EP0888449B1 - Solid surfactant and builder-containing washing and cleaning agent with a high bulk density or compound for such an agent - Google Patents

Solid surfactant and builder-containing washing and cleaning agent with a high bulk density or compound for such an agent Download PDF

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Publication number
EP0888449B1
EP0888449B1 EP97907093A EP97907093A EP0888449B1 EP 0888449 B1 EP0888449 B1 EP 0888449B1 EP 97907093 A EP97907093 A EP 97907093A EP 97907093 A EP97907093 A EP 97907093A EP 0888449 B1 EP0888449 B1 EP 0888449B1
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EP
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Prior art keywords
weight
zeolite
detergent
alkyl
water
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Application number
EP97907093A
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German (de)
French (fr)
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EP0888449A1 (en
Inventor
Katrin Burmeister
Roswitha Pawelczyk
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • 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
    • C11D1/66—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to a solid detergent and builder-containing detergent and cleaning agent with a high bulk density or compound therefor, which contains water-soluble silicate and zeolite as a builder and C 9 -C 13 alkylbenzenesulfonates and C 8 -C 22 alkyl sulfates as anionic surfactants.
  • zeolite in particular, are used as inorganic builder substances Zeolite NaA and Zeolite P, and alkali silicates used.
  • inorganic builder substances Zeolite NaA and Zeolite P
  • alkali silicates used.
  • mixtures of zeolite with alkali silicates and alkali carbonates are used and organic builders, such as polymeric carboxylates.
  • EP-A-0 291 869 describes combinations of builders from zeolite, aminoalkane polyphosphonate and / or polymeric polycarboxylate and 1-hydroxyethane-1,1-diphosphonate (HEDP), with certain weight ratios of the last three components a synergism regarding the change in the training of Show fiber incrustations.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • crystalline, layered sodium silicates as a builder is described, for example, in European patent application EP-A-164 514, which discloses a builder combination which mainly contains crystalline sheet silicates of the formula (I) NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • layered silicates can be used as water softeners both separately and in detergents and cleaning agents together with other builders such as phosphates, zeolite, other silicates, phosphonates and polycarboxylates.
  • EP-A-0 405 122 a builder combination is used described for a textile detergent which is a mixture of zeolite and crystalline Contains layered sodium silicate in a ratio of 4: 1 to 1: 4.
  • the zeolites are used in the production of detergents at the same time their absorbency, i.e. the adsorption capacity by acting as a carrier material for some surfactants, e.g. nonionic surfactants.
  • zeolites are replaced by the water-soluble silicates in products containing large amounts of sticky substances, for example alkylbenzenesulfonates, this leads to increased stickiness.
  • the alkyl benzene sulfonates can be replaced, for example, by the fatty alkyl sulfates.
  • Japanese patent application JP-A-4036398 discloses high bulk density detergent compositions in which zeolite is completely replaced by crystalline layered sodium silicate and a mixture of an alkylbenzenesulfonate and a fatty alkyl sulfate is used.
  • Examples 3 and 8 describe compositions of 20% by weight ⁇ -Na 2 Si 2 O 5 , 10% by weight of a C 10 -C 14 alkylbenzenesulfonate and 10% by weight of a C 12 alkyl sulfate.
  • the fatty alkyl sulfates have the disadvantage that they have a lower solubility than the alkyl benzene sulfonates and in particular the C 12 -C 14 fatty alkyl sulfates foam very strongly.
  • zeolite is necessary to process the surfactants in the spray tower can.
  • the tower powder Solid removed, so that correspondingly smaller amounts of surfactant are incorporated can.
  • the surfactants must then partly as separate additional components Detergent can be added.
  • solid and liquid Detergent raw materials in particular anionic surfactants, builder substances, alkalizing agents and liquid nonionic surfactants and optionally water or aqueous solutions of the preceding, with simultaneous or subsequent shaping and If necessary, drying can be combined by first all solid Components mixed together and then the liquid components be added, an additive to improve the dissolution behavior from the group of fatty alkyl sulfates, olefin sulfonates, alkyl aromatic sulfonates and Mixtures of these after mixing the solid ingredients in the process is introduced.
  • Both organic and inorganic come as builder substances Substances into consideration, e.g. Zeolites, layered silicates, and polymers Polycarboxylates.
  • the agents described contain up to 50% by weight of zeolite.
  • German patent application DE-A-195 25 378 describes a method for Manufacture of readily soluble washing and cleaning agents with bulk density above 600 g / l, in which zeolite is completely or partially dispensed with.
  • a Compound made by powdered alkali metal carbonate, or alkali metal silicate a mixture thereof is agglomerated using an aqueous preparation.
  • This aqueous preparation contains, inter alia, one or more anionic surfactants, advantageously Alkylbenzenesulfonates and / or alk (en) ylsulfates.
  • the compound can be added later liquid ingredients, especially nonionic surfactants are treated.
  • the washing or cleaning agent then contains the compound, between 0 and 30% by weight of zeolite and is produced by granulation, roller compaction, extrusion or mixing.
  • the present invention had the object of a powdery washing and see To provide cleaning agents that are easy to manufacture and that are easy to use.
  • S. 3a availability i.e. good powder properties, e.g. low stickiness and good Solubility, the zeolite at least partially by a water-soluble silicate can be replaced.
  • the present invention relates to a solid detergent and builder-containing washing and cleaning agent with a high bulk density or compound therefor, this agent being an anionic surfactant from 0.1% by weight to 10% by weight of C 9 -C 13 alkylbenzenesulfonates and 10% by weight to 50% by weight of C 8 -C 22 alkyl sulfates and as a builder contains 10% by weight to 45% by weight of water-soluble silicates and up to 30% by weight of zeolite.
  • the weight percentages given here relate to the total funds.
  • the total of the ingredients adds up to 100% by weight.
  • the water-soluble alkali silicates contained according to the invention can be amorphous, X-ray amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 1.8 to 1: 3.5.
  • Such crystalline layered silicates are described, for example, in European patent application 164 514.
  • Preferred crystalline sheet silicates of the formula (I) are those in which M represents sodium and x assumes the values 2 or 3.
  • M represents sodium
  • x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 • yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in the international patent application WO-A-91/08171.
  • the content of water-soluble alkali silicates in the agents is preferably 10% by weight to 40% by weight and in particular 10% by weight to 35% by weight, based on the anhydrous active substance.
  • the agents according to the invention contain C 8 -C 22 alkyl sulfates as further substances, which are preferably contained in an amount of 12 wt.% To 30 wt.% In the agent according to the invention.
  • Particularly suitable C 8 -C 22 alkyl sulfates are the sulfuric acid monoesters of the fatty alcohols, in particular the C 6 -C 18 fatty alcohols, such as lauryl, myristyl, cetyl or stearyl alcohol or the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil may also contain proportions of unsaturated alcohols, for example oleyl alcohol.
  • Preferred mixtures are those in which the proportion of the alkyl radicals is 15 to 40% by weight on C 12 , 5 to 15% by weight on C 14 , 15 to 25% by weight on C 16 , 30 to 60% by weight on C 18 and less than 1% by weight on C 10 are distributed.
  • alkylbenzenesulfonates are preferably present in the agent according to the invention in an amount of 0.5 wt.% To 5 wt.
  • Preferred alkylbenzenesulfonates are those cuts which contain large amounts of C 12 -alkylbenzenesulfonate.
  • the C 8 -C 22 alkyl sulfates and the C 9 -C 13 alkyl benzene sulfonates are present in a weight ratio of 20: 1 to 2: 1, in particular 10: 1 to 2: 1, in the agent according to the invention.
  • the detergents and cleaning agents according to the invention can be used as further ingredients other builders and surfactants and others, usually in such agents have contained substances.
  • the agent according to the invention can also contain zeolites as optional builder substances.
  • Zeolite A for example, but also zeolite are suitable X and zeolite P and mixtures of A, X and / or P.
  • Zeolite is preferably from A type in detergent quality.
  • Mixtures of zeolite NaA are also suitable and NaX, the proportion of the zeolite NaX in such mixtures expediently is below 30%. They have practically no particles larger than 30 ⁇ m and exist preferably at least 80% of particles smaller than 10 microns in size.
  • Suitable Zeolites have an average particle size of less than 10 ⁇ m (measurement method: Eisenhofer diffraction; Average volume distribution), preferably between 1.5 and 4.5 ⁇ m, in particular between 2.0 and 4.0 ⁇ m.
  • Your calcium binding capacity is in the range from 100 to 200 mg CaO / g.
  • the zeolite generally has a water content of 17 up to 25% by weight, preferably 18 to 22, in particular 20 to 22% by weight.
  • the salary the average of finely divided, in particular crystalline, hydrated zeolite preferably 0.5 to 30 wt .-%, based on anhydrous active substance.
  • the weight ratio of water-soluble silicates to zeolite between 1: 0.01 and 1: 1.5.
  • Polymeric carboxylates or polymeric carboxylic acids can also be used as additional builders be included. These polymeric carboxylates or carboxylic acids can in the invention Detergent is present in an amount of 1 to 15 wt .-%.
  • 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 especially 50,000 to 100,000.
  • the (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution are used, 20 to 55% by weight aqueous solutions being preferred.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 1 to 12 % By weight, in particular 2 to 10% by weight.
  • biodegradable terpolymers for example those those according to DE-A-43 00 772 as monomers salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or as according to DE-C-42 21 381 Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those described in the German patent applications DE-A-43 03 320 and P 44 17 734.8 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • Further usable organic builders are, for example, those preferred in Form of their sodium salts used polycarboxylic acids, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acid, aminocarboxylic acid, nitrilotriacetic acid (NTA), as long as there is no objection to such use for ecological reasons is, and mixtures of these.
  • Preferred salts are the salts of the polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Suitable anionic surfactants agent C of the invention can -Alkylpolyglykolethersulfonate 6 -C 18, C 6 -C 18 -Fettklareestersulfonate, C 6 -C 18 -Fettalkylethersulfate, olefin sulfonates, glycerol ether, Glycerol ether sulfates, alkenyl sulfates, Hydroxymischethersulfate, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, amide acids, C 6 -C 18 fatty acid amide ether sulfates, 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 - Contain alkyl
  • soaps can be contained in the agents according to the invention, in particular saturated fatty acid soaps, the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut-, Palm kernel or tallow fatty acids, derived soap mixtures, are suitable.
  • the further surfactants and the soaps can be used in a total amount of 1 to 15 % By weight, in particular 1 to 10% by weight, alone or in any mixtures in the agents according to the invention are present.
  • the total surfactant content is in the Agents according to the invention preferably over 20 wt .-%.
  • the agent according to the invention can also contain nonionic surfactants in an amount of 1 to 25% by weight, preferably 2% by weight to 20% by weight.
  • the preferred nonionic surfactants are liquid, alkoxylated, preferably ethoxylated, especially primary alcohols with preferably 8 to 18 carbon atoms (alkyl polyglycol ether) and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or in 2- Position may be methyl branched, or may contain linear and methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms for example from coconut oil, tallow oil or oleyl alcohol, which can have an average of 2 to 8 EO units per mole of alcohol, are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO units or 7 EO units, C 9 -C 11 alcohols with 3 EO units, 5 EO units or 7 EO units and mixtures of these this, such as mixtures of C 12 -C 14 alcohol with 3 EO units and C 12 -C 18 alcohol with 5 EO units.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol alkoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • the agent according to the invention can be alkyl polyglycosides, Fatty acid alkyl esters; Contain amine oxides and polyhydroxy fatty acid amides.
  • Structure breakers can be used as further components. Structure breakers are usually used to improve the processability of funds. Suitable structure breakers are particularly ethoxylated C 8 -C 18 fatty alcohols with 20 to 45 EO, preferably tallow fatty alcohols with 30 and 40 EO, polyethylene glycol or polypropylene glycol, sulfates and / or disulfates of polyethylene glycol or polypropylene glycol, sulfosuccinates and / or disulfosuccinates of polyethylene glycol or polypropylene glycol or mixtures of these.
  • the nonionic surfactants and the structure breakers can be used in a ratio of nonionic surfactant to structure breaker of 1: 1 to 15: 1.
  • the detergents produced according to the invention preferably contain peroxy bleaching agents and in particular peroxy bleaching agents in combination with bleach activators.
  • peroxy bleaching agents sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or diperoxydodecanedioic acid.
  • the detergents preferably contain 5 to 25% by weight and in particular 10 to 20% by weight of bleaching agent, sodium percarbonate and / or sodium perborate monohydrate being preferably used.
  • bleach activators can be incorporated into the preparations which form organic peracids with H 2 O 2 .
  • these are N- or O-acyl compounds, for example multi-acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanuric acid hydrides, and also carboxylic acid hydrides , Carboxylic acid esters, especially sodium isonanoyloxybenzenesulfonate, and acylated sugar derivatives, especially pentaacetyl glucose.
  • N- or O-acyl compounds for example multi-acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular
  • the bleach activator can be coated with coating substances in a known manner or, if necessary with the aid of auxiliaries, granulated or extruded / pelletized and, if desired, contain further additives, for example dye.
  • Such granules preferably contain over 70% by weight, in particular from 90% by weight to 99% by weight, of bleach activator.
  • a bleach activator is preferably used which forms peracetic acid under the washing conditions.
  • TAED tetraacetylethylenediamine
  • DADHT 1,5- Diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • Extruded TAED which contains 70 70% by weight of TAED, 15 to 25% by weight of C 12-18 fatty alcohol sulfate and 2 to 6% by weight of soda can also be used.
  • the content of bleach activators in the detergents containing bleach is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Suitable ingredients of the agents according to the invention are water-soluble inorganic salts such as bicarbonates, carbonates or mixtures thereof; in particular alkali carbonate and 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.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously 5 and 15% by weight.
  • the other detergent ingredients include foam inhibitors, optical brighteners, enzymes, fabric softening agents, colors and fragrances.
  • Neutral salts can also be found in an amount up to 20 wt .-% may be contained, their proportion is preferably ⁇ 10 wt .-%.
  • the agent can contain additional graying inhibitors in an amount of 0.1 to 5 % By weight, based on the composition.
  • additional graying inhibitors are Suitable water-soluble colloids mostly organic, for example soluble starch preparations and Z.
  • Enzymes come from the class of proteases, lipases or lipolytic acting enzymes, amylases, cellulases or mixtures thereof in question. Particularly good are suitable from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens Active ingredients. Proteases of the subtilisin type and in particular are preferred 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 Celiulase 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.
  • lipolytic enzymes are the well-known cutinases. Peroxidases too or oxidases have been found to be suitable in some cases.
  • the enzymes can adsorbed on carriers and / or embedded in coating substances to counter them to protect 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 % By weight.
  • the stabilizers come in particular for peroxygen compounds and enzymes Salts, such as neutral sodium salts, of polyphosphonic acids, especially of 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DETPMP diethylenetriaminepentamethylenephosphonic acid
  • ethylenediaminetetramethylenephosphonic acid ethylenediaminetetramethylenephosphonic acid.
  • the phosphonates can be in Amounts of up to 1.5% by weight are used, but preference is given to these additives dispensed with, so that the detergents according to the invention have a mathematical calculation Have phosphorus content of 0%.
  • the agents can contain enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1 wt .-% sodium formate can be used.
  • proteases those with soluble calcium seeds and a calcium content of preferably about 1.2 % By weight, based on the enzyme, are stabilized.
  • boron compounds for example boric acid, boron oxide, borax and others Alkali metal borates.
  • Suitable foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica as well as paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica.
  • Can with advantage mixtures of different foam inhibitors can also be used, e.g. those made of silicone oil, Paraffin oil or waxing.
  • the foam inhibitors are preferably attached to a granular, water-soluble or dispersible carrier substance bound.
  • the powder detergents can be used as optical brighteners, for example derivatives of Contain diaminostilbenedisulfonic acid or its alkali metal salts, which are good in dispersions Have it incorporated (see below).
  • the maximum amount of brightener in the invention Average is 0.5 wt .-%, preferably amounts from 0.02 to 0.25 wt .-% used.
  • Another object of the present invention relates to the production of detergents and cleaning agents containing surfactants and builders which contain 0.1% by weight to 10% by weight of C 9 -C 13 alkylbenzenesulfonate and 10% by weight to 50 % By weight of C 8 -C 22 alkyl sulfate as anionic surfactants and 10 to 45% by weight of water-soluble silicates and 0 to 30% by weight of zeolite as a builder, in which a premix is prepared from solid and liquid detergent constituents and this Premix is then pressed.
  • liquid non-ionic substances in particular come as liquid detergent components Surfactants into consideration.
  • the combination of the solid and liquid detergent raw materials under simultaneous or subsequent shaping and, if desired, drying can be carried out according to all known Processes in which washing and cleaning agents with a high bulk density, i.e. with a bulk density above 500 g / l, preferably above 600 g / l and in particular between 700 and 1,000 g / l, are carried out.
  • Examples of such known and preferred processes are granulation processes, in which either contain the solid ingredients of a detergent or cleaning agent spray-dried washing and cleaning agent or a mixture of spray-dried and non-spray-dried ingredients of washing and Detergents, if necessary including the additive, in a quick running mixer compacted and simultaneously in this mixer or after it in a further device, for example in a fluidized bed, with the liquid Components are mixed or applied.
  • a premix is first is made from detergent ingredients.
  • This solid, preferably homogeneous premix is with the addition of a plasticizer and / or lubricant over hole shapes with opening widths the predetermined granule dimension at high pressures between 25 and 200 bar extruded.
  • the strand is immediately after exiting the hole shape cut to the predetermined granule dimension by means of a cutting device.
  • the application of the high working pressure causes the premix to be plasticized in the formation of granules and provides the cutting ability of the freshly extruded strands for sure.
  • the premix consists at least partly of solid, preferably finely divided usual ingredients of detergents and cleaning agents, where appropriate liquid components are mixed.
  • the solid ingredients can go through Spray drying obtained tower powders, but also agglomerates, the selected one Mixture components as pure substances that mix with each other in the finely divided state will be, as well as mixtures of these. Subsequently, if necessary added the liquid ingredients and then the one selected according to the invention Plasticizers and / or lubricants mixed. As a plasticizer and / or lubricant aqueous solutions of polymeric polycarboxylates as well as highly concentrated anionic surfactant pastes and nonionic surfactants are preferred. For a detailed description of the Process and the appropriate ingredients of the premix and the appropriate Plasticizer and / or lubricant is based on the disclosure of the international Patent application WO 91/02047 referenced.
  • the liquid Nonionic surfactants also as a liquid component or as a plasticizer and / or Lubricants can be added to the solid premix or they are an ingredient a solid mixture component of the premix, this solid Mixture component can consist of a carrier bead, which with a solution or a dispersion was applied.
  • the addition of the liquid component, that is not bound to a carrier bead, can at any point in the process to Example in the production of the premix, but also in the processing of the plasticized Premix, but before passing through the hole shape (perforated nozzle plate) respectively.
  • Kneaders of any configuration are preferably used as the homogenizing device, For example, 2-screw kneaders can be selected.
  • the intensive mixing process can itself lead to a desired temperature increase. Moderately elevated temperatures of, for example, 60 to 70 ° C are usually not exceeded.
  • the premix preferably fed continuously to a 2-screw kneader (extruder), the Housing and its extruder pelletizing head to the predetermined extrusion temperature tempered, for example heated to 40 to 60 ° C. Under the action of shear the extruder screws, the premix is plasticized at pressures of 25 to 200 bar, in the form of fine strands through the perforated nozzle plate in the extruder head and finally the extrudate, preferably in a rotating knife, in reduced spherical to cylindrical granules.
  • the hole diameter in the Perforated nozzle plate and the strand cut length are based on the selected granulate dimension Voted.
  • the production of Granules of a substantially uniformly predeterminable particle size in which individual the absolute particle sizes to be adapted to the intended application can.
  • particle diameters up to at most 0.8 cm are preferred.
  • Important embodiments see the production of uniform granules Diameters in the millimeter range, for example in the range from 0.5 to 5 mm and especially in the range of 0.8 to 3 mm.
  • the length / diameter ratio of the In an important embodiment, the chopped off primary granulate lies in Range from 1: 1 to about 3: 1.
  • the still plastic, moist To supply primary granulate to a further shaping processing step be there edges present on the raw granulate are rounded, so that ultimately spherical or at least approximately spherical granules can be obtained.
  • small amounts of dry powder for example, can be used at this stage Zeolite powder such as zeolite NaA powder can also be used. This shape can be used in standard rounding machines, for example in rotary machines with rotating Bottom disc.
  • the granules are then preferably one Drying step, for example a fluidized bed dryer, supplied.
  • Tablets can, for example, be produced in such a way that the builder substances, in particular the water-soluble alkali silicates and possibly all other components mixed together in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses, hydraulic presses or rotary presses with pressures in the range from 1 to 300 bar, advantageously in the range from about 5 to 200 bar and in particular between 10 and 150 bar.
  • the compression is preferably carried out without the addition of water.
  • the premixes provided for compression however, by mixing the individual ingredients, which are at least partially in Pre-assembled form as a granular compound.
  • a tablet produced in this way preferably has a weight from 10 to 120 g, in particular from 20 to 100 g, the diameter of the Tablets is usually less than 100 mm.
  • the Diameter / height ratio of the tablets should be optimized so that a as little abrasion as possible on the vertical walls of the tabletting apparatus (higher Diameter / low height) with sufficient stability and not too large Surface (small diameter / high height) is guaranteed.
  • Preferred diameter / height ratios the cylindrical compacts are about 0.5: 1 to 10: 1, especially at 1: 1 to 8: 1.
  • dry powders of this type are zeolite NaA powder, but also precipitated or pyrogenic silica, as for example as Aerosil® or Sipernat® (products from Degussa) in Are commercially available. Highly concentrated, at least 90, are also preferred % By weight alcohol sulfate powder which is essentially, i.e. at least 90% particles exist with a particle size smaller than 100 microns. In particular are Mixtures of zeolite and alcohol sulfate powder are preferred.
  • the washing and cleaning agents can be produced uniformly from extrudates, which have the above-mentioned ingredients.
  • the finished funds can, however also from a mixture of several different solids, in particular several various granules, of which, for example, the Powdered washing and cleaning agents according to the invention the main ingredient form.
  • the bleach, the bleach activator, the enzymes and Dyes and fragrances are subsequently added to the extrudates. It is preferred that the bleach, the bleach activator and the enzymes are each in compacted granular form, for example as extrudates produced separately, by means of a kneader of the configuration described above or via a pellet press be obtained.
  • the mixture was homogenized for 2 minutes and then in a twin-screw extruder fed, its housing including the extruder pelletizing head was tempered to 45 ° C.
  • the premix was plasticized under the shear action of the extruder screws and then extruded at a pressure of 120 bar through the extruder perforated die plates into fine strands with a diameter of 1.2 mm, which were chopped into approximately spherical granules using a knock-out knife . (Length / diameter ratio about 1, hot cut).
  • the product obtained was rounded off for about 1 minute in a commercially available rounding machine of the type Marumerizer® with the addition of small amounts of zeolite NaA and then dried at a supply air temperature of 70 ° C. in a fluidized bed dryer until an exhaust air temperature of 53 ° C. was reached.
  • Example 1 (comparison)
  • Example 2 composition End product 1 Premix 1 End product 2
  • Premix 2 Premix 2 C 11 -C 13 alkyl benzene sulfonate 1.00 1.19 C 12-18 fatty alcohol sulfate 17.77 21.26 16.77 20.05 C 12-18 fatty alcohol x 7 EO 3.55 4.24 3.55 4.24 optical brightener 0.04 0.05 0.04 0.05 Perfume 0.36 0.36
  • Zeolite 3.15 3.15 Na perborate monohydrate 17.53 20.96 17.53 20.96 TAED 7.00 7.00

Abstract

The washing and cleaning agent proposed contains 0.1 to 10 % by wt. of C9-C13 alkylbenzene sulphonate and 10 to 50 % by wt. of C8-C22 alkyl sulphate as anionic surfactants and 10 to 45 % by wt. of water-soluble silicates and up to 30 % by wt. of zeolite as builders. The agent exhibits excellent powder properties, such as a low tendency to stick and ease of solubility.

Description

Die Erfindung betrifft ein festes Tensid- und Builder-haltiges Wasch- und Reinigungsmittel mit hohem Schüttgewicht oder Compound hierfür, das als Builder wasserlösliches Silikat und Zeolith und als anionische Tenside C9-C13-Alkylbenzolsulfonate und C8-C22-Alkylsulfate enthält.The invention relates to a solid detergent and builder-containing detergent and cleaning agent with a high bulk density or compound therefor, which contains water-soluble silicate and zeolite as a builder and C 9 -C 13 alkylbenzenesulfonates and C 8 -C 22 alkyl sulfates as anionic surfactants.

In der Praxis werden als anorganische Buildersubstanzen vor allem Zeolith, insbesondere Zeolith NaA und Zeolith P, und Alkalisilikate eingesetzt. Zur Reduzierung von Inkrustationen verwendet man beispielsweise Mischungen von Zeolith mit Alkalisilikaten und Alkalicarbonaten sowie organischen Gerüstsubstanzen, wie polymeren Carboxylaten.In practice, zeolite, in particular, are used as inorganic builder substances Zeolite NaA and Zeolite P, and alkali silicates used. To reduce incrustations for example, mixtures of zeolite with alkali silicates and alkali carbonates are used and organic builders, such as polymeric carboxylates.

Die europäische Patentanmeldung EP-A-0 291 869 beschreibt Gerüststoffkombinationen aus Zeolith, Aminoalkanpolyphosphonat und/oder polymerem Polycarboxylat sowie 1-Hydroxyethan-1,1-diphosphonat (HEDP), wobei bestimmte Gewichtsverhältnisse der letzten drei Komponenten einen Synergismus bezüglich der Veränderung der Ausbildung von Faserinkrustationen zeigen.European patent application EP-A-0 291 869 describes combinations of builders from zeolite, aminoalkane polyphosphonate and / or polymeric polycarboxylate and 1-hydroxyethane-1,1-diphosphonate (HEDP), with certain weight ratios of the last three components a synergism regarding the change in the training of Show fiber incrustations.

Der Einsatz von kristallinen, schichtförmigen Natriumsilikaten als Gerüstsubstanz wird beispielsweise in der europäischen Patentanmeldung EP-A-164 514 beschrieben, worin eine Gerüststoffkombination offenbart wird, die hauptsächlich kristalline Schichtsilikate der Formel (I) NaMSixO2x+1.yH2O enthält, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 und bevorzugte Werte für x 2, 3 oder 4 sind. Diese Schichtsilikate können als Wasserenthärtungsmittel sowohl separat als auch in Wasch- und Reinigungsmitteln zusammen mit anderen Gerüststoffen wie Phosphaten, Zeolith, weiteren Silikaten, Phosphonaten und Polycarboxylaten eingesetzt werden.The use of crystalline, layered sodium silicates as a builder is described, for example, in European patent application EP-A-164 514, which discloses a builder combination which mainly contains crystalline sheet silicates of the formula (I) NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. These layered silicates can be used as water softeners both separately and in detergents and cleaning agents together with other builders such as phosphates, zeolite, other silicates, phosphonates and polycarboxylates.

So wird zum Beispiel in der europäischen Patentanmeldung EP-A-0 405 122 eine Builderkombination für ein Textilwaschmittel beschrieben, das ein Gemisch aus Zeolith und kristallinem Natriumschichtsilikat in einem Verhältnis von 4 : 1 bis 1 : 4 enthält. For example, in European patent application EP-A-0 405 122 a builder combination is used described for a textile detergent which is a mixture of zeolite and crystalline Contains layered sodium silicate in a ratio of 4: 1 to 1: 4.

Von Buildersystemen auf Basis von Zeolith, wie sie in den voranstehend genannten Druckschriften beschrieben werden, sind zwar keine ökologisch nachteiligen Wirkungen bekannt, die modernen Haushaltswaschmaschinen benötigen aber pro Waschgang immer weniger Wasser, so daß die Gefahr besteht, daß sich die relativ schwerlöslichen Buildersysteme nicht vollständig auflösen und es zur Bildung von Inkrustationen kommen kann.From builder systems based on zeolite, such as those mentioned above Descriptions of publications are not ecologically disadvantageous effects known, but modern household washing machines always need one wash less water, so that there is a risk that the relatively sparingly soluble Do not completely dissolve builder systems and incrustations form can.

Neben dem Ca-Bindevermögen der Zeolithe nutzt man bei der Herstellung von Waschmitteln gleichzeitig ihre Saugfähigkeit, d.h. das Adsorptionsvermögen, indem sie als Trägermaterial für einige Tenside, z.B. nichtionische Tenside, dienen.In addition to the Ca binding capacity of the zeolites, they are used in the production of detergents at the same time their absorbency, i.e. the adsorption capacity by acting as a carrier material for some surfactants, e.g. nonionic surfactants.

Der Austausch von Zeolith gegen wasserlösliche Substanzen, beispielsweise wasserlösliche Silikate, ist nicht ohne weiteres möglich. Werden beispielsweise in Produkten, die in größeren Mengen klebrige Substanzen, z.B. Alkylbenzolsulfonate, enthalten, Zeolithe durch die wasserlöslichen Silikate ersetzt, führt das zu einer erhöhten Klebrigkeit. Um die Klebrigkeit der Produkte zu verringern, können die Alkylbenzolsulfonate beispielsweise durch die Fettalkylsulfate ersetzt werden. In der japanischen Patentanmeldung JP-A-4036398 werden Waschmittelzusammensetzungen hoher Schüttdichte offenbart, bei denen Zeolith gänzlich gegen kristallines Natriumschichtsilicat ausgetauscht ist sowie eine Mischung aus einem Alkylbenzolsulfonat und einem Fettalkylsulfat eingesetzt wird. So werden in den Beispielen 3 und 8 Zusammensetzungen aus 20 Gew.-% δ-Na2Si2O5, 10 Gew.-% eines C10-C14 Alkylbenzolsulfonates sowie 10 Gew.-% eines C12-Alkylsulfates beschrieben. Die Fettalkylsulfate haben jedoch den Nachteil, siehe daß sie eine geringere Löslichkeit als die Alkylbenzolsulfonate haben und insbesondere die C12-C14-Fettalkylsulfate sehr stark schäumen.The exchange of zeolite for water-soluble substances, for example water-soluble silicates, is not easily possible. If, for example, zeolites are replaced by the water-soluble silicates in products containing large amounts of sticky substances, for example alkylbenzenesulfonates, this leads to increased stickiness. In order to reduce the stickiness of the products, the alkyl benzene sulfonates can be replaced, for example, by the fatty alkyl sulfates. Japanese patent application JP-A-4036398 discloses high bulk density detergent compositions in which zeolite is completely replaced by crystalline layered sodium silicate and a mixture of an alkylbenzenesulfonate and a fatty alkyl sulfate is used. Examples 3 and 8 describe compositions of 20% by weight δ-Na 2 Si 2 O 5 , 10% by weight of a C 10 -C 14 alkylbenzenesulfonate and 10% by weight of a C 12 alkyl sulfate. However, the fatty alkyl sulfates have the disadvantage that they have a lower solubility than the alkyl benzene sulfonates and in particular the C 12 -C 14 fatty alkyl sulfates foam very strongly.

Der Austausch von Zeolith gegen wasserlösliche Substanzen führt auch bei der Herstellung über ein Sprühtrocknungsverfahren im sogenannten Sprühturm zu Problemen. Wie bereits bechrieben, ist Zeolith notwendig, um die Tenside im Sprühturm mitverarbeiten zu können. Beim Austausch von Zeolith gegen wasserlösliche Silikate wird dem Turmpulver Feststoff entzogen, so daß entsprechend geringere Mengen an Tensid eingearbeitet werden können. Die Tenside müssen dann teilweise als separate Zusatzkomponenten dem Waschmittel zugesetzt werden.The exchange of zeolite for water-soluble substances also leads to the production via a spray drying process in the so-called spray tower to problems. How Already described, zeolite is necessary to process the surfactants in the spray tower can. When replacing zeolite with water-soluble silicates, the tower powder Solid removed, so that correspondingly smaller amounts of surfactant are incorporated can. The surfactants must then partly as separate additional components Detergent can be added.

In der internationalen Patentanmeldung WO-A-93/15180 wird beispielsweise ein Verfahren zur Herstellung fester Wasch- und Reinigungsmittel mit hohem Schüttgewicht und verbesserter Lösegeschwindigkeit beschrieben, worin feste und flüssige Waschmittelrohstoffe, insbesondere Aniontenside, Buildersubstanzen, Alkalisierungsmittel und flüssige Niotenside sowie gegebenenfalls Wasser oder wäßrige Lösungen der voranstehenden, unter gleichzeitiger oder anschließender Formgebung und gegebenenfalls Trocknung zusammengegeben werden, indem zunächst alle festen Bestandteile miteinander vermischt und anschließend die flüssigen Bestandteile hinzugegeben werden, wobei zur Verbesserung des Auflöseverhaltens ein Zusatzstoff aus der Gruppe der Fettalkylsulfate, Olefinsulfonate, alkylaromatischen Sulfonaten und Mischungen aus diesen nach dem Vermischen der festen Bestandteile in das Verfahren eingebracht wird. Als Buildersubstanzen kommen sowohl organische als auch anorganische Substanzen in Betracht, z.B. Zeolithe, Schichtsilikate, und polymere Polycarboxylate. Die beschriebenen Mittel enthalten bis 50 Gew.-% Zeolith.For example, in international patent application WO-A-93/15180 Process for the production of solid washing and cleaning agents with a high bulk density and improved dissolving speed, wherein solid and liquid Detergent raw materials, in particular anionic surfactants, builder substances, alkalizing agents and liquid nonionic surfactants and optionally water or aqueous solutions of the preceding, with simultaneous or subsequent shaping and If necessary, drying can be combined by first all solid Components mixed together and then the liquid components be added, an additive to improve the dissolution behavior from the group of fatty alkyl sulfates, olefin sulfonates, alkyl aromatic sulfonates and Mixtures of these after mixing the solid ingredients in the process is introduced. Both organic and inorganic come as builder substances Substances into consideration, e.g. Zeolites, layered silicates, and polymers Polycarboxylates. The agents described contain up to 50% by weight of zeolite.

Außerdem beschreibt die deutsche Offenlegungsschrift DE-A-195 25 378 ein Verfahren zur Herstellung von gut löslichen Wasch- und Reinigungsmitteln mit Schüttgewicht oberhalb von 600 g/l, bei denen ganz oder teilweise auf Zeolith verzichtet wird. Dabei wird zunächst ein Compound hergestellt, indem pulverförmiges Alkalimetallcarbonat, Alkalimetallsilicat oder eine Mischung daraus unter Verwendung einer wäßrigen Zubereitung agglomeriert wird. Diese wäßrige Zubereitung enthält u.a eines oder mehrere Aniontenside, vorteilhafterweise Alkylbenzolsulfonate und/oder Alk(en)ylsulfate. Das Compound kann nachträglich mit flüssigen Inhaltsstoffen, insbesondere nichtionischen Tensiden behandelt werden. Das Wasch- oder Reinigungsmittel enthält dann das Compound, zwischen 0 und 30 Gew.% Zeolith und wird durch Granulierung, Walzenkompaktierung, Extrusion oder Mischen hergestellt.In addition, the German patent application DE-A-195 25 378 describes a method for Manufacture of readily soluble washing and cleaning agents with bulk density above 600 g / l, in which zeolite is completely or partially dispensed with. First, a Compound made by powdered alkali metal carbonate, or alkali metal silicate a mixture thereof is agglomerated using an aqueous preparation. This aqueous preparation contains, inter alia, one or more anionic surfactants, advantageously Alkylbenzenesulfonates and / or alk (en) ylsulfates. The compound can be added later liquid ingredients, especially nonionic surfactants are treated. The washing or cleaning agent then contains the compound, between 0 and 30% by weight of zeolite and is produced by granulation, roller compaction, extrusion or mixing.

Der vorliegenden Erfindung lag die Aufgabe zugrunde, ein pulverförmiges Wasch- und siehe Reinigungsmittel zur Verfügung zu stellen, das gut herstellbar ist und eine gute Hand- S. 3a habbarkeit, d.h. gute Pulvereigenschaften, wie z.B. eine geringe Klebrigkeit und eine gute Löslichkeit, aufweist, wobei der Zeolith zumindest teilweise durch ein wasserlösliches Silikat ersetzt werden kann.The present invention had the object of a powdery washing and see To provide cleaning agents that are easy to manufacture and that are easy to use. S. 3a availability, i.e. good powder properties, e.g. low stickiness and good Solubility, the zeolite at least partially by a water-soluble silicate can be replaced.

Gegenstand der vorliegenden Erfindung ist ein festes Tensid- und Builder-haltiges Wasch- und Reinigungsmittel mit hohem Schüttgewicht oder Compound hierfür, wobei dieses Mittel als anionische Tenside 0,1 Gew.-% bis 10 Gew.-% C9-C13-Alkybenzolsulfonate und 10 Gew.-% bis 50 Gew.-% C8-C22-Alkylsulfate und als Builder 10 Gew.-% bis 45 Gew.-% wasserlösliche Silikate und bis zu 30 Gew.-% Zeolith enthält.The present invention relates to a solid detergent and builder-containing washing and cleaning agent with a high bulk density or compound therefor, this agent being an anionic surfactant from 0.1% by weight to 10% by weight of C 9 -C 13 alkylbenzenesulfonates and 10% by weight to 50% by weight of C 8 -C 22 alkyl sulfates and as a builder contains 10% by weight to 45% by weight of water-soluble silicates and up to 30% by weight of zeolite.

Die hier angegebenen Mengenangaben in Gewichtsprozent beziehen sich jeweils auf das gesamte Mittel. Die Gesamtsumme der Inhaltstoffe addiert sich auf 100 Gew.-%.The weight percentages given here relate to the total funds. The total of the ingredients adds up to 100% by weight.

Die erfindungsgemäß enthaltenen wasserlöslichen Alkalisilikate können amorph, röntgenamorph oder kristallin vorliegen. Bevorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die amorphen Natriumsilikate, mit einem molaren Verhältnis Na2O:SiO2 von 1:1,8 bis 1:3,5. Als kristalline Silikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können, werden vorzugsweise kristalline Schichtsilikate der Formel (I) NaMSixO2x+1+yH2O eingesetzt, in denen M für Natrium steht, 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 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate der Formel (I) sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl β- als auch δ-Natriumdisilikate Na2Si2O5•yH2O bevorzugt, wobei β-Natriumdisilikat beispielsweise nach dem Verfahren erhalten werden kann, das in der intemationalen Patentanmeldung WO-A-91/08171 beschrieben ist. Der Gehalt der Mittel an wasserlöslichen Alkalisilikaten beträgt vorzugsweise 10 Gew.-% bis 40 Gew.-% und insbesondere 10 Gew.-% bis 35 Gew.-%, bezogen auf wasserfreie Aktivsubstanz.The water-soluble alkali silicates contained according to the invention can be amorphous, X-ray amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 1.8 to 1: 3.5. Crystalline layered silicates of the formula (I) NaMSi x O 2x + 1 + yH 2 O, in which M represents sodium, x is a number of 1.9, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application 164 514. Preferred crystalline sheet silicates of the formula (I) are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na 2 Si 2 O 5 • yH 2 O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in the international patent application WO-A-91/08171. The content of water-soluble alkali silicates in the agents is preferably 10% by weight to 40% by weight and in particular 10% by weight to 35% by weight, based on the anhydrous active substance.

Als weitere Substanzen enthalten die erfindungsgemäßen Mittel C8-C22-Alkylsulfate, die vorzugsweise in einer Menge von 12 Gew.-% bis 30 Gew.-% im erfindungsgemäßen Mittel enthalten sind.The agents according to the invention contain C 8 -C 22 alkyl sulfates as further substances, which are preferably contained in an amount of 12 wt.% To 30 wt.% In the agent according to the invention.

Als C8-C22-Alkylsulfate eignen sich insbesondere die Schwefelsäuremonoester der Fettalkohole, insbesondere der C6-C18-Fettalkohole, wie Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der aus Kokosöl, Palm- und Palmkemöl gewonnenen Fettalkoholgemische, die zusätzlich noch Anteile an ungesättigten Alkoholen, z.B. an Oleylalkohol, enthalten können. Bevorzugte Gemische sind solche, in denen der Anteil der Alkylreste zu 15 bis 40 Gew.-% auf C12, zu 5 bis 15 Gew.-% auf C14, zu 15 bis 25 Gew.-% auf C16, zu 30 bis 60 Gew.-% auf C18 und unter 1 Gew.-% auf C10 verteilt sind.Particularly suitable C 8 -C 22 alkyl sulfates are the sulfuric acid monoesters of the fatty alcohols, in particular the C 6 -C 18 fatty alcohols, such as lauryl, myristyl, cetyl or stearyl alcohol or the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil may also contain proportions of unsaturated alcohols, for example oleyl alcohol. Preferred mixtures are those in which the proportion of the alkyl radicals is 15 to 40% by weight on C 12 , 5 to 15% by weight on C 14 , 15 to 25% by weight on C 16 , 30 to 60% by weight on C 18 and less than 1% by weight on C 10 are distributed.

Aus 2,3-Alkylsulfate, welche beispielsweise gemäß den US-Patentschriften 3,234,258 oder 5,075,041 hergestellt werden und als Handelsprodukte der Shell Oil Company unter dem Namen DAN® erhalten werden können, sind geeignete Alkylsulfate.From 2,3-alkyl sulfates, which, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 are manufactured and sold as Shell Oil Company's commercial products Suitable alkyl sulfates can be obtained under the name DAN®.

Es wurde festgestellt, daß die Löslichkeit der Alkylsulfate erheblich verbessert werden kann, wenn das Mittel geringe Mengen C9-C13-Alkylbenzosulfonate enthält. Die Alkylbenzolsulfonate sind vorzugsweise in einer Menge von 0,5 Gew.-% bis 5 Gew.-% im erfindungsgemäßen Mittel enthalten. Als Alkylbenzolsulfonate kommen vorzugsweise solche Schnitte in Betracht, die große Anteile C12-Alkylbenzolsulfonat enthalten.It has been found that the solubility of the alkyl sulfates can be significantly improved if the agent contains small amounts of C 9 -C 13 alkyl benzosulfonates. The alkylbenzenesulfonates are preferably present in the agent according to the invention in an amount of 0.5 wt.% To 5 wt. Preferred alkylbenzenesulfonates are those cuts which contain large amounts of C 12 -alkylbenzenesulfonate.

Die C8-C22-Alkylsulfate und die C9-C13-Alkylbenzolsulfonate liegen in einem Gewichtsverhältnis von 20:1 bis 2:1, insbesondere von 10:1 bis 2:1, im erfindungsgemäßen Mittel vor. The C 8 -C 22 alkyl sulfates and the C 9 -C 13 alkyl benzene sulfonates are present in a weight ratio of 20: 1 to 2: 1, in particular 10: 1 to 2: 1, in the agent according to the invention.

Als weitere Inhaltsstoffe können die erfindungsgemäßen Wasch- und Reinigungsmittel weitere Gerüstsubstanzen und Tenside sowie andere, üblicherweise in derartigen Mitteln enthaltene Substanzen aufweisen.The detergents and cleaning agents according to the invention can be used as further ingredients other builders and surfactants and others, usually in such agents have contained substances.

Als fakultative Buildersubstanzen kann das erfindungsgemäße Mittel auch Zeolithe enthalten. Üblicherweise wird feinkristalliner, synthetischer und gebundenes Wasser enthaltender Zeolith eingesetzt. Geeignet sind beispielsweise Zeolith A, jedoch auch Zeolith X und Zeolith P sowie Mischungen aus A, X und/oder P. Vorzugsweise wird Zeolith vom A-Typ in Waschmittelqualität, eingesetzt. Geeignet sind auch Gemische aus Zeolith NaA und NaX, wobei der Anteil des Zeoliths NaX in derartigen Gemischen zweckmäßigerweise unter 30 % liegt. Sie weisen praktisch keine Teilchen größer als 30 µm auf und bestehen vorzugsweise zu wenigstens 80 % aus Teilchen einer Größe kleiner als 10 µm. Geeignete Zeolithe weisen eine mittlere Teilchengröße von weniger als 10 µm (Meßmethode: Frauenhofer-Beugung; Mittelwert der Volumenverteilung), bevorzugt zwischen 1,5 und 4,5 µm, insbesondere zwischen 2,0 und 4,0 µm auf. Ihr Calciumbindevermögen, das nach den Angaben der deutschen Patentanmeldung 24 12 837 bestimmt wird, liegt im Bereich von 100 bis 200 mg CaO/g. Der Zeolith weist im allgemeinen einen Wassergehalt von 17 bis 25 Gew.-% auf, vorzugsweise 18 bis 22, insbesondere 20 bis 22 Gew.-%. Der Gehalt der Mittel an feinteiligem, insbesondere kristallinem, hydratisiertem Zeolith beträgt vorzugsweise 0,5 bis 30 Gew.-%, bezogen auf wasserfreie Aktivsubstanz. In einer bevorzugten Ausführungsform der Erfindung liegt das Gewichtsverhältnis der wasserlöslichen Silikate zu Zeolith zwischen 1 : 0,01 und 1 : 1,5.The agent according to the invention can also contain zeolites as optional builder substances. Usually fine crystalline, synthetic and bound water containing Zeolite used. Zeolite A, for example, but also zeolite are suitable X and zeolite P and mixtures of A, X and / or P. Zeolite is preferably from A type in detergent quality. Mixtures of zeolite NaA are also suitable and NaX, the proportion of the zeolite NaX in such mixtures expediently is below 30%. They have practically no particles larger than 30 µm and exist preferably at least 80% of particles smaller than 10 microns in size. Suitable Zeolites have an average particle size of less than 10 µm (measurement method: Frauenhofer diffraction; Average volume distribution), preferably between 1.5 and 4.5 µm, in particular between 2.0 and 4.0 µm. Your calcium binding capacity, according to the details of the German patent application 24 12 837 is determined, is in the range from 100 to 200 mg CaO / g. The zeolite generally has a water content of 17 up to 25% by weight, preferably 18 to 22, in particular 20 to 22% by weight. The salary the average of finely divided, in particular crystalline, hydrated zeolite preferably 0.5 to 30 wt .-%, based on anhydrous active substance. In a preferred embodiment of the invention is the weight ratio of water-soluble silicates to zeolite between 1: 0.01 and 1: 1.5.

Als weitere Gerüststoffe können auch polymere Carboxylate bzw. polymere Carbonsäuren enthalten sein. Diese polymeren Carboxylate bzw. Carbonsäuren können im erfindungsgemäßen Waschmittel in einer Menge von 1 bis 15 Gew.-% vorliegen.Polymeric carboxylates or polymeric carboxylic acids can also be used as additional builders be included. These polymeric carboxylates or carboxylic acids can in the invention Detergent is present in an amount of 1 to 15 wt .-%.

Geeignete polymere Polycarboxylate sind beispielsweise die Natriumsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 800 bis 150.000 (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 5.000 bis 200.000, vorzugsweise 10.000 bis 120.000 und insbesondere 50.000 bis 100.000.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 especially 50,000 to 100,000.

Die (co-)polymeren Polycarboxylate können entweder als Pulver oder als wäßrige Lösung eingesetzt werden, wobei 20 bis 55 Gew.-%ige wäßrige Lösungen bevorzugt sind.The (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution are used, 20 to 55% by weight aqueous solutions being preferred.

Der Gehalt der Mittel an (co-)polymeren Polycarboxylaten beträgt vorzugsweise 1 bis 12 Gew.-%, insbesondere 2 bis 10 Gew.-%.The content of (co) polymeric polycarboxylates in the agents is preferably 1 to 12 % By weight, in particular 2 to 10% by weight.

Insbesondere bevorzugt sind auch biologisch abbaubare Terpolymere, 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-C-42 21 381 als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zuckerderivate enthalten.Also particularly preferred are biodegradable terpolymers, for example those those according to DE-A-43 00 772 as monomers salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or as according to DE-C-42 21 381 Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Weitere bevorzugte Copolymere sind solche, die in den deutschen Patentanmeldungen DE-A-43 03 320 und P 44 17 734.8 beschrieben werden und als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäuresalze bzw. Acrolein und Vinylacetat aufweisen.Other preferred copolymers are those described in the German patent applications DE-A-43 03 320 and P 44 17 734.8 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Weitere brauchbare organische Gerüstsubstanzen sind beispielsweise die bevorzugt in Form ihrer Natriumsalze eingesetzten Polycarbonsäuen, wie Citronensäure, Adipinsäure, Bemsteinsäure, Glutarsäure, Weinsäure, Zuckersäure, Aminocarbonsäure, Nitrilotriessigsäure (NTA), sofem 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.Further usable organic builders are, for example, those preferred in Form of their sodium salts used polycarboxylic acids, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acid, aminocarboxylic acid, nitrilotriacetic acid (NTA), as long as there is no objection to such use for ecological reasons is, and mixtures of these. Preferred salts are the salts of the polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Als weitere anionische Tenside kann das erfindungsgemäße Mittel C6-C18-Alkylpolyglykolethersulfonate, C6-C18-Fettsäureestersulfonate, C6-C18-Fettalkylethersulfate, Olefinsulfonate, Glycerinethersulfonate, Glycerinethersulfate, Alkenylsulfate, Hydroxymischethersulfate, Monoglyceridsulfate, Sulfosuccinate, Sulfotriglyceride, Amidsäuren, C6-C18-Fettsäureamid-Ethersulfate, C6-C18-Alkyl(ether)carboxylate, Fettsäureisethionate, N-C6-C16-Acyl-Sarcosinate, N-C6-C18-Acyl-Tauride, C6-C18-Alkyloligoglycosidsulfate, C6-C18-Alkyl-Phosphate sowie deren Mischungen enthalten. Other suitable anionic surfactants agent C of the invention can -Alkylpolyglykolethersulfonate 6 -C 18, C 6 -C 18 -Fettsäureestersulfonate, C 6 -C 18 -Fettalkylethersulfate, olefin sulfonates, glycerol ether, Glycerol ether sulfates, alkenyl sulfates, Hydroxymischethersulfate, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, amide acids, C 6 -C 18 fatty acid amide ether sulfates, 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 - Contain alkyl oligoglycoside sulfates, C 6 -C 18 alkyl phosphates and mixtures thereof.

Ferner können in den erfindungsgemäßen Mitteln Seifen enthalten sein, wobei insbesondere gesättigte Fettsäureseifen, die Salze der Laurinsäure, Myristinsäure, Palmitinsäure oder Stearinsäure, sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische, geeignet sind.Furthermore, soaps can be contained in the agents according to the invention, in particular saturated fatty acid soaps, the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut-, Palm kernel or tallow fatty acids, derived soap mixtures, are suitable.

Die weiteren Tenside und die Seifen können insgesamt in einer Menge von 1 bis 15 Gew.-%, insbesondere 1 bis 10 Gew.-%, alleine oder in beliebigen Mischungen im erfindungsgemäßen Mittel vorliegen. Der Gesamttensidgehalt liegt in den erfindungsgemäßen Mitteln vorzugsweise über 20 Gew.-%.The further surfactants and the soaps can be used in a total amount of 1 to 15 % By weight, in particular 1 to 10% by weight, alone or in any mixtures in the agents according to the invention are present. The total surfactant content is in the Agents according to the invention preferably over 20 wt .-%.

Das erfindungsgemäße Mittel kann auch nichtionische Tenside in einer Menge von 1 bis 25 Gew.-%, bevorzugt 2 Gew.-% bis 20 Gew.-% enthalten. Als nichtionische Tenside werden vorzugsweise flüssige, alkoxylierte, bevorzugt ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen (Alkylpolyglykolether) und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder 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 bevorzugt, z.B. aus Kokos-, Talgfett- oder Oleylalkohol, die durchschnittlich 2 bis 8 EO-Einheiten pro Mol Alkohol haben können. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-C14-Alkohole mit 3 EO-Einheiten oder 7 EO-Einheiten, C9-C11-Alkohole mit 3 EO-Einheiten, 5 EO-Einheiten oder 7 EO-Einheiten und Mischungen aus diesen, wie Mischungen aus C12-C14-Alkohol mit 3 EO-Einheiten und C12-C18-Alkohol mit 5 EO-Einheiten. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholalkoxylate weisen eine eingeengte Homologenverteilung auf (Narrow Range Ethoxylates, NRE).The agent according to the invention can also contain nonionic surfactants in an amount of 1 to 25% by weight, preferably 2% by weight to 20% by weight. The preferred nonionic surfactants are liquid, alkoxylated, preferably ethoxylated, especially primary alcohols with preferably 8 to 18 carbon atoms (alkyl polyglycol ether) and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or in 2- Position may be methyl branched, 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 from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut oil, tallow oil or oleyl alcohol, which can have an average of 2 to 8 EO units per mole of alcohol, are particularly preferred. The preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO units or 7 EO units, C 9 -C 11 alcohols with 3 EO units, 5 EO units or 7 EO units and mixtures of these this, such as mixtures of C 12 -C 14 alcohol with 3 EO units and C 12 -C 18 alcohol with 5 EO units. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol alkoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

Als weitere nichtionische Tenside kann das erfindungsgemäße Mittel Alkylpolyglykoside, Fettsäurealkylester; Aminoxide sowie Polyhydroxyfettsäureamide enthalten.As further nonionic surfactants, the agent according to the invention can be alkyl polyglycosides, Fatty acid alkyl esters; Contain amine oxides and polyhydroxy fatty acid amides.

Als weitere Komponenten können Strukturbrecher eingesetzt werden. Strukturbrecher werden üblicherweise eingesetzt, um die Verarbeitbarkeit der Mittel zu verbessern. Als Strukturbrecher eignen sich besonders ethoxylierte C8-C18-Fettalkohole mit 20 bis 45 EO, vorzugsweise Talgfettalkohole mit 30 und 40 EO, Polyethylenglykol oder Polypropylenglykol, Sulfate und/oder Disulfate von Polyethylenglykol oder Polypropylenglykol, Sulfosuccinate und/oder Disulfosuccinate von Polyethylenglykol oder Polypropylenglykol oder Mischungen aus diesen. Die nichtionischen Tenside und die Strukturbrecher können in einem Verhältnis von nichtionischem Tensid zu Strukturbrecher von 1:1 bis 15:1 eingesetzt werden.Structure breakers can be used as further components. Structure breakers are usually used to improve the processability of funds. Suitable structure breakers are particularly ethoxylated C 8 -C 18 fatty alcohols with 20 to 45 EO, preferably tallow fatty alcohols with 30 and 40 EO, polyethylene glycol or polypropylene glycol, sulfates and / or disulfates of polyethylene glycol or polypropylene glycol, sulfosuccinates and / or disulfosuccinates of polyethylene glycol or polypropylene glycol or mixtures of these. The nonionic surfactants and the structure breakers can be used in a ratio of nonionic surfactant to structure breaker of 1: 1 to 15: 1.

Die erfindungsgemäß hergestellten Waschmittel enthalten vorzugsweise Peroxybleichmittel und insbesondere Peroxybleichmittel in Kombination mit Bleichaktivatoren. Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumperborattetrahydrat, das Natriumperboratmonohydrat und Natriumpercarbonat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperoxyazelainsäure oder Diperoxydodecandisäure. Die Waschmittel enthalten vorzugsweise 5 bis 25 Gew.-% und insbesondere 10 bis 20 Gew.-% Bleichmittel, wobei Natriumpercarbonat und/oder Natriumperboratmonohydrat bevorzugt eingesetzt werden.The detergents produced according to the invention preferably contain peroxy bleaching agents and in particular peroxy bleaching agents in combination with bleach activators. Among the compounds which serve as bleaching agents and supply H 2 O 2 in water, sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or diperoxydodecanedioic acid. The detergents preferably contain 5 to 25% by weight and in particular 10 to 20% by weight of bleaching agent, sodium percarbonate and / or sodium perborate monohydrate being preferably used.

Um beim Waschen bei Temperaturen von 60°C und darunter eine verbesserte Bleichwirkung zu erreichen, können Bleichaktivatoren in die Präparate eingearbeitet werden, die mit H2O2 organische Persäuren bilden. Beispiele hierfür sind N- oder O-Acyl-Verbindungen, beispielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin, acylierte Glykolurile, insbesondere Tetraacetylglykoluril, N-acylierte Hydantoine, Hydrazide, Triazole, Triazine, Urazole, Diketopiperazine, Sulfurylamide und Cyanurate, außerdem Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, Carbonsäureester, insbesondere Natriumisononanoyloxybenzolsulfonat, und acylierte Zuckerderivate, insbesondere Pentaacetylglucose. Der Bleichaktivator kann in bekannter Weise mit Hüllsubstanzen überzogen oder, gegebenenfalls unter Einsatz von Hilfsmitteln, granuliert oder extrudiert/pelletiert worden sein und gewünschtenfalls weitere Zusatzstoffe, beispielsweise Farbstoff, enthalten. Vorzugsweise enthält ein derartiges Granulat über 70 Gew.-%, insbesondere von 90 Gew.-% bis 99 Gew.-%, Bleichaktivator. Vorzugsweise wird ein Bleichaktivator eingesetzt, der unter den Waschbedingungen Peressigsäure bildet. Unter diesen ist mit Hilfe von Carboxymethylcellulose granuliertes Tetraacetylethylendiamin (TAED) mit mittleren Korngrößen von 0,01 bis 0,8 mm, wie es nach dem in der europäischen Patentschrift EP 037 026 beschriebenen Verfahren hergestellt werden kann, und/oder granuliertes 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), wie es nach dem in der deutschen Patentschrift DD 255 884 beschriebenen Verfahren hergestellt werden kann, besonders bevorzugt. Es kann auch extrudiertes TAED eingesetzt werden, welches ≥ 70 Gew.-% TAED, 15 bis 25 Gew.-% C12-18-Fettalkoholsulfat und 2 bis 6 Gew.-% Soda enthält. Der Gehalt an Bleichaktivatoren in den bleichmittelhaltigen Waschmitteln liegt in dem üblichen Bereich, vorzugsweise zwischen 1 und 10 Gew.-% und insbesondere zwischen 3 und 8 Gew.-%.In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the preparations which form organic peracids with H 2 O 2 . Examples of these are N- or O-acyl compounds, for example multi-acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanuric acid hydrides, and also carboxylic acid hydrides , Carboxylic acid esters, especially sodium isonanoyloxybenzenesulfonate, and acylated sugar derivatives, especially pentaacetyl glucose. The bleach activator can be coated with coating substances in a known manner or, if necessary with the aid of auxiliaries, granulated or extruded / pelletized and, if desired, contain further additives, for example dye. Such granules preferably contain over 70% by weight, in particular from 90% by weight to 99% by weight, of bleach activator. A bleach activator is preferably used which forms peracetic acid under the washing conditions. Among these is tetraacetylethylenediamine (TAED) with average grain sizes of 0.01 to 0.8 mm, granulated with the help of carboxymethyl cellulose, as can be produced by the process described in European Patent EP 037 026, and / or granulated 1,5- Diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), as can be prepared by the process described in German Patent DD 255 884, is particularly preferred. Extruded TAED which contains 70 70% by weight of TAED, 15 to 25% by weight of C 12-18 fatty alcohol sulfate and 2 to 6% by weight of soda can also be used. The content of bleach activators in the detergents containing bleach is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.

Weitere geeignete Inhaltsstoffe der erfindungsgemäßen Mittel sind wasserlösliche anorganische Salze wie Bicarbonate, Carbonate oder Mischungen aus diesen; insbesondere Alkalicarbonat und 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 5 und 15 Gew.-%.Other suitable ingredients of the agents according to the invention are water-soluble inorganic salts such as bicarbonates, carbonates or mixtures thereof; in particular alkali carbonate and 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. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously 5 and 15% by weight.

Zu den sonstigen Waschmittelbestandteilen, deren Anteil je nach Zusammensetzung der Waschmittel 0,1 bis 5 Gew.-% beträgt, zählen Schauminhibitoren, optische Aufheller, Enzyme, textilweichmachende Stoffe, Farb- und Duftstoffe. Es können auch Neutralsalze in einer Menge bis zu 20 Gew.-% enthalten sein, ihr Anteil ist bevorzugt ≤ 10 Gew.-%.The other detergent ingredients, the proportion of which depends on the composition of the Detergent is 0.1 to 5 wt .-% include foam inhibitors, optical brighteners, enzymes, fabric softening agents, colors and fragrances. Neutral salts can also be found in an amount up to 20 wt .-% may be contained, their proportion is preferably ≤ 10 wt .-%.

Ferner kann das Mittel zusätzliche Vergrauungsinhibitoren in einer Menge von 0,1 bis 5 Gew.-%, bezogen auf die Mittel, enthalten. Als zusätzliche Vergrauungsinhibitoren sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise lösliche Stärkepräparate und z. B. abgebaute Stärke, Aldehydstärken usw. Carboxymethylcellulose (Na-Salz), Methylcellulose, Methylhydroxyethylcellulose und deren Gemische sowie Polyvinylpyrrolidon werden bevorzugt eingesetzt.Furthermore, the agent can contain additional graying inhibitors in an amount of 0.1 to 5 % By weight, based on the composition. As additional graying inhibitors are Suitable water-soluble colloids mostly organic, for example soluble starch preparations and Z. B. degraded starch, aldehyde starches etc. carboxymethyl cellulose (sodium salt), Methyl cellulose, methyl hydroxyethyl cellulose and their mixtures and polyvinyl pyrrolidone are preferred.

Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen bzw. lipolytisch wirkenden Enzyme, Amylasen, Cellulasen bzw. deren Gemische in Frage. 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 Celiulase 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. 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.Enzymes come from the class of proteases, lipases or lipolytic acting enzymes, amylases, cellulases or mixtures thereof in question. Particularly good are suitable from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens Active ingredients. Proteases of the subtilisin type and in particular are preferred 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 Celiulase 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 for Such lipolytic enzymes are the well-known cutinases. Peroxidases too or oxidases have been found to be suitable in some cases. The enzymes can adsorbed on carriers and / or embedded in coating substances to counter them to protect 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 % By weight.

Als Stabilisatoren insbesondere für Persauerstoffverbindungen und Enzyme kommen die Salze, wie neutral reagierende Natriumsalze, von Polyphosphonsäuren, insbesondere von 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), Diethylentriaminpentamethylenphosphonsäure (DETPMP) oder Ethylendiamintetramethylenphosphonsäure in Betracht. Diese Verbindung wirken auch als wasserlösliche Komplexbildner. Die Phosphonate können in Mengen bis zu 1,5 Gew.-% eingesetzt werden, bevorzugt wird jedoch auf diese Zusätze verzichtet, so daß die erfindungsgemäßen Waschmittel einen rechnerischen Phosphorgehalt von 0 % aufweisen.The stabilizers come in particular for peroxygen compounds and enzymes Salts, such as neutral sodium salts, of polyphosphonic acids, especially of 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid. This connection also act as water-soluble complexing agents. The phosphonates can be in Amounts of up to 1.5% by weight are used, but preference is given to these additives dispensed with, so that the detergents according to the invention have a mathematical calculation Have phosphorus content of 0%.

Zusätzlich können die Mittel Enzymstabilisatoren enthalten. Beispielsweise können 0,5 bis 1 Gew.-% Natriumformiat eingesetzt werden. Möglich ist auch der Einsatz von Proteasen, die mit löslichen Calciumsaizen und einem Calciumgehalt von vorzugsweise etwa 1,2 Gew.-%, bezogen auf das Enzym, stabilisiert sind. Besonders vorteilhaft ist jedoch der Einsatz von Borverbindungen, beispielsweise von Borsäure, Boroxid, Borax und anderen Alkalimetallboraten.In addition, the agents can contain enzyme stabilizers. For example, 0.5 to 1 wt .-% sodium formate can be used. It is also possible to use proteases, those with soluble calcium seeds and a calcium content of preferably about 1.2 % By weight, based on the enzyme, are stabilized. However, the is particularly advantageous Use of boron compounds, for example boric acid, boron oxide, borax and others Alkali metal borates.

Geeignete Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure. Mit Vorteil können auch Gemische verschiedener Schauminhibitoren verwendet werden, z.B. solche aus Silikonöl, Paraffinöl oder Wachsen. Vorzugsweise sind die Schauminhibitoren an eine granulare, in Wasser lösliche bzw. dispergierbare Trägersubstanz gebunden.Suitable foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica as well as paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Can with advantage mixtures of different foam inhibitors can also be used, e.g. those made of silicone oil, Paraffin oil or waxing. The foam inhibitors are preferably attached to a granular, water-soluble or dispersible carrier substance bound.

Die pulverförmigen Waschmittel können als optische Aufheller beispielsweise Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten, die sich gut in Dispersionen einarbeiten lassen (siehe unten). Der maximale Gehalt an Aufhellem in den erfindungsgemäßen Mitteln beträgt 0,5 Gew.-%, vorzugsweise werden Mengen von 0,02 bis 0,25 Gew.-% eingesetzt.The powder detergents can be used as optical brighteners, for example derivatives of Contain diaminostilbenedisulfonic acid or its alkali metal salts, which are good in dispersions Have it incorporated (see below). The maximum amount of brightener in the invention Average is 0.5 wt .-%, preferably amounts from 0.02 to 0.25 wt .-% used.

Ein weiterer Gegenstand der vorliegenden Erfindung betrifft die Herstellung von Tensid- und Builder-haltigen Wasch- und Reinigungsmitteln, die 0,1 Gew.-% bis 10 Gew.-% C9-C13-Alkylbenzolsulfonat und 10 Gew.-% bis 50 Gew.-% C8-C22-Alkylsulfat als anionische Tenside und 10 bis 45 Gew.-% wasserlösliche Silikate und 0 bis zu 30 Gew.-% Zeolith als Builder enthalten, worin ein Vorgemisch aus festen und flüssigen Waschmittelbetandteilen hergestellt wird und dieses Vorgemisch anschließend verpreßt wird.Another object of the present invention relates to the production of detergents and cleaning agents containing surfactants and builders which contain 0.1% by weight to 10% by weight of C 9 -C 13 alkylbenzenesulfonate and 10% by weight to 50 % By weight of C 8 -C 22 alkyl sulfate as anionic surfactants and 10 to 45% by weight of water-soluble silicates and 0 to 30% by weight of zeolite as a builder, in which a premix is prepared from solid and liquid detergent constituents and this Premix is then pressed.

Als flüssige Waschmittelbestandteile kommen insbesondere die flüssigen nichtionischen Tenside in Betracht.The liquid non-ionic substances in particular come as liquid detergent components Surfactants into consideration.

Das Zusammenfügen der festen und flüssigen Waschmittelrohstoffe unter gleichzeitiger oder anschließender Formgebung und gewünschtenfalls Trocknung kann nach allen bekannten Verfahren, bei denen Wasch- und Reinigungsmittel mit hohem Schüttgewicht, d.h. mit einem Schüttgewicht oberhalb 500 g/l, vorzugsweise oberhalb 600 g/l und insbesondere zwischen 700 und 1.000 g/l, hergestellt werden, durchgeführt werden. Beispiele für derartige bekannte und bevorzugte Verfahren sind Granulierverfahren, in denen entweder die festen Inhaltsstoffe eines Wasch- und Reinigungsmittels oder ein sprühgetrocknetes Wasch- und Reinigungsmittel oder eine Mischung aus sprühgetrockneten und nichtsprühgetrockneten Inhaltsstoffen von Wasch- und Reinigungsmitteln, gegebenenfalls einschließlich des Zusatzstoffes, in einem schnell laufenden Mischer kompaktiert und gleichzeitig in diesem Mischer oder im Anschluß daran in einer weiteren Vorrichtung, beispielsweise in einer Wirbelschicht, mit den flüssigen Bestandteilen vermischt bzw. beaufschlagt wird. The combination of the solid and liquid detergent raw materials under simultaneous or subsequent shaping and, if desired, drying can be carried out according to all known Processes in which washing and cleaning agents with a high bulk density, i.e. with a bulk density above 500 g / l, preferably above 600 g / l and in particular between 700 and 1,000 g / l, are carried out. Examples of such known and preferred processes are granulation processes, in which either contain the solid ingredients of a detergent or cleaning agent spray-dried washing and cleaning agent or a mixture of spray-dried and non-spray-dried ingredients of washing and Detergents, if necessary including the additive, in a quick running mixer compacted and simultaneously in this mixer or after it in a further device, for example in a fluidized bed, with the liquid Components are mixed or applied.

Bei der Durchführung des erfindungsgemäßen Verfahrens können insbesondere Granulate und Tabletten erhalten werden.When carrying out the method according to the invention, in particular Granules and tablets can be obtained.

Zur Herstellung von Granulaten ist ein Verfahren bevorzugt, worin zuerst ein Vorgemisch aus Waschmittelbestandteilen hergestellt wird. Dieses feste, bevorzugt homogene Vorgemisch, wird unter Zusatz eines Plastifizier- und/oder Gleitmittels über Lochformen mit Öffnungsweiten der vorbestimmten Granulatdimension bei hohen Drucken zwischen 25 und 200 bar strangförmig verpreßt. Der Strang wird direkt nach dem Austritt aus der Lochform mittels einer Schneidevorrichtung auf die vorbestimmte Granulatdimension zugeschnitten. Die Anwendung des hohen Arbeitsdrucks bewirkt die Plastifizierung des Vorgemisches bei der Granulatbildung und stellt die Schneidfähigkeit der frisch extrudierten Stränge sicher. Das Vorgemisch besteht wenigstens anteilsweise aus festen, vorzugsweise feinteiligen üblichen Inhaltsstoffen von Wasch- und Reinigungsmitteln, denen gegebenenfalls flüssige Bestandteile zugemischt sind. Die festen Inhaltsstoffe können durch Sprühtrocknung gewonnene Turmpulver, aber auch Agglomerate, die jeweils gewählten Mischungsbestandteile als reine Stoffe, die im feinteiligen Zustand miteinander vermischt werden, sowie Mischungen aus diesen sein. Im Anschluß daran werden gegebenenfalls die flüssigen Inhaltsstoffe zugegeben und dann das erfindungsgemäß ausgewählte Plastifizier- und /oder Gleitmittel eingemischt. Als Plastifizier- und/oder Gleitmittel werden wäßrige Lösungen von polymeren Polycarboxylaten sowie hochkonzentrierte Aniontensidpasten und nichtionische Tenside bevorzugt. Zur ausführlichen Beschreibung des Verfahrens sowie der geeigneten Inhaltsstoffe des Vorgemisches und der geeigneten Plastifizier- und/oder Gleitmittels wird auf die Offenbarung der internationalen Patentanmeldung WO 91/02047 verwiesen.For the production of granules, a method is preferred in which a premix is first is made from detergent ingredients. This solid, preferably homogeneous premix, is with the addition of a plasticizer and / or lubricant over hole shapes with opening widths the predetermined granule dimension at high pressures between 25 and 200 bar extruded. The strand is immediately after exiting the hole shape cut to the predetermined granule dimension by means of a cutting device. The application of the high working pressure causes the premix to be plasticized in the formation of granules and provides the cutting ability of the freshly extruded strands for sure. The premix consists at least partly of solid, preferably finely divided usual ingredients of detergents and cleaning agents, where appropriate liquid components are mixed. The solid ingredients can go through Spray drying obtained tower powders, but also agglomerates, the selected one Mixture components as pure substances that mix with each other in the finely divided state will be, as well as mixtures of these. Subsequently, if necessary added the liquid ingredients and then the one selected according to the invention Plasticizers and / or lubricants mixed. As a plasticizer and / or lubricant aqueous solutions of polymeric polycarboxylates as well as highly concentrated anionic surfactant pastes and nonionic surfactants are preferred. For a detailed description of the Process and the appropriate ingredients of the premix and the appropriate Plasticizer and / or lubricant is based on the disclosure of the international Patent application WO 91/02047 referenced.

In einer weiteren möglichen Ausführungsform dieses Verfahrens können die flüssigen Niotenside auch als flüssiger Bestandteil beziehungsweise als Plastifizier- und/oder Gleitmittel zu dem festen Vorgemisch zugegeben werden, oder sie sind ein Bestandteil einer festen Mischungskomponente des Vorgemisches, wobei diese feste Mischungskomponente aus einem Trägerbead bestehen kann, das mit einer Lösung oder einer Dispersion beaufschlagt wurde. Die Zugabe der flüssigen Komponente, das heißt nicht an ein Trägerbead gebunden, kann an jeder beliebigen Stelle des Verfahrens, zum Beispiel bei der Herstellung des Vorgemisches, aber auch bei der Verarbeitung des plastifizierten Vorgemisches, jedoch vor dem Durchtritt durch die Lochform (Lochdüsenplatte) erfolgen. Als Homogenisiervorrichtung können bevorzugt Kneter beliebiger Ausgestaltung, beispielsweise 2-Schnecken-Kneter gewählt werden. Der intensive Mischungsvorgang kann dabei bereits aus sich heraus zu einer gewünschten Temperatursteigerung führen. Dabei werden mäßig erhöhte Temperaturen von beispielsweise 60 bis 70 °C in der Regel nicht überschritten. In einer bevorzugten Ausführungsform wird das Vorgemisch vorzugsweise kontinuierlich einem 2-Schnecken-Kneter (Extruder) zugeführt, dessen Gehäuse und dessen Extruder-Granulierkopf auf die vorbestimmte Extrudiertemperatur temperiert, beispielsweise auf 40 bis 60 °C aufgeheizt sind. Unter der Schereinwirkung der Extruder-Schnecken wird das Vorgemisch bei Drucken von 25 bis 200 bar plastifiziert, in Form feiner Stränge durch die Lochdüsenplatte im Extruderkopf extrudiert und schließlich das Extrudat mittels eines rotierenden Abschlagmessers vorzugsweise in kugelförmigen bis zylindrischen Granulatkömem verkleinert. Der Lochdurchmesser in der Lochdüsenplatte und die Strangschnittlänge werden dabei auf die gewählte Granulatdimension abgestimmt. In dieser Ausführungsform gelingt die Herstellung von Granulaten einer im wesentlichen gleichmäßig vorbestimmbaren Teilchengröße, wobei im einzelnen die absoluten Teilchengrößen dem beabsichtigten Einsatzzweck angepaßt sein können. Im allgemeinen werden Teilchendurchmesser bis höchstens 0,8 cm bevorzugt. Wichtige Ausführungsformen sehen hier die Herstellung von einheitlichen Granulaten mit Durchmessem im Millimeterbereich, beispielsweise im Bereich von 0,5 bis 5 mm und insbesondere im Bereich von 0,8 bis 3 mm vor. Das Länge/Durchmesser-Verhältnis des abgeschlagenen primären Granulats liegt dabei in einer wichtigen Ausführungsform im Bereich von 1 : 1 bis etwa 3 : 1. Weiterhin ist es bevorzugt, das noch plastische, feuchte Primärgranulat einem weiteren formgebenden Verarbeitungsschritt zuzuführen; dabei werden am Rohgranulat vorliegende Kanten abgerundet, so daß letztlich kugelförmige oder wenigstens annähernd kugelförmige Granulatkömer erhalten werden können. Falls gewünscht oder erforderlich, können in dieser Stufe geringe Mengen an Trockenpulver, beispielsweise Zeolithpulver wie Zeolith NaA-Pulver, mit verwendet werden. Diese Formgebung kann in marktgängigen Rondiergeräten, beispielsweise in Rondiergeräten mit rotierender Bodenscheibe, erfolgen. Vorzugsweise werden die Granulate dann einem Trocknungsschritt, beispielsweise einem Wirbelschichttrockner, zugeführt.In a further possible embodiment of this method, the liquid Nonionic surfactants also as a liquid component or as a plasticizer and / or Lubricants can be added to the solid premix or they are an ingredient a solid mixture component of the premix, this solid Mixture component can consist of a carrier bead, which with a solution or a dispersion was applied. The addition of the liquid component, that is not bound to a carrier bead, can at any point in the process to Example in the production of the premix, but also in the processing of the plasticized Premix, but before passing through the hole shape (perforated nozzle plate) respectively. Kneaders of any configuration are preferably used as the homogenizing device, For example, 2-screw kneaders can be selected. The intensive mixing process can itself lead to a desired temperature increase. Moderately elevated temperatures of, for example, 60 to 70 ° C are usually not exceeded. In a preferred embodiment, the premix preferably fed continuously to a 2-screw kneader (extruder), the Housing and its extruder pelletizing head to the predetermined extrusion temperature tempered, for example heated to 40 to 60 ° C. Under the action of shear the extruder screws, the premix is plasticized at pressures of 25 to 200 bar, in the form of fine strands through the perforated nozzle plate in the extruder head and finally the extrudate, preferably in a rotating knife, in reduced spherical to cylindrical granules. The hole diameter in the Perforated nozzle plate and the strand cut length are based on the selected granulate dimension Voted. In this embodiment, the production of Granules of a substantially uniformly predeterminable particle size, in which individual the absolute particle sizes to be adapted to the intended application can. In general, particle diameters up to at most 0.8 cm are preferred. Important embodiments see the production of uniform granules Diameters in the millimeter range, for example in the range from 0.5 to 5 mm and especially in the range of 0.8 to 3 mm. The length / diameter ratio of the In an important embodiment, the chopped off primary granulate lies in Range from 1: 1 to about 3: 1. It is further preferred that the still plastic, moist To supply primary granulate to a further shaping processing step; be there edges present on the raw granulate are rounded, so that ultimately spherical or at least approximately spherical granules can be obtained. if desired or required, small amounts of dry powder, for example, can be used at this stage Zeolite powder such as zeolite NaA powder can also be used. This shape can be used in standard rounding machines, for example in rotary machines with rotating Bottom disc. The granules are then preferably one Drying step, for example a fluidized bed dryer, supplied.

Tabletten können beispielsweise derart hergestellt werden, daß man die Buildersubstanzen, insbesondere die wasserlöslichen Alkalisilikate und gegebenenfalls alle anderen Bestandteile in einem Mischer miteinander vermischt und das Gemisch mittels herkömmlicher Tablettenpressen beispielsweise Exzenterpressen, hydraulischen Pressen oder Rundläuferpressen mit Preßdrucken im Bereich von 1 bis 300 bar, vorteilhafterweise im Bereich von etwa 5 bis 200 bar und insbesondere zwischen 10 und 150 bar verpreßt. Vorzugsweise erfolgt die Verpressung dabei ohne die Zugabe von Wasser. In einer bevorzugten Ausführungsform können die zur Verpressung vorgesehenen Vorgemische jedoch durch Vermischen der einzelnen Inhaltsstoffe, die wenigstens anteilsweise in vorkonfektionierter Form als granulares Compound vorliegen, hergestellt. Hierzu zählen beispielsweise walzenkompaktierte kristalline schichtförmige oder amorphe Natriumdisilikate, die gegebenenfalls mit flüssigen bis wachsartigen Komponenten, beispielsweise nichtionischen Tensiden imprägniert wurden. Insbesondere wird hierdurch eine wasserfreie Vorkonfektionierung ermöglicht, welche besonders vorteilhaft ist. Man erhält so problemlos bruchfeste und dennoch unter Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit guter Bruchfestigkeit. Die Preßbedingungen sind im jeweiligen Fall üblicherweise auf die Einstellung der gewünschten Löslichkeit der Tablette bei gleichzeitig ausreichender Festigkeit bzw. Härte der Tablette zu optimieren. Dabei gilt in an sich bekannter Weise, daß höhere Preßdrucke eine Verminderung der Löslichkeit der Tablette bewirken. Bevorzugte Tabletten weisen eine Bruchfestigkeit von mindestens 55 N und insbesondere von mindestens 60 N auf. Es sind auch Tabletten mit Bruchfestigkeiten über 150 N möglich.Tablets can, for example, be produced in such a way that the builder substances, in particular the water-soluble alkali silicates and possibly all other components mixed together in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses, hydraulic presses or rotary presses with pressures in the range from 1 to 300 bar, advantageously in the range from about 5 to 200 bar and in particular between 10 and 150 bar. The compression is preferably carried out without the addition of water. In a preferred embodiment, the premixes provided for compression however, by mixing the individual ingredients, which are at least partially in Pre-assembled form as a granular compound. Which includes for example roll-compacted crystalline layered or amorphous Sodium disilicates, which may contain liquid to waxy components, For example, nonionic surfactants have been impregnated. In particular, this will enables water-free pre-assembly, which is particularly advantageous. Man thus easily gets unbreakable and yet under conditions of use sufficiently quickly soluble tablets with good breaking strength. The pressing conditions are usually in the respective case on the setting of the desired solubility of the To optimize the tablet with sufficient strength or hardness of the tablet. It applies in a manner known per se that higher pressures reduce the Cause solubility of the tablet. Preferred tablets have a breaking strength of at least 55 N and in particular at least 60 N. There are also tablets with Breaking strengths above 150 N possible.

Als Raumform kommen praktisch alle sinnvollen handhabbaren Ausgestaltungsformen in Betracht, solange sie den Anforderung entsprechen, daß der Kontakt zur Tablettierapparatur während des Herstellungsprozesses relativ gering ist. Bevorzugt sind hierbei zylinderförmige Ausgestaltungen mit ovalem oder kreisförmigem Querschnitt der unten angegebenen Art. Vorzugsweise weist eine derart hergestellte Tablette ein Gewicht von 10 bis 120 g, insbesondere von 20 bis 100 g auf, wobei der Durchmesser der Tabletten üblicherweise kleiner als 100 mm ist. Bevorzugte Waschmitteltabletten weisen einen Durchmesser von maximal 80 mm und insbesondere von 30 bis 80 mm auf. Es ist jedoch auch möglich und insbesondere auch im Hinblick auf verbesserte Löslichkeiten bevorzugt, mehrere, also mindestens 2 Tabletten mit gleicher oder unterschiedlicher Zusammensetzung einzusetzen. diese Tabletten besitzen vorzugsweise ein Gewicht von 10 bis 40 g, wobei Durchmesser von 20 bis 50 mm bevorzugt sind. Das Durchmesser/Höhe-Verhältnis der Tabletten soll dahingehend optimiert sein, daß eine möglichst geringe Abrasion an den vertikalen Wänden der Tablettierapparatur (hoher Durchmesser/geringe Höhe) mit einer ausreichenden Stabilität und einer nicht zu großen Oberfläche (kleiner Durchmesser/große Höhe) gewährleistet ist. Bevorzugte Durchmesser/Höhe-Verhältnisse der zylindrischen Preßlinge liegen bei etwa 0,5:1 bis 10:1, insbesondere bei 1:1 bis 8:1.Practically all sensible, manageable design forms come in as the spatial form Consider as long as they meet the requirement that contact with the Tableting equipment is relatively small during the manufacturing process. Are preferred here cylindrical configurations with an oval or circular cross section Art specified below. A tablet produced in this way preferably has a weight from 10 to 120 g, in particular from 20 to 100 g, the diameter of the Tablets is usually less than 100 mm. Have preferred detergent tablets a maximum diameter of 80 mm and in particular from 30 to 80 mm. It is however also possible and in particular also with regard to improved solubilities preferred, several, ie at least 2 tablets with the same or different Use composition. these tablets preferably have a weight of 10 to 40 g, with diameters of 20 to 50 mm being preferred. The Diameter / height ratio of the tablets should be optimized so that a as little abrasion as possible on the vertical walls of the tabletting apparatus (higher Diameter / low height) with sufficient stability and not too large Surface (small diameter / high height) is guaranteed. Preferred diameter / height ratios the cylindrical compacts are about 0.5: 1 to 10: 1, especially at 1: 1 to 8: 1.

Zur Erreichung eines erhöhten Schüttgewichts ist es von Vorteil, die getrockneten Granulate gegebenenfalls noch einmal mit feinteilgen Trockenpulvern abzupudern. Beispiele für derartige Trockenpulver sind Zeolith-NaA-Pulver, aber auch gefällte oder pyrogene Kieselsäure, wie sie beispielsweise als Aerosil® oder Sipernat® (Produkte der Firma Degussa) im Handel-erhältlich sind. Bevorzugt sind hierbei auch hochkonzentrierte, mindestens 90 Gew.-%ige Alkoholsulfat-Pulver, die im wesentlichen, d.h. zu mindestens 90 % aus Teilchen mit einer Teilchengröße kleiner als 100 µm bestehen. Insbesondere sind Mischungen aus Zeolith und Alkoholsulfat-Pulver bevorzugt.To achieve an increased bulk density, it is advantageous to use the dried granules if necessary, powder again with finely divided dry powders. examples for dry powders of this type are zeolite NaA powder, but also precipitated or pyrogenic silica, as for example as Aerosil® or Sipernat® (products from Degussa) in Are commercially available. Highly concentrated, at least 90, are also preferred % By weight alcohol sulfate powder which is essentially, i.e. at least 90% particles exist with a particle size smaller than 100 microns. In particular are Mixtures of zeolite and alcohol sulfate powder are preferred.

Die Wasch- und Reinigungsmittel können einheitlich aus Extrudaten hergestellt werden, welche die oben genannten Inhaltsstoffe aufweisen. Die fertigen Mittel können jedoch auch aus einem Gemisch mehrerer verschiedener Feststoffe, insbesondere mehrerer verschiedener Granulate, erhalten werden, von denen beispielsweise die erfindungsgemäßen pulverförmigen Wasch- und Reinigungsmittel den Hauptbestandteil bilden. So können beispielsweise das Bleichmittel, der Bleichaktivator, die Enzyme sowie Farb- und Duftstoffe nachträglich zu den Extrudaten zugemischt werden. Dabei ist es bevorzugt, daß das Bleichmittel, der Bleichaktivator und die Enzyme jeweils in kompaktierter granularer Form, beispielsweise als jeweils separat hergestellte Extrudate, die mittels eines Kneters der oben beschriebenen Ausgestaltung oder über eine Pellet-Presse erhalten werden, einzusetzen. The washing and cleaning agents can be produced uniformly from extrudates, which have the above-mentioned ingredients. The finished funds can, however also from a mixture of several different solids, in particular several various granules, of which, for example, the Powdered washing and cleaning agents according to the invention the main ingredient form. For example, the bleach, the bleach activator, the enzymes and Dyes and fragrances are subsequently added to the extrudates. It is preferred that the bleach, the bleach activator and the enzymes are each in compacted granular form, for example as extrudates produced separately, by means of a kneader of the configuration described above or via a pellet press be obtained.

BeispieleExamples

In einem Chargenmischer, der mit einem Messerkopf-Zerkleinerer (Zerhacker) ausgerüstet war, wurde ein festes Vorgemisch aus den in den unten stehenden Tabellen aufgeführten festen Bestandteilen hergestellt.In a batch mixer equipped with a cutter head chopper was a solid pre-mix from those listed in the tables below solid components.

Bei laufenden Mischwerkzeugen wurde dieses Gemisch mit C12-C18-Fettalkohol mit 7 EO versetzt. Anschließend wurde eine 30 Gew.-%ige wäßrige Sokalan CP® -5-Lösung zudosiert.With mixing tools running, this mixture was mixed with C 12 -C 18 fatty alcohol with 7 EO. A 30% by weight aqueous Sokalan CP® -5 solution was then metered in.

Die Mischung wurde 2 Minuten homogenisiert und im Anschluß daran einem Zwei-Schnecken-Extruder zugeführt, dessen Gehäuse einschließlich des Extruder-Granulierkopfes auf 45° C temperiert war.The mixture was homogenized for 2 minutes and then in a twin-screw extruder fed, its housing including the extruder pelletizing head was tempered to 45 ° C.

Unter der Schereinwirkung der Extruder-Schnecken wurde das Vorgemisch plastifiziert und anschließend bei einem Druck von 120 bar durch die Extruder-Lochdüsenplatten zu feinen Strängen mit einem Durchmesser von 1,2 mm extrudiert, welche nach dem Düsenaustritt mittels eines Abschlagmessers zu angenähert kugelförmigen Granulaten zerkleinert wurden. (Länge/Durchmesser-Verhältnis etwa 1, Heißabschlag). Das anfallende Produkt wurde etwa 1 Minute in einem handelsüblichen Rondiergerät vom Typ Marumerizer® unter Zugabe geringer Mengen Zeolith NaA verrundet und anschließend bei einer Zulufttemperatur von 70° C im Wirbelschichttrockner bis zum Erreichen einer Ablufttemperatur von 53° C getrocknet. Die erhaltenen extrudierten und getrockneten Granulate besaßen die in den Tabellen 1-4 wiedergegebenen Zusammensetzungen. Beispiel 1 (Vergleich) Beispiel 2 Zusammensetzung Endprodukt 1 Vorgemisch 1 Endprodukt 2 Vorgemisch 2 C11-C13-Alkylbenzolsulfonat 1,00 1,19 C12-18-Fettalkoholsulfat 17,77 21,26 16,77 20,05 C12-18-Fettalkohol x 7 EO 3,55 4,24 3,55 4,24 optischer Aufheller 0,04 0,05 0,04 0,05 Parfüm 0,36 0,36 Enzyme 1,56 1,56 HEDP 0,51 0,61 0,51 0,61 Sokalan® CP5 5,00 5,98 5,00 5,98 Silikonentschäumergranulat 3,64 3,64 C12/18-Fettsäureseife 0,71 0,85 0,61 0,85 amorphes Natriumdisilikat 25,46 30,44 25,46 30,44 Zeolith 3,15 3,15 Na-Perborat-Monohydrat 17,53 20,96 17,53 20,96 TAED 7,00 7,00 Polyethylenglykol, MG 400 1,52 1,82 1,52 1,82 Natriumsulfat 1,71 0,85 1,76 0,91 Wasser + sonst. Salze ad 100 ad 100 ad 100 ad 100 Summe 100,00 100,00 100,00 100,00 Tensidgehalt 21,32 25,50 21,32 25,48 Beispiel 3 Beispiel 4 Zusammensetzung Endprodukt 3 Vorgemisch 3 Endprodukt 4 Vorgemisch 4 C11-C13-Alkylbenzolsulfonat 2,00 2,41 3,00 3,62 Protease 0,68 0,68 C12-18-Fettalkoholsulfat 15,77 19,00 14,77 17,86 C12-18-Fettalkohol x 7 EO 3,55 4,27 3,55 4,29 optischer Aufheller 0,04 0,05 0,04 0,05 Parfüm 0,36 0,36 feinteilige Kieselsäure 0,24 0,24 Enzyme 0,88 0,88 HEDP 0,51 0,61 0,51 0,62 Sokalan® CP5 5,00 6,03 5,02 6,07 Silikonentschäumergranulat 3,64 3,64 C16-18-Fettsäureseife 0,71 0,85 0,71 0,86 amorphes Natriumdisilikat 25,46 30,67 25,46 30,78 Zeolith 3,15 3,15 Na-Perborat-Monohydrat 17,53 21,12 17,53 21,20 TAED 7,00 7,00 Polyethylenglykol, MG 400 1,52 1,83 1,52 1,84 Natriumsulfat 1,81 0,98 1,86 1,04 Wasser + sonst. Salze ad 100 ad 100 ad 100 ad 100 Summe 100,00 100,00 100,00 100,00 Tensidgehalt 21,32 25,68 21,32 25,77 Beispiel 5 (Vergleich) Beispiel 6 Zusammensetzung Endprodukt 5 Vorgemisch 5 Endprodukt 6 Vorgemisch 6 C11/13-Alkylbenzolsulfonat 3,00 4,64 C12-18-Fettalkoholsulfat 17,60 26,59 14,60 22,61 C12-18-Fettalkohol x 7 EO 3,51 5,30 3,51 5,43 Wasserglas A 25,20 38,08 25,20 39,03 Parfüm 0,36 0,36 Aerosil 200 0,24 0,24 Enzyme 1,81 2,06 optischer Aufheller 0,54 0,82 0,54 0,82 Sokalan CP5 5,00 7,56 5,01 7,75 Silikonentschäumer 3,64 3,64 C16/18-Fettsäureseife 0,70 1,06 0,70 1,08 Zeolith 3,15 3,34 Na-Percarbonat-Gran. 19,00 19,00 TAED 7,00 7,00 Polyethylenglykol, MG 400 1,50 2,27 1,50 2,32 Natriumsulfat 1,21 1,07 1,35 1,32 Wasser + sonst. Salze ad 100 ad 100 ad 100 ad 100 Summe 100,00 100,00 100,00 100,00 Tensidgehalt 21,11 31,97 21,11 32,68 Beispiel 7 (Vergleich) Beispiel 8 Zusammensetzung Endprodukt 7 Vorgemisch 7 Endprodukt 8 Vorgemisch 8 C11/13-Alkylbenzolsulfonat 3,00 4,61 Enzyme 1,80 1,80 C12-18-Fettalkoholsulfat 17,60 27,11 14,60 22,47 C12-18-Fettalkohol x 7 EO 3,12 4,81 3,12 4,80 Wasserglas 2,0 12,00 18,49 12,00 18,47 optischer Aufheller 0,76 1,18 0,76 1,18 Parfüm 0,36 0,36 Aerosil 200 0,24 0,24 Sokalan CP5(R) 5,00 7,71 5,00 7,70 Silikonentschäumer 3,64 3,64 C16/18-Fettsäureseife 0,70 1,08 0,70 1,08 Zeolith 17,31 22,18 17,31 22,16 Na-Percarbonat-Gran. 19,50 19,50 TAED 7,00 7,00 Polyethylenglykol, MG 400 1,50 2,31 1,50 2,31 Natriumsulfat 1,21 1,09 1,35 1,31 Wasser + sonst. Salze ad 100 ad 100 ad 100 ad 100 Summe 100,00 100,00 100,00 100,00 Tensidgehalt 20,72 31,92 20,72 31,88 The premix was plasticized under the shear action of the extruder screws and then extruded at a pressure of 120 bar through the extruder perforated die plates into fine strands with a diameter of 1.2 mm, which were chopped into approximately spherical granules using a knock-out knife . (Length / diameter ratio about 1, hot cut). The product obtained was rounded off for about 1 minute in a commercially available rounding machine of the type Marumerizer® with the addition of small amounts of zeolite NaA and then dried at a supply air temperature of 70 ° C. in a fluidized bed dryer until an exhaust air temperature of 53 ° C. was reached. The extruded and dried granules obtained had the compositions shown in Tables 1-4. Example 1 (comparison) Example 2 composition End product 1 Premix 1 End product 2 Premix 2 C 11 -C 13 alkyl benzene sulfonate 1.00 1.19 C 12-18 fatty alcohol sulfate 17.77 21.26 16.77 20.05 C 12-18 fatty alcohol x 7 EO 3.55 4.24 3.55 4.24 optical brightener 0.04 0.05 0.04 0.05 Perfume 0.36 0.36 Enzymes 1.56 1.56 HEDP 0.51 0.61 0.51 0.61 Sokalan® CP5 5.00 5.98 5.00 5.98 Silicone defoamer granulate 3.64 3.64 C 12/18 fatty acid soap 0.71 0.85 0.61 0.85 amorphous sodium disilicate 25.46 30.44 25.46 30.44 Zeolite 3.15 3.15 Na perborate monohydrate 17.53 20.96 17.53 20.96 TAED 7.00 7.00 Polyethylene glycol, MG 400 1.52 1.82 1.52 1.82 Sodium sulfate 1.71 0.85 1.76 0.91 Water + other salts ad 100 ad 100 ad 100 ad 100 total 100.00 100.00 100.00 100.00 Surfactant content 21.32 25.50 21.32 25.48 Example 3 Example 4 composition Final product 3 Premix 3 Final product 4 Premix 4 C 11 -C 13 alkyl benzene sulfonate 2.00 2.41 3.00 3.62 Protease 0.68 0.68 C 12-18 fatty alcohol sulfate 15.77 19.00 14.77 17.86 C 12-18 fatty alcohol x 7 EO 3.55 4.27 3.55 4.29 optical brightener 0.04 0.05 0.04 0.05 Perfume 0.36 0.36 finely divided silica 0.24 0.24 Enzymes 0.88 0.88 HEDP 0.51 0.61 0.51 0.62 Sokalan® CP5 5.00 6.03 5.02 6.07 Silicone defoamer granulate 3.64 3.64 C 16-18 fatty acid soap 0.71 0.85 0.71 0.86 amorphous sodium disilicate 25.46 30.67 25.46 30.78 Zeolite 3.15 3.15 Na perborate monohydrate 17.53 21.12 17.53 21.20 TAED 7.00 7.00 Polyethylene glycol, MG 400 1.52 1.83 1.52 1.84 Sodium sulfate 1.81 0.98 1.86 1.04 Water + other salts ad 100 ad 100 ad 100 ad 100 total 100.00 100.00 100.00 100.00 Surfactant content 21.32 25.68 21.32 25.77 Example 5 (comparison) Example 6 composition Final product 5 Premix 5 Final product 6 Premix 6 C 11/13 alkylbenzenesulfonate 3.00 4.64 C 12-18 fatty alcohol sulfate 17.60 26.59 14.60 22.61 C 12-18 fatty alcohol x 7 EO 3.51 5.30 3.51 5.43 Water glass A 25.20 38.08 25.20 39.03 Perfume 0.36 0.36 Aerosil 200 0.24 0.24 Enzymes 1.81 2.06 optical brightener 0.54 0.82 0.54 0.82 Sokalan CP5 5.00 7.56 5.01 7.75 Silicone defoamer 3.64 3.64 C 16/18 fatty acid soap 0.70 1.06 0.70 1.08 Zeolite 3.15 3.34 Na percarbonate gran. 19.00 19.00 TAED 7.00 7.00 Polyethylene glycol, MG 400 1.50 2.27 1.50 2.32 Sodium sulfate 1.21 1.07 1.35 1.32 Water + other salts ad 100 ad 100 ad 100 ad 100 total 100.00 100.00 100.00 100.00 Surfactant content 21.11 31.97 21.11 32.68 Example 7 (comparison) Example 8 composition End product 7 Premix 7 End product 8 Premix 8 C 11/13 alkylbenzenesulfonate 3.00 4.61 Enzymes 1.80 1.80 C 12-18 fatty alcohol sulfate 17.60 27.11 14.60 22.47 C 12-18 fatty alcohol x 7 EO 3.12 4.81 3.12 4.80 Water glass 2.0 12.00 18.49 12.00 18.47 optical brightener 0.76 1.18 0.76 1.18 Perfume 0.36 0.36 Aerosil 200 0.24 0.24 Sokalan CP5 (R) 5.00 7.71 5.00 7.70 Silicone defoamer 3.64 3.64 C 16/18 fatty acid soap 0.70 1.08 0.70 1.08 Zeolite 17.31 22.18 17.31 22.16 Na percarbonate gran. 19.50 19.50 TAED 7.00 7.00 Polyethylene glycol, MG 400 1.50 2.31 1.50 2.31 Sodium sulfate 1.21 1.09 1.35 1.31 Water + other salts ad 100 ad 100 ad 100 ad 100 total 100.00 100.00 100.00 100.00 Surfactant content 20.72 31.92 20.72 31.88

Die Löslichkeit der in den obigen Tabellen dargestellten Produkte wurden in einem Leitfähigkeitstest (die Zeit, bis 90 % des Mittels gelöst waren, wurde bestimmt) sowie durch Bestimmung des Rückstandsverhaltens im simulierten Handwaschtest (L-Test) bestimmt. The solubility of the products shown in the tables above were tested in a conductivity test (the time until 90% of the agent was dissolved was determined) and by determination of the residue behavior in the simulated hand wash test (L test).

1. Bestimmung des Löseverhaltens (Leitfähigkeitstest)1. Determination of the dissolving behavior (conductivity test)

In einem 1-1-Gefäß wurden 500 ml demineralisiertes Wasser (20°C) eingefüllt, der Propellerrührer mit einer Drehzahl von 900 Umdrehungen pro Minute eingeschaltet und die Leitfähigkeitsmeßzelle eingetaucht. Danach wurden 5 g des Mittels zugegeben. Die Änderung der Leitfähigkeit wurde über einen Schreiber festgehalten. Die Messung erfolgte, bis kein Anstieg der Leitfähigkeit mehr feststellbar war. Die Zeit zum Erreichen der Leitfähigkeitskonstanz ist die Lösezeit des Mittels (100%). Die Lösezeit bei 90%iger Auflösung wurde rechnerisch ermittelt. Die ermittelten Werte sind in Tabelle 5 aufgeführt.500 ml of demineralized water (20 ° C.) were poured into a 1 l vessel Propeller stirrer switched on at a speed of 900 revolutions per minute and the conductivity measuring cell is immersed. Then 5 g of the agent were added. The Changes in conductivity were recorded by a clerk. The measurement until there was no increase in conductivity. The time to reach the constant conductivity is the dissolving time of the agent (100%). The release time at 90% The resolution was calculated. The values determined are listed in Table 5.

2. Bestimmung des Rückstandsverhaltens im simulierten Handwaschtest (HW in %) (L-Test)2. Determination of the residue behavior in the simulated hand wash test (HW in%) (L test)

In einer Schüssel wurden 32 g des Mittels in 4 l Wasser (16 °d) bei einer Temperatur von 30°C 15 Sekunden mit der Hand vorgelöst. Dann wurde ein Nicki-Pullover dreimal untergetaucht, gedrückt und um 90° gedreht. Nach einer Minute wurde der Pullover aus der Waschlauge genommen und ausgewrungen. Die Waschlauge wurde abdekantiert, die Rückstände auf ein Sieb überführt und bei 40°C getrocknet. Die Rückstände werden in Gew.-% angegeben. Die Versuchsergebnisse sind ebenfalls in Tabelle 5 wiedergegeben. Beispiel 90 % Lösezeit im Leitfähigkeitstest L - Test (% Rückstand) 1 (Vgl.) 7 min 46 s 44 2 5 min 29 s 24 3 4 min 23 s 21 4 4 min 18 s 23 5 (Vgl.) 8 min 15 s 47 6 3 min 45 s 23 7 (Vgl.) 6 min 13 s -- 8 2 min 36 s -- In a bowl, 32 g of the agent were pre-dissolved in 4 l of water (16 ° d) at a temperature of 30 ° C for 15 seconds by hand. Then a Nicki sweater was submerged three times, pressed and turned by 90 °. After a minute, the sweater was removed from the soapy water and wrung out. The wash liquor was decanted off, the residues were transferred to a sieve and dried at 40 ° C. The residues are given in% by weight. The test results are also shown in Table 5. example 90% dissolving time in the conductivity test L test (% residue) 1 (see) 7 min 46 s 44 2 5 min 29 s 24th 3rd 4 min 23 s 21 4th 4 min 18 s 23 5 (see) 8 min 15 s 47 6 3 min 45 s 23 7 (See) 6 min 13 s - 8th 2 min 36 s -

Aus den obigen Beispielen wird deutlich, daß sich die Löslichkeit der Mittel durch Zusatz von geringen Mengen Alkylbenzolsulfonat deutlich steigern läßt, wenn große Mengen an Alkylsulfaten enthalten sind.From the above examples it is clear that the solubility of the agents is due to the addition of small amounts of alkyl benzene sulfonate can increase significantly when large amounts of Alkyl sulfates are included.

Claims (11)

  1. A solid surfactant- and builder-containing detergent of high bulk density or a compound therefor, characterized in that it contains as anionic surfactants 0.1% by weight to 10% by weight of C9-13 alkyl benzenesulfonate and 10% by weight to 50% by weight of C8-22 alkyl sulfate, the C8-22 alkyl sulfate and C9-13 alkyl benzenesulfonate being present in quantity ratios of 20:1 to 2:1, and as builders 10% by weight to 45% by weight of water-soluble silicates and up to 30% by weight of zeolite.
  2. A detergent as claimed in claim 1, characterized in that the water-soluble silicates and the zeolite are present in a ratio by weight of 1:0.01 to 1:1.5.
  3. A detergent as claimed in claim 1 or 2, characterized in that nonionic surfactants are present in a quantity of 1% by weight to 25% by weight.
  4. A detergent as claimed in any of claims 1 to 3, characterized in that it contains 5 to 25% by weight of bleaching agents.
  5. A detergent as claimed in any of claims 1 to 4, characterized in that it contains enzymes from the class of proteases, lipases, amylases, cellulases or mixtures thereof in the form of granules in a quantity of 0.1% by weight to 5% by weight.
  6. A process for the production of a solid surfactant- and builder-containing detergent of high bulk density or a compound therefor, characterized in that it contains as anionic surfactants 0.1% by weight to 10% by weight of C9-13 alkyl benzenesulfonate and from 10% by weight to 50% by weight of C8-22 alkyl sulfate, the C8-22 alkyl sulfate and C9-13 alkyl benzenesulfonate being present in quantity ratios of 20:1 to 2:1, and as builders 10% by weight to 45% by weight of water-soluble silicates and 0 to 30% by weight of zeolite, the solid and liquid detergent ingredients being mixed to form a homogeneous premix and then compressed.
  7. A process as claimed in claim 6, characterized in that the premix is extruded through a multiple-bore die - with bore diameters corresponding to the predetermined granule size - to form strands, the extrusion process being carried out under high pressures of 25 to 200 bar in the presence of an added plasticizer and/or lubricant, and the strands thus formed are cut to the predetermined granule size by a cutting unit immediately after leaving the extrusion die.
  8. A process as claimed in claim 6, characterized in that the premix is tabletted.
  9. A process as claimed in any of claims 6 to 8, characterized in that nonionic surfactants are used as liquid detergent ingredients.
  10. A process as claimed in any of claims 6 to 9, characterized in that anionic surfactants are used in solid or liquid to paste-like form.
  11. A process as claimed in any of claims 6 to 10, characterized in that a bulk density of the detergents of 600 to 1,000 g/l is established.
EP97907093A 1996-03-21 1997-03-12 Solid surfactant and builder-containing washing and cleaning agent with a high bulk density or compound for such an agent Revoked EP0888449B1 (en)

Applications Claiming Priority (3)

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DE19611013 1996-03-21
DE19611013A DE19611013A1 (en) 1996-03-21 1996-03-21 Solid detergent or builder-containing detergent or cleaning agent with a high bulk density or compound therefor
PCT/EP1997/001241 WO1997034994A1 (en) 1996-03-21 1997-03-12 Solid surfactant and builder-containing washing and cleaning agent with a high bulk density or compound for such an agent

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EP0888449A1 EP0888449A1 (en) 1999-01-07
EP0888449B1 true EP0888449B1 (en) 2001-12-05

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
US7910538B2 (en) 2008-06-04 2011-03-22 The Procter & Gamble Company Detergent composition

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US5961663A (en) * 1997-05-29 1999-10-05 Colgate-Palmolive Co. Microwave-dried amorphous alkali metal silicate powders and their use as builders in detergent compositions
US6559115B1 (en) * 1998-07-10 2003-05-06 The Procter & Gamble Company Detergent tablet with high mechanical and dissolution characteristics
ATE289347T1 (en) * 1998-07-10 2005-03-15 Procter & Gamble DETERGENT TABLET WITH HIGH MECHANICAL AND SOLUTION PROPERTIES
EP0971028A1 (en) * 1998-07-10 2000-01-12 The Procter & Gamble Company Detergent tablet with high dissolution and mechanical characteristics
DE19903290A1 (en) * 1999-01-28 2000-08-03 Henkel Kgaa Detergent tablets with defined anionic surfactant behavior
DE19911570A1 (en) * 1999-03-16 2000-09-28 Henkel Kgaa Anionic surfactant granules
WO2001025391A1 (en) * 1999-10-06 2001-04-12 The Procter & Gamble Company Detergent tablet with high dissolution and mechanical characteristics
DE10031619A1 (en) * 2000-06-29 2002-01-10 Cognis Deutschland Gmbh Surfactant granules with an improved dissolution rate
DE102015002877A1 (en) * 2015-03-09 2016-09-15 Henkel Ag & Co. Kgaa Granular detergent or cleaner with improved dissolution rate
US11767495B2 (en) * 2020-03-13 2023-09-26 YFY Consumer Products, Co. Systems and methods for manufacturing solid granules

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JPH0436398A (en) * 1990-06-01 1992-02-06 Lion Corp High bulk density granular detergent composition
DE4125178A1 (en) * 1991-07-30 1993-02-04 Henkel Kgaa POWDERED ANIONSIDE PREPARATION
DE19525378A1 (en) * 1995-07-12 1997-01-16 Henkel Kgaa Amorphous alkali silicate compound

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7910538B2 (en) 2008-06-04 2011-03-22 The Procter & Gamble Company Detergent composition

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WO1997034994A1 (en) 1997-09-25
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DE59705671D1 (en) 2002-01-17
ES2169357T3 (en) 2002-07-01
EP0888449A1 (en) 1999-01-07

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