EP1348756A1 - Process for making solid compositions - Google Patents

Process for making solid compositions Download PDF

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Publication number
EP1348756A1
EP1348756A1 EP03006430A EP03006430A EP1348756A1 EP 1348756 A1 EP1348756 A1 EP 1348756A1 EP 03006430 A EP03006430 A EP 03006430A EP 03006430 A EP03006430 A EP 03006430A EP 1348756 A1 EP1348756 A1 EP 1348756A1
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EP
European Patent Office
Prior art keywords
solid mixture
mixture according
alcohol
solid
weight
Prior art date
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Granted
Application number
EP03006430A
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German (de)
French (fr)
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EP1348756B1 (en
Inventor
Rainer Dr. Eskuchen
Franz Wenin
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Cognis IP Management GmbH
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Cognis Deutschland GmbH and Co KG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives 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
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust

Definitions

  • the present invention relates to solid mixtures which have at least one liquid or gelling Contain component, as well as a process for the preparation of such mixtures, and the Use of the mixtures.
  • the object of the present invention was to provide fixed offer forms that contain higher proportions of liquid components at room temperature and yet flowable and are not adhesive.
  • a solid mixture which comprises at least a) a solid mixture is claimed Carrier, b) a surfactant component, c) a component liquid at room temperature Hydrocolloid d) and e) optionally contain auxiliaries and additives.
  • the solid carrier substance a) used is, in particular, finely crystalline, synthetic and bound water-containing zeolite such as zeolite NaA in detergent quality.
  • zeolite NaX and mixtures of NaA and NaX are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production.
  • the zeolite can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.
  • Suitable substitutes or partial substitutes for zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates are those in which M in the general formula represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred.
  • the agents according to the invention preferably contain 10 to 60% by weight of zeolite and / or crystalline layered silicates as solid component a), mixtures of zeolite and crystalline layered silicates in any ratio being particularly advantageous.
  • the agents contain 20 to 50% by weight of zeolite and / or crystalline layered silicates.
  • Particularly preferred agents contain up to 40% by weight of zeolite and in particular up to 35% by weight of zeolite, in each case based on the anhydrous active substance.
  • Suitable ingredients for a) are water-soluble amorphous silicates; they are preferably used in combination with zeolite and / or crystalline layered silicates.
  • Particularly preferred are agents which contain, above all, sodium silicate with a molar ratio (module) Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5.
  • the content of amorphous sodium silicates in the agents is preferably up to 15% by weight and preferably between 2 and 8% by weight.
  • Phosphates such as tripolyphosphates, pyrophosphates and orthophosphates can also be present in small amounts in the compositions.
  • the content of the phosphates in the compositions is preferably up to 15% by weight, but in particular 0 to 10% by weight.
  • the compositions can additionally contain layered silicates of natural and synthetic origin. However, smectites, in particular bentonites, are preferred here.
  • small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas.
  • the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca 2+ .
  • the amount of water of hydration is usually in the range from 8 to 20% by weight and depends on the swelling condition or the type of processing.
  • Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
  • Usable organic builders 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, tartaric acid, sugar acids, aminocarboxylic acids, nitricotrylic acid (NTA), provided that such use is not objectionable for ecological reasons. and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • 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 use of polymeric polycarboxylates is not absolutely necessary.
  • agents are preferred which are biodegradable polymers, for example terpolymers, the monomers acrylic acid and maleic acid or salts thereof, and vinyl alcohol or vinyl alcohol derivatives, or the monomers acrylic acid and 2-alkylallylsulfonic acid or salts thereof as well as sugar derivatives.
  • Further 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.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Other suitable solids a) are urea and its solid derivatives as well as phyrophosphates, sucrose, dextrose, cyclodextrins, glucose syrup, sorbitol, aldehydes, amines, organic and inorganic Ca salts.
  • suitable components a) must be able to absorb or bind component c) due to their structure.
  • the use of water glasses and zeolites or of sucrose is particularly preferred.
  • mixtures of component a) is particularly preferred.
  • water glass together with sucrose is particularly preferred.
  • sucrose is particularly preferred.
  • Quantities of sucrose to water glass from 3: 1 to 1: 1 preferred.
  • the agents according to the invention contain as component b) a surfactant component, selected from anionic, non-ionic and / or amorphous surfactants. be preferred surfactants solid at room temperature are used as component b).
  • Suitable anionic surfactants are, for example, alkylbenzenesulfonates, which preferably follow the formula (I) R'-Ph-SO 3 X (I) in which R 'is a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • alkylbenzenesulfonates which preferably follow the formula (I) R'-Ph-SO 3 X (I) in which R 'is a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are preferably used.
  • Alkyl and / or alkenyl sulfates which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary alcohols which follow the formula (II) R "-O-SO 3 X (II) in which R "represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, eradyl alcohol, arachyl alcohol, petroyl alcohol, petroyl alcohol, petroyl alcohol, aryl alcohol alcohol, petroyl alcohol, and their technical mixtures which are obtained from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis
  • the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts f Basis of C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts.
  • ether sulfates are known anionic surfactants which are produced on an industrial scale by SO 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
  • SO 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
  • ether sulfates which follow the formula (III) are suitable R '''O- (CH 2 CH 2 O) m SO 3 X (IV) in which R '"stands for a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, n for numbers from 1 to 10 and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Typical Examples are the sulfates of addition products with an average of 1 to 10 and in particular 2 to 5 moles of ethylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, elaalyl alcohol, oleyl alcohol , Gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures in the form of their sodium and / or magnesium salts
  • the ether sulfates can have both a conventional and a narrow homolog distribution, and the use of ether sulfates based on adducts with an average of 2 is particularly preferred up to 3 moles of ethylene oxide on technical grade C 12/14 or C 12/18 coconut fatty alcohol fractions in the form of their sodium and / or magnesium salts.
  • Acylglutamates are known anionic surfactants which follow the formula (V) in which R "" CO represents a linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds and X represents hydrogen, an alkali metal and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. They are produced, for example, by Schotten-Baumann acylation of glutamic acid with fatty acids, fatty acid esters or chlorides. Sales products are available, for example, from Hoechst AG, Frankfurt / DE or Ajinomoto Co. Inc., Tokyo / JP.
  • acylglutamates which are suitable for the purposes of the invention are anionic surfactants which are derived from fatty acids having 6 to 22, preferably 12 to 18, carbon atoms, such as, for example, C 12/14 or C 12/18 coconut fatty acid, Lauric acid, myristic acid, palmitic acid and / or stearic acid.
  • anionic surfactants which are derived from fatty acids having 6 to 22, preferably 12 to 18, carbon atoms, such as, for example, C 12/14 or C 12/18 coconut fatty acid, Lauric acid, myristic acid, palmitic acid and / or stearic acid.
  • Sodium N-cocoyl and sodium N-stearoyl-L-glutamate are particularly preferred.
  • Alcohol ethoxylates are to be mentioned as non-ionic surfactants.
  • alcohol ethoxylates are referred to as fatty alcohol or oxo alcohol ethoxylates and preferably follow the formula (VI), R ''''O (CH 2 CH 2 O) n H (VI) in which R '"" represents a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and n is a number from 1 to 50.
  • Typical examples are the adducts of on average 1 to 50, preferably 5 to 40 and in particular 10 to 25 moles of capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol Petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, which are used, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols.
  • Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation, of aminic compounds.
  • the starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine.
  • unsaturated carboxylic acids such as acrylic acid, is also possible.
  • betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (VII) in the R b for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R a for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R c for alkyl radicals with 1 to 4 carbon atoms, n for numbers from 1 to 6 and X for a Alkali and / or alkaline earth metal or ammonium.
  • R b for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms
  • R a for hydrogen or alkyl radicals with 1 to 4 carbon atoms
  • R c for alkyl radicals with 1 to 4 carbon atoms
  • n for numbers from 1 to 6
  • X for a Alkali and / or alkaline earth metal or ammonium.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C 12/14 -Kokosalkyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearyl, oleyl, C 16/18 tallow alkyl dimethyl amine and technical mixtures thereof.
  • surfactants used are alkoligoglycosides of the formula R 1 O- [G] p in which R 1 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number of 1 to 10.
  • Preferred agents of the present invention contain as the surfactant component b) alkyl oligoglycosides of the above formula.
  • Soybean oil is particularly preferred as component c). Soybean oil is a yellowish to brownish-yellow, fat, semi-drying oil, which can be obtained by pressing and / or extraction Hydrocarbons (e.g. hexane) is obtained from soybeans (Glycine max) or soybean meal. Soybean oil content: 17-22%. 55-65% of the total fatty acids in soybean oil are multiple unsaturated fatty acids. The sterol content of soybean oil averages 0.37% (of which Cholesterol 0.3-0.5%).
  • soybean oil v. a Ergost-5-en-3b-ol, campesterin and the like.
  • Sitosterol. Refining can reduce the sterol content by approx. 30%. It also contains Soybean oil free fatty acids, lecithin and up to 0.8% tocopherol. Soybean oil goes through like most oils that The individual steps of refining are processed for nutritional purposes, with the Entlecithination (enrichment of the phospholipids after adding water to the boundary layer u. Separation in separators) is of particular importance for the production of soy lecithin.
  • hydrocolloids d) are used simultaneously or at different times, preferably selected from the group gelatin, alginates, pectins, modified starch, carrageenans, agar, Xanthan, galactomanane, gum arabic. These compounds show a viscosity build-up in Water and are therefore also used as thickeners.
  • the component to a) is in amounts of 1 to 90, preferably 5 to 90, in particular 5 to 75 and particularly preferably in amounts of 20 to 65 wt .-%, based on the solid agent.
  • the Surfactant component b) is preferably in amounts of 1 to 60% by weight, in particular 10 to 55 % By weight and very particularly in amounts of 15 to 45% by weight in the compositions.
  • the Components c) and d) are preferably in a total amount of 2 to 65, preferably 5 to 50 % By weight, particularly preferably 5 to 40% by weight and in particular 10 to 35% by weight. It can be advantageous, a weight ratio between components c) and d) of 3: to 1: 1 adjust.
  • Component c) is preferably used in excess compared to component d) used.
  • auxiliaries and additives are contained, these are in amounts of typically 1 to 15, preferably 1 to 10% by weight and particularly preferably in amounts of 1 to 5% by weight.
  • agents also contain water, but in minor amounts. The exact one Content depends on the type of drying. Water contents below 10% by weight are typical, preferably below 5% by weight and in particular below 3% by weight.
  • Another object of the present invention relates to a method for producing Solid mixtures as described above.
  • the process is characterized in that an aqueous emulsion is first prepared from components a) to d) and optionally e) and these Emulsion then dries at elevated temperature. Drying can all be done by a specialist common processes are used, in particular spray drying or the use of a Wirbel Anlagengranulationstrockners.
  • the agents according to the invention can consequently be used as powder or preferably present as granules.
  • Table 1 describes the compositions (in% by weight) of the aqueous emulsions.

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  • Engineering & Computer Science (AREA)
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Abstract

A solid mixture comprises (A) a solid carrier; (B) a surfactant component; (C) a room temperature liquid component; (D) a hydrocolloid; and optionally also (E) conventional aids and additives. Also included is an Independent claim for production of the mixture by heating an aqueous emulsion of the components to dry it.

Description

Die vorliegende Erfindung betrifft Feststoffmischungen, die mindestens eine flüssige oder gelierende Komponente enthalten, sowie eine Verfahren zur Herstellung derartiger Mischungen, sowie die Verwendung der Mischungen.The present invention relates to solid mixtures which have at least one liquid or gelling Contain component, as well as a process for the preparation of such mixtures, and the Use of the mixtures.

Bei der Herstellung fester Angebotsformen von beispielsweise Wasch- und Reinigungsmitteln treten dann Probleme auf, wenn neben den festen Bestandteilen auch bei Raumtemperatur (21°C) flüssige Substanzen verarbeitet werden sollen insbesondere dann, wenn diese flüssigen Komponenten in höheren Konzentrationen mitverarbeitet werden sollen.In the production of solid forms of offer of detergents and cleaning agents, for example then problems arise if, in addition to the solid components, liquid also at room temperature (21 ° C) Substances should be processed especially when these liquid components are in higher concentrations should be processed.

Die Aufgabe der vorliegenden Erfindung bestand darin, feste Angebotsformen bereitzustellen, die höhere Anteile bei Raumtemperatur flüssiger Bestandteile enthalten und trotzdem rieselfähig und nichtklebend sind.The object of the present invention was to provide fixed offer forms that contain higher proportions of liquid components at room temperature and yet flowable and are not adhesive.

Es wurde gefunden, daß durch Zugabe der flüssigen Komponenten in Kombination mit sogenannten Hydrokolloiden die Aufgabe gelöst wurde.It was found that by adding the liquid components in combination with so-called Hydrocolloids the task was solved.

In einer ersten Ausführungsform werden Feststoffmischung beansprucht die mindestens a) einen festen Trägerstoff, b) einen tensidischen Bestandteil, c) einen bei Raumtemperatur flüssigen Bestandteil, ein Hydrokolloid d) und e) optional Hilfs- und Zusatzstoffe enthalten.In a first embodiment, a solid mixture which comprises at least a) a solid mixture is claimed Carrier, b) a surfactant component, c) a component liquid at room temperature Hydrocolloid d) and e) optionally contain auxiliaries and additives.

Als feste Trägersubstanz a) wird insbesondere feinkristalliner, synthetisches und gebundenes Wasser enthaltender Zeolith wie Zeolith NaA in Waschmittelqualität eingesetzt. Geeignet sind jedoch auch Zeolith NaX sowie Mischungen aus NaA und NaX. Der Zeolith kann als sprühgetrocknetes Pulver oder 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 nicht-ionischen Tensiden als Stabilisatoren enthalten, beispielsweise 1 bis 3 Gew.-%, bezogen auf Zeolith, an ethoxylierten C12-C18-Fettalkoholen mit 2 bis 5 Ethylenoxidgruppen oder ethoxylierte Isotridecanole. Geeignete Zeolithe weisen eine mittlere Teilchengröße von weniger als 10 µm (Volumenverteilung; Meßmethode: Coulter Counter) auf und enthalten vorzugsweise 18 bis 22, insbesondere 20 bis 22 Gew.-% an gebundenem Wasser. Geeignete Substitute bzw. Teilsubstitute für Zeolithe sind kristalline, schichtförmige Natriumsilicate der allgemeinen Formel NaMSixO2x+1·yH2O, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Bevorzugte kristalline Schichtsilicate sind solche, in denen M in der allgemeinen Formel für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl β- als auch γ-Natriumdisilicate Na2Si2O5·yH2O bevorzugt. Die erfindungsgemäßen Mittel enthalten als feste Komponente a) vorzugsweise 10 bis 60 Gew.-% Zeolith und/oder kristalline Schichtsilicate, wobei Mischungen von Zeolith und kristallinen Schichtsilicaten in einem beliebigen Verhältnis besonders vorteilhaft sein können. Insbesondere ist es bevorzugt, daß die Mittel 20 bis 50 Gew.-% Zeolith und/oder kristalline Schichtsilicate enthalten. Besonders bevorzugte Mittel enthalten bis 40 Gew.-% Zeolith und insbesondere bis 35 Gew.-% Zeolith, jeweils bezogen auf wasserfreie Aktivsubstanz.The solid carrier substance a) used is, in particular, finely crystalline, synthetic and bound water-containing zeolite such as zeolite NaA in detergent quality. However, zeolite NaX and mixtures of NaA and NaX are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water. Suitable substitutes or partial substitutes for zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which M in the general formula represents sodium and x assumes the values 2 or 3. In particular, both β- and γ-sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred. The agents according to the invention preferably contain 10 to 60% by weight of zeolite and / or crystalline layered silicates as solid component a), mixtures of zeolite and crystalline layered silicates in any ratio being particularly advantageous. In particular, it is preferred that the agents contain 20 to 50% by weight of zeolite and / or crystalline layered silicates. Particularly preferred agents contain up to 40% by weight of zeolite and in particular up to 35% by weight of zeolite, in each case based on the anhydrous active substance.

Weitere geeignete Inhaltsstoffe zu a) sind wasserlösliche amorphe Silicate; vorzugsweise werden sie in Kombination mit Zeolith und/oder kristallinen Schichtsilicaten eingesetzt. Insbesondere bevorzugt sind dabei Mittel, welche vor allem Natriumsilicat mit einem molaren Verhältnis (Modul) Na2O : SiO2 von 1:1 bis 1:4,5, vorzugsweise von 1:2 bis 1:3,5, enthalten. Der Gehalt der Mittel an amorphen Natriumsilicaten beträgt dabei vorzugsweise bis 15 Gew.-% und vorzugsweise zwischen 2 und 8 Gew.-%. Auch Phosphate wie Tripolyphosphate, Pyrophosphate und Orthophosphate können in geringen Mengen in den Mitteln enthalten sein. Vorzugsweise beträgt der Gehalt der Phosphate in den Mitteln bis 15 Gew.-%, jedoch insbesondere 0 bis 10 Gew.-%. Außerdem können die Mittel auch zusätzlich Schichtsilicate natürlichen und synthetischen Ursprungs enthalten. Bevorzugt sind hier jedoch Smectite, insbesondere Bentonite. Geeignete Schichtsilicate, die zur Gruppe der mit Wasser quellfähigen Smectite zählen, sind z.B. solche der allgemeinen Formeln (OH)4Si8-yAly(MgxAl4-x)O20 (OH)4Si8-yAly(Mg6-zLiz)O20 (OH)4Si8-yAly(Mg6-z Alz)O20 mit x = 0 bis 4, y = 0 bis 2, z = 0 bis 6. Zusätzlich kann in das Kristallgitter der Schichtsilicate gemäß den vorstehenden Formeln geringe Mengen an Eisen eingebaut sein. Ferner können die Schichtsilicate aufgrund ihrer ionenaustauschenden Eigenschaften Wasserstoff-, Alkali-, Erdalkaliionen, insbesondere Na+ und Ca2+ enthalten. Die Hydratwassermenge liegt meist im Bereich von 8 bis 20 Gew.-% und ist vom Quellzustand bzw. von der Art der Bearbeitung abhängig. Vorzugsweise werden Schichtsilicate verwendet, die aufgrund einer Alkalibehandlung weitgehend frei von Cal-ciumionen und stark färbenden Eisenionen sind. Brauchbare organische Gerüstsubstanzen sind bei-spielsweise die bevorzugt in Form ihrer Natriumsalze eingesetzten Polycarbonsäuren, wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren, Aminocarbonsäuren, Nitri-lotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citro-nensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren und Mischungen aus diesen. Geeignete polymere Polycarboxylate sind beispielsweise die Natriumsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 800 bis 150000 (auf Säure bezogen). Geeignete copolymere Polycarboxylate sind insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 5000 bis 200000, vorzugsweise 10000 bis 120000 und insbesondere 50000 bis 100000. Der Einsatz polymerer Polycarboxylate ist nicht zwingend erforderlich. Falls jedoch polymere Polycarboxylate eingesetzt werden, so sind Mittel bevorzugt, welche biologisch abbaubare Polymere, beispielsweise Terpolymere, die als Monomere Acrylsäure und Maleinsäure bzw. deren Salze sowie Vinylalkohol bzw. Vinylalkohol-Derivate oder die als Monomere Acrylsäure und 2-Alkylallylsulfonsäure bzw. deren Salze sowie Zuckerderivate enthalten. Weitere geeignete Buildersubstanzen sind Polyacetale, welche durch Umsetzung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 Kohlenstoffatome und mindestens 3 Hydroxyl-gruppen aufweisen erhalten werden können. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Gluconsäure und/oder Glucoheptonsäure erhalten. Weitere geeignete Feststoffe a) sind Harnstoff und dessen feste Derivate sowie Phyrophosphate, Saccharose, Dextrose, Cyclodextrine, Glucosesirup, Sorbit, Aldehyde, Amine, organische und anorganische Ca-Salze.
Generell gilt, daß geeignete Komponenten a) aufgrund ihrer Struktur in der Lage sein müssen, die Komponente c) aufzusaugen bzw. zu binden. Besonders bevorzugt ist die Verwendung von Wassergläsern und Zeolithen oder von Saccharose.Other suitable ingredients for a) are water-soluble amorphous silicates; they are preferably used in combination with zeolite and / or crystalline layered silicates. Particularly preferred are agents which contain, above all, sodium silicate with a molar ratio (module) Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5. The content of amorphous sodium silicates in the agents is preferably up to 15% by weight and preferably between 2 and 8% by weight. Phosphates such as tripolyphosphates, pyrophosphates and orthophosphates can also be present in small amounts in the compositions. The content of the phosphates in the compositions is preferably up to 15% by weight, but in particular 0 to 10% by weight. In addition, the compositions can additionally contain layered silicates of natural and synthetic origin. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are, for example, those of the general formulas (OH) 4 Si 8-y Al y (Mg x Al 4-x ) O 20 (OH) 4 Si 8-y Al y (Mg 6-z Li z ) O 20 (OH) 4 Si 8-y Al y (Mg 6-z Al z ) O 20 with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, due to their ion-exchanging properties, the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca 2+ . The amount of water of hydration is usually in the range from 8 to 20% by weight and depends on the swelling condition or the type of processing. Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment. Usable organic builders 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, tartaric acid, sugar acids, aminocarboxylic acids, nitricotrylic acid (NTA), provided that such use is not objectionable for ecological reasons. and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. 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 use of polymeric polycarboxylates is not absolutely necessary. However, if polymeric polycarboxylates are used, agents are preferred which are biodegradable polymers, for example terpolymers, the monomers acrylic acid and maleic acid or salts thereof, and vinyl alcohol or vinyl alcohol derivatives, or the monomers acrylic acid and 2-alkylallylsulfonic acid or salts thereof as well as sugar derivatives. Further 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. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid. Other suitable solids a) are urea and its solid derivatives as well as phyrophosphates, sucrose, dextrose, cyclodextrins, glucose syrup, sorbitol, aldehydes, amines, organic and inorganic Ca salts.
In general, suitable components a) must be able to absorb or bind component c) due to their structure. The use of water glasses and zeolites or of sucrose is particularly preferred.

Besonders bevorzugt ist die Verwendung von Mischungen der Komponente a). Beispielsweise ist es bevorzugt, Wasserglas zusammen mit Saccharose als Komponente a) einzusetzen. Dabei sind Mengenverhältnisse Saccharose zu Wasserglas von 3:1 bis 1:1 bevorzugt. The use of mixtures of component a) is particularly preferred. For example it is preferred to use water glass together with sucrose as component a). Are Quantities of sucrose to water glass from 3: 1 to 1: 1 preferred.

Weiterhin enthalten die erfindungsgemäßen Mittel als Komponente b) einen tensidischen Bestandteil, ausgewählt aus anionischen-, nicht-ionischen und/oder amophteren Tensiden. vorzugsweise werden bei Raumtemperatur feste Tenside als Komponente b) eingesetzt.Furthermore, the agents according to the invention contain as component b) a surfactant component, selected from anionic, non-ionic and / or amorphous surfactants. be preferred surfactants solid at room temperature are used as component b).

Geeignete anionische Tenside sind z.B. Alkylbenzolsulfonate die vorzugsweise der Formel (I) folgen R'-Ph-SO3X   (I) in der R' für einen verzweigten, vorzugsweise jedoch linearen Alkylrest mit 10 bis 18 Kohlenstoffatomen, Ph für einen Phenylrest und X für X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Vorzugsweise werden Dodecylbenzolsulfonate, Tetradecylbenzolsulfonate, Hexadecylbentolsulfonate sowie deren technische Gemische in Form der Natriumsalze eingesetzt.Suitable anionic surfactants are, for example, alkylbenzenesulfonates, which preferably follow the formula (I) R'-Ph-SO 3 X (I) in which R 'is a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are preferably used.

Unter Alkyl- und/oder Alkenylsulfaten, die auch häufig als Fettalkoholsulfate bezeichnet werden, sind die Sulfatierungsprodukte primärer Alkohole zu verstehen, die der Formel (II) folgen, R"-O-SO3X   (II) in der R" für einen linearen oder verzweigten, aliphatischen Alkyl- und/oder Alkenylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Typische Beispiele für Alkylsulfate, die im Sinne der Erfindung Anwendung finden können, sind die Sulfatierungsprodukte von Capronalkohol, Caprylalkohol, Caprinalkohol, 2-Ethylhexylalkohol, Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol und Erucylalkohol sowie deren technischen Gemischen, die durch Hochdruckhydrierung technischer Methylesterfraktionen oder Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Die Sulfatierungsprodukte können vorzugsweise in Form ihrer Alkalisalze und insbesondere ihrer Natriumsalze eingesetzt werden. Besonders bevorzugt sind Alkylsulfate auf Basis von C16/18-Talgfettalkoholen bzw. pflanzliche Fettalkohole vergleichbarer C-Kettenverteilung in Form ihrer Natriumsalze.Alkyl and / or alkenyl sulfates, which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary alcohols which follow the formula (II) R "-O-SO 3 X (II) in which R "represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of Alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, eradyl alcohol, arachyl alcohol, petroyl alcohol, petroyl alcohol, petroyl alcohol, aryl alcohol alcohol, petroyl alcohol, and their technical mixtures which are obtained from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis The sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts f Basis of C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts.

Alkylethersulfate ("Ethersulfate") stellen bekannte anionische Tenside dar, die großtechnisch durch SO3- oder Chlorsulfonsäure (CSA)-Sulfatierung von Fettalkohol- oder Oxoalkoholpolyglycolethern und nachfolgende Neutralisation hergestellt werden. Im Sinne der Erfindung kommen Ethersulfate in Betracht, die der Formel (III) folgen, R'''O-(CH2CH2O)mSO3X   (IV) in der R'" für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen, n für Zahlen von 1 bis 10 und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Typische Beispiele sind die Sulfate von Anlagerungsprodukten von durchschnittlich 1 bis 10 und insbesondere 2 bis 5 Mol Ethylenoxid an Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen in Form ihrer Natrium- und/oder Magnesiumsalze. Die Ethersulfate können dabei sowohl eine konventionelle als auch eine eingeengte Homologenverteilung aufweisen. Besonders bevorzugt ist der Einsatz von Ethersulfaten auf Basis von Addukten von durchschnittlich 2 bis 3 Mol Ethylenoxid an technische C12/14- bzw. C12/18- Kokosfettalkoholfraktionen in Form ihrer Natrium- und/oder Magnesiumsalze.Alkyl ether sulfates ("ether sulfates") are known anionic surfactants which are produced on an industrial scale by SO 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization. For the purposes of the invention, ether sulfates which follow the formula (III) are suitable R '''O- (CH 2 CH 2 O) m SO 3 X (IV) in which R '"stands for a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, n for numbers from 1 to 10 and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical Examples are the sulfates of addition products with an average of 1 to 10 and in particular 2 to 5 moles of ethylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, elaalyl alcohol, oleyl alcohol , Gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures in the form of their sodium and / or magnesium salts The ether sulfates can have both a conventional and a narrow homolog distribution, and the use of ether sulfates based on adducts with an average of 2 is particularly preferred up to 3 moles of ethylene oxide on technical grade C 12/14 or C 12/18 coconut fatty alcohol fractions in the form of their sodium and / or magnesium salts.

Acylglutamate stellen bekannte anionische Tenside dar, die der Formel (V) folgen,

Figure 00050001
in der R""CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 und/oder 1, 2 oder 3 Doppelbindungen und X für Wasserstoff, ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Ihre Herstellung erfolgt beispielsweise durch Schotten-Baumann Acylierung von Glutaminsäure mit Fettsäuren, Fettsäureestern oder -chloriden. Verkaufsprodukte sind beispielsweise von der Hoechst AG, Frankfurt/DE oder der Ajinomoto Co. Inc., Tokyo/JP erhältlich. Typische Beispiele für geeignete Acylglutamate, die im Sinne der Erfindung in Betracht kommen, sind Aniontenside, die sich von Fettsäuren mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen ableiten, wie beispielsweise C12/14- bzw. C12/18-Kokosfettsäure, Laurinsäure, Myristinsäure, Palmitinsäure und/oder Stearinsäure. Besonders bevorzugt sind Natrium-N-cocoyl- und Natrium-N-stearoyl-L-glutamat. Acylglutamates are known anionic surfactants which follow the formula (V)
Figure 00050001
in which R "" CO represents a linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds and X represents hydrogen, an alkali metal and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. They are produced, for example, by Schotten-Baumann acylation of glutamic acid with fatty acids, fatty acid esters or chlorides. Sales products are available, for example, from Hoechst AG, Frankfurt / DE or Ajinomoto Co. Inc., Tokyo / JP. Typical examples of suitable acylglutamates which are suitable for the purposes of the invention are anionic surfactants which are derived from fatty acids having 6 to 22, preferably 12 to 18, carbon atoms, such as, for example, C 12/14 or C 12/18 coconut fatty acid, Lauric acid, myristic acid, palmitic acid and / or stearic acid. Sodium N-cocoyl and sodium N-stearoyl-L-glutamate are particularly preferred.

Als nicht-ionische Tenside sind Alkoholeethoxylate zu nennen. Alkoholethoxylate werden herstellungsbedingt als Fettalkohol- oder Oxoalkoholethoxylate bezeichnet und folgen vorzugsweise der Formel (VI), R'''''O(CH2CH2O)nH   (VI) in der R'"" für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen und n für Zahlen von 1 bis 50 steht. Typische Beispiele sind die Addukte von durchschnittlich 1 bis 50, vorzugsweise 5 bis 40 und insbesondere 10 bis 25 Mol an Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen, die z.B. bei der Hochdruckhydrierung von technischen Methylestern auf Basis von Fetten und Ölen oder Aldehyden aus der Roelen'schen Oxosynthese sowie als Monomerfraktion bei der Dimerisierung von ungesättigten Fettalkoholen anfallen. Bevorzugt sind Addukte von 10 bis 40 Mol Ethylenoxid an technische Fettalkohole mit 12 bis 18 Kohlenstoffatomen, wie beispielsweise Kokos-, Palm-, Palmkern- oder Talgfettalkohol.Alcohol ethoxylates are to be mentioned as non-ionic surfactants. For production reasons, alcohol ethoxylates are referred to as fatty alcohol or oxo alcohol ethoxylates and preferably follow the formula (VI), R '''''O (CH 2 CH 2 O) n H (VI) in which R '"" represents a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and n is a number from 1 to 50. Typical examples are the adducts of on average 1 to 50, preferably 5 to 40 and in particular 10 to 25 moles of capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol Petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, which are used, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Adducts of 10 to 40 moles of ethylene oxide with technical fatty alcohols with 12 to 18 carbon atoms, such as, for example, coconut, palm, palm kernel or tallow fatty alcohol, are preferred.

Betaine stellen bekannte Tenside dar, die überwiegend durch Carboxyalkylierung, vorzugsweise Carboxymethylierung von aminischen Verbindungen hergestellt werden. Vorzugsweise werden die Ausgangsstoffe mit Halogencarbonsäuren oder deren Salzen, insbesondere mit Natriumchloracetat kondensiert, wobei pro Mol Betain ein Mol Salz gebildet wird. Ferner ist auch die Anlagerung von ungesättigten Carbonsäuren, wie beispielsweise Acrylsäure möglich. Beispiele für geeignete Betaine stellen die Carboxyalkylierungsprodukte von sekundären und insbesondere tertiären Aminen dar, die der Formel (VII) folgen,

Figure 00060001
in der Rb für Alkyl- und/oder Alkenylreste mit 6 bis 22 Kohlenstoffatomen, Ra für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, Rc für Alkylreste mit 1 bis 4 Kohlenstoffatomen, n für Zahlen von 1 bis 6 und X für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind die Carboxymethylierungsprodukte von Hexylmethylamin, Hexyldimethylamin, Octyldimethylamin, Decyldimethylamin, Dodecylmethylamin, Dodecyldimethylamin, Dodecylethylmethylamin, C12/14-Kokosalkyldimethylamin, Myristyldimethylamin, Cetyldimethylamin, Stearyldimethylamin, Stearylethylmethylamin, Oleyldimethylamin, C16/18-Talgalkyldimethylamin sowie deren technische Gemische.Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation, of aminic compounds. The starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine. The addition of unsaturated carboxylic acids, such as acrylic acid, is also possible. Examples of suitable betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (VII)
Figure 00060001
in the R b for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R a for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R c for alkyl radicals with 1 to 4 carbon atoms, n for numbers from 1 to 6 and X for a Alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C 12/14 -Kokosalkyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearyl, oleyl, C 16/18 tallow alkyl dimethyl amine and technical mixtures thereof.

Weitere, vorzugsweise verwendetes Tenside sind Alkloligoglycoside der Formel R1O-[G]p in der R1 für einen Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht. Bevorzugte Mittel der vorliegenden Erfindung enthalten als tensidische Komponente b) Alkyloligoglycoside der obigen Formel.Further preferred surfactants used are alkoligoglycosides of the formula R 1 O- [G] p in which R 1 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number of 1 to 10. Preferred agents of the present invention contain as the surfactant component b) alkyl oligoglycosides of the above formula.

Erfindungswesentlich ist die Gegenwart an bei Raumtemperatur flüssigen Substanzen c) in den Mitteln. Es handelt sich dabei vorzugsweise um bei Raumtemperatur (21 °C) flüssige Fette und Öle sowie flüssige nichtionische Tenside. Besonders bevorzugt ist Sojaöl als Komponente c). Sojaöl ist ein gelbliches bis braungelbes, fettes, halbtrocknendes Öl, das durch Pressen und/oder Extraktion mit Kohlenwasserstoffen (z. B. Hexan) aus Sojabohnen (Glycine max) oder Sojaschrot gewonnen wird. Ölgehalt der Sojabohnen: 17-22%. 55-65% der Gesamtfettsäuren des Sojaöls sind mehrfach ungesättigte Fettsäuren. Der Sterin-Gehalt von Sojaöl beträgt durchschnittlich 0,37% (davon Cholesterin 0,3-0,5%). Neben Cholesterin finden sich in Sojaöl v. a. Ergost-5-en-3b-ol, Campesterin u. Sitosterin . Durch Raffination läßt sich der Sterin-Gehalt um ca. 30% senken. Darüber hinaus enthält Sojaöl freie Fettsäuren, Lecithin und bis zu 0,8% Tocopherol. Sojaöl durchläuft, wie die meisten Öle, die zu Ernährungszwecken bearbeitet werden, die einzelnen Schritte der Raffination, wobei der Entlecithinierung (Anreicherung der Phospholipide nach Wasserzusatz an der Grenzschicht u. Abtrennung in Separatoren) besondere Bedeutung zur Herst. von Sojalecithin zukommt. Analytik: Dichte 0,916-0,922, Schmelzpunkt -15 bis -8 °C, Festpunkt 282 °C, VZ 188-195, IZ 120-136, SZ 0,3-3,0, unverseifbarer Anteil 0,5-1,5%. Neben dem Sojaöl können auch andere bei Raumtemperatur flüssige Öle, insbesondere Parfümöle, eingesetzt werden.The presence of substances c) which are liquid at room temperature is essential to the invention. These are preferably fats and oils which are liquid at room temperature (21 ° C.) and liquid non-ionic surfactants. Soybean oil is particularly preferred as component c). Soybean oil is a yellowish to brownish-yellow, fat, semi-drying oil, which can be obtained by pressing and / or extraction Hydrocarbons (e.g. hexane) is obtained from soybeans (Glycine max) or soybean meal. Soybean oil content: 17-22%. 55-65% of the total fatty acids in soybean oil are multiple unsaturated fatty acids. The sterol content of soybean oil averages 0.37% (of which Cholesterol 0.3-0.5%). In addition to cholesterol, soybean oil v. a. Ergost-5-en-3b-ol, campesterin and the like. Sitosterol. Refining can reduce the sterol content by approx. 30%. It also contains Soybean oil free fatty acids, lecithin and up to 0.8% tocopherol. Soybean oil goes through like most oils that The individual steps of refining are processed for nutritional purposes, with the Entlecithination (enrichment of the phospholipids after adding water to the boundary layer u. Separation in separators) is of particular importance for the production of soy lecithin. analytics: Density 0.916-0.922, melting point -15 to -8 ° C, fixed point 282 ° C, VZ 188-195, IZ 120-136, SZ 0.3-3.0, unsaponifiable fraction 0.5-1.5%. In addition to soybean oil, others can also be used at room temperature liquid oils, especially perfume oils, are used.

Weiterhin werden gleichzeitig oder zeitlich versetzt Hydrokolloide d) eingesetzt, vorzugsweise ausgewählt aus der Gruppe Gelatine, Alginate, Pektine, modifizierte Stärke, Carrageenane, Agar, Xanthan, Galactomanane, Gummi arabicum. Diese Verbindungen zeigen einen Viskositätsaufbau in Wasser und werden daher auch als Verdicker eingesetzte.Furthermore, hydrocolloids d) are used simultaneously or at different times, preferably selected from the group gelatin, alginates, pectins, modified starch, carrageenans, agar, Xanthan, galactomanane, gum arabic. These compounds show a viscosity build-up in Water and are therefore also used as thickeners.

Die Komponente zu a) ist in Mengen von 1 bis 90 , vorzugsweise 5 bis 90, insbesondere 5 bis 75 und besonders bevorzugt in Mengen von 20 bis 65 Gew.-%, bezogen auf die festen Mittel enthalten. Die tensidische Komponente b) ist vorzugsweise in Mengen von 1 bis 60 Gew.-%, insbesondere 10 bis 55 Gew.-% und ganz besonders in Mengen von 15 bis 45 Gew.-% in den Mitteln enthalten. Die Komponenten c) und d) sind vorzugsweise in Mengen von insgesamt 2 bis 65, vorzugsweise 5 bis 50 Gew.-%, besonders bevorzugt 5 bis 40 Gew.-% und insbesondere 10 bis 35 Gew.-% enthalten. Es kann vorteilhaft sein, ein Gewichtsverhältnis zwischen den Komponenten c) und d) von 3 : bis 1 : 1 einzustellen. Vorzugsweise wird die Komponente c) im Überschuss im Vergleich zur Komponente d) eingesetzt.The component to a) is in amounts of 1 to 90, preferably 5 to 90, in particular 5 to 75 and particularly preferably in amounts of 20 to 65 wt .-%, based on the solid agent. The Surfactant component b) is preferably in amounts of 1 to 60% by weight, in particular 10 to 55 % By weight and very particularly in amounts of 15 to 45% by weight in the compositions. The Components c) and d) are preferably in a total amount of 2 to 65, preferably 5 to 50 % By weight, particularly preferably 5 to 40% by weight and in particular 10 to 35% by weight. It can be advantageous, a weight ratio between components c) and d) of 3: to 1: 1 adjust. Component c) is preferably used in excess compared to component d) used.

Sofern weitere Hilfs- und Zusatzstoffe enthalten sind, liegen diese in Mengen von typischerweise 1 bis 15, vorzugsweise 1 bis 10 Gew.-% und besonders bevorzugt in Mengen von 1 bis 5 Gew.-% vor. Die Mittel enthalten nach Trocknung auch Wasser, allerdings in untergeordneten Mengen. Der genaue Gehalt hängt von der Art der Trocknung ab. Typische sind Wassergehalte unter 10 Gew.-%, vorzugsweise unter 5 Gew.-% und insbesondere unter 3 Gew.-%.If further auxiliaries and additives are contained, these are in amounts of typically 1 to 15, preferably 1 to 10% by weight and particularly preferably in amounts of 1 to 5% by weight. The After drying, agents also contain water, but in minor amounts. The exact one Content depends on the type of drying. Water contents below 10% by weight are typical, preferably below 5% by weight and in particular below 3% by weight.

Ein weiterer Gegenstand der vorliegenden Erfindung betrifft ein Verfahren zu Herstellung von Feststoffmischungen gemäß der obigen Beschreibung. Das Verfahren zeichnet sich dadurch aus, daß man zunächst eine wässerige Emulsion aus den Komponenten a) bis d) und ggf. e) herstellt und diese Emulsion anschließend bei erhöhter Temperatur trocknet. Zum Trocknen können alle dem Fachmann geläufigen Verfahren eingesetzt werden, insbesondere die Sprühtrocknung oder der Einsatz eines Wirbelschichtgranulationstrockners. Folgerichtig können die erfindungsgemäßen Mittel als Pulver oder, vorzugsweise als Granulate vorliegen. Another object of the present invention relates to a method for producing Solid mixtures as described above. The process is characterized in that an aqueous emulsion is first prepared from components a) to d) and optionally e) and these Emulsion then dries at elevated temperature. Drying can all be done by a specialist common processes are used, in particular spray drying or the use of a Wirbelschichtgranulationstrockners. The agents according to the invention can consequently be used as powder or preferably present as granules.

BeispieleExamples

Im folgenden wird die Herstellung der erfindungsgemäßen Mischungen beschrieben: Zunächst wird Wasser auf 75 °C erwärmt und anschließend wird die Komponente d) und dann a) zudosiert. Anschließend erfolgt die Zugabe der Komponente b) sowie der Komponente c). Die Emulsion wurde in den Beispielen 1 bis 7 anschließend im Vakuumtrockenschrank bei 75 °C getrocknet.
Die Emulsion zu Versuch 10 wurde dagegen mit 700 g/h in einen Wirbelschichtgranulationstrockner (Fa. Glatt AGT 150) dosiert und über eine 2-Stoffdüse versprüht. Nach der Emulsion wurden noch 160 g/h einer Mischung aus Harnstoff, Kaliumpyrophosphat und Wasserglas über eine Feststoffdosierschnecke in den Trockner dosiert. Die Trocknung wurde bei einer Wirbelschichttemperatur von 75 °C und einer Lufttemperatur von 115 °C durchgeführt. Es wurden in jedem Fall ein freifließende, nichtklebende Feststoff erhalten.
In der Tabelle 1 sind die Zusammensetzungen (in Gew.-%) der wässerigen Emulsionen beschrieben.

Figure 00100001
The preparation of the mixtures according to the invention is described below: First, water is heated to 75 ° C. and then component d) and then a) are metered in. Then component b) and component c) are added. In Examples 1 to 7, the emulsion was then dried in a vacuum drying cabinet at 75 ° C.
In contrast, the emulsion for test 10 was metered at 700 g / h into a fluidized bed granulation dryer (Glatt AGT 150) and sprayed through a two-component nozzle. After the emulsion, 160 g / h of a mixture of urea, potassium pyrophosphate and water glass were metered into the dryer via a solids metering screw. The drying was carried out at a fluidized bed temperature of 75 ° C. and an air temperature of 115 ° C. A free-flowing, non-sticky solid was obtained in each case.
Table 1 describes the compositions (in% by weight) of the aqueous emulsions.
Figure 00100001

Claims (15)

Feststoffmischung, enthaltend mindestens a) einen festen Trägerstoff b) einen tensidischen Bestandteil c) einen bei Raumtemperatur flüssige Bestandteil d) ein Hydrokolloid und e) optional Hilfs- und Zusatzstoffe Solid mixture containing at least a) a solid carrier b) a surfactant component c) a liquid component at room temperature d) a hydrocolloid and e) optional auxiliaries and additives Feststoffmischung nach Anspruch 1, dadurch gekennzeichnet, daß der feste Trägerstoff a) ausgewählt ist aus der Gruppe der Zeolithe, Wasssergläser, feste Polycarbonsäuren und Polycarboxylate, Saccharose, Dextrose, Cyclodextrine, Glucosesirup, Sorbit, Aldehyde, Amine, organische und anorganische Ca-Salze, Harnstoff oder PhyrophosphateSolid mixture according to claim 1, characterized in that the solid carrier a) is selected from the group of zeolites, water glasses, solid polycarboxylic acids and polycarboxylates, sucrose, dextrose, cyclodextrins, glucose syrup, sorbitol, aldehydes, amines, organic and inorganic calcium salts, Urea or phyrophosphates Feststoffmischung nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß der tensidischen Bestandteil ausgewählt ist aus der Gruppe der anionischen, nichtionischen und/oder amophteren Tenside.Solid mixture according to claims 1 and 2, characterized in that the surfactant component is selected from the group of anionic, nonionic and / or amophore surfactants. Feststoffmischung nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß als tensidischer Bestandteil Alkyloligoglycoside der allgemeinen Formel R1O-[G]p in der R1 für einen Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht, enthalten sind.Solid mixture according to Claims 1 to 3, characterized in that alkyl oligoglycosides of the general formula R 1 O- [G] p in R 1 as an surfactant constituent for an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G for a sugar radical 5 or 6 carbon atoms and p represents numbers from 1 to 10, are included. Feststoffmischung nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß die Bestandteile zu c) ausgewählt sind aus der Gruppe Lecithine, bei Raumtemperatur flüssige Fette und Öle, Parfümöle, flüssige nichtionische Tenside.Solid mixture according to Claims 1 to 4, characterized in that the constituents to c) are selected from the group lecithins, fats and oils which are liquid at room temperature, perfume oils, liquid nonionic surfactants. Feststoffmischung nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß die Bestandteile zu d) ausgewählt sind aus gelierenden Substanzen, vorzugsweise Gelatine, Alginate, Pektine, modifizierte Stärke, Carrageenane, Agar, Xanthan, Galactomanane, Gummi arabicum. Solid mixture according to claims 1 to 5, characterized in that the constituents to d) are selected from gelling substances, preferably gelatin, alginates, pectins, modified starch, carrageenans, agar, xanthan, galactomanans, gum arabic. Feststoffmischung nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß die Komponenten zu a) in Mengen von 1 bis 90, vorzugsweise 5 bis 75 und insbesondere 20 bis 65 Gew.-% enthalten sind.Solid mixture according to Claims 1 to 6, characterized in that the components for a) are present in amounts of 1 to 90, preferably 5 to 75 and in particular 20 to 65% by weight. Feststoffmischung nach den Ansprüchen 1 bis 7, dadurch gekennzeichnet, daß die tensidischen Komponente b) in Mengen von 1 bis 60, vorzugsweise 10 bis 55 und insbesondere 15 bis 45 Gew.-% enthalten ist.Solid mixture according to Claims 1 to 7, characterized in that the surfactant component b) is present in amounts of 1 to 60, preferably 10 to 55 and in particular 15 to 45% by weight. Feststoffmischung nach den Ansprüchen 1 bis 8, dadurch gekennzeichnet, daß die Komponenten c) und d) in Mengen von 2 bis 65, vorzugsweise 5 bis 50 und insbesondere 5 bis 40 Gew.-% enthalten sind.Solid mixture according to Claims 1 to 8, characterized in that components c) and d) are present in amounts of 2 to 65, preferably 5 to 50 and in particular 5 to 40% by weight. Feststoffmischung nach den Ansprüchen 1 bis 9, dadurch gekennzeichnet, daß die optionalen Hilfsund Zusatzstoffe in Mengen von insgesamt 1 bis 15, vorzugsweise 1 bis 10 und insbesondere 1 bis 5 Gew.-% enthalten sind.Solid mixture according to Claims 1 to 9, characterized in that the optional auxiliaries and additives are present in amounts of 1 to 15, preferably 1 to 10 and in particular 1 to 5% by weight. Feststoffmischung nach den Ansprüchen 1 bis 10, dadurch gekennzeichnet, daß es als Granulat vorliegt.Solid mixture according to claims 1 to 10, characterized in that it is in the form of granules. Verfahren zur Herstellung von Feststoffen, enthaltend mindestens die Bestandteile a) bis d) und ggf. e) gemäß Anspruch 1, dadurch gekennzeichnet, daß man zunächst eine wässerige Emulsion aus den Komponenten a) bis d) und ggf. e) herstellt und diese Emulsion anschließend bei erhöhter Temperatur trocknet.A process for the production of solids containing at least components a) to d) and optionally e) according to claim 1, characterized in that an aqueous emulsion is first prepared from components a) to d) and optionally e) and this emulsion then dries at elevated temperature. Verfahren nach Anspruch 12, dadurch gekennzeichnet, daß die Emulsion mittels eines Wirbelschichtgranulationstrockner getrocknet wird.A method according to claim 12, characterized in that the emulsion is dried by means of a fluidized bed granulation dryer. Verfahren nach Anspruch 12, dadurch gekennzeichnet, daß die Emulsion mittels Sprühtrocknung getrocknet wird.A method according to claim 12, characterized in that the emulsion is dried by spray drying. Verwendung von Feststoffmischungen gemäß Anspruch 1 zur Herstellung von Wasch- und Reinigungsmitteln.Use of solid mixtures according to claim 1 for the production of washing and Detergents.
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