EP0814070A1 - Compositions pour boutons d'allumettes - Google Patents

Compositions pour boutons d'allumettes Download PDF

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Publication number
EP0814070A1
EP0814070A1 EP97303819A EP97303819A EP0814070A1 EP 0814070 A1 EP0814070 A1 EP 0814070A1 EP 97303819 A EP97303819 A EP 97303819A EP 97303819 A EP97303819 A EP 97303819A EP 0814070 A1 EP0814070 A1 EP 0814070A1
Authority
EP
European Patent Office
Prior art keywords
match head
iron
citrate
dry weight
formulation
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.)
Granted
Application number
EP97303819A
Other languages
German (de)
English (en)
Other versions
EP0814070B1 (fr
Inventor
Michael Graham Carey Cox
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.)
Republic Technologies UK Ltd
Original Assignee
Swedish Match UK Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Swedish Match UK Ltd filed Critical Swedish Match UK Ltd
Publication of EP0814070A1 publication Critical patent/EP0814070A1/fr
Application granted granted Critical
Publication of EP0814070B1 publication Critical patent/EP0814070B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/002—Sensitisers or density reducing agents, foam stabilisers, crystal habit modifiers
    • C06B23/004—Chemical sensitisers
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
    • C06B29/02—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate of an alkali metal
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06F—MATCHES; MANUFACTURE OF MATCHES
    • C06F3/00—Chemical features in the manufacture of matches

Definitions

  • the present invention relates to match head formulations suitable for the production of safety matches as well as matches that may be struck anywhere and to matches formed when coated with the said formulations.
  • match head formulations have contained chromium compounds, phosphorus sesquisulphide, sulphur and/or sulphur compounds and zinc oxide. These compounds are now widely recognised as having undesirable environmental properties both in relation to the manufacture of such formulations and in relation to their use and it is therefore an object of the present invention to provide a match head formulation in which these compounds are substantially absent.
  • match head formulation which is ignited by an abrasive contact with any suitable roughened surface. These are referred to as 'strike anywhere' matches.
  • a second type of match in common use has a match head formulation which is ignited by an abrasive contact with a surface containing a formulation for initiating ignition of the match head. These are referred to as 'safety matches'.
  • UK-A-2252312 discloses compositions which comprise phosphorus or ferrophosphorus and excluding environmentally harmful components containing sulphur, chromium or zinc.
  • Phosphorus match compositions for safety matches as well as strike anywhere matches are disclosed, the strike anywhere formulations comprising larger proportions of phosphorus. Matches made using these formulations have excellent environmentally friendly properties.
  • the purpose of this invention is to improve the control of the sensitivity properties whilst at the same time retaining the environmentally friendly properties of the match head.
  • Control of the sensitivity influences the striking force required to be applied by the user in order to ignite the match head. If it is too high, this may result in breakage of the head, or alternatively breakage of the splint before ignition has occurred. In addition if the strike force required is too high this may increase the risk of accidents by flying heads or broken splints where the heads have ignited. This is also the case with conventional match compositions that the matches may be too difficult to ignite. Altematively if the match head is too easy to light this may lead to premature ignition creating the danger of fires. It is possible to come across matches having different properties and a problem is to achieve a guaranteed consistent desired balance of the ignition sensitivity.
  • a match head formulation suitable for the production of strike anywhere matches or safety matches
  • the match head formulation comprises a component which is a chelating agent such as EDTA (ethylene diamine tetra-acetic acid), citric acid, lactic acid, tartaric acid, malic acid, or gluconic or other alpha hydroxy carboxylic acids, said chelating agent being complexed with a metal which may be selected from the following: manganese, Iron, cobalt, nickel, chromium, copper or vanadium.
  • the metal chelate is iron citrate which is preferably in the form of ammonium iron III citrate which is soluble in water.
  • the density of the formulation when in the form of a wet composition is in a range from 1.1 to 1.4 g/cm 3 .
  • the composition includes potassium chlorate present is in the range from 40 to 60 percent dry weight while the red amorphous phosphorus is present in a proportion of up to 9 percent dry weight for strike anywhere matches and up to 2 per cent dry weight for safety matches.
  • Gelatine may provide a suitable binder if present in proportions ranging from 3 to 18 percent dry weight or alternatively the binder may be in the form of animal glue.
  • the thickener is preferably a starch present in proportions of up to 5 percent dry weight while feldspar or other siliceous minerals may be chosen as the filler.
  • the formulation may also include an ash improver, a pigment and a bleaching agent.
  • a foaming agent may be Arylan PWS an amine salt of an alkyl aryl sulphonic acid present in proportions of up to 0.2 percent dry weight.
  • the formulation may also include an ash improver such as infusoria in proportions of up to 6 percent dry weight or a cellulose flour such as olivestone flour in proportions of up to 7 percent dry weight and a pigment such as iron oxide in proportions ranging from 3 to 10 percent dry weight.
  • the composition may also include ferrophosphorus (a mixture of iron phosphides containing typically between 18 and 25 percent phosphorus).
  • the iron citrate is provided in the form of ammonium iron III citrate.
  • the iron citrate is provided in the form of Iron (III) citrate.
  • the iron citrate is provided in the form of ferrous citrate monohydrate.
  • the proportion of iron citrate of the match head composition is 0.01 % to 2.14 % by dry weight. In a further preferred embodiment of the invention the proportion of iron citrate in the match head composition is 0.15 % to 1.5 % by dry weight. In a further preferred embodiment of the invention the proportion of iron citrate in the match head composition is 0.4 % to 0.9 % by dry weight.
  • the proportion of phosphorus in the match head composition in the range from 0.01 % to 9 % by dry weight.
  • a match head formulation suitable for the production of strike anywhere matches is prepared in which 48.34 percent dry weight of potassium chlorate is mixed with 12.43 percent dry weight of gelatine, 2.76 percent dry weight of starch, 20.72 percent dry weight of feldspar, 0.35 percent dry weight of Eosin, 2.76 percent dry weight of titanium dioxide, 6.90 percent dry weight of limestone, and 0.21 percent dry weight of sodium dithionite ensuring good wetting and dispersion of all the ingredients before adding 5 percent dry weight of red amorphous phosphorus as an aqueous slurry and 0.57 per cent dry weight iron citrate in the form of ammonium iron (iii) citrate.
  • the above formulation combines a satisfactory sensitivity and bum rate and has no propensity to produce burning fragments or dropping of hot ash.
  • the formulation also provides cost benefits over other existing formulations.
  • the sensitivity is improved markedly when compared to formulations not comprising the iron citrate.
  • the water content of the above formulation may be in the range from 40 to 50g per 100g of solids but is typically 45.6g/100g solids.
  • the density of the formulation when in the form of a wet composition may be in the range of 1.1 to 1.4 g/cm 3 but is typically 1.2 to 1.35 g/cm 3 .
  • This figure is lower than is usual for match head formulations of this type as a result of being more highly aerated and contributes towards an improved sensitivity and a faster drying rate.
  • the formulation is thus able to dry even during sympathetic spells of high atmospheric humidity.
  • the proportions of potassium chlorate present may range from 40 to 60 percent dry weight while the red amorphous phosphorus may be present in proportions of up to 9 and as low as 1 percent dry weight for the formulation to maintain a satisfactory performance.
  • the iron citrate may be present in proportions between 0.01 % and 2.5 % dry weight.
  • iron citrate is provided in the form of ammonium iron (III) citrate.
  • iron citrate may be provided in the form of Iron (III) citrate or ferrous citrate monohydrate.
  • iron citrate will be used a the general term throughout this specification to describe chelating complexes containing iron and citrate which may not be definite compounds.
  • the iron content can vary widely from 15 % to 28 % depending on which form of iron citrate is used.
  • the water soluble complexes for example, also contain ammonia. The effectiveness of any particular complex depends upon and is proportional to the iron content. The same is true if different metals are used.
  • the iron citrate complex may also be formed in situ by the addition of any citrate such as for example potassium citrate to the composition and an iron salt such as for example iron III sulphate. These two compounds will react together to form the soluble iron citrate complex. Many other alternative compounds could be used with the corresponding reactions producing the desired complex. This is also true for the other complexes envisaged by the invention formed from any of the metals namely, manganese, cobalt, nickel, chromium, copper or vanadium with the chelating agents; lactic acid, tartaric acid, malic acid, gluconic or other alpha hydroxy carboxylic acids or EDTA.
  • the gelatine is present as a binder.
  • the binder content of the formulation is lower than is usual and consequently improves the sensitivity of the formulation as well as the drying rate.
  • the gelatine may be present in proportions ranging from 8 to 18 percent dry weight. In place of gelatine animal glue may provide a satisfactory binding agent.
  • Starch is present as a thickener to improve the head formulation during dipping and may be present in proportions ranging from I to 4 percent dry weight and still serve its function satisfactorily.
  • amorphous phosphorus makes it difficult to achieve the clear bright colours characteristic of match head formulations based on phosphorus sesquisulphide.
  • the muddy colour of amorphous phosphorus in the above formulation is particularly difficult to mask in the orange/yellow spectral region and consequently a colourant such as Eosin may be required to be present in proportions of up to 7 percent dry weight.
  • An alternative colourant to produce a match head formulation in the blue/red spectral region such as Rhodamine may not need to be present to such an extent.
  • sodium dithionite may be used to bleach the gelatine while titanium dioxide may be employed as a masking agent. The titanium dioxide may be present in proportions of up to 7 percent dry weight.
  • Limestone may be present in proportions ranging from 3 to 14 percent dry weight to control the pH of the formulation while feldspar is used as a filler and serves to make up the balance of the formulation.
  • the above formulation is free of phosphorus sesquisulphide, zinc oxide and di-chromates.
  • the absence of sulphur from the formulation reduces the smell produced on striking a match coated with the formulation.
  • the absence of phosphorus sesquisulphide is advantageous because it is difficult to handle during manufacture. It is possible to include these components in the formulation in lower proportions than conventionally used with the inclusion of iron citrate in proportions from 0.01 % to 2.5 % to improve and control the sensitivity.
  • match head formulations suitable for the production of safety matches have contained chromium compounds, sulphur compounds and zinc oxide and in particular have contained potassium dichromate, sulphur powder and zinc oxide. In the second example all these are absent from the formulation and have been replaced in the formulations of the present invention by red amorphous phosphorus and iron citrate.
  • a match head formulation suitable for the production of safety matches is prepared in which 54.18 percent dry weight of potassium chlorate is mixed with 4.06 percent dry weight of gelatine, 4.06 percent dry weight of starch, 20.32 percent dry weight of feldspar, 2.71 percent dry weight of infusoria, 6.77 percent dry weight of iron oxide, 0.09 percent dry weight of Arylan PWS, and 6.77 percent dry weight of limestone ensuring good wetting and dispersion of all the ingredients before adding 0.5 percent dry weight of amorphous phosphorus as an aqueous slurry and 0.5 per cent dry weight iron (iii) citrate in the form of ammonium iron(iii) citrate.
  • the water content of the above formulation may be in the range 40 to 55g per 100g of solids but is typically 48.8g /100g solids.
  • the density of the formulation when in the form of a wet composition may be in the range from 1.0 to 1.4 g/cm 3 but is typically 1.15 g/cm 3 .
  • this figure is lower than is usual for match head formulations of this type as a result of being more highly aerated and contributes towards an improved sensitivity and a faster drying rate.
  • the proportion of potassium chlorate present may range from 40 to 60 percent dry weight and the proportion of amorphous phosphorus may range from 0.01 to 2.0 percent dry weight for the formulation to maintain a satisfactory performance.
  • the proportion of iron citrate may range from 0.01 % to 2.5 % dry weight.
  • a match head formulation suitable for the production of safety matches is prepared in which 57.98 percent dry weight of potassium chlorate is mixed with 9.28 percent dry weight of glue, 30.97 percent dry weight of an uncoloured pre-mixture of inert materials including silica, alumino-silicates and alkaline earth carbonates, 0.09 percent dry weight of Arylan PWS, and 0.14 percent dry weight of Eosin dye before adding 1.1 percent dry weight of amorphous phosphorus and 0.43 per cent dry weight ammonium iron (iii) citrate.
  • This example provides safety matches which red in colour.
  • a match head formulation suitable for the production of safety matches is prepared in which 55.93 percent dry weight of potassium chlorate is mixed with 8.95 percent dry weight of glue, 33.56 percent dry weight of a brown pre-mixture of inert materials including silica, alumino-silicates, alkaline earth carbonates and iron oxides (the iron oxides functioning to provide the brown head colour), 0.08 percent dry weight of Arylan PWS, before adding 1.06 percent dry weight of amorphous phosphorus and 0.42 per cent dry weight ammonium iron (iii) citrate.
  • This example provides safety matches which are brown in colour.
  • iron citrate is provided in the form of ferrous citrate monohydrate.
  • iron citrate may be provided in the form of Iron (III) citrate or ammonium iron (III) citrate.
  • the gelatine is present as a binder.
  • the binder content of the formulation is lower than is usual and consequently improves the sensitivity of the formulation as well as the drying rate.
  • Gelatine may be present in proportions ranging from 3 to 12 percent dry weight. In place of gelatine animal glue may provide a satisfactory binding agent.
  • iron oxide is used as a pigment and may be present in proportions ranging from 3 to 10 percent dry weight.
  • the above formulation is free of potassium dichromate, sulphur and zinc oxide.
  • the absence of sulphur from the formulation reduces the smell produced on striking a match coated with the formulation.
  • the absence of potassium dichromate is advantageous because potassium dichromate is difficult to handle during manufacture.
  • Such safety match compositions may be formulated along the lines of the above example to combine a satisfactory sensitivity and bum rate with no propensity to produce burning fragments or dropping of hot ash.
  • the formulation meets all the requirements of BS 3795 and provides cost benefits over other existing formulations.
  • iron citrate is provided in the form of ferrous citrate monohydrate.
  • iron citrate may be provided in the form of Iron (III) citrate or ammonium iron (III) citrate.
  • Example 2 This formulation is similar to that described in Example 2 above and differs essentially only in that it may be more brightly coloured. Consequently the proportions of the chlorate, amorphous phosphorus, gelatine, starch, infusoria, Arylan PWS, limestone, and feldspar may vary within substantially the same ranges as disclosed in Example 2.
  • olivestone flour acts as an ash improver and may be present in proportions of up to 7 percent dry weight while titanium dioxide may also be present in proportions of up to 7 percent dry weight and acts as a masking agent as described in Example 1.
  • Olivestone flour may be substituted by other cellulose flours.
  • the amorphous phosphorus of the formulations described in Examples 2 and 3 may be replaced by ferrophosphorus, a mixture of iron phosphides containing typically between 18 and 25 percent phosphorus.
  • Ferrophosphorus is relatively inexpensive and easy to handle but is a dense black powder and therefore limits the range of colours attainable.
  • a match head formulation of this type suitable for the production of safety matches is provided by mixing 52.63 percent dry weight of potassium chlorate with 3.95 percent dry weight of gelatine, 3.95 percent dry weight of starch, 19.73 percent dry weight of feldspar, 6.57 percent dry weight of iron oxide and 12.66 percent dry weight of ferrophosphorus and 0.5 per cent dry weight iron citrate.
  • iron citrate is provided in the form of ferrous citrate monohydrate.
  • iron citrate may be provided in the form of Iron (III) citrate or ammonium iron (III) citrate.
  • the ferrophosphorus is preferably ground to a particle size of up to 100 microns.
  • the preferred size for the formulation given in example 6 is less than 5 microns. It is to be noted that with a particle size between 20 and 65 microns it is possible to produce a composition with a colour other than black by using dyes. Ferrophosphorus in this range of particle size has been found to be beneficial in a range of pyrotechnic applications.
  • the proportion of gelatine present in the formulation was found to be able to range from 3 to 12 percent dry weight while the starch could be present in proportions of up to 10 percent dry weight.
  • feldspar is used as a filler and serves to make up the balance of the formulation.
  • iron oxide may be omitted and replaced by titanium dioxide and a suitable pigment each in proportions of up to 7 percent dry weight.
  • iron citrate was shown to be effective as a controller of the sensitivity of the match head composition and also is the most environmentally friendly and the most cost effective.
EP97303819A 1996-06-18 1997-06-04 Compositions pour boutons d'allumettes Expired - Lifetime EP0814070B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9612729A GB2314325B (en) 1996-06-18 1996-06-18 Match head formulations
GB9612729 1996-06-18

Publications (2)

Publication Number Publication Date
EP0814070A1 true EP0814070A1 (fr) 1997-12-29
EP0814070B1 EP0814070B1 (fr) 2001-10-17

Family

ID=10795482

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97303819A Expired - Lifetime EP0814070B1 (fr) 1996-06-18 1997-06-04 Compositions pour boutons d'allumettes

Country Status (11)

Country Link
EP (1) EP0814070B1 (fr)
AT (1) ATE207048T1 (fr)
DE (1) DE69707360T2 (fr)
DK (1) DK0814070T3 (fr)
ES (1) ES2166047T3 (fr)
GB (1) GB2314325B (fr)
HU (1) HUP9701062A3 (fr)
NO (1) NO308354B1 (fr)
PL (1) PL184658B1 (fr)
PT (1) PT814070E (fr)
TR (1) TR199700489A2 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3492176A (en) * 1968-09-11 1970-01-27 T O Paine Ammonium perchlorate composite propellant containing an organic transitional metal chelate catalytic additive
US3923564A (en) * 1971-06-22 1975-12-02 Us Army Double base propellant with thorium containing ballistic modifier
EP0496996A2 (fr) * 1991-01-08 1992-08-05 BRYANT & MAY LIMITED Compositions pour boutons d'allumette

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3492176A (en) * 1968-09-11 1970-01-27 T O Paine Ammonium perchlorate composite propellant containing an organic transitional metal chelate catalytic additive
US3923564A (en) * 1971-06-22 1975-12-02 Us Army Double base propellant with thorium containing ballistic modifier
EP0496996A2 (fr) * 1991-01-08 1992-08-05 BRYANT & MAY LIMITED Compositions pour boutons d'allumette
GB2252312A (en) * 1991-01-08 1992-08-05 Bryant & May Ltd Match head formulations.

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 109, no. 14, 3 October 1988, Columbus, Ohio, US; abstract no. 112935j, Y. HAGIHARA ET AL.: "Effects of organoiron compounds on burning rate and slurry viscosity of AP-HTPB composite propellants." page 147; XP002041508 *
KOGYO KAYAKU, vol. 49, no. 2, 1988, pages 119 - 123 *

Also Published As

Publication number Publication date
EP0814070B1 (fr) 2001-10-17
ATE207048T1 (de) 2001-11-15
HUP9701062A3 (en) 2002-02-28
HUP9701062A2 (hu) 1999-06-28
NO308354B1 (no) 2000-09-04
DE69707360T2 (de) 2002-07-04
DE69707360D1 (de) 2001-11-22
GB2314325A (en) 1997-12-24
NO972399D0 (no) 1997-05-27
NO972399L (no) 1997-12-19
DK0814070T3 (da) 2001-12-27
TR199700489A2 (xx) 1998-01-21
HU9701062D0 (en) 1997-08-28
GB9612729D0 (en) 1996-08-21
PL184658B1 (pl) 2002-11-29
PL320604A1 (en) 1997-12-22
GB2314325B (en) 2000-07-12
PT814070E (pt) 2002-03-28
ES2166047T3 (es) 2002-04-01

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