EP0340847A2 - Procédé de préparation de corps contenant un composé d'un peroxyacide et compositions comprenant les dits corps - Google Patents

Procédé de préparation de corps contenant un composé d'un peroxyacide et compositions comprenant les dits corps Download PDF

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Publication number
EP0340847A2
EP0340847A2 EP19890201076 EP89201076A EP0340847A2 EP 0340847 A2 EP0340847 A2 EP 0340847A2 EP 19890201076 EP19890201076 EP 19890201076 EP 89201076 A EP89201076 A EP 89201076A EP 0340847 A2 EP0340847 A2 EP 0340847A2
Authority
EP
European Patent Office
Prior art keywords
process according
forming
temperature
acid
hydration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19890201076
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German (de)
English (en)
Other versions
EP0340847A3 (fr
Inventor
Timothy David Finch
William John Iley
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0340847A2 publication Critical patent/EP0340847A2/fr
Publication of EP0340847A3 publication Critical patent/EP0340847A3/fr
Withdrawn legal-status Critical Current

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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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C11D3/062—Special methods concerning phosphates
    • 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

Definitions

  • This invention relates to a process for preparing dry particulate bodies containing a solid organic peroxyacid compound, and to compositions comprising said bodies.
  • organic peroxyacids as a class are very effective bleaches, and the use of organic peroxyacid compounds as the bleach system in detergent compositions has been proposed in the art.
  • the solid peroxyacids are of particular importance as they can be handled more easily than the liquid forms for use as a bleach component in bleaching and detergent compositions. Even so, because of their high reactivity, the greatest caution should be exercised in handling and working with peroxyacids, and, especially in the dry solid or highly concentrated state, organic peroxyacids can be very hazardous.
  • organic peroxyacids are therefore usually provided in the form of less concentrated, granular compositions or agglomerates, with or without a protective coating.
  • DPDA diperoxydodecanedioic acid
  • Wet-mixture peroxyacid granulation has the advantage of being able to handle high moisture content systems. It has the further advantage of being easy to scale up without involvement of any particularly hazardous operations.
  • the present invention provides an improvement of the wet-mixture peroxyacid granulation process and produces peroxyacid-containing bodies of excellent quality with high grades of homogeneity, mechanical and chemical stability and especially attrition resistance combined with good dispersibility.
  • the process of the invention comprises the steps of
  • an important feature of the process is the incorporation and intimate mixing of a film-forming material with the water-wet mixture of step (A).
  • This mix has a pH of below 7.
  • the water-wet mixture of (A) including the film-forming material should have an acid pH of below 7, preferably from 3 to 6.5.
  • This pH can be adjusted by using an acidic, film-forming material and/or by adding a solid, pH-regulating, acid substance, e.g. citric acid, succinic acid, adipic acid, glutaric acid etc.
  • the film-forming material should preferably be non-oxidizable.
  • suitable film-forming materials are, for example, the non-oxidizable polymers, which can be in the acid form or in the form of their alkali metal salts.
  • Acidic polymers usable in this invention can be any non-cellulosic homo- or copolymeric mono- and polycarboxylic acids having an average molecular weight of from 500 to about 1,000,000, preferably from 2,000 to 250,000, more preferably from 10,000 to 50,000.
  • Suitable polymers include those derived from acrylic acid, methacrylic acid, maleic acid, citraconic acid, aconitic acid, fumaric acid, mesaconic acid, phenyl maleic acid, benzyl maleic acid, itaconic acid, methylene malonic acid, alpha-Ci-C 4 . alkyl acrylic acid, alpha-hydroxy acrylic acid and acetalcarboxylic acid monomers, or from the anhydrides of the above monomers where these exist.
  • the polymers can be homopolymers of the above mono- or polycarboxylic monomers; or copolymers of two or more of the above mono- or polycarboxyl monomers; or copolymers of one or more of the above carboxyl monomers with an unsaturated polymerizable monomer other than the specified mono- and polycarboxyl monomers; or modified homo- or copolymers of the above classes having, for example, a non-oxidizable phosphinic acid or sulphinic acid group.
  • Preferred acidic, polymeric materials are the polyacrylic acids, phosphinate-modified polyacrylic acids, such as described in GB Patents 1,485,235 and 1,595,688 and EP-A-0182411; copolymers of maleic acid (anhydride) and acrylic or methacrylic acid; and acidic copolymers containing hydrophobic groups, such as copolymers based on polymethacrylic acid and polyacrylic acid esters in which the ratio of free carboxyl groups to ester groups is at least 1:1.
  • Copolymers of the latter group can be advantageously used for preparing peroxyacid-containing bodies for use in aqueous liquid bleaching compositions, where they could further reduce the solubility of the organic peroxyacid, and hence improve its storage stability.
  • non-acidic, film-forming polymers may also be used, so long as they are sufficiently resistant to oxidation; their selection can be routinely made without difficulty by the skilled artisan.
  • molecular weights are from 2,000 to 250,000, more preferably from 10,000 to 50,000.
  • Another suitable class of film-forming materials is that of the so-called glassy or amorphous phosphates having the general formula : wherein M is hydrogen, alkali metal, ammonium or a substituted ammonium group; Y has a value in the range of from 2 to 50; and the ratio x:y is from 0.7:1 to 1.7:1.
  • a representative example of a glassy phosphate is sodium hexametaphosphate. - (Na 2 O) 3 (P 2 O 5 ) 3 .
  • the amount of film-forming material which can be added for the purpose of the invention is such that it will give a material level in the final granule of about 0.5-10% by weight. Optimally, this should be within the range of about 2.5-6% by weight.
  • the peroxyacid compound usable in this invention should be solid at room temperature and preferably has a melting point of at least 50° C.
  • Such peroxyacid compounds are the organic peroxyacids and water-soluble salts thereof having the general formula: wherein R is an alkylene or substituted alkylene group containing 1 to 20 carbon atoms or an arylene group containing from 6 to 8 carbon atoms, and Y is hydrogen, halogen, alkyl, aryl or any group which provides an anionic moiety in aqueous solution.
  • Y groups can include, for example : wherein M is H or a water-soluble, salt-forming cation. They can contain either one, two or more peroxy groups and can be either aliphatic or aromatic.
  • the organic peroxyacid is aliphatic
  • the unsubstituted acid can have the general formula : wherein Y can be H, -CH s , -CH 2 CI, or and n can be an integer from 6 to 20.
  • Peroxydodecanoic acids, peroxytetradecanoic acids and peroxyhexadecanoic acids are preferred compounds of this type, particularly 1,12-diperoxydodecanedioic acid (DPDA), 1,14-diperoxytetradecanedioic acid and 1,16-diperoxy- hexadecanedioic acids.
  • DPDA 1,12-diperoxydodecanedioic acid
  • 1,14-diperoxytetradecanedioic acid 1,16-diperoxy- hexadecanedioic acids.
  • Examples of other suitable compounds of this type are diperoxyazelaic acid, diperoxyadipic acid and diperoxysebacic acid.
  • the unsubstituted acid can have the general formula : wherein Y is, for example, hydrogen, halogen, alkyl,
  • the percarboxy and Y groupings can be in any relative position around the aromatic ring.
  • the ring and/or Y group (if alkyl) can contain any non-interfering substituents, such as halogen or sulphonate groups.
  • suitable aromatic peroxyacids and salts thereof include monoperoxyphthalic acid, diperox- yterephthalic acid, 4-chlorodiperoxyphthalic acid, diperoxyisophthalic acid, peroxy benzoic acids and ring- substituted peroxy benzoic acids, such as peroxy-alphanaphthoic acid.
  • a preferred aromatic peroxyacid is diperoxyisophthalic acid.
  • the hydratable material usable in the present invention will have a hydration temperature of up to 40. C, so as to allow working at relatively low temperatures, thereby minimizing peracid decomposition. It should also preferably be non-alkaline.
  • Hydration temperature is the transition temperature for dehydration of the hydrate to its anhydrous state.
  • a preferred hydratable material is sodium sulphate, which is neutral and has a hydration temperature to the decahydrate of about 32.4° C. (see International Critical Tables, Volume IV, published by McGraw Hill).
  • the convenient working temperatures are about 40° C in step (A) and from 10 to about 20 C in step (B).
  • Drying of the particles in step (C) should preferably be carried out under dynamic conditions, such as in a fluidized bed drier. Drying in a static bed, such as e.g. using a tray drier, is not recommended since the solid particles will tend to revert to a slurry or pasty mass, due to dehydration of the hydrates at the high drying temperature.
  • the granules are preferably dried to a state in which all hydratable material has been converted to its anhydrous form.
  • the amount of water in the water-wet mixture of step (A) is not critical and may amount to about 10-35% by weight.
  • the amount of hydratable material in the water-wet mixture is dependent upon the water content and should be such that it is sufficient to take up a substantial amount of the free water as water of hydration.
  • the process of the invention can be conveniently applied directly to 1,12-diperoxydodecanedioic acid (DPDA) suspensions as obtained from the usual process of manufacturing DPDA from the reaction of 1,12-dodecanedioic acid with hydrogen peroxide under the influence of sulphuric acid in an aqueous medium.
  • DPDA 1,12-diperoxydodecanedioic acid
  • Such usual preparation methods are described, among others, in US Patent 4,119,660, US Patent 4,314,949 and DE-A-2,930,546.
  • Such suspensions as supplied from manufacturers usually comprise from 25-35% DPDA, 50-70% water, and 5-15% sodium sulphate.
  • a convenient way of using these suspensions as the starting material is by heating the suspension to about 40 C and adding sufficient anhydrous sodium sulphate for binding the water upon hydration and thereafter adding the film-forming material, whilst ensuring that the slurry is well agitated. This is then followed by the cooling and shaping step (B) and subsequently the drying step (C), which can be further followed by screening to the desired particle size range, if necessary.
  • the resultant granules exhibit good stability in detergent bases.
  • a desirable particle size range for peroxyacid-containing bodies usable in detergent and bleaching compositions is between 150 ⁇ m and 2,000 u.m, particularly between 350 ⁇ m and 1700 ⁇ m.
  • particulate bodies can be obtained containing from about 15% to about 30% by weight of peroxyacid compound.
  • the process is suitably used for preparing particulate bodies containing from 17% to 25% by weight of peroxyacid, the balance being formed by one or more hydratable material(s), film-forming material and minor amounts of any optional ingredients as desired.
  • the peroxyacid-containing bodies (particles or granules) obtained by the process of the invention are extremely suitable for use as a bleach additive and for the incorporation in bleaching and/or detergent powder compositions.
  • detergent compositions comprising the peroxyacid-containing bodies as described herein are within the purview of the present invention.
  • Such detergent compositions will usually also contain surface-active materials, detergency builders and other known ingredients of such formulations.
  • the surface-active material may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof. Many suitable actives are commercially available and are fully described in literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
  • the total level of the surface-active material may range up to 50% by weight, preferably being from about 1% ⁇ to 40% by weight of the composition, most preferably 4% to 25%.
  • the detergent compositions of the invention will normally also contain a detergency builder.
  • Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ionexchange materials and 4) mixtures thereof.
  • Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its water-soluble salts; the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid; and polyacetal carboxylates as disclosed in U.S. patents 4,144,226 and 4,146,495.
  • alkali metal polyphosphates such as sodium tripolyphosphate
  • the alkali metal salts of carboxymethyloxy succinic acid ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid
  • polyacetal carboxylates as disclosed in U.S. patents 4,144,226 and 4,146
  • precipitating builder materials examples include sodium orthophosphate, sodium carbonate and long- chain fatty acid soaps.
  • Examples of calcium ion-exchanging builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives.
  • compositions of the invention may contain any one of the organic or inorganic builder materials, such as sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl malonate, carboxymethyloxy succinate and the water-insoluble crystalline or amorphous aluminosilicate builder materials, or mixtures thereof.
  • organic or inorganic builder materials such as sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl malonate, carboxymethyloxy succinate and the water-insoluble crystalline or amorphous aluminosilicate builder materials, or mixtures thereof.
  • These builder materials may be present at a level of, for example, from 5 to 80% by weight, preferably from 10 to 60% by weight.
  • the detergent compositions of the invention can contain any of the conventional additives - if not already included in the instant peroxyacid granules - in the amounts in which such materials are normally employed in fabric-washing detergent compositions.
  • these additives include lather boosters, such as alkanolamides, particularly the monoethanol amides derived from palm kernel fatty acids and coconut fatty acids, lather depressants, such as alkyl phosphates and silicones, anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers, peroxide stabilizers, such as ethylene diamine tetraacetic acid and preferably phosphonates, e.g.
  • ethylene diamine tetra-methylene phosphonic acid and diethylene triamine pentamethylene phosphonic acid or their salts fabric-softening agents, inorganic salts, such as sodium sulphate, and, usually present in very small amounts, fluorescent agents, perfumes, enzymes, such as proteases, cellulases, lipases and amylases, germicides and colourants.
  • Granules containing 1,12-diperoxydodecanedioic acid are prepared and processed in the following manner :
  • Polyacrylic acid of MW 30,000 was added in an amount to give a final polyacrylic acid level of about 5% in the final granule, whilst ensuring that the slurry was well agitated and the temperature of 40 . C was maintained.
  • the slurry was then transferred to a mixer/cooler (a Lodige @ mixer with cooling jacket) and the temperature was reduced to 10°C. A granule/crumb was slowly formed from the mixture, which was then discharged to a fluidized bed drier for drying.
  • the dry granules from the fluidized bed drier were screened to a particle size range of between 150 nm and 2,000 um. Any oversize (>2,000 ⁇ m) and undersize ( ⁇ 150 ⁇ m) were collected for recycling to the mixer / cooler. The following granule composition was obtained :
  • the granules have a bulk density of 600 kg/m 3 and show good attrition resistance, good stability on storage and an excellent dispersibility, showing no sign of high local concentration of DPDA.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP19890201076 1988-05-05 1989-04-26 Procédé de préparation de corps contenant un composé d'un peroxyacide et compositions comprenant les dits corps Withdrawn EP0340847A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8810630 1988-05-05
GB888810630A GB8810630D0 (en) 1988-05-05 1988-05-05 Process for preparing bodies containing peroxyacid & compositions comprising said bodies

Publications (2)

Publication Number Publication Date
EP0340847A2 true EP0340847A2 (fr) 1989-11-08
EP0340847A3 EP0340847A3 (fr) 1990-10-03

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ID=10636393

Family Applications (1)

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EP19890201076 Withdrawn EP0340847A3 (fr) 1988-05-05 1989-04-26 Procédé de préparation de corps contenant un composé d'un peroxyacide et compositions comprenant les dits corps

Country Status (6)

Country Link
EP (1) EP0340847A3 (fr)
JP (1) JPH0623186B2 (fr)
AU (1) AU613745B2 (fr)
BR (1) BR8902095A (fr)
GB (1) GB8810630D0 (fr)
ZA (1) ZA893330B (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0396341A2 (fr) * 1989-05-01 1990-11-07 The Procter & Gamble Company Granulé de blanchiment aggloméré à base de peroxyacide et procédé de préparation
EP0429108A2 (fr) * 1989-11-13 1991-05-29 Unilever N.V. Procédé pour la préparation des particules solides d'un adjuvant de détergente et leur utilisations dans les compositions détergentes
TR25837A (tr) * 1990-05-31 1993-09-01 Procter & Gamble KüLCELENDIRILMIS PEROKSIASIT AGARTICI GRANüLü VE BUNU YAPMAYA MAHSUS YÖNTEM.
EP0570881A2 (fr) * 1992-05-19 1993-11-24 Hoechst Aktiengesellschaft Procédé de fabrication de granulés pauvres en poussière
EP0592033A1 (fr) * 1992-10-07 1994-04-13 The Procter & Gamble Company Procédé pour fabriquer des particules contenant des peroxyacides
US5409632A (en) * 1992-11-16 1995-04-25 The Procter & Gamble Company Cleaning and bleaching composition with amidoperoxyacid
US5932532A (en) * 1993-10-14 1999-08-03 Procter & Gamble Company Bleach compositions comprising protease enzyme

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB456591A (en) * 1935-06-04 1936-11-12 Henry Edward Cox Mixing machines
US4497757A (en) * 1983-01-31 1985-02-05 The Procter & Gamble Company Energy efficient hydration process
EP0200163A2 (fr) * 1985-05-02 1986-11-05 Henkel Kommanditgesellschaft auf Aktien Agent de blanchiment, sa préparation et son utilisation
EP0256443A2 (fr) * 1986-08-15 1988-02-24 Unilever N.V. Composition à base d'acide peroxydé et son utilisation dans des compositions détergentes

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4091544A (en) * 1977-02-11 1978-05-30 The Procter & Gamble Company Drying process
US4379080A (en) * 1981-04-22 1983-04-05 The Procter & Gamble Company Granular detergent compositions containing film-forming polymers
GB8607387D0 (en) * 1986-03-25 1986-04-30 Unilever Plc Activator compositions
GB8607388D0 (en) * 1986-03-25 1986-04-30 Unilever Plc Activator compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB456591A (en) * 1935-06-04 1936-11-12 Henry Edward Cox Mixing machines
US4497757A (en) * 1983-01-31 1985-02-05 The Procter & Gamble Company Energy efficient hydration process
EP0200163A2 (fr) * 1985-05-02 1986-11-05 Henkel Kommanditgesellschaft auf Aktien Agent de blanchiment, sa préparation et son utilisation
EP0256443A2 (fr) * 1986-08-15 1988-02-24 Unilever N.V. Composition à base d'acide peroxydé et son utilisation dans des compositions détergentes

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0396341A2 (fr) * 1989-05-01 1990-11-07 The Procter & Gamble Company Granulé de blanchiment aggloméré à base de peroxyacide et procédé de préparation
EP0396341A3 (fr) * 1989-05-01 1992-01-22 The Procter & Gamble Company Granulé de blanchiment aggloméré à base de peroxyacide et procédé de préparation
EP0429108A2 (fr) * 1989-11-13 1991-05-29 Unilever N.V. Procédé pour la préparation des particules solides d'un adjuvant de détergente et leur utilisations dans les compositions détergentes
EP0429108A3 (en) * 1989-11-13 1991-10-16 Unilever Nv Process for preparing particulate detergent additive bodies and use thereof in detergent compositions
TR24785A (tr) * 1989-11-13 1992-05-01 Unilever Nv Tanecikli deterjan katki maddesi cisimcikleri hazirlamaya mahsus yoentem ve bunla
US5167852A (en) * 1989-11-13 1992-12-01 Lever Brothers Company, Division Of Conopco Inc. Process for preparing particulate detergent additive bodies and use thereof in detergent compositions
TR25837A (tr) * 1990-05-31 1993-09-01 Procter & Gamble KüLCELENDIRILMIS PEROKSIASIT AGARTICI GRANüLü VE BUNU YAPMAYA MAHSUS YÖNTEM.
EP0570881A2 (fr) * 1992-05-19 1993-11-24 Hoechst Aktiengesellschaft Procédé de fabrication de granulés pauvres en poussière
EP0570881A3 (en) * 1992-05-19 1994-08-24 Hoechst Ag Process for manufacture of low-dust granules
US6066365A (en) * 1992-05-19 2000-05-23 Hoechst Aktiengesellschaft Process for the preparation of low-dust granules
EP0592033A1 (fr) * 1992-10-07 1994-04-13 The Procter & Gamble Company Procédé pour fabriquer des particules contenant des peroxyacides
US5536435A (en) * 1992-10-07 1996-07-16 The Procter & Gamble Company Process for making peroxyacid containing particles
US5409632A (en) * 1992-11-16 1995-04-25 The Procter & Gamble Company Cleaning and bleaching composition with amidoperoxyacid
US5932532A (en) * 1993-10-14 1999-08-03 Procter & Gamble Company Bleach compositions comprising protease enzyme

Also Published As

Publication number Publication date
EP0340847A3 (fr) 1990-10-03
BR8902095A (pt) 1989-12-05
GB8810630D0 (en) 1988-06-08
JPH0211564A (ja) 1990-01-16
AU613745B2 (en) 1991-08-08
JPH0623186B2 (ja) 1994-03-30
AU3393189A (en) 1989-11-09
ZA893330B (en) 1991-01-30

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