EP0337523B1 - Compositions détergentes en poudre et leur procédé de préparation - Google Patents

Compositions détergentes en poudre et leur procédé de préparation Download PDF

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Publication number
EP0337523B1
EP0337523B1 EP89200587A EP89200587A EP0337523B1 EP 0337523 B1 EP0337523 B1 EP 0337523B1 EP 89200587 A EP89200587 A EP 89200587A EP 89200587 A EP89200587 A EP 89200587A EP 0337523 B1 EP0337523 B1 EP 0337523B1
Authority
EP
European Patent Office
Prior art keywords
powder
weight
paraffin wax
spray
slurry
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
EP89200587A
Other languages
German (de)
English (en)
Other versions
EP0337523B2 (fr
EP0337523A1 (fr
Inventor
Peter Willem Appel
Hendrik Simon Kielman
Seeng Djiang Liem
Marco Waas
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
Original Assignee
Unilever PLC
Unilever NV
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Publication date
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0337523A1 publication Critical patent/EP0337523A1/fr
Publication of EP0337523B1 publication Critical patent/EP0337523B1/fr
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Publication of EP0337523B2 publication Critical patent/EP0337523B2/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
    • C11D3/18—Hydrocarbons
    • 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
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions

Definitions

  • the present invention relates to detergent powders prepared at least in part by spray-drying and intended for use in drum-type front-loading washing machines.
  • the invention is of especial applicability to powders containing no, or reduced levels of, phosphate builders and to powders of high bulk density.
  • the incorporation of the materials via the slurry also improves powder structure and raises the bulk density.
  • the invention comprises a spray-dried detergent powder being substantially free from inorganic phosphate and comprising at least 5% by weight of one or more anionic surfactants, from 20 to 80% by weight of crystalline or amorphous alumino-silicate detergency builder and no more than 10% by weight of alkali metal silicate, characterized in that the powder further comprises from 0.1 to 6.0% by weight of a paraffin wax which is water-insoluble and substantially insoluble in anionic and nonionic surfactants and has a melting point within the range of from 30 to 100 ° C and a contact angle to water of at least 75 °.
  • the invention provides a process for the preparation of a detergent powder being substantially free from inorganic phosphate and comprising at least 5% by weight of one or more anionic surfactants, from 20 to 80% by weight crystalline or amorphous alumino-silicate detergency builder and no more than 10% by weight of alkali metal silicate, the process including the step of spray-drying an aqueous slurry, characterized in that the powder further comprises a paraffin wax which is water-insoluble and substantially insoluble in anionic and nonionic surfactants and has a melting point within the range of from 30 to 100°C and a contact angle to water of at least 75°, and this paraffin wax is incorporated in the slurry or sprayed onto the powder in an amount of from 0.1 to 6.0% by weight based on the powder.
  • a paraffin wax which is water-insoluble and substantially insoluble in anionic and nonionic surfactants and has a melting point within the range of from 30 to 100°C and a contact angle
  • FR-A-2 257 680 discloses phosphate containing granular detergent compositions which include a microcrystalline paraffin wax as a foam control agent. It is generally mentioned in this document that suitable waxes appear to be those which can be solubilized by the surfactant employed.
  • detergent compositions containing foam control systems that include hydrocarbon waxes are given in EP-A-87 233, EP-A-109 247 and EP-A-206 522 (Unilever); GB 1 492 939, GB-B-2 040 982, EP-A-8 829, EP-A-8 830 and JP-A-56 034797 (Procter & Gamble); DE-A-3 436 194, US 4 590 194 and EP-A-150 386 (Henkel).
  • US 4 196 104 (Procter & Gamble) discloses spraying an antistatic composition comprising a quaternary ammonium compound and a paraffin wax (as dispersion inhibitor) onto detergent base granules.
  • the first aspect of the invention is a detergent powder prepared at least in part by spray-drying.
  • the composition of the invention may be a fully formulated detergent composition prepared wholly by spray-drying; a spray-dried base to which other ingredients may be admixed to form a finished product; or a finished product of that type, comprising a spray-dried base in admixture with other ingredients.
  • the detergent powder of the invention contains at least 5% by weight of one or more anionic and/or nonionic surfactants, from 20 to 80% by weight of crystalline or amorphous aluminosilicate detergency builder, and a specified paraffin wax that influences its dispensing behaviour in a particular manner.
  • composition of the invention may also contain any of the materials conventionally included in detergent compositions. These are described in more detail below.
  • the surfactant component is the surfactant component
  • the total amount of surfactant present in the composition of the invention will generally range from 5 to 40% by weight, more preferably from 10 to 30% by weight and especially from 12 to 20% by weight. These figures are typical for fully formulated detergent compositions, and where a spray-dried base forms only part of such a composition the surfactant content of that base, as a percentage, may of course be higher.
  • the invention relates to compositions containing anionic surfactant.
  • the high-foaming anionic surfactant tends to cause "puffing" (entrainment of air) in the slurry, so that highly porous particles are formed in the spray-drying tower. These particles may be very crisp and free-flowing, but may be of lower bulk density than desired.
  • the incorporation in the slurry of a paraffin wax, in accordance with the present invention has been found to result in an increase in bulk density.
  • the amount of anionic surfactant present is at least 5% by weight, and may suitably be in the range of from 5 to 30% by weight, preferably from 5 to 10% by weight, these figures again being based on a fully formulated detergent composition.
  • Anionic surfactants are well known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 ; primary and secondary alkyl sulphates, particularly sodium C 12 -C15 primary alcohol sulphates; olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates: and fatty acid ester sulphonates.
  • alkylbenzene sulphonates particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15
  • primary and secondary alkyl sulphates particularly sodium C 12 -C15 primary alcohol sulphates
  • olefin sulphonates alkane sulphonates
  • dialkyl sulphosuccinates and fatty acid ester sulphonates.
  • the composition of the invention also contains one or more nonionic surfactants.
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 12 -C 15 primary and secondary alcohols ethoxylated with an average of from 3 to 20 moles of ethylene oxide per mole of alcohol.
  • the weight ratio of anionic surfactant to nonionic surfactant is preferably at least 0.67:1, more preferably at least 1:1, and most preferably within the range of from 1:1 to 10:1, in order to obtain the optimum detergency and foaming properties appropriate for front-loading automatic washing machines. These ratios of course apply to fully formulated products.
  • a spray-dried base that is to form only part of a product may contain a lower proportion of, or no, nonionic surfactant, the balance of the nonionic surfactant being added after the spray-drying tower.
  • the paraffin wax is The paraffin wax
  • the characterising feature of the composition of the present invention is the presence of a low level (0.1-6.0% by weight) of a paraffin wax.
  • the hydrophobicity of this material is expressed in terms of its contact angle to water, which must be at least 750, preferably at least 85°.
  • the melting point of the paraffin wax is also important: it appears that the wax should be solid at ambient temperature but liquid at slurry-processing temperature (generally in the range of from 60 to 100°C).
  • the melting point of the paraffin wax should lie within the range of from 30 to 100°C, preferably from 40 to 80 °C, more preferably within the range of from 50 to 60 °C.
  • Paraffin oil liquid at ambient temperature has been found to be ineffective in the context of the present invention, and also tends to give wet, sticky powders with unacceptable flow properties.
  • paraffin wax be substantially insoluble in the anionic and nonionic surfactant system present in the composition: the microcrystalline waxes of FR-A-2 257 680 and GB 1 492 939 (Procter & Gamble) are stated to be chosen for their solubility in the surfactant present, and are unsuitable for use in the present invention for that reason as well as for the reason that their melting points are too high.
  • the paraffin wax is preferably present in an amount of from 0.2 to 4% by weight. In a fully formulated product the optimum level for paraffin wax appears to be from 0.3 to 2% by weight.
  • composition of the invention is prepared by a process which includes the step of spray-drying an aqueous crutcher slurry.
  • This slurry will normally contain all those desired ingredients sufficiently heat- stable to survive the spray-drying process, notably anionic surfactants, builders, inorganic salts, sodium silicate, Polymers and fluorescers. More heat-sensitive ingredients can be postdosed to, or sprayed onto, the spray-dried base.
  • the paraffin wax characteristic of the invention may be incorporated. It may be included in the slurry, in which case it is preferably used in an amount of from 0.2 to 4.0% by weight, more preferably from 0.3 to 2.0% by weight, based on the final powder including any postdosed ingredients. It may be advantageous to premix the paraffin wax with surfactant, especially nonionic surfactant, before admixture with other slurry ingredients.
  • the second method by which the paraffin wax may be incorporated in a detergent composition of the invention is by spraying it in liquefied form onto the spray-dried powder. If the final product is to include postdosed solid ingredients, for example, sodium perborate, bleach activator granules, enzyme granules or antifoam granules, the paraffin wax should be sprayed on after addition of those ingredients so as to cover the whole powder.
  • postdosed solid ingredients for example, sodium perborate, bleach activator granules, enzyme granules or antifoam granules
  • the paraffin wax may be melted and sprayed directly onto the powder.
  • the paraffin wax is then preferably used in an amount of from 2.0 to 6.0% by weight, more preferably from 3.0 to 4.0% by weight.
  • the paraffin wax is premixed with nonionic surfactant to form a coating composition which may then be sprayed onto the detergent powder.
  • Lower levels of the paraffin wax for example, 0.2 to 4.0%, preferably 0.3 to 2.0%, are then found to be effective.
  • the coating composition consists essentially of 2-50% by weight of the paraffin wax and 50-98% by weight of nonionic surfactant.
  • the coating composition desirably contains 8-15% by weight of paraffin wax and 85-92% by weight of nonionic surfactant.
  • the paraffin wax, and if necessary the nonionic surfactant are melted to form the coating composition, which is applied as a liquid, suitably at a temperature of 40-60 ° C.
  • the coating composition should be substantially free of other ingredients that might interfere with the beneficial effect of the paraffin wax on dispensing.
  • the incorporation of the paraffin wax should effect a reduction in the residue of at least 10 percentage points, preferably at least 20 percentage points.
  • a powder having essentially the same composition but with an inorganic salt (sodium carbonate or sodium sulphate) to make up the difference should be used.
  • the present invention is therefore especially applicable to powders which, without the paraffin wax, give dispenser residues of at least 10%, more especially at least 20%, by weight. That is especially likely to be the case if the powder is a zero-phosphate composition built with crystalline (zeolite) or amorphous sodium aluminosilicate; if it contains less than 10% sodium silicate; or if it has a bulk density of 450 g/litre or more, preferably 600 g/litre or more.
  • the detergent powder of the invention can contain any of the ingredients conventionally present in compositions intended for the washing of fabrics in front-loading automatic washing machines.
  • examples of such components include inorganic and organic detergency builders, other inorganic salts, bleaches, fluorescers, polymers, lather control agents, enzymes and perfumes.
  • the powder of the invention may contain one or more soaps of fatty acids, in addition to the non-soap anionic surfactant mentioned above.
  • the powder will also contain one or more detergency builders.
  • the invention is of especial applicability to zero-phosphate powders containing from 20 to 80 % by weight of crystalline (zeolite) or amorphous aluminosilicate.
  • Other supplementary, builders may also be present, for example, polycarboxylate polymers such as polyacrylates, acrylic-maleic copolymers, or acrylic phosphinates; momomeric polycarboxylates such as nitrilotriacetates and ethylene diamine tetraacetates; inorganic salts such as sodium carbonate; and many other materials familiar to the skilled detergent formulator.
  • the powder of the invention may contain sodium silicate.
  • High levels of silicate can in themselves have a beneficial effect on dispensing, as well as on powder structure and prevention of machine corrosion, but are undesirable in powders containing aluminosilicate because the two components react together to form insoluble siliceous species.
  • the present invention enables the dispensing behaviour of zeolite-built powders to be improved without a corresponding increase in the level of insoluble material. Accordingly, the invention relates to powders containing less that 10% by weight, more especially less than 5% by weight, of sodium silicate.
  • fluorescers include fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, enzymes, lather control agents, bleaches, bleach activators, and bleach stabilisers. These may be included in the spray-dried base powder or postdosed according to their known suitability for undergoing spray-drying processes and their compatibility with other slurry ingredients.
  • Zero-phosphate detergent base powders containing various amounts of paraffin wax (melting point 52-54 ° C) or paraffin oil were prepared, by slurry-making and spray-drying, to the following nominal composition:
  • the full formulation of the base powder of Comparative Example B was identical to that of Example 3, except that the paraffin wax was replaced by paraffin oil.
  • the dispensing residues of the base powders, determined by the test described above, and their powder properties were as follows: The dispenser residue of the base powder of Comparative Example B was 15%.
  • Zero-phosphate detergent powders similar to those of Examples 1-4 but containing a higher level of anionic surfactant were prepared, to the following formulations (in weight %):
  • a zero-phosphate detergent base powder similar to that of Comparative Example A was prepared, by slurry-making and spray-drying, to the following formulation:
  • Dispensing and powder properties were as follows:

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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)
  • Detergent Compositions (AREA)

Claims (13)

1. Une composition détergente en poudre séchée par vaporisation ne contenant substantiellement pas de phosphate inorganique et comprenant au moins 5% en masse d'un ou de plusieurs agents tensio-actifs anioniques, de 20 à 80% en masse d'édificateur de détergence aluminosilicate cristallin ou amorphe et pas plus de 10% en masse de silicate de métal alcalin, caractérisé en ce que la poudre comprend en outre de 0,1 à 6,0% en masse de cire de paraffine non soluble dans l'eau et substantiellement non soluble dans les agents tensio-actifs anioniques et non ioniques, dont le point de fusion est compris dans la gamme allant de 30 à 100 ° C et dont l'angle de contact avec l'eau est d'au moins 750.
2. Une composition détergente en poudre selon la revendication 1, caractérisée en ce que la cire de paraffine a un angle de contact avec l'eau d'au moins 85°.
3. Une composition détergente en poudre selon la revendication 1 ou 2, caractérisée en ce que la cire de paraffine a un point de lusion compris dans la gamme allant de 40 à 80 ° C.
4. Une composition détergente en poudre selon l'une des revendications précédentes, caractérisée en ce que la quantité de cire de paraffine incorporée à la composition détergente en poudre est comprise dans la gamme allant de 0,2 à 4,0% en masse.
5. Une composition détergente en poudre selon l'une des revendications précédentes, caractérisée en ce que sa densité est d'au moins 450 g/I.
6. Une composition détergente en poudre selon la revendication 5, caractérisée en ce que sa densité est d'au moins 600 g/I.
7. Un procédé pour la préparation d'une composition détergente en poudre ne contenant substantiellement pas de phosphate inorganique et comprenant au moins 5% en masse d'un ou de plusieurs agents tensio-actifs anioniques, de 20 à 80% en masse d'un édificateur de détergence aluminosilicate amorphe ou cristallin et pas plus de 10% en masse de silicate de métal alcalin, le procédé comprenant l'étape consistant à sécher par vaporisation une pâte aqueuse, caractérisé en ce que la composition détergente en poudre comprend en outre une cire de paraffine qui est non soluble dans l'eau et substantiellement non soluble dans les agents tensio-actifs anioniques et non ioniques et dont le point de fusion est compris dans la gamme allant de 30 à 100°C et dont l'angle de contact avec l'eau est d'au moins 75°, cette cire de paraffine étant incorporée à la pâte ou vaporisée sur la composition détergente en poudre dans une quantité allant de 0,1 à 6,0% en masse par rapport à la masse de la composition détergente en poudre.
8. Un procédé selon la revendication 7, caractérisé en ce que la cire de paraffine est incorporée par l'intermédiaire de la pâte dans une quantité allant de 0,2 à 4,0% en masse par rapport à la composition détergente en poudre.
9. Un procédé selon la revendication 8, caractérisé en ce que la cire de paraffine est pré-mélangée à l'agent tensio-actif non ionique avant d'être mélangée aux autres ingrédients de la pâte.
10. Un procédé selon la revendication 9, caractérisé en ce que la cire de paraffine sous forme liquéfiée est vaporisée sur la poudre séchée par vaporisation, dans une quantité allant de 0,2 à 0,4% en masse par rapport à la poudre ainsi obtenue.
11. Un procédé selon la revendication 10, caractérisé en ce qu'il comprend le fait de vaporiser sur la composition détergente en poudre, une composition d'enrobage essentiellement composée de :
(i) de 2 à 50% en masse de la cire de paraffine dispersée dans
(ii) de 50 à 98% en masse d'agent tensio-actif non ionique, les pourcentages se basant sur la composition d'enrobage.
12. Un procédé selon la revendication 11, caractérisé en ce que la composition d'enrobage est essentiellement composée de 5 à 30% en masse de cire de paraffine et de 70 à 95% en masse d'agent tensio-actif non ionique.
13. Une composition détergente en poudre selon la revendication 12, caractérisée en ce que la composition d'enrobage est essentiellement composée de 8 à 15% en masse de cire de paraffine et de 85 à 92% en masse d'agent tensio-actif non ionique.
EP89200587A 1988-03-21 1989-03-09 Compositions détergentes en poudre et leur procédé de préparation Expired - Lifetime EP0337523B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB888806702A GB8806702D0 (en) 1988-03-21 1988-03-21 Detergent powders & processes for preparing them
GB8806702 1988-03-21

Publications (3)

Publication Number Publication Date
EP0337523A1 EP0337523A1 (fr) 1989-10-18
EP0337523B1 true EP0337523B1 (fr) 1993-06-09
EP0337523B2 EP0337523B2 (fr) 2002-05-29

Family

ID=10633813

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89200587A Expired - Lifetime EP0337523B2 (fr) 1988-03-21 1989-03-09 Compositions détergentes en poudre et leur procédé de préparation

Country Status (8)

Country Link
EP (1) EP0337523B2 (fr)
AU (1) AU620381B2 (fr)
CA (1) CA1317188C (fr)
DE (1) DE68906949T3 (fr)
ES (1) ES2042963T5 (fr)
GB (1) GB8806702D0 (fr)
TR (1) TR26791A (fr)
ZA (1) ZA892134B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7279453B2 (en) 2001-02-22 2007-10-09 Henkel Kommanditgesellschaft Auf Aktien Foam regulating granulate

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9025673D0 (en) * 1990-11-26 1991-01-09 Unilever Plc Detergent powders and process for preparing them
EP0679178A1 (fr) * 1993-01-18 1995-11-02 The Procter & Gamble Company Compositions detersives pour lave-vaisselle
US5776874A (en) * 1993-01-18 1998-07-07 The Procter & Gamble Company Anti-tarnishing machine dishwashing detergent compositions containing a paraffin oil
EP0679177A1 (fr) * 1993-01-18 1995-11-02 The Procter & Gamble Company Compositions detersives pour lave-vaisselle
EP0706559B1 (fr) * 1993-07-01 2001-08-08 The Procter & Gamble Company Composition pour lave-vaisselle contenant un agent de blanchiment oxygene, de l'huile de paraffine et un compose benzotriazole pour inhiber le ternissement de l'argent
AU699818B2 (en) * 1993-07-02 1998-12-17 Unilever Plc Process for the production of high bulk density detergent composition
DE69328679T2 (de) * 1993-07-16 2001-01-11 The Procter & Gamble Company, Cincinnati Waschmittelzusammensetzungen für Geschirrspülmaschinen
ATE187487T1 (de) * 1994-02-18 1999-12-15 Henkel Ecolab Gmbh & Co Ohg Verfahren zur herstellung von sprühgetrockneten granulaten
EP0772670A4 (fr) * 1994-07-21 1998-01-28 Procter & Gamble Agents de blanchiment contenant une huile ou cire de paraffine dans des particules separees
DE19615824A1 (de) * 1996-04-20 1997-10-23 Igus Gmbh Gleitlager
DE19857204A1 (de) 1998-12-11 2000-06-15 Henkel Kgaa Wäßrige Schaumregulatoremulsion
WO2013093877A2 (fr) 2011-12-23 2013-06-27 Koninklijke Philips Electronics N.V. Système d'encapsulation pour la libération contrôlée d'un agent de blanchiment
WO2013128328A2 (fr) 2012-02-28 2013-09-06 Koninklijke Philips N.V. Système et procédé d'éclaircissement des dents
WO2014097053A1 (fr) 2012-12-18 2014-06-26 Koninklijke Philips N.V. Procédé amélioré de blanchiment des dents contenant un vernis à libération prolongée et activé par la lumière

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Publication number Priority date Publication date Assignee Title
US2423450A (en) * 1941-04-17 1947-07-08 Colgate Palmolive Peet Co Preparation of synthetic organic detergent particles having only slight dust-forming tendencies
AU496849B2 (en) * 1974-01-11 1978-11-02 Procter & Gamble Company, The LOW sudsing DETERGENT COMPOSITIONS
US4363740A (en) * 1980-07-29 1982-12-14 Lever Brothers Company Process for making controlled sudsing detergent powder
GB8513074D0 (en) * 1985-05-23 1985-06-26 Unilever Plc Antifoam ingredient

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7279453B2 (en) 2001-02-22 2007-10-09 Henkel Kommanditgesellschaft Auf Aktien Foam regulating granulate

Also Published As

Publication number Publication date
DE68906949T2 (de) 1993-09-16
GB8806702D0 (en) 1988-04-20
TR26791A (tr) 1994-08-08
AU620381B2 (en) 1992-02-20
ZA892134B (en) 1990-11-28
ES2042963T5 (es) 2002-12-16
EP0337523B2 (fr) 2002-05-29
DE68906949D1 (de) 1993-07-15
EP0337523A1 (fr) 1989-10-18
ES2042963T3 (es) 1993-12-16
AU3149889A (en) 1989-09-21
DE68906949T3 (de) 2002-09-05
CA1317188C (fr) 1993-05-04

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