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EP1305386B1 - Activateurs de blanchiment enrobes - Google Patents

Activateurs de blanchiment enrobes 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
European Patent Office
Prior art keywords
alkyl
formula
weight
bleach activator
sulphate
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.)
Expired - Lifetime
Application number
EP01969508A
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German (de)
English (en)
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EP1305386A1 (fr
Inventor
Horst-Dieter Speckmann
Bernd Larson
Jörg Poethkow
Peter Schmiedel
Lars Züchner
Oliver Mogck
Manfred Schreiber
Frank Weinelt
Georg Borchers
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.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP1305386A1 publication Critical patent/EP1305386A1/fr
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Anticipated expiration legal-status Critical
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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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Claims (14)

  1. Procédé de préparation de particules enrobées, contenant un activateur de blanchiment selon la formule (I)
    Figure imgb0006
     dans laquelle R1 représente -H, -CH3, un radical alkyle ou alcényle en C2 à C24, un radical alkyle ou alcényle en C2 à C24 substitué comprenant au moins un substituant du groupe formé par -Cl, -Br, -OH, -NH2, -CN, un radical alkylaryle ou alcénylaryle comprenant un groupe alkyle en C1 à C24, ou un radical alkylaryle ou alcénylaryle substitué par un groupe alkyle en C1 à C24 et au moins un autre substituant sur le cycle aromatique, et R2 et R3 sont choisis indépendamment l'un de l'autre parmi -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 avec n = 1, 2, 3, 4, 5 ou 6, R4 et R5 présentent, indépendamment l'un de l'autre, une signification indiquée ci-dessus pour R1, R2 ou R3 et X est un anion équilibrant la charge, en ce qu'on pulvérise sur l'activateur de blanchiment se trouvant sous forme solide, en particulier sous forme de poudre, selon la formule (I), si souhaité en mélange avec un liant et/ou une charge solide, un matériau d'enrobage organique liquide ou fluidifié par chauffage, le matériau à enrober étant en particulier maintenu en mouvement.
  2. Procédé selon la revendication 1, caractérisé en ce qu'il est réalisé dans un lit tourbillonnant, un mélangeur ou un granulateur.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le matériau d'enrobage est choisi parmi les sels inorganiques, tels que les sulfates de métal alcalin, les chlorures de métal alcalin, les silicates de métal alcalin, les phosphates de métal alcalin, les phosphonates de métal alcalin, les sulfates de métal alcalino-terreux et les silicates de métal alcalino-terreux, les cires de paraffine, les composés polymères solubles dans l'eau à base de saccharide, tels que les amidons ou les dérivés d'amidon ou de cellulose, les alcools polymères tels que les poly(alcools vinyliques) et les polyéthylèneglycols, les polycarboxylates homopolymères et copolymères, les polyesters d'acides dicarboxyliques et d'alcools le cas échéant oligomères ou polymères, les agents tensioactifs non ioniques, les agents tensioactifs anioniques, les acides hydroxycarboxyliques, tels que l'acide glycolique et l'acide citrique et/ou les acides gras.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'on transporte le matériau d'enrobage au préalable dans une solution ou du moins une suspension pouvant être pompée et pulvérisable et on élimine à nouveau, du moins partiellement, si souhaité, le solvant ou l'agent de mise en suspension en même temps que le processus d'enrobage ou après celui-ci par une étape de séchage.
  5. Procédé selon la revendication 1, caractérisé en ce qu'on introduit l'activateur de blanchiment selon la formule (I) dans du matériau d'enrobage fluidifié par chauffage, on refroidit le mélange formé sous le point de fusion ou sous la température de ramollissement du matériau d'enrobage et on le transforme, simultanément ou consécutivement, en granulats de manière en principe connue.
  6. Procédé selon la revendication 5, caractérisé en ce que le matériau d'enrobage est une cire, un polyester ou un acide gras, en particulier l'acide stéarique.
  7. Particule contenant l'activateur de blanchiment selon la formule générale (I),
    Figure imgb0007
     dans laquelle R1 représente -H, -CH3, un radical alkyle ou alcényle en C2 à C24, un radical alkyle ou alcényle en C2 à C24 substitué par au moins un substituant du groupe formé par -CI, -Br, -OH, -NH2, -CN, un radical alkylaryle ou alcénylaryle comprenant un groupe alkyle en C1 à C24 ou un groupe alkylaryle ou alcénylaryle substitué comprenant un groupe alkyle en C1 à C24 et au moins un autre substituant sur le cycle aromatique, R2 et R3 sont choisis, indépendamment l'un de l'autre parmi -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 avec n = 1, 2, 3, 4, 5 ou 6, R4 et R5 présentent, indépendamment l'un de l'autre une signification indiquée ci-dessus pour R1, R2 ou R3 et X est un anion équilibrant la charge, qui peut être obtenue selon le procédé selon l'une quelconque des revendications 1 à 6, qui est enrobée le plus complètement possible par le matériau d'enrobage et qui présente un diamètre moyen de particule dans la plage de 0,2 mm à 3 mm.
  8. Particule selon la revendication 7, caractérisée en ce qu'elle contient au moins 40% en poids et en particulier de 50% en poids à 92% en poids d'activateur de blanchiment selon la formule (I) et du matériau de revêtement en des quantités jusqu'à 60% en poids, en particulier de 8% en poids à 50% en poids et de manière particulièrement avantageuse de 10% en poids à 25% en poids, par rapport à la somme d'activateur de blanchiment et de matériau de revêtement.
  9. Particule selon la revendication 7 ou 8, caractérisée en ce que, dans le composé selon la formule I, R1, R2 et R3 sont identiques.
  10. Particule selon la revendication 9, caractérisée en ce que dans le composé selon la formule I, R1, R2 et R3 signifient des groupes méthyle.
  11. Particule selon l'une quelconque des revendications 7 à 10, caractérisée en ce que dans le composé selon la formule I, parmi les radicaux R1, R2 et R3 au moins 1 ou 2 des radicaux mentionnés sont des groupes méthyle et les autres présentent plusieurs atomes de carbone.
  12. Particule selon l'une quelconque des revendications 7 à 11, caractérisée en ce que dans le composé selon la formule I l'anion X- représente un halogénure, tel que le chlorure, le fluorure, l'iodure et le bromure, un nitrate, un hydroxyde, un phosphaté, un hydrogénophosphate, un dihydrogénophosphate, un pyrophosphate, un métaphosphate, un hexafluorophosphate, un carbonate, un hydrogénocarbonate, un sulfate, un hydrogénosulfate, un C1-20-alkylsulfate, un C1-20-alkylsulfonate, un arylsulfonate le cas échéant substitué par C1-18-alkyle, un chlorate, un perchlorate et/ou un anion d'acides C1-24-carboxyliques, tel que le formiate, l'acétate, le laurate, le benzoate ou le citrate, seuls ou dans des mélanges quelconques.
  13. Particule selon la revendication 12, caractérisée en ce que dans le composé selon la formule I, l'anion X- représente chlorure, sulfate, hydrogénosulfate, éthosulfate, C12/18-alkylsulfate, C12/16-alkylsulfate ou C13/15-alkylsulfate, laurylsulfate, dodécylbenzènesulfonate, toluènesulfonate, cumènesulfonate, xylènesulfonate ou méthosulfate ou des mélanges de ceux-ci.
  14. Utilisation de particules selon l'une quelconque des revendications 7 à 13 pour la préparation d'agents de lavage et de nettoyage, en particulier sous forme de particules.
EP01969508A 2000-08-04 2001-07-25 Activateurs de blanchiment enrobes Expired - Lifetime EP1305386B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10038832 2000-08-04
DE10038832A DE10038832A1 (de) 2000-08-04 2000-08-04 Umhüllte Bleichaktivatoren
PCT/EP2001/008598 WO2002012426A1 (fr) 2000-08-04 2001-07-25 Activateurs de blanchiment enrobes

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EP1305386A1 EP1305386A1 (fr) 2003-05-02
EP1305386B1 true EP1305386B1 (fr) 2006-12-20

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EP (1) EP1305386B1 (fr)
JP (1) JP2004517160A (fr)
AT (1) ATE348870T1 (fr)
AU (1) AU2001289747A1 (fr)
DE (2) DE10038832A1 (fr)
ES (1) ES2277940T3 (fr)
WO (1) WO2002012426A1 (fr)

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DE10159388A1 (de) * 2001-12-04 2003-06-12 Henkel Kgaa Verfahren zur Herstellung von umhüllten Bleichaktivatorgranulaten
WO2003101940A2 (fr) 2002-05-31 2003-12-11 Henkel Kommanditgesellschaft Auf Aktien Desodorisation de derives d'acetonitriles cationiques
WO2004029187A1 (fr) * 2002-09-20 2004-04-08 Henkel Kommanditgesellschaft Auf Aktien Compositions de detergent de lave-vaisselle (mgsm) contenant des activateurs de blanchiment speciaux (iii)
BR0317351A (pt) 2002-12-18 2005-11-16 Procter & Gamble Ativador orgânico, processo para a produção, composição de limpeza e método de limpeza do mesmo
EP1572851B1 (fr) 2002-12-20 2007-03-21 Henkel Kommanditgesellschaft auf Aktien Produits de lavage et de nettoyage contenant un agent de blanchiment
DE502004003835D1 (de) * 2003-02-10 2007-06-28 Henkel Kgaa Bleichmittelhaltige wasch- oder reinigungsmittel mit wasserlöslichem buildersystem und schmutzablösevermögendem cellulosederivat
DE10351325A1 (de) * 2003-02-10 2004-08-26 Henkel Kgaa Wasch- oder Reinigungsmittel mit wasserlöslichem Buildersystem und schmutzablösevermögendem Cellulosederivat
ES2279344T3 (es) * 2003-02-10 2007-08-16 Henkel Kommanditgesellschaft Auf Aktien Aumento de la capacidad de absorcion de agua de textiles.
WO2004069976A2 (fr) * 2003-02-10 2004-08-19 Henkel Kommanditgesellschaft Auf Aktien Utilisation de derives cellulosiques en tant que regulateurs de moussage
DE10351321A1 (de) * 2003-02-10 2004-08-26 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch eine Kombination von Cellulosderivaten
WO2005116179A1 (fr) * 2004-05-17 2005-12-08 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage comprenant un complexe de metal de transition qui renforce le blanchiment et est produit eventuellement in situ
DE102004028494A1 (de) * 2004-06-11 2005-12-29 Clariant Gmbh Mischungen von Ammoniumnitril-Bleichaktivatoren und Aminosäuren
DE102005026522B4 (de) * 2005-06-08 2007-04-05 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch Polymer
DE102005026544A1 (de) 2005-06-08 2006-12-14 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch Polymer
JP2007172716A (ja) * 2005-12-20 2007-07-05 Sony Corp 再生装置、再生方法および再生プログラム、記録媒体およびデータ構造、ならびに、オーサリング装置、オーサリング方法およびオーサリングプログラム
US8182785B2 (en) * 2008-06-11 2012-05-22 Nutech Ventures Methods and compositions for generating singlet oxygen
US20110009305A1 (en) * 2009-07-09 2011-01-13 Nigel Patrick Somerville Roberts Layered Particles and Compositions Comprising Same
EP2451926A1 (fr) * 2009-07-09 2012-05-16 The Procter & Gamble Company Compositions contenant des co-particules d agent de blanchiment
EP2447350A1 (fr) * 2010-10-29 2012-05-02 The Procter & Gamble Company Coparticule de blanchiment
DE102014110847A1 (de) * 2013-08-14 2015-02-19 Budich International Gmbh Mehrphasige Reinigungstablette

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ATE348870T1 (de) 2007-01-15
EP1305386A1 (fr) 2003-05-02
ES2277940T3 (es) 2007-08-01
JP2004517160A (ja) 2004-06-10
WO2002012426A1 (fr) 2002-02-14
US20040067863A1 (en) 2004-04-08
DE50111695D1 (de) 2007-02-01
US20050148484A9 (en) 2005-07-07
AU2001289747A1 (en) 2002-02-18
DE10038832A1 (de) 2002-03-28

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