EP0490912A1 - Liquid detergents containing zeolite. - Google Patents

Liquid detergents containing zeolite.

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Publication number
EP0490912A1
EP0490912A1 EP90912599A EP90912599A EP0490912A1 EP 0490912 A1 EP0490912 A1 EP 0490912A1 EP 90912599 A EP90912599 A EP 90912599A EP 90912599 A EP90912599 A EP 90912599A EP 0490912 A1 EP0490912 A1 EP 0490912A1
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EP
European Patent Office
Prior art keywords
weight
zeolite
sodium
composition according
contain
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.)
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Application number
EP90912599A
Other languages
German (de)
French (fr)
Other versions
EP0490912B1 (en
Inventor
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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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—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, then the problem of suspension stabilization must also be solved for this insoluble and finely divided component. For this purpose, German patent application 3605978 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).
  • aluminum tristearate aluminum tristearate
  • non-aqueous liquid heavy-duty detergents which contain 25-45% by weight of one or more liquid nonionic surfactants, 10-20% by weight of salts of nitrilotriacetic acid, 10-25% by weight of zeolite and an antigelling agent, for example a nonionic surfactant reacted with succinic anhydride or an alkylene glycol monoalkyl ether, and aluminum tristearate as stabilizing agents.
  • an antigelling agent for example a nonionic surfactant reacted with succinic anhydride or an alkylene glycol monoalkyl ether, and aluminum tristearate as stabilizing agents.
  • 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 a Alkali metal sulfates as a stabilizer and, if appropriate, 1-10% by weight of one
  • alkylbenzenesulfonate as anionic surfactant also leads to physically unstable compositions such as the addition of solvents such as alcohols or glycols.
  • Canadian patent application 1 202857 discloses stable aqueous liquid detergents which contain 13-38% by weight of zeolite, 5-40% by weight of unsaturated Ci5-C22 fatty acid soap, and 7-20% by weight of 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.
  • amphoteric and other anionic surfactants which also include saturated soaps, can also be present in the compositions.
  • European patent application 75976 describes alkaline aqueous liquid detergents which contain 7-30% by weight of zeolite, 5-40% by weight of an unsaturated Ci6-C22 _ ' r fatty acid soap, 1-30% by weight of a nonionic surfactant, 5 15% by weight of a water-soluble polycarboxylate and 20-82% by weight of water, but which are free from synthetic anionic surfactants, which would otherwise destabilize the perfume esters 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 sulphate 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 sulphate 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 builder substances were Contained zeolite and 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.
  • 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 compositions: significant phase separations occurred after 15 days of storage at room temperature.
  • 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 in each case to stabilize a specific 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 are also known from European patent application 170 091, which include surfactants, electrolytes, including water-soluble builder substances, but which contain less than 3% by weight sodium sulfate, and contain suspended builder substances.
  • tripolyphosphate is preferably used as the builder substance for the same reasons of stability as in European patent applications 86614 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 traces and in the latter case is introduced into the concentrates as an impurity of the anionic surfactants.
  • the concentrates can be diluted rapidly 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 builder substances such as phosphates and zeolite and which contains viscosity-reducing (co) polymers, for example polyethylene glycol, polyacrylates, polyaleates, 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 has a shelf life of at least 3 months both at room temperature and at 40 ° C., not even during transport at temperatures between 5 and 60 ° C. Sedimentation tends and meets the requirements for the performance of modern liquid detergents.
  • the invention accordingly relates to a phosphate-free, zeolite-containing liquid detergent which contains 10-30% by weight of anionic and nonionic surfactants, 10-25% by weight of zeolite, 1-10% by weight of an electrolyte system consisting of at least 2 electrolytes from the Group of carbonates, sulfates, chlorides, acetates and citrates, and contains 40-60% by weight of water, the electrolyte system consisting of at least one carbonate and one sulfate.
  • 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 Cg-Ci3-alkylbenzenesulfonates, in particular Ci2-alkylbenzenesulfonate, and sulfonates based on oleochemicals, such as the esters of oc- Sulfofatty acids (ester sulfonates), e.g. B. the oc-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. B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, pal ityl or stearyl alcohol, or the C ⁇ o-C2 ⁇ "0 oa1 alcohols, and those secondary alcohols of this chain length, the sulfuric acid monoesters of the primary alcohols being preferred on a fat-chemical basis.
  • fatty alcohols such as. B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, pal ityl or stearyl alcohol, or the C ⁇ o-C2 ⁇ "0 oa1 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 the alcohols ethoxylated with 1-6 moles of ethylene oxide such as linear C 12 -C 18 fatty alcohols or 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide, are also suitable.
  • the sulfates and sulfonates can be present individually or in a mixture.
  • Preferred agents contain 5-17% by weight, in particular 8-16% by weight of Cg-Ci3-alkylbenzenesulfonates or 10-20% by weight of a mixture ⁇ mixture of Cg-Ci3-alkylbenzenesulfonates with one or more other sulfonates and / or sulfates in any mixture ratio.
  • Soaps preferably saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid and stearic acid, can also be used as anionic surfactants.
  • natural fatty acids e.g. B. coconut, palm kernel or taig fatty acids derived soap mixtures.
  • those soaps which are composed of 50-100% by weight saturated C12-C] _g fatty acid soaps and 0-50% by weight 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, conventional ethoxylated fatty alcohols, in particular addition products of 2-7 moles of ethylene oxide (E0) with linear primary alcohols, such as. B. on coconut oil, tallow or oleyl alcohol, or on primary alcohols (oxo alcohols) branched with methyl in the 2-position.
  • E0 ethylene oxide
  • linear primary alcohols such as. B. on coconut oil, tallow or oleyl alcohol
  • oxo alcohols oxo alcohols
  • the agents according to the invention contain 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 with a size of more than 30 ⁇ m and consist of at least 80% of particles with a size of less 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 ⁇ m.
  • Their calcium binding capacity which is determined according to the information in German patent application 24 12837, 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 consists at least of a carbonate and a sulfate.
  • the proportion of the electrolyte system, based on the total agent, is 1-10% by weight.
  • 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.
  • citrate for example sodium citrate or triethanolammonium citrate, or from 0.5-1.5% by weight of sodium carbonate, 3.5-5.5% by weight of 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.
  • 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 preferably from 1.1 to 1.25 g / ml from 1.15 - 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. Its viscosity (Brookfield viscometer, spindle no. 6, 10 rpm) is 2,000 to 11,000 Pas, preferably between 3,000 and 9,000 mPas and in particular between 3,500 and 8,500 mPas.
  • the storage stability of the agent was tested at both 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 different foam inhibitors are also advantageously used, e.g. B. those made of 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 furthermore 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 which are stable in aqueous agents, hydrotropes and colorants and fragrances, in the customary amounts which provide stability do not affect the suspensions of the invention.
  • the neutral-reacting sodium salts of, for example, l-hydroxyethane-1,1-diphosphonate and diethylenetriamine pentamethylene phosphonate in amounts of 0.1-1.5% by weight are preferably used as salts of polyphosphonic acids.
  • 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.
  • B salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which Instead of the morpholino group, wear a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted 4,4'-distyryl-diphenyl type can also be used to be present; z. B.
  • the compound ⁇ 4,4'-bis (4-chloro-3-sulfostyryl) 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, and quantities of 0.02-0.1% by weight are preferably 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-Ci3-alkylbenzenesulfonate, in particular Ci2-alkylbenzenesulfonate, 1-3.0% by weight of saturated C 1 -C -cig 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 wt .-% l-hydroxyethane-l, l-d ⁇ phosphonate and / or diethylenetriaminepenta ethylene phosphonate, 0.1 wt .-% silicone oil and 43 - 54 wt .-% 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.
  • the invention further relates to a method for producing the liquid detergents described above.
  • the liquid detergents can be prepared in a manner known per se. 35 to 60%, preferably 40-58%, based on the total amount of water provided on average, and the foam inhibitor are preferably introduced into a reactor which is provided with a stirring system. The other components are added in such a way that the stirring in of a large amount of air bubbles is avoided. 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 optionally chloride and acetate can also be metered in in powder form or in the form of an aqueous solution.
  • Liquid detergent (WL) in a 900 kg batch Liquid detergent (WL) in a 900 kg batch.
  • Taig fatty alcohol was stabilized with 5 E0, 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 of glycerin and 4.5 kg of perfume, 0.45 kg of optical brightener, 4.50 kg of protease, and 9.00 kg of l-hydroxyethane-l, l-diphosphonate disodium salt.
  • Viscosity (Brookfield viscometer, spindle No. 6, 10 rpm): 4000 mPas
  • Storage stability The storage time was 7 months. At storage temperatures of 40 ° C and room temperature, no sedimentation occurred in both cases within this time.
  • W2 contained 9.5% by weight of dodecylbenzenesulfonate, 1.7% by weight of C ⁇ 2 fatty acid, 6% by weight of Ci3-Ci5 alcohol with 7 E0, 3% by weight of Ci2-Ci4 alcohol with 3 E0, 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 % Glycerin and 52.05% 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-C14-alcohol with 5 E0, 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 occurs 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 Ci2-Ci8 alcohol with 5 EO and Ci2- Ci4 alcohol with 3 EO, 17% by weight zeolite NaA, 0.5% by weight sodium carbonate, 5.5% by weight sodium sulfate, 2.0% by weight sodium acetate, 3% by weight 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 Ci2-Ci4 alcohol with 5 E0, 4.9% by weight of Ci2 fatty acid, 1.1% by weight of sodium hydroxide, 17 , 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 Citric acid, 0.5% by weight of protease, 0.1% by weight of silicone oil and 47.7% by weight of water.
  • the storage time was 6 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 (WI) 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:

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

"Zeolithhaltiqes Flüssiowaschmittel" "Zeolite-containing liquid detergent"
Die Erfindung betrifft ein phosphatfreies, wäßriges Flüssigwasch¬ mittel, das Zeolith als Buildersubstanz enthält, sowie ein Ver¬ fahren 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. Natriumtripoly- phosphat 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 Suspensi¬ onsstabilisierung zu lösen. Dazu schlägt die deutsche Patentan¬ meldung 3605978 vor, die Zeolithteilchen in einer nicht-wäßrigen Flüssigkeit (flüssiges Niotensid) zu suspendieren und durch Zugabe des Alumiπiumsalzes 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 Nitrilo- triessigsäure, 10 - 25 Gew.-% Zeolith sowie ein Antigeliermittel, beispielsweise ein mit Bernsteinsäureanhydrid umgesetztes nicht ionisches Tensid oder einen Alkylenglykolmonoalkylether, sowi Aluminiumtristearat als Stabilisierungsmittel enthalten. Die US-amerikanische Patentschrift 4 018 720 beschreibt wäßrige Flüssigwaschmittel, die 7 - 25 Gew.-% einer Mischung aus Alkyl- sulfaten bzw. Alkylethersulfaten und Alkylbenzolsulfonaten, 6 - 25 Gew.-% einer Phosphatbuildersubstanz, 3 - 20 Gew.-% eines Alka¬ limetallsulfates als Stabilisator und ggf. 1 - 10 Gew.-% einesLiquid 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, then the problem of suspension stabilization must also be solved for this insoluble and finely divided component. For this purpose, German patent application 3605978 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 of salts of nitrilotriacetic acid, 10-25% by weight of zeolite and an antigelling agent, for example a nonionic surfactant reacted with succinic anhydride or an alkylene glycol monoalkyl ether, and aluminum tristearate as stabilizing agents. 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 a Alkali metal sulfates as a stabilizer and, if appropriate, 1-10% by weight of one
Aluminosilikates als Co-Builder enthalten. Die alleinige Verwen¬ dung von Alkylbenzolsulfonat als Aniontensid führt ebenso zu phy¬ sikalisch instabilen Zusammensetzungen wie die Zugabe von Lö¬ sungsmitteln wie Alkoholen oder Glykolen.Contain aluminosilicates as co-builders. The sole use of alkylbenzenesulfonate as anionic surfactant also leads to physically unstable compositions such as the addition of solvents such as alcohols or glycols.
Aus der kanadischen Patentanmeldung 1 202857 sind stabile wäßrige Flüssigwaschmittel bekannt, die 13 - 38 Gew.-% Zeolith, 5 - 40 Gew.-% ungesättigte Ci5-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.Canadian patent application 1 202857 discloses stable aqueous liquid detergents which contain 13-38% by weight of zeolite, 5-40% by weight of unsaturated Ci5-C22 fatty acid soap, and 7-20% by weight of 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 75976 beschreibt alkalische wä߬ rige Flüssigwaschmittel, die 7 - 30 Gew.-% Zeolith, 5 - 40 Gew.-% einer ungesättigten Ci6-C22_'rettsäureseife, 1 - 30 Gew.-% eines nichtionischen Tensids, 5 - 15 Gew.-% eines wasserlöslichen Poly- carboxylats und 20 - 82 Gew.-% Wasser enthalten, die aber frei sind von synthetischen Aniontensiden, die sonst die in dieser stabilen flüssigen Mischung vorhandenen Parfümester destabilisie¬ ren.European patent application 75976 describes alkaline aqueous liquid detergents which contain 7-30% by weight of zeolite, 5-40% by weight of an unsaturated Ci6-C22 _ ' r fatty acid soap, 1-30% by weight of a nonionic surfactant, 5 15% by weight of a water-soluble polycarboxylate and 20-82% by weight of water, but which are free from synthetic anionic surfactants, which would otherwise destabilize the perfume esters present in this stable liquid mixture.
In der europäischen Patentanmeldung 86 614 werden wäßrige Flüs- sigwaschmittel beschrieben, die anionische und ggf. und/oder nichtionische, kationische und amphotere Tenside, wasserunlösliche, suspendierte und ggf. wasserlösliche Buildersubstanzen sowie weitere Elektrolyte enthalten, wobei Na¬ triumsulfat 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.-% Si¬ likat 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 sulphate 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 builder substances were Contained zeolite and 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 Suspen¬ sionen besitzen einen pH-Wert von 7 - 9. Die Mittel enthalten 1 - 60 Gew.-% Tenside, 0,5 - 30 Gew.-% Phosphat und/oder Nitrilotri¬ acetat 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 Phasentren¬ nungen 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. 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 compositions: significant phase separations occurred after 15 days of storage at room temperature.
In der europäischen Patentanmeldung 151 884 werden wäßrige Flüs¬ sigwaschmittel 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 Buil¬ dersubstanzen benötigte Menge an Elektrolyt wird durch Kondukti- vitätsmessungen 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 in each case to stabilize a specific 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 wä߬ rige Flüssigwaschmittel bekannt, die Tenside, Elektrolyte, zu de¬ nen auch wasserlösliche Buildersubstanzen zählen, die aber weniger als 3 Gew.-% Natriumsulfat beinhalten, und suspendierte Builder¬ substanzen enthalten. Auch hier wird aus denselben Stabilitäts¬ gründen wie in den europäischen Patentanmeldungen 86614 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.Aqueous liquid detergents are also known from European patent application 170 091, which include surfactants, electrolytes, including water-soluble builder substances, but which contain less than 3% by weight sodium sulfate, and contain suspended builder substances. Here too, tripolyphosphate is preferably used as the builder substance for the same reasons of stability as in European patent applications 86614 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 Tensidkonzen- trate, die ohne Stabilitätsverlust transportiert und gelagert werden können, 25 - 80 Gew.-% Tenside sowie bis zu 10 Gew.-%, be¬ zogen auf die Tensidmenge, an Elektrolyten. Natriumsulfat ist je¬ doch gar nicht oder nur in Spuren zugegen und wird im letzteren Fall als Verunreinigung der Aniontenside in die Konzentrate ein¬ getragen. Die Konzentrate können schnell verdünnt oder durch Zu¬ gabe anderer Waschmittelbestandteile, beispielsweise durch Zugabe von suspendierbaren Buildersubstanzen, vorzugsweise Tripolyphos¬ phat, und ggf. von Elektrolyten, zu Flüssigwaschmitteln vermengt werden. Dabei ist der Einsatz von Elektrolyten, die keine Buil- dereigenschaften besitzen, weniger bevorzugt. Die europäische Patentanmeldung 301 882 beschreibt ein Flüssig¬ waschmittel, das Buildersubstanzen wie Phosphate und Zeolith ent¬ halten kann und das die Viskosität reduzierende (Co-)Polymere, beispielsweise Polyethylenglykol, Polyacrylate, Poly aleate, Po- lysaccharide 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 Pha¬ sentrennung auftritt, die mehr als 2 % beträgt.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 traces and in the latter case is introduced into the concentrates as an impurity of the anionic surfactants. The concentrates can be diluted rapidly 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 builder substances such as phosphates and zeolite and which contains viscosity-reducing (co) polymers, for example polyethylene glycol, polyacrylates, polyaleates, 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, wä߬ riges 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 has a shelf life of at least 3 months both at room temperature and at 40 ° C., not even during transport at temperatures between 5 and 60 ° C. Sedimentation tends and meets the requirements for the performance of modern liquid detergents.
Gegenstand der Erfindung ist dementsprechend ein phosphatfreies, zeolithhaltiges Flüssigwaschmittel, das 10 - 30 Gew.-% anionische und nichtionische Tenside, 10 - 25 Gew.-% Zeolith, 1 - 10 Gew.-% eines Elektrolytsystems, bestehend aus mindestens 2 Elektrolyten aus der Gruppe der Carbonate, Sulfate, Chloride, Acetate und Ci¬ trate, und 40 - 60 Gew.-% Wasser enthält, wobei das Elektrolyt¬ system wenigstens aus einem Carbonat und einem Sulfat besteht.The invention accordingly relates to a phosphate-free, zeolite-containing liquid detergent which contains 10-30% by weight of anionic and nonionic surfactants, 10-25% by weight of zeolite, 1-10% by weight of an electrolyte system consisting of at least 2 electrolytes from the Group of carbonates, sulfates, chlorides, acetates and citrates, and contains 40-60% by weight of water, the electrolyte system consisting of at least one carbonate and one sulfate.
Die erfindungsgemäßen Mittel beinhalten vorzugsweise 5 - 20 Gew.-% übliche anionische Tenside aus der Klasse der Sulfonate und Sul¬ fate. Als Tenside vom Sulfonattyp kommen vorzugsweise Cg-Ci3-Al- kylbenzolsulfonate, insbesondere Ci2-Alkylbenzolsulfonat, und Sulfonate auf fettchemischer Basis wie die Ester von oc- Sulfofettsäuren (Estersulfonate), z. B. die oc-sulfonierten Me¬ thylester der hydrierten Kokos-, Palmkern- oder Taigfettsäuren 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, Taigfettalkoholen, Oleylalkohol, Lauryl-, Myristyl-, Pal ityl- oder Stearylalkohol, oder den Cιo-C2θ"0 oa1koholen, und diejenigen sekundärer Alkohole dieser Kettenlänge, wobei die Schwefelsäuremonoester der primären Alko¬ hole auf fettchemischer Basis bevorzugt sind. Auch die Schwefel¬ säuremonoester der mit 1 - 6 Mol Ethylenoxid ethoxylierten Alko¬ hole, wie lineare Cχ2~Ci8-Fettalkohole oder 2-Methyl-verzweigte Cg-Cn-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid, sind ge¬ eignet. 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.-% Cg-Ci3-Alkylbenzolsulfonate oder 10 - 20 Gew.-% einer Mi¬ schung aus Cg-Ci3-Alkylbenzolsulfonaten mit einem oder mehreren anderen Sulfonaten und/oder Sulfaten in einem beliebigen Mi¬ schungsverhältnis.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 Cg-Ci3-alkylbenzenesulfonates, in particular Ci2-alkylbenzenesulfonate, and sulfonates based on oleochemicals, such as the esters of oc- Sulfofatty acids (ester sulfonates), e.g. B. the oc-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. B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, pal ityl or stearyl alcohol, or the Cιo-C2θ "0 oa1 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 the alcohols ethoxylated with 1-6 moles of ethylene oxide, such as linear C 12 -C 18 fatty alcohols or 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide, are also suitable The sulfates and sulfonates can be present individually or in a mixture. Preferred agents contain 5-17% by weight, in particular 8-16% by weight of Cg-Ci3-alkylbenzenesulfonates or 10-20% by weight of a mixture ¬ mixture of Cg-Ci3-alkylbenzenesulfonates with one or more other sulfonates and / or sulfates in any mixture ratio.
Als anionische Tenside sind weiterhin Seifen, vorzugsweise gesät¬ tigte Fettsäureseifen wie die Salze der Laurinsäure, Myristinsäu- re, Palmitinsäure und Stearinsäure, brauchbar. Geeignet sind ins¬ besondere aus natürlichen Fettsäuren, z. B. Kokos-, Palmkern- oder Taigfettsäuren abgeleitete Seifengemische. Geeignet sind auch solche Seifen, die zu 50 - 100 Gew.-% aus gesättigten Ci2-C]_g- Fettsäureseifen und zu 0 - 50 Gew.-% aus Ölsäureseife zusammen¬ gesetzt sind. Die erfindungsgemäßen Mittel können 0 - 5 Gew.-% an Seifen enthalten. Bevorzugte Mittel besitzen einen Gehalt an Seife von 1 - 3,5 Gew.-%. Die anionischen Tenside können in Form ihrer Natrium-, Kalium¬ oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen.Soaps, preferably saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid and stearic acid, can also be used as anionic surfactants. From natural fatty acids, e.g. B. coconut, palm kernel or taig fatty acids derived soap mixtures. Also suitable are those soaps which are composed of 50-100% by weight saturated C12-C] _g fatty acid soaps and 0-50% by weight 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.
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 (E0) an lineare primäre Alkohole, wie z. B. an Kokos-, Taigfett- oder Oleylalko- hol, oder an in 2-Stellung methylverzweigte primäre Alkohole (Oxoalkohole). Insbesondere werden Ci2-Ci4-Alkohole mit 3 E0 oderThe agents according to the invention further preferably contain 5-10% by weight from the class of the nonionic surfactants. Suitable are, for example, conventional ethoxylated fatty alcohols, in particular addition products of 2-7 moles of ethylene oxide (E0) with linear primary alcohols, such as. B. on coconut oil, tallow or oleyl alcohol, or on primary alcohols (oxo alcohols) branched with methyl in the 2-position. In particular, Ci2-Ci4 alcohols with 3 E0 or
4 E0, Ci3-Ci5-Alkohole mit 3, 5 oder 7 E0, Ci2-Ci8-Alkohole mit 3,4 E0, Ci3-Ci5 alcohols with 3, 5 or 7 E0, Ci2-Ci8 alcohols with 3,
5 oder 7 E0 und Mischungen aus diesen, wie Mischungen aus C12- ' Ci4~Alkohol mit 3 E0 und Ci2-Cιg-Alkohole mit 5 E0, in Mengen von 5 - 9 Gew.-% eingesetzt.5 or 7 E0 and mixtures of these, such as mixtures of C12- 'Ci4 ~ alcohol with 3 E0 and Ci2-Cιg alcohols with 5 E0, used in amounts of 5-9 wt .-%.
Als Buildersubstanz enthalten die erfindungsgemäßen Mittel 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. Ge¬ eignete 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. Be¬ vorzugte Zeolithe haben eine mittlere Teilchengröße von 2 - 4 μm. Ihr Calciumbindevermögen, das nach den Angaben der deutschen Pa¬ tentanmeldung 24 12837 bestimmt wird, liegt im Bereich von 100 - 200 mg CaO/g. Die Zeolithe, die zu 10 - 25 Gew.-% in den erfin¬ dungsgemäßen 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 be¬ trägt vorzugsweise 0,8 : 1 bis 1,4 : 1 und insbesondere 1 : 1 bis 1,4 : 1.The agents according to the invention contain 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 with a size of more than 30 μm and consist of at least 80% of particles with a size of less 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 μm. Their calcium binding capacity, which is determined according to the information in German patent application 24 12837, 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 Zeo¬ lith werden durch ein Elektrolytsystem stabilisiert, das aus min¬ destens 2 Salzen, vorzugsweise Natriumsalzen und/oder Triethanol- arnmonium-Salzen, aus der Gruppe der Carbonate, Chloride, Sulfate, Acetate und Citrate besteht, wobei das Elektrolytsystem aber we¬ nigstens 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 einge¬ bracht wird und durch Reaktion mit überschüssigem Alkali entsteht. Bevorzugt verwendete Elektrolytsysteme bestehen aus 3 oder 4 ver¬ schiedenen Elektrolyten, insbesondere (bezogen auf das gesamte Mittel) aus 0,5 - 2 Gew.-% Natriumcarbonat, 4 - 6 Gew.-% Natrium¬ sulfat und 0,8 - 1,5 Gew.-% Citrat, beispielsweise Natriumeitrat oder Triethanolammoniumcitrat, oder aus 0,5 - 1,5 Gew.-% Natrium¬ carbonat, 3,5 - 5,5 Gew.-% Natriumsulfat und 1,0 - 2,0 Gew.-% Na¬ triumchlorid oder aus 0,5 - 1 Gew.-% Natriumcarbonat, 4 - 6 Gew.-% Natriumsulfat und 0,5 - 4 Gew.-% Natriu acetat 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. Die erfindungsgemäßen Mittel enthalten 40 - 60 Gew.-% und vor¬ zugsweise 42 - 55 Gew.-% Wasser.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 consists at least 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 of citrate, for example sodium citrate or triethanolammonium citrate, or from 0.5-1.5% by weight of sodium carbonate, 3.5-5.5% by weight of 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. 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 zwi¬ schen 8,5 und 10,5 und insbesondere zwischen 9 und 10. Die Dichte der Mittel hat einen Wert von 1,1 bis 1,25 g/ml, vorzugsweise von 1,15 - 1,22 g/ml. Die erfindungsgemäßen Mittel weisen eine Flie߬ grenze von mindestens 3 Pa auf. Bevorzugte Mittel besitzen Flie߬ grenzen zwischen 4 und 35 Pa. Ihre Viskosität (Brookfield-Visko- simeter, Spindel Nr. 6, 10 Upm) liegt bei 2 000 bis 11 000 Pas, vorzugsweise zwischen 3 000 und 9 000 mPas und insbesondere zwi¬ schen 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 trans¬ portieren.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 preferably from 1.1 to 1.25 g / ml from 1.15 - 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. Its viscosity (Brookfield viscometer, spindle no. 6, 10 rpm) is 2,000 to 11,000 Pas, preferably between 3,000 and 9,000 mPas and in particular between 3,500 and 8,500 mPas. The storage stability of the agent was tested at both 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 Poly- siloxanKieselsäureGemische, wobei die darin enthaltene feinteilige Kieselsäure vorzugsweise silaniert ist. Die Polysiloxane können sowohl aus linearen Verbindungen (Silikonöle) als auch aus ver¬ netzten 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 Par- affinöl. Insbesondere ist der Einsatz von 0,1 Gew.-%, bezogen auf das gesamte Mittel, an Silikonöl bevorzugt. Vorzugsweise enthalten die Mittel 0,5 - 5 Gew.-% Alkohole mit 2 - 3 Kohlenstoffatomen und 1 - 3 Hydroxylgruppen, wie Ethanol, Pro- panol, Propylenglykol und Glycerin. Vorzugsweise werden Propylen- glykol und Glycerin, allein oder im Gemisch mit Ethanol, in Mengen von 2 - 3,5 Gew.-% eingesetzt.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 different foam inhibitors are also advantageously used, e.g. B. those made of 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. 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 zwi¬ schen 9 und 12 zu halten.The agents can furthermore 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 Färb- 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 which are stable in aqueous agents, hydrotropes and colorants and fragrances, 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 l-Hydroxyethan-1,1- diphosphonat und Diethylentriamin-pentamethylenphosphonat in Men¬ gen 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, l-hydroxyethane-1,1-diphosphonate and diethylenetriamine pentamethylene phosphonate in amounts of 0.1-1.5% by weight are preferably used as salts of polyphosphonic acids. The total phosphorus content in the compositions is preferably less than 0.5%.
Die Waschmittel können als optische Aufheller Derivate der Di- aminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z. B. Salze der 4,4'-Bis(2-anilino-4-morpholino- l,3,5-triazin-6-yl-amino)-stilben-2,2'-disulfonsäure oder gleich¬ artig aufgebaute Verbindungen, die anstelle der Morpholinogruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilino- gruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin kön¬ nen 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 erfin¬ dungsgemäßen Mitteln beträgt 0,5 Gew.-%, vorzugsweise werden Men¬ gen 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-l, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which Instead of the morpholino group, wear a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted 4,4'-distyryl-diphenyl type can also be used to be present; z. B. the compound ■ 4,4'-bis (4-chloro-3-sulfostyryl) 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, and quantities of 0.02-0.1% by weight are preferably 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-Ci3-Alkylbenzolsulfonat, insbesondere Ci2-Alkylbenzol- sulfonat, 1 - 3,0 Gew.-% gesättigte C^-Cig-Fettsäureseife in Form der Natrium- und/oder Triethanolammoniumsalze, 5 - 9 Gew.-% nichtionische Tenside, 14 - 19 Gew.-% gebundenes Wasser enthal¬ tenden Zeolith, 0,5 - 1,5 Gew.-% Natriumcarbonat, 3 - 6 Gew.-% Natriumsulfat, 0 - 1,5 Gew.-% l-Hydroxyethan-l,l-dιphosphonat und/oder Diethylentriaminpenta ethylenphosphonat, 0,1 Gew.-% Silikonöl und 43 - 54 Gew.-% Wasser.In a preferred embodiment, the agents contain 8-16% by weight of C9-Ci3-alkylbenzenesulfonate, in particular Ci2-alkylbenzenesulfonate, 1-3.0% by weight of saturated C 1 -C -cig 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 wt .-% l-hydroxyethane-l, l-dιphosphonate and / or diethylenetriaminepenta ethylene phosphonate, 0.1 wt .-% silicone oil and 43 - 54 wt .-% 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 Propylen- glykol.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 Na- triumcitrat und/oder Triethanolam oniumcitrat, und 2 - 3 Gew.-% Glycerin oder einer Mischung aus 2/3 Glycerin und 1/3 Ethanol enthalten.Likewise preferred is the use of agents which contain 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 triethanolamium citrate, and 2 - 3% by weight 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 Flüssig¬ waschmittel in an sich bekannter Weise hergestellt werden. Vor¬ zugsweise werden in einem Reaktor, der mit einem Rührsystem ver¬ sehen ist, 35 bis 60 %, vorzugsweise 40 - 58 % Wasser, bezogen auf die im Mittel vorgesehene Gesamtmenge an Wasser, sowie der Schauminhibitor vorgelegt. Die Zudosierung der übrigen Komponenten erfolgt derart, daß das Einrühren einer größeren Menge Luftblasen vermieden wird. 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 ein¬ gerührt. Im Anschluß daran wird die Fettsäure zweckmäßigerweise mit Triethanolamin und/oder Natriumhydroxid, das vorzugsweise in Form einer wäßrigen Lösung hinzugefügt wird, neutralisiert. Zeo¬ lith 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 Elek¬ trolytsalze Carbonat und Sulfat sowie ggf. Chlorid und Acetat können ebenfalls in Pulverform oder in Form einer wäßrigen Lösung hinzudosiert werden. The invention further relates to a method for producing the liquid detergents described above. The liquid detergents can be prepared in a manner known per se. 35 to 60%, preferably 40-58%, based on the total amount of water provided on average, and the foam inhibitor are preferably introduced into a reactor which is provided with a stirring system. The other components are added in such a way that the stirring in of a large amount of air bubbles is avoided. 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 optionally chloride and acetate can also be metered in in powder form or in the form of an aqueous solution.
BeispieleExamples
Beispiel 1:Example 1:
Dieses Beispiel beschreibt die Herstellung eines erfindungsgemäßenThis example describes the preparation of an inventive
Flüssigwaschmittels (Wl) im 900 kg-Ansatz.Liquid detergent (WL) in a 900 kg batch.
In einem 800-1-Kesselreaktor, der mit einem Rührsystem versehen war, wurden 195,25 kg Wasser und 0,9 kg Silikonöl (Silikonanti- schaummittel VP 1132, Produkt der Fa. Wacker-Chemie GmbH) vorge¬ legt. Nach dem Aufheizen der Wasser-Silikonöl-Mischung auf 70 °C wurden 16,00 kg ebenfalls auf 70 °C erwärmte C^-Fettsäure (94 %ig) zugegeben.195.25 kg of water and 0.9 kg of silicone oil (silicone anti-foaming agent VP 1132, product from Wacker-Chemie GmbH) were placed in an 800-liter boiler reactor which was provided with a stirring system. After the water-silicone oil mixture had been heated to 70 ° C., 16.00 kg of C 1-4 fatty acid (94% strength), likewise heated to 70 ° C., were added.
Als weitere Bestandteile wurden folgende Komponenten in den ange¬ geben Mengen zugegeben: 150,00 kg einer 55 Gew.-%igen wäßrigen Lösung von Natriu dodecyl- benzolsulfonat, 60,00 kg Ci3-Ci5-Alkohol mit 7 Ethylenoxidgruppen (E0), 305,00 kg einer 52 Gew.-%igen wäßrigen Zeolith-Suspension, die mitThe following components were added as further constituents in the amounts stated: 150.00 kg of a 55% strength by weight aqueous solution of sodium dodecylbenzenesulfonate, 60.00 kg of C13-C15-alcohol with 7 ethylene oxide groups (E0), 305 , 00 kg of a 52 wt .-% aqueous zeolite suspension with
Taigfettalkohol mit 5 E0 stabilisiert war, 100,00 kg einer 50 Gew.-%igen wäßrigen Natriumsulfatlösung, 10,00 kg einer 50 Gew.-%igen wäßrigen Natriu carbonatlösung, 7,20 kg Citronensäure, 12,20 kg Triethanolamin, 25,00 kg Glycerin sowie 4,5 kg Parfüm, 0,45 kg optische Aufheller, 4,50 kg Protease, und 9,00 kg l-Hydroxyethan-l,l-diphosphonat-dinatriumsalz.Taig fatty alcohol was stabilized with 5 E0, 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 of glycerin and 4.5 kg of perfume, 0.45 kg of optical brightener, 4.50 kg of protease, and 9.00 kg of l-hydroxyethane-l, l-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.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.
Dichte: 1,2 g/ml pH-Wert: 9,20Density: 1.2 g / ml pH: 9.20
Viskosität (Brookfield-Viskosimeter, Spindel Nr. 6, 10 Upm): 4000 mPasViscosity (Brookfield viscometer, spindle No. 6, 10 rpm): 4000 mPas
Fließgrenze: 4,2 PaYield point: 4.2 Pa
Lagerstabilität: Die Lagerzeit betrug 7 Monate. Bei Lagertempera¬ turen von 40 °C und Raumtemperatur trat in beiden Fällen innerhalb dieser Zeit keine Sedimentation auf.Storage stability: The storage time was 7 months. At storage temperatures of 40 ° C and room temperature, no sedimentation occurred in both cases within this time.
Beispiel 2:Example 2:
Weitere erfindungsgemäße Mittel W2 - W5 wurden analog zu BeispielOther agents W2-W5 according to the invention were analogous to Example
1 hergestellt.1 manufactured.
W2 enthielt 9,5 Gew.-% Dodecylbenzolsulfonat, 1,7 Gew.-% Cχ2-Fett- säure, 6 Gew.-% Ci3-Ci5-Alkohol mit 7 E0, 3 Gew.-% Ci2-Ci4-Alkohol mit 3 E0, 1,3 Gew.-% Triethanolamin, 17 Gew.-% Zeolith NaA, 2,0 Gew.-% Natriumcarbonat, 4,0 Gew.-% Natriumsulfat, 1,0 Gew.-% Ci- tronensäure, 3 Gew.-% Glycerin und 52,05 Gew.-% Wasser. Die La¬ gerzeit betrug 5 Monate. Innerhalb dieser Zeit trat bei Lagertem¬ peraturen von 40 °C und Raumtemperatur keine Sedimentation auf.W2 contained 9.5% by weight of dodecylbenzenesulfonate, 1.7% by weight of Cχ2 fatty acid, 6% by weight of Ci3-Ci5 alcohol with 7 E0, 3% by weight of Ci2-Ci4 alcohol with 3 E0, 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 % Glycerin and 52.05% 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-AI- kohol mit 5 E0, 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 Sedimen¬ tation auf.W3 contained 14% by weight of dodecylbenzenesulfonate, 8% by weight of C12-C14-alcohol with 5 E0, 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 occurs 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 Ci2-Ci8-Alkohol mit 5 EO und Ci2-Ci4-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 Sedimen¬ tation 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 Ci2-Ci8 alcohol with 5 EO and Ci2- Ci4 alcohol with 3 EO, 17% by weight zeolite NaA, 0.5% by weight sodium carbonate, 5.5% by weight sodium sulfate, 2.0% by weight sodium acetate, 3% by weight 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.-% Ci2-Ci4-Alkohol mit 5 E0, 4,9 Gew.-% Ci2-Fettsäure, 1,1 Gew.-% Natriumhydroxid, 17,5 Gew.-% Zeolith NaA, 2 Gew.-% Gly¬ cerin, 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 6 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 Ci2-Ci4 alcohol with 5 E0, 4.9% by weight of Ci2 fatty acid, 1.1% by weight of sodium hydroxide, 17 , 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 Citric acid, 0.5% by weight of protease, 0.1% by weight of silicone oil and 47.7% by weight of water. The storage time was 6 2 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 (Wl), die in einer Haushaltswaschma¬ schine mit horizontal angeordneter Wäschetrommel (Typ Miele W 433) unter folgenden Bedingungen durchgeführt wurde:This example describes the application test of the agent (WI) 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:
Waschtemperatur: 60 °CWashing temperature: 60 ° C
Einlaugenverfahren - BuntwaschprogrammSoak-in process - colored washing program
Wasserhärte: 16 °d (160 mg CaO pro Liter) Waschmitteldosierung: 224 gWater hardness: 16 ° d (160 mg CaO per liter) Detergent dosage: 224 g
Textilproben: je zwei Teststreifen mit gleicher Anschmutzung sowie 3,5 kg normal verschmutzte Haushaltswäsche VierfachbestitrroungTextile samples: two test strips with the same soiling and 3.5 kg of normally soiled household laundry
Die optische Auswertung der Waschergebnisse (Tabelle 1) erfolgte mit einem Zeiss-Reflektometer bei 460 nm (Ausblendung des Aufhel¬ ler-Effektes). Remissionsunterschiede von 2 % und mehr können di¬ rekt vom Verbraucher wahrgenommen werden.The optical evaluation of the washing results (Table 1) was carried out using a Zeiss reflectometer at 460 nm (masking out of the brightener effect). Differences in remission of 2% and more can be perceived directly by the consumer.
Anschmutzunqen: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 Baumwolle VIII Cosmetics on refined cotton
Tabel le 1Table 1
Die Ergebnisse sind vergleichbar bis besser als die mit handels¬ üblichen Produkten erzielbaren Werte. The results are comparable to better than the values that can be achieved with commercially available products.

Claims

Patentansprüche Claims
1. Zeolithhaltiges und phosphatfreies Flüssigwaschmittel, ent¬ haltend 10 -30 Gew.-% anionische und nichtionische Tenside, 10 - 25 Gew.- Zeolith, 1 - 10 Gew.-% eines Elektrolytsystems, bestehend aus mindestens 2 Elektrolyten aus der Gruppe der Carbonate, Sulfate, Chloride, Acetate und Citrate, und 40 - 60 Gew.-% Wasser, wobei das Elektrolytsystem wenigstens aus einem Carbonat und einem Sulfat besteht.1. Zeolite-containing and phosphate-free liquid detergent, containing 10-30% by weight of anionic and nonionic surfactants, 10-25% by weight of zeolite, 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, and 40-60% by weight of water, the electrolyte system consisting of at least one carbonate and one sulfate.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß es 5 - 17 Gew.-% Cg-Ci3-Alkylbenzolsulfonate oder 10 - 20 Gew.-% einer Mischung aus Cg-Ci3-Alkylbenzolsulfonaten mit einem oder meh¬ reren anderen Sulfonaten und/oder Sulfaten in einem beliebigen Mischungsverhältnis enthält.2. Composition according to claim 1, characterized in that there are 5-17% by weight of Cg-Ci3-alkylbenzenesulfonates or 10-20% by weight of a mixture of Cg-Ci3-alkylbenzenesulfonates with one or more other sulfonates and / or contains sulfates in any mixing ratio.
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es 1 - 3,5 Gew.-% gesättigte Fettsäureseifen in Form der Natrium¬ oder Triethanolammoniumsalze enthält.3. Composition according to claim 1 or 2, characterized in that it contains 1 - 3.5 wt .-% saturated fatty acid soaps in the form of sodium or triethanolammonium salts.
4. Mittel nach einem der Ansprüche 1 - 3, dadurch gekennzeichnet, daß das Verhältnis Zeolith : Elektrolytsystem 10 : 3 bis4. Composition according to one of claims 1-3, characterized in that the ratio zeolite: electrolyte system 10: 3 to
10 : 6, insbesondere 10 : 4 bis 10 : 5 beträgt.10: 6, in particular 10: 4 to 10: 5.
5. Mittel nach einem der Ansprüche 1 - 4, dadurch gekennzeichnet, daß es 0,5 - 2 Gew.-% Natriumcarbonat, 4 - 6 Gew.-% Natrium¬ sulfat und 0,8 - 1,5 Gew.-% Citrat enthält. 5. Composition according to one of claims 1-4, characterized in that it contains 0.5-2% by weight sodium carbonate, 4-6% by weight sodium sulfate and 0.8-1.5% by weight citrate contains.
6. Mittel nach einem der Ansprüche 1 - 4-, dadurch gekennzeichnet, daß es 0,5 bis 1 Gew.-% Natriumcarbonat, 4 - 6 Gew.-% Natrium¬ sulfat und 0,5 - 4 Gew.-% Natriumacetat enthält.6. Composition according to one of claims 1-4, characterized in that it contains 0.5 to 1 wt .-% sodium carbonate, 4 - 6 wt .-% sodium sulfate and 0.5 - 4 wt .-% sodium acetate .
7. Mittel nach einem der Ansprüche 1 - 4, dadurch gekennzeichnet, daß es 0,5 - 1 Gew.-% Natriumcarbonat, 3 - 5,5 Gew.-% Natrium¬ sulfat, 0,5 - 1,5 Gew.-% Natriumchlorid und 0,5 - 2,5 Gew.-% Natriumacetat enthält.7. Composition according to one of claims 1-4, characterized in that it contains 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.
8. Mittel nach einem der Ansprüche 1 - 7, dadurch gekennzeichnet, daß es 2 - 3,5 Gew.-% Propylenglykol , Glycerin oder ein Ge¬ misch aus Glycerin und Ethanol oder aus Propylenglykol und Ethanol enthält.8. Composition according to one of claims 1-7, characterized in that it contains 2 - 3.5 wt .-% propylene glycol, glycerol or a mixture of glycerol and ethanol or from propylene glycol and ethanol.
9. Verfahren zur Herstellung eines zeolithhaltigen und phosphat¬ freien Flüssigwaschmittels, enthaltend 10 - 30 Gew.-% anio¬ nische und nichtionische Tenside, 10 - 25 Gew.-% Zeolith, 1 - 10 Gew.-% eines Elektrolytsystems, bestehend aus mindestens 2 Elektrolyten aus der Gruppe der Carbonate, Sulfate, Chloride, Acetate und Citrate, und 40 - 60 Gew.-% Wasser, wobei das Elektrolytsystem wenigstens aus einem Carbonat und einem Sul¬ fat besteht, dadurch gekennzeichnet, daß es in an sich üb¬ licher Weise hergestellt wird. 9. A process for the preparation of a zeolite-containing and phosphate-free liquid detergent, containing 10-30% by weight of anionic and nonionic surfactants, 10-25% by weight of zeolite and 1-10% by weight of an electrolyte system consisting of at least 2 electrolytes from the group of carbonates, sulfates, chlorides, acetates and citrates, and 40-60% by weight of water, the electrolyte system consisting at least of a carbonate and a sulfate, characterized in that it is in itself known Licher way is made.
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
DE3929591A DE3929591A1 (en) 1989-09-06 1989-09-06 LIQUID DETERGENT WITH ZEOLITE
DE3929591 1989-09-06
PCT/EP1990/001435 WO1991003541A1 (en) 1989-09-06 1990-08-29 Liquid detergents containing zeolite

Publications (2)

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

Family

ID=6388738

Family Applications (1)

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)

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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
MX2012004686A (en) 2009-11-04 2012-05-22 Colgate Palmolive Co Microfibrous cellulose having a particle size distribution for structured surfactant compositions.
MX2012004761A (en) 2009-11-04 2012-05-23 Colgate Palmolive Co Process to produce stable suspending system.
EP2773736B1 (en) 2011-11-02 2018-10-10 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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Also Published As

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ES2062547T3 (en) 1994-12-16
DE3929591A1 (en) 1991-03-07
ATE111509T1 (en) 1994-09-15
KR927003773A (en) 1992-12-18
WO1991003541A1 (en) 1991-03-21
US5252244A (en) 1993-10-12
EP0490912B1 (en) 1994-09-14
JPH05500381A (en) 1993-01-28
PT95189A (en) 1991-05-22
DE59007161D1 (en) 1994-10-20

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