EP0369317A1 - Washing and cleaning agents containing sec. dialkylether sulfates - Google Patents
Washing and cleaning agents containing sec. dialkylether sulfates Download PDFInfo
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- EP0369317A1 EP0369317A1 EP19890120755 EP89120755A EP0369317A1 EP 0369317 A1 EP0369317 A1 EP 0369317A1 EP 19890120755 EP19890120755 EP 19890120755 EP 89120755 A EP89120755 A EP 89120755A EP 0369317 A1 EP0369317 A1 EP 0369317A1
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Classifications
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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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/65—Mixtures of anionic with cationic compounds
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the present invention relates to detergents and cleaning agents which, as anionic surfactant component, have salts of sec. Contains dialkyl ether sulfates.
- This new surfactant compound is excellently suitable as an exchange component for alkylbenzenesulfonates, since, with comparable good application properties, it has much more favorable ecological properties, i. H. develops better biodegradability and less toxicity to fish and small organisms in wastewater. In addition, it can essentially be produced from natural, renewable raw materials.
- M in the abovementioned general formula (I) is Na, K, Mg, ammonium, alkylammonium, alkanolammonium, where the alkyl and alkanol radicals of the organic ammonium ions mentioned can each have 1 to 4 carbon atoms.
- the sodium salts are preferred.
- the salts of triethanolamine are particularly useful for liquid agents.
- R1 represents a linear alkyl radical having 1 to 16 carbon atoms.
- the substituents R 1 for the compounds according to the invention are therefore methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n- Hendecyl n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl and n-hexadecyl in question.
- Alkyl radicals having 6 to 14 carbon atoms are preferred.
- R2 in the general formula (I) mentioned above is hydrogen or a linear alkyl radical having 1 to 16 carbon atoms.
- the same alkyl radicals as for R1 are suitable for R2.
- the sum of the C atoms contained in R1 and R2 is 1 to 18, preferably 6 to 14.
- R1 is linear alkyl radicals having 8 to 12 C atoms and R2 is hydrogen.
- R3 represents a linear or branched, saturated alkyl radical having 1 to 22 carbon atoms.
- the substituents R 3 are therefore methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-hendecyl, n- Dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl and n-docosyl as well as the branched chain isomers of the alkyl radicals in question .
- R3 stands for linear, saturated alkyl radicals with 1 to 22 carbon atoms.
- a preferred embodiment comprises compounds in which R 3 represents linear, saturated alkyl radicals having 1 to 12 carbon atoms, in particular alkyl radicals having 1 to 4 carbon atoms.
- R4 represents a methyl group and preferably hydrogen.
- the index n stands for a number from 0 to 15, the range from 1 to 10 being preferred for n.
- ethoxy radicals and propoxy radicals it is also possible for ethoxy radicals and propoxy radicals to be incorporated next to one another in the molecule chain in any ratio and in any order. Such mixed ethers also fall under the general formula (I).
- dialkyl ether sulfates not claimed here can be carried out in such a way that epoxides of the general formula II in which R1 and R2 have the meanings given above, with alcohol alkoxylates of the general formula III in which R3, R4 and n have the meanings given above, at elevated temperature in the presence of a catalyst to give hydroxyalkyl polyethylene and hydroxyalkyl polypropylene glycol ethers of the general formula VI implements.
- This reaction takes place at temperatures from 100 to 180 ° C., preferably 120 to 160 ° C.
- Alkali metal alcoholates, such as sodium methylate are preferably used as catalysts.
- the amount of the catalyst is 0.01 to 2% by weight of the reaction mixture.
- the compounds of the formula IV obtained in this way are reacted with known sulfonating agents, such as chlorosulfonic acid, amidosulfonic acid or - preferably - with sulfur trioxide which is diluted with inert gases or air, the temperature being advantageously 10 to 40 ° C. during the sulfation.
- the crude sulfation product is then converted into a basic one Excess aqueous solution containing neutralizing agents added or continuously neutralized. This solution is then advantageously post-treated for 20 minutes to 1 hour at temperatures of 60 to 100 ° C.
- the aqueous solutions of the compounds obtained can, if appropriate after neutralizing excess basic compounds, be further processed immediately or else dried, in particular spray-dried.
- Detailed manufacturing information can be found in EP-A-299 370 or US Application No. 210 719 with priority from 07/15/1987.
- the dialkyl ether sulfates can be used in amounts of 1 to 50% by weight, preferably 2 to 25% by weight, in customary washing and cleaning agents and in particular in those in which alkylbenzenesulfonates have hitherto been used as surfactants. Because of their comparable, inexpensive cleaning properties and their good solubility properties, they can advantageously replace all or part of the alkylbenzenesulfonates in such compositions. In order that the advantageous ecological properties of the dialkyl ether sulfates are sufficiently effective, agents are preferred in which at least 50% by weight of conventional alkylbenzenesulfonates are replaced by the dialkyl ether sulfates. Agents without a content of alkylbenzenesulfonates are particularly preferred.
- the agents containing dialkyl ether sulfates can be solid, i. H. Powdery, granular or also as shaped pieces or in liquid or pasty form.
- the agents according to the invention can contain additional anionic or nonionic surfactants.
- additional anionic or nonionic surfactants include in particular soaps, as well as surfactants from Sulfonate and sulfate type as well as non-ionic compounds, e.g. B. from the class of polyglycol ether derivatives.
- surfactants with high biodegradation rates and low toxicity in aquatic systems are preferred.
- Suitable soaps are derived from natural or synthetic, saturated or monounsaturated fatty acids with 12 to 22 carbon atoms. Are particularly suitable from natural fatty acids such. B. coconut, palm kernel or tallow fatty acid derived soap mixtures. Preferred are those which are composed of 50 to 100% of saturated C12 ⁇ 18 fatty acid soaps and 0 to 50% of oleic acid soap.
- Useful surfactants of the sulfonate type are - taking into account the above reservations - linear alkylbenzenesulfonates (C9 ⁇ 13-alkyl) and olefin sulfonates, d.
- H Mixtures of alkene and hydroxyalkanesulfonates and disulfonates as obtained, for example, from C12 ⁇ 18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline hydrolysis of the sulfonation products.
- alkanesulfonates which are obtainable from C12 ⁇ 18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization, and also alpha-sulfofatty acids and their esters, e.g. B. the alpha-sulfonated hydrogenated coconut, palm kernel or tallow fatty acids and their methyl or ethyl esters and mixtures thereof.
- alpha sulfoesters and alpha sulfo fatty acid disalts are preferred.
- Particularly suitable surfactants of the sulfate type are 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, palmityl or stearyl alcohol or the C10 ⁇ 18 oxo alcohols.
- Sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated alcohols ethoxylated with 1 to 6, preferably 1 to 2, moles of ethylene oxide are also very suitable.
- Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
- the anionic surfactants are usually in the form of their sodium salts. Their proportion, based on the composition, is generally 0 to 25% by weight, preferably 3 to 20% by weight, including the dialkyl ether sulfates.
- Addition products of 2 to 20, preferably 3 to 15 moles of ethylene oxide with 1 mole of a compound having essentially 10 to 20 carbon atoms from the group of alcohols are preferably used as nonionic surfactants.
- These include water-soluble adducts of 7 to 15 moles of ethylene oxide with primary alcohols, such as. B. on coconut or tallow fatty alcohols, on oleyl alcohol, on oxo alcohols or on secondary alcohols having 8 to 18, preferably 12 to 20 carbon atoms.
- non-completely or not completely water-soluble polyglycol ethers with 2 to 6 ethylene glycol ether residues and the same C chain length are also of interest, which are distinguished by an increased cleaning ability against greasy soiling.
- nonionic surfactants are alkyl glycosides or alkyl oligoglycosides, the alkyl group of which has 8 to 18, preferably 10 to 16, carbon atoms.
- the content of the agents in nonionic surfactants or nonionic surfactant mixtures is 0 to 25 % By weight, preferably 1 to 20% by weight and in particular 2 to 15% by weight.
- Suitable zwitterionic surfactants are those with a betaine structure and the known sulfobetaines.
- Cationic surfactants for example quaternary ammonium salts with a C10 ⁇ 16 alkyl chain and three lower alkyl groups, preferably methyl groups, can also be used.
- anionic surfactant including dialkyl ether sulfate
- cationic surfactant of 3: 1 to 25: 1, they can increase the washing power of the detergents, especially in relation to fatty stains.
- the total content of surfactants in the detergents depends on the intended use and is 1 to 50% by weight. In solid compositions it is preferably 5 to 30% by weight and in particular 8 to 25% by weight. In liquid, builder salt-free agents, it is generally higher and is 15 to 50% by weight, preferably 20 to 45% by weight.
- Component (b) consists of builder salts and sequestering agents, which, individually or in a mixture, bind or precipitate the lime hardness of the water or precipitate or complexly bind disruptive heavy metal ions and thus increase the cleaning power and prevent undesired decomposition of sensitive components such as per-compounds and enzymes.
- Suitable components of component (b) are, in particular, ecologically harmless builder salts, such as finely crystalline, synthetic water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 22 24 837).
- Their particle size is usually in the range from 1 to 10 ⁇ m.
- their content is generally 0 to 40, preferably 10 to 30,% by weight, based on the anhydrous substance.
- component (b) which are used in particular together with the zeolites are (co) polymeric polycarboxylates, such as polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50% to 10% maleic acid.
- the molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on free acid.
- a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
- Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, in which the proportion of acid is at least 50%.
- polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, which are obtained by polymerizing esters of glycolic acid, introducing stable terminal end groups, and saponifying to give the sodium or potassium salts.
- polymeric acids which are obtained by polymerizing acrolein and disproportionating the polymer according to Canizzaro using strong alkalis. They are essentially made up of acrylic acid units and vinyl alcohol units or acrolein units.
- the content of (co) polymeric polycarboxylic acids in the composition, based on free acid, is 0 to 15% by weight, preferably 0.5 to 10% by weight and in particular 1 to 5% by weight.
- the components of component (b) also include nitrilotriacetate (NTA), preferably in the form of the sodium salt, and polycarboxylic acids, such as citric acid, likewise preferably as the sodium salt.
- NTA nitrilotriacetate
- polycarboxylic acids such as citric acid
- the salts of polyphosphonic acids in particular 1-hydroxyethane-1,1-diphosphonic acid, possibly also aminoalkane polyphosphonic acid, such as aminotrimethylenephosphonic acid (ATP), ethylenediamine-tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMPe) and their higher homologue are also suitable.
- ATP aminotrimethylenephosphonic acid
- ETMP ethylenediamine-tetramethylenephosphonate
- DTPMPe diethylenetriaminepentamethylenephosphonate
- They are preferably in the form of the neutral sodium salts, e.g. B.
- compositions as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP.
- Their proportion in the compositions, calculated on free acid, is generally 0 to 3% by weight, in particular 0.1 to 1.5% by weight.
- phosphates can also be used, in particular pentasodium triphosphate, possibly also pyrophosphates, which due to their solubility properties can be used in liquid detergents, as well as orthophosphates, which primarily act as precipitants for lime salts.
- the phosphate content based on pentasodium triphosphate, should preferably be below 30% by weight, in particular below 20% by weight.
- Their proportion in the agents can be 0 to 8% by weight, in particular 2 to 5% by weight, with their proportion preferably not substantially exceeding 3% by weight in the presence of zeolites.
- washing alkali is sodium carbonate, the proportion of which is up to 20% by weight, preferably 2 to 15% by weight and in particular 5 to 10% by weight.
- graying inhibitors Dirt carriers
- bleaching agents bleach activators
- optical brighteners optical brighteners
- Foam inhibitors enzymes
- fabric softening agents colors and fragrances as well as neutral salts, solvents and water.
- the washing and cleaning agents can contain graying inhibitors, which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying.
- graying inhibitors water-soluble colloids of mostly organic nature are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
- Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. B. degraded starch, aldehyde starches, etc.
- Polyvinylpyrrolidone is also useful.
- Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof are preferably used.
- the proportion of the compounds is generally 0.2 to 2, preferably 0.5 to 1.5,% by weight.
- NaBO2 ⁇ H2O2 ⁇ 3 H2O sodium perborate tetrahydrate
- NaBO2 ⁇ H2O2 ⁇ 3 H2O monohydrate
- Peroxy carbonate (Na2CO3 ⁇ 1.5 H2O2), peroxypyrophosphates, citrate perhydrates, urea perhydrate or melamine perhydrate as well as H2O2-delivering peracidic salts or peracids such as perbenzoates, peroxyphathalates, diperazelaic acid or diperdodecanedioic acid can also be used.
- bleach activators can be incorporated into the preparations.
- Examples include N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetyl-ethylenediamine, furthermore carboxylic anhydrides and esters of polyols such as glucose pentaacetate.
- the detergents can contain, as optical brighteners for cotton, in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
- B salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure, which instead of Morpholino group carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group.
- Possible brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type, for example the compound 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline.
- Brighteners of the substituted 4,4'-distyryl-diphenyl type may also 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.
- Enzymes from the class of proteases, lipases and amylases or mixtures thereof are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
- Suitable foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica.
- Bis-acylamides derived from C12 ⁇ 20 alkylamines and C2 ⁇ 6 dicarboxylic acids are also useful.
- Mixtures of different foam inhibitors are also advantageously used, e.g. B. from silicone and paraffins or waxes.
- the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
- Layered silicates from the bentonite and smectite class e.g. B. those according to DE 23 34 899 and EP 265 529. Also suitable are synthetic finely divided sheet silicates with smectite-like crystal phase and reduced swelling capacity, as are characterized in more detail in DE 35 26 405 (US 4,737,306).
- the layered silicate content can be, for example, up to 20% by weight.
- the preparation of powdery to granular agents can be carried out in a conventional manner, ie by spray drying them Conditions resistant components and then admixing the heat-sensitive components such as bleach, enzymes, fragrances and foam inhibitors.
- Other suitable processes are the granulation of the constituents, water, salt solutions, polymer solutions and / or nonionic surfactants being able to be used as the granulation liquid.
- test mixtures The following granular or liquid detergents were used as test mixtures. In order to avoid interference from optical brighteners in the remission measurement, brightener-free mixtures and non-optically brightened test fabrics were used. In practice the mixtures would contain between 0.1 and 0.5% by weight of conventional brighteners. Table I component medium I. II III synthesized.
- phosphate-reduced powder detergent I a phosphate-free powder detergent II and a phosphate-free liquid detergent III.
- AA-MA copolymer Na salt of an acrylic acid-maleic acid copolymer
- Phosphonate Na salt of diethylenetriamine-pentamethylene-phosphonic acid
- Cellulose ether mixtures of carboxymethyl cellulose and hydroxyethyl methyl cellulose
- Water total water content including water bound to zeolite and crystal water.
- the percentage remission (abbreviation% R) was determined photometrically.
- the values given in the following tables are mean values from 3 determinations within a range of 2%. A remission difference of 2% is still clearly visible to the naked eye and therefore corresponds to an effect perceptible by the consumer.
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Abstract
Description
Die vorliegende Erfindung betrifft Wasch- und Reinigungsmittel, die als anionische Tensidkomponente Salze von sek. Dialkylethersulfaten enthält. Diese neue Tensidverbindung eignet sich hervorragend als Austauschkomponente für Alkylbenzolsulfonate, da sie bei vergleichbar guten anwendungstechnischen Eigenschaften sehr viel günstigere ökologische Eigenschaften, d. h. eine bessere Biodegradibilität und eine geringere Toxicität gegenüber Fischen und Kleinlebewesen im Abwasser entfaltet. Sie kann überdies im wesentlichen aus natürlichen, nachwachsenden Rohstoffen hergestellt werden.The present invention relates to detergents and cleaning agents which, as anionic surfactant component, have salts of sec. Contains dialkyl ether sulfates. This new surfactant compound is excellently suitable as an exchange component for alkylbenzenesulfonates, since, with comparable good application properties, it has much more favorable ecological properties, i. H. develops better biodegradability and less toxicity to fish and small organisms in wastewater. In addition, it can essentially be produced from natural, renewable raw materials.
Gegenstand der Erfindung sind Wasch und Reinigungsmittel fester oder flüssiger Form, enthaltend
- a) 1 bis 50 Gew.-% mindestens eines anionischen oder kationischen Tensids,
- b) 1 bis 90 Gew.-% mindestens einer Verbindung aus der Klasse der Buildersalze und Sequestrierungsmittel und
- c) Differenz bis 100 Gew.-% an sonstigen üblichen Wasch- und Reinigungsmittelbestandteilen,
- a) 1 to 50% by weight of at least one anionic or cationic surfactant,
- b) 1 to 90% by weight of at least one compound from the class of the builder salts and sequestering agents and
- c) difference of up to 100% by weight of other usual detergent and cleaning agent components,
Die Bedeutung von M in der oben genannten allgemeinen Formel (I) ist Na, K, Mg, Ammonium, Alkylammonium, Alkanolammonium, wobei die Alkyl- und Alkanolreste der genannten organischen Ammoniumionen je 1 bis 4 C-Atome haben können. Bevorzugt sind die Natriumsalze. Für flüssige Mittel sind insbesondere die Salze des Triethanolamins gut brauchbar.The meaning of M in the abovementioned general formula (I) is Na, K, Mg, ammonium, alkylammonium, alkanolammonium, where the alkyl and alkanol radicals of the organic ammonium ions mentioned can each have 1 to 4 carbon atoms. The sodium salts are preferred. The salts of triethanolamine are particularly useful for liquid agents.
In der allgemeinen Formel (I) steht R¹ für einen linearen Alkylrest mit 1 bis 16 C-Atomen . Es kommen also für die erfindungsgemäßen Verbindungen als Substituent R¹ die Reste Methyl, Ethyl, n-Propyl, n-Butyl, n-Pentyl, n-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl, n-Hendecyl n-Dodecyl, n-Tridecyl, n-Tetradecyl, n-Pentadecyl und n-Hexadecyl in Frage. Bevorzugt sind Alkylreste mit 6 bis 14 C-Atomen.In the general formula (I), R1 represents a linear alkyl radical having 1 to 16 carbon atoms. The substituents R 1 for the compounds according to the invention are therefore methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n- Hendecyl n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl and n-hexadecyl in question. Alkyl radicals having 6 to 14 carbon atoms are preferred.
Die Bedeutung von R² in der oben genannten allgemeinen Formel (I) ist Wasserstoff oder ein lineare Alkylrest mit 1 bis 16 C-Atomen. Neben Wasserstoff kommen also für R² dieselben Alkylreste wie für R¹ in Frage. Die Summe der in R¹ und R² enthaltenen C-Atome beträgt 1 bis 18, vorzugsweise 6 bis 14. Insbesondere steht R¹ für lineare Alkylreste mit 8 bis 12 C-Atomen und R² für Wasserstoff. In der oben genannten Formel (I) steht R³ für einen linearen oder verzweigten, gesättigten Alkylrest mit 1 bis 22 C-Atomen. Es kommen somit als Substituent R³ die Reste Methyl, Ethyl, n-Propyl, n-Butyl, n-Pentyl, n-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl, n-Hendecyl, n-Dodecyl, n-Tridecyl, n-Tetradecyl, n-Pentadecyl, n-Hexadecyl, n-Heptadecyl, n-Octadecyl, n-Nonadecyl, n-Eicosyl, n-Heneicosyl und n-Docosyl sowie die verzweigtkettigen Isomeren der genannten Alkylreste in Frage.The meaning of R² in the general formula (I) mentioned above is hydrogen or a linear alkyl radical having 1 to 16 carbon atoms. In addition to hydrogen, the same alkyl radicals as for R¹ are suitable for R². The sum of the C atoms contained in R¹ and R² is 1 to 18, preferably 6 to 14. In particular, R¹ is linear alkyl radicals having 8 to 12 C atoms and R² is hydrogen. In the above formula (I), R³ represents a linear or branched, saturated alkyl radical having 1 to 22 carbon atoms. The substituents R 3 are therefore methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-hendecyl, n- Dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl and n-docosyl as well as the branched chain isomers of the alkyl radicals in question .
R³ steht für lineare, gesättigte Alkylreste mit 1 bis 22 C-Atomen. Eine bevorzugte Ausführungsform umfaßt Verbindungen, in der R³ für lineare, gesättigte Alkylreste mit 1 bis 12 C-Atomen, insbesondere für Alkylreste mit 1 bis 4 C-Atomen, steht.R³ stands for linear, saturated alkyl radicals with 1 to 22 carbon atoms. A preferred embodiment comprises compounds in which R 3 represents linear, saturated alkyl radicals having 1 to 12 carbon atoms, in particular alkyl radicals having 1 to 4 carbon atoms.
In der oben genannten allgemeinen Formel (I) steht R⁴ für eine Methylgruppe und vorzugsweise für Wasserstoff. Der Index n steht für eine Zahl von 0 bis 15, wobei der Bereich von 1 bis 10 für n bevorzugt ist. Es ist jedoch auch möglich, daß in den genannten Verbindungen Ethoxyreste und Propoxyreste nebeneinander in beliebigem Verhältnis und beliebiger Reihenfolge in die Molekülkette eingebaut sind. Derartige gemischte Ether fallen ebenfalls unter die allgemeine Formel (I).In the above general formula (I) R⁴ represents a methyl group and preferably hydrogen. The index n stands for a number from 0 to 15, the range from 1 to 10 being preferred for n. However, it is also possible for ethoxy radicals and propoxy radicals to be incorporated next to one another in the molecule chain in any ratio and in any order. Such mixed ethers also fall under the general formula (I).
Die hier nicht beanspruchte Herstellung der Dialkylethersulfate kann in der Weise erfolgen, daß man Epoxide der allgemeinen Formel II
Die Dialkylethersulfate können in Mengen von 1 bis 50 Gew.-%, vorzugsweise 2 bis 25 Gew.-% in üblichen Wasch- und Reinigungsmitteln eingesetzt werden und insbesondere in solchen, in denen bisher Alkylbenzolsulfonate als Tenside verwendet wurden. Auf Grund ihrer ihres vergleichbaren günstigen Reinigungsvermögens und ihrer guten Löslichkeitseigenschaften können sie in derartigen Mitteln mit Vorteil die Alkylbenzolsulfonate ganz oder teilweise ersetzen. Damit die vorteilhaften ökologischen Eigenschaften der Dialkylethersulfate hinreichend zum Tragen kommen, werden solche Mittel bevorzugt, in denen mindestens 50 Gew.-% an herkömmlichen Alkylbenzolsulfonaten durch die Dialkylethersulfate ersetzt sind. Besonders bevorzugt sind Mittel ohne einen Gehalt an Alkylbenzolsulfonaten.The dialkyl ether sulfates can be used in amounts of 1 to 50% by weight, preferably 2 to 25% by weight, in customary washing and cleaning agents and in particular in those in which alkylbenzenesulfonates have hitherto been used as surfactants. Because of their comparable, inexpensive cleaning properties and their good solubility properties, they can advantageously replace all or part of the alkylbenzenesulfonates in such compositions. In order that the advantageous ecological properties of the dialkyl ether sulfates are sufficiently effective, agents are preferred in which at least 50% by weight of conventional alkylbenzenesulfonates are replaced by the dialkyl ether sulfates. Agents without a content of alkylbenzenesulfonates are particularly preferred.
Die Mittel mit einem Gehalt an Dialkylethersulfaten können fest, d. h. pulverförmig, granular oder auch als geformte Stücke oder auch in flüssiger bzw. pastöser Form vorliegen.The agents containing dialkyl ether sulfates can be solid, i. H. Powdery, granular or also as shaped pieces or in liquid or pasty form.
Als Bestandteile der Komponente (a) können die erfindungsgemäßen Mittel zusätzliche anionische bzw. nichtionische Tenside enthalten. Hierzu zählen insbesondere Seifen, ferner Tenside vom Sulfonat- und Sulfat-Typ sowie nichtionische Verbindugnen, z. B. aus der Klasse der Polyglykoletherderivate. Tenside mit hohen biologischen Abbauraten und niedriger Toxicität in aquatischen Systemen sind bevorzugt.As components of component (a), the agents according to the invention can contain additional anionic or nonionic surfactants. These include in particular soaps, as well as surfactants from Sulfonate and sulfate type as well as non-ionic compounds, e.g. B. from the class of polyglycol ether derivatives. Surfactants with high biodegradation rates and low toxicity in aquatic systems are preferred.
Geeignete Seifen leiten sich von natürlichen oder synthetischen, gesättigten oder einfach ungesättigten Fettsäuren mit 12 bis 22 C-Atomen ab. Geeignet sind insbesondere aus natürlichen Fettsäuren, z. B. Kokos-, Palmkern oder Talgfettsäuren abgeleitete Seifengemische. Bevorzugt sind solche, die zu 50 bis 100 % aus gesättigten C₁₂₋₁₈-Fettsäureseifen und zu 0 bis 50 % aus Ölsäureseife zusammengesetzt sind.Suitable soaps are derived from natural or synthetic, saturated or monounsaturated fatty acids with 12 to 22 carbon atoms. Are particularly suitable from natural fatty acids such. B. coconut, palm kernel or tallow fatty acid derived soap mixtures. Preferred are those which are composed of 50 to 100% of saturated C₁₂₋₁₈ fatty acid soaps and 0 to 50% of oleic acid soap.
Brauchbare Tenside vom Sulfonattyp sind - unter Berücksichtigung der obengenannten Vorbehalte - lineare Alkylbenzolsulfonate (C₉₋₁₃-Alkyl) und Olefinsulfonate, d. h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C₁₂₋₁₈-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische Hydrolyse der Sulfonierungsprodukte erhält. Geeignet sind auch Alkansulfonate, die aus C₁₂₋₁₈-Alkanen durch Sulfochlorierung oder Sulfoxydation und anschließende Hydrolyse bzw. Neutralisation erhältlich sind, sowie alpha-Sulfofettsäuren und deren Ester, z. B. die alpha-sulfonierte hydrierte Kokos-, Palmkern- oder Talgfettsäuren und deren Methyl- oder Ethylester sowie deren Gemische. Die alpha-Sulfoester und alpha-Sulfofettsäure-Disalze sind bevorzugt.Useful surfactants of the sulfonate type are - taking into account the above reservations - linear alkylbenzenesulfonates (C₉₋₁₃-alkyl) and olefin sulfonates, d. H. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates as obtained, for example, from C₁₂₋₁₈ monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline hydrolysis of the sulfonation products. Also suitable are alkanesulfonates, which are obtainable from C₁₂₋₁₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization, and also alpha-sulfofatty acids and their esters, e.g. B. the alpha-sulfonated hydrogenated coconut, palm kernel or tallow fatty acids and their methyl or ethyl esters and mixtures thereof. The alpha sulfoesters and alpha sulfo fatty acid disalts are preferred.
Besonders geeignete Tenside vom Sulfattyp sind die Schwefelsäuremonoester aus primären Alkoholen natürlichen und synthetischen Ursprungs, d. h. aus Fettalkoholen, wie z. B. Kokosfettalkoholen, Talgfettalkoholen, Oleylalkohol, Lauryl-, Myristyl-, Palmityl- oder Stearylalkohol oder den C₁₀₋₁₈-Oxoalkoholen. Schwefelsäuremonoester der mit 1 bis 6, vorzugsweise 1 bis 2 Mol Ethylenoxid ethoxylierten aliphatischen primären Alkohole bzw. ethoxylierten Alkohole sind ebenfalls gut geeignet. Ferner eignen sich sulfatierte Fettsäurealkanolamide und sulfatierte Fettsäuremonoglyceride.Particularly suitable surfactants of the sulfate type are 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, palmityl or stearyl alcohol or the C₁₀₋₁₈ oxo alcohols. Sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated alcohols ethoxylated with 1 to 6, preferably 1 to 2, moles of ethylene oxide are also very suitable. Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
Die anionischen Tenside liegen üblicherweise in Form ihrer Natriumsalze vor. Ihr Anteil, bezogen auf das Mittel, beträgt im allgemeinen 0 bis 25 Gew.-%, vorzugsweise 3 bis 20 Gew.-% einschließlich der Dialkylethersulfate.The anionic surfactants are usually in the form of their sodium salts. Their proportion, based on the composition, is generally 0 to 25% by weight, preferably 3 to 20% by weight, including the dialkyl ether sulfates.
Als nichtionische Tenside werden vorzugsweise Anlagerungsprodukte von 2 bis 20, vorzugsweise 3 bis 15 Mol Ethylenoxid an 1 Mol einer Verbindung mit im wesentlichen 10 bis 20 Kohlenstoffatomen aus der Gruppe der Alkohole verwendet. Hierzu zählen wasserlösliche Anlagerungsprodukte von 7 bis 15 Mol Ethylenoxid an primäre Alkohole, wie z. B. an Kokos- oder Talgfettalkohole, an Oleylalkohol, an Oxoalkohole oder an sekundäre Alkohole mit 8 bis 18, vorzugsweise 12 bis 20 C-Atomen. Neben diesen wasserlöslichen Nonionics sind aber auch nicht bzw. nicht vollständig wasserlösliche Polyglykolether mit 2 bis 6 Ethylenglykoletherresten und gleicher C-Kettenlänge von Interesse, die sich durch ein erhöhtes Reinigungsvermögen gegenüber fettartigen Verschmutzungen auszeichnen.Addition products of 2 to 20, preferably 3 to 15 moles of ethylene oxide with 1 mole of a compound having essentially 10 to 20 carbon atoms from the group of alcohols are preferably used as nonionic surfactants. These include water-soluble adducts of 7 to 15 moles of ethylene oxide with primary alcohols, such as. B. on coconut or tallow fatty alcohols, on oleyl alcohol, on oxo alcohols or on secondary alcohols having 8 to 18, preferably 12 to 20 carbon atoms. In addition to these water-soluble nonionics, non-completely or not completely water-soluble polyglycol ethers with 2 to 6 ethylene glycol ether residues and the same C chain length are also of interest, which are distinguished by an increased cleaning ability against greasy soiling.
Weitere geeignete nichtionische Tenside sind Alkylglycoside bzw. Alkyloligoglycoside, deren Alkylgruppe 8 bis 18, vorzugsweise 10 bis 16 C-Atome aufweist. Der Gehalt der Mittel an nichtionischen Tensiden bzw. nichtionischen Tensidgemischen beträgt 0 bis 25 Gew.-%, vorzugsweise 1 bis 20 Gew.-% und insbesondere 2 bis 15 Gew.-%.Further suitable nonionic surfactants are alkyl glycosides or alkyl oligoglycosides, the alkyl group of which has 8 to 18, preferably 10 to 16, carbon atoms. The content of the agents in nonionic surfactants or nonionic surfactant mixtures is 0 to 25 % By weight, preferably 1 to 20% by weight and in particular 2 to 15% by weight.
Als zwitterionische Tenside eignen sich solche mit Betain-Struktur sowie die bekannten Sulfobetaine. Kationische Tenside, beispielsweise quartäre Ammoniumsalze mit einer C₁₀₋₁₆-Alkylkette und drei niederen Alkylgruppen, vorzugsweise Methylgruppen, können ebenfalls mitverwendet werden. Bei einem Gewichtsverhältnis von Aniontensid (einschließlich Dialkylethersulfat) zu Kationtensid von 3 : 1 bis 25 : 1 können sie die Waschkraft der Mittel erhöhen, insbesondere gegenüber fetthaltigen Anschmutzungen.Suitable zwitterionic surfactants are those with a betaine structure and the known sulfobetaines. Cationic surfactants, for example quaternary ammonium salts with a C₁₀₋₁₆ alkyl chain and three lower alkyl groups, preferably methyl groups, can also be used. With a weight ratio of anionic surfactant (including dialkyl ether sulfate) to cationic surfactant of 3: 1 to 25: 1, they can increase the washing power of the detergents, especially in relation to fatty stains.
Der Gesamtgehalt der Mittel an Tensiden hängt vom Verwendungszweck ab und beträgt 1 bis 50 Gew.-%. In festen Mitteln beträgt er vorzugsweise 5 bis 30 Gew.-% und insbesondere 8 bis 25 Gew.-%. In flüssigen, buildersalzfreien Mitteln ist er in der Regel höher und beträgt 15 bis 50 Gew.-%, vorzugsweise 20 bis 45 Gew.-%.The total content of surfactants in the detergents depends on the intended use and is 1 to 50% by weight. In solid compositions it is preferably 5 to 30% by weight and in particular 8 to 25% by weight. In liquid, builder salt-free agents, it is generally higher and is 15 to 50% by weight, preferably 20 to 45% by weight.
Die Komponente (b) besteht aus Buildersalzen und Sequestrierungsmitteln, die einzeln oder im Gemisch untereinander die Kalkhärte des Wassers binden oder ausfällen oder störende Schwermetallionen komplex binden und damit die Reinigungskraft erhöhen und eine unerwünschte Zersetzung empfindlicher Bestandteile, wie Perverbindungen und Enzyme, verhindern.Component (b) consists of builder salts and sequestering agents, which, individually or in a mixture, bind or precipitate the lime hardness of the water or precipitate or complexly bind disruptive heavy metal ions and thus increase the cleaning power and prevent undesired decomposition of sensitive components such as per-compounds and enzymes.
Geeignete Bestandteile der Komponente (b) sind insbesondere ökologisch unbedenkliche Buildersalze, wie feinkristalline, synthetische wasserhaltige Zeolithe vom Typ NaA, die ein Calciumbindevermögen im Bereich von 100 bis 200 mg CaO/g (gemäß den Angaben in DE 22 24 837) aufweisen. Ihre Teilchengröße liegt üblicherweise im Bereich von 1 bis 10 µm. In festen oder pastenförmigen Mitteln beträgt ihr Gehalt im allgemeinen 0 bis 40, vorzugsweise 10 bis 30 Gew.-%, bezogen auf wasserfreie Substanz.Suitable components of component (b) are, in particular, ecologically harmless builder salts, such as finely crystalline, synthetic water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 22 24 837). Their particle size is usually in the range from 1 to 10 μm. In solid or pasty form their content is generally 0 to 40, preferably 10 to 30,% by weight, based on the anhydrous substance.
Als weitere Bestandteile der Komponente (b), die insbesondere zusammen mit den Zeolithen eingesetzt werden, kommen (co-)polymere Polycarboxylate in Betracht, wie Polyacrylate, Polymethacrylate und insbesondere Copolymere der Acrylsäure mit Maleinsäure, vorzugsweise solche aus 50 % bis 10 % Maleinsäure. Das Molekulargewicht der Homopolymeren liegt im allgemeinen zwischen 1 000 und 100 000, das der Copolymeren zwischen 2 000 und 200 000, vorzugsweise 50 000 bis 120 000, bezogen auf freie Säure. Ein besonders bevorzugtes Acrylsäure-Maleinsäure-Copolymer weist ein Molekulargewicht von 50 000 bis 100 000 auf.Other components of component (b) which are used in particular together with the zeolites are (co) polymeric polycarboxylates, such as polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50% to 10% maleic acid. The molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copolymere der Acrylsäure oder Methacrylsäure mit Vinylethern, wie Vinylmethylether, in denen der Anteil der Säure mindestens 50 % beträgt. Brauchbar sind ferner Polyacetalcarbonsäuren, wie sie beispielsweise in den US-Patentschriften 4 144 226 und 4 146 495 beschrieben sind und durch Polymerisation von Estern der Glykolsäure, Einführung stabiler terminaler Endgruppen und Verseifung zu den Natrium- oder Kaliumsalzen erhalten werden. Geeignet sind ferner polymere Säuren, die durch Polymerisation von Acrolein und Disproportionierung des Polymers nach Canizzaro mittels starker Alkalien erhalten werden. Sie sind im wesentlichen aus Acrylsäureeinheiten und Vinylalkoholeinheiten beziehungsweise Acroleineinheiten aufgebaut.Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, in which the proportion of acid is at least 50%. Also useful are polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, which are obtained by polymerizing esters of glycolic acid, introducing stable terminal end groups, and saponifying to give the sodium or potassium salts. Also suitable are polymeric acids which are obtained by polymerizing acrolein and disproportionating the polymer according to Canizzaro using strong alkalis. They are essentially made up of acrylic acid units and vinyl alcohol units or acrolein units.
Der Gehalt der Mittel an (co-)polymeren Polycarbonsäuren beträgt, auf freie Säure bezogen 0 bis 15 Gew.-%, vorzugsweise 0,5 bis 10 Gew.-% und insbesondere 1 bis 5 Gew.-%.The content of (co) polymeric polycarboxylic acids in the composition, based on free acid, is 0 to 15% by weight, preferably 0.5 to 10% by weight and in particular 1 to 5% by weight.
Zu den Bestandteilen der Komponente (b) zählen weiterhin Nitrilotriacetat (NTA), vorzugsweise in Form des Natriumsalzes, sowie Polycarbonsäuren, wie Citronensäure, ebenfalls bevorzugt als Natriumsalz. Weiterhin kommen die Salze von Polyphosphonsäuren, insbesondere 1-Hydroxyethan-1,1-diphosphonsäure, ggf. auch Aminoalkanpolyphosphonsäure in Betracht, wie Aminotrimethylenphosphonsäure (ATP), Ethylendiamin-tetramethylenphosphonat (EDTMP), Diethylentriamin-pentamethylenphosphonat (DTPMP), sowie deren höhere Homologe. Sie werden vorzugsweise in Form der neutral reagierenden Natriumsalze, z. B. als Hexanatriumsalz der EDTMP bzw. als Hepta- und Octa-Natriumsalz der DTPMP, eingesetzt. Ihr Anteil in den Mitteln, auf freie Säure berechnet, beträgt allgemein 0 bis 3 Gew.-%, insbesondere 0,1 bis 1,5 Gew.-%.The components of component (b) also include nitrilotriacetate (NTA), preferably in the form of the sodium salt, and polycarboxylic acids, such as citric acid, likewise preferably as the sodium salt. Furthermore, the salts of polyphosphonic acids, in particular 1-hydroxyethane-1,1-diphosphonic acid, possibly also aminoalkane polyphosphonic acid, such as aminotrimethylenephosphonic acid (ATP), ethylenediamine-tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMPe) and their higher homologue are also suitable. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. Their proportion in the compositions, calculated on free acid, is generally 0 to 3% by weight, in particular 0.1 to 1.5% by weight.
In Fällen, in denen ein Phosphat-Gehalt toleriert wird, können auch Phosphate mitverwendet werden, insbesondere Pentanatriumtriphosphat, ggf. auch Pyrophosphate, die aufgrund ihrer Löslichkeitseigenschaften in Flüssigwaschmitteln eingesetzt werden können, sowie Orthophosphate, die in erster Linie als Fällungsmittel für Kalksalze wirken. Vorzugsweise soll jedoch der Gehalt an Phosphaten, bezogen auf Pentanatriumtriphosphat, unter 30 Gew.-%, insbesondere unter 20 Gew.-% liegen.In cases where a phosphate content is tolerated, phosphates can also be used, in particular pentasodium triphosphate, possibly also pyrophosphates, which due to their solubility properties can be used in liquid detergents, as well as orthophosphates, which primarily act as precipitants for lime salts. However, the phosphate content, based on pentasodium triphosphate, should preferably be below 30% by weight, in particular below 20% by weight.
Zu den Bestandteilen der Komponente (b) zählen ferner Waschalkalien wie Alkalimetallsilicate, insbesondere Natriumsilicate der Zusammensetzung Na₂O : SiO₂ = 1 : 1 bis 1 : 3,5, vorzugsweise 1 : 2 bis 1 : 3,35. Ihr Anteil in den Mitteln kann 0 bis 8 Gew.-%, insbesondere 2 bis 5 Gew.-% betragen, wobei in Gegenwart von Zeolithen ihr Anteil vorzugsweise 3 Gew.-% nicht wesentlich übersteigt.The components of component (b) also include washing alkalis such as alkali metal silicates, in particular sodium silicates of the composition Na₂O: SiO₂ = 1: 1 to 1: 3.5, preferably 1: 2 to 1: 3.35. Their proportion in the agents can be 0 to 8% by weight, in particular 2 to 5% by weight, with their proportion preferably not substantially exceeding 3% by weight in the presence of zeolites.
Als Waschalkali kommt ferner Natriumcarbonat in Frage, dessen Anteil bis zu 20 Gew.-%, vorzugsweise 2 bis 15 Gew.-% und insbesondere 5 bis 10 Gew.-% beträgt.Also suitable as washing alkali is sodium carbonate, the proportion of which is up to 20% by weight, preferably 2 to 15% by weight and in particular 5 to 10% by weight.
Zu den sonstigen Waschmittelbestandteilen (Komponente c), deren Anteil je nach Zusammensetzung der Mittel bis 80, vorzugsweise bis 50 Gew.-% und insbesondere 5 bis 40 Gew.-% beträgt, zählen Vergrauungsinhibitoren (Schmutzträger), Bleichmittel, Bleichaktivatoren, optische Aufheller, Schauminhibitoren, Enzyme, textilweichmachende Stoffe, Farb- und Duftstoffe sowie Neutralsalze, Lösungsmittel und Wasser.The other detergent components (component c), the proportion of which, depending on the composition of the detergent, is up to 80, preferably up to 50% by weight and in particular 5 to 40% by weight, include graying inhibitors (dirt carriers), bleaching agents, bleach activators, optical brighteners, Foam inhibitors, enzymes, fabric softening agents, colors and fragrances as well as neutral salts, solvents and water.
Als Bestandteil dieser Komponente (c) können die Wasch- und Reinigungsmittel Vergrauungsinhibitoren enthalten, die den von der Faser abgelösten Schmutz in der Flotte suspendiert halten und so das Vergrauen verhindern. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, wie beispielsweise die wasserlöslichen Salze polymerer Carbonsäuren, Leim, Gelantine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich lösliche Stärkepräparate und andere als die oben genannten Stärkeprodukte verwenden, wie z. B. abgebaute Stärke, Aldehydstärken usw.. Auch Polyvinylpyrrolidon ist brauchbar. Carboxymethylcellulose (Na-Salz), Methylcellulose, Methylhydroxyethylcellulose und deren Gemische werden bevorzugt eingesetzt. Der Anteil der Verbindungen beträgt im allgemeinen 0,2 bis 2, vorzugsweise 0,5 bis 1,5 Gew.-%.As a component of this component (c), the washing and cleaning agents can contain graying inhibitors, which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying. For this purpose, water-soluble colloids of mostly organic nature are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof are preferably used. The proportion of the compounds is generally 0.2 to 2, preferably 0.5 to 1.5,% by weight.
Unter den als Bleichmittel dienenden, in Wasser H₂O₂ liefernden Verbindungen haben das Natriumperborat-tetrahydrat (NaBO₂ ·H₂O₂ · 3 H₂O) und das -monohydrat (NaBO₂ · H₂O₂) besondere Bedeutung. Brauchbar sind auch Peroxycarbonat (Na₂CO₃ · 1,5 H₂O₂), Peroxypyrophosphate, Citratperhydrate, Harnstoffperhydrat oder Melaminperhydrat sowie H₂O₂ liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxyphathalate, Diperazelainsäure oder Diperdodekandisäure.Of the compounds used as bleaching agents which supply H₂O₂ in water, sodium perborate tetrahydrate (NaBO₂ · H₂O₂ · 3 H₂O) and monohydrate (NaBO₂ · H₂O₂) are of particular importance. Peroxy carbonate (Na₂CO₃ · 1.5 H₂O₂), peroxypyrophosphates, citrate perhydrates, urea perhydrate or melamine perhydrate as well as H₂O₂-delivering peracidic salts or peracids such as perbenzoates, peroxyphathalates, diperazelaic acid or diperdodecanedioic acid can also be used.
Um beim Waschen bei Temperaturen unterhalb 80 °C, insbesondere im Bereich von 40 bis 60 °C, eine verbesserte Bleichwirkung zu erreichen, können Bleichaktivatoren in die Präparate eingearbeitet werden. Beispiele hierfür sind mit H₂O₂ organische Persäuren bildende N-Acyl- bzw. O-Acyl-Verbindungen, vorzugsweise N,N′-tetraacylierte Diamine, wie N,N,N′,N′-Tetraacetyl-ethylendiamin, ferner Carbonsäureanhydride und Ester von Polyolen, wie Glucosepentaacetat.In order to achieve an improved bleaching effect when washing at temperatures below 80 ° C., in particular in the range from 40 to 60 ° C., bleach activators can be incorporated into the preparations. Examples include N-acyl or O-acyl compounds which form organic peracids with H₂O₂, preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetyl-ethylenediamine, furthermore carboxylic anhydrides and esters of polyols such as glucose pentaacetate.
Die Waschmittel können als optische Aufheller für Baumwolle insbesondere Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z. B. Salze der 4,4′-Bis(2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino)-stilben-2,2′-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholinogruppe eine Diethanolaminogruppe, eine Methylaminogruppe oder eine 2-Methoxyethylaminogruppe tragen. Als Aufheller für Polyamidfasern kommen solche vom Typ der 1,3-Diaryl-2-pyrazoline in Frage, beispielsweise die Verbindung 1-(p-Sulfamoylphenyl)-3-(p-chlorphenyl)-2-pyrazolin. Weiterhin können Aufheller vom Typ des substituierten 4,4′-Distyryl-diphenyls anwesend sein; z. B. die Verbindung 4,4′-Bis-(4-chlor-3-sulfo styryl)-diphenyl. Auch Gemische der vorgenannten Aufheller können verwendet werden.The detergents can contain, as optical brighteners for cotton, in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Are suitable for. B. salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure, which instead of Morpholino group carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Possible brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type, for example the compound 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline. Brighteners of the substituted 4,4'-distyryl-diphenyl type may also 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.
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen und Amylasen bzw. deren Gemische in Frage. Besonders geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheniformis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen.Enzymes from the class of proteases, lipases and amylases or mixtures thereof are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
Geeignete Schauminhibitoren sind Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure, Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure. Auch von C₁₂₋₂₀-Alkylaminen und C₂₋₆-Dicarbonsäuren abgeleitete Bis-acylamide sind brauchbar. Mit Vorteil werden auch Gemische verschiedener Schauminhibitoren verwendet, z. B. solche aus Silikonen und Paraffinen oder Wachsen. Vorzugsweise sind die Schauminhibitoren an eine granulare, in Wasser lösliche bzw. dispergierbare Trägersubstanz gebunden.Suitable foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Bis-acylamides derived from C₁₂₋₂₀ alkylamines and C₂₋₆ dicarboxylic acids are also useful. Mixtures of different foam inhibitors are also advantageously used, e.g. B. from silicone and paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
Als textilweichmachende Zusätze eignen sich Schichtsilikate aus der Klasse der Bentonite und Smectite, z. B. solche gemäß DE 23 34 899 und EP 265 529. Geeignet sind ferner synthetische feinteilige Schichtsilikate mit smectitähnlicher Kristallphase und verringertem Quellvermögen, wie sie in DE 35 26 405 (US 4 737 306) näher gekennzeichnet sind. Der Gehalt an Schichtsilikaten kann beispielsweise bis 20 Gew.-% betragen.Layered silicates from the bentonite and smectite class, e.g. B. those according to DE 23 34 899 and EP 265 529. Also suitable are synthetic finely divided sheet silicates with smectite-like crystal phase and reduced swelling capacity, as are characterized in more detail in DE 35 26 405 (US 4,737,306). The layered silicate content can be, for example, up to 20% by weight.
Die Herstellung pulverförmiger bis granularer Mittel kann in üblicher Weise, d. h. durch Sprühtrocknen der unter diesen Bedingungen beständigen Bestandteile und anschließendes Zumischen der hitzeempfindlichen Komponenten, wie Bleichmittel, Enzyme, Duftstoffe und Schauminhibitoren erfolgen. Weitere geeignete Verfahren sind das Granulieren der Bestandteile, wobei Wasser, Salzlösungen, Polymerlösungen und/oder nichtionische Tenside als Granulierflüssigkeit verwendet werden können.The preparation of powdery to granular agents can be carried out in a conventional manner, ie by spray drying them Conditions resistant components and then admixing the heat-sensitive components such as bleach, enzymes, fragrances and foam inhibitors. Other suitable processes are the granulation of the constituents, water, salt solutions, polymer solutions and / or nonionic surfactants being able to be used as the granulation liquid.
Als Testgemische wurden die folgenden granularen bzw. flüssigen Waschmittel verwendet. Um bei der Remissionsmessung keine Störungen durch optische Aufheller zu erhalten, wurden aufhellerfreie Gemische und nicht optisch aufgehellte Testgewebe verwendet. In der Praxis würden die Gemische zwischen 0,1 und 0,5 Gew.-% herkömmlicher Aufheller enthalten.
Es handelt sich demnach um ein phosphatreduziertes pulverförmiges Waschmittel I, ein phosphatfreies pulverförmiges Waschmittel II und ein phosphatfreies Flüssigwaschmittel III. Es bedeuten
AA-MA-Copolymer = Na-Salz eines Acrylsäure-Maleinsäure-Copolymer, Molekulargewicht 70 000
Phosphonat = Na-Salz der Diethylentriamin-pentamethylen-phosphonsäure
Celluloseether = Gemische aus Carboxymethylcellulose und Hydroxyethylmethylcellulose
Wasser = Gesamter Wassergehalt einschließlich des an Zeolith und als Kristallwasser gebundenen Wassers.It is therefore a phosphate-reduced powder detergent I, a phosphate-free powder detergent II and a phosphate-free liquid detergent III. Mean it
AA-MA copolymer = Na salt of an acrylic acid-maleic acid copolymer, molecular weight 70,000
Phosphonate = Na salt of diethylenetriamine-pentamethylene-phosphonic acid
Cellulose ether = mixtures of carboxymethyl cellulose and hydroxyethyl methyl cellulose
Water = total water content including water bound to zeolite and crystal water.
Als synthetisches Aniontensid wurde in den Vergleichsversuchen (Bezeichnung V) lineares C₁₀₋₁₃-Alkylbenzolsulfonat-Na-Salz (Abkürzung LAS) verwendet, das in den erfindungsgemäßen Versuchen durch Dialkylethersulfate (Na-Salze) gemäß Formel I ersetzt wurden. In allen Verbindungen waren R² und R⁴ = H und M = Na. Die übrigen Symbole hatten die in Tabelle 2 angegebene Bedeutung, wobei die Zahlen die Anzahl der C-Atome in R¹ und R³ bzw. der EO-Gruppen (n) bedeuten.
Die Mittel wurden im Launderometer (Abkürzung LM) sowie in einer Haushaltsmaschine (Abkürzung WM) mit horizontal angeordneter frontbeladener Trommel verwendet, wobei im letzteren Fall ein automatisches Einlaugen-Verfahren (ohne Vorwäsche) einprogrammiert wurde. Die Wasserhärte betrug 16 °d (entsprechend 160 mg CaO pro Liter). Die Waschtemperatur und die Waschmittelkonzentration (in g/l) sind in der Tabelle aufgeführt. Es wurden unter standardisierten Bedingungen angeschmutzte Textillappen verwendet, die bei Verwendung der Waschmaschine zusammen mit 3 kg sauberer Füllwäsche gewaschen wurden. Es kamen folgende Testanschmutzungen zum Einsatz:
- A1 Pigment/Hautfettanschmutzung auf Baumwolle und veredelter Baumwolle,
- A2 Mineralölanschmutzung auf Mischgewebe aus Polyesterfäser und veredelter Baumwolle,
- A3 Make up auf Mischgewebe gemäß A2.
- A1 pigment / skin fat contamination on cotton and finished cotton,
- A2 mineral oil contamination on mixed fabrics made of polyester fiber and finished cotton,
- A3 make-up on blended fabrics according to A2.
Die prozentuale Remission (Abkürzung % R) wurde photometrisch bestimmt. Die in den folgenden Tabellen angegebenen Werte sind Mittelwerte aus 3 Bestimmungen innerhalb eines Streuungsbereiches von 2 %. Ein Remissionsunterschied von 2 % ist auch mit dem bloßen Auge noch gut erkennbar und entspricht somit einem vom Verbraucher wahrnehmbaren Effekt.The percentage remission (abbreviation% R) was determined photometrically. The values given in the following tables are mean values from 3 determinations within a range of 2%. A remission difference of 2% is still clearly visible to the naked eye and therefore corresponds to an effect perceptible by the consumer.
Die Ergebnisse zeigen, daß die Waschkraft der Dialkylethersulfate in der Größenordnung von kommerziellen Dodecylbenzolsufonat liegt und diese sogar teilweise übertrifft.The results show that the washing power of the dialkyl ether sulfates is of the order of magnitude of commercial dodecylbenzenesulfonate and even exceeds it in some cases.
Bei der Prüfung auf biologische Abbaufähigkeit ergaben sich nach Standardtests angegeben in % MBAS (Methylenblau-aktive Substanz) und % BiAS (Wismut-aktive Substanz) im OECD-Screening-Test Werte für den Primärabbau zwischen 92 und 99 %. Die Fischtoxicität (in Milligramm Aktivsubstanz pro Liter) ergab Werte für LCo von 2 mg/l bis 22 mg/l und 118 mg/l mit Mittelwerten von LCo = 7,5 g/l und LC₁₀₀ = 22 g/l. Die Vergleichswerte für Dodecylbenzolsulfonat sind um ca. das 3fache bis 5fache niedriger und somit entsprechend ungünstiger. Gegenüber üblichen Nonionics ist die Fischtoxicität um den Faktor 6fach bis 8fach geringer. Die Bakterientoxicität aller Proben, die nach dem Sauerstoffzehrungstest gegenüber B. Robra getestet wurde, lag über 10 000 mg AS/l (Aktivsubstanz pro Liter) und ist damit als sehr gering einzustufen.
Claims (8)
a) 1 bis 50 Gew.-% mindestens eines anionischen oder kationischen Tensids,
b) 1 bis 90 Gew.-% mindestens einer Verbindung aus der Klasse der Buildersalze und Sequestrierungsmittel und
c) Differenz bis 100 Gew.-% an sonstigen üblichen Wasch- und Reinigungsmittelbestandteilen,
dadurch gekennzeichnet, daß die Komponente (a) ganz oder teilweise aus einem sekundären Dialkylethersulfat der allgemeinen Formel I besteht:
a) 1 to 50% by weight of at least one anionic or cationic surfactant,
b) 1 to 90% by weight of at least one compound from the class of the builder salts and sequestering agents and
c) difference of up to 100% by weight of other usual detergent and cleaning agent components,
characterized in that component (a) consists wholly or partly of a secondary dialkyl ether sulfate of the general formula I:
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3839016A DE3839016A1 (en) | 1988-11-18 | 1988-11-18 | WASHING AND CLEANING AGENTS WITH SEK CONTENT. Dialkyl ether sulfates |
DE3839016 | 1988-11-18 |
Publications (1)
Publication Number | Publication Date |
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EP0369317A1 true EP0369317A1 (en) | 1990-05-23 |
Family
ID=6367416
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89912966A Pending EP0444094A1 (en) | 1988-11-18 | 1989-11-09 | Washing and cleansing agents containing secondary dialkyl ether sulphates |
EP19890120755 Withdrawn EP0369317A1 (en) | 1988-11-18 | 1989-11-09 | Washing and cleaning agents containing sec. dialkylether sulfates |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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EP89912966A Pending EP0444094A1 (en) | 1988-11-18 | 1989-11-09 | Washing and cleansing agents containing secondary dialkyl ether sulphates |
Country Status (6)
Country | Link |
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EP (2) | EP0444094A1 (en) |
JP (1) | JPH04501735A (en) |
KR (1) | KR900701985A (en) |
DE (1) | DE3839016A1 (en) |
DK (1) | DK94191A (en) |
WO (1) | WO1990005769A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004058664A2 (en) * | 2002-12-20 | 2004-07-15 | Cognis Ip Management Gmbh | Alkyl monoglycerin ether derivatives |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP4699726B2 (en) * | 2004-09-15 | 2011-06-15 | 株式会社Adeka | Surfactant composition |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2333974A1 (en) * | 1972-07-20 | 1974-01-31 | Colgate Palmolive Co | LIQUID DETERGENT |
DE2132300B2 (en) * | 1970-06-29 | 1979-06-07 | Ethyl Corp., Richmond, Va. (V.St.A.) | Detergent mixture |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5959212A (en) * | 1982-09-28 | 1984-04-05 | Toyobo Co Ltd | Cellulose ether gas separation membrane |
JPS6227025A (en) * | 1985-07-29 | 1987-02-05 | Teijin Ltd | Composite membrane for separating gas |
-
1988
- 1988-11-18 DE DE3839016A patent/DE3839016A1/en not_active Withdrawn
-
1989
- 1989-11-09 JP JP2500161A patent/JPH04501735A/en active Pending
- 1989-11-09 WO PCT/EP1989/001337 patent/WO1990005769A1/en not_active Application Discontinuation
- 1989-11-09 KR KR1019900701541A patent/KR900701985A/en not_active Application Discontinuation
- 1989-11-09 EP EP89912966A patent/EP0444094A1/en active Pending
- 1989-11-09 EP EP19890120755 patent/EP0369317A1/en not_active Withdrawn
-
1991
- 1991-05-17 DK DK094191A patent/DK94191A/en not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2132300B2 (en) * | 1970-06-29 | 1979-06-07 | Ethyl Corp., Richmond, Va. (V.St.A.) | Detergent mixture |
DE2333974A1 (en) * | 1972-07-20 | 1974-01-31 | Colgate Palmolive Co | LIQUID DETERGENT |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004058664A2 (en) * | 2002-12-20 | 2004-07-15 | Cognis Ip Management Gmbh | Alkyl monoglycerin ether derivatives |
WO2004058664A3 (en) * | 2002-12-20 | 2004-09-02 | Cognis Deutschland Gmbh | Alkyl monoglycerin ether derivatives |
Also Published As
Publication number | Publication date |
---|---|
DK94191D0 (en) | 1991-05-17 |
DE3839016A1 (en) | 1990-05-23 |
EP0444094A1 (en) | 1991-09-04 |
KR900701985A (en) | 1990-12-05 |
DK94191A (en) | 1991-05-17 |
JPH04501735A (en) | 1992-03-26 |
WO1990005769A1 (en) | 1990-05-31 |
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