Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • 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
• • 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
• • 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
• • 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
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—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
• • 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
• • 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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• 1988
  • 1988-11-18 DE DE3839016A patent/DE3839016A1/de not_active Withdrawn
• 1989
  • 1989-11-09 JP JP2500161A patent/JPH04501735A/ja active Pending
  • 1989-11-09 WO PCT/EP1989/001337 patent/WO1990005769A1/fr not_active Application Discontinuation
  • 1989-11-09 EP EP89912966A patent/EP0444094A1/fr active Pending
  • 1989-11-09 EP EP19890120755 patent/EP0369317A1/fr not_active Withdrawn
  • 1989-11-09 KR KR1019900701541A patent/KR900701985A/ko not_active Application Discontinuation
• 1991
  • 1991-05-17 DK DK91941A patent/DK94191D0/da not_active Application Discontinuation

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