EP1276837A1 - Wäscheweichspülmittel enthaltende dosierungseinheit zur verwendung in einem waschgang - Google Patents
Wäscheweichspülmittel enthaltende dosierungseinheit zur verwendung in einem waschgangInfo
- Publication number
- EP1276837A1 EP1276837A1 EP01928752A EP01928752A EP1276837A1 EP 1276837 A1 EP1276837 A1 EP 1276837A1 EP 01928752 A EP01928752 A EP 01928752A EP 01928752 A EP01928752 A EP 01928752A EP 1276837 A1 EP1276837 A1 EP 1276837A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- softening
- unit dose
- composition
- fatty
- pentaerythritol
- 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- Withdrawn
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
- 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
- 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
- C11D17/0047—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
- C11D17/0086—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
- C11D3/12—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
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 softemng compositions which are compacted granular compositions or encapsulated liquid or granular compositions suitable for use in the wash cycle of an automatic washing machine.
- detergent compositions in the form of compacted granular tablets of various shapes have received much attention in the patent literature, the use of such tablets to provide a unit dose fabric softener which will soften or condition fabrics in the wash cycle without impairing detergency or otherwise compromise the cleaning benefits provided by the detergent composition is not known.
- a unit dose composition for the rinse cycle 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.
- Laundry detergent compositions which further include a fabric softener to provide softening or conditioning of fabrics in the wash cycle of the laundering operation are well- known in the art and described in the patent literature. See, for example, U.S. Patent 4,605,506 to Wixon; U.S. Patent 4,818,421 to Boris et al. and U.S. Patent 4,569,773 to Ramachandran et al., all assigned to Colgate-Palmolive Co., and U.S. Patent 4,851,138 assigned to Akzo.
- U.S. Patent 5,972,870 to Anderson describes a multi-layered laundry tablet for washing which may include a detergent in the outer layer and a fabric softener, or water softener or fragrance in the inner layer.
- wash cycle active fabric softeners typically in powder form. But, these type products are characterized by the same inconvenience inherent with the use of powered detergents, namely, problems of handling, caking in the container or wash cycle dispenser, and the need for a dosing device to deliver the desired amount of active softener material to the wash water. It has now been found that softening of laundry can be effected in the wash cycle with a flexibility which is independent of the detergent dosage, and with great convenience by the consumer by the use of a unit dose wash cycle softener which avoids the common problems associated with the pouring and handling of granular or liquid detergent compositions.
- the present invention provides a unit dose wash cycle fabric softening composition for softening or conditioning fabrics in the wash cycle of an automatic washing machine, said unit dose comprising (a) a compacted granular fabric softener composition or (b) an encapsulated liquid and/or granular fabric softener composition, the amount of (a) or (b) being sufficient to form a unit dose capable of providing effective softening or conditioning of fabrics in the wash cycle of said washing machine.
- the unit dose fabric softening composition is characterized by being in the form of a tablet and having no discrete outer layer surrounding the fabric softener comprised of an alkaline material such that the pH of the wash water is increased upon dissolution of said outer layer in said wash water.
- the unit dose comprises a compacted granular softener composition which is essentially free of a soap surfactant.
- granular as used herein in describing the fabric softener is intended to encompass relatively coarser granules varying in size from about 150. to 2,000 microns as well as finer powder having a size as small as 30 to 50 microns.
- fabric softener is used herein for purposes of convenience to refer to materials which provide softening and/or conditioning benefits to fabrics in the wash cycle of a home or automatic laundering machine.
- the compacted granular fabric softener composition of the invention is preferably comprised of a fabric softemng clay optionally in combination with an organic fatty softening material.
- Especially preferred fabric softeners comprise a clay mineral softener, such as bentonite, in combination with a pentaerythritol ester compound as further described herein.
- Useful combinations of such softener may vary from about 80%, to about 90%, by weight, of clay, and from about 10% to about 20%, by weight, of fatty softening material such as a pentaerythritol compound (often abbreviated herein as "PEC").
- PEC pentaerythritol compound
- the encapsulated liquid or granular fabric softener composition contemplated for use herein comprises a gelatin capsule containing a nonionic softener or clay to avoid any reaction with anionic surfactants which may be present in the wash liquor.
- useful liquid softening compositions include fatty alcohols, fatty acids, fatty esters, silicones (e.g. linear, grafted, crosslinked or ethoxylated), polyethylene waxes and fatty amides.
- 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, cationic or nonionic fatty chains (C 10 -C 22 preferably C 12 - C 18 ).
- 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 alkoxylated 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 liydroxyls 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 atom
- 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.
- 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 andbehenic 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 2 CH 3 - (CH 2 ) ⁇ o -COO-
- R 3 OH
- R 4 OH
- R! CH 3 - (CH 2 )i6 -COO-
- R 2 CH 3 - (CH 2 )i6 -COO-
- R 3 OH
- R 4 OH
- R! CH 3 - (CH 2 ) 20 -COO- R 2 OH
- R4OH Dipentaerythritol Esters
- R! CH 3 - (CH 2 ) ⁇ o -CO
- R 2 CH 3 - (CH 2 ) ⁇ o -CO
- R 3 CH 3 - (CH 2 ) ⁇ 0 -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 may also be employed herein, including such as pentaerythritol dihydrogenated tallowate, pentaerythritol ditallowate, pentaerythritol dipalmitate, and dipentaerythritol tetratallowate.
- cationic softeners such as conventional quaternary ammonium softening compounds may optionally be added in minor amounts.
- the combination of bentonite and organic fatty softening material is generally from about 10% to about 99% bentonite and from about 1% to about 90% fatty softening material, preferably from about 50% to about 95% bentonite and about 5% to about 50% fatty softening material, and most preferably from about 80% to 90% bentonite and from about 10% to about 20% fatty softeningjnaterial.
- compositions of the invention include disintegration materials to enhance the disintegration of the unit dose in the wash water.
- disintegration 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.
- the encapsulation provided for the liquid or granular softening or conditioning materials is preferably a gelatin shell which is readily soluble in the wash water and compatible with detergents used in the wash cycle.
- the manufacture of such gelatin capsules utilizes technology well known in the art and is described, for example, in the following publications which are incorporated herein by reference: "Softgels: Manufacturing Considerations", Paul Wilkinson and Foo Song Horn, Drugs Pharmaceutical Science (1990), pps.
- liquid softeners of the invention include fatty alcohols, such as oleyl alcohol, fatty acids, such as oleyl carboxylic acid; fatty esters, such as oleyl esters or vegetable fatty esters such as sunflower oil ; silicones, such as polydimethylsiloxanes, linear or crosslinked, ethoxylated or without ethoxylation and optionally including an amide functionality; polyethylene waxes, having a molecular weight of from 8,000 to 60,000; and fatty amides, such as dioleyl amide formed by the reaction of diethylene triamine with oleic acid having predominantly the following structure:
- Ri represents an oleyl alkyl carbon chain
- R 2 represents H or (EO) x with x varying from 0 to 6 (the degree of ethoxylation).
- oleyl carbon chain length is most preferred for purposes of providing softening efficacy and dispersion in the wash water, other higher alkyl chain lengths may also be used for the invention.
- Typical unit dose compositions for use herein may vary from about 5 to about 10 ml corresponding on a weight basis to about 5 to about 10 grams (which includes the weight of the capsule), and the number of doses per wash is two.
- the corresponding volume and weight is from about 10 to about 20 ml and from about 10 to about 20 grams (including the capsule weight), respectively.
- Example 1 A compacted granular 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.
- a gelatin encapsulated unit dose liquid softener composition was prepared comprising the following ingredients:
- the softness provided by the unit dose composition was evaluated on cotton tee-shirts and towels in a European washing machine and compared with a commercial liquid fabric softener.
- the unit dose composition provided essentially equivalent softness.
Landscapes
- 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)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US558822 | 2000-04-26 | ||
US09/558,822 US6258767B1 (en) | 2000-04-26 | 2000-04-26 | Spherical compacted unit dose softener |
US09/620,515 US6294516B1 (en) | 2000-04-26 | 2000-07-20 | Wash cycle unit dose softener |
US620515 | 2000-07-20 | ||
US821231 | 2001-03-29 | ||
US09/821,231 US6589930B2 (en) | 2000-04-26 | 2001-03-29 | Wash cycle unit dose softener |
PCT/US2001/013007 WO2001081520A1 (en) | 2000-04-26 | 2001-04-23 | Wash cycle unit dose softener |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1276837A1 true EP1276837A1 (de) | 2003-01-22 |
Family
ID=27415783
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01928752A Withdrawn EP1276837A1 (de) | 2000-04-26 | 2001-04-23 | Wäscheweichspülmittel enthaltende dosierungseinheit zur verwendung in einem waschgang |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1276837A1 (de) |
JP (1) | JP2003531311A (de) |
CN (1) | CN1439046A (de) |
AU (1) | AU2001255577A1 (de) |
BR (1) | BR0110354A (de) |
CA (1) | CA2406174A1 (de) |
MX (1) | MXPA02010229A (de) |
WO (1) | WO2001081520A1 (de) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6664226B2 (en) * | 2000-04-26 | 2003-12-16 | Colgate-Palmolive Co | Spherical compacted unit dose softener |
US6670320B1 (en) * | 2002-06-11 | 2003-12-30 | Colgate-Palmolive | Wash cycle unit dose softener containing a disintegrating agent |
US6746995B2 (en) * | 2002-06-13 | 2004-06-08 | Colgate-Palmolive Company | Wash cycle unit dose softener containing a controlled amount of moisture |
US6664222B1 (en) * | 2002-06-13 | 2003-12-16 | Colgate-Palmolive Co. | Wash cycle unit dose softener |
AU2003259284A1 (en) * | 2002-07-31 | 2004-02-16 | Colgate-Palmolive Company | Unit dose softener disposed in water soluble container |
CA2494721A1 (en) * | 2002-07-31 | 2004-02-05 | Colgate-Palmolive Company | Unit dose nonaqueous softener disposed in water soluble container |
EP1431384B2 (de) | 2002-12-19 | 2009-02-11 | The Procter & Gamble Company | Einkammer-Einzelportion Textilbehandlungsmittel enthaltend in Beuteln verpackte Zusammensetzungen mit nicht-kationischen Weichspülmitteln |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4081384A (en) * | 1975-07-21 | 1978-03-28 | The Proctor & Gamble Company | Solvent-free capsules and fabric conditioning compositions containing same |
US4082678A (en) * | 1976-11-10 | 1978-04-04 | The Procter & Gamble Company | Fabric conditioning articles and process |
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 |
US4659496A (en) * | 1986-01-31 | 1987-04-21 | Amway Corporation | Dispensing pouch containing premeasured laundering compositions |
US5091105A (en) * | 1989-10-10 | 1992-02-25 | Dow Corning Corporation | Liquid detergent fabric softening laundering composition |
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 |
ZA9886B (en) * | 1997-01-17 | 1998-07-08 | Gordon Glasgow | Washing aid |
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 (de) * | 1999-04-30 | 2000-11-02 | The Procter & Gamble Company | Waschmittelzusammensetzungen |
DE19931399A1 (de) * | 1999-07-07 | 2001-01-11 | Henkel Kgaa | Kapsel für die kontrollierte Freisetzung von Aktivstoffen |
-
2001
- 2001-04-23 EP EP01928752A patent/EP1276837A1/de not_active Withdrawn
- 2001-04-23 CA CA002406174A patent/CA2406174A1/en not_active Abandoned
- 2001-04-23 WO PCT/US2001/013007 patent/WO2001081520A1/en not_active Application Discontinuation
- 2001-04-23 AU AU2001255577A patent/AU2001255577A1/en not_active Abandoned
- 2001-04-23 CN CN 01811700 patent/CN1439046A/zh active Pending
- 2001-04-23 BR BR0110354-7A patent/BR0110354A/pt not_active Application Discontinuation
- 2001-04-23 MX MXPA02010229A patent/MXPA02010229A/es active IP Right Grant
- 2001-04-23 JP JP2001578592A patent/JP2003531311A/ja active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO0181520A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU2001255577A1 (en) | 2001-11-07 |
JP2003531311A (ja) | 2003-10-21 |
BR0110354A (pt) | 2003-01-21 |
CA2406174A1 (en) | 2001-11-01 |
MXPA02010229A (es) | 2003-04-25 |
WO2001081520A1 (en) | 2001-11-01 |
CN1439046A (zh) | 2003-08-27 |
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