EP0783035B1 - Bleichmittelsysteme enthaltend Bis- und Tris-(mu-oxo)-di-Mangan-Komplexsalze - Google Patents
Bleichmittelsysteme enthaltend Bis- und Tris-(mu-oxo)-di-Mangan-Komplexsalze Download PDFInfo
- Publication number
- EP0783035B1 EP0783035B1 EP96120743A EP96120743A EP0783035B1 EP 0783035 B1 EP0783035 B1 EP 0783035B1 EP 96120743 A EP96120743 A EP 96120743A EP 96120743 A EP96120743 A EP 96120743A EP 0783035 B1 EP0783035 B1 EP 0783035B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bis
- bleach
- formula
- bleach system
- oxo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- NYCVCXMSZNOGDH-UHFFFAOYSA-N pyrrolidine-1-carboxylic acid Chemical class OC(=O)N1CCCC1 NYCVCXMSZNOGDH-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 235000020095 red wine Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3932—Inorganic compounds or complexes
Definitions
- Bleaches that release active oxygen are an essential ingredient modern washing and cleaning agents. Your main job is distance stubborn stains such as tea, coffee, red wine or fruit juices from textile fibers or solid surfaces. This is done by oxidative destruction of the chromophoric system; adhering microorganisms are killed at the same time and neutralizes odors.
- Hydrogen peroxide organic or inorganic peracid used.
- powdered products is used as a source for active oxygen mostly used a persalt.
- Typical examples are Sodium perborates or percarbonates or urea adducts.
- bleach activators are often added.
- examples for this are Tetraacetylethylenediamine (TAED), diacetyldioxohexahydrotriazine (DADHT), Pentaacetylglycose (PAG), benzoyloxybenzenesulfonate (BOBS) and Nonanoyloxybenzenesulfonate (NOBS).
- TAED Tetraacetylethylenediamine
- DADHT diacetyldioxohexahydrotriazine
- PAG Pentaacetylglycose
- BBS benzoyloxybenzenesulfonate
- NOBS Nonanoyloxybenzenesulfonate
- transition metals are free or complex Form catalyze the decomposition of hydrogen peroxides.
- the effectiveness of is unsatisfactory in most cases.
- the addition of metal salts leads to catalytic decomposition of hydrogen peroxide, however, no bleaching effect is observed. Most is this is associated with damage to the textile fabric.
- the appearance of free Transition metals during the washing and cleaning process is therefore undesirable. If, on the other hand, the metal salt is used in a complex form, the corresponding complex during storage and under Conditions of use to be stable to hydrolysis and oxidation Suppress side effects.
- EP A 458 397 and 458 398 describes the use of macrocyclic Polyamines as complex ligands in multinuclear, oxygen-bridged Manganese complexes. In combination with oxidizing agents, these complexes show especially on tea stains, good bleaching properties. As a disadvantage however, the difficult to access complex ligand of the triazacyclononane type has an effect out. It is only in a multi-stage, by-product-rich manufacturing process accessible. Similar complexes are described in EP 544 519, again the Synthesis of the complex ligand is very complex and difficult on an industrial scale realize.
- anion A are Cl - , Br - , J - , NO 3 - , ClO 4 - , NCS - , PF 6 - , RSO 3 - , RSO 4 - , SO 4 2- , BPh 4 - , OAc - .
- Preferred anions are PF 6 - , ClO 4 - , tosylate.
- the ligands of the formula II contained in these manganese complex salts are prepared by reacting 2- (chloromethyl) pyridinium chloride with an alkylenediamine in the presence of a phase transfer catalyst (see Synthesis, June 1992, p. 539-540) or in an analogous manner for the substituted other ligands of the formula II.
- the manganese complex salts of the formula I are prepared in accordance with the information in Inorg. Chem. 1989, 28, 3606-3608, by oxidizing an aqueous solution containing MnCl 2 and the ligand with H 2 O 2 or analogously to that in Inorg. Chem. 1994, 33, 4105-4111 described method, in which the oxidation is carried out with ammonium peroxodisulfate.
- the metal complexes can be either pre-washed and Detergent added or ligand and during the washing process Transition metal can be generated in situ.
- These complex salts have catalytic properties and are capable of Bleaching performance of peracids, persalts or hydrogen peroxide in washing and To significantly increase the cleaning process.
- the bleaching catalysts are in Combination with an oxidizing agent used.
- Oxidizing agents that can be used are hydrogen peroxide, Alkali metal perborates, percarbonates, perphosphates or persulfates.
- the catalysts are used in powdered products be, sodium perborate mono- or tetrahydrate, caroate in the form of the triple salt and sodium percarbonate, the latter in particular in coated form.
- This Compounds can either with the catalysts alone or according to one preferred embodiment, additionally together with a bleach activator be used. This extends the range of applications and the germicidal properties of the formulation enhanced.
- Bleach activators are known from numerous patent applications. Examples for this are reactive esters and amides as in GB 836,988, 864,798, 907,356, 1,003,310 and 1,519,351; EP 284,292, 331,229, 303,520, 185,522, 174,132, 120,591 and US 1,246,339, 3,332,882, 4,128,494, 4,412,934, 4,675,393, 4,751,015 and 4,397,757.
- Tetraacetylethylenediamine is particularly preferred, Nonanoyloxibenzenesulfonate, benzoyloxibenzenesulfonate, nonanoyl and Benzoylcaprolactam, isatoic, maleic, succinic and citric anhydrides and acylated sugar or sugar derivatives, in addition alkyl or aryl nitriles.
- peroxibenzoic acid and substituted derivatives Typical representatives are peroxibenzoic acid and substituted derivatives, aliphatic mono- and dicarboxylic acids such as pemonanoic acid, perlauric acid, 1,9-diperoxiazeldic acid and 1,12-dodecanediperic acid.
- N, N'-phthaloylaminoperoxycarboxylic acids such as N, N'-phthaloylaminoperoxyhexanoic acid (PAP), 6-octylamino-6-oxoperoxihexanoic acid, monoperoxiphthalic acid and their Salts, 2-alkylperoxy-1,4-butanedioic acids or 4,4'-sulphonylbisperoxybenzoic acid.
- composition of the bleach system according to the invention can vary widely Limits fluctuate and are generally between 0.0005 and 2% by weight, preferably 0.001 to 0.5% by weight of the bleaching catalyst described and 1 to 99.9995%, preferably 5 to 99.999% of an oxidizing agent from the group inorganic or organic peracids or salts, and optionally 0 to 70%, preferably 10 to 60% of a bleach activator.
- the bleaching systems according to the invention are used in heavy-duty detergents, Multi-component detergents (modular systems), stain salts, Stain pretreatment agents, dishwasher detergents, cleaning agents for hard surfaces, disinfectants, and denture cleaners. Beside the bleach the catalysts also take on the function of dye transfer inhibitors. Usually the catalysts are in granular form for washing and Detergent added. Inorganic pelletizers can be used Salts such as sodium sulfate, chloride, phosphate or silicates can be used. In a preferred application form, they are incorporated into the activator granules.
- granulation can be inorganic or organic auxiliaries are used, film-forming materials are preferred such as surfactants, fatty acids, celulose derivatives, or polymers.
- the granules can additionally be provided with a coating, which on the one hand ensures their storage stability increases and interactions with other detergent ingredients during the Storage can be prevented, but also their release kinetics can be influenced.
- the bleach system according to the invention can be used in detergents and cleaning agents in the form of a powder or as granules.
- the detergents and cleaning agents contain usually still surface-active compounds such as anionic, non-ionic, zwitterionic, amphoteric or cationic surfactants, builders, Enzymes and additives.
- Surfactants can be of natural or synthetic origin and are e.g. in "Surface Active Agents and Detergents" Volume and II by Schwanz, Perry and Berch described. Examples are alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, alpha-sulfofatty acid methyl esters, soaps and alkyl ether sulfonates. nonionic Surfactants such as alkyl polyglycol ethers, alkyl polyglucosides, glucamides, sugar esters and Amine oxides can also be used.
- Important builder and cobuilder substances which in combination with the bleach systems according to the invention can be used Phosphates such as sodium tripolyphosphate, type A, X and P zeolites, Alkali metal carbonates and bicarbonates, amorphous and crystalline silicates, especially layered silicates such as SKS-6, 7, 9 or 10 from Hoechst AG or disilicates as sold by Akzo under the trade name Britesil7.
- a co-builder can include organic carboxylic acids such as citric acid or amino acids are used, but also polymers of the type of polyacrylic acid or Copolymers of acrylic acid and maleic acid or their derivatives. Farther phosphonate or other complexing agents can be added.
- Amylase, proteases, lipases, cellulases and peroxidases can be used as enzymes other additives cellulose ethers, silicones, bentonites, optical brighteners and perfume be used.
- N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine were dissolved in 30 ml of a mixture of ethanol and water (5: 1) and then Mn (acetate) 3 . 2H 2 O (0.96 g; 3.6 mmol) was added. Then 2.2 g (20 mmol) sodium butyrate was added and then 2 ml HClO 4 (70%). A pH of 7.5 was established. Then 3 g (24.48 mmol) NaClO 4 were added and this mixture was stirred for 4 hours at room temperature.
- Manganese (II) sulfate and the 4-dentate were used as comparative compounds
- Example 3 Washing tests in a Linitest device
- Example 4 Washing tests in a Linitest device
- Example 3 The tests were carried out as described in Example 3. Instead of the test soil tea (BC-1), beetroot and curry on cotton (manufacturer laundry research Krefeld) were used. catalyst Beetroot ⁇ RE Curry ⁇ RE without 0 0 K1 + 2.0 + 0.6 K2 + 4.0 + 0.9
- the washing tests were carried out in the Linitest réelle at 40 ° C; Washing time 30 min. 1.5 g / l WMP were pre-dissolved in 200 ml water (15 ° dH) and 0.5 g / l sodium perborate monohydrate was added. Before the start of the washing tests, 0; 1.5; 3; 6; 12; 25 mg / l of the catalysts added. The washing tests were carried out analogously to Example 3.
- the table shows the reflectance differences ⁇ RE of the washes with and without a catalyst.
- Catalyst concentration [mg / l] catalyst 0 1.5 3 6 12 25 K1 0 + 2.0 + 2.0 + 3.2 + 2.6 + 2.7 K2 0 + 1.6 + 2.3 + 3.2 + 4.8 +5.1
- Example 7 Influence of various oxidizing agents on the bleaching result
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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)
- Catalysts (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19600159A DE19600159A1 (de) | 1996-01-04 | 1996-01-04 | Bleichmittelsysteme enthaltend Bis- und Tris-(mu-oxo)-di-Mangan-Komplexsalze |
| DE19600159 | 1996-01-04 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0783035A2 EP0783035A2 (de) | 1997-07-09 |
| EP0783035A3 EP0783035A3 (de) | 1998-02-25 |
| EP0783035B1 true EP0783035B1 (de) | 2003-09-24 |
Family
ID=7782152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96120743A Expired - Lifetime EP0783035B1 (de) | 1996-01-04 | 1996-12-23 | Bleichmittelsysteme enthaltend Bis- und Tris-(mu-oxo)-di-Mangan-Komplexsalze |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5942152A (es) |
| EP (1) | EP0783035B1 (es) |
| JP (1) | JPH09194886A (es) |
| AT (1) | ATE250660T1 (es) |
| CA (1) | CA2194342A1 (es) |
| DE (2) | DE19600159A1 (es) |
| ES (1) | ES2207663T3 (es) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19605688A1 (de) * | 1996-02-16 | 1997-08-21 | Henkel Kgaa | Übergangsmetallkomplexe als Aktivatoren für Persauerstoffverbindungen |
| CA2264047A1 (en) * | 1996-08-26 | 1998-03-05 | Alfred Busch | Cellulase activity control by a terminator |
| CA2248476A1 (en) * | 1997-10-01 | 1999-04-01 | Unilever Plc | Bleach activation |
| US6274122B1 (en) * | 1999-01-07 | 2001-08-14 | Mclaughlin Gerald | Device and method using dry mixtures for whitening teeth |
| WO2002071968A2 (en) * | 2001-03-14 | 2002-09-19 | Gerald Mclaughlin | Strips for treating teeth |
| GB2386616A (en) * | 2002-03-21 | 2003-09-24 | Unilever Plc | Bleaching composition |
| JP2005194244A (ja) * | 2004-01-09 | 2005-07-21 | Shigenobu Yano | 亜鉛イオン蛍光センサー |
| EP2286845B1 (en) | 2004-03-05 | 2016-11-16 | Gen-Probe Incorporated | Reagents and method for use in deactivating nucleic acids |
| KR100647976B1 (ko) * | 2004-05-03 | 2006-11-23 | 애경산업(주) | 표백촉매로서 거대고리 망간 착화합물 및 이를 함유한표백제 및 표백세제 조성물 |
| US8492324B2 (en) | 2008-04-09 | 2013-07-23 | Basf Se | Use of metal hydrazide complex compounds as oxidation catalysts |
| WO2009141258A1 (de) * | 2008-05-23 | 2009-11-26 | Henkel Ag & Co. Kgaa | Textilschonendes waschmittel |
| WO2010131227A2 (en) * | 2009-05-14 | 2010-11-18 | Ecolab Usa Inc. | Compositions, systems and method for in situ generation of alkalinity |
| WO2012000846A1 (en) | 2010-06-28 | 2012-01-05 | Basf Se | Metal free bleaching composition |
| WO2013060708A1 (en) | 2011-10-25 | 2013-05-02 | Basf Se | Use of comb or block copolymers as soil antiredeposition agents and soil release agents in laundry processes |
| IN2014CN03742A (es) | 2011-10-25 | 2015-09-04 | Basf Se | |
| US10837949B1 (en) * | 2012-03-22 | 2020-11-17 | Piers Richard Warburton | Peracetic acid sensor with filter to remove hydrogen peroxide |
| US9790452B2 (en) | 2013-03-27 | 2017-10-17 | Basf Se | Block copolymers as soil release agents in laundry processes |
| KR20160105790A (ko) | 2013-11-27 | 2016-09-07 | 바스프 에스이 | 세탁 방법에서 오염물 방출제로서의 랜덤 공중합체 |
| WO2017186480A1 (en) | 2016-04-26 | 2017-11-02 | Basf Se | Metal free bleaching composition |
Family Cites Families (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1246339A (en) | 1916-08-21 | 1917-11-13 | Isaac J Smit | Self-illuminating depresser for dental and surgical work. |
| NL113890C (es) | 1955-07-27 | |||
| GB864798A (en) | 1958-03-20 | 1961-04-06 | Unilever Ltd | Bleaching processes and compositions |
| NL252798A (es) | 1959-06-19 | 1900-01-01 | ||
| US3156654A (en) | 1961-06-19 | 1964-11-10 | Shell Oil Co | Bleaching |
| GB1003310A (en) | 1963-01-15 | 1965-09-02 | Unilever Ltd | Bleaching processes and compositions |
| US3332882A (en) | 1964-12-18 | 1967-07-25 | Fmc Corp | Peroxygen compositions |
| GB1182143A (en) | 1966-03-01 | 1970-02-25 | United States Borax Chem | Bleaching Compositions and Methods. |
| GB1519351A (en) | 1975-01-29 | 1978-07-26 | Unilever Ltd | Preparation of acetoxy arylene sulphonates |
| US4128494A (en) | 1976-09-01 | 1978-12-05 | Produits Chimiques Ugine Kuhlmann | Activators for percompounds |
| US4397757A (en) | 1979-11-16 | 1983-08-09 | Lever Brothers Company | Bleaching compositions having quarternary ammonium activators |
| GR76237B (es) | 1981-08-08 | 1984-08-04 | Procter & Gamble | |
| DE3360762D1 (en) | 1982-04-02 | 1985-10-17 | Unilever Nv | Process for preparing sugar acetates |
| US4412934A (en) | 1982-06-30 | 1983-11-01 | The Procter & Gamble Company | Bleaching compositions |
| US4478733A (en) | 1982-12-17 | 1984-10-23 | Lever Brothers Company | Detergent compositions |
| GB8304990D0 (en) | 1983-02-23 | 1983-03-30 | Procter & Gamble | Detergent ingredients |
| GB8422158D0 (en) | 1984-09-01 | 1984-10-03 | Procter & Gamble Ltd | Bleach compositions |
| TR22733A (tr) | 1984-12-14 | 1988-05-24 | Clorox Co | Fenilen mono-ve diester perasit iptidai maddeler |
| US4728455A (en) | 1986-03-07 | 1988-03-01 | Lever Brothers Company | Detergent bleach compositions, bleaching agents and bleach activators |
| US4751015A (en) | 1987-03-17 | 1988-06-14 | Lever Brothers Company | Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions |
| US4933103A (en) | 1987-03-23 | 1990-06-12 | Kao Corporation | Bleaching composition |
| US4915863A (en) | 1987-08-14 | 1990-04-10 | Kao Corporation | Bleaching composition |
| GB8720863D0 (en) | 1987-09-04 | 1987-10-14 | Unilever Plc | Metalloporphyrins |
| EP0331229B1 (en) | 1988-03-01 | 1993-08-18 | Unilever N.V. | Quaternary ammonium compounds for use in bleaching systems |
| GB8908416D0 (en) * | 1989-04-13 | 1989-06-01 | Unilever Plc | Bleach activation |
| GB8915781D0 (en) | 1989-07-10 | 1989-08-31 | Unilever Plc | Bleach activation |
| US5114688A (en) | 1990-01-23 | 1992-05-19 | L'air Liquide, Societe Anonyme Pour L'etude Et Exploitation Des Procedes Georges Claude | Binuclear metal macrocyclic and macrobicyclic complexes for oxygen separation and transport |
| GB9003741D0 (en) | 1990-02-19 | 1990-04-18 | Unilever Plc | Bleach activation |
| DE69125309T2 (de) * | 1990-05-21 | 1997-07-03 | Unilever Nv | Bleichmittelaktivierung |
| US5194416A (en) | 1991-11-26 | 1993-03-16 | Lever Brothers Company, Division Of Conopco, Inc. | Manganese catalyst for activating hydrogen peroxide bleaching |
| US5256779A (en) * | 1992-06-18 | 1993-10-26 | Lever Brothers Company, Division Of Conopco, Inc. | Synthesis of manganese oxidation catalyst |
| EP0754219B1 (en) * | 1994-04-07 | 1998-09-09 | The Procter & Gamble Company | Bleach compositions comprising bleach activators and bleach catalysts |
| US5686014A (en) * | 1994-04-07 | 1997-11-11 | The Procter & Gamble Company | Bleach compositions comprising manganese-containing bleach catalysts |
| GB9407533D0 (en) * | 1994-04-13 | 1994-06-08 | Procter & Gamble | Detergent compositions |
| US5720897A (en) * | 1995-01-25 | 1998-02-24 | University Of Florida | Transition metal bleach activators for bleaching agents and detergent-bleach compositions |
-
1996
- 1996-01-04 DE DE19600159A patent/DE19600159A1/de not_active Withdrawn
- 1996-12-23 ES ES96120743T patent/ES2207663T3/es not_active Expired - Lifetime
- 1996-12-23 AT AT96120743T patent/ATE250660T1/de not_active IP Right Cessation
- 1996-12-23 DE DE59610733T patent/DE59610733D1/de not_active Expired - Lifetime
- 1996-12-23 EP EP96120743A patent/EP0783035B1/de not_active Expired - Lifetime
- 1996-12-27 JP JP8350981A patent/JPH09194886A/ja not_active Withdrawn
-
1997
- 1997-01-03 US US08/775,354 patent/US5942152A/en not_active Expired - Lifetime
- 1997-01-03 CA CA002194342A patent/CA2194342A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| DE19600159A1 (de) | 1997-07-10 |
| ES2207663T3 (es) | 2004-06-01 |
| US5942152A (en) | 1999-08-24 |
| ATE250660T1 (de) | 2003-10-15 |
| EP0783035A3 (de) | 1998-02-25 |
| JPH09194886A (ja) | 1997-07-29 |
| EP0783035A2 (de) | 1997-07-09 |
| CA2194342A1 (en) | 1997-07-05 |
| DE59610733D1 (de) | 2003-10-30 |
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