EP0490912B1 - Detergents liquides a teneur en zeolite - Google Patents

Detergents liquides a teneur en 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)
English (en)
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EP0490912A1 (fr
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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    • 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)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Claims (9)

  1. Agent de lavage liquide contenant de la zéolithe et exempt de phosphates, présentant un pH compris entre 8 et 12 et une limite d'écoulement d'au moins 3 Pa, renfermant
    10 à 30 % en poids de tensioactifs anioniques et non ioniques, un maximum 5 % en poids de savons étant contenu par rapport à la totalité de l'agent et les savons étant composés à raison de 50 à 100 % en poids de savons d'acides gras saturés en C₁₂ à C₁₈,
    10 à 25 % en poids de zéolithe, ne présentant pas de particules d'une grosseur supérieure à 30 µm, constituée à raison de 80 % au moins de particules d'une grosseur inférieure à 10 µm et possédant une grosseur de particule moyenne située dans l'intervalle de 1 à 10 µm,
    1 à 10 % en poids d'un système électrolytique, constitué d'au moins 2 électrolytes appartenant au groupe des carbonates, sulfates, chlorures, acétates et citrates, le système électrolytique renferment 0,5 à 4 % en poids de carbonate et 0,5 à 8 % an poids de sulfate, dans chaque cas par rapport à le totalité du mélange, et
    40 à 60 % en poids d'eau.
  2. Agent selon la revendication 1, caractérisé en ce qu'il renferme 5 à 17 % en poids d'(alkyl en C₉-C₁₃)-benzènesulfonates ou 10 à 20 % en poids d'un mélange d'(alkyl en C₉-C₁₃)-benzènesulfonates avec un ou plusieurs autres sulfonates et/ou sulfates dans un rapport de mélange quelconque.
  3. Agent selon la revendication 1 ou 2, caractérisé on ce qu'il renferme 1 à 3,5 % en poids de savons d'acides gras saturés, sous la forme de sels de sodium ou de triéthanolammonium.
  4. Agent selon une des revendications 1 à 3, caractérisé en ce que le rapport pondéral zéolithe:système électrolytique atteint 10:3 à 10:6, an particulier 10:4 à 10:5.
  5. Agent selon une des revendications 1 à 4, caractérisé en ce qu'il renferme 0,5 à 2 % en poids de carbonate de sodium, 4 à 6 % en poids de sulfate de sodium et 0,8 à 1,5 % en poids de citrate.
  6. Agent selon une des revendications 1 à 4, caractérisé en ce qu'il renferme 0,5 à 1 % en poids de carbonate de sodium, 4 à 6 % en poids de sulfate de sodium et 0,5 à 4 % en poids d'acétate de sodium.
  7. Agent selon une des revendications 1 à 4, caractérisé en, ce qu'il renferme 0,5 à 1 % en poids de carbonate de sodium, 3 à 5,5 % en poids de sulfate de sodium, 0,5 à 1,5 % en poids de chlorure de sodium et 0,5 à 2,5 % en poids d'acétate de sodium.
  8. Agent selon une des revendications 1 à 7, caractérisé en qu'il renferme 2 à 3,5 % en poids de propylèneglycol, de glycérine ou un mélange de glycérine et d'éthanol ou de propylèneglycol et d'éthanol.
  9. Procédé de fabrication d'un agent de lavage liquide conforme à la revendication 1, caractérisé en ce qui 35 à 60 % d'eau, par rapport à la quantité totale d'eau prévue dans l'agent, ainsi qu'éventuellement un inhibiteur de mousse, sont disposés (préalablement) dans un réacteur équipé d'un système d'agitation, des tensioactifs anioniques et non ioniques sont additionnés, un acide gras ou un mélange d'acides gras éventuellement chauffé à 60 - 80 °C est délayé dans l'eau également chauffée à 60 - 80 °C dans ce cas, une neutralisation est ensuite opérée a l'aide de triéthanolamine et/ou d'hydroxyde de sodium, de la zéolithe sous la forme d'une poudre ou d'une suspension aqueuse est additionnée, les sels électrolytiques sous la forme d'une poudre ou d'une solution aqueuse, ainsi qu'éventuellement d'autres additifs, sont (finalement) ajoutés, l'adjonction dosée des composants à l'eau disposée au préalable se déroulant de manière telle que le délayage d'une quantité importante de bulles d'air est évité.
EP90912599A 1989-09-06 1990-08-29 Detergents liquides a teneur en zeolite Expired - Lifetime EP0490912B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3929591A DE3929591A1 (de) 1989-09-06 1989-09-06 Zeolithhaltiges fluessigwaschmittel
DE3929591 1989-09-06
PCT/EP1990/001435 WO1991003541A1 (fr) 1989-09-06 1990-08-29 Detergents liquides a teneur en zeolite

Publications (2)

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

Family

ID=6388738

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90912599A Expired - Lifetime EP0490912B1 (fr) 1989-09-06 1990-08-29 Detergents liquides a teneur en zeolite

Country Status (9)

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

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4128426A1 (de) * 1991-08-27 1993-03-04 Henkel Kgaa Zeolithhaltiges fluessigwaschmittel
DE4203789A1 (de) * 1992-02-10 1993-08-12 Henkel Kgaa Verfahren zur stabilisierung von waessrigen zeolith-suspensionen
DE4210073A1 (de) * 1992-03-27 1993-09-30 Henkel Kgaa Verfahren zur Verminderung des Gehaltes an freiem Formaldehyd und Ameisensäure in nichtionischen und anionischen Tensiden
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
US8541355B2 (en) 2009-11-04 2013-09-24 Colgate-Palmolive Company Process to produce stable suspending system
AU2010315146B2 (en) 2009-11-04 2013-05-09 Colgate-Palmolive Company Microfibrous cellulose having a particle size distribution for structured surfactant compositions
EP2773736B1 (fr) 2011-11-02 2018-10-10 Henkel AG & Co. KGaA Produit de lavage ou de nettoyage structuré à limite d'écoulement
CN104911046A (zh) * 2015-07-03 2015-09-16 陈明志 一种柔顺型衣服洗涤剂
WO2024135128A1 (fr) * 2022-12-19 2024-06-27 ライオン株式会社 Composition détergente liquide pour produits textiles

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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 (fr) * 1978-03-02 1979-08-23 Unilever Nv Procede de production de compositions detergentes
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 (ja) * 1980-10-02 1985-10-31 水澤化学工業株式会社 ゼオライト水性懸濁組成物及びその製法
US4440663A (en) * 1981-09-14 1984-04-03 The Procter & Gamble Company Alkaline aqueous liquid detergent compositions containing normally unstable ester perfumes
EP0075976B1 (fr) * 1981-09-14 1985-06-19 THE PROCTER & GAMBLE COMPANY Composition détergente alkaline aqueuse contenant des parfums d'esters normalement instables
DE3139858A1 (de) * 1981-10-02 1983-04-21 Colgate-Palmolive Co., 10022 New York, N.Y. Verfahren zur hemmung der gelbildung in bicarbonat-carbonat-zeolith-silikat-crutcher- aufschlaemmungen
EP0079646B1 (fr) * 1981-11-16 1986-05-21 Unilever N.V. Composition détergente liquide
IS1740B (is) * 1982-02-05 1999-12-31 Albright & Wilson Uk Limited Samsetning á hreinsivökva
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 (ja) * 1983-12-26 1985-03-01 ライオン株式会社 ゼオライトスラリ−
GB8515720D0 (en) * 1985-06-21 1985-07-24 Unilever Plc Detergent compositions
DE3621536A1 (de) * 1986-06-27 1988-01-07 Henkel Kgaa Fluessiges waschmittel und verfahren zu seiner herstellung
DE3643895A1 (de) * 1986-12-22 1988-06-30 Henkel Kgaa Fluessige nichtionische tensidmischungen

Also Published As

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

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