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EP0253151A2 - Liquid washing agent and process for its production - Google Patents

Liquid washing agent and process for its production Download PDF

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Publication number
EP0253151A2
EP0253151A2 EP87108777A EP87108777A EP0253151A2 EP 0253151 A2 EP0253151 A2 EP 0253151A2 EP 87108777 A EP87108777 A EP 87108777A EP 87108777 A EP87108777 A EP 87108777A EP 0253151 A2 EP0253151 A2 EP 0253151A2
Authority
EP
European Patent Office
Prior art keywords
detergent
detergent according
component
constituents
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP87108777A
Other languages
German (de)
French (fr)
Other versions
EP0253151A3 (en
Inventor
Paul Dr. Schulz
Karl Schwadtke
Eduard Dr. Smulders
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0253151A2 publication Critical patent/EP0253151A2/en
Publication of EP0253151A3 publication Critical patent/EP0253151A3/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C11D1/831—Mixtures of non-ionic with anionic compounds of sulfonates with ethers of polyoxyalkylenes without phosphates
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043—Liquid or thixotropic (gel) compositions
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • nonionic surfactants in detergents primarily serves to improve the washability of oily and greasy soiling.
  • the amount of the generally liquid nonionic surfactants is limited by the ability of the solid detergent constituents to absorb liquid constituents.
  • the free-flowing properties of the detergents usually deteriorate if you want to use a quantity of nonionic liquid surfactants which is desirable per se.
  • the nonionic surfactants are difficult to process using the hot spray method widely used for the production of detergents.
  • Detergents with a high content of nonionic surfactants can be produced without problems as liquid to pasty detergents - referred to in the context of this invention as liquid detergents.
  • detergents contain builders that are essential for washing. Support the washing performance in various ways.
  • builders are powders or granules, which tend to settle in liquid systems after prolonged storage.
  • the solids are completely ground to very small particle sizes (below 10 microns) according to the teaching of DE-OS 28 25 218.
  • EP-PS 34 387 such detergents for encryption is known rin g augmentation of settling of solids clays having chain structure to add.
  • EP-OS 158 464 describes liquid detergents whose solids have a particle size of over Have 10 microns and their nonionic surfactants have a pour point of less than about 24 ° C.
  • the known liquid detergents have the disadvantage that they contain constituents (ballast components) which are inert with regard to the washing performance or that their viscosity is unstable when stored, which generally leads to a deterioration in the dissolving rate under washing conditions.
  • the long-term sedimentation stability of most products is unsatisfactory.
  • Another disadvantage of the liquid detergents described so far is the poor storage stability of chemically sensitive components, such as. B. perborate, bleach activator and the enzymes used. The more or less pronounced degradation of these components leads to a significant loss in washing performance and causes the well-known "gassing" of some liquid detergents, inter alia, in airtight containers, e.g. B. in portion packs.
  • the object of the present invention is therefore to provide a liquid detergent based on nonionic surfactants and builders which does not have the disadvantages of the known liquid detergents.
  • the fatty alcohol of component a) can be straight or branched, it can contain an even or odd number of carbon atoms and it can be both saturated and unsaturated.
  • branched alcohols are particularly suitable, in particular oxo alcohols.
  • the term "practically anhydrous" means that the detergent contains at most 5 percent by weight of unbound water.
  • the detergent can also contain bound water, i.e. H. e.g. B. water in the form of water of crystallization in inorganic salts or water which is adsorptively bound and can only be removed by vigorous heating to, for example, above 400 ° C. or water which is part of the raw materials used for the detergent according to the invention.
  • Practically gas-free means that the detergent contains at most 5, preferably less than 3 percent by volume of gaseous components at room temperature.
  • Practically gas-free, liquid detergents in the context of this invention have a viscosity behavior which has hardly changed even after prolonged storage and permit the setting of a specific, desired viscosity within wide limits more easily than detergents with a higher gas content. They have a high, constant density and represent the most compact form of supply for the recipe in question. The low gas content therefore promotes the production of stable, flowable and pumpable detergents. This also improves the dissolving speed of the detergents in the wash liquor.
  • Suitable anionic surfactants of the sulfate and sulfonate type are alkylbenzenesulfonates with a Cq to C 15 alkyl radical, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C 12 -C 18 monoolefins with terminal or internal ones Double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • dialcan sulfonates which are obtainable from C 12 -C 18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of alpha sulfo fatty acids, e.g. B. the alpha-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural or synthetic origin, ie from fatty alcohols such as. B.
  • coconut fatty alcohols coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10 -C 20 oxo alcohols and the secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated secondary alcohols ethoxylated with 1 to 6 mol of ethylene oxide are also suitable.
  • Sulfated fatty acid alkanolamides and sulfated fatty acid ranoglycerides are also suitable.
  • Suitable soaps in the context of this invention are the alkali metal salts of saturated or unsaturated fatty acids with 10 to 24 carbon atoms: soaps with a higher number of carbon atoms, in particular with 14 to 24 carbon atoms, are used to dampen the foam. Soaps of the saturated C 20 -C 24 fatty acids are particularly suitable as foam suppressants for detergents based on sodium triphosphate as builders, while in detergents containing predominantly zeolite, C 14 -C 18 soaps already show good foam inhibition, especially at low washing temperatures.
  • Particulate builders are organic and inorganic substances, preferably alkaline salts, in particular alkali salts, which not only are able to precipitate or bind complex calcium ions, but also, if possible, bring about a synergistic increase in washing power and have dirt-carrying capacity.
  • alkaline salts in particular alkali salts
  • the water-soluble alkali metaphosphates or Alkalipoly - phosphates, especially pentasodium triphosphate are still of particular importance.
  • organic complexing agents for calcium ions and heavy metal ions can be present.
  • Suitable phosphorus-containing organic complexing agents are the water-soluble salts of alkane polyphosphonic acids, amino and hydroxyalkane polyphonic acids and phosphonopolycarboxylic acids, such as. B.
  • methanediphosphonic acid dimethylaminomethane1,1-diphosphonic acid, aminotrimethylene triphosphonic acid, ethylenediaminetetramethylene tetraphosphonic acid, diethylenetriaminepentamethylenepentaphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-i, 2,4-tricarboxylic acid
  • the N- and P-free polycarboxylic acids forming calcium ion complex salts which also include polymers containing carboxyl groups, are of particular importance.
  • Low molecular weight compounds such as citric acid, 2,2-oxydisuccinic acid or carboxymethyloxysuccinic acid are suitable.
  • Suitable polymeric polycarboxylic acids have a molecular weight of 350 to about 1,500,000 in the form of the water-soluble salts.
  • Particularly preferred polymeric polycarboxylates have a molecular weight in the range from 500 to 175,000, and in particular in the range from 10,000 to 100,000.
  • polyacrylic acid poly-alpha hydroxyacrylic acid, polymaleic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds, such as, for example, vinyl methyl ether.
  • ethylenically unsaturated compounds such as, for example, vinyl methyl ether.
  • the water-soluble salts of polyglyoxylic acid can also be used.
  • Suitable water-insoluble inorganic builders are the finely divided synthetic zeolite A-type sodium aluminosilicates containing bound water described in German patent application DE 24 12 837 as phosphate substitutes for detergents and cleaning agents.
  • the cation-exchanging sodium aluminosilicates are used in the usual hydrated, finely crystalline form, i. H. they have practically no particles larger than 30 microns and preferably consist at least 80% of particles smaller than 10 microns.
  • Their calcium binding capacity which is determined according to the information in DE 24 12 837, is in the range from 100 to 2DO mg CaO / g.
  • the zeolite NaA can be used in particular, also the zeolite NaX and mixtures of zeolite NaA and NaX.
  • Suitable inorganic, non-complexing salts are the - also referred to as "washing alkalis" - bicarbonates, carbonates, borates, sulfates or silicates of the alkalis; Of the alkali silicates, especially the sodium silicates with a Na 2 O: SiO 2 ratio of 1: 1 to 1: 3.5 can be used.
  • salts of the non-capillary-active sulfonic acids carboxylic acids and sulfocarboxylic acids containing 2 to 9 carbon atoms, for example the alkali salts of alkane, benzene, toluene, xylene - Or cumene sulfonic acids, sulfobenzoic acids, sulfophthalic acid, sulfoacetic acid, sulfosuccinic acid and the salts of acetic acid or lactic acid.
  • Acetamide and urea are also suitable as solubilizers.
  • Detergents which have particularly favorable properties with regard to their cleaning ability, their foaming behavior and their water solubility contain, as component b), a sulfonate together with soap.
  • the soap is in particular those alkali salts of fatty acids that have foam-suppressing properties, i.e. of fatty acids with 18 to 24 carbon atoms.
  • particularly valuable detergents contain, as component a), nonionic surfactants which are addition products of 3 to 5 moles of ethylene oxide with one mole of fatty alcohol. Addition products to fatty alcohols with 12 to 18 C atoms and in particular mixtures of adducts with fatty alcohols with different chain length ranges give the detergents particularly valuable properties.
  • particularly interesting compounds of component c) are polyethylene glycols with a mole weight of about 300 to 400, i.e. Compounds with about 7 to about 9 ethoxy units in the molecule.
  • These hydrotropic liquid phase additives can, as usual, carry terminal hydroxyl groups or they can, e.g. B. with methyl residues, end groups.
  • the ratio of components a), b) and c) to one another is particularly important for the detergents according to the invention.
  • detergents which contain component a) in a ratio to component b) of 1.1: 1 to 1.5: 1 and contain component c) in an amount of 2 to 10 percent by weight are preferred.
  • Particularly powerful detergents according to the invention contain components a), b) and c) in an amount of 25 to 40 percent by weight.
  • detergents have two types of particulate constituents, namely a first, finely divided fraction with a particle size in the range from dust fineness to 30 microns and a second, coarser fraction with a particle size in the range from 200 to 2000 microns included.
  • “Dust fineness” stands for particles with a size of more than 0.01 micron, in particular with a particle size of more than 0.1 micron.
  • Particles with a size in the range of 200 to 2000 microns are mainly granules.
  • certain detergent ingredients are added to the liquid detergents. These are detergent constituents, which are in granular form either for handling reasons, but above all to prevent their interaction with other detergent constituents. These include, for example, anti-graying substances, optical brighteners, enzymes, bleaching agents and bleach activators, foam inhibitors.
  • Suitable graying inhibitors are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Mixtures of various cellulose ethers are also suitable, in particular mixtures of carboxymethyl cellulose and methyl cellulose. Enzymes from the class of proteases, lipases and amylases or mixtures thereof are possible. Enzymes obtained from bacterial strains or fungi, such as bacillus substilis, bacillus lichenififormis and streptomyces griseus, are particularly suitable. In order to protect the enzymes against premature decomposition, they are usually embedded in coating substances.
  • perhydrates and per compounds commonly used in detergents and bleaching agents are suitable as bleaching components.
  • Perhydrates preferably include sodium perborate, the is used as a monohydrate or in particular as a tetrahydrate.
  • the perhydrates of sodium carbonate (sodium percarbonate), sodium pyrophosphate (perpyrophosphate), sodium silicate (persilicate) and urea are also suitable. These perhydrates are preferably used together with bleach activators.
  • Sodium perborate tetrahydrate and sodium perborate monohydrate in combination with bleach activators are preferred as bleaching components.
  • the bleach activators include in particular N-acyl compounds and O-acyl compounds.
  • N-acyl compounds are multiply acylated alkylenediamines, such as tetraacetylmethylene diamine, tetraacetylethylenediamine and their higher homologues, and acylated glycolurils, such as tetraacetylglycoluril.
  • acylated glycolurils such as tetraacetylglycoluril.
  • Further examples are Na-cyanamide, N-alkyl-N-sulfonylcarbonamides, N-acylhydantoins, N-acylated cyclic hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and imidazolines.
  • acylated sugars such as glucose pentaacetate are suitable as O-acyl compounds.
  • Preferred bleach activators are tetraacetylethylene diamine and glucose pentaacetate.
  • the bleach activators can also be used to avoid interactions with per compounds or other substances, e.g. B. with enzymes, coated with H-üllsubstanzen.
  • Such detergent components used in the form of granules or granules coated with coating substances lead to products with particularly valuable properties.
  • the special composition of the detergents and the presence of particulate constituents with two different particle size ranges result in detergents with particularly high viscosity stability and sedimentation stability.
  • the agents according to the invention with a viscosity in the range of 10,000 to 1,000,000 mPas, measured using a Brookfield RVT viscometer Use of spindle 6 at 1 to 10 revolutions per minute and 20 ° C are particularly preferred detergents.
  • Another object of the present invention is a method for producing a liquid detergent of the composition and properties described above.
  • the liquid constituents of the detergent and those particulate constituents which do not interact chemically with one another and with the liquid constituents even after comminution are intimately mixed in a first mixing stage and the suspension thus obtained is subjected to wet grinding, so that the average grain diameter of these solid components in the suspension thus obtained after grinding is at most 30 microns, whereupon the suspension is degassed.
  • the remaining particulate constituents with a particle size between 200 and 2000 microns are degassed in vacuo, this degassed solid mixture is mixed with the ground suspension of the first mixing stage in a second mixing stage with further degassing, and optionally added to this mixture in vacuo further auxiliaries such as fragrances, dyes or hydrotropic compounds or other compounds for setting the desired viscosity are added.
  • the degassing of liquid and solid components has the effect that the liquid detergents according to the invention are practically gas-free, which results in a particularly stable viscosity behavior of the detergents.
  • the average grain diameter of the solids of the finely ground suspension should be of the order of magnitude mean pore size of the coarse-particle solid recipe components incorporated under grain retention or below.
  • a special handling advantage is obtained if the detergents are packed in portions in bags from a water-soluble film.
  • Particularly preferred as a form of supply are detergents which are contained in bags made of film based on polyvinyl alcohol.
  • the bags contain so much of the detergents according to the invention that they are sufficient for washing the amount of laundry in a washing machine filling.
  • Suitable films are, for example, polyvinyl alcohol films with a film thickness of 65 microns, which are formed by heat or wet sealing into closed bags containing the detergent.
  • a phosphate-free detergent of the following composition was prepared in a manner comparable to that described above:
  • This detergent had a viscosity of 38,000 mPas.
  • the dissolution behavior was as described in Example 1.
  • the detergents from Examples 1 and 2 had excellent washing performance both against fat / pigment, enzymatic and against bleachable stains in hard and soft water. If the water hardness is high, up to 3 sachets of detergent were used, if the water hardness was low only one.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • Detergent Compositions (AREA)

Abstract

The liquid washing agent based on non-ionic surfactants and particulate builders contains a surfactant liquid component from adducts of 2 to 8 mol of ethylene oxide and 1 mol of fatty alcohol with 10 to 12 C atoms, anionic surfactants and low molecular weight polyethylene glycol. The surfactant liquid component comprises at least 20% by weight of the complete washing agent. The ratio of fatty alcohol ethoxylate to anionic surfactant is in the range 1:1 to 2:1. The washing agent has a density between 1.4 and 1.8 and is virtually free of water and gases.

Description

Der Einsatz nichtionischer Tenside in Waschmitteln dient vor allem der verbesserten Auswaschbarkeit öliger und fettiger Verschmutzungen. In rieselfähigen Waschmitteln ist aber die Menge der in der Regel flüssigen nichtionischen Tenside durch die Aufnähmefähigkeit der festen Waschmittelbestandteile an flüssigen Bestandteilen begrenzt. Meistens verschlechtert sich die Rieselfähigkeit der Waschmittel, wenn man eine an sich wünschenswerte Menge nichtionischer flüssiger Tenside verwenden möchte. Außerdem lassen sich die nichtionischen Tenside schlecht nach der in großem Umfang zur Waschmittelherstellung verwendeten Heißsprüh-Methode verarbeiten. Waschmittel mit einem hohen Gehalt an nichtionischen Tensiden können dagegen problemlos als flüssige bis pastöse Waschmittel - im Rahmen dieser Erfindung als flüssige Waschmittel bezeichnet - hergestellt werden.The use of nonionic surfactants in detergents primarily serves to improve the washability of oily and greasy soiling. In free-flowing detergents, however, the amount of the generally liquid nonionic surfactants is limited by the ability of the solid detergent constituents to absorb liquid constituents. The free-flowing properties of the detergents usually deteriorate if you want to use a quantity of nonionic liquid surfactants which is desirable per se. In addition, the nonionic surfactants are difficult to process using the hot spray method widely used for the production of detergents. Detergents with a high content of nonionic surfactants, on the other hand, can be produced without problems as liquid to pasty detergents - referred to in the context of this invention as liquid detergents.

Üblicherweise enthalten Waschmittel Gerüststoffe, die beim Waschen. auf vielfältige Weise die Waschleistung unterstützen. In ihrer üblichen Einsatzform sind Gerüststoffe Pulver bzw. Granulate, die in flüssigen Systemen bei längerer Lagerung zum Absetzen neigen'. Um diesen Nachteil zu vermeiden, werden die Feststoffe nach der Lehre der DE-OS 28 25 218 vollständig auf sehr geringe Teilchengrößen (unter 10 Mikron) vermahlen. Aus der EP-PS 34 387 ist bekannt, derartigen Waschmitteln zur Ver- ringerung des Absetzens von Feststoffen Tone mit Ketten-Struktur zuzusetzen. In der EP-OS 158 464 sind flüssige Waschmittel beschrieben, deren Feststoffe eine Teilchengröße von über 10 Mikron haben und deren nichtionische Tenside einen "pour point" von weniger als etwa 24 °C haben. Die bekannten flüssigen Waschmittel haben aber den Nachteil, daß sie hinsichtlich der Waschleistung inerte Bestandteile (Ballastkomponenten) enthalten oder daß ihre Viskosität beim Lagern instabil ist, was im allgemeinen zu einer Verschlechterung der Lösegeschwindigkeit unter Waschbedingungen führt. Außerdem ist die Langzeit-Sedimentationsstabilität der meisten Produkte unbefriedigend. Ein weiterer Nachteil der bisher beschriebenen flüssigen Waschmittel ist die mangelhafte Lagerstabilität chemisch empfindlicher Komponenten, wie z. B. Perborat, Bleichaktivator und der eingesetzten Enzyme. Der mehr oder minder ausgeprägte Abbau dieser Komponenten führt zu einem signifikanten Verlust an Waschleistung und verursacht das bekannte "Gasen" mancher flüssiger Waschmittel u. a. in luftdicht verschlossenen Gebinden, z. B. in Portionspackungen.Usually, detergents contain builders that are essential for washing. Support the washing performance in various ways. In their usual form of use, builders are powders or granules, which tend to settle in liquid systems after prolonged storage. In order to avoid this disadvantage, the solids are completely ground to very small particle sizes (below 10 microns) according to the teaching of DE-OS 28 25 218. From EP-PS 34 387 such detergents for encryption is known rin g augmentation of settling of solids clays having chain structure to add. EP-OS 158 464 describes liquid detergents whose solids have a particle size of over Have 10 microns and their nonionic surfactants have a pour point of less than about 24 ° C. However, the known liquid detergents have the disadvantage that they contain constituents (ballast components) which are inert with regard to the washing performance or that their viscosity is unstable when stored, which generally leads to a deterioration in the dissolving rate under washing conditions. In addition, the long-term sedimentation stability of most products is unsatisfactory. Another disadvantage of the liquid detergents described so far is the poor storage stability of chemically sensitive components, such as. B. perborate, bleach activator and the enzymes used. The more or less pronounced degradation of these components leads to a significant loss in washing performance and causes the well-known "gassing" of some liquid detergents, inter alia, in airtight containers, e.g. B. in portion packs.

Aufgabe der vorliegenden Erfindung ist daher, ein flüssiges Waschmittel auf Basis nichtionischer Tenside und Gerüststoffe bereitzustellen, das die Nachteile der bekannten flüssigen Waschmittel nicht aufweist.The object of the present invention is therefore to provide a liquid detergent based on nonionic surfactants and builders which does not have the disadvantages of the known liquid detergents.

Die Lösung dieser Aufgabe besteht in einem Waschmittel, das eine Tensid-Flüssigkomponente aus

  • a) Anlagerungsprodukten von 2 bis 8 Mol Ethylenoxid an 1 Mol Fettalkohol mit 10 bis 20 Kohlenstoffatomen,
  • b) Aniontensiden vom Typ der Sulfate, Sulfonate und Seife,
  • c) Polyethylenglykol mit einem Molgewicht von etwa 200 bis 600,
  • enthält, mit der Maßgabe, daß die Menge der Bestandteile a) + b) + c) größer als 20 Gewichtsprozent, insbesondere 20 bis 50 Gewichtsprozent des gesamten Waschmittels ist, und daß das Verhältnis von a) : b) im Bereich von 1 :, 1 bis 2 : 1 liegt, daß das Waschmittel eine Dichte von 1,4 bis 1,8 hat und praktisch wasserfrei und gasfrei ist.
The solution to this problem consists in a detergent comprising a surfactant liquid component
  • a) addition products of 2 to 8 moles of ethylene oxide with 1 mole of fatty alcohol with 10 to 20 carbon atoms,
  • b) anionic surfactants of the sulfate, sulfonate and soap type,
  • c) polyethylene glycol with a molecular weight of about 200 to 600,
  • contains, with the proviso that the amount of components a) + b) + c) greater than 20 percent by weight, in particular 20 to 50 % By weight of the total detergent, and that the ratio of a): b) is in the range from 1: 1 to 2: 1, that the detergent has a density of 1.4 to 1.8 and is practically water-free and gas-free.

Der Fettalkohol der Komponente a) kann geradlinig oder verzweigt sein, er kann eine gerade oder ungerade Anzahl von C-Atomen enthalten und sowohl gesättigt als auch ungesättigt sein. Außer Fettalkoholen, die sich von in der Natur vorkommenden Fettsäuren ableiten, kommen vor allem verzweigte Alkohole in Frage, insbesondere Oxoalkohole. Der Ausdruck "praktisch wasserfrei" bedeutet, daß das Waschmittel höchstens 5 Gewichtsprozent nichtgebundenes Wasser enthält, darüber hinaus kann das Waschmittel zusätzlich gebundenes Wasser, d. h. z. B. Wasser in Form von Kristallwasser in anorganischen Salzen oder Wasser, das adsorptiv gebunden ist und erst durch stärkeres Erhitzen auf beispielsweise über 400 °C entfernt werden kann oder Wasser, das Bestandteil der für das erfindungsgemäße Waschmittel verwendeten Rohstoffen ist, enthalten.The fatty alcohol of component a) can be straight or branched, it can contain an even or odd number of carbon atoms and it can be both saturated and unsaturated. In addition to fatty alcohols derived from naturally occurring fatty acids, branched alcohols are particularly suitable, in particular oxo alcohols. The term "practically anhydrous" means that the detergent contains at most 5 percent by weight of unbound water. In addition, the detergent can also contain bound water, i.e. H. e.g. B. water in the form of water of crystallization in inorganic salts or water which is adsorptively bound and can only be removed by vigorous heating to, for example, above 400 ° C. or water which is part of the raw materials used for the detergent according to the invention.

Der Ausdruck "praktisch gasfrei" bedeutet, daß das Waschmittel höchstens 5, vorzugsweise weniger als 3 Volumenprozent bei Raumtemperatur gasförmige Bestandteile enthält. Praktisch gasfreie, flüssige Waschmittel im Rahmen dieser Erfindung weisen ein auch bei längerer Lagerung kaum verändertes Viskositätsverhalten auf und gestatten die Einstellung einer bestimmten, gewünschten Viskosität innerhalb weiter Grenzen leichter als Waschmittel mit einem höheren- Gasgehalt. Sie besitzen eine hohe, gleichbleibende Dichte und stellen die kompakteste Anbietungsform für die betreffende Rezeptur dar. Der niedrige Gasgehalt fördert demnach die Herstellung von stabilen, fließ- und pumpfähigen Waschmitteln. Dadurch wird auch die Lösegeschwindigkeit der Waschmittel in der Waschflotte verbessert.The expression "practically gas-free" means that the detergent contains at most 5, preferably less than 3 percent by volume of gaseous components at room temperature. Practically gas-free, liquid detergents in the context of this invention have a viscosity behavior which has hardly changed even after prolonged storage and permit the setting of a specific, desired viscosity within wide limits more easily than detergents with a higher gas content. They have a high, constant density and represent the most compact form of supply for the recipe in question. The low gas content therefore promotes the production of stable, flowable and pumpable detergents. This also improves the dissolving speed of the detergents in the wash liquor.

Als geeignete Aniontenside vom Typ der Sulfate und Sulfonate kommen Alkylbenzolsulfonate mit einem Cq- bis C15-Alkylrest, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C12-C18-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Dialkansulfonate, die aus C12-C18-Alkanen durch Sulfochlorierung oder Sulfoxidation und anschließende Hydrolyse bzw. Neutralisation bzw. durch Bisulfitaddition an Olefine erhältlich sind, sowie die Ester von Alpha-Sulfofettsäuren, z. B. die alpha-sulfonierten Methyl- oder Ethylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren. Geeignete Tenside vom Sulfattyp sind die Schwefelsäuremonoester aus primären Alkoholen natürlichen oder synthetischen Ursprungs, d. h. aus Fettalkoholen, wie z. B. Kokosfettalkoholen, Talgfettalkoholen, Oleylalkohol-, Lauryl-, Myristyl-, Palmityl-oder Stearylalkohol, oder den C10-C20-Oxoalkoholen und die sekundären Alkohole dieser Kettenlänge. Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten aliphatischen primären Alkohole bzw. ethoxylierten sekundären AIkohole sind geeignet. Ferner eignen sich sulfatierte Fettsäurealkanolamide und sulfatierte Fettsäurerranoglyceride.Suitable anionic surfactants of the sulfate and sulfonate type are alkylbenzenesulfonates with a Cq to C 15 alkyl radical, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C 12 -C 18 monoolefins with terminal or internal ones Double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are dialcan sulfonates which are obtainable from C 12 -C 18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of alpha sulfo fatty acids, e.g. B. the alpha-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural or synthetic origin, ie from fatty alcohols such as. B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10 -C 20 oxo alcohols and the secondary alcohols of this chain length. The sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated secondary alcohols ethoxylated with 1 to 6 mol of ethylene oxide are also suitable. Sulfated fatty acid alkanolamides and sulfated fatty acid ranoglycerides are also suitable.

Geeignete Seifen-sind im Rahmen dieser Erfindung die Alkalimetallsalze von gesättigten oder ungesättigten Fettsäuren mit 10 bis 24 C-Atomen: Zur Schaumdämpfung werden Seifen mit einer höheren Anzahl an C-Atomen, insbesondere mit 14 bis 24 C-Atomen eingesetzt. Seifen der gesättigten C20-C24-Fettsäuren eignen sich besonders als Schaumdämpfer für Waschmittel auf Basis von Natriumtriphosphat als Builder, während in überwiegend Zeolith enthaltenden Waschmitteln bereits C14-C18-Seifen gute Schauminhibierung zeigen, insbesondere bei niederen Waschtemperaturen.Suitable soaps in the context of this invention are the alkali metal salts of saturated or unsaturated fatty acids with 10 to 24 carbon atoms: soaps with a higher number of carbon atoms, in particular with 14 to 24 carbon atoms, are used to dampen the foam. Soaps of the saturated C 20 -C 24 fatty acids are particularly suitable as foam suppressants for detergents based on sodium triphosphate as builders, while in detergents containing predominantly zeolite, C 14 -C 18 soaps already show good foam inhibition, especially at low washing temperatures.

Teilchenförmige Gerüststoffe sind organische und anorganische Substanzen, vorzugsweise alkalisch reagierende Salze, insbesondere Alkalisalze, die nicht nur Calciumionen auszufällen oder komplex zu binden vermögen, sondern möglichst auch mit den Tensiden eine synergistische Steigerung der Waschkraft bewirken und ein Schmutztragevermögen besitzen. Von den anorganischen Salzen sind die wasserlöslichen Alkalimeta- oder Alkalipoly- phosphate, insbesondere das Pentanatriumtriphosphat, immer noch von besonderer Bedeutung. Neben diesen Phosphaten können organische Komplexbildner für Calciumionen und Schwermetallionen vorhanden sein. Dazu gehören Verbindungen vom Typ der Aminopolycarbonsäuren, wie z.B. Nitrilotriessigsäure, Ethylendiamintetraessigsäure, Diethylentriaminpentaessigsäure sowie höhere Homologe. Geeignete phosphorhaltige organische Komplexbildner sind die wasserlöslichen Salze der Alkanpolyphosphonsäuren, Amino- und Hydroxyalkanpolyphonphonsäuren und Phosphonopolycarbonsäuren, wie z. B. die Verbindungen Methandiphosphonsäure, Dimethylaminomethan1,1-diphosphonsäure, Aminotrimethylentriphosphonsäure, Ethylendiamintetramethylentetraphosphonsäure, Diethylentriaminpentamethylenpentaphosphonsäure, 1-Hydroxyethan-1,1-dip-hosphonsäure, 2-Phosphonobutan-i ,2,4-tricarbonsäureParticulate builders are organic and inorganic substances, preferably alkaline salts, in particular alkali salts, which not only are able to precipitate or bind complex calcium ions, but also, if possible, bring about a synergistic increase in washing power and have dirt-carrying capacity. Of the inorganic salts, the water-soluble alkali metaphosphates or Alkalipoly - phosphates, especially pentasodium triphosphate, are still of particular importance. In addition to these phosphates, organic complexing agents for calcium ions and heavy metal ions can be present. These include compounds of the aminopolycarboxylic acid type, such as, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and higher homologues. Suitable phosphorus-containing organic complexing agents are the water-soluble salts of alkane polyphosphonic acids, amino and hydroxyalkane polyphonic acids and phosphonopolycarboxylic acids, such as. B. the compounds methanediphosphonic acid, dimethylaminomethane1,1-diphosphonic acid, aminotrimethylene triphosphonic acid, ethylenediaminetetramethylene tetraphosphonic acid, diethylenetriaminepentamethylenepentaphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-i, 2,4-tricarboxylic acid

Unter den organischen Gerüstsubstanzen sind die N- und P-freien, mit Calciumionen Komplexsalze bildenden Polycarbonsäuren, wozu auch Carboxylgruppen enthaltende Polymerisate zählen, von besonderer Bedeutung. Geeignet sind niedermolekulare Verbindungen, wie -z.B. Citronensäure, 2,2-Oxydibernsteinsäure oder Carboxymethyloxybernsteinsäure. Geeignete polymere Polycarbonsäuren haben ein Molgewicht von 350 bis etwa 1 500 000 in Form der wasserlöslichen Salze. Besonders bevorzugte polymere Polycarboxylate haben ein Molgewicht im Bereich von 500 bis 175 000, und insbesondere im Bereich von 10 000 bis 100 000. Dazu gehören Verbindungen wie z. B. Polyacrylsäure, Poly-alphahydroxyacrylsäure, Polymaleinsäure sowie die Copolymerisate der entsprechenden monomeren Carbonsäuren untereinander oder mit ethylenisch ungesättigten Verbindungen, wie z.B. Vinylmethylether. Weiterhin brauchbar sind auch die wasserlöslichen Salze der Polyglyoxylsäure.Among the organic framework substances, the N- and P-free polycarboxylic acids forming calcium ion complex salts, which also include polymers containing carboxyl groups, are of particular importance. Low molecular weight compounds such as citric acid, 2,2-oxydisuccinic acid or carboxymethyloxysuccinic acid are suitable. Suitable polymeric polycarboxylic acids have a molecular weight of 350 to about 1,500,000 in the form of the water-soluble salts. Particularly preferred polymeric polycarboxylates have a molecular weight in the range from 500 to 175,000, and in particular in the range from 10,000 to 100,000. B. polyacrylic acid, poly-alpha hydroxyacrylic acid, polymaleic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds, such as, for example, vinyl methyl ether. The water-soluble salts of polyglyoxylic acid can also be used.

Als in Wasser unlösliche anorganische Gerüstsubstanzen eignen sich die in der deutschen Patentanmeldung DE 24 12 837 als Phosphatsubstitute für Wasch- und Reinigungsmitteln näher beschriebenen feinteiligen synthetischen, gebundenes Wasser enthaltenden Natriumalumosilikate von Zeolith-A-Typ. Die kationenaustauschenden Natriumalumosilikate kommen in der üblichen hydratisierten, fein kristallinen Form zum Einsatz, d. h. sie weisen praktisch keine Teilchen größer als 30 micron auf und bestehen vorzugsweise zu wenistens 80 % aus Teilchen einer Größe von weniger als 10 micron. Ihr Calciumbindevermögen, das nach den Angaben der DE 24 12 837 bestimmt wird, liegt im Bereich von 100 bis 2DO mg CaO/g. Brauchbar ist insbesondere der Zeolith NaA, ferner auch der Zeolith NaX und Mischungen aus Zeolith NaA und NaX.Suitable water-insoluble inorganic builders are the finely divided synthetic zeolite A-type sodium aluminosilicates containing bound water described in German patent application DE 24 12 837 as phosphate substitutes for detergents and cleaning agents. The cation-exchanging sodium aluminosilicates are used in the usual hydrated, finely crystalline form, i. H. they have practically no particles larger than 30 microns and preferably consist at least 80% of particles smaller than 10 microns. Their calcium binding capacity, which is determined according to the information in DE 24 12 837, is in the range from 100 to 2DO mg CaO / g. The zeolite NaA can be used in particular, also the zeolite NaX and mixtures of zeolite NaA and NaX.

Geeignete anorganische, nichtkomplexbildende Salze sind die - auch als "Waschalkalien" bezeichneten - Bicarbonate, Carbonate, Borate, Sulfate oder Silikate- der Alkalien; von den Alkalisilikaten sind vor allem die Natriumsilikate mit einem Verhältnis Na2O : SiO2 wie 1 : 1 bis 1 : 3,5 brauchbar.Suitable inorganic, non-complexing salts are the - also referred to as "washing alkalis" - bicarbonates, carbonates, borates, sulfates or silicates of the alkalis; Of the alkali silicates, especially the sodium silicates with a Na 2 O: SiO 2 ratio of 1: 1 to 1: 3.5 can be used.

Weitere Gerüstsubstanzen, die wegen ihrer hydrotropen Eigenschaften meist in flüssigen Mitteln eingesetzt werden, sind die Salze der nicht kapillaraktiven, 2 bis 9 C-Atome enthaltenden Sulfonsäuren,-Carbonsäuren und Sulfocarbonsäuren, beispielsweise die Alkalisalze der Alkan-, Benzol-, Toluol-, Xylol- oder Cumolsulfonsäuren, der Sulfobenzoesäuren, Sulfophthalsäure, Sulfoessigsäure, Sulfobernsteinsäure sowie die Salze der Essigsäure oder Milchsäure. Als Lösungsvermittler sind auch Acetamid und Harnstoff geeignet.Other structural substances that are mostly used in liquid agents because of their hydrotropic properties are the salts of the non-capillary-active sulfonic acids, carboxylic acids and sulfocarboxylic acids containing 2 to 9 carbon atoms, for example the alkali salts of alkane, benzene, toluene, xylene - Or cumene sulfonic acids, sulfobenzoic acids, sulfophthalic acid, sulfoacetic acid, sulfosuccinic acid and the salts of acetic acid or lactic acid. Acetamide and urea are also suitable as solubilizers.

Waschmittel, die hinsichtlich ihres Reinigungsvermögens ihres Schaumverhaltens und ihrer Wasserlöslichkeit besonders günstige Eigenschaften aufweisen, enthalten als Komponente b) ein Sulfonat zusammen mit Seife. Bei der Seife handelt es sich insbesondere um solche Alkalisalze von Fettsäuren, die schaumdämpfende Eigenschaften aufweisen, d.h., von Fettsäuren mit 18 bis 24 C-Atomen. Hinsichtlich ihrer Reinigungswirkung und ihres Viskositätsverhaltens besonders wertvolle Waschmittel enthalten als Komponente a) nichtionische Tenside, die Anlagerungsprodukte von 3 bis 5 Mol Ethylenoxid an ein Mol Fettalkohol darstellen. Anlagerungsprodukte an Fettalkohole mit 12 bis 18 C-Atomen und insbesondere Gemische von Anlagerungsprodukten an Fettalkohole mit unterschiedlichem Kettenlängenbereich verleihen den Waschmitteln besonders wertvolle Eigenschaften. Hinsichtlich ihres Einflusses auf das Viskositätsverhalten und die Lösegeschwindkeit der erfindungsgemäßen Waschmittel besonders interessante Verbindungen der Komponente c) sind Polyethylenglykole mit einem Moigewicht von etwa 300 bis 400, d.h. Verbindungen mit etwa 7 bis etwa 9 Ethoxy-Einheiten im Molekül. Diese hydrotrop wirkenden Flüssigphasenzusätze können., wie üblich, terminale Hydroxylgr-uppen tragen oder sie können, z. B. mit Methylresten, endgruppenverschlossen sein.Detergents which have particularly favorable properties with regard to their cleaning ability, their foaming behavior and their water solubility contain, as component b), a sulfonate together with soap. The soap is in particular those alkali salts of fatty acids that have foam-suppressing properties, i.e. of fatty acids with 18 to 24 carbon atoms. With regard to their cleaning action and their viscosity behavior, particularly valuable detergents contain, as component a), nonionic surfactants which are addition products of 3 to 5 moles of ethylene oxide with one mole of fatty alcohol. Addition products to fatty alcohols with 12 to 18 C atoms and in particular mixtures of adducts with fatty alcohols with different chain length ranges give the detergents particularly valuable properties. With regard to their influence on the viscosity behavior and the dissolving speed of the detergents according to the invention, particularly interesting compounds of component c) are polyethylene glycols with a mole weight of about 300 to 400, i.e. Compounds with about 7 to about 9 ethoxy units in the molecule. These hydrotropic liquid phase additives can, as usual, carry terminal hydroxyl groups or they can, e.g. B. with methyl residues, end groups.

Für die erfindungsgemäßen Waschmittel ist das Verhältnis der Komponenten a), b) und c) zueinander besonders wichtig. Bevorzugt werden im Rahmen dieser Erfindung Waschmittel, die die Komponente a) in einem Verhältnis zu Komponente b) von 1,1 : 1 bis 1,5 : 1 enthält und die Komponente c) in einer Menge von 2 bis 10 Gewichtsprozent enthalten. Besonders leistungsfähige erfindungsgemäße Waschmittel enthalten die Komponenten a), b) und c) in einer Menge von 25 bis 40 Gewichtsprozent.The ratio of components a), b) and c) to one another is particularly important for the detergents according to the invention. In the context of this invention, detergents which contain component a) in a ratio to component b) of 1.1: 1 to 1.5: 1 and contain component c) in an amount of 2 to 10 percent by weight are preferred. Particularly powerful detergents according to the invention contain components a), b) and c) in an amount of 25 to 40 percent by weight.

Ein weiteres Merkmal von erfindungsgemäßen Waschmitteln mit besonders wertvollen Eigenschaften besteht darin, daß die Waschmittel zwei Typen von teilchenförmigen Bestandteilen, und zwar einen ersten, feinverteilten Anteil mit einer Teilchengröße im Bereich von Staubfeinheit bis 30 Mikron und einen zweiten, gröberen Anteil mit einer Teilchengröße im Bereich von 200 bis 2000 Mikron enthalten. "Staubfeinheit" steht für Teilchen mit einer Größe von mehr als 0,01 Mikron, insbesondere mit einer Teilchengröße von über 0,1 Mikron. Teilchen mit einer Größe im Bereich von 200 bis 2000 Mikron sind vor allem Granulate. In dieser Form werden bestimmte Waschmittelbestandteile den flüssigen Waschmitteln hinzugefügt. Dabei handelt es sich um Waschmittelbestanteile, die entweder aus Handhabungsgründen, vor allem aber um ihre Wechselwirkung mit anderen Waschmittelbestandteilen zu verhindern, in Granulatform vorliegen. Hierzu zählen beispielsweise vergrauungsverhütende Stoffe, optische Aufheller, Enzyme, Bleichmittel und Bleichaktivatoren, Schauminhibitoren.Another feature of detergents according to the invention with particularly valuable properties is that the detergents have two types of particulate constituents, namely a first, finely divided fraction with a particle size in the range from dust fineness to 30 microns and a second, coarser fraction with a particle size in the range from 200 to 2000 microns included. "Dust fineness" stands for particles with a size of more than 0.01 micron, in particular with a particle size of more than 0.1 micron. Particles with a size in the range of 200 to 2000 microns are mainly granules. In this form, certain detergent ingredients are added to the liquid detergents. These are detergent constituents, which are in granular form either for handling reasons, but above all to prevent their interaction with other detergent constituents. These include, for example, anti-graying substances, optical brighteners, enzymes, bleaching agents and bleach activators, foam inhibitors.

Geeignete Vergrauungsverhüter sind Celluloseether, wie Carboxymethylcellulose, Methylcellulose, Hydroxyalkylcellulosen und Mischether, wie Methylhydroxyethylcellulose, MethylhydroxypropylcelluIose und Methyl-Carboxymethylcellulose. Geeignet sind ferner Gemische verschiedener Celluloseether, insbesondere Gemische aus Carboxymethylcellulose- und Methylcellulose. Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen und Amylasen bzw. deren Gemische in Frage. Besonders geeignet sind aus Bakterienstämmen oder Pilzen, wie bacillus substilis, bacillus licheniförmis und streptomyces griseus gewonnene enzymatische Wirkstoffe. Um die Enzyme gegen vorzeitige Zersetzung zu schützen, sind diese in der Regel in Hüllsubstanzen eingebettet.Suitable graying inhibitors are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Mixtures of various cellulose ethers are also suitable, in particular mixtures of carboxymethyl cellulose and methyl cellulose. Enzymes from the class of proteases, lipases and amylases or mixtures thereof are possible. Enzymes obtained from bacterial strains or fungi, such as bacillus substilis, bacillus lichenififormis and streptomyces griseus, are particularly suitable. In order to protect the enzymes against premature decomposition, they are usually embedded in coating substances.

Als Bleichkomponente kommen die üblicherweise in Wasch- und Bleichmittel verwendeten Perhydrate und Perverbindungen in Frage. Zu den Perhydraten zählt bevorzugt Natriumperborat, das als Monohydrat oder insbesondere als Tetrahydrat eingesetzt wird. Ferner kommen die Perhydrate des Natriumcarbonats (Natriumpercarbonat), des Natriumpyrophosphats (Perpyrophosphat), des Natriumsilikats (Persilikat) sowie des Harnstoffes in Betracht. Diese Perhydrate kommen bevorzugt zusammen mit Bleichaktivatoren zum Einsatz. Bevorzugt kommt Natriumperborat-tetrahydrat und Natriumperborat-monohydrat in Verbindung mit Bleichaktivatoren als Bleichkomponente in Frage. Zu den Bleichaktivatoren zählen insbesondere N-Acylverbindungen und O-Acylverbindungen. Beispiele für geeignete N-Acylverbindungen sind mehrfach acylierte Alkylendiamine, wie Tetraacetylmethylendiamin, Tetraacetylethylendiamin und deren höhere Homologen, sowie acylierte Glykolurile, wie Tetraacetylglykoluril. Weitere Beispiele sind Na-Cyanamid, N-Alkyl-N-sulfonylcarbonamide, N-Acylhydantoine, N-acylierte cyclische Hydrazide, Triazole, Urazole, Diketopiperazine, Sulfurylamide, Cyanurate und Imidazoline. Als O-Acylverbindungen kommen neben Carbonsäureanhydriden, wie Phthalsäureanhydrid und Estern, wie Na-(iso)-nonanoylphenolsulfonat, insbesondere acylierte Zucker, wie Glucosepentaacetat in Frage. Bevorzugte Bleichaktivatoren sind Tetraacetylethylendiamin und Glucosepentaacetat. Auch die Bleichaktivatoren können zur Vermeidung von Wechselwirkungen mit Perverbindungen oder anderen Substanzen, z. B. mit Enzymen, mit H-üllsubstanzen überzogen sein. In Form- von Granulaten oder mit Hüllsubstanzen überzogenen Granulaten eingesetzte derartige Waschmittelbestanteile führen zu Produkten mit besonders wertvollen Eigenschaften. Durch die besondere Zusammensetzung der Waschmittel und durch die Anwesenheit von teilchenförmigen Bestandteilen mit zwei verschiedenen Teilchengrößen-Bereichen, erhält man Waschmittel mit besonders hoher Viskositätsstabilität und Sedimentationsstabilität. Die erfindungsgemäßen Mittel mit einer Viskosität im Bereich von 10 000 bis 1 000 000 mPas, gemessen mit einem Brookfield-RVT-Viskosimeter unter Verwendung von Spindel 6 bei 1 bis 10 Umdrehungen pro Minute und 20 °C, sind besonders bevorzugte Waschmittel.The perhydrates and per compounds commonly used in detergents and bleaching agents are suitable as bleaching components. Perhydrates preferably include sodium perborate, the is used as a monohydrate or in particular as a tetrahydrate. The perhydrates of sodium carbonate (sodium percarbonate), sodium pyrophosphate (perpyrophosphate), sodium silicate (persilicate) and urea are also suitable. These perhydrates are preferably used together with bleach activators. Sodium perborate tetrahydrate and sodium perborate monohydrate in combination with bleach activators are preferred as bleaching components. The bleach activators include in particular N-acyl compounds and O-acyl compounds. Examples of suitable N-acyl compounds are multiply acylated alkylenediamines, such as tetraacetylmethylene diamine, tetraacetylethylenediamine and their higher homologues, and acylated glycolurils, such as tetraacetylglycoluril. Further examples are Na-cyanamide, N-alkyl-N-sulfonylcarbonamides, N-acylhydantoins, N-acylated cyclic hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and imidazolines. In addition to carboxylic anhydrides such as phthalic anhydride and esters such as Na (iso) nonanoylphenol sulfonate, in particular acylated sugars such as glucose pentaacetate are suitable as O-acyl compounds. Preferred bleach activators are tetraacetylethylene diamine and glucose pentaacetate. The bleach activators can also be used to avoid interactions with per compounds or other substances, e.g. B. with enzymes, coated with H-üllsubstanzen. Such detergent components used in the form of granules or granules coated with coating substances lead to products with particularly valuable properties. The special composition of the detergents and the presence of particulate constituents with two different particle size ranges result in detergents with particularly high viscosity stability and sedimentation stability. The agents according to the invention with a viscosity in the range of 10,000 to 1,000,000 mPas, measured using a Brookfield RVT viscometer Use of spindle 6 at 1 to 10 revolutions per minute and 20 ° C are particularly preferred detergents.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung eines flüssigen Waschmittels der vorbeschriebenen Zusammensetzung und Eigenschaften. Bei der Herstellung mischt man die flüssigen Bestandteile des Waschmittels und diejenigen teilchenförmigen Bestandteile, die auch nach einer Zerkleinerung nicht in chemische Wechselwirkung miteinander und mit dem flüssigen Bestandteilen treten, in einer ersten Mischstufe innig miteinander und unterzieht die so erhaltene Suspension einer Naßvermahlung, so daß der mittlere Korndurchmesser dieser festen Bestandteile in der so erhaltenen Suspension nach dem Vermahlen höchstens 30 Mikron beträgt, worauf man die Suspension entgast. In einem zweiten Prozeßschritt entgast man unter Kornerhaltung die übrigen teilchenförmigen Bestandteile mit einer Teilchengröße zwischen 200 und 2000 Mikron im Vakuum, vermischt dieses entgaste Feststoffgemisch mit der aemahlenen Suspension der ersten Mischstufe in einer zweiten Mischstufe unter erneutem Entgasen, und fügt zu dieser Mischung gegebenenfalls im Vakuum weitere Hilfsmittel wie Duftstoffe, Farbstoffe oder hydrotrope Verbindungen oder sonstige Verbindungen zur Einstellung der gewünschten Viskosität hinzu. Durch die Entgasung von Flüssig- und Festkomponenten wird bewirkt, daß die flüssigen erfindungsgemäßen Waschmittel praktisch gasfrei sind, was sich in einem besonders stabilen Viskositätsverhalten der Waschmittel auswirkt. Es wird angenommen, daß durch diese besondere Verfahrensweise die nach der Naßvermahlung erhaltene Suspension mit feinvermahlenem Feststoffen in die Poren der groben Feststoffe als Ganzes eindringen und dadurch die Viskositätsstabilität des flüssigen Waschmittels bewirkt wird. Daher sollte der mittlere Korndurchmesser der Feststoffe der feinvermahlenen Suspension ungefähr in der Größenordnung der mittleren Porengröße der unter Kornerhaltung eingearbeiteten grobteiligen festen Rezepturbestandteile oder darunter liegen.Another object of the present invention is a method for producing a liquid detergent of the composition and properties described above. In the preparation, the liquid constituents of the detergent and those particulate constituents which do not interact chemically with one another and with the liquid constituents even after comminution are intimately mixed in a first mixing stage and the suspension thus obtained is subjected to wet grinding, so that the the average grain diameter of these solid components in the suspension thus obtained after grinding is at most 30 microns, whereupon the suspension is degassed. In a second process step, the remaining particulate constituents with a particle size between 200 and 2000 microns are degassed in vacuo, this degassed solid mixture is mixed with the ground suspension of the first mixing stage in a second mixing stage with further degassing, and optionally added to this mixture in vacuo further auxiliaries such as fragrances, dyes or hydrotropic compounds or other compounds for setting the desired viscosity are added. The degassing of liquid and solid components has the effect that the liquid detergents according to the invention are practically gas-free, which results in a particularly stable viscosity behavior of the detergents. It is believed that this special procedure allows the suspension obtained after the wet grinding with finely ground solids to penetrate into the pores of the coarse solids as a whole, and thereby the viscosity stability of the liquid detergent is brought about. Therefore, the average grain diameter of the solids of the finely ground suspension should be of the order of magnitude mean pore size of the coarse-particle solid recipe components incorporated under grain retention or below.

Einen besonderen Handhabungsvorteil erhält man, wenn man die Waschmittel in Beuteln aus einer wasserlöslichen Folie portionsweise abpackt. Als Anbietungsform besonders bevorzugt sind Waschmittel, die in Beuteln aus Folie auf Basis von Polyvinylalkohol enthalten sind. Für die Handhabung in Haushaltswaschmitteln ist es ein besonderer Vorteil, wenn die Beutel soviel der erfindungsgemäßen Waschmittel enthalten, daß sie zum Waschen der Wäschemenge einer Waschmaschienfüllung ausreichen. Geeignete Folien sind beispielsweise Polyvinylalkoholfolien mit einer Foliendicke von 65 Mikron, die durch Heiß- oder Naßversiegelung zu geschlossenen, das Waschmittel enthaltenden Beuteln geformt werden.A special handling advantage is obtained if the detergents are packed in portions in bags from a water-soluble film. Particularly preferred as a form of supply are detergents which are contained in bags made of film based on polyvinyl alcohol. For handling in household detergents, it is a particular advantage if the bags contain so much of the detergents according to the invention that they are sufficient for washing the amount of laundry in a washing machine filling. Suitable films are, for example, polyvinyl alcohol films with a film thickness of 65 microns, which are formed by heat or wet sealing into closed bags containing the detergent.

B e i s p i e l eExample Beispiel 1example 1

In einem Rührbehälter wurden 25,2 kg C12/18-Fettalkohol + 5 Mol Ethylenoxid, 100,8 kg C12/14-Fettalkohol + 3 Mol Ethylenoxid, 120,0 kg Alkylbenzolsulfonat-Pulver, 75,0 kg Polyethylenglykol Molgewicht 400, 326,5 kg Natriumtripolyphosphat, 50,0 kg pulverförmiges Natronwasserglas mit einem SiO2 : Na20-Verhältnis von 2,0 und einem Restwassergehalt von ca. 20 Gew.-%, 5,0 kg eines 3 : 7-Gemisches von Methylcellulose und Carboxymethylcellulose, miteinander vermischt. Anschließend wurde dieses Gemisch in einer SZEGO-Mühle naßvermahlen (mittlere Korngröße ca. 17 Mikron) und in einem Rührkessel mit Ankerrührung und Teflonabstreifern nach Zugabe von 3,0 kg Silikonentschäumer durch Anlegen eines Vakuums von 20 mbar bis auf einen Restgasgehalt von 2 Vol.-% entgast.In a stirred vessel were 25.2 kg C 12/18 -fatty alcohol + 5 moles of ethylene oxide, 100 8 kg C 12/14 -fatty alcohol + 3 moles ethylene oxide, 120.0 kg alkyl benzene sulfonate powder, 75.0 kg of polyethylene glycol molecular weight of 400, 326.5 kg of sodium tripolyphosphate, 50.0 kg of powdered sodium silicate with an SiO 2 : Na 2 0 ratio of 2.0 and a residual water content of approx. 20% by weight, 5.0 kg of a 3: 7 mixture of methyl cellulose and carboxymethyl cellulose mixed together. This mixture was then wet-ground in a SZEGO mill (average particle size approx. 17 microns) and in a stirred tank with anchor stirring and Teflon wipers after adding 3.0 kg of silicone defoamer by applying a vacuum of 20 mbar to a residual gas content of 2 vol. % degassed.

In einen evakuierbaren Kessel wurden 8,0 kg granulierte und umhüllte Alkalase, 250,0 kg Natriumperborat-Tetrahydrat (mittlere Teiichengröße ca. 1500 micron, Porengröße 10 bis 40 micron, gemessen mit Hilfe der Quecksilberporosimetrie) und 30,0 kg Seife auf Basis von C16- bis C22-Fettsäuren eingewogen und entgast. Der Inhalt dieses Kessels wurde dann unter Vakuum (20 mbar) in einen ebenfalls evakuierten Mischkessel eingerührt. Abschließend werden zugegeben 3,0 kg optische Aufheller, 0,5 kg Farbstoff und 3,0 kg Duftstoff. Man erhielt ein Waschmittel mit einer Viskosität von 132 000 mPas. Der pH-Wert einer 1 %igen Lösung dieses Mittels in Wasser betrug bei 20 °C 10,5.8.0 kg of granulated and coated alkalase, 250.0 kg of sodium perborate tetrahydrate (average particle size approx. 1500 micron, pore size 10 to 40 micron, measured with the aid of mercury porosimetry) and 30.0 kg of soap based on were placed in an evacuable kettle C16 to C 22 fatty acids weighed and degassed. The contents of this kettle were then stirred under vacuum (20 mbar) into a mixing kettle which was also evacuated. Finally, 3.0 kg of optical brighteners, 0.5 kg of dye and 3.0 kg of fragrance are added. A detergent with a viscosity of 132,000 mPas was obtained. The pH of a 1% solution of this agent in water was 10.5 at 20 ° C.

Je 75g dieses Waschmittels wurden in Beutel aus einer in borathaltigen wäßrigen Lösungen löslichen Polyvinylalkoholfolie mit einer Stärke von 65 micron abgefüllt; die Beutel wurden durch thermisches Verschweißen verschlossen. Legte man einen solchen Beutel in die Trommel einer automatischen Haushaltswaschmaschine, füllte die Trommel dann mit 3,5 kg Textilien und prüfte die Auflösegeschwindigkeit der Beutel unter Benutzung des Buntwaschprogramms (30 °C, 1-Laugenverfahren), stellte man fest, daß Beutel und Waschmittel nach 10 Minuten Waschdauer vollständig gelöst waren.75 g each of this detergent were filled into bags made of a polyvinyl alcohol film with a thickness of 65 microns, which was soluble in borate-containing aqueous solutions; the bags were sealed by thermal sealing. If you put one Bags in the drum of an automatic household washing machine, then filled the drum with 3.5 kg of textiles and checked the dissolving speed of the bags using the colored washing program (30 ° C., 1-lye method), it was found that bags and detergent after 10 minutes of washing were completely solved.

Beispiel 2Example 2

In vergleichbarer Weise wie zuvor beschrieben wurde ein phosphatfreies Waschmittel der folgenden Zusammensetzung hergestellt:

Figure imgb0001
A phosphate-free detergent of the following composition was prepared in a manner comparable to that described above:
Figure imgb0001

Dieses Waschmittel hatte eine Viskosität von 38 000 mPas. Das Auflöseverhalten war wie in Beispiel 1 beschrieben. Die Waschmittel aus den Beispielen 1 und 2 hatten ausgezeichnete Waschleistung sowohl gegenüber Fett/Pigment-, enzymatischen als auch gegenüber bleichbaren Anschmutzungen in hartem wie in weichem Wasser. Bei großer Wasserhärte wurden bis zu 3 Beutel Waschmittel eingesetzt, bei niedriger Härte nur einer.This detergent had a viscosity of 38,000 mPas. The dissolution behavior was as described in Example 1. The detergents from Examples 1 and 2 had excellent washing performance both against fat / pigment, enzymatic and against bleachable stains in hard and soft water. If the water hardness is high, up to 3 sachets of detergent were used, if the water hardness was low only one.

Claims (12)

1. Flüssiges Waschmittel auf Basis von nichtionischen Tensiden und teilchenförmigen Gerüststoffen, dadurch gekennzeichnet, daß es eine Tensid-Flüssigkomponente aus a) Anlagerungsprodukten von 2 bis 8 Mol Ethylenoxid an 1 Mol Fettalkohol mit 10 bis 20 Kohlenstoffatomen, b) Aniontensiden vom Typ der Sulfate, Sulfonate und Seife, c) Polyethylenglykol mit einem Molgewicht von etwa 200 bis 600, enthält, mit der Maßgabe, daß die Menge der Bestandteile a) + b) + c) größer als 20 Gew.-%, insbesondere 20 - 50 Gew.-% des gesamten Waschmittels ist u.nd daß das Verhältnis von a) : b) im Bereich von 1 : 1 bis 2 : 1 liegt, daß das Waschmittel eine Dichte zwischen 1,4 und 1,8 hat und praktisch wasserfrei und praktisch gasfrei ist. 1. Liquid detergent based on nonionic surfactants and particulate builders, characterized in that it consists of a surfactant liquid component a) addition products of 2 to 8 moles of ethylene oxide with 1 mole of fatty alcohol with 10 to 20 carbon atoms, b) anionic surfactants of the sulfate, sulfonate and soap type, c) polyethylene glycol with a molecular weight of about 200 to 600, contains, with the proviso that the amount of the components a) + b) + c) is greater than 20 wt .-%, in particular 20-50 wt .-% of the total detergent and that the ratio of a): b ) in the range of 1: 1 to 2: 1, that the detergent has a density between 1.4 and 1.8 and is practically water-free and practically gas-free. 2. Waschmittel nach Anspruch 1, dadurch gekennzeichnet, daß es als Komponente b) ein Sulfonat zusammen mit Seife enthält.2. Detergent according to claim 1, characterized in that it contains a sulfonate together with soap as component b). 3. Waschmittel nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß es als Komponente a) nichtionische Tenside, die Anlagerungsprodukte von 3 bis 5 Mol Ethylenoxid an 1 Mol Fettalkohol sind, enthält.3. Detergent according to one of claims 1 and 2, characterized in that it contains as component a) nonionic surfactants which are adducts of 3 to 5 moles of ethylene oxide with 1 mole of fatty alcohol. 4. Waschmittel nach einem der Ansprüche 1 bis 3, dadurch ge-kennzeichnet, daß es Polyethylenglykol mit einem Molgewicht von etwa 300 bis 400 enthält.4. A detergent composition according to any one of claims 1 to 3, characterized g e-denotes that it contains polyethylene glycol having a molecular weight of about 300 to 400 bar. 5. Waschmittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es die Komponente a) in einem Verhältnis zur Komponente b) von 1,1 : 1 bis 1,5 : 1 und Komponente c) in einer Menge von 2 bis 10 Gew.-% enthält.5. Detergent according to one of claims 1 to 4, characterized in that it contains component a) in a ratio to component b) of 1.1: 1 to 1.5: 1 and component c) in an amount of 2 to 10 Wt .-% contains. 6. Waschmittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es die Komponenten a) + b) + c) in einer Menge von 25 bis 40 Gew.-% enthält.6. Detergent according to one of claims 1 to 5, characterized in that it contains the components a) + b) + c) in an amount of 25 to 40 wt .-%. 7. Waschmittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es 2 Typen von teilchenförmigen Bestandteilen und zwar einen ersten feinverteilten Anteil mit einer Teilchengröße im Bereich von Staubfeinheit bis 30 Mikron und und einer zweiten gröberen Anteil mit einer Teilchengröße von 200 bis 2000 Mikron enthält-7. Detergent according to one of claims 1 to 6, characterized in that there are 2 types of particulate constituents, namely a first finely divided portion with a particle size in the range from dust fineness to 30 microns and a second coarser portion with a particle size of 200 to 2000 Micron contains 8. Waschmittel nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es eine Viskosität im Bereich von 10 000 bis 1 000 000 mPas hat.8. Detergent according to one of claims 1 to 7, characterized in that it has a viscosity in the range of 10,000 to 1,000,000 mPas. 9. Verfahren zur Herstellung eines Waschmittels nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man die flüssigen Bestandteile und diejenigen teilchenförmigen Bestandteile, die auch nach Zerkleinerung nicht in chemische Wechselwirkung miteinander und mit den flüssigen Bestandteilen treten, in einer ersten Mischstufe miteinander vermischt, die so erhaltene Suspension einer Naßvermahlung unterzieht-, so daß der mittlere Korndurchmesser der festen Bestandteile der Suspension nach dem Vermahlen höchstens 30 Mikron beträgt, worauf man die Suspension im Vakuum entgast, daß man die übrigen teilchenförmigen Bestandteile mit einer Teilchengröße zwischen 200 und 2000 Mikron in einem weiteren Prozeßschritt unter Kornerhaltung entgast, das entgaste Feststoffgemisch zusammen mit der gemahlenen Suspension der ersten Mischstufe in einer zweiten Mischstufe unter erneuter Entgasung vermischt und zu dieser Mischung im Vakuum ggf. weitere Hilfsmittel hinzufügt.9. A process for the preparation of a detergent according to any one of claims 1 to 8, characterized in that the liquid constituents and those particulate constituents which do not interact chemically with one another and with the liquid constituents even after comminution are mixed together in a first mixing stage , the suspension thus obtained is subjected to wet grinding, so that the mean grain diameter of the solid constituents of the suspension after grinding is at most 30 microns, whereupon the suspension is degassed in vacuo to give the other particulate constituents having a particle size between 200 and 2000 microns degassed in a further process step, grain condition, the degassed solid emic g together with the milled Suspension of the first mixing stage is mixed in a second mixing stage with further degassing and, if necessary, additional auxiliaries are added to this mixture in vacuo. 10. Waschmittel nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß es in Beuteln aus wasserlöslicher Folie enthalten ist.10. Detergent according to one of claims 1 to 8, characterized in that it is contained in bags made of water-soluble film. 11. Waschmittel nach Anspruch 10, dadurch gekennzeichnet, daß es in Beuteln aus Folie auf Basis von Polyvinylalkohol enthalten ist.11. Detergent according to claim 10, characterized in that it is contained in bags made of film based on polyvinyl alcohol. 12. Waschmittel nach einem der Ansprüche 10 und 11, dadurch gekennzeichnet, daß es in Beuteln in einer Menge, die zum Waschen der Wäschemenge einer Waschmaschinenfüllung ausreicht, enthalten ist.12. Detergent according to one of claims 10 and 11, characterized in that it is contained in bags in an amount sufficient to wash the amount of laundry in a washing machine filling.
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DK330887D0 (en) 1987-06-26
EP0253151A3 (en) 1990-06-13
DE3621536A1 (en) 1988-01-07
JPS638495A (en) 1988-01-14
US4929380A (en) 1990-05-29

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