EP1276836A2 - Adoucissant en dose unitaire compactee spherique - Google Patents

Adoucissant en dose unitaire compactee spherique

Info

Publication number
EP1276836A2
EP1276836A2 EP01927303A EP01927303A EP1276836A2 EP 1276836 A2 EP1276836 A2 EP 1276836A2 EP 01927303 A EP01927303 A EP 01927303A EP 01927303 A EP01927303 A EP 01927303A EP 1276836 A2 EP1276836 A2 EP 1276836A2
Authority
EP
European Patent Office
Prior art keywords
unit dose
pentaerythritol
softening
composition
fabric
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.)
Ceased
Application number
EP01927303A
Other languages
German (de)
English (en)
Inventor
Alain Jacques
Juliette Rousselet
Hoai-Chau Cao
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.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive Co
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
Priority claimed from US09/558,822 external-priority patent/US6258767B1/en
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Publication of EP1276836A2 publication Critical patent/EP1276836A2/fr
Ceased legal-status Critical Current

Links

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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0086—Laundry tablets
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/044—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening 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
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols

Definitions

  • This invention relates to wash cycle unit dose laundry compositions for softening or conditioning fabrics. More particularly, this invention relates to unit dose fabric softening compositions which are compacted granular compositions spherical in shape and suitable for use in the wash cycle of an automatic washing machine.
  • Detergent compositions manufactured in the form of tablets of compacted detergent powder are known in the art.
  • U.S . 5 ,225 , 100 for example, describes a tablet of compacted powder comprising an anionic detergent compound which will adequately disperse in the wash water.
  • unit dose softener One possible option for providing a unit dose softener is to introduce the softening ingredients directly into the rinse cycle. But, for this type of product to be effective several practical requirements must be met. To begin with, the size and shape of the unit dose container must be readily compatible with the geometry of a wide variety of rinse cycle dispensers designed for home washing machines in order to insure its easy introduction into the dispenser.
  • the unit dose composition must be formulated to readily dispense its contents upon contact with water in a period of time corresponding to the residence time of the unit dose in the dispenser, namely, the period of time during which water enters and flows through the rinse cycle dispenser.
  • Wash cycle softeners are known in the art which condition fabrics during the period of the wash cycle.
  • Tablet unit doses for detergent compositions are also known.
  • Such tablets are typically flat compacted unit compositions which conceptually offer numerous advantages to the consumer such as: ease of dosing; cleaner wash cycle dispensers resulting from not being dosed with loose powder; less bulk to carry and dispense; ease of handling relative to liquids; and environmental benefits attendant to reduced packaging requirements.
  • Some tablet manufacturers provide a net or sachet designed to contain the tablet unit dose, and thereby avoid the problem of direct contact between the tablet and the seal.
  • Another proposed solution involves providing a rapidly dispersible tablet in the wash water by incorporating an effervescent matrix and/or a disintegration agent into the tablet. But, these proposed options are generally uneconomical and often result in an unduly fragile tablet unable to readily withstand normal handling by the consumer without fracturing.
  • an economical unit dose tablet capable of providing conditioning of fabrics, and which retains its physical integrity during normal handling prior to being introduced into the washing machine.
  • the present invention provides a unit dose ' laundry composition for softening or conditioning fabrics which is suitable as an additive to the wash cycle of an automatic washing machine, said unit dose composition comprising a compacted granular composition comprising a fabric softener or a fabric conditioner, said compacted granular composition being characterized by having a spherical shape and having no discrete outer layer surrounding said fabric softener or conditioner, which outer layer is comprised of an alkaline material such that the pH of the wash water is increased upon the dissolution of said outer layer in said wash water.
  • the fabric softener or conditioner is comprised of a fabric softening clay and an organic fatty softening material.
  • a fabric softening clay such as bentonite
  • apentaerythritol compound as further described herein.
  • Useful combinations of such softener may very from about 83%, to about 90%, by weight, of clay, and from about 10% to about 17%, by weight, of fatty softening material such as a pentaerythritol compound (often abbreviated herein as "PEC").
  • PEC pentaerythritol compound
  • the fabric softener or conditioner is free of a soap surfactant.
  • a process for softening or conditioning laundry which comprises contacted the laundry with an effective amount of the unit dose laundry composition defined above.
  • the clays that are useful components of the invented products are those which cooperate with the organic fatty softener materials to provide enhanced softening of laundry.
  • Such clays include the montmorillonite-containing clays which have swelling properties (in water) and which are of smectite structure, so that they deposit on fibrous materials, especially cotton and cotton/synthetic blends, such as cotton/polyester, to give such fibers and fabrics made from them a surface lubricity or softness.
  • the best of the smectite clays for use in the present invention is bentonite and the best of the bentonites are those which have a substantial swelling capability in water, such as the sodium and potassium bentonites.
  • Such swelling bentonites are also known as western or Wyoming bentonites, which are essentially sodium bentonite.
  • Other bentonites such as calcium bentonite, are normally non-swelling and usually are, in themselves, unacceptable as fabric softening agents.
  • a source of alkali metal or other solubilizing ion such as sodium (which may come from sodium hydroxide, added to the composition, or from sodium salts, such as builders and fillers, which may be functional components of the composition).
  • bentonites are those of sodium and potassium, which are normally swelling, and calcium and magnesium, which are normally non-swelling. Of these it is preferred to utilize calcium (with a source of sodium being present) and sodium bentonites.
  • the bentonites employed may be produced in the United States of America, such as Wyoming bentonite, but also may be obtained from Europe, including Italy and Spain, as calcium bentonite, which may be converted to sodium bentonite by treatment with sodium carbonate, or may be employed as calcium bentonite.
  • other montmorillonite-containing smectite clays of properties like those of the bentonites described may be substituted in whole or in part for the bentonites described herein and similar fabric softening results will be obtained.
  • the swellable bentonites and similarly operative clays are of ultimate particle sizes in the micron range, e.g., 0.01 to 20 microns and of actual particle sizes in the range of No's. 100 to 400 sieves, preferably 140 to 325 sieves, U.S. Sieve Series.
  • the bentonite and other such suitable swellable clays may be agglomerated to larger particle sizes too, such as 60 to 120 sieves, but such agglomerates are not preferred unless they include the PEC('s) too (in any particulate products).
  • a main component of the invented compositions and articles of the present invention, and which is used in combination with the fabric softening clay is an organic fatty softener.
  • the organic softener can be anionic or nonionic fatty chains (C ⁇ o-C 2 2 preferably C 12 -C ⁇ 8 ).
  • Anionic softeners include fatty acids soaps.
  • Preferred organic softeners are nonionics such as fatty esters, ethoxylated fatty esters, fatty alcohols and polyols polymers.
  • the organic softener is most preferably a higher fatty acid ester of a pentaerythritol compound, which term is used in this specification to describe higher fatty acid esters of pentaerythritol, higher fatty acid esters of pentaerythritol oligomers, higher fatty acid esters of lower alkylene oxide derivatives of pentaerythritol and higher fatty acid esters of lower alkylene oxide derivatives of pentaerythritol oligomers.
  • Pentaerythritol compound is often abbreviated as PEC herein, which description and abbreviation may apply to any or all of pentaerythritol, oligomers, thereof and allcoxylated derivatives thereof, as such, or more preferably and more usually, as the esters, as may be indicated by the context.
  • the oligomers of pentaerythritol are preferably those of two to five pentaerythritol moieties, more preferably 2 or 3, with such moieties being joined together through etheric bonds.
  • the lower alkylene oxide derivatives thereof are preferably of ethylene oxide or propylene oxide monomers, dimers or polymers, which terminate in hydroxyls and are joined to the pentaerythritol or oligomer of pentaerythritol through etheric linkages.
  • At least one of the PEC OH groups and preferably at least two, e.g., 1 or 2 to 4, are esterified by a higher fatty acid or other higher aliphatic acid, which can be of an odd number of carbon atoms.
  • the higher fatty acid esters of the pentaerythritol compounds are preferably partial esters. And more preferably there will be at least two free hydroxyls thereon after esterification (on the pentaerythritol, oligomer or alkoxyalkane groups). Frequently, the number of such free hydroxyls is two or about two but sometimes it may by one, as in pentaerythritol tristearate, or as many ' as eight, as in pentaerythritol tetrapalmitate.
  • the higher aliphatic or fatty acids that may be employed as esterifying acids are those of carbon atom contents in the range of 8 to 24, preferably 12 to 22 and more preferably 12 to 18, e.g., lauric, myristic, palmitic, oleic, stearic and behenic acids. Such may be mixtures of such fatty acids, obtained from natural sources, such as tallow or coconut oil, or from such natural materials that have been hydrogenated. Synthetic acids of odd or even numbers of carbon atoms may also be employed. Of the fatty acids lauric and stearic acids are often preferred, and such preference may depend on the pentaerythritol compound being esterified.
  • R ! CH 3 - (CH 2 ) 20 -COO-
  • R 2 CH 3 - (CH 2 ) 20 -COO-
  • R 3 OH
  • R 2 CH 3 - (CH 2 ) 10 -CO
  • R 3 CH 3 - (CH 2 ) ⁇ o -CO
  • R4 CH 3 - (CH 2 ) 10 -CO
  • pentaerythritol compounds that are useful in the practice of this invention are illustrated it will be understood that various other such pentaerythritol compounds within the description thereof herein may be employed too, including such as pentaerythritol dihydrogenated tallowate, pentaerythritol ditallowate, pentaerythritol dipahnitate, and dipentaerythritol tetratallowate.
  • fabric softening materials may be incorporated into the presently described unit dose laundry compositions provided they are not ecologically unacceptable and if they do not interfere with the fiber softening action of the clay and organic fatty softener material.
  • antistatic action when antistatic action is desirable in the product, such additions may be important because although PEC's, for example, have some antistatic properties it is generally insufficient for the intended purposes.
  • PEC's for example, have some antistatic properties it is generally insufficient for the intended purposes.
  • fabric softening compositions and articles with the PEC supplemented by other antistatic agents and also by fabric softeners.
  • the foremost of such antistatic materials are the quaternary ammonium salts but when they are present there can be ecological problems, due to their alleged toxicities to aquatic organisms.
  • antistats and fabric softeners include: higher alkyl neoalkanamides, e.g., N-stearyl neodecanamide; isostearamides; amines, such as N,N-ditallowalkyl N-methyl a ine; esterified quaternary salts or esterquats: amidoamines; amidoquats; imidazolines; imidazolinium salts.
  • Other useful ingredients for the unit dose laundry compositions of the invention include disintegration materials to enhance the disintegration of the unit dose in the wash water. Such materials include an effervescent matrix such as citric acid combined with baking soda, or materials such as PVP polymer and cellulose.
  • Granulating agents may be used such as polyethylene glycol; bactericides, perfumes, dyes and materials to protect against color fading, dye transfer, anti-pilling and anti-shrinkage.
  • cosmetic ingredients such as dyes, micas and waxes may be used as coating ingredients to improve the appearance and feel of the unit dose.
  • a unit dose composition was prepared from the following ingredients:
  • This method of manufacture consisted of mixing all the ingredients with the exception of perfume in a Loedige-type mixer. The resulting blend was dried in an oven and perfume was then added to the dried powder. The powder was then compacted using an alternative or rotative press mounted with appropriate dyes. The weight of the spherical unit dose was 60g and such unit dose dispersed in water within 20 minutes when introduced in the wash load at the beginning of the wash in a European Miele W832 front loading washing machine set a Program White Colors at 40°C.
  • Unit dose softener compositions were prepared as described in Example 1 to provide 60 gram spherical softeners having a diameter of 44 mm.
  • the typical range of spherical dose diameters is from about 5 to about 60 mm; preferably from about 20 to about 40 mm; and most preferably from about 30 to about 35 mm.
  • the dissolution behavior of the unit dose softener in the washing machine was compared to a compacted tablet of 35 grams.
  • the European washing machine and conditions of laundering were as described in Example 1.
  • the spherical unit dose softener of the invention and the tablet were introduced into the washing machine before the start of the wash. Results were as follows:

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

L'invention concerne une composition de lavage en dose unitaire pour adoucir ou assouplir les textiles, apte à être ajoutée au cycle de lavage d'un lave-linge automatique. Cette composition en dose unitaire comprend une composition granulaire compactée constituée d'un adoucissant ou d'un assouplissant pour textile. Cette composition granulaire compactée est caractérisée en ce qu'elle présente une forme sphérique et ne présente pas de couche extérieure discrète entourant ledit adoucissant ou assouplissant, la couche extérieure étant constituée d'un matériau alcalin, qui augmente le pH de l'eau de lavage lors de la dissolution de ladite couche extérieure dans cette eau.
EP01927303A 2000-04-26 2001-04-23 Adoucissant en dose unitaire compactee spherique Ceased EP1276836A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US09/558,822 US6258767B1 (en) 2000-04-26 2000-04-26 Spherical compacted unit dose softener
US558822 2000-04-26
US821233 2001-03-29
US09/821,233 US20020010118A1 (en) 2000-04-26 2001-03-29 Spherical compacted unit dose softener
PCT/US2001/013080 WO2001081521A2 (fr) 2000-04-26 2001-04-23 Adoucissant en dose unitaire compactee spherique

Publications (1)

Publication Number Publication Date
EP1276836A2 true EP1276836A2 (fr) 2003-01-22

Family

ID=27071870

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01927303A Ceased EP1276836A2 (fr) 2000-04-26 2001-04-23 Adoucissant en dose unitaire compactee spherique

Country Status (8)

Country Link
EP (1) EP1276836A2 (fr)
JP (1) JP2003531312A (fr)
CN (1) CN1439048A (fr)
AU (2) AU5377001A (fr)
BR (1) BR0110345A (fr)
CA (1) CA2405862A1 (fr)
MX (1) MXPA02010287A (fr)
WO (1) WO2001081521A2 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6670320B1 (en) * 2002-06-11 2003-12-30 Colgate-Palmolive Wash cycle unit dose softener containing a disintegrating agent
US6664222B1 (en) * 2002-06-13 2003-12-16 Colgate-Palmolive Co. Wash cycle unit dose softener
US6746995B2 (en) * 2002-06-13 2004-06-08 Colgate-Palmolive Company Wash cycle unit dose softener containing a controlled amount of moisture
EP1746152A1 (fr) 2005-07-20 2007-01-24 Unilever N.V. Compositions détergentes
EP1746151A1 (fr) 2005-07-20 2007-01-24 Unilever N.V. Pastilles de composition détergente
FR2969171B1 (fr) * 2010-12-17 2013-01-04 Eurotab Tablette adoucissante pour textile
AU2014414847B2 (en) * 2014-12-22 2018-02-01 Colgate-Palmolive Company Unit dose fabric softener
EP4157983B1 (fr) * 2020-05-27 2024-02-14 Unilever IP Holdings B.V. Composition d'adoucissant pour tissus

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4328110A (en) * 1980-09-17 1982-05-04 Beecham Inc. Fabric conditioning articles and methods of use
JPS61276896A (ja) * 1985-06-03 1986-12-06 花王株式会社 洗濯浴用柔軟剤錠剤
FI921148A (fi) * 1991-09-06 1993-03-07 Colgate Palmolive Co Tygmjukgoerande produkter baserade pao en kombination av en pentaerytritolfoerining och bentonit
JPH0987696A (ja) * 1995-09-27 1997-03-31 Lion Corp 錠剤型ノニオン洗剤組成物
US5972870A (en) * 1997-08-21 1999-10-26 Vision International Production, Inc. Multi-layered laundry tablet
GB9802390D0 (en) * 1998-02-04 1998-04-01 Unilever Plc Detergent compositions
EP1048718A1 (fr) * 1999-04-30 2000-11-02 The Procter & Gamble Company Compositions détergentes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0181521A3 *

Also Published As

Publication number Publication date
WO2001081521A2 (fr) 2001-11-01
CN1439048A (zh) 2003-08-27
AU5377001A (en) 2001-11-07
AU2001253770B2 (en) 2005-08-18
JP2003531312A (ja) 2003-10-21
CA2405862A1 (fr) 2001-11-01
WO2001081521A3 (fr) 2002-02-07
MXPA02010287A (es) 2003-04-25
BR0110345A (pt) 2003-05-13

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