WO1992015662A1 - Verfahren zur teppichreinigung - Google Patents
Verfahren zur teppichreinigung Download PDFInfo
- Publication number
- WO1992015662A1 WO1992015662A1 PCT/EP1992/000427 EP9200427W WO9215662A1 WO 1992015662 A1 WO1992015662 A1 WO 1992015662A1 EP 9200427 W EP9200427 W EP 9200427W WO 9215662 A1 WO9215662 A1 WO 9215662A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cleaning
- cleaning liquid
- water
- fatty acid
- surfactants
- 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.)
- Ceased
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
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
-
- 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
- C11D1/83—Mixtures of non-ionic with 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
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0031—Carpet, upholstery, fur or leather cleansers
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
Definitions
- the present invention relates to a method for cleaning carpets by means of spray extraction.
- the devices have a row of nozzles at the front in the working direction, with which the very dilute surfactant solution is blown into the textile material under high pressure, and behind it a wide suction nozzle or a series of suction nozzles with which the liquid just introduced into the textile largely removed from the textile and transferred to a storage tank of the device.
- a brushing device can be provided between the application nozzles and the suction nozzles. Because of the relatively large amounts of liquid which are enforced in the liquid extraction process, it is necessary to use only slightly foaming or non-foaming surfactants in the cleaning solutions in order not to exhaust the capacity of the collecting container too quickly.
- Adducts of long-chain alcohols, ethylene oxide (EO) and propylene oxide (PO) are therefore predominantly used, which are naturally extremely low-foaming and make the use of large amounts of defoamers unnecessary.
- a disadvantage of these surfactants is their comparatively poor biodegradability and their limited extent Cleaning ability. Overcoming these drawbacks was one of the objects of the present invention.
- the invention relates to a process for cleaning carpets by spray extraction, in which the sprayed-on cleaning liquid, in addition to synthetic anionic or nonionic surfactants, contains 0.005 to 0.2% by weight of a water-soluble salt of a fatty acid having 12 to 18 carbon atoms.
- the ammonium salts of the fatty acids are preferably used as water-soluble salts.
- the soap content in the cleaning liquid of the process according to the invention has the effect that even when strongly foaming anionic surfactants are used, the foam formation is reduced so much that the existing collecting tanks can be optimally used for the solutions to be extracted. Due to the extensive freedom in the choice of synthetic surfactants, it is possible to fall back on those surfactants that are characterized by particularly high cleaning power and low tendency to re-soiling. While the cleaning liquid is extremely low in foam at the concentration used in the spray extraction process, a corresponding liquid concentrate from which this cleaning liquid is used shows can be produced in normal operation, with undiluted use and application of brushes a strong foam development. The liquid concentrate can therefore be used undiluted or with a low dilution for the shampooing process, so that there are advantages for warehousing, above all for commercial users.
- the cleaning method according to the invention can easily be carried out with the aid of conventional spray extraction devices.
- the work processes differ from the conventional method only in so far as the agents to be used according to the invention are used. Because of the low foam content of the compositions, the addition of silicone defoamers can generally be dispensed with.
- the synthetic surfactants used in the cleaning liquid are nonionic and, preferably, anionic surfactants, although the use of other types of surfactants may also be appropriate in individual cases.
- the content of synthetic anionic and / or nonionic surfactants in the cleaning solution is preferably between 0.005 and 0.2% by weight, in particular between 0.04 and 0.08% by weight.
- the cleaning solution is preferably produced predominantly or exclusively with those surfactants which, together with the other constituents of the cleaning solution, lead to solid, brittle residues after the liquor remaining on the carpets has dried on.
- Suitable anionic surfactants are in particular those of the sulfate or sulfonate type, but other types such as long-chain N-acyl sarcosinates, salts of fatty acid cyanamides or salts of ether carboxylic acids, as are obtainable from long-chain alkyl or alkylphenyl polyglycol ethers and chloroacetic acid, can also be used. be used.
- the anionic surfactants are preferably used in the form of the sodium salts.
- Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of long-chain primary alcohols of natural and synthetic origin with 10 to 20 carbon atoms, ie of fatty alcohols such as, for example, B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the Cio - C20-OXO alcohols and those of secondary alcohols of these chain lengths. she are also known as alkyl sulfates.
- the sulfuric acid monoesters of the aliphatic primary alcohols, secondary alcohols or alkylphenols (ether sulfates) ethoxylated with 1 to 6 moles of ethylene oxide come into consideration. Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
- the surfactants of the sulfonate type are primarily sulfosuccinic acid monoesters and diesters with 6 to 22 carbon atoms in the alcohol parts, the alkylbenzenesulfonates with Cg-Cis-alkyl groups and the esters of ⁇ -sulfofatty acids, e.g. B. the ⁇ -sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
- alkanesulfonates which are obtainable from C12-Ci8-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins
- olefinsulfonates which are mixtures of alkene and hydroxyalkanesulfonates and disulfonates as obtained for example from long-chain monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
- alkyl sulfates with 12 to 18 carbon atoms the salts of sulfosuccinic acid monoesters with 15 to 20 carbon atoms in the alcohol part, the alkylbenzenesulfonates with 10 to 13 carbon atoms in the alkyl chain, the sulfates of those ethoxylated with 1 to 3 mol E0 Fatty alcohols with 12 - 18 carbon atoms and mixtures of these surfactants are used.
- the fatty alcohol sulfates with 12 to 18 carbon atoms are particularly preferred.
- Suitable nonionic surfactants for the process according to the invention are, in particular, addition products of 1 to 30, preferably 3 to 15, moles of ethylene oxide to 1 mole of a long-chain compound having 10 to 20 carbon atoms from the group of alcohols, alkylphenols, carboxylic acids and carboxamides.
- the addition products of ethylene oxide (E0) with long-chain primary or secondary alcohols, such as, for example, fatty alcohols or oxo alcohols, and with mono- or dialkylphenols with 6 to 14 C atoms in the alkyl groups are particularly important.
- other nonionic surfactants for example long-chain amine oxides and, can also be used Alkyl glycosides.
- nonionic surfactants are fatty alcohols or oxo alcohols with 10 to 20 carbon atoms, which are ethoxylated with 3 to 10 mol of EO, and mixtures of compounds of this type with different degrees of ethoxylation.
- the cleaning liquid used contains a water-soluble salt of a fatty acid with 12 to 18 carbon atoms.
- the alkali soaps of this chain length can be used, i. H. the lithium, sodium and potassium salts of the fatty acids, but also the salts of fatty acids with ammonia or suitable amines, for example triethanolamine.
- the ammonium soaps accessible from fatty acids and ammonia are particularly preferred.
- the content of fatty acid salts in the cleaning liquid is usually 0.005 to 0.2% by weight, preferably 0.03 to 0.06% by weight.
- the ratio of soap to other surfactants in the cleaning liquids is preferably between about 0.2: 1 and 3: 1, in particular between about 0.5: 1 and about 2: 1.
- the cleaning liquid can be used for the method according to the invention without further additives. In many cases, however, it can be expedient to add further auxiliaries customary in carpet cleaning agents to the cleaning solution. Particularly noteworthy are sequestering agents, anti-pollution agents, antistatic agents, hydrotropes, organic solvents, preservatives and perfume. Also in the selection of auxiliary substances, especially those which are contained in large quantities in the cleaning agent, preference is given to those which, after the liquid residues have dried on the carpet, lead to solid residues, since these can later be vacuumed dry.
- the auxiliaries which are intended to reduce re-soiling of the carpet are primarily water-soluble or water-dispersible polymers which have film-forming temperatures above 70 ° C. and which after drying do not lead to films but to brittle residues.
- Corresponding polyacrylates and polymethacrylates are preferably used.
- Their concentration in the cleaning liquid is normally not more than 0.5% by weight, preferably between 0.01 and 0.3% by weight.
- Quaternary ammonium compounds which attach to the textile material are usually used as active ingredients which are intended to provide the carpet with a certain antistatic finish.
- Inorganic salts can also have an antistatic effect on the carpet.
- the total content of auxiliaries in the cleaning agent solution, calculated without organic solvents, is generally not more than 1% by weight, preferably between 0.01 and 0.5% by weight.
- the cleaning liquids sprayed in the cleaning process according to the invention can be mixed directly from the components. Since it is a matter of very dilute cleaning agent solutions, it had been established in practice to prepare these solutions by dilution with water before use from more concentrated preparations containing the active ingredients in appropriate proportions in higher concentrations.
- the concentrates can be solid, powdery products; However, more common are concentrates in liquid form which contain all active ingredients. For the production of stable liquid concentrates, it may be necessary to add solubilizers that ensure the perfect miscibility of all ingredients.
- Suitable solubilizing additives are primarily hydrotropes, for example the salts of short-chain alkylbenzenesulfonic acids or low-boiling, water-miscible organic solvents, for example ethanol and isopropanol.
- the concentration of the active ingredients in the concentrates is generally chosen so that the desired use concentrations can be achieved by dilution with water in a ratio of from 1:30 to 1: 300, preferably from 1:50 to 1: 100.
- each piece of carpet was uniformly sprayed and sucked off from all sides.
- the cleaning speed was chosen so that the product consumption per test specimen was 700 ml (i 50 ml).
- the carpet samples were sucked off (against the pile direction without spraying) so that the carpet fiber was set up to dry.
- test specimens were suctioned off from each side in a cross-way with a brush suction device (Siemens Universal Plus). Finally, the fibers of the carpet specimens were all brushed in the same direction using a soft brush.
- the test is carried out on polyamide velor carpets. 500 g of the agents diluted with water in a ratio of 1: 4 (concentrate: water) were applied per ⁇ .2 using a shaving machine (Shampooer Hoover F 4002) and brushed in. Enough foam for uniform distribution and gentle brushing only developed in cases la - d.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Central Heating Systems (AREA)
- Control Of Washing Machine And Dryer (AREA)
- Manufacturing Of Electric Cables (AREA)
- Treatment Of Fiber Materials (AREA)
Abstract
Description
Claims
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92905154A EP0574431B1 (de) | 1991-03-06 | 1992-02-27 | Verfahren zur teppichreinigung |
| DE59204768T DE59204768D1 (de) | 1991-03-06 | 1992-02-27 | Verfahren zur teppichreinigung |
| GR950403628T GR3018508T3 (en) | 1991-03-06 | 1995-12-21 | Method of cleaning carpets |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4107118.2 | 1991-03-06 | ||
| DE4107118A DE4107118A1 (de) | 1991-03-06 | 1991-03-06 | Verfahren zur teppichreinigung |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1992015662A1 true WO1992015662A1 (de) | 1992-09-17 |
Family
ID=6426587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1992/000427 Ceased WO1992015662A1 (de) | 1991-03-06 | 1992-02-27 | Verfahren zur teppichreinigung |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0574431B1 (de) |
| AT (1) | ATE131861T1 (de) |
| DE (2) | DE4107118A1 (de) |
| DK (1) | DK0574431T3 (de) |
| ES (1) | ES2081100T3 (de) |
| GR (1) | GR3018508T3 (de) |
| WO (1) | WO1992015662A1 (de) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994020594A1 (de) * | 1993-03-10 | 1994-09-15 | Henkel-Ecolab Gmbh & Co. Ohg | Wischpflegemittel |
| US7261742B2 (en) | 2005-10-13 | 2007-08-28 | S.C. Johnson & Son, Inc. | Method of deodorizing a textile |
| US7407922B2 (en) | 2005-10-13 | 2008-08-05 | S.C. Johnson & Son, Inc. | Deodorizing compositions |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6262022B1 (en) | 1992-06-25 | 2001-07-17 | Novartis Ag | Pharmaceutical compositions containing cyclosporin as the active agent |
| DE4202549A1 (de) * | 1992-01-30 | 1993-08-05 | Peter Marsilius | Verfahren und mittel zur beseitigung von hausmilben und deren ueberresten in wohnungseinrichtungen |
| DE4403290A1 (de) * | 1994-02-03 | 1995-08-10 | Licentia Gmbh | Bodenpflegegerät |
| DE4406320A1 (de) * | 1994-02-25 | 1995-08-31 | Schaefer Juergen | Verfahren, Vorrichtung und Flüssigkeit zum Reinigen von textilen Flächen-Bespannungstuchen |
| DE102011054215A1 (de) | 2011-10-06 | 2013-04-11 | Alfred Kärcher Gmbh & Co. Kg | Verfahren zur Desinfektion von Textilmaterialien |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2118820A1 (en) * | 1971-04-19 | 1972-11-09 | Henkel & Cie GmbH, 4000 Düsseldorf | Carpet/upholstery cleaning agent - based on surfactants and contg dispersed polymethylmethacrylate to avoid rapid soiling aft |
| US3734686A (en) * | 1971-08-12 | 1973-05-22 | Cosden Oil & Chem Co | Composition and method for treating carpets and pile fabrics |
| GB1430204A (en) * | 1973-09-18 | 1976-03-31 | Johnson & Son Inc S C | Aqueous cleaning composition |
| FR2296685A1 (fr) * | 1975-01-02 | 1976-07-30 | Procter & Gamble Europ | Composition liquide pour nettoyages menagers |
| US4219333A (en) * | 1978-07-03 | 1980-08-26 | Harris Robert D | Carbonated cleaning solution |
| EP0021799A1 (de) * | 1979-06-22 | 1981-01-07 | S.C. Johnson & Son, Inc. | Extraktionsreinigungsverfahren für Teppiche |
| US4552692A (en) * | 1982-01-08 | 1985-11-12 | Gillespie Thomas W | Concentrated composition for cleaning rugs and carpets |
-
1991
- 1991-03-06 DE DE4107118A patent/DE4107118A1/de not_active Withdrawn
-
1992
- 1992-02-27 DE DE59204768T patent/DE59204768D1/de not_active Expired - Fee Related
- 1992-02-27 EP EP92905154A patent/EP0574431B1/de not_active Expired - Lifetime
- 1992-02-27 WO PCT/EP1992/000427 patent/WO1992015662A1/de not_active Ceased
- 1992-02-27 AT AT92905154T patent/ATE131861T1/de not_active IP Right Cessation
- 1992-02-27 DK DK92905154.8T patent/DK0574431T3/da active
- 1992-02-27 ES ES92905154T patent/ES2081100T3/es not_active Expired - Lifetime
-
1995
- 1995-12-21 GR GR950403628T patent/GR3018508T3/el unknown
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2118820A1 (en) * | 1971-04-19 | 1972-11-09 | Henkel & Cie GmbH, 4000 Düsseldorf | Carpet/upholstery cleaning agent - based on surfactants and contg dispersed polymethylmethacrylate to avoid rapid soiling aft |
| US3734686A (en) * | 1971-08-12 | 1973-05-22 | Cosden Oil & Chem Co | Composition and method for treating carpets and pile fabrics |
| GB1430204A (en) * | 1973-09-18 | 1976-03-31 | Johnson & Son Inc S C | Aqueous cleaning composition |
| FR2296685A1 (fr) * | 1975-01-02 | 1976-07-30 | Procter & Gamble Europ | Composition liquide pour nettoyages menagers |
| US4219333A (en) * | 1978-07-03 | 1980-08-26 | Harris Robert D | Carbonated cleaning solution |
| US4219333B1 (de) * | 1978-07-03 | 1984-02-28 | ||
| EP0021799A1 (de) * | 1979-06-22 | 1981-01-07 | S.C. Johnson & Son, Inc. | Extraktionsreinigungsverfahren für Teppiche |
| US4552692A (en) * | 1982-01-08 | 1985-11-12 | Gillespie Thomas W | Concentrated composition for cleaning rugs and carpets |
Non-Patent Citations (1)
| Title |
|---|
| Database WPIL,DERWENT PUBLICATIONS,LONDON UK. ACC. NO. : 88-320551 [45] & KR,A,8 801 145 (LUCKY CO.) 1. Juli 1988 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994020594A1 (de) * | 1993-03-10 | 1994-09-15 | Henkel-Ecolab Gmbh & Co. Ohg | Wischpflegemittel |
| US5683975A (en) * | 1993-03-10 | 1997-11-04 | Henkel Ecolab Gmbh & Co Ohg | Floor wiping composition |
| US7261742B2 (en) | 2005-10-13 | 2007-08-28 | S.C. Johnson & Son, Inc. | Method of deodorizing a textile |
| US7407922B2 (en) | 2005-10-13 | 2008-08-05 | S.C. Johnson & Son, Inc. | Deodorizing compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| DK0574431T3 (da) | 1996-05-06 |
| DE59204768D1 (de) | 1996-02-01 |
| EP0574431B1 (de) | 1995-12-20 |
| GR3018508T3 (en) | 1996-03-31 |
| ES2081100T3 (es) | 1996-02-16 |
| EP0574431A1 (de) | 1993-12-22 |
| ATE131861T1 (de) | 1996-01-15 |
| DE4107118A1 (de) | 1992-09-10 |
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