EP0633927A1 - Reinigungsmittel für harte oberflächen. - Google Patents
Reinigungsmittel für harte oberflächen.Info
- Publication number
- EP0633927A1 EP0633927A1 EP93906597A EP93906597A EP0633927A1 EP 0633927 A1 EP0633927 A1 EP 0633927A1 EP 93906597 A EP93906597 A EP 93906597A EP 93906597 A EP93906597 A EP 93906597A EP 0633927 A1 EP0633927 A1 EP 0633927A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- cleaning
- foam
- fatty alcohol
- azr
- 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.)
- Granted
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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
-
- 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
-
- 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
- C11D1/02—Anionic 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
- C11D1/662—Carbohydrates or derivatives
-
- 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 invention relates to low-foaming cleaning agents for hard surfaces. All non-textile surfaces occurring in the household and commercial sector, with the exception of dishes, are to be understood as such.
- the term all-purpose cleaner hereinafter referred to as AZR
- Low-foaming AZR are those that develop a small volume of foam when used manually, which significantly reduces within a few minutes.
- AZR have been known for a long time. These are essentially aqueous surfactant solutions of various types with or without the addition of builders and with or without the addition of water-soluble solvents or solubilizers.
- a disadvantage of manual application in practice has been its high foaming power. Although the consumer wants to perceive a certain amount of foam in the application solution at the start of his cleaning work in order to prove effectiveness, the foam should then collapse as quickly as possible, so that once cleaned surfaces do not have to be wiped down.
- alkyl polyglucosides (hereinafter referred to as APG) in washing and cleaning agents is becoming increasingly popular.
- alkyl polyglucosides are known to be highly foaming surfactants. In particular, however, they are used for products with the desired foaming capacity, for example for manually used products dishwashing detergent or recommended for shampooing.
- EP 70074, 70075, 70076 and 70 077 (Procter & Gamble) describe such high-foaming detergents and cleaning agents based on various APG-containing surfactant combinations. Consequently, these combinations are not recommended for the AZR area.
- the object of the invention was to provide means for the manual cleaning of hard surfaces, with the exception of dishes, which at the same time have good cleaning properties, good biodegradability and a distinctly low foaming capacity.
- the criterion should be that foam that initially forms visibly reduces within 5 minutes.
- a) 0.1-50, preferably 0.1-45% of alkyl polyglucosides of the formula R 0 Z x with R Cg-Cio
- a preferred embodiment of the invention includes AZR of the above type with an additional content of conventional anionic surfactants such as fatty alcohol sulfates, fatty alcohol ether sulfates, olefin sulfonates, paraffin sulfonates or mixtures thereof, their amounts being less than 25%, preferably less than 20% of the total surfactant a) + b) + c), so as not to impair the foaming behavior of the cleaning agent.
- conventional anionic surfactants such as fatty alcohol sulfates, fatty alcohol ether sulfates, olefin sulfonates, paraffin sulfonates or mixtures thereof, their amounts being less than 25%, preferably less than 20% of the total surfactant a) + b) + c), so as not to impair the foaming behavior of the cleaning agent.
- the APGs to be used in the AZR according to the invention are fatty alcohol polyglycosides of the composition R 0 (Z), where
- R is an alkyl radical with 8-10 carbon atoms
- the alkyl radical means the alkyl chains from fatty alcohols of natural or synthetic origin.
- the fatty alcohol alkoxylates to be used according to the invention are those which have an HLB value greater than 10, preferably greater than or equal to 11. These compounds are even more biodegradable than those with HLB values of less than 10, as described in WO 88/09369 (Staley). According to Griffin, the HLB value is defined as
- fatty alcohol alkoxylate Addition products of about 3 to 20, preferably about 4 to 10, moles of ethylene oxide (EO) with 1 mole of fatty alcohol having 6 to 16, preferably 8 to 10, carbon atoms in the alkyl chain are particularly preferred.
- EO ethylene oxide
- the fatty alcohols used as raw materials can be produced from natural oils and fats as well as synthetically.
- the fatty acids to be used according to the invention are carboxylic acids with 8 to 22, preferably 10 to 18, carbon atoms in the alkyl chain. Depending on the pH of the agents according to the invention, they are either in free form or partially or completely neutralized, that is to say in salt form. Suitable cations of these salts are alkali metal cations or nitrogen-containing cations such as ammonium or alkanol monium ions.
- the optional auxiliaries are substances which are used in AZR as builders, solvents, hydrotropes, cleaning enhancers, viscosity regulators, pH regulators, preservatives, colorants and fragrances, opacifiers etc.
- the AZR according to the invention do not contain any foam-promoting surfactants such as amoxides or fatty acid alkanolamides.
- Cleaning agents containing 1 to 90 wt .-% Cß - Cis-alkyl polyglucosides with 1.5 to 10 glucose units in the molecule, 1 to 90 wt .-% C8-C22 fatty alcohol ethoxylates with 2 to 12 moles of ethylene oxide and HLB values of 6 to 15, 1 to 15 wt .-% Cß - C24 fatty acids and optionally contain further synthetic anionic surfactants are known from EP 75995 (Procter &Gamble); however, they are only used for and on textile cleaning Foam behavior is not discussed in detail.
- Liquid cleaning agents with 2 to 60% by weight of C8-Ci8 alkyl monoglucosides, 0.1 to 10% by weight of nonionic surfactants with an HLB value of less than 5 and 0.1 to 10% by weight of nonionic surfactants with a HLB values of not less than 5 and 0.001 to 8% by weight of one or more intentional organic or inorganic salts are known from EP 408 965 (Kao). You foam strongly. The prior art did not suggest the new and inventive use of the special agents.
- the test method described below according to "Soap-Oil-Fat-Waxes", 112 .. 371, (1986) was used to test the cleaning power and gives very reproducible results.
- the cleaning agent to be tested was then placed on an artificially soiled plastic surface.
- a mixture of carbon black, machine oil, triglyceride, saturated fatty acids and low-boiling aliphatic hydrocarbon was used as artificial soiling for the dilute use of the cleaning agent.
- the test area of 26 x 28 cm was coated evenly with 2 g of the artificial soiling with the aid of a surface brush.
- a plastic sponge was soaked in each case with 10 ml of the cleaning agent solution to be tested and moved mechanically on the test surface which was also coated with 10 ml of the cleaning agent solution to be tested. After 10 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning effect, ie the whiteness of the plastic surface cleaned in this way, was measured using a "Microcolor" color difference measuring device (Dr. B. Lange). The clean white plastic surface served as the white standard.
- the read values for the cleaned plastic areas were to be equated with the percentage of cleaning power (% RV).
- % RV values given are the values determined by this method for the cleaning ability of the cleaning agents examined. They represent mean values from triplicate determinations.
- the measured values were set in relation to the cleaning result of a commercially available, low-foaming AZR used as standard.
- the standard AZR used at the time of the invention had the composition:
- test product is placed in a large glass beaker. Then, from a height of 30 cm, the amount of tap water is allowed to flow in freely, which, with the amount of product presented, is the recommended application. solution of the product.
- the foam height in the beaker is read off immediately after the addition of water and after 3 minutes. The foam height after 3 minutes is related to the initial foam and the foam breakdown is calculated as follows:
- a typical low-foaming AZR has a foam breakdown of over 50%.
- the example shows an AZR that is used in a 1% solution. Is at this concentration
- the AZR according to the invention is therefore, despite the extreme lack of foam, significantly more cleaning-efficient than the commercially available comparative product.
- Example 2 20.0% by weight C8 - Cio fatty alcohol + 4 E0 5.0% by weight palm kernel fatty acid 1.0% by weight citric acid 10.0% by weight cumosulfonate
- Example 2 represents an AZR high concentrate which is used in 0.1% solution. With this concentration the remedy has
- Succinic acid 0.05% by weight polyethylene oxide, MW 600000 2.0% by weight butylglycol
- the example shows a 1% application solution
- Example 3 0.5% fatty alcohol ether sulfate was added in order to deliberately not let the foam break down to 100%. The content of additional surfactant had no effect on the cleaning performance. The foam disintegration was 90%.
- the relative cleaning power compared to the 1% application solution of the standard was 180%.
- Cs-alkyl xyloside with approximately 1.2 xylose units 12.5% by weight
- Cio-alkyl xyloside with approximately 1.5 xylose units 11.1% by weight Cs-fatty alcohol + 4 EO 2.8% by weight %
- coconut fatty acid 2.4% by weight citric acid 5.6% by weight cumene sulfonate
- X% by weight potassium hydroxide solution for adjusting the pH of the finished product to pH 7.5 ad 100% by weight water, color and fragrances.
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)
- Detergent Compositions (AREA)
- Physical Vapour Deposition (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Glass Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Lubricants (AREA)
- Polishing Bodies And Polishing Tools (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4210365A DE4210365C2 (de) | 1992-03-30 | 1992-03-30 | Verwendung von Reinigungsmitteln für harte Oberflächen |
| DE4210365 | 1992-03-30 | ||
| PCT/EP1993/000707 WO1993020179A1 (de) | 1992-03-30 | 1993-03-24 | Reinigungsmittel für harte oberflächen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0633927A1 true EP0633927A1 (de) | 1995-01-18 |
| EP0633927B1 EP0633927B1 (de) | 1996-05-01 |
Family
ID=6455410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93906597A Expired - Lifetime EP0633927B1 (de) | 1992-03-30 | 1993-03-24 | Reinigungsmittel für harte oberflächen |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5591376A (de) |
| EP (1) | EP0633927B1 (de) |
| JP (1) | JPH07505183A (de) |
| AT (1) | ATE137531T1 (de) |
| BR (1) | BR9306163A (de) |
| DE (2) | DE4210365C2 (de) |
| DK (1) | DK0633927T3 (de) |
| ES (1) | ES2086223T3 (de) |
| WO (1) | WO1993020179A1 (de) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE9300955L (sv) * | 1993-03-23 | 1994-09-24 | Berol Nobel Ab | Alkylglykosid och dess användning |
| DE4404199A1 (de) * | 1994-02-10 | 1995-08-17 | Henkel Kgaa | Reinigungsmittel für harte Oberflächen |
| JPH093498A (ja) * | 1995-06-20 | 1997-01-07 | Th Goldschmidt Ag | 貯蔵安定性の濃縮水性界面活性剤組成物 |
| DE19644252A1 (de) * | 1996-10-24 | 1998-04-30 | Henkel Ecolab Gmbh & Co Ohg | Reinigung harter Oberflächen mit rheopexen wäßrigen Reinigungsmitteln |
| US5952287A (en) * | 1997-06-03 | 1999-09-14 | Henkel Corporation | Microemulsion composition for cleaning hard surfaces |
| US6224685B1 (en) * | 1997-06-03 | 2001-05-01 | Henkel Corporation | Microemulsion composition for cleaning hard surfaces |
| US6384010B1 (en) * | 2000-06-15 | 2002-05-07 | S.C. Johnson & Son, Inc. | All purpose cleaner with low organic solvent content |
| US6300300B1 (en) * | 2001-03-09 | 2001-10-09 | Mwj, L.L.C. | Liquid cleaning, degreasing, and disinfecting concentrate and methods of use |
| US8673865B2 (en) * | 2005-03-03 | 2014-03-18 | Kao Corporation | Agent for enhancing antiseptic power |
| US8980813B2 (en) | 2008-02-21 | 2015-03-17 | S. C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion on a vertical hard surface and providing residual benefits |
| US9410111B2 (en) | 2008-02-21 | 2016-08-09 | S.C. Johnson & Son, Inc. | Cleaning composition that provides residual benefits |
| US9481854B2 (en) | 2008-02-21 | 2016-11-01 | S. C. Johnson & Son, Inc. | Cleaning composition that provides residual benefits |
| US8993502B2 (en) | 2008-02-21 | 2015-03-31 | S. C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion to a vertical hard surface and providing residual benefits |
| DE102012221021A1 (de) * | 2012-11-19 | 2014-05-22 | Henkel Ag & Co. Kgaa | Wasch- und Reinigungsmittel mit Alkylpolypentosiden |
| US20160244623A1 (en) * | 2015-02-21 | 2016-08-25 | Geo-Tech Polymers, Llc | Coating Removal from Polyethylene Film |
| US10196591B2 (en) | 2015-07-10 | 2019-02-05 | S. C. Johnson & Sons, Inc. | Gel cleaning composition |
| US10000728B2 (en) | 2015-07-17 | 2018-06-19 | S. C. Johnson & Son, Inc. | Cleaning composition with propellant |
| US10358625B2 (en) | 2015-07-17 | 2019-07-23 | S. C. Johnson & Son, Inc. | Non-corrosive cleaning composition |
| US10604724B2 (en) | 2015-08-27 | 2020-03-31 | S. C. Johnson & Son, Inc. | Cleaning gel with glycine betaine amide/nonionic surfactant mixture |
| US10723978B2 (en) | 2015-08-27 | 2020-07-28 | S. C. Johnson & Son, Inc. | Cleaning gel with glycine betaine ester and nonionic surfactant mixture |
| US10246569B2 (en) | 2015-10-20 | 2019-04-02 | Geo-Tech Polymers, Llc | Recycling of fibrous surface coverings |
| WO2017099933A1 (en) | 2015-12-07 | 2017-06-15 | S.C. Johnson & Son, Inc. | Acidic hard surface cleaner with glycine betaine ester |
| US10836980B2 (en) | 2015-12-07 | 2020-11-17 | S. C. Johnson & Son, Inc. | Acidic hard surface cleaner with glycine betaine amide |
| RU2019117744A (ru) * | 2016-11-08 | 2020-12-10 | Басф Се | Композиция, подходящая в качестве поверхностно-активного вещества |
Family Cites Families (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1370377A (en) * | 1971-11-15 | 1974-10-16 | Procter & Gamble Ltd | Composition and method for cleaning hard surfaces |
| US4079078A (en) * | 1974-06-21 | 1978-03-14 | The Procter & Gamble Company | Liquid detergent compositions |
| US4065409A (en) * | 1975-08-01 | 1977-12-27 | Corporate Brands, Inc. | Hard surface detergent composition |
| CA1083911A (en) * | 1976-12-13 | 1980-08-19 | Thaddeus J. Kaniecki | Liquid cleaning compositions and process therefor |
| DE3275200D1 (en) * | 1981-07-13 | 1987-02-26 | Procter & Gamble | Foaming surfactant compositions |
| DE3275201D1 (en) * | 1981-07-13 | 1987-02-26 | Procter & Gamble | Foaming surfactant compositions |
| AU556758B2 (en) * | 1981-07-13 | 1986-11-20 | Procter & Gamble Company, The | Foaming compositions based on alkylpolysaccharide |
| DE3275199D1 (en) * | 1981-07-13 | 1987-02-26 | Procter & Gamble | Foaming surfactant compositions |
| GR76286B (de) * | 1981-09-28 | 1984-08-04 | Procter & Gamble | |
| US4483780A (en) * | 1982-04-26 | 1984-11-20 | The Procter & Gamble Company | Detergent compositions containing polyglycoside and polyethoxylate detergent surfactants |
| US4488981A (en) * | 1983-09-06 | 1984-12-18 | A. E. Staley Manufacturing Company | Lower alkyl glycosides to reduce viscosity in aqueous liquid detergents |
| JPH0676595B2 (ja) * | 1984-11-06 | 1994-09-28 | ヘンケル・コーポレーシヨン | 洗剤におけるモノグリコシド粘度調整剤 |
| US4627931A (en) * | 1985-01-29 | 1986-12-09 | A. E. Staley Manufacturing Company | Method and compositions for hard surface cleaning |
| US4606850A (en) * | 1985-02-28 | 1986-08-19 | A. E. Staley Manufacturing Company | Hard surface cleaning composition and cleaning method using same |
| DE3518672A1 (de) * | 1985-05-24 | 1986-11-27 | Basf Ag, 6700 Ludwigshafen | Fluessiges reinigungskonzentrat fuer stark alkalische reinigungsformulierungen |
| USH468H (en) * | 1985-11-22 | 1988-05-03 | A. E. Staley Manufacturing Company | Alkaline hard-surface cleaners containing alkyl glycosides |
| DE3708330A1 (de) * | 1987-03-14 | 1988-09-22 | Henkel Kgaa | Fluessige, alkalische reinigerkonzentrate |
| WO1988009369A1 (en) * | 1987-05-18 | 1988-12-01 | Staley Continental, Inc. | Low foaming detergent composition |
| DE3928602A1 (de) * | 1989-08-30 | 1991-03-07 | Henkel Kgaa | Alkalistabile und stark alkalisch formulierbare antischaummittel fuer die gewerbliche reinigung, insbesondere fuer die flaschen- und cip-reinigung |
| GB8927956D0 (en) * | 1989-12-11 | 1990-02-14 | Unilever Plc | Detergent composition |
| DE4009533A1 (de) * | 1990-03-24 | 1991-09-26 | Henkel Kgaa | Schwachschaeumendes nichtionisches tensidgemisch |
| DE4029035A1 (de) * | 1990-09-13 | 1992-03-19 | Huels Chemische Werke Ag | Waschmittel |
| US5290472A (en) * | 1992-02-21 | 1994-03-01 | The Procter & Gamble Company | Hard surface detergent compositions |
| US5223179A (en) * | 1992-03-26 | 1993-06-29 | The Procter & Gamble Company | Cleaning compositions with glycerol amides |
| DE4216380A1 (de) * | 1992-05-18 | 1993-11-25 | Henkel Kgaa | Verfahren zur Reinigung von Badezimmerarmaturen |
| US5342534A (en) * | 1992-12-31 | 1994-08-30 | Eastman Kodak Company | Hard surface cleaner |
-
1992
- 1992-03-30 DE DE4210365A patent/DE4210365C2/de not_active Expired - Fee Related
-
1993
- 1993-03-24 ES ES93906597T patent/ES2086223T3/es not_active Expired - Lifetime
- 1993-03-24 DK DK93906597.5T patent/DK0633927T3/da active
- 1993-03-24 BR BR9306163A patent/BR9306163A/pt not_active Application Discontinuation
- 1993-03-24 JP JP5517043A patent/JPH07505183A/ja active Pending
- 1993-03-24 AT AT93906597T patent/ATE137531T1/de not_active IP Right Cessation
- 1993-03-24 DE DE59302457T patent/DE59302457D1/de not_active Expired - Lifetime
- 1993-03-24 EP EP93906597A patent/EP0633927B1/de not_active Expired - Lifetime
- 1993-03-24 WO PCT/EP1993/000707 patent/WO1993020179A1/de not_active Ceased
- 1993-04-08 US US08/325,323 patent/US5591376A/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9320179A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE137531T1 (de) | 1996-05-15 |
| DK0633927T3 (da) | 1996-09-09 |
| WO1993020179A1 (de) | 1993-10-14 |
| DE4210365C2 (de) | 1995-06-08 |
| JPH07505183A (ja) | 1995-06-08 |
| US5591376A (en) | 1997-01-07 |
| ES2086223T3 (es) | 1996-06-16 |
| DE59302457D1 (de) | 1996-06-05 |
| EP0633927B1 (de) | 1996-05-01 |
| BR9306163A (pt) | 1998-01-13 |
| DE4210365A1 (de) | 1993-10-07 |
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Legal Events
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