EP0641381B2 - Verfahren zur herstellung pastenförmiger waschmittel - Google Patents

Verfahren zur herstellung pastenförmiger waschmittel Download PDF

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Publication number
EP0641381B2
EP0641381B2 EP93909938A EP93909938A EP0641381B2 EP 0641381 B2 EP0641381 B2 EP 0641381B2 EP 93909938 A EP93909938 A EP 93909938A EP 93909938 A EP93909938 A EP 93909938A EP 0641381 B2 EP0641381 B2 EP 0641381B2
Authority
EP
European Patent Office
Prior art keywords
weight
nonionic
mixture
quantities
detergent
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
Application number
EP93909938A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0641381B1 (de
EP0641381A1 (de
Inventor
Hans-Josef Beaujean
Jens Bode
Norbert Schäfer
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0641381A1 publication Critical patent/EP0641381A1/de
Publication of EP0641381B1 publication Critical patent/EP0641381B1/de
Application granted granted Critical
Publication of EP0641381B2 publication Critical patent/EP0641381B2/de
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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
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid 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
    • 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
    • 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
    • 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 present patent application relates to a process for the production of pasty, anhydrous or low-water Detergents and cleaning agents that, despite their insoluble content, are stable to sedimentation.
  • Paste-like detergents and cleaning agents have advantages with regard to them easy handling and relatively easy to manufacture on the apparatus side, with a further advantage is that you have a relatively wide margin with regard to the recipe components and thus the composition can largely adapt to specific washing requirements.
  • Differentiate in this regard are pasty detergents from pourable detergents, which, if no suitable measures are taken will have undesirable sedimentation if they contain insoluble components.
  • active oxygen compounds In addition, as a rule, such detergents do not have an application component in the formulation acceptable depletion of active oxygen. This is caused by unbound water, by multifunctional alcohols (preferably with adjacent OH groups or also with residual monomer components in polyols). Sedimentation-stable pasty detergents behave more favorably in this regard.
  • the object of the present invention was therefore to provide a method for simple manufacture paste-like detergents that are sedimentation-stable despite the content of insoluble components.
  • An essential feature of the paste-like detergents to be produced is their low or no water.
  • the present invention relates to a process for producing pasty, low-water or anhydrous Detergents containing non-ionic and anionic surfactants, soap, builders and bleaches, which is characterized in that sodium salts of linear fatty acid with 12 to 22 carbon atoms in amounts of 0.5 to 10% by weight, based on the finished detergent, in particle form with a particle size of at most 0.4 mm in the to 70-90 ° C. heated mixture of nonionic and anionic Surfactants incorporated and after cooling this mixture to below 30 ° C the rest Detergent ingredients incorporated.
  • “Wasseram” means that one Adds at most 3% by weight of water to the detergents during manufacture.
  • Suitable anionic Surfactants are, for example, synthetic surfactants of the sulfonate, sulfate or succinate type.
  • the surfactants of the sulfonate type are alkylbenzenesulfonates (C 9 -C 15 -alkyl), mixtures of alkane and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis Receives sulfonation products.
  • Afanesulfonates which are obtainable from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins are also suitable.
  • esters of alpha sulfo fatty acids e.g. B. the alpha-sulfonic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or tallow fatty acid.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols (e.g. from coconut fatty alcohols, Tallow fatty alcohols or oleyl alcohols) and those of secondary alcohols.
  • the alkoxylation products are also suitable of the aforementioned sulfate type surfactants.
  • Sulfated fatty acid alkanolamides are also suitable, Fatty acid monoglycerides or reaction products of 1 to 4 moles of ethylene oxide with primary or secondary fatty alcohols.
  • Other suitable anionic surfactants are the fatty acid esters or amides of hydroxy or aminocarboxylic acids, such as B. the fatty acid sarcosides, glycocate, lactate, tauride or isethionate.
  • Anionic succinate-type surfactants are, for example, alkyl succinates with long-chain alkyl radicals or alkyl sulfosuccinates.
  • the anionic surfactants can be in the form of their sodium, potassium and ammonium salts as well as soluble salts organic bases, such as mono-, di- or triethanolamine.
  • Nonionic surfactants are, for example, addition products of 4 to 40, preferably 4 to 20, moles of ethylene oxide 1 mol of fatty alcohol, alkytphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide. Particularly important are the adducts of 5 to 16 moles of ethylene oxide with coconut or tallow fatty alcohol, with oleyl alcohol or with secondary alcohols with 8 to 18, preferably 12 to 18, carbon atoms, and with mono- or dialkylphenols 6 to 14 carbon atoms in the alkyl radicals.
  • water-soluble nonionic surfactants not or not completely water-soluble polyglycol ethers with 1 to 4 ethylene glycol ether residues in the molecule of interest, especially when used together with water-soluble nonionic or anionic surfactants.
  • non-ionic surfactants are the water-soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 Addition products containing propylene glycol ether groups onto ethylene oxide or propylene oxide, alkylenediamine-polypropylene glycol and alkyl polypropylene glycols having 1 to 10 carbon atoms in the alkyl chain, in which the Polypropylene glycol chain acts as a hydrophobic residue.
  • nonionic surfactants of the amine oxide or sulfoxide type are usable.
  • alkylene oxide with long-chain alcohols examples include mixtures of oeyl alcohol and cetyl alcohol with an iodine number in the range from 50 to 55, to which about 7 moles of ethylene oxide have been added per mole of alcohol, C 12 -C 18 -fatty alcohol, to which about 5 moles of ethylene oxide have been attached and C 13 to C 15 oxo alcohol to which 5 to 8 moles of ethylene oxide have been attached.
  • Other interesting nonionic surfactants of this type are addition products of ethylene oxide and propylene oxide with fatty alcohols.
  • alkyl glucosides with a C 8 to C 18 alkyl radical, preferably with an alkyl radical consisting essentially of C 10 to C 16 , which is derived from decyl, lauryl, myristyl, cetyl and stearyl alcohol and derived from technical fractions, which preferably contain saturated alcohols.
  • alkyl glucosides is particularly suitable, the alkyl radical of which contains 50 to 70% by weight of C 12 and 18 to 30% by weight of C 14 alkyl radicals.
  • the degree of oligomerization of suitable alkyl glucosides is between 1 and 10, preferably between 1 and 6.
  • soap is also an anionic surfactant, it is used in the context of the present patent application as treated separate component.
  • Suitable soaps are the salts of saturated fatty acids 12 to 22 carbon atoms, which can also be in the form of their mixtures.
  • Suitable builders are in particular zeolite A, polycarboxylates, citrate, phosphonates, carbonates, silicates, Aminopolycarboxylic acid and polymers made from acrylic acid and maleic anhydride.
  • Suitable bleaching agents which release hydrogen peroxide in the wash liquor are, for example, sodium perborate tetrahydrate (NaBO 2 .H 2 O 2 • 3 H 2 O) and the monohydrate (NaBO 2 .H 2 O 2).
  • sodium perborate tetrahydrate NaBO 2 .H 2 O 2 • 3 H 2 O
  • monohydrate NaBO 2 .H 2 O 2
  • other borates which supply hydrogen peroxide can also be used, for example the perborax (Na 2 B 4 O 7 .H 2 O).
  • peroxy hydrates such as peroxycarbonates (Na 2 CO 3 .1.5 H 2 O 2 ), peroxypyrophosphates, citrate perhydrates, urea-H 2 O 2 - or melamine-H 2 O 2 - Compounds as well as by peracid salts providing hydrogen peroxide, e.g. As caroates (KHSO 5 ), perbenzoates or peroxyphthalates can be replaced.
  • KHSO 5 As caroates
  • perbenzoates or peroxyphthalates can be replaced.
  • water-soluble and / or water-insoluble stabilizers for the peroxy compounds together with these in amounts of 0.25 to 10% by weight.
  • examples of possible insoluble stabilizers are alkaline earth metal silicates and water-soluble stabilizers are, for example, organic complexing agents.
  • TAED tetraacetylethylene diamine
  • TAGU tetraacetylglycoluril
  • the soap is incorporated in a finely divided form.
  • finely divided means a particle size of less than 0.4 mm.
  • the soap can be made without the addition of water and without the use of powerful dispersants incorporate. It is preferred that the mixture of nonionic and anionic surfactants before incorporating the soap heated to 80 to 85 ° C.
  • a preferred embodiment of the method according to the invention is characterized in that in the mixture of nonionic and anionic surfactants uses at least two different nonionic surfactants.
  • These nonionic surfactants are preferably fatty alcohol ethoxylates with 12 to 18 carbon atoms in the Fatty alcohol residue and with different degrees of ethoxylation in the range from 2 to 7 moles of ethylene oxide per mole of fatty alcohol, which are used in amounts of 3 to 60% by weight, based on the finished detergent.
  • the type and the The amount of soap used is important.
  • Sodium salts of linear fatty acids are used as soap with 12 to 22 carbon atoms in amounts of 0.5 to 10 wt .-%, based on the finished detergent.
  • Procedure using the nonionic and anionic surfactants and soap mentioned the paste-like consistency of the detergents is established within 24 hours after mixing. Until then, the detergent produced according to the invention is pourable and can be easily conveyed, pumped and filled.
  • polycarboxylates and / or are preferably used as the framework substances Phosphonates and / or carbonates and / or silicates in amounts of 10 to 50% by weight, based on the finished detergent, on.
  • Another preferred builder is water-insoluble zeolite A.
  • sodium perborate is preferably used as the bleaching agent and / or sodium percarbonate, if desired in combination with activators, of which tetraacetylethylenediamine or diperoxydodecanedioic anhydride in addition to tetraacetylglycoluril in amounts of 10 to 30% by weight on the finished detergent, are preferred.
  • detergent components can be used in the preparation of the pasty detergents according to the invention.
  • the advantage of the detergents produced according to the invention is that they have reliable sedimentation stability the detergents are initially flowable and are easily pumped, conveyed and filled in this state can and that after about 24 hours, the pasty consistency sets, whereby the handling advantages described above are guaranteed.
  • detergents produced according to the invention have a negligible low breakdown of active oxygen.
  • a mixture of nonionic and anionic surfactants of the following composition was prepared at 80 to 85 ° C: 33.5% by weight C 12 - 15 oxo alcohol + 2 moles of ethylene oxide 16.5% by weight C 12-18 fatty alcohol + 7 moles of ethylene oxide 6.5% by weight C 13-17 alkane sulfonate - sodium salt 6.5% by weight C 12-16 alkyl sulphate - sodium salt 1% by weight C12 - 18 fatty acid - sodium salt.
  • the soap was incorporated as a fine-particle soap powder ( ⁇ 0.4 mm) with a mixer using the stator / rotor principle ("Supraton").
  • the surfactant mixture thus obtained was mixed with 2.1 wt 1-hydroxyethane-1,1-diphosphonic acid, disodium salt 5.5% by weight Copolymer of acrylic acid and maleic anhydride ("Sokalan CP 5" (R), company BASF, Germany) 10.0% by weight Sodium perborate monohydrate 3.0% by weight Tetraacetylethylenediamine 5.5% by weight Zeolite A 8.1% by weight sodium Rest up to 100% in total optical brightener, foam regulator, fragrance, enzyme in small quantities.
  • the mixture was liquid and was easy to pump, pump and fill.
  • the sodium perborate monohydrate had the following particle size distribution: > 1.0 mm 0.1% > 0.5 mm 14.7% > 0.4 mm 37.4% > 0.2 mm 90.7% > 0.1 mm 99.99%.
  • the sodium carbonate was 60.7% with a grain size of> 0.1 mm.

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  • 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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
EP93909938A 1992-05-19 1993-05-11 Verfahren zur herstellung pastenförmiger waschmittel Expired - Lifetime EP0641381B2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4216453A DE4216453A1 (de) 1992-05-19 1992-05-19 Verfahren zur Herstellung pastenförmiger Waschmittel
DE4216453 1992-05-19
PCT/EP1993/001146 WO1993023521A1 (de) 1992-05-19 1993-05-11 Verfahren zur herstellung pastenförmiger waschmittel

Publications (3)

Publication Number Publication Date
EP0641381A1 EP0641381A1 (de) 1995-03-08
EP0641381B1 EP0641381B1 (de) 1996-02-21
EP0641381B2 true EP0641381B2 (de) 1999-09-29

Family

ID=6459194

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93909938A Expired - Lifetime EP0641381B2 (de) 1992-05-19 1993-05-11 Verfahren zur herstellung pastenförmiger waschmittel

Country Status (13)

Country Link
US (1) US5518645A (ko)
EP (1) EP0641381B2 (ko)
JP (1) JPH07506607A (ko)
KR (1) KR950701679A (ko)
AT (1) ATE134384T1 (ko)
CA (1) CA2136173A1 (ko)
DE (2) DE4216453A1 (ko)
DK (1) DK0641381T4 (ko)
ES (1) ES2083285T5 (ko)
FI (1) FI945417A0 (ko)
GR (2) GR3019219T3 (ko)
NO (1) NO306560B1 (ko)
WO (1) WO1993023521A1 (ko)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6756181B2 (en) 1993-06-25 2004-06-29 Polyfibron Technologies, Inc. Laser imaged printing plates
US6916596B2 (en) 1993-06-25 2005-07-12 Michael Wen-Chein Yang Laser imaged printing plates
US5506201A (en) * 1994-04-29 1996-04-09 International Flavors & Fragrances Inc. Formulation of a fat surfactant vehicle containing a fragrance
DE4436151A1 (de) * 1994-08-16 1996-05-02 Henkel Kgaa Verfahren zur Herstellung eines Flüssigwaschmittels mit Bleiche
EP0784669A1 (en) * 1994-09-26 1997-07-23 The Procter & Gamble Company Process for preparing non-aqueous, bleach-containing liquid detergent compositions
EP0783563B1 (en) * 1994-09-26 2000-01-26 The Procter & Gamble Company Nonaqueous bleach-containing liquid detergent compositions
DE19535082A1 (de) * 1995-09-21 1997-03-27 Henkel Ecolab Gmbh & Co Ohg Pastenförmiges Wasch- und Reinigungsmittel
US6083488A (en) * 1996-12-04 2000-07-04 The Block Drug Company Barrier to plaque formation
DE19703364A1 (de) * 1997-01-30 1998-08-06 Henkel Ecolab Gmbh & Co Ohg Pastenförmiges Wasch- und Reinigungsmittel
US5863887A (en) * 1997-12-01 1999-01-26 Precision Fabrics Group, Inc. Laundry compositions having antistatic and fabric softening properties, and laundry detergent sheets containing the same
US6130193A (en) * 1998-02-06 2000-10-10 Precision Fabrics Group, Inc. Laundry detergent compositions containing silica for laundry detergent sheets
DE10017540C2 (de) * 2000-04-08 2002-07-04 Henkel Kgaa Verfahren zur Herstellung von flüssigen bis gelförmigen Reinigungsmitteln
US7694583B2 (en) * 2005-05-05 2010-04-13 Control Gaging, Inc. Gripper gage assembly
JP5868747B2 (ja) * 2012-03-19 2016-02-24 花王株式会社 界面活性剤混合物の製造方法
DE102012015826A1 (de) 2012-08-09 2014-02-13 Clariant International Ltd. Flüssige tensidhaltige Alkanolamin-freie Zusammensetzungen
DE102017208559A1 (de) 2017-05-19 2018-11-22 Henkel Ag & Co. Kgaa Verfahren zur Herstellung gelförmiger Substanzen

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8522621D0 (en) * 1985-09-12 1985-10-16 Unilever Plc Detergent powder
DE3621536A1 (de) * 1986-06-27 1988-01-07 Henkel Kgaa Fluessiges waschmittel und verfahren zu seiner herstellung
DE3842007A1 (de) * 1988-12-14 1990-06-21 Henkel Kgaa Fluessiges bis pastoeses, bleichmittelhaltiges waschmittel
DE3914504A1 (de) * 1989-05-02 1990-11-08 Henkel Kgaa Pastoeses, phosphatfreies, im wesentlichen wasserfreies waschmittel
GB2237285A (en) * 1989-10-27 1991-05-01 Unilever Plc Liquid soap composition
DE4009532A1 (de) * 1990-03-24 1991-09-26 Henkel Kgaa Waschmittel-formkoerper
US5244593A (en) * 1992-01-10 1993-09-14 The Procter & Gamble Company Colorless detergent compositions with enhanced stability

Also Published As

Publication number Publication date
DE4216453A1 (de) 1993-11-25
WO1993023521A1 (de) 1993-11-25
NO943320L (no) 1994-09-08
US5518645A (en) 1996-05-21
DE59301689D1 (de) 1996-03-28
NO943320D0 (no) 1994-09-08
DK0641381T3 (da) 1996-06-24
CA2136173A1 (en) 1993-11-25
ES2083285T5 (es) 1999-11-16
EP0641381B1 (de) 1996-02-21
NO306560B1 (no) 1999-11-22
FI945417A (fi) 1994-11-17
GR3019219T3 (en) 1996-06-30
FI945417A0 (fi) 1994-11-17
KR950701679A (ko) 1995-04-28
GR3031777T3 (en) 2000-02-29
ES2083285T3 (es) 1996-04-01
DK0641381T4 (da) 2000-01-03
ATE134384T1 (de) 1996-03-15
JPH07506607A (ja) 1995-07-20
EP0641381A1 (de) 1995-03-08

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