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EP0813591A1 - Produit de nettoyage pateux - Google Patents

Produit de nettoyage pateux

Info

Publication number
EP0813591A1
EP0813591A1 EP96905805A EP96905805A EP0813591A1 EP 0813591 A1 EP0813591 A1 EP 0813591A1 EP 96905805 A EP96905805 A EP 96905805A EP 96905805 A EP96905805 A EP 96905805A EP 0813591 A1 EP0813591 A1 EP 0813591A1
Authority
EP
European Patent Office
Prior art keywords
formula
weight
group
compound
viscosity
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
Application number
EP96905805A
Other languages
German (de)
English (en)
Other versions
EP0813591B1 (fr
Inventor
Dieter Hemm
Günter Hellmann
Klaus Wilbert
Horst Prühs
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ecolab GmbH and Co OHG
Original Assignee
Henkel Ecolab GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Ecolab GmbH and Co KG filed Critical Henkel Ecolab GmbH and Co KG
Publication of EP0813591A1 publication Critical patent/EP0813591A1/fr
Application granted granted Critical
Publication of EP0813591B1 publication Critical patent/EP0813591B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/06—Hydroxides
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/263—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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3218—Alkanolamines or alkanolimines
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3227—Ethers thereof
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids

Definitions

  • the present invention relates to water-containing paste-like cleaning agents based on NaOH.
  • the cleaning agents contain glycols, glycol derivatives and / or certain alkanolamines.
  • Highly alkaline cleaning agents are commercially available in a wide variety of forms, z. B. as a powder, as granules, as a liquid, as a melting block or as a tablet produced by compression.
  • Pasty cleaning agents have already been described in the prior art, e.g. B. in the German Offenlegungsschrift DE-OS-31 38 425.
  • the theological behavior of the cleaners described there is such that a gel-like paste by the action of mechanical forces, for example by shaking or pressure on a deformable storage bottle or tube or by means of a Liquefied dosing pump and easily squeezed out of a spray nozzle.
  • Silicates are primarily used as alkali carriers, whereas the cleaning agents according to the present invention should be pasty and should preferably be based on the very inexpensive raw material sodium hydroxide as alkali carriers.
  • US Pat. No. 3,607,764 describes glass cleaning agents in solid form, which are diluted to form a sprayable solution; these agents contain, inter alia sodium or potassium hydroxide, sodium or Kaliumthpolyphosphat, sodium or potassium pyrophosphate, hydroxycarboxylic acid builders, a water-soluble nonionic surfactant, alkylene glycol ether and optionally Nat ⁇ 'carbonate.
  • a paste form in the sense of the present invention is not described.
  • Japanese patent specification JA 84/182870 describes solutions of small amounts of alkali metal hydroxides (below 2% by weight) in glycols or alcohols, which become viscous when neutralized with long-chain carboxylic acids have from 7-11 and can be used as a paste in leather greasing by adding silicone oil.
  • the object of the present invention is to provide water-containing, highly alkaline, sodium hydroxide-based cleaning agents of a general type for textile surfaces, e.g. B. butcher's laundry, but preferably those for cleaning hard surfaces, e.g. B. dishes, and in particular cleaning agents for the commercial cleaning of dishes, which combine the advantages of powders and liquids on the one hand and the advantages of tablets and melting blocks on the other.
  • cleaning agents are to be provided which have a solubility which is precisely defined under the most varied of application conditions, but on the other hand are transport-stable and storage-stable and, moreover, can be dosed quickly, easily and precisely, and are not dusty and can be produced without great technical effort.
  • the present invention relates to water-containing, highly alkaline paste-like cleaning agents
  • R 1 represents a hydrogen atom or a methyl group and R 2 independently of it a hydrogen atom, a Ci to C 4 alkyl group, a group CH 2 CH (R 3 ) OR 4 or a group CH 2 CH (R 5 ) OCH 2 CH (R 6 ) OR 7 , wherein R 3 , R 5 and R ⁇ are hydrogen atoms or methyl groups and R 4 and R 7 are hydrogen atoms or Ci to C 4 alkyl groups stand, and / or compounds of formula II,
  • the cleaning agent has a viscosity of 20 ° C
  • the paste-like form in the sense of the present invention manifests itself in such a way that cleaning agents according to the invention do not emerge from a container, e.g. B. a screw cap glass flow out.
  • the pasty consistency can even manifest itself in the form of cut resistance.
  • the viscosity is measured in the manner described above. At the defined speed of 5 rpm, the following spindles can be used to measure the viscosities: Spindle 3: viscosity range from 2,000 to 20,000 spindle 4: viscosity range from 4,000 to 40,000 spindle 5: viscosity range from 8,000 to 80,000 spindle 6: viscosity range from 20,000 to 200,000 spindle 7: viscosity range from 80,000 to 800,000
  • the spindle with which the viscosity value displayed on the measuring device is closest to the center of the scale range is preferably used.
  • the compounds of the formulas I and II are preferably selected from the group consisting of ethylene glycol, 1,2-propylene glycol, butyl glycol and butyl diglycol or from the group ethanolamine, diethanolamine, triethanolamine.
  • 1,2-propylene glycol and diethanolamine are preferred.
  • these compounds must not be present in higher proportions by weight than NaOH, ie the weight ratio of the sum of all the compounds of the formulas I and / or II to the NaOH contained is always less than 1.
  • composition of the substance is selected according to the invention, surprisingly, no further additives apart from I and / or II are required in order to achieve a thickening effect in aqueous sodium hydroxide solution.
  • the water content is also a critical parameter; it is between 16 and 55% by weight, advantageously between 28 and 40% by weight.
  • the water content also includes the bound water contained in other optional ingredients. Accordingly, the percentages by weight of all other ingredients always relate to the anhydrous active substance.
  • the pH of the cleaning agents according to the invention is above 11.5, preferably above 13.
  • the cleaning agents can optionally additionally contain a builder substance in an amount of up to 50% by weight, preferably 15 to 40% by weight.
  • the builder substance contained in the cleaning agents according to the invention can in principle be any substance which is known in the prior art as a builder suitable in the broadest sense for detergents and cleaning agents; water-soluble builder substances are preferably used.
  • builder substances come e.g. B. alkali phosphates, which may be in the form of their sodium or potassium salts, in question. Examples include: tetrasodium diphosphate, pentasodium triphosphate, so-called sodium hexamaphosphate and the corresponding potassium salts or mixtures of sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • Other possible water-soluble builder components are e.g. B. organic polymers native or synthetic origin, especially polycarboxylates. For example, polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids are suitable.
  • Commercial products are e.g. B. Sokalan® CP 5 and PA 30 from BASF, Alcosperse® 175 and 177 from Alco, LMW® 45 N and SP02 ND from Norsohaas.
  • Aminoacetates such as. B. nitrilotriacetate or ethylenediaminetetraacetate. Soda and borax are also among the builder substances in the context of the present invention.
  • Suitable native polymers include, for example, oxidized starch (e.g. DE 42 28 786) and polyamino acids such as polyglutamic acid or polyaspartic acid, e.g. B. from Cygnus, Bayer, Rohm & Haas, Rhône-Poulenc or SRCHEM.
  • Other possible builder components are naturally occurring hydroxycarboxylic acids such as. B. mono-, dihydroxysuccinic acid, ⁇ -hydroxypropionic acid, citric acid, gluconic acid, and their salts.
  • Citrates are preferably used in the form of trisodium citrate dihydrate.
  • Amorphous metal silicates or layered silicates can also be mentioned as builder substances.
  • Crystalline layered silicates are also suitable builders insofar as they are are are sufficiently stable to alkali; Crystalline layered silicates are sold by Hoechst AG (Germany) under the trade name Na-SKS, e.g. B. Na-SKS-1
  • Na 2 Si 8 0 7 xH2 ⁇ Na-SKS ⁇ (a 2 Si4 ⁇ 9 xH2 ⁇ ), Makatit), Na-SKS-5 ( ⁇ - Na 2 Si 2 ⁇ 5), Na-SKS-7 (ß-Na 2 Si 2 05, natrosilite), Na-SKS-11 ( ⁇ -Na 2 Si 2 0 5 ) and Na-SKS-6 ( ⁇ -Na 2 Si 2 0 5 ).
  • Particularly preferred builder substances are those selected from the group consisting of pentasodium triphosphate, trinate umcitrate, nitrilotriacetate, ethylenediaminetetraacetate and mixtures thereof.
  • Bleaches customary in cleaning agents can also be present in the agents according to the invention. These can be selected from the group of oxygen-based bleaches, such as. B Sodium perborate also in the form of its hydrates, or sodium percarbonate, or from the group of chlorine-based bleaches, such as Trichlo socyanuric acid, Alkalidichlo socyanurate, alkali hypochlorites, and alkali hypochlorite-releasing agents, with alkali-stable bleaching agent compositions being particularly preferred. These can be both alkali-stable substances or components stabilized by suitable processes such as surface coating or passivation.
  • Optional ingredients are other common ingredients
  • Detergent ingredients such as. B. defoamers (such as silicone oils, paraffins or waxes), dyes or alkali-stable perfume substances.
  • Low-foaming surfactants especially nonionic surfactants, may also be present in an amount of up to 5% by weight.
  • Extremely low-foam connections are usually used. These preferably include C 2 -C 8 - alkyl polyethylene glycol polypropylene glycol ether, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. But you can also use other non-foaming non-foaming surfactants known, such as. B.
  • abrasive ingredients can be present, but the cleaning agents according to the invention are preferably free of them.
  • thickeners such as B. swellable layered silicates of the Montmoriilonit type, bentonite, kaolin, talc or carboxymethyl cellulose can be used optionally to vary the viscosity, they are not necessary to achieve the desired pasty properties and the viscosities of the cleaning agents according to the invention, d. H. such thickeners can be dispensed with.
  • a process for thickening aqueous 42 to 55% by weight NaOH solution is claimed.
  • the process is characterized in that a compound of the formula I and / or a compound of the formula II is added to such a NaOH solution with stirring, and a paste-like preparation is thus obtained.
  • the process is carried out at 20 ° C to 25 ° C.
  • the NaOH content in the aqueous solution can then also be more than 55% by weight.
  • the NaOH content can also be below 42% by weight at lower temperatures.
  • the restriction to 42 to 55% by weight NaOH Solutions are therefore essentially limited to temperatures from 20 ° C to 25 ° C.
  • stirring is continued for at least 3 minutes.
  • the thickened, paste-like preparation is to contain builder substances, these can be contained in the NaOH solution to be thickened from the outset.
  • the builder substances are preferably added to the already thickened, paste-like preparation.
  • Other optional ingredients are also preferably added to the already thickened, paste-like preparation.
  • the use of the pasty preparations as a cleaning agent can, for. B. in such a way that the pasty detergent located in a bucket (capacity z. B. 0.5 to 10 kg) is sprayed with water and the detergent thus used is used, for. B. is metered into a dishwasher.
  • a dosing device sold by Henkel Hygiene GmbH under the name Topmater® P40 is ideal. Dosing from a 200 I barrel is also possible, e.g. B. via the Compactomix device from Lang.
  • the preparation of the paste-like cleaning agents according to the invention can be carried out directly in the containers used, e.g. B. sales containers; but it is also possible to produce a larger amount of cleaning agents according to the invention in a stirred kettle, then depending on the viscosity, possibly with slight heating, for. B. to 45 ° to 50 ° C, in a flowable state, in the containers used, for. B. sales containers to fill and then to cool again to about 20 ° C to achieve the viscosity of the invention.
  • the containers used e.g. B. sales containers
  • Viscosity 720,000 mPa s Detergent 8 Viscosity 720,000 mPa s Detergent 8:
  • V1 does not produce a paste, but a moist, lumpy powder.
  • V2, V3 and V4 are subject to phase separation after 1 day of storage at 25 ° C. H. Separation of the aqueous phase.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Noodles (AREA)
  • Gyroscopes (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Inorganic Insulating Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Afin d'obtenir des produits de nettoyage pâteux et aqueux à base de NaOH qui restent stables pendant leur transport et leur stockage, qui sont faciles à traiter et aisément solubles, on exploite l'effet épaississant de certains glycols, dérivés de glycol et/ou alcanolamines sur une solution alcaline huileuse et aqueuse. Les produits de nettoyage peuvent le cas échéant contenir des adjuvants usuels et d'autres constituants.
EP96905805A 1995-03-03 1996-02-27 Produit de nettoyage pateux Expired - Lifetime EP0813591B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19507532A DE19507532C2 (de) 1995-03-03 1995-03-03 Pastenförmiges Reinigungsmittel
DE19507532 1995-03-03
PCT/EP1996/000792 WO1996027653A1 (fr) 1995-03-03 1996-02-27 Produit de nettoyage pateux

Publications (2)

Publication Number Publication Date
EP0813591A1 true EP0813591A1 (fr) 1997-12-29
EP0813591B1 EP0813591B1 (fr) 1999-07-07

Family

ID=7755598

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96905805A Expired - Lifetime EP0813591B1 (fr) 1995-03-03 1996-02-27 Produit de nettoyage pateux

Country Status (16)

Country Link
US (1) US5958862A (fr)
EP (1) EP0813591B1 (fr)
JP (1) JPH11501072A (fr)
AT (1) ATE181957T1 (fr)
CA (1) CA2214592A1 (fr)
CZ (1) CZ288780B6 (fr)
DE (2) DE19507532C2 (fr)
DK (1) DK0813591T3 (fr)
ES (1) ES2135876T3 (fr)
FI (1) FI973586A0 (fr)
GR (1) GR3030783T3 (fr)
HU (1) HUP9702412A3 (fr)
NO (1) NO973079L (fr)
PL (1) PL321708A1 (fr)
SK (1) SK115297A3 (fr)
WO (1) WO1996027653A1 (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19617215A1 (de) * 1996-04-30 1997-11-06 Henkel Ecolab Gmbh & Co Ohg Kompaktreiniger für gewerbliche Geschirrspülmaschinen
JP2001500915A (ja) * 1996-09-24 2001-01-23 ヘンケル―エコラープ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・ウント・コンパニー・オッフェネ・ハンデルスゲゼルシャフト 界面活性剤を含むコンパクトな清浄剤
DE19741874A1 (de) * 1997-09-23 1999-04-01 Henkel Ecolab Gmbh & Co Ohg Alkoholathaltiger Reiniger
DE19828578C2 (de) * 1998-06-26 2000-04-20 Henkel Ecolab Gmbh & Co Ohg Verfahren zur Herstellung von cremeförmigen alkalisch-wäßrigen Reinigungsmitteln
US20040166043A1 (en) * 2003-02-24 2004-08-26 Vandine Robert W. Gas scrubbing reagent and methods for using same
CA2678624C (fr) * 2003-05-16 2012-11-06 Exciton Technologies Inc. Produits de revetement par depot, materiaux composites et methodes de production connexes
US20050059565A1 (en) * 2003-09-03 2005-03-17 Sutton David C. Cleaning composition
KR100651366B1 (ko) * 2003-09-05 2006-11-28 삼성전기주식회사 세정력과 폴리이미드면 접착력을 지닌 브라운 옥사이드전처리제 조성물 및 브라운 옥사이드 공정을 통한폴리이미드면 접착력 향상 방법
CN102317458B (zh) 2008-12-04 2018-01-02 库尔纳公司 通过红细胞生成素(epo)天然反义转录物的抑制对epo相关疾病的治疗
US20120115766A1 (en) * 2009-06-01 2012-05-10 Yuken Industry Co., Ltd. Degreasing composition and production method thereof
US8946182B2 (en) 2010-01-25 2015-02-03 Curna, Inc. Treatment of RNASE H1 related diseases by inhibition of natural antisense transcript to RNASE H1
DE102015109017A1 (de) 2015-06-08 2016-12-08 Budich International Gmbh Reinigungsmittel zur Reinigung von gewerblichen Gargeräten
DE102015109019A1 (de) 2015-06-08 2016-12-08 Budich International Gmbh Reinigungsvorrichtung für gewerbliche Gargeräte
HUE038978T2 (hu) * 2015-10-16 2018-12-28 Hans Georg Hagleitner Folyékony tisztítószer koncentrátum

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Publication number Priority date Publication date Assignee Title
DD289065A5 (de) 1989-08-09 1991-04-18 Carl Zeiss Gmbh Werk Entwicklung Wiss.-Techn. Ausruestungen Patentbuero,De Verfahren zur erzeugung einer dielektrischen schicht auf leichtmetallen oder deren legierungen
DE4139006C2 (de) 1991-11-27 1996-10-24 Electro Chem Eng Gmbh Verfahren zur Erzeugung von Oxidkeramikschichten auf sperrschichtbildenden Metallen und Gegenstände aus Aluminium, Magnesium, Titan oder deren Legierungen mit einer Oxidkeramikschicht

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US4784788A (en) * 1985-12-14 1988-11-15 Colgate-Palmolive Co. Cleaning paste with soluble abrasive
US5019290A (en) * 1988-03-22 1991-05-28 Dubois Chemicals, Inc. Method of formulating high caustic paste dishwashing compositions made compositions thereby, wherein phosphate reversion is minimized
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DE4228786A1 (de) * 1992-08-29 1994-03-03 Henkel Kgaa Geschirrspülmittel mit ausgewähltem Builder-System
GB9302855D0 (en) * 1993-02-12 1993-03-31 Laporte Esd Ltd Cleaning composition
ATE194380T1 (de) * 1993-06-01 2000-07-15 Ecolab Inc Verdickte reiniger fuer harte oberflaechen
US5510051A (en) * 1994-08-01 1996-04-23 Lam; Tony Preparation of a multi-purpose cleaner

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
DD289065A5 (de) 1989-08-09 1991-04-18 Carl Zeiss Gmbh Werk Entwicklung Wiss.-Techn. Ausruestungen Patentbuero,De Verfahren zur erzeugung einer dielektrischen schicht auf leichtmetallen oder deren legierungen
DE4139006C2 (de) 1991-11-27 1996-10-24 Electro Chem Eng Gmbh Verfahren zur Erzeugung von Oxidkeramikschichten auf sperrschichtbildenden Metallen und Gegenstände aus Aluminium, Magnesium, Titan oder deren Legierungen mit einer Oxidkeramikschicht

Also Published As

Publication number Publication date
HUP9702412A3 (en) 2001-04-28
ATE181957T1 (de) 1999-07-15
CZ276897A3 (cs) 1998-02-18
NO973079D0 (no) 1997-07-02
DE59602390D1 (de) 1999-08-12
ES2135876T3 (es) 1999-11-01
JPH11501072A (ja) 1999-01-26
NO973079L (no) 1997-07-02
US5958862A (en) 1999-09-28
HUP9702412A2 (hu) 1998-03-30
WO1996027653A1 (fr) 1996-09-12
DE19507532A1 (de) 1996-09-12
EP0813591B1 (fr) 1999-07-07
FI973586L (fi) 1997-09-02
DK0813591T3 (da) 2000-01-03
DE19507532C2 (de) 2000-01-05
SK115297A3 (en) 1998-02-04
GR3030783T3 (en) 1999-11-30
CZ288780B6 (cs) 2001-08-15
CA2214592A1 (fr) 1996-09-12
PL321708A1 (en) 1997-12-22
FI973586A7 (fi) 1997-09-02
FI973586A0 (fi) 1997-09-02

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