EP0745119B1 - Process of preparing spray-dried granulates - Google Patents

Process of preparing spray-dried granulates Download PDF

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Publication number
EP0745119B1
EP0745119B1 EP95909694A EP95909694A EP0745119B1 EP 0745119 B1 EP0745119 B1 EP 0745119B1 EP 95909694 A EP95909694 A EP 95909694A EP 95909694 A EP95909694 A EP 95909694A EP 0745119 B1 EP0745119 B1 EP 0745119B1
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EP
European Patent Office
Prior art keywords
weight
salts
acids
acid
spray
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Expired - Lifetime
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EP95909694A
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German (de)
French (fr)
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EP0745119A1 (en
Inventor
Elmar Wilms
Thomas Merz
Chris De Jong
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Ecolab GmbH and Co oHG
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Henkel Ecolab GmbH and Co KG
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Priority claimed from DE4408502A external-priority patent/DE4408502A1/en
Application filed by Henkel Ecolab GmbH and Co KG filed Critical Henkel Ecolab GmbH and Co KG
Publication of EP0745119A1 publication Critical patent/EP0745119A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • 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

Definitions

  • the invention relates to a spray drying process by which heavy granules can be produced, which can be used as a detergent or cleaning agent suitable for use in detergents or cleaning agents.
  • EP-A-0 120 492 special spray dried Granules described which bulk densities of at least Achieve 550 g / l up to 800 g / l without post-treatment of the granules, whereby with aftertreatment, spraying the porous granules with, for example non-ionic surfactants or powdering with finely divided powders, for example zeolite powders is understood.
  • These contain granules ethoxylated alcohols with 12 to 24 carbon atoms and average 3 to 20 ethylene oxide groups.
  • the Granules are produced by a process in which a slurry is used a content of 55 to 35 wt .-% water (including the adsorptive or sprayed as hydrate bound water).
  • the water content is not below 42 wt .-%, because lower Contents lead to a strong increase in viscosity of the slurry and the Addition of viscosity reducing agents such as toluene, xylene or cumene sulfonate make necessary. Slurry viscosities up to a maximum of 15000 mPas under operating conditions are considered acceptable.
  • An object of the invention was to make the spray drying process energetic to make it cheaper or to increase the performance of the spray towers and thus an increase in capacity of the existing systems to achieve constant energy requirements. To do this, it should be possible to spray more concentrated slurries. However, these slurries were allowed do not have such high viscosities that spraying is no longer possible was. In addition, additives such as toluene, xylene or cumene sulfonate should be considered usual means of lowering viscosity can be dispensed with.
  • Another The object of the invention was to provide granules which anionic surfactants in amounts of at least 1 wt .-% as well optionally additional soaps in quantities of at least 0.2% by weight included and one for spray-dried products without after-treatment mechanical and / or chemical processing increased bulk density exhibit.
  • the invention accordingly relates to a process for the production of spray-dried granules, which are particularly suitable for washing or Detergents or as a component for this, characterized in that a slurry is used in the spray drying, less than 40% by weight of water, but there are quantities of anionic surfactants of at least 1% by weight, based on the spray-dried granules, and Contains sugar acids or salts of sugar acids and a viscosity of has a maximum of 15000 mPas (under operating conditions).
  • Granules produced with preference have a bulk density of at least 600 g / l, preferably from 650 to 1000 g / l and in particular at least 700 g / l.
  • a bulk density of at least 600 g / l, preferably from 650 to 1000 g / l and in particular at least 700 g / l.
  • these granules are used exclusively produced by a spray drying process.
  • Spray drying processes like Impregnation with liquid to waxy components, for example Nonionic surfactants, powdering with finely divided powders or use of the granules in optionally further compacting mixing and / or granulation or Extrusion processes are not excluded, but are not essential to the invention.
  • the details of the bulk weights therefore relate always on the base granules obtained by spray drying.
  • the anionic surfactants in the granules produced according to the invention such as usual alkylbenzenesulfonates and / or alkyl (ether) sulfates is preferably 1.5 to 10% by weight.
  • the granules can also be added to soaps Contain quantities of at least 0.2 wt .-%. Contain preferred granules about 0.5 to 15% by weight, in particular up to 10% by weight Fatty acid soaps or natural fatty acid soap mixtures.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the readily biodegradable alkanesulfonates are obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the sulfonate group is statistically distributed over the entire carbon chain, with the secondary alkanesulfonates predominating.
  • the esters of ⁇ -sulfofatty acids are also suitable, for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C 16 -C 18 alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 12 -C 14 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates and in particular C 12 -C 16 -Fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 2 to 4 E0 are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable soaps are in particular saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants and soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, Di- or triethanolamine.
  • the anionic are preferably located Surfactants in the form of their sodium or potassium salts, especially in the form of Sodium salts.
  • the agents preferably contain as sugar acids or salts of sugar acids Polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts with 4 to 6 carbon atoms, each carbon atom which has no carboxyl group or carries a keto group, has a hydroxy group, and / or Polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts with 4 to 6 Carbon atoms and at least 2 hydroxyl groups per molecule or mixtures from these acids and salts.
  • polyhydroxymonocarboxylic acids form or polyhydroxymonocarboxylic acid salts, which one keto group per Have molecule, preferably lactones.
  • Preferred polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts are those which have 4 to 6 carbon atoms contain and on each carbon atom that has no carboxyl group or carries a keto group, have a hydroxy group.
  • polyhydroxymonocarboxylic acids and or polyhydroxymonocarboxylic acid salts with 4 carbon atoms and 3 hydroxyl groups, with 5 carbon atoms and 4 hydroxyl groups and with 6 carbon atoms and 4 or 5 hydroxyl groups prefers.
  • Polyhydroxymonocarboxylic acids have particularly advantageous properties or polyhydroxymonocarboxylic acid salts with 6 carbon atoms and 5 hydroxy groups, such as D-gluconic acid (also maltonic acid or called dextronic acid) or their salts, and polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts with 6 carbon atoms, one Keto group and 4 hydroxy groups, such as L-ascorbic acid, which is present as a lactone, and L-ascorbic acid salts.
  • Mixtures of acids can also be used and / or the salts are used, the latter preferably in the form their sodium or potassium salts.
  • polyhydroxydicarboxylic acids are also preferred or polyhydroxydicarboxylic acid salts, which 4 to 6 Contain carbon atoms and on each carbon atom that has no carboxyl group carries, have a hydroxy group.
  • polyhydroxydicarboxylic acids and polyhydroxydicarboxylic acid salts with 4 Carbon atoms and 2 hydroxy groups, such as tartaric acid and tartaric acid salts, and with 6 carbon atoms and 4 hydroxy groups, such as galactaric acid (also Called mucic acid or mucic acid) and galactaric acid salts as well as glucaric acid (also called saccharic acid) and glucaric acid salts, preferred.
  • the content of the spray-dried granules in sugar acids and preferably the salts of the sugar acids are preferably 0.2 to 20% by weight and in particular 0.5 to 15% by weight.
  • the granules produced according to the invention can also contain further ingredients which are usually used in detergents or cleaning agents which can be used either in the home or in the commercial sector.
  • the granules can also contain nonionic surfactants.
  • Their content is preferably 1 to 30% by weight, in particular 2 to 25% by weight. In granules which contain more than 10% by weight of anionic surfactants and soaps, the content of nonionic is advantageously up to 20% by weight.
  • the nonionic surfactants used are preferably alkoxylated, advantageously liquid ethoxylated, in particular primary alcohols having preferably 8 to 24 carbon atoms, in particular 8 to 18 carbon atoms, and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol, in which the alcohol radical may be linear or preferably methyl-branched in the 2-position, or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 E0 or 4 E0, C 9 -C 11 alcohol with 7 E0, C 13 -C 15 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C 12 -C 18 alcohols with 3 E0, 5 E0 or 7 E0 and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 E0 and C 12 -C 18 alcohol with 5 E0.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • nonionic surfactants are, in particular, tallow fatty alcohols with up to 80 E0, preferably tallow fatty alcohols with 11 E0, 14 E0, 25 E0, 30 E0 or 40 E0. Because of the known pluming problem in the spray drying of ethoxylated alcohols, which is caused by the steam volatility of unreacted alcohol and low-ethoxylated alcohols, the preferred ethoxylated fatty alcohols contain at least 5 E0 groups in the molecule on average. For the same reason, preferred alcohol ethoxylates also have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • Suitable alkoxylated alcohols can also be propoxylated or both ethoxylated be propoxylated as well. However, within the scope of this invention the only ethoxylated alcohols due to the better resulting Product characteristics preferred.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • Granules produced with preference preferably contain inorganic ones or inorganic and organic builder substances.
  • inorganic Builder substances primarily include phosphates, in particular the well-known tripolyphosphates and zeolite.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality.
  • zeolite NaX, zeolite P and mixtures of NaA, NaX and possibly P are also suitable.
  • the zeolite can be used as a spray-dried powder, but advantageously also as an undried stabilized suspension which is still moist from its production.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.
  • Layer substitutes are suitable substitutes or partial substitutes for the zeolite natural and synthetic origin.
  • Such layered silicates are, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405.
  • Their usability is not one special composition or structural formula limited. Are preferred here, however, smectites, especially bentonites.
  • the phosphate and / or zeolite content of the spray-dried granules is preferably 20 to 60% by weight and in particular 25 to 50 % By weight, based in each case on anhydrous active substance, lower quantities between 20 and 25% by weight can be particularly advantageous, if phosphates and zeolites are used.
  • Usable organic builders in addition to the sugar acids or their salts can be used, for example, are preferred polycarboxylic acids such as citric acid used in the form of their sodium salts, Adipic acid, succinic acid, glutaric acid, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use from ecological Reasons is not objectionable, as well as mixtures of these.
  • Preferred Salts are the salts of polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid and mixtures thereof.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
  • Their relative molecular mass, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, 20 up to 55% by weight aqueous solutions are preferred.
  • Particularly preferred are also biodegradable terpolymers, for example those that are considered Monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or Vinyl alcohol derivatives according to DE-A-43 00 772 or as the monomers salts of Acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives according to DE-C-42 21 381 included.
  • polyacetals which by reaction of dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and have at least 3 hydroxyl groups, for example as in European Patent application EP-A-0 280 223 can be obtained.
  • Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable ingredients of the granules are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
  • alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
  • the sodium carbonate content of the granules is preferably up to 20% by weight, advantageously between 5 and 15% by weight if the granules are to be used in the home, and can preferably be up to 50% by weight in the commercial sector. , in particular up to 45% by weight.
  • the sodium silicate content of the granules is generally up to 10% by weight and preferably between 2 and 8% by weight, silicate-containing granules of at most 3% by weight being preferred in zeolite-containing granules.
  • Alkali carbonates also by sulfur-free, 2 to 11 carbon atoms and optionally having a further carboxyl and / or amino group Amino acids and / or their salts are replaced.
  • a partial to complete exchange the alkali carbonates are made by glycine or glycinate.
  • the other detergent ingredients contained in the granules may include graying inhibitors, foam inhibitors, optical Brighteners, enzymes, fabric softening agents, colors and fragrances as well Neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and Diethylenetriaminepentamethylenephosphonate in amounts of 0.1 to 1.5% by weight used.
  • Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Are particularly well suited Strains of bacteria or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably become proteases of the subtilisin type and in particular proteases that are obtained from Bacillus lentus.
  • enzyme mixtures for example from protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, Amylase and lipase or protease, lipase and cellulase, but especially Mixtures of cellulase of particular interest. Oxidases too and peroxidases have been found to be suitable in some cases.
  • enzyme mixtures or enzyme granules can, for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • Graying inhibitors have the task of removing the fiber Keep dirt suspended in the fleet and prevent graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose.
  • soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as carboxymethyl cellulose are preferred.
  • Methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof and polyvinylpyrrolidone.
  • the agents can contain 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-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl.
  • Mixtures of the aforementioned brighteners can also be used. It has been found that uniform white granules are obtained if, apart from the customary brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight. also contain small amounts, for example 10 -6 to 10 -3 % by weight, preferably around 10 -5 % by weight, of a blue dye.
  • a particularly preferred dye is Tinolux (R) (commercial product from Ciba-Geigy).
  • the spray-dried granules without bleach, bleach activator and enzymes and optionally produced without a foam inhibitor.
  • Ingredients of household detergents can preferably be added later either as a raw material or in a pre-assembled processing form (Compound) are mixed with the spray-dried granules.
  • the spray-dried granules as basic granules for the production of detergents used for the commercial sector.
  • the proportion of spray-dried granules in household detergents or for the commercial sector is preferably 40 to 90% by weight and in particular 50 to 85% by weight.
  • the granules are produced in the process according to the invention via the Spray drying a slurry that contains less than 40% by weight of water anionic surfactants in amounts of at least 1% by weight, based on the spray-dried granules, as well as sugar acids or salts of sugar acids contains, with the viscosity of the slurries not under the operating conditions should be above 15000 mPas in order to process the slurries safely Enable tower.
  • such slurries are preferably used under the operating conditions a viscosity below 12000 mPas and especially below Have 10,000 mPas.
  • Such slurries are obtained when they are according to the invention Polyhydroxymonocarboxylic acids or their salts, polyhydroxydicarboxylic acids or their salts or mixtures of these mono- and / or Di compounds as indicated above contained in the amounts indicated.
  • polyhydroxymononecarboxylic acids or Polyhydroxymonocarboxylic acid salts and in particular the use of gluconic acid and advantageously preferred by gluconate.
  • the sugar acids and in particular the salts of the sugar acids can be in solid form or in form an aqueous solution, for example in the form of a 60 to 80% by weight aqueous solution can be incorporated into the slurry.
  • the spray to dry Slurry advantageously contains 0.5 to 15% by weight, preferably 1 to 10 % By weight and in particular 2 to 5% by weight of gluconic acid, gluconate or mixtures from these, each based on the spray-dried granules.
  • the bulk weights of the granules so produced can be in a wide range Frames vary. The person skilled in the art knows which parameter changes in the spray drying process to lighter and which lead to heavier granules. For example, granules with a bulk density can also be below of 550 g / l. However, it is preferred that in this Spray drying process Bulk weights of at least 550 g / l, preferably of at least 600 g / l and in particular from 650 to 1000 g / l be, these bulk weights easily in conventional Spray towers can be reached.
  • This process not only solves the tasks, but also the services and to increase the capacities of the spray towers while maintaining the same energy requirements (performance increases of 20% and above are possible) and at others to ensure the processability of highly concentrated slurries (Concentration by 10% and more possible compared to the prior art), but in the case of spray drying of tripolyphoshate-containing ones Granules also achieve a higher degree of phosphate conservation.
  • Another Advantage of this method is that slurries that have no polycarboxylate content cannot be sprayed as there will be phase separations comes, and for which the addition of citrate no training homogeneous phase caused by the addition of the sugar acids or their Salts now become homogeneous and can thus be sprayed.
  • the concentration of the sprayed slurry was 75.7% by weight and the viscosity under operating conditions 7400 mPas.
  • the bulk density achieved was 600 g / l.
  • Example M1 / 1 was repeated, the operating conditions of the Spray tower remained the same and 2 wt .-%, based on the spray-dried Granules, sodium gluconate in solid form (100% by weight) in exchange for Sodium carbonate were used.
  • the slurry concentration became 76.2 % By weight increased, the viscosity decreased to 5000 mPas.
  • the bulk density of the spray dried granules M1 / 2 was 647 g / l.
  • Example M1 / 2 was used at a slurry concentration of 79.7% by weight repeated.
  • the viscosity of the slurry was below 10,000 mPas.
  • the Bulk weight of the spray-dried granules M1 / 3 was 730 g / l.
  • sodium citrate sodium gluconate was used in the same way as above added, the viscosity of the slurry dropped to 6500 mPas. It there was a phase-stable slurry that could be sprayed.

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Abstract

Spray-dried granulates useful as washing or cleaning products or as components of such products, both for household and industrial use, contain at least 1 % by weight anionic surfactants and may have apparent densities of at least 550 g/l. These granulates may be produced by spraying slurries that contain saccharic acids or salts of saccharic acids. The use of saccharic acids or their salts at the same time lowers the viscosity of the slurries, so that more concentrated slurries may be sprayed, increasing the output of spraying towers without increasing their energy consumption.

Description

Die Erfindung betrifft ein Sprühtrocknungsverfahren, durch das schwere Granulate hergestellt werden können, die sich als Wasch- oder Reinigungsmittel oder zum Einsatz in Wasch- oder Reinigungsmitteln eignen.The invention relates to a spray drying process by which heavy granules can be produced, which can be used as a detergent or cleaning agent suitable for use in detergents or cleaning agents.

In der europäischen Patentanmeldung EP-A-0 120 492 werden spezielle sprühgetrocknete Granulate beschrieben, welche Schüttgewichte von mindestens 550 g/l bis zu 800 g/l ohne Nachbehandlung der Granulate erreichen, wobei unter Nachbehandlung das Besprühen der porösen Granulate mit beispielsweise nichtionischen Tensiden oder das Abpudern mit feinteiligen Pulvern, beispielsweise Zeolith-Pulvern, verstanden wird. Diese Granulate enthalten ethoxylierte Alkohole mit 12 bis 24 Kohlenstoffatomen und durchschnittlich 3 bis 20 Ethylenoxidgruppen. Um ein derartig hohes Schüttgewicht zu erreichen, ist es essentiell, daß der Gehalt an Aniontensiden in diesen Granulaten weniger als 1 Gew.-% und der Gehalt an Seife weniger als 0,2 Gew.-% beträgt, da bereits geringe Mengen an derartigen Zusätzen bei der Sprühtrocknung zu einem Aufblähen der Granulate und damit zu einer Abnahme des erwünschten hohen Schüttgewichts sowie der Rieselfähigkeit führen. Die Granulate werden durch ein Verfahren hergestellt, bei dem ein Slurry mit einem Gehalt von 55 bis 35 Gew.-% Wasser (einschließlich des adsorptiv bzw. als Hydrat gebundenen Wassers) versprüht wird. Jedoch ist es bevorzugt, daß der Wassergehalt nicht unterhalb 42 Gew.-% liegt, da niedrigere Gehalte zu einer starken Viskositätserhöhung des Slurries führen und den Zusatz viskositätserniedrigender Mittel wie Toluol-, Xylol- oder Cumolsulfonat erforderlich machen. Slurryviskositäten bis maximal 15000 mPas unter Betriebsbedingungen werden als akzeptabel angesehen.In the European patent application EP-A-0 120 492 special spray dried Granules described which bulk densities of at least Achieve 550 g / l up to 800 g / l without post-treatment of the granules, whereby with aftertreatment, spraying the porous granules with, for example non-ionic surfactants or powdering with finely divided powders, for example zeolite powders is understood. These contain granules ethoxylated alcohols with 12 to 24 carbon atoms and average 3 to 20 ethylene oxide groups. In order to achieve such a high bulk density, it is essential that the content of anionic surfactants in these granules less than 1% by weight and the soap content less than 0.2% by weight is, since even small amounts of such additives during spray drying to inflate the granules and thus decrease the desired high bulk density and flowability. The Granules are produced by a process in which a slurry is used a content of 55 to 35 wt .-% water (including the adsorptive or sprayed as hydrate bound water). However, it is preferred that the water content is not below 42 wt .-%, because lower Contents lead to a strong increase in viscosity of the slurry and the Addition of viscosity reducing agents such as toluene, xylene or cumene sulfonate make necessary. Slurry viscosities up to a maximum of 15000 mPas under operating conditions are considered acceptable.

Eine Aufgabe der Erfindung bestand darin, den Sprühtrocknungsprozeß energetisch günstiger zu gestalten oder eine Leistungssteigerung der Sprühtürme und damit eine Kapazitätssteigerung der vorhandenen Anlagen bei gleichbleibendem Energiebedarf zu erzielen. Dazu sollte es möglich sein, höherkonzentrierte Slurries zu versprühen. Diese Slurries durften jedoch nicht so hohe Viskositäten aufweisen, daß ein Versprühen nicht mehr möglich war. Außerdem sollte auf Zusätze wie Toluol-, Xylol- oder Cumolsulfonat als übliche Mittel zur Viskositätserniedrigung verzichtet werden können. Eine weitere Aufgabe der Erfindung bestand darin, daß Granulate bereitgestellt werden sollten, welche anionische Tenside in Mengen von mindestens 1 Gew.-% sowie gegebenenfalls zusätzlich Seifen in Mengen von mindestens 0,2 Gew.-% enthalten und ein für sprühgetrocknete Produkte ohne Nachbehandlung durch mechanische und/oder chemische Bearbeitung erhöhtes Schüttgewicht aufweisen.An object of the invention was to make the spray drying process energetic to make it cheaper or to increase the performance of the spray towers and thus an increase in capacity of the existing systems to achieve constant energy requirements. To do this, it should be possible to spray more concentrated slurries. However, these slurries were allowed do not have such high viscosities that spraying is no longer possible was. In addition, additives such as toluene, xylene or cumene sulfonate should be considered usual means of lowering viscosity can be dispensed with. Another The object of the invention was to provide granules which anionic surfactants in amounts of at least 1 wt .-% as well optionally additional soaps in quantities of at least 0.2% by weight included and one for spray-dried products without after-treatment mechanical and / or chemical processing increased bulk density exhibit.

Es wurde nun gefunden, daß konzentriertere Slurries in herkömmlichen Sprühtürmen versprüht werden können, wenn sie bestimmte zusätzliche Stoffe enthalten, die aber bereits bekannte Inhaltsstoffe von Wasch- oder Reinigungsmitteln sind und dort insbesondere als Cobuilder eingesetzt werden.It has now been found that more concentrated slurries in conventional Spray towers can be sprayed if they contain certain additional substances contain, but the already known ingredients of detergents or cleaning agents are and are used there in particular as cobuilders.

Gegenstand der Erfindung ist dementsprechend ein Verfahren zur Herstellung von sprühgetrockneten Granulaten, welche insbesondere für Wasch- oder Reinigungsmittel oder als Komponente hierfür eingesetzt werden können, dadurch gekennzeichnet, daß bei der Sprühtrocknung ein Slurry eingesetzt wird, der weniger als 40 Gew.-% Wasser, dafür aber anionische Tenside in Mengen von mindestens 1 Gew.-%, bezogen auf das sprühgetrocknete Granulat, sowie Zuckersäuren bzw. Salze von Zuckersäuren enthält und eine Viskosität von maximal 15000 mPas (unter Betriebsbedingungen) aufweist.The invention accordingly relates to a process for the production of spray-dried granules, which are particularly suitable for washing or Detergents or as a component for this, characterized in that a slurry is used in the spray drying, less than 40% by weight of water, but there are quantities of anionic surfactants of at least 1% by weight, based on the spray-dried granules, and Contains sugar acids or salts of sugar acids and a viscosity of has a maximum of 15000 mPas (under operating conditions).

Bevorzugt hergestellte Granulate weisen dabei ein Schüttgewicht von mindestens 600 g/l, vorzugsweise von 650 bis 1000 g/l und insbesondere von mindestens 700 g/l auf. Wenn im Rahmen dieser Erfindung von sprühgetrockneten Granulaten mit hohen Schüttgewichten, insbesondere mit Schüttgewichten von mindestens 700 g/l, gesprochen wird, so werden diese Granulate ausschließlich durch einen Sprühtrocknungsprozeß hergestellt. Nachbehandlungen wie Imprägnierungen mit flüssigen bis wachsartigen Komponenten, beispielsweise Niotensiden, Abpuderungen mit feinteiligen Pulvern oder Einsatz der Granulate in gegebenenfalls weiter verdichtend wirkenden Misch- und/oder Granulations- bzw. Extrusionsverfahren werden dabei nicht ausgeschlossen, sind jedoch nicht erfindungswesentlich. Die Angaben zu den Schüttgewichten beziehen sich somit immer auf die durch Sprühtrocknung erhaltenen Basisgranulate.Granules produced with preference have a bulk density of at least 600 g / l, preferably from 650 to 1000 g / l and in particular at least 700 g / l. When spray dried within the scope of this invention Granules with high bulk densities, especially with bulk densities of at least 700 g / l, these granules are used exclusively produced by a spray drying process. Follow-up treatments like Impregnation with liquid to waxy components, for example Nonionic surfactants, powdering with finely divided powders or use of the granules in optionally further compacting mixing and / or granulation or Extrusion processes are not excluded, but are not essential to the invention. The details of the bulk weights therefore relate always on the base granules obtained by spray drying.

Der Gehalt der erfindungsgemäß hergestellten Granulate an Aniontensiden wie üblichen Alkylbenzolsulfonaten und/oder Alkyl(ether)sulfaten beträgt vorzugsweise 1,5 bis 10 Gew.-%. Zusätzlich können die Granulate auch noch Seifen in Mengen von mindestens 0,2 Gew.-% enthalten. Bevorzugte Granulate enthalten dabei zusätzlich etwa 0,5 bis 15 Gew.-%, insbesondere bis 10 Gew.-% an Fettsäureseifen bzw. natürlichen Fettsäureseifengemischen.The anionic surfactants in the granules produced according to the invention, such as usual alkylbenzenesulfonates and / or alkyl (ether) sulfates is preferably 1.5 to 10% by weight. The granules can also be added to soaps Contain quantities of at least 0.2 wt .-%. Contain preferred granules about 0.5 to 15% by weight, in particular up to 10% by weight Fatty acid soaps or natural fatty acid soap mixtures.

Als anionische Tenside werden beispielsweise solche vom Typ der Sulfonate und Sulfate eingesetzt. Als Tenside vom Sulfonat-Typ kommen vorzugsweise C9-C13-Alkylbenzolsulfonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C12-C18-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus C12-C18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden. Die biologisch gut abbaubaren Alkansulfonate werden aus C12-C18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen. Die Sulfonatgruppe ist dabei über die gesamte Kohlenstoffkette statistisch verteilt, wobei die sekundären Alkansulfonate überwiegen. Geeignet sind auch die Ester von α-Sulfofettsäuren (Estersulfonate), z.B. die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren.Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The readily biodegradable alkanesulfonates are obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The sulfonate group is statistically distributed over the entire carbon chain, with the secondary alkanesulfonates predominating. The esters of α-sulfofatty acids (ester sulfonates) are also suitable, for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C10-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlänge bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind C16-C18-Alk(en)ylsulfate insbesondere bevorzugt. Dabei kann es auch von besonderem Vorteil und insbesondere für maschinelle Waschmittel von Vorteil sein, C16-C18-Alk(en)ylsulfate in Kombination mit niedriger schmelzenden Aniontensiden und insbesondere mit solchen Aniontensiden, die einen niedrigeren Krafft-Punkt aufweisen und bei relativ niedrigen Waschtemperaturen von beispielsweise Raumtemperatur bis 40 °C eine geringe Kristallisationsneigung zeigen, einzusetzen. In einer bevorzugten Ausführungsform der Erfindung enthalten die Mittel daher Mischungen aus kurzkettigen und langkettigen Fettalkylsulfaten, vorzugsweise Mischungen aus C12-C14-Fettalkylsulfaten oder C12-C18-Fettalkylsulfaten mit C16-C18-Fettalkylsulfaten und insbesondere C12-C16-Fettalkylsulfaten mit C16-C18-Fettalkylsulfaten. In einer weiteren bevorzugten Ausführungsform der Erfindung werden jedoch nicht nur gesättigte Alkylsulfate, sondern auch ungesättigte Alkenylsulfate mit einer Alkenylkettenlänge von vorzugsweise C16 bis C22 eingesetzt. Dabei sind insbesondere Mischungen aus gesättigten, überwiegend aus C16 bestehenden sulfierten Fettalkoholen und ungesättigten, überwiegend aus C18 bestehenden sulfierten Fettalkoholen bevorzugt, beispielsweise solche, die sich von festen oder flüssigen Fettalkoholmischungen des Typs HD-Ocenol (R) (Handelsprodukt des Anmelders) ableiten. Dabei sind Gewichtsverhältnisse von Alkylsulfaten zu Alkenylsulfaten von 10:1 bis 1:2 und insbesondere von etwa 5:1 bis 1:1 bevorzugt. Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-C21-Alkohole, wie 2-Methyl-verzweigte C9-C11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-C18-Fettalkohole mit 2 bis 4 E0, sind geeignet. Sie werden in Waschmitteln aufgrund ihres hohen Schaumverhaltens nur in relativ geringen Mengen, beispielsweise in Mengen von 1 bis 5 Gew.-%, eingesetzt.As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C 16 -C 18 alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize. In a preferred embodiment of the invention, the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 12 -C 14 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates and in particular C 12 -C 16 -Fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates. In a further preferred embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used. Mixtures of saturated sulfonated fatty alcohols predominantly consisting of C 16 and unsaturated sulfated fatty alcohols predominantly consisting of C 18 are particularly preferred, for example those derived from solid or liquid HD-Ocenol (R) fatty alcohol mixtures (commercial product of the applicant) . Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred. The sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 2 to 4 E0 are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Als Seifen eignen sich insbesondere gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierte Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische. Insbesondere sind solche Seifengemische bevorzugt, die zu 50 bis 100 Gew.-% aus gesättigten C12-C24-Fettsäureseifen und zu 0 bis 50 Gew.-% aus Ölsäureseife zusammengesetzt sind.Suitable soaps are in particular saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.

Die anionischen Tenside und Seifen können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor. The anionic surfactants and soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, Di- or triethanolamine. The anionic are preferably located Surfactants in the form of their sodium or potassium salts, especially in the form of Sodium salts.

Als Zuckersäuren bzw. Salze von Zuckersäuren enthalten die Mittel vorzugsweise Polyhydroxymonocarbonsäuren bzw. Polyhydroxymonocarbonsäuresalze mit 4 bis 6 Kohlenstoffatomen, wobei jedes Kohlenstoffatom, welches keine Carboxylgruppe oder Ketogruppe trägt, eine Hydroxy-Gruppe aufweist, und/oder Polyhydroxydicarbonsäuren bzw. Polyhydroxydicarbonsäuresalze mit 4 bis 6 Kohlenstoffatomen und mindestens 2 Hydroxy-Gruppen pro Molekül oder Mischungen aus diesen Säuren und Salzen. Dabei bilden Polyhydroxymonocarbonsäuren bzw. Polyhydroxymonocarbonsäuresalze, welche eine Ketogruppe pro Molekül aufweisen, vorzugsweise Lactone. Bevorzugte Polyhydroxymonocarbonsäuren bzw. Polyhydroxymonocarbonsäuresalze sind solche, die 4 bis 6 Kohlenstoffatome enthalten und an jedem Kohlenstoffatom, das keine Carboxylgruppe oder Ketogruppe trägt, eine Hydroxy-Gruppe aufweisen. Insbesondere sind dabei Polyhydroxymonocarbonsäuren bzw. und Polyhydroxymonocarbonsäuresalze mit 4 Kohlenstoffatomen und 3 Hydroxy-Gruppen, mit 5 Kohlenstoffatomen und 4 Hydroxygruppen und mit 6 Kohlenstoffatomen und 4 oder 5 Hydroxy-Gruppen bevorzugt. Besonders vorteilhafte Eigenschaften weisen Polyhydroxymonocarbonsäuren bzw. Polyhydroxymonocarbonsäuresalze mit 6 Kohlenstoffatomen und 5 Hydroxy-Gruppen, wie D-Gluconsäure (auch Maltonsäure oder Dextronsäure genannt) bzw. deren Salze, und Polyhydroxymonocarbonsäuren bzw. Polyhydroxymonocarbonsäuresalze mit 6 Kohlenstoffatomen, einer Ketogruppe und 4 Hydroxy-Gruppen, wie L-Ascorbinsäure, die als Lacton vorliegt, und L-Ascorbinsäuresalze auf. Dabei können auch Mischungen der Säuren und/oder der Salze eingesetzt werden, letztere vorzugsweise in Form ihrer Natrium- oder Kaliumsalze. Weiterhin bevorzugt sind jedoch auch Polyhydroxydicarbonsäuren bzw. Polyhydroxydicarbonsäuresalze, welche 4 bis 6 Kohlenstoffatome enthalten und an jedem Kohlenstoffatom, das keine Carboxylgruppe trägt, eine Hydroxy-Gruppe aufweisen. Insbesondere sind dabei also Polyhydroxydicarbonsäuren und Polyhydroxydicarbonsäuresalze mit 4 Kohlenstoffatomen und 2 Hydroxy-Gruppen, wie Weinsäure und Weinsäuresalze, und mit 6 Kohlenstoffatomen und 4 Hydroxy-Gruppen, wie Galactarsäure (auch Mucinsäure oder Schleimsäure genannt) und Galactarsäuresalze sowie Glucarsäure (auch Saccharinsäure genannt) und Glucarsäuresalze, bevorzugt. Dabei können auch Mischungen der Säuren, der Monosalze und/oder der Disalze eingesetzt werden. Die Salze werden vorzugsweise als Natrium- oder Kaliumsalze eingesetzt. Zu den besonders vorteilhaften Polyhydroxydicarbonsäuresalzen gehören daher die Mononatriumsalze und Dinatriumsalze sowie die Monokalium- und Dikaliumsalze der Weinsäure, der Galactarsäure und der D-Glucarsäure.The agents preferably contain as sugar acids or salts of sugar acids Polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts with 4 to 6 carbon atoms, each carbon atom which has no carboxyl group or carries a keto group, has a hydroxy group, and / or Polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts with 4 to 6 Carbon atoms and at least 2 hydroxyl groups per molecule or mixtures from these acids and salts. Here, polyhydroxymonocarboxylic acids form or polyhydroxymonocarboxylic acid salts, which one keto group per Have molecule, preferably lactones. Preferred polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts are those which have 4 to 6 carbon atoms contain and on each carbon atom that has no carboxyl group or carries a keto group, have a hydroxy group. Especially are polyhydroxymonocarboxylic acids and or polyhydroxymonocarboxylic acid salts with 4 carbon atoms and 3 hydroxyl groups, with 5 carbon atoms and 4 hydroxyl groups and with 6 carbon atoms and 4 or 5 hydroxyl groups prefers. Polyhydroxymonocarboxylic acids have particularly advantageous properties or polyhydroxymonocarboxylic acid salts with 6 carbon atoms and 5 hydroxy groups, such as D-gluconic acid (also maltonic acid or called dextronic acid) or their salts, and polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts with 6 carbon atoms, one Keto group and 4 hydroxy groups, such as L-ascorbic acid, which is present as a lactone, and L-ascorbic acid salts. Mixtures of acids can also be used and / or the salts are used, the latter preferably in the form their sodium or potassium salts. However, polyhydroxydicarboxylic acids are also preferred or polyhydroxydicarboxylic acid salts, which 4 to 6 Contain carbon atoms and on each carbon atom that has no carboxyl group carries, have a hydroxy group. In particular are there thus polyhydroxydicarboxylic acids and polyhydroxydicarboxylic acid salts with 4 Carbon atoms and 2 hydroxy groups, such as tartaric acid and tartaric acid salts, and with 6 carbon atoms and 4 hydroxy groups, such as galactaric acid (also Called mucic acid or mucic acid) and galactaric acid salts as well as glucaric acid (also called saccharic acid) and glucaric acid salts, preferred. Mixtures of the acids, the mono salts and / or the disalts can also be used be used. The salts are preferably as sodium or Potassium salts used. To the particularly advantageous polyhydroxydicarboxylic acid salts therefore include the monosodium and disodium salts as well the monopotassium and dipotassium salts of tartaric acid, galactaric acid and D-glucaric acid.

Der Gehalt der sprühgetrockneten Granulate an Zuckersäuren und vorzugsweise an den Salzen der Zuckersäuren beträgt dabei vorzugsweise 0,2 bis 20 Gew.-% und insbesondere 0,5 bis 15 Gew.-%. Besonders bevorzugt werden dabei sprühgetrocknete Granulate hergestellt, welche 1 bis 10 Gew.-% und vorteilhafterweise 2 bis 5 Gew.-% Gluconsäure, Gluconat oder Mischungen aus diesen enthalten.The content of the spray-dried granules in sugar acids and preferably the salts of the sugar acids are preferably 0.2 to 20% by weight and in particular 0.5 to 15% by weight. Are particularly preferred spray-dried granules produced, which 1 to 10 wt .-% and advantageously 2 to 5% by weight of gluconic acid, gluconate or mixtures of contain this.

Die erfindungsgemäß hergestellten Granulate können noch weitere Inhaltsstoffe enthalten, die üblicherweise in Wasch- oder Reinigungsmitteln, die entweder im Haushalt oder im gewerblichen Bereich eingesetzt werden können, verwendet werden. Neben den anionischen Tensiden können die Granulate auch nichtionische Tenside enthalten. Ihr Gehalt beträgt vorzugsweise 1 bis 30 Gew.-%, insbesondere 2 bis 25 Gew.-%. In Granulaten, welche mehr als 10 Gew.-% an Aniontensiden und Seifen enthalten, beträgt der Gehalt an nichtionischen vorteilhafterweise bis 20 Gew.-%. Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise flüssige ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 24 C-Atomen, insbesondere 8 bis 18 C-Atomen, und durchschnittlich 1 bis 12 Mol Ethylenoxid (E0) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann, bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen bevorzugt, z.B. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 E0 pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-C14-Alkohole mit 3 E0 oder 4 E0, C9-C11-Alkohol mit 7 E0, C13-C15-Alkohole mit 3 E0, 5 E0, 7 E0 oder 8 E0, C12-C18-Alkohole mit 3 E0, 5 E0 oder 7 E0 und Mischungen aus diesen, wie Mischungen aus C12-C14-Alkohol mit 3 E0 und C12-C18-Alkohol mit 5 E0. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Weitere bevorzugte Niotenside sind dabei insbesondere Talgfettalkohole mit bis zu 80 E0, vorzugsweise Talgfettalkohole mit 11 E0, 14 E0, 25 E0, 30 E0 oder 40 E0. Aufgrund des bekannten Pluming-Problems bei der Sprühtrocknung von ethoxylierten Alkoholen, welches durch die Wasserdampfflüchtigkeit von nicht-umgesetzten Alkohol und niedrigethoxylierten Alkoholen hervorgerufen wird, enthalten die bevorzugt eingesetzten ethoxylierten Fettalkohole mindestens durchschnittlich 5 E0-Gruppen im Molekül. Bevorzugte Alkoholethoxylate weisen aus demselben Grund auch eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Insbesondere bevorzugt werden Talgfettalkohole oder C12-C18-Fettalkohole mit 5 bis 25 E0, vorzugsweise Mischungen aus Alkoholen mit 5 E0 und/oder 7 E0 und 25 E0 oder Mischungen aus Alkoholen mit 5 E0 und 14 E0.The granules produced according to the invention can also contain further ingredients which are usually used in detergents or cleaning agents which can be used either in the home or in the commercial sector. In addition to the anionic surfactants, the granules can also contain nonionic surfactants. Their content is preferably 1 to 30% by weight, in particular 2 to 25% by weight. In granules which contain more than 10% by weight of anionic surfactants and soaps, the content of nonionic is advantageously up to 20% by weight. The nonionic surfactants used are preferably alkoxylated, advantageously liquid ethoxylated, in particular primary alcohols having preferably 8 to 24 carbon atoms, in particular 8 to 18 carbon atoms, and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol, in which the alcohol radical may be linear or preferably methyl-branched in the 2-position, or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 E0 or 4 E0, C 9 -C 11 alcohol with 7 E0, C 13 -C 15 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C 12 -C 18 alcohols with 3 E0, 5 E0 or 7 E0 and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 E0 and C 12 -C 18 alcohol with 5 E0. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Further preferred nonionic surfactants are, in particular, tallow fatty alcohols with up to 80 E0, preferably tallow fatty alcohols with 11 E0, 14 E0, 25 E0, 30 E0 or 40 E0. Because of the known pluming problem in the spray drying of ethoxylated alcohols, which is caused by the steam volatility of unreacted alcohol and low-ethoxylated alcohols, the preferred ethoxylated fatty alcohols contain at least 5 E0 groups in the molecule on average. For the same reason, preferred alcohol ethoxylates also have a narrow homolog distribution (narrow range ethoxylates, NRE). Tallow fatty alcohols or C 12 -C 18 fatty alcohols with 5 to 25 E0, preferably mixtures of alcohols with 5 E0 and / or 7 E0 and 25 E0 or mixtures of alcohols with 5 E0 and 14 E0 are particularly preferred.

Geeignete alkoxylierte Alkohole können auch propoxyliert oder sowohl ethoxyliert als auch propoxyliert sein. Im Rahmen dieser Erfindung sind jedoch die nur ethoxylierten Alkohole aufgrund der besseren resultierenden Produkteigenschaften bevorzugt. Der Gehalt der Granulate an ethoxylierten Alkoholen, insbesondere an Talgfettalkoholen mit 5 bis 25 E0, beträgt insbesondere 10 bis 15 Gew.-%.Suitable alkoxylated alcohols can also be propoxylated or both ethoxylated be propoxylated as well. However, within the scope of this invention the only ethoxylated alcohols due to the better resulting Product characteristics preferred. The content of the granules in ethoxylated Alcohols, especially on tallow fatty alcohols with 5 to 25 E0, is in particular 10 to 15% by weight.

Außerdem können als weitere nichtionische Tenside auch Alkylglykoside der allgemeinen Formel RO(G)x eingesetzt werden, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4.In addition, alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Bevorzugt hergestellte Granulate enthalten dabei vorzugsweise noch anorganische oder anorganische und organische Buildersubstanzen. Zu den anorganischen Buildersubstanzen zählen dabei in erster Linie Phosphate, insbesondere die bekannten Tripolyphosphate und Zeolith.Granules produced with preference preferably contain inorganic ones or inorganic and organic builder substances. To the inorganic Builder substances primarily include phosphates, in particular the well-known tripolyphosphates and zeolite.

Der eingesetzte feinkristalline, synthetische und gebundenes Wasser enthaltende Zeolith ist vorzugsweise Zeolith NaA in Waschmittelqualität. Geeignet sind jedoch auch Zeolith NaX, Zeolith P sowie Mischungen aus NaA, NaX und gegebenenfalls P. Der Zeolith kann als sprühgetrocknetes Pulver, vorteilhafterweise aber auch als ungetrocknete, von ihrer Herstellung noch feuchte, stabilisierte Suspension zum Einsatz kommen. Für den Fall, daß der Zeolith als Suspension eingesetzt wird, kann diese geringe Zusätze an nichtionischen Tensiden als Stabilisatoren enthalten, beispielsweise 1 bis 3 Gew.-%, bezogen auf Zeolith, an ethoxylierten C12-C18-Fettalkoholen mit 2 bis 5 Ethylenoxidgruppen oder ethoxylierte Isotridecanole. Geeignete Zeolithe weisen eine mittlere Teilchengröße von weniger als 10 µm (Volumenverteilung; Meßmethode: Coulter Counter) auf und enthalten vorzugsweise 18 bis 22, insbesondere 20 bis 22 Gew.-% an gebundenem Wasser.The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. However, zeolite NaX, zeolite P and mixtures of NaA, NaX and possibly P are also suitable. The zeolite can be used as a spray-dried powder, but advantageously also as an undried stabilized suspension which is still moist from its production. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.

Geeignete Substitute bzw. Teilsubstitute für den Zeolith sind Schichtsilikate natürlichen und synthetischen Ursprungs. Derartige Schichtsilikate sind beispielsweise aus den Patentanmeldungen DE-B-23 34 899, EP-A-0 026 529 und DE-A-35 26 405 bekannt. Ihre Verwendbarkeit ist nicht auf eine spezielle Zusammensetzung bzw. Strukturformel beschränkt. Bevorzugt sind hier jedoch Smectite, insbesondere Bentonite.Layer substitutes are suitable substitutes or partial substitutes for the zeolite natural and synthetic origin. Such layered silicates are, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405. Their usability is not one special composition or structural formula limited. Are preferred here, however, smectites, especially bentonites.

Der Gehalt der sprühgetrockneten Granulate an Phosphaten und/oder Zeolith beträgt dabei vorzugsweise 20 bis 60 Gew.-% und insbesondere 25 bis 50 Gew.-%, jeweils bezogen auf wasserfreie Aktivsubstanz, wobei geringere mengen zwischen 20 und 25 Gew.-% insbesondere dann vorteilhaft sein können, wenn Phosphate und Zeolithe eingesetzt werden.The phosphate and / or zeolite content of the spray-dried granules is preferably 20 to 60% by weight and in particular 25 to 50 % By weight, based in each case on anhydrous active substance, lower quantities between 20 and 25% by weight can be particularly advantageous, if phosphates and zeolites are used.

Brauchbare organische Gerüstsubstanzen, die zusätzlich zu den Zuckersäuren bzw. deren Salzen eingesetzt werden können, sind beispielsweise die bevorzugt in Form ihrer Natriumsalze eingesetzten Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure und Mischungen aus diesen. Dabei ist zu beachten, daß diese üblicherweise in Wasch- oder Reinigungsmitteln eingesetzten Polycarboxylate, insbesondere Citronensäure bzw. Citrat, weder die gewünschte Viskositätserniedrigung des zu versprühenden Slurries noch die gewünschte Schüttgewichtserhöhung der sprühgetrockneten Granulate bewirkt. Usable organic builders, in addition to the sugar acids or their salts can be used, for example, are preferred polycarboxylic acids such as citric acid used in the form of their sodium salts, Adipic acid, succinic acid, glutaric acid, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use from ecological Reasons is not objectionable, as well as mixtures of these. Preferred Salts are the salts of polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid and mixtures thereof. It should be noted, that these are usually used in washing or cleaning agents Polycarboxylates, especially citric acid or citrate, neither Desired viscosity reduction of the slurry to be sprayed still the desired increase in bulk density of the spray-dried granules.

Geeignete polymere Polycarboxylate sind beispielsweise die Natriumsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 800 bis 150000 (auf Säure bezogen). Geeignete copolymere Polycarboxylate sind insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 5000 bis 200000, vorzugsweise 10000 bis 120000 und insbesondere 50000 bis 100000. Die (co-)polymeren Polycarboxylate können entweder als Pulver oder als wäßrige Lösung eingesetzt werden, wobei 20 bis 55 Gew.-%ige wäßrige Lösungen bevorzugt sind. Insbesondere bevorzugt sind auch biologisch abbaubare Terpolymere, beispielsweise solche, die als Monomere Salze der Acrylsäure und der Maleinsäure sowie Vinylalkohol bzw. Vinylalkohol-Derivate gemäß DE-A-43 00 772 oder die als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zucker-Derivate gemäß DE-C-42 21 381 enthalten.Suitable polymeric polycarboxylates are, for example, the sodium salts polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain. Their relative molecular mass, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. The (co) polymeric polycarboxylates can can be used either as a powder or as an aqueous solution, 20 up to 55% by weight aqueous solutions are preferred. Particularly preferred are also biodegradable terpolymers, for example those that are considered Monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or Vinyl alcohol derivatives according to DE-A-43 00 772 or as the monomers salts of Acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives according to DE-C-42 21 381 included.

Weitere geeignete Buildersubstanzen sind Polyacetale, welche durch Umsetzung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 C-Atome und mindestens 3 Hydroxylgruppen aufweisen, beispielsweise wie in der europäischen Patentanmeldung EP-A-0 280 223 beschrieben erhalten werden können. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Gluconsäure und/oder Glucoheptonsäure erhalten.Other suitable builder substances are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and have at least 3 hydroxyl groups, for example as in European Patent application EP-A-0 280 223 can be obtained. Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Weitere geeignete Inhaltsstoffe der Granulate sind wasserlösliche anorganische Salze wie Bicarbonate, Carbonate, amorphe Silikate oder Mischungen aus diesen; insbesondere werden Alkalicarbonat und amorphes Alkalisilikat, vor allem Natriumsilikat mit einem molaren Verhältnis Na2O : SiO2 von 1:1 bis 1:4,5, vorzugsweise von 1:2 bis 1:3,5, eingesetzt. Der Gehalt der Granulate an Natriumcarbonat beträgt dabei vorzugsweise bis zu 20 Gew.-%, vorteilhafterweise zwischen 5 und 15 Gew.-%, wenn die Granulate im Haushalt verwendet werden sollen, und kann im gewerblichen Bereich auf vorzugsweise bis zu 50 Gew.-%, insbesondere bis zu 45 Gew.-% ansteigen. Der Gehalt der Granulate an Natriumsilikat beträgt im allgemeinen bis zu 10 Gew.-% und vorzugsweise zwischen 2 und 8 Gew.-%, wobei in zeolithhaltigen Granulaten Silikatmengen von maximal 3 Gew.-% bevorzugt sind.Other suitable ingredients of the granules are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; In particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used. The sodium carbonate content of the granules is preferably up to 20% by weight, advantageously between 5 and 15% by weight if the granules are to be used in the home, and can preferably be up to 50% by weight in the commercial sector. , in particular up to 45% by weight. The sodium silicate content of the granules is generally up to 10% by weight and preferably between 2 and 8% by weight, silicate-containing granules of at most 3% by weight being preferred in zeolite-containing granules.

Nach der Lehre der älteren deutschen Patentanmeldung P 43 19 578.4 können Alkalicarbonate auch durch schwefelfreie, 2 bis 11 Kohlenstoffatome und gegebenenfalls eine weitere Carboxyl- und/oder Aminogruppe aufweisende Aminosäuren und/oder deren Salze ersetzt werden. Im Rahmen dieser Erfindung ist es dabei bevorzugt, daß ein teilweiser bis vollständiger Austausch der Alkalicarbonate durch Glycin bzw. Glycinat erfolgt.According to the teaching of the older German patent application P 43 19 578.4 Alkali carbonates also by sulfur-free, 2 to 11 carbon atoms and optionally having a further carboxyl and / or amino group Amino acids and / or their salts are replaced. Within the scope of this invention it is preferred that a partial to complete exchange the alkali carbonates are made by glycine or glycinate.

Zu den sonstigen Waschmittelbestandteilen, die in den Granulaten enthalten sein können, zählen Vergrauungsinhibitoren, Schauminhibitoren, optische Aufheller, Enzyme, textilweichmachende Stoffe, Farb- und Duftstoffe sowie Neutralsalze wie Sulfate und Chloride in Form ihrer Natrium- oder Kaliumsalze.The other detergent ingredients contained in the granules may include graying inhibitors, foam inhibitors, optical Brighteners, enzymes, fabric softening agents, colors and fragrances as well Neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts.

Beim Einsatz in maschinellen Waschverfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Als Schauminhibitoren eignen sich beispielsweise Seifen natürlicher oder synthetischer Herkunft, die einen hohen Anteil an C18-C24-Fettsäuren aufweisen. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, ggf. silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure oder Bistearylethylendiamid. Mit Vorteilen werden auch Gemische aus verschiedenen Schauminhibitoren verwendet, z.B. solche aus Silikonen, Paraffinen oder Wachsen.When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.

Als Salze von Polyphosphonsäuren werden vorzugsweise die neutral reagierenden Natriumsalze von beispielsweise 1-Hydroxyethan-1,1-diphosphonat und Diethylentriaminpentamethylenphosphonat in Mengen von 0,1 bis 1,5 Gew.-% verwendet.The salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and Diethylenetriaminepentamethylenephosphonate in amounts of 0.1 to 1.5% by weight used.

Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen, Cellulasen bzw. deren Gemische in Frage. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheniformis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Dabei sind Enzymmischungen, beispielsweise aus Protease und Amylase oder Protease und Lipase oder Protease und Cellulase oder aus Cellulase und Lipase oder aus Protease, Amylase und Lipase oder Protease, Lipase und Cellulase, insbesondere jedoch Cellulase-haltige Mischungen von besonderem Interesse. Auch Oxidasen und Peroxidasen haben sich in einigen Fällen als geeignet erwiesen. Der Anteil der Enzyme, Enzymmischungen oder Enzymgranulate kann beispielsweise etwa 0,1 bis 5 Gew.-%, vorzugsweise 0,1 bis etwa 2 Gew.-% betragen.Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Are particularly well suited Strains of bacteria or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably become proteases of the subtilisin type and in particular proteases that are obtained from Bacillus lentus. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, Amylase and lipase or protease, lipase and cellulase, but especially Mixtures of cellulase of particular interest. Oxidases too and peroxidases have been found to be suitable in some cases. Of the Proportion of the enzymes, enzyme mixtures or enzyme granules can, for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

Vergrauungsinhibitoren haben die Aufgabe, den von der Faser abgelösten Schmutz in der Flotte suspendiert zu halten und so das Vergrauen zu verhindern. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise die wasserlöslichen Salze polymerer Carbonsäuren, Leim, Gelatine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich lösliche Stärkepräparate und andere als die obengenannten Stärkeprodukte verwenden, z.B. abgebaute Stärke, Aldehydstärken usw.. Auch Polyvinylpyrrolidon ist brauchbar. Bevorzugt werden jedoch Celluloseether, wie Carboxymethylcellulose, Methylcellulose, Hydroxyalkylcellulose und Mischether, wie Methylhydroxyethylcellulose, Methylhydroxypropylcellulose, Methylcarboxymethylcellulose und deren Gemische sowie Polyvinylpyrrolidon eingesetzt.Graying inhibitors have the task of removing the fiber Keep dirt suspended in the fleet and prevent graying. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Furthermore, soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, cellulose ethers such as carboxymethyl cellulose are preferred. Methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof and polyvinylpyrrolidone.

Die Mittel können als optische Aufheller Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z.B. Salze der 4,4'-Bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholino-Gruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle anwesend sein, z.B. die Alkalisalze des 4,4'-Bis(2-sulfostyryl)-diphenyls, 4,4'-Bis(4-chlor-3-sulfostyryl)-diphenyls, oder 4-(4-Chlorstyryl)-4'-(2-sulfostyryl)-diphenyls. Auch Gemische der vorgenannten Aufheller können verwendet werden. Es wurde gefunden, daß einheitlich weiße Granulate erhalten werden, wenn die Mittel außer den üblichen Aufhellern in üblichen Mengen, beispielsweise zwischen 0,1 und 0,5 Gew.-%, vorzugsweise zwischen 0,1 und 0,3 Gew.-%, auch geringe Mengen, beispielsweise 10-6 bis 10-3 Gew.-%, vorzugsweise um 10-5 Gew.-%, eines blauen Farbstoffs enthalten. Ein besonders bevorzugter Farbstoff ist Tinolux(R) (Handelsprodukt der Ciba-Geigy).As optical brighteners, the agents can contain 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-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. It has been found that uniform white granules are obtained if, apart from the customary brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight. also contain small amounts, for example 10 -6 to 10 -3 % by weight, preferably around 10 -5 % by weight, of a blue dye. A particularly preferred dye is Tinolux (R) (commercial product from Ciba-Geigy).

In einer bevorzugten Ausführungsform der Erfindung werden die sprühgetrockneten Granulate jedoch ohne Bleichmittel, Bleichaktivator und Enzyme sowie gegebenenfalls ohne Schauminhibitor hergestellt. Diese an sich üblichen Inhaltsstoffe von Haushaltswaschmitteln können vorzugsweise nachträglich entweder als Rohstoff oder in einer vorkonfektionierten Verarbeitungsform (Compound) mit den sprühgetrockneten Granulaten vermischt werden.In a preferred embodiment of the invention, the spray-dried However, granules without bleach, bleach activator and enzymes and optionally produced without a foam inhibitor. These usual in themselves Ingredients of household detergents can preferably be added later either as a raw material or in a pre-assembled processing form (Compound) are mixed with the spray-dried granules.

In einer weiteren bevorzugten Ausführungsform der Erfindung werden die sprühgetrockneten Granulate als Basisgranulate zur Herstellung von Waschmitteln für den gewerblichen Bereich eingesetzt. Sie können dabei beispielsweise mit alkalischen Stoffen wie Metasilikat vermischt werden.In a further preferred embodiment of the invention, the spray-dried granules as basic granules for the production of detergents used for the commercial sector. For example, you can can be mixed with alkaline substances such as metasilicate.

Der Anteil des sprühgetrockneten Granulats in Waschmitteln für den Haushalt oder für den gewerblichen Bereich beträgt dabei vorzugsweise 40 bis 90 Gew.-% und insbesondere 50 bis 85 Gew.-%.The proportion of spray-dried granules in household detergents or for the commercial sector is preferably 40 to 90% by weight and in particular 50 to 85% by weight.

Die Herstellung der Granulate erfolgt im erfindungsgemäßen Verfahren über die Sprühtrocknung eines Slurries, der weniger als 40 Gew.-% Wasser, dafür aber anionische Tenside in Mengen von mindestens 1 Gew.-%, bezogen auf das sprühgetrocknete Granulat, sowie Zuckersäuren bzw. Salze von Zuckersäuren enthält, wobei die Viskosität des Slurries unter den Betriebsbedingungen nicht oberhalb 15000 mPas liegen soll, um ein sicheres Verarbeiten des Slurries im Turm zu ermöglichen. Im Rahmen der vorliegenden Erfindung ist es möglich und daher auch bevorzugt, den Wassergehalt des Slurries weiter zu senken. So sind Wassergehalte von maximal 35 Gew.-% bevorzugt. In einer weiteren Ausführungsform der Erfindung werden dabei solche Slurries bevorzugt eingesetzt, die unter den Betriebsbedingungen eine Viskosität unterhalb 12000 mPas und insbesondere unterhalb 10000 mPas aufweisen. Derartige Slurries werden erhalten, wenn sie erfindungsgemäß Polyhydroxymonocarbonsäuren bzw. deren Salze, Polyhydroxydicarbonsäuren bzw. deren Salze oder Mischungen aus diesen Mono- und/oder Di-Verbindungen wie oben angegeben in den angegebenen Mengen enthalten. Dabei ist jedoch der Einsatz der Polyhydroxymononcarbonsäuren bzw. der Polyhydroxymonocarbonsäuresalze und insbesondere der Einsatz von Gluconsäure und vorteilhafterweise von Gluconat bevorzugt. Die Zuckersäuren und insbesondere die Salze der Zuckersäuren können in fester Form oder in Form einer wäßrigen Lösung, beispielsweise in Form einer 60 bis 80 Gew.-%igen wäßrigen Lösung in den Slurry eingearbeitet werden. Der sprühzutrocknende Slurry enthält vorteilhafterweise 0,5 bis 15 Gew.-%, vorzugsweise 1 bis 10 Gew.-% und insbesondere 2 bis 5 Gew.-% Gluconsäure, Gluconat oder Mischungen aus diesen, jeweils bezogen auf die sprühgetrockneten Granulate.The granules are produced in the process according to the invention via the Spray drying a slurry that contains less than 40% by weight of water anionic surfactants in amounts of at least 1% by weight, based on the spray-dried granules, as well as sugar acids or salts of sugar acids contains, with the viscosity of the slurries not under the operating conditions should be above 15000 mPas in order to process the slurries safely Enable tower. Within the scope of the present invention it is possible and therefore also preferred to further reduce the water content of the slurry. So are Water content of a maximum of 35 % By weight preferred. In another embodiment of the invention such slurries are preferably used under the operating conditions a viscosity below 12000 mPas and especially below Have 10,000 mPas. Such slurries are obtained when they are according to the invention Polyhydroxymonocarboxylic acids or their salts, polyhydroxydicarboxylic acids or their salts or mixtures of these mono- and / or Di compounds as indicated above contained in the amounts indicated. However, the use of polyhydroxymononecarboxylic acids or Polyhydroxymonocarboxylic acid salts and in particular the use of gluconic acid and advantageously preferred by gluconate. The sugar acids and in particular the salts of the sugar acids can be in solid form or in form an aqueous solution, for example in the form of a 60 to 80% by weight aqueous solution can be incorporated into the slurry. The spray to dry Slurry advantageously contains 0.5 to 15% by weight, preferably 1 to 10 % By weight and in particular 2 to 5% by weight of gluconic acid, gluconate or mixtures from these, each based on the spray-dried granules.

Die Schüttgewichte der so hergestellten Granulate können in einem breiten Rahmen variieren. Der Fachmann weiß, welche Parameteränderungen im Sprühtrocknungsprozeß zu leichteren und welche zu schwereren Granulaten führen. So können beispielsweise Granulate mit einem Schüttgewicht auch unterhalb von 550 g/l hergestellt werden. Bevorzugt ist es jedoch, daß in diesem Sprühtrocknungsverfahren Schüttgewichte von mindestens 550 g/l, vorzugsweise von mindestens 600 g/l und insbesondere von 650 bis 1000 g/l eingestellt werden, wobei diese Schüttgewichte ohne weiteres in herkömmlichen Sprühtürmen erreicht werden können.The bulk weights of the granules so produced can be in a wide range Frames vary. The person skilled in the art knows which parameter changes in the spray drying process to lighter and which lead to heavier granules. For example, granules with a bulk density can also be below of 550 g / l. However, it is preferred that in this Spray drying process Bulk weights of at least 550 g / l, preferably of at least 600 g / l and in particular from 650 to 1000 g / l be, these bulk weights easily in conventional Spray towers can be reached.

Dieses Verfahren löst dabei nicht nur die Aufgaben, einmal die Leistungen und Kapazitäten der Sprühtürme bei gleichbleibendem Energiebedarf zu erhöhen (es sind Leistungssteigerungen von 20 % und darüber möglich) und zum anderen die Verarbeitbarkeit hochkonzentrierter Slurries sicherzustellen (Aufkonzentration gegenüber dem Stand der Technik um 10 % und mehr möglich), sondern im Falle der Sprühtrocknung von Tripolyphoshat-haltigen Granulaten wird auch ein höherer Phosphaterhaltungsgrad erreicht. Ein weiterer Vorteil dieses Verfahrens besteht darin, daß Slurries, die ohne Polycarboxylatgehalt nicht versprüht werden können, da es zu Phasentrennungen kommt, und bei denen auch der Zusatz von Citrat keine Ausbildung einer homogenen Phase bewirkt, durch den Zusatz der Zuckersäuren bzw. von deren Salzen nun homogen werden und sich somit versprühen lassen. This process not only solves the tasks, but also the services and to increase the capacities of the spray towers while maintaining the same energy requirements (performance increases of 20% and above are possible) and at others to ensure the processability of highly concentrated slurries (Concentration by 10% and more possible compared to the prior art), but in the case of spray drying of tripolyphoshate-containing ones Granules also achieve a higher degree of phosphate conservation. Another Advantage of this method is that slurries that have no polycarboxylate content cannot be sprayed as there will be phase separations comes, and for which the addition of citrate no training homogeneous phase caused by the addition of the sugar acids or their Salts now become homogeneous and can thus be sprayed.

Beispiele:Examples: Beispiele M1/1:Examples M1 / 1:

Es wurde ein Granulat M1/1 der unten angegebenen Zusammensetzung mittels Sprühtrocknung hergestellt:

  • Talgfettalkohol mit 5 E0 6 Gew.-%
  • Talgfettalkohol mit 14 E0 6 Gew.-%
  • Alkylbenzolsulfonat 6 Gew.-%
  • Natriumcarbonat 37 Gew.-%
  • Natriumtripolyphosphat 30 Gew.-%
  • Natriumsilikat (Na2O:SiO2 1:3,0) 4 Gew.-%
  • Carboxymethylcellulose (CMC) und Methylcellulose (MC) 0,9 Gew.-%
  • Optischer Aufheller 0,2 Gew.-%
  • 1-Hydroxyethan-1,1-diphosphonat (HEDP) 0,3 Gew.-%
  • Wasser und Salz aus Lösungen Rest zu 100 Gew.-%
    • Granules M1 / 1 of the composition given below were produced by spray drying:
  • Tallow fatty alcohol with 5 E0 6% by weight
  • Tallow fatty alcohol with 14 E0 6% by weight
  • Alkylbenzenesulfonate 6% by weight
  • Sodium carbonate 37% by weight
  • Sodium tripolyphosphate 30% by weight
  • Sodium silicate (Na 2 O: SiO 2 1: 3.0) 4% by weight
  • Carboxymethyl cellulose (CMC) and methyl cellulose (MC) 0.9% by weight
  • Optical brightener 0.2% by weight
  • 1-hydroxyethane-1,1-diphosphonate (HEDP) 0.3% by weight
  • Water and salt from solutions 100% remainder

    • Die Konzentration des versprühten Slurries betrug 75,7 Gew.-%, die Viskosität unter Betriebsbedingungen 7400 mPas. Das erzielte Schüttgewicht betrug 600 g/l.The concentration of the sprayed slurry was 75.7% by weight and the viscosity under operating conditions 7400 mPas. The bulk density achieved was 600 g / l.

    Beispiel M1/2:Example M1 / 2:

    Das Beispiel M1/1 wurde wiederholt, wobei die Betriebsbedingungen des Sprühturms gleich blieben und 2 Gew.-%, bezogen auf das sprühgetrocknete Granulat, Natriumgluconat in fester Form (100 Gew.-%ig) im Austausch gegen Natriumcarbonat eingesetzt wurden. Die Slurry-Konzentration wurde auf 76,2 Gew.-% erhöht, die Viskosität sank auf 5000 mPas. Das Schüttgewicht der sprühgetrockneten Granulate M1/2 betrug 647 g/l.Example M1 / 1 was repeated, the operating conditions of the Spray tower remained the same and 2 wt .-%, based on the spray-dried Granules, sodium gluconate in solid form (100% by weight) in exchange for Sodium carbonate were used. The slurry concentration became 76.2 % By weight increased, the viscosity decreased to 5000 mPas. The bulk density of the spray dried granules M1 / 2 was 647 g / l.

    Beispiel M1/3:Example M1 / 3:

    Das Beispiel M1/2 wurde bei einer Slurry-Konzentration von 79,7 Gew.-% wiederholt. Die Viskosität des Slurries lag unterhalb 10000 mPas. Das Schüttgewicht der sprühgetrockneten Granulate M1/3 betrug 730 g/l.Example M1 / 2 was used at a slurry concentration of 79.7% by weight repeated. The viscosity of the slurry was below 10,000 mPas. The Bulk weight of the spray-dried granules M1 / 3 was 730 g / l.

    Beispiel M2:Example M2:

    In analoger Weise zu den Beispielen M1/1 bis M1/3 wurde ein Slurry versprüht, welcher 8,5 Gew.-% C12-C18-Fettsäureseife und 2,2 Gew.-% Alkylbenzolsulfonat, jeweils bezogen auf das sprühgetrocknete Granulat, enthielt, wobei der Anteil an nichtionischen Tensiden auf 7 Gew.-% gesenkt worden war. Die Viskosität eines 60 Gew.-%igen Slurries lag oberhalb 20000 mPas. Es fand eine Phasentrennung statt, so daß die Viskositätsmessungen fraglich erschienen. Durch die Zugabe von 2 Gew.-% Natriumcitrat, bezogen auf das sprühgetrocknete Granulat, das im Austausch gegen Natriumcarbonat eingesetzt wurde, konnte keine Aufhebung der Phasentrennung erwirkt werden.In a manner analogous to Examples M1 / 1 to M1 / 3, a slurry was sprayed which contains 8.5% by weight of C 12 -C 18 fatty acid soap and 2.2% by weight of alkylbenzenesulfonate, in each case based on the spray-dried granules, contained, the proportion of nonionic surfactants had been reduced to 7 wt .-%. The viscosity of a 60% by weight slurry was above 20,000 mPas. There was a phase separation, so that the viscosity measurements appeared questionable. By adding 2% by weight of sodium citrate, based on the spray-dried granules which were used in exchange for sodium carbonate, the phase separation could not be eliminated.

    Wurden statt Natriumcitrat Natriumgluconat in derselben Weise wie oben angegeben zugegeben, so sank die Viskosität des Slurries auf 6500 mPas. Es lag ein phasenstabiler Slurry vor, der versprüht werden konnte.Instead of sodium citrate, sodium gluconate was used in the same way as above added, the viscosity of the slurry dropped to 6500 mPas. It there was a phase-stable slurry that could be sprayed.

    Claims (5)

    1. A process for the production of spray-dried granules which may be used in particular for detergents or as a detergent component, characterized in that a slurry which contains less than 40% by weight of water but at least 1% by weight, based on the spray-dried granules, of anionic surfactants and also sugar acids or salts thereof and which has a viscosity of at most 15,000 mPas (under operating conditions) is used for spray drying.
    2. A process as claimed in claim 1, characterized in that a slurry containing polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts containing 4 to 6 carbon atoms and at least 3 hydroxy groups per molecule or mixtures of these acids and/or salts and/or polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts containing 4 to 6 carbon atoms and at least 2 hydroxy groups per molecule or mixtures of these acids and salts is used.
    3. A process as claimed in claim 1 or 2, characterized in that a slurry containing 0.2 to 20% by weight, based on the spray-dried granules, of polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts containing 4 to 6 carbon atoms, each carbon atom without a carboxyl group or keto group containing a hydroxy group, is used.
    4. A process as claimed in any of claims 1 to 3, characterized in that a slurry containing 0.5 to 15% by weight, preferably 1 to 10% by weight and more preferably 2 to 5% by weight of gluconic acid, gluconate or mixtures thereof, based on the spray-dried granules, is used.
    5. A process as claimed in any of claims 1 to 4, characterized in that a bulk density of at least 600 g/l and preferably in the range from 650 to 1,000 g/l is adjusted.
    EP95909694A 1994-02-18 1995-02-09 Process of preparing spray-dried granulates Expired - Lifetime EP0745119B1 (en)

    Applications Claiming Priority (5)

    Application Number Priority Date Filing Date Title
    DE4405125 1994-02-18
    DE4405125 1994-02-18
    DE4408502A DE4408502A1 (en) 1994-02-18 1994-03-14 Spray-dried granules with high bulk density
    DE4408502 1994-03-14
    PCT/EP1995/000465 WO1995022596A1 (en) 1994-02-18 1995-02-09 Spray-dried granulate with high apparent density

    Publications (2)

    Publication Number Publication Date
    EP0745119A1 EP0745119A1 (en) 1996-12-04
    EP0745119B1 true EP0745119B1 (en) 1999-12-08

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    ID=25933884

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP95909694A Expired - Lifetime EP0745119B1 (en) 1994-02-18 1995-02-09 Process of preparing spray-dried granulates

    Country Status (7)

    Country Link
    EP (1) EP0745119B1 (en)
    AT (1) ATE187487T1 (en)
    DK (1) DK0745119T3 (en)
    ES (1) ES2141336T3 (en)
    GR (1) GR3032349T3 (en)
    PL (1) PL180293B1 (en)
    WO (1) WO1995022596A1 (en)

    Family Cites Families (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    GB8626082D0 (en) * 1986-10-31 1986-12-03 Unilever Plc Detergent powders
    GB8806702D0 (en) * 1988-03-21 1988-04-20 Unilever Plc Detergent powders & processes for preparing them
    DE3818829A1 (en) * 1988-06-03 1989-12-14 Henkel Kgaa KOENIGES ADSORPTIONSMITTEL WITH IMPROVED SPOONING BEHAVIOR
    DE4220387A1 (en) * 1992-06-22 1993-12-23 Henkel Kgaa Granular detergent and cleaner

    Also Published As

    Publication number Publication date
    ATE187487T1 (en) 1999-12-15
    GR3032349T3 (en) 2000-04-27
    PL180293B1 (en) 2001-01-31
    DK0745119T3 (en) 2000-05-08
    PL315788A1 (en) 1996-12-09
    WO1995022596A1 (en) 1995-08-24
    EP0745119A1 (en) 1996-12-04
    ES2141336T3 (en) 2000-03-16

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