EP0540372B1 - Match head formulations containing iron phosphides - Google Patents

Match head formulations containing iron phosphides Download PDF

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Publication number
EP0540372B1
EP0540372B1 EP92402242A EP92402242A EP0540372B1 EP 0540372 B1 EP0540372 B1 EP 0540372B1 EP 92402242 A EP92402242 A EP 92402242A EP 92402242 A EP92402242 A EP 92402242A EP 0540372 B1 EP0540372 B1 EP 0540372B1
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EP
European Patent Office
Prior art keywords
mass
dry mixture
composition according
composition
weight
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
EP92402242A
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German (de)
French (fr)
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EP0540372A1 (en
Inventor
Jean-Paul Bernard
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.)
Societe Nationale dExploitation Industrielle des Tabacs et Allumettes SAS
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Societe Nationale dExploitation Industrielle des Tabacs et Allumettes SAS
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B39/00—Compositions containing free phosphorus or a binary compound of phosphorus, except with oxygen
    • C06B39/02—Compositions containing free phosphorus or a binary compound of phosphorus, except with oxygen with an inorganic oxygen-halogen salt
    • C06B39/04—Compositions containing free phosphorus or a binary compound of phosphorus, except with oxygen with an inorganic oxygen-halogen salt with a binary compound of phosphorus, except with oxygen
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06F—MATCHES; MANUFACTURE OF MATCHES
    • C06F3/00—Chemical features in the manufacture of matches

Definitions

  • the invention relates to match buttons and, more particularly, but not exclusively, to so-called safety matches.
  • a safety match consists of a rod comprising, at one end, a button designed to ignite by friction on a special support comprising red phosphorus.
  • a button designed to ignite by friction on a special support comprising red phosphorus.
  • matches of the so-called “strike-anywhere” type the button of which ignites by friction on the most diverse rough supports.
  • Sulfur is used in safety matches, phosphorus sulfide in "strike-anywhere" matches.
  • the odor of sulfur dioxide released at the time of combustion may be perceived as irritating for some users, and especially the traces of potassium dichromate and zinc salts generally present in the washing water of production equipment may be considered polluting if they are released into the natural environment.
  • the object of the present invention is to overcome this drawback by making it possible to substitute for sulfur a primary fuel which is non-toxic and not capable of producing an irritating emanation and to suppress the introduction of potassium dichromate and, preferably, that of oxide. of zinc in the composition of the button.
  • composition for match button according to the invention is defined in a first set of claims 1 to 10 in which claim 1 specifies that this composition comprises an oxidizer, a fuel, a binder as well as possible fillers and adjuvants and is characterized in that the fuel comprises an iron phosphide in a proportion ranging from 3 to 60% by weight.
  • composition according to the invention is defined in a second set of claims 1 to 13, in which claim 1 specifies that this composition comprises an oxidizer , a fuel, a binder as well as fillers and any additives, and is characterized in that the fuel comprises an iron phosphide in a proportion ranging from 3 to 60% by weight, and in that the charge comprises flours diatoms, and / or bentonite and / or mica and / or silica.
  • the average particle size of the iron phosphides used will be less than 250 ⁇ m and, preferably, of the order of ten ⁇ m.
  • the components are mixed in aqueous dispersion with, for example, 25% of water and the matches are manufactured by soaking according to a conventional technique.
  • the iron phosphide used is commercially available in the form of a fine powder (majority particle size of a few microns), which is used in the prior art as a conductive pigment in the field of anti-corrosion paints.
  • This powder contains iron phosphides in the form F2P or F3P.
  • the phosphide oxidation reaction begins with friction on a special surface which can be identical to that found in traditional safety matchboxes using sulfur as fuel.
  • the particle size of the phosphides has been found to be an important parameter (it must be less than 200 microns on average to obtain satisfactory reactivity and sensitivity), which is probably explained by the role played by the interface between the particles of phosphides and potassium chlorate crystals in combustion.
  • combustion speed does not reach values high enough to require the use of an energetic phlegmatizer, such as zinc oxide or zinc salt.
  • This ignition violence could be reduced in particular thanks to an addition of celite, for example by 1% by mass and / or by the replacement of a phosphide fraction, for example of the order of 4% with mica.
  • celite for example by 1% by mass and / or by the replacement of a phosphide fraction, for example of the order of 4% with mica.
  • phosphide fraction for example of the order of 4% with mica.
  • This composition makes it possible to obtain a good sensitivity, which remains good even in the case where the bentonite is removed and where 3% of celite is added.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Pretreatment Of Seeds And Plants (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (AREA)
  • Adornments (AREA)
  • Golf Clubs (AREA)
  • Thermotherapy And Cooling Therapy Devices (AREA)

Abstract

The composition according to the invention comprises an oxidising agent, a fuel, a binder and optional fillers and adjuvants. As fuel, it employs an iron phosphide in a proportion ranging from 3 to 60 % by weight. The invention makes it possible in particular to do away with the odour of sulphur dioxide released by conventional matches at the time of burning.

Description

L'invention concerne les boutons d'allumettes et, plus particulièrement, mais non exclusivement, d'allumettes dites de sûreté.The invention relates to match buttons and, more particularly, but not exclusively, to so-called safety matches.

On sait qu'une allumette de sûreté est constituée d'une tige comportant, à une extrémité, un bouton conçu pour s'enflammer par frottement sur un support spécial comportant du phosphore rouge. Il existe, par ailleurs, des allumettes de type dit "strike-anywhere" dont le bouton s'enflamme par frottement sur les supports rugueux les plus divers.We know that a safety match consists of a rod comprising, at one end, a button designed to ignite by friction on a special support comprising red phosphorus. There are, moreover, matches of the so-called "strike-anywhere" type, the button of which ignites by friction on the most diverse rough supports.

Une composition traditionnelle pour bouton d'allumette répond à la formulation suivante :

Comburant
: Chlorate de potassium   28 à 62 % en poids
Combustible
: Soufre ou sulfure de phosphore   2 à 7 % en poids
Liant
: Gélatine pure ou avec des additifs   8 à 18 % en poids
Charges
: Matières siliciques ou organiques   15 à 25 % en poids
Adjuvants
: Catalyseurs, pigments, colorants
(dont bichromate de potassium et oxyde de zinc)   0,5 à 25 % en poids
A traditional composition for match button corresponds to the following formulation:
Oxidizer
: Potassium chlorate 28 to 62% by weight
Combustible
: Sulfur or sulfide of phosphorus 2 to 7% by weight
Binder
: Pure gelatin or with additives 8 to 18% by weight
Charges
: Silicic or organic materials 15 to 25% by weight
Adjuvants
: Catalysts, pigments, dyes
(including potassium dichromate and zinc oxide) 0.5 to 25% by weight

Le soufre est utilisé dans les allumettes de sûreté, le sulfure de phosphore dans les allumettes "strike-anywhere".Sulfur is used in safety matches, phosphorus sulfide in "strike-anywhere" matches.

Les allumettes actuelles ne présentent pas de toxicité effective ni pour l'utilisateur, ni pour le personnel de production.Current matches do not present any effective toxicity either for the user or for the production personnel.

Toutefois, l'odeur d'anhydride sulfureux dégagée au moment de la combustion peut être perçue comme irritante pour certains utilisateurs, et surtout les traces de bichromate de potassium et de sels de zinc généralement présents dans les eaux de lavage du matériel de production peuvent être considérées comme polluantes si elles sont rejetées dans le milieu naturel.However, the odor of sulfur dioxide released at the time of combustion may be perceived as irritating for some users, and especially the traces of potassium dichromate and zinc salts generally present in the washing water of production equipment may be considered polluting if they are released into the natural environment.

La présente invention a pour but de s'affranchir de cet inconvénient en permettant de substituer au soufre un combustible primaire atoxique et non susceptible de produire une émanation irritante et de supprimer l'introduction de bichromate de potassium et, de préférence, celle d'oxyde de zinc dans la composition du bouton.The object of the present invention is to overcome this drawback by making it possible to substitute for sulfur a primary fuel which is non-toxic and not capable of producing an irritating emanation and to suppress the introduction of potassium dichromate and, preferably, that of oxide. of zinc in the composition of the button.

Toutefois, par la demande de brevet européen 0496996 A2 publiée le 5 Août 1992, c'est à dire postérieurement à la date de priorité de la présente demande, on a déjà proposé une composition pour bouton d'allumette dans laquelle les composés de chrome et les composés à base de sesqui-phosphores, les composés sulfureux et les oxydes de zinc sont absents et sont remplacés par du phosphure de fer.However, by European patent application 0496996 A2 published on August 5, 1992, that is to say after the priority date of the present application, a composition for match button has already been proposed in which the chromium and sesqui-phosphorus compounds, sulfur compounds and zinc oxides are absent and are replaced by iron phosphide.

En conséquence, pour les pays désignés dans la présente demande et qui ne le sont pas dans la demande de brevet européen précitée, la composition pour bouton d'allumette selon l'invention est définie dans un premier jeu de revendications 1 à 10 dans lequel la revendication 1 précise que cette composition comprend un comburant, un combustible, un liant ainsi que d'éventuels charges et adjuvants et est caractérisée en ce que le combustible comprend un phosphure de fer dans une proportion allant de 3 à 60 % en poids.Consequently, for the countries designated in the present application and which are not in the patent application European aforementioned, the composition for match button according to the invention is defined in a first set of claims 1 to 10 in which claim 1 specifies that this composition comprises an oxidizer, a fuel, a binder as well as possible fillers and adjuvants and is characterized in that the fuel comprises an iron phosphide in a proportion ranging from 3 to 60% by weight.

Pour les pays désignés dans la présente demande et qui le sont dans la demande de brevet européen précitée, la composition selon l'invention est définie dans un second jeu de revendications 1 à 13, dans lequel la revendication 1 précise que cette composition comprend un comburant, un combustible, un liant ainsi que des charges et d'éventuels adjuvants, et est caractérisée en ce que le combustible comprend un phosphure de fer dans une proportion allant de 3 à 60 % en poids, et en ce que la charge comprend des farines de diatomées, et/ou de la bentonite et/ou du mica et/ou de la silice.For the countries designated in the present application and which are in the aforementioned European patent application, the composition according to the invention is defined in a second set of claims 1 to 13, in which claim 1 specifies that this composition comprises an oxidizer , a fuel, a binder as well as fillers and any additives, and is characterized in that the fuel comprises an iron phosphide in a proportion ranging from 3 to 60% by weight, and in that the charge comprises flours diatoms, and / or bentonite and / or mica and / or silica.

Dans un mode d'exécution préféré, la granulométrie moyenne des phosphures de fer utilisés, sera inférieure à 250 µm et, de préférence, de l'ordre d'une dizaine de µm.In a preferred embodiment, the average particle size of the iron phosphides used will be less than 250 μm and, preferably, of the order of ten μm.

Dans son application aux allumettes de sûreté, la composition suivant l'invention aura avantageusement la formulation suivante :

Comburant
: Chlorate ou perchlorate de potassium   30 à 62 % en poids
Combustible
: Phosphures de fer   3 à 60 % en poids
Liant
: Gélatine ou liants de synthèse   5 à 18 % en poids
Charges
: Matières siliciques ou organiques   0 à 25 % en poids
Adjuvants
: Pigments - flegmatisants - stabilisants   0 à 25 % en poids
In its application to safety matches, the composition according to the invention will advantageously have the following formulation:
Oxidizer
: Potassium chlorate or perchlorate 30 to 62% by weight
Combustible
: Iron phosphides 3 to 60% by weight
Binder
: Gelatin or synthetic binders 5 to 18% by weight
Charges
: Silicic or organic materials 0 to 25% by weight
Adjuvants
: Pigments - phlegmatizers - stabilizers 0 to 25% by weight

L'invention sera mieux comprise à la lumière des exemples décrits ci-après, donnés à titre non limitatif, qui se rapportent à la fabrication d'allumettes de sûreté.The invention will be better understood in the light of the examples described below, given without limitation, which relate to the manufacture of safety matches.

Exemple 1Example 1

On part de la composition suivante :

Chlorate de potassium
50% en masse du mélange sec
Gélatine
13 % en masse du mélange sec
Farine de diatomées
5 % en masse du mélange sec
Phosphure de fer
32 % en masse du mélange sec
We start from the following composition:
Potassium chlorate
50% by mass of the dry mixture
Gelatin
13% by mass of the dry mixture
Diatom flour
5% by mass of the dry mixture
Iron phosphide
32% by mass of the dry mixture

Les composants sont mélangés en dispersion aqueuse avec par exemple 25 % d'eau et la fabrication des allumettes s'effectue par trempage suivant une technique classique.The components are mixed in aqueous dispersion with, for example, 25% of water and the matches are manufactured by soaking according to a conventional technique.

Après séchage pendant 1 heure 30 à 40°C, la réactivité et la sensibilité obtenues sont comparables à celles d'une formulation classique pour allumettes de sûreté.After drying for 1 hour 30 minutes at 40 ° C., the reactivity and sensitivity obtained are comparable to that of a conventional formulation for safety matches.

On soulignera qu'aucun ajout de bichromate de potassium ou d'oxyde de zinc n'a été fait. Le phosphure de fer utilisé est disponible dans le commerce à l'état de poudre fine (granulométrie majoritaire de quelques microns), laquelle est utilisée dans l'art antérieur comme pigment conducteur dans le domaine des peintures anti-corrosion.It should be noted that no addition of potassium dichromate or zinc oxide was made. The iron phosphide used is commercially available in the form of a fine powder (majority particle size of a few microns), which is used in the prior art as a conductive pigment in the field of anti-corrosion paints.

Cette poudre contient des phosphures de fer sous la forme F₂P ou F₃P.This powder contains iron phosphides in the form F₂P or F₃P.

La réaction d'oxydation des phosphures s'amorce par la friction sur une surface spéciale qui peut être identique à celle que possèdent les boîtes d'allumettes de sûreté traditionnelles utilisant le soufre comme combustible. On constate de manière surprenante que la combustion des phosphures se poursuit quand on arrête le frottement, en dépit de l'absence de l'effet catalytique - indispensable dans l'art antérieur - du bichromate de potassium.The phosphide oxidation reaction begins with friction on a special surface which can be identical to that found in traditional safety matchboxes using sulfur as fuel. We surprisingly notes that the combustion of phosphides continues when the friction is stopped, despite the absence of the catalytic effect - essential in the prior art - of potassium dichromate.

La granulométrie des phosphures s'est révélée constituer un paramètre important (elle doit être inférieure à 200 microns en moyenne pour obtenir une réactivité et une sensibilité satisfaisantes), ce qui s'explique probablement par le rôle joué par l'interface entre les particules de phosphures et les cristaux de chlorate de potassium dans la combustion.The particle size of the phosphides has been found to be an important parameter (it must be less than 200 microns on average to obtain satisfactory reactivity and sensitivity), which is probably explained by the role played by the interface between the particles of phosphides and potassium chlorate crystals in combustion.

On constate également que la vitesse de combustion n'atteint pas des valeurs suffisamment élevées pour exiger l'emploi d'un flegmatisant énergique, tel qu'oxyde de zinc ou sel de zinc.It is also noted that the combustion speed does not reach values high enough to require the use of an energetic phlegmatizer, such as zinc oxide or zinc salt.

Toutefois, l'allumage demeure relativement violent, la flamme partant dans tous les sens avec des projections.However, the ignition remains relatively violent, the flame going in all directions with projections.

Cette violence de l'allumage a pu être réduite notamment grâce à un rajout de célite, par exemple de 1 % en masse et/ou au remplacement d'une fraction de phosphure, par exemple de l'ordre de 4 % par du mica. Cette dernière solution permet de réduire notablement les projections lors de l'allumage.This ignition violence could be reduced in particular thanks to an addition of celite, for example by 1% by mass and / or by the replacement of a phosphide fraction, for example of the order of 4% with mica. The latter solution significantly reduces splashes during ignition.

Exemple 2Example 2

Dans cet exemple, la composition présente la formulation suivante :

Chlorate de potassium
50 % en masse du mélange sec
Gélatine
13 % en masse du mélange sec
Farine de diatomées
5 % en masse du mélange sec
Phosphure de fer
32 % en masse du mélange sec
Bentonite
5 % en masse du mélange sec
In this example, the composition has the following formulation:
Potassium chlorate
50% by mass of the dry mixture
Gelatin
13% by mass of the dry mixture
Diatom flour
5% by mass of the dry mixture
Iron phosphide
32% by mass of the dry mixture
Bentonite
5% by mass of the dry mixture

Cette composition permet d'obtenir une bonne sensibilité, laquelle reste bonne même dans le cas où l'on supprime la bentonite et où l'on rajoute 3 % de célite.This composition makes it possible to obtain a good sensitivity, which remains good even in the case where the bentonite is removed and where 3% of celite is added.

Aucun changement notable n'est constaté si l'on ramène à 11 % la quantité de gélatine, avec des ajouts de 2 % de silice C 600, de 3 % de célite, la quantité de phosphure étant alors ramenée à 29 %.No significant change is noted if the amount of gelatin is reduced to 11%, with the addition of 2% of silica C 600, of 3% of celite, the amount of phosphide then being reduced to 29%.

Exemple 3Example 3

La composition définie dans cet exemple est celle qui a donné les meilleurs résultats, aussi bien au niveau de son industrialisation que sur le plan qualitatif. Sa formulation est la suivante :

Chlorate de potassium
55 % en masse du mélange sec
Gélatine
13 % en masse du mélange sec
Farine de diatomées
5 % en masse du mélange sec
Silice
16 % en masse du mélange sec
Phosphure de fer
5 % en masse du mélange sec
Célite
2 % en masse du mélange sec
Oxyde de titane
4 % en masse du mélange sec
The composition defined in this example is that which gave the best results, both in terms of its industrialization and in terms of quality. Its formulation is as follows:
Potassium chlorate
55% by mass of the dry mixture
Gelatin
13% by mass of the dry mixture
Diatom flour
5% by mass of the dry mixture
Silica
16% by mass of the dry mixture
Iron phosphide
5% by mass of the dry mixture
Celite
2% by mass of the dry mixture
Titanium oxide
4% by mass of the dry mixture

Cette composition a permis d'obtenir une très bonne sensibilité sur tous frottoirs, aucune projection ni de formation de dards, une bonne transmission avec une fumée et une flamme normale, le bouton présentant un bon aspect après allumage : Ces résultats sont restés inchangés à la suite d'un rajout de 1 % d'oxyde de fer pour colorer le bouton.This composition made it possible to obtain a very good sensitivity on all rubbers, no projection or formation of darts, a good transmission with a smoke and a normal flame, the button having a good appearance after lighting: These results remained unchanged at following an addition of 1% iron oxide to color the button.

Des essais sur une composition similaire à la précédente avec, en moins 1 % de silice et 1 % de phosphure (ce qui ramène à 4 % le pourcentage de phosphure) et, en plus 2 % de célite, ont permis d'obtenir des résultats satisfaisants, avec cependant un léger retard à l'allumage et une légère difficulté des allumettes à s'enflammer.Tests on a composition similar to the previous one with, in less 1% of silica and 1% of phosphide (which brings back to 4% the percentage of phosphide) and, in addition 2% of celite, made it possible to obtain results satisfactory, with however a slight delay in lighting and a slight difficulty of the matches to ignite.

Claims (13)

  1. Composition for match head of the type comprising an oxygen carrier, a fuel, a binder as well as filling material and possibly additives, characterized in that the fuel comprises an iron phosphide in a proportion ranging from 3 to 60% by weight, and in that the filling materials comprise diatomaceous earth, and/or bentonite and/or mica and/or silica.
  2. Composition according to claim 1, characterized in that the average granulometry of the iron phosphides used is less than 250 µm.
  3. Composition according to claim 2, characterized in that the average granulometry of the iron phosphides used is of the order of ten µm.
  4. Composition according to one of the previous claims, characterized in that, in its application to safety matches, it is formulated as follows:
    Oxygen carrier   : Potassium chlorate or perchlorate   30 to 62% by weight
    Fuel   : Iron phosphides   3 to 60% by weight
    Binder   : Gelatine or synthetic binders   5 to 18% by weight
    Filling materials   : Silicious or organic matter   ≦ 25% by weight
    Additives   : Pigments-combustion regulators-stabilisers   0 to 25% by weight
  5. Composition according to claim 4, characterized in that it comprises iron oxide in a proportion of the order of 1%.
  6. Composition according to one of the previous claims, characterized in that the binder is gelatine which is used in the composition in a proportion of approximately 13%.
  7. Composition according to one of the previous claims, characterized in that the filling materials comprise diatomaceous earth used in the composition in a proportion of approximately 5% by weight.
  8. Composition according to one of the previous claims, characterized in that filling materials comprise silica, mica and titanium oxide which are used in the composition in a proportion of approximately 3 to 6% by weight.
  9. Composition according to one of the previous claims, characterized in that the above-mentioned composition comprises cellite.
  10. Composition according to claim 9, characterized in that the quantity of cellite is included between 1 and 5%.
  11. Composition according to claim 4, characterized in that it is formulated as follows:
    Potassium chlorate   55% by mass of the dry mixture
    Gelatine   13% by mass of the dry mixture
    Diatomaceous earth   5% by mass of the dry mixture
    Silica   16% by mass of the dry mixture
    Iron phosphide   5% by mass of the dry mixture
    Cellite   2% by mass of the dry mixture
    Titanium oxide   4% by mass of the dry mixture
  12. Composition for match head, characterized in that it comprises:
    Potassium chlorate   50% by mass of the dry mixture
    Gelatine   13% by mass of the dry mixture
    Diatomaceous earth   5% by mass of the dry mixture
    Iron phosphide   32% by mass of the dry mixture
  13. Composition for match head, characterized in that it comprises:
    Potassium chlorate   50% by mass of the dry mixture
    Gelatine   13% by mass of the dry mixture
    Diatomaceous earth   5% by mass of the dry mixture
    Iron phosphide   32% by mass of the dry mixture
    Bentonite   5% by mass of the dry mixture
EP92402242A 1991-10-10 1992-08-06 Match head formulations containing iron phosphides Expired - Lifetime EP0540372B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9112458A FR2682375B1 (en) 1991-10-10 1991-10-10 COMPOSITION FOR MATCH BUTTONS CONTAINING IRON PHOSPHIDES.
FR9112458 1991-10-10

Publications (2)

Publication Number Publication Date
EP0540372A1 EP0540372A1 (en) 1993-05-05
EP0540372B1 true EP0540372B1 (en) 1994-01-05

Family

ID=9417764

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92402242A Expired - Lifetime EP0540372B1 (en) 1991-10-10 1992-08-06 Match head formulations containing iron phosphides

Country Status (6)

Country Link
EP (1) EP0540372B1 (en)
AT (1) ATE99661T1 (en)
DE (1) DE69200035T2 (en)
DK (1) DK0540372T3 (en)
ES (1) ES2062876T3 (en)
FR (1) FR2682375B1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITFI20110204A1 (en) * 2011-09-22 2013-03-23 Veronica Giuntoli MATCH.

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL38522C (en) * 1932-11-28
US2132996A (en) * 1936-02-12 1938-10-11 Samuel D Ehrlich Ignition and priming compound
GB2098975B (en) * 1981-05-27 1985-07-31 Immobiliere Financiere Et Des Improvements in the manufacture of socalled safety matches
GB2273702B (en) * 1991-01-08 1995-02-08 Bryant & May Ltd Match head formulations

Also Published As

Publication number Publication date
FR2682375B1 (en) 1993-11-26
FR2682375A1 (en) 1993-04-16
DE69200035T2 (en) 1994-06-23
DK0540372T3 (en) 1994-05-16
ES2062876T3 (en) 1994-12-16
DE69200035D1 (en) 1994-02-17
EP0540372A1 (en) 1993-05-05
ATE99661T1 (en) 1994-01-15

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