EP0490912B1 - Liquid detergents containing zeolite - Google Patents

Liquid detergents containing zeolite Download PDF

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Publication number
EP0490912B1
EP0490912B1 EP90912599A EP90912599A EP0490912B1 EP 0490912 B1 EP0490912 B1 EP 0490912B1 EP 90912599 A EP90912599 A EP 90912599A EP 90912599 A EP90912599 A EP 90912599A EP 0490912 B1 EP0490912 B1 EP 0490912B1
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Prior art keywords
weight
detergent
sodium
zeolite
water
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German (de)
French (fr)
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EP0490912A1 (en
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Hans Josef Beaujean
Jens Bode
Stefan Paasch
Karl Schwadtke
Eduard Smulders
Eric Sung
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

  • the invention relates to a phosphate-free, aqueous liquid detergent which contains zeolite as builder substance, and to a process for its preparation.
  • Liquid detergents containing builder substances are known in large numbers. In these aqueous concentrates, water-soluble builder substances such as sodium tripolyphosphate are also partially undissolved and are present as fine particles. For reasons of application safety, such liquid detergents must be formulated as stabilized, homogeneous suspensions. If the tripolyphosphate is replaced by zeolite NaA, the problem of suspension stabilization must also be solved for this insoluble and finely divided component. For this purpose, German patent application 36 05 978 suggests suspending the zeolite particles in a non-aqueous liquid (liquid nonionic surfactant) and increasing the stability of the suspension by adding the aluminum salt of a higher aliphatic carboxylic acid (aluminum tristearate).
  • a non-aqueous liquid liquid nonionic surfactant
  • non-aqueous liquid heavy-duty detergents which contain 25-45% by weight of one or more liquid nonionic surfactants, 10-20% by weight salts of nitrilotriacetic acid, 10-25% by weight zeolite and a Antigelling agents, for example a nonionic surfactant reacted with succinic anhydride or an alkylene glycol monoalkyl ether, and aluminum tristearate as stabilizing agents.
  • European patent application EP 038 591 describes nibbling agents which contain 1-20% by weight of synthetic surfactant, 5-50% by weight of a water-insoluble builder, which can be a zeolite and / or an amorphous aluminosilicate, and 5-60% by weight. % of a water-soluble salt of an unsaturated fatty acid.
  • the proportion of salts of saturated fatty acids in the agents described there must be kept as low as possible and preferably does not exceed half the amount of unsaturated soap present.
  • the US Pat. No. 4,018,720 describes aqueous liquid detergents which contain 7-25% by weight of a mixture of alkyl sulfates or alkyl ether sulfates and alkylbenzenesulfonates, 6-25% by weight of a phosphate builder substance, 3-20% by weight of an alkali metal sulfate Stabilizer and optionally 1 - 10 wt .-% of an aluminosilicate as a co-builder.
  • alkylbenzenesulfonate as an anionic surfactant leads to physically unstable compositions as does the addition of solvents such as alcohols or glycols.
  • European patent application 75 976 describes alkaline aqueous liquid detergents which contain 7-30% by weight of zeolite, 5-40% by weight of an unsaturated C16-C22 fatty acid soap, 1-30% by weight of a nonionic surfactant, 5-15% by weight .-% of a water-soluble polycarboxylate and 20 - 82 wt .-% water, but which are free of synthetic anionic surfactants, which otherwise destabilize the perfume ester present in this stable liquid mixture.
  • European patent application 86 614 describes aqueous liquid detergents which contain anionic and optionally and / or nonionic, cationic and amphoteric surfactants, contain water-insoluble, suspended and, if appropriate, water-soluble builder substances and further electrolytes, sodium sulfate not being present in amounts above 3% by weight.
  • aqueous liquid detergents which contain anionic and optionally and / or nonionic, cationic and amphoteric surfactants, contain water-insoluble, suspended and, if appropriate, water-soluble builder substances and further electrolytes, sodium sulfate not being present in amounts above 3% by weight.
  • tripolyphosphate or mixtures of tripolyphosphate and other builder substances are preferably used as the builder substance.
  • phosphate-containing suspensions sometimes showed no signs of sedimentation even after 12 months of storage at room temperature
  • phosphate-free agents which were 13.4% by weight of zeolite and 8.9% by weight of silicate or 13.6% by weight of zeolite and Contained 9.0 wt .-% silicate, stable for one month at room temperature.
  • European patent application 142 185 discloses stable aqueous liquid detergents which contain condensed phosphates and / or nitrilotriacetate together with zeolite NaY.
  • the suspensions have a pH of 7-9.
  • the compositions contain 1-60% by weight of surfactants, 0.5-30% by weight of phosphate and / or nitrilotriacetate and 1-45% by weight of zeolite.
  • the surfactants can consist of anionic and nonionic surfactants, these preferably being used in a ratio of 10: 1 to 1:10.
  • the zeolite NaA proved to be unsuitable for use in these agents: after 15 days of storage at room temperature, there were clear phase separations.
  • European patent application 151 884 describes aqueous liquid detergents which contain builder substances, preferably phosphates, and surfactants in a ratio of at least 1.5: 1 and electrolytes.
  • the amount of electrolyte required to stabilize a certain predetermined suspension of water, surfactants and builder substances is determined by conductivity measurements: with continuous addition of Electrolyte salts pass through the electrical conductivity at a first minimum, in which the suspension is stable.
  • aqueous liquid detergents which contain surfactants, electrolytes, which also include water-soluble builder substances, but which contain less than 3% by weight sodium sulfate, and suspended builder substances.
  • tripolyphosphate is preferably used as builder substance for the same reasons of stability as in European patent applications 86 614 and 151 884.
  • the agents can be separated into at least 2 layers, at least one of which is an aqueous layer, by centrifugation at 800 times gravity for 17 hours at 25 ° C.
  • Stable agents contain such amounts of dissolved electrolyte that there are 2-4.5 gram ions of alkali metal ion per liter in this aqueous layer.
  • aqueous non-sedimenting, liquid-crystalline surfactant concentrates which can be transported and stored without loss of stability contain 25-80% by weight of surfactants and up to 10% by weight, based on the amount of surfactant, of electrolytes .
  • sodium sulfate is not present at all or only in trace amounts and in the latter case is introduced into the concentrates as an impurity in the anionic surfactants.
  • the concentrates can be quickly diluted or mixed into liquid detergents by adding other detergent constituents, for example by adding suspendable builder substances, preferably tripolyphosphate, and optionally electrolytes. The use of electrolytes that have no builder properties is less preferred.
  • European patent application 301 882 describes a liquid detergent which can contain builders such as phosphates and zeolite and which contains viscosity-reducing (co) polymers, for example polyethylene glycol, polyacrylates, polymaleates, polysaccharides and sulfonated polysaccharides.
  • the polymers are only partially dissolved in the aqueous phase, the rest is part of a phase dispersed in the aqueous phase.
  • the agents are already considered to be sufficiently stable if there is no phase separation of more than 2% within 21 days when stored at 25 ° C.
  • the object of the invention was to provide a phosphate-free, aqueous and zeolite-containing liquid detergent which is stable for at least 3 months both at room temperature and at 40 ° C. and does not tend to sedimentation during transport at temperatures between 5 and 60 ° C. and meets the requirements for the performance of modern liquid detergents.
  • the invention accordingly relates to a phosphate-free, zeolite-containing liquid detergent with a pH between 8 and 12 and a flow limit of at least 3 Pa, containing 10-30% by weight of anionic and nonionic surfactants, with a maximum of 5% by weight, based on the total composition of soaps is contained and the soaps are composed of 50-100% by weight of saturated C12-C18 fatty acid soaps, 10-25% by weight of zeolite which has no particles with a size greater than 30 ⁇ m at least 80% consists of particles less than 10 ⁇ m in size and has an average particle size in the range of 1-10 ⁇ m, 1-10% by weight of an electrolyte system consisting of at least 2 electrolytes from the group of the carbonates, sulfates, chlorides , Acetates and citrates, the electrolyte system containing 0.5-4% by weight of carbonate and 0.5-8% by weight of sulfate, in each case based on the total composition, and 40-60% by
  • the agents according to the invention preferably contain 5-20% by weight of conventional anionic surfactants from the class of the sulfonates and sulfates.
  • Preferred surfactants of the sulfonate type are C9-C13-alkylbenzenesulfonates, especially C12-alkylbenzenesulfonate, and sulfonates based on oleochemicals, such as the esters of ⁇ -sulfofatty acids (Ester sulfonates), e.g. B. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids into consideration.
  • Suitable surfactants of the sulfate type are, for example, the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols such as. Example, coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C10-C20 oxo alcohols, and those secondary alcohols of this chain length, the sulfuric acid monoesters of the primary alcohols being preferred on a fat-chemical basis.
  • the sulfuric acid monoesters of alcohols ethoxylated with 1-6 moles of ethylene oxide such as linear C12-C18 fatty alcohols or 2-methyl-branched C9-C11 alcohols with an average of 3.5 moles of ethylene oxide, are suitable.
  • Sulfated fatty acid monoglycerides are also suitable.
  • the sulfates and sulfonates can be present individually or in a mixture.
  • Preferred agents contain 5 - 17 wt .-%, in particular 8 - 16 wt .-% C9-C13-alkylbenzenesulfonates or 10 - 20 wt .-% of a mixture of C9-C13-alkylbenzenesulfonates with one or more other sulfonates and / or sulfates in any mixing ratio.
  • soaps preferably saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid and stearic acid.
  • Particularly suitable are natural fatty acids, e.g. B. coconut, palm kernel or tallow fatty acid derived soap mixtures.
  • those soaps which are composed of 50-100% by weight of saturated C12-C18 fatty acid soaps and 0-50% by weight of oleic acid soap.
  • the agents according to the invention can contain 0-5% by weight of soaps. Preferred agents have a soap content of 1-3.5% by weight.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the agents according to the invention further preferably contain 5-10% by weight from the class of the nonionic surfactants.
  • Suitable are, for example, customary ethoxylated fatty alcohols, in particular addition products of 2-7 moles of ethylene oxide (EO) with linear primary alcohols, such as. B. on coconut oil, tallow or oleyl alcohol, or on primary alcohols (oxo alcohols) branched methyl in the 2-position.
  • EO ethylene oxide
  • C12-C14 alcohols with 3 EO or 4 EO C13-C15 alcohols with 3, 5 or 7 EO
  • C12-C18 alcohols with 3, 5 or 7 EO and mixtures of these such as mixtures of C12-C14 -Alcohol with 3 EO and C12-C18 alcohols with 5 EO, used in amounts of 5 - 9 wt .-%.
  • the agents according to the invention contain, for example, the zeolite NaA as builder substance. Mixtures of zeolite NaA and NaX can also be used, the proportion of the zeolite NaX in such mixtures advantageously being below 30%, in particular below 20%.
  • Suitable zeolites have no particles larger than 30 ⁇ m and consist of at least 80% particles smaller than 10 ⁇ m. Their average particle size (volume distribution, measurement method: Coulter Counter) is in the range of 1 - 10 ⁇ m. Preferred zeolites have an average particle size of 2-4 microns. Your calcium binding capacity, which is determined according to the information in German patent application 24 12 837, is in the range of 100-200 mg CaO / g.
  • the zeolites which contain 10-25% by weight in the agents according to the invention, can still contain excess alkali from their production.
  • the zeolite content of the agents according to the invention is preferably 12-20% by weight and in particular 14-19% by weight.
  • the ratio of surfactants: zeolite is preferably 0.8: 1 to 1.4: 1 and in particular 1: 1 to 1.4: 1.
  • the suspensions of water, surfactants and zeolite according to the invention are stabilized by an electrolyte system which consists of at least 2 salts, preferably sodium salts and / or triethanolammonium salts, from the group of carbonates, chlorides, sulfates, acetates and citrates, but the electrolyte system at least consists of a carbonate and a sulfate.
  • the proportion of the electrolyte system, based on the total agent, is 1-10% by weight.
  • It consists of 0.5-4% by weight, preferably 0.5-2% by weight, of carbonate, 0.5-8% by weight, preferably 1-6% by weight, of sulfate, 0 - 4% by weight, preferably 0.1 - 2% by weight, of chloride, 0 - 4% by weight, preferably 0.1 - 2.5% by weight, of acetate and 0 1.5% by weight, preferably 0.1-1% by weight, of citrate, which is introduced into the suspension in the form of citric acid and is formed by reaction with excess alkali.
  • Electrolyte systems used with preference consist of 3 or 4 different electrolytes, in particular (based on the total composition) of 0.5-2% by weight sodium carbonate, 4-6% by weight sodium sulfate and 0.8-1.5% by weight.
  • % Citrate for example sodium citrate or triethanolammonium citrate, or from 0.5-1.5% by weight sodium carbonate, 3.5-5.5% by weight sodium sulfate and 1.0-2.0% by weight sodium chloride or from 0.5-1% by weight sodium carbonate, 4-6% by weight sodium sulfate and 0.5-4% by weight sodium acetate or from 0.5-1% by weight sodium carbonate, 3-5.5% by weight.
  • the ratio of zeolite: electrolyte system is preferably 10: 3 to 10: 6 and in particular 10: 4 to 10: 5.
  • the agents according to the invention contain 40-60% by weight and preferably 42-55% by weight of water.
  • the pH of the compositions is between 8 and 12, preferably between 8.5 and 10.5 and in particular between 9 and 10.
  • the density of the compositions is generally from 1.1 to 1.25 g / ml, preferably from 1.15 to 1.22 g / ml.
  • the agents according to the invention have a yield point of at least 3 Pa. Preferred agents have flow limits between 4 and 35 Pa.
  • Their viscosity (Brookfield viscometer, spindle no. 6, 10 rpm) is generally 2,000 to 11,000 mPas, preferably between 3,000 and 9,000 mPas and in particular between 3,500 and 8,500 mPas.
  • the storage stability of the compositions was tested both at room temperature and at 40 ° C. over a period of 7 months. The agents were stable on storage for at least 3 months. With batches that had been stored for a long time, no discontinuation was observed even after 4 months and even after 7 months. The agents can be transported at temperatures between 5 and 60 ° C.
  • the foaming power of the surfactants can be reduced by adding 0.05-2% by weight of non-surfactant-like organic substances.
  • Suitable foam inhibitors are, for example, known polysiloxane / silica mixtures, the fine-particle silica contained therein preferably being silanated.
  • the polysiloxanes can consist both of linear compounds (silicone oils) and of crosslinked polysiloxane resins and of their mixtures.
  • Other suitable defoamers are paraffin oils, microparaffins and paraffin waxes.
  • Mixtures of various foam inhibitors are also advantageously used, for example those made from silicone oil and paraffin oil. In particular, the use of 0.1% by weight, based on the total agent, of silicone oil is preferred.
  • the agents preferably contain 0.5-5% by weight of alcohols with 2-3 carbon atoms and 1-3 hydroxyl groups, such as ethanol, propanol, propylene glycol and glycerol.
  • Alcohols with 2-3 carbon atoms and 1-3 hydroxyl groups such as ethanol, propanol, propylene glycol and glycerol.
  • Propylene glycol and glycerol, alone or in a mixture with ethanol, are preferably used in amounts of 2 to 3.5% by weight.
  • the agents can contain small amounts of free base, such as triethanolamine or sodium hydroxide solution, in order to maintain the pH between 9 and 12.
  • free base such as triethanolamine or sodium hydroxide solution
  • the agents can optionally contain other known additives commonly used in detergents, for example salts of polyphosphonic acids, optical brighteners, enzymes, bleaches, hydrotropes and dyes and fragrances which are stable in aqueous agents, in the customary amounts which provide stability do not affect the suspensions of the invention.
  • the neutral-reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and diethylenetriamine pentamethylene phosphonate are preferably used as salts of polyphosphonic acids in amounts of 0.1-1.5% by weight.
  • the total phosphorus content in the compositions is preferably less than 0.5%.
  • the detergents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Are suitable for.
  • Brighteners of the substituted 4,4'-distyryl-diphenyl type can also be used to be present; e.g. B.
  • the compound 4,4'-bis (4-chloro-3-sulfo-styryl) diphenyl Mixtures of the aforementioned brighteners can also be used.
  • the maximum content of brighteners in the agents according to the invention is 0.5% by weight, preferably amounts of 0.02-0.1% by weight are used.
  • Enzymes from the class of proteases, lipases, amylases or mixtures thereof are possible. Their proportion can be 0.2-1% by weight.
  • the agents contain 8-16% by weight of C9-C13-alkylbenzenesulfonate, in particular C12-alkylbenzenesulfonate, 1-3.0% by weight of saturated C12-C18-fatty acid soap in the form of the sodium and / or triethanolammonium salts, 5-9% by weight of nonionic surfactants, 14-19% by weight of bound water-containing zeolite, 0.5-1.5% by weight of sodium carbonate, 3-6% by weight of sodium sulfate, 0-1.5% by weight % 1-hydroxyethane-1,1-diphosphonate and / or diethylenetriaminepentamethylenephosphonate, 0.1% by weight silicone oil and 43-54% by weight water.
  • the agents contain surfactants, zeolite, phosphonate, silicone oil and water as above and also 0.5-1% by weight sodium carbonate, 4-6% by weight sodium sulfate, 1.5-2% by weight sodium acetate and 2-3% by weight of glycerin or propylene glycol.
  • agents containing surfactants, zeolite, phosphonate, silicone oil, sodium carbonate, sodium sulfate and water as above, and 0.8-1.5% by weight of citrate, for example sodium citrate and / or triethanolammonium citrate, and 2-3% .-% Contain glycerin or a mixture of 2/3 glycerin and 1/3 ethanol.
  • the invention further relates to a method for producing the liquid detergents described above.
  • the liquid detergents can be produced in a manner known per se. 35 to 60%, in particular 40-58% water, based on the total amount of water provided on average, and, if appropriate, a foam inhibitor are preferably introduced into a reactor which is provided with a stirring system, and anionic and nonionic surfactants are mixed in. If soap is provided as a constituent of the composition, the corresponding fatty acid or the corresponding fatty acid mixture is heated to 60-80 ° C. and stirred into the water provided, which in this case is also heated to 60-80 ° C.
  • the fatty acid is then advantageously neutralized with triethanolamine and / or sodium hydroxide, which is preferably added in the form of an aqueous solution.
  • Zeolite NaA can be added both in the form of a powder and in the form of an aqueous suspension, the addition of a 40-55% by weight aqueous zeolite suspension being preferred.
  • the electrolyte salts carbonate and sulfate and, if appropriate, chloride and acetate can also be metered in in powder form or in the form of an aqueous solution. The components are added to the water initially introduced in such a way that the stirring in of a large amount of air bubbles is avoided.
  • This example describes the production of a liquid detergent according to the invention (W1) in a 900 kg batch.
  • W2 contained 9.5% by weight dodecylbenzenesulfonate, 1.7% by weight C12 fatty acid, 6% by weight C13-C15 alcohol with 7 EO, 3% by weight C12-C14 alcohol with 3 EO, 1.3% by weight of triethanolamine, 17% by weight of zeolite NaA, 2.0% by weight of sodium carbonate, 4.0% by weight of sodium sulfate, 1.0% by weight of citric acid, 3% by weight of glycerin and 52.05 wt% water.
  • the storage period was 5 months. During this time, no sedimentation occurred at storage temperatures of 40 ° C and room temperature.
  • W3 contained 14% by weight of dodecylbenzenesulfonate, 8% by weight of C12-C1 mit alcohol with 5 EO, 0.5% by weight of sodium hydroxide, 18% by weight of zeolite NaA, 0.5% by weight of sodium carbonate, 5 , 0% by weight sodium sulfate, 2.0% by weight sodium chloride, 2% by weight glycerin, 1% by weight ethanol and 47% by weight water.
  • the storage period was 4 months. Stepped within that time no sedimentation at storage temperatures of 40 ° C and room temperature.
  • W4 contained 10% by weight of dodecylbenzenesulfonate, 1.8% by weight of C12-C14 fatty acid, 1.4% by weight of triethanolamine, 6% by weight of a mixture of C12-C18 alcohol with 5 EO and C12- C14 alcohol with 3 EO, 17 wt .-% zeolite NaA, 0.5 wt .-% sodium carbonate, 5.5 wt .-% sodium sulfate, 2.0 wt .-% sodium acetate, 3 wt .-% propylene glycol and 50 , 1 wt .-% water.
  • the storage period was 5 months. During this time, no sedimentation occurred at storage temperatures of 40 ° C and room temperature.
  • W5 was produced from 9.8% by weight of dodecylbenzenesulfonate, 8.0% by weight of C12-C14 alcohol with 5 EO, 4.9% by weight of C12 fatty acid, 1.1% by weight of sodium hydroxide, 17th , 5% by weight of zeolite NaA, 2% by weight of glycerol, 1% by weight of ethanol, 0.5% by weight of sodium carbonate, 6.0% by weight of sodium sulfate, 0.9% by weight of citric acid, 0.5 wt% protease, 0.1 wt% silicone oil and 47.7 wt% water.
  • the storage time was 61 ⁇ 2 months. At both 40 ° C and room temperature, there was no sedimentation in either time.
  • This example describes the application test of the agent (W1) according to the invention, which was carried out in a household washing machine with a horizontally arranged laundry drum (type Miele W 433) under the following conditions: Washing temperature : 60 ° C Soaking process - colored washing program Water hardness : 16 ° d (160 mg CaO per liter) Detergent dosage : 224 g Textile samples : two test strips with the same soiling and 3.5 kg of normally soiled household laundry Quadruple determination The optical evaluation of the washing results (Table 1) was carried out using a: Zeiss reflectometer at 460 nm (suppression of the brightener effect). Remission differences of 2% and more can be noticed directly by the consumer.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

PCT No. PCT/EP90/01435 Sec. 371 Date Mar. 6, 1992 Sec. 102(e) Date Mar. 6, 1992 PCT Filed Aug. 29, 1990 PCT Pub. No. WO91/03541 PCT Pub. Date Mar. 21, 1991.A phosphate-free liquid detergent containing anionic and nonionic surfactants, zeolite, and electrolyte system selected from carbonates, sulfates, chlorides, acetates and citrates with the proviso that the electrolyte system contain at least one carbonate and one sulfate, and water.

Description

Die Erfindung betrifft ein phosphatfreies, wäßriges Flüssigwaschmittel, das Zeolith als Buildersubstanz enthält, sowie ein Verfahren zu seiner Herstellung.The invention relates to a phosphate-free, aqueous liquid detergent which contains zeolite as builder substance, and to a process for its preparation.

Flüssige Waschmittel, die Buildersubstanzen enthalten, sind in großer Zahl bekannt. In diesen wäßrigen Konzentraten sind auch an sich wasserlösliche Buildersubstanzen wie z.B. Natriumtripolyphosphat teilweise ungelöst und liegen als feine Teilchen vor. Aus Gründen der Anwendungssicherheit müssen solche Flüssigwaschmittel als stabilisierte homogene Suspensionen formuliert sein. Ersetzt man das Tripolyphosphat durch Zeolith NaA, dann ist auch für diese unlösliche und feinteilige Komponente das Problem der Suspensionsstabilisierung zu lösen. Dazu schlägt die deutsche Patentanmeldung 36 05 978 vor, die Zeolithteilchen in einer nicht-wäßrigen Flüssigkeit (flüssiges Niotensid) zu suspendieren und durch Zugabe des Aluminiumsalzes einer höheren aliphatischen Carbonsäure (Aluminiumtristearat) die Stabilität der Suspension zu erhöhen. Aus der deutschen Patentanmeldung 36 25 189 sind nicht-wäßrige flüssige Grobwaschmittel bekannt, die 25 - 45 Gew.-% eines oder mehrerer flüssiger Niotenside, 10 - 20 Gew.-% Salze der Nitrilotriessigsäure, 10 - 25 Gew.-% Zeolith sowie ein Antigeliermittel, beispielsweise ein mit Bernsteinsäureanhydrid umgesetztes nichtionisches Tensid oder einen Alkylenglykolmonoalkylether, sowie Aluminiumtristearat als Stabilisierungsmittel enthalten.Liquid detergents containing builder substances are known in large numbers. In these aqueous concentrates, water-soluble builder substances such as sodium tripolyphosphate are also partially undissolved and are present as fine particles. For reasons of application safety, such liquid detergents must be formulated as stabilized, homogeneous suspensions. If the tripolyphosphate is replaced by zeolite NaA, the problem of suspension stabilization must also be solved for this insoluble and finely divided component. For this purpose, German patent application 36 05 978 suggests suspending the zeolite particles in a non-aqueous liquid (liquid nonionic surfactant) and increasing the stability of the suspension by adding the aluminum salt of a higher aliphatic carboxylic acid (aluminum tristearate). From German patent application 36 25 189 non-aqueous liquid heavy-duty detergents are known which contain 25-45% by weight of one or more liquid nonionic surfactants, 10-20% by weight salts of nitrilotriacetic acid, 10-25% by weight zeolite and a Antigelling agents, for example a nonionic surfactant reacted with succinic anhydride or an alkylene glycol monoalkyl ether, and aluminum tristearate as stabilizing agents.

Die europäische Patentanmeldung EP 038 591 beschreibt Naschmittel, die 1 - 20 Gew.-% synthetisches Tensid, 5 - 50 Gew.-% eines wasserunlöslichen Builders, der ein Zeolith und/oder ein amorphes Alumosilikat sein kann, und 5 - 60 Gew.-% eines wasserlöslichen Salzes einer ungesättigten Fettsäure enthalten. Der Anteil an Salzen gesättigter Fettsäuren muß in den dort beschriebenen Mitteln so niedrig wie möglich gehalten werden und übersteigt vorzugsweise nicht die Hälfte der Menge an vorhandener ungesättiger Seife.European patent application EP 038 591 describes nibbling agents which contain 1-20% by weight of synthetic surfactant, 5-50% by weight of a water-insoluble builder, which can be a zeolite and / or an amorphous aluminosilicate, and 5-60% by weight. % of a water-soluble salt of an unsaturated fatty acid. The proportion of salts of saturated fatty acids in the agents described there must be kept as low as possible and preferably does not exceed half the amount of unsaturated soap present.

Die US-amerikanische Patentschrift 4 018 720 beschreibt wäßrige Flüssigwaschmittel, die 7 - 25 Gew.-% einer Mischung aus Alkylsulfaten bzw. Alkylethersulfaten und Alkylbenzolsulfonaten, 6 - 25 Gew.-% einer Phosphatbuildersubstanz, 3 - 20 Gew.-% eines Alkalimetallsulfates als Stabilisator und ggf. 1 - 10 Gew.-% eines Aluminosilikates als Co-Builder enthalten. Die alleinige Verwendung von Alkylbenzolsulfonat als Aniontensid führt ebenso zu physikalisch instabilen Zusammensetzungen wie die Zugabe von Lösungsmitteln wie Alkoholen oder Glykolen.The US Pat. No. 4,018,720 describes aqueous liquid detergents which contain 7-25% by weight of a mixture of alkyl sulfates or alkyl ether sulfates and alkylbenzenesulfonates, 6-25% by weight of a phosphate builder substance, 3-20% by weight of an alkali metal sulfate Stabilizer and optionally 1 - 10 wt .-% of an aluminosilicate as a co-builder. The sole use of alkylbenzenesulfonate as an anionic surfactant leads to physically unstable compositions as does the addition of solvents such as alcohols or glycols.

Aus der kanadischen Patentanmeldung 1 202 857 sind stabile wäßrige Flüssigwaschmittel bekannt, die 13 - 38 Gew.-% Zeolith, 5 - 40 Gew.-% ungesättigte C₁₆-C₂₂-Fettsäureseife, 7 - 20 Gew.-% Tenside wie alkoxylierte nichtionische Tenside und Aminoxide, 5 - 15 Gew.-% wasserlösliche Buildersubstanzen wie Polycarboxylate und Pyrophosphat und 30 - 70 Gew.-% Wasser enthalten. In den Mitteln können zusätzlich auch amphotere und weitere anionische Tenside, zu denen auch gesättigte Seifen zählen, zugegen sein.From Canadian patent application 1 202 857 stable aqueous liquid detergents are known, the 13 - 38 wt .-% zeolite, 5 - 40 wt .-% unsaturated C₁₆-C₂₂ fatty acid soap, 7 - 20 wt .-% surfactants such as alkoxylated nonionic surfactants and Amine oxides, 5-15% by weight of water-soluble builder substances such as polycarboxylates and pyrophosphate and 30-70% by weight of water. In addition, amphoteric and other anionic surfactants, which also include saturated soaps, can also be present in the compositions.

Die europäische Patentanmeldung 75 976 beschreibt alkalische wäßrige Flüssigwaschmittel, die 7 - 30 Gew.-% Zeolith, 5 - 40 Gew.-% einer ungesättigten C₁₆-C₂₂-Fettsäureseife, 1 - 30 Gew.-% eines nichtionischen Tensids, 5 - 15 Gew.-% eines wasserlöslichen Polycarboxylats und 20 - 82 Gew.-% Wasser enthalten, die aber frei sind von synthetischen Aniontensiden, die sonst die in dieser stabilen flüssigen Mischung vorhandenen Parfümester destabilisieren.European patent application 75 976 describes alkaline aqueous liquid detergents which contain 7-30% by weight of zeolite, 5-40% by weight of an unsaturated C₁₆-C₂₂ fatty acid soap, 1-30% by weight of a nonionic surfactant, 5-15% by weight .-% of a water-soluble polycarboxylate and 20 - 82 wt .-% water, but which are free of synthetic anionic surfactants, which otherwise destabilize the perfume ester present in this stable liquid mixture.

In der europäischen Patentanmeldung 86 614 werden wäßrige Flüssigwaschmittel beschrieben, die anionische und ggf. und/oder nichtionische, kationische und amphotere Tenside, wasserunlösliche, suspendierte und ggf. wasserlösliche Buildersubstanzen sowie weitere Elektrolyte enthalten, wobei Natriumsulfat nicht in Mengen oberhalb 3 Gew.-% enthalten sein darf. Vorzugsweise wird aus Gründen der Stabilität als Buildersubstanz Tripolyphosphat oder Mischungen aus Tripolyphosphat und anderen Buildersubstanzen eingesetzt. Während phosphathaltige Suspensionen teilweise auch nach 12 Monaten Lagerung bei Raumtemperatur keine Sedimentationserscheinungen aufwiesen, waren phosphatfreie Mittel, die als Buildersubstanzen 13,4 Gew.-% Zeolith und 8,9 Gew.-% Silikat bzw. 13,6 Gew.-% Zeolith und 9,0 Gew.-% Silikat enthielten, einen Monat bei Raumtemperatur lagerstabil.European patent application 86 614 describes aqueous liquid detergents which contain anionic and optionally and / or nonionic, cationic and amphoteric surfactants, contain water-insoluble, suspended and, if appropriate, water-soluble builder substances and further electrolytes, sodium sulfate not being present in amounts above 3% by weight. For reasons of stability, tripolyphosphate or mixtures of tripolyphosphate and other builder substances are preferably used as the builder substance. While phosphate-containing suspensions sometimes showed no signs of sedimentation even after 12 months of storage at room temperature, phosphate-free agents which were 13.4% by weight of zeolite and 8.9% by weight of silicate or 13.6% by weight of zeolite and Contained 9.0 wt .-% silicate, stable for one month at room temperature.

Aus der europäischen Patentanmeldung 142 185 sind stabile wäßrige Flüssigwaschmittel bekannt, die kondensierte Phosphate und/oder Nitrilotriacetat zusammen mit Zeolith NaY enthalten. Die Suspensionen besitzen einen pH-Wert von 7 - 9. Die Mittel enthalten 1 - 60 Gew.-% Tenside, 0,5 - 30 Gew.-% Phosphat und/oder Nitrilotriacetat und 1 - 45 Gew.-% Zeolith. Die Tenside können aus Anion- und Niotensiden bestehen, wobei diese vorzugsweise im Verhältnis 10 : 1 bis 1 : 10 eingesetzt werden. Der Zeolith NaA erwies sich für den Einsatz in diesen Mitteln als nicht geeignet: bereits nach 15 Tagen Lagerung bei Raumtemperatur traten deutliche Phasentrennungen auf.European patent application 142 185 discloses stable aqueous liquid detergents which contain condensed phosphates and / or nitrilotriacetate together with zeolite NaY. The suspensions have a pH of 7-9. The compositions contain 1-60% by weight of surfactants, 0.5-30% by weight of phosphate and / or nitrilotriacetate and 1-45% by weight of zeolite. The surfactants can consist of anionic and nonionic surfactants, these preferably being used in a ratio of 10: 1 to 1:10. The zeolite NaA proved to be unsuitable for use in these agents: after 15 days of storage at room temperature, there were clear phase separations.

In der europäischen Patentanmeldung 151 884 werden wäßrige Flüssigwaschmittel beschrieben, die Buildersubstanzen, vorzugsweise Phosphate, und Tenside in einem Verhältnis von mindestens 1,5 : 1 sowie Elektrolyte enthalten. Die jeweils zur Stabilisierung einer bestimmten vorgegebenen Suspension aus Wasser, Tensiden und Buildersubstanzen benötigte Menge an Elektrolyt wird durch Konduktivitätsmessungen ermittelt: bei kontinuierlicher Zugabe an Elektrolytsalzen durchläuft die elektrische Konduktivität ein erstes Minimum, in dem die Suspension stabil ist.European patent application 151 884 describes aqueous liquid detergents which contain builder substances, preferably phosphates, and surfactants in a ratio of at least 1.5: 1 and electrolytes. The amount of electrolyte required to stabilize a certain predetermined suspension of water, surfactants and builder substances is determined by conductivity measurements: with continuous addition of Electrolyte salts pass through the electrical conductivity at a first minimum, in which the suspension is stable.

Aus der europäischen Patentanmeldung 170 091 sind ebenfalls wäßrige Flüssigwaschmittel bekannt, die Tenside, Elektrolyte, zu denen auch wasserlösliche Buildersubstanzen zählen, die aber weniger als 3 Gew.-% Natriumsulfat beinhalten, und suspendierte Buildersubstanzen enthalten. Auch hier wird aus denselben Stabilitätsgründen wie in den europäischen Patentanmeldungen 86 614 und 151 884 bevorzugt Tripolyphosphat als Buildersubstanz verwendet. Die Mittel sind durch Zentrifugieren bei 800facher Erdanziehung während 17 Stunden bei 25 °C in mindestens 2 Schichten trennbar, von denen mindestens eine eine wäßrige Schicht ist. Stabile Mittel enthalten derartige Mengen an gelöstem Elektrolyt, daß in dieser wäßrigen Schicht 2 - 4,5 Grammionen Alkalimetallion pro Liter vorliegen.From European patent application 170 091, aqueous liquid detergents are also known which contain surfactants, electrolytes, which also include water-soluble builder substances, but which contain less than 3% by weight sodium sulfate, and suspended builder substances. Here too, tripolyphosphate is preferably used as builder substance for the same reasons of stability as in European patent applications 86 614 and 151 884. The agents can be separated into at least 2 layers, at least one of which is an aqueous layer, by centrifugation at 800 times gravity for 17 hours at 25 ° C. Stable agents contain such amounts of dissolved electrolyte that there are 2-4.5 gram ions of alkali metal ion per liter in this aqueous layer.

Nach der Lehre der europäischen Patentanmeldung 295 021 enthalten wäßrige nicht-sedimentierende, flüssigkristalline Tensidkonzentrate, die ohne Stabilitätsverlust transportiert und gelagert werden können, 25 - 80 Gew.-% Tenside sowie bis zu 10 Gew.-%, bezogen auf die Tensidmenge, an Elektrolyten. Natriumsulfat ist jedoch gar nicht oder nur in Spuren zugegen und wird im letzteren Fall als Verunreinigung der Aniontenside in die Konzentrate eingetragen. Die Konzentrate können schnell verdünnt oder durch Zugabe anderer Waschmittelbestandteile, beispielsweise durch Zugabe von suspendierbaren Buildersubstanzen, vorzugsweise Tripolyphosphat, und ggf. von Elektrolyten, zu Flüssigwaschmitteln vermengt werden. Dabei ist der Einsatz von Elektrolyten, die keine Buildereigenschaften besitzen, weniger bevorzugt.According to the teaching of European patent application 295 021, aqueous non-sedimenting, liquid-crystalline surfactant concentrates which can be transported and stored without loss of stability contain 25-80% by weight of surfactants and up to 10% by weight, based on the amount of surfactant, of electrolytes . However, sodium sulfate is not present at all or only in trace amounts and in the latter case is introduced into the concentrates as an impurity in the anionic surfactants. The concentrates can be quickly diluted or mixed into liquid detergents by adding other detergent constituents, for example by adding suspendable builder substances, preferably tripolyphosphate, and optionally electrolytes. The use of electrolytes that have no builder properties is less preferred.

Die europäische Patentanmeldung 301 882 beschreibt ein Flüssigwaschmittel, das Buildersubstanzen wie Phosphate und Zeolith enthalten kann und das die Viskosität reduzierende (Co-)Polymere, beispielsweise Polyethylenglykol, Polyacrylate, Polymaleate, Polysaccharide und sulfonierte Polysaccharide, enthält. Dabei sind die Polymeren nur zum Teil in der wäßrigen Phase gelöst, der Rest ist ein Bestandteil einer in der wäßrigen Phase dispergierten Phase. Die Mittel werden bereits als ausreichend stabil angesehen, wenn bei der Lagerung bei 25 °C innerhalb von 21 Tagen keine Phasentrennung auftritt, die mehr als 2 % beträgt.European patent application 301 882 describes a liquid detergent which can contain builders such as phosphates and zeolite and which contains viscosity-reducing (co) polymers, for example polyethylene glycol, polyacrylates, polymaleates, polysaccharides and sulfonated polysaccharides. The polymers are only partially dissolved in the aqueous phase, the rest is part of a phase dispersed in the aqueous phase. The agents are already considered to be sufficiently stable if there is no phase separation of more than 2% within 21 days when stored at 25 ° C.

Die Aufgabe der Erfindung bestand darin, ein phosphatfreies, wäßriges und Zeolith-haltiges Flüssigwaschmittel zu schaffen, das sowohl bei Raumtemperatur als auch bei 40 °C mindestens 3 Monate lagerstabil ist, auch beim Transport bei Temperaturen zwischen 5 und 60 °C nicht zur Sedimentation neigt und den Anforderungen an die Leistung moderner Flüssigwaschmittel genügt.The object of the invention was to provide a phosphate-free, aqueous and zeolite-containing liquid detergent which is stable for at least 3 months both at room temperature and at 40 ° C. and does not tend to sedimentation during transport at temperatures between 5 and 60 ° C. and meets the requirements for the performance of modern liquid detergents.

Gegenstand der Erfindung ist dementsprechend ein phosphatfreies, zeolithhaltiges Flüssigwaschmittel mit einem pH-Wert zwischen 8 und 12 und einer Fließgrenze von mindestens 3 Pa, enthaltend 10 - 30 Gew.-% anionische und nichtionische Tenside, wobei höchstens 5 Gew.-%, bezogen auf das gesamte Mittel, an Seifen enthalten sind und die Seifen zu 50 - 100 Gew.-% aus gesättigten C₁₂-C₁₈-Fettsäureseifen zusammengesetzt sind, 10 - 25 Gew.-% Zeolith, der keine Teilchen mit einer Größe über 30 µm aufweist, zu wenigstens 80 % aus Teilchen einer Größe von weniger als 10 µm besteht und eine mittlere Teilchengröße im Bereich von 1 - 10 µm besitzt, 1 - 10 Gew.-% eines Elektrolytsystems, bestehend aus mindestens 2 Elektrolyten aus der Gruppe der Carbonate, Sulfate, Chloride, Acetate und Citrate, wobei das Elektrolytsystem 0,5 - 4 Gew.-% Carbonat und 0,5 - 8 Gew.-% Sulfat, jeweils bezogen auf das gesamte Mittel, enthält, und 40 - 60 Gew.-% Wasser.The invention accordingly relates to a phosphate-free, zeolite-containing liquid detergent with a pH between 8 and 12 and a flow limit of at least 3 Pa, containing 10-30% by weight of anionic and nonionic surfactants, with a maximum of 5% by weight, based on the total composition of soaps is contained and the soaps are composed of 50-100% by weight of saturated C₁₂-C₁₈ fatty acid soaps, 10-25% by weight of zeolite which has no particles with a size greater than 30 µm at least 80% consists of particles less than 10 µm in size and has an average particle size in the range of 1-10 µm, 1-10% by weight of an electrolyte system consisting of at least 2 electrolytes from the group of the carbonates, sulfates, chlorides , Acetates and citrates, the electrolyte system containing 0.5-4% by weight of carbonate and 0.5-8% by weight of sulfate, in each case based on the total composition, and 40-60% by weight of water.

Die erfindungsgemäßen Mittel beinhalten vorzugsweise 5 - 20 Gew.-% übliche anionische Tenside aus der Klasse der Sulfonate und Sulfate. Als Tenside vom Sulfonattyp kommen vorzugsweise C₉-C₁₃-Alkylbenzolsulfonate, insbesondere C₁₂-Alkylbenzolsulfonat, und Sulfonate auf fettchemischer Basis wie die Ester von α-Sulfofettsäuren (Estersulfonate), z. B. die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren in Betracht. Geeignete Tenside vom Sulfattyp sind beispielsweise die Schwefelsäuremonoester aus primären Alkoholen natürlichen und synthetischen Ursprungs, d. h. aus Fettalkoholen, wie z. B. Kokosfettalkoholen, Talgfettalkoholen, Oleylalkohol, Lauryl-, Myristyl-, Palmityl- oder Stearylalkohol, oder den C₁₀-C₂₀-Oxoalkoholen, und diejenigen sekundärer Alkohole dieser Kettenlänge, wobei die Schwefelsäuremonoester der primären Alkohole auf fettchemischer Basis bevorzugt sind. Auch die Schwefelsäuremonoester der mit 1 - 6 Mol Ethylenoxid ethoxylierten Alkohole, wie lineare C₁₂-C₁₈-Fettalkohole oder 2-Methyl-verzweigte C₉-C₁₁-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid, sind geeignet. Ferner eignen sich sulfatierte Fettsäuremonoglyceride. Die Sulfate und Sulfonate können einzeln oder im Gemisch vorliegen. Bevorzugte Mittel enthalten 5 - 17 Gew.-%, insbesondere 8 - 16 Gew.-% C₉-C₁₃-Alkylbenzolsulfonate oder 10 - 20 Gew.-% einer Mischung aus C₉-C₁₃-Alkylbenzolsulfonaten mit einem oder mehreren anderen Sulfonaten und/oder Sulfaten in einem beliebigen Mischungsverhältnis.The agents according to the invention preferably contain 5-20% by weight of conventional anionic surfactants from the class of the sulfonates and sulfates. Preferred surfactants of the sulfonate type are C₉-C₁₃-alkylbenzenesulfonates, especially C₁₂-alkylbenzenesulfonate, and sulfonates based on oleochemicals, such as the esters of α-sulfofatty acids (Ester sulfonates), e.g. B. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids into consideration. Suitable surfactants of the sulfate type are, for example, the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols such as. Example, coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C₁₀-C₂₀ oxo alcohols, and those secondary alcohols of this chain length, the sulfuric acid monoesters of the primary alcohols being preferred on a fat-chemical basis. The sulfuric acid monoesters of alcohols ethoxylated with 1-6 moles of ethylene oxide, such as linear C₁₂-C₁₈ fatty alcohols or 2-methyl-branched C₉-C₁₁ alcohols with an average of 3.5 moles of ethylene oxide, are suitable. Sulfated fatty acid monoglycerides are also suitable. The sulfates and sulfonates can be present individually or in a mixture. Preferred agents contain 5 - 17 wt .-%, in particular 8 - 16 wt .-% C₉-C₁₃-alkylbenzenesulfonates or 10 - 20 wt .-% of a mixture of C₉-C₁₃-alkylbenzenesulfonates with one or more other sulfonates and / or sulfates in any mixing ratio.

Als anionische Tenside sind weiterhin Seifen, vorzugsweise gesättigte Fettsäureseifen wie die Salze der Laurinsäure, Myristinsäu re, Palmitinsäure und Stearinsäure, brauchbar, Geeignet sind insbesondere aus natürlichen Fettsäuren, z. B. Kokos-, Palmkern- oder Talgfettsäuren abgeleitete Seifengemische. Geeignet sind auch solche Seifen, die zu 50 - 100 Gew.-% aus gesättigten C₁₂-C₁₈-Fettsäureseifen und zu 0 - 50 Gew.-% aus Ölsäureseife zusammengesetzt sind. Die erfindungsgemäßen Mittel können 0 - 5 Gew.-% an Seifen enthalten. Bevorzugte Mittel besitzen einen Gehalt an Seife von 1 - 3,5 Gew.-%.Also useful as anionic surfactants are soaps, preferably saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid and stearic acid. Particularly suitable are natural fatty acids, e.g. B. coconut, palm kernel or tallow fatty acid derived soap mixtures. Also suitable are those soaps which are composed of 50-100% by weight of saturated C₁₂-C₁₈ fatty acid soaps and 0-50% by weight of oleic acid soap. The agents according to the invention can contain 0-5% by weight of soaps. Preferred agents have a soap content of 1-3.5% by weight.

Die anionischen Tenside können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen.The anionic surfactants can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.

Die erfindungsgemäßen Mittel beinhalten weiterhin vorzugsweise 5 - 10 Gew.-% aus der Klasse der nichtionischen Tenside. Geeignet sind beispielsweise übliche ethoxylierte Fettalkohole, insbesondere Anlagerungsprodukte von 2 - 7 Mol Ethylenoxid (EO) an lineare primäre Alkohole, wie z. B. an Kokos-, Talgfett- oder Oleylalkohol, oder an in 2-Stellung methylverzweigte primäre Alkohole (Oxoalkohole). Insbesondere werden C₁₂-C₁₄-Alkohole mit 3 EO oder 4 EO, C₁₃-C₁₅-Alkohole mit 3, 5 oder 7 EO, C₁₂-C₁₈-Alkohole mit 3, 5 oder 7 EO und Mischungen aus diesen, wie Mischungen aus C₁₂-C₁₄-Alkohol mit 3 EO und C₁₂-C₁₈-Alkohole mit 5 EO, in Mengen von 5 - 9 Gew.-% eingesetzt.The agents according to the invention further preferably contain 5-10% by weight from the class of the nonionic surfactants. Suitable are, for example, customary ethoxylated fatty alcohols, in particular addition products of 2-7 moles of ethylene oxide (EO) with linear primary alcohols, such as. B. on coconut oil, tallow or oleyl alcohol, or on primary alcohols (oxo alcohols) branched methyl in the 2-position. In particular, C₁₂-C₁₄ alcohols with 3 EO or 4 EO, C₁₃-C₁₅ alcohols with 3, 5 or 7 EO, C₁₂-C₁₈ alcohols with 3, 5 or 7 EO and mixtures of these, such as mixtures of C₁₂-C₁₄ -Alcohol with 3 EO and C₁₂-C₁₈ alcohols with 5 EO, used in amounts of 5 - 9 wt .-%.

Als Buildersubstanz enthalten die erfindungsgemäßen Mittel z.B. den Zeolith NaA. Brauchbar sind ferner Gemische aus Zeolith NaA und NaX, wobei der Anteil des Zeoliths NaX in derartigen Gemischen zweckmäßigerweise unter 30 %, insbesondere unter 20 %, liegt. Geeignete Zeolithe weisen keine Teilchen mit einer Größe über 30 µm auf und bestehen zu wenigstens 80 % aus Teilchen einer Größe von weniger als 10 µm. Ihre mittlere Teilchengröße (Volumenverteilung, Meßmethode: Coulter Counter) liegt im Bereich von 1 - 10 µm. Bevorzugte Zeolithe haben eine mittlere Teilchengröße von 2 - 4 µm. Ihr Calciumbindevermögen, das nach den Angaben der deutschen Patentanmeldung 24 12 837 bestimmt wird, liegt im Bereich von 100 - 200 mg CaO/g. Die Zeolithe, die zu 10 - 25 Gew.-% in den erfindungsgemäßen Mitteln enthalten sind, können von ihrer Herstellung her noch überschüssiges Alkali enthalten. Vorzugsweise beträgt der Gehalt der erfindungsgemäßen Mittel an Zeolith 12 - 20 Gew.-% und insbesondere 14 - 19 Gew.-%. Das Verhältnis Tenside : Zeolith beträgt vorzugsweise 0,8 : 1 bis 1,4 : 1 und insbesondere 1 : 1 bis 1,4 : 1.The agents according to the invention contain, for example, the zeolite NaA as builder substance. Mixtures of zeolite NaA and NaX can also be used, the proportion of the zeolite NaX in such mixtures advantageously being below 30%, in particular below 20%. Suitable zeolites have no particles larger than 30 µm and consist of at least 80% particles smaller than 10 µm. Their average particle size (volume distribution, measurement method: Coulter Counter) is in the range of 1 - 10 µm. Preferred zeolites have an average particle size of 2-4 microns. Your calcium binding capacity, which is determined according to the information in German patent application 24 12 837, is in the range of 100-200 mg CaO / g. The zeolites, which contain 10-25% by weight in the agents according to the invention, can still contain excess alkali from their production. The zeolite content of the agents according to the invention is preferably 12-20% by weight and in particular 14-19% by weight. The ratio of surfactants: zeolite is preferably 0.8: 1 to 1.4: 1 and in particular 1: 1 to 1.4: 1.

Die erfindungsgemäßen Suspensionen aus Wasser, Tensiden und Zeolith werden durch ein Elektrolytsystem stabilisiert, das aus mindestens 2 Salzen, vorzugsweise Natriumsalzen und/oder Triethanolammonium-Salzen, aus der Gruppe der Carbonate, Chloride, Sulfate, Acetate und Citrate besteht, wobei das Elektrolytsystem aber wenigstens aus einem Carbonat und einem Sulfat besteht. Der Anteil des Elektrolytsystems, bezogen auf das gesamte Mittel, beträgt 1 - 10 Gew.-%. Es besteht zu 0,5 - 4 Gew.-%, vorzugsweise 0,5 - 2 Gew.-%, aus Carbonat, zu 0,5 - 8 Gew.-%, vorzugsweise 1 - 6 Gew.-%, aus Sulfat, zu 0 - 4 Gew.-%, vorzugsweise 0,1 - 2 Gew.-%, aus Chlorid, zu 0 - 4 Gew.-%, vorzugsweise 0,1 - 2,5 Gew.-%, aus Acetat und zu 0 - 1,5 Gew.-%, vorzugsweise 0,1 - 1 Gew.-%, aus Citrat, das in Form von Citronensäure in die Suspension eingebracht wird und durch Reaktion mit überschüssigem Alkali entsteht. Bevorzugt verwendete Elektrolytsysteme bestehen aus 3 oder 4 verschiedenen Elektrolyten, insbesondere (bezogen auf das gesamte Mittel) aus 0,5 - 2 Gew.-% Natriumcarbonat, 4 - 6 Gew.-% Natriumsulfat und 0,8 - 1,5 Gew.-% Citrat, beispielsweise Natriumcitrat oder Triethanolammoniumcitrat, oder aus 0,5 - 1,5 Gew.-% Natriumcarbonat, 3,5 - 5,5 Gew.-% Natriumsulfat und 1,0 - 2,0 Gew.-% Natriumchlorid oder aus 0,5 - 1 Gew.-% Natriumcarbonat, 4 - 6 Gew.-% Natriumsulfat und 0,5 - 4 Gew.-% Natriumacetat oder aus 0,5 - 1 Gew.-% Natriumcarbonat, 3 - 5,5 Gew.-% Natriumsulfat, 0,5 - 1,5 Gew.-% Natriumchlorid und 0,5 - 2,5 Gew.-% Natriumacetat. Das Verhältnis Zeolith : Elektrolytsystem beträgt vorzugsweise 10 : 3 bis 10 : 6 und insbesondere 10 : 4 bis 10 : 5.The suspensions of water, surfactants and zeolite according to the invention are stabilized by an electrolyte system which consists of at least 2 salts, preferably sodium salts and / or triethanolammonium salts, from the group of carbonates, chlorides, sulfates, acetates and citrates, but the electrolyte system at least consists of a carbonate and a sulfate. The proportion of the electrolyte system, based on the total agent, is 1-10% by weight. It consists of 0.5-4% by weight, preferably 0.5-2% by weight, of carbonate, 0.5-8% by weight, preferably 1-6% by weight, of sulfate, 0 - 4% by weight, preferably 0.1 - 2% by weight, of chloride, 0 - 4% by weight, preferably 0.1 - 2.5% by weight, of acetate and 0 1.5% by weight, preferably 0.1-1% by weight, of citrate, which is introduced into the suspension in the form of citric acid and is formed by reaction with excess alkali. Electrolyte systems used with preference consist of 3 or 4 different electrolytes, in particular (based on the total composition) of 0.5-2% by weight sodium carbonate, 4-6% by weight sodium sulfate and 0.8-1.5% by weight. % Citrate, for example sodium citrate or triethanolammonium citrate, or from 0.5-1.5% by weight sodium carbonate, 3.5-5.5% by weight sodium sulfate and 1.0-2.0% by weight sodium chloride or from 0.5-1% by weight sodium carbonate, 4-6% by weight sodium sulfate and 0.5-4% by weight sodium acetate or from 0.5-1% by weight sodium carbonate, 3-5.5% by weight. -% sodium sulfate, 0.5-1.5% by weight sodium chloride and 0.5-2.5% by weight sodium acetate. The ratio of zeolite: electrolyte system is preferably 10: 3 to 10: 6 and in particular 10: 4 to 10: 5.

Die erfindungsgemäßen Mittel enthalten 40 - 60 Gew.-% und vorzugsweise 42 - 55 Gew.-% Wasser.The agents according to the invention contain 40-60% by weight and preferably 42-55% by weight of water.

Der pH-Wert der Mittel liegt zwischen 8 und 12, vorzugsweise zwischen 8,5 und 10,5 und insbesondere zwischen 9 und 10. Die Dichte der Mittel hat in der Regel einen Wert von 1,1 bis 1,25 g/ml, vorzugsweise von 1,15 - 1,22 g/ml. Die erfindungsgemäßen Mittel weisen eine Fließgrenze von mindestens 3 Pa auf. Bevorzugte Mittel besitzen Fließgrenzen zwischen 4 und 35 Pa. Ihre Viskosität (Brookfield-Viskosimeter, Spindel Nr. 6, 10 Upm) liegt in der Regel bei 2 000 bis 11 000 mPas, vorzugsweise zwischen 3 000 und 9 000 mPas und insbesondere zwischen 3 500 und 8 500 mPas. Die Lagerstabilität der Mittel wurde sowohl bei Raumtemperatur als auch bei 40 °C über einen Zeitraum von 7 Monaten getestet. Die Mittel waren mindestens 3 Monate lang lagerstabil. Bei schon länger gelagerten Ansätzen wurde auch nach 4 Monaten und sogar nach 7 Monaten kein Absetzen beobachtet. Die Mittel lassen sich bei Temperaturen zwischen 5 und 60 °C transportieren.The pH of the compositions is between 8 and 12, preferably between 8.5 and 10.5 and in particular between 9 and 10. The density of the compositions is generally from 1.1 to 1.25 g / ml, preferably from 1.15 to 1.22 g / ml. The agents according to the invention have a yield point of at least 3 Pa. Preferred agents have flow limits between 4 and 35 Pa. Their viscosity (Brookfield viscometer, spindle no. 6, 10 rpm) is generally 2,000 to 11,000 mPas, preferably between 3,000 and 9,000 mPas and in particular between 3,500 and 8,500 mPas. The storage stability of the compositions was tested both at room temperature and at 40 ° C. over a period of 7 months. The agents were stable on storage for at least 3 months. With batches that had been stored for a long time, no discontinuation was observed even after 4 months and even after 7 months. The agents can be transported at temperatures between 5 and 60 ° C.

Das Schaumvermögen der Tenside läßt sich durch die Zugabe von 0,05 - 2 Gew.-% nicht tensidartiger organischer Substanzen verringern. Geeignete Schauminhibitoren sind beispielsweise bekannte PolysiloxanKieselsäureGemische, wobei die darin enthaltene feinteilige Kieselsäure vorzugsweise silaniert ist. Die Polysiloxane können sowohl aus linearen Verbindungen (Silikonöle) als auch aus vernetzten Polysiloxan-Harzen sowie aus deren Gemischen bestehen. Weitere geeignete Entschäumer sind Paraffinöle, Mikroparaffine und Paraffinwachse. Mit Vorteil werden auch Gemische verschiedener Schauminhibitoren verwendet, z.B. solche aus Silikonöl und Paraffinöl. Insbesondere ist der Einsatz von 0,1 Gew.-%, bezogen auf das gesamte Mittel, an Silikonöl bevorzugt.The foaming power of the surfactants can be reduced by adding 0.05-2% by weight of non-surfactant-like organic substances. Suitable foam inhibitors are, for example, known polysiloxane / silica mixtures, the fine-particle silica contained therein preferably being silanated. The polysiloxanes can consist both of linear compounds (silicone oils) and of crosslinked polysiloxane resins and of their mixtures. Other suitable defoamers are paraffin oils, microparaffins and paraffin waxes. Mixtures of various foam inhibitors are also advantageously used, for example those made from silicone oil and paraffin oil. In particular, the use of 0.1% by weight, based on the total agent, of silicone oil is preferred.

Vorzugsweise enthalten die Mittel 0,5 - 5 Gew.-% Alkohole mit 2 - 3 Kohlenstoffatomen und 1 - 3 Hydroxylgruppen, wie Ethanol, Propanol, Propylenglykol und Glycerin. Vorzugsweise werden Propylenglykol und Glycerin, allein oder im Gemisch mit Ethanol, in Mengen von 2 - 3,5 Gew.-% eingesetzt.The agents preferably contain 0.5-5% by weight of alcohols with 2-3 carbon atoms and 1-3 hydroxyl groups, such as ethanol, propanol, propylene glycol and glycerol. Propylene glycol and glycerol, alone or in a mixture with ethanol, are preferably used in amounts of 2 to 3.5% by weight.

Weiterhin können die Mittel geringe Mengen an freier Base, wie Triethanolamin oder Natronlauge, enthalten, um den pH-Wert zwischen 9 und 12 zu halten.In addition, the agents can contain small amounts of free base, such as triethanolamine or sodium hydroxide solution, in order to maintain the pH between 9 and 12.

Außer den genannten Inhaltsstoffen können die Mittel ggf. weitere bekannte, in Waschmitteln üblicherweise eingesetzte Zusatzstoffe, beispielsweise Salze von Polyphosphonsäuren, optische Aufheller, Enzyme, in wäßrigen Mitteln stabile Bleichmittel, Hydrotrope sowie Farb- und Duftstoffe, in den üblichen Mengen enthalten, welche die Stabilität der erfindungsgemäßen Suspensionen nicht beeinflussen.In addition to the ingredients mentioned, the agents can optionally contain other known additives commonly used in detergents, for example salts of polyphosphonic acids, optical brighteners, enzymes, bleaches, hydrotropes and dyes and fragrances which are stable in aqueous agents, in the customary amounts which provide stability do not affect the suspensions of the invention.

Als Salze von Polyphosphonsäuren werden vorzugsweise die neutral reagierenden Natriumsalze von beispielsweise 1-Hydroxyethan-1,1-diphosphonat und Diethylentriamin-pentamethylenphosphonat in Mengen von 0,1 - 1,5 Gew.-% verwendet. Vorzugsweise beträgt der Phosphor-Gesamtanteil in den Mitteln weniger als 0,5 %.The neutral-reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and diethylenetriamine pentamethylene phosphonate are preferably used as salts of polyphosphonic acids in amounts of 0.1-1.5% by weight. The total phosphorus content in the compositions is preferably less than 0.5%.

Die Waschmittel können als optische Aufheller Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z. B. Salze der 4,4'-Bis(2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino)-stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholinogruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ des substituierten 4,4'-Distyryl-diphenyls anwesend sein; z. B. die Verbindung 4,4'-Bis-(4-chlor-3-sulfo-styryl)-diphenyl. Auch Gemische der vorgenannten Aufheller können verwendet werden. Der maximale Gehalt an Aufhellern in den erfindungsgemäßen Mitteln beträgt 0,5 Gew.-%, vorzugsweise werden Mengen von 0,02 - 0,1 Gew.-% eingesetzt.The detergents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which instead of Morpholino group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted 4,4'-distyryl-diphenyl type can also be used to be present; e.g. B. the compound 4,4'-bis (4-chloro-3-sulfo-styryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. The maximum content of brighteners in the agents according to the invention is 0.5% by weight, preferably amounts of 0.02-0.1% by weight are used.

Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen bzw. deren Gemische in Frage. Ihr Anteil kann 0,2 - 1 Gew.-% betragen.Enzymes from the class of proteases, lipases, amylases or mixtures thereof are possible. Their proportion can be 0.2-1% by weight.

In einer bevorzugten Ausführungsform enthalten die Mittel 8 - 16 Gew.-% C₉-C₁₃-Alkylbenzolsulfonat, insbesondere C₁₂-Alkylbenzolsulfonat, 1 - 3,0 Gew.-% gesättigte C₁₂-C₁₈-Fettsäureseife in Form der Natrium- und/oder Triethanolammoniumsalze, 5 - 9 Gew.-% nichtionische Tenside, 14 - 19 Gew.-% gebundenes Wasser enthaltenden Zeolith, 0,5 - 1,5 Gew.-% Natriumcarbonat, 3 - 6 Gew.-% Natriumsulfat, 0 - 1,5 Gew.-% 1-Hydroxyethan-1,1-diphosphonat und/oder Diethylentriaminpentamethylenphosphonat, 0,1 Gew.-% Silikonöl und 43 - 54 Gew.-% Wasser.In a preferred embodiment, the agents contain 8-16% by weight of C₉-C₁₃-alkylbenzenesulfonate, in particular C₁₂-alkylbenzenesulfonate, 1-3.0% by weight of saturated C₁₂-C₁₈-fatty acid soap in the form of the sodium and / or triethanolammonium salts, 5-9% by weight of nonionic surfactants, 14-19% by weight of bound water-containing zeolite, 0.5-1.5% by weight of sodium carbonate, 3-6% by weight of sodium sulfate, 0-1.5% by weight % 1-hydroxyethane-1,1-diphosphonate and / or diethylenetriaminepentamethylenephosphonate, 0.1% by weight silicone oil and 43-54% by weight water.

In einer weiteren bevorzugten Ausführungsform enthalten die Mittel Tenside, Zeolith, Phosphonat, Silikonöl und Wasser wie oben sowie 0,5 - 1 Gew.-% Natriumcarbonat, 4 - 6 Gew.-% Natriumsulfat, 1,5 - 2 Gew.-% Natriumacetat und 2 - 3 Gew.-% Glycerin oder Propylenglykol.In a further preferred embodiment, the agents contain surfactants, zeolite, phosphonate, silicone oil and water as above and also 0.5-1% by weight sodium carbonate, 4-6% by weight sodium sulfate, 1.5-2% by weight sodium acetate and 2-3% by weight of glycerin or propylene glycol.

Ebenso bevorzugt ist die Verwendung von Mitteln, die Tenside, Zeolith, Phosphonat, Silikonöl, Natriumcarbonat, Natriumsulfat und Wasser wie oben sowie 0,8 - 1,5 Gew.-% Citrat, beispielsweise Natriumcitrat und/oder Triethanolammoniumcitrat, und 2 - 3 Gew.-% Glycerin oder einer Mischung aus 2/3 Glycerin und 1/3 Ethanol enthalten.Also preferred is the use of agents containing surfactants, zeolite, phosphonate, silicone oil, sodium carbonate, sodium sulfate and water as above, and 0.8-1.5% by weight of citrate, for example sodium citrate and / or triethanolammonium citrate, and 2-3% .-% Contain glycerin or a mixture of 2/3 glycerin and 1/3 ethanol.

Die Erfindung betrifft ferner ein Verfahren zur Herstellung der oben beschriebenen Flüssigwaschmittel. Dabei können die Flüssigwaschmittel in an sich bekannter Weise hergestellt werden. Vorzugsweise werden in einem Reaktor, der mit einem Rührsystem versehen ist, 35 bis 60 %, insbesondere 40 - 58 % Wasser, bezogen auf die im Mittel vorgesehene Gesamtmenge an Wasser, sowie gegebenenfalls ein Schauminhibitor vorgelegt, anionische und nichtionische Tenside werden zugemischt. Falls Seife als Bestandteil der Mittel vorgesehen ist, wird die entsprechende Fettsäure bzw. das entsprechende Fettsäuregemisch auf 60 - 80 °C aufgeheizt und in das für diesen Fall ebenfalls auf 60 - 80 °C aufgeheizte, vorgelegte Wasser eingerührt. Im Anschluß daran wird die Fettsäure zweckmäßigerweise mit Triethanolamin und/oder Natriumhydroxid, das vorzugsweise in Form einer wäßrigen Lösung hinzugefügt wird, neutralisiert. Zeolith NaA kann sowohl in Form eines Pulvers als auch in Form einer wäßrigen Suspension zugegeben werden, wobei die Zugabe einer 40 - 55 Gew.-%igen wäßrigen Zeolith-Suspension bevorzugt ist. Die Elektrolytsalze Carbonat und Sulfat sowie ggf. Chlorid und Acetat können ebenfalls in Pulverform oder in Form einer wäßrigen Lösung hinzudosiert werden. Die Zudosierung der Komponenten zum vorgelegten Wasser erfolgt dabei derart, daß das Einrühren einer größeren Menge Luftblasen vermieden wird.The invention further relates to a method for producing the liquid detergents described above. The liquid detergents can be produced in a manner known per se. 35 to 60%, in particular 40-58% water, based on the total amount of water provided on average, and, if appropriate, a foam inhibitor are preferably introduced into a reactor which is provided with a stirring system, and anionic and nonionic surfactants are mixed in. If soap is provided as a constituent of the composition, the corresponding fatty acid or the corresponding fatty acid mixture is heated to 60-80 ° C. and stirred into the water provided, which in this case is also heated to 60-80 ° C. The fatty acid is then advantageously neutralized with triethanolamine and / or sodium hydroxide, which is preferably added in the form of an aqueous solution. Zeolite NaA can be added both in the form of a powder and in the form of an aqueous suspension, the addition of a 40-55% by weight aqueous zeolite suspension being preferred. The electrolyte salts carbonate and sulfate and, if appropriate, chloride and acetate can also be metered in in powder form or in the form of an aqueous solution. The components are added to the water initially introduced in such a way that the stirring in of a large amount of air bubbles is avoided.

BeispieleExamples Beispiel 1:Example 1:

Dieses Beispiel beschreibt die Herstellung eines erfindungsgemäßen Flüssigwaschmittels (W1) im 900 kg-Ansatz.This example describes the production of a liquid detergent according to the invention (W1) in a 900 kg batch.

In einem 800-l-Kesselreaktor, der mit einem Rührsystem versehen war, wurden 195,25 kg Wasser und 0,9 kg Silikonöl (Silikonantischaummittel VP 1132, Produkt der Fa. Wacker-Chemie GmbH) vorgelegt. Nach dem Aufheizen der Wasser-Silikonöl-Mischung auf 70 °C wurden 16,00 kg ebenfalls auf 70 °C erwärmte C₁₂-Fettsäure (94 %ig) zugegeben.195.25 kg of water and 0.9 kg of silicone oil (silicone antifoam agent VP 1132, product from Wacker-Chemie GmbH) were placed in an 800 l tank reactor which was provided with a stirring system. After heating the water-silicone oil mixture to 70 ° C 16.00 kg were also heated to 70 ° C C₁₂ fatty acid (94%) added.

Als weitere Bestandteile wurden folgende Komponenten in den angegeben Mengen zugegeben:
150,00 kg einer 55 Gew.-%igen wäßrigen Lösung von Natriumdodecylbenzolsulfonat,
60,00 kg C₁₃-C₁₅-Alkohol mit 7 Ethylenoxidgruppen (EO),
305,00 kg einer 52 Gew.-%igen wäßrigen Zeolith-Suspension, die mit Talgfettalkohol mit 5 EO stabilisiert war,
100,00 kg einer 50 Gew.-%igen wäßrigen Natriumsulfatlösung,
10,00 kg einer 50 Gew.-%igen wäßrigen Natriumcarbonatlösung,
7,20 kg Citronensäure,
12,20 kg Triethanolamin,
25,00 kg Glycerin
sowie 4,5 kg Parfum, 0,45 kg optische Aufheller, 4,50 kg Protease, und 9,00 kg 1-Hydroxyethan-1,1-diphosphonat-dinatriumsalz.The following components were added as further constituents in the amounts indicated:
150.00 kg of a 55% by weight aqueous solution of sodium dodecylbenzenesulfonate,
60.00 kg of C₁₃-C₁₅ alcohol with 7 ethylene oxide groups (EO),
305.00 kg of a 52% by weight aqueous zeolite suspension which was stabilized with tallow fatty alcohol with 5 EO,
100.00 kg of a 50% by weight aqueous sodium sulfate solution,
10.00 kg of a 50% by weight aqueous sodium carbonate solution,
7.20 kg citric acid,
12.20 kg triethanolamine,
25.00 kg glycerin
and 4.5 kg of perfume, 0.45 kg of optical brightener, 4.50 kg of protease, and 9.00 kg of 1-hydroxyethane-1,1-diphosphonate disodium salt.

Nach Beendigung des Mischvorganges wurde 20 Minuten nachgerührt. Anschließend wurde die erhaltene Suspension im Vakuum (120 mm Hg-Säule) entgast, um während des Dispergiervorganges eingetragene Luft zu entfernen.
Dichte: 1,2 g/ml
pH-Wert: 9,20
Viskosität (Brookfield-Viskosimeter, Spindel Nr. 6, 10 Upm): 4000 mPas
Fließgrenze: 4,2 Pa
Lagerstabilität: Die Lagerzeit betrug 7 Monate. Bei Lagertemperaturen von 40 °C und Raumtemperatur trat in beiden Fällen innerhalb dieser Zeit keine Sedimentation auf.After the mixing process had ended, stirring was continued for 20 minutes. The suspension obtained was then removed in vacuo (120 mm Hg column) degassed to remove air introduced during the dispersing process.
Density : 1.2 g / ml
pH : 9.20
Viscosity (Brookfield viscometer, spindle No. 6, 10 rpm): 4000 mPas
Yield point : 4.2 Pa
Storage stability : The storage time was 7 months. At both 40 ° C and room temperature, there was no sedimentation in either time.

Beispiel 2:Example 2:

Weitere erfindungsgemäße Mittel W2 - W5 wurden analog zu Beispiel 1 hergestellt.Further agents W2-W5 according to the invention were produced analogously to Example 1.

W2 enthielt 9,5 Gew.-% Dodecylbenzolsulfonat, 1,7 Gew.-% C₁₂-Fettsäure, 6 Gew.-% C₁₃-C₁₅-Alkohol mit 7 EO, 3 Gew.-% C₁₂-C₁₄-Alkohol mit 3 EO, 1,3 Gew.-% Triethanolamin, 17 Gew.-% Zeolith NaA, 2,0 Gew.-% Natriumcarbonat, 4,0 Gew.-% Natriumsulfat, 1,0 Gew.-% Citronensäure, 3 Gew.-% Glycerin und 52,05 Gew.-% Wasser. Die Lagerzeit betrug 5 Monate. Innerhalb dieser Zeit trat bei Lagertemperaturen von 40 °C und Raumtemperatur keine Sedimentation auf.W2 contained 9.5% by weight dodecylbenzenesulfonate, 1.7% by weight C₁₂ fatty acid, 6% by weight C₁₃-C₁₅ alcohol with 7 EO, 3% by weight C₁₂-C₁₄ alcohol with 3 EO, 1.3% by weight of triethanolamine, 17% by weight of zeolite NaA, 2.0% by weight of sodium carbonate, 4.0% by weight of sodium sulfate, 1.0% by weight of citric acid, 3% by weight of glycerin and 52.05 wt% water. The storage period was 5 months. During this time, no sedimentation occurred at storage temperatures of 40 ° C and room temperature.

W3 enthielt 14 Gew.-% Dodecylbenzolsulfonat, 8 Gew.-% C₁₂-C₁₄-Alkohol mit 5 EO, 0,5 Gew.-% Natriumhydroxid, 18 Gew.-% Zeolith NaA, 0,5 Gew.-% Natriumcarbonat, 5,0 Gew.-% Natriumsulfat, 2,0 Gew.-% Natriumchlorid, 2 Gew.-% Glycerin, 1 Gew.-% Ethanol und 47 Gew.-% Wasser. Die Lagerzeit betrug 4 Monate. Innerhalb dieser Zeit trat bei Lagertemperaturen von 40 °C und Raumtemperatur keine Sedimentation auf.W3 contained 14% by weight of dodecylbenzenesulfonate, 8% by weight of C₁₂-C₁ mit alcohol with 5 EO, 0.5% by weight of sodium hydroxide, 18% by weight of zeolite NaA, 0.5% by weight of sodium carbonate, 5 , 0% by weight sodium sulfate, 2.0% by weight sodium chloride, 2% by weight glycerin, 1% by weight ethanol and 47% by weight water. The storage period was 4 months. Stepped within that time no sedimentation at storage temperatures of 40 ° C and room temperature.

W4 enthielt 10 Gew.-% Dodecylbenzolsulfonat, 1,8 Gew.-% C₁₂-C₁₄-Fettsäure, 1,4 Gew.-% Triethanolamin, 6 Gew.-% eines Gemisches aus C₁₂-C₁₈-Alkohol mit 5 EO und C₁₂-C₁₄-Alkohol mit 3 EO, 17 Gew.-% Zeolith NaA, 0,5 Gew.-% Natriumcarbonat, 5,5 Gew.-% Natriumsulfat, 2,0 Gew.-% Natriumacetat, 3 Gew.-% Propylenglykol und 50,1 Gew.-% Wasser. Die Lagerzeit betrug 5 Monate. Innerhalb dieser Zeit trat bei Lagertemperaturen von 40 °C und Raumtemperatur keine Sedimentation auf.W4 contained 10% by weight of dodecylbenzenesulfonate, 1.8% by weight of C₁₂-C₁₄ fatty acid, 1.4% by weight of triethanolamine, 6% by weight of a mixture of C₁₂-C₁₈ alcohol with 5 EO and C₁₂- C₁₄ alcohol with 3 EO, 17 wt .-% zeolite NaA, 0.5 wt .-% sodium carbonate, 5.5 wt .-% sodium sulfate, 2.0 wt .-% sodium acetate, 3 wt .-% propylene glycol and 50 , 1 wt .-% water. The storage period was 5 months. During this time, no sedimentation occurred at storage temperatures of 40 ° C and room temperature.

W5 wurde hergestellt aus 9,8 Gew.-% Dodecylbenzolsulfonat, 8,0 Gew.-% C₁₂-C₁₄-Alkohol mit 5 EO, 4,9 Gew.-% C₁₂-Fettsäure, 1,1 Gew.-% Natriumhydroxid, 17,5 Gew.-% Zeolith NaA, 2 Gew.-% Glycerin, 1 Gew.-% Ethanol, 0,5 Gew.-% Natriumcarbonat, 6,0 Gew.-% Natriumsulfat, 0,9 Gew.-% Citronensäure, 0,5 Gew.-% Protease, 0,1 Gew.-% Silikonöl und 47,7 Gew.-% Wasser. Die Lagerzeit betrug 6¹/₂ Monate. Bei Lagertemperaturen von 40 °C und Raumtemperatur trat in beiden Fällen innerhalb dieser Zeit keine Sedimentation auf.W5 was produced from 9.8% by weight of dodecylbenzenesulfonate, 8.0% by weight of C₁₂-C₁₄ alcohol with 5 EO, 4.9% by weight of C₁₂ fatty acid, 1.1% by weight of sodium hydroxide, 17th , 5% by weight of zeolite NaA, 2% by weight of glycerol, 1% by weight of ethanol, 0.5% by weight of sodium carbonate, 6.0% by weight of sodium sulfate, 0.9% by weight of citric acid, 0.5 wt% protease, 0.1 wt% silicone oil and 47.7 wt% water. The storage time was 6½ months. At both 40 ° C and room temperature, there was no sedimentation in either time.

Beispiel 3:Example 3:

Dieses Beispiel beschreibt die anwendungstechnische Prüfung des erfindungsgemäßen Mittels (W1), die in einer Haushaltswaschmaschine mit horizontal angeordneter Wäschetrommel (Typ Miele W 433) unter folgenden Bedingungen durchgeführt wurde:
Waschtemperatur: 60 °C
Einlaugenverfahren - Buntwaschprogramm
Wasserhärte: 16 °d (160 mg CaO pro Liter)
Waschmitteldosierung: 224 g
Textilproben: je zwei Teststreifen mit gleicher Anschmutzung sowie 3,5 kg normal verschmutzte Haushaltswäsche
Vierfachbestimmung
Die optische Auswertung der Waschergebnisse (Tabelle 1) erfolgte mit ein: Zeiss-Reflektometer bei 460 nm (Ausblendung des Aufheller-Effektes). Remissionsunterschiede von 2 % und mehr können direkt vom Verbraucher wahrgenommen werden.This example describes the application test of the agent (W1) according to the invention, which was carried out in a household washing machine with a horizontally arranged laundry drum (type Miele W 433) under the following conditions:
Washing temperature : 60 ° C
Soaking process - colored washing program
Water hardness : 16 ° d (160 mg CaO per liter)
Detergent dosage : 224 g
Textile samples : two test strips with the same soiling and 3.5 kg of normally soiled household laundry
Quadruple determination
The optical evaluation of the washing results (Table 1) was carried out using a: Zeiss reflectometer at 460 nm (suppression of the brightener effect). Remission differences of 2% and more can be noticed directly by the consumer.

Anschmutzungen:Soiling:

  • I Staub/Hautfett auf BaumwolleI dust / skin fat on cotton
  • II Staub/Hautfett auf veredelter BaumwolleII Dust / skin fat on refined cotton
  • III Staub/Hautfett auf Mischgewebe aus Polyester und veredelter Baumwolle (50/50)III Dust / skin fat on mixed fabrics made of polyester and finished cotton (50/50)
  • IV Staub/Hautfett auf PolyesterIV dust / skin oil on polyester
  • V Mineralöl auf BaumwolleV mineral oil on cotton
  • VI Tee auf BaumwolleVI tea on cotton
  • VII Rotwein auf BaumwolleVII red wine on cotton
  • VIII Kosmetik auf veredelter BaumwolleVIII Cosmetics on refined cotton

Tabelle 1Table 1 % Remission für Anschmutzung% Remission for soiling AnfangswertInitial value W1W1 II. 30,930.9 64,564.5 IIII 27,727.7 69,769.7 IIIIII 22,822.8 44,844.8 IVIV 30,430.4 71,771.7 VV 17,417.4 74,674.6 VIVI 28,128.1 48,248.2 VIIVII 28,728.7 55,455.4 VIIVII 22,422.4 65,765.7

Die Ergebnisse sind vergleichbar bis besser als die mit handelsüblichen Produkten erzielbaren Werte.The results are comparable to better than the values that can be achieved with commercially available products.

Claims (9)

  1. A zeolite-containing and phosphate-free liquid detergent with a pH value of 8 to 12 and a yield point of at least 3 Pa, containing
    10 to 30% by weight of anionic and nonionic surfactants, at most 5% by weight - based on the detergent as a whole - of soaps being present and 50 to 100% by weight of the soaps consisting of saturated C₁₂₋₁₈ fatty acid soaps,
    10 to 25% by weight of zeolite which does not contain any particles larger than 30 µm in size, in which at least 80% of the particles are smaller than 10 µm in size and which has an average particle size of 1 to 10 µm,
    1 to 10% by weight of an electrolyte system consisting of at least 2 electrolytes from the group of carbonates, sulfates, chlorides, acetates and citrates, the electrolyte system containing 0.5 to 4% by weight of carbonate and 0.5 to 8% by weight of sulfate, based on the detergent as a whole, and
    40 to 60% by weight of water.
  2. A detergent as claimed in claim 1, characterized in that it contains 5 to 17% by weight of C₉₋₁₃ alkyl benzenesulfonates or 10 to 20% by weight of a mixture of C₉₋₁₃ alkyl benzenesulfonates with one or more other sulfonates and/or sulfates in any mixing ratio.
  3. A detergent as claimed in claim 1 or 2, characterized in that it contains 1 to 3.5% by weight of saturated fatty acid soaps in the form of the sodium or triethanolammonium salts.
  4. A detergent as claimed in any of claims 1 to 3, characterized in that the ratio by weight of zeolite to the electrolyte system is 10:3 to 10:6 and, more particularly, 10:4 to 10:5.
  5. A detergent as claimed in any of claims 1 to 4, characterized in that it contains 0.5 to 2% by weight of sodium carbonate, 4 to 6% by weight of sodium sulfate and 0.8 to 1.5% by weight of citrate.
  6. A detergent as claimed in any of claims 1 to 4, characterized in that it contains 0.5 to 1% by weight of sodium carbonate, 4 to 6% by weight of sodium sulfate and 0.5 to 4% by weight of sodium acetate.
  7. A detergent as claimed in any of claims 1 to 4, characterized in that it contains 0.5 to 1% by weight of sodium carbonate, 3 to 5.5% by weight of sodium sulfate, 0.5 to 1.5% by weight of sodium chloride and 0.5 to 2.5% by weight of sodium acetate.
  8. A detergent as claimed in any of claims 1 to 7, characterized in that it contains 2 to 3.5% by weight of propylene glycol, glycerol or a mixture of glycerol and ethanol or of propylene glycol and ethanol.
  9. A process for the production of the liquid detergent claimed in claim 1, characterized in that 35 to 60% of water, based on the total quantity of water envisaged for the detergent, and optionally a foam inhibitor are introduced into a reactor equipped with a stirring system, anionic and nonionic surfactants are added, fatty acid optionally heated to 60-80°C or a fatty acid mixture is stirred into the water, which has also been heated to 60-80°C for this case, and subsequently neutralized with triethanolamine and/or sodium hydroxide, zeolite is added in the form of a powder or an aqueous suspension and the electrolyte salts are added in powder form or in the form of an aqueous solution and optionally other additives, the components being added to the water in such a way that no significant quantities of air bubbles are stirred in.
EP90912599A 1989-09-06 1990-08-29 Liquid detergents containing zeolite Expired - Lifetime EP0490912B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3929591 1989-09-06
DE3929591A DE3929591A1 (en) 1989-09-06 1989-09-06 LIQUID DETERGENT WITH ZEOLITE
PCT/EP1990/001435 WO1991003541A1 (en) 1989-09-06 1990-08-29 Liquid detergents containing zeolite

Publications (2)

Publication Number Publication Date
EP0490912A1 EP0490912A1 (en) 1992-06-24
EP0490912B1 true EP0490912B1 (en) 1994-09-14

Family

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Application Number Title Priority Date Filing Date
EP90912599A Expired - Lifetime EP0490912B1 (en) 1989-09-06 1990-08-29 Liquid detergents containing zeolite

Country Status (9)

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US (1) US5252244A (en)
EP (1) EP0490912B1 (en)
JP (1) JPH05500381A (en)
KR (1) KR927003773A (en)
AT (1) ATE111509T1 (en)
DE (2) DE3929591A1 (en)
ES (1) ES2062547T3 (en)
PT (1) PT95189A (en)
WO (1) WO1991003541A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4128426A1 (en) * 1991-08-27 1993-03-04 Henkel Kgaa LIQUID DETERGENT WITH ZEOLITE
DE4203789A1 (en) * 1992-02-10 1993-08-12 Henkel Kgaa METHOD FOR STABILIZING AQUEOUS ZEOLITE SUSPENSIONS
DE4210073A1 (en) * 1992-03-27 1993-09-30 Henkel Kgaa Process for reducing the free formaldehyde and formic acid content in nonionic and anionic surfactants
US5876514A (en) * 1997-01-23 1999-03-02 Ecolab Inc. Warewashing system containing nonionic surfactant that performs both a cleaning and sheeting function and a method of warewashing
US8216989B2 (en) * 2009-08-26 2012-07-10 Ecolab Usa Inc. Cleaning composition for removing/preventing redeposition of protein soils
CA2776996C (en) 2009-11-04 2015-06-30 Colgate-Palmolive Company Microfibrous cellulose having a particle size distribution for structured surfactant compositions
NZ599223A (en) 2009-11-04 2013-07-26 Colgate Palmolive Co Process to produce stable composition of surfactant and suspending agent with gas level determined by gas bubble test
WO2013064357A1 (en) 2011-11-02 2013-05-10 Henkel Ag & Co. Kgaa Structured detergent or cleaning agent having a flow limit ii
CN104911046A (en) * 2015-07-03 2015-09-16 陈明志 Soft-type clothes detergent

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4083793A (en) * 1973-05-23 1978-04-11 Henkel Kommanditgesellschaft Auf Aktien Washing compositions containing aluminosilicates and nonionics and method of washing textiles
GB1589971A (en) * 1976-10-11 1981-05-20 Unilever Ltd Built liquid detergent
BE874420A (en) * 1978-03-02 1979-08-23 Unilever Nv PROCESS FOR THE PRODUCTION OF DETERGENT COMPOSITIONS
US4265777A (en) * 1980-04-17 1981-05-05 The Procter & Gamble Company Detergent compositions containing an aluminosilicate detergency builder and an unsaturated fatty acid soap
JPS6049128B2 (en) * 1980-10-02 1985-10-31 水澤化学工業株式会社 Zeolite aqueous suspension composition and its manufacturing method
EP0075976B1 (en) * 1981-09-14 1985-06-19 THE PROCTER & GAMBLE COMPANY Alkaline aqueous liquid detergent compositions containing normally unstable ester perfumes
US4440663A (en) * 1981-09-14 1984-04-03 The Procter & Gamble Company Alkaline aqueous liquid detergent compositions containing normally unstable ester perfumes
DE3139858A1 (en) * 1981-10-02 1983-04-21 Colgate-Palmolive Co., 10022 New York, N.Y. Process for inhibiting gel formation in bicarbonate/carbonate/ zeolite/silicate Crutcher suspensions
DE3271270D1 (en) * 1981-11-16 1986-06-26 Unilever Nv Liquid detergent composition
IS1740B (en) * 1982-02-05 1999-12-31 Albright & Wilson Uk Limited Composition of cleaning liquid
US4405483A (en) * 1982-04-27 1983-09-20 The Procter & Gamble Company Stable liquid detergents containing aluminosilicate ion exchange material
GB8327271D0 (en) * 1983-10-12 1983-11-16 Unilever Plc Built liquid detergent compositions
JPS608278B2 (en) * 1983-12-26 1985-03-01 ライオン株式会社 Zeolite slurry
GB8515720D0 (en) * 1985-06-21 1985-07-24 Unilever Plc Detergent compositions
DE3621536A1 (en) * 1986-06-27 1988-01-07 Henkel Kgaa LIQUID DETERGENT AND METHOD FOR THE PRODUCTION THEREOF
DE3643895A1 (en) * 1986-12-22 1988-06-30 Henkel Kgaa LIQUID NON-ionic surfactant blends

Also Published As

Publication number Publication date
EP0490912A1 (en) 1992-06-24
US5252244A (en) 1993-10-12
ES2062547T3 (en) 1994-12-16
DE3929591A1 (en) 1991-03-07
JPH05500381A (en) 1993-01-28
WO1991003541A1 (en) 1991-03-21
DE59007161D1 (en) 1994-10-20
KR927003773A (en) 1992-12-18
ATE111509T1 (en) 1994-09-15
PT95189A (en) 1991-05-22

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