EP1275709B1 - Procédé de préparation de granulés d'activateur de blanchiment - Google Patents

Procédé de préparation de granulés d'activateur de blanchiment Download PDF

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Publication number
EP1275709B1
EP1275709B1 EP02015331A EP02015331A EP1275709B1 EP 1275709 B1 EP1275709 B1 EP 1275709B1 EP 02015331 A EP02015331 A EP 02015331A EP 02015331 A EP02015331 A EP 02015331A EP 1275709 B1 EP1275709 B1 EP 1275709B1
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EP
European Patent Office
Prior art keywords
spheronizer
bleach activator
granules
extrudates
weight
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
EP02015331A
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German (de)
English (en)
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EP1275709A1 (fr
Inventor
Georg Dr. Borschers
Torsten Dr. Pilz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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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
    • C11D3/3907—Organic compounds
    • C11D3/3915—Sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds

Definitions

  • the present invention relates to a process for the production of cylindrical to spherical extrudates containing bleach activators, with defined particle sizes and narrow particle size distribution, which exhibit a low abrasion behavior and a good flow behavior.
  • EP 486 592 describes the production of extruded moldings in which a solid and free-flowing premix is extruded using a plasticizer and / or lubricant at relatively high pressures of between about 25 and 200 bar.
  • the strand has such a consistency that it can be cut directly onto a predetermined granule dimension after leaving the hole shape by means of a cutting device.
  • the plasticizers and / or lubricants mentioned are in particular aqueous anionic surfactant pastes, aqueous polymer solutions and / or nonionic surfactants which are liquid at room temperature.
  • the extruded shaped articles which can be produced in this way generally have a size of up to 2 cm, preferably up to 0.8 cm, the length-diameter ratio advantageously being between 1: 1 and 3: 1.
  • bleach activators are advantageously formulated in the form of cylindrical extrudates in order to ensure compatibility with other detergent constituents and a sufficient storage stability. It is assumed that the highly reactive bleach activator is predominantly embedded in the interior of the cylindrical granules and the surface predominantly consists of binding materials and plasticizer. To avoid segregation of the different particles in the detergent formulation during transport and storage, the particle diameter should be between 0.2 mm and 2 mm, preferably between 0.5 mm and 0.8 mm, the particle length is in the range of 0.5 mm to 3.5 mm, ideally between 0.9 mm and 2.5 mm.
  • the object of the invention was to produce cylindrical to spherical extrudates containing bleach activators for use in detergents or cleaners, which have a very narrow particle size distribution and at the same time a low Abriebtendenz, low dust formation, a favorable flow behavior, and a good dissolving behavior show during the washing and cleaning process.
  • the invention relates to a process for the preparation of bleach activator granules, characterized in that a mixture of bleach activator, anionic or nonionic surfactant and polyalkylene glycol at temperatures of 40 to 90 ° C, preferably 60 to 80 ° C and a pressure of 10 to Extruded at 30 bar and granulated the extrudates obtained at a temperature of 60 to 90 ° C, preferably 60 to 80 ° C on a Rondier.
  • Suitable bleach activators are, for example, N, N, N ', N'-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulphonate (SBOBS), sodium trimethylhexanoyloxybenzenesulphonate (STHOBS), tetraacetylglycoluril (TAGU), Tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxime (ADMG), 1-phenyl-3-acetylhydantoin (PAH), nonanoylcaprolactam phenylsulfonate ester (APES), nitrilotriacetate (NTA), preferably the sodium salt of nonanoyloxybenzenesulphonate (NOBS), the sodium salt of 3,5,5-trimethylhexanoyloxyphenylsulfon
  • Preferred anionic surfactants are alkali salts, ammonium salts, amine salts and salts of amino alcohols of the following compounds: alkyl sulfates, alkyl ether sulfates, alkyl amide sulfates and ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkyl sulfonates, alkyl amide sulfonates, alkylaryl sulfonates, alpha-olefin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl amide sulfosuccinates, alkyl sulfoacetates, Alkyl polyglycerol carboxylates, alkyl phosphates, alkyl ether phosphates, alkyl sarcosinates, alkyl polypeptides, alkyl amid
  • the alkyl radical of all these compounds normally contains 8-32, preferably 8-22 C atoms.
  • Particularly preferred are linear straight-chain alkylbenzenesulfonates, in particular having a C 8 -C 20 -, more preferably having a C 11-13 -alkyl group.
  • Preferred nonionic surfactants are polyethoxylated, polypropoxylated or polyglycerolated ethers of fatty alcohols, polyethoxylated, polypropoxylated and polyglycerinated fatty acid esters, polyethoxylated esters of fatty acids and of sorbitol, polyethoxylated or polyglycerolated fatty amides.
  • Suitable polyalkylene glycols are polyethylene glycols, 1,2-polypropylene glycols and also modified polyethylene glycols and polypropylene glycols.
  • the modified polyalkylene glycols include in particular sulfates and / or disulfates of polyethylene glycols or polypropylene glycols having a molecular weight between 600 and 12000 and in particular between 1000 and 4000.
  • Another group consists of mono- and / or disuccinates of polyalkylene glycols, which in turn have molecular weights between 600 and 6000, preferably between 1000 and 4000.
  • ethoxylated derivatives such as trimethylolpropane having 5 to 30 EO.
  • the polyethylene glycols preferably used may be a linear or have branched structure, in particular linear polyethylene glycols are preferred.
  • Particularly preferred polyethylene glycols include those having molecular weights between 2,000 and 12,000, advantageously about 4,000, wherein polyethylene glycols having molecular weights below 3500 and above 5000, especially in combination with polyethylene glycols having a molecular weight of 4000, can be used and advantageously such combinations are more than 50 wt .-%, based on the total amount of polyethylene glycols, polyethylene glycols having a molecular weight between 3500 and 5000 have.
  • the modified polyethylene glycols also include one or more end-capped polyethylene glycols, the end groups preferably being C 1 -C 12 -alkyl chains, preferably C 1 -C 6 , which may be linear or branched. Unilaterally end-capped polyethylene glycol derivatives may also correspond to the formula Cx (EO) y (PO) z, where Cx may be an alkyl chain having a C chain length of 1 to 20, y 50 to 500 and z 0 to 20. Likewise suitable are low molecular weight polyvinylpyrrolidones and derivatives of these having molecular weights of up to a maximum of 30,000. Preferred here are molecular weight ranges between 3,000 and 30,000. Polyvinyl alcohols are preferably used in combination with polyethylene glycols.
  • the abrasion resistance of the bleach activator granules may additionally one or more components added, which are liquid at room temperature or present under the processing conditions as a melt, for example linear or branched fatty acids, especially nonanoic acid or ethoxylated fatty acids 2 to 100 EO.
  • the mixture of all components described above may additionally contain small amounts of a solvent, preferably less than 15 wt .-%, preferably less than 10 wt .-%, more preferably less than 7 wt .-%.
  • a solvent preferably less than 15 wt .-%, preferably less than 10 wt .-%, more preferably less than 7 wt .-%.
  • Preferred solvent is water.
  • additives are substances that increase the pH during storage and Affect application. These include organic carboxylic acids or their salts, such as citric acid in anhydrous or hydrated form, glycolic acid, succinic acid, maleic acid or lactic acid.
  • additives are possible which influence the bleaching ability, such as complexing agents and transition metal complexes, for example iron, cobalt or manganese-containing metal complexes as described in EP-A-0 458 397 and EP-A-0 458 398.
  • Particularly advantageous embodiments of the invention contain as bleach activator the sodium salt of nonanoyloxyphenylsulphonate (NOBS), as solubilizer linear straight-chain alkylbenzenesulphonates, in particular with a C 8 -C 20 -, more preferably with a C 11-13 -alkyl group (LAS), as well as nonanoic acid and polyethylene glycol ( PEG) 4000 as consistency regulator and plasticizer, wherein the proportion of NOBS 70 wt .-% to 90 wt .-%, preferably 80 wt .-% to 87 wt .-%, particularly preferably 81 wt .-% to 85 wt.
  • NOBS nonanoyloxyphenylsulphonate
  • LAS solubilizer linear straight-chain alkylbenzenesulphonates
  • PEG polyethylene glycol
  • LAS 2 wt .-% to 10 wt .-% preferably 3 wt .-% to 5 wt .-%, particularly preferably 3.7 wt .-% to 4.5 wt .-%, of nonanoic acid 0 , 1 wt .-% to 6 wt .-%, preferably 1 wt .-% to 4 wt .-%, particularly preferably 2.5 wt .-% to 3.5 wt .-%, of PEG 4000 1 wt. -% to 15 wt .-%, preferably 5 wt .-% to 10 wt .-%, particularly preferably 7 wt .-% to 8 wt .-% is.
  • bleach activator for example nonanoyloxyphenylsulphonate (NOBS) and anionic or nonionic surfactant, for example alkylbenzenesulphonate (LAS) are mixed in powder form, plasticizers, for example nonanoic acid and PEG 4000 at 50 to 70 ° C, preferably 60 to 65 ° C and registered at a temperature in the range from 60 to 70 ° C and a pressure of 14 bar to 22 bar extruded strand-shaped.
  • NOBS nonanoyloxyphenylsulphonate
  • LAS alkylbenzenesulphonate
  • the mixture is fed continuously to a 1-shaft extruder, 2-shaft extruder or 2-screw extruder with concurrent or counter-rotating screw guide whose housing and its extruder granulating head to be heated to the predetermined extrusion temperature can.
  • the mixture is compacted under pressure, plasticized, extruded in the form of strands through the hole die plate in the extruder head, optionally with fine-grained anti-caking agent, For example, TiO2, silica, zeolite, dusted own dust, crushed into coarse straw pieces and transferred to a to 40 to 90 ° C, preferably 60 to 80 ° C, especially 60 to 65 ° C heated Rondierer.
  • fine-grained anti-caking agent For example, TiO2, silica, zeolite, dusted own dust, crushed into coarse straw pieces and transferred to a to 40 to 90 ° C, preferably 60 to 80 ° C, especially 60 to 65 ° C heated Rondierer.
  • the subsequent Rondier compiler cylindrical to spherical granules are obtained with defined particle sizes and very narrow particle size distribution, wherein the particle diameter between 0.2 mm and 2 mm, preferably between 0.5 mm and 0.8 mm, the particle length in the range of 0.5 mm to 3.5 mm, ideally between 0.9 mm and 2.5 mm.
  • the extrudates are placed directly on the Rondierer or possibly coarsely pre-crushed.
  • the molding process according to the invention is carried out continuously in cascade operation, but also a batch-wise work is possible.
  • the size and shape of the particles can be influenced and brought about in the Rondiermaschine by several parameters.
  • the forming process is determined by the filling quantity, the temperature of the mixture, the residence time of the mixture in the Rondier, by the rotation speed of the Rondierusion, as well as by the plastic deformability of the mixture.
  • the residence time of the mixture in the ringer depends not only on the plasticity of the filling amount and is preferably 10 sec. To 120 sec., Particularly preferably 20 sec. To 60 sec., The peripheral speed 10 m / sec. to 30 m / sec., preferably 12 m / sec. up to 20 m / sec.
  • the temperature in the ringer is controlled by supplying air or gas (N2), preferably via the cleavage device.
  • the temperature of the air or gas streams is 50 to 120 ° C, preferably 60 to 90 ° C, so that depending on the design of the Rondierers the desired working temperature can be maintained in Rondierer.
  • the cylindrically shaped and rounded Particles in a downstream apparatus preferably cooled in a fluid bed cooler in cold air or gas stream to temperatures below 40 ° C in order to avoid sticking of the granules.
  • the granules thus obtained are characterized by a favorable flow behavior, low dust content, high abrasion resistance.
  • the bulk density is in the range 300 g / l to 2000 g / l, preferably in the range 400 g / l to 1500 g / l and particularly preferably in the range of 500-800 g / l.
  • the resulting granules according to the invention are suitable directly for use in detergents and cleaners. If necessary, they can be provided with a coating cover.
  • additives are substances which react with the peroxycarboxylic acid released from the activator in the wash liquor to form reactive intermediates, such as dioxiranes or oxaziridines, and in this way can increase the reactivity.
  • Corresponding compounds are ketones and sulfonimines according to US-A-3 822 114 and EP-A-0 446 982.
  • the amount of the additive depends in particular on its nature.
  • acidifying additives and organic catalysts to increase the performance of the peracid in amounts of 0 to 20 wt .-%, in particular in amounts of 1 to 10 wt .-%, based on the total weight, added, metal complexes in concentrations in the ppm range.
  • the resulting granules are characterized by a very good abrasion resistance and storage stability in powdered detergent, cleaning and disinfectant formulations. They are ideal for use in heavy-duty detergents, stain salts, machine dishwashing detergents, powdered all-purpose cleaners and denture cleaners.
  • the granules of the invention are usually used in combination with a hydrogen peroxide source.
  • a hydrogen peroxide source examples include perborate monohydrate, perborate tetrahydrate, percarbonates and Hydrogen peroxide adducts on urea or amine oxides.
  • the formulation according to the prior art may have other detergent ingredients, such as organic and inorganic builders and co-builders, surfactants, enzymes, brighteners and perfume.
  • Granule diameter d 0.7 mm
  • Granule length I 1.4 mm
  • Granule diameter d 0.7 mm
  • Granule length I 1.4 mm
  • Granule diameter d 0.7 mm
  • Granule length I 1.4 mm
  • Nonanoylcaprolactamphenylsulfonatester APES
  • 10.7 g of sodium citrate and 7.5 g of water are in the ploughshare mixer (manufacturer Lödige) at room temperature at room speed homogeneously blended at 120 per minute with cutter head engaged within a period of 150 seconds, transferred to a single-screw dome extruder (manufactured by Fitzpatrick) with a bore diameter of 0.7 mm in the punching die, and an extruder screw speed of 45 per minute, throughput of 199 g / min, extruded.
  • APES Nonanoylcaprolactamphenylsulfonatester
  • the extrudates at room temperature in a batch-Rondierer (manufacturer Schlüter) with a diameter of 0.3 m at a speed of 1000 per minute, a peripheral speed of 22.3 m / sec and a residence time of 40 seconds to the previously specified particle shape brought.
  • a batch-Rondierer manufactured by the manufacturer Schlüter
  • the cylindrically shaped and rounded particles are dried in a downstream apparatus, preferably in a fluid bed dryer and cooled

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (12)

  1. Procédé de production de granulés d'activateur de blanchiment, caractérisé en ce que l'on extrude un mélange composé d'un activateur de blanchiment, d'un tensio-actif anionique ou non ionique et de polyalkylèneglycol à des températures de 40°C à 90°C, de préférence de 60°C à 80°C et sous une pression de 10 à 30 bars, et en ce que l'on transforme les extrudats obtenus en granulés à une température de 60°C à 90°C, de préférence de 60°C à 80°C dans une machine de sphéronisation.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise en outre des acides gras linéaires ou ramifiés ou des acides gras éthoxylés avec 2 à 100 OE.
  3. Procédé selon la revendication 1, caractérisé en ce que l'on met en oeuvre, en tant que tensio-actif anionique, un alkylarylsulfonate.
  4. Procédé selon la revendication 1, caractérisé en ce que l'on met en oeuvre, en tant que polyalkylèneglycol, le polyéthylèneglycol.
  5. Procédé selon la revendication 1, caractérisé en ce que l'on met en oeuvre, en tant qu'activateur de blanchiment, le nonanoyloxybenzènesulfonate de sodium.
  6. Procédé selon la revendication 1, caractérisé en ce que l'on fabrique des granulés composés de 70% à 90% en poids de nonanoyloxybenzènesulfonate de sodium, de 2% à 10% en poids d'alkylbenzènesulfonate, de 0,1% à 6% en poids d'acide nonanoïque et de 1% à 15% en poids de polyéthylèneglycol 4000.
  7. Procédé selon la revendication 1, caractérisé en ce que les extrudats sont déposés directement dans la machine de sphéronisation ou sont grossièrement préconcassés.
  8. Procédé selon la revendication 1, caractérisé en ce que l'on régule la température au moyen d'un courant d'air ou de gaz dans la machine de sphéronisation.
  9. Procédé selon la revendication 1, caractérisé en ce que l'on travaille à une vitesse périphérique dans la machine de sphéronisation de 10 à 30 m/s.
  10. Procédé selon la revendication 1, caractérisé en ce que l'on travaille avec un temps de maintien de 10 à 120 s dans la machine de sphéronisation.
  11. Procédé selon la revendication 1, caractérisé en ce que l'on réalise le procédé de sphéronisation en discontinu ou en continu selon un mode en cascade.
  12. Procédé selon la revendication 1, caractérisé en ce que l'on saupoudre les extrudats d'un agent anti-agglomérant.
EP02015331A 2001-07-14 2002-07-10 Procédé de préparation de granulés d'activateur de blanchiment Expired - Lifetime EP1275709B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10134364 2001-07-14
DE10134364A DE10134364A1 (de) 2001-07-14 2001-07-14 Verfahren zur Herstellung von Bleichaktivator-Granulaten

Publications (2)

Publication Number Publication Date
EP1275709A1 EP1275709A1 (fr) 2003-01-15
EP1275709B1 true EP1275709B1 (fr) 2006-06-07

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EP02015331A Expired - Lifetime EP1275709B1 (fr) 2001-07-14 2002-07-10 Procédé de préparation de granulés d'activateur de blanchiment

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US (1) US6897192B2 (fr)
EP (1) EP1275709B1 (fr)
JP (1) JP2003129100A (fr)
DE (2) DE10134364A1 (fr)
ES (1) ES2266354T3 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10136805A1 (de) 2001-07-25 2003-02-13 Clariant Gmbh Verfahren zur Herstellung von Bleichaktivator-Granulaten
DE10334046A1 (de) * 2003-07-25 2005-02-10 Clariant Gmbh Verfahren zur Herstellung von granulierten Acyloxybenzolsulfonaten oder Acyloxybenzolcarbonsäuren und deren Salze
US20140243252A1 (en) * 2013-02-28 2014-08-28 Futurefuel Chemical Company Laundry detergent formulation

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Publication number Priority date Publication date Assignee Title
GB1368400A (en) * 1971-08-05 1974-09-25 Procter & Gamble Bleaching process and compositions therefor
US4126573A (en) * 1976-08-27 1978-11-21 The Procter & Gamble Company Peroxyacid bleach compositions having increased solubility
US4126673A (en) * 1977-05-13 1978-11-21 Cromwell Metals, Inc. Method for processing dross
US4486327A (en) * 1983-12-22 1984-12-04 The Procter & Gamble Company Bodies containing stabilized bleach activators
DE59006160D1 (de) 1989-08-09 1994-07-21 Henkel Kgaa Herstellung verdichteter granulate für waschmittel.
US5047163A (en) 1990-03-16 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with sulfonimines
DE69125309T2 (de) 1990-05-21 1997-07-03 Unilever Nv Bleichmittelaktivierung
US5458801A (en) * 1991-09-27 1995-10-17 Kao Corporation Process for producing granular bleach activator composition and granular bleach activator composition
DE4143016A1 (de) * 1991-12-24 1993-07-01 Henkel Kgaa Bleichaktivatoren in granulatform (ii)
US5206207A (en) * 1992-03-18 1993-04-27 Westvaco Corporation Preparation for high activity high density carbon
EP0880581A4 (fr) * 1996-01-29 2001-10-10 Procter & Gamble Procede de fabrication d'activateurs de blanchiment particulaires
US5843879A (en) * 1996-02-06 1998-12-01 Lion Corporation Bleaching activator granulate
CA2311378C (fr) 1997-11-20 2004-04-20 The Procter & Gamble Company Composition detergente contenant des particules activatrices de blanchiment a taille optimale
DE19844523A1 (de) * 1998-09-29 2000-03-30 Henkel Kgaa Granulationsverfahren
AR027014A1 (es) * 1999-12-20 2003-03-12 Procter & Gamble Particula de acitvador de blanqueo, composicion detergente que la comrende y metodo de incremento de la hidroligancia promedio de una molecula de sal
DE10136805A1 (de) * 2001-07-25 2003-02-13 Clariant Gmbh Verfahren zur Herstellung von Bleichaktivator-Granulaten

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US20030040452A1 (en) 2003-02-27
JP2003129100A (ja) 2003-05-08
ES2266354T3 (es) 2007-03-01
DE10134364A1 (de) 2003-01-23
DE50207069D1 (de) 2006-07-20
EP1275709A1 (fr) 2003-01-15
US6897192B2 (en) 2005-05-24

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