EP0540372A1 - Match head formulations containing iron phosphides - Google Patents

Match head formulations containing iron phosphides Download PDF

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Publication number
EP0540372A1
EP0540372A1 EP92402242A EP92402242A EP0540372A1 EP 0540372 A1 EP0540372 A1 EP 0540372A1 EP 92402242 A EP92402242 A EP 92402242A EP 92402242 A EP92402242 A EP 92402242A EP 0540372 A1 EP0540372 A1 EP 0540372A1
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Prior art keywords
mass
composition according
weight
dry mixture
composition
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EP92402242A
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German (de)
French (fr)
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EP0540372B1 (en
Inventor
Jean-Paul Bernard
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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 having, at one end, a congruent button to ignite by friction on a special support comprising red phosphorus.
  • a congruent button 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.
  • a traditional composition for match button corresponds to the following formulation: Oxidizer: Potassium chlorate 28 to 62% by weight Fuel: Sulfur or sulfide of phosphorus 2 to 7% by weight Binder: Pure gelatin or with additives 8 to 18% by weight Fillers: 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
  • 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 buttons according to the invention is mainly characterized in that it comprises from 3 to 60% by weight of iron phosphides.
  • the average particle size of the iron phosphides used will be less than 250 microns and, preferably, about ten microns.
  • composition according to the invention will advantageously have the following formulation:
  • the components are mixed in aqueous dispersion with, for example, 25% water and the matches are made 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% by mica.
  • celite for example by 1% by mass and / or by the replacement of a phosphide fraction, for example of the order of 4% by mica.
  • 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
  • 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.
  • 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

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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)
  • Adornments (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (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 congru 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 having, at one end, a congruent button 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 Fuel: Sulfur or sulfide of phosphorus 2 to 7% by weight Binder: Pure gelatin or with additives 8 to 18% by weight Fillers: 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 to the user or to 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.

La composition pour boutons d'allumettes suivant l'invention se caractérise principalement en ce qu'elle comporte de 3 à 60 % en poids de phosphures de fer.The composition for match buttons according to the invention is mainly characterized in that it comprises from 3 to 60% by weight of iron phosphides.

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

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

Figure imgb0001
Figure imgb0002
 In its application to safety matches, the composition according to the invention will advantageously have the following formulation:
Figure imgb0001
Figure imgb0002

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% water and the matches are made 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 found 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% by mica. This latter solution makes it possible to significantly reduce the projections 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 (10)

Composition pour bouton d'allumette du type comprenant un comburant, un combustible, un liant ainsi que d'éventuels charges et adjuvants,
caractérisée en ce que le combustible comprend un phosphure de fer dans une proportion allant de 3 à 60 % en poids.Composition for match button of the type comprising an oxidizer, a fuel, a binder as well as any fillers and adjuvants,
characterized in that the fuel comprises an iron phosphide in a proportion ranging from 3 to 60% by weight. Composition selon la revendication 1,
caractérisée en ce que la granulométrie moyenne des phosphures de fer utilisés est inférieure à 250 microns.Composition according to claim 1,
characterized in that the average particle size of the iron phosphides used is less than 250 microns. Composition selon la revendication 2,
caractérisée en ce que la granulométrie moyenne des phosphures de fer utilisés est de l'ordre d'une dizaine de microns.Composition according to claim 2,
characterized in that the average particle size of the iron phosphides used is of the order of ten microns. Composition selon l'une des revendications précédentes,
caractérisée en ce que, dans son application aux allumettes de sécurité, elle possède 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
Composition according to one of the preceding claims,
characterized in that, in its application to safety matches, it has the following formulation: Oxidizer: Potassium chlorate or perchlorate 30 to 62% by weight Fuel: Iron phosphides 3 to 60% by weight Binder: Gelatin or synthetic binders 5 to 18% by weight Fillers: Silicic or organic materials 0 to 25% by weight Adjuvants: Pigments - phlegmatizers - stabilizers 0 to 25% by weight
Composition selon la revendication 4,
caractérisée en ce que le liant est de la gélatine qui rentre dans la composition dans une proportion d'environ 13 %.Composition according to claim 4,
characterized in that the binder is gelatin which is included in the composition in a proportion of about 13%. Composition selon la revendication 4,
caractérisée en ce que les charges comprennent de la farine de diatomées rentrant dans la composition dans une proportion d'environ 5 % en poids.Composition according to claim 4,
characterized in that the fillers comprise diatomaceous flour entering the composition in a proportion of about 5% by weight. Composition selon la revendication 4,
caractérisée en ce que les charges comprennent de la silice, du mica, et de l'oxyde de titane qui rentre au sein de la composition dans un pourcentage d'environ 3 à 6 % en poids.Composition according to claim 4,
characterized in that the fillers include silica, mica, and titanium oxide which enters the composition in a percentage of about 3 to 6% by weight. Composition selon la revendication 4,
caractérisée en ce qu'elle comprend en outre de 2 à 5 % de célite.Composition according to claim 4,
characterized in that it further comprises from 2 to 5% of celite. Composition selon la revendication 4,
caractérisée en ce qu'elle présente la formulation 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
Composition according to claim 4,
characterized in that it has the following formulation: 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
Composition selon la revendication 4,
caractérisée en ce qu'elle comprend en outre de l'oxyde de fer dans une proportion de l'ordre de 1 %.Composition according to claim 4,
characterized in that it further comprises iron oxide in a proportion of the order of 1%.
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
FR9112458 1991-10-10
FR9112458A FR2682375B1 (en) 1991-10-10 1991-10-10 COMPOSITION FOR MATCH BUTTONS CONTAINING IRON PHOSPHIDES.

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EP0540372A1 true EP0540372A1 (en) 1993-05-05
EP0540372B1 EP0540372B1 (en) 1994-01-05

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

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* 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.

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB414938A (en) * 1932-11-28 1934-08-16 Larsson Lars Erik Improved method of making water-proof matches
US2132996A (en) * 1936-02-12 1938-10-11 Samuel D Ehrlich Ignition and priming compound
GB2098975A (en) * 1981-05-27 1982-12-01 Immobiliere Financiere Et Des Improvements in the manufacture of so-called safety matches
EP0496996A2 (en) * 1991-01-08 1992-08-05 BRYANT & MAY LIMITED Match head formulations

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB414938A (en) * 1932-11-28 1934-08-16 Larsson Lars Erik Improved method of making water-proof matches
US2132996A (en) * 1936-02-12 1938-10-11 Samuel D Ehrlich Ignition and priming compound
GB2098975A (en) * 1981-05-27 1982-12-01 Immobiliere Financiere Et Des Improvements in the manufacture of so-called safety matches
EP0496996A2 (en) * 1991-01-08 1992-08-05 BRYANT & MAY LIMITED Match head formulations

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FR2682375B1 (en) 1993-11-26
DE69200035T2 (en) 1994-06-23
EP0540372B1 (en) 1994-01-05
ATE99661T1 (en) 1994-01-15
FR2682375A1 (en) 1993-04-16
DE69200035D1 (en) 1994-02-17
ES2062876T3 (en) 1994-12-16
DK0540372T3 (en) 1994-05-16

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