EP0745119A1 - Spray-dried granulate with high apparent density - Google Patents

Spray-dried granulate with high apparent density

Info

Publication number
EP0745119A1
EP0745119A1 EP95909694A EP95909694A EP0745119A1 EP 0745119 A1 EP0745119 A1 EP 0745119A1 EP 95909694 A EP95909694 A EP 95909694A EP 95909694 A EP95909694 A EP 95909694A EP 0745119 A1 EP0745119 A1 EP 0745119A1
Authority
EP
European Patent Office
Prior art keywords
acids
salts
spray
weight
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP95909694A
Other languages
German (de)
French (fr)
Other versions
EP0745119B1 (en
Inventor
Elmar Wilms
Thomas Merz
Chris De Jong
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ecolab GmbH and Co oHG
Original Assignee
Henkel Ecolab GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from 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
Application granted granted Critical
Publication of EP0745119B1 publication Critical patent/EP0745119B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 spray-dried granules which are particularly suitable as detergents or cleaners or for use in detergents or cleaners and have a bulk density of at least 550 g / l, and to a spray-drying process by which these heavy granules ⁇ late can be produced.
  • European spray application EP-A-0 120492 describes special spray-dried granules which achieve bulk densities of at least 550 g / 1 up to 800 g / 1 without aftertreatment of the granules, with the treatment of the porous granules with, for example, undertreatment nonionic surfactants or powdering with finely divided powders, for example zeolite powders. These granules contain ethoxylated alcohols with 12 to 24 carbon atoms and an average of 3 to 20 ethylene oxide groups.
  • the anionic surfactant content in these granules is less than 1% by weight and the soap content is less than 0.2% by weight, since this is already low Amounts of such additives in the spray drying cause the granules to swell and thus to a decrease in the desired high bulk density and in the flowability.
  • the granules are produced by a process in which a slurry with a content of 55 to 35% by weight of water (including the water adsorptively or bound as hydrate) is sprayed.
  • the water content is not below 42% by weight, since lower contents lead to a sharp increase in the viscosity of the slurry and necessitate the addition of viscosity-reducing agents such as toluene, xylene or cumene sulfonate. Slurry viscosities up to a maximum of 15000 Pas under operating conditions are considered acceptable.
  • a further object of the invention was to provide granules which contain anionic surfactants in amounts of at least 1% by weight and, if appropriate, additionally soaps in amounts of at least 0.2% by weight, and one for spray-dried products without aftertreatment mechanical and / or chemical processing have increased bulk density.
  • the invention accordingly relates in a first embodiment to spray-dried granules which can be used in particular as detergents or cleaning agents or as a component therefor, the granules containing anionic surfactants in amounts of at least 1% by weight and a bulk density of at least 550 g / 1.
  • Preferred granules have a bulk density of at least 600 g / 1, preferably from 650 to 1000 g / 1 and in particular at least 700 g / 1.
  • these granules are produced exclusively by a spray drying process.
  • Aftertreatments such as impregnation with liquid to wax-like components, for example niotene surfactants, powdering with finely divided powders or use of the granules in mixing and / or granulation or extrusion processes which may have a further densifying effect are not excluded, but are not essential to the invention.
  • the details of the bulk weights therefore always refer to the base granules obtained by spray drying.
  • the content of anionic surfactants in the granules according to the invention is preferably 1.5 to 10% by weight.
  • the granules can also be added to soaps Contain quantities of at least 0.2 wt .-%.
  • Preferred granules additionally contain about 0.5 to 15% by weight, in particular up to 10% by weight, of 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 Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, i.e. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from Ci2-C ⁇ 8 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the readily biodegradable alkanesulfonates are obtained from Ci2-Ci8-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.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), e.g. the oc-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • alkali and, in particular, the sodium salts of the sulfuric acid semiesters of the for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ⁇ o-C20 ⁇ 0- * oal- ⁇ ° h ° l e 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 1 -C 8 -alk (en) yl sulfates are particularly preferred. It can also be particularly advantageous and particularly advantageous for machine washing agents to use C 1 -C 8 -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 with relatively low washing ⁇ temperatures from, for example, room temperature to 40 ° C a low temperature Show inclination to install.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of Ci2-Ci4-fatty alkyl sulfates or Ci2-Ci8-fatty alkyl sulfates with Ciö-C j ⁇ -fatty alkyl sulfates and in particular Ci2-Ci6 -Fatty alkyl sulfates with Ci6-Ci8-fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 5 to C 22 are used.
  • the sulfuric acid monoesters of the straight-chain or branched C7 ⁇ C2i alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide (E0) or C ⁇ -Ci ⁇ - 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 from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated Ci2-C24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants and soaps can be present 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 surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the agents preferably contain, as sugar acids or salts of sugar acids, polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts having 4 to 6 carbon atoms, each carbon atom which has no carboxyl group or keto group having a hydroxyl group and / or polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts 4 to 6 carbon atoms and at least 2 hydroxyl groups per molecule or mixtures of these acids and salts.
  • Polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts, which have one keto group per molecule preferably form lactones.
  • Preferred polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts are those which contain 4 to 6 carbon atoms and have a hydroxyl group on each carbon atom which has no carboxyl group or keto 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 are particularly preferred.
  • polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts with 6 carbon atoms and 5 hydroxy groups such as D-gluconic acid (also called maltonic acid or dextronic acid) or their salts
  • Mixtures of the acids and / or the salts can also be used, the latter preferably in the form of their sodium or potassium salts.
  • polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts which contain 4 to 6 carbon atoms and have a hydroxyl group on each carbon atom which does not carry a carboxyl 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 and glucaric acid (also called saccharic acid) ) and glucaric acid salts, preferred.
  • Mixtures of acids, mono salts and / or disalts can also be used.
  • the salts are preferably used as sodium or potassium salts.
  • the particularly advantageous polyhydroxydicarboxylic acid salts therefore include the monosodium salts and disodium salts as well the monopotassium and dipotassium salts of tartaric acid, galactaric acid and D-glucaric acid.
  • the content of the spray-dried granules in sugar acids and preferably in the salts of sugar acids is preferably 0.2 to 20% by weight and in particular 0.5 to 15% by weight.
  • Spray-dried granules which contain 1 to 10% by weight and advantageously 2 to 5% by weight of gluconic acid, gluconate or mixtures thereof are particularly preferred.
  • the granules 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 household 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 residue can be methyl-branched linearly or preferably in the 2-position, or can contain linear and methyl-branched residues in the mixture, as is usually present in oxo alcohol residues.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 E0 or 4 E0, Cg-C ⁇ alcohol with 7 E0, Ci3-Ci5 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, Ci2-Ci8- Alcohols with 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of Ci2-Ci4 alcohol with 3 E0 and Ci2-Ci8 alcohol with 5 E0.
  • the degrees of ethoxylation given represent statistical mean values which can be an integer or a fraction for a special 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.
  • the ethoxylated fatty alcohols preferably used contain at least 5 EO groups on average in the molecule.
  • preferred alcohol ethoxylates also have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • tallow fatty alcohols or Ci2-Ci8 fatty alcohols with 5 to 25 EO preferably mixtures of alcohols with 5 EO and / or 7 EO and 25 EO or mixtures of alcohols with 5 EO and 14 EO.
  • Suitable alkoxylated alcohols can also be propoxylated or both ethoxylated and propoxylated. In the context of this invention, however, the only ethoxylated alcohols are preferred because of the better resulting product properties.
  • alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 ° C.
  • -Atoms means and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligo erization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • Preferred granules preferably contain inorganic or inorganic and organic builder substances.
  • the inorganic builder substances include primarily phosphates, in particular the known tripolyphosphates and zeolite.
  • the fine 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 also be produced as a spray-dried powder, but advantageously also as an undried one moist, stabilized suspension are used.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated Ci2-Ci8 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.
  • Suitable substitutes or partial substitutes for the zeolite are layer silicates of natural and synthetic origin.
  • Layered silicates of this type are known, 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 limited to a special composition or structural formula.
  • smectites, in particular bentonites, are preferred here.
  • 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, in each case based on anhydrous active substance, smaller amounts between 20 and 25% by weight in particular then can be advantageous if phosphates and zeolites are used.
  • Usable organic builders which can be used in addition to the sugar acids or their salts are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such Use for 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 of these.
  • polycarboxylates particularly citric acid or citrate, which are usually used in detergents or cleaning agents, do not bring about the desired reduction in viscosity of the slurry to be sprayed or the desired increase in the bulk density of the spray-dried granules.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of 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 of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, 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 to 55% by weight. % aqueous solutions are preferred.
  • biodegradable terpolymers for example those containing the mono salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives according to DE-A-4300772 or the monomer salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives according to DE-C-4221 381 included.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223 .
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic 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 Na2 ⁇ : Si ⁇ 2 from 1: 1 to 1: 4.5, preferably from 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 used in the commercial sector up to 50 wt .-%, in particular up to 45 wt .-% increase.
  • 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 metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and, if appropriate, a further carboxyl and / or amino group and amino acids and / or their salts.
  • the alkali metal carbonates be partially or completely replaced by glycine or glycinate.
  • the other detergent constituents which can be contained in the granules include graying inhibitors, foam inhibitors, optical brighteners, enzymes, textile-softening substances, colorants and fragrances, and 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 Ci8-C24 ⁇ 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 different foam inhibitors are also used with advantages, e.g. those made of silicones, paraffins or waxes.
  • the salts of polyphosphonic acids which are preferably used are the neutral-reacting sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate and diethylenetriapentamethylenephosphonate in amounts of 0.1 to 1.5% by weight.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Preferred Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Oxidases and peroxidases have also proven to be suitable in some cases.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures and polyvinylpyrrolidone are preferably used.
  • 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-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which contain an replace the morpholino group with a diethanola ino group, a methylamino group, an anilino group or a 2-methoxyethylarino 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.
  • the agents in addition to the usual brighteners, in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, also in small amounts, for example 10% up to 10 "3% by weight, preferably around 10" 5% by weight, of a blue dye.
  • a particularly preferred dye is Tinolu ⁇ (R) (commercial product from Ciba-Geigy).
  • the spray-dried granules are produced without bleach, bleach activator and enzymes and, if appropriate, without a foam inhibitor.
  • These ingredients of household detergents, which are known per se, can preferably be subsequently mixed with the spray-dried granules either as a raw material or in a prefabricated processing form (compound).
  • the spray-dried granules are used as basic granules for the production of detergents for the commercial sector.
  • they can be mixed with alkaline substances such as metasilicate.
  • the proportion of the spray-dried granules in detergents for household or for commercial use is preferably 40 to 90% by weight and in particular 50 to 85% by weight.
  • the invention also relates to a process for the production of spray-dried granules and in particular for the production of the above-mentioned granules according to the invention, which can be used in particular as a washing or cleaning agent or as a component therefor.
  • They are produced by spray drying a slurry which contains less than 40% by weight of water, but instead contains anionic surfactants in amounts of at least 1% by weight, based on the spray-dried granules, and also sugar acids or salts of sugar acids.
  • the viscosity of the slurry under the operating conditions should not be above 15000 mPas in order to enable the slurry to be processed safely in the tower.
  • water contents are a maximum of 35 % By weight preferred.
  • those slurries are preferably used which have a viscosity below 12000 mPas and in particular below 10000 mPas under the operating conditions. Slurries of this type are obtained if they contain polyhydroxymonocarboxylic acids or their salts, polyhydroxydicarboxylic acids or their salts or mixtures of these mono- and / or di-compounds as stated above in the amounts stated.
  • the use of the polyhydroxy ononcarboxylic acids or the polyhydroxymonocarboxylic acid salts, and in particular the use of gluconic acid and advantageously gluconate, is preferred.
  • the sugar acids and in particular the salts of the sugar acids can be incorporated into the slurry in solid form or in the form of an aqueous solution, for example in the form of a 60 to 80% by weight aqueous solution.
  • the slurry to be spray-dried 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 thereof, based in each case on the spray-dried granules.
  • the bulk weights of the granules produced in this way can vary within a wide range.
  • the person skilled in the art knows which parameter changes in the spray drying process lead to lighter ones and which lead to heavier granules.
  • granules with a bulk density below 550 g / l can also be produced.
  • This process not only solves the tasks of increasing the performance and capacities of the spray towers while maintaining the same energy requirement (performance increases of 20% and above are possible) and on the other hand ensuring the processability of highly concentrated slurries (concentration over the prior art 10% and more possible), but in the case of spray drying tripolyphoshate-containing granules, a higher degree of phosphate maintenance is also achieved.
  • a further advantage of this process is that slurries which cannot be sprayed without polycarboxylate content, since it leads to phase separation gen comes, and in which the addition of citrate does not cause a homogeneous phase, the addition of the sugar acids or their salts now become homogeneous and can thus be sprayed.
  • Granules Ml / 1 of the composition given below were produced by spray drying:
  • the concentration of the sprayed slurry was 75.7% by weight and the viscosity was 7400 mPas under operating conditions.
  • the bulk density achieved was 600 g / l.
  • Example Ml / 1 was repeated, the operating conditions of the spray tower remaining the same and 2% by weight, based on the spray-dried granules, of sodium gluconate in solid form (100% by weight) being used in exchange for sodium carbonate.
  • the slurry concentration was increased to 76.2% by weight and the viscosity decreased to 5000 mPas.
  • the bulk density of the spray-dried Ml / 2 granules was 647 g / 1.
  • Example Ml / 3 Example Ml / 2 was repeated at a slurry concentration of 79.7% by weight. The viscosity of the slurry was below 10,000 mPas. The bulk density of the spray-dried Ml / 3 granules was 730 g / 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Detergent Compositions (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Glanulating (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

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

"Sprühgetrocknetes Granulat mit hohem Schüttqewicht" "Spray-dried granules with high bulk density"
Die Erfindung betrifft ein sprühgetrocknetes Granulat, das sich insbeson¬ dere als Wasch- oder Reinigungsmittel oder zum Einsatz in Wasch- oder Rei¬ nigungsmitteln eignet und ein Schüttgewicht von mindestens 550 g/1 auf¬ weist, sowie ein Sprühtrocknungsverfahren, durch das diese schweren Granu¬ late hergestellt werden können.The invention relates to spray-dried granules which are particularly suitable as detergents or cleaners or for use in detergents or cleaners and have a bulk density of at least 550 g / l, and to a spray-drying process by which these heavy granules ¬ late can be produced.
In der europäischen Patentanmeldung EP-A-0 120492 werden spezielle sprüh¬ getrocknete Granulate beschrieben, welche Schüttgewichte von mindestens 550 g/1 bis zu 800 g/1 ohne Nachbehandlung der Granulate erreichen, wobei unter Nachbehandlung das Besprühen der porösen Granulate mit beispiels¬ weise 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 errei¬ chen, ist es essentiell, daß der Gehalt an Aniontensiden in diesen Granu¬ laten weniger als 1 Gew.-% und der Gehalt an Seife weniger als 0,2 Gew.-% beträgt, da bereits geringe Mengen an derartigen Zusätzen bei der Sprüh¬ trocknung 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 bevor¬ zugt, 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 Cumol- sulfonat erforderlich machen. Slurryviskositäten bis maximal 15000 Pas unter Betriebsbedingungen werden als akzeptabel angesehen.European spray application EP-A-0 120492 describes special spray-dried granules which achieve bulk densities of at least 550 g / 1 up to 800 g / 1 without aftertreatment of the granules, with the treatment of the porous granules with, for example, undertreatment nonionic surfactants or powdering with finely divided powders, for example zeolite powders. These granules contain ethoxylated alcohols with 12 to 24 carbon atoms and an average of 3 to 20 ethylene oxide groups. In order to achieve such a high bulk density, it is essential that the anionic surfactant content in these granules is less than 1% by weight and the soap content is less than 0.2% by weight, since this is already low Amounts of such additives in the spray drying cause the granules to swell and thus to a decrease in the desired high bulk density and in the flowability. The granules are produced by a process in which a slurry with a content of 55 to 35% by weight of water (including the water adsorptively or bound as hydrate) is sprayed. However, it is preferred that the water content is not below 42% by weight, since lower contents lead to a sharp increase in the viscosity of the slurry and necessitate the addition of viscosity-reducing agents such as toluene, xylene or cumene sulfonate. Slurry viscosities up to a maximum of 15000 Pas under operating conditions are considered acceptable.
Eine Aufgabe der Erfindung bestand darin, den Sprühtrocknungsprozeß ener¬ getisch günstiger zu gestalten oder eine Leistungssteigerung der Sprüh¬ türme 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 ög- lieh war. Außerdem sollte auf Zusätze wie Toluol-, Xylol- oder Cumolsul- fonat 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.It was an object of the invention to make the spray drying process more energy-efficient or to increase the performance of the spray towers and thus to increase the capacity of the existing plants while maintaining the same energy requirement. For this, it should be possible to spray slurries with a higher concentration. However, these slurries were not allowed to have such high viscosities that spraying was no longer possible. was borrowed. In addition, it should be possible to dispense with additives such as toluene, xylene or cumene sulfonate as customary agents for lowering the viscosity. A further object of the invention was to provide granules which contain anionic surfactants in amounts of at least 1% by weight and, if appropriate, additionally soaps in amounts of at least 0.2% by weight, and one for spray-dried products without aftertreatment mechanical and / or chemical processing have increased bulk density.
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 Reini¬ gungsmitteln sind und dort insbesondere als Cobuilder eingesetzt werden.It has now been found that more concentrated slurries can be sprayed in conventional spray towers if they contain certain additional substances, but which are already known ingredients of detergents or cleaners and are used there in particular as cobuilders.
Gegenstand der Erfindung ist dementsprechend in einer ersten Ausführungs¬ form ein sprühgetrocknetes Granulat, welches insbesondere als Wasch- oder Reinigungsmittel oder als Komponente hierfür eingesetzt werden kann, wobei das Granulat anionische Tenside in Mengen von mindestens 1 Gew.-% enthält sowie ein Schüttgewicht von mindestens 550 g/1 aufweist.The invention accordingly relates in a first embodiment to spray-dried granules which can be used in particular as detergents or cleaning agents or as a component therefor, the granules containing anionic surfactants in amounts of at least 1% by weight and a bulk density of at least 550 g / 1.
Bevorzugte Granulate weisen dabei ein Schüttgewicht von mindestens 600 g/1, vorzugsweise von 650 bis 1000 g/1 und insbesondere von mindestens 700 g/1 auf. Wenn im Rahmen dieser Erfindung von sprühgetrockneten Granulaten mit hohen Schüttgewichten, insbesondere mit Schüttgewichten von mindestens 700 g/1, gesprochen wird, so werden diese Granulate ausschließlich durch einen Sprühtrocknungsprozeß hergestellt. Nachbehandlungen wie Imprägnie¬ rungen mit flüssigen bis wachsartigen Komponenten, beispielsweise Nioten- siden, 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.Preferred granules have a bulk density of at least 600 g / 1, preferably from 650 to 1000 g / 1 and in particular at least 700 g / 1. When spray-dried granules with high bulk densities, in particular with bulk densities of at least 700 g / l, are used in the context of this invention, these granules are produced exclusively by a spray drying process. Aftertreatments such as impregnation with liquid to wax-like components, for example niotene surfactants, powdering with finely divided powders or use of the granules in mixing and / or granulation or extrusion processes which may have a further densifying effect are not excluded, but are not essential to the invention. The details of the bulk weights therefore always refer to the base granules obtained by spray drying.
Der Gehalt der erfindungsgemäßen 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 content of anionic surfactants in the granules according to the invention, such as customary 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 .-%. Preferred granules additionally contain about 0.5 to 15% by weight, in particular up to 10% by weight, of 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 Cg-Ci3-Alkylbenzolsulfonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus Ci2-Cχ8-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sul- fonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus Ci2-Ci8-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neu¬ tralisation gewonnen werden. Die biologisch gut abbaubaren Alkansulfonate werden aus Ci2-Ci8-Alkanen beispielsweise durch Sulfochlorierung oder Sul¬ foxidation 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 oc-sulfo- nierten Methylester der hydrierten Kokos-, Palmkern- oder Taigfettsäuren.Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, i.e. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from Ci2-Cχ8 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The readily biodegradable alkanesulfonates are obtained from Ci2-Ci8-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. Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), e.g. the oc-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 beispielsweise aus Kokosfettalkohol, Taigfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stea- rylalkohol oder der Cιo-C20~0-*oal-<°h°le und diejenigen Halbester sekundä¬ rer 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 Inter¬ esse sind Ciö-Ci8-Alk(en)ylsulfate insbesondere bevorzugt. Dabei kann es auch von besonderem Vorteil und insbesondere für maschinelle Waschmittel von Vorteil sein, Cι§-Ci8-Alk(en)ylsulfate in Kombination mit niedriger schmelzenden Aniontensiden und insbesondere mit solchen Aniontensiden, die einen niedrigeren Krafft-Punkt aufweisen und bei relativ niedrigen Wasch¬ temperaturen von beispielsweise Raumtemperatur bis 40 °C eine geringe Kri- stallisationsneigung zeigen, einzusetzen. In einer bevorzugten Ausfüh¬ rungsform der Erfindung enthalten die Mittel daher Mischungen aus kurz- kettigen und langkettigen Fettalkylsulfaten, vorzugsweise Mischungen aus Ci2-Ci4-Fettalkylsulfaten oder Ci2-Ci8-Fettalkylsulfaten mit Ciö-Cjβ-Fett- alkylsulfaten und insbesondere Ci2-Ci6-Fettalkylsulfaten mit Ci6-Ci8-Fett- alkylsulfaten. In einer weiteren bevorzugten Ausführungsform der Erfindung werden jedoch nicht nur gesättigte Alkylsulfate, sondern auch ungesättigte Alkenylsulfate mit einer Alkenylkettenlänge von vorzugsweise C 5 bis C22 eingesetzt. Dabei sind insbesondere Mischungen aus gesättigten, überwie¬ gend aus Ciö bestehenden sulfierten Fettalkoholen und ungesättigten, über¬ wiegend aus Ci8 bestehenden sulfierten Fettalkoholen bevorzugt, beispiels¬ weise 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 Schwefelsäure¬ monoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7~C2i-Alkohole, wie 2-Methyl-verzweigte Cg-Cn-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (E0) oder C^-Ciδ-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.The alkali and, in particular, the sodium salts of the sulfuric acid semiesters of the for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Cιo-C20 ~ 0- * oal- <° h ° l e 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. From the point of view of washing technology, C 1 -C 8 -alk (en) yl sulfates are particularly preferred. It can also be particularly advantageous and particularly advantageous for machine washing agents to use C 1 -C 8 -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 with relatively low washing ¬ temperatures from, for example, room temperature to 40 ° C a low temperature Show inclination to install. In a preferred embodiment of the invention, the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of Ci2-Ci4-fatty alkyl sulfates or Ci2-Ci8-fatty alkyl sulfates with Ciö-C j β-fatty alkyl sulfates and in particular Ci2-Ci6 -Fatty alkyl sulfates with Ci6-Ci8-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 5 to C 22 are used. Mixtures of saturated sulfated fatty alcohols consisting predominantly of Ciö and unsaturated, predominantly consisting of Ci8 sulfated fatty alcohols are particularly preferred, for example those which are derived from solid or liquid fatty alcohol mixtures of the HD-Ocenol ( R ) type (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 C7 ~ C2i alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide (E0) or C ^ -Ciδ- 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, hy¬ drierte Erucasäure und Behensäure sowie insbesondere aus natürlichen Fett¬ säuren, z.B. Kokos-, Palmkern- oder Taigfettsäuren, abgeleitete Seifenge¬ mische. Insbesondere sind solche Seifengemische bevorzugt, die zu 50 bis 100 Gew.-% aus gesättigten Ci2-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 from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated Ci2-C24 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. Als Zuckersäuren bzw. Salze von Zuckersäuren enthalten die Mittel vorzugs¬ weise Polyhydroxymonocarbonsäuren bzw. Polyhydroxymonocarbonsäuresalze mit 4 bis 6 Kohlenstoffatomen, wobei jedes Kohlenstoffatom, welches keine Car- boxylgruppe 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 Mi¬ schungen aus diesen Säuren und Salzen. Dabei bilden Polyhydroxymonocarbon¬ säuren bzw. Polyhydroxymonocarbonsäuresalze, welche eine Ketogruppe pro Molekül aufweisen, vorzugsweise Lactone. Bevorzugte Polyhydroxymonocarbon¬ säuren bzw. Polyhydroxymonocarbonsäuresalze sind solche, die 4 bis 6 Koh¬ lenstoffatome enthalten und an jedem Kohlenstoffatom, das keine Carboxyl- gruppe oder Ketogruppe trägt, eine Hydroxy-Gruppe aufweisen. Insbesondere sind dabei Polyhydroxymonocarbonsäuren bzw. und Polyhydroxymonocarbonsäu- resalze mit 4 Kohlenstoffatomen und 3 Hydroxy-Gruppen, mit 5 Kohlenstoff¬ atomen und 4 Hydroxygruppen und mit 6 Kohlenstoffatomen und 4 oder 5 Hy¬ droxy-Gruppen bevorzugt. Besonders vorteilhafte Eigenschaften weisen Poly¬ hydroxymonocarbonsäuren bzw. Polyhydroxymonocarbonsäuresalze mit 6 Kohlen¬ stoffatomen und 5 Hydroxy-Gruppen, wie D-Gluconsäure (auch Maltonsäure oder Dextronsäure genannt) bzw. deren Salze, und Polyhydroxymonocarbon¬ säuren bzw. Polyhydroxy onocarbonsäuresalze mit 6 Kohlenstoffatomen, einer Ketogruppe und 4 Hydroxy-Gruppen, wie L-Ascorbinsäure, die als Lacton vor¬ liegt, und L-Ascorbinsäuresalze auf. Dabei können auch Mischungen der Säu¬ ren und/oder der Salze eingesetzt werden, letztere vorzugsweise in Form ihrer Natrium- oder Kaliumsalze. Weiterhin bevorzugt sind jedoch auch Po¬ lyhydroxydicarbonsäuren bzw. Polyhydroxydicarbonsäuresalze, welche 4 bis 6 Kohlenstoffatome enthalten und an jedem Kohlenstoffatom, das keine Carbo- xylgruppe 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 Glucar- säure (auch Saccharinsäure genannt) und Glucarsäuresalze, bevorzugt. Dabei können auch Mischungen der Säuren, der Monosalze und/oder der Disal- ze eingesetzt werden. Die Salze werden vorzugsweise als Natrium- oder Kaliumsalze eingesetzt. Zu den besonders vorteilhaften Polyhydroxydicar- bonsäuresalzen gehören daher die Mononatriumsalze und Dinatriumsalze sowie die Monokalium- und Dikaliumsalze der Weinsäure, der Galactarsäure und der D-Glucarsäure.The anionic surfactants and soaps can be present 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 surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts. The agents preferably contain, as sugar acids or salts of sugar acids, polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts having 4 to 6 carbon atoms, each carbon atom which has no carboxyl group or keto group having a hydroxyl group and / or polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts 4 to 6 carbon atoms and at least 2 hydroxyl groups per molecule or mixtures of these acids and salts. Polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts, which have one keto group per molecule, preferably form lactones. Preferred polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts are those which contain 4 to 6 carbon atoms and have a hydroxyl group on each carbon atom which has no carboxyl group or keto 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 are particularly preferred. Particularly advantageous properties are shown by polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts with 6 carbon atoms and 5 hydroxy groups, such as D-gluconic acid (also called maltonic acid or dextronic acid) or their salts, and polyhydroxymonocarboxylic acids or polyhydroxy onocarboxylic acid salts with 6 carbon atoms, one Keto group and 4 hydroxyl groups, such as L-ascorbic acid, which is present as lactone, and L-ascorbic acid salts. Mixtures of the acids and / or the salts can also be used, the latter preferably in the form of their sodium or potassium salts. However, further preferred are also polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts which contain 4 to 6 carbon atoms and have a hydroxyl group on each carbon atom which does not carry a carboxyl group. In particular, 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 and glucaric acid (also called saccharic acid) ) and glucaric acid salts, preferred. Mixtures of acids, mono salts and / or disalts can also be used. The salts are preferably used as sodium or potassium salts. The particularly advantageous polyhydroxydicarboxylic acid salts therefore include the monosodium salts 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 vorzugs¬ weise an den Salzen der Zuckersäuren beträgt dabei vorzugsweise 0,2 bis 20 Gew.-% und insbesondere 0,5 bis 15 Gew.-%. Besonders bevorzugt sind dabei sprühgetrocknete Granulate, 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 in the salts of sugar acids is preferably 0.2 to 20% by weight and in particular 0.5 to 15% by weight. Spray-dried granules which contain 1 to 10% by weight and advantageously 2 to 5% by weight of gluconic acid, gluconate or mixtures thereof are particularly preferred.
Die erfindungsgemäßen Granulate können noch weitere Inhaltsstoffe enthal¬ ten, 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 nichtio¬ nische 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 vor¬ zugsweise alkoxylierte, vorteilhafterweise flüssige ethoxylierte, insbe¬ sondere 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 Oxoalkohol- resten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen bevorzugt, z.B. aus Kokos-, Palm-, Taigfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 E0 pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise Ci2-Ci4-Alkohole mit 3 E0 oder 4 E0, Cg- Cπ-Alkohol mit 7 E0, Ci3-Ci5-Alkohole mit 3 E0, 5 E0, 7 E0 oder 8 E0, Ci2-Ci8-Alkohole mit 3 E0, 5 E0 oder 7 E0 und Mischungen aus diesen, wie Mischungen aus Ci2-Ci4-Alkohol mit 3 E0 und Ci2-Ci8-Alkohol mit 5 E0. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein kön¬ nen. Weitere bevorzugte Niotenside sind dabei insbesondere Talgfettalko- hole mit bis zu 80 E0, vorzugsweise Taigfettalkohole 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 Wasserdampf¬ flüchtigkeit von nicht-umgesetzten Alkohol und niedrigethoxylierten Alko¬ holen hervorgerufen wird, enthalten die bevorzugt eingesetzten ethoxylier¬ ten Fettalkohole mindestens durchschnittlich 5 EO-Gruppen im Molekül. Be¬ vorzugte Alkoholethoxylate weisen aus demselben Grund auch eine eingeengte HomologenVerteilung auf (narrow ränge ethoxylates, NRE). Insbesondere be¬ vorzugt werden Taigfettalkohole oder Ci2-Ci8-Fettalkohole mit 5 bis 25 EO, vorzugsweise Mischungen aus Alkoholen mit 5 EO und/oder 7 EO und 25 EO oder Mischungen aus Alkoholen mit 5 EO und 14 EO.The granules 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 household 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 residue can be methyl-branched linearly or preferably in the 2-position, or can contain linear and methyl-branched residues in the mixture, as is usually present in oxo alcohol residues. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 E0 or 4 E0, Cg-Cπ alcohol with 7 E0, Ci3-Ci5 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, Ci2-Ci8- Alcohols with 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of Ci2-Ci4 alcohol with 3 E0 and Ci2-Ci8 alcohol with 5 E0. The degrees of ethoxylation given represent statistical mean values which can be an integer or a fraction for a special 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 with the Spray drying of ethoxylated alcohols, which is caused by the water vapor volatility of unreacted alcohol and low-ethoxylated alcohols, the ethoxylated fatty alcohols preferably used contain at least 5 EO groups on average in the molecule. For the same reason, preferred alcohol ethoxylates also have a narrow homolog distribution (narrow range ethoxylates, NRE). Particularly preferred are tallow fatty alcohols or Ci2-Ci8 fatty alcohols with 5 to 25 EO, preferably mixtures of alcohols with 5 EO and / or 7 EO and 25 EO or mixtures of alcohols with 5 EO and 14 EO.
Geeignete alkoxylierte Alkohole können auch propoxyliert oder sowohl eth- oxyliert als auch propoxyliert sein. Im Rahmen dieser Erfindung sind je¬ doch die nur ethoxylierten Alkohole aufgrund der besseren resultierenden Produkteigenschaften bevorzugt. Der Gehalt der Granulate an ethoxylierten Alkoholen, insbesondere an Taigfettalkoholen mit 5 bis 25 EO, beträgt ins¬ besondere 10 bis 15 Gew.-%.Suitable alkoxylated alcohols can also be propoxylated or both ethoxylated and propoxylated. In the context of this invention, however, the only ethoxylated alcohols are preferred because of the better resulting product properties. The content of the granules in ethoxylated alcohols, in particular tallow fatty alcohols with 5 to 25 EO, is in particular 10 to 15% by weight.
Außerdem können als weitere nichtionische Tenside auch Alkylglykoside der allgemeinen Formel R0(G)x eingesetzt werden, in der R einen primären ge¬ radkettigen oder methylverzweigten, insbesondere in 2-Stellung methylver¬ zweigten 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 Oligo erisierungsgrad 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 R0 (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 ° C. -Atoms means and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligo erization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
Bevorzugte Granulate enthalten dabei vorzugsweise noch anorganische oder anorganische und organische Buildersubstanzen. Zu den anorganischen Buil- dersubstanzen zählen dabei erster Linie Phosphate, insbesondere die be¬ kannten Tripolyphosphate und Zeolith.Preferred granules preferably contain inorganic or inorganic and organic builder substances. The inorganic builder substances include primarily phosphates, in particular the known tripolyphosphates and zeolite.
Der eingesetzte feinkristalline, synthetische und gebundenes Wasser ent¬ haltende Zeolith ist vorzugsweise Zeolith NaA in Waschmittelqualität. Ge¬ eignet 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 Ci2-Ci8-Fettalkoholen mit 2 bis 5 Ethylenoxidgruppen oder ethoxylierte Isotridecanole. Geeignete Zeolithe weisen eine mittlere Teilchengröße von weniger als 10 μm (Volu¬ menverteilung; Meßmethode: Coulter Counter) auf und enthalten vorzugsweise 18 bis 22, insbesondere 20 bis 22 Gew.-% an gebundenem Wasser.The fine 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 also be produced as a spray-dried powder, but advantageously also as an undried one moist, stabilized suspension are used. 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 Ci2-Ci8 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 Schichtsi¬ likate 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.Suitable substitutes or partial substitutes for the zeolite are layer silicates of natural and synthetic origin. Layered silicates of this type are known, 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 limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here.
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 kön¬ nen, 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, in each case based on anhydrous active substance, smaller amounts between 20 and 25% by weight in particular then can be advantageous if phosphates and zeolites are used.
Brauchbare organische Gerüstsubstanzen, die zusätzlich zu den Zuckersäuren bzw. deren Salzen eingesetzt werden können, sind beispielsweise die be¬ vorzugt in Form ihrer Natriumsalze eingesetzten Polycarbonsäuren wie Ci- tronensäure, 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 be¬ achten, daß diese üblicherweise in Wasch- oder Reinigungsmitteln einge¬ setzten Polycarboxylate, insbesondere Citronensäure bzw. Citrat, weder die gewünschte Viskositätserniedrigung des zu versprühenden Slurries noch die gewünschte Schüttgewichtserhöhung der sprühgetrockneten Granulate bewirkt. 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). Ge¬ eignete 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 Malein¬ säure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Ma¬ leinsäure 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 Mono ere Salze der Acrylsäure und der Maleinsäure sowie Vinylalkohol bzw. Vinylalkohol-Derivate gemäß DE-A-4300772 oder die als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zucker-Derivate gemäß DE-C-4221 381 enthalten.Usable organic builders which can be used in addition to the sugar acids or their salts are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such Use for 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 of these. It should be noted that these polycarboxylates, particularly citric acid or citrate, which are usually used in detergents or cleaning agents, do not bring about the desired reduction in viscosity of the slurry to be sprayed or the desired increase in the bulk density of the spray-dried granules. Suitable polymeric polycarboxylates are, for example, the sodium salts of 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 of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, 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 to 55% by weight. % aqueous solutions are preferred. Also particularly preferred are biodegradable terpolymers, for example those containing the mono salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives according to DE-A-4300772 or the monomer salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives according to DE-C-4221 381 included.
Weitere geeignete Buildersubstanzen sind Polyacetale, welche durch Umset¬ zung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 C-Atome und mindestens 3 Hydroxylgruppen aufweisen, beispielsweise wie in der euro¬ päischen Patentanmeldung EP-A-0 280 223 beschrieben erhalten werden kön¬ nen. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutar- aldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäu¬ ren wie Gluconsäure und/oder Glucoheptonsäure erhalten.Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223 . Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
Weitere geeignete Inhaltsstoffe der Granulate sind wasserlösliche anorga¬ nische Salze wie Bicarbonate, Carbonate, amorphe Silikate oder Mischungen aus diesen; insbesondere werden Alkalicarbonat und amorphes Alkalisilikat, vor allem Natriumsilikat mit einem molaren Verhältnis Na2θ : Siθ2 von 1:1 bis 1:4,5, vorzugsweise von 1:2 bis 1:3,5, eingesetzt. Der Gehalt der Gra¬ nulate an Natriu carbonat beträgt dabei vorzugsweise bis zu 20 Gew.-%, vorteilhafterweise zwischen 5 und 15 Gew.-%, wenn die Granulate im Haus¬ halt verwendet werden sollen, und kann im gewerblichen Bereich auf vor¬ zugsweise 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 Na2θ: Siθ2 from 1: 1 to 1: 4.5, preferably from 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 used in the commercial sector up to 50 wt .-%, in particular up to 45 wt .-% increase. 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 Erfin¬ dung ist es dabei bevorzugt, daß ein teilweiser bis vollständiger Aus¬ tausch der Alkalicarbonate durch Glycin bzw. Glycinat erfolgt.According to the teaching of the older German patent application P 43 19 578.4, alkali metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and, if appropriate, a further carboxyl and / or amino group and amino acids and / or their salts. In the context of this invention, it is preferred that the alkali metal carbonates be partially or completely replaced by glycine or glycinate.
Zu den sonstigen Waschmittelbestandteilen, die in den Granulaten enthalten sein können, zählen Vergrauungsinhibitoren, Schauminhibitoren, optische Aufheller, Enzyme, textilweichmachende Stoffe, Färb- und Duftstoffe sowie Neutralsalze wie Sulfate und Chloride in Form ihrer Natrium- oder Kalium¬ salze.The other detergent constituents which can be contained in the granules include graying inhibitors, foam inhibitors, optical brighteners, enzymes, textile-softening substances, colorants and fragrances, and 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 Ci8-C24~Fettsäuren aufweisen. Geeignete nichttensid- artige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, ggf. silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kiesel¬ säure oder Bistearylethylendiamid. Mit Vorteilen werden auch Gemische aus verschiedenen Schauminhibitoren verwendet, z.B. solche aus Silikonen, Pa¬ raffinen 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 Ci8-C24 ~ 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 different foam inhibitors are also used with advantages, e.g. those made of silicones, paraffins or waxes.
Als Salze von Polyphosphonsäuren werden vorzugsweise die neutral reagie¬ renden Natriumsalze von beispielsweise l-Hydroxyethan-l,l-diphosphonat und Diethylentria inpentamethylenphosphonat in Mengen von 0,1 bis 1,5 Gew.-% verwendet.The salts of polyphosphonic acids which are preferably used are the neutral-reacting sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate and diethylenetriapentamethylenephosphonate in amounts of 0.1 to 1.5% by weight.
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 lichenifor- mis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Vorzugs- weise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Dabei sind Enzymmischun¬ gen, 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 je¬ doch 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.Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Preferred Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Oxidases and peroxidases have also proven to be suitable in some cases. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, 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 ver¬ hindern. Hierzu sind wasserlösliche Kolloide meist organischer Natur ge¬ eignet, 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 Carboxymethylcellu¬ lose, Methylcellulose, Hydroxyalkylcellulose und Mischether, wie Methyl- hydroxyethy1cel1u1ose, Methylhydroxypropy1cel1ulose, Methylcarboxymethyl- cellulose und deren Gemische sowie Polyvinylpyrrolidon eingesetzt.Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures and polyvinylpyrrolidone are preferably used.
Die Mittel können als optische Aufheller Derivate der Diaminostilbendi- sulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z.B. Salze der 4,4'-Bis(2-anilino-4-morpholino-l,3,5-triazinyl-6-amino)stil- ben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die an¬ stelle der Morpholino-Gruppe eine Diethanola inogruppe, eine Methylamino- gruppe, eine Anilinogruppe oder eine 2-Methoxyethylarπinogruppe 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 er- halten 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"^ bis 10"3 Gew.-%, vorzugsweise um 10"5 Gew.-%, eines blauen Farbstoffs enthalten. Ein besonders bevorzugter Farbstoff ist Tinoluχ(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-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which contain an replace the morpholino group with a diethanola ino group, a methylamino group, an anilino group or a 2-methoxyethylarino 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 was found that uniform white granules will hold if the agents, in addition to the usual brighteners, in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, also in small amounts, for example 10% up to 10 "3% by weight, preferably around 10" 5% by weight, of a blue dye. A particularly preferred dye is Tinoluχ (R) (commercial product from Ciba-Geigy).
In einer bevorzugten Ausführungsform der Erfindung werden die sprühge¬ trockneten Granulate jedoch ohne Bleichmittel, Bleichaktivator und Enzyme sowie gegebenenfalls ohne Schauminhibitor hergestellt. Diese an sich üb¬ lichen Inhaltsstoffe von Haushaltswaschmitteln können vorzugsweise nach¬ träglich entweder als Rohstoff oder in einer vorkonfektionierten Verarbei¬ tungsform (Co pound) mit den sprühgetrockneten Granulaten vermischt wer¬ den.In a preferred embodiment of the invention, however, the spray-dried granules are produced without bleach, bleach activator and enzymes and, if appropriate, without a foam inhibitor. These ingredients of household detergents, which are known per se, can preferably be subsequently mixed with the spray-dried granules either as a raw material or in a prefabricated processing form (compound).
In einer weiteren bevorzugten Ausführungsform der Erfindung werden die sprühgetrockneten Granulate als Basisgranulate zur Herstellung von Wasch¬ mitteln für den gewerblichen Bereich eingesetzt. Sie können dabei bei¬ spielsweise mit alkalischen Stoffen wie Metasilikat vermischt werden.In a further preferred embodiment of the invention, the spray-dried granules are used as basic granules for the production of detergents for the commercial sector. For example, they can be mixed with alkaline substances such as metasilicate.
Der Anteil des sprühgetrockneten Granulats in Waschmitteln für den Haus¬ halt oder für den gewerblichen Bereich beträgt dabei vorzugsweise 40 bis 90 Gew.-% und insbesondere 50 bis 85 Gew.-%.The proportion of the spray-dried granules in detergents for household or for commercial use is preferably 40 to 90% by weight and in particular 50 to 85% by weight.
Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung von sprüh¬ getrockneten Granulaten und insbesondere zur Herstellung der obengenannten erfindungsgemäßen Granulate, die insbesondere als Wasch- oder Reinigungs¬ mittel oder als Komponente hierfür eingesetzt werden können. Die Herstel¬ lung erfolgt 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 si¬ cheres Verarbeiten des Slurries im Turm zu ermöglichen. Im Rahmen der vor¬ liegenden Erfindung ist es möglich und daher auch bevorzugt, den Wasser¬ gehalt 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 Betriebsbedin¬ gungen eine Viskosität unterhalb 12000 mPas und insbesondere unterhalb 10000 mPas aufweisen. Derartige Slurries werden erhalten, wenn sie erfin¬ dungsgemäß Polyhydroxymonocarbonsäuren bzw. deren Salze, Polyhydroxydi¬ carbonsäuren 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 Polyhydroxy ononcarbonsäuren bzw. der Polyhydroxymonocarbonsäuresalze und insbesondere der Einsatz von Glucon- säure 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 Mischun¬ gen aus diesen, jeweils bezogen auf die sprühgetrockneten Granulate.The invention also relates to a process for the production of spray-dried granules and in particular for the production of the above-mentioned granules according to the invention, which can be used in particular as a washing or cleaning agent or as a component therefor. They are produced by spray drying a slurry which contains less than 40% by weight of water, but instead contains anionic surfactants in amounts of at least 1% by weight, based on the spray-dried granules, and also sugar acids or salts of sugar acids. the viscosity of the slurry under the operating conditions should not be above 15000 mPas in order to enable the slurry to be processed safely in the tower. In the context of the present invention, it is possible and therefore also preferred to further reduce the water content of the slurry. So water contents are a maximum of 35 % By weight preferred. In a further embodiment of the invention, those slurries are preferably used which have a viscosity below 12000 mPas and in particular below 10000 mPas under the operating conditions. Slurries of this type are obtained if they contain polyhydroxymonocarboxylic acids or their salts, polyhydroxydicarboxylic acids or their salts or mixtures of these mono- and / or di-compounds as stated above in the amounts stated. However, the use of the polyhydroxy ononcarboxylic acids or the polyhydroxymonocarboxylic acid salts, and in particular the use of gluconic acid and advantageously gluconate, is preferred. The sugar acids and in particular the salts of the sugar acids can be incorporated into the slurry in solid form or in the form of an aqueous solution, for example in the form of a 60 to 80% by weight aqueous solution. The slurry to be spray-dried 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 thereof, based in each case on the spray-dried granules.
Die Schüttgewichte der so hergestellten Granulate können in einem breiten Rahmen variieren. Der Fachmann weiß, welche Parameteränderungen im Sprüh¬ trocknungsprozeß zu leichteren und welche zu schwereren Granulaten führen. So können beispielsweise Granulate mit einem Schüttgewicht auch unterhalb von 550 g/1 hergestellt werden. Bevorzugt ist es jedoch, daß in diesem Sprühtrocknungsverfahren Schüttgewichte von mindestens 550 g/1, vorzugs¬ weise von mindestens 600 g/1 und insbesondere von 650 bis 1000 g/1 einge¬ stellt werden, wobei diese Schüttgewichte ohne weiteres in herkömmlichen Sprühtürmen erreicht werden können.The bulk weights of the granules produced in this way can vary within a wide range. The person skilled in the art knows which parameter changes in the spray drying process lead to lighter ones and which lead to heavier granules. For example, granules with a bulk density below 550 g / l can also be produced. However, it is preferred that in this spray drying process bulk densities of at least 550 g / 1, preferably at least 600 g / 1 and in particular from 650 to 1000 g / 1 are set, these bulk weights being easily achieved in conventional spray towers can.
Dieses Verfahren löst dabei nicht nur die Aufgaben, einmal die Leistungen und Kapazitäten der Sprühtürme bei gleichbleibendem Energiebedarf zu er¬ höhen (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 mög¬ lich), sondern im Falle der Sprühtrocknung von Tripolyphoshat-haltigen Granulaten wird auch ein höherer Phosphaterhaltungsgrad erreicht. Ein wei¬ terer Vorteil dieses Verfahrens besteht darin, daß Slurries, die ohne Po- lycarboxylatgehalt nicht versprüht werden können, da es zu Phasentrennun- gen 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 of increasing the performance and capacities of the spray towers while maintaining the same energy requirement (performance increases of 20% and above are possible) and on the other hand ensuring the processability of highly concentrated slurries (concentration over the prior art 10% and more possible), but in the case of spray drying tripolyphoshate-containing granules, a higher degree of phosphate maintenance is also achieved. A further advantage of this process is that slurries which cannot be sprayed without polycarboxylate content, since it leads to phase separation gen comes, and in which the addition of citrate does not cause a homogeneous phase, the addition of the sugar acids or their salts now become homogeneous and can thus be sprayed.
Beispiele:Examples:
Beispiele Ml/1:Examples Ml / 1:
Es wurde ein Granulat Ml/1 der unten angegebenen Zusammensetzung mittels Sprühtrocknung hergestellt:Granules Ml / 1 of the composition given below were produced by spray drying:
Taigfettalkohol mit 5 EO 6 Gew.-Daily fat alcohol with 5 EO 6 wt.
Taigfettalkohol mit 14 EO 6 Gew.-%Taig fat alcohol with 14 EO 6 wt .-%
Alkylbenzolsulfonat 6 Gew.-%Alkylbenzenesulfonate 6% by weight
Natriumcarbonat 37 Gew.-%Sodium carbonate 37% by weight
Natriu tripolyphosphat 30 Gew.-%Sodium tripolyphosphate 30% by weight
Natriumsilikat (Na2θ:Siθ2 1:3,0) 4 Gew.-%Sodium silicate (Na2θ: Siθ2 1: 3.0) 4% by weight
Carboxymethylcellulose (CMC) und Methylcellulose (MC) 0,9 Gew.-%Carboxymethyl cellulose (CMC) and methyl cellulose (MC) 0.9% by weight
Optischer Aufheller 0,2 Gew.-%Optical brightener 0.2% by weight
1-Hydroxyethan-l.l-diphosphonat (HEDP) 0,3 Gew.-%1-hydroxyethane-l. L-diphosphonate (HEDP) 0.3% by weight
Wasser und Salz aus Lösungen Rest zu 100 Gew.-%Water and salt from solutions 100% remainder
Die Konzentration des versprühten Slurries betrug 75,7 Gew.-%, die Visko¬ sität unter Betriebsbedingungen 7400 mPas. Das erzielte Schüttgewicht be¬ trug 600 g/1.The concentration of the sprayed slurry was 75.7% by weight and the viscosity was 7400 mPas under operating conditions. The bulk density achieved was 600 g / l.
Beispiel Ml/2:Example Ml / 2:
Das Beispiel Ml/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 Ml/2 betrug 647 g/1.Example Ml / 1 was repeated, the operating conditions of the spray tower remaining the same and 2% by weight, based on the spray-dried granules, of sodium gluconate in solid form (100% by weight) being used in exchange for sodium carbonate. The slurry concentration was increased to 76.2% by weight and the viscosity decreased to 5000 mPas. The bulk density of the spray-dried Ml / 2 granules was 647 g / 1.
Beispiel Ml/3: Das Beispiel Ml/2 wurde bei einer Slurry-Konzentration von 79,7 Gew.-% wiederholt. Die Viskosität des Slurries lag unterhalb 10000 mPas. Das Schüttgewicht der sprühgetrockneten Granulate Ml/3 betrug 730 g/1.Example Ml / 3: Example Ml / 2 was repeated at a slurry concentration of 79.7% by weight. The viscosity of the slurry was below 10,000 mPas. The bulk density of the spray-dried Ml / 3 granules was 730 g / 1.
Beispiel M2:Example M2:
In analoger Weise zu den Beispielen Ml/1 bis Ml/3 wurde ein Slurry ver¬ sprüht, welcher 8,5 Gew.-% Cχ2-Ci8-Fettsäureseife und 2,2 Gew.-% Alkylben- zolsulfonat, 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 frag¬ lich erschienen. Durch die Zugabe von 2 Gew.-% Natriumcitrat, bezogen auf das sprühgetrocknete Granulat, das im Austausch gegen Natriumcarbonat ein¬ gesetzt wurde, konnte keine Aufhebung der Phasentrennung erwirkt werden.In a manner analogous to Examples Ml / 1 to Ml / 3, a slurry was sprayed containing 8.5% by weight of Cχ2-Ci8 fatty acid soap and 2.2% by weight of alkylbenzenesulfonate, based in each case 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. If sodium gluconate was added instead of sodium citrate in the same way as stated above, the viscosity of the slurry dropped to 6500 mPas. There was a phase-stable slurry that could be sprayed.

Claims

Patentansprüche claims
1. Sprühgetrocknetes Granulat, welches insbesondere als Wasch- oder Rei¬ nigungsmittel oder als Komponente hierfür eingesetzt werden kann, wo¬ bei das Granulat anionische Tenside in Mengen von mindestens 1 Gew.-% enthält sowie ein Schüttgewicht von mindestens 550 g/1 aufweist.1. Spray-dried granules, which can be used in particular as detergents or cleaning agents or as a component therefor, the granules containing anionic surfactants in amounts of at least 1% by weight and having a bulk density of at least 550 g / l.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß es Alkylbenzol- sulfonate und/oder Alkyl(ether)sulfate in Mengen von 1,5 bis 10 Gew.-% enthält.2. Composition according to claim 1, characterized in that it contains alkylbenzene sulfonates and / or alkyl (ether) sulfates in amounts of 1.5 to 10 wt .-%.
3. Mittel nach Anpruch 1 oder 2, dadurch gekennzeichnet, daß es Seifen in Mengen von mindestens 0,2 Gew.-% enthält, wobei bevorzugte Granulate 0,5 bis 15 Gew.-%, insbesondere bis 10 Gew.-% an Fettsäureseifen bzw. natürlichen Fettsäureseifengemischen enthalten.3. Composition according to claim 1 or 2, characterized in that it contains soaps in amounts of at least 0.2 wt .-%, with preferred granules 0.5 to 15 wt .-%, in particular up to 10 wt .-% of fatty acid soaps or natural fatty acid soap mixtures.
4. Mittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es 0,2 bis 20 Gew.-% Polyhydroxymonocarbonsäuren bzw. Polyhydroxymono- carbonsäuresalze mit 4 bis 6 Kohlenstoffatomen, wobei jedes Kohlen¬ stoffatom, welches keine Carboxylgruppe oder Ketogruppe trägt, eine Hydroxy-Gruppe aufweist, und/oder Polyhydroxydicarbonsäuren bzw. Poly¬ hydroxydicarbonsäuresalze mit 4 bis 6 Kohlenstoffatomen und mindestens 2 Hydroxy-Gruppen pro Molekül oder Mischungen aus diesen Säuren und Salzen aufweist, enthält.4. Agent according to one of claims 1 to 3, characterized in that it contains 0.2 to 20 wt .-% polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts with 4 to 6 carbon atoms, each carbon atom which does not carry a carboxyl group or keto group, has a hydroxyl group, and / or has polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts with 4 to 6 carbon atoms and at least 2 hydroxyl groups per molecule or mixtures of these acids and salts.
5. Mittel nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß es 0,5 bis 15 Gew.-%, vorzugsweise 1 bis 10 Gew.-% und insbesondere 2 bis 5 Gew.-% Gluconsäure, Gluconat oder Mischungen aus diesen enthält.5. Composition according to claim 3 or 4, characterized in that it contains 0.5 to 15 wt .-%, preferably 1 to 10 wt .-% and in particular 2 to 5 wt .-% gluconic acid, gluconate or mixtures thereof.
6. Granuläres Waschmittel, gekennzeichnet durch einen Gehalt an sprühge¬ trockneten Granulaten gemäß einem der Ansprüche 1 bis 5 von 40 bis 90 Gew.-%, vorzugsweise von 50 bis 85 Gew.-%.6. Granular detergent, characterized by a content of spray-dried granules according to one of claims 1 to 5 from 40 to 90% by weight, preferably from 50 to 85% by weight.
7. 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.7. A process for the production of spray-dried granules, which can be used in particular for detergents or cleaning agents or as a component therefor, characterized in that at Spray drying uses a slurry which contains less than 40% by weight of water, but instead contains 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 and a viscosity of at most 15000 mPas (under operating conditions).
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß ein Slurry ein¬ gesetzt wird, welcher Polyhydroxymonocarbonsäuren bzw. Polyhydroxy- monocarbonsäuresalze mit 4 bis 6 Kohlenstoffatomen und mindestens 3 Hydroxy-Gruppen pro Molekül oder Mischungen aus diesen Säuren und/oder Salzen und/oder Polyhydroxydicarbonsäuren bzw. Polyhydroxydicarbon¬ säuresalze mit 4 bis 6 Kohlenstoffatomen und mindestens 2 Hydroxy- Gruppen pro Molekül oder Mischungen aus diesen Säuren und Salzen ent¬ hält.8. The method according to claim 7, characterized in that a slurry is used which polyhydroxymonocarboxylic acids or polyhydroxy monocarboxylic acid salts having 4 to 6 carbon atoms and at least 3 hydroxy groups per molecule or mixtures of these acids and / or salts and / or Contains polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid salts with 4 to 6 carbon atoms and at least 2 hydroxyl groups per molecule or mixtures of these acids and salts.
9. Verfahren nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß ein Slurry eingesetzt wird, welcher 0,2 bis 20 Gew.-%, bezogen auf die sprühgetrockneten Granulate, Polyhydroxymonocarbonsäuren bzw. Poly- hydroxymonocarbonsäuresalze mit 4 bis 6 Kohlenstoffatomen enthält, wobei jedes Kohlenstoffatom, welches eine Carboxylgruppe oder Keto¬ gruppe trägt, eine Hydroxygruppe aufweist.9. The method according to claim 7 or 8, characterized in that a slurry is used which contains 0.2 to 20 wt .-%, based on the spray-dried granules, polyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid salts having 4 to 6 carbon atoms, each Carbon atom which carries a carboxyl group or keto group has a hydroxy group.
10. Verfahren nach einem der Ansprüche 7 bis 9, dadurch gekennzeichnet, daß ein Slurry eingesetzt wird, welcher 0,5 bis 15 Gew.-%, vorzugs¬ weise 1 bis 10 Gew.-% und insbesondere 2 bis 5 Gew.-% Gluconsäure, Gluconat oder Mischungen aus diesen, jeweils bezogen auf die sprüh¬ getrockneten Granulate, enthält.10. The method according to any one of claims 7 to 9, characterized in that a slurry is used which 0.5 to 15 wt .-%, preferably 1 to 10 wt .-% and in particular 2 to 5 wt .-% Contains gluconic acid, gluconate or mixtures of these, in each case based on the spray-dried granules.
11. Verfahren nach einem der Ansprüche 7 bis 10, dadurch gekennzeichnet, daß ein Schüttgewicht von mindestens 600 g/1 und vorzugsweise von 650 bis 1000 g/1 eingestellt wird. 11. The method according to any one of claims 7 to 10, characterized in that a bulk density of at least 600 g / 1 and preferably from 650 to 1000 g / 1 is set.
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
DE4408502 1994-03-14
DE4408502A DE4408502A1 (en) 1994-02-18 1994-03-14 Spray-dried granules with high bulk density
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 true EP0745119A1 (en) 1996-12-04
EP0745119B1 EP0745119B1 (en) 1999-12-08

Family

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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9522596A1 *

Also Published As

Publication number Publication date
WO1995022596A1 (en) 1995-08-24
PL180293B1 (en) 2001-01-31
EP0745119B1 (en) 1999-12-08
GR3032349T3 (en) 2000-04-27
ES2141336T3 (en) 2000-03-16
DK0745119T3 (en) 2000-05-08
PL315788A1 (en) 1996-12-09
ATE187487T1 (en) 1999-12-15

Similar Documents

Publication Publication Date Title
EP0642576B1 (en) Continuous production process of a granulated washing and/or cleaning agent
WO1995020029A1 (en) Builders for washing or cleaning agents
WO1995022592A1 (en) Washing agent with amorphous silicate builder substances
WO1993002176A1 (en) Method of producing high-bulk-density washing agents with improved dissolving speed
WO1993015180A1 (en) Process for producing solid washing and cleaning agents with a high powder density and improved rates of dissolution
DE69730222T2 (en) METHOD FOR PRODUCING DETERGENTS WITH HIGH BULK WEIGHT
WO1994013771A1 (en) Granulated washing and cleaning agents with a high surfactant content
DE19500644B4 (en) Spray-dried detergent or component thereof
EP0716687B1 (en) Spray-dried granulate with high apparent density
WO1994014946A1 (en) Granulated washing and/or cleaning agents
EP0840780B1 (en) High bulk density granulated washing or cleaning product
EP0745119B1 (en) Process of preparing spray-dried granulates
DE4408502A1 (en) Spray-dried granules with high bulk density
EP1141186B1 (en) Tenside granulates
EP0874684B1 (en) Process for producing a granular additive
WO1993005133A1 (en) Washing and/or cleaning process
EP0713524A1 (en) Detergent containing non-ionic cellulose ethers
WO1995033684A1 (en) Granulated, water-soluble, silicic-acid-containing alkaline silicate
WO1994000544A1 (en) Washing and cleaning granules
EP0893492B1 (en) Process for making a storage stable and flowable granulate from anionic detergent compositions
EP0936267A2 (en) Alkali metal silicate/ nonionic surfactant compound
EP0888444A1 (en) Method of manufacturing free-flowing granular washing or cleaning agents
WO2000023550A1 (en) Non-ionic surfactant mixtures
EP0710273A1 (en) Powdery or granulated washing agents with improved secondary detergent power
EP1123373A1 (en) Non-ionic surfactant mixtures

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19960809

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI NL SE

17Q First examination report despatched

Effective date: 19971208

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI NL SE

REF Corresponds to:

Ref document number: 187487

Country of ref document: AT

Date of ref document: 19991215

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59507389

Country of ref document: DE

Date of ref document: 20000113

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN P. & C. S.N.C.

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2141336

Country of ref document: ES

Kind code of ref document: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20000410

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20040108

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20040112

Year of fee payment: 10

Ref country code: DK

Payment date: 20040112

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20040116

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20040203

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20040319

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20040518

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050209

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050210

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050228

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050228

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050228

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050228

BERE Be: lapsed

Owner name: *HENKEL-ECOLAB G.M.B.H. & CO. OHG

Effective date: 20050228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050905

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

EUG Se: european patent has lapsed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20050901

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20060109

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20060202

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20060210

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20060228

Year of fee payment: 12

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20070209

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20071030

BERE Be: lapsed

Owner name: *HENKEL-ECOLAB G.M.B.H. & CO. OHG

Effective date: 20050228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070209

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070228

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20070210

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070210

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070209

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 59507389

Country of ref document: DE

Representative=s name: GODEMEYER BLUM LENZE PARTNERSCHAFT, PATENTANWA, DE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20140417

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59507389

Country of ref document: DE