödige, Schugi or Eirich type, or in conventional fluidized bed devices.
  • the invention relates to a solid washing, rinsing and / or cleaning agent which contains a treated alkali carbonate.
  • agents in particular heavy powder with a bulk density between 600 and 1 100 g / 1, the treated alkali carbonate, preferably sodium carbonate, in amounts of 1 to 20% by weight, preferably in amounts of 3 to 15% by weight and in particular in amounts of 5 to 10 wt .-%, based on the detergent, as well as other usual ingredients of detergents, dishwashing detergents or cleaning agents.
  • the agents can be produced using the known granulation and extrusion methods and by mixing several base powders or base granules. For example, the agents can be obtained by adding an agent without alkali carbonate, Drying, granulating or extruding methods was produced, the treated alkali carbonate is dry mixed.
  • the other usual ingredients of washing, spraying or cleaning agents include, in particular, surfactants such as anionic surfactants, nonionic surfactants, amphoteric surfactants or cationic surfactants.
  • surfactants such as anionic surfactants, nonionic surfactants, amphoteric surfactants or cationic surfactants.
  • Anionic and nonionic surfactants are particularly preferred.
  • Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are alkylbenzenesulfonates (Cg-Ci5-alkyl), olefin sulfonates, ie. H. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from Ci2 "Ci8 monoolefins with terminal and internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, are also suitable.
  • Dialkane sulfonates are also suitable which are obtainable from Ci2-Ci8-Al anen by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and in particular the esters of ⁇ -sulfofatty acids (ester sulfonates), for example the ⁇ -sulfonated ones Methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, that is to say from fatty alcohols, for example coconut oil alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C ⁇ o 20 ⁇ 0 % alcohols, and those of secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of ethylene oxide, are also suitable.
  • Sulfated fatty acid monoglycerides are also suitable.
  • Soaps from natural or synthetic, preferably saturated, fatty acids can also be used.
  • Soap mixtures derived from natural fatty acids for example coconut, palm kernel or tallow fatty acids, are particularly suitable.
  • Preferred are those which are 50 to 100% saturated Ci2-Ci8 fatty acid soaps and 0 to 50% composed of oleic acid soaps.
  • the anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the detergent content according to the invention of anionic surfactants or of anionic surfactant mixtures is preferably 5 to 40, in particular 8 to 35,% by weight. It is particularly advantageous if the content of sulfonates and / or sulfates in the compositions is 10 to 35% by weight, in particular 15 to 30% by weight, and the soap content is up to 8% by weight. , in particular 0.5 to 5 wt .-%.
  • nonionic surfactants are those which can also be used as a coating substance.
  • the content of the agents in ethoxylated alcohols preferably used as nonionic surfactants is preferably 1 to 10% by weight and in particular 2 to 8% by weight.
  • Suitable and, in particular, ecologically harmless builder substances such as finely crystalline, synthetic water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g, are preferably used. Their average particle size is usually in the range from 1 to 10 ⁇ m (measurement method: Coulter Counter, volume distribution).
  • the zeolite content of the compositions is generally up to 60% by weight, preferably at least 10% by weight and in particular 20 to 55% by weight, based on the anhydrous substance.
  • builder components which can be used together with the zeolites are (co) polymeric polycarboxylates, such as polyacrylates, polyethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those from 50% to 10% maleic acid.
  • the relative molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on free acid.
  • a particularly added 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 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, and polymeric acids which are obtained by polymerizing acrolein and subsequent disproportionation using alkalis and are composed of acrylic acid units and vinyl alcohol units or acrolein units.
  • the content of (co) polymeric polycarboxylates in the agents can be, for example, up to 10% by weight, preferably 2 to 8% by weight.
  • a particularly preferred embodiment of the invention provides, however, that the washing and / or cleaning agents are free of (co) polymeric polycarboxylates.
  • Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid and nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons.
  • NTA nitrilotriacetic acid
  • alkali silicate especially sodium silicate with a molar ratio Na2 ⁇ : S ⁇ 2 of 1: 1 to 1: 4.5, is used.
  • the content of sodium silicate in the compositions is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • graying inhibitors Dirt carriers
  • foam inhibitors foam inhibitors
  • bleaching agents and bleach activators optical brighteners
  • enzymes enzymes
  • textile-softening substances colorants and fragrances, and neutral salts.
  • bleaching agents that can be used are, for example, peroxycarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracid salts or peracids, such as perbenzoates, Peroxaphthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetylethylene diamine, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • the bleach activator content of the bleach-containing agents is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone are preferably used, for example in amounts of 0.1 to 5% by weight, based on the composition.
  • the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like organic substances.
  • a reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, for example sulfates and / or sulfonates with nonionic surfactants and / or with soaps.
  • soaps the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid residue. Soaps of natural and synthetic origin which contain a high proportion of C ⁇ 8-C24 fatty acids are therefore suitable as foam-inhibiting soaps.
  • Suitable non-surfactant foam inhibitors are the organopolysiloxanes already mentioned as coating substances and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of various foam inhibitors are also used with advantage, for example those composed of silicones and paraffins or waxes.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • the detergents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • derivatives of diaminostilbenedisulfonic acid or its alkali metal salts for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure are suitable which, instead of the morpholino group, carry a diethanola ino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted 4,4'-distyryl-di-phenyl type may also be present; for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • Enzymes from the class of proteases, lipases, cellulases and amylases or mixtures thereof are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Strepto yces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. The enzymes can be adsorbed on carriers and / or embedded in shell substances in order to protect them against premature decomposition.
  • the salts of polyphosphonic acids are suitable as stabilizers, in particular for per-compounds and enzymes. Examples
  • V-soda compressed calcined soda with a bulk density of approximately 900 g / l was used as the untreated alkali carbonate, 0.1% by weight of the particles having a diameter above 2 mm and 2% by weight of the particles having a diameter below 0.2 mm (commercial product from Matthes & Weber, Federal Republic of Germany).
  • This untreated alkali carbonate was - as listed in Examples 1 to 5 - converted into a treated alkali carbonate.
  • the treated alkali carbonate provided the carbonate ions with a time delay in comparison to the untreated alkali carbonate, ie the dissolution rate of the treated alkali carbonates was less than the dissolution rate of the untreated alkali carbonate.
  • the dissolving speed of the alkali carbonate samples was determined by means of conductivity measurements.
  • Table 2 lists the reduced formation of calcium carbonate in a zeolite / treated alkali carbonate system.
  • the formation of calcium carbonate as a competitive reaction between calcium ion exchange and calcium carbonate precipitation was determined as follows:
  • the carbonate content (calculated) determined as calcium carbonate) microanalytically For this purpose, the dried filter cake was mixed with a dilute 10% by weight sulfuric acid. The resulting carbon dioxide was passed into an aqueous, 25% by weight, weighed potassium hydroxide solution, weighed back and converted to precipitated calcium carbonate.
  • Treated alkali carbonate consisting of 100 parts by weight of V-soda and 8.1 parts by weight of a 1: 1 mixture of Cs-Cio-fatty acid and stearic acid
  • Treated alkali carbonate consisting of 100 parts by weight of V-soda and 8.1 parts by weight of a 1: 1 mixture of stearic acid and iso-stearic acid.
  • 100 parts by weight of V-soda were mixed with 8.1 parts by weight of the specified melted fatty acids at 120 ° C. in a Lödige mixer for 20 minutes.
  • Treated alkali carbonate consisting of 100 parts by weight of V-soda and 5 parts by weight of calcium stearate.
  • V-soda 100 parts by weight of V-soda were mixed with the stated amounts of calcium stearate in a Turbula mixer. The shaking times were 10 minutes.
  • Treated alkali carbonate consisting of 100 parts by weight of V soda and 2 parts by weight of Hoechst wax C ( R ) (micropowder)
  • Treated alkali carbonate consisting of 100 parts by weight of V soda and 5 parts by weight of Hoechst wax C ( R ) (micropowder).
  • Treated alkali carbonate consisting of 100 parts by weight of V-soda and 4.2 parts by weight of a sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 of 1: 2.0.
  • Treated alkali carbonate consisting of 100 parts by weight of V-soda and 7 parts by weight of a sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 of 1: 3.4
  • Treated alkali carbonate consisting of 100 parts by weight of V-soda and 5 parts by weight of a sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 of 1: 4.0
  • Treated alkali carbonate consisting of 100 parts by weight of V-soda and 10 parts by weight of a sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 of 1: 4.0.
  • V-soda 100 parts by weight of V-soda were sprayed in a Lödige mixer with a 30% by weight water glass solution of the type specified and dried at 120 ° C. for 2 hours.
  • Treated alkali carbonate consisting of 100 parts by weight of V soda, 7.5 parts by weight of a sodium silicate with a molar ratio a ⁇ : S ⁇ 2 of 1: 2.0 and 10 parts by weight of a 1: 1 mixture from C ⁇ -Cin fatty acid and stearic acid
  • Treated alkali carbonate consisting of 100 parts by weight of V-soda, 4 parts by weight of a sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 of 1: 2.0 and 5.5 parts by weight of stearic acid.
  • 100 parts by weight of V-soda were sprayed in a Lödige mixer with a 30% by weight waterglass solution of the type specified, as in Example 4, and dried at 120.degree.
  • the dried alkali carbonate was then treated as described in Example 1 with the fatty acid or the fatty acid mixture.

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Abstract

Procédé de lavage et/ou de nettoyage destiné à combattre la formation d'incrustations sans qu'il soit nécessaire d'utiliser des substances qui empêchent ou retardent le dépôt de carbonate de calcium sur des surfaces dures ou des tissus textiles, par exemple des polycarboxylates polymères. Selon l'invention, on réduit ou l'on évite la formation de carbonate de calcium dans des quantités excédant le produit de solubilité de carbonate de calcium à des températures comprises entre 15 et 95 °C, en retardant l'apport de carbonate alcalin à la préparation de lavage, de rinçage et de nettoyage. A cet effet, l'on ajoute plus tard le carbonate alcalin à la préparation, ou bien l'on utilise un carbonate alcalin traité dont la vitesse de dissolution à des températures comprises entre 15 et 95 °C est inférieure à celle du carbonate alcalin non traité.
PCT/EP1992/001934 1991-08-30 1992-08-22 Procede de lavage et/ou de nettoyage WO1993005133A1 (fr)

Applications Claiming Priority (2)

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DE19914128826 DE4128826A1 (de) 1991-08-30 1991-08-30 Wasch- und/oder reinigungsverfahren
DEP4128826.2 1991-08-30

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WO1993005133A1 true WO1993005133A1 (fr) 1993-03-18

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000037596A3 (fr) * 1998-12-19 2000-11-23 Henkel Kgaa Procede permettant d'empecher les depots

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69635927T2 (de) * 1995-09-04 2006-12-21 Kao Corp. Waschverfahren und zusammensetzung hierfür
JP3705392B2 (ja) * 1997-03-12 2005-10-12 花王株式会社 洗濯方法
DE19957038A1 (de) * 1999-11-26 2001-05-31 Henkel Kgaa Wasch- und Reinigungsmittel
DE19957036A1 (de) * 1999-11-26 2001-05-31 Henkel Kgaa Verfahren zur Herstellung teilchenförmiger Wasch- oder Reinigungsmittel

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2437173A1 (de) * 1974-06-01 1976-02-12 Karl Hans Dipl Chem D Heinlein Verfahren zum aufbereiten von textilem material
FR2396076A1 (fr) * 1977-06-27 1979-01-26 Akzo Nv Composition detergente contenant un carbonate alcalin
US4347152A (en) * 1976-12-02 1982-08-31 Colgate-Palmolive Company Phosphate-free concentrated particulate heavy duty laundry detergent
EP0094723A1 (fr) * 1982-05-12 1983-11-23 De Blauwe Lier B.V. Procédé pour le lavage de textiles dans de l'eau dure et utilisation de compositions détergentes sans phosphates à cet effet

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2437173A1 (de) * 1974-06-01 1976-02-12 Karl Hans Dipl Chem D Heinlein Verfahren zum aufbereiten von textilem material
US4347152A (en) * 1976-12-02 1982-08-31 Colgate-Palmolive Company Phosphate-free concentrated particulate heavy duty laundry detergent
FR2396076A1 (fr) * 1977-06-27 1979-01-26 Akzo Nv Composition detergente contenant un carbonate alcalin
EP0094723A1 (fr) * 1982-05-12 1983-11-23 De Blauwe Lier B.V. Procédé pour le lavage de textiles dans de l'eau dure et utilisation de compositions détergentes sans phosphates à cet effet

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000037596A3 (fr) * 1998-12-19 2000-11-23 Henkel Kgaa Procede permettant d'empecher les depots

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