EP0574436B1 - Detergents - Google Patents

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Publication number
EP0574436B1
EP0574436B1 EP92905355A EP92905355A EP0574436B1 EP 0574436 B1 EP0574436 B1 EP 0574436B1 EP 92905355 A EP92905355 A EP 92905355A EP 92905355 A EP92905355 A EP 92905355A EP 0574436 B1 EP0574436 B1 EP 0574436B1
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EP
European Patent Office
Prior art keywords
weight
detergent
zeolite
silicate
alkali metal
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EP92905355A
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German (de)
French (fr)
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EP0574436A1 (en
Inventor
Horst Upadek
Jörg Poethkow
Rainer Salz
Hans-Jürgen Riebe
Wolfgang Seiter
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/08Silicates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/128Aluminium silicates, e.g. zeolites
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3942Inorganic per-compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3945Organic per-compounds

Definitions

  • the invention relates to a phosphate-free detergent based on zeolite and alkali silicate and a process for its production.
  • zeolite in particular zeolite NaA, and in particular mixtures of zeolite with alkali silicates and alkali carbonates and polymeric polycarboxylates have been used as phosphate substitutes in washing and cleaning agents and to reduce incrustations.
  • complexing agents such as the salts of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA) and phosphonic acids.
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • the mostly selectively acting complexing agents have the task of eliminating heavy metal ions, which, even in traces, can have a very negative effect on the washing process, in particular on the bleaching process (Ullmann, 1987, Vol. 8, pp. 351 to 354).
  • European patent application 291 869 (Henkel) describes phosphate-free builders combinations of zeolite and aminoalkane polyphosphonate and / or polymeric polycarboxylate and 1-hydroxyethane-1,1-diphosphonate (HEDP), certain weight ratios of the last three components being synergistic with regard to preventing the formation of fiber incrustations demonstrate.
  • Crystalline, layered sodium silicates have also been described as substitutes or partial substitutes for phosphates and zeolites.
  • European patent application 164 514 discloses a phosphate-free builder combination which mainly contains crystalline phyllosilicates of the formula (I) NaMSi x O 2 + 1 .yH2O, where M is sodium or hydrogen means x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • These layered silicates can be used as water softeners both separately and in detergents and cleaning agents together with other builders such as phosphates, zeolite, other silicates, phosphonates and polycarboxylates.
  • German patent application 24 12 837 (Henkel), which, in combination with zeolite, contains various complexing agents such as polymeric polycarboxylates and phosphonates as well as alkaline framework substances, such as carbonates and silicates, which are not capable of complex formation.
  • "microcrystalline" zeolites are preferably used, which are at least 80% by weight of particles having a size between 10 and 0.01 ⁇ m and in particular between 8 and 0.1 ⁇ m.
  • washing and cleaning agents which contain 0.5 to 3 wt .-% alkali silicate (calculated as a solid). These agents are prepared either by a conventional mixing process in which the solid silicates or a corresponding amount of a water glass solution are mixed together with the other main components, or by a spray drying process in which the slurry contains both zeolite and the corresponding amount of alkali silicate.
  • the alkali silicates serve as corrosion inhibitors.
  • a detergent is known from German patent application 26 56 009 (Colgate) which contains 12 to 25% by weight of zeolite, in particular of type 4A, 5 to 20% by weight of a sodium silicate with the composition Na 2 O: SiO 2 of 1: 1 to 1 : 3.2, in particular from 1: 2.0 to 1: 2.6, and contains a peroxy bleach.
  • undesired deposits of the water-insoluble zeolite particles on the laundry are to be prevented by 0.3 to 3% by weight of a polymer from the group carboxymethyl cellulose, lower alkyl cellulose, hydroxy-lower alkyl-lower alkyl cellulose, polyvinyl alcohol, polyvinyl acetate and Polyvinyl pyrrolidone can be used.
  • the zeolite has an average particle diameter of 0.5 to 12 ⁇ m, preferably 5 to 9 ⁇ m.
  • European patent application 10 247 describes a detergent which contains surfactants in conventional amounts, zeolite, alkali silicate and optionally a peroxy bleach.
  • zeolite zeolite
  • alkali silicate alkali silicate
  • peroxy bleach zeolite
  • water-soluble organic complexing agents from the group of substituted alkanedi- and alkanetri-phosphonic acids, which are present in the form of their alkali and / or alkaline earth salts
  • a detergent is obtained which not only has a good primary washing action, but also the formation of fiber incrustations reduced.
  • the addition of these phosphonates results in increased bleaching stability despite the absence of conventional stabilizers such as magnesium silicate and aminopolycarboxylate.
  • the agent contains 20 to 65 wt .-% of a finely divided zeolite, as described in German patent application DE 24 12 837, and 1 to 7 wt .-% solid, powdered sodium silicate of the molar composition Na2O: SiO2 from 1: 2 to 1: 2.2.
  • the composition consists of a mixture of at least 2 powder constituents, the first of which is obtained by spray drying an aqueous slurry containing the zeolite, surfactants and optionally the water-soluble organic complex-forming framework substances, and the second powder constituent from the sodium silicate powder and optionally from the water-soluble phosphonates and other detergent additives that are sensitive to hydrolysis and / or temperature.
  • European patent application 240 356 discloses detergents which, in addition to zeolite and water-soluble sodium silicates, as described in European patent application 10 247, contain polymeric polycarboxylates and their derivatives, for example polyacrylates and salts of acrylic acid-maleic acid copolymers. These polymeric polycarboxylates are spray dried together with the zeolite during the production of the detergent.
  • builder combinations for detergents which contain crystalline phyllosilicates and optionally phosphates and polycarboxylates such as citrates, glykonates, NTA and / or iminodiacetates, but no zeolite.
  • the agents which contain 10 to 50% by weight of crystalline layered silicate, are characterized by a storage-stabilized bleaching system.
  • European patent application 405 122 (Hoechst) specifies a builder combination for textile detergents, the builder combination consisting of a mixture of zeolite and crystalline sodium phyllosilicate in a ratio of 4: 1 to 1: 4.
  • the incrustation of the fabric can be reduced.
  • the object of the invention was to further develop the field of phosphate-free builders combinations for use in textile detergents with the aim of reducing the proportion of organic synthetic compounds.
  • detergents which contain a special combination of finely divided zeolite with a relatively narrow particle size spectrum and alkali silicate as builders meet the high demands placed on modern detergents.
  • the invention relates to a detergent which contains surfactants, zeolite, alkali silicate and optionally a peroxy bleach and which is characterized in that it comprises 30 to 65% by weight of a finely divided, hydrated zeolite with an average particle size of 1 to 5 ⁇ m, 1 to 15 wt .-% of a solid alkali silicate of the molar composition M2O: Si2O from 1: 2.0 to 1: 3.0, wherein M is sodium and / or potassium, with the proviso that the agent is free of water-soluble organic Complexing agents from the group of substituted phosphonates, free of polymeric polycarboxylates and essentially free of alkali carbonates.
  • the finely divided, hydrated zeolite generally has a water content of 17 to 25% by weight.
  • the quantities for zeolite relate to the anhydrous active substance.
  • Suitable zeolites are those of the zeolite A type. Mixtures of zeolite NaA and NaX can also be used, the proportion of the zeolite NaX in such mixtures advantageously being less than 30%.
  • Preferred zeolites have an average particle size between 1.8 and 4.5 ⁇ m, in particular between 2.0 and 4.0 ⁇ m (measurement method: Fraunhofer diffraction; mean volume distribution).
  • the content of the agents in finely divided, in particular crystalline, hydrated zeolite is preferably 30 to 55 wt .-% and in particular 32 to 54 wt .-%, based on anhydrous active substance.
  • the solid alkali silicates can be amorphous or crystalline, as powder or as granules, for example as roller-compacted chip granules, or as a spray-dried compound.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 2 to 1: 2.8.
  • Such amorphous alkali metal silicates are commercially available, for example, under the name Portil (R) (Henkel).
  • crystalline sheet silicates of the formula (I) NaMSi x O 2 + 1 .yH2O are preferably used, in which M represents sodium, x assumes the values 2 or 3 and y is a number from 0 to 20. Both ⁇ - and ⁇ -sodium disilicates Na2Si2O5 are particularly preferred.
  • the content of alkali silicates in the compositions is preferably 2 to 10% by weight and in particular 3 to 10% by weight, based on the anhydrous substance.
  • the amorphous sodium silicate content of the agents is 3.5 to 8% by weight, based on the anhydrous substance.
  • the weight ratio of zeolite: amorphous silicate, based in each case on anhydrous substance is preferably 4: 1 to 10: 1.
  • the crystalline layered silicates are preferably used in amounts of 2 to 7% by weight, the weight ratio of zeolite to crystalline layered silicate, based in each case on the anhydrous substance, being at least 5: 1.
  • the weight ratio of amorphous alkali silicate: crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • the agents do not contain any water-soluble organic complexing agents from the group of the phosphonates, so that the agents have a calculated phosphorus content of 0%.
  • Polymeric polycarboxylates for example polyacrylates, polymethacrylates, polymaleates or copolymers of acrylic acid with maleic acid or maleic anhydride, which are usually used in combination with zeolite, are also not present in the product according to the invention, since they do not improve its primary and secondary washability.
  • the agents are also essentially free of alkali carbonates, which means that they contain no more than about 5% by weight, preferably no more than 4% by weight and particularly advantageously no more than 3% by weight of alkali carbonates, in particular of sodium carbonate.
  • alkali carbonate content in the range mentioned also contributes to increased incrustation.
  • alkali carbonate may only be added in the amounts in which it does not contribute to increased incrustation.
  • Preferred detergents contain peroxy bleach and in particular peroxy bleach in combination with bleach activators.
  • bleaching agents which supply H2O2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other bleaches that can be used are, for example, peroxycarbonate or peracidic salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid.
  • Suitable bleach activators for these peroxy bleaches are, for example, the N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines such as N, N, N'N'-tetraacetylethylenediamine.
  • the content of peroxy bleaching agent in the agents is preferably 12 to 30% by weight, in particular in combination with 1 to 10% by weight, preferably 2 to 8% by weight, of a bleach activator.
  • the detergents according to the invention are not only distinguished by a reduced formation of fiber incrustations compared to agents of the prior art which usually contain polymeric polycarboxylates and / or alkali metal carbonates in larger amounts. Surprisingly, they also have an improved bleaching action or an improved stabilization of the peroxy bleaching agent, although they contain no conventional stabilizers such as phosphonate, magnesium silicate or other complexing agents such as the salts of nitrilotriacetic acid and ethylenediaminetetraacetic acid.
  • the detergents and cleaning agents contain known compounds from the group of anionic, nonionic and zwitterionic surfactants as further constituents.
  • sulfonates come as anionic surfactants and sulfates and soaps from preferably natural fatty acids or fatty acid mixtures.
  • C Tens-C13 alkylbenzenesulfonates, olefin sulfonates, esters of ⁇ -sulfofatty acids or ⁇ -sulfofatty acid disalts are used, for example, as surfactants of the sulfonate type.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural or synthetic origin, ie from C12-C18 fatty alcohols or from C10-C20 oxo alcohols, and those of secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the alcohols reacted with 1 to 6 mol of ethylene oxide (EO) are also suitable.
  • Addition products of preferably 2 to 20 moles of EO to 1 mole of an aliphatic compound with essentially 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides and alkanesulfonamides are of particular interest as nonionic surfactants.
  • polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule that are not or not completely water-soluble are also important, in particular when they are used together with water-soluble nonionic or anionic surfactants.
  • alkyl polyglycosides of the general formula RO- (G) x can also be used as nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, C-atoms, methyl-branched, G is a symbol is a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10.
  • the total content of surfactants in the compositions is generally between 5 and 40% by weight. It is preferably 5 to 30% by weight and in particular 8 to 25% by weight.
  • detergent and cleaning agent components include foam inhibitors, optical brighteners, enzymes, fabric softening agents, dyes and fragrances as well as neutral salts, solvents and water.
  • foam inhibitors include foam inhibitors, optical brighteners, enzymes, fabric softening agents, dyes and fragrances as well as neutral salts, solvents and water.
  • graying inhibitors which are usually used in modern textile detergents, is not necessary and, in particular, is also not preferred.
  • Enzymes from the class of proteases, lipases, cellulases and amylases or their mixtures are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • Suitable non-surfactant-like and preferably used foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica. Mixtures of different foam inhibitors are also advantageously used, e.g. B. from silicone and paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • powdery or granular detergents contain 10 to 30% by weight of surfactants, 30 to 45% by weight of a finely divided, hydrated zeolite with an average particle size of 2.0 to 3.8 ⁇ m, 2 to 10% by weight.
  • the detergents according to the invention can be prepared in a conventional manner, for example by mixing, granulating and / or by spray drying. It is possible to incorporate the builders zeolite and solid alkali silicate into the agents individually in a conventional manner and in any order.
  • the pourable powder or granular preparations preferably consist of a dry homogeneous mixture of at least 2 powder components, at least the first of which is in the form of spray-dried granules. It is done by a conventional way Spray drying of a slurry available which contains at least the anionic surfactants and optionally nonionic surfactants.
  • This slurry preferably additionally contains at least part of the zeolite and / or the silicate.
  • the slurry can contain a portion, but not more than 3% by weight and in particular not more than 2% by weight, in each case based on the total finished composition of the amorphous silicates contain.
  • the rest of the amorphous alkali silicates present as powder or granules, like the crystalline sheet silicates which may be present, which are in granular form or adsorbed on a carrier which consists, for example, of sodium sulfate, are subsequently mixed into the spray product.
  • the zeolite-containing slurry be free of amorphous alkali silicates and that these are subsequently added to the spray-dried product.
  • the slurry does not contain zeolite, it is possible to incorporate the entire proportion of the amorphous alkali silicates into the slurry and to spray-dry them.
  • the crystalline layered silicates which may be present are preferably not spray-dried, but are added subsequently in granular form or adsorbed onto a carrier.
  • the zeolite is then also incorporated into the compositions as a powder or, preferably, as a commercially available compound, for example as Wessalith (R) CS or Wessalith (R) CB (commercial products from Degussa, Federal Republic of Germany).
  • zeolite-containing and a silicate-containing slurry it is also possible for a zeolite-containing and a silicate-containing slurry to be spray-dried separately and then mixed. However, it is particularly advantageous if the zeolite-containing slurry and the silicate-containing slurry are introduced into a spray tower at the same time.
  • bleaching agents such as perborate are not spray-dried together with the constituents of the first powder component, but are also only added to the spray product afterwards.
  • Granular detergents of the following composition were produced and tested.
  • the perborate, the bleach activator, the alkali silicate as well as enzyme granulate and silicone oil granulate were subsequently mixed into the spray-dried product from a slurry which contained the remaining constituents.
  • the test was carried out under practical conditions in household washing machines (Miele W 717). The washing conditions are specified in more detail in the individual examples.
  • the degree of whiteness was measured in a Zeiss reflectometer at 460 nm (suppression of the brightener effect). Remission differences of 2% and more are significant and directly understandable by the consumer.
  • Table 1 shows that in the test series a) (detergent without the addition of copper), agents E and V have comparable performances.
  • the detergent E according to the invention performed significantly better than V in all soiling.
  • the performance difference between E and V in favor of E was even greater .
  • Table 1 Trial series % Remission for detergent E V a) Detergent 73.9 74.4 b) Detergent + 5ppm Cu2+ 68.1 63.3 c) Detergent + 10ppm Cu2+ 53.3 47.7
  • Washing conditions tap water of 23 ° d, 3.5 kg of clean laundry, dosage of detergent 146 g, 25 washes; all other parameters as in example 1.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Wood Science & Technology (AREA)
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  • Detergent Compositions (AREA)

Abstract

Detergents which contain 30 to 65 wt. % of a fine-particle, hydrated zeolite with a mean particle size of 1 to 5 $g(m)m and 1 to 15 wt. % of a solid alkali silicate with a molar composition M2?O:SiO2? of 1:2.0 to 1:3.0 and are free from water-soluble organic complex builders from the group of the substituted phosphonates, free from polymeric polycarboxylates and substantially free from alkali carbonates can be used as substitutes for ordinary commercial detergents which contain large amounts of phosphonates, polymeric polycarboxylates and/or alkali carbonates, without any loss of detergency. The proportion of organic synthetic compounds in detergents can thus be reduced.

Description

Die Erfindung betrifft ein phosphatfreies Waschmittel auf Basis Zeolith und Alkalisilikat sowie ein Verfahren zu seiner Herstellung.The invention relates to a phosphate-free detergent based on zeolite and alkali silicate and a process for its production.

In der Praxis wurden als Phosphatsubstitute in Wasch- und Reinigungsmitteln vor allem Zeolith, insbesondere Zeolith NaA, und zur Reduzierung von Inkrustationen Mischungen von Zeolith mit Alkalisilikaten und Alkalicarbonaten sowie polymeren Polycarboxylaten verwendet. Dazu kommen noch Komplexbildner wie die Salze der Nitrilotriessigsäure (NTA), der Ethylendiamintetraessigsäure (EDTA) und der Phosphonsäuren. Die meist selektiv wirkenden Komplexbildner haben die Aufgabe, Schwermetallionen, die schon in Spuren eine sehr negative Auswirkung auf den Waschvorgang, insbesondere auf den Bleichvorgang, haben können, zu eliminieren (Ullmann, 1987, Vol. 8, S. 351 bis 354). Von den Phosphonaten ist bekannt, daß sie auch der Ausfällung schwerlöslicher Calciumsalze und somit der durch schwerlösliche Calciumsalze hervorgerufenen Inkrustation und der Vergrauung des Gewebes entgegenwirken ("Einsatz von Phosphonaten in flüssigen Vollwaschmitteln", M. Paladini, G. Schnorbus, Seifen-Öle-Fette-Wachse, 115. Jahrgang (1989), S. 508 bis 511). Schließlich bewirkt der kombinierte Einsatz von Phosphonaten und Copolymeren auf Basis der Acrylsäure und Maleinsäure im Vergleich mit Formulierungen, die nur einen dieser beiden Bestandteile enthalten, einen höheren Weißgrad der Textilien ("Einsatz von Phosphonaten in Haushaltswaschmitteln mit niedrigem Phosphorgehalt (1 %)", M. Paladini, G. Schnorbus, Seifen-Öle-Fette-Wachse, 114. Jahrgang (1988), S. 756 bis 760). Die europäische Patentanmeldung 291 869 (Henkel) beschreibt phosphatfreie Gerüststoffkombinationen aus Zeolith und Aminoalkanpolyphosphonat und/oder polymerem Polycarboxylat sowie 1-Hydroxyethan-1,1-diphosphonat (HEDP), wobei bestimmte Gewichtsverhältnisse der letzten drei Komponenten einen Synergismus bezüglich der Verhinderung der Ausbildung von Faserinkrustationen zeigen.In practice, zeolite, in particular zeolite NaA, and in particular mixtures of zeolite with alkali silicates and alkali carbonates and polymeric polycarboxylates have been used as phosphate substitutes in washing and cleaning agents and to reduce incrustations. There are also complexing agents such as the salts of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA) and phosphonic acids. The mostly selectively acting complexing agents have the task of eliminating heavy metal ions, which, even in traces, can have a very negative effect on the washing process, in particular on the bleaching process (Ullmann, 1987, Vol. 8, pp. 351 to 354). It is known that the phosphonates also counteract the precipitation of poorly soluble calcium salts and thus the incrustation caused by poorly soluble calcium salts and the graying of the fabric ("Use of phosphonates in heavy duty liquid detergents", M. Paladini, G. Schnorbus, soap oil fats - Waxes, 115th year (1989), pp. 508 to 511). Finally, the combined use of phosphonates and copolymers based on acrylic acid and maleic acid results in a higher degree of whiteness of the textiles compared to formulations containing only one of these two components ("Use of phosphonates in household detergents with a low phosphorus content (1%)", Paladini, G. Schnorbus, Seifen-Öle-Fette-Wwachs, 114th year (1988), pp. 756 to 760). European patent application 291 869 (Henkel) describes phosphate-free builders combinations of zeolite and aminoalkane polyphosphonate and / or polymeric polycarboxylate and 1-hydroxyethane-1,1-diphosphonate (HEDP), certain weight ratios of the last three components being synergistic with regard to preventing the formation of fiber incrustations demonstrate.

Als Substitute bzw. als Teilsubstitute für Phosphate und Zeolithe sind auch kristalline, schichtförmige Natriumsilikate beschrieben worden. So offenbart die europäische Patenanmeldung 164 514 (Hoechst) eine phosphatfreie Gerüststoffkombination, die hauptsächlich kristalline Schichtsilikate der Formel (I) NaMSixO2+1·yH₂O enthält, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 und bevorzugte Werte für x 2, 3 oder 4 sind. Diese Schichtsilikate können als Wasserenthärtungsmittel sowohl separat als auch in Wasch- und Reinigungsmitteln zusammen mit anderen Gerüststoffen wie Phosphaten, Zeolith, weiteren Silikaten, Phosphonaten und Polycarboxylaten eingesetzt werden.Crystalline, layered sodium silicates have also been described as substitutes or partial substitutes for phosphates and zeolites. For example, European patent application 164 514 (Hoechst) discloses a phosphate-free builder combination which mainly contains crystalline phyllosilicates of the formula (I) NaMSi x O 2 + 1 .yH₂O, where M is sodium or hydrogen means x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. These layered silicates can be used as water softeners both separately and in detergents and cleaning agents together with other builders such as phosphates, zeolite, other silicates, phosphonates and polycarboxylates.

Bereits in der deutschen Patentanmeldung 24 12 837 (Henkel) werden Waschmittel beschrieben, die in Kombination mit Zeolith verschiedenartige Komplexbildner wie polymere Polycarboxylate und Phosphonate sowie alkalische, nicht zur Komplexbildung befähigte Gerüstsubstanzen wie Carbonate und Silikate enthalten. Dabei werden vorzugsweise "mikrokristalline" Zeolithe verwendet, die zu wenigstens 80 Gew.-% aus Teilchen einer Größe zwischen 10 und 0,01 µm und insbesondere zwischen 8 und 0,1 µm liegen.Detergent is already described in German patent application 24 12 837 (Henkel), which, in combination with zeolite, contains various complexing agents such as polymeric polycarboxylates and phosphonates as well as alkaline framework substances, such as carbonates and silicates, which are not capable of complex formation. In this case, "microcrystalline" zeolites are preferably used, which are at least 80% by weight of particles having a size between 10 and 0.01 µm and in particular between 8 and 0.1 µm.

Aus der deutschen Patentanmeldung 25 25 778 (P&G) sind Wasch- und Reinigungsmittel bekannt, die 0,5 bis 3 Gew.-% Alkalisilikat (berechnet als Feststoff) enthalten. Diese Mittel werden entweder durch ein übliches Mischverfahren, bei dem die festen Silikate oder eine entsprechende Menge einer Wasserglaslösung zusammen mit den anderen Hauptbestandteilen vermischt werden, oder durch ein Sprühtrocknungsverfahren, bei dem der Slurry sowohl Zeolith als auch die entsprechende Menge Alkalisilikat enthält, hergestellt. Die Alkalisilikate dienen dabei als Korrosionsinhibitoren.From the German patent application 25 25 778 (P&G) washing and cleaning agents are known which contain 0.5 to 3 wt .-% alkali silicate (calculated as a solid). These agents are prepared either by a conventional mixing process in which the solid silicates or a corresponding amount of a water glass solution are mixed together with the other main components, or by a spray drying process in which the slurry contains both zeolite and the corresponding amount of alkali silicate. The alkali silicates serve as corrosion inhibitors.

Aus der deutschen Patentanmeldung 26 56 009 (Colgate) ist ein Waschmittel bekannt, das 12 bis 25 Gew.-% Zeolith, insbesondere des Typs 4A, 5 bis 20 Gew.-% eines Natriumsilikats der Zusammensetzung Na₂O:SiO₂ von 1:1 bis 1:3,2, insbesondere von 1:2,0 bis 1:2,6, sowie ein Peroxybleichmittel enthält. Nach den Angaben dieser Literaturstelle sollen unerwünschte Ablagerungen der wasserunlöslichen Zeolith-Teilchen auf der Wäsche dadurch verhindert werden, daß 0,3 bis 3 Gew.-% eines Polymeren aus der Gruppe Carboxymethylcellulose, niedere Alkylcellulose, Hydroxy-Niederalkyl-NiederalkylCellulose, Polyvinylalkohol, Polyvinylacetat und Polyvinylpyrrolidon eingesetzt werden. Der Zeolith besitzt einen mittleren Teilchendurchmesser von 0,5 bis 12 µm, vorzugsweise von 5 bis 9 µm.A detergent is known from German patent application 26 56 009 (Colgate) which contains 12 to 25% by weight of zeolite, in particular of type 4A, 5 to 20% by weight of a sodium silicate with the composition Na 2 O: SiO 2 of 1: 1 to 1 : 3.2, in particular from 1: 2.0 to 1: 2.6, and contains a peroxy bleach. According to the information in this reference, undesired deposits of the water-insoluble zeolite particles on the laundry are to be prevented by 0.3 to 3% by weight of a polymer from the group carboxymethyl cellulose, lower alkyl cellulose, hydroxy-lower alkyl-lower alkyl cellulose, polyvinyl alcohol, polyvinyl acetate and Polyvinyl pyrrolidone can be used. The zeolite has an average particle diameter of 0.5 to 12 μm, preferably 5 to 9 μm.

Die europäische Patentanmeldung 10 247 (Henkel) beschreibt ein Waschmittel, das Tenside in üblichen Mengen, Zeolith, Alkalisilikat und gegebenenfalls ein Peroxybleichmittel enthält. Durch den Zusatz wasserlöslicher organischer Komplexbildner aus der Gruppe der substituierten Alkandi- und Alkantri-Phosphonsäuren, die in Form ihrer Alkali- und/oder Erdalkalisalze vorliegen, wird ein Waschmittel erhalten, das nicht nur eine gute Primärwaschwirkung aufweist, sondern das auch die Bildung von Faserinkrustationen reduziert. Außerdem wird durch den Zusatz dieser Phosphonate eine erhöhte Bleichstabilität trotz Abwesenheit üblicher Stabilisatoren wie Magnesiumsilikat und Aminopolycarboxylat erzielt. Das Mittel enthält 20 bis 65 Gew.-% eines feinteiligen Zeoliths, wie er in der deutschen Patentanmeldung DE 24 12 837 beschrieben wird, und 1 bis 7 Gew.-% festes, pulverförmiges Natriumsilikat der molaren Zusammensetzung Na₂O:SiO₂ von 1:2 bis 1:2,2. Das Mittel besteht aus einem Gemisch aus wenigstens 2 Pulverbestandteilen, von denen der erste durch Sprühtrocknung einer wäßrigen Aufschlämmung, die den Zeolith, Tenside und gegebenenfalls die wasserlöslichen organischen komplexbildenden Gerüstsubstanzen enthält, erhalten wird und der zweite Pulverbestandteil aus dem Natriumsilikatpulver sowie gegebenenfalls aus den wasserlöslichen Phosphonaten und weiteren Waschmittelzusätzen, die hydrolyse- und/oder temperaturempfindlich sind, besteht.European patent application 10 247 (Henkel) describes a detergent which contains surfactants in conventional amounts, zeolite, alkali silicate and optionally a peroxy bleach. By adding water-soluble organic complexing agents from the group of substituted alkanedi- and alkanetri-phosphonic acids, which are present in the form of their alkali and / or alkaline earth salts, a detergent is obtained which not only has a good primary washing action, but also the formation of fiber incrustations reduced. In addition, the addition of these phosphonates results in increased bleaching stability despite the absence of conventional stabilizers such as magnesium silicate and aminopolycarboxylate. The agent contains 20 to 65 wt .-% of a finely divided zeolite, as described in German patent application DE 24 12 837, and 1 to 7 wt .-% solid, powdered sodium silicate of the molar composition Na₂O: SiO₂ from 1: 2 to 1: 2.2. The composition consists of a mixture of at least 2 powder constituents, the first of which is obtained by spray drying an aqueous slurry containing the zeolite, surfactants and optionally the water-soluble organic complex-forming framework substances, and the second powder constituent from the sodium silicate powder and optionally from the water-soluble phosphonates and other detergent additives that are sensitive to hydrolysis and / or temperature.

Aus der europäischen Patentanmeldung 240 356 (Unilever) sind Waschmittel bekannt, die außer Zeolith und wasserlöslichen Natriumsilikaten, wie sie in der europäischen Patentanmeldung 10 247 beschrieben wurden, polymere Polycarboxylate und deren Derivate, beispielsweise Polyacrylate und Salze von Acrylsäure-Maleinsäure-Copolymeren, enthalten. Dabei werden diese polymeren Polycarboxylate bei der Herstellung des Waschmittels zusammen mit dem Zeolith sprühgetrocknet.European patent application 240 356 (Unilever) discloses detergents which, in addition to zeolite and water-soluble sodium silicates, as described in European patent application 10 247, contain polymeric polycarboxylates and their derivatives, for example polyacrylates and salts of acrylic acid-maleic acid copolymers. These polymeric polycarboxylates are spray dried together with the zeolite during the production of the detergent.

Aus den europäischen Patentanmeldungen 337 217 und 337 219 (Hoechst) sind Gerüststoffkombinationen für Waschmittel bekannt, die kristalline Schichtsilikate und gegebenenfalls Phosphate und Polycarboxylate wie Citrate, Glykonate, NTA und/oder Iminodiacetate, aber keinen Zeolith enthalten. Die Mittel, die 10 bis 50 Gew.-% kristallines Schichtsilikat enthalten, zeichnen sich durch ein lagerstabilisiertes Bleichsystem aus.From European patent applications 337 217 and 337 219 (Hoechst), builder combinations for detergents are known which contain crystalline phyllosilicates and optionally phosphates and polycarboxylates such as citrates, glykonates, NTA and / or iminodiacetates, but no zeolite. The agents, which contain 10 to 50% by weight of crystalline layered silicate, are characterized by a storage-stabilized bleaching system.

In der europäischen Patentanmeldung 405 122 (Hoechst) wird eine Builderkombination für Textilwaschmittel angegeben, wobei die Builderkombination aus einem Gemisch aus Zeolith und kristallinem Natriumschichtsilikat in einem Verhältnis von 4:1 bis 1:4 besteht. Durch die Verwendung eines Textilwaschmittels, das diese Builderkombination enthält, kann die Inkrustation des Gewebes verringert werden.European patent application 405 122 (Hoechst) specifies a builder combination for textile detergents, the builder combination consisting of a mixture of zeolite and crystalline sodium phyllosilicate in a ratio of 4: 1 to 1: 4. By using a textile detergent that contains this builder combination, the incrustation of the fabric can be reduced.

Die Aufgabe der Erfindung bestand darin, das Gebiet der phosphatfreien Gerüststoffkombinationen für die Anwendung in Textilwaschmitteln weiter zu entwickeln mit dem Ziel, den Anteil der organischen synthetischen Verbindungen zu reduzieren. Überraschenderweise wurde nun gefunden, daß Waschmittel, die als Gerüststoffe eine spezielle Kombination aus feinteiligem Zeolith mit relativ engem Teilchengrößenspektrum und Alkalisilikat enthalten, die hohen Anforderungen, die an moderne Waschmittel gestellt werden, erfüllen.The object of the invention was to further develop the field of phosphate-free builders combinations for use in textile detergents with the aim of reducing the proportion of organic synthetic compounds. Surprisingly, it has now been found that detergents which contain a special combination of finely divided zeolite with a relatively narrow particle size spectrum and alkali silicate as builders meet the high demands placed on modern detergents.

Gegenstand der Erfindung ist ein Waschmittel, das Tenside, Zeolith, Alkalisilikat und gegebenenfalls ein Peroxybleichmittel enthält und das dadurch gekennzeichnet ist, daß es 30 bis 65 Gew.-% eines feinteiligen, hydratisierten Zeoliths mit einer mittleren Teilchengröße von 1 bis 5 µm, 1 bis 15 Gew.-% eines festen Alkalisilikats der molaren Zusammensetzung M₂O : Si₂O von 1:2,0 bis 1:3,0, worin M für Natrium und/oder Kalium steht, enthält, mit der Maßgabe, daß das Mittel frei von wasserlöslichen organischen Komplexbildnern aus der Gruppe der substituierten Phosphonate, frei von polymeren Polycarboxylaten und im wesentlichen frei von Alkalicarbonaten ist.The invention relates to a detergent which contains surfactants, zeolite, alkali silicate and optionally a peroxy bleach and which is characterized in that it comprises 30 to 65% by weight of a finely divided, hydrated zeolite with an average particle size of 1 to 5 µm, 1 to 15 wt .-% of a solid alkali silicate of the molar composition M₂O: Si₂O from 1: 2.0 to 1: 3.0, wherein M is sodium and / or potassium, with the proviso that the agent is free of water-soluble organic Complexing agents from the group of substituted phosphonates, free of polymeric polycarboxylates and essentially free of alkali carbonates.

Der feinteilige, hydratisierte Zeolith weist im allgemeinen einen Wassergehalt von 17 bis 25 Gew.-% auf. Die Mengenangaben für Zeolith beziehen sich jedoch auf die wasserfreie Aktivsubstanz. Geeignete Zeolithe sind solche vom Zeolith A-Typ. Brauchbar sind ferner Gemische aus Zeolith NaA und NaX, wobei der Anteil des Zeoliths NaX in derartigen Gemischen zweckmäßigerweise unter 30 % liegt. Bevorzugte Zeolithe besitzen eine mittlere Teilchengröße zwischen 1,8 und 4,5 µm, insbesondere zwischen 2,0 und 4,0 µm (Meßmethode: Fraunhofer-Beugung; Mittelwert der Volumenverteilung). Der Gehalt der Mittel an feinteiligem, insbesondere kristallinem, hydratisiertem Zeolith beträgt vorzugsweise 30 bis 55 Gew.-% und insbesondere 32 bis 54 Gew.-%, bezogen auf wasserfreie Aktivsubstanz.The finely divided, hydrated zeolite generally has a water content of 17 to 25% by weight. However, the quantities for zeolite relate to the anhydrous active substance. Suitable zeolites are those of the zeolite A type. Mixtures of zeolite NaA and NaX can also be used, the proportion of the zeolite NaX in such mixtures advantageously being less than 30%. Preferred zeolites have an average particle size between 1.8 and 4.5 μm, in particular between 2.0 and 4.0 μm (measurement method: Fraunhofer diffraction; mean volume distribution). The content of the agents in finely divided, in particular crystalline, hydrated zeolite is preferably 30 to 55 wt .-% and in particular 32 to 54 wt .-%, based on anhydrous active substance.

Die festen Alkalisilikate können amorph oder kristallin, als Pulver oder als Granulat, beispielsweise als walzenkompaktiertes Splittergranulat, oder als sprühgetrocknetes Compound vorliegen. Bevorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die amorphen Natriumsilikate, mit einem molaren Verhältnis Na₂O:SiO₂ von 1:2 bis 1:2,8 . Derartige amorphe Alkalisilkate sind beispielsweise unter dem Namen Portil(R) (Henkel) im Handel erhältlich. Als kristalline Silikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können, werden vorzugsweise kristalline Schichtsilikate der Formel (I) NaMSixO2+1·yH₂O eingesetzt, in denen M für Natrium steht, x die Werte 2 oder 3 annimmt und y eine Zahl von 0 bis 20 ist. Insbesondere bevorzugt sind sowohl β- als auch δ-Natriumdisilikate Na₂Si₂O₅. Der Gehalt der Mittel an Alkalisilikaten beträgt vorzugsweise 2 bis 10 Gew.-% und insbesondere 3 bis 10 Gew.-%, bezogen auf wasserfreie Substanz. Insbesondere beträgt der Gehalt der Mittel an amorphen Natriumsilikaten 3,5 bis 8 Gew.-%, bezogen auf wasserfreie Substanz. Das Gewichtsverhältnis Zeolith : amorphem Silikat, jeweils bezogen auf wasserfreie Substanz, beträgt vorzugsweise 4:1 bis 10:1. Die kristallinen Schichtsilikate werden vorzugsweise in Mengen von 2 bis 7 Gew.-% eingesetzt, wobei das Gewichtsverhältnis Zeolith zu kristallinem Schichtsilikat, jeweils bezogen auf wasserfreie Substanz, mindestens 5:1 beträgt. In Mitteln, die sowohl amorphe als auch kristalline Alkalisilikate enthalten, beträgt das Gewichtsverhältnis amorphes Alkalisilikat : kristallinem Alkalisilikat vorzugsweise 1:2 bis 2:1 und insbesondere 1:1 bis 2:1.The solid alkali silicates can be amorphous or crystalline, as powder or as granules, for example as roller-compacted chip granules, or as a spray-dried compound. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 2 to 1: 2.8. Such amorphous alkali metal silicates are commercially available, for example, under the name Portil (R) (Henkel). As crystalline silicates, which may be present alone or in a mixture with amorphous silicates, crystalline sheet silicates of the formula (I) NaMSi x O 2 + 1 .yH₂O are preferably used, in which M represents sodium, x assumes the values 2 or 3 and y is a number from 0 to 20. Both β- and δ-sodium disilicates Na₂Si₂O₅ are particularly preferred. The content of alkali silicates in the compositions is preferably 2 to 10% by weight and in particular 3 to 10% by weight, based on the anhydrous substance. In particular, the amorphous sodium silicate content of the agents is 3.5 to 8% by weight, based on the anhydrous substance. The weight ratio of zeolite: amorphous silicate, based in each case on anhydrous substance, is preferably 4: 1 to 10: 1. The crystalline layered silicates are preferably used in amounts of 2 to 7% by weight, the weight ratio of zeolite to crystalline layered silicate, based in each case on the anhydrous substance, being at least 5: 1. In compositions which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate: crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

Die Mittel enthalten keine wasserlöslichen organischen Komplexbildner aus der Gruppe der Phosphonate, so daß die Mittel einen rechnerischen Phosphorgehalt von 0 % aufweisen.The agents do not contain any water-soluble organic complexing agents from the group of the phosphonates, so that the agents have a calculated phosphorus content of 0%.

Auch polymere Polycarboxylate, beispielsweise Polyacrylate, Polymethacrylate, Polymaleate oder Copolymere der Acrylsäure mit Maleinsäure bzw. Maleinsäureanhydrid, die üblicherweise in Kombination mit Zeolith eingesetzt werden, sind in dem erfindungsgemäßen Erzeugnis nicht enthalten, da sie dessen Primär- und Sekundärwaschvermögen nicht verbessern.Polymeric polycarboxylates, for example polyacrylates, polymethacrylates, polymaleates or copolymers of acrylic acid with maleic acid or maleic anhydride, which are usually used in combination with zeolite, are also not present in the product according to the invention, since they do not improve its primary and secondary washability.

Die Mittel sind außerdem im wesentlichen frei von Alkalicarbonaten, dies bedeutet, daß sie nicht mehr als etwa 5 Gew.-% , vorzugsweise nicht mehr als 4 Gew.-% und mit besonderem Vorteil nicht mehr als 3 Gew.-% an Alkalicarbonaten, insbesondere an Natriumcarbonat, enthalten. In Abhängigkeit von der Rezeptur ist es nicht ausgeschlossen, daß auch ein Gehalt an Alkalicarbonat in dem genannten Bereich zu einer verstärkten Inkrustationsbildung beiträgt. Im Rahmen dieser Erfindung ist deshalb vorgesehen, daß Alkalicarbonat nur in den Mengen zugesetzt werden darf, in denen es nicht zu einer verstärkten Inkrustationsbildung beiträgt.The agents are also essentially free of alkali carbonates, which means that they contain no more than about 5% by weight, preferably no more than 4% by weight and particularly advantageously no more than 3% by weight of alkali carbonates, in particular of sodium carbonate. Depending on the recipe, it cannot be ruled out that an alkali carbonate content in the range mentioned also contributes to increased incrustation. In the context of this invention it is therefore provided that alkali carbonate may only be added in the amounts in which it does not contribute to increased incrustation.

Bevorzugte Waschmittel enthalten Peroxybleichmittel und insbesondere Peroxybleichmittel in Kombination mit Bleichaktivatoren. Unter den als Bleichmittel dienenden, in Wasser H₂O₂ liefernden Verbindungen haben das Natriumperborat-Tetrahydrat und das Natriumperborat-Monohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Peroxycarbonat oder persaure Salze organischer Säuren, wie Perbenzoate oder Salze der Diperdodecandisäure. Geeignete Bleichaktivatoren für diese Peroxybleichmittel sind beispielsweise die mit H₂O₂ organische Persäuren bildenden N-Acyl- bzw. O-Acyl-Verbindungen, vorzugsweise N,N'-tetraacylierte Diamine wie N,N,N'N'-Tetraacetylethylendiamin. Der Gehalt der Mittel an Peroxybleichmittel beträgt vorzugsweise 12 bis 30 Gew.-%, insbesondere in Kombination mit 1 bis 10 Gew.-%, vorzugsweise 2 bis 8 Gew.-%, eines Bleichaktivators.Preferred detergents contain peroxy bleach and in particular peroxy bleach in combination with bleach activators. Of the compounds used as bleaching agents, which supply H₂O₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaches that can be used are, for example, peroxycarbonate or peracidic salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid. Suitable bleach activators for these peroxy bleaches are, for example, the N-acyl or O-acyl compounds which form organic peracids with H₂O₂, preferably N, N'-tetraacylated diamines such as N, N, N'N'-tetraacetylethylenediamine. The content of peroxy bleaching agent in the agents is preferably 12 to 30% by weight, in particular in combination with 1 to 10% by weight, preferably 2 to 8% by weight, of a bleach activator.

Die erfindungsgemäßen Waschmittel zeichnen sich gegenüber Mitteln des Standes der Technik, die üblicherweise polymere Polycarboxylate und/oder Alkalicarbonate in größeren Mengen enthalten, nicht nur durch eine verringerte Bildung von Faserinkrustationen aus. Überraschenderweise weisen sie auch eine verbesserte Bleichwirkung bzw. eine verbesserte Stabilisierung des Peroxybleichmittels auf, obwohl sie keine üblichen Stabilisatoren wie Phosphonat, Magnesiumsilikat oder weitere Komplexbildner wie die Salze der Nitrilotriessigsäure und der Ethylendiamintetraessigsäure enthalten.The detergents according to the invention are not only distinguished by a reduced formation of fiber incrustations compared to agents of the prior art which usually contain polymeric polycarboxylates and / or alkali metal carbonates in larger amounts. Surprisingly, they also have an improved bleaching action or an improved stabilization of the peroxy bleaching agent, although they contain no conventional stabilizers such as phosphonate, magnesium silicate or other complexing agents such as the salts of nitrilotriacetic acid and ethylenediaminetetraacetic acid.

Als weitere Bestandteile enthalten die Wasch- und Reinigungsmittel bekannte Verbindungen aus der Gruppe der anionischen, nichtionischen und zwitterionischen Tenside. Insbesondere kommen als Aniontenside Sulfonate und Sulfate sowie Seifen aus vorzugsweise natürlichen Fettsäuren bzw. Fettsäuregemischen in Betracht. Als Tenside vom Sulfonattyp werden beispielsweise C₉-C₁₃-Alkylbenzolsulfonate, Olefinsulfonate, Ester von α-Sulfofettsäuren oder α-Sulfofettsäure-disalze eingesetzt. Geeignete Tenside vom Sulfattyp sind die Schwefelsäuremonoester aus primären Alkoholen natürlichen oder synthetischen Ursprungs, d. h. aus C₁₂-C₁₈-Fettalkoholen oder aus C₁₀-C₂₀-Oxoalkoholen, und diejenigen sekundärer Alkohole dieser Kettenlänge. Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid (EO) umgesetzten Alkohole kommen in Betracht. Als nichtionische Tenside sind vor allem Anlagerungsprodukte von vorzugsweise 2 bis 20 Mol EO an 1 Mol einer aliphatischen Verbindung mit im wesentlichen 10 bis 20 Kohlenstoffatomen aus der Gruppe der Alkohole, Carbonsäuren, Fettamine, Carbonsäureamide und Alkansulfonamide von Interesse. Wichtig sind neben den wasserlöslichen Niotensiden aber auch nicht bzw. nicht vollständig wasserlösliche Polyglykolether mit 2 bis 7 Ethylenglykoletherresten im Molekül, insbesondere dann, wenn sie zusammen mit wasserlöslichen nichtionischen oder anionischen Tensiden eingesetzt werden. Außerdem können als nichtionische Tenside auch Alkylpolyglykoside der allgemeinen Formel R-O-(G)x eingesetzt werden, in der R einen primären geradkettigen oder in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet, G ein Symbol ist, das für eine Glykose-Einheit mit 5 oder 6 C-Atomen steht, und der Oligomerisierungsgrad x zwischen 1 und 10 liegt.The detergents and cleaning agents contain known compounds from the group of anionic, nonionic and zwitterionic surfactants as further constituents. In particular, sulfonates come as anionic surfactants and sulfates and soaps from preferably natural fatty acids or fatty acid mixtures. C Tens-C₁₃ alkylbenzenesulfonates, olefin sulfonates, esters of α-sulfofatty acids or α-sulfofatty acid disalts are used, for example, as surfactants of the sulfonate type. Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural or synthetic origin, ie from C₁₂-C₁₈ fatty alcohols or from C₁₀-C₂₀ oxo alcohols, and those of secondary alcohols of this chain length. The sulfuric acid monoesters of the alcohols reacted with 1 to 6 mol of ethylene oxide (EO) are also suitable. Addition products of preferably 2 to 20 moles of EO to 1 mole of an aliphatic compound with essentially 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides and alkanesulfonamides are of particular interest as nonionic surfactants. In addition to the water-soluble nonionic surfactants, polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule that are not or not completely water-soluble are also important, in particular when they are used together with water-soluble nonionic or anionic surfactants. In addition, alkyl polyglycosides of the general formula RO- (G) x can also be used as nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, C-atoms, methyl-branched, G is a symbol is a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10.

Der Gesamtgehalt der Mittel an Tensiden liegt im allgemeinen zwischen 5 und 40 Gew.-%. Vorzugsweise beträgt er 5 bis 30 Gew.-% und insbesondere 8 bis 25 Gew.-%.The total content of surfactants in the compositions is generally between 5 and 40% by weight. It is preferably 5 to 30% by weight and in particular 8 to 25% by weight.

Zu den sonstigen Wasch- und Reinigungsmittelbestandteilen, deren Anteil je nach Zusammensetzung der Mittel bis zu 40 Gew.-%, vorzugsweise 5 bis 30 Gew.-% und insbesondere 8 bis 20 Gew.-% beträgt, zählen Schauminhibitoren, optische Aufheller, Enzyme, textilweichmachende Stoffe, Farb- und Duftstoffe sowie Neutralsalze, Lösungsmittel und Wasser. Der Einsatz von Vergrauungsinhibitoren, die üblicherweise in modernen Textilwaschmitteln verwendet werden, ist nicht erforderlich und insbesondere auch nicht bevorzugt.Other detergent and cleaning agent components, the proportion of which, depending on the composition of the detergent, is up to 40% by weight, preferably 5 to 30% by weight and in particular 8 to 20% by weight, include foam inhibitors, optical brighteners, enzymes, fabric softening agents, dyes and fragrances as well as neutral salts, solvents and water. The use of graying inhibitors, which are usually used in modern textile detergents, is not necessary and, in particular, is also not preferred.

Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Cellulasen und Amylasen bzw. deren Gemische in Frage. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheniformis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen.Enzymes from the class of proteases, lipases, cellulases and amylases or their mixtures are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.

Geeignete nichttensidartige und bevorzugt eingesetzte Schauminhibitoren sind Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure. Mit Vorteil werden auch Gemische verschiedener Schauminhibitoren verwendet, z. B. solche aus Silikonen und Paraffinen oder Wachsen. Vorzugsweise sind die Schauminhibitoren an eine granulare, in Wasser lösliche bzw. dispergierbare Trägersubstanz gebunden.Suitable non-surfactant-like and preferably used foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica. Mixtures of different foam inhibitors are also advantageously used, e.g. B. from silicone and paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.

In einer bevorzugten Ausführungsform enthalten pulverförmige oder granulare Waschmittel 10 bis 30 Gew.-% Tenside, 30 bis 45 Gew.-% eines feinteiligen, hydratisierten Zeoliths mit einer mittleren Teilchengröße von 2,0 bis 3,8 µm, 2 bis 10 Gew.-% amorphes Natriumsilikat mit einem molaren Verhältnis Na₂O : SiO₂ von 2,0 bis 2,8 oder einer Mischung aus dem genannten amorphen Natriumsilikat mit kristallinem Schichtsilikat, vorzugsweise β-Natriumdisilikat oder δ-Natriumdisilikat, sowie 18 bis 30 Gew.-% Peroxybleichmittel, vorzugsweise Perborat, und 2 bis 8 Gew.-% eines Bleichaktivators, vorzugsweise TAED.In a preferred embodiment, powdery or granular detergents contain 10 to 30% by weight of surfactants, 30 to 45% by weight of a finely divided, hydrated zeolite with an average particle size of 2.0 to 3.8 μm, 2 to 10% by weight. % amorphous sodium silicate with a molar ratio Na₂O: SiO₂ of 2.0 to 2.8 or a mixture of the above amorphous sodium silicate with crystalline layered silicate, preferably β-sodium disilicate or δ-sodium disilicate, and 18 to 30% by weight peroxy bleach, preferably Perborate, and 2 to 8% by weight of a bleach activator, preferably TAED.

Die erfindungsgemäßen Waschmittel können in an sich üblicher Weise, beispielsweise durch Mischen, Granulieren und/oder durch Sprühtrocknung hergestellt werden. Dabei ist es möglich, die Gerüststoffe Zeolith und festes Alkalisilikat einzeln in an sich üblicher Weise und beliebiger Reihenfolge in die Mittel einzuarbeiten.The detergents according to the invention can be prepared in a conventional manner, for example by mixing, granulating and / or by spray drying. It is possible to incorporate the builders zeolite and solid alkali silicate into the agents individually in a conventional manner and in any order.

Die schüttfähigen pulverförmigen oder granularen Präparate bestehen vorzugsweise aus einem trockenen homogenen Gemisch von mindestens 2 Pulverkomponenten, wovon zumindest die erste als sprühgetrocknetes Granulat vorliegt. Es ist durch eine in konventioneller Weise durchgeführte Sprühtrocknung eines Slurries erhältlich, der zumindest die anionischen Tenside sowie gegebenenfalls nichtionische Tenside enthält.The pourable powder or granular preparations preferably consist of a dry homogeneous mixture of at least 2 powder components, at least the first of which is in the form of spray-dried granules. It is done by a conventional way Spray drying of a slurry available which contains at least the anionic surfactants and optionally nonionic surfactants.

Vorzugsweise enthält dieser Slurry zusätzlich wenigstens einen Teil des Zeoliths und/oder des Silikats. Für den Fall, daß der Slurry Zeolith-haltig ist, kann der Slurry einen Teil, aber nicht mehr als 3 Gew.-% und insbesondere nicht mehr als 2 Gew.-%, jeweils bezogen auf das gesamte, fertige Mittel, der amorphen Silikate enthalten. Der Rest der als Pulver oder Granulat vorliegenden amorphen Alkalisilikate wird ebenso wie die gegebenenfalls vorhandenen kristallinen Schichtsilikate, die in granularer Form oder adsorbiert an einen Träger, der beispielsweise aus Natriumsulfat besteht, nachträglich dem Sprühprodukt zugemischt. Insbesondere ist es jedoch bevorzugt, daß der Zeolith-haltige Slurry frei von amorphen Alkalisilikaten ist und diese insgesamt dem sprühgetrockneten Produkt nachträglich zugegeben werden.This slurry preferably additionally contains at least part of the zeolite and / or the silicate. In the event that the slurry contains zeolite, the slurry can contain a portion, but not more than 3% by weight and in particular not more than 2% by weight, in each case based on the total finished composition of the amorphous silicates contain. The rest of the amorphous alkali silicates present as powder or granules, like the crystalline sheet silicates which may be present, which are in granular form or adsorbed on a carrier which consists, for example, of sodium sulfate, are subsequently mixed into the spray product. In particular, however, it is preferred that the zeolite-containing slurry be free of amorphous alkali silicates and that these are subsequently added to the spray-dried product.

Falls der Slurry jedoch keinen Zeolith enthält, so ist es möglich, den gesamten Anteil der amorphen Alkalisilikate in den Slurry einzuarbeiten und sprühzutrocknen. Die gegebenenfalls vorhandenen kristallinen Schichtsilikate werden jedoch auch in diesem Fall vorzugsweise nicht sprühgetrocknet, sondern in granularer Form oder an einen Träger adsorbiert nachträglich zugegeben. Der Zeolith wird dann ebenfalls als Pulver oder vorzugsweise als handelsübliches Compound, beispielsweise als Wessalith (R) CS oder Wessalith (R) CB (Handelsprodukte der Firma Degussa, Bundesrepublik Deutschland) in die Mittel eingearbeitet.However, if the slurry does not contain zeolite, it is possible to incorporate the entire proportion of the amorphous alkali silicates into the slurry and to spray-dry them. In this case, however, the crystalline layered silicates which may be present are preferably not spray-dried, but are added subsequently in granular form or adsorbed onto a carrier. The zeolite is then also incorporated into the compositions as a powder or, preferably, as a commercially available compound, for example as Wessalith (R) CS or Wessalith (R) CB (commercial products from Degussa, Federal Republic of Germany).

Ebenso ist es möglich, daß ein Zeolith-haltiger und ein Silikat-haltiger Slurry getrennt sprühgetrocknet und im Anschluß daran vermischt werden. Insbesondere ist es jedoch von Vorteil, wenn der Zeolith-haltige Slurry und der Silikat-haltige Slurry gleichzeitig in einen Sprühturm eingebracht werden.It is also possible for a zeolite-containing and a silicate-containing slurry to be spray-dried separately and then mixed. However, it is particularly advantageous if the zeolite-containing slurry and the silicate-containing slurry are introduced into a spray tower at the same time.

Bleichmittel wie Perborat werden wie üblich wegen ihrer thermischen Empfindlichkeit nicht zusammen mit den Bestandteilen der ersten Pulverkomponente sprühgetrocknet, sondern ebenfalls erst nachträglich dem Sprühprodukt zugemischt.Because of their thermal sensitivity, bleaching agents such as perborate are not spray-dried together with the constituents of the first powder component, but are also only added to the spray product afterwards.

BeispieleExamples

Es wurden granulare Waschmittel nachstehender Zusammensetzung hergestellt und getestet. Das Perborat, der Bleichaktivator, das Alkalisilikat sowie Enzymgranulat und Silikonölgranulat wurden dem sprühgetrockneten Produkt aus einem Slurry, der die restlichen Bestandteile enthielt, nachträglich zugemischt. Die Prüfung erfolgte unter praxisnahen Bedingungen in Haushaltswaschmaschinen (Miele W 717). Die Waschbedingungen werden in den einzelnen Beispielen genauer angegeben. Die Messung des Weißgrades erfolgte in einem Zeiß-Reflektometer bei 460 nm (Ausblendung des Aufheller-Effektes). Hierbei sind Remissionsunterschiede von 2 % und mehr signifikant und direkt vom Verbraucher nachvollziehbar.Granular detergents of the following composition were produced and tested. The perborate, the bleach activator, the alkali silicate as well as enzyme granulate and silicone oil granulate were subsequently mixed into the spray-dried product from a slurry which contained the remaining constituents. The test was carried out under practical conditions in household washing machines (Miele W 717). The washing conditions are specified in more detail in the individual examples. The degree of whiteness was measured in a Zeiss reflectometer at 460 nm (suppression of the brightener effect). Remission differences of 2% and more are significant and directly understandable by the consumer.

Das erfindungsgemäße Mittel E und das Vergleichsmittel V besaßen folgende Zusammensetzung: E V C₁₂-Alkylbenzolsulfonat-Natriumsalz 8,0 8,0 C₁₂-C₁₈-Fettalkohol mit 5 EO 5,5 5,5 C₁₂-C₁₈-Fettsäureseife-Natriumsalz 1,5 1,5 Zeolith NaA (wasserfreie AS) mittlere Teilchengröße 4,2 µm - 24,0 Zeolith NaA (wasserfreie AS) mittlere Teilchengröße 3,3 µm 38,0 - amorphes Natriumsilikat Na₂O:SiO₂ = 1:2,0 5,5 - amorphes Natriumsilikat Na₂O:SiO₂ = 1:3,3 - 3,5 Natriumcarbonat (wasserfrei) - 12,5 Acrylsäure-Maleinsäure-Copolymer-Natriumsalz (Sokalan CP5(R), Handelsprodukt der Firma BASF, Deutschland) - 3,5 Natriumperborat-Tetrahydrat 25,0 25,0 TAED 2,0 2,0 1-Hydroxyethan-1,1-diphosphonat - 0,4 Magnesiumsilikat - 1,1 Rest (Enzym, Parfüm, Silikonöl, optischer Aufheller, Natriumsulfat, Wasser) 14,5 13,0 Agent E according to the invention and comparative agent V had the following composition: E V C₁₂-alkylbenzenesulfonate sodium salt 8.0 8.0 C₁₂-C₁₈ fatty alcohol with 5 EO 5.5 5.5 C₁₂-C₁₈ fatty acid soap sodium salt 1.5 1.5 Zeolite NaA (anhydrous AS) average particle size 4.2 µm - 24.0 Zeolite NaA (anhydrous AS) average particle size 3.3 µm 38.0 - amorphous sodium silicate Na₂O: SiO₂ = 1: 2.0 5.5 - amorphous sodium silicate Na₂O: SiO₂ = 1: 3.3 - 3.5 Sodium carbonate (anhydrous) - 12.5 Acrylic acid-maleic acid copolymer sodium salt (Sokalan CP5 ( R) , commercial product from BASF, Germany) - 3.5 Sodium perborate tetrahydrate 25.0 25.0 TAED 2.0 2.0 1-hydroxyethane-1,1-diphosphonate - 0.4 Magnesium silicate - 1.1 Rest (enzyme, perfume, silicone oil, optical brightener, sodium sulfate, water) 14.5 13.0

Beispiel 1: Stabilisierung des Peroxybleichmittels Example 1: Stabilization of the peroxy bleach

Waschbedingungen :Washing conditions:
Leitungswasser von 17°d (äquivalent 170 mg CaO/l), Hauptwaschgang bei 25 - 90°C (Aufheizzeit 60 Minuten, 15 Minuten bei 90°C), Flottenverhältnis (kg Wäsche: 1 Waschlauge im Hauptwaschgang) 1:4, 5maliges Nachspülen mit Leitungswasser, Abschleudern und Trocknen; Dosierung des Waschmittels: 146 g.Tap water of 17 ° d (equivalent to 170 mg CaO / l), main wash at 25 - 90 ° C (heating up time 60 minutes, 15 minutes at 90 ° C), liquor ratio (kg of laundry: 1 wash liquor in the main wash) 1: 4, rinse 5 times with tap water, spinning and drying; Dosage of the detergent: 146 g.

Die Maschinen wurden mit 3,5 kg normal verschmutzter Haushaltswäsche (Bettwäsche, Tischwäsche, Leibwäsche) und 0,5 kg Testgewebe beschickt. Als Testgewebe wurden Streifen aus standardisiertem Baumwollgewebe (Wäscheforschungsanstalt Krefeld), aus veredeltem Baumwollgewebe und aus einem Mischgewebe aus Polyester und veredelter Baumwolle verwendet.

Anschmutzungen:
Fett-/Pigment-Anschmutzungen und bleichbare Anschmutzungen wie Rotwein, Tee, Kakao, Waldbeere
Der Versuch wurde dreimal wiederholt. Die angebenen Remissionswerte spiegeln die Durchschnittswerte über alle Messungen wider.The machines were loaded with 3.5 kg of normally soiled household linen (bed linen, table linen, underwear) and 0.5 kg of test fabric. Strips of standardized cotton fabric (Krefeld laundry research institute), of refined cotton fabric and of a mixed fabric of polyester and refined cotton were used as the test fabric.
Soiling:
Fat / pigment stains and bleachable stains such as red wine, tea, cocoa, wild berries
The experiment was repeated three times. The specified reflectance values reflect the average values across all measurements.

In zwei weiteren Versuchsreihen wurden zu der Waschflotte jeweils 5ppm bzw. 10ppm zweiwertige Kupferionen (Cu²⁺ in Form von Kupfersulfat) hinzugegeben. Die angegebenen Remissionswerte entsprechen auch hier den Durchschnittswerten über alle Messungen.In two further test series, 5ppm and 10ppm divalent copper ions (Cu²⁺ in the form of copper sulfate) were added to the wash liquor added. The specified reflectance values also correspond to the average values across all measurements.

Aus Tabelle 1 geht hervor, daß in der Versuchsreihe a) (Waschmittel ohne Kupfer-Zugabe) die Mittel E und V vergleichbare Leistungen aufweisen. In der Versuchsreihe b) (Waschmittel und 5ppm Cu²⁺) zeigte das erfindungsgemäße Waschmittel E bei allen Anschmutzungen signifikant bessere Leistungen als V. In der Versuchsreihe c) (Waschmittel und 10ppm Cu²⁺) wurde der Leistungsunterschied zwischen E und V zugunsten von E noch größer. Tabelle 1 Versuchsreihe % Remission für Waschmittel E V a) Waschmittel 73,9 74,4 b) Waschmittel + 5ppm Cu²⁺ 68,1 63,3 c) Waschmittel + 10ppm Cu²⁺ 53,3 47,7 Table 1 shows that in the test series a) (detergent without the addition of copper), agents E and V have comparable performances. In the test series b) (detergent and 5ppm Cu²⁺), the detergent E according to the invention performed significantly better than V in all soiling. In the test series c) (detergent and 10ppm Cu²⁺) the performance difference between E and V in favor of E was even greater . Table 1 Trial series % Remission for detergent E V a) Detergent 73.9 74.4 b) Detergent + 5ppm Cu²⁺ 68.1 63.3 c) Detergent + 10ppm Cu²⁺ 53.3 47.7

Beispiel 2: Sekundärwirkungen Example 2 : secondary effects

Waschbedingungen: Leitungswasser von 23°d, 3,5 kg saubere Füllwäsche, Dosierung des Waschmittels 146 g, 25 Wäschen; alle weiteren Parameter wie in Beispiel 1.Washing conditions: tap water of 23 ° d, 3.5 kg of clean laundry, dosage of detergent 146 g, 25 washes; all other parameters as in example 1.

Aus Tabelle 2 geht hervor, daß sowohl der Aschegehalt (gemessen an Frottiergewebe) als auch die Inkrustation (gemessene Gewichtszunahme an Bleichnesselgewebe) bei dem Vergleichsmittel V höher ausfallen als bei dem erfindungsgemäßen Mittel E. Tabelle 2 Mittel % Asche (Frottier) % Inkrustation (Bleichnessel) E 1,37 2,54 V 2,82 3,40 From Table 2 it can be seen that both the ash content (measured on terry cloth) and the incrustation (measured weight gain on bleaching nettle tissue) are higher for the comparative agent V than for the agent E. Table 2 medium % Ash (terry) % Incrustation (bleaching nettle) E 1.37 2.54 V 2.82 3.40

Vergleichbare Ergebnisse wurden bei der Remissionsmessung erzielt, wenn statt 5,5 Gew.-% eines amorphen Natriumsilikats mit dem molaren Verhältnis Na₂O:SiO₂ von 1:2,0 ein amorphes Natriumsilikat mit einem molaren Verhältnis von 1:2,6, ein kristallines β-Disilikat oder eine Mischung aus 3,5 Gew.-% eines amorphen Natriumsilikats und 2 Gew.-% eines kristallinen δ-Disilikats eingesetzt wurden.Comparable results were obtained in the remission measurement if, instead of 5.5% by weight of an amorphous sodium silicate with the molar ratio Na₂O: SiO₂ of 1: 2.0, an amorphous sodium silicate with a molar ratio of 1: 2.6, a crystalline β Disilicate or a mixture of 3.5% by weight of an amorphous sodium silicate and 2% by weight of a crystalline δ-disilicate were used.

Claims (11)

  1. A detergent containing surfactants, zeolite, alkali metal silicate and optionally a peroxy bleaching agent, characterized in that it contains 30 to 65% by weight of a fine-particle hydrated zeolite having an average particle size of 1 to 5 µm, 1 to 15% by weight of a solid alkali metal silicate of the molar composition M₂O:SiO₂ = 1:2.0 to 1:3.0, where M is sodium and/or potassium, with the proviso that the detergent is free from water-soluble organic complexing agents from the group of substituted phosphonates, free from polymeric polycarboxylates and substantially free from alkali metal carbonates.
  2. A detergent as claimed in claim 1, characterized in that it contains 30 to 50% by weight and preferably 32 to 45% by weight of a fine-particle hydrated zeolite having a mean particle size of 1.8 to 4.5 µm and preferably 2.0 to 4.0 µm and 2 to 10% by weight and preferably 3 to 8% by weight sodium silicate with a molar ratio of Na₂O to SiO₂ of 1:2.0 to 1:2.8.
  3. A detergent as claimed in claim 1 or 2, characterized in that it contains 12 to 30% by weight of a peroxy bleaching agent, preferably in combination with 1 to 5% by weight of an activator for the peroxy bleaching agent.
  4. A detergent as claimed in any of claims 1 to 3, characterized in that it contains 2 to 7% by weight of a crystalline layer silicate having the formula Na₂Si₂O₅·yH₂O, where y is a number of 0 to 20, and the ratio of zeolite to crystalline layer silicate is at least 5:1.
  5. A detergent as claimed in any of claims 1 to 3, characterized in that it contains zeolite and amorphous alkali metal silicate in a ratio by weight of 4:1 to 10:1.
  6. A detergent as claimed in any of claims 1 to 5, characterized in that it contains amorphous alkali metal silicate and crystalline alkali metal silicate in a ratio by weight of 1:2 to 2:1 and preferably 1:1 to 2:1.
  7. A detergent as claimed in any of claims 1 to 6, characterized in that it contains no more than 4% by weight and preferably no more than 3% by weight alkali metal carbonates, particularly sodium carbonate, with the proviso that the alkali metal carbonate is only added in quantities in which it does not contribute to increased incrustation.
  8. A process for the production of the detergent claimed in any of claims 1 to 7, characterized in that a slurry containing the anionic surfactants, at least part of the zeolite, a part, but no more than 3% by weight and preferably no more than 2% by weight, based on the final detergent as a whole, of the amorphous silicates and optionally nonionic surfactants is spray-dried.
  9. A process as claimed in claim 8, characterized in that the zeolite-containing slurry is free from amorphous alkali metal silicates which are subsequently added as a whole to the spray-dried product together with the crystalline layer silicates optionally present.
  10. A process for the production of the detergent claimed in any of claims 1 to 7, characterized in that a slurry containing the anionic surfactants, amorphous silicates and optionally nonionic surfactants is spray-dried and the zeolite is subsequently added to the spray-dried product.
  11. A process for the production of the detergent claimed in any of claims 1 to 7, characterized in that a zeolite-containing slurry and a silicate-containing slurry are simultaneously introduced into a spray drying tower.
EP92905355A 1991-03-05 1992-02-25 Detergents Revoked EP0574436B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4106880 1991-03-05
DE4106880A DE4106880A1 (en) 1991-03-05 1991-03-05 LAUNDRY DETERGENT
PCT/EP1992/000390 WO1992015663A1 (en) 1991-03-05 1992-02-25 Detergents

Publications (2)

Publication Number Publication Date
EP0574436A1 EP0574436A1 (en) 1993-12-22
EP0574436B1 true EP0574436B1 (en) 1995-11-02

Family

ID=6426447

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92905355A Revoked EP0574436B1 (en) 1991-03-05 1992-02-25 Detergents

Country Status (6)

Country Link
EP (1) EP0574436B1 (en)
JP (1) JPH06505045A (en)
AT (1) ATE129743T1 (en)
DE (2) DE4106880A1 (en)
ES (1) ES2079858T3 (en)
WO (1) WO1992015663A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9021761D0 (en) * 1990-10-06 1990-11-21 Procter & Gamble Detergent compositions
DE4134914A1 (en) * 1991-10-23 1993-04-29 Henkel Kgaa DETERGENT AND CLEANING AGENT WITH SELECTED BUILDER SYSTEMS
DE4304474A1 (en) * 1993-02-15 1994-08-18 Henkel Kgaa Detergent additive containing surfactants and builders
ES2373300B1 (en) 2011-12-14 2012-12-20 Soro Internacional, S.A. DETERGENT FOR DISHWASHERS.

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA767170B (en) * 1975-12-15 1978-07-26 Colgate Palmolive Co Detergent composition and method for use
US4129511A (en) * 1976-09-24 1978-12-12 The Lion Fat & Oil Co., Ltd. Method of spray drying detergents containing aluminosilicates
DE2965075D1 (en) * 1978-10-12 1983-04-28 Henkel Kgaa Phosphate-free washing agent and process for its production
EP0061296B1 (en) * 1981-03-20 1984-10-24 Unilever Plc Process for the manufacture of detergent compositions containing sodium aluminosilicate
GB8334017D0 (en) * 1983-12-21 1984-02-01 Unilever Plc Detergent composition
CA1286563C (en) * 1986-04-04 1991-07-23 Jan Hendrik Eertink Detergent powders and processes for preparing them
GB8622565D0 (en) * 1986-09-19 1986-10-22 Unilever Plc Detergent composition
DE3920704A1 (en) * 1989-06-24 1991-01-03 Hoechst Ag BUILDER FOR TEXTILE DETERGENTS

Also Published As

Publication number Publication date
EP0574436A1 (en) 1993-12-22
ES2079858T3 (en) 1996-01-16
ATE129743T1 (en) 1995-11-15
JPH06505045A (en) 1994-06-09
DE59204203D1 (en) 1995-12-07
DE4106880A1 (en) 1992-09-10
WO1992015663A1 (en) 1992-09-17

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