EP0574431B1 - Procede pour le nettoyage de tapis et moquettes - Google Patents
Procede pour le nettoyage de tapis et moquettes Download PDFInfo
- Publication number
- EP0574431B1 EP0574431B1 EP92905154A EP92905154A EP0574431B1 EP 0574431 B1 EP0574431 B1 EP 0574431B1 EP 92905154 A EP92905154 A EP 92905154A EP 92905154 A EP92905154 A EP 92905154A EP 0574431 B1 EP0574431 B1 EP 0574431B1
- Authority
- EP
- European Patent Office
- 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.)
- Expired - Lifetime
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 with the aid of spray extraction.
- the devices have a row of nozzles at the front in the working direction, with the aid of 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 that has just been introduced into the textile is largely expelled again the textile is removed and transferred to a storage tank of the device.
- a brushing device can be provided between the application nozzles and the suction nozzles.
- European patent application 21 799, German patent application 21 18 820 and US patent 4,219,333 describe such methods and agents which can be used in this method.
- the invention relates to a process for cleaning carpets by spray extraction, in which the sprayed-on cleaning liquid contains, in addition to synthetic anionic or nonionic surfactants, 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 foaming is reduced to such an extent that the existing collecting tanks for the solutions to be extracted can be optimally used. 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-foaming 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 without further ado for the shampooing process, so that there are advantages in 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. Due to the low foam content of the agents, 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.
- 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. B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the C10 - C20 oxo alcohols and those of secondary alcohols of these chain lengths.
- fatty alcohols such as, for. B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the C10 - C20 oxo alcohols and those of secondary alcohols of these chain lengths.
- the sulfuric acid monoesters of the aliphatic primary alcohols, secondary alcohols or alkylphenols (ether sulfates) ethoxylated with 1 to 6 moles of ethylene oxide are also suitable.
- Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
- the surfactants of sulfonate type are primarily sulfosuccinic acid monoesters and diesters with 6 to 22 carbon atoms in the alcohol parts, the alkylbenzenesulfonates with C9 - C15 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-C18 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, such as they are 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 the fatty alcohols ethoxylated with 1 to 3 mol EO with 12 - 18 carbon atoms and mixtures of these surfactants.
- 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 with 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 (EO) 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 can also be used, for example long-chain amine oxides and 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 0.2: 1 and 3: 1, in particular between 0.5: 1 and 2: 1.
- the cleaning liquid can be used for the process 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.
- sequestering agents especially those that are contained in large quantities in the cleaning agent, preference is also given to those which lead to solid residues on the carpet after the liquid residues have dried off, since these can later also be vacuumed dry.
- the auxiliaries which are intended to reduce the re-soiling of the carpet are primarily water-soluble or water-dispersible polymers which have film-forming temperatures above 70 ° C. and do not lead to films after drying, 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. However, since these are very dilute cleaning agent solutions, it had been established in practice to prepare these solutions before use from more concentrated preparations, which contain the active ingredients in appropriate proportions in higher concentrations, by dilution with water.
- 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.
- concentration of the active compounds in the concentrates is generally chosen so that the desired use concentrations can be achieved by dilution with Nasser in a ratio of from 1:30 to 1: 300, preferably from 1:50 to 1: 100.
- Table 1 The following agents (Table 1) were prepared by dissolving the active ingredients in water and, if appropriate, organic solvent. The content is given in percent by weight, in each case calculated as a pure active substance. Table 1 concentrate a b c d e Sodium Lauryl Sulfate (Texapon (R) K 12) 3.8 3.8 - 5.0 - Sodium lauryl ether sulfate (2EO) (Texapon (R) N 25) - - 4.0 - - C 10/12 fatty alcohol + 6 PO + 4 EO - - - - 8.0 Polymethyl methacrylate (Ubatol (R) TR 1138) 6.4 6.4 6.4 10.0 - NH4 soap from coconut palm kernel fatty acid ( Edenor (R) KPK) 2.8 - 2.5 - - K-Soap from Coconut Palm Kernel Fatty Acid ( Edenor (R) KPK) - - - 3.5 - Sodium cumene sulfonate - - -
- Example 1 The agents according to Example 1 (a - e) were compared both with regard to their cleaning power and their foaming behavior in the spray extraction process and also checked for their usability in the shampooing process.
- a) Checking the cleaning effect Uniform, naturally soiled carpets (polyamide velor, beige) were cut into test specimens measuring 33 cm x 79 cm, only test specimens with the same degree of soiling being used for the test.
- the products (a, c, d) used according to the invention, as well as a comparison product (b) and a commercially available product (e) were diluted 1: 100 with tap water to the application concentration. With a spray extraction device (Kärcher Puzzi S), each piece of carpet was sprayed and vacuumed evenly from all sides.
- the cleaning speed was chosen so that the product consumption per test specimen was 700 ml ( ⁇ 50 ml).
- the carpet samples were sucked off (against the pile direction without spraying) so that the carpet fiber was set up to dry.
- the test specimens were suctioned off from each side in a cross-way with a brush suction device (Siemens Universal Plus).
- the fibers of the carpet specimens were all brushed in the same direction using a soft brush.
- the individual pieces of carpet were assessed visually in comparison to one another and to an uncleaned pattern. The assessment was carried out by 5 examiners who assessed each piece individually on a scale from 1 (completely clean) to 5 (no cleaning recognizable).
- Table 2 contains the results in the form of the mean values from 3 individual experiments.
- Procedure for determining the suction quantity (without defoamer additive) The fresh water tank was filled with 7.00 kg of the detergent solution to be tested (dilution of the concentrates 1: 100 with tap water) in a commercially available spray extraction device (Kärcher Puzzi S). The product to be tested was transferred to the dirty water tank by spraying the product onto a hard, clean plastic floor and simultaneously vacuuming it off. When the dirty water tank had reached its maximum filling quantity, the total weight of the extracted quantity was determined. Ideally (no foam formation), the amount of solution used could be sucked up without changing the dirty water tank.
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)
- Central Heating Systems (AREA)
- Control Of Washing Machine And Dryer (AREA)
- Manufacturing Of Electric Cables (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treatment Of Fiber Materials (AREA)
Claims (7)
- Procédé de nettoyage des moquettes et des tapis de sol par pulvérisation-extraction, caractérisé en ce que le liquide nettoyant pulvérisé contient en plus d'un tensioactif anionique et/ou non ionique, également 0,005 à 0,2 % en poids d'un sel soluble dans l'eau d'un acide gras comportant 12 à 18 atomes de C.
- Procédé selon la revendication 1 avec un liquide nettoyant dans lequel on utilise un sel d'ammonium comme sel d'acide gras.
- Procédé selon une des revendications 1 ou 2 avec un liquide nettoyant, dans lequel le rapport entre les sels d'acides gras et les tensioactifs synthétiques est compris entre 0,2:1 et 3:1, en particulier entre 0,5:1 et 2:1.
- Procédé selon une des revendications 1 ou 2 avec un liquide nettoyant, qui contient un surfactif anionique comme tensioactif synthétique.
- Procédé selon la revendications 4 avec un liquide nettoyant, qui contient un alkylsulfate comme tensioactif anionique.
- Procédé selon une des revendications 1 ou 2 avec un liquide nettoyant, qui contient en plus un polymère soluble dans l'eau présentant une température de formation de film supérieure à 70 °C, de préférence un polyméthacrylate.
- Procédé selon une des revendications 1 à 6, dans lequel le liquide nettoyant est fabriqué par dilution avec de l'eau, dans un rapport compris entre 1:30 et 1:300, de préférence entre 1:50 et 1:100, d'un concentré d'agent nettoyant de composition correspondante.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4107118A DE4107118A1 (de) | 1991-03-06 | 1991-03-06 | Verfahren zur teppichreinigung |
DE4107118 | 1991-03-06 | ||
PCT/EP1992/000427 WO1992015662A1 (fr) | 1991-03-06 | 1992-02-27 | Procede pour le nettoyage de tapis et moquettes |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0574431A1 EP0574431A1 (fr) | 1993-12-22 |
EP0574431B1 true EP0574431B1 (fr) | 1995-12-20 |
Family
ID=6426587
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92905154A Expired - Lifetime EP0574431B1 (fr) | 1991-03-06 | 1992-02-27 | Procede pour le nettoyage de tapis et moquettes |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0574431B1 (fr) |
AT (1) | ATE131861T1 (fr) |
DE (2) | DE4107118A1 (fr) |
DK (1) | DK0574431T3 (fr) |
ES (1) | ES2081100T3 (fr) |
GR (1) | GR3018508T3 (fr) |
WO (1) | WO1992015662A1 (fr) |
Families Citing this family (6)
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 |
DE4307473A1 (de) * | 1993-03-10 | 1994-09-15 | Henkel Ecolab Gmbh & Co Ohg | Wischpflegemittel |
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 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2118820C3 (de) * | 1971-04-19 | 1980-01-31 | Henkel Kgaa, 4000 Duesseldorf | Reinigungs- und Shampooniermittel für textile Oberflächenbeläge |
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 |
LU71583A1 (fr) * | 1975-01-02 | 1976-11-11 | Procter & Gamble Europ | |
US4219333A (en) * | 1978-07-03 | 1980-08-26 | Harris Robert D | Carbonated cleaning solution |
US4304610A (en) * | 1979-06-22 | 1981-12-08 | S. C. Johnson & Son, Inc. | Carpet cleaning method |
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 DK DK92905154.8T patent/DK0574431T3/da active
- 1992-02-27 EP EP92905154A patent/EP0574431B1/fr not_active Expired - Lifetime
- 1992-02-27 ES ES92905154T patent/ES2081100T3/es not_active Expired - Lifetime
- 1992-02-27 WO PCT/EP1992/000427 patent/WO1992015662A1/fr active IP Right Grant
- 1992-02-27 AT AT92905154T patent/ATE131861T1/de not_active IP Right Cessation
- 1992-02-27 DE DE59204768T patent/DE59204768D1/de not_active Expired - Fee Related
-
1995
- 1995-12-21 GR GR950403628T patent/GR3018508T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
GR3018508T3 (en) | 1996-03-31 |
DE59204768D1 (de) | 1996-02-01 |
DE4107118A1 (de) | 1992-09-10 |
ES2081100T3 (es) | 1996-02-16 |
ATE131861T1 (de) | 1996-01-15 |
WO1992015662A1 (fr) | 1992-09-17 |
DK0574431T3 (da) | 1996-05-06 |
EP0574431A1 (fr) | 1993-12-22 |
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