EP1305386B1 - Enclosed bleach activators - Google Patents

Enclosed bleach activators Download PDF

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Publication number
EP1305386B1
EP1305386B1 EP01969508A EP01969508A EP1305386B1 EP 1305386 B1 EP1305386 B1 EP 1305386B1 EP 01969508 A EP01969508 A EP 01969508A EP 01969508 A EP01969508 A EP 01969508A EP 1305386 B1 EP1305386 B1 EP 1305386B1
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EP
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Prior art keywords
alkyl
formula
weight
bleach activator
sulphate
Prior art date
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EP01969508A
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German (de)
French (fr)
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EP1305386A1 (en
Inventor
Horst-Dieter Speckmann
Bernd Larson
Jörg Poethkow
Peter Schmiedel
Lars Züchner
Oliver Mogck
Manfred Schreiber
Frank Weinelt
Georg Borchers
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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 enveloped bleach activators of the quaternized aminoalkyl nitrile type.
  • detergents In addition to the ingredients indispensable for the washing process, such as surfactants and builders, detergents generally contain further constituents, which can be summarized by the term washing aids and which comprise such different active ingredient groups as foam regulators, grayness inhibitors, bleaching agents and color transfer inhibitors. Such auxiliaries also include substances which promote the surfactant performance by the oxidative degradation of soils or those present in the liquor. The same applies mutatis mutandis to cleaners for hard surfaces.
  • inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water releasing hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 60 ° C, a sufficiently fast bleaching of soiled textiles.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N- acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfururamides and cyanurates, in addition carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benz
  • International Patent Application WO 99/14296 relates to coated granules containing ammonium nitriles obtainable by coating a so-called ammonium nitrile base granules with a coating substance.
  • the preparation of the basic granulate is carried out by mixing the dry ammonium nitrile with a dry granulation aid, pressing this mixture into larger agglomerates and crushing these agglomerates to the desired particle size.
  • European Patent Application EP 0 464 880 discloses bleach-enhancing cationic nitriles of the general formula R'R "R '" N + -CR 1 R 2 -CN X - in which R 1 and R 2 are hydrogen or a substituent having at least one C Atom, R 'is a C 1-24 alkyl, alkenyl or alkyl ether group or a group -CR 1 R 2 -CN, and R "and R'” are each a C 1-24 alkyl or hydroxyalkyl group, and the Counteranion X - is an organic sulfonate, an organic sulfate or a carboxylate.
  • R 1 is -H, -CH 3 , a C 2-24 alkyl or alkenyl radical, a substituted C 2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 -alkyl group and at least one further substituent on the aromatic ring
  • R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 - OH, -CH 2 -CH 2 -OH, -CH 2 -CH 2 -OH, -CH
  • the anions X - include in particular the halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, bicarbonate, sulfate, hydrogen sulfate, C 1-20 alkyl sulfate, C 1-20 alkyl sulfonate, optionally C 1-18 alkyl-substituted aryl sulfonate, chlorate, perchlorate and / or the anions of C 1-24 carboxylic acids such as formate, acetate, laurate, benzoate or citrate, alone or in any mixtures.
  • halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate
  • toluenesulfonate or cumene sulfonate be while the anion of the ortho, meta or para isomers of methylbenzenesulfonic acid or isopropylbenzenesulfonic acid and any mixtures thereof understood.
  • Para- isopropylbenzenesulfonic acid is particularly preferred.
  • the compound according to general formula I can be used in solid form as such or particulate form, that is applied to an organic and / or inorganic support material, be used as starting material in the enclosure according to the invention.
  • the application of the compound of formula (I) can be carried out on the support material such that stirred into a solution of the compound of formula I, as obtained in the preparation thereof, the support material and the optionally aqueous solvent in vacuo, if desired at elevated Temperature, subtracts.
  • the solution of the compound according to formula I can also be sprayed onto the support material and, if appropriate, subsequently subjected to a drying process. It is preferred if the particles resulting from the manufacturing process have a diameter in the range from 0.4 mm to 3 mm.
  • Suitable carrier materials are all substances which do not interact in unduly negative ways with the compound according to formula I, for example alkali metal sulfonate, surfactants, organic acids and polymers, alkali metal carbonates, alkali metal sulfates, alkali metal hydrogensulfates, alkali metal bicarbonates, alkali metal phosphates, alkali metal hydrogenphosphates, dialkalihydrogenphosphates and alkali metal silicates and theirs mixtures.
  • such support materials are used whose inner surface is in the range of 10 m 2 / g to 500 m 2 / g, in particular 100 m 2 / g to 450 m 2 / g.
  • silicate carrier materials which are particularly suitable for the purposes of the present invention include, for example, both alkali metal silicates and also silicic acids, silica gels and clays as well as mixtures thereof.
  • the carrier material is preferably free of zeolites.
  • Silicate-containing support material optionally contains, in addition to the silicate component, further particulate inert constituents which do not affect the stability of the compounds according to formula I unreasonably.
  • Silicas prepared by a thermal process flame hydrolysis of SiCl 4
  • fumed silicas are useful as well as silicas prepared by wet processes.
  • Silica gels are colloidal silicas with elastic to solid consistency and a largely loose pore structure, resulting in a high remplissigauballmescale. They can be prepared by the action of mineral acids on water glass. Clays are naturally occurring crystalline or amorphous silicates of aluminum, iron, magnesium, calcium, potassium and sodium, for example kaolin, talc, pyrophyllite, attapulgite, sepiolite, montmorillonite and bauxite. The use of aluminum silicate as a carrier material or as a component of a carrier material mixture is possible. The carrier material preferably has particle sizes in the range from 100 ⁇ m to 1.5 mm.
  • the coating materials should prove to be as chemically inert as possible to the bleach activator, that is to say the degradation rate for the particles to be used according to the invention, containing the bleach activator according to formula (I), which are stored for about 4 months, should be as low as possible.
  • the coating materials must be sufficiently rapidly soluble in water or aqueous solutions so that the granules as constituents of detergents or cleaners when used in corresponding aqueous washing or cleaning solutions release the bleach activator at the desired time or over the desired period of time.
  • the use of the correspondingly coated particles in textile detergents often shows a greater avoidance of color damage to textiles washed with them than when the pure substance according to formula (I) is used.
  • Suitable coating materials for the purposes of this invention are in particular inorganic salts such as alkali metal sulfates, alkali metal chlorides, alkali metal silicates, alkali metal phosphates and Alkaliphosphonate, Erdallcalisulfate and alkaline earth metal silicates, paraffin waxes, water-soluble polymeric compounds based on saccharide, such as starch or starch or cellulose derivatives, polymeric alcohols, for example Polyvinyl alcohols and polyethylene glycols, homo- and copolymeric polycarboxylates, polyesters of dicarboxylic acids and optionally oligomeric or polymeric alcohols, nonionic surfactants, anionic surfactants, hydroxycarboxylic acids such as glycolic acid and citric acid, and / or fatty acids.
  • inorganic salts such as alkali metal sulfates, alkali metal chlorides, alkali metal silicates, alkali metal phosphates and Alkaliphosphonate,
  • sodium is the preferred alkali metal ion and magnesium is the preferred alkaline earth metal ion.
  • Paraffin wax generally represents a complex mixture without sharp melting point. For characterization is usually determined its melting range by differential thermal analysis (DTA), as described in "The Analyst” 87 (1962), 420, and / or its solidification point. This is the temperature at which molten material passes from the liquid to the solid state by slow cooling.
  • DTA differential thermal analysis
  • waxes are used which solidify in the range of 20 ° C to 70 ° C. It should be noted that even at room temperature appearing paraffin wax mixtures may contain different proportions of liquid paraffin. In the case of the paraffin waxes which are particularly useful according to the invention, the proportion of liquid at 40 ° C. is as high as possible, without already being 100% at this temperature.
  • Particularly preferred paraffin wax mixtures have at 40 ° C a liquid content of at least 50 wt .-%, in particular from 55 wt .-% to 80 wt .-%, and at 60 ° C, a liquid content of at least 90 wt .-%. In addition, it must be ensured that the paraffins contain the lowest possible volatile components.
  • Preferred paraffin waxes contain less than 1 wt .-%, in particular less than 0.5 wt .-% at 110 ° C and atmospheric pressure vaporizable fractions.
  • Particularly suitable paraffin waxes according to the invention can be obtained, for example, under the trade names Lunaflex® from Fuller and Deawax® from DEA Mineralöl AG.
  • water-soluble starch or cellulose derivatives useful as coating materials are, in particular, starch ethers and cellulose ethers.
  • cellulose ethers are methylcellulose, ethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose and carboxymethylcellulose, which is normally used as the sodium salt.
  • Suitable starch ethers are, for example, carboxymethyl starch, hydroxyethyl starch and methyl starch.
  • Sodium carboxymethyl cellulose and starch have proven particularly suitable.
  • Gelatin is also used with particular advantage as a coating material.
  • Polyvinyl alcohols are not accessible by direct polymerization, since the necessary basic monomer vinyl alcohol does not exist. Polyvinyl alcohols are therefore polymer-analogous reactions by hydrolysis, but technically especially by alkaline catalyzed transesterification of polyvinyl acetates with alcohols (For example, methanol) prepared in solution.
  • Polyvinyl alcohols used in accordance with the invention which are generally commercially available as white-yellowish powders or granules have molar masses in the range from 3000 g / mol to 320 000 g / mol, in particular 8000 g / mol to 200000 g / mol (corresponding degrees of polymerisation in Range of about 75-8000, especially about 200 to 5000).
  • polyvinyl alcohol esters in particular polyvinyl acetates, with a residual content of acyl groups, in particular acetyl groups, up to about 80 wt .-%, in particular from 10 wt .-% to 70 wt .-%.
  • the polyvinyl alcohols can be characterized in more detail by specifying the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
  • Conversion temperatures of the polyvinyl alcohols are dependent on the acetyl group content, the distribution of the acetyl groups along the chain and the tacticity of the polymers.
  • Fully saponified polyvinyl alcohols have a glass transition temperature of 85 ° C, with the value for partially hydrolyzed (87-89%) products at about 58 ° C is significantly lower.
  • Polyvinyl alcohols which are usually have a density of about 1.2-1.3 g / cm 3 depending on the degree of hydrolysis normally soluble in water and strongly polar organic solvents such as formamide, dimethylformamide and dimethylsulfoxide, by (chlorinated) hydrocarbons, esters, fats and oils they are not attacked.
  • Polyvinyl alcohols are classified as toxicologically harmless and are biodegradable.
  • Other suitable coating materials are polyethylene glycols, for example, having a molecular weight between 10,000 and 20,000.
  • homo- and copolymeric carboxylates such as polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those with about 50 wt .-% to 10 wt .-% maleic acid.
  • the molecular weight of these homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • suitable compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as Vinyhnethylethem, in which the proportion of the acid is preferably at least 50 wt .-%.
  • a further embodiment of the invention results from the use of so-called host molecules or compounds which, owing to their structure or arrangement, can protect bleach activators which, if appropriate, can enclose molecules such as the specified bleach activators in their interior.
  • a preferred cage compound is cyclodextrin.
  • nonionic surfactants as coating materials, which are to be understood in particular as solid polyalkoxylates of fatty alcohols at room temperature, and anionic surfactants, in particular C 9 -C 13 -alkylbenzenesulfonates, C 12 -C 18 -fatty alcohol sulfates and C 12 -C 18 -fatty acids and their salts, and to use mixtures of these, wherein the anionic surfactants are generally present as alkali metal salts, in particular sodium salts.
  • the particles according to the invention have a content of bleach activator according to formula (I) of preferably at least 40% by weight and in particular from 50% by weight to 92% by weight; the coating material is preferably in amounts up to 60% by weight, in particular from 3% by weight to 50% by weight and with particular advantage of 10% by weight. to 25 wt .-%, based on the sum of bleach activator and coating material, contained in the granules.
  • the granules may contain small amounts of free water, not bound as water of crystallization or in comparable form. These should be as low as possible, with normally amounts up to about 5% by weight being tolerable. Preferably, however, the granules contain 0 to 3 wt .-% water.
  • the invention further relates to a process for the preparation of coated bleach activator according to formula (I) containing granules characterized in that the present in solid, especially powder form bleach activator of formula (I), if desired in admixture with binder and / or solid filler or as prefabricated Granules, sprayed with a liquefied or liquid by heating organic cladding material, wherein the material to be encased is preferably kept in motion, for example by being in a fluidized bed, a mixer or granulator.
  • the desired particle size or particle size distribution of the resulting coated particles can be adjusted in a simple manner substantially over the duration of the mixing or granulation.
  • Organic and also inorganic coating materials such as the alkali or alkaline earth salts mentioned, especially if they are solid at room temperature, can also be applied in this way if previously converted into a solution or at least a pumpable and sprayable slurry, water being the preferred solution or slurry, and if desired, the solvent or slurry may be at least partially removed by a drying step subsequent to the wrapping operation.
  • the drying step can also be carried out simultaneously with the coating process, in particular if the coating is carried out in a fluidized bed with compressed air at temperatures of preferably 25 ° C. to 80 ° C. and in particular 45 ° C. to 75 ° C.
  • a further embodiment of the method according to the invention is the Bleach activator according to formula (I) in by heating liquefied wrapping material to cool the resulting mixture below the melting point or the softening temperature of the wrapping material and thereby or subsequently in a known manner by, for example pelleting, pastillation, extrusion or grinding, if desired, granules.
  • Preferred wrapping materials in this process variant are the abovementioned waxes, polyesters and fatty acids, in particular stearic acid.
  • coated granules are too strong for sticking, they can be aftertreated with conventional powdering agents, for example finely divided silica or zeolites.
  • Coated particles produced according to the invention or produced by the process according to the invention preferably have average particle diameters in the range from 0.2 mm to 3 mm, in particular from 0.4 mm to 1.8 mm. They are stable when stored for long periods, especially against hydrolysis of the bleach activator according to formula (I), and are preferably used in particular particulate detergents and cleaners in amounts such that these agents levels of 0.1 wt .-% to 10 wt .-%, in particular from 0.2 wt .-% to 7 wt .-% of bleach activator according to formula (I).

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Abstract

The aim of the invention is to improve the stability in storage of bleach activators of the quaternized amino alkyl nitrile type. To this end, the invention provides that a particle containing these bleach activators is enclosed in the most complete possible manner by an enclosing material.

Description

Die vorliegende Erfindung betrifft umhüllte Bleichaktivatoren vom Typ der quatemisierten Aminoalkylnitrile.The present invention relates to enveloped bleach activators of the quaternized aminoalkyl nitrile type.

Waschmittel enthalten neben den für den Waschprozess unverzichtbaren Inhaltsstoffen wie Tensiden und Buildermaterialien in der Regel weitere Bestandteile, die man unter dem Begriff Waschhilfsstoffe zusammenfassen kann und die so unterschiedliche Wirkstoffgruppen wie Schaumregulatoren, Vergrauungsinhibitoren, Bleichmittel und Farbübertragungsinhibitoren umfassen. Zu derartigen Hilfsstoffen gehören auch Substanzen, welche die Tensidleistung durch den oxidativen Abbau von auf dem Textil befindlichen Anschmutzungen oder solchen in der Flotte unterstützen. Gleiches gilt sinngemäß auch für Reinigungsmittel für harte Oberflächen. So werden anorganische Persauerstoffverbindungen, insbesondere Wasserstoffperoxid und feste Persauerstoffverbindungen, die sich in Wasser unter Freisetzung von Wasserstoffperoxid lösen, wie Natriumperborat und Natriumcarbonat-Perhydrat, seit langem als Oxidationsmittel zu Desinfektions- und Bleichzwecken verwendet. Die Oxidationswirkung dieser Substanzen hängt in verdünnten Lösungen stark von der Temperatur ab; so erzielt man beispielsweise mit H2O2 oder Perborat in alkalischen Bleichflotten erst bei Temperaturen oberhalb von etwa 60 °C eine ausreichend schnelle Bleiche verschmutzter Textilien. Bei niedrigeren Temperaturen kann die Oxidationswirkung der anorganischen Persauerstoffverbindungen durch Zusatz sogenannter Bleichaktivatoren verbessert werden, für die zahlreiche Vorschläge, vor allem aus den Stoffklassen der N- oder O-Acylverbindungen, beispielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin, acylierte Glykolurile, insbesondere Tetraacetylglykoluril, N-acylierte Hydantoine, Hydrazide, Triazole, Hydrotriazine, Urazole, Diketopiperazine, Sulfurylamide und Cyanurate, außerdem Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, Carbonsäureester, insbesondere Natrium-nonanoyloxy-benzolsulfonat, Natrium-isononanoyloxy-benzolsulfonat und acylierte Zuckerderivate, wie Pentaacetylglukose, in der Literatur bekannt geworden sind. Durch Zusatz dieser Substanzen kann die Bleichwirkung wäßriger Peroxidflotten so weit gesteigert werden, daß bereits bei Temperaturen unterhalb 60 °C im wesentlichen die gleichen Wirkungen wie mit der Peroxidflotte allein bei 95 °C eintreten.
Die internationale Patentanmeldung WO 99/14296 betrifft umhüllte Granulate, die Ammoniumnitrile enthalten und durch Umhüllen eines sogenannten Ammoniumnitril-Basisgranulats mit einer Coatingsubstanz erhältlich sind. Die Herstellung des Basisgranulats erfolgt durch Vermischen des trockenen Ammoniumnitrils mit einem trockenen Granulierhilfsmittel, Verpressen dieser Mischung zu größeren Agglomeraten und Zerkleinern dieser Agglomerate auf die gewünschte Korngröße.
Aus der europäischen Patentanmeldung EP 0 464 880 sind bleichverstärkende kationische Nitrile der allgemeinen Formel R'R"R'"N+-CR1R2-CN X- bekannt, in der R1 und R2 Wasserstoff oder ein Substituent mit mindestens einem C-Atom, R' eine C1-24-Alkyl-, Alkenyl- oder Alkylethergruppe oder eine Gruppe -CR1R2-CN, und R" sowie R'" jeweils eine C1-24-Alkyl- oder Hydroxyalkylgruppe ist und das Gegenanion X- ein organisches Sulfonat, ein organisches Sulfat oder ein Carboxylat ist.
Aus der internationalen Patentanmeldung WO 98/23719 ist bekannt, daß Verbindungen der allgemeinen Formel R1R2R3N+CH2CN X-, in denen R1, R2 und R3 unabhängig voneinander eine Alkyl-, Alkenyl oder Arylgruppe mit 1 bis 18 C-Atomen ist, wobei die Gruppen R2 und R3 auch Teil eines das N-Atom und gegebenenfalls weitere Heteroratome einschließenden Heterocyclusses sein können, und X ein ladungsausgleichendes Anion ist, als Aktivatoren für insbesondere anorganische Persauerstoffverbindungen in wäßrigen Reinigungslösungen für Geschirr verwendet werden können. Dadurch erhält man eine Verbesserung der Oxidations- und Bleichwirkung insbesondere anorganischer Persauerstoffverbindungen bei niedrigen Temperaturen unterhalb von 80 °C, insbesondere im Temperaturbereich von ca. 15 °C bis 55 °C. Die kationischen Nitrile sind jedoch insbesondere in Kombination mit weiteren Inhaltsstoffen von Wasch- und Reinigungsmitteln normalerweise wenig lagerstabil und insbesondere empfindlich gegenüber Feuchtigkeit.
Die verliegende Erfindung, mit der dieses Problem gelöst werden kann, betrifft Teilchen mit Bleichaktivator der allgemeinen Formel (I),

Figure imgb0001
in der R1 für -H, -CH3, einen C2-24-Alkyl- oder -Alkenylrest, einen substituierten C2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH2, -CN, einen Alkyl- oder Alkenylarylrest mit einer C1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R2 und R3 unabhängig voneinander ausgewählt sind aus -CH2-CN, -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2CH3, -(CH2CH2-O)nH mit n = 1, 2, 3, 4, 5 oder 6, R4 und R5 unabhängig voneinander eine voranstehend für R1, R2 oder R3 angegebene Bedeutung haben und X ein ladungsausgleichendes Anion ist, die nach dem im folgenden beschriebenen Verfahren erhältlich sind und die mit einem Umhüllungsmaterial möglichst vollständig umhüllt sind und einen mittleren Teilchen durchmesser im Bereich von 0,2 mm bis 3,0 mm aufweisen.
Die Herstellung von Verbindungen gemäß Formel I kann nach bekannten Verfahren oder in Anlehnung an diese erfolgen, wie sie zum Beispiel in der genannten Patentliteratur oder von Abraham in Progr. Phys. Org. Chem. 11 (1974), S. 1ff, oder von Arnett in J. Am. Chem. Soc. 102 (1980), S. 5892ff. veröffentlicht worden sind.
Bevorzugt ist die Verwendung von Verbindungen gemäß Formel I, in denen R1, R2 und R3 gleich sind. Unter diesen sind solche Verbindungen bevorzugt, in denen die genannten Reste Methylgruppen bedeuten. Andererseits sind auch solche Verbindungen bevorzugt, bei denen mindestens 1 oder 2 der genannten Reste Methylgruppen sind und die anderen mehrere C-Atome aufweisen.
Zu den Anionen X- gehören insbesondere die Halogenide wie Chlorid, Fluorid, Iodid und Bromid, Nitrat, Hydroxid, Phosphat, Hydrogenphosphat, Dihydrogenphosphat, Pyrophosphat, Metaphosphat, Hexafluorophosphat, Carbonat, Hydrogencarbonat, Sulfat, Hydrogensulfat, C1-20-Alkylsulfat, C1-20-Alkylsulfonat, gegebenenfalls C1-18-alkylsubstituiertes Arylsulfonat, Chlorat, Perchlorat und/oder die Anionen von C1-24-Carbonsäuren wie Formiat, Acetat, Laurat, Benzoat oder Citrat, allein oder in beliebigen Mischungen.
Bevorzugt sind Verbindungen gemäß Formel I, in denen X- Chlorid, Sulfat, Hydrogensulfat, Ethosulfat, C12/18-, C12/16- oder C13/15-Alkylsulfat, Laurylsulfat, Dodecylbenzolsulfonat, Toluolsulfonat, Cumolsulfonat, Xylolsulfonat oder Methosulfat oder Mischungen aus diesen ist. Unter Toluolsulfonat beziehungsweise Cumolsulfonat werden dabei das Anion des ortho-, meta- oder para-Isomeren der Methylbenzolsulfonsäure beziehungsweise Isopropylbenzolsulfonsäure und beliebige Mischungen aus diesen verstanden. Para-Isopropylbenzolsulfonsäure ist besonders bevorzugt.In addition to the ingredients indispensable for the washing process, such as surfactants and builders, detergents generally contain further constituents, which can be summarized by the term washing aids and which comprise such different active ingredient groups as foam regulators, grayness inhibitors, bleaching agents and color transfer inhibitors. Such auxiliaries also include substances which promote the surfactant performance by the oxidative degradation of soils or those present in the liquor. The same applies mutatis mutandis to cleaners for hard surfaces. Thus, inorganic peroxygen compounds, particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water releasing hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes. The oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 60 ° C, a sufficiently fast bleaching of soiled textiles. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N- acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfururamides and cyanurates, in addition carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetylglucose, have become known in the literature , By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased so much that already at Temperatures below 60 ° C substantially the same effects as with the peroxide solution alone at 95 ° C occur.
International Patent Application WO 99/14296 relates to coated granules containing ammonium nitriles obtainable by coating a so-called ammonium nitrile base granules with a coating substance. The preparation of the basic granulate is carried out by mixing the dry ammonium nitrile with a dry granulation aid, pressing this mixture into larger agglomerates and crushing these agglomerates to the desired particle size.
European Patent Application EP 0 464 880 discloses bleach-enhancing cationic nitriles of the general formula R'R "R '" N + -CR 1 R 2 -CN X - in which R 1 and R 2 are hydrogen or a substituent having at least one C Atom, R 'is a C 1-24 alkyl, alkenyl or alkyl ether group or a group -CR 1 R 2 -CN, and R "and R'" are each a C 1-24 alkyl or hydroxyalkyl group, and the Counteranion X - is an organic sulfonate, an organic sulfate or a carboxylate.
From the international patent application WO 98/23719 it is known that compounds of the general formula R 1 R 2 R 3 N + CH 2 CN X - , in which R 1 , R 2 and R 3 are independently an alkyl, alkenyl or aryl group with 1 to 18 carbon atoms, wherein the groups R 2 and R 3 may also be part of a N-atom and optionally further heteroatoms enclosing heterocycle, and X is a charge-balancing anion, as activators for in particular inorganic peroxygen compounds in aqueous cleaning solutions for crockery can be used. This results in an improvement of the oxidation and bleaching action of inorganic peroxygen compounds in particular at low temperatures below 80 ° C, in particular in the temperature range of about 15 ° C to 55 ° C. However, the cationic nitriles, especially in combination with other ingredients of detergents and cleaners are usually less stable on storage and especially sensitive to moisture.
The present invention, with which this problem can be solved, concerns particles with bleach activator of the general formula (I),
Figure imgb0001
 in the R 1 is -H, -CH 3 , a C 2-24 alkyl or alkenyl radical, a substituted C 2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 -alkyl group and at least one further substituent on the aromatic ring, R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 - OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) - CH 2 CH 3 , - (CH 2 CH 2 -O) n H with n = 1, 2, 3, 4, 5 or 6, R 4 and R 5 independently of one another above for R 1 , R 2 or R 3 X and X is a charge-balancing anion, which are obtainable by the method described below and which are as completely enveloped with a wrapping material sin d and have an average particle diameter in the range of 0.2 mm to 3.0 mm.
The preparation of compounds of the formula I can be carried out by known processes or by analogy thereto, as described, for example, in the abovementioned patent literature or by Abraham in Progr. Phys. Org. Chem. 11 (1974), p. 1ff, or Arnett in J. Am. Chem. Soc. 102 (1980), p. 5892ff. have been published.
Preference is given to the use of compounds of the formula I in which R 1 , R 2 and R 3 are identical. Among these, preference is given to those compounds in which the radicals mentioned are methyl groups. On the other hand, those compounds are preferred in which at least 1 or 2 of the radicals mentioned are methyl groups and the others have a plurality of carbon atoms.
The anions X - include in particular the halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, bicarbonate, sulfate, hydrogen sulfate, C 1-20 alkyl sulfate, C 1-20 alkyl sulfonate, optionally C 1-18 alkyl-substituted aryl sulfonate, chlorate, perchlorate and / or the anions of C 1-24 carboxylic acids such as formate, acetate, laurate, benzoate or citrate, alone or in any mixtures.
Preference is given to compounds of the formula I in which X-chloride, sulfate, hydrogensulfate, ethosulfate, C 12/18 , C 12/16 or C 13/15 -alkyl sulfate, lauryl sulfate, dodecylbenzenesulfonate, toluenesulfonate, cumene sulfonate, xylenesulfonate or methosulfate or Mixtures of these is. Under toluenesulfonate or cumene sulfonate be while the anion of the ortho, meta or para isomers of methylbenzenesulfonic acid or isopropylbenzenesulfonic acid and any mixtures thereof understood. Para- isopropylbenzenesulfonic acid is particularly preferred.

Die Verbindung gemäß allgemeiner Formel I kann in fester Form als solche oder teilchenförmig konfektioniert, das heißt aufgebracht auf ein organisches und/oder anorganisches Trägermaterial, als Ausgangsmaterial bei der erfindungsgemäßen Umhüllung eingesetzt werden. Dabei kann das Aufbringen der Verbindung gemäß Formel (I) auf das Trägermaterial derart geschehen, daß man in eine Lösung der Verbindung gemäß Formel I, wie sie im Rahmen deren Herstellung anfällt, das Trägermaterial einrührt und das gegebenenfalls wäßrige Lösungsmittel im Vakuum, gewünschtenfalls bei erhöhter Temperatur, abzieht. Man kann die Lösung der Verbindung gemäß Formel I aber auch auf das Trägermaterial aufsprühen und dabei oder gegebenenfalls anschließend einem Trocknungsprozeß unterwerfen. Dabei ist es bevorzugt, wenn die durch den Konfektionierungsprozeß entstehenden Teilchen einen Durchmesser im Bereich von 0,4 mm bis 3 mm aufweisen. Als Trägermaterialien kommen alle Substanzen in Betracht, die nicht in unzumutbar negativer Weise mit der Verbindung gemäß Formel I wechselwirken, zum Beispiel Alkalicumolsulfonat, Tenside, organische Säuren und Polymere, Alkalicarbonate, Alkalisulfate, Alkalihydrogensulfate, Alkalihydrogencarbonate, Alkaliphosphate, Alkalidihydrogenphosphate, Dialkalihydrogenphosphate und Alkalisilikate und deren Mischungen. Es werden vorzugsweise solche Trägermaterialien verwendet, deren innere Oberfläche im Bereich von 10 m2/g bis 500 m2/g, insbesondere 100 m2/g bis 450 m2/g liegt. Zu den im Rahmen der vorliegenden Erfindung besonders geeigneten silikatischen Trägermaterialien gehören beispielsweise sowohl Alkalisilikate wie auch Kieselsäuren, Kieselgele und Tone sowie deren Gemische. Das Trägermaterial ist jedoch vorzugsweise frei von Zeolithen. Silikatenthaltendes Trägermaterial enthält neben der Silikat-Komponente gegebenenfalls weitere teilchenförmige inerte Bestandteile, welche die Stabilität der Verbindungen gemäß Formel I nicht unzumutbar beeinträchtigen. Kieselsäuren, die nach einem 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 Flüssigkeitsauballmevermögen ergibt. Sie können durch Einwirken von Mineralsäuren auf 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 100 µm bis 1,5 mm auf.The compound according to general formula I can be used in solid form as such or particulate form, that is applied to an organic and / or inorganic support material, be used as starting material in the enclosure according to the invention. In this case, the application of the compound of formula (I) can be carried out on the support material such that stirred into a solution of the compound of formula I, as obtained in the preparation thereof, the support material and the optionally aqueous solvent in vacuo, if desired at elevated Temperature, subtracts. However, the solution of the compound according to formula I can also be sprayed onto the support material and, if appropriate, subsequently subjected to a drying process. It is preferred if the particles resulting from the manufacturing process have a diameter in the range from 0.4 mm to 3 mm. Suitable carrier materials are all substances which do not interact in unduly negative ways with the compound according to formula I, for example alkali metal sulfonate, surfactants, organic acids and polymers, alkali metal carbonates, alkali metal sulfates, alkali metal hydrogensulfates, alkali metal bicarbonates, alkali metal phosphates, alkali metal hydrogenphosphates, dialkalihydrogenphosphates and alkali metal silicates and theirs mixtures. Preferably, such support materials are used whose inner surface is in the range of 10 m 2 / g to 500 m 2 / g, in particular 100 m 2 / g to 450 m 2 / g. The silicate carrier materials which are particularly suitable for the purposes of the present invention include, for example, both alkali metal silicates and also silicic acids, silica gels and clays as well as mixtures thereof. However, the carrier material is preferably free of zeolites. Silicate-containing support material optionally contains, in addition to the silicate component, further particulate inert constituents which do not affect the stability of the compounds according to formula I unreasonably. Silicas prepared by a thermal process (flame hydrolysis of SiCl 4 ) (so-called fumed silicas) are useful as well as silicas prepared by wet processes. Silica gels are colloidal silicas with elastic to solid consistency and a largely loose pore structure, resulting in a high Flüssigauballmevermögen. They can be prepared by the action of mineral acids on water glass. Clays are naturally occurring crystalline or amorphous silicates of aluminum, iron, magnesium, calcium, potassium and sodium, for example kaolin, talc, pyrophyllite, attapulgite, sepiolite, montmorillonite and bauxite. The use of aluminum silicate as a carrier material or as a component of a carrier material mixture is possible. The carrier material preferably has particle sizes in the range from 100 μm to 1.5 mm.

Die Überzugsmaterialien sollten sich gegenüber dem Bleichaktivator als möglichst weitgehend chemisch inert erweisen, das heißt die Abbaurate für die erfindungsgemäß zu verwendenden, den Bleichaktivator gemäß Formel (I) enthaltenden Teilchen, die über etwa 4 Monate gelagert werden, soll möglichst gering sein. Weiterhin müssen die Überzugsmaterialien in Wasser beziehungsweise wäßrigen Lösungen ausreichend schnell löslich sein, damit die Granulate als Bestandteile von Wasch- oder Reinigungsmitteln bei deren Anwendung in entsprechenden wäßrigen Wasch- oder Reinigungslösungen den Bleichaktivator zum gewünschten Zeitpunkt beziehungsweise über den gewünschten Zeitraum freisetzen. Außerdem zeigt sich beim Einsatz der entsprechend umhüllten Teilchen in Textilwaschmitteln oft eine höhere Vermeidung von Farbschädigungen damit gewaschener Textilien als beim Einsatz der reinen Substanz gemäß Formel (I).The coating materials should prove to be as chemically inert as possible to the bleach activator, that is to say the degradation rate for the particles to be used according to the invention, containing the bleach activator according to formula (I), which are stored for about 4 months, should be as low as possible. Furthermore, the coating materials must be sufficiently rapidly soluble in water or aqueous solutions so that the granules as constituents of detergents or cleaners when used in corresponding aqueous washing or cleaning solutions release the bleach activator at the desired time or over the desired period of time. In addition, the use of the correspondingly coated particles in textile detergents often shows a greater avoidance of color damage to textiles washed with them than when the pure substance according to formula (I) is used.

Als Überzugsmaterialien im Sinne dieser Erfindung eignen sich insbesondere anorganische Salze wie Alkalisulfate, Alkalichloride, Alkalisilikate, Alkaliphosphate und Alkaliphosphonate, Erdallcalisulfate und Erdalkalisililcate, Paraffinwachse, wasserlösliche polymere Verbindungen auf Saccharid-Basis, wie Stärke beziehungsweise Stärke- oder Cellulose-Derivate, polymere Alkohole, beispielsweise Polyvinylalkohole und Polyethylenglykole, homo- und copolymere Polycarboxylate, Polyester aus Dicarbonsäuren und gegebenenfalls oligo- oder polymeren Alkoholen, nichtionische Tenside, anionische Tenside, Hydroxycarbonsäuren wie Glykolsäure und Citronensäure, und/oder Fettsäuren.Suitable coating materials for the purposes of this invention are in particular inorganic salts such as alkali metal sulfates, alkali metal chlorides, alkali metal silicates, alkali metal phosphates and Alkaliphosphonate, Erdallcalisulfate and alkaline earth metal silicates, paraffin waxes, water-soluble polymeric compounds based on saccharide, such as starch or starch or cellulose derivatives, polymeric alcohols, for example Polyvinyl alcohols and polyethylene glycols, homo- and copolymeric polycarboxylates, polyesters of dicarboxylic acids and optionally oligomeric or polymeric alcohols, nonionic surfactants, anionic surfactants, hydroxycarboxylic acids such as glycolic acid and citric acid, and / or fatty acids.

In den genannten anorganischen Salzen ist Natrium das bevorzugte Alkaliion und Magnesium das bevorzugte Erdalkaliion.In the said inorganic salts, sodium is the preferred alkali metal ion and magnesium is the preferred alkaline earth metal ion.

Paraffinwachs stellt im allgemeinen ein komplexes Stoffgemisch ohne scharfen Schmelzpunkt dar. Zur Charakterisierung bestimmt man üblicherweise seinen Schmelzbereich durch Differential-Thermo-Analyse (DTA), wie in "The Analyst" 87 (1962), 420, beschrieben, und/oder seinen Erstarrungspunkt. Darunter versteht man die Temperatur, bei der geschmolzenes Material durch langsames Abkühlen aus dem flüssigen in den festen Zustand übergeht. Vorzugsweise werden Wachse verwendet, die im Bereich von 20°C bis 70 °C erstarren. Dabei ist zu beachten, daß auch bei Raumtemperatur fest erscheinende Paraffinwachsgemische unterschiedliche Anteile an flüssigem Paraffin enthalten können. Bei den erfindungsgemäß besonders brauchbaren Paraffinwachsen liegt der Flüssiganteil bei 40 °C möglichst hoch, ohne bei dieser Temperatur schon 100 % zu betragen. Besonders bevorzugte Paraffinwachsgemische weisen bei 40 °C einen Flüssiganteil von mindestens 50 Gew.-%, insbesondere von 55 Gew.-% bis 80 Gew.-%, und bei 60 °C einen Flüssiganteil von mindestens 90 Gew.-% auf. Außerdem ist darauf zu achten, daß die Paraffine möglichst geringe flüchtige Anteile enthalten. Bevorzugte Paraffinwachse enthalten weniger als 1 Gew.-%, insbesondere weniger als 0,5 Gew.-% bei 110 °C und Normaldruck verdampfbare Anteile. Erfindungsgemäß besonders brauchbare Paraffinwachse können beispielsweise unter den Handelsbezeichnungen Lunaflex® der Firma Fuller sowie Deawax® der DEA Mineralöl AG bezogen werden.Paraffin wax generally represents a complex mixture without sharp melting point. For characterization is usually determined its melting range by differential thermal analysis (DTA), as described in "The Analyst" 87 (1962), 420, and / or its solidification point. This is the temperature at which molten material passes from the liquid to the solid state by slow cooling. Preferably, waxes are used which solidify in the range of 20 ° C to 70 ° C. It should be noted that even at room temperature appearing paraffin wax mixtures may contain different proportions of liquid paraffin. In the case of the paraffin waxes which are particularly useful according to the invention, the proportion of liquid at 40 ° C. is as high as possible, without already being 100% at this temperature. Particularly preferred paraffin wax mixtures have at 40 ° C a liquid content of at least 50 wt .-%, in particular from 55 wt .-% to 80 wt .-%, and at 60 ° C, a liquid content of at least 90 wt .-%. In addition, it must be ensured that the paraffins contain the lowest possible volatile components. Preferred paraffin waxes contain less than 1 wt .-%, in particular less than 0.5 wt .-% at 110 ° C and atmospheric pressure vaporizable fractions. Particularly suitable paraffin waxes according to the invention can be obtained, for example, under the trade names Lunaflex® from Fuller and Deawax® from DEA Mineralöl AG.

Zu den als Überzugsmaterialien brauchbaren wasserlöslichen Stärke- beziehungsweise Cellulose-Derivaten zählen insbesondere Stärkeether und Celluloseether. Beispiele für Celluloseether sind Methylcellulose, Ethylcellulose, Hydroxyethylcellulose, Methylliydroxyethylcellulose, Methylhydroxypropylcellulose und Carboxymethylcellulose, die normalerweise als Natriumsalz eingesetzt wird. Als Stärke kommt beispielsweise depolymerisierte Stärke in Betracht. Geeignete Stärkeether sind beispielsweise Carboxymethylstärke, Hydroxyethylstärke und Methylstärke. Als besonders geeignet haben sich Natriumcarboxymethylcellulose und Stärke erwiesen. Mit besonderem Vorteil wird auch Gelatine als Überzugsmaterial eingesetzt.Among the water-soluble starch or cellulose derivatives useful as coating materials are, in particular, starch ethers and cellulose ethers. Examples of cellulose ethers are methylcellulose, ethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose and carboxymethylcellulose, which is normally used as the sodium salt. As a strength, for example, depolymerized starch comes into consideration. Suitable starch ethers are, for example, carboxymethyl starch, hydroxyethyl starch and methyl starch. Sodium carboxymethyl cellulose and starch have proven particularly suitable. Gelatin is also used with particular advantage as a coating material.

Polyvinylalkohole sind durch direkte Polymerisationsverfahren nicht zugänglich, da das dafür notwendige Basis-Monomere Vinylalkohol nicht existiert. Polyvinylalkohole werden daher über polymeranaloge Reaktionen durch Hydrolyse, technisch insbesondere aber durch alkalisch katalysierte Umesterung von Polyvinylacetaten mit Alkoholen (beispielsweise Methanol) in Lösung hergestellt. Erfindungsgemäß bevorzugt eingesetzte Polyvinylalkohole, die im Handel in der Regel als weiß-gelbliche Pulver oder Granulate angeboten werden, haben Molmassen im Bereich von 3000 g/mol bis 320000 g/mol, insbesondere 8000 g/mol bis 200000 g/mol (entsprechend Polymerisationsgraden im Bereich von ca. 75-8000, insbesondere ca. 200 bis 5000). Sie weisen vorzugsweise Hydrolysegrade von 20 Gew.-% bis 100 Gew.-%, insbesondere von 30 Gew.-% bis 90 Gew.-% auf. Anders ausgedrückt handelt es sich dabei um ganz oder teilweise verseifte Polyvinylalkoholester, insbesondere Polyvinylacetate, mit einem Restgehalt an Acylgruppen, insbesondere Acetyl-Gruppen, bis zu etwa 80 Gew.-%, insbesondere von 10 Gew.-% bis 70 Gew.-%. Näher charakterisiert werden können die Polyvinylalkohole durch Angabe des Polymerisationsgrades des Ausgangspolymeren, des Hydrolysegrades, der Verseifungszahl beziehungsweise der Lösungs-Viskosität. Umwandlungstemperaturen der Polyvinylalkohole sind abhängig vom AcetylgruppenGehalt, der Verteilung der Acetyl-Gruppen entlang der Kette und der Taktizität der Polymeren. Vollverseifte Polyvinylalkohole haben eine Glasübergangstemperatur von 85° C, wobei der Wert für teilverseifte (87-89%) Produkte mit ca. 58° C deutlich niedriger liegt. Polyvinylalkohole, die normalerweise eine Dichte von etwa 1,2-1,3 g/cm3 aufweisen, sind abhängig vom Hydrolysegrad normalerweise löslich in Wasser und stark polaren organischen Lösungsmitteln wie Formamid, Dimethylformamid und Dimethylsulfoxid, von (chlorierten) Kohlenwasserstoffen, Estern, Fetten und Ölen werden sie nicht angegriffen. Polyvinylalkohole werden als toxikologisch unbedenklich eingestuft und sind biologisch abbaubar. Weitere geeignete Überzugsmaterialien sind Polyethylenglykole, die beispielsweise eine relative Molekülmasse zwischen 10 000 und 20 000 besitzen. Ebenso brauchbar sind homo- und copolymere Carboxylate, wie Polyacrylate, Polymethacrylate und insbesondere Copolymere der Acrylsäure mit Maleinsäure, vorzugsweise solche mit ca. 50 Gew.-% bis 10 Gew.-% Maleinsäure. Die relative Molekülmasse dieser Homopolymeren liegt im allgemeinen zwischen 1 000 und 100 000, die der Copolymeren zwischen 2 000 und 200 000, vorzugsweise 50 000 bis 120 000, bezogen auf freie Säure. Ein besonders bevorzugtes Acrylsäure-Maleinsäure-Copolymer weist eine relative Molekülmasse von 50 000 bis 100 000 auf. Außerdem geeignete Verbindungen dieser Klasse sind Copolymere der Acrylsäure oder Methacrylsäure mit Vinylethem, wie Vinyhnethylethem, in denen der Anteil der Säure vorzugsweise mindestens 50 Gew.-% beträgt.Polyvinyl alcohols are not accessible by direct polymerization, since the necessary basic monomer vinyl alcohol does not exist. Polyvinyl alcohols are therefore polymer-analogous reactions by hydrolysis, but technically especially by alkaline catalyzed transesterification of polyvinyl acetates with alcohols (For example, methanol) prepared in solution. Polyvinyl alcohols used in accordance with the invention which are generally commercially available as white-yellowish powders or granules have molar masses in the range from 3000 g / mol to 320 000 g / mol, in particular 8000 g / mol to 200000 g / mol (corresponding degrees of polymerisation in Range of about 75-8000, especially about 200 to 5000). They preferably have degrees of hydrolysis of from 20% by weight to 100% by weight, in particular from 30% by weight to 90% by weight. In other words, these are completely or partially saponified polyvinyl alcohol esters, in particular polyvinyl acetates, with a residual content of acyl groups, in particular acetyl groups, up to about 80 wt .-%, in particular from 10 wt .-% to 70 wt .-%. The polyvinyl alcohols can be characterized in more detail by specifying the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity. Conversion temperatures of the polyvinyl alcohols are dependent on the acetyl group content, the distribution of the acetyl groups along the chain and the tacticity of the polymers. Fully saponified polyvinyl alcohols have a glass transition temperature of 85 ° C, with the value for partially hydrolyzed (87-89%) products at about 58 ° C is significantly lower. Polyvinyl alcohols, which are usually have a density of about 1.2-1.3 g / cm 3 depending on the degree of hydrolysis normally soluble in water and strongly polar organic solvents such as formamide, dimethylformamide and dimethylsulfoxide, by (chlorinated) hydrocarbons, esters, fats and oils they are not attacked. Polyvinyl alcohols are classified as toxicologically harmless and are biodegradable. Other suitable coating materials are polyethylene glycols, for example, having a molecular weight between 10,000 and 20,000. Likewise useful are homo- and copolymeric carboxylates, such as polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those with about 50 wt .-% to 10 wt .-% maleic acid. The molecular weight of these homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Also suitable compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as Vinyhnethylethem, in which the proportion of the acid is preferably at least 50 wt .-%.

Eine weitere Ausführungsform der Erfindung ergibt sich durch den Einsatz sogenannter Wirts-Moleküle beziehungsweise Verbindungen, die aufgrund ihrer Struktur beziehungsweise Anordnung Bleichaktivatoren schützen können die Moleküle wie die angegebenen Bleichaktivatoren gegebenenfalls in ihrem Inneren einzuschließen vermögen. Eine bevorzugte Käfigverbindung ist Cyclodextrin. Mit besonderem Vorteil werden der Bleichaktivator gemäß Formel (I) und Cyclodextrin in einem molaren Verhältnis von 1:1 bis 1:2 eingesetzt.A further embodiment of the invention results from the use of so-called host molecules or compounds which, owing to their structure or arrangement, can protect bleach activators which, if appropriate, can enclose molecules such as the specified bleach activators in their interior. A preferred cage compound is cyclodextrin. With particular advantage, the bleach activator according to formula (I) and cyclodextrin in a molar ratio of 1: 1 to 1: 2 are used.

Unter den als Überzugsmaterialien zum Einsatz kommenden Polyestern sind solche bevorzugt, welche der Wäschefaser schmutzabstoßende Eigenschaften verleihen und die, falls während des Waschvorgangs anwesend, das Schmutzablösevermögen der übrigen Waschmittelbestandteile unterstützen. Diese werden oft als "Soil-Release"-Wirkstoffe oder wegen ihres Vermögens, die behandelte Oberfläche der Faser schmutzabstoßend auszurüsten, als "Soil-Repellents" bezeichnet. Der gleiche Effekt kann auch bei deren Einsatz in Reinigungsmitteln für harte Oberflächen beobachtet werden. Wegen ihrer chemischen Ähnlichkeit zu Polyesterfasern besonders wirksame und daher bevorzugte schmutzablösevermögende Wirkstoffe, die aber auch bei Geweben beziehungsweise Oberflächen aus anderem Material die erwünschte Wirkung zeigen können, sind Copolyester, die Dicarbonsäureeinheiten, Alkylenglykoleinheiten und Polyalkylenglykoleinheiten enthalten. Schmutzablösevermögende Copolyester der genannten Art wie auch ihr Einsatz in Waschmitteln sind seit langer Zeit bekannt. So beschreibt zum Beispiel die deutsche Offenlegungsschrift DT 16 17 141 ein Waschverfahren unter Einsatz von Polyethylenterephthalat-Polyoxyethylenglykol-Copolymeren. Die deutsche Offenlegungsschrift DT 22 00 911 betrifft Waschmittel, die Niotensid und ein Mischpolymer aus Polyoxyethylenglykol und Polyethylenterephthalat enthalten. In der deutschen Offenlegungsschrift DT 22 53 063 sind saure Textilausrüstungsmittel genannt, die ein Copolymer aus einer dibasigen Carbonsäure und einem Alkylen- oder Cycloalkylenpolyglykol sowie gegebenenfalls einem Alkylen- oder Cycloalkylenglykol enthalten. Polymere aus Ethylenterephthalat und Polyethylenoxid-terephthalat, in denen die Polyethylenglykol-Einheiten Molgewichte von 750 bis 5000 aufweisen und das Molverhältnis von Ethylenterephthalat zu Polyethylenoxid-terephthalat 50:50 bis 90:10 beträgt, und deren Einsatz in Waschmitteln ist in der deutschen Patentschrift DE 28 57 292 beschrieben. Polymere mit Molgewicht 15000 bis 50 000 aus Ethylenterephthalat und Polyethylenoxid-terephthalat, wobei die Polyethylenglykol-Einheiten Molgewichte von 1000 bis 10 000 aufweisen und das Molverhältnis von Ethylenterephthalat zu Polyethylenoxid-terephthalat 2:1 bis 6:1 beträgt, können gemäß der deutschen Offenlegungsschrift DE 33 24 258 in Waschmitteln eingesetzt werden. Das europäische Patent EP 066 944 betrifft Textilbehandlungsmittel, die einen Copolyester aus Ethylenglykol, Polyethylenglykol, aromatischer Dicarbonsäure und sulfonierter aromatischer Dicarbonsäure in bestimmten Molverhältnissen enthalten. Aus dem europäischen Patent EP 0 185 427 sind Methyl- oder Ethylgruppen-endverschlossene Polyester mit Ethylen-und/oder Propylen-terephthalat- und Polyethylenoxid-terephthalat-Einheiten und Waschmitel, die derartiges Soil-release-Polymer enthalten, bekannt. Das europäische Patent EP 0 241 984 betrifft einen Polyester, der neben Oxyethylen-Gruppen und Terephthalsäureeinheiten auch substituierte Ethyleneinheiten sowie Glycerineinheiten enthält. Aus dem europäischen Patent EP 0 241 985 sind Polyester bekannt, die neben Oxyethylen-Gruppen und Terephthalsäureeinheiten 1,2-Propylen-, 1,2-Butylen- und/oder 3-Methoxy-1,2-propylengruppen sowie Glycerineinheiten enthalten und mit C1- bis C4-Alkylgruppen endgruppenverschlossen sind. Die europäische Patentschrift EP 0 253 567 betrifft Soil-release-Polymere mit einer Molmasse von 900 bis 9000 aus Ethylenterephthalat und Polyethylenoxid-terephthalat, wobei die Polyethylenglykol-Einheiten Molgewichte von 300 bis 3000 aufweisen und das Molverhältnis von Ethylenterephthalat zu Polyethylenoxid-terephthalat 0,6 bis 0,95 beträgt. Aus der europäischen Patentanmeldung EP 0 272 033 sind zumindest anteilig durch C1-4-Alkyl- oder Acylreste endgruppenverschlossene Polyester mit Poly-propylenterephthalat- und PolyoxyethylenterephthalatEinheiten bekannt. Das europäische Patent EP 0 274 907 beschreibt sulfoethyl-endgruppenverschlossene terephthalathaltige Soil-release-Polyester. In der europäischen Patentanmeldung EP 0 357 280 werden durch Sulfonierung ungesättigter Endgruppen Soil-Release-Polyester mit Terephthalat-, Alkylenglykol- und Poly-C2-4-Glylkol-Einheiten hergestellt. Die internationale Patentanmeldung WO 95/32232 betrifft schmutzablösevermögende Polyester der allgemeinen Formel

        X-(O-(CHR-)a)b[O-OC-Ph-CO-(O-(CHR-)o)p]yO-Y     (II)

in der

a
eine Zahl von 2 bis 8,
b
eine Zahl von 1 bis 300,
o
eine Zahl von 2 bis 8,
p
eine Zahl von 1 bis 300 und
y
eine Zahl von 1 bis 500 bedeutet,
Ph
ein o-, m- oder p-Phenylenrest ist, der 1 bis 4 Substituenten, ausgewählt aus Alkylresten mit 1 bis 22 C-Atomen, Sulfonsäuregruppen, Carboxylgruppen und deren Mischungen, tragen kann,
R
ausgewählt wird aus Wasserstoff, einem Alkylrest mit 1 bis 22 C-Atomen und deren Mischungen, und
X und Y
unabhängig voneinander aus Wasserstoff, Alkyl- und Arylmonocarbonsäureresten mit 5 bis 32 C-Atomen, Hydroxymonocarbonsäureresten mit 2 bis 22 C-Atomen und einem Oligomerisierungsgrad von 1 bis 100 sowie Dicarbonsäurehalbesterresten, deren zweite Carbonsäuregruppe mit einem Alkohol A-(OCHZCH2)d-OH verestert ist, bei dem A einen Alkyl- oder Alkenylrest mit 8 bis 22 C-Atomen, Z Wasserstoff oder einen Alkylrest mit 1 bis 2 C-Atomen und d eine Zahl von 1 bis 40 bedeutet, mit der Maßgabe, daß X und Y nicht gleichzeitig Wasserstoff sind, wenn R Wasserstoff oder ein Alkylrest mit 1 C-Atom, a und/oder o 2 und b und/oder p 1 ist, ausgewählt werden.
Among the polyesters used as coating materials, those which give the laundry fiber soil repellency and which, if present during the washing process, promote the soil releasing ability of the remaining detergent ingredients are preferred. These are often referred to as soil release agents or because of their ability to render the treated surface of the fiber dirt-repellant, so-called "soil repellents". The same effect can also be observed in their use in hard surface cleaners. Because of their chemical similarity to polyester fibers particularly effective and therefore preferred soil release agents, but also in tissues or surfaces of other materials can show the desired effect, are copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Dirt-releasing copolyesters of the type mentioned as well as their use in detergents have been known for a long time. For example, German Offenlegungsschrift DT 16 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers. German laid-open specification DT 22 00 911 relates to detergents which contain nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate. In the German patent application DT 22 53 063 acidic textile finishing agents are mentioned which contain a copolymer of a dibasic carboxylic acid and an alkylene or Cycloalkylenpolyglykol and optionally an alkylene or cycloalkylene glycol. Polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 and the Molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 50:50 to 90:10, and their use in detergents is described in German Patent DE 28 57 292. Polymers having a molecular weight of 15,000 to 50,000 of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 2: 1 to 6: 1, can according to the German patent application DE 33 24 258 are used in detergents. European patent EP 066 944 relates to textile treatment compositions containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. European Patent EP 0 185 427 discloses methyl or ethyl group end-capped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and laundry detergents containing such soil release polymer. European patent EP 0 241 984 relates to a polyester which, besides oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and also glycerine units. European Patent EP 0 241 985 discloses polyesters which, in addition to oxyethylene groups and terephthalic acid units, contain 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and also glycerol units, and C 1 - to C 4 alkyl groups are endgruppenverschlossen. European Patent EP 0 253 567 relates to soil release polymers having a molecular weight of 900 to 9000 of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 0.6 to 0.95. European Patent Application EP 0 272 033 discloses at least proportionally polyesters with poly-propylene terephthalate and polyoxyethylene terephthalate units which are end-capped by C 1-4 -alkyl or acyl radicals. European Patent EP 0 274 907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters. In the European patent application EP 0 357 280, soil-release polyesters with terephthalate-, alkylene glycol- and poly-C 2-4 -glycol units are prepared by sulfonation of unsaturated end groups. International Patent Application WO 95/32232 relates to soil release polyesters of the general formula

X- (O- (CHR-) a ) b [O-OC-Ph-CO- (O- (CHR-) o ) p ] y OY (II)

in the
a
a number from 2 to 8,
b
a number from 1 to 300,
O
a number from 2 to 8,
p
a number from 1 to 300 and
y
a number from 1 to 500 means
Ph
is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof,
R
is selected from hydrogen, an alkyl radical having 1 to 22 carbon atoms and mixtures thereof, and
X and Y
independently of one another from hydrogen, alkyl and aryl monocarboxylic acid residues having 5 to 32 C atoms, hydroxymonocarboxylic acid residues having 2 to 22 C atoms and a degree of oligomerization of 1 to 100 and dicarboxylic acid half-ester residues whose second carboxylic acid group is substituted by an alcohol A- (OCHZCH 2 ) d -OH esterified in which A is an alkyl or alkenyl radical having 8 to 22 C atoms, Z is hydrogen or an alkyl radical having 1 to 2 C atoms and d is a number from 1 to 40, with the proviso that X and Y are not are simultaneously hydrogen when R is hydrogen or an alkyl group with 1 C atom, a and / or o 2 and b and / or p 1 are selected.

Ebenso ist es auch möglich, als Überzugsmaterialien nichtionische Tenside, worunter insbesondere bei Raumtemperatur feste Polyalkoxylate von Fettalkoholen zu verstehen sind, und Aniontenside, insbesondere C9-C13-Alkylbenzolsulfonate, C12-C18-Fettalkoholsulfate sowie C12-C18-Fettsäuren und deren Salze, und Mischungen aus diesen einzusetzen, wobei die Aniontenside in der Regel als Alkalisalze, insbesondere Natriumsalze vorliegen.Likewise, it is also possible to use nonionic surfactants as coating materials, which are to be understood in particular as solid polyalkoxylates of fatty alcohols at room temperature, and anionic surfactants, in particular C 9 -C 13 -alkylbenzenesulfonates, C 12 -C 18 -fatty alcohol sulfates and C 12 -C 18 -fatty acids and their salts, and to use mixtures of these, wherein the anionic surfactants are generally present as alkali metal salts, in particular sodium salts.

Die erfindungsgemäßen Teilchen besitzen einen Gehalt an Bleichaktivator gemäß Formel (I) von vorzugsweise mindestens 40 Gew.-% und insbesondere von 50 Gew.-% bis 92 Gew.-%; das Überzugsmaterial ist vorzugsweise in Mengen bis zu 60 Gew.-%, insbesondere von 3 Gew.-% bis 50 Gew.-% und mit besonderem Vorteil von 10 Gew.-% bis 25 Gew.-%, bezogen auf die Summe aus Bleichaktivator und Überzugsmaterial, in den Granulaten enthalten.The particles according to the invention have a content of bleach activator according to formula (I) of preferably at least 40% by weight and in particular from 50% by weight to 92% by weight; the coating material is preferably in amounts up to 60% by weight, in particular from 3% by weight to 50% by weight and with particular advantage of 10% by weight. to 25 wt .-%, based on the sum of bleach activator and coating material, contained in the granules.

Herstellungsbedingt können die Granulate geringe Mengen an freiem, nicht als Kristallwasser oder in vergleichbarer Form gebundenem Wasser enthalten. Diese sollten möglichst gering sein, wobei normalerweise Mengen bis zu etwa 5 Gew.-% tolerierbar sein können. Vorzugsweise enthalten die Granulate jedoch 0 bis 3 Gew.-% Wasser.Due to the production, the granules may contain small amounts of free water, not bound as water of crystallization or in comparable form. These should be as low as possible, with normally amounts up to about 5% by weight being tolerable. Preferably, however, the granules contain 0 to 3 wt .-% water.

Die Erfindung betrifft weiterhin ein Verfahren zur Herstellung von umhüllten Bleichaktivator gemäß Formel (I) enthaltenden Granulaten dadurch, daß man den in fester, insbesondere pulverförmiger Form vorliegenden Bleichaktivator gemäß Formel (I), gewünschtenfalls in Abmischung mit Bindemittel und/oder festem Füllstoff oder als vorgefertigtes Granulat, mit einem flüssigen beziehungsweise durch Erwärmen verflüssigten organischen Umhüllungsmaterial besprüht, wobei das zu umhüllende Material vorzugsweise in Bewegung gehalten wird, beispielsweise dadurch, daß es sich in einer Wirbelschicht, einem Mischer oder Granulator befindet. Bei letzteren kann, insbesondere wenn Bindemittel anwesend sind oder das Umhüllungsmaterial auch Bindemittel-Eigenschaften aufweist, in einfacher Weise eine Einstellung der gewünschten Teilchengröße beziehungsweise Teilchengrößenverteilung der resultierenden umhüllten Partikel im wesentlichen über die Zeitdauer der Mischung beziehungsweise Granulation erfolgen. Organische und auch anorganische Umhüllungsmaterialien wie die genannten Alkali- oder Erdalkalisalze, insbesondere wenn sie bei Raumtemperatur fest sind, können auch auf diese Weise aufgebracht werden, wenn man sie zuvor in eine Lösung oder zumindest eine pumpbare und sprühfähige Aufschlämmung überführt, wobei Wasser das bevorzugte Lösungs- beziehungsweise Aufschlämmungsmittel ist, und gewünschtenfalls das Lösungs- beziehungsweise Aufschlämmungsmittel anschließend an den Umhüllungsvorgang durch einen Trocknungsschritt zumindest teilweise wieder entfernt werden kann. Der Trocknungsschritt kann auch, insbesondere wenn die Umhüllung in einer Wirbelschicht mit eingetragener Luft bei Temperaturen von vorzugsweise 25 °C bis 80 °C und insbesondere 45 °C bis 75 °C vorgenommen wird, gleichzeitig mit dem Umhüllungsvorgang erfolgen.The invention further relates to a process for the preparation of coated bleach activator according to formula (I) containing granules characterized in that the present in solid, especially powder form bleach activator of formula (I), if desired in admixture with binder and / or solid filler or as prefabricated Granules, sprayed with a liquefied or liquid by heating organic cladding material, wherein the material to be encased is preferably kept in motion, for example by being in a fluidized bed, a mixer or granulator. In the case of the latter, in particular if binders are present or the coating material also has binder properties, the desired particle size or particle size distribution of the resulting coated particles can be adjusted in a simple manner substantially over the duration of the mixing or granulation. Organic and also inorganic coating materials such as the alkali or alkaline earth salts mentioned, especially if they are solid at room temperature, can also be applied in this way if previously converted into a solution or at least a pumpable and sprayable slurry, water being the preferred solution or slurry, and if desired, the solvent or slurry may be at least partially removed by a drying step subsequent to the wrapping operation. The drying step can also be carried out simultaneously with the coating process, in particular if the coating is carried out in a fluidized bed with compressed air at temperatures of preferably 25 ° C. to 80 ° C. and in particular 45 ° C. to 75 ° C.

Eine weitere Ausgestaltung des erfindungsgemäßen Verfahrens besteht darin, den Bleichaktivator gemäß Formel (I) in durch Erwärmen verflüssigtes Umhüllungsmaterial einzubringen, die entstehende Mischung unter den Schmelzpunkt beziehungsweise die Erweichungstemperatur des Umhüllungsmaterials abzukühlen und dabei oder anschließend in im Prinzip bekannter Art durch beispielsweise Pelletieren, Pastillieren, Extrudieren oder gewünschtenfalls Mahlen in Granulate zu überführen. Bevorzugte Umhüllungsmaterialien in dieser Verfahrensvariante sind die oben genannten Wachse, Polyester und Fettsäuren, insbesondere Stearinsäure.A further embodiment of the method according to the invention is the Bleach activator according to formula (I) in by heating liquefied wrapping material to cool the resulting mixture below the melting point or the softening temperature of the wrapping material and thereby or subsequently in a known manner by, for example pelleting, pastillation, extrusion or grinding, if desired, granules. Preferred wrapping materials in this process variant are the abovementioned waxes, polyesters and fatty acids, in particular stearic acid.

Sofern die umhüllten Granulate zu stark zum Kleben neigen, können sie mit üblichen Abpuderungsmitteln, beispielsweise feinteiliger Kieselsäure oder Zeolithen, nachbehandelt werden.If the coated granules are too strong for sticking, they can be aftertreated with conventional powdering agents, for example finely divided silica or zeolites.

Erfindungsgemäße beziehungsweise durch das erfindungsgemäße Verfahren hergestellte umhüllte Teilchen weisen vorzugsweise mittlere Teilchendurchmesser im Bereich von 0,2 mm bis 3 mm, insbesondere 0,4 mm bis 1,8 mm auf. Sie sind bei Lagerung über längere Zeiträume stabil, insbesondere gegenüber Hydrolyse des Bleichaktivators gemäß Formel (I), und werden in insbesondere teilchenförmigen Wasch- und Reinigungsmitteln vorzugsweise in solchen Mengen eingesetzt, daß diese Mittel Gehalte von 0,1 Gew.-% bis 10 Gew.-%, insbesondere von 0,2 Gew.-% bis 7 Gew.-% an Bleichaktivator gemäß Formel (I) aufweisen.Coated particles produced according to the invention or produced by the process according to the invention preferably have average particle diameters in the range from 0.2 mm to 3 mm, in particular from 0.4 mm to 1.8 mm. They are stable when stored for long periods, especially against hydrolysis of the bleach activator according to formula (I), and are preferably used in particular particulate detergents and cleaners in amounts such that these agents levels of 0.1 wt .-% to 10 wt .-%, in particular from 0.2 wt .-% to 7 wt .-% of bleach activator according to formula (I).

Claims (14)

  1. Method for producing enclosed particles containing bleach activator according to formula (I),
    Figure imgb0004
     in which R1 is -H, -CH3, a C2-24-alkyl or -alkenyl radical, a substituted C2-24-alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH2, -CN, an alkyl- or alkenylaryl radical with a C1-24-alkyl group, or is a substituted alkyl- or alkenylaryl radical with a C1-24-alkyl group and at least one other substituent on the aromatic ring, R2 and R3, independently of one another, are chosen from -CH2-CN, -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2-CH3, -(CH2CH2-O)nH where n = 1, 2, 3, 4, 5 or 6, R4 and R5, independently of one another, have an abovementioned meaning given for R1, R2 or R3, and X is a charge-balancing anion, by spraying the bleach activator according to formula (I) present in solid, in particular pulverulent, form, if desired in a mixture with binder and/or solid filler, with an organic enclosing material which is liquid or liquefied by heating, where the material to be enclosed is, in particular, kept in motion.
  2. Method according to Claim 1, characterized in that it is carried out in a fluidized bed, a mixer or granulator.
  3. Method according to Claim 1 or 2, characterized in that the coating material is chosen from the inorganic salts, such as alkali metal sulphates, alkali metal chlorides, alkali metal silicates, alkali metal phosphates, alkali metal phosphonates, alkaline earth metal sulphates and alkaline earth metal silicates, paraffin waxes, water-soluble saccharide based polymeric compounds, such as starch or starch derivatives or cellulose derivatives, polymeric alcohols, such as polyvinyl alcohols and polyethylene glycols, homo- and copolymeric polycarboxylates, polyesters of dicarboxylic acids and optionally oligo- or polymeric alcohols, nonionic surfactants, anionic surfactants, hydroxy carboxylic acids, such as glycolic acid and citric acid, and/or fatty acids.
  4. Method according to one of Claims 1 to 3, characterized in that the enclosing material is converted beforehand into a solution or at least a pumpable and sprayable slurry and, if desired, the solvent or slurrying agent is at least partially removed again during or subsequently to the enclosing operation by a drying step.
  5. Method according to Claim 1, characterized in that the bleach activator according to formula (I) is introduced into enclosing material liquefied by heating, the resulting mixture is cooled to below the melting point or the softening point of the enclosing material and, during this or subsequently, converted into granules in a manner known in principle.
  6. Method according to Claim 5, characterized in that the enclosing material is wax, polyester or fatty acid, in particular stearic acid.
  7. Particle containing bleach activator of the general formula (I),
    Figure imgb0005
     in which R1 is -H, -CH3, a C2-24-alkyl or -alkenyl radical, a substituted C2-24-alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH2, -CN, an alkyl- or alkenylaryl radical with a C1-24-alkyl group, or is a substituted alkyl- or alkenylaryl radical with a C1-24-alkyl group and at least one other substituent on the aromatic ring, R2 and R3, independently of one another, are chosen from -CH2-CN, -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2-CH3, -(CH2CH2-O)nH where n = 1, 2, 3, 4, 5 or 6, R4 and R5, independently of one another, have an abovementioned meaning given for R1, R2 or R3, and X is a charge-balancing anion, which is obtainable by the method according to one of Claims 1 to 6 and is enclosed in the most complete manner possible with the enclosing material and has an average particle diameter in the range from 0.2mm to 3mm.
  8. Particle according to Claim 7, characterized in that it comprises at least 40% by weight and in particular from 50% by weight to 92% by weight of bleach activator according to formula (I) and coating material in amounts up to 60% by weight, in particular from 8% by weight to 50% by weight and particularly advantageously from 10% by weight to 25% by weight, based on the sum of bleach activator and coating material.
  9. Particle according to Claim 7 or 8, characterized in that, in the compound according to formula I, R1, R2 and R3 are identical.
  10. Particle according to Claim 9, characterized in that, in the compound according to formula I, R1, R2 and R3 are methyl groups.
  11. Particle according to one of Claims 7 to 10, characterized in that, in the compound according to formula I, among the radicals R1, R2 and R3, at least 1 or 2 of said radicals are methyl groups and the others have two or more carbon atoms.
  12. Particle according to one of Claims 7 to 11, characterized in that, in the compound according to formula I, the anion X- is a halide such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, hydrogen carbonate, sulphate, hydrogen sulphate, C1-20-alkyl sulphate, C1-20-alkylsulphonate, optionally C1-18-alkylsubstituted arylsulphonate, chlorate, perchlorate and/or an anion of C1-24-carboxylic acids, such as formate, acetate, laurate, benzoate or citrate, alone or in any desired mixtures.
  13. Particle according to Claim 12, characterized in that, in the compound according to formula I, the anion X- is chloride, sulphate, hydrogen sulphate, ethosulphate, C12/18-, C12/16- or C13/15-alkyl sulphate, lauryl sulphate, dodecylbenzenesulphonate, toluenesulphonate, cumenesulphonate, xylenesulphonate or methosulphate or mixtures thereof.
  14. Use of particles according to one of Claims 7 to 13 for the production of, in particular, particulate detergents and cleaners.
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DE10159388A1 (en) * 2001-12-04 2003-06-12 Henkel Kgaa Process for the production of coated bleach activator granules
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AU2003270171A1 (en) * 2002-09-20 2004-04-19 Henkel Kommanditgesellschaft Auf Aktien Dishwasher compositions (mgsm) provided with specially formulated bleach activators (iii)
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EP1305386A1 (en) 2003-05-02
US20040067863A1 (en) 2004-04-08
DE10038832A1 (en) 2002-03-28
DE50111695D1 (en) 2007-02-01
JP2004517160A (en) 2004-06-10
ATE348870T1 (en) 2007-01-15
US20050148484A9 (en) 2005-07-07
ES2277940T3 (en) 2007-08-01
WO2002012426A1 (en) 2002-02-14
AU2001289747A1 (en) 2002-02-18

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