EP1058722B1 - Tenside combination containing special anionic tensides - Google Patents

Tenside combination containing special anionic tensides Download PDF

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Publication number
EP1058722B1
EP1058722B1 EP99910234A EP99910234A EP1058722B1 EP 1058722 B1 EP1058722 B1 EP 1058722B1 EP 99910234 A EP99910234 A EP 99910234A EP 99910234 A EP99910234 A EP 99910234A EP 1058722 B1 EP1058722 B1 EP 1058722B1
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EP
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Prior art keywords
weight
alkyl
alkyl sulfates
carbon atoms
percentage
Prior art date
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EP99910234A
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German (de)
French (fr)
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EP1058722A1 (en
Inventor
Georg Meine
Andreas Syldath
Dieter Nickel
Thomas Müller-Kirschbaum
Dagmar Zaika
Ansgar Behler
Hans-Christian Raths
Peter Sandkühler
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D1/37—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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • 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
    • 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
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • 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
    • C11D1/75—Amino oxides

Definitions

  • the present invention relates to a surfactant combination, the special fatty alkyl sulfates contains in combination with alkylbenzenesulfonates.
  • the laundry detergent the claim directed that at the washing temperatures applied over the whole Range of soiling found in household laundry, such as dust and Skin fat, cosmetics and pigments, which are essentially from the food, means decorative cosmetics (lipstick, make-up, ointments, etc.) care products, such as Shoe polish or from general (street) dirt, an even and have very high washing activity.
  • the washing activity of most of the prior art Technology-known surfactant combinations have a maximum performance at higher Temperatures.
  • alkylbenzenesulfonates are for example especially effective against lipstick stains, they show however a weakness against dust and skin fat.
  • a surfactant system described which is based on alkyl sulfates derived from natural raw materials, the contain a mixture of alkyl chain lengths, the alkyl sulfates Weight distribution of the alkyl chain lengths have less than 20% by weight Alkyl chains with 12 carbon atoms, from 30 to 80% by weight alkyl chains with 14 Carbon atoms, from 30 to 50 wt .-% alkyl chains with 16 carbon atoms and contain less than 10% by weight alkyl chains with 18 carbon atoms.
  • alkyl sulfates are known to be at lower washing temperatures have no uniform activity towards all stains. Your The best are dust / skin fat / soiling.
  • composition contains (a) an alkyl sulfate surfactant system that is a mixture of alkyl chain lengths contains, the weight distribution of the alkyl chains is such that less than 20 % By weight of the alkyl chains have a chain length of less than 14.
  • composition (b) contains a nonionic surfactant and (c) one Zeolite builder, the zeolite P with a ratio of Si: Al not greater than 1.33 (Zeolite MAP).
  • GB-A-2 289 687 discloses a powder detergent with a density of Described at least 650 g / l, which (a) from 1 to 50 wt .-% of a surfactant system contains, (b) from 2 to 25% by weight of a potassium salt and (c) at least 1% by weight of one Builders.
  • the surfactant system contains at least 30% by weight of a sulfated surfactant which is selected from the group of alkyl sulfates, alkyl ethoxy sulfates, secondary Alkyl sulfates and mixtures thereof. Examples of alkyl sulfates are alkyl sulfates with 14 to 16 carbon atoms in the carbon chain.
  • the object of the present invention was to provide a surfactant system to provide that in powdery to granular as well as in liquid washing and Detergents can be used and improved washing performance over a The largest possible selection of different types of contamination is available put. Furthermore, the surfactant system should contain components that are commercially available reasonable prices are available and have ecologically favorable properties.
  • the present invention accordingly relates to a surfactant combination for use in detergents and cleaning agents containing C 12 -C 18 alkyl sulfates, the proportion of carbon chains with less than 14 carbon atoms being less than 10%, based on the content of C 12 - C 18 alkyl sulfate, and C 9 -C 13 alkyl benzene sulfonates in a ratio of 1:10 to 10: 1.
  • the proportion of carbon chains with more than 16 carbon atoms in the C 12 -C 18 alkyl sulfates used is less than 10% by weight, based on the content of C 12 -C 18 alkyl sulfates.
  • the proportion of carbon chains with more than 16 carbon atoms in the C 12 -C 18 alkyl sulfates used is above 10 and below 20% by weight, based on the content of C 12 -C 18 alkyl sulfates.
  • the C 12 -C 18 alkyl sulfates contained in the surfactant combination according to the invention are known anionic surfactants which can be obtained by sulfonating the corresponding alcohols.
  • the desired carbon chain cut can be set by using the corresponding alcohols produced from natural raw material sources or synthetically with an appropriate chain length distribution or by using corresponding, pure starting compounds.
  • the C 9 -C 13 alkylbenzenesulfonates are also known anionic surfactants which can be obtained by sulfonating the C 9 -C 13 monoolefins with a terminal or internal double bond with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • the C 9 -C 13 alkylbenzenesulfonates are usually used; Higher-chain alkylbenzenesulfonates are largely avoided.
  • the C 12 -C 18 alkyl sulfates and the C 9 -C 13 alkyl benzene sulfonates are preferably in a ratio of 1: 1 to 4: 1.
  • the surfactant combination according to the invention is for use in powdery bis granular as well as liquid detergents and cleaning agents.
  • the surfactants can be used as individual substances as well as in the form of compounds be added.
  • the compounds are preferably produced using a granulation process, especially in the fluidized bed.
  • Another subject is accordingly powdery to granular detergents and cleaning agents, the surfactant combination according to the invention in combination with others contain common ingredients.
  • liquid detergents and cleaning agents which are the inventive ones Combination of surfactants, a suitable solvent and possibly other Contain common ingredients.
  • the powdery to granular or liquid washing and cleaning agents according to the invention preferably contain the C 12 -C 18 alkyl sulfates from the surfactant combination in an amount of 1 to 20% by weight, based on the total agent.
  • the C 9 -C 13 alkylbenzenesulfonates are preferably present in the agents according to the invention in an amount of 1 to 20 wt.
  • the agents according to the invention can contain further anionic agents as further constituents Surfactants, nonionic surfactants, builders and possibly other substances that are usually contained in detergents and cleaning agents.
  • anionic surfactants are the C 8 -C 22 olefin sulfonates, C 8 -C 22 alkane sulfonates, C 8 -C 22 alkenyl sulfates, monoesters and / or diesters of alkyl sulfosuccinic acid (sulfosuccinates), C 6 -C 18 alkyl polyglycol ether sulfonates, C 8 -C 22 -Fettklareestersulfonate, C 8 -C 22 -alkyl ether sulfates, glycerol ether, Glycerol ether, Hydroxymischethersulfate, monoglyceride sulfates, Sulfoglyceride, amic acids, C 6 -C 18 -Fettklaramidethersulfate, C 6 -C 18 alkyl (ether) carboxylates, fatty acid isethionates, NC 6
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the content of the agents in further anionic surfactants is preferably up to 10 Wt .-%.
  • the agents C 8 -C 18 alcohol alkoxylates, alkyl polyglycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated alkyl C 8 -C 18 fatty acid esters, N-fatty alkyl amine oxides, polyhydroxy fatty acid amides or mixtures thereof can be used as nonionic surfactants.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as these, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO ,
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • the agents contain as nonionic surfactant C 12 -C 16 fatty alcohol alkoxylates with an average degree of alkoxylation between 5.2 and 5.8, preferably between 5.4 and 5.6.
  • alkyl glycosides of the general formula RO (G) x are alkyl glycosides of the general formula RO (G) x , in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • the content of the nonionic surfactants in the finished compositions is preferably 2 to 45 wt .-%, preferably over 20 wt .-%, the content of nonionic Surfactants in liquid agents are generally above 10% by weight.
  • Suitable inorganic builder substances are, for example, phosphates, preferably Tripolyphosphates, but also orthophosphates and pyrophosphates, as well as zeolite and crystalline Phyllosilicates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) and zeolite A are particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • a cocrystallized sodium / potassium aluminum silicate made of zeolite A and zeolite X which as VEGOBOND AX® (commercial product from Condea Augusta SpA) im Trade is available.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 • y H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number of Is 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline sheet silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 • y H 2 O are preferred.
  • Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and Mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and Mixtures of these.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of Polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 800 to 150,000 (based on acid).
  • Suitable copolymers Polycarboxylates are especially those of acrylic acid with methacrylic acid and Acrylic acid or methacrylic acid with maleic acid.
  • Have proven to be particularly suitable Copolymers of acrylic acid with maleic acid have proven to be 50 to 90% by weight of acrylic acid and contain 50 to 10% by weight of maleic acid.
  • Their relative molecular mass, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • the content of the agents in (co) polymers Polycarboxylates is preferably 1 to 8% by weight, in particular 2 to 6% by weight.
  • biodegradable polymers made from more than two different ones Monomer units, for example those which according to DE-A-43 00 772 as Monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C42 21 381 as monomer salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives.
  • polyacetals which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups, for example as in the European patent application EP-A-0 280 223 can be obtained.
  • Preferred polyacetals will be from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
  • alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 2 and 15% by weight.
  • the sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • bleaching agents that serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • the bleach content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.
  • Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, 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, acidic Group-containing polyamides are suitable for this purpose.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt) are preferred.
  • Methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their Mixtures and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the funds used.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • the salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepenta-methylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5 wt .-% used.
  • the agents can be derivatives of diaminostilbenedisulfonic acid or whose alkali metal salts contain. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds which instead of the morpholino group a diethanolamino group, a Carry a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g.
  • bleach activators are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably polyacrylicized alkylenediamines such as N, N'tetraacylated diamines, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles , Triazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid esters such as p- (alkanoyloxy) benzenesulfonate, in particular sodium isononoyloxybenzenesulfonate, and the p- (alkenoyloxy) benzenesulfonate, also caprolactam derivatives, carbonic acid anhydride such as phthalic acid anhydride such as phthalates.
  • polyacrylicized alkylenediamines such as N, N
  • bleach activators are acetylated mixtures of sorbitol and mannitol, as described for example in European patent application EP-A-0 525 239, and acetylated pentaerythritol.
  • the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All these Hydrolases help to remove stains, such as protein, fat or in the laundry starchy stains and graying. Cellulases and others Glycosyl hydrolases can be removed by removing pilling and
  • subtilisin type and in particular proteases obtained from Bacillus lentus are used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and Lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic Enzymes and cellulase, but especially protease and / or lipase-containing Mixtures or mixtures with lipolytically active enzymes of particular Interest.
  • lipolytically active enzymes are the known ones Cutinases. Peroxidases or oxidases have also been found to be suitable in some cases proved.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, Pullulanases and pectinases.
  • Cellobiohydrolases are preferably used as cellulases, Endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or Mixtures of these are used. Because the different types of cellulase are characterized by their CMCase and Avicelase activities can be distinguished by targeted mixtures the desired activities are set for the cellulases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
  • the agents present in liquid form in addition to the Nonionic surfactants usually present as a liquid component also organic solvents, e.g. B. mono- or polyhydric alcohols with 1 to 4 carbon atoms contain.
  • Preferred alcohols are ethanol, 1,2-propanediol, glycerol and their Mixtures.
  • the compositions preferably contain 2 to 12% by weight and in particular 3 to 10 % By weight of ethanol or any mixture of ethanol and glycerin.
  • non-aqueous liquid detergents in addition to the mono- and / or polyfunctional ones short chain alcohols such as ethanol, propylene glycol and / or glycerin liquid organic ethers, for example diisopropyl monomethyl ether, are also preferred.
  • short chain alcohols such as ethanol, propylene glycol and / or glycerin liquid organic ethers, for example diisopropyl monomethyl ether
  • a powdery to granular washing and cleaning agent according to the present invention preferably contains 2 to 20 wt .-% C 12 -C 18 alkyl sulfates, the proportion of carbon chains with less than 14 carbon atoms being less than 10%, based on the content C 12 -C 18 alkyl sulfate, 2 to 20% by weight of C 9 -C 13 alkyl benzene sulfonates, where C 12 -C 18 alkyl sulfates and the C 9 -C 13 alkyl benzene sulfonates in a ratio of 1:10 to 10: 1 are present, 15% by weight to 55% by weight of inorganic and / or organic builders, up to 10% by weight of further anionic surfactants, 1% by weight to 20% by weight of nonionic surfactants, up to 25% by weight .-%, in particular 1% by weight to 15% by weight of bleach, up to 8% by weight, in particular 0.5% by weight to 6% by weight of bleach activator and up to
  • a liquid washing and cleaning agent according to the present invention preferably contains 2 to 20% by weight of C 12 -C 18 alkyl sulfates, the proportion of carbon chains with less than 14 carbon atoms being less than 10%, based on the C 12 content -C 18 alkyl sulfate, 2 to 20% by weight of C 9 -C 13 alkyl benzene sulfonates, the C 12 -C 18 alkyl sulfates and the C 9 -C 13 alkyl benzene sulfonates in a ratio of 1:10 to 10: 1 4 to 25% by weight of liquid nonionic surfactants, up to 10% by weight of solvent, up to 10% by weight of builder substances, up to 3% by weight of enzymes and up to 2% by weight of others in washing - and cleaning agents usual ingredients.
  • Fragrances can also be in the form of solid compounds in particular Powdery to granular detergents and cleaning agents can be incorporated. Such concentrated fragrance compounds can be separated, for example Granulation, compacting, extrusion, pelleting or other agglomeration processes produce. Cyclodextrins, for example, have been used as carrier materials proven, the cyclodextrin-perfume complexes additionally with others Auxiliaries can be coated.
  • the special production of perfume moldings is, for example, in the older German patent application DE-A-197 46 780.6, in which a method is disclosed in which a fixed, in essential anhydrous premix of carriers, optionally auxiliaries and 5 to 25% by weight of perfume is subjected to granulation or press agglomeration.
  • the washing performance was checked under practical conditions in household washing machines type Miele W 918 Novotronic.
  • the machines were weighing 3.5 kg Household linen (bed linen, table linen, underwear) and 0.5 kg test fabric loaded. Both commercially available artificially soiled were used as test fabrics Cotton fabric and polyester / cotton blend as well as with a machine Process of naturally soiled cotton fabrics and polyester / cotton blended fabrics used.
  • test fabrics were with the different stains given below Mistake.
  • the washing effect was determined by measuring the reflectance. (Measurement degree of whiteness: Zeiss reflectometer, 465 nm, suppression of the brightener effect).
  • the Experiments were repeated five times each.
  • the specified remission values are the Average values across all measurements. The results are in Tables 2 and 3 played.
  • Table 3 column 2 shows the average values for the individual types of soiling and column 3 shows the total remission values for all types of soiling.

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Abstract

Surfactant combinations containing C12-18 alkyl sulfates wherein less than 10% by weight of the C12-18 alkyl sulfates, based on the C12-18 alkyl sulfates, have carbon chains with fewer than 14 carbon atoms and C9-13 alkyl benzenesulfonates in a weight ratio of 1:10 to 10:1. The combinations are useful in powder and granular as well as liquid washing and cleaning detergents.

Description

Die vorliegende Erfindung betrifft eine Tensidkombination, die spezielle Fettalkylsulfate in Kombination mit Alkylbenzolsulfonaten enthält.The present invention relates to a surfactant combination, the special fatty alkyl sulfates contains in combination with alkylbenzenesulfonates.

Im Bereich der Textilwäsche in den privaten Haushalten ist in den letzten Jahren die Tendenz zu beobachten, daß die Wäsche bei immer niedrigeren Temperaturen gewaschen wird. Die Hauptwaschtemperaturen liegen zwischen 40 und 60 °C. Auf Kochwäsche wird in den meisten Haushalten verzichtet. Auf der anderen Seite wird aber an die Waschmittel der Anspruch gerichtet, daß die bei den angewendeten Waschtemperaturen über die ganze Bandbreite der in der Haushaltswäsche vorkommenden Verschmutzungen, wie Staub und Hautfett, Kosmetika und Pigmente, die im Wesentlichen aus den Lebensmitteln, Mitteln der dekorativen Kosmetik (Lippenstift, Make-up, Salben etc.) Pflegeartikel, wie Schuhcreme oder aus allgemeinem (Straßen-)Schmutz stammen, eine gleichmäßige und sehr hohe Waschaktivität aufweisen. Die Waschaktivität der meisten aus dem Stand der Technik bekannten Tensidkombinationen hat ein Leistungsmaximum bei höheren Temperaturen. Auch die besonders leistungsstarken waschaktiven Substanzen, wie einige anionische Tenside zeigen ihr Aktivitätsmaximum gegenüber bestimmten Anschmutzungen, nicht aber über die gesamte Bandbreite der im Haushalt vorkommenden Anschmutzungen. So sind die Alkylbenzolsulfonate beispielsweise insbesondere gegenüber Lippenstift-Anschmutzungen besonders wirksam, sie zeigen jedoch eine Schwäche gegenüber Staub und Hautfett.In the field of textile laundry in private households, this has been the case in recent years Tendency to observe that the laundry is washed at ever lower temperatures becomes. The main washing temperatures are between 40 and 60 ° C. On hot laundry waived in most households. On the other hand, the laundry detergent the claim directed that at the washing temperatures applied over the whole Range of soiling found in household laundry, such as dust and Skin fat, cosmetics and pigments, which are essentially from the food, means decorative cosmetics (lipstick, make-up, ointments, etc.) care products, such as Shoe polish or from general (street) dirt, an even and have very high washing activity. The washing activity of most of the prior art Technology-known surfactant combinations have a maximum performance at higher Temperatures. Even the particularly powerful detergent substances, like some anionic surfactants show their maximum activity against certain Soiling, but not across the entire range of household chores occurring soiling. The alkylbenzenesulfonates are for example especially effective against lipstick stains, they show however a weakness against dust and skin fat.

In der internationalen Patentanmeldung WO 95/02390 wird ein Tensidsystem beschrieben, das auf aus natürlichen Rohstoffen stammenden Alkylsulfaten basiert, die ein Gemisch aus Alkylkettenlängen enthalten, wobei die Alkylsulfate eine solche Gewichtsverteilung der Alkylkettenlängen aufweisen, daß sie weniger als 20 Gew.-% Alkylketten mit 12 Kohlenstoffatomen, von 30 bis 80 Gew.-% Alkylketten mit 14 Kohlenstoffatomen, von 30 bis 50 Gew.-% Alkylketten mit 16 Kohlenstoffatomen und weniger als 10 Gew.-% Alkylketten mit 18 Kohlenstoffatomen enthalten. In international patent application WO 95/02390 a surfactant system described, which is based on alkyl sulfates derived from natural raw materials, the contain a mixture of alkyl chain lengths, the alkyl sulfates Weight distribution of the alkyl chain lengths have less than 20% by weight Alkyl chains with 12 carbon atoms, from 30 to 80% by weight alkyl chains with 14 Carbon atoms, from 30 to 50 wt .-% alkyl chains with 16 carbon atoms and contain less than 10% by weight alkyl chains with 18 carbon atoms.

Von den Alkylsulfaten ist jedoch bekannt, daß sie bei niedrigeren Waschtemperaturen keine gleichmäßige Aktivität gegenüber allen Anschmutzungen aufweisen. Ihre Leistungsstärke sind Staub/Hautfett/Anschmutzungen.However, the alkyl sulfates are known to be at lower washing temperatures have no uniform activity towards all stains. Your The best are dust / skin fat / soiling.

Ein weiteres Tensidsystem, das spezielle Fettalkylsulfate enthält, ist in der intern. Patentanmeldung WO 96/21705 offenbart. Die dort beschriebene Tensidzusammensetzung enthält (a) ein Alkylsulfat-Tensidsystem, das ein Gemisch aus Alkylkettenlängen enthält, wobei die Gewichtsverteilung der Alkylketten derart ist, daß weniger als 20 Gew.-% der Alkylketten eine Kettenlänge kleiner als 14 aufweisen. Als weitere Komponenten enthält die Zusammensetzung (b) ein nichtionisches Tensid und (c) einen Zeolithbuilder, der Zeolith P mit einem Verhältnis von Si : Al nicht größer als 1,33 (Zeolith MAP) umfaßt.Another surfactant system that contains special fatty alkyl sulfates is in the intern. Patent application WO 96/21705 disclosed. The surfactant composition described there contains (a) an alkyl sulfate surfactant system that is a mixture of alkyl chain lengths contains, the weight distribution of the alkyl chains is such that less than 20 % By weight of the alkyl chains have a chain length of less than 14. As another Components, composition (b) contains a nonionic surfactant and (c) one Zeolite builder, the zeolite P with a ratio of Si: Al not greater than 1.33 (Zeolite MAP).

In der GB-A-2 289 687 wird ein pulverförmiges Waschmittel mit einer Dichte von mindestens 650 g/l beschrieben, das (a) von 1 bis 50 Gew.-% eines Tensidsystems enthält, (b) von 2 bis 25 Gew.-% eines Caliumsalzes und (c) mindestens 1 Gew.-% eines Builders. Das Tensidsystem enthält mindestens 30 Gew.-% eines sulfatierten Tensids, das ausgewählt ist aus der Gruppe der Alkylsulfate, Alkylethoxysulfate, sekundären Alkylsulfate und Gemischen daraus. Als Alkylsulfate werden beispielsweise Alkylsulfate mit 14 bis 16 C-Atomen in der Kohlenstoffkette eingesetzt.GB-A-2 289 687 discloses a powder detergent with a density of Described at least 650 g / l, which (a) from 1 to 50 wt .-% of a surfactant system contains, (b) from 2 to 25% by weight of a potassium salt and (c) at least 1% by weight of one Builders. The surfactant system contains at least 30% by weight of a sulfated surfactant which is selected from the group of alkyl sulfates, alkyl ethoxy sulfates, secondary Alkyl sulfates and mixtures thereof. Examples of alkyl sulfates are alkyl sulfates with 14 to 16 carbon atoms in the carbon chain.

Der vorliegenden Erfindung lag die Aufgabe zugrunde, ein Tensidsystem zur Verfügung zu stellen, das sowohl in pulverförmigen bis granularen als auch in flüssigen Wasch- und Reinigungsmitteln eingesetzt werden kann und eine verbesserte Waschleistung über eine möglichst große Auswahl verschiedener Arten an Verschmutzungen zur Verfügung zu stellen. Ferner sollte das Tensidsystem Komponenten enthalten, die im Handel zu günstigen Preisen erhältlich sind und ökologisch günstige Eigenschaften aufweisen.The object of the present invention was to provide a surfactant system to provide that in powdery to granular as well as in liquid washing and Detergents can be used and improved washing performance over a The largest possible selection of different types of contamination is available put. Furthermore, the surfactant system should contain components that are commercially available reasonable prices are available and have ecologically favorable properties.

Überraschenderweise wurde festgestellt, daß durch Einsatz einer speziellen Kombination aus anionischen Tensiden in Wasch- und Reinigungsmitteln, ein Optimum an Waschaktivität, bezogen auf verschiedenartige Anschmutzungen, bei gleichbleibender Konzentration der waschaktiven Komponenten aufweisen.Surprisingly, it was found that by using a special combination from anionic surfactants in washing and cleaning agents, an optimum Washing activity, based on different types of soiling, with the same Have concentration of active detergent components.

Gegenstand der vorliegenden Erfindung ist demgemäß eine Tensidkombination für den Einsatz in Wasch- und Reinigungsmitteln, enthaltend C12-C18-Alkylsulfate, wobei der Anteil der Kohlenstoffketten mit weniger als 14 Kohlenstoffatomen kleiner ist als 10 %, bezogen auf den Gehalt an C12-C18-Alkylsulfat, und C9-C13-Alkylbenzolsulfonate in einem Verhältnis von 1 : 10 bis 10 : 1.The present invention accordingly relates to a surfactant combination for use in detergents and cleaning agents containing C 12 -C 18 alkyl sulfates, the proportion of carbon chains with less than 14 carbon atoms being less than 10%, based on the content of C 12 - C 18 alkyl sulfate, and C 9 -C 13 alkyl benzene sulfonates in a ratio of 1:10 to 10: 1.

In einer bevorzugten Ausführungsform ist in den verwendeten C12-C18-Alkylsulfaten der Anteil der Kohlenstoffketten mit mehr als 16 Kohlenstoffatomen kleiner als 10 Gew.-%, bezogen auf den Gehalt an C12-C18-Alkylsulfaten.In a preferred embodiment, the proportion of carbon chains with more than 16 carbon atoms in the C 12 -C 18 alkyl sulfates used is less than 10% by weight, based on the content of C 12 -C 18 alkyl sulfates.

In einer weiteren bevorzugten Ausführungsform liegt in den verwendeten C12-C18-Alkylsulfaten der Anteil der Kohlenstoffketten mit mehr als 16 Kohlenstoffatomen über 10 und unter 20 Gew.-%, bezogen auf den Gehalt an C12-C18-Alkylsulfaten.In a further preferred embodiment, the proportion of carbon chains with more than 16 carbon atoms in the C 12 -C 18 alkyl sulfates used is above 10 and below 20% by weight, based on the content of C 12 -C 18 alkyl sulfates.

Besonders gute Waschergebnisse werden erhalten, wenn in den C12-C18-Alkylsulfaten der Anteil der Alkylsulfate mit einer mit einer Kettenlänge von 14 Kohlenstoffatomen von 40 bis 80 Gew.-%, bezogen auf die C12-C18-Alkylsulfate, beträgt.Particularly good washing results are obtained when the proportion of alkyl sulfates with a chain length of 14 carbon atoms in the C 12 -C 18 alkyl sulfates is from 40 to 80% by weight, based on the C 12 -C 18 alkyl sulfates.

Die in der erfindungsgemäßen Tensidkombination enthaltenen C12-C18-Alkylsulfate sind bekannte anionische Tenside, die durch Sulfierung der entsprechenden Alkohole erhalten werden können. Der gewünschte Kohlenstoffkettenschnitt kann eingestellt werden, indem die entsprechenden aus natürlichen Rohstoffquellen oder synthetische hergestellte Alkohole mit entsprechender Kettenlängenverteilung oder wenn entsprechende, reine Ausgangsverbindungen eingesetzt werden.The C 12 -C 18 alkyl sulfates contained in the surfactant combination according to the invention are known anionic surfactants which can be obtained by sulfonating the corresponding alcohols. The desired carbon chain cut can be set by using the corresponding alcohols produced from natural raw material sources or synthetically with an appropriate chain length distribution or by using corresponding, pure starting compounds.

Auch die C9-C13-Alkylbenzolsulfonate sind bekannte anionische Tenside, die durch Sulfonieren der C9-C13-Monoolefine mit end- oder innenständiger Doppelbindung mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, erhalten werden können. Üblicherweise werden die C9-C13-Alkylbenzolsulfonate eingesetzt; auf höherkettige Alkylbenzolsulfonate wird weitestgehend verzichtet.The C 9 -C 13 alkylbenzenesulfonates are also known anionic surfactants which can be obtained by sulfonating the C 9 -C 13 monoolefins with a terminal or internal double bond with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. The C 9 -C 13 alkylbenzenesulfonates are usually used; Higher-chain alkylbenzenesulfonates are largely avoided.

In einer bevorzugten Ausführungsform liegen die C12-C18-Alkylsulfate und die C9-C13-Alkylbenzolsulfonate vorzugsweise in einem Verhältnis von 1 : 1 bis 4 : 1 vor.In a preferred embodiment, the C 12 -C 18 alkyl sulfates and the C 9 -C 13 alkyl benzene sulfonates are preferably in a ratio of 1: 1 to 4: 1.

Die erfindungsgemäße Tensidkombination ist zum Einsatz in pulverförmigen bis granularen als auch flüssigen Wasch- und Reinigungsmitteln geeignet.The surfactant combination according to the invention is for use in powdery bis granular as well as liquid detergents and cleaning agents.

Die Tenside können den Mitteln sowohl als Einzelsubstanzen als auch in Form von Compounds zugesetzt werden. Die Compounds werden vorzugsweise mittels Granulierverfahren, insbesondere in der Wirbelschicht, hergestellt.The surfactants can be used as individual substances as well as in the form of compounds be added. The compounds are preferably produced using a granulation process, especially in the fluidized bed.

Ein weiterer Gegenstand sind demgemäß pulverförmige bis granulare Wasch- und Reinigungsmittel, die die erfindungsgemäße Tensidkombination in Kombination mit weiteren üblichen Bestandteilen enthalten.Another subject is accordingly powdery to granular detergents and cleaning agents, the surfactant combination according to the invention in combination with others contain common ingredients.

Noch ein weiterer Gegenstand sind flüssige Wasch- und Reinigungsmittel, die die erfindungsgemäße Tensidkombination, ein geeignetes Lösungsmittel sowie ggf. weitere übliche Bestandteile enthalten.Still another object are liquid detergents and cleaning agents which are the inventive ones Combination of surfactants, a suitable solvent and possibly other Contain common ingredients.

Die erfindungsgemäßen pulverförmigen bis granularen oder flüssigen Wasch- und Reinigungsmittel enthalten die C12-C18-Alkylsulfate aus der Tensidkombination vorzugsweise in einer Menge von 1 bis 20 Gew.-%, bezogen auf das gesamte Mittel. Die C9-C13-Alkylbenzolsulfonate sind in den erfindungsgemäßen Mitteln vorzugsweise in einer Menge von 1 bis 20 Gew.-%, bezogen auf das gesamte Mittel, enthalten.The powdery to granular or liquid washing and cleaning agents according to the invention preferably contain the C 12 -C 18 alkyl sulfates from the surfactant combination in an amount of 1 to 20% by weight, based on the total agent. The C 9 -C 13 alkylbenzenesulfonates are preferably present in the agents according to the invention in an amount of 1 to 20 wt.

Als weitere Bestandteile können die erfindungsgemäßen Mittel weitere anionische Tenside, nichtionische Tenside, Builder sowie ggf. noch weitere Substanzen, die üblicherweise in Wasch- und Reinigungsmitteln enthalten sind, enthalten. The agents according to the invention can contain further anionic agents as further constituents Surfactants, nonionic surfactants, builders and possibly other substances that are usually contained in detergents and cleaning agents.

Als weitere anionische Tenside kommen beispielsweise die C8-C22-Olefinsulfonate, C8-C22-Alkansulfonate, C8-C22-Alkenylsulfate, Monoester und/oder Diester der Alkylsulfobernsteinsäure (Sulfosuccinate), C6-C18-Alkylpolyglykolethersulfonate, C8-C22-Fettsäureestersulfonate, C8-C22-Alkylethersulfate, Glycerinethersulfonate, Glycerinethersulfate, Hydroxymischethersulfate, Monoglyceridsulfate, Sulfoglyceride, Amidsäuren, C6-C18-Fettsäureamidethersulfate, C6-C18-Alkyl(ether)carboxylate, Fettsäureisethionate, N-C6-C16-Acyl-Sarcosinate, N-C6-C18-Acyl-Tauride, C6-C18-Alkyloligoglycosidsulfate, C6-C18-Alkyl-Phosphate, Seifen sowie deren Mischungen in Betracht. Die anionischen Tenside können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze, vor.Examples of further anionic surfactants are the C 8 -C 22 olefin sulfonates, C 8 -C 22 alkane sulfonates, C 8 -C 22 alkenyl sulfates, monoesters and / or diesters of alkyl sulfosuccinic acid (sulfosuccinates), C 6 -C 18 alkyl polyglycol ether sulfonates, C 8 -C 22 -Fettsäureestersulfonate, C 8 -C 22 -alkyl ether sulfates, glycerol ether, Glycerol ether, Hydroxymischethersulfate, monoglyceride sulfates, Sulfoglyceride, amic acids, C 6 -C 18 -Fettsäureamidethersulfate, C 6 -C 18 alkyl (ether) carboxylates, fatty acid isethionates, NC 6 -C 16 acyl sarcosinates, NC 6 -C 18 acyl taurides, C 6 -C 18 alkyl oligoglycoside sulfates, C 6 -C 18 alkyl phosphates, soaps and mixtures thereof. The anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Der Gehalt der Mittel an weiteren anionischen Tensiden beträgt vorzugsweise bis zu 10 Gew.-%.The content of the agents in further anionic surfactants is preferably up to 10 Wt .-%.

Als nichtionische Tenside können die Mittel C8-C18-Alkoholalkoxylate, Alkylpolyglykoside, alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte C8-C18-Fettsäurealkylester, N-Fettalkyl-Aminoxide, Polyhydroxyfettsäureamide oder deren Gemische eingesetzt werden.The agents C 8 -C 18 alcohol alkoxylates, alkyl polyglycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated alkyl C 8 -C 18 fatty acid esters, N-fatty alkyl amine oxides, polyhydroxy fatty acid amides or mixtures thereof can be used as nonionic surfactants.

Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-C14-Alkohole mit 3 EO oder 4 EO, C9-C11-Alkohole mit 7 EO, C13-C15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-C18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie diesen, wie Mischungen aus C12-C14-Alkohol mit 3 EO und C12-C18-Alkohol mit 7 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind (Talg-) Fettalkohole mit 14 EO, 16 EO, 20 EO, 25 EO, 30 EO oder 40 EO.The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as these, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO , The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

In einer besonders bevorzugten Ausführungsform enthalten die Mittel als nichtionisches Tensid C12-C16-Fettalkoholalkoxylate mit einem mittleren Alkoxylierungsgrad zwischen 5,2 und 5,8, vorzugsweise zwischen 5,4 und 5,6.In a particularly preferred embodiment, the agents contain as nonionic surfactant C 12 -C 16 fatty alcohol alkoxylates with an average degree of alkoxylation between 5.2 and 5.8, preferably between 5.4 and 5.6.

Als weitere bevorzugt eingesetzte nichtionische Tenside können auch Alkylglykoside der allgemeinen Formel RO(G)x genannt werden, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4.Other preferred nonionic surfactants that can be used are alkyl glycosides of the general formula RO (G) x , in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Der Gehalt der nichtionischen Tenside beträgt in den fertigen Mitteln vorzugsweise von 2 bis 45 Gew.-%, vorzugsweise über 20 Gew.-%, wobei der Gehalt an nichtionischen Tensiden in flüssigen Mitteln in der Regel über 10 Gew.-% liegt.The content of the nonionic surfactants in the finished compositions is preferably 2 to 45 wt .-%, preferably over 20 wt .-%, the content of nonionic Surfactants in liquid agents are generally above 10% by weight.

Als anorganische Buildersubstanzen eignen sich beispielsweise Phosphate, vorzugsweise Tripolyphosphate, aber auch Orthophosphate und Pyrophosphate, sowie Zeolith und kristalline Schichtsilikate.Suitable inorganic builder substances are, for example, phosphates, preferably Tripolyphosphates, but also orthophosphates and pyrophosphates, as well as zeolite and crystalline Phyllosilicates.

Der eingesetzte feinkristalline, synthetische und gebundenes Wasser enthaltende Zeolith ist vorzugsweise Zeolith A und/oder P. Als Zeolith P werden Zeolith MAP® (Handelsprodukt der Firma Crosfield) und Zeolith A besonders bevorzugt. Geeignet sind jedoch auch Zeolith X sowie Mischungen aus A, X und/oder P. Von besonderem Interesse ist auch ein cokristallisiertes Natrium/Kalium-Aluminiumsilikat aus Zeolith A und Zeolith X, welches als VEGOBOND AX® (Handelsprodukt der Firma Condea Augusta S.p.A.) im Handel erhältlich ist. Der Zeolith kann als sprühgetrocknetes Pulver oder auch als ungetrocknete, von ihrer Herstellung noch feuchte, stabilisierte Suspension zum Einsatz kommen. Für den Fall, daß der Zeolith als Suspension eingesetzt wird, kann diese geringe Zusätze an nichtionischen Tensiden als Stabilisatoren enthalten, beispielsweise 1 bis 3 Gew.-%, bezogen auf Zeolith, an ethoxylierten C12-C18-Fettalkoholen mit 2 bis 5 Ethylenoxidgruppen, C12-C14-Fettalkoholen mit 4 bis 5 Ethylenoxidgruppen oder ethoxylierten Isotridecanolen. Geeignete Zeolithe weisen eine mittlere Teilchengröße von weniger als 10 µm (Volumenverteilung; Meßmethode: Coulter Counter) auf und enthalten vorzugsweise 18 bis 22 Gew.-%, insbesondere 20 bis 22 Gew.-% an gebundenem Wasser.The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) and zeolite A are particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Of particular interest is also a cocrystallized sodium / potassium aluminum silicate made of zeolite A and zeolite X, which as VEGOBOND AX® (commercial product from Condea Augusta SpA) im Trade is available. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Geeignete Substitute bzw. Teilsubstitute für Phosphate und Zeolithe sind kristalline, schichtförmige Natriumsilikate der allgemeinen Formel NaMSixO2x+1•y H2O, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Derartige kristalline Schichtsilikate werden beispielsweise in der europäischen Patentanmeldung EP-A-0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate der angegebenen Formel sind solche, in denen M flir Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl β- als auch δ-Natriumdisilikate Na2Si2O5•y H2O bevorzugt.Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 • y H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number of Is 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline sheet silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na 2 Si 2 O 5 • y H 2 O are preferred.

Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren und Mischungen aus diesen.Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and Mixtures of these. Preferred salts are the salts of polycarboxylic acids such as Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and Mixtures of these.

Geeignete polymere Polycarboxylate sind beispielsweise die Natriumsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 800 bis 150000 (auf Säure bezogen). Geeignete copolymere Polycarboxylate sind insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 5000 bis 200000, vorzugsweise 10000 bis 120000 und insbesondere 50000 bis 100000. Der Gehalt der Mittel an (co-)polymeren Polycarboxylaten beträgt vorzugsweise 1 bis 8 Gew.-%, insbesondere 2 bis 6 Gew.-%.Suitable polymeric polycarboxylates are, for example, the sodium salts of Polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 800 to 150,000 (based on acid). Suitable copolymers Polycarboxylates are especially those of acrylic acid with methacrylic acid and Acrylic acid or methacrylic acid with maleic acid. Have proven to be particularly suitable Copolymers of acrylic acid with maleic acid have proven to be 50 to 90% by weight of acrylic acid and contain 50 to 10% by weight of maleic acid. Their relative molecular mass, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. The content of the agents in (co) polymers Polycarboxylates is preferably 1 to 8% by weight, in particular 2 to 6% by weight.

Insbesondere bevorzugt sind auch biologisch abbaubare Polymere aus mehr als zwei verschiedenen Monomereinheiten, beispielsweise solche, die gemäß der DE-A-43 00 772 als Monomere Salze der Acrylsäure und der Maleinsäure sowie Vinylalkohol bzw. Vinylalkohol-Derivate oder gemäß der DE-C42 21 381 als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zucker-Derivate enthalten.Also particularly preferred are biodegradable polymers made from more than two different ones Monomer units, for example those which according to DE-A-43 00 772 as Monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C42 21 381 as monomer salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives.

Weitere geeignete Buildersubstanzen sind Polyacetale, welche durch Umsetzung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 C-Atome und mindestens 3 Hydroxylgruppen aufweisen, beispielsweise wie in der europäischen Patentanmeldung EP-A-0 280 223 beschrieben, erhalten werden können. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Gluconsäure und/oder Glucoheptonsäure erhalten.Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups, for example as in the European patent application EP-A-0 280 223 can be obtained. Preferred polyacetals will be from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Weitere geeignete Inhaltsstoffe der Mittel sind wasserlösliche anorganische Salze wie Bicarbonate, Carbonate, amorphe Silikate oder Mischungen aus diesen; insbesondere werden Alkalicarbonat und amorphes Alkalisilikat, vor allem Natriumsilikat mit einem molaren Verhältnis Na2O : SiO2 von 1:1 bis 1:4,5, vorzugsweise von 1:2 bis 1:3,5, eingesetzt. Der Gehalt der Mittel an Natriumcarbonat beträgt dabei vorzugsweise bis zu 20 Gew.-%, vorteilhafterweise zwischen 2 und 15 Gew.-%. Der Gehalt der Mittel an Natriumsilikat beträgt im allgemeinen bis zu 10 Gew.-% und vorzugsweise zwischen 2 und 8 Gew.-%. Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; In particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 2 and 15% by weight. The sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.

Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumperborattetrahydrat und das Natriumperboratmonohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Natriumpercarbonat, Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandisäure. Der Gehalt der Mittel an Bleichmitteln beträgt vorzugsweise 5 bis 25 Gew.-% und insbesondere 10 bis 20 Gew.-%, wobei vorteilhafterweise Perboratmonohydrat oder Percarbonat eingesetzt wird.Among the compounds which serve as bleaching agents and supply H 2 O 2 in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. The bleach content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.

Vergrauungsinhibitoren haben die Aufgabe, den von der Faser abgelösten Schmutz in der Flotte suspendiert zu halten und so das Wiederaufziehen des Schmutzes zu verhindern. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise die wasserlöslichen Salze polymerer Carbonsäuren, Leim, Gelatine, 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 obengenannten Stärkeprodukte verwenden, z.B. abgebaute Stärke, Aldehydstärken usw. Auch Polyvinylpyrrolidon ist brauchbar. Bevorzugt werden jedoch Celluloseether, wie Carboxymethylcellulose (Na-Salz), Methylcellulose, Hydroxyalkylcellulose und Mischether, wie Methylhydroxyethylcellulose, Methylhydroxypropylcellulose, Methylcarboxymethylcellulose und deren Gemische, sowie Polyvinylpyrrolidon beispielsweise in Mengen von 0,1 bis 5 Gew.-%, bezogen auf die Mittel, eingesetzt.Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening. Water-soluble colloids of mostly organic nature are suitable for this purpose, 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. Also water-soluble, acidic Group-containing polyamides are suitable for this purpose. Furthermore, use soluble starch preparations and starch products other than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers, such as carboxymethyl cellulose (sodium salt), are preferred. Methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their Mixtures and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the funds used.

Beim Einsatz in maschinellen Waschverfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Als Schauminhibitoren eignen sich beispielsweise Seifen natürlicher oder synthetischer Herkunft, die einen hohen Anteil an C18-C24-Fettsäuren aufweisen. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, ggf. silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure oder Bistearylethylendiamid. Mit Vorteilen werden auch Gemische aus verschiedenen Schauminhibitoren verwendet, z.B. solche aus Silikonen, Paraffinen oder Wachsen. Vorzugsweise sind die Schauminhibitoren, insbesondere Silikon- und/oder Paraffin-haltige Schauminhibitoren, an eine granulare, in Wasser lösliche bzw. dispergierbare Trägersubstanz gebunden. Insbesondere sind dabei Mischungen aus Paraffinen und Bistearylethylendiamiden bevorzugt.When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

Als Salze von Polyphosphonsäuren werden vorzugsweise die neutral reagierenden Natriumsalze von beispielsweise 1-Hydroxyethan-1,1-diphosphonat, Diethylentriaminpenta-methylenphosphonat oder Ethylendiamintetramethylenphosphonat in Mengen von 0,1 bis 1,5 Gew.-% verwendet.The salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepenta-methylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5 wt .-% used.

Die Mittel können als optische Aufheller Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z.B. Salze der 4,4'-Bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholino-Gruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle anwesend sein, z.B. die Alkalisalze des 4,4'-Bis(2-sulfostyryl)-diphenyls, 4,4'-Bis(4-chlor-3-sulfostyryl)-diphenyls, oder 4-(4-Chlorstyryl)-4'-(2-sulfostyryl)-diphenyls. Auch Gemische der vorgenannten Aufheller können verwendet werden.As optical brighteners, the agents can be derivatives of diaminostilbenedisulfonic acid or whose alkali metal salts contain. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds which instead of the morpholino group a diethanolamino group, a Carry a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned Brighteners can be used.

Beispiele für Bleichaktivatoren sind mit H2O2 organische Persäuren bildende N-Acyl- bzw. O-Acyl-Verbindungen, vorzugsweise mehrfach acylierte Alkylendiamine wie N,N'tetraacylierte Diamine, acylierte Glykolurile, insbesondere Tetraacetylglykoluril, N-acylierte Hydantoine, Hydrazide, Triazole, Triazine, Urazole, Diketopiperazine, Sulfurylamide und Cyanurate, außerdem Carbonsäureester wie p-(Alkanoyloxy)benzolsulfonate, insbesondere Natriumisononanoyloxybenzolsulfonat, und der p-(Alkenoyloxy)-benzolsulfonate, ferner Caprolactam-Derivate, Carbonsäureanhydride wie Phthalsäureanhydrid und Ester von Polyolen wie Glucosepentaacetat. Weitere bekannte Bleichaktivatoren sind acetylierte Mischungen aus Sorbitol und Mannitol, wie sie beispielsweise in der europäischen Patentanmeldung EP-A-0 525 239 beschrieben werden, und acetyliertes Pentaerythrit. Der Gehalt der bleichmittelhaltigen Mittel an Bleichaktivatoren liegt in dem üblichen Bereich, vorzugsweise zwischen 1 und 10 Gew.-% und insbesondere zwischen 3 und 8 Gew.-%. Besonders bevorzugte Bleichaktivatoren sind N,N,N',N'-Tetraacetylethylendiamin (TAED), 1,5-Diacetyl-2,4-dioxo-hexahydro-1,3,5-triazin (DADHT) und acetylierte Sorbitol-Mannitol-Mischungen (SORMAN).Examples of bleach activators are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably polyacrylicized alkylenediamines such as N, N'tetraacylated diamines, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles , Triazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid esters such as p- (alkanoyloxy) benzenesulfonate, in particular sodium isononoyloxybenzenesulfonate, and the p- (alkenoyloxy) benzenesulfonate, also caprolactam derivatives, carbonic acid anhydride such as phthalic acid anhydride such as phthalates. Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described for example in European patent application EP-A-0 525 239, and acetylated pentaerythritol. The bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).

Als Enzyme kommen insbesondere solche aus der Klasse der Hydrolasen, wie der Proteasen, Esterasen, Lipasen bzw. lipolytisch wirkenden Enzyme, Amylasen, Cellulasen bzw. andere Glykosylhydrolasen und Gemische der genannten Enzyme in Frage. Alle diese Hydrolasen tragen in der Wäsche zur Entfernung von Verfleckungen, wie protein-, fettoder stärkehaltigen Verfleckungen, und Vergrauungen bei. Cellulasen und andere Glykosylhydrolasen können durch das Entfernen von Pilling und Mikrofibrillen zur Farberhaltung und zur Erhöhung der Weichheit des Textils beitragen. Zur Bleiche bzw. zur Hemmung der Farbübertragung können auch Oxidoreduktasen eingesetzt werden. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus und Humicola insolens gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Dabei sind Enzymmischungen, beispielsweise aus Protease und Amylase oder Protease und Lipase bzw. lipolytisch wirkenden Enzymen oder Protease und Cellulase oder aus Cellulase und Lipase bzw. lipolytisch wirkenden Enzymen oder aus Protease, Amylase und Lipase bzw. lipolytisch wirkenden Enzymen oder Protease, Lipase bzw. lipolytisch wirkenden Enzymen und Cellulase, insbesondere jedoch Protease- und/oder Lipase-haltige Mischungen bzw. Mischungen mit lipolytisch wirkenden Enzymen von besonderem Interesse. Beispiele für derartige lipolytisch wirkende Enzyme sind die bekannten Cutinasen. Auch Peroxidasen oder Oxidasen haben sich in einigen Fällen als geeignet erwiesen. Zu den geeigneten Amylasen zählen insbesondere α-Amylasen, Iso-Amylasen, Pullulanasen und Pektinasen. Als Cellulasen werden vorzugsweise Cellobiohydrolasen, Endoglucanasen und β-Glucosidasen, die auch Cellobiasen genannt werden, bzw. Mischungen aus diesen eingesetzt. Da sich die verschiedenen Cellulase-Typen durch ihre CMCase- und Avicelase-Aktivitäten unterscheiden, können durch gezielte Mischungen der Cellulasen die gewünschten Aktivitäten eingestellt werden. Enzymes in particular come from the class of hydrolases, such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All these Hydrolases help to remove stains, such as protein, fat or in the laundry starchy stains and graying. Cellulases and others Glycosyl hydrolases can be removed by removing pilling and microfibrils Color preservation and increase the softness of the textile. For bleaching or Oxidoreductases can also be used to inhibit color transfer. From bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens enzymatic agents. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are used. Are there Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and Lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic Enzymes and cellulase, but especially protease and / or lipase-containing Mixtures or mixtures with lipolytically active enzymes of particular Interest. Examples of such lipolytically active enzymes are the known ones Cutinases. Peroxidases or oxidases have also been found to be suitable in some cases proved. Suitable amylases include in particular α-amylases, iso-amylases, Pullulanases and pectinases. Cellobiohydrolases are preferably used as cellulases, Endoglucanases and β-glucosidases, which are also called cellobiases, or Mixtures of these are used. Because the different types of cellulase are characterized by their CMCase and Avicelase activities can be distinguished by targeted mixtures the desired activities are set for the cellulases.

Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen. Der Anteil der Enzyme, Enzymmischungen oder Enzymgranulate kann beispielsweise etwa 0,1 bis 5 Gew.-%, vorzugsweise 0,1 bis etwa 2 Gew.-% betragen.The enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.

Als Lösungsmittel können die in flüssiger Form vorliegenden Mittel neben den üblicherweise als flüssige Komponente vorliegenden nichtionischen Tensiden auch organische Lösungsmittel, z. B. ein- oder mehrwertige Alkohole mit 1 bis 4 C-Atomen enthalten. Bevorzugte Alkohole sind Ethanol, 1,2-Propandiol, Glycerin sowie deren Gemische. Die Mittel enthalten vorzugsweise 2 bis 12 Gew.-% und insbesondere 3 bis 10 Gew.-% Ethanol oder ein beliebiges Gemisch aus Ethanol und Glycerin.As a solvent, the agents present in liquid form in addition to the Nonionic surfactants usually present as a liquid component also organic solvents, e.g. B. mono- or polyhydric alcohols with 1 to 4 carbon atoms contain. Preferred alcohols are ethanol, 1,2-propanediol, glycerol and their Mixtures. The compositions preferably contain 2 to 12% by weight and in particular 3 to 10 % By weight of ethanol or any mixture of ethanol and glycerin.

Insbesondere in nicht-wäßrigen Flüssigwaschmitteln sind neben den mono- und/oder polyfunktionellen kurzkettigen Alkoholen wie Ethanol, Propylenglykol und/oder Glycerin auch flüssige organische Ether, beispielsweise Diisopropylmonomethylether bevorzugt.In particular in non-aqueous liquid detergents, in addition to the mono- and / or polyfunctional ones short chain alcohols such as ethanol, propylene glycol and / or glycerin liquid organic ethers, for example diisopropyl monomethyl ether, are also preferred.

Ein pulverförmiges bis granulares Wasch- und Reinigungsmittel gemäß der vorliegenden Erfindung enthält vorzugsweise 2 bis 20 Gew.-% C12-C18-Alkylsulfate, wobei der Anteil der Kohlenstoffketten mit weniger als 14 Kohlenstoffatomen kleiner ist als 10 %, bezogen auf den Gehalt an C12-C18-Alkylsulfat, 2 bis 20 Gew.-% C9-C13-Alkylbenzolsulfonate, wobei C12-C18-Alkylsulfate und die C9-C13-Alkylbenzolsulfonate in einem Verhältnis von 1 : 10 bis 10 : 1 vorliegen, 15 Gew.-% bis 55 Gew.-% anorganischen und/oder organischen Builder, bis zu 10 Gew.-% weitere anionische Tenside, 1 Gew.-% bis 20 Gew.-% nichtionische Tenside, bis zu 25 Gew.-%, insbesondere 1 Gew.-% bis 15 Gew.-% Bleichmittel, bis zu 8 Gew.-%, insbesondere 0,5 Gew.-% bis 6 Gew.-% Bleichaktivator und bis zu 20 Gew.-%, insbesondere 0,1 Gew.-% bis 15 Gew.-% anorganische Salze, insbesondere Alkalicarbonat, -sulfat und/oder -silikat, sowie bis zu 2 Gew.-%, insbesondere 0,4 Gew.-% bis 1,2 Gew.-% Enzyme und weitere, in Wasch- und Reinigungsmitteln übliche Inhaltsstoffe, wie Strukturbrecher, Schauminhibitoren, optische Aufheller, Enzyme, Stabilisatoren, insbesondere für Persauerstoffverbindungen und Enzyme, textilweichmachende Stoffe, Vergrauungsinhibitoren, Schauminhibitoren und Farb- und Duftstoffe. A powdery to granular washing and cleaning agent according to the present invention preferably contains 2 to 20 wt .-% C 12 -C 18 alkyl sulfates, the proportion of carbon chains with less than 14 carbon atoms being less than 10%, based on the content C 12 -C 18 alkyl sulfate, 2 to 20% by weight of C 9 -C 13 alkyl benzene sulfonates, where C 12 -C 18 alkyl sulfates and the C 9 -C 13 alkyl benzene sulfonates in a ratio of 1:10 to 10: 1 are present, 15% by weight to 55% by weight of inorganic and / or organic builders, up to 10% by weight of further anionic surfactants, 1% by weight to 20% by weight of nonionic surfactants, up to 25% by weight .-%, in particular 1% by weight to 15% by weight of bleach, up to 8% by weight, in particular 0.5% by weight to 6% by weight of bleach activator and up to 20% by weight, in particular 0.1% by weight to 15% by weight of inorganic salts, in particular alkali metal carbonate, sulfate and / or silicate, and up to 2% by weight, in particular 0.4% by weight to 1.2% by weight .-% enzymes and others, ingredients common in detergents and cleaning agents, such as structure breakers, foam inhibitors, optical brighteners, enzymes, stabilizers, in particular for peroxygen compounds and enzymes, textile-softening substances, graying inhibitors, foam inhibitors and colorants and fragrances.

Ein flüssiges Wasch- und Reinigungsmittel gemäß der vorliegenden Erfindung enthält vorzugsweise 2 bis 20 Gew.-% C12-C18-Alkylsulfate, wobei der Anteil der Kohlenstoffketten mit weniger als 14 Kohlenstoffatomen kleiner ist als 10 %, bezogen auf den Gehalt an C12-C18-Alkylsulfat, 2 bis 20 Gew.-% C9-C13-Alkylbenzolsulfonate, wobei die C12-C18-Alkylsulfate und die C9-C13-Alkylbenzolsulfonate in einem Verhältnis von 1 : 10 bis 10 : 1 vorliegen, 4 bis 25 Gew.-% flüssige nichtionische Tenside, bis zu 10 Gew.-% Lösungsmittel, bis zu 10 Gew.-% Buildersubstanzen, bis zu 3 Gew.-% Enzyme und bis zu 2 Gew.-% weitere in Wasch- und Reinigungsmitteln übliche Inhaltsstoffe.A liquid washing and cleaning agent according to the present invention preferably contains 2 to 20% by weight of C 12 -C 18 alkyl sulfates, the proportion of carbon chains with less than 14 carbon atoms being less than 10%, based on the C 12 content -C 18 alkyl sulfate, 2 to 20% by weight of C 9 -C 13 alkyl benzene sulfonates, the C 12 -C 18 alkyl sulfates and the C 9 -C 13 alkyl benzene sulfonates in a ratio of 1:10 to 10: 1 4 to 25% by weight of liquid nonionic surfactants, up to 10% by weight of solvent, up to 10% by weight of builder substances, up to 3% by weight of enzymes and up to 2% by weight of others in washing - and cleaning agents usual ingredients.

Duftstoffe können auch in Form von festen Compounds in die insbesondere pulverförmigen bis granularen Wasch- und Reinigungsmittel eingearbeitet werden. Solche konzentrierten Duftstoff-Compounds lassen sich beispielsweise separat durch Granulation, Kompaktierung, Extrusion, Pelletierung oder über andere Agglomerationsverfahren herstellen. Als Trägermaterialien haben sich beispielsweise Cyclodextrine bewährt, wobei die Cyclodextrin-Parfüm-Komplexe zusätzlich noch mit weiteren Hilfsstoffen beschichtet werden können. Die besondere Herstellung von Duftstoff-Formkörpern wird beispielsweise in der älteren deutschen Patentanmeldung DE-A-197 46 780.6 beschrieben, in welcher ein Verfahren offenbart wird, bei dem ein festes, im wesentlichen wasserfreies Vorgemisch aus Trägerstoffen, gegebenenfalls Hilfsstoffen und 5 bis 25 Gew.-% Parfüm einer Granulation oder Preßagglomeration unterworfen wird. Fragrances can also be in the form of solid compounds in particular Powdery to granular detergents and cleaning agents can be incorporated. Such concentrated fragrance compounds can be separated, for example Granulation, compacting, extrusion, pelleting or other agglomeration processes produce. Cyclodextrins, for example, have been used as carrier materials proven, the cyclodextrin-perfume complexes additionally with others Auxiliaries can be coated. The special production of perfume moldings is, for example, in the older German patent application DE-A-197 46 780.6, in which a method is disclosed in which a fixed, in essential anhydrous premix of carriers, optionally auxiliaries and 5 to 25% by weight of perfume is subjected to granulation or press agglomeration.

BeispieleExamples

Die Prüfung der Waschleistung erfolgte unter praxisnahen Bedingungen in Haushaltswaschmaschinen des Typs Miele W 918 Novotronic. Die Maschinen wurden mit 3,5 kg Haushaltswäsche (Bettwäsche, Tischwäsche, Leibwäsche) und 0,5 kg Testgewebe beschickt. Als Testgewebe wurden sowohl kommerziell erhältliche künstlich angeschmutzte Baumwollgewebe und Polyester/Baumwoll-Mischgewebe sowie mit einem maschinellen Verfahren natürlich angeschmutzte Baumwollgewebe und Polyester/Baumwoll-Mischgewebe eingesetzt.The washing performance was checked under practical conditions in household washing machines type Miele W 918 Novotronic. The machines were weighing 3.5 kg Household linen (bed linen, table linen, underwear) and 0.5 kg test fabric loaded. Both commercially available artificially soiled were used as test fabrics Cotton fabric and polyester / cotton blend as well as with a machine Process of naturally soiled cotton fabrics and polyester / cotton blended fabrics used.

Waschbedingungen:Washing conditions:

Leitungswasser von 16°d (Äquivalent 160 mg CaO/l), wurden im Hauptwaschgang bei 40 °C und 60 °C mit 4,3 g/l Waschmittel und 60 Minuten Waschzeit gewaschen. Es wurde dreimal mit Leitungswasser nachgespült, anschließend geschleudert und getrocknet. Das Flottenverhältnis, kg Wäsche: Liter (1) Waschlauge, betrug 1: 4,5. Beispiel (Pulver) Komponente 1 2 C11-13-Alkylbenzolsulfonat 14,8 12,0 C14-16-Alkylsulfat 3,6 C12-18-Alkohol x 7 EO 3,8 C12-14-Alkohol x 5,5 EO 3,0 Talgalkohol x 5 EO 0,53 0,53 C12-C18-Seife (Na-Salz) 0,9 0,9 Soda 11,8 11,8 Soil-Repellent Polymer 0,75 0,75 Wasserglas 1,6 1,6 Na-Perboratmonohydrat 12,05 12,05 Hydroxyethyldiphosphonat 0,5 0,5 Silikonöl 0,6 0,6 Zeolith 20,61 20,61 polymeres Polycarboxylat 5,15 5,15 TAED 8,0 8,0 Enzym 3,99 3,99 Wasser und Salze ad 100 ad 100 Tap water of 16 ° d (equivalent to 160 mg CaO / l) was washed in the main wash at 40 ° C and 60 ° C with 4.3 g / l detergent and a washing time of 60 minutes. It was rinsed three times with tap water, then spun and dried. The liquor ratio, kg laundry: liter (1) wash liquor, was 1: 4.5. Example (powder) component 1 2 C 11 - 13 alkyl benzene sulfonate 14.8 12.0 C 14-16 alkyl sulfate 3.6 C 12-18 alcohol x 7 EO 3.8 C 12-14 alcohol x 5.5 EO 3.0 Tallow alcohol x 5 EO 0.53 0.53 C 12 -C 18 soap (Na salt) 0.9 0.9 soda 11.8 11.8 Soil repellent polymer 0.75 0.75 water glass 1.6 1.6 Na-perborate 12.05 12.05 Hydroxyethyldiphosphonat 0.5 0.5 silicone oil 0.6 0.6 zeolite 20.61 20.61 polymeric polycarboxylate 5.15 5.15 TAED 8.0 8.0 enzyme 3.99 3.99 Water and salts ad 100 ad 100

Die Testgewebe waren mit den unten angegebenen verschiedenen Anschmutzungen versehen. Die Waschwirkung wurde durch Messung der Remission bestimmt. (Messung des Weißgrades: Zeiss-Reflektometer, 465 nm, Ausblendung des Aufheller-Effektes). Die Versuche wurden jeweils fünfmal wiederholt. Die angegebenen Remissionswerte sind die Durchschnittswerte über alle Messungen. Die Ergebnisse sind in den Tabellen 2 und 3 wiedergegeben. The test fabrics were with the different stains given below Mistake. The washing effect was determined by measuring the reflectance. (Measurement degree of whiteness: Zeiss reflectometer, 465 nm, suppression of the brightener effect). The Experiments were repeated five times each. The specified remission values are the Average values across all measurements. The results are in Tables 2 and 3 played.

Die in den Tabellen verwendetet Abkürzungen haben folgende Bedeutung:
Gewebe:

  • B = Baumwolle
  • P = Polyester
  • PBV = Polyester/Baumwolle veredelt
    • Anschmutzungen:
  • SW = Staub/Wollfett
  • SH = Staub/Hautfett
  • RF4 = Ruß/Wollfett
  • MU = Make up
  • LS = Lippenstift
  • T = Tee Beispiel Anschmutzung Fett/Pigment-Flecken Fett/Ruß-Flecken SW-B SH-B SH-BV SH-PBV RF4-PBV 1 (Vergleich) 60,3 77,3 78,7 74,2 72,4 2 (Erfindung) 61,3 78,0 80,1 74,3 74,4 Anschmutzung Kosmetik-Flecken bleichbare Flecken LS1-PBV MU-PBV T-B 1 (Vergleich) 74,3 58,6 63,0 2 (Erfindung) 76,4 56,1 62,6
    • The abbreviations used in the tables have the following meanings:
    Tissue:
  • B = cotton
  • P = polyester
  • PBV = polyester / cotton refined
    • stains:
  • SW = dust / wool fat
  • SH = dust / skin fat
  • RF4 = soot / wool fat
  • MU = make up
  • LS = lipstick
  • T = tea example soiling Grease / pigment spots Fat / soot stains SW-B SH-B SH-BV SH-PBV RF4-PBV 1 (comparison) 60.3 77.3 78.7 74.2 72.4 2 (invention) 61.3 78.0 80.1 74.3 74.4 soiling Cosmetic stains bleachable stains LS1 PBV MU PBV TB 1 (comparison) 74.3 58.6 63.0 2 (invention) 76.4 56.1 62.6

    • In Tabelle 3, Spalte 2 sind die Durchschnittswerte über die einzelnen Arten an Verschmutzungen und in Spalte 3 die summierten Remissionswerte über alle Arten Anschmutzungen wiedergegeben. Beispiel Durchschnittswert der Remission summierte Remissionswerte 1 (Vergleich) 69,6 556,8 2 (Erfindung) 70,4 563,2 Table 3, column 2 shows the average values for the individual types of soiling and column 3 shows the total remission values for all types of soiling. example Average remission value summed remission values 1 (comparison) 69.6 556.8 2 (invention) 70.4 563.2

    Aus Tabelle 3 wird deutlich, daß die Rezepturen, die die speziellen Alkylsulfate gemäß der Erfindung enthalten, über die Bandbreite der am häufigsten anfallenden Arten an Anschmutzungen eine verbesserte Waschleistung zeigen.From Table 3 it is clear that the recipes that the special alkyl sulfates according to of the invention included across the range of the most commonly occurring species Soiling shows an improved washing performance.

    Claims (10)

    1. A surfactant combination for use in detergents containing C12-18 alkyl sulfates, the percentage of carbon chains with fewer than 14 carbon atoms being less than 10%, based on the content of C12-18 alkyl sulfate, and C9-13 alkyl benzenesulfonates in a ratio of 1:10 to 10:1.
    2. A surfactant combination as claimed in claim 1, characterized in that the percentage of carbon chains with more than 16 carbon atoms in the C12-18 alkyl sulfates is less than 10% by weight, based on the C12-18 alkyl sulfates.
    3. A surfactant combination as claimed in claim 1, characterized in that the percentage of carbon chains with more than 16 carbon atoms in the C12-18 alkyl sulfates is above 10 and below 20% by weight, based on the C12-18 alkyl sulfates.
    4. A surfactant combination as claimed in any of claims 1 to 3, characterized in that the percentage of carbon chains with a chain length of 14 carbon atoms in the C12-18 alkyl sulfates is between 40 and 80% by weight.
    5. A surfactant combination as claimed in any of claims 1 to 4, characterized in that the C12-18 alkyl sulfates and the alkyl benzenesulfonates are present in a ratio of 1:1 to 4:1.
    6. A surfactant system as claimed in any of claims 1 to 5, characterized in that it contains nonionic surfactants selected from the group consisting of alkoxylated C8-18 alcohols, alkoxylated fatty acid alkyl esters, amine oxides, polyhydroxyfatty acid amines and mixtures thereof.
    7. A detergent as claimed in claim 6, characterized in that the alkoxylated C8-18 alcohols are selected from C12-16 fatty alcohol alkoxylates with an average degree of alkoxylation of 5.2 to 5.8.
    8. A powder-form or granular detergent containing the surfactant combination claimed in any of claims 1 to 7, characterized in that it contains 2 to 20% by weight of C12-18 alkyl sulfates, the percentage of carbon chains with fewer than 14 carbon atoms being less than 10%, based on the C12-18 alkyl sulfate content, 2 to 20% by weight of C9-13 alkyl benzenesulfonates, the C12-18 alkyl sulfates and the C9-13 alkyl benzenesulfonates being present in a ratio of 1:10 to 10:1, 15% by weight to 55% by weight of inorganic and/or organic builders, up to 10% by weight of other anionic surfactants, 1% by weight to 20% by weight of nonionic surfactants, up to 25% by weight and more particularly from 1% by weight to 15% by weight of bleaching agents, up to 8% by weight and more particularly from 0.5% by weight to 6% by weight of bleach activator, up to 20% by weight and more particularly from 0.1% by weight to 15% by weight of inorganic salts, more particularly alkali metal carbonate, sulfate and/or silicate, and up to 2% by weight and more particularly from 0.4% by weight to 1.2% by weight of enzymes and other typical detergent ingredients.
    9. A powder-form or granular detergent as claimed in claim 8, characterized in that it contains builders selected from the group of phosphates, zeolites, water-soluble alkali metal silicates and organic builders, such as polycarboxylates, (co)polymeric polycarboxylates or biodegradable terpolymers and quatemary polymers.
    10. A liquid detergent containing the surfactant combination claimed in any of claims 1 to 7, characterized in that it contains 2 to 20% by weight of C12-18 alkyl sulfates, the percentage of carbon chains with fewer than 14 carbon atoms being less than 10%, based on the C12-18 alkyl sulfate content, 2 to 20% by weight of C9-13 alkyl benzenesulfonates, the C12-18 alkyl sulfates and the C9-13 alkyl benzenesulfonates being present in a ratio of 1:10 to 10:1,4 to 25% by weight of liquid nonionic surfactants, up to 10% by weight of solvent, up to 10% by weight of builders, up to 3% by weight of enzymes and up to 2% by weight of other typical detergent ingredients.
    EP99910234A 1998-02-26 1999-02-17 Tenside combination containing special anionic tensides Revoked EP1058722B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE19807805A DE19807805A1 (en) 1998-02-26 1998-02-26 A combination of surfactants containing special anionic surfactants
    DE19807805 1998-02-26
    PCT/EP1999/001053 WO1999043772A2 (en) 1998-02-26 1999-02-17 Tenside combination containing special anionic tensides

    Publications (2)

    Publication Number Publication Date
    EP1058722A1 EP1058722A1 (en) 2000-12-13
    EP1058722B1 true EP1058722B1 (en) 2002-08-21

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    EP (1) EP1058722B1 (en)
    JP (1) JP2002504621A (en)
    AT (1) ATE222597T1 (en)
    DE (2) DE19807805A1 (en)
    ES (1) ES2180283T3 (en)
    WO (1) WO1999043772A2 (en)

    Family Cites Families (9)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE3413571A1 (en) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt USE OF CRYSTALLINE LAYERED SODIUM SILICATES FOR WATER SOFTENING AND METHOD FOR WATER SOFTENING
    DE3706036A1 (en) 1987-02-25 1988-09-08 Basf Ag POLYACETALS, METHOD FOR THE PRODUCTION THEREOF FROM DIALDEHYDES AND POLYOLCARBONIC ACIDS AND USE OF THE POLYACETALS
    ATE155165T1 (en) 1991-07-31 1997-07-15 Ausimont Spa METHOD FOR INCREASING THE BLEACHING EFFECTIVENESS OF AN INORGANIC PER SALT
    DE4221381C1 (en) 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Graft copolymers of unsaturated monomers and sugars, process for their preparation and their use
    DE4300772C2 (en) 1993-01-14 1997-03-27 Stockhausen Chem Fab Gmbh Water-soluble, biodegradable copolymers based on unsaturated mono- and dicarboxylic acids, process for their preparation and their use
    AU7062494A (en) * 1993-07-12 1995-02-13 Procter & Gamble Company, The Surfactant system
    GB2289687A (en) 1994-04-11 1995-11-29 Procter & Gamble Agglomerated Detergent Composition Containing High Levels Of Anionic Surfactants And Potassium Salt For Improved Solubility In Cold Temperature Laundering Sol
    GB2296919A (en) * 1995-01-12 1996-07-17 Procter & Gamble Detergent composition
    DE19746780A1 (en) 1997-10-23 1999-04-29 Henkel Kgaa Production of perfumed moldings especially beads with high bulk density useful in detergent

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    US6531439B1 (en) 2003-03-11
    DE19807805A1 (en) 1999-09-02
    ES2180283T3 (en) 2003-02-01
    WO1999043772A3 (en) 1999-11-11
    DE59902409D1 (en) 2002-09-26
    WO1999043772A2 (en) 1999-09-02
    ATE222597T1 (en) 2002-09-15
    EP1058722A1 (en) 2000-12-13

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