EP0763594B1 - Verfahren zur Herstellung von körnigen Reinigungsmitteln - Google Patents

Verfahren zur Herstellung von körnigen Reinigungsmitteln Download PDF

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Publication number
EP0763594B1
EP0763594B1 EP95306547A EP95306547A EP0763594B1 EP 0763594 B1 EP0763594 B1 EP 0763594B1 EP 95306547 A EP95306547 A EP 95306547A EP 95306547 A EP95306547 A EP 95306547A EP 0763594 B1 EP0763594 B1 EP 0763594B1
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EP
European Patent Office
Prior art keywords
weight
aqueous slurry
inorganic salt
sodium
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP95306547A
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English (en)
French (fr)
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EP0763594A1 (de
Inventor
Andrew Dorset
Kay Emma Fitzgibbon
Zayeed Alam
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Procter and Gamble Co
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Procter and Gamble Co
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Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to DE69531207T priority Critical patent/DE69531207T2/de
Priority to EP95306547A priority patent/EP0763594B1/de
Priority to AT95306547T priority patent/ATE244294T1/de
Priority to ES95306547T priority patent/ES2202343T3/es
Priority to ZA967561A priority patent/ZA967561B/xx
Priority to BR9610630A priority patent/BR9610630A/pt
Priority to US09/043,183 priority patent/US5998356A/en
Priority to PCT/US1996/014864 priority patent/WO1997011149A1/en
Priority to CZ98708A priority patent/CZ70898A3/cs
Priority to TR1998/00489T priority patent/TR199800489T1/xx
Priority to CA002231577A priority patent/CA2231577C/en
Priority to HU9901581A priority patent/HUP9901581A3/hu
Priority to IL12365196A priority patent/IL123651A0/xx
Priority to CNB96198239XA priority patent/CN1168814C/zh
Priority to ARP960104387A priority patent/AR003608A1/es
Publication of EP0763594A1 publication Critical patent/EP0763594A1/de
Priority to MX9802108A priority patent/MX9802108A/es
Application granted granted Critical
Publication of EP0763594B1 publication Critical patent/EP0763594B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the present invention relates to a process for preparing a particulate detergent composition, in particular by spray drying an aqueous slurry. Particulate detergent compositions are also disclosed.
  • powder structurants useful to achieve a crisp, free-flowing spray-dried powder.
  • film-forming polymer for example, polycarboxylates (for example, US-A-4 379 080); polyacrylates (for example, JP204098/1983); sucrose and derivatives (for example, EP-A-0 215 637) ; sodium sesquicarbonate (for example, EP-A-0 242 138).
  • powder structurants are required by the formulator as active ingredients, then they are an expensive processing aid.
  • aqueous slurry which does not comprise either water-soluble silicate, or one of the alternative powder structurants is difficult to spray dry.
  • high water concentrations are generally needed in order to maintain the viscosity of the slurry low enough to provide crisp, free-flowing particles of the desired particle size when spray-dried.
  • the disadvantage of high water concentrations is that the excess water must be removed during the drying step and a lot of energy is needed to do this.
  • WO90/04630 published on 3rd May 1990, describes a process for preparing a carbonate containing detergent slurry comprising an alkylpolyglycoside and an alkali metal chloride.
  • Zeolite A is suggested as one possible builder albeit in the presence of silicate (at 7% by weight in Table VI).
  • EP-A-0,326,208 describes porous pouched granular detergents having improved dispensing properties and reduced dusting due to the incorporation of a hygroscopic builder salt selected from a specified group of a large number of organic salts.
  • EP-A-0,257,514 describes detergents comprising surfactant and zeolite, alkali silicate, anionic functional organosiliconate and complexing agent for trivalent aluminium. The combination of the organosiliconate and the complexing agent is said to give improved dissolution characteristics.
  • the object of the present invention is to avoid residue problems by substantially omitting silicate from an aqueous slurry which comprises anionic surfactant and aluminosilicate, and at the same time to provide a low viscosity slurry suitable for spray-drying to form crisp, free-flowing powder.
  • a process for preparing a particulate detergent composition comprising less than 2% by weight silicate, the process comprising forming an aqueous slurry comprising at least 0.5% by weight sodium aluminosilicate and which further comprises less than 5% by weight of silicate and an inorganic salt, or a mixture of inorganic salts, and whereby the inorganic salt is added in an amount of at least 1% by weight and sufficient to increases the ionic conductivity of the aqueous slurry, and subsequently drying the aqueous slurry to form the particulate detergent composition.
  • the inorganic salt is an alkali metal or alkaline earth metal salt, or mixtures thereof of halide or, nitrate most preferably sodium chloride.
  • the step of adding the inorganic salt raises the ionic conductivity of the aqueous slurry by at least 3 milliSiemens, and preferably by at least 5 milliSiemens.
  • a further aspect of the invention concerns spray-dried detergent powder compositions.
  • Preferred compositions comprise:
  • Essential components of the compositions of the present invention are aluminosilicate builders such as those having the empirical formula: M z (zAlO 2 ) y ] ⁇ x H 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in US Patent 3,985,669, Krummel et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations zeolite A, zeolite P(B), zeolite MAP, zeolite X and zeolite Y.
  • the crystalline aluminosilicate ion exchange material has the formula : Na 12 [(AlO 2 ) 12 (SiO2) 12 ] ⁇ x H 2 O wherein x is from about 20 to about 30, especially about 27.
  • This material is known as zeolite A.
  • the "overdried" zeolites are particularly useful when a low moisture environment is required, for example to improve stability of detergent bleaches such as perborate and percarbonate.
  • the aluminosilicate has a particle size of about 0.1-10 micrometers in diameter.
  • Preferred ion exchange materials have a particle size diameter of from about 0.2 micrometers to about 4 micrometers.
  • particle size diameter herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
  • the crystalline zeolite A materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg equivalent of CaCO 3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg eq./g to about 352 mg eq./g.
  • the zeolite A materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /gallon/minute/gram/gallon (0.13g Ca ++ /litre/minute/gram/litre) of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon(0.13g Ca ++ /litre/minute/gram/litre) to about 6 grains/gallon/minute/gram/gallon (0.39g Ca ++ /litre/minute/gram/litre), based on calcium ion hardness.
  • Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon (0.26g Ca ++ /litre/minute/gram/litre).
  • the granular agglomerates of the present invention also comprise other detergent ingredients.
  • Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
  • Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
  • Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of acyl groups.
  • this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkyl benzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight or branched chain configuration, e.g., those of the type described in U.S. Pat. Nos. 2,220,099 and 2,477,383; and methyl ester sulphonates.
  • Especially valuable are linear straight chain alkyl benzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C 11 -C 13 LAS.
  • anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
  • Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; watersoluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms in the alkane moiety.
  • Water-soluble nonionic surfactants are also useful as surfactants in the compositions of the invention. Indeed, preferred processes use anionic/nonionic blends.
  • Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from about 4 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 1 to 25 moles of ethylene oxide per mole of alcohol, especially 2 to 7 moles of ethylene oxide per mole of alcohol.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms; and condensation products of propylene glycol with ethylene oxide.
  • polyhydroxy fatty acid amides which may be prepared by reacting a fatty acid ester and an N-alkyl polyhydroxy amine.
  • the preferred amine for use in the present invention is N-(Rl)-CH2(CH2OH)4-CH2-OH and the preferred ester is a C12-C20 fatty acid methyl ester.
  • Most preferred is the reaction product of N-methyl glucamine (which may be derived from glucose) with C12-C20 fatty acid methyl ester.
  • Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
  • Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be either straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
  • Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
  • Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R 4 R 5 R 6 R 7 N + X - , wherein R 4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R 5 , R 6 and R 7 are each C 1 to C 7 alkyl preferably methyl; X - is an anion, e.g. chloride.
  • Examples of such trimethyl ammonium compounds include C 12-14 alkyl trimethyl ammonium chloride and cocalkyl trimethyl ammonium methosulfate.
  • the granular detergents of the present invention can contain neutral or alkaline salts which have a pH in solution of seven or greater, and can be either organic or inorganic in nature.
  • the builder salt assists in providing the desired density and bulk to the detergent granules herein. While some of the salts are inert, many of them also function as detergency builder materials in the laundering solution.
  • Useful water-soluble salts include the compounds commonly known as detergent builder materials.
  • Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, and polyhydroxysulfonates.
  • alkali metal especially sodium, salts of the above.
  • inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate.
  • polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid.
  • Other phosphorus builder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148.
  • nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of SiO 2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
  • organic polymers are also useful as builders to improve detergency. Included among such polymers may be mentioned sodium carboxy-lower alkyl celluloses, sodium lower alkyl celluloses and sodium hydroxy-lower alkyl celluloses, such as sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose, homo & co polymers of amino acids (particularly homo and co polymers of aspartic acid glutamic acid), polyvinyl alcohols (which often also include some polyvinyl acetate), polyacrylamides, polyacrylates and various copolymers, such as those of maleic and acrylic acids, in particular maleic/acrylic/vinyl alcohol terpolymers.
  • sodium carboxy-lower alkyl celluloses sodium lower alkyl celluloses and sodium hydroxy-lower alkyl celluloses
  • amino acids particularly homo and co polymers of aspartic acid glutamic acid
  • polyvinyl alcohols which often also include some polyvinyl acetate
  • polyacrylamides polyacryl
  • polystyrene resin polystyrene resin
  • suitable polymers are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
  • Polymeric polycarboxyate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid, methylenemalonic acid, methyl acrylic and PEG.
  • polymeric polycarboxylates are substantially omitted from the aqueous slurry. By substantially omitted, less than 5% by weight of the aqueous slurry is preferred, and less than 2% by weight is more preferred.
  • the inorganic salt should result in an increased ionic conductivity of the aqueous slurry.
  • the ionic conductivity of the aqueous slurry depends not only on the inorganic salt used, but also on the amount of inorganic salt used, and also on the composition of the aqueous slurry.
  • Halides, especially chlorides and nitrates have been found to be particularly effective inorganic salts which when used at the preferred levels, have the effect of increasing the ionic conductivity of the aqueous slurry.
  • Carbonates and sulphates are less effective, and may well cause a decrease in the ionic conductivity of the slurry.
  • the higher ionic conductivity of the aqueous slurry suppresses the formation of highly viscous surfactant phases which are subsequently difficult to dry. By promoting less viscous surfactant phases the aqueous slurry is more readily formed into free-flowing, crisp particles having a good particle size distribution.
  • Particulate suds suppressors may also be incorporated into the finished composition by dry adding.
  • the suds suppressing activity of these particles is based on fatty acids or silicones.
  • compositions of the present invention can be included in the compositions of the present invention. These include flow aids, color speckles, bleaching agents and bleach activators, suds boosters or suds suppressors, antitarnish and anticorrosion agents, soil suspending agents, anionic and nonionic soil release agents, dyes, clays, flocculating agents, STS, fillers, optical brighteners, germicides, pH adjusting agents, nonbuilder alkalinity sources, hydrotropes, enzymes, enzyme-stabilizing agents, chelating agents, (including EDDS) and perfumes.
  • flow aids include color speckles, bleaching agents and bleach activators, suds boosters or suds suppressors, antitarnish and anticorrosion agents, soil suspending agents, anionic and nonionic soil release agents, dyes, clays, flocculating agents, STS, fillers, optical brighteners, germicides, pH adjusting agents, nonbuilder alkalinity sources, hydrotropes, enzymes, enzyme-stabilizing agents,
  • These optional ingredients may be incorporated either directly in the agglomerates herein or may be components of separate particles suitable for dry adding to the agglomerates of the present invention.
  • the aqueous slurry may be prepared by a batch or continuous process. Most conveniently a batch mixer, or “crutcher” is used in which the various detergent components or dissolved in, or slurried with, water. Typically the aqueous slurry contains from about 20% to about 60% by weight of water, in particular from about 30% to about 40% by weight of water. This is referred to as the crutcher mix moisture. In the process of the present invention, the order of addition of the inorganic salt and the other components of the aqueous slurry (or “crutcher mix") is not considered to be critical.
  • the ionic conductivity of the aqueous slurry which comprises the inorganic salt must be greater than the ionic conductivity of the aqueous slurry in the absence of the inorganic salt. It is preferred that the addition of the inorganic salt results in an aqueous slurry having an ionic conductivity which is at least 3 milliSiemens higher than a corresponding aqueous slurry from which the inorganic salt has been omitted.
  • the drying of the aqueous slurry may be achieved by any one of several processes known to the skilled man, but it is preferably prepared by spray drying. Following the spray drying route, an aqueous slurry is prepared comprising the solids. The slurry is then pumped at high pressure through atomising nozzles into a drying tower where excess water is driven off, producing a flowable powder. The resulting powder may then be oversprayed with liquid ingredients, especially nonionic surfactants for which the powder has a high adsorption capacity before it loses its good flow characteristics. Other powdered components of the finished laundry detergent may be dry mixed with the flowable powder produced by the above process.
  • the aqueous slurry is heated to 70°C and is fed through to a series of pressure pumps. This increases the pressure of the mix up to 80 bar. Air is then injected into the mix at a pressure of 100 bar. The high pressure mix is then directed to the top of the spray drying tower. Here it is blown through a set of nozzles, which range in aperture diameter up to 1mm. These atomise the slurry into droplets. The moisture is driven off these particles as they fall through the tower with a residence time of up to 180 seconds by contact with hot air at 275°C. At the bottom of the tower a blown powder is collected with a density in the range of 300 - 550g/l. The resulting blown powder has a moisture in the range of 5 -_15% with the majority of the particles having a size in the range of 150 - 1200 micrometers.

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  • Engineering & Computer Science (AREA)
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Claims (11)

  1. Verfahren zur Herstellung einer teilchenförmigen Detergenszusammensetzung, umfassend weniger als 2 Gew.-% Silicat, wobei das Verfahren umfasst:
    (a) Bilden einer wässrigen Aufschlämmung, umfassend Wasser, anionisches Tensid und mindestens 0,5% Natriumaluminosillcat.
    (b) Zugeben eines anorganischen Salzes oder einer Mischung anorganischer Salze zu der wässrigen Aufschlämmung,
    (c) Trocknen der Aufschlämmung
    dadurch gekennzeichnet, dass das anorganische Salz in einer Menge von mindestens 1 Gew.-% der wässrigen Aufschlämmung zugegeben wird und ausreichend ist, um die ionische Leitfähigkeit der wässrigen Aufschlämmung zu erhöhen, und wobei die wässrige Aufschlämmung weniger als 5 Gew.-% Silicat umfasst.
  2. Verfahren nach Anspruch 1, wobei das anorganische Salz aus der Gruppe gewählt ist, bestehend aus Alkalimetallsalzen von Halogeniden, Nitraten oder Mischungen hiervon.
  3. Verfahren nach Anspruch 1, wobei das anorganische Salz aus der Gruppe gewählt ist, bestehend aus Erdalkalimetallsalzen von Halogeniden, Nitraten oder Mischungen hiervon.
  4. Verfahren nach Anspruch 2, wobei das anorganische Salz Natriumchlorid ist.
  5. Verfahren nach mindestens einem der vorangehenden Ansprüche, wobei der Schritt des Zugebens des anorganischen Salzes die ionische Leitfähigkeit der wässrigen Aufschlämmung um mindestens 3 milliSiemens erhöht.
  6. Verfahren nach Anspruch 1, wobei der Bereich des anionischen Tensids 1% bis 50%, weiter vorzugsweise 5 bis 20 Gew.-% beträgt.
  7. Verfahren nach Anspruch 1, wobei der Bereich an Natriumaluminosilicat 1% bis 50%, weiter vorzugsweise 5 bis 30 Gew.-% beträgt.
  8. Verfahren nach Anspruch 1, wobei der Bereich des anorganischen Salzes 1% bis 50%, weiter vorzugsweise 1 bis 10 Gew.-% beträgt.
  9. Verfahren nach mindestens einem der vorangehenden Ansprüche, wobei die Aufschlämmung in einem Sprühtrocknungsschritt getrocknet wird.
  10. Sprühgetrocknetes Pulver, umfassend:
    (a) mindestens ein Tensid,
    (b) 2 bis 80 Gew.-% Aluminosilicat,
    (c) 1 bis 20 Gew.-% anorganisches Salz, gewählt aus der Gruppe, bestehend aus Alkalimetall-, Erdalkalimetallsalzen oder Mischungen hiervon aus Halogenid, Nitraten oder Mischungen hiervon, und
    (d) weniger als 2 Gew.-% Silicat.
  11. Sprühgetrocknetes Pulver nach Anspruch 10, umfassend:
    (a) mindestens 5 Gew.-% Tensid,
    (b) 10 bis 50 Gew.-% Aluminosilicat,
    (c) 2 bis 10 Gew.-% eines Alkalimetall- vorzugsweise Natrium-, -Chlorids, und
    (d) weniger als 2 Gew.-% Silicat.
EP95306547A 1995-09-18 1995-09-18 Verfahren zur Herstellung von körnigen Reinigungsmitteln Expired - Lifetime EP0763594B1 (de)

Priority Applications (16)

Application Number Priority Date Filing Date Title
DE69531207T DE69531207T2 (de) 1995-09-18 1995-09-18 Verfahren zur Herstellung von körnigen Reinigungsmitteln
EP95306547A EP0763594B1 (de) 1995-09-18 1995-09-18 Verfahren zur Herstellung von körnigen Reinigungsmitteln
AT95306547T ATE244294T1 (de) 1995-09-18 1995-09-18 Verfahren zur herstellung von körnigen reinigungsmitteln
ES95306547T ES2202343T3 (es) 1995-09-18 1995-09-18 Procedimiento para preparar detergentes en granulos.
ZA967561A ZA967561B (en) 1995-09-18 1996-09-06 Process for making granular detergents
TR1998/00489T TR199800489T1 (xx) 1995-09-18 1996-09-13 Gran�ll� deterjanlar�n imali i�in i�lem.
PCT/US1996/014864 WO1997011149A1 (en) 1995-09-18 1996-09-13 Process for making granular detergents
CZ98708A CZ70898A3 (cs) 1995-09-18 1996-09-13 Způsob výroby granulovaných detergentů
BR9610630A BR9610630A (pt) 1995-09-18 1996-09-13 Processo para a fabricação de detergentes granulares
CA002231577A CA2231577C (en) 1995-09-18 1996-09-13 Process for making granular detergents
HU9901581A HUP9901581A3 (en) 1995-09-18 1996-09-13 Process for making granular detergents
IL12365196A IL123651A0 (en) 1995-09-18 1996-09-13 Process for making granular detergents
CNB96198239XA CN1168814C (zh) 1995-09-18 1996-09-13 制备粒状洗涤剂的方法
US09/043,183 US5998356A (en) 1995-09-18 1996-09-13 Process for making granular detergents
ARP960104387A AR003608A1 (es) 1995-09-18 1996-09-18 Proceso para fabricar una composicion detergente en particulas y polvo secado por pulverizacion obtenido mediante el mismo.
MX9802108A MX9802108A (es) 1995-09-18 1998-03-17 Procedimiento para hacer detergentes granulados.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP95306547A EP0763594B1 (de) 1995-09-18 1995-09-18 Verfahren zur Herstellung von körnigen Reinigungsmitteln

Publications (2)

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EP0763594A1 EP0763594A1 (de) 1997-03-19
EP0763594B1 true EP0763594B1 (de) 2003-07-02

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EP95306547A Expired - Lifetime EP0763594B1 (de) 1995-09-18 1995-09-18 Verfahren zur Herstellung von körnigen Reinigungsmitteln

Country Status (15)

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EP (1) EP0763594B1 (de)
CN (1) CN1168814C (de)
AR (1) AR003608A1 (de)
AT (1) ATE244294T1 (de)
BR (1) BR9610630A (de)
CA (1) CA2231577C (de)
CZ (1) CZ70898A3 (de)
DE (1) DE69531207T2 (de)
ES (1) ES2202343T3 (de)
HU (1) HUP9901581A3 (de)
IL (1) IL123651A0 (de)
MX (1) MX9802108A (de)
TR (1) TR199800489T1 (de)
WO (1) WO1997011149A1 (de)
ZA (1) ZA967561B (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19936614B4 (de) * 1999-08-04 2008-12-24 Henkel Ag & Co. Kgaa Verfahren zur Herstellung eines Waschmittels
DE19936613B4 (de) * 1999-08-04 2010-09-02 Henkel Ag & Co. Kgaa Verfahren zur Herstellung eines Waschmittels mit löslichem Buildersystem
CN1109579C (zh) * 1999-08-17 2003-05-28 中国石油化工集团公司 催化剂用分子筛浆液的制备方法
CN1164611C (zh) 2002-06-17 2004-09-01 厦门大学 丙-谷二肽合成方法
EP2669001B1 (de) * 2012-06-01 2015-01-14 The Procter and Gamble Company Sprühtrockenverfahren
CN103937620A (zh) * 2014-04-04 2014-07-23 广州立白企业集团有限公司 一种中性洗衣粉组合物及其制备方法
DE102014218805A1 (de) * 2014-09-18 2016-03-24 Henkel Ag & Co. Kgaa Verfahren zur Herstellung von sprühgetrockneten Waschmittelpulvern

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2220099A (en) 1934-01-10 1940-11-05 Gen Aniline & Flim Corp Sulphonic acids
US2477383A (en) 1946-12-26 1949-07-26 California Research Corp Sulfonated detergent and its method of preparation
NL132418C (de) 1962-04-13
CA777769A (en) 1963-03-18 1968-02-06 H. Roy Clarence Substituted methylene diphosphonic acid compounds and detergent compositions
US3213030A (en) 1963-03-18 1965-10-19 Procter & Gamble Cleansing and laundering compositions
US3308067A (en) 1963-04-01 1967-03-07 Procter & Gamble Polyelectrolyte builders and detergent compositions
US3400148A (en) 1965-09-23 1968-09-03 Procter & Gamble Phosphonate compounds
US3400176A (en) 1965-11-15 1968-09-03 Procter & Gamble Propanepolyphosphonate compounds
CA790610A (en) 1965-12-28 1968-07-23 T. Quimby Oscar Diphosphonate compounds and detergent compositions
US3985669A (en) 1974-06-17 1976-10-12 The Procter & Gamble Company Detergent compositions
US5080820A (en) * 1981-02-26 1992-01-14 Colgate-Palmolive Co. Spray dried base beads for detergent compositions containing zeolite, bentonite and polyphosphate
US4379080A (en) 1981-04-22 1983-04-05 The Procter & Gamble Company Granular detergent compositions containing film-forming polymers
JPS6042279B2 (ja) 1982-05-25 1985-09-20 花王株式会社 洗浄剤組成物
GB8328017D0 (en) * 1983-10-19 1983-11-23 Unilever Plc Detergent powders
GB8522621D0 (en) 1985-09-12 1985-10-16 Unilever Plc Detergent powder
US4675127A (en) * 1985-09-26 1987-06-23 A. E. Staley Manufacturing Company Process for preparing particulate detergent compositions
GB8609044D0 (en) 1986-04-14 1986-05-21 Unilever Plc Detergent powders
US4741862A (en) * 1986-08-22 1988-05-03 Dow Corning Corporation Zeolite built detergent compositions
EP0326208A3 (de) * 1988-01-26 1990-11-28 The Procter & Gamble Company Zu einem Beutel befindliche körnige Detergentzusammensetzungen die hygroskopische Verstärker enthalten
WO1990004630A1 (en) 1988-10-21 1990-05-03 Henkel Corporation A process for preparing a detergent slurry and particulate detergent composition
US5118439A (en) * 1988-10-21 1992-06-02 Henkel Corporation Process for preparing a detergent slurry and particulate detergent composition
US5194639A (en) 1990-09-28 1993-03-16 The Procter & Gamble Company Preparation of polyhydroxy fatty acid amides in the presence of solvents
RU2088645C1 (ru) * 1990-09-28 1997-08-27 Дзе Проктер Энд Гэмбл Компани Моющая композиция и способ улучшения очищающего действия по отношению к тканям моющей композиции
MX9202828A (es) * 1991-06-28 1992-12-01 Colgate Palmolive Co Composiciones detergentes secadas por rociado a base de zeolita y proceso para la preparacion de las mismas.
US5565422A (en) * 1995-06-23 1996-10-15 The Procter & Gamble Company Process for preparing a free-flowing particulate detergent composition having improved solubility

Also Published As

Publication number Publication date
BR9610630A (pt) 1999-03-16
CZ70898A3 (cs) 1998-10-14
DE69531207T2 (de) 2004-04-22
AR003608A1 (es) 1998-08-05
DE69531207D1 (de) 2003-08-07
ES2202343T3 (es) 2004-04-01
TR199800489T1 (xx) 1998-06-22
CA2231577A1 (en) 1997-03-27
HUP9901581A2 (hu) 1999-08-30
IL123651A0 (en) 1998-10-30
MX9802108A (es) 1998-08-30
ATE244294T1 (de) 2003-07-15
EP0763594A1 (de) 1997-03-19
CN1168814C (zh) 2004-09-29
CN1202195A (zh) 1998-12-16
CA2231577C (en) 2002-11-19
WO1997011149A1 (en) 1997-03-27
HUP9901581A3 (en) 2000-10-30
ZA967561B (en) 1997-06-10

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