WO2000022091A1 - Detergent compositions - Google Patents
Detergent compositions Download PDFInfo
- Publication number
- WO2000022091A1 WO2000022091A1 PCT/US1999/022474 US9922474W WO0022091A1 WO 2000022091 A1 WO2000022091 A1 WO 2000022091A1 US 9922474 W US9922474 W US 9922474W WO 0022091 A1 WO0022091 A1 WO 0022091A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- detergent
- detergent composition
- water
- disintegrant
- Prior art date
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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- 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
- 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
- C11D3/2082—Polycarboxylic 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
- 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
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
-
- 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
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
Definitions
- detergent compositions It is a particular requirement of detergent compositions that they should deliver the detergent actives to the wash water as soon as possible on contact with water.
- detergent compositions have tended to have increased densities above 650g/l, or above 700g/l or even above 750g/l, or are even provided in the form of tablets. This has tended to inhibit dispensing and/or distribution and consequently rapid delivery of the detergent actives to the wash water.
- EP- A-466484 describes the use of disintegrants and their mechanisms. It is stated that
- Suitable polymers should be heat stable up to at least the temperature for the appropriate detergent processing.
- the disintegrants are generally present in the detergent composition in amounts from 1 to 20 wt%, preferably in amounst of 2 to 15 wt%, most preferably from 2 to 10 wt% based on the weight of the detergent composition. It may be particularly advantageous to use the water-swellable cationic polymer in combination with an additional disintegrant, such as any of those discussed in EP-A- 466484. In such cases, it may be preferred to from a pre-mix of the water-swellable cationic polymer and additional disintegrant prior to incorporation into a detergent composition.
- suitable phosphate-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta- phosphates).
- Preferred phosphate builders are tetrasodium pyrophosphate or more preferably anhydrous or partially hydrated sodium tripolyphosphate at levels of from 0.5% to 50%, more preferably from 5% to 45% by weight based on the detergent composition as a whole.
- polymeric or oligomeric polycarboxylates are present at levels of less than 5%, preferably less than 3% or even less than 2% or even 0% by weight of the compositions.
- Chelants are also useful as the polyanionic builder for use in the detergent compositions of the invention.
- chelant is meant sequester (chelate) metal ions.
- These components are generally present at a level of from 0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most preferably from 0.3% to 2% by weight of the compositions.
- the particulate material used for making the tablet of this invention can be made by any particulation or granulation process.
- An example of such a process is spray drying (in a co-current or counter current spray drying tower) which typically gives low bulk densities 600g/l or lower.
- Particulate materials of higher density can be prepared by granulation and densification in a high shear batch mixer/granulator or by a continuous granulation and densification process (e.g. using Lodige® CB and/or Lodige® KM mixers).
- Other suitable processes include fluid bed processes, compaction processes (e.g. roll compaction), extrusion, as well as any particulate material made by any chemical process like flocculation, crystallisation sentering, etc.
- Suitable coating materials are fatty acids, C2-C13 dicarboxylic acids, fatty alcohols, diols, esters and ethers.
- Preferred fatty acids are those having a carbon chain length of from C12 to C22 and most preferably from C18 to C22.
- a coating of any desired thickness can be applied according to the present invention.
- the coating forms from 1% to 10%, preferably from 1.5% to 5%, of the tablet or detergent component weight.
- composition or component thereof according to the present invention will contain additional detergent ingredients.
- additional detergent ingredients The precise nature of these additional ingredients, and levels of incorporation thereof will depend on the application of the component or compositions and the physical form of the components and the compositions.
- AE X S especially EO 1-7 ethoxy sulfates
- Cig N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the Ci2-Ci8 N-methylglucamides. See WO 9,206,154.
- Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C1 Q-C ⁇ N-(3- methoxypropyl) glucamide.
- the N-propyl through N-hexyl C ⁇ 2-C ⁇ glucamides can be used for low sudsing.
- C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C ⁇ Q-CI g soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful.
- Suitable cationic surfactants for incorporation into the detergent composition of the invention include the quaternary ammonium surfactants.
- the quaternary ammonium surfactant is a mono C6-C16, preferably Cg-Cio N- alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
- Preferred are also the mono-alkoxylated and bis- alkoxylated amine surfactants.
- Aluminosilicate builders may be useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
- aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally- occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X, zeolite MAP may be particularly useful. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
- This material is known as Zeolite A.
- the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
- R ⁇ is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
- Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof.
- Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from about 0.001%) to about 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
- AU Anson units
- proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo.
- proteases suitable for removing protein- based stains that are commercially available include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
- Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and
- Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.” Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
- Patent 3,600,319 issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas.
- Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570.
- Other components which are commonly used in detergent compositions and which may be incorporated into the detergent tablets of the present invention include, soil release agents, soil antiredeposition agents, dispersing agents, brighteners, suds suppressors, fabric softeners, dye transfer inhibition agents and perfumes.
- cationic polymer IPR 88 (ex. Rohm & Haas) was used as disintegrant, a tablet having a total weight of 46g and a diametral fracture stress of 28 kPa was produced. This tablet was immersed in de-ionised water at 20°C and the time taken for the coating to begin to disintegrate was measured to be 4 seconds.
- detergent compositions according to the invention may be particulate or may be compressed in a tablet press into tablets.
- R C 10 -C 18 , condensed with z mol ethylene oxide
- PB1 Anhydrous sodium perborate bleach of nominal formula NaBO 2 .H 2 O 2
- DOBS Decanoyl oxybenzene sulfonate in the form of the sodium salt
- NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt
- NACA-OBS (6-nonamidocaproyl) oxybenzene sulfonate
- DOBS Decanoyloxybenzene sulfonate in the form of the sodium salt
- DOBA Decanoyl oxybenzoic acid
- DTPMP Diethylene triamine penta (methylene phosphonate), marketed by
- EDDS Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt.
- Photoactivated Sulfonated zinc phthlocyanine encapsulated in bleach (1) dextrin soluble polymer
- PVP Polyvinylpyrolidone polymer
- PVNO Polyvinylpyridine N-oxide polymer
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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)
- Detergent Compositions (AREA)
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU10971/00A AU1097100A (en) | 1998-10-09 | 1999-09-28 | Detergent compositions |
BR9914354-2A BR9914354A (pt) | 1998-10-09 | 1999-09-28 | Composições detergentes |
EP99954680A EP1119610B1 (en) | 1998-10-09 | 1999-09-28 | Detergent compositions |
DE69929223T DE69929223T2 (de) | 1998-10-09 | 1999-09-28 | Reinigungsmittelzusammensetzungen |
JP2000575984A JP2002527580A (ja) | 1998-10-09 | 1999-09-28 | 洗剤組成物 |
AT99954680T ATE314455T1 (de) | 1998-10-09 | 1999-09-28 | Reinigungsmittelzusammensetzungen |
CA002346187A CA2346187A1 (en) | 1998-10-09 | 1999-09-28 | Detergent compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9822023.9 | 1998-10-09 | ||
GB9822023A GB2342358A (en) | 1998-10-09 | 1998-10-09 | Detergent compositions comprising cationic polymers |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000022091A1 true WO2000022091A1 (en) | 2000-04-20 |
Family
ID=10840263
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/022474 WO2000022091A1 (en) | 1998-10-09 | 1999-09-28 | Detergent compositions |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP1119610B1 (pt) |
JP (1) | JP2002527580A (pt) |
CN (1) | CN1329662A (pt) |
AR (1) | AR020747A1 (pt) |
AT (1) | ATE314455T1 (pt) |
AU (1) | AU1097100A (pt) |
BR (1) | BR9914354A (pt) |
CA (1) | CA2346187A1 (pt) |
DE (1) | DE69929223T2 (pt) |
ES (1) | ES2255312T3 (pt) |
GB (1) | GB2342358A (pt) |
WO (1) | WO2000022091A1 (pt) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1162257A1 (en) * | 2000-06-09 | 2001-12-12 | The Procter & Gamble Company | A process of treating fabrics with a detergent tablet comprising an ion exchange resin |
EP1186649A1 (de) * | 2000-09-08 | 2002-03-13 | Cognis Deutschland GmbH | Waschmitteltabletten |
EP1188819A1 (de) * | 2000-09-08 | 2002-03-20 | Cognis Deutschland GmbH | Waschmitteltabletten |
EP1188817A2 (de) * | 2000-09-08 | 2002-03-20 | Cognis Deutschland GmbH | Waschmittel |
EP1191094A2 (de) * | 2000-09-08 | 2002-03-27 | Cognis Deutschland GmbH | Waschmittel |
WO2004046292A1 (en) * | 2002-11-15 | 2004-06-03 | Unilever N.V. | Improved detergent composition |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2376692A (en) * | 2001-06-22 | 2002-12-24 | Reckitt Benckiser Nv | Fabric softening laundry tablet |
EP1275371A1 (en) * | 2001-07-13 | 2003-01-15 | Johnson and Johnson GmbH | Dry products comprising a sheet and two phases |
MX2012002748A (es) * | 2009-09-02 | 2012-04-19 | Unilever Nv | Composicion y proceso para tratamiento de un genero. |
MY182371A (en) * | 2014-09-17 | 2021-01-21 | Lion Corp | Powder detergent for clothing |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4761249A (en) * | 1985-12-23 | 1988-08-02 | Henkel Kommanditgesellschaft Auf Aktien | Soil-collecting cleaning enhancers in aqueous surfactant laundering and cleaning solutions |
US4773939A (en) * | 1986-02-22 | 1988-09-27 | Henkel Kommanditgesellschaft Auf Aktien | Use of insoluble soil collectors for at least partial regeneration of laundering and cleaning solutions |
EP0466484A2 (en) * | 1990-07-13 | 1992-01-15 | Unilever Plc | Detergent compositions |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2911857A1 (de) * | 1979-03-26 | 1980-10-16 | Henkel Kgaa | Appretierend wirkendes textilwaschmittel |
EP0111965B1 (en) * | 1982-12-23 | 1989-07-26 | THE PROCTER & GAMBLE COMPANY | Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties |
US5478501A (en) * | 1994-04-07 | 1995-12-26 | The Andrew Jergens Company | Bathing composition containing coated cationic polymer |
GB2318799A (en) * | 1996-10-31 | 1998-05-06 | Procter & Gamble | Detergent compositions |
-
1998
- 1998-10-09 GB GB9822023A patent/GB2342358A/en not_active Withdrawn
-
1999
- 1999-09-28 DE DE69929223T patent/DE69929223T2/de not_active Expired - Lifetime
- 1999-09-28 EP EP99954680A patent/EP1119610B1/en not_active Expired - Lifetime
- 1999-09-28 AT AT99954680T patent/ATE314455T1/de not_active IP Right Cessation
- 1999-09-28 BR BR9914354-2A patent/BR9914354A/pt not_active IP Right Cessation
- 1999-09-28 WO PCT/US1999/022474 patent/WO2000022091A1/en active IP Right Grant
- 1999-09-28 AU AU10971/00A patent/AU1097100A/en not_active Abandoned
- 1999-09-28 JP JP2000575984A patent/JP2002527580A/ja not_active Withdrawn
- 1999-09-28 CA CA002346187A patent/CA2346187A1/en not_active Abandoned
- 1999-09-28 CN CN99814114.3A patent/CN1329662A/zh active Pending
- 1999-09-28 ES ES99954680T patent/ES2255312T3/es not_active Expired - Lifetime
- 1999-10-08 AR ARP990105090A patent/AR020747A1/es unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4761249A (en) * | 1985-12-23 | 1988-08-02 | Henkel Kommanditgesellschaft Auf Aktien | Soil-collecting cleaning enhancers in aqueous surfactant laundering and cleaning solutions |
US4773939A (en) * | 1986-02-22 | 1988-09-27 | Henkel Kommanditgesellschaft Auf Aktien | Use of insoluble soil collectors for at least partial regeneration of laundering and cleaning solutions |
EP0466484A2 (en) * | 1990-07-13 | 1992-01-15 | Unilever Plc | Detergent compositions |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1162257A1 (en) * | 2000-06-09 | 2001-12-12 | The Procter & Gamble Company | A process of treating fabrics with a detergent tablet comprising an ion exchange resin |
WO2001096522A1 (en) * | 2000-06-09 | 2001-12-20 | The Procter & Gamble Company | A process of treating fabrics with a detergent tablet comprising an ion exchange resin |
EP1186649A1 (de) * | 2000-09-08 | 2002-03-13 | Cognis Deutschland GmbH | Waschmitteltabletten |
EP1188819A1 (de) * | 2000-09-08 | 2002-03-20 | Cognis Deutschland GmbH | Waschmitteltabletten |
EP1188817A2 (de) * | 2000-09-08 | 2002-03-20 | Cognis Deutschland GmbH | Waschmittel |
EP1191094A2 (de) * | 2000-09-08 | 2002-03-27 | Cognis Deutschland GmbH | Waschmittel |
EP1188817A3 (de) * | 2000-09-08 | 2003-06-11 | Cognis Deutschland GmbH & Co. KG | Waschmittel |
EP1191094A3 (de) * | 2000-09-08 | 2003-06-11 | Cognis Deutschland GmbH & Co. KG | Waschmittel |
WO2004046292A1 (en) * | 2002-11-15 | 2004-06-03 | Unilever N.V. | Improved detergent composition |
CN100393863C (zh) * | 2002-11-15 | 2008-06-11 | 荷兰联合利华有限公司 | 改进的洗涤剂组合物 |
Also Published As
Publication number | Publication date |
---|---|
DE69929223T2 (de) | 2006-08-31 |
ES2255312T3 (es) | 2006-06-16 |
AR020747A1 (es) | 2002-05-29 |
EP1119610B1 (en) | 2005-12-28 |
CN1329662A (zh) | 2002-01-02 |
CA2346187A1 (en) | 2000-04-20 |
EP1119610A1 (en) | 2001-08-01 |
AU1097100A (en) | 2000-05-01 |
ATE314455T1 (de) | 2006-01-15 |
GB2342358A (en) | 2000-04-12 |
DE69929223D1 (de) | 2006-02-02 |
GB9822023D0 (en) | 1998-12-02 |
BR9914354A (pt) | 2001-06-26 |
JP2002527580A (ja) | 2002-08-27 |
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