EP1207195A2 - Particulate bleach activators comprising acetonitril - Google Patents

Particulate bleach activators comprising acetonitril Download PDF

Info

Publication number
EP1207195A2
EP1207195A2 EP01126661A EP01126661A EP1207195A2 EP 1207195 A2 EP1207195 A2 EP 1207195A2 EP 01126661 A EP01126661 A EP 01126661A EP 01126661 A EP01126661 A EP 01126661A EP 1207195 A2 EP1207195 A2 EP 1207195A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
bleach activators
acetonitrile
contain
particulate bleach
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01126661A
Other languages
German (de)
French (fr)
Other versions
EP1207195A3 (en
Inventor
Georg Dl. Borchers
Robert Dr. Milbradt
Oliver Dr. Mogck
Frank Dr. Weinelt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant GmbH filed Critical Clariant GmbH
Publication of EP1207195A2 publication Critical patent/EP1207195A2/en
Publication of EP1207195A3 publication Critical patent/EP1207195A3/en
Withdrawn legal-status Critical Current

Links

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
    • 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
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles

Definitions

  • the present invention relates to particulate bleach activators based on Acetonitriles, a process for their preparation, which consists in that Applies acetonitrile to silicon containing substrates and the Use of these products as bleach activators in solid washing and Detergents.
  • Bleach activators are important components in compact detergents, Stain removal salts and machine dishwashing detergents. They already enable at 40 to 60 ° C a bleaching result comparable to that of hot laundry by using Hydrogen peroxide dispensers (mostly perborates, percarbonates, persilicates and Perphosphate) react with the release of peroxyacids.
  • Hydrogen peroxide dispensers mostly perborates, percarbonates, persilicates and Perphosphate
  • bleach activators Many substances are known in the art as bleach activators. Usually these are reactive organic compounds with a O-acyl or N-acyl group in alkaline solution together with a source form the corresponding peroxyacids for hydrogen peroxide.
  • bleach activators are, for example, N, N, N ', N'-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), Sodium trimethylhexanoyloxybenzenesulfonate (STHOBS), tetraacetylglucoluril (TAGU), tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxin (ADMG) and 1-phenyl-3-acetylhydantoin (PAH).
  • TAED N, N, N ', N'-tetraacetylethylenediamine
  • GPA glucose pentaacetate
  • TAX xylose tetraacetate
  • SBOBS sodium 4-benzoyloxybenzenesulfonate
  • STHOBS Sodium trimethyl
  • Ammonium nitriles are a special class of cationic bleach activators. Compounds of this type and their use as bleach activators in bleaching agents are described in EP-A-0 303 520, EP-A-0 464 880, EP-A-0 458 396, EP-A-0 897 974 and EP-A-0 790 244.
  • ammonium nitriles as bleach activators in detergents and cleaning agents, the hygroscopicity of ammonium nitriles and the sensitivity to hydrolysis in the presence of alkaline detergent components and a correspondingly low storage stability are of great disadvantage.
  • acetonitrile derivatives in particular cyclic acetonitrile compounds, for incorporation in solid washing and cleaning agents can be converted into a solid form by a carrier material with the largest possible surface, for example silica, in an aqueous Stirred acetonitrile solution or sprayed the aqueous solution onto the carrier and the resulting mixture is dried in a vacuum at elevated Subjected to temperatures.
  • a carrier material with the largest possible surface, for example silica
  • the granular or particulate Packaging of the acetonitrile derivatives in a very gentle, but also economically and ecologically very advantageous can that at room temperature saturated, aqueous solutions of acetonitrile derivatives on a silicon-containing carrier material, in particular silica, can be sprayed on without subsequent drying.
  • the Active substance concentration of those produced by the process according to the invention Products is higher than conventional products, the hygroscopicity of the Acetonitrile derivatives assembled according to the invention are significantly lower.
  • the invention relates to particulate bleach activators containing 15 to 60, preferably 20 to 50, in particular 35 to 45% by weight of an acetonitrile, 20 to 70, preferably 30 to 50, in particular 35 to 45% by weight of a silicon containing carrier material and 20 to 30, preferably 22 to 25 wt .-% Water.
  • Suitable acetonitriles are compounds of the formula in which R 1 , R 2 , R 3 are identical or different and for linear or branched C 1 -C 24 alkyl groups, C 2 -C 24 alkenyl groups or for C 1 -C 4 alkoxy-C 1 -C 4 - Alkyl groups, substituted or unsubstituted benzyl, or in which R 1 and R 2 together with the nitrogen atom to which they are attached form a ring having 4 to 6 C atoms, which is substituted by C 1 -C 5 alkyl, C 1 - C 5 -alkoxy, C 1 - to C 5 -alkanoyl, phenyl, amino, ammonium, cyano, cyanamino, chlorine or bromine can be substituted and in addition to the nitrogen atom instead of carbon atoms one or two oxygen or nitrogen atoms, a group NR 6 or can contain a group R 3 -NR 6 , in which R 6 is hydrogen, C
  • Cumene sulfonate and C 12/18 alcohol sulfate are particularly preferred as anions.
  • Particularly preferred are compounds of the above formula in which R 1 , R 2 and R 3 are C 1 -C 4 alkyl and R 4 and R 5 are hydrogen and A is any cation, preferably chloride, methosulfate, cumene sulfonate, lauryl sulfate or fatty acid alkyl carboxylates or Mixtures of these cations.
  • a saturated aqueous solution is prepared from these acetonitriles the silicon-containing carrier material is applied, preferably by Spray on, for example via a two-component nozzle.
  • the temperature of this saturated aqueous solution is preferably 10 to 40, particularly preferred at 20 to 25 ° C.
  • the material can then be mixed.
  • the amount of saturated aqueous solution is measured so that the above mentioned limits for acetonitrile, carrier material and water are observed.
  • the silicon-containing carrier materials used are preferably those whose inner surface is in the range from 10 m 2 / g to 500 m 2 / g, in particular 100 m 2 / g to 450 m 2 / g.
  • silicates, silicas, silica gels and clays and their mixtures are suitable.
  • the carrier material is preferably free of strongly alkaline components.
  • Silicas produced by the thermal process (flame hydrolysis of SiCl 4 ) can be used as well as silicas produced by wet processes.
  • Silica gels are colloidal silicas with elastic to firm consistency and a largely loose pore structure, which results in a high fluid absorption capacity.
  • Clays are naturally occurring crystalline or amorphous silicates of aluminum, iron, magnesium, calcium, potassium and sodium, for example kaolin, talc, pyrophyllite, attapulgite, sepiolite, montmorillionite and bauxite.
  • the use of aluminum silicate as a carrier material or as a component of a carrier material mixture is also possible.
  • the carrier material preferably has particle sizes in the range from 10 ⁇ m to 1.5 mm.
  • the Granulate acetonitrile-loaded carrier material can also do that carrier material loaded with the acetonitrile with or without the addition of a binder compressed, compacted and gentle up to granulate sizes from 200 to 2000 ⁇ m be crushed.
  • a build-up granulation in the mixer for example in the Ploughshare mixer, ring layer mixer or intensive mixer with or without additive a binder, for example a water-based binder such as tylose (Carboxymethyl cellulose) or an anhydrous binding system, such as Fettalkoholpolyglykolether.
  • a binder for example a water-based binder such as tylose (Carboxymethyl cellulose) or an anhydrous binding system, such as Fettalkoholpolyglykolether.
  • this can be done by spraying on a saturated Solution of the acetonitrile on a carrier material obtained with particulate product or without the addition of a binder of a form granulation by means of dies in the extruder, but also in ring roller presses, roller mills, possibly with downstream rounder.
  • the particulate bleach activators obtained according to the invention are directly for Suitable for use in detergents and cleaning agents.
  • tissue and To avoid color damage it is advantageous to use the particulate Bleach activators, however, according to methods known per se with a coating envelope to provide.
  • the granules are processed in a manner known per se an additional step coated with a film-forming substance, whereby the Product properties can be significantly influenced.
  • All film-forming substances such as waxes, are suitable as coating material.
  • anionic and cationic polymers e.g. B. polyacrylic acids.
  • Coating substances with a melting point of 30 to 100 ° C. are preferred used. Examples of this and a method of application are described in EP-A-0 835 926.
  • the coating materials are applied in the Usually by spraying the melted or dissolved in a solvent Coating materials.
  • the coating material can be in amounts from 0 to 30, preferably 5 to 20 wt .-%, based on the total weight on the granulate core according to the invention are applied.
  • the particulate bleach activators according to the invention contain other suitable additives, such as anionic and nonionic Surfactants which lead to a faster dissolution of the granules according to the invention contribute.
  • Preferred anionic surfactants are alkali salts, ammonium salts, Amine salts and salts of amino alcohols from the following compounds: Alkyl sulfates, alkyl ether sulfates, alkyl amide sulfates and ether sulfates, Alkylaryl polyether sulfates, monoglyceride sulfates, alkyl sulfonates, alkyl amide sulfonates, Alkyl aryl sulfonates, ⁇ -olefin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, Alkyl amide sulfosuccinates, alkyl sulfo acetates,
  • nonionic surfactants are polyethoxylated, polypropoxylated or polyglycerolated ethers of fatty alcohols, polyethoxylated, polypropoxylated and polyglycerolated fatty acid esters, polyethoxylated esters of fatty acids and of Sorbitol, polyethoxylated or polyglycerolated fatty amides are preferred.
  • suitable additives are substances that adjust the pH during storage and Affect application. These include organic carboxylic acids or their salts, such as citric acid in anhydrous or hydrated form, glycolic acid, Succinic acid, maleic acid or lactic acid.
  • organic carboxylic acids or their salts such as citric acid in anhydrous or hydrated form, glycolic acid, Succinic acid, maleic acid or lactic acid.
  • additions are possible that influence the bleaching capacity, such as complexing agents and Transition metal complexes, e.g. Contains iron, cobalt and manganese Metal complexes as described in EP-A-0 458 397 and EP-A-0 458 398.
  • the amount of the additive depends in particular on its type acidifying additives and organic catalysts to increase the performance of the Peracid in amounts of 0 to 20% by weight, in particular in amounts of 1 to 10% by weight, based on the total weight, was added, but metal complexes in concentrations in the ppm range.
  • the particulate bleach activators according to the invention can be incorporated into tableted detergent and cleaning agent formulations by customary methods.
  • the procedure is preferably such that all the constituents are mixed with one another in a mixer and the mixture is pressed by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 ⁇ 10 5 Pa to 1500 ⁇ 10 5 Pa , In this way, break-resistant tablets are obtained with ease, which nevertheless dissolve sufficiently quickly under conditions of use, with bending strengths of over 150 N.
  • a tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.
  • the acetonitrile derivatives made up according to the invention can be in Heavy duty detergents, stain removal salts, machine dishwashing detergents, powdered All-purpose cleaners and denture cleaners are used.
  • the detergents and cleaning agents containing the above-described particulate Assembled acetonitrile derivatives are used in combination with a Source of hydrogen peroxide, for example perborate monohydrate, perborate tetrahydrate, Percarbonate and hydrogen peroxide adducts with urea or Amine oxides are used and can contain all ingredients common in these agents, such as Builder substances, surface-active surfactants, enzymes, sequestering agents, Electrolytes, pH regulators, foam regulators, abrasives Brighteners, silver corrosion inhibitors, preservatives, perfumes and fragrances contain.
  • a Source of hydrogen peroxide for example perborate monohydrate, perborate tetrahydrate, Percarbonate and hydrogen peroxide adducts with urea or Amine oxides are used and can contain all ingredients common in these agents, such as Builder substances, surface-active surfactants, enzymes, sequestering agents, Electrolytes, pH regulators, foam regulators, abrasives Brighten
  • Suitable builders are both phosphate-free builder systems as well systems containing phosphates, for example alkali metal phosphates, in the form of their alkaline neutral or acidic sodium or potassium salts may be present, such as Trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen phosphate, Pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric Trisodium phosphate with amounts of oligomerization in the range from 5 to 1000, especially 5 to 50, and mixtures of sodium and potassium salts.
  • phosphates for example alkali metal phosphates
  • alkali metal phosphates in the form of their alkaline neutral or acidic sodium or potassium salts
  • Trisodium phosphate such as Trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen phosphate, Pentasodium triphosphate, so-called sodium hexameta
  • Fine crystalline, synthetic water-containing zeolites of the type NaA the one Have calcium binding capacity in the range of 100 to 200 mg CaO / g a preferred use. These zeolites can be in an amount up to 20 wt .-% may be included in the average.
  • Useful builders are also the preferred ones in Form of their sodium salts used percarboxylic acids, such as citric acid and Nitriloacetate (NTA), ethylenediaminetetraacetic acid. Analogous to this, too polymeric carboxylates and their salts are used.
  • the relative molecular mass of the Homopolymers are generally between 1000 and 100,000, the Copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid.
  • water-soluble polyacrylates are also suitable, for example, with about 1% of a polyallyl ether of sucrose are cross-linked and have a relative molecular mass above one million have. Examples of this are those under the name Carbopol® 940 and 941 available polymers.
  • the cross-linked polyacrylates are not over in quantities 1 wt .-%, preferably used in amounts of 0.2 to 0.7 wt .-%. This Builders can be used in amounts up to 5% by weight.
  • Preferred anionic surfactants are C 8 -C 20 fatty acid- ⁇ -methyl ester sulfonates, alkyl sulfates, alkyl ether sulfates and sec. Alkanesulfonates.
  • the alkyl ether sulfates used in the agents according to the invention are water-soluble salts or acids of the formula RO (A) m SO 3 M, in which R is an unsubstituted C 10 -C 24 -alkyl or C 10 -C 24 -hydroxyalkyl radical, preferably a C 12 -C 20 alkyl or C 12 -C 20 hydroxyalkyl radical, particularly preferably C 12 -C 18 alkyl or C 12 -C 18 hydroxyalkyl radical.
  • A is an ethoxy or propoxy unit
  • m is a number greater than 0, preferably between 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3
  • M is a hydrogen atom or a cation such as, for example a metal cation (e.g. sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a substituted ammonium cation.
  • substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine.
  • alkyl ether sulfates are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate, (C 12 -C 18 E (1.0) M), C 12 -C 18 alkyl polyethoxylate (2, 25) sulfate (C 12 -C 18 E (2.25) M), C 12 -C 18 alkyl polyethoxylate (3.0) sulfate (C 12 -C 18 E (3.0) M), C 12 -C 18 alkyl polyethoxylate (4.0) sulfate (C 12 -C 18 E (4.0) M).
  • the alkyl group can either be saturated or unsaturated, branched or linear and optionally with a hydroxyl group be substituted.
  • the sulfo group is statistically distributed over the entire C chain, with the primary methyl groups at the beginning and end of the chain none Possess sulfonate groups.
  • the preferred secondary alkanesulfonates contain linear alkyl chains with 9 to 25 carbon atoms, preferably from 10 to 20 Carbon atoms and particularly preferably 13 to 17 carbon atoms.
  • the cation is sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. Sodium as a cation is simplicity preferred for the sake of it.
  • the Detergents and cleaning agents also other types of anionic surfactants contain, such as alkyl sulfates, sulfonates, carboxylates, phosphates and Mixtures of the compounds mentioned.
  • Suitable cations are e.g. Sodium, potassium, calcium or magnesium, as well as ammonium Ammonium compounds, including mono-, di- or Triethanolammonium cations, as well as mixtures of these cations.
  • Alkyl sulfates here are water-soluble salts or acids of the formula ROSO 3 M, in which R is preferably a C 10 -C 24 hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with C 10 -C 20 alkyl components, particularly preferably a C 12 -C 18 alkyl radical or hydroxyalkyl radical.
  • M is hydrogen or a cation, for example sodium, potassium, lithium or ammonium or substituted ammonium, for example methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations, derived from alkylamines such as ethylamine, diethylamine, triethylamine and Mixtures of these.
  • alkylamines such as ethylamine, diethylamine, triethylamine and Mixtures of these.
  • alkylbenzenesulfonate is alkylbenzenesulfonate.
  • the alkyl group can be either saturated or unsaturated, branched or linear and optionally be substituted with a hydroxyl group.
  • the preferred alkylbenzenesulfonates contain linear alkyl chains with 9 to 25 Carbon atoms, preferably from 10 to 13 carbon atoms, which is cation Sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or Magnesium and mixtures thereof.
  • Suitable anionic surfactants are carboxylates, for example fatty acid soaps and comparable surfactants.
  • the soaps can be saturated or unsaturated and can contain various substituents, such as hydroxyl groups or alpha sulfonate groups. Linear saturated or unsaturated hydrocarbon residues are preferred as the hydrophobic component in the soaps.
  • the hydrophobic components usually contain 6 to 30 carbon atoms, preferably 10 to 18 carbon atoms.
  • anionic surfactants are salts of acylaminocarboxylic acids, which are formed by reacting fatty acid chlorides with sodium sarcosinate in an alkaline medium (acylsarcosinates), and fatty acid-protein condensation products, which are obtained by reacting fatty acid chlorides with oligopeptides.
  • the salts of alkylsulfamidocarboxylic acids and the salts of alkyl and alkylaryl ether carboxylic acids also have surfactant properties.
  • anionic surfactants which are useful for use in detergents and cleaning agents are C 8 -C 24 -olefin sulfonates, sulfonated polycarboxylic acids, prepared by sulfonating the pyrolysis products of alkaline earth metal citrates, as described, for example, in GB 1 082 179, alkyl glycerol sulfates, fatty acyl glycerol sulfates, oleyl glycerol sulfates , alkylphenol ether sulfates, primary paraffinsulfonates, alkyl phosphates, alkyl ether phosphates, isethionates such as the acyl isethionates, N-acyl taurides, alkyl succinamates, sulfosuccinates, monoester of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 monoesters) and diesters of sul
  • Resin acids or hydrogenated resin acids such as rosin or hydrogenated rosin or tall oil resins and tall oil resin acids can also be used. Further examples are described in "Surface Active Agents and Detergents” (Vol. I and II, Schwartz, Perry and Berch). A large number of such surfactants are also described in US 3,929,678.
  • anionic surfactants are also alkyl ether sulfonates, glycerol ether, sulfofatty acids, Glycerol ether, Hydroxymischethersulfat, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, alkyl oligoglucoside sulfates, Alkylaminozuckersulfate and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional or narrow homolog distribution.
  • nonionic surfactants such as fatty acid alkyl ester, alkyl and / or alkenyl oligoglycosides, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide, fatty amine polyglycol ethers, alkoxylated triglycerides, Fett Textreglucamiden, PolyölfettTexreester, Zuckerester, sorbitan esters and polysorbates and / or alkoxylated fatty alcohols may be used ,
  • Co-surfactants from the group alkyl betaines, alkyl amido betaines, Aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines, Amine oxides and fatty acid alkanolamides or polyhydroxyamides are used.
  • bleach activating acetonitrile derivatives known ones conventional bleach activators, that is compounds that are under Perhydrolysis conditions aliphatic peroxocarboxylic acids and / or optionally substituted perbenzoic acids are used.
  • Suitable substances are organic compounds with a 0-acyl or N-acyl group, especially from the group of activated carboxylic acid esters, in particular sodium nonanoyloxy benzenesulfonate, sodium isononanoyloxy benzenesulfonate, Sodium 4-benzoyloxy-benzenesulfonate, sodium trimethylhexanoyloxy-benzenesulfonate, Carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, lactones, acylates, carboxamides, acyl lactams, acyl lac
  • bleach activators listed above or on in their place can also sulfonimines and / or bleach-enhancing Transition metal salts or transition metal complexes as so-called Bleach catalysts, as described in DE 196 49 375, may be included.
  • Enzymes come from the class of proteases such as BLAP, Optimase, Opticlean, Maxacal, Maxapem, Esperase, Savinase, Purifect OxP and / or Durazym, lipases such as Lipolase, Lipomax, Lumafast and / or Lipozym, amylases such as Termamyl, Ainylase-LT, Maxamyl, Duramyl and / or Purafect OxAm, as well Cutinases, pullulanases or their mixture in question. Their share can range from 0.2 to 1% by weight.
  • the enzymes can be adsorbed on carrier substances and / or be embedded in coating substances.
  • foam regulators 0.5 to 4 wt .-% foam suppressing compounds, preferably from the Group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffins, paraffin-alcohol combinations, hydrophobicized silica, the Bis fatty acid amides and other other known commercially available Defoamers can be added.
  • the inventive System and environmentally compatible acids especially citric acid, Acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, Glutaric acid and / or adipic acid, but also mineral acids, in particular Sulfuric acid or alkali hydrogen sulfates or bases, especially ammonium or alkali hydroxides.
  • Such pH regulators are in the Agents according to the invention preferably do not exceed 10% by weight, especially 0.5 to 6 wt .-% included.
  • Suitable preservatives are, for example, phenoxyethanol, Formaldehyde solution, pentanediol or sorbic acid.
  • Abrasives that can be used are Quartz flours, wood flours, plastic flours, chalks and micro glass balls.
  • Typical examples of other additives are sodium borate, starch, Sucrose, polydextrose, stilbene compounds, methyl cellulose, toluenesulfonate, Cumene sulfonate, soaps and silicones.
  • the preparation of the agents according to the invention in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range of 800 to 1000 g / l can be done by first Process stage the builder components with at least a portion of liquid Mix components while increasing the bulk density of this premix mixed and then - if necessary after an intermediate drying - the other components of the agent, including the bleach activator, with the so obtained premix combined.
  • silica Sipernat® 50 S (Degussa-Hüls) were placed in the Lödige mixer. submitted and at about 20 ° C over a period of 27 minutes 780 ml of a aqueous, about 67 wt .-% solution of trimethylacetonitrile ammonium chloride with sprayed on a two-component nozzle. After spraying it was 2 minutes remixed.
  • Aerosil® 380 silica (Degussa Hüls) were placed in the Lödige mixer. submitted and at about 20 ° C over a period of 9 minutes 320 ml aqueous, about 67 wt .-% solution of trimethylacetonitrile ammonium chloride with sprayed on a two-component nozzle. After spraying it was 2 minutes remixed.
  • Example 1 Dishwasher detergent (% by weight)
  • Example 2 Dishwasher tablets (% by weight)
  • Second phase sodium tripolyphosphate 31 Na perborate monohydrate 10 Acetonitrile / sipernate (52/48% by weight) 3 Polycarboxylate (Sokalan® CP5) 1 glucamide 2 sodium 15 Layered Silicate (SKS-6) 6
  • Second phase sodium tripolyphosphate 26% by weight Complexing agent (Turpinal® 2NZ) 1% by weight Protease granules (Blap® 200) 2% by weight Amylase granules (Duranyl® 60 T) 2% by weight dye 0.9% by weight Perfume 0.1% by weight

Abstract

Particulate bleach activators comprise 15-60 wt.% of an acetonitrile, 20-70 wt.% of a silicon-containing carrier and 20-30 wt.% water. An Independent claim is also included for production of the bleach activators by applying a saturated aqueous solution of the acetonitrile onto the carrier.

Description

Vorliegende Erfindung betrifft teilchenförmige Bleichaktivatoren auf der Basis von Acetonitrilen, ein Verfahren zu deren Herstellung, das darin besteht, daß man Acetonitrile auf Silizium enthaltende Trägermaterialien aufbringt und die Verwendung dieser Produkte als Bleichaktivatoren in festen Wasch- und Reinigungsmitteln.The present invention relates to particulate bleach activators based on Acetonitriles, a process for their preparation, which consists in that Applies acetonitrile to silicon containing substrates and the Use of these products as bleach activators in solid washing and Detergents.

Bleichaktivatoren sind wichtige Bestandteile in Kompaktwaschmitteln, Fleckensalzen und Maschinengeschirrspülmitteln. Sie ermöglichen bereits bei 40 bis 60°C ein der Kochwäsche vergleichbares Bleichergebnis, indem sie mit Wasserstoffperoxydspendern (meist Perborate, Percarbonate, Persilicate und Perphosphate) unter Freisetzung von Peroxysäuren reagieren.Bleach activators are important components in compact detergents, Stain removal salts and machine dishwashing detergents. They already enable at 40 to 60 ° C a bleaching result comparable to that of hot laundry by using Hydrogen peroxide dispensers (mostly perborates, percarbonates, persilicates and Perphosphate) react with the release of peroxyacids.

Viele Substanzen sind nach dem Stand der Technik als Bleichaktivatoren bekannt. Gewöhnlich handelt es sich dabei um reaktive organische Verbindungen mit einer O-Acyl- oder N-Acyl-Gruppe, die in alkalischer Lösung zusammen mit einer Quelle für Wasserstoffperoxid die entsprechenden Peroxysäuren bilden.Many substances are known in the art as bleach activators. Usually these are reactive organic compounds with a O-acyl or N-acyl group in alkaline solution together with a source form the corresponding peroxyacids for hydrogen peroxide.

Repräsentative Beispiele für Bleichaktivatoren sind etwa N,N,N',N'-Tetraacetylethylendiamin (TAED), Glucosepentaacetat (GPA), Xylosetetraacetat (TAX), Natrium-4-benzoyloxybenzolsulfonat (SBOBS), Natriumtrimethylhexanoyloxybenzolsulfonat (STHOBS), Tetraacetylglucoluril (TAGU), Tetraacetylcyansäure (TACA), Di-N-acetyldimethylglyoxin (ADMG) und 1-Phenyl-3-acetylhydantoin (PAH).Representative examples of bleach activators are, for example, N, N, N ', N'-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), Sodium trimethylhexanoyloxybenzenesulfonate (STHOBS), tetraacetylglucoluril (TAGU), tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxin (ADMG) and 1-phenyl-3-acetylhydantoin (PAH).

Ammoniumnitrile bilden eine besondere Klasse kationischer Bleichaktivatoren. Verbindungen dieser Art und deren Verwendung als Bleichaktivator in Bleichmitteln sind in EP-A-0 303 520, EP-A-0 464 880, EP-A-0 458 396, EP-A-0 897 974 und EP-A-0 790 244 beschrieben.
Für den Einsatz der Ammoniumnitrile als Bleichaktivator in Wasch- und Reinigungsmitteln ist die Hygroskopizität der Ammoniumnitrile und die Hydrolyseempfindlichkeit in Gegenwart alkalischer Waschmittelbestandteile und eine damit verbundene entsprechend geringe Lagerstabilität von großem Nachteil.Ammonium nitriles are a special class of cationic bleach activators. Compounds of this type and their use as bleach activators in bleaching agents are described in EP-A-0 303 520, EP-A-0 464 880, EP-A-0 458 396, EP-A-0 897 974 and EP-A-0 790 244.
For the use of ammonium nitriles as bleach activators in detergents and cleaning agents, the hygroscopicity of ammonium nitriles and the sensitivity to hydrolysis in the presence of alkaline detergent components and a correspondingly low storage stability are of great disadvantage.

In WO 98/23531 und WO 00/36061 wird beschrieben, dass Acetonitril-Derivate, insbesondere cyclische Acetonitrilverbindungen, zur Einarbeitung in feste Wasch- und Reinigungsmittel in eine feste Form überführt werden, indem ein Trägermaterial mit möglichst großer Oberfläche, beispielsweise Kieselsäure, in eine wässrige Acetonitrillösung eingerührt bzw. die wässrige Lösung auf den Träger aufgesprüht wird und die resultierende Mischung einer Trocknung im Vakuum bei erhöhten Temperaturen unterzogen wird. Die in diesen Schriften beschriebenen Granulate bzw. Partikel haben Wassergehalte von bis zu 20 Gew.-%, bevorzugt weniger als 1 Gewichtsprozent. Unbefriedigend ist die Hygroskopizität und folglich die Lagerstabilität der Produkte, insbesondere der linearen Acetonitril-Derivate bei schwankender Luftfeuchtigkeit, sowie die teilweise Zersetzung der hydrolyseempfindlichen Acetonitrilverbindungen während des thermischen Trocknungsprozesses.WO 98/23531 and WO 00/36061 describe that acetonitrile derivatives, in particular cyclic acetonitrile compounds, for incorporation in solid washing and cleaning agents can be converted into a solid form by a carrier material with the largest possible surface, for example silica, in an aqueous Stirred acetonitrile solution or sprayed the aqueous solution onto the carrier and the resulting mixture is dried in a vacuum at elevated Subjected to temperatures. The granules described in these documents or particles have water contents of up to 20% by weight, preferably less than 1 Weight. The hygroscopicity and consequently that is unsatisfactory Storage stability of the products, especially the linear acetonitrile derivatives fluctuating air humidity, as well as the partial decomposition of the hydrolysis sensitive acetonitrile compounds during thermal Drying process.

Überraschenderweise wurde gefunden, dass die granulat- bzw. teilchenförmige Konfektionierung der Acetonitril-Derivate in einer für den Wirkstoff sehr schonenden, aber auch ökonomisch und ökologisch sehr vorteilhaften Weise dadurch erfolgen kann, dass bei Raumtemperatur gesättigte, wässrige Lösungen aus Acetonitril-Derivaten auf ein Silizium enthaltendes Trägermaterial, insbesondere Kieselsäure, aufgesprüht werden ohne anschließende Trocknung. Man erhält feste Produkte mit einem Wasseranteil von 20 bis 30 Gew.-%. Auf ein energieintensives und für den Wirkstoff belastendes Trockenverfahren kann verzichtet werden. Die Wirkstoffkonzentration der nach dem erfindungsgemäßen Verfahren hergestellten Produkte ist gegenüber herkömmlichen Produkten höher, die Hygroskopizität der erfindungsgemäß konfektionierten Acetonitril-Derivate signifikant geringer. Surprisingly, it was found that the granular or particulate Packaging of the acetonitrile derivatives in a very gentle, but also economically and ecologically very advantageous can that at room temperature saturated, aqueous solutions of acetonitrile derivatives on a silicon-containing carrier material, in particular silica, can be sprayed on without subsequent drying. You get solid products a water content of 20 to 30 wt .-%. On an energy-intensive and for the Drying process that stresses the active ingredient can be dispensed with. The Active substance concentration of those produced by the process according to the invention Products is higher than conventional products, the hygroscopicity of the Acetonitrile derivatives assembled according to the invention are significantly lower.

Gegenstand der Erfindung sind teilchenförmige Bleichaktivatoren, enthaltend 15 bis 60, vorzugsweise 20 bis 50, insbesondere 35 bis 45 Gew.-% eines Acetonitrils, 20 bis 70, bevorzugt 30 bis 50, insbesondere 35 bis 45 Gew.-% eines Silizium enthaltenden Trägermaterials und 20 bis 30, vorzugsweise 22 bis 25 Gew.-% Wasser.The invention relates to particulate bleach activators containing 15 to 60, preferably 20 to 50, in particular 35 to 45% by weight of an acetonitrile, 20 to 70, preferably 30 to 50, in particular 35 to 45% by weight of a silicon containing carrier material and 20 to 30, preferably 22 to 25 wt .-% Water.

Als Acetonitrile kommen infrage Verbindungen der Formel

Figure 00030001
worin R1, R2, R3 gleich oder verschieden sind, und für lineare oder verzweigte C1-C24-Alkylgruppen, C2-C24-Alkenylgruppen oder für C1-C4-Alkoxy-C1-C4-Alkylgruppen, substituiertes oder unsubstituiertes Benzyl stehen, oder worin R1 und R2 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Ring mit 4 bis 6 C-Atomen bilden, der mit C1-C5-Alkyl, C1-C5-Alkoxy, C1- bis C5-Alkanoyl, Phenyl, Amino, Ammonium, Cyano, Cyanamino, Chlor oder Brom substituiert sein kann und zusätzlich zum Stickstoffatom anstelle von Kohlenstoffatomen ein oder zwei Sauerstoff- oder Stickstoffatome, eine Gruppe N-R6 oder eine Gruppe R3-N-R6 enthalten kann, worin R6 Wasserstoff, C1- bis C5-Alkyl, C2- bis C5-Alkenyl, C2- bis C5-Alkinyl, Phenyl, C7- bis C9-Aralkyl, C5- bis C7-Cycloalkyl, C1- bis C6-Alkanoyl, Cyanomethyl oder Cyan ist, R4 und R5 Wasserstoff, C1-C4-Alkyl, C2-C4-Alkenyl, C1-C4-Alkoxy-C1-C4-alkyl, Phenyl oder C1-C3-Alkylphenyl, vorzugsweise Wasserstoff, Methyl oder Phenyl sind, wobei insbesondere R4 Wasserstoff bedeutet, wenn R5 keinen Wasserstoff bedeutet, und A für ein beliebiges Anion, beispielsweise Chlorid, Bromid, lodid, Fluorid, Sulfat, Hydrogensulfat, Carbonat, Hydrogencarbonat, Phosphat, Mono- und Di-Hydrogenphosphat, Pyrophosphat, Metaphosphat, Nitrat, Methylsulfat, Phosphonat, Methylphosphonat, Methandisulfonat, Methylsulfonat, Ethansulfonat oder für ein Anion der Formeln RSO3 ⊖, R1SO4 ⊖ oder R2COO⊖ steht, wobei R, R1 und R2 C8-C20-, vorzugsweise C10-C18-Alkyl, und R1 zusätzlich auch substituiertes Aryl, vorzugsweise C1-C18-Alkylphenyl bedeuten. Besonders bevorzugt sind Cumolsulfonat und C12/18-Alkoholsulfat als Anion.
Besonders bevorzugt sind Verbindungen der obigen Formel, worin R1, R2 und R3 C1-C4-Alkyl und R4 und R5 Wasserstoff bedeuten und A ein beliebiges Kation ist, bevorzugt Chlorid, Methosulfat, Cumolsulfonat, Laurylsulfat oder Fettsäurealkylcarboxylate oder Mischungen dieser Kationen.Suitable acetonitriles are compounds of the formula
Figure 00030001
in which R 1 , R 2 , R 3 are identical or different and for linear or branched C 1 -C 24 alkyl groups, C 2 -C 24 alkenyl groups or for C 1 -C 4 alkoxy-C 1 -C 4 - Alkyl groups, substituted or unsubstituted benzyl, or in which R 1 and R 2 together with the nitrogen atom to which they are attached form a ring having 4 to 6 C atoms, which is substituted by C 1 -C 5 alkyl, C 1 - C 5 -alkoxy, C 1 - to C 5 -alkanoyl, phenyl, amino, ammonium, cyano, cyanamino, chlorine or bromine can be substituted and in addition to the nitrogen atom instead of carbon atoms one or two oxygen or nitrogen atoms, a group NR 6 or can contain a group R 3 -NR 6 , in which R 6 is hydrogen, C 1 - to C 5 -alkyl, C 2 - to C 5 -alkenyl, C 2 - to C 5 -alkynyl, phenyl, C 7 - to C 9 Aralkyl, C 5 to C 7 cycloalkyl, C 1 to C 6 alkanoyl, cyanomethyl or cyan, R 4 and R 5 is hydrogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, phenyl or C 1 -C 3 -alkylphenyl, preferably hydrogen, methyl or phenyl, where in particular R 4 is hydrogen if R 5 is not hydrogen, and A for any anion, for example chloride, bromide, iodide, fluoride, sulfate, hydrogen sulfate, carbonate, Hydrogen carbonate, phosphate, mono- and di-hydrogen phosphate, pyrophosphate, metaphosphate, nitrate, methyl sulfate, phosphonate, methyl phosphonate, methane disulfonate, methyl sulfonate, ethanesulfonate or for an anion of the formulas RSO 3 ⊖ , R 1 SO 4 ⊖ or R 2 COO ⊖ , where R, R 1 and R 2 are C 8 -C 20 -, preferably C 10 -C 18 alkyl, and R 1 additionally also substituted aryl, preferably C 1 -C 18 alkylphenyl. Cumene sulfonate and C 12/18 alcohol sulfate are particularly preferred as anions.
Particularly preferred are compounds of the above formula in which R 1 , R 2 and R 3 are C 1 -C 4 alkyl and R 4 and R 5 are hydrogen and A is any cation, preferably chloride, methosulfate, cumene sulfonate, lauryl sulfate or fatty acid alkyl carboxylates or Mixtures of these cations.

Die Synthese dieser Acetonitrile kann nach bekannten Verfahren erfolgen, wie z.B. von Abraham in Progr. Phys. Org. Chem. 11 (1974), S 1 ff, oder von Arnett in J. Am Chem. Soc. 102 (1980), S 5892 ff veröffentlicht.The synthesis of these acetonitriles can be carried out by known methods, e.g. by Abraham in Progr. Phys. Org. Chem. 11 (1974), S 1 ff, or by Arnett in J. Am Chem. Soc. 102 (1980), S 5892 ff.

Aus diesen Acetonitrilen wird eine gesättigte wässrige Lösung hergestellt, die auf das Silizium enthaltende Trägermaterial aufgebracht wird, vorzugsweise durch Aufsprühen, beispielsweise über eine Zweistoffdüse. Die Temperatur dieser gesättigten wässrigen Lösung liegt vorzugswese bei 10 bis 40, besonders bevorzugt bei 20 bis 25°C. Anschließend daran kann das Material nachgemischt werden. Die Menge an gesättigter wässriger Lösung wird dabei so bemessen, dass die oben genannten Grenzen für Acetonitril, Trägermaterial und Wasser eingehalten werden.A saturated aqueous solution is prepared from these acetonitriles the silicon-containing carrier material is applied, preferably by Spray on, for example via a two-component nozzle. The temperature of this saturated aqueous solution is preferably 10 to 40, particularly preferred at 20 to 25 ° C. The material can then be mixed. The The amount of saturated aqueous solution is measured so that the above mentioned limits for acetonitrile, carrier material and water are observed.

Als Silizium enthaltende Trägermaterialien werden vorzugsweise solche verwendet, deren innere Oberfläche im Bereich von 10 m2/g bis 500 m2/g, insbesondere 100 m2/g bis 450 m2/g liegt. Geeignet sind beispielsweise Silikate, Kieselsäuren, Kieselgele und Tone, sowie deren Gemische. Das Trägermaterial ist vorzugsweise frei von stark alkalischen Bestandteilen.
Kieselsäuren, die nach dem Thermalprozess (Flammenhydrolyse von SiCl4) hergestellt worden sind (sogenannte pyrogene Kieselsäuren), sind ebenso brauchbar wie durch Nassverfahren hergestellte Kieselsäuren. Kieselgele sind colloidale Kieselsäuren mit elastischer bis fester Konsistenz und einer weitgehend losen Porenstruktur, wodurch sich ein hohes Flüssigkeitsaufnahmevermögen ergibt. Sie können durch Einwirken von Mineralsäuren aus Wasserglas hergestellt werden. Tone sind natürlich vorkommende kristalline oder amorphe Silikate des Aluminiums, Eisens, Magnesiums, Calciums, Kaliums und Natriums, zum Beispiel Kaolin, Talkum, Pyrophyllit, Attapulgit, Sepiolit, Montmorillionit und Bauxit. Auch der Einsatz von Aluminiumsilikat als Trägermaterial oder als Komponente einer Trägermaterialmischung ist möglich. Vorzugsweise weist das Trägermaterial Teilchengrößen im Bereich von 10 µm bis 1,5 mm auf.The silicon-containing carrier materials used are preferably those whose inner surface is in the range from 10 m 2 / g to 500 m 2 / g, in particular 100 m 2 / g to 450 m 2 / g. For example, silicates, silicas, silica gels and clays and their mixtures are suitable. The carrier material is preferably free of strongly alkaline components.
Silicas produced by the thermal process (flame hydrolysis of SiCl 4 ) (so-called pyrogenic silicas) can be used as well as silicas produced by wet processes. Silica gels are colloidal silicas with elastic to firm consistency and a largely loose pore structure, which results in a high fluid absorption capacity. They can be made from water glass by the action of mineral acids. Clays are naturally occurring crystalline or amorphous silicates of aluminum, iron, magnesium, calcium, potassium and sodium, for example kaolin, talc, pyrophyllite, attapulgite, sepiolite, montmorillionite and bauxite. The use of aluminum silicate as a carrier material or as a component of a carrier material mixture is also possible. The carrier material preferably has particle sizes in the range from 10 μm to 1.5 mm.

Um eine ausreichende Lagerstabilität zu gewährleisten und die bleichaktivierende Wirkung erst beim Waschvorgang freizusetzen, ist es vorteilhaft, das mit dem Acetonitril beladene Trägermaterial anschließend zu granulieren. Ebenso kann das mit dem Acetonitril beladene Trägermaterial mit oder ohne Zusatz eines Binders verpresst, kompaktiert und schonend bis zu Granulatgrößen von 200 bis 2000 µm zerkleinert werden.To ensure adequate storage stability and the bleach activating To release effect only during the washing process, it is advantageous to use the Granulate acetonitrile-loaded carrier material. It can also do that carrier material loaded with the acetonitrile with or without the addition of a binder compressed, compacted and gentle up to granulate sizes from 200 to 2000 µm be crushed.

Ebenso geeignet ist eine Aufbaugranulierung im Mischer, beispielsweise im Pflugscharmischer, Ringschichtmischer oder Intensivmischer mit oder ohne Zusatz eines Binders, beispielsweise eines wasserbasierenden Binders, wie Tylose (Carboxymethylcellulose) oder eines wasserfreien Bindesystems, wie Fettalkoholpolyglykolether.A build-up granulation in the mixer, for example in the Ploughshare mixer, ring layer mixer or intensive mixer with or without additive a binder, for example a water-based binder such as tylose (Carboxymethyl cellulose) or an anhydrous binding system, such as Fettalkoholpolyglykolether.

In einer weiteren Ausführungsform kann das durch Aufsprühen einer gesättigten Lösung des Acetonitrils auf ein Trägermaterial erhaltene teilchenförmige Produkt mit oder ohne Zusatz eines Binders einer Formgranulierung durch Matrizen im Extruder, aber auch in Ringkollerpressen, Kollergängen, gegebenenfalls mit nachgeschaltetem Rondierer, unterzogen werden.In a further embodiment, this can be done by spraying on a saturated Solution of the acetonitrile on a carrier material obtained with particulate product or without the addition of a binder of a form granulation by means of dies in the extruder, but also in ring roller presses, roller mills, possibly with downstream rounder.

Die erfindungsgemäß erhaltenen teilchenförmigen Bleichaktivatoren sind direkt zum Einsatz in Wasch- und Reinigungsmitteln geeignet. Um Gewebe- und Farbschädigungen zu vermeiden ist es vorteilhaft, die teilchenförmigen Bleichaktivatoren jedoch nach an sich bekannten Verfahren mit einer Coatinghülle zu versehen. Hierzu wird das Granulat nach in an sich bekannten Verfahren in einem zusätzlichen Schritt mit einer filmbildenden Substanz umhüllt, wodurch die Produkteigenschaften erheblich beeinflusst werden können.The particulate bleach activators obtained according to the invention are directly for Suitable for use in detergents and cleaning agents. To tissue and To avoid color damage, it is advantageous to use the particulate Bleach activators, however, according to methods known per se with a coating envelope to provide. For this purpose, the granules are processed in a manner known per se an additional step coated with a film-forming substance, whereby the Product properties can be significantly influenced.

Als Coatingmaterial geeignet sind alle filmbildenden Substanzen, wie Wachse, Silikone, Fettsäuren, Seifen, anionische Tenside, nichtionische Tenside, kationische Tenside, sowie anionische und kationische Polymere, z. B. Polyacrylsäuren. Durch Verwendung dieser Coatingmaterialien kann u. a. das Auflöseverhalten verzögert werden, um auf diese Weise auch Wechselwirkungen zwischen dem Bleichaktivator und dem Enzymsystem zu Beginn des Waschprozesses zu unterbinden. Soll das Granulat in Maschinengeschirrspülmitteln Verwendung finden, eignen sich hierzu vor allem Wachse mit Schmelzpunkten von 40 bis 50°C.All film-forming substances, such as waxes, are suitable as coating material. Silicones, fatty acids, soaps, anionic surfactants, nonionic surfactants, cationic Surfactants, as well as anionic and cationic polymers, e.g. B. polyacrylic acids. By Use of these coating materials can u. a. the dissolution behavior is delayed interactions between the bleach activator and to stop the enzyme system at the beginning of the washing process. Should that Granules used in machine dishwashing detergents are suitable for this all waxes with melting points from 40 to 50 ° C.

Bevorzugt werden Coatingsubstanzen mit einem Schmelzpunkt von 30 bis 100°C verwendet. Beispiele hierfür sowie ein Verfahren zur Aufbringung werden in EP-A-0 835 926 beschrieben. Das Aufbringen der Coatingmaterialien erfolgt in der Regel durch Aufsprühen der geschmolzenen oder in einem Lösemittel gelösten Coatingmaterialien. Das Coatingmaterial kann in Mengen von 0 bis 30, vorzugsweise 5 bis 20 Gew.-%, bezogen auf das Gesamtgewicht, auf den erfindungsgemäßen Granulatkern aufgebracht werden.Coating substances with a melting point of 30 to 100 ° C. are preferred used. Examples of this and a method of application are described in EP-A-0 835 926. The coating materials are applied in the Usually by spraying the melted or dissolved in a solvent Coating materials. The coating material can be in amounts from 0 to 30, preferably 5 to 20 wt .-%, based on the total weight on the granulate core according to the invention are applied.

Darüber hinaus können die erfindungsgemäßen teilchenförmigen Bleichaktivatoren noch weitere geeignete Zusätze enthalten, wie anionische und nichtionische Tenside, die zu einer schnelleren Auflösung der erfindungsgemäßen Granulate beitragen. Bevorzugte anionische Tenside sind Alkalisalze, Ammoniumsalze, Aminsalze und Salze von Aminoalkoholen von folgenden Verbindungen: Alkylsulfate, Alkylethersulfate, Alkylamid-sulfate und -ethersulfate, Alkylarylpolyethersulfate, Monoglyceridsulfate, Alkylsulfonate, Alkylamidsulfonate, Alkylarylsulfonate, α-Olefinsulfonate, Alkylsulfosuccinate, Alkylethersulfosuccinate, Alkylamidsulfosuccinate, Alkylsulfoacetate, Alkylpolyglycerincarboxylate, Alkylphosphate, Alkyletherphosphaten, Alkylsarcosinate, Alkylpolypeptidate, Alkylamidopolypeptidate, Alkylisethionate, Alkyltaurate, Alkylpolyglykolethercarbonsäuren oder Fettsäuren, wie Oleinsäure, Ricinoleinsäure, Palmitinsäure, Stearinsäure, Kopraölsäuresalze oder hydrierte Kopraölsäuresalze. Der Alkylrest all dieser Verbindungen enthält normalerweise 8 bis 32, vorzugsweise 8 bis 22 C-Atome. In addition, the particulate bleach activators according to the invention contain other suitable additives, such as anionic and nonionic Surfactants which lead to a faster dissolution of the granules according to the invention contribute. Preferred anionic surfactants are alkali salts, ammonium salts, Amine salts and salts of amino alcohols from the following compounds: Alkyl sulfates, alkyl ether sulfates, alkyl amide sulfates and ether sulfates, Alkylaryl polyether sulfates, monoglyceride sulfates, alkyl sulfonates, alkyl amide sulfonates, Alkyl aryl sulfonates, α-olefin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, Alkyl amide sulfosuccinates, alkyl sulfo acetates, alkyl polyglycerol carboxylates, Alkyl phosphates, alkyl ether phosphates, alkyl sarcosinates, alkyl polypeptidates, Alkylamidopolypeptidates, alkylisethionates, alkyl taurates, Alkyl polyglycol ether carboxylic acids or fatty acids, such as oleic acid, ricinoleic acid, Palmitic acid, stearic acid, copraic acid salts or hydrogenated copraic acid salts. The alkyl radical of all these compounds normally contains 8 to 32, preferably 8 to 22 carbon atoms.

Als nichtionische Tenside werden polyethoxylierte, polypropoxylierte oder polyglycerinierte Ether von Fettalkoholen, polyethoxilierte, polypropoxylierte und polyglycerinierte Fettsäureester, polyethoxylierte Ester von Fettsäuren und von Sorbit, polyethoxilierte oder polyglycerinierte Fettamide bevorzugt.As nonionic surfactants are polyethoxylated, polypropoxylated or polyglycerolated ethers of fatty alcohols, polyethoxylated, polypropoxylated and polyglycerolated fatty acid esters, polyethoxylated esters of fatty acids and of Sorbitol, polyethoxylated or polyglycerolated fatty amides are preferred.

Ebenfalls geeignete Zusätze sind Stoffe, die den pH-Wert während Lagerung und Anwendung beeinflussen. Dazu zählen organische Carbonsäuren oder deren Salze, wie Zitronensäure in wasserfreier oder hydratisierter Form, Glykolsäure, Bernsteinsäure, Maleinsäure oder Milchsäure. Daneben sind Zusätze möglich, die das Bleichvermögen beeinflussen, wie Komplexbildner und Übergangsmetallkomplexe, z.B. Eisen-, Cobalt- bzw. Mangan-haltige Metallkomplexe wie in EP-A-0 458 397und EP-A-0 458 398 beschrieben.Also suitable additives are substances that adjust the pH during storage and Affect application. These include organic carboxylic acids or their salts, such as citric acid in anhydrous or hydrated form, glycolic acid, Succinic acid, maleic acid or lactic acid. In addition, additions are possible that influence the bleaching capacity, such as complexing agents and Transition metal complexes, e.g. Contains iron, cobalt and manganese Metal complexes as described in EP-A-0 458 397 and EP-A-0 458 398.

Weitere mögliche Zusätze sind Stoffe, die in der Waschlauge mit der durch den Aktivator freigesetzten Peroxicarbonsäure unter Bildung reaktiver Zwischenstufen, wie Dioxiranen oder Oxaziridinen, reagieren und auf diese Weise die Reaktivität erhöhen können. Entsprechende Verbindungen sind Ketone und Sulfonimine entsprechend US-A-3 822 114 und EP-A-0 446 982.Other possible additives are substances in the wash liquor with the by the Activator released peroxycarboxylic acid with formation of reactive intermediates, such as dioxiranes or oxaziridines, and thus reactivity can increase. Corresponding compounds are ketones and sulfonimines corresponding to US-A-3 822 114 and EP-A-0 446 982.

Die Menge des Zusatzstoffes richtet sich insbesondere nach seiner Art. So werden acidifizierende Zusätze und organische Katalysatoren zur Leistungssteigerung der Persäure in Mengen von 0 bis 20 Gew.-%, insbesondere in Mengen von 1 bis 10 Gew.-%, bezogen auf das Gesamtgewicht, zugesetzt, Metallkomplexe hingegen in Konzentrationen im ppm Bereich.The amount of the additive depends in particular on its type acidifying additives and organic catalysts to increase the performance of the Peracid in amounts of 0 to 20% by weight, in particular in amounts of 1 to 10% by weight, based on the total weight, was added, but metal complexes in concentrations in the ppm range.

In einer weiteren bevorzugten Ausführungsform können die erfindungsgemäßen teilchenförmigen Bleichaktivatoren in tablettierte Wasch- und Reinigungsmittelformulierungen nach gängigen Methoden eingearbeitet werden. Zur Herstellung von Reinigungsmitteln in Tablettenform geht man vorzugsweise derart vor, dass man alle Bestandteile in einem Mischer miteinander vermischt und das Gemisch mittels herkömmlicher Tablettenpresser, beispielsweise Exzenterpressen oder Rundläuferpressen, mit Pressdrücken im Bereich von 200 x 105 Pa bis 1500 x 105 Pa verpresst. Man erhält so problemlos bruchfeste und dennoch unter Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Biegefestigkeiten von über 150 N. Vorzugsweise hat eine derart hergestellte Tablette ein Gewicht von 15 g bis 40 g, insbesondere von 20 g bis 30 g, bei einem Durchmesser von 35 mm bis 40 mm.In a further preferred embodiment, the particulate bleach activators according to the invention can be incorporated into tableted detergent and cleaning agent formulations by customary methods. To produce cleaning agents in tablet form, the procedure is preferably such that all the constituents are mixed with one another in a mixer and the mixture is pressed by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 × 10 5 Pa to 1500 × 10 5 Pa , In this way, break-resistant tablets are obtained with ease, which nevertheless dissolve sufficiently quickly under conditions of use, with bending strengths of over 150 N. A tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.

Die erfindungsgemäß konfektionierten Acetonitril-Derivate können in Vollwaschmitteln, Fleckensalzen, Maschinengeschirrspülmitteln, pulverförmigen Allzweckreinigern und Gebissreinigern eingesetzt werden.The acetonitrile derivatives made up according to the invention can be in Heavy duty detergents, stain removal salts, machine dishwashing detergents, powdered All-purpose cleaners and denture cleaners are used.

Die Wasch- und Reinigungsmittel, enthaltend oben beschriebene teilchenförmig konfektionierte Acetonitril-Derivate werden in Kombination mit einer Wasserstoffperoxidquelle, beispielsweise Perborat-Monohydrat, Perborat-Tetrahydrat, Percarbonat sowie Wasserstoffperoxid-Adukte an Harnstoff oder Aminoxiden eingesetzt und können alle in diesen Mitteln üblichen Inhaltsstoffe, wie Buildersubstanzen, oberflächenaktive Tenside, Enzyme, Sequestriermittel, Elektrolyte, pH-Regulatoren, Schaumregulatoren, Abrasivstoffe Aufheller, Silberkorrosionsinhibitoren, Konservierungsmittel, Parfüm- und Duftstoffe enthalten.The detergents and cleaning agents containing the above-described particulate Assembled acetonitrile derivatives are used in combination with a Source of hydrogen peroxide, for example perborate monohydrate, perborate tetrahydrate, Percarbonate and hydrogen peroxide adducts with urea or Amine oxides are used and can contain all ingredients common in these agents, such as Builder substances, surface-active surfactants, enzymes, sequestering agents, Electrolytes, pH regulators, foam regulators, abrasives Brighteners, silver corrosion inhibitors, preservatives, perfumes and fragrances contain.

Geeignete Builder sind sowohl phosphatfreie Buildersysteme als auch phosphathaltige Systeme, beispielsweise Alkaliphosphate, die in Form ihrer alkalischen neutralen oder sauren Natrium- oder Kaliumsalze vorliegen können, wie Trinatriumphosphat, Tetranatriumdiphosphat, Dinatriumdihydrogenphosphat, Pentanatriumtriphosphat, sogenanntes Natriumhexametaphosphat, oligomeres Trinatriumphosphat mit Oligomerisierungsmengen im Bereich von 5 bis 1000, insbesondere 5 bis 50, sowie Gemische aus Natrium- und Kaliumsalzen. Feinkristalline, synthetische wasserhaltige Zeolithe vom Typ NaA, die ein Calciumbindevermögen im Bereich von 100 bis 200 mg CaO/g aufweisen, finden eine bevorzugte Verwendung. Diese Zeolithe können in einer Menge bis zu 20 Gew.-% im Mittel enthalten sein. Brauchbare Builder sind auch die bevorzugt in Form ihrer Natriumsalze eingesetzten Percarbonsäuren, wie Zitronensäure und Nitriloacetat (NTA), Ethylendiamintetraessigsäure. Analog hierzu können auch polymere Carboxylate und deren Salze eingesetzt werden. Hierzu gehören beispielsweise die Salze homopolymerer oder copolymerer Polyacrylate, Polymethacrylate und insbesondere Copolymere der Acrylsäure mit Maleinsäure, und auch Polyvinylpyrrolidon und Urethane. Die relative Molekülmasse der Homopolymeren liegt im allgemeinen zwischen 1000 und 100 000, die der Copolymeren zwischen 2000 und 200 000, vorzugsweise 50 000 bis 120 000, bezogen auf die freie Säure. Insbesondere sind auch wasserlösliche Polyacrylate geeignet, die beispielsweise mit etwa 1 % eines Polyallylethers der Sucrose quervernetzt sind und die eine relative Molekülmasse oberhalb einer Million besitzen. Beispiele hierfür sind die unter dem Namen Carbopol® 940 und 941 erhältlichen Polymere. Die quervernetzten Polyacrylate werden in Mengen nicht über 1 Gew.-%, vorzugsweise in Mengen von 0,2 bis 0,7 Gew.-% eingesetzt. Diese Gerüstsubstanzen können in Mengen bis zu 5 Gew.-% eingesetzt werden.Suitable builders are both phosphate-free builder systems as well systems containing phosphates, for example alkali metal phosphates, in the form of their alkaline neutral or acidic sodium or potassium salts may be present, such as Trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen phosphate, Pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric Trisodium phosphate with amounts of oligomerization in the range from 5 to 1000, especially 5 to 50, and mixtures of sodium and potassium salts. Fine crystalline, synthetic water-containing zeolites of the type NaA, the one Have calcium binding capacity in the range of 100 to 200 mg CaO / g a preferred use. These zeolites can be in an amount up to 20 wt .-% may be included in the average. Useful builders are also the preferred ones in Form of their sodium salts used percarboxylic acids, such as citric acid and Nitriloacetate (NTA), ethylenediaminetetraacetic acid. Analogous to this, too polymeric carboxylates and their salts are used. This includes for example the salts of homopolymeric or copolymeric polyacrylates, Polymethacrylates and in particular copolymers of acrylic acid with maleic acid, and also polyvinyl pyrrolidone and urethanes. The relative molecular mass of the Homopolymers are generally between 1000 and 100,000, the Copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid. In particular, water-soluble polyacrylates are also suitable, for example, with about 1% of a polyallyl ether of sucrose are cross-linked and have a relative molecular mass above one million have. Examples of this are those under the name Carbopol® 940 and 941 available polymers. The cross-linked polyacrylates are not over in quantities 1 wt .-%, preferably used in amounts of 0.2 to 0.7 wt .-%. This Builders can be used in amounts up to 5% by weight.

Als anionische Tensiden bevorzugt sind C8-C20-Fettsäure-α-methylestersulfonate, Alkylsulfate, Alkylethersulfate und sek. Alkansulfonate.
Die in den erfindungsgemäßen Mitteln eingesetzten Alkylethersulfate sind wasserlösliche Salze oder Säuren der Formel RO(A)mSO3M, worin R einen unsubstituierten C10-C24-Alkyl- oder C10-C24-Hydroxyalkylrest, bevorzugt einen C12-C20-Alkyl- oder C12-C20-Hydroxyalkylrest, besonders bevorzugt C12-C18-Alkyl- oder C12-C18-Hydroxyalkylrest darstellt. "A" ist eine Ethoxy- oder Propoxyeinheit, m ist eine Zahl größer als 0, vorzugsweise zwischen 0,5 und ca. 6, besonders bevorzugt zwischen ca. 0,5 und ca. 3 und M ist ein Wasserstoffatom oder ein Kation wie z.B. ein Metallkation (z.B. Natrium, Kalium, Lithium, Calcium, Magnesium, etc.), Ammonium oder ein substituiertes Ammoniumkation. Spezifische Beispiele von substituierten Ammoniumkationen sind Methyl-, Dimethyl-, Trimethylammonium- und quaternäre Ammoniumkationen, wie Tetramethylammonium und Dimethylpiperidiniumkationen sowie solche, die von Alkylaminen, wie Ethylamin, Diethylamin, Triethylamin abgeleitet sind. Als Beispiele für diese Alkylethersulfate seien genannt C12-C18-Alkyl-polyethoxylat(1,0)sulfat, (C12-C18E(1,0)M), C12-C18-Alkyl-polyethoxylat(2,25)sulfat (C12-C18E(2,25)M), C12-C18-Alkyl-polyethoxylat(3,0)sulfat (C12-C18E(3,0)M), C12-C18-Alkyl-polyethoxylat(4,0)sulfat (C12-C18E(4,0)M). Preferred anionic surfactants are C 8 -C 20 fatty acid-α-methyl ester sulfonates, alkyl sulfates, alkyl ether sulfates and sec. Alkanesulfonates.
The alkyl ether sulfates used in the agents according to the invention are water-soluble salts or acids of the formula RO (A) m SO 3 M, in which R is an unsubstituted C 10 -C 24 -alkyl or C 10 -C 24 -hydroxyalkyl radical, preferably a C 12 -C 20 alkyl or C 12 -C 20 hydroxyalkyl radical, particularly preferably C 12 -C 18 alkyl or C 12 -C 18 hydroxyalkyl radical. "A" is an ethoxy or propoxy unit, m is a number greater than 0, preferably between 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3, and M is a hydrogen atom or a cation such as, for example a metal cation (e.g. sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a substituted ammonium cation. Specific examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine. Examples of these alkyl ether sulfates are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate, (C 12 -C 18 E (1.0) M), C 12 -C 18 alkyl polyethoxylate (2, 25) sulfate (C 12 -C 18 E (2.25) M), C 12 -C 18 alkyl polyethoxylate (3.0) sulfate (C 12 -C 18 E (3.0) M), C 12 -C 18 alkyl polyethoxylate (4.0) sulfate (C 12 -C 18 E (4.0) M).

Bei den sekundären Alkansulfonaten kann die Alkylgruppe entweder gesättigt oder ungesättigt, verzweigt oder linear und gegebenenfalls mit einer Hydroxylgruppe substituiert sein. Die Sulfogruppe ist statistisch über die gesamte C-Kette verteilt, wobei die primären Methylgruppen am Kettenanfang und Kettenende keine Sulfonatgruppen besitzen. Die bevorzugten sekundären Alkansulfonate enthalten lineare Alkylketten mit 9 bis 25 Kohlenstoffatomen, bevorzugt von 10 bis 20 Kohlenstoffatome und besonders bevorzugt 13 bis 17 Kohlenstoffatome. Das Kation ist Natrium, Kalium, Ammonium, Mono-, Di- oder Triethanolammonium, Calcium oder Magnesium und Mischungen davon. Natrium als Kation ist der Einfachheit halber bevorzugt.In the secondary alkanesulfonates, the alkyl group can either be saturated or unsaturated, branched or linear and optionally with a hydroxyl group be substituted. The sulfo group is statistically distributed over the entire C chain, with the primary methyl groups at the beginning and end of the chain none Possess sulfonate groups. The preferred secondary alkanesulfonates contain linear alkyl chains with 9 to 25 carbon atoms, preferably from 10 to 20 Carbon atoms and particularly preferably 13 to 17 carbon atoms. The cation is sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. Sodium as a cation is simplicity preferred for the sake of it.

Neben diesen oder anstelle dieser bevorzugten anionischen Tenside können die Wasch- und Reinigungsmittel auch andere Typen von anionischen Tensiden enthalten, wie zum Beispiel Alkylsulfate, -Sulfonate, -Carboxylate, -Phosphate und Mischungen aus den genannten Verbindungen. Geeignete Kationen sind z.B. Natrium, Kalium, Calcium oder Magnesium, sowie Ammonium, substituierte Ammoniumverbindungen, einschließlich Mono-, Di- oder Triethanolammoniumkationen, sowie Mischungen dieser Kationen.In addition to these or instead of these preferred anionic surfactants, the Detergents and cleaning agents also other types of anionic surfactants contain, such as alkyl sulfates, sulfonates, carboxylates, phosphates and Mixtures of the compounds mentioned. Suitable cations are e.g. Sodium, potassium, calcium or magnesium, as well as ammonium Ammonium compounds, including mono-, di- or Triethanolammonium cations, as well as mixtures of these cations.

Alkylsulfate sind hier wasserlösliche Salze oder Säuren der Formel ROSO3M, worin R bevorzugt ein C10-C24-Kohlenwasserstoffrest, bevorzugt ein Alkyl oder Hydroxyalkylrest mit C10-C20-Alkylkomponenten, besonders bevorzugt ein C12-C18-Alkyl- oder Hydroxyalkylrest darstellt. M ist Wasserstoff oder ein Kation, z.B. Natrium, Kalium, Lithium oder Ammonium oder substituiertes Ammonium, z.B. Methyl-, Dimethyl- und Trimethylammoniumkationen und quaternäre Ammoniumkationen, wie Tetramethylammonium- und Dimethylpiperidiniumkationen und quartäre Ammoniumkationen, abgeleitet von Alkylaminen wie Ethylamin, Diethylamin, Triethylamin und Mischungen davon.Alkyl sulfates here are water-soluble salts or acids of the formula ROSO 3 M, in which R is preferably a C 10 -C 24 hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with C 10 -C 20 alkyl components, particularly preferably a C 12 -C 18 alkyl radical or hydroxyalkyl radical. M is hydrogen or a cation, for example sodium, potassium, lithium or ammonium or substituted ammonium, for example methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations, derived from alkylamines such as ethylamine, diethylamine, triethylamine and Mixtures of these.

Ein weiteres geeignetes anionisches Tensid ist Alkylbenzolsulfonat. Die Alkylgruppe kann entweder gesättigt oder ungesättigt, verzweigt oder linear und gegebenenfalls mit einer Hydroxylgruppe substituiert sein. Another suitable anionic surfactant is alkylbenzenesulfonate. The alkyl group can be either saturated or unsaturated, branched or linear and optionally be substituted with a hydroxyl group.

Die bevorzugten Alkylbenzolsulfonate enthalten lineare Alkylketten mit 9 bis 25 Kohlenstoffatomen, bevorzugt von 10 bis 13 Kohlenstoffatomen, das Kation ist Natrium, Kalium, Ammonium, Mono-, Di- oder Triethanolammonium, Calcium oder Magnesium und Mischungen davon.The preferred alkylbenzenesulfonates contain linear alkyl chains with 9 to 25 Carbon atoms, preferably from 10 to 13 carbon atoms, which is cation Sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or Magnesium and mixtures thereof.

Weitere geeignete anionische Tenside sind Carboxylate, z.B. Fettsäureseifen und vergleichbare Tenside. Die Seifen können gesättigt oder ungesättigt sein und können verschiedene Substituenten, wie Hydroxylgruppen oder Alpha-Sulfonatgruppen enthalten. Bevorzugt sind lineare gesättigte oder ungesättigte Kohlenwasserstoffreste als hydrophobe Komponente in den Seifen. Üblicherweise enthalten die hydrophoben Komponenten 6 bis 30 Kohlenstoffatome, bevorzugt 10 bis 18 Kohlenstoffatome.
Weitere anionische Tenside sind Salze von Acylaminocarbonsäuren, die durch Umsetzung von Fettsäurechloriden mit Natriumsarkosinat im alkalischen Medium entstehen (Acylsarcosinate) sowie Fettsäure-Eiweiß-Kondensationsprodukte, die durch Umsetzung von Fettsäurechloriden mit Oligopeptiden erhalten werden. Tensidcharakter haben auch die Salze von Alkylsulfamidocarbonsäuren und die Salze von Alkyl- und Alkylarylethercarbonsäuren.Other suitable anionic surfactants are carboxylates, for example fatty acid soaps and comparable surfactants. The soaps can be saturated or unsaturated and can contain various substituents, such as hydroxyl groups or alpha sulfonate groups. Linear saturated or unsaturated hydrocarbon residues are preferred as the hydrophobic component in the soaps. The hydrophobic components usually contain 6 to 30 carbon atoms, preferably 10 to 18 carbon atoms.
Other anionic surfactants are salts of acylaminocarboxylic acids, which are formed by reacting fatty acid chlorides with sodium sarcosinate in an alkaline medium (acylsarcosinates), and fatty acid-protein condensation products, which are obtained by reacting fatty acid chlorides with oligopeptides. The salts of alkylsulfamidocarboxylic acids and the salts of alkyl and alkylaryl ether carboxylic acids also have surfactant properties.

Andere anionische Tenside, die nützlich für den Einsatz in Wasch- und Reinigungsmitteln sind, sind C8-C24-Olefinsulfonate, sulfonierte Polycarboxylsäuren, hergestellt durch Sulfonierung der Pyrolyseprodukte von Erdalkalimetallcitraten, wie z.B. beschrieben in GB 1 082 179, Alkylglycerinsulfate, Fettacylglycerinsulfate, Oleylglycerinsulfate, Alkylphenolethersulfate, primäre Paraffinsulfonate, Alkylphosphate, Alkyletherphosphate, Isethionate, wie Acylisethionate, N-Acyltauride, Alkylsuccinamate, Sulfosuccinate, Monoester der Sulfosuccinate (besonders gesättigte und ungesättigte C12-C18-Monoester) und Diester der Sulfosuccinate (besonders gesättigte und ungesättigte C12-C18-Diester), Acylsarcosinate, Sulfate von Alkylpolysacchariden wie Sulfate von Alkylglycosiden, verzweigte primäre Alkylsulfate und Alkylpolyethoxycarboxylate wie die der Formel RO(CH2CH2)kCH2COO-M+ worin R C8-C22-Alkyl, k eine Zahl von 0 bis 10 und M ein ein lösliches Salz bildendes Kation ist. Harzsäuren oder hydrierte Harzsäuren, wie Rosin oder hydriertes Rosin oder Tallölharze und Tallölharzsäuren sind ebenfalls einsetzbar. Weitere Beispiele sind in "Surface Active Agents and Detergents" (Vol. I und II, Schwartz, Perry und Berch) beschrieben. Eine Vielzahl solcher Tenside sind auch in US 3 929 678 beschrieben.Other anionic surfactants which are useful for use in detergents and cleaning agents are C 8 -C 24 -olefin sulfonates, sulfonated polycarboxylic acids, prepared by sulfonating the pyrolysis products of alkaline earth metal citrates, as described, for example, in GB 1 082 179, alkyl glycerol sulfates, fatty acyl glycerol sulfates, oleyl glycerol sulfates , alkylphenol ether sulfates, primary paraffinsulfonates, alkyl phosphates, alkyl ether phosphates, isethionates such as the acyl isethionates, N-acyl taurides, alkyl succinamates, sulfosuccinates, monoester of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as sulfates of alkyl glycosides, branched primary alkyl sulfates and alkyl polyethoxy carboxylates such as those of the formula RO (CH 2 CH 2 ) k CH 2 COO-M + wherein RC 8 -C 22 alkyl, k a number from 0 to 10 and M is a cation which forms a soluble salt is. Resin acids or hydrogenated resin acids such as rosin or hydrogenated rosin or tall oil resins and tall oil resin acids can also be used. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II, Schwartz, Perry and Berch). A large number of such surfactants are also described in US 3,929,678.

Typische Beispiele für anionische Tenside sind auch Alkylethersulfonate, Glycerinethersulfonate, Sulfofettsäuren, Glycerinethersulfate, Hydroxymischethersulfat, Fettsäureamid-(ether)sulfate, Mono- und Dialkylsulfosuccinate, Mono- und Dialkylsulfosuccinamate, Sulfotriglyceride, Amidseifen, Alkyloligoglucosidsulfate, Alkylaminozuckersulfate und Alkyl(ether)phosphate. Sofern die anionischen Tenside Polyglykoletherketten enthalten, können sie eine konventionelle oder auch eingeengte Homologenverteilung aufweisen.
In den Wasch- und Reinigungsmittel können ebenfalls nichtionischen Tenside, wie Fettsäurealkylesteralkoxylate, Alkyl- und/oder Alkenyloligoglykosiden, Fettalkoholpolyglycolether, Alkylphenolpolyglycolether, Fettsäurepolyglykolester, Fettsäureamidpolyglycolether, Fettaminpolyglycolether, alkoxylierte Triglyceriden, Fettsäureglucamiden, Polyölfettsäureester, Zuckerester, Sorbitanester und Polysorbaten und/oder alkoxylierten Fettalkoholen eingesetzt werden.Typical examples of anionic surfactants are also alkyl ether sulfonates, glycerol ether, sulfofatty acids, Glycerol ether, Hydroxymischethersulfat, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, alkyl oligoglucoside sulfates, Alkylaminozuckersulfate and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional or narrow homolog distribution.
In the washing and cleaning agents are also nonionic surfactants such as fatty acid alkyl ester, alkyl and / or alkenyl oligoglycosides, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide, fatty amine polyglycol ethers, alkoxylated triglycerides, Fettsäureglucamiden, Polyölfettsäureester, Zuckerester, sorbitan esters and polysorbates and / or alkoxylated fatty alcohols may be used ,

Des weiteren können Co-Tenside aus der Gruppe Alkylbetaine, Alkylamidobetaine, Aminopropionate, Aminoglycinate, Imidazoliniumbetaine und Sulfobetaine, Aminoxide und Fettsäurealkanolamide oder Polyhydroxyamide eingesetzt werden.Co-surfactants from the group alkyl betaines, alkyl amido betaines, Aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines, Amine oxides and fatty acid alkanolamides or polyhydroxyamides are used.

Zusätzlich zu den bleichaktivierenden Acetonitril-Derivaten können bekannte konventionelle Bleichaktivatoren, das heißt Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren und/oder gegebenenfalls substituierte Perbenzoesäuren ergeben, eingesetzt werden. Geeignete Substanzen sind organische Verbindungen mit einer 0-Acyl- oder N-Acyl-Gruppe, insbesondere aus der Gruppe der aktivierten Carbonsäureester, insbesondere Natrium-nonanoyloxy-benzolsulfonat, Natrium-isononanoyloxy-benzolsulfonat, Natrium-4-benzoyloxy-benzolsulfonat, Natrium-trimethylhexanoyloxy-benzolsulfonat, Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat, 2,5-Diacetoxy-2,5-dihydrofuran, Lactone, Acylate, Carbonsäureamide, Acyllactame, acylierte Harnstoffe und Oxamide, N-acylierte Hydantoine, beispielsweise 1-Phenyl-3-acetylhydantoin, Hydrazide, Triazole, Hydrotriazine, Urazole, Diketopiperazide, Sulfurylamide, mehrfach acylierte Alkylendiamine beispielsweise N,N,N',N'-Tetraacetylethylendiamin, acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin, acylierte Glykolurile, insbesondere Tetraacetylglykoluril, N-Acylimide, insbesondere N-Nonanoylsuccinimid, und acylierte Zuckerderivate, insbesondere Pentaacetylglukose, Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose, sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton und/oder N-acylierte Lactame, beispielsweise N-Benzoylcaprolactam.In addition to the bleach activating acetonitrile derivatives, known ones conventional bleach activators, that is compounds that are under Perhydrolysis conditions aliphatic peroxocarboxylic acids and / or optionally substituted perbenzoic acids are used. Suitable substances are organic compounds with a 0-acyl or N-acyl group, especially from the group of activated carboxylic acid esters, in particular sodium nonanoyloxy benzenesulfonate, sodium isononanoyloxy benzenesulfonate, Sodium 4-benzoyloxy-benzenesulfonate, sodium trimethylhexanoyloxy-benzenesulfonate, Carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, lactones, acylates, carboxamides, acyl lactams, acylated ureas and oxamides, N-acylated hydantoins, for example 1-phenyl-3-acetylhydantoin, Hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazides, Sulfurylamides, multiple acylated alkylenediamines, for example N, N, N ', N'-tetraacetylethylenediamine, acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, acylated glycolurils, especially Tetraacetylglycoluril, N-acylimides, especially N-nonanoylsuccinimide, and acylated sugar derivatives, in particular pentaacetyl glucose, pentaacetyl fructose, Tetraacetylxylose and Octaacetyllactose, as well as acetylated, if necessary N-alkylated glucamine and gluconolactone and / or N-acylated lactams, for example N-benzoylcaprolactam.

Zusätzlich zu den oben aufgeführten konventionellen Bleichaktivatoren oder an deren Stelle können auch Sulfonimine und/oder bleichverstärkende Übergangsmetallsalze beziehungsweise Übergangsmetallkomplexe als sogenannte Bleichkatalysatoren, wie in DE 196 49 375 beschrieben, enthalten sein.In addition to the conventional bleach activators listed above or on in their place can also sulfonimines and / or bleach-enhancing Transition metal salts or transition metal complexes as so-called Bleach catalysts, as described in DE 196 49 375, may be included.

Als Enzyme kommen solche aus der Klasse der Proteasen wie BLAP, Optimase, Opticlean, Maxacal, Maxapem, Esperase, Savinase, Purifect OxP und/oder Durazym, Lipasen, wie Lipolase, Lipomax, Lumafast und/oder Lipozym, Amylasen wie Termamyl, Ainylase-LT, Maxamyl, Duramyl und/oder Purafect OxAm, sowie Cutinasen, Pullulanasen bzw. deren Gemisch in Frage. Ihr Anteil kann 0,2 bis 1 Gew.-% betragen. Die Enzyme können an Trägersubstanzen adsorbiert werden und/oder in Hüllsubstanzen eingebettet sein.Enzymes come from the class of proteases such as BLAP, Optimase, Opticlean, Maxacal, Maxapem, Esperase, Savinase, Purifect OxP and / or Durazym, lipases such as Lipolase, Lipomax, Lumafast and / or Lipozym, amylases such as Termamyl, Ainylase-LT, Maxamyl, Duramyl and / or Purafect OxAm, as well Cutinases, pullulanases or their mixture in question. Their share can range from 0.2 to 1% by weight. The enzymes can be adsorbed on carrier substances and / or be embedded in coating substances.

Als Silberkorrosionsinhibitoren können die in DE 196 49 375 genannten Verbindungen, eingesetzt werden.Silver corrosion inhibitors which can be mentioned in DE 196 49 375 Connections are used.

Als Schaumregulatoren können vorzugsweise bis zu 6 Gew.-%, insbesondere etwa 0,5 bis 4 Gew.-% schaumunterdrückende Verbindungen, vorzugsweise aus der Gruppe der Silikonöle, Gemische aus Silikonöl und hydrophobierter Kieselsäure, Paraffine, Paraffin-Alkohol-Kombinationen, hydrophobierte Kieselsäure, der Bisfettsäureamide und sonstige weiterer bekannter im Handel erhältliche Entschäumer zugesetzt werden.Up to 6% by weight, in particular approximately, can preferably be used as foam regulators 0.5 to 4 wt .-% foam suppressing compounds, preferably from the Group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffins, paraffin-alcohol combinations, hydrophobicized silica, the Bis fatty acid amides and other other known commercially available Defoamers can be added.

Zur Einstellung eines gewünschten pH-Wertes können die erfindungsgemäßen Mittel system- und umweltverträgliche Säuren, insbesondere Zitronensäure, Essigsäure, Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure oder Alkalihydrogensulfate oder Basen, insbesondere Ammonium- oder Alkalihydroxide, enthalten. Derartige pH-Regulatoren sind in den erfindungsgemäßen Mittel vorzugsweise nicht über 10 Gew.-%, insbesondere von 0,5 bis 6 Gew.-%, enthalten.To set a desired pH, the inventive System and environmentally compatible acids, especially citric acid, Acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, Glutaric acid and / or adipic acid, but also mineral acids, in particular Sulfuric acid or alkali hydrogen sulfates or bases, especially ammonium or alkali hydroxides. Such pH regulators are in the Agents according to the invention preferably do not exceed 10% by weight, especially 0.5 to 6 wt .-% included.

Als Konservierungsmittel eignen sich beispielsweise Phenoxyethanol, Formaldehydlösung, Pentandiol oder Sorbinsäure. Einsetzbare Abrasivstoffe sind Quarzmehle, Holzmehle, Kunststoffmehle, Kreiden und Mikroglaskugeln.Suitable preservatives are, for example, phenoxyethanol, Formaldehyde solution, pentanediol or sorbic acid. Abrasives that can be used are Quartz flours, wood flours, plastic flours, chalks and micro glass balls.

Als typische Einzelbeispiele für weitere Zusatzstoffe sind Natriumborat, Stärke, Saccharose, Polydextrose, Stilbenverbindungen, Methylcellulose, Toluolsulfonat, Cumolsulfonat, Seifen und Silicone zu nennen.Typical examples of other additives are sodium borate, starch, Sucrose, polydextrose, stilbene compounds, methyl cellulose, toluenesulfonate, Cumene sulfonate, soaps and silicones.

Die Herstellung der erfindungsgemäßen Mittel in Form von nicht staubenden, lagerstabilen rieselfähigen Pulvern und/oder Granulaten mit hohen Schüttgewichten im Bereich von 800 bis 1000 g/l kann dadurch erfolgen, dass man in einer ersten Verfahrensstufe die Builder-Komponenten mit wenigstens einem Anteil flüssiger Mischungskomponenten unter Erhöhung der Schüttdichte dieses Vorgemisches vermischt und nachfolgend - gewünschtenfalls nach einer Zwischentrocknung - die weiteren Bestandteile des Mittels, darunter den Bleichaktivator, mit dem so gewonnenen Vorgemisch vereinigt.The preparation of the agents according to the invention in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range of 800 to 1000 g / l can be done by first Process stage the builder components with at least a portion of liquid Mix components while increasing the bulk density of this premix mixed and then - if necessary after an intermediate drying - the other components of the agent, including the bleach activator, with the so obtained premix combined.

Die nachfolgenden Beispiele dienen der Erläuterung der Erfindung, ohne sie jedoch darauf einzuschränken. The following examples serve to illustrate the invention, but without it to limit it.

Konfektionierung von Trimethylacetonitrilammoniumchlorid/KieselsäureAssembly of trimethylacetonitrile ammonium chloride / silica

Beispiel 1example 1

Im Lödige Mischer wurden 300 g der Kieselsäure Sipernat® 50 S (Degussa-Hüls) vorgelegt und bei ca. 20°C über einen Zeitraum von 27 Minuten 780 ml einer wässrigen, ca. 67 gew.-%igen Lösung von Trimethylacetonitrilammoniumchlorid mit einer Zweistoffdüse aufgesprüht. Nach dem Aufsprühen wurde 2 Minuten nachgemischt.300 g of the silica Sipernat® 50 S (Degussa-Hüls) were placed in the Lödige mixer. submitted and at about 20 ° C over a period of 27 minutes 780 ml of a aqueous, about 67 wt .-% solution of trimethylacetonitrile ammonium chloride with sprayed on a two-component nozzle. After spraying it was 2 minutes remixed.

Parameter:Parameter:

Drehzahl MischwerkzeugSpeed mixing tool 120 pro min120 per min Füllmengecapacity 0,3 kg0.3 kg Füllgrad MischerFill level mixer 65 %65% Temperatur MischraumMixing room temperature 23°C23 ° C Temperatur der Acetonitril-LösungTemperature of the acetonitrile solution 23°C23 ° C ZugabegeschwindigkeitslösungAddition rate solution ca. 20 - 40 ml/minapprox. 20 - 40 ml / min

Beispiel 2Example 2

Im Lödige Mischer wurden 150 g der Kieselsäure Aerosil® 380 (Degussa Hüls) vorgelegt und bei ca. 20°C über einen Zeitraum von 9 Minuten 320 ml einer wässrigen, ca. 67 gew.-%igen Lösung von Trimethylacetonitrilammoniumchlorid mit einer Zweistoffdüse aufgesprüht. Nach dem Aufsprühen wurde 2 Minuten nachgemischt.150 g of Aerosil® 380 silica (Degussa Hüls) were placed in the Lödige mixer. submitted and at about 20 ° C over a period of 9 minutes 320 ml aqueous, about 67 wt .-% solution of trimethylacetonitrile ammonium chloride with sprayed on a two-component nozzle. After spraying it was 2 minutes remixed.

Parameter:Parameter:

Drehzahl MischwerkzeugSpeed mixing tool 120 pro min120 per min Füllmengecapacity 0,15 kg0.15 kg Füllgrad MischerFill level mixer 70 %70% Temperatur MischraumMixing room temperature 21°C 21 ° C Temperatur der Acetonitril-LösungTemperature of the acetonitrile solution 18°C18 ° C ZugabegeschwindigkeitslösungAddition rate solution ca. 20 - 40 ml/mirapprox. 20 - 40 ml / me

Formulierungsbeispieleformulation Examples Beispiel 1: Maschinengeschirrspülmittel (Gew.-%)Example 1: Dishwasher detergent (% by weight)

Natriumcitratsodium citrate 4141 Natriumcarbonatsodium 55 Natriumhydrogencarbonatsodium 3030 Proteaseprotease 11 Amylaseamylase 11 Glucamidglucamide 22 Natriumperborat-MonohydratSodium perborate monohydrate 1010 Acetonitril/Sipernat (52/48 Gew.-%)Acetonitrile / sipernate (52/48% by weight) 1010

Beispiel 2: Maschinengeschirrspülmitteltabletten (Gew.-%)Example 2: Dishwasher tablets (% by weight)

Erste Phase:First phase: Natriumtripolyphosphatsodium tripolyphosphate 3131 Na-Perborat-MonohydratNa perborate monohydrate 1010 Acetonitril/Sipernat (52/48 Gew.-%)Acetonitrile / sipernate (52/48% by weight) 33 Polycarboxylat (Sokalan® CP5)Polycarboxylate (Sokalan® CP5) 11 Glucamidglucamide 22 Natriumcarbonatsodium 1515 Schichtsilikat (SKS-6)Layered Silicate (SKS-6) 66 Zweite Phase:Second phase: Natriumtripolyphosphatsodium tripolyphosphate 26 Gew.-%26% by weight Komplexbildner (Turpinal® 2NZ)Complexing agent (Turpinal® 2NZ) 1 Gew.-%1% by weight Proteasegranulat (Blap® 200)Protease granules (Blap® 200) 2 Gew.-%2% by weight Amylasegranulat (Duranyl® 60 T)Amylase granules (Duranyl® 60 T) 2 Gew.-%2% by weight Farbstoffdye 0,9 Gew.-% 0.9% by weight ParfümPerfume 0,1 Gew.-%0.1% by weight

Beispiel 3: Textilwaschmittel (in Gew.-%)Example 3: Textile detergent (in% by weight)

Natrium-PercarbonatSodium percarbonate 20,020.0 Acetonitril/Sipernat (52/48 Gew.-%)Acetonitrile / sipernate (52/48% by weight) 6,06.0 Fettalkoholsulfat-Na-SalzFatty alcohol sulfate sodium salt 10,010.0 SeifeSoap 1,01.0 C13/C15-Oxalkohol, 3EOC 13 / C 15 oxalcohol, 3EO 4,04.0 Glucamidglucamide 1,51.5 Zeolith AZeolite A 20,020.0 Kristallines SchichtsilikatCrystalline layered silicate 10,010.0 Acryl-/Maleinsäure, Copolymer MG 70 000)Acrylic / maleic acid, copolymer MG 70 000) 5,05.0 Natriumsulfatsodium sulphate 8,08.0 Natriumcarbonatsodium 6,06.0 Zitronensäurecitric acid 5,05.0 Carboxymethylcellulosecarboxymethylcellulose 1,51.5 Lipaselipase 0,50.5 Proteaseprotease 0,50.5 Wasserwater ad 100ad 100

Claims (11)

Teilchenförmige Bleichaktivatoren, enthaltend 15 bis 60 Gew.-% eines Acetonitrils, 20 bis 70 Gew.-% eines Silizium enthaltenden Trägermaterials und 20 bis 30 Gew.-% Wasser.Particulate bleach activators containing 15 to 60 wt .-% of one Acetonitrile, 20 to 70% by weight of a carrier material containing silicon and 20 up to 30% by weight of water. Teilchenförmige Bleichaktivatoren nach Anspruch 1, dadurch gekennzeichnet, dass sie ein Acetonitril enthalten der Formel
Figure 00180001
worin R1, R2, R3 gleich oder verschieden sind, und für lineare oder verzweigte C1-C24-Alkylgruppen, C2-C24-Alkenylgruppen oder für C1-C4-Alkoxy-C1-C4-Alkylgruppen, substituiertes oder unsubstituiertes Benzyl stehen, oder worin R1 und R2 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Ring mit 4 bis 6 C-Atomen bilden, der mit C1-C5-Alkyl, C1-C5-Alkoxy, C1-C5-Alkanoyl, Phenyl, Amino, Ammonium, Cyano, Cyanamino, Chlor oder Brom substituiert sein kann und zusätzlich zum Stickstoffatom anstelle von Kohlenstoffatomen ein oder zwei Sauerstoff- oder Stickstoffatome, eine Gruppe N-R6 oder eine Gruppe R3-N-R6 enthalten kann, worin R6 Wasserstoff, C1-C5-Alkyl, C2-C5-Alkenyl, C2-C5-Alkinyl, Phenyl, C7-C9-Aralkyl, C5-C7-Cycloalkyl, C1-C6-Alkanoyl, Cyanomethyl oder Cyan ist, R4 und R5 Wasserstoff, C1-C4-Alkyl, C2-C4-Alkenyl, C1-C4-Alkoxy-C1-C4-alkyl, Phenyl oder C1-C3-Alkylphenyl, vorzugsweise Wasserstoff, Methyl oder Phenyl sind, wobei insbesondere R4 Wasserstoff bedeutet, wenn R5 keinen Wasserstoff bedeutet, und A ein Anion bedeutet.Particulate bleach activators according to claim 1, characterized in that they contain an acetonitrile of the formula
Figure 00180001
in which R 1 , R 2 , R 3 are identical or different and for linear or branched C 1 -C 24 alkyl groups, C 2 -C 24 alkenyl groups or for C 1 -C 4 alkoxy-C 1 -C 4 - Alkyl groups, substituted or unsubstituted benzyl, or in which R 1 and R 2 together with the nitrogen atom to which they are attached form a ring having 4 to 6 C atoms, which is substituted by C 1 -C 5 alkyl, C 1 - C 5 alkoxy, C 1 -C 5 alkanoyl, phenyl, amino, ammonium, cyano, cyanamino, chlorine or bromine can be substituted and in addition to the nitrogen atom instead of carbon atoms one or two oxygen or nitrogen atoms, a group NR 6 or one Group R 3 -NR 6 may contain, wherein R 6 is hydrogen, C 1 -C 5 alkyl, C 2 -C 5 alkenyl, C 2 -C 5 alkynyl, phenyl, C 7 -C 9 aralkyl, C 5 -C 7 cycloalkyl, C 1 -C 6 alkanoyl, cyanomethyl or cyan, R 4 and R 5 is hydrogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 1 -C 4 alkoxy- C 1 -C 4 alkyl, phenyl or C 1 -C 3 alkylphenyl, preferably what are hydrogen, methyl or phenyl, in particular R 4 being hydrogen when R 5 is not hydrogen and A being an anion. Teilchenförmige Bleichaktivatoren nach Anspruch 1, dadurch gekennzeichnet, dass sie ein Acetonitril der Formel gemäß Anspruch 2 enthalten, worin R1, R2 und R3 C1-C4-Alkyl und R4 und R5 Wasserstoff und A ein Anion bedeuten. Particulate bleach activators according to claim 1, characterized in that they contain an acetonitrile of the formula according to claim 2, wherein R 1 , R 2 and R 3 are C 1 -C 4 alkyl and R 4 and R 5 are hydrogen and A is an anion. Teilchenförmige Bleichaktivatoren nach Anspruch 1, dadurch gekennzeichnet, dass sie 20 bis 50 Gew.-% des Acetonitrils enthalten.Particulate bleach activators according to claim 1, characterized in that they contain 20 to 50 wt .-% of the acetonitrile. Teilchenförmige Bleichaktivatoren nach Anspruch 1, dadurch gekennzeichnet, dass sie 35 bis 45 Gew.-% des Acetonitrils enthalten.Particulate bleach activators according to claim 1, characterized in that they contain 35 to 45 wt .-% of the acetonitrile. Teilchenförmige Bleichaktivatoren nach Anspruch 1, dadurch gekennzeichnet, dass sie 30 bis 50 Gew.-% des Silizium enthaltenden Trägermaterials enthalten.Particulate bleach activators according to claim 1, characterized in that they contain 30 to 50 wt .-% of the silicon-containing carrier material. Teilchenförmige Bleichaktivatoren nach Anspruch 1, dadurch gekennzeichnet, dass sie 35 bis 45 Gew.-% des Silizium enthaltenden Trägermaterials enthalten.Particulate bleach activators according to claim 1, characterized in that they contain 35 to 45 wt .-% of the silicon-containing carrier material. Teilchenförmige Bleichaktivatoren nach Anspruch 1, dadurch gekennzeichnet, dass sie 22 bis 25 Gew.-% Wasser enthalten.Particulate bleach activators according to claim 1, characterized in that they contain 22 to 25 wt .-% water. Verfahren zur Herstellung der teilchenförmigen Bleichaktivatoren nach Anspruch 1, dadurch gekennzeichnet, dass man eine gesättigte wässrige Lösung eines Acetonitrils auf ein Silizium enthaltendes Trägermaterial aufbringt.A process for the preparation of the particulate bleach activators according to claim 1, characterized in that a saturated aqueous solution of an acetonitrile is applied to a silicon-containing carrier material. Verfahren zur Herstellung der teilchenförmigen Bleichaktivatoren nach Anspruch 1, dadurch gekennzeichnet, dass man eine bei 10 bis 40°C gesättigte wässrige Lösung eines Acetonitrils auf ein Silizium enthaltendes Trägermaterial aufbringt.A process for the production of the particulate bleach activators according to claim 1, characterized in that an aqueous solution of an acetonitrile saturated at 10 to 40 ° C is applied to a silicon-containing carrier material. Wasch- und Reinigungsmittel enthaltend einen teilchenförmigen Bleichaktivator nach Anspruch 1.Detergent and cleaning agent containing a particulate Bleach activator according to claim 1.
EP01126661A 2000-11-17 2001-11-08 Particulate bleach activators comprising acetonitril Withdrawn EP1207195A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10057045 2000-11-17
DE10057045A DE10057045A1 (en) 2000-11-17 2000-11-17 Particulate bleach activators based on acetonitriles

Publications (2)

Publication Number Publication Date
EP1207195A2 true EP1207195A2 (en) 2002-05-22
EP1207195A3 EP1207195A3 (en) 2003-06-11

Family

ID=7663661

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01126661A Withdrawn EP1207195A3 (en) 2000-11-17 2001-11-08 Particulate bleach activators comprising acetonitril

Country Status (4)

Country Link
US (1) US6498133B2 (en)
EP (1) EP1207195A3 (en)
JP (1) JP2002226892A (en)
DE (1) DE10057045A1 (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10038086A1 (en) * 2000-08-04 2002-02-14 Clariant Gmbh Process for the preparation of hydrolysis-stable ammonium nitriles
DE10159388A1 (en) * 2001-12-04 2003-06-12 Henkel Kgaa Process for the production of coated bleach activator granules
WO2003101940A2 (en) * 2002-05-31 2003-12-11 Henkel Kommanditgesellschaft Auf Aktien Deodorisation of cationic ammonium acetonitrile derivatives
AU2003297077A1 (en) * 2002-12-18 2004-07-29 The Procter And Gamble Company Organic activator
US20040156742A1 (en) * 2003-02-11 2004-08-12 Milan Jolanda Bianca Synergistically-effective cyclohexylethan-1-yl ester mixtures as malodour counteractants as measured physiologically and psychometrically and methods for using same
US20050106192A1 (en) * 2003-11-13 2005-05-19 Parekh Prabodh P. Synergistically-effective composition of zinc ricinoleate and one or more substituted monocyclic organic compounds and use thereof for preventing and/or suppressing malodors
DE102005005016A1 (en) 2005-02-03 2006-08-10 Basf Ag Polymers hydrophobic aminonitrile quats for bleach activation
DE102006036889A1 (en) * 2006-08-04 2008-02-07 Clariant International Limited Use of aminoacetones and their salts as bleaching force enhancers for peroxygen compounds
US8012554B2 (en) 2007-09-12 2011-09-06 Pactiv Corporation Bags having odor management capabilities
US8124793B2 (en) * 2007-11-27 2012-02-28 Gail Marie Cronyn, legal representative Derivatives of ethylene methanedisulfonate as cancer chemotherapeutic agents
BR112014013868A2 (en) * 2011-12-09 2017-06-13 Clariant Finance Bvi Ltd automatic dishwashing detergent compositions comprising etercarboxylic acids or their high cloud point salts and surfactants

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0458396A1 (en) * 1990-05-24 1991-11-27 Unilever N.V. Bleaching composition
WO1996007650A1 (en) * 1994-09-02 1996-03-14 Basf Aktiengesellschaft Process for producing quaternary glycine nitriles
WO1996040661A1 (en) * 1995-06-07 1996-12-19 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
EP0790244A1 (en) * 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Ammonium nitriles and use thereof as bleach activators
WO1998023718A2 (en) * 1996-11-29 1998-06-04 Basf Aktiengesellschaft Textile detergent formulation on the basis of quaternized glycine nitriles, bleaching agents, nonionic and/or anionic tensides and calcium ion and/or magnesium ion sequestering compounds
WO1998023531A1 (en) * 1996-11-29 1998-06-04 The Clorox Company Granular n-alkyl ammonium acetonitrile compositions
WO2000036061A2 (en) * 1998-12-15 2000-06-22 Henkel Kommanditgesellschaft Auf Aktien Acetonitrile derivatives formulated in particulate form as bleach activators in solid detergents
DE19908069A1 (en) * 1999-02-25 2000-08-31 Henkel Kgaa Compounded acetonitrile derivatives as bleach activators in detergents
US6235218B1 (en) * 1995-06-07 2001-05-22 The Clorox Company Process for preparing N-alkyl ammonium acetonitrile compounds

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1368400A (en) 1971-08-05 1974-09-25 Procter & Gamble Bleaching process and compositions therefor
DE2437090A1 (en) 1974-08-01 1976-02-19 Hoechst Ag CLEANING SUPPLIES
US4915863A (en) 1987-08-14 1990-04-10 Kao Corporation Bleaching composition
US5047163A (en) 1990-03-16 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with sulfonimines
GB9012001D0 (en) 1990-05-30 1990-07-18 Unilever Plc Bleaching composition
US6183665B1 (en) * 1995-06-07 2001-02-06 The Clorox Company Granular N-alkyl ammonium acetonitrile compositions
DE19641708A1 (en) 1996-10-10 1998-04-16 Clariant Gmbh Process for the preparation of a coated bleach activator granulate
DE19649375A1 (en) 1996-11-29 1998-06-04 Henkel Kgaa Acetonitrile derivatives as bleach activators in detergents
US6211130B1 (en) 1997-08-21 2001-04-03 Henkel Kommanditgesellschaft Auf Aktien Use of quaternary acetonitrile compounds as activators for detergents
US6168077B1 (en) 1998-10-21 2001-01-02 Litronic, Inc. Apparatus and method of providing a dual mode card and reader

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0458396A1 (en) * 1990-05-24 1991-11-27 Unilever N.V. Bleaching composition
WO1996007650A1 (en) * 1994-09-02 1996-03-14 Basf Aktiengesellschaft Process for producing quaternary glycine nitriles
WO1996040661A1 (en) * 1995-06-07 1996-12-19 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
US6235218B1 (en) * 1995-06-07 2001-05-22 The Clorox Company Process for preparing N-alkyl ammonium acetonitrile compounds
EP0790244A1 (en) * 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Ammonium nitriles and use thereof as bleach activators
WO1998023718A2 (en) * 1996-11-29 1998-06-04 Basf Aktiengesellschaft Textile detergent formulation on the basis of quaternized glycine nitriles, bleaching agents, nonionic and/or anionic tensides and calcium ion and/or magnesium ion sequestering compounds
WO1998023531A1 (en) * 1996-11-29 1998-06-04 The Clorox Company Granular n-alkyl ammonium acetonitrile compositions
WO2000036061A2 (en) * 1998-12-15 2000-06-22 Henkel Kommanditgesellschaft Auf Aktien Acetonitrile derivatives formulated in particulate form as bleach activators in solid detergents
DE19908069A1 (en) * 1999-02-25 2000-08-31 Henkel Kgaa Compounded acetonitrile derivatives as bleach activators in detergents

Also Published As

Publication number Publication date
EP1207195A3 (en) 2003-06-11
US6498133B2 (en) 2002-12-24
JP2002226892A (en) 2002-08-14
DE10057045A1 (en) 2002-05-23
US20020107163A1 (en) 2002-08-08

Similar Documents

Publication Publication Date Title
EP1209221B1 (en) Use of cyclic sugar ketons as catalysts for peroxy compounds
EP1557457B1 (en) Use of transition metal complexes as bleach catalysts in washing and cleaning agents
EP1017773B1 (en) Bleaching activators based on ammonium nitrile in the form of coated granules
EP2049643A1 (en) Use of aminoacetones and salts thereof as bleaching boosters for peroxygen compounds
EP1791939B1 (en) Bleach activator mixtures
EP1445305B1 (en) Use of transition metal complexes as bleach catalysts
DE19740671A1 (en) Bleach activator granulate containing ammonium nitrile and layered silicate
EP1319705B1 (en) Bleach activator cogranulates
EP1225215B1 (en) Use of transition metal complexes with oxime ligands as bleach catalysts
EP0985728B1 (en) Bleach activator granulate
EP1207195A2 (en) Particulate bleach activators comprising acetonitril
EP1305384B1 (en) Particle-shaped acetonitrile derivatives as bleach activators in solid detergents
EP0710716B1 (en) Granulated bleach activators and production thereof
EP1487955B1 (en) Ammonium nitriles and the use thereof as hydrophobic bleaching activators
WO2000032731A1 (en) Use of transition metal complexes with nitrogen-containing heterocyclic ligands for improving the bleaching effect of peroxy compounds
EP1309542B1 (en) Method for producing hydrolysis-stable ammonium nitriles
WO2002026927A1 (en) Coated, granular n-alkylammonium acetonitrile salts and their use as bleach activators
DE19625495A1 (en) Quaternary ammonium compounds as bleach activators and their production
EP1794272B1 (en) Mixtures of bleaching agents
EP1784385A1 (en) Diethyl methyl ammonium nitriles and detergents and cleaning agents containing said ammonium nitriles
WO2007017216A1 (en) Washing and cleaning agents containing 1,3,5-triacetyl-2,4-dioxo-1,3,5-hexahydrotriazine as a bleach activator
DE102004043359A1 (en) Bleaching activator-granulates, useful e.g. in washing-, cleaning- and disinfecting agents, comprises hydroxybenzoicacid derivatives, quaternary hydroxyalkyl ammonium compounds and granulation auxiliary- and/or coating agents
WO2006092246A1 (en) Ammonium nitriles and the use thereof as bleaching activators
EP1622864A1 (en) Method for producing granulated ammonium nitrile

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

17P Request for examination filed

Effective date: 20031211

AKX Designation fees paid

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

17Q First examination report despatched

Effective date: 20050506

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20050920