EP0888425B1 - Verfahren zur herstellung eines freifliessenden agglomerisierten niotensidhaltigen waschmittels - Google Patents

Verfahren zur herstellung eines freifliessenden agglomerisierten niotensidhaltigen waschmittels Download PDF

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Publication number
EP0888425B1
EP0888425B1 EP97908065A EP97908065A EP0888425B1 EP 0888425 B1 EP0888425 B1 EP 0888425B1 EP 97908065 A EP97908065 A EP 97908065A EP 97908065 A EP97908065 A EP 97908065A EP 0888425 B1 EP0888425 B1 EP 0888425B1
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EP
European Patent Office
Prior art keywords
alkali metal
surfactant
carboxylic acid
water
detergent
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
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EP97908065A
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English (en)
French (fr)
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EP0888425A1 (de
EP0888425A4 (de
Inventor
David S. Staley
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Amway Corp
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Amway Corp
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Publication of EP0888425A4 publication Critical patent/EP0888425A4/de
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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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof

Definitions

  • U.S. Pat. No. 4,473,485 to Green reports that a free-flowing granular detergent can be prepared by mixing a polycarboxylic structuring agent solution with a micronized carbonate followed by the addition to the mixture of a nonionic surfactant and water, followed by removal of the excess water.
  • the preferred micronized carbonate is calcium or sodium carbonate.
  • a disadvantage of this process is that the micronized carbonate used by Greene to enhance the flowability of the detergent product is quite expensive as compared to standard sodium carbonate. Without the use of the micronized carbonate, Greene's product would not have such good flowability. In addition, where the micronized carbonate is calcium carbonate, the building capability of the detergent is reduced.
  • coated is used in the specification and claims to mean that the surfactant is present on the surface of the carbonate (and other particles) as well as within the carbonate (and other particles), e.g. by absorption.
  • the anionic surfactants useful in the present invention may also include the potassium, sodium, calcium, magnesium, ammonium or lower alkanolammonium, such as triethanolammonium, monoethanolammonium, or diisopropanolammonium paraffin or olefin sulfonates in which the alkyl group contains from 10 to 20 carbon atoms.
  • the lower alkanol of such alkanolammonium will normally be of 2 to 4 carbon atoms and is preferably ethanol.
  • the alkyl group can be straight or branched and, in addition, the sulfonate is preferably joined to any secondary carbon atom, i.e., the sulfonate is not terminally joined.
  • anionic surfactants useful herein are the sodium alkyl glycerol ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from 1 to 10 units of ethylene oxide per molecule and wherein the alkyl group contains from 10 to 20 carbon atoms.
  • the nonionic detergent surfactant may be any of the conventional materials of this type which are very well known and fully described in the literature, for example in "Surface Active Agents and Detergents” Volumes I and II by Schwartz, Perry & Berch, "Nonionic Surfactants” by M. J. Schick, and McCutcheon's "Emulsifiers & Detergents,"
  • the nonionic materials may include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Alkyl saccharides may also find use in the composition.
  • the alkyl saccharides are those having a hydrophobic group containing from 8 to 20 carbon atoms, preferably from 10 to 16 carbon atoms, and a polysaccharide hydrophillic group containing from 1 (mono) to 10 (poly), saccharide units (e.g., galactoside, glucoside, fructoside, glucosyl, fructosyl, and/or galactosyl units).
  • saccharide units e.g., galactoside, glucoside, fructoside, glucosyl, fructosyl, and/or galactosyl units.
  • Mixtures of saccharide moieties may be used in the alkyl saccharide surfactants.
  • Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
  • Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from 8 to 18 carbon atoms.
  • the later admixed carboxylic add may be coated with the excess nonionic surfactant.
  • the amount of carboxylic add available to solubilize and neutralize with the alkali metal carbonate will be reduced, which, in tum will reduce the agglomeration efficiency and require additional carboxylic add to achieve the desired particle size.
  • the premix is formed by mixing from 30% to 65% of sodium carbonate, from 0.5% to 4% of a silica, from 2% to 3% of carboxymethylcellulose, and a minor amount of other optional detergent ingredients; and spraying from 20% to 30% of a nonionic surfactant wherein the nonionic surfactant is the sole detergent surfactant present, onto the mixed carbonate, silica, carboxymethylcellulose, and optional ingredients.
  • the surfactant particularly the nonionic surfactant is added in an amount so that it is within a particular ratio with respect to the sodium carbonate. Within this ratio range, the surfactant adequately coats the sodium carbonate yet does not provide a substantial excess of surfactant which would then undesirably coat the carboxylic acid. Moreover, it is believed that the order of addition is important to achieving the desired agglomeration. By loading the alkali metal carbonate with the surfactant prior to the admixture of carboxylic acid and introduction of water, the desired particle size is achieved while still producing a free-flowing powder.
  • the alkali metal carboxylate is present in the detergent composition at a level of up to 25%, preferably from 4% to 18% and is provided solely by the reaction of the carboxylic acid corresponding to the alkali metal carboxylate, and the alkali metal carbonate. It is believed that when the amount of alkali metal carboxylate is within this range, the desired agglomeration of the nonionic surfactant loaded alkali metal carbonate will be efficiently achieved and will produce the desired particle size. More preferably, the alkali metal carboxylate is present at a level of from 5% to 13% and in the most preferred embodiment is present at a level of 9% to 11%.
  • the carboxylic acid should be substantially completely neutralized by reaction with the alkali metal carbonate to its corresponding alkali metal salt during processing.
  • malic add should be substantially completely neutralized to an alkali metal malate.
  • the carboxylic acid is not completely neutralized. Therefore, it is desirable to neutralize at least 90%, preferably at least 95% and more preferably at least 99% of the carboxylic acid to its alkali metal carboxylate.
  • the substantially completely neutralized carboxylic acid will be selected from the group consisting of the alkali metal salts of citric acid, malic acid, and mixtures thereof.
  • the substantially completely neutralized carboxylic acid is selected from the group consisting of sodium citrate, sodium malate, and mixtures thereof.
  • the carboxylic acid is admixed with the premix at a level of up to 18% by weight of the final product.
  • the preferred range of admixed acid is from 3% to 13% by weight of the final product, more preferably from 4% to 10% and most preferably from 7% to 9%.
  • the carboxylic acid is only lightly admixed with the premix prior to the later introduction of water to minimize the potential for coating of the carboxylic acid by the nonionic surfactant.
  • the carboxylic acid is lightly admixed with the premix, a small amount of water is incorporated to accomplish agglomeration of the particles.
  • the water may be incorporated as a mist, steam, or in another suitable fashion. Desirably, the amount of water used is as small as practical in order to minimize subsequent drying time, energy and thus cost.
  • the water is therefore incorporated at a level from 0.1% to no more than 7%, preferably no more than 5%. In a more preferred embodiment, the water is incorporated in a range between 4% and 5%.
  • the larger particles move from the inlet end to the outlet end of the agglomerator where they exit and are conveyed to a dryer to remove the free water from the agglomerated particles.
  • the agglomerator is preferably inclined from the inlet to the outlet so that as the particles agglomerate, the larger agglomerated particles move from the inlet end to the outlet end where they are dried.
  • hydration of sodium carbonate is exothermic and excessive hydration of sodium carbonate will generate undesirable heat and increase the temperature of the mixture above the first temperature.
  • an excess of surfactant present in the premix may cause coating of the carboxylic acid resulting in a reduction of agglomeration efficiency.
  • additional carboxylic acid and water may be required to achieve the desired agglomerated particle size. Consequently, the order of addition as well as the temperature are believed to be important to achieving the desired agglomeration and particle size.
  • the preferred carboxylic acid has a greater water solubility than its corresponding alkali metal salt below a first temperature.
  • An increase in temperature above the first temperature therefore adversely affects the relative solubility of the acid form of the carboxylic acid in comparison to the salt form which, in turn, adversely affects the agglomeration efficiency.
  • the formation of the alkali metal salt of the carboxylic acid is controlled so as to prevent the temperature of the mixture from rising above the first temperature.
  • agglomerate size e.g., feed rate to the drum, angle of the drum, rotational speed of the drum, the number and location of the water spray.
  • the result of manipulating such factors is desired control of the particle size and density of the agglomerates.
  • the preferred embodiment of the agglomerated detergent composition of the present invention includes from 20% to 70% of sodium carbonate, from 20% to 40% of a surfactant, particularly a nonionic detergent surfactant and from 3% to 13% of a sodium carboxylate selected from the group consisting of sodium citrate, sodium malate, and mixtures thereof, wherein the sodium carboxylate is provided solely by the reaction, at a temperature, below a first temperature, or (a) a premix comprising a surfactant and sodium carbonate, (b) a carboxylic acid selected from the group consisting of citric acid, malic acid, and mixtures thereof, and (c) water.
  • the agglomerated detergent composition resulting from the process of the present invention includes from 20% to 70% of sodium carbonate, from 20% to 40% of a nonionic detergent surfactant, wherein the nonionic surfactant is the sole detergent surfactant present, and from 4% to 18% of a sodium salt of a carboxylic add selected from the group consisting of sodium citrate, sodium malate, and mixtures thereof, wherein the sodium salt of the carboxylic acid is formed by the reaction at a temperature below a first temperature of (a) a premix comprising a nonionic surfactant loaded sodium carbonate, (b) a carboxylic add selected from the group consisting of citric acid, malic acid, and mixtures thereof, and (c) water.
  • optional additives are lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants such as alkyl phosphates and silicone oils, anti-redeposition agents such as sodium carboxymethyl cellulose, oxygen releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine releasing bleaching agents such as trichloroisocyanuric add and alkali metal salts of dichloroisocyanuric add, fabric softening agents, inorganic salts such as sodium sulfate, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes, enzyme stabilizing agents and germicides.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids
  • lather depressants such as alkyl phosphates and silicone
  • a low level of silicate for example up to 5% by weight, is usually advantageous in decreasing the corrosion of metal parts in fabric washing machines.
  • Useful silicates such as an alkali metal silicate, particularly sodium neutral, alkaline, meta- or orthosilicate can be used.
  • Aluminosilicate ion exchange materials may be useful in the detergent composition of this invention and may include the naturally-occurring aluminosilicates or synthetically derived, a method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat No. 3,985,669, Such synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, and Zeolite X. In addition, layered or structured silicates such as those sold under the designation SKS-6 by Hoechst-Celanese may also find use in the detergent composition.
  • Smectite clays may be suitable for use herein and are described in U.S. Pat. No. 4,762,645, at column 6, line 3 through column 7, line 24.
  • whitening agent particles may be added to the dried powder detergent described above.
  • the whitening agent particles comprise a fluorescent whitening agent and an anionic surfactant that substantially protects the whitening agent from degradation caused by the presence of nonionic surfactant.
  • the preferred whitening agent particle composition and method of making it is more fully described in US-A-5 714 452 and US-A-5 714 452), respectively.
  • the detergent composition may also contain a post-added acidulant for improved solubility, as more particularly described in US-A-5 995 068.
  • the ingredients listed in Table 1 were agglomerated into an acceptable free-flowing powder detergent in the following manner.
  • the sodium carbonate, whitener, silica, and carboxymethylcellulose were mixed for 1 minute in a ribbon mixer to achieve a uniform mixture.
  • Neodol 25-7 (a C 12 -C 15 alcohol ethoxylated with 7 moles of ethylene oxide) was poured into the above mixture while mixing to uniformly coat the sodium carbonate and other ingredients.
  • the loaded sodium carbonate (and other ingredients) were transferred to a laboratory scale agglomerator (O'Brien Industrial Equip. Co., 3 foot diameter, 1 foot long) which was rotated at 9 rpm for 2 minutes after which water was sprayed on the mixture to cause agglomeration of the particles.
  • Example No. 2 3 Material Amount (Formula Weight) Sodium Carbonate 55.88 55.88 53.18 Silica 3.0 3.0 3.0 Carboxymethylcellulose 2.0 --- 2.0 Brightener 0.02 0.02 0.02 Citric Acid 7.5 7.5 7.5 Water (added for agglomeration) 4.0 4.0 4.0 Water (after drying) 2.2 1.2 1.2 Density 0.85 0.87 0.84 Flodex 12 9 10

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (7)

  1. Verfahren zum Herstellen einer rieselfähigen agglomerierten Waschmittelpulverzusammensetzung, umfassend die Schritte:
    a) Herstellen einer homogenen, mit oberflächenaktivem Stoff beschichteten bzw. imprägnierten Alkalimetallcarbonat-Vormischung, umfassend:
    i. ein Alkalimetallcarbonat in einer Menge von 5 Gew.-% bis 80 Gew.-%, bezogen auf die Waschmittelpulverzusammensetzung;
    ii. einen waschaktiven (oberflächenaktiven) Stoff, ausgewählt aus der Gruppe bestehend aus anionischen, nichtionischen, zwitterionischen, ampholytischen, kationischen Verbindungen und Gemischen davon, in einer Menge von 5 Gew.-% bis 50 Gew.-%, bezogen auf die Waschmittelpulverzusammensetzung,
    b) anschließend Vermischen einer Carbonsäure mit der Vormischung, um ein Gemisch zu ergeben, wobei unterhalb einer ersten Temperatur, welche weniger als 42°C beträgt, die Carbonsäure eine Wasserlöslichkeit aufweist, die größer ist als die Wasserlöslichkeit ihres entsprechenden Alkalimetallsalzes, und wobei die Carbonsäure in einer Menge bis zu 25 Gew.-% zugemischt wird; und
    c) anschließend Zugeben von Wasser zu dem Gemisch, wodurch die Carbonsäure löslich gemacht wird und mit dem Alkalimetallcarbonat unterhalb der ersten Temperatur reagiert.
  2. Verfahren nach Anspruch 1, wobei das Alkalimetallcarbonat Natriumcarbonat ist.
  3. Verfahren nach Anspruch 1, wobei der oberflächenaktive Stoff aus einem nichtionischen oberflächenaktiven Stoff besteht.
  4. Verfahren nach Anspruch 3, wobei das Verhältnis von Natriumcarbonat zu nichtionischem oberflächenaktiven Stoff im Bereich von 2 : 1 bis 3,5 : 1 liegt.
  5. Verfahren nach Anspruch 1, wobei die Carbonsäure ausgewählt wird aus der Gruppe bestehend aus Citronensäure, Äpfelsäure und Gemischen davon.
  6. Verfahren nach Anspruch 1, wobei die Menge der Carbonsäure so ist, dass das Verhältnis des Alkalimetallcarbonats zu der Carbonsäure 6,5 : 1 bis 12 : 1 beträgt.
  7. Verfahren nach Anspruch 1, wobei die erste Temperatur 15°C bis 40°C beträgt.
EP97908065A 1996-03-15 1997-03-10 Verfahren zur herstellung eines freifliessenden agglomerisierten niotensidhaltigen waschmittels Expired - Lifetime EP0888425B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US61644396A 1996-03-15 1996-03-15
US61656896A 1996-03-15 1996-03-15
US616568 1996-03-15
PCT/US1997/003741 WO1997033959A1 (en) 1996-03-15 1997-03-10 Free-flowing agglomerated nonionic surfactant detergent composition and process for making same
US616443 2000-07-14

Publications (3)

Publication Number Publication Date
EP0888425A1 EP0888425A1 (de) 1999-01-07
EP0888425A4 EP0888425A4 (de) 2000-08-23
EP0888425B1 true EP0888425B1 (de) 2002-09-04

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EP97908065A Expired - Lifetime EP0888425B1 (de) 1996-03-15 1997-03-10 Verfahren zur herstellung eines freifliessenden agglomerisierten niotensidhaltigen waschmittels

Country Status (10)

Country Link
EP (1) EP0888425B1 (de)
JP (1) JP2002511107A (de)
CN (1) CN1233275A (de)
AR (1) AR006251A1 (de)
AT (1) ATE223472T1 (de)
AU (1) AU715795B2 (de)
CA (1) CA2248994C (de)
DE (1) DE69715170T2 (de)
HK (1) HK1017707A1 (de)
WO (1) WO1997033959A1 (de)

Families Citing this family (10)

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Publication number Priority date Publication date Assignee Title
GB2315763A (en) * 1996-07-31 1998-02-11 Procter & Gamble Preparation of an agglomerated detergent composition comprising a surfactant a an acid source
GB9807477D0 (en) * 1998-04-07 1998-06-10 Unilever Plc Coloured granular composition for use in particulate detergent compositions
GB9826105D0 (en) † 1998-11-27 1999-01-20 Unilever Plc Detergent compositions
CA2456095C (en) 2001-08-31 2010-05-11 Morepen Laboratories Ltd. An improved process for the preparation of amorphous atorvastatin calcium salt (2:1)
US8105628B2 (en) 2003-09-23 2012-01-31 Orthocon, Inc. Absorbable implants and methods for their use in hemostasis and in the treatment of osseous defects
US7955616B2 (en) 2003-09-23 2011-06-07 Orthocon, Inc. Absorbable implants and methods for their use in hemostasis and in the treatment of osseous defects
US7759300B2 (en) * 2007-07-02 2010-07-20 Ecolab Inc. Solidification matrix including a salt of a straight chain saturated mono-, di-, or tri- carboxylic acid
DE102008028229A1 (de) * 2008-06-16 2009-12-17 Fit Gmbh Zusammensetzung zur Herstellung von Reinigungsmitteln, Tablettiermischung, Polymerkombination, Reinigunsmittel-Formkörper und Verfahren zur deren Herstellung
EP3694967B1 (de) * 2017-10-13 2021-10-27 Unilever Global IP Limited Betaine bezogenen partikel aus hydratebildendem salz für aschmittelzusammensetzung
US11377626B2 (en) * 2018-03-08 2022-07-05 Ecolab Usa Inc. Solid enzymatic detergent compositions and methods of use and manufacture

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Publication number Priority date Publication date Assignee Title
GB1398263A (en) * 1971-08-17 1975-06-18 Unilever Ltd Detergent compositions
US3920586A (en) * 1972-10-16 1975-11-18 Procter & Gamble Detergent compositions
US4666740A (en) * 1976-12-02 1987-05-19 The Colgate-Palmolive Co. Phosphate-free concentrated particulate heavy duty laundry detergent
US4473485A (en) * 1982-11-05 1984-09-25 Lever Brothers Company Free-flowing detergent powders
GB9120657D0 (en) * 1991-09-27 1991-11-06 Unilever Plc Detergent powders and process for preparing them
US5259994A (en) * 1992-08-03 1993-11-09 The Procter & Gamble Company Particulate laundry detergent compositions with polyvinyl pyrollidone
DE4435743C2 (de) * 1994-02-17 1998-11-26 Chemolux Sarl Verfahren zur Herstellung eines Mehrkomponenten-Granulates
US5496486A (en) * 1994-06-30 1996-03-05 Amway Corporation Process for increasing liquid surfactant loading in free flowing powder detergents

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AU1990697A (en) 1997-10-01
JP2002511107A (ja) 2002-04-09
CN1233275A (zh) 1999-10-27
EP0888425A1 (de) 1999-01-07
HK1017707A1 (en) 1999-11-26
DE69715170D1 (de) 2002-10-10
WO1997033959A1 (en) 1997-09-18
CA2248994A1 (en) 1997-09-18
AU715795B2 (en) 2000-02-10
EP0888425A4 (de) 2000-08-23
ATE223472T1 (de) 2002-09-15
DE69715170T2 (de) 2003-05-28
AR006251A1 (es) 1999-08-11
CA2248994C (en) 2001-05-15

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