WO1998028391A1 - Cleaning composition comprising monoalkyl cationic surfactants - Google Patents
Cleaning composition comprising monoalkyl cationic surfactants Download PDFInfo
- Publication number
- WO1998028391A1 WO1998028391A1 PCT/EP1997/007152 EP9707152W WO9828391A1 WO 1998028391 A1 WO1998028391 A1 WO 1998028391A1 EP 9707152 W EP9707152 W EP 9707152W WO 9828391 A1 WO9828391 A1 WO 9828391A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- surfactant
- composition according
- fatty alkyl
- composition
- mono
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/835—Mixtures of non-ionic with cationic compounds
-
- 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
- C11D3/30—Amines; Substituted amines ; Quaternized 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- 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
-
- 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
Definitions
- the present invention relates to an alkaline cleaning composition for hard surfaces, wherein said composition comprises both a fatty alkyl cationic surfactant and a nonionic surfactant.
- soil release agents including polymers, siloxanes and dialkyl quaternary cationic surfactants in cleaning compositions so as to provide a secondary cleaning benefit. It is believed that these soil release agents function by deposition of a layer of of polymer, siloxane or surfactant on the surface during cleaning. This layer of material is believed to facilitate further cleaning operations by reducing the extent to which soil adheres to the surface.
- compositions are strongly alkaline, so as to assist cleaning.
- quaternary, cationic surfactants are available at the lowest cost.
- These quaternary salts generally comprise a quaternised nitrogen with one or two pendant fatty alkyl chains and three or two pendant lower alkyl chains.
- dialkyl quaternary cationic surfactants it has been found difficult to stabilize the products against flocculation and or phase-separation due to the interaction of the components present.
- the present invention provides an aqueous, hard- surface cleaning composition
- a surfactant mixture comprising:
- a cationic surfactant which is a mono fatty alkyl quaternary ammonium compound wherein the alkyl chains comprise at least 10%wt of C18-C26 alky groups
- composition further comprise, at least 0.5%wt of of an organic amine having a pKa of at least 8.0.
- compositions of the present invention modify the surface energy of surfaces to which the composition is applied so as to raise the contact angle of soil subsequently deposited on the modified surface.
- a range of cationic mono-fatty alkyl quaternary ammonium compounds find useful appliaction in the compositions of the present invention.
- Particularly suitable cationic surfactants are of the general formula:
- R l t R 2 and R 3 are independently C j _ 6 alkyl, R 4 is a fatty alkyl chain and X is an monovalent anion equivalent, the distribution of chain lengths in the material being such that in at least 10%wt of the material the fatty alkyl chain comprises C18-26 carbon atoms. It is preferable that less than 60% of the material comprises mono-fatty alkyl quaternary ammonium compounds in which the fatty alkyl chain is C16 or shorter.
- the fatty alkyl chain can be derived from synthetic or natural feedstocks. If the fatty alkyl chain is derived from natural feedstocks it will generally comprise a mixture of materials with a range of alkyl chain lengths in the fatty-alkyl chain. Preferably the fatty alkyl chains are fully saturated. It is envisaged that saturated alkyl chains will show effective properties due to packing of the alkyl chains at surfaces and interfaces.
- Materials of this general nature, in which the lower alkyl groups are methyl groups are available in the marketplace.
- a particularly preferred material is trimethyl behenyl ammonium bromide. We have determined that this material will flocculate over time in the presence of significant quantities of inorganic salts, including alkali's such as sodium hydroxide and sodium or potassium carbonate. As is further described herein, this difficulty is avoided in the compositions of the present invention.
- Nonionic Surfactants :
- compositions of the present invention comprise a nonionic surfactant.
- nonionic surfactant is believed to contribute significantly to the cleaning effectiveness of the compositions of the invention.
- Suitable nonionic detergent active compounds can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.
- the length of the hydrophilic or polyoxyalkylene radical 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 .
- Particular examples include the condensation product of aliphatic alcohols having from 6 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut oil ethylene oxide condensate having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; condensates of alkylphenols whose alkyl group contains from 6 to 12 carbon atoms with 5 to 25 moles of ethylene oxide per mole of alkylphenol; condensates of the reaction product of ethylenediamine and propylene oxide with ethylene oxide, the condensates containing from 40 to 80% of polyoxyethylene radicals by weight and having a molecular weight of from 5,000 to 11,000; tertiary amine oxides of structure R 3 N0, where one group R is an alkyl group of 8 to 18 carbon atoms and the others are each methyl, ethyl or hydroxy-ethyl groups, for instance dimethyldodecylamine oxide; tertiary phosphine oxides of
- nonionic surfactants are the ethoxylated alcohols having 6-14 carbons and 2-9 moles of ethoxylation.
- Suitable materials include IMBENTIN 91/35 OFA (TM) , a C 9.n nonionic having on average five moles of ethoxylation and NONIDET 91-6T (TM) a topped C 9 _ n nonionic with an average of six moles of ethoxylation.
- nonionic surfactants are known to the skilled worker, as set forth in M.J.Schick 'Nonionic Surfactants', Marcel Dekker (1967) and subsequent editions of the same work.
- the amount of nonionic detergent active to be employed in the composition of the invention will generally be from 1 to 30%wt, preferably from 2 to 20%wt, and most preferably from 5 to 10%wt.
- the ratio of nonionic surfactant to anionic and cationic surfactant is such that > 75% of the total surfactant present in the composition is nonionic.
- compositions of the present invention only comprise low levels of anionic detergent actives or that these actives are absent in so far as is practical. It is believed that the presence of anionic detergents will cause the formation of a complex between the cationic and anionic detergents which will reduce the effectiveness of the compositions.
- the overall surfactant content of compositions according to the present invention will generally be 1 to 30%wt.
- compositions of the invention comprise at least 0.5%wt of an organic amine, with a pK a of at least 8.0.
- This component is believed to function as ester- cleavage agent which assists cleaning of recalcitrant soils such as the pyrolised soils which are produced when fatty and/or proteinaceous foodstuffs are heated at the surface.
- the composition comprises 1-10% of an alkanolamine, with levels of 2-6%wt being particularly preferred.
- alkanolamines include: 2- amino-2-methyl-1-propanol, mono-ethanolamine and di- ethanolamine .
- 2-amino-2-methyl-l-propanol is the most preferred organic amine.
- compositions of the present invention comprise less than 1% of electrolyte salts, including sodium and/or potassium carbonates, bicarbonates and/or hydroxides. Minors and other components:
- compositions of the present invention can contain other ingredients which aid in their cleaning performance and/or improve the physical properties of the composition. These components are not essential to the functioning of the invention.
- Hydrophobic oils are optional components of compositions according to the present invention. Suitable oils include oils which rapidly dissolve triglyceride. When oils are present preferred oils include limonene, para-cymene, di-butyl ether and butyl butyrate.
- a further optional ingredient for compositions according to the invention is a suds regulating material, which can be employed in those compositions according to the invention which have a tendency to produce excessive suds in use.
- suds regulating materials are organic solvents, hydrophobic silica and silicone oils or hydrocarbons.
- Solvents are optional components of compositions according to the present invention. Where solvents are present, preferred solvents are of the form R : -0- (E0) m - (PO) n -R 2 , wherein R x and R 2 are independently C2-6 alkyl or H, but not both hydrogen, m and n are independently 0-5. More preferably, the solvent is selected from the group comprising di-ethylene glycol mono n- butyl ether, mono-ethylene glycol mono n-butyl ether, propylene glycol n-butyl ether, isopropanol, ethanol, butanol and mixtures thereof.
- Alternative solvents include the pyrrolid (in) ones, for example N-methyl pyrrolidinone.
- a long-chain fatty alcohol particularly C16 or longer, more preferably C16-C20 such as tallow alcohol gives an improvement in cleaning performance.
- these alcohols will be present at levels of 0.001-2%, and preferably less than 1%.
- compositions according to the invention can also contain, in addition to the ingredients already mentioned, various other optional ingredients such as pH regulants, colourants, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents, gel-control agents, freeze-thaw stabilisers, bactericides, preservatives, detergent hydrotropes, perfumes and opacifiers.
- various other optional ingredients such as pH regulants, colourants, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents, gel-control agents, freeze-thaw stabilisers, bactericides, preservatives, detergent hydrotropes, perfumes and opacifiers.
- compositions according to the invention are packaged in a container adapted to produce a spray of 0.1-1.5ml of product per spraying operation, said spray having an average drop size in the range 30-300 microns.
- Suitable polymers include polyvinyl pyrrolidone, available in the marketplace as Polymer PVP K-90.
- Suitable levels of PVP polymer range upwards from 50ppm. Levels of 300-2000ppm are particularly preferred.
- compositions have a pH of >10 and comprise, in admixture with water, : a) 3-15% nonionic surfactant (preferably, C9-C12 E05-8 nonionic surfactant)
- solvent preferably, diethylene glycol mono-n-butyl ether
- a cationic surfactant comprises a cation of the general formula: [R t R 2 R 3 R 4 N] + X "
- R ⁇ r R 2 and R 3 are independently C j.6 alkyl, R 4 is a fatty alkyl chain comprising at least 10% C18-26 carbon atoms and X is an monovalent anion equivalent.
- Aqueous compositions comprising nonionic surfactant, and a relatively low level of cationic surfactant were prepared as in Tables 1 below: using the following materials (all compositions are given in terms of wt% unless otherwise stated) : NONI : NONIDET 91-6T (TM: ex. Nippon Shell): a C9-C11 ethoxylated alcohol with 6 moles of ethoxylation, and topped to reduce the quantity of low ethoxylates, VBM: Behenyl trimethyl ammonium chloride (ex Nippon
- Fats di hardened tallow dimethyl ammonium chloride.
- the required amounts of all of the ingredients were mixed at room temperature.
- examples 2 & 5 VBM was added to hot water at 80C and stirred using a Heidolph mixer at 80C for 2 hours, to give a 15.5% solution by weight.
- the required amount of this solution was then added to the required amount of a solution containing all the remaining ingredients, at room temperature, and the solution stirred for a further 10 minutes.
- equal amounts of nonionic surfactant (NONI) and dihardened tallow dimethyl ammonium chloride were melted together at 60C.
- the required amount of this comelt was added (still at 60C) to the required amount of a solution containing all the remaining ingredients, at room temperature, and the solution stirred for a further 30 minutes.
- the required amounts of all of the ingredients were mixed at room temperature. The solution was then warmed briefly to 60 C to homogenise.
- Tiles were cleaned by hand using damp J-cloths and the compositions listed in Table 1. The effort required to clean the tiles was determined as 'ETh' in Table 1. ETh measurements are expressed in Newton. seconds, higher values indicate that more effort was required to clean the tile.
- Stability was determined by placing samples on storage at 5, 25 an 37 Celcius for three months. In the cases indicated as unstable in Table 1 a cloudy precipitate was formed under one or more of the storage conditions.
- Example 2 which is an embodiment of the invention using the longer chain fatty alkyl containing quaternary cationic VBM.
- Examples 3 and 4 also showed an improvement over the control formulation provide as example 1. It can be seen that this improvment was either slight, as with the shorter fatty alkyl chain (CTAB: as used in example 4) or that product stability on storage was lost, as with the di fatty alkyl material (2HT: as used in example 3) .
- Example 5 shows that the combination of an alkaline salt with VBM did not lead to a stable product .
- This mixture was then sprayed using a Humbrol [RTM] airbrush paint sprayer onto the cleaned tiles, using a circular mask, to give 5.5cm diameter patches of soil.
- the acetone was allowed to evaporate to give 0.04-0.05g of soil per tile.
- the soiled tiles were heated at 175 Celcius for 34 minutes and left overnight prior to cleaning.
- the soil tile was placed in the 'WIRA' tester and 0.5ml of test product applied.
- the tile was then cleaned using a 'J-cloth' [RTM] (ex. Johnson and Johnson, UK) , folded to give eight layers, at a head pressure of 657g/cm 2 , for one full cycle (17 passes of the head) .
- CB is the contact angle on glass which has been contacted with the composition according to the example, using bromonaphthalene .
- Example 6 is in accordance with the invention, whereas the remaining examples are comparative.
- Example 11 is a commercially successful kitchen cleaner.
- examples 6 and 7 with clean a surface with reduced effort and leave the surface energy modified so as to prevent or reduce re-soiling.
- Example 8 is less effective especially as regards thermally aged soils.
- the formulation of example 9 will attack the thermally aged soil used to determine ETh but is poor as a general cleaner.
- Example 10 is acceptable but it is preferable that carbonate is absent.
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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)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9713967-0A BR9713967A (pt) | 1996-12-20 | 1997-12-15 | Composição aquosa e processo para limpeza de superfìcies duras compreendendo uma mistura tensoativa. |
DE69706314T DE69706314T2 (de) | 1996-12-20 | 1997-12-15 | Reinigungsmittel mit kationischen monoalkkytensiden |
EP97952956A EP0946695B1 (en) | 1996-12-20 | 1997-12-15 | Cleaning composition comprising monoalkyl cationic surfactants |
JP52836398A JP2001506694A (ja) | 1996-12-20 | 1997-12-15 | モノアルキル陽イオン界面活性剤を含む洗浄剤組成物 |
AU56638/98A AU719564B2 (en) | 1996-12-20 | 1997-12-15 | Cleaning composition comprising monoalkyl cationic surfactants |
SK811-99A SK81199A3 (en) | 1996-12-20 | 1997-12-15 | Aqueous cleaning composition for hard surfaces and hard surfaces cleaning method |
CA002272607A CA2272607A1 (en) | 1996-12-20 | 1997-12-15 | Cleaning composition comprising monoalkyl cationic surfactants |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9626610.1A GB9626610D0 (en) | 1996-12-20 | 1996-12-20 | Cleaning composition comprising monoalkyl cationic surfactants |
GB9626610.1 | 1996-12-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998028391A1 true WO1998028391A1 (en) | 1998-07-02 |
Family
ID=10804833
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1997/007152 WO1998028391A1 (en) | 1996-12-20 | 1997-12-15 | Cleaning composition comprising monoalkyl cationic surfactants |
Country Status (16)
Country | Link |
---|---|
EP (1) | EP0946695B1 (es) |
JP (1) | JP2001506694A (es) |
KR (1) | KR20000069596A (es) |
AR (1) | AR009668A1 (es) |
AU (1) | AU719564B2 (es) |
BR (1) | BR9713967A (es) |
CA (1) | CA2272607A1 (es) |
DE (1) | DE69706314T2 (es) |
ES (1) | ES2163209T3 (es) |
GB (1) | GB9626610D0 (es) |
HU (1) | HUP0000687A3 (es) |
SK (1) | SK81199A3 (es) |
TR (1) | TR199901318T2 (es) |
TW (1) | TW374798B (es) |
WO (1) | WO1998028391A1 (es) |
ZA (1) | ZA9710996B (es) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003031549A1 (en) * | 2001-10-10 | 2003-04-17 | 3M Innovative Properties Company | Cleaning composition |
EP1818389A2 (en) | 2006-02-13 | 2007-08-15 | Air Liquide Santé (International) | Alkaline disinfecting and cleaning compositions having improved cleaning efficiency |
JP2018536061A (ja) * | 2015-11-12 | 2018-12-06 | エコラブ ユーエスエイ インク | 向上した油性汚れ除去のための混合カチオン性/非イオン性界面活性剤系を含有する低泡性物品洗浄洗剤 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6585145B2 (ja) * | 2016-12-13 | 2019-10-02 | アース製薬株式会社 | 水洗トイレ用洗浄組成物 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0036720A1 (en) * | 1980-03-11 | 1981-09-30 | Unilever Plc | Detergent composition |
JPS5876477A (ja) * | 1981-10-30 | 1983-05-09 | Lion Corp | 陶磁器、ガラス表面のケイ酸スケールによる汚れを防止する方法 |
WO1995014765A1 (en) * | 1993-11-22 | 1995-06-01 | Colgate-Palmolive Company | Microemulsion all purpose liquid cleaning compositions |
US5522942A (en) * | 1993-04-19 | 1996-06-04 | Reckitt & Colman Inc. | Method for cleaning hard surfaces using an aqueous solution of quaternary ammonium compound, combination of nonionic surfactant and glycol ether solvent |
WO1996026263A1 (en) * | 1995-02-23 | 1996-08-29 | Unilever Plc | Process and composition for cleaning surfaces |
-
1996
- 1996-12-20 GB GBGB9626610.1A patent/GB9626610D0/en active Pending
-
1997
- 1997-12-08 ZA ZA9710996A patent/ZA9710996B/xx unknown
- 1997-12-15 DE DE69706314T patent/DE69706314T2/de not_active Expired - Fee Related
- 1997-12-15 TR TR1999/01318T patent/TR199901318T2/xx unknown
- 1997-12-15 AU AU56638/98A patent/AU719564B2/en not_active Ceased
- 1997-12-15 SK SK811-99A patent/SK81199A3/sk unknown
- 1997-12-15 ES ES97952956T patent/ES2163209T3/es not_active Expired - Lifetime
- 1997-12-15 CA CA002272607A patent/CA2272607A1/en not_active Abandoned
- 1997-12-15 BR BR9713967-0A patent/BR9713967A/pt not_active Application Discontinuation
- 1997-12-15 KR KR1019997005578A patent/KR20000069596A/ko not_active Application Discontinuation
- 1997-12-15 JP JP52836398A patent/JP2001506694A/ja not_active Ceased
- 1997-12-15 HU HU0000687A patent/HUP0000687A3/hu unknown
- 1997-12-15 WO PCT/EP1997/007152 patent/WO1998028391A1/en not_active Application Discontinuation
- 1997-12-15 EP EP97952956A patent/EP0946695B1/en not_active Expired - Lifetime
- 1997-12-17 AR ARP970105932A patent/AR009668A1/es unknown
-
1998
- 1998-01-16 TW TW087100569A patent/TW374798B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0036720A1 (en) * | 1980-03-11 | 1981-09-30 | Unilever Plc | Detergent composition |
JPS5876477A (ja) * | 1981-10-30 | 1983-05-09 | Lion Corp | 陶磁器、ガラス表面のケイ酸スケールによる汚れを防止する方法 |
US5522942A (en) * | 1993-04-19 | 1996-06-04 | Reckitt & Colman Inc. | Method for cleaning hard surfaces using an aqueous solution of quaternary ammonium compound, combination of nonionic surfactant and glycol ether solvent |
WO1995014765A1 (en) * | 1993-11-22 | 1995-06-01 | Colgate-Palmolive Company | Microemulsion all purpose liquid cleaning compositions |
WO1996026263A1 (en) * | 1995-02-23 | 1996-08-29 | Unilever Plc | Process and composition for cleaning surfaces |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Section Ch Week 8324, Derwent World Patents Index; Class A97, AN 83-57656K, XP002062525 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003031549A1 (en) * | 2001-10-10 | 2003-04-17 | 3M Innovative Properties Company | Cleaning composition |
CN100415860C (zh) * | 2001-10-10 | 2008-09-03 | 3M创新有限公司 | 清洁组合物 |
EP1818389A2 (en) | 2006-02-13 | 2007-08-15 | Air Liquide Santé (International) | Alkaline disinfecting and cleaning compositions having improved cleaning efficiency |
EP1818389A3 (en) * | 2006-02-13 | 2007-12-05 | Air Liquide Santé (International) | Alkaline disinfecting and cleaning compositions having improved cleaning efficiency |
JP2018536061A (ja) * | 2015-11-12 | 2018-12-06 | エコラブ ユーエスエイ インク | 向上した油性汚れ除去のための混合カチオン性/非イオン性界面活性剤系を含有する低泡性物品洗浄洗剤 |
Also Published As
Publication number | Publication date |
---|---|
BR9713967A (pt) | 2000-04-11 |
DE69706314T2 (de) | 2002-01-03 |
AR009668A1 (es) | 2000-04-26 |
KR20000069596A (ko) | 2000-11-25 |
EP0946695B1 (en) | 2001-08-22 |
GB9626610D0 (en) | 1997-02-05 |
TR199901318T2 (xx) | 1999-08-23 |
DE69706314D1 (de) | 2001-09-27 |
TW374798B (en) | 1999-11-21 |
ZA9710996B (en) | 1999-06-08 |
AU5663898A (en) | 1998-07-17 |
EP0946695A1 (en) | 1999-10-06 |
ES2163209T3 (es) | 2002-01-16 |
HUP0000687A3 (en) | 2003-02-28 |
HUP0000687A2 (hu) | 2000-08-28 |
AU719564B2 (en) | 2000-05-11 |
CA2272607A1 (en) | 1998-07-02 |
SK81199A3 (en) | 1999-12-10 |
JP2001506694A (ja) | 2001-05-22 |
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