EP1735422B1 - Particules d'agent de blanchiment a enrobage soluble dans l'eau - Google Patents

Particules d'agent de blanchiment a enrobage soluble dans l'eau Download PDF

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Publication number
EP1735422B1
EP1735422B1 EP05728973A EP05728973A EP1735422B1 EP 1735422 B1 EP1735422 B1 EP 1735422B1 EP 05728973 A EP05728973 A EP 05728973A EP 05728973 A EP05728973 A EP 05728973A EP 1735422 B1 EP1735422 B1 EP 1735422B1
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EP
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Prior art keywords
acid
weight
core
water
polyvinyl alcohol
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EP05728973A
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German (de)
English (en)
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EP1735422A1 (fr
EP1735422B2 (fr
Inventor
Georg Assmann
Horst-Dieter Speckmann
Frank Meier
Helga Werner
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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
    • C11D3/3945—Organic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof

Definitions

  • the present patent application relates to water-soluble coated peroxycarboxylic acid particles, processes for their preparation and their use in particular liquid detergents or cleaners.
  • Imidoperoxycarboxylic acids are known as bleaching components in detergents and cleaners. Their problematic, however, is their low storage stability, especially in liquid formulations and at higher pH values. To solve this problem, proposals have already been made in the prior art.
  • the US patent US 3,770,816 relates to mixtures of diperisophthalic acid and magnesium sulfate which have hydration water contents of 0.25 to 5 parts by weight per part by weight of diperisophthalic acid.
  • Polyvinyl alcohol can be applied as a wrapping material to a peroxycarboxylic acid-containing particle.
  • From the US patent US 4,225,451 are percarboxy- and optionally additionally carboxy-substituted benzenes known as Blleichwirk für having at least 2 percarboxy. These may be in contact with desensitizing agents such as hydrocarbons having melting points above 30 ° C, fatty acids, aromatic acids, their alkyl esters, proteins, starch materials, alkali and alkaline earth salts.
  • the European patent application 0 074 730 A1 relates to a process for granulating magnesium salts of organic peracids with the aid of a binder which, based on the finished granules, contains at least 0.1% hydroxylated organic polymer.
  • the European patent application EP 0 653 485 discloses capsule compositions in which 6-phthalimidoperoxihexanoic acid is present as a dispersion in oil. The preparation of these capsules therefore requires an upstream emulsification process for the preparation of the peracid dispersion.
  • the present invention which seeks to remedy this, is a coated Blleichffenchen consisting of a bleach active ingredient-containing core and a core at least partially surrounding coating of water-soluble material, wherein the particle is characterized in that the core peroxycarboxylic acid and the coating material polyvinyl alcohol and additionally containing an acid and wherein the peroxycarboxylic acid is 4-phthalimidoperoxobutyric acid. 5-phthalimidoperoxopentanoic acid, 6-phthalimidoperoxohexanoic acid, 7-phthalimidoperoxoheptanoic acid, or a mixture of these.
  • water-soluble should be understood to mean that the so-called material dissolves without residue to at least 3 g / l, in particular at least 6 g / l in water of pH 7 at room temperature.
  • the coating material solvent especially water, in amounts of optionally up to 10 wt .-%, preferably 0.1 wt .-% to 5 wt .-% and particularly preferably below 4 wt. %, in each case based on the coated particle. If the following is the amount of coating material, a possible solvent content is not taken into account.
  • Suitable peroxycarboxylic acids present in the core of the coated particle according to the invention include 4-phthalimidoperoxobutanoic acid, 5-phthalimidoperoxopentanoic acid, 6-phthalimidoperoxohexanoic acid, 7-phthalimidoperoxoheptanoic acid and mixtures thereof. If the peroxycarboxylic acid is not in solid form at room temperature, it may, if desired, have been formulated in particulate form prior to wrapping with the water-soluble material in a manner known in the art using inert carrier materials; However, a peroxycarboxylic acid which is solid at room temperature is preferably used. Preferred peracids include 6-phthalimidoperoxohexanoic acid.
  • the content of peroxycarboxylic acid in the particles according to the invention is preferably from 20% by weight to 90% by weight, in particular from 40% by weight to 80% by weight and particularly preferably from 50% to 70% by weight.
  • Polyvinyl alcohol is an essential component of the coating material. Polyvinyl alcohols are not accessible by direct polymerization, since the necessary basic monomers vinyl alcohol does not exist. Polyvinyl alcohols are therefore prepared via polymer-analogous reactions by hydrolysis, but in particular technically by alkali-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol) in solution. Commercially available polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range of about 500-2500 (corresponding to molar masses of about 20000-100000 g / mol) have different degrees of hydrolysis of 98-99 wt .-% or 87-89 mole%.
  • polyvinyl acetates with a residual content of acetyl groups of about 1-2 wt .-% and 11-13 mol%.
  • the polyvinyl alcohols are characterized by the manufacturer by indicating 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 ° and a melting point of 228 °. The corresponding values for partially hydrolyzed (87-89%) products are considerably lower at approx.
  • Polyvinyl alcohols which normally have a density of about 1.2-1.3 g / cm 3 , are soluble in water and a few highly polar organic solvents such as formamide, dimethylformamide, and dimethylsulfoxide, of (chlorinated) hydrocarbons, esters, depending on the degree of hydrolysis. Fats and oils are not attacked. Polyvinyl alcohols are classified as toxicologically harmless and are at least partially biodegradable. Preferably, polyvinyl alcohols are used which have a saponification number in the range from 20 to 350, in particular in the range from 100 to 300 and particularly preferably from 150 to 250. The degree of polymerization is preferably in the range from 100 to 3000, in particular from 150 to 2000 and particularly preferably from 250 to 500.
  • Optionally contained additional coating materials for the peroxycarboxylic acids must have said water solubility and be capable of being melted or dissolved in water or other vaporizable solvent, in devices commonly used for particle coating. For example, granulators or fluidized bed plants to be applied to the peroxycarboxylic acid.
  • Suitable additional coating materials include, for example, nonionic surfactants mentioned below, mineral acids, carboxylic acids and / or organic polymers.
  • Polymeric polycarboxylates in particular polymerization products of acrylic acid, methacrylic acid or maleic acid or copolymers of at least two of these, are suitable, which can also be used in completely or at least partially neutralized form, in particular in the form of the alkali metal salts.
  • Commercial products are, for example Sokalan ® CP 5, CP 10 and PA 30 from BASF.
  • phosphonic acids or optionally functionally modified phosphonic acids for example hydroxy- or aminoalkanephosphonic acids, and / or their alkali metal salts.
  • suitable phosphonic acids are 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or the dialkali salt or the tetraalkali salt of this acid, ethylenediamine tetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and their higher homologs.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • ETMP ethylenediamine tetramethylenephosphonic acid
  • DTPMP diethylenetriaminepentamethylenephosphonic acid
  • sodium is the respectively preferred alkali metal.
  • Mandatory are acids, such as mineral acids such as phosphoric acid, sulfuric acid and / or hydrochloric acid, and / or carboxylic acids such as adipic acid, ascorbic acid, citric acid and / or C 10 - to C 18 fatty acid, in the coating material whereby the stability of the peroxycarboxylic acid is further increased.
  • mineral acids such as phosphoric acid, sulfuric acid and / or hydrochloric acid
  • carboxylic acids such as adipic acid, ascorbic acid, citric acid and / or C 10 - to C 18 fatty acid
  • the stated mineral acids essentially serve for adjusting the pH of the coating material usually applied as an aqueous preparation and therefore only in small amounts of normally at most 0.5% by weight, preferably not more than 0.1% by weight, in accordance with the invention coated particles are present
  • the phosphonic acids in higher amounts, for example, up to 10 wt .-%, preferably not more than 5 wt .-%
  • the carboxylic acids in still higher amounts, for example up to 35%, preferably not more than 25 wt. -%, be present in accordance with the invention coated particles.
  • anionic or nonionic modified celluloses especially alkali carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose or methylhydroxypropyl cellulose, alone or in mixtures with one another, or corresponding starch derivatives can be used as additional constituents of the coating material.
  • the coating material is preferably applied to the particulate peroxycarboxylic acid in amounts such that the coated peroxycarboxylic acid particles consist of from 5% to 50% by weight of the coating material.
  • the diameters of the coated Peroxocarbonchureteilchen are preferably in the range of 100 microns to 2000 microns, in particular in the range of 100 microns to 800 microns or in the range of 800 microns to 1600 microns; Therefore, it is based on correspondingly finely divided PeroxocarbonTexrematerial and covers it with the coating material.
  • the procedure is preferably such that a fluidized bed of the peroxycarboxylic acid particles to be coated is sprayed with a solvent-containing preparation, preferably an aqueous preparation, of the coating material, thereby or subsequently carrying out a drying, wherein the solvent, preferably water, is at least partially removed by evaporation, and discharges the enveloped PeroxocarbonTalkreteilchen in principle conventional manner from the fluidized bed.
  • a solvent-containing preparation preferably an aqueous preparation
  • Another object of the invention is therefore a process for the preparation of coated Blleichstoffteitchen consisting of a bleach active ingredient-containing core and a core at least partially surrounding coating of water-soluble material by introducing a particulate peroxocarboxylic acid, the 4-Phthalimidoperoxobutanklare, 5-Phthalimidoperoxopentan Textre, 6-Phthalimidoperoxohexanklare , 7-Phthalimidoperoxoheptanoic acid or a mixture of these is in a fluidized bed, spraying an aqueous solution containing polyvinyl alcohol and additionally an acid, and drying.
  • the temperature of the bleach particle does not exceed 50 ° C, especially 35 ° C, during the auto-spraying of the aqueous solution and during drying. This can be achieved in particular by not selecting the temperature of the fluidizing means too high, for example less than 65 ° C.
  • an enveloped peroxycarboxylic acid particle according to the invention may also be prepared by spray-drying.
  • Another object of the invention is therefore a process for the preparation of coated bleach particles consisting of a bleach-containing core and a core at least partially surrounding coating of water-soluble material, by spray-drying an aqueous preparation containing peroxycarboxylic acid and polyvinyl alcohol and additionally an acid and wherein the Peroxycarboxylic acid is 4-phthalimidoperoxobutanoic acid, 5-phthalimidoperoxopentanoic acid, 6-phthalimidoperoxohexanoic acid, 7-phthalimidoperoxoheptanoic acid or a mixture of these.
  • a further embodiment of the invention therefore relates to a particle enveloped according to the invention, in which the core contains, in addition to the peroxycarboxylic acid, support material which is identical to the coating material. It is preferred if the proportion of the sum of the coating material and the carrier material amounts to 5% by weight to 50% by weight of the coated particle
  • An agent according to the invention or produced by the process according to the invention is preferably used for the production of detergents or cleaners.
  • the coating avoids direct contact of alkaline components usually contained therein with the acidic bleach.
  • the coating can control the water access to the bleach component.
  • the dissolution of the bleaching agent can be readily controlled by the choice of coating material and layer thickness, that is, the relative amount of coating material applied.
  • such detergent or cleaning agent may contain all conventional ingredients in such agents, such as surfactants, solvents, builders, enzymes and other auxiliaries such as soil repellants, thickeners, dyes and perfumes or the like. It can be both in solid form or as a liquid, wherein it is preferably anhydrous in the latter case.
  • anhydrous is meant an agent which contains not more than 10% by weight, in particular not more than 5% by weight, of water.
  • it contains nonionic surfactants and / or organic solvents and optionally anionic surfactants, cationic surfactants and / or amphoteric surfactants.
  • the solvents or solvent mixtures used in the liquid phase of the agent are surfactants or at least contain a proportion which corresponds in particular to 10% by weight to 99% by weight of the total solvent to surfactants.
  • Surfactants of the sulfonate type, alk (en) ylsulfates, alkoxylated alk (en) ylsulfates, ester sulfonates and / or soaps are preferably used as anionic surfactants.
  • surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and Hydroxyalkansulfonaten and disulfonates, such as those from C 12 -C 18 monoolefins having terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 10 -C 18 fatty alcohols, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 8 -C 20 -oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis.
  • C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and C 14 -C 15 -alkyl sulfates and C 14 -C 16 -alkyl sulfates are particularly preferred.
  • 2,3-alkyl sulfates which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 are manufactured and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 -alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 -alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 -C 18 Fatty alcohols containing 1 to 4 EO are suitable. Due to their high foaming behavior, they are usually used in detergents only in relatively small amounts, for example in amounts of from 0 to 5% by weight.
  • esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • anionic surfactants are particularly soaps into consideration.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, for. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • those soap mixtures are preferred which are composed of 50 to 100 wt .-% of saturated C 12 -C 24 fatty acid soaps and 0 to 50 wt .-% of oleic acid soap.
  • Ether carboxylic acids are water hardness insensitive and have excellent surfactant properties , Production and application are for example in Soaps, oils, fats, waxes 101, 37 (1975 ); 115, 235 (1989 ) and Surfactants Deterg. 25, 308 (1988 ).
  • Cationic surfactants contain the surface activity of the high molecular weight hydrophobic residue upon dissociation in aqueous solution in the cation.
  • the most important representatives of the cationic surfactants are the quaternary ammonium compounds of the general formula: (R 1 R 2 R 3 R 4 N + ) X - .
  • R 1 is C 1 -C 8 -alk (en) yl
  • R 2 to R 4 are each independently C n H 2n + 1-px - (Y 1 (CO) R 5 ) p - (Y 2 H) x
  • n stands for integers without 0 and p and x stand for integers or 0.
  • Y 1 and Y 2 are each independently O, N or NH.
  • R 5 denotes a C 3 -C 23 -alk (en) yl chain.
  • X is one Counterion, which is preferably selected from the group of halides, alkyl sulfates and alkyl carbonates. Particularly preferred are cationic surfactants in which the nitrogen group is substituted by two long acyl and two short alk (en) yl radicals.
  • Amphoteric or ampholytic surfactants have a plurality of functional groups which can ionize in aqueous solution and - depending on the conditions of the medium - give the compounds anionic or cationic character (see DIN 53900, July 1972). Near the isoelectric point (around pH 4), the amphoteric surfactants form internal salts, making them difficult or insoluble in water. Amphoteric surfactants are subdivided into ampholytes and betaines, the latter being present in solution as zwitterions. Ampholytes are amphoteric electrolytes, ie, compounds that have both acidic and basic hydrophilic groups and thus behave acidic or basic depending on the condition. Betaine refers to compounds with the atomic grouping R 3 N + -CH 2 -COO - , which show typical properties of zwitterions.
  • the nonionic surfactants used are preferably alkoxylated and / or propoxylated, in particular primary, alcohols having preferably 8 to 18 C atoms and on average 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per mole of alcohol.
  • EO ethylene oxide
  • PO propylene oxide
  • C 8 -C 16 -alcohol alkoxylates advantageously ethoxylated and / or propoxylated C 10 -C 15 -alcohol alkoxylates, in particular C 12 -C 14 -alcohol alkoxylates, having a degree of ethoxylation of between 2 and 10, preferably between 3 and 8, and / or a degree of propoxylation between 1 and 6, preferably between 1.5 and 5.
  • the stated degrees of ethoxylation and propoxylation represent statistical averages, which may be an integer or a fractional number for a particular product.
  • Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow range ethoxylates / propoxylates, NRE / NRP).
  • fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x , z. B. as compounds, especially with anionic surfactants used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol that is suitable for a glycose unit having 5 or 6 C atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.1 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in the Japanese patent application JP-A-58/217 598 are described or preferably according to the in the international patent application WO-A-90113533 be prepared described methods.
  • Particularly preferred are C 12 -C 18 fatty acid methyl esters having an average of 3 to 15 EO, in particular having an average of 5 to 12 EO.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • gemini surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called “spacer”. This spacer is usually a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to control the surface tension of the water to greatly reduce, out. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimer alcohol bis- and trimeralcohol tris-sulfates and ether sulfates according to the international patent application WO-A-96/23768 , End-capped dimeric and trimeric mixed ethers according to the German patent application DE-A-195 13 391 They are characterized by their bi- and multi-functionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides as described in international patent applications WO 95/19953 .
  • WO 95/19954 and WO95-A- / 19955 to be discribed.
  • the amount of surfactants contained in the agents according to the invention is preferably from 0.1% by weight to 90% by weight, in particular from 10% by weight to 80% by weight, and particularly preferably from 20% by weight to 70% by weight. -%.
  • Such surfactants can make up the entire liquid fraction of the composition according to the invention, but can also be completely or at least partially replaced or supplemented by other organic solvents which are preferably water-miscible. In this latter case, solid representatives of the surfactants mentioned can also be used at room temperature in amounts such that a liquid agent still results.
  • organic solvents here are preferably polydiols, ethers, alcohols, ketones, amides and / or esters, in amounts of 0 to 90 wt .-%, preferably 0.1 to 70 wt .-%, in particular 0.1 to 60 wt. -% used.
  • Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains, and graying. Cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities.
  • the proportion of enzymes or enzyme mixtures may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 3 wt .-%.
  • Further detergent ingredients may be builders, cobuilders, soil repellents, alkaline salts and foam inhibitors, complexing agents, enzyme stabilizers, grayness inhibitors, optical brighteners and UV absorbers.
  • fine crystalline, synthetic and bound water-containing zeolite can be used, preferably zeolite A and / or P.
  • zeolite P zeolite MAP ® commercial product from Crosfield
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite may preferably be used as a spray-dried powder.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates can also be used as builders.
  • Suitable substitutes or sub-substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in the European patent application EP-A-0 164 514 described.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the process described in International Patent Application WO-A-91/08171 is described.
  • the preferred builder substances also include amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delay-delayed and have secondary washing properties.
  • the dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray-amorphous silicates which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in the German patent application DE-A-44 00 024 described.
  • Especially preferred are densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
  • Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.
  • Their content is generally not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished agent.
  • tripolyphosphates even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing power.
  • Preferred amounts of phosphates are below 10% by weight, especially at 0% by weight.
  • Suitable organic builder substances which are useful as co-builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and their derivatives and mixtures thereof.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • Further useable acidulants are known pH regulators, such as sodium bicarbonate and sodium hydrogen sulfate.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar mass measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 2,000 to 20,000 g / mol. Because of their superior solubility can from this group in turn the short-chain polyacrylates, the molecular weights of 2,000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 g / mol, have to be preferred.
  • Suitable polymers may also include substances consisting partly or wholly of units of vinyl alcohol or its derivatives.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as an aqueous solution or, preferably, as a powder.
  • the polymers may also allylsulfonic acids, such as in the EP-B-0 727 448 Allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
  • biodegradable polymers of more than two different monomer units for example, those according to the DE-A-43 00 772 as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to the DE-C-42 21 381 as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those described in the German patent applications DE-A-43 03 320 and DE-A-4417734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • Particularly preferred Polyaspartic acids or their salts and derivatives of which in the German patent application DE-A-195 40 086 is disclosed that they also have a bleach-stabilizing effect in addition to Cobuilder properties.
  • polyacetals which are prepared by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as in the European patent application EP-A-0 280 223 described, can be obtained.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500 000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • Both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also yellow dextrins and white dextrins with relatively high molecular weights in the range from 2 000 to 30 000 g / mol are useful.
  • a preferred dextrin is in the British patent application 94 19 091 described.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and methods of their preparation are, for example, from the European patent applications EP-A-0 232 202 . EP-A-0 427 349 . EP-A-0 472 042 and EP-A-0 542 496 as well as the international patent applications WO-A-92/18542 . WO-A-93/08251 . WO-A-93/16110 . WO 94/28030 . WO-A-95/07303 . WO 95/12619 and WO 95/20608 known. Also suitable is an oxidized oligosaccharide according to German patent application DE-A-196 00 018 , A product
  • ethylenediamine-N, N'-disuccinate (EDDS) the synthesis of which, for example, in US 3,158,615 is described, preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such co-builders are described, for example, in the international patent application WO 95/20029 described.
  • compositions may also contain components which positively influence the oil and Fettauswaschles from textiles, so-called soil repellents. This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component.
  • the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, and polymers of phthalic acid and / or terephthalic acid or derivatives thereof known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Especially preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • compositions are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures thereof;
  • alkali metal carbonate and amorphous alkali metal silicate especially sodium silicate with a molar ratio of Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
  • Preferred agents include alkaline salts, builder and / or co-builders, preferably sodium carbonate, zeolite, crystalline layered sodium silicates and / or trisodium citrate, in amounts of from 0.5 to 70% by weight, preferably 0.5 to 50% by weight. , in particular 0.5 to 30 wt .-% anhydrous substance.
  • foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. It is also advantageous to use mixtures of different foam inhibitors, for example those of silicones, paraffins or waxes.
  • foam inhibitors in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • a granular, water-soluble or dispersible carrier substance In particular, mixtures of paraffins and bistearylethylenediamides are preferred.
  • Suitable complexing agents or stabilizers in particular for per compounds and enzymes which are sensitive to heavy metal ions, are the salts of polyphosphonic acids.
  • the sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriamine penta-methylenephosphonate or ethylenediamine tetramethylenephosphonate in amounts of from 0.1 to 5% by weight are preferably used.
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of (co) polymeric carboxylic acids, glue, gelatin, salts of ethercarboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, for. Degraded starch, aldehyde levels, etc. Also, polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and polyvinylpyrrolidone, for example, in amounts of from 0.1 to 5% by weight, based on the compositions, used.
  • the funds can optical brighteners such.
  • brighteners of the substituted diphenylstyrene type may be present, e.g.
  • UV absorbers can also be used. These are compounds with pronounced ultraviolet radiation absorptivity which contribute to improving the light fastness of dyes and pigments as well as textile fibers as light stabilizers (UV stabilizers) and also protect the wearer's skin from textile exposure to UV radiation.
  • the compounds which are active by radiationless deactivation are derivatives of benzophenone whose substituents, such as hydroxyl and / or alkoxy groups, are usually in the 2- and / or 4-position.
  • UV absorbers absorb UV-A and UV-B radiation and optionally UV-C radiation and radiate back with wavelengths of blue light, so that they additionally have the effect of an optical brightener.
  • Preferred UV absorbers are also those in the European patent applications EP-A-0 374 751 .
  • UV absorbers such as triazine derivatives, eg. B. hydroxyaryl-1,3,5-triazine, sulfonated 1,3,5-triazine, o-hydroxyphenylbenzotriazole and 2-aryl-2H-benzotriazole and bis (anilinotriazinylamino) stilbene disulfonic acid and derivatives thereof.
  • UV absorbers it is also possible to use pigments which absorb ultraviolet radiation, such as titanium dioxide.
  • compositions may contain other conventional thickeners and anti-settling agents and viscosity regulators such as polyacrylates, polycarboxylic acids, polysaccharides and their derivatives, polyurethanes, polyvinylpyrrolidones, castor oil derivatives, polyamine derivatives such as quaternized and / or ethoxylated hexamethylenediamines and any mixtures thereof.
  • Preferred agents have a viscosity of less than 10,000 mPa.s when measured with a Brookfield viscometer at a temperature of 20 ° C and a shear rate of 50 min -1 .
  • compositions may contain other typical detergent and cleaner components such as perfumes and / or dyes, preference being given to those dyes which have no or negligible coloring action on the textiles to be washed.
  • Preferred quantitative ranges of the totality of the dyes used are less than 1% by weight, preferably less than 0.1% by weight, based on the agent.
  • the agents can also white pigments such.
  • Preferred agents have densities of 0.5 to 2.0 g / cm 3 , in particular 0.7 to 1.5 g / cm 3 , on.
  • the density difference between the coated peroxycarboxylic acid particles and the liquid phase of the composition is preferably not more than 10% of the density of either, and in particular is so low that the coated peroxycarboxylic acid particles and preferably also, if appropriate, other suspended solids particles in the liquid phase in the liquid phase, which may optionally be facilitated by the use of a thickening agent mentioned above.
  • this dispersion was dried in a Buchi spray dryer (Type 190). With a spray flow of 700 liters per hour of air, a stage 6 output, a stage 20 aspirator output and inlet and outlet temperatures of 101 ° C and 57 ° C, respectively, a fine white powder was obtained. The yield was 13.2 g and thus corresponded to 88% of the theoretical value. The particle size of the product was 5 to 30 microns, it showed few agglomerates. The residual moisture was less than 4%.
  • the exact active content of the powder was determined by elemental analysis (nitrogen value) and was 69%.
  • the quality of the product was determined by the active oxygen content ("AO" via titration determination) after different times.
  • the active oxygen loss was 17% after 2 days.
  • this dispersion was dried in a Buchi spray dryer (Type 190). With a spray flow of 700 liters per hour of air, a stage 6 output, a stage 20 aspirator output and inlet and outlet temperatures of 101 ° C and 57 ° C, respectively, a fine white powder was obtained. The yield was 12.8 g and corresponds to 85% of the theoretical value.
  • the exact active content of the powder was determined by elemental analysis (nitrogen value) and was 55% here.
  • the quality of the product was determined by the active oxygen content ("AO" via titration determination) after different times.
  • the active oxygen loss was 14% after 2 days.
  • this dispersion was dried in a Buchi spray dryer (Type 190). With a spray flow of 700 liters per hour of air, a stage 6 delivery, a stage 20 aspirator performance and inlet and outlet temperatures of 107 ° C and 53 ° C, respectively, a fine white powder was obtained. The yield was 8.3 g and thus corresponded to 55% of the theoretical value.
  • the exact active content of the powder was determined by elemental analysis (nitrogen value) and was 70% here.
  • the quality of the product was determined by the active oxygen content ("AO" via titration determination) after different times.
  • the active oxygen loss was 19% after 2 days.
  • this dispersion was dried in a Buchi spray dryer (Type 190). With a spray flow of 700 liters per hour of air, a stage 6 output, a stage 20 aspirator output and input / output
  • the exact active content of the powder was determined by elemental analysis (nitrogen value) and was 55% here.
  • the quality of the product was determined by the active oxygen content ("AO" via titration determination) after different times.
  • the active oxygen loss was 15% after 2 days.
  • this dispersion was dried in a Buchi spray dryer (Type 190). With a spray flow of 800 liters per hour of air, a stage 8 delivery, a stage 20 aspirator performance, and inlet and outlet temperatures of 86 ° C and 45 ° C, respectively, a fine white powder was obtained. The yield was 7.0 g and thus corresponded to 47% of the theoretical value.
  • the particle size of the product was 20-150 ⁇ m, it showed agglomerates.
  • the residual moisture was 1.3%.
  • the exact active content of the powder was determined by elemental analysis (nitrogen value) and was 86% here.
  • the quality of the product was determined by the active oxygen content ("AO" via titration determination) after different times.
  • the active oxygen loss was 12% after 2 days and 15% after 42 days.
  • this dispersion was dried in a Buchi spray dryer (Type 190). With a spray flow of 800 liters per hour of air, a stage 8 delivery, a stage 20 aspirator performance, and inlet and outlet temperatures of 86 ° C and 45 ° C, respectively, a fine white powder was obtained. The yield was 4, 1 g and thus corresponded to 27% of the theoretical value.
  • the particle size of the product was 5-25 ⁇ m, it showed agglomerates.
  • the residual moisture was 2.5%.
  • the exact active content of the powder was determined by elemental analysis (nitrogen value) and was 86% here.
  • the quality of the product was determined by the active oxygen content ("AO" via titration determination) after different times.
  • the active oxygen loss was 6% after 2 days and 17% after 42 days.
  • this dispersion was dried in a Buchi spray dryer (Type 190). With a spray flow of 800 liters per hour of air, a stage 7 output, a stage 20 aspirator output, and inlet and outlet temperatures of 91 ° C and 51 ° C, respectively, a fine white powder was obtained.
  • the particle size of the product was 2-25 ⁇ m, it showed agglomerates.
  • the exact active content of the powder was determined by elemental analysis (nitrogen value) and was 55% here.
  • the quality of the product was determined by the active oxygen content ("AO" via titration determination) after different times.
  • the active oxygen loss was 21% after 2 days and 60% after 42 days.
  • this dispersion was dried in a Buchi spray dryer (Type 190). With a spray flow of 800 liters per hour of air, a stage 7 output, a stage 20 aspirator performance, and inlet and outlet temperatures of 89 ° C and 47 ° C, respectively, a fine white powder was obtained.
  • the particle size of the product was 2-30 ⁇ m, it showed agglomerates.
  • the residual moisture was 2.5%.
  • the exact active content of the powder was determined by elemental analysis (nitrogen value) and was 58%.
  • the quality of the product was determined by the active oxygen content ("AO" via titration determination) after different times.
  • the active oxygen loss was 18% after 2 days and 21% after 42 days.

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Claims (11)

  1. Particule d'agent de blanchiment enrobée constituée par une partie centrale contenant une substance active d'agent de blanchiment et par un enrobage constitué par une matière soluble dans l'eau, entourant cette partie centrale au moins en partie, caractérisé en ce que la partie centrale contient de l'acide peroxocarboxylique et la matière d'enrobage contient de l'alcool polyvinylique et en outre un acide, l'acide peroxocarboxylique représentant l'acide 4-phtalimidoperoxobutanoïque, l'acide 5-phtalimidoperoxopentanoïque, l'acide 6-phtalimidoperoxohexanoïque, l'acide 7-phtalimidoperoxoheptanoïque ou un mélange desdits acides.
  2. Particule selon la revendication 1, caractérisée en ce que, dans la matière d'enrobage, le rapport pondéral de l'alcool polyvinylique à l'acide se situe dans la plage de 1000 : 1 à 1 : 2.
  3. Particule selon la revendication 1 ou 2, caractérisée en ce que, dans la matière d'enrobage, le rapport pondéral de l'alcool polyvinylique à l'acide se situe dans la plage de 500 : 1 à 1 : 1.
  4. Particule selon l'une quelconque des revendications 1 à 3, caractérisée en ce que la partie centrale contient, en plus de l'acide peroxocarboxylique, une matière de support qui est identique à la matière d'enrobage.
  5. Particule selon l'une quelconque des revendications 1 à 4, caractérisée en ce que la fraction de la matière d'enrobage ou la fraction de la somme de la matière d'enrobage et de la matière de support représente de 5 % en poids à 50 % en poids de la particule enrobée.
  6. Particule selon l'une quelconque des revendications 1 à 5, caractérisée en ce que la teneur en acide peroxocarboxylique s'élève de 20 % en poids à 90 % en poids, en particulier de 40 % en poids à 80 % en poids.
  7. Procédé pour la fabrication de particules d'agents de blanchiment enrobées constituées par une partie centrale contenant une substance active d'agent de blanchiment et par un enrobage constitué par une matière soluble dans l'eau, entourant cette partie centrale au moins en partie, par incorporation d'un acide peroxocarboxylique particulaire, qui représente l'acide 4-phtalimidoperoxobutanoïque, l'acide 5-phtalimidoperoxopentanoïque, l'acide 6-phtalimidoperoxohexanoïque, l'acide 7-phtalimidoperoxoheptanoïque ou un mélange desdits acides, dans un lit fluidisé, par aspersion d'une solution aqueuse qui contient l'alcool polyvinylique et en outre un acide, et par séchage.
  8. Procédé selon la revendication 7, caractérisé en ce que la température de la particule d'agents de blanchiment lors de l'aspersion de la solution aqueuse et lors du séchage ne dépasse pas 50 °C, en particulier 35 °C.
  9. Procédé pour la fabrication de particules d'agents de blanchiment enrobées constituées par une partie centrale contenant une substance active d'agent de blanchiment et par un enrobage constitué par une matière soluble dans l'eau, entourant cette partie centrale au moins en partie, par séchage par pulvérisation d'une préparation aqueuse qui contient de l'acide peroxocarboxylique, de l'alcool polyvinylique et en outre un acide, l'acide peroxocarboxylique représentant l'acide 4-phtalimidoperoxobutanoïque, l'acide 5-phtalimidoperoxopentanoïque, l'acide 6-phtalimidoperoxohexanoïque, l'acide 7-phtalimidoperoxoheptanoïque ou un mélange desdits acides,
  10. Particule selon l'une quelconque des revendications 1 à 6 ou procédé selon l'une quelconque des revendications 7 à 9, caractérisé en ce que l'acide peroxocarboxylique représente l'acide 6-phtalimidoperoxohexanoïque.
  11. Utilisation de particules selon l'une quelconque des revendications 1 à 6 ou 10 ou bien que l'on obtient conformément au procédé selon l'une quelconque des revendications 7 à 10, pour la fabrication d'agents de lavage ou de nettoyage.
EP05728973.8A 2004-04-15 2005-04-08 Particules d'agent de blanchiment a enrobage soluble dans l'eau Not-in-force EP1735422B2 (fr)

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DE102004018790A DE102004018790B4 (de) 2004-04-15 2004-04-15 Wasserlöslich umhüllte Bleichmittelteilchen
PCT/EP2005/003699 WO2005100525A1 (fr) 2004-04-15 2005-04-08 Particules d'agent de blanchiment a enrobage soluble dans l'eau

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EP1735422A1 EP1735422A1 (fr) 2006-12-27
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US (1) US7897556B2 (fr)
EP (1) EP1735422B2 (fr)
JP (1) JP4920576B2 (fr)
AT (1) ATE405629T1 (fr)
DE (2) DE102004018790B4 (fr)
ES (1) ES2309737T5 (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9796954B2 (en) 2010-11-19 2017-10-24 Reckitt Benckiser Finish B.V. Dyed coated bleach materials
US10240113B2 (en) 2010-11-19 2019-03-26 Reckitt Benckiser Finish B.V. Dyed coated bleach materials

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DE102004018790A1 (de) 2005-11-10
EP1735422A1 (fr) 2006-12-27
WO2005100525A1 (fr) 2005-10-27
ATE405629T1 (de) 2008-09-15
US7897556B2 (en) 2011-03-01
ES2309737T5 (es) 2014-11-19
ES2309737T3 (es) 2008-12-16
EP1735422B2 (fr) 2014-10-15
JP2007532727A (ja) 2007-11-15
JP4920576B2 (ja) 2012-04-18
DE102004018790B4 (de) 2010-05-06
US20070093402A1 (en) 2007-04-26
DE502005005113D1 (de) 2008-10-02

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