EP0414285B1 - Coacervats de polymères adjuvants et leur utilisation - Google Patents

Coacervats de polymères adjuvants et leur utilisation Download PDF

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Publication number
EP0414285B1
EP0414285B1 EP19900201944 EP90201944A EP0414285B1 EP 0414285 B1 EP0414285 B1 EP 0414285B1 EP 19900201944 EP19900201944 EP 19900201944 EP 90201944 A EP90201944 A EP 90201944A EP 0414285 B1 EP0414285 B1 EP 0414285B1
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EP
European Patent Office
Prior art keywords
coacervate
weight
copolymer
fraction
liquid 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
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EP19900201944
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German (de)
English (en)
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EP0414285A1 (fr
Inventor
Cornelis Johannes Buytenhek
Marianne Meyer
Cornelis Johannes Van De Pas
Johannes Henricus Maria Rek
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.)
Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Publication of EP0414285A1 publication Critical patent/EP0414285A1/fr
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in 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
    • 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
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase

Definitions

  • the present invention is concerned with coacervate fractions of builder polymers, more in particular of copolymers of acrylic acid and maleic acid, and the use of these fractions to formulate structured liquid detergent compositions.
  • Such structured liquids can be 'internally structured', whereby the structure is formed by primary ingredients, and/or they can be structured by secondary additives, such as certain cross-linked polyacrylates, or clays, which can be added to a composition as 'external structurants'.
  • External structuring is usually used for the purpose of suspending solid particles and/or droplets of nonionic surfactant. Examples of externally structured liquid detergent compositions are given in EP-A-120 533.
  • Internal structuring is usually used to suspend particles and/or to endow properties such as consumer-preferred flow properties and/or turbid appearance.
  • the most common suspended particulate solids are detergency builders and abrasive particles.
  • Examples of internally structured liquids without suspended solids are given in U.S. patent 4 244 840.
  • Examples of internally structured liquids having solid particles suspended therein are disclosed in specifications EP-A-160 342; EP-A-38 101; EP-A-140 452 and also in the aforementioned U.S. patent 4 244 840.
  • the first is high viscosity, rendering the products difficult to pour and the second is instability, i.e. a tendency for the dispersed and aqueous phases to undergo separation of the active ingredients or sedimentation of the solid particles and/or creaming of the nonionic, upon storage at elevated or even at ambient temperatures.
  • instability i.e. a tendency for the dispersed and aqueous phases to undergo separation of the active ingredients or sedimentation of the solid particles and/or creaming of the nonionic, upon storage at elevated or even at ambient temperatures.
  • EP-A-301 882 discloses that for internally structured liquid detergent compositions, the amount of stably incorporated polymer can be increased by adjusting the composition such that only part of the polymer is in solution whilst the rest is incorporated in a stable 'non-dissolved' phase within the composition.
  • the obtained compositions are sometimes of relatively high viscosity, furthermore compositions comprising higher levels of polymer tend to be instable.
  • this object may be achieved by incorporating the builder polymer in the composition at least partially in the form of a coacervate fraction containing said copolymer.
  • a coacervate fraction of a coacervate forming detergency copolymer of acrylic acid and maleic acid is provided.
  • Coacervate formation is a well-known phenomenon in physical chemistry, more in particular in colloid chemistry.
  • coacervation is a specific way of aggregation of active materials, whereby a relatively highly concentrated dispersed phase of the active materials is obtained.
  • Typical circumstances for the formation of such a coacervate fraction are circumstances wherein hydration of the active materials is reduced and the charge of the active materials is reduced or shielded.
  • coacervate fraction from a colloidal system of actives involves dehydration and neutralization of the electrical charge at the same time. When doing this, part of the actives form a coacervate fraction. Starting with a homogeneous colloidal solution, coacervation leads to phase separation. The coacervate fractions formed as a separate viscous liquid phase with a high concentration of dispersed material, which may for instance be as high as 35 % by weight. This does not exclude residual solubility of the colloid in the remaining solution.
  • the presence of materials in coacervate form may be detected by any means well-known in the art for the detection of structure formation, suitable methods for example involve: centrifugation, preferably at high speed, chromatography, X-ray and light scattering techniques or light microscopy, each separately or in combination with one another and chemical analysis.
  • a coacervate may be formed from an aqueous solution containing the copolymer by adding electrolyte, preferably concentrated sodium hydroxide solution, to a colloidal system of copolymer in a solvent until at a certain concentration of electrolyte material the coacervate fraction separates out, followed separating the formed coacervate fraction, for example by sedimentation or centrifugation.
  • electrolyte preferably concentrated sodium hydroxide solution
  • a preferred method for obtaining a coacervate fraction of the copolymer involves the preparation of an aqueous solution containing from 2-20% by weight of the copolymer, adding electrolyte, preferably concentrated sodium hydroxide solution, to a final concentration of at least 1% (w/w) of the electrolyte and separating the formed coacervate fraction by sedimentation or centrifugation.
  • electrolyte preferably concentrated sodium hydroxide solution
  • the aqueous solution more preferably contains from 5 - 10% by weight of the copolymer.
  • Coacervate fractions isolated by this or any other method for obtaining a similar fraction preferably contain at least 15 % by weight of the copolymer, and more preferably from 20 to 50 % by weight of the copolymer. TABLE A COACERVATION CONCENTRATION OF ELECTROLYTES FOR ACRYLIC ACID/MALEIC ACID COPOLYMERS (5% W/V) Polymer Mol.
  • Coacervate fractions according to the invention advantageously comprise an aqueous base and have a pH of more than 8.0, preferably of more than 9.0, a pH of above 11.0 being especially preferred.
  • copolymers are used wherein the molar ratio of acrylic acid to maleic acid in the copolymer is from 1 to 10. Also preferred is the use of copolymers having molecular weight of the copolymer is at least 5,000, preferably more than 20,000, especially preferred more than 40,000. The molecular weight of the copolymer is preferably less than 1,000,000, more preferably less than 150,000, most preferred less than 100,000. Copolymers having a molecular weight from 40,000 to 100,000 are particularly preferred, especially because of their excellent builder capacity.
  • the coacervate fraction obtained may be used to manufacture internally or externally structured liquid detergent compositions, which may be used for dish washing or fabric washing purposes, for example.
  • an externally structured liquid detergent composition comprising : 2-30% by weight of an alkaline agent, 2-60% by weight of the coacervate fraction according to the invention, and 0.1-5% by weight of a thickening agent.
  • an alkaline agent is any chemical agent suitable for use in liquid detergent compositions and capable of rendering said compositions alkaline.
  • the alkaline agent is present in an amount of from 2% to 30% by weight, preferably 10% to 25% by weight of the total composition.
  • suitable agents are the alkali metal hydroxides and silicates, such as alkali metal orthosilicates, metasilicates and disilicates, sodium metasilicate being preferred.
  • mixtures of alkaline agents may be used, such as a combination of sodium silicate and sodium hydroxide.
  • the externally structured liquid detergent compositions according to the invention comprise from 2 to 30 % by weight of a coacervate fraction as defined before, preferably from 5 to 10 %.
  • These externally structured compositions further contain a structuring or thickening agent.
  • Suitable agents are found among the alkali-stable polymers. Especially suitable are the water-soluble polymers of acrylic acid, cross-linked with about 1% of a polyallyl ether of sucrose having an average of about 5.8 allyl groups for each sucrose molecule, the polymer having a molecular weight in excess of 1,000,000. Examples of such polymers are Carbopol 934, 940 and 941. Carbopol is the Registered Trademark of B.F. Goodrich Co. Ltd, the manufacturers of these polymers. The preferred polymer is Carbopol 941. Depending on the viscosity which is desired, they may be included in the range of from 0.1% to 5% by weight, but preferably their amount varies from 0.2% to 0.8% by weight, and in particular from 0.2 to 0.6% by weight of the total composition.
  • the liquid detergent composition further comprises 0.5-25% by weight of a nonionic surfactant or a mixture thereof. If a nonionic surfactant is incorporated, it is normally present in an amount of at least 0.5%, and in particular of at least 2% by weight, the amount preferably ranging from 5 to 15% by weight of the total composition.
  • Nonionic detergents for use in compositions of the present invention can be readily obtained commercially, such as e.g. those sold under the trade names Lutensol LF 400 to 1300 (ex BASF AG) and Plurafac RA 30 to 343 (ex Produits Chimiques Ugine-Kuhlmann).
  • nonionic surfactant is an ethoxylated and propoxylated and/or butoxylated alcohol, the overall ratio in the alkylene oxide radical between the number of ethylene oxide units and the number of propylene and/or butylene oxide units being less than 9.
  • nonionics are for instance described in EP-A-120 533.
  • the nonionic detergent can be used as sole detergent, but other detergent-active ingredients, such as e.g. the water-soluble anionic sulphate or sulphonate detergents, can be tolerated provided their amount does not exceed 5% by weight, preferably 3% by weight or even 1% by weight of the total composition.
  • compositions of the invention may further contain 2% to 20%, preferably 5% to 15% by weight of an additional detergency builder.
  • suitable detergency builders are the phosphate builders such as the alkali metal salts of triphosphoric acid, pyrophosphoric acid, orthophosphoric acid, polymetaphosphoric acid and mixtures thereof. Sodium and potassium triphosphates are preferred.
  • Other suitable builders include carbonates, zeolites and organic builders such as citrates and polycarboxylates such as nitrilotriacetate, polyacrylates, polymaleinates and mixtures thereof.
  • an internally structured liquid detergent composition comprising a structured phase containing detergent-active material dispersed in an aqueous phase containing dissolved electrolyte and a copolymer of acrylic acid and maleic acid in the form of a coacervate fraction according to the invention.
  • more than 90% of the copolymer present in the compositions is in the form of a coacervate according to the invention.
  • the term 'electrolyte' means any inorganic or organic salt which is capable of ionising in aqueous solution.
  • the electrolyte may be dissolved in the compositions of the present invention and/or it may be present as suspended solid particles. In the great majority of cases where solid particles are suspended by an internal structure, it is necessary to have some dissolved electrolyte in order that the surfactant will exist in a structured form. Usually, the electrolyte will have another function, most often as a detergency builder, although it is possible to use electrolytes having no other role than to bring about internal structuring.
  • the composition is only internally structured and/or it contains an external structuring system, according to the particular ingredients and, sometimes, the order of mixing, it is possible to have the same electrolyte in solution and as suspended solids.
  • Either or both of the dissolved and suspended electrolyte materials may be a single electrolyte or a mixture of different electrolytes and, in any event, can be the same or different from one another.
  • the electrolyte material in suspension will be the same as that in solution, being an excess of same beyond the solubility limit.
  • the detergent active materials for use in externally structured compositions according to the present invention may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof.
  • surfactants may be selected from any of the classes, sub-classes and specific materials described in "Surface Active Agents” Vol. I, by Schwartz & Perry, Interscience 1949 and "Surface Active Agents" Vol.
  • Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are alkyl (C6-C18) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phospine oxides and dialkyl sulphoxides.
  • Suitable anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C8-C18) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monos
  • an alkali metal salt of a fatty acid especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof.
  • the sodium or potassium soaps of these acids can be used.
  • the liquid detergent compositions of the invention may further contain any of the adjuvants normally used in fabric-washing detergent compositions, e.g. sequestering agents such as ethylene diamine tetra-acetate and diethylene tetramine methylene phosphoric acid; soil-suspending and anti-redeposition agents such as carboxymethylcellulose, polyvinyl pyrrolidone and the maleic anhydride/vinylmethyl ether copolymer; fluorescent agents; hydrotropes; conditioning agents; lather boosters; perfumes, germicides and colorants.
  • sequestering agents such as ethylene diamine tetra-acetate and diethylene tetramine methylene phosphoric acid
  • soil-suspending and anti-redeposition agents such as carboxymethylcellulose, polyvinyl pyrrolidone and the maleic anhydride/vinylmethyl ether copolymer
  • fluorescent agents such as carboxymethylcellulose, polyvinyl pyrrolidone and the maleic anhydr
  • lather-depressors such as liquid polysiloxane anti-foam compounds; alkali-stable enzymes; bleaches, such as e.g. sodium sulphite, and potassium dichlorocyanurate, may be necessary or desirable to formulate a complete heavy-duty detergent composition suitable for use in machine washing operations.
  • These ingredients can be employed in the liquid detergent without the risk of undue decomposition during storage, especially if a proper protective coating is applied.
  • compositions of the present invention normally have viscosities within the range of 0.3 to 3.0 Pa.s (at 20°C and 21 sec ⁇ 1), in particular within the range of 0.5 to 2.0 Pa.s and preferably within the range of 0.6-1.2 Pa.s.
  • Externally structured compositions of the present invention are especially advantageous having pH-values within the high alkaline region, in particular values equal to or above 11, but preferred are pH-values above 12 or even above 13.
  • Internally structured compositions preferably have a pH of between 7.0 and 11.0.
  • the following externally structured liquid detergent formulations were prepared by adding the ingredients in the given order.
  • the copolymer was a copolymer of acrylic acid and maleic acid sold by BASF under the trade name CP7, in the form of a 40 % by weight solution in water. The amounts indicated below are in % by weight.
  • Example 4 NaOH 20.0 20.0 20.0 STP 2.5 2.5 2.5 Carbopol 941 0.50 0.55 0.60 Copolymer 7.5 7.5 7.5 Water -Balance -
  • the copolymer was again CP7 ex BASF. In these Examples it was added in the form of a coacervate fraction which was prepared from an aqueous solution containing 22.8 % by weight sodium hydroxide, 8.6 % CP7 and 68.6 % water. This solution was allowed to stand for one day and then the bottom layer was separated and used.
  • compositions were: Examples 4 5 6 Viscosity(mPa.s, 21s ⁇ 1, 25°C) 1500 1600 2200 Stability at 20°C (months) > 3 > 3 > 3 Stability at 37°C (months) ⁇ 1 ⁇ 1 ⁇ 3 S(kPa.s, 10 ⁇ 5s ⁇ 1, 25°C) 16 18 42
  • Marlon AS3 is dodecyl benzene sulphonic acid
  • LES is lauryl ether sulphate (about 3 EO)
  • Synperonic A3 is an ethoxylated C13-C15 fatty alcohol having 3 EO moieties.
  • To 480 g of this product various amounts were added of an acrylic acid/maleic acid copolymer sold by BASF under the trade name Sokalan CP5. The copolymer was added in the form of its coacervate, which was prepared by isolation of the bottom fraction which separates as a bottom layer after storage of the following composition for one day (the percentages are % by weight). Water 72.0 % Glycerol 10.1 % Borax 8.6 % NaOH 1.8 % Citric acid 2.3 % Copolymer (CP5) 5.2 %
  • the coacervate contained approximately 33% by weight of the copolymer. After the addition, the viscosity and stability of the product were investigated. Example grams of coacervate added final conc. copolymer viscosity (mPa.s, 21s ⁇ 1, 25°C) 7 0 0 1530 8 4.9 0.3 1180 9 10.0 0.7 990 10 20.4 1.3 650 11 42.6 2.7 460 12 66.7 4.0 390 13 93.2 5.6 300
  • the pH of the liquids was 8.7. In all cases, the stability after storage for three weeks at room temperature was good, showing less than 2% phase separation.

Claims (14)

  1. Fraction de coacervat isolée d'un copolymère de détergence d'acides acrylique et maléique formant coacervat.
  2. Fraction de coacervat selon la revendication 1, dans laquelle le rapport molaire de l'acide acrylique à l'acide maléique dans le copolymère est de 1 à 10.
  3. Fraction de coacervat selon la revendication 1 ou 2, dans laquelle la masse moléculaire du copolymère est d'au moins 5000.
  4. Fraction de coacervat selon les revendications 1, 2 et 3 qu'on obtient en préparant une solution aqueuse de 2 à 20% en puis du copolymère, en ajoutant un électrolyte jusqu'à une concentration finale d'au moins 1% en poids d'électrolyte et en séparant la fraction de coacervat formée par sédimentation ou centrifugation.
  5. Fraction de coacervat selon une ou plusieurs des revendications précédentes, qu'on obtient en préparant une solution aqueuse de 5 à 10% en poids de copolymère, en ajoutant une solution aqueuse concentrée d'hydroxyde de sodium jusqu'à une concentration finale d'au moins 1% en poids d'hydroxyde de sodium et en séparant la fraction de coacervat formée par sédimentation ou centrifugation.
  6. Fraction de coacervat selon une ou plusieurs des revendications précédentes, qui contient de 20 à 50% en poids de polymère.
  7. Fraction de coacervat selon une ou plusieurs des revendications précédentes, comprenant une base aqueuse ayant un pH supérieur à 8,0.
  8. Utilisation d'une fraction de coacervat selon une au plusieurs des revendications précédentes pour la formulation des compositions de détergents liquides structurés.
  9. Composition détergente liquide extérieurement structurée qu'on obtient selon la revendication 8 et qui comprend :
    2 à 30% en poids d'un agent alcalin ;
    2 à 60% en poids d'une fraction de coacervat selon les revendications 1 à 6 ; et
    0,1 à 5% en poids d'un agent structurant au épaississant.
  10. Composition détergente liquide extérieurement structurée selon les revendications 8 et/au 9, qui comprend en outre de 0,5 à 25% en poids d'une ou plusieurs matières tensioactives non ioniques.
  11. Composition détergente liquide extérieurement structurée selon une ou plusieurs des revendications 8 à 10, qui comprend en outre de 2 à 20% en poids d'un adjuvant.
  12. Composition détergente liquide intérieurement structurée obtenue selon la revendication 7, qui comprend une phase structurée contenant un détergent actif dispersé dans une phase aqueuse contenant l'électrolyte dissous.
  13. Composition détergente liquide selon la revendication 11, dans laquelle au moins 90% du copolymère sont présents sous forme d'une fraction de coacervat selon une ou plusieurs des revendications 1 à 7.
  14. Utilisation d'une composition selon l'une quelconque des revendications 9 à 13, pour le lavage de la vaisselle au le lavage des textiles.
EP19900201944 1989-08-15 1990-07-18 Coacervats de polymères adjuvants et leur utilisation Expired - Lifetime EP0414285B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8918575 1989-08-15
GB898918575A GB8918575D0 (en) 1989-08-15 1989-08-15 Liquid detergent composition

Publications (2)

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EP0414285A1 EP0414285A1 (fr) 1991-02-27
EP0414285B1 true EP0414285B1 (fr) 1995-05-24

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EP (1) EP0414285B1 (fr)
CA (1) CA2022902A1 (fr)
DE (1) DE69019632T2 (fr)
DK (1) DK0414285T3 (fr)
FI (1) FI903955A0 (fr)
GB (1) GB8918575D0 (fr)
NO (1) NO174815B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11248192B2 (en) 2019-01-22 2022-02-15 Ecolab Usa Inc. Polymer blend to stabilize highly alkaline laundry detergent

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1707624A3 (fr) 1993-10-08 2007-01-03 Novozymes A/S Variants d'amylase
EP0675194A1 (fr) * 1994-03-28 1995-10-04 The Procter & Gamble Company Additifs pour détergents dans des liquides structurés
DE19752454B4 (de) * 1997-11-26 2008-07-31 Henkel Ag & Co. Kgaa Geschirrspülmittel mit spezifischem Viskositätsprofil
US7390776B2 (en) 2002-09-13 2008-06-24 Nippon Shokubai Co., Ltd. Liquid detergent builder and liquid detergent containing the same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2936984A1 (de) * 1979-09-13 1981-04-02 Basf Ag, 6700 Ludwigshafen Verwendung von (meth)acrylsaeure-maleinsaeure-copolymerisaten als inkrustierungsinhibitoren in waschmitteln
GB8308263D0 (en) * 1983-03-25 1983-05-05 Unilever Plc Aqueous liquid detergent composition
DE3528460A1 (de) * 1985-08-08 1987-02-19 Basf Ag Verwendung von neutralisierten und amidierten, carboxylgruppen enthaltenden polymerisaten als zusatz zu waschmitteln und reinigungsmitteln

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11248192B2 (en) 2019-01-22 2022-02-15 Ecolab Usa Inc. Polymer blend to stabilize highly alkaline laundry detergent
US11773349B2 (en) 2019-01-22 2023-10-03 Ecolab Usa Inc. Polymer blend to stabilize highly alkaline laundry detergent

Also Published As

Publication number Publication date
CA2022902A1 (fr) 1991-02-16
NO903553L (no) 1991-02-18
DK0414285T3 (da) 1995-10-09
NO174815B (no) 1994-04-05
DE69019632D1 (de) 1995-06-29
NO174815C (fr) 1994-07-13
FI903955A0 (fi) 1990-08-10
EP0414285A1 (fr) 1991-02-27
GB8918575D0 (en) 1989-09-27
DE69019632T2 (de) 1995-10-12
NO903553D0 (no) 1990-08-14

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