BG62766B1 - Formulations for match heads - Google Patents

Abstract

The formulations are used in the manufacture of safety matches and matches which can be lighted from all surfaces. They contain metal chelate complexes of iron, copper, chromium or vanadium and citric, tartaric and ethylenediaminotetraacetic acid. The metallic chelate complexes can be combined with the standard compositions for matchstick heads in which there are chromium compounds, compounds based on sesquiphosphorus, sulphur compounds and zinc oxides or preferably be combined with environmental favourable compositions by making use of either amorphous phosphorus, or optionally ferrophosphorus. The manufacture and use of the formulations meet with the requirements for environmental protection. The invention also relates to matchstrick head formulations which are ecological and can be died in bright colouring. 10 claims

Description

Field of application

The invention relates to match heads suitable for the production of a safe match and a light matchable match, and matches obtained when covered with such a composition.

So far, match heads have chromium compounds, phosphorus sesquisulfide, sulfur and / or sulfur compounds and zinc oxide. These compounds are considered to have environmentally undesirable effects, which also relates to the production and use of such compositions. Therefore, it is an object of the invention to provide a composition for matched heads in which these compounds are practically absent.

BACKGROUND OF THE INVENTION

A match is known for its comb composition, which ignites upon abrasive contact with any suitable rough surface and is known as "burning everywhere". A second type of match has such a composition on its head, by which it ignites upon abrasive contact with a surface containing a composition for initiating the ignition of the match head. This type of match is called "safe".

A composition (UK-A-2252312) is known that contains phosphorus or ferrophosphorus and does not contain environmentally harmful components including sulfur, chromium or zinc. Phosphorous matches are described for safe and burning matches, with those for burning matches containing larger quantities of phosphorus. The matches made with these formulations have excellent environmental properties. The aim of the invention is to improve the control of the ignition sensitivity while maintaining the environmentally friendly characteristics of the matched heads. Sensitivity control affects the burning force required by the user to ignite the cymbal head. If it is very high, it may break or alternatively break the stick itself before ignition occurs. In addition, if very high teasing power is required, the risk of accidents may be increased by knocking the head off or breaking the ignition. This happens with the usual matchmaking compositions, in which the stick is very difficult to ignite. Alternatively. if the head ignites very easily, it may lead to a pre-ignition, creating a fire hazard. Matches with different properties may be encountered and it is a problem to achieve the guaranteed constant desired balance of the ignition sensitivity.

SUMMARY OF THE INVENTION

The problem to be solved with the invention is to provide a composition for matched heads that is sufficiently sensitive to ensure consistency in ignition. It is also an object of the invention to provide precise control over the sensitivity of the cymbal head so that the desired constancy of that sensitivity can be guaranteed. These problems must be solved on the one hand without affecting the other properties of the hub and, on the other, be capable of being carried out with the same production technique without incurring significant additional production costs.

According to the first aspect of the present invention there is provided a composition for comb heads that is suitable for the production of flamboyant everywhere or safe matches, which contains a compound that is a chelating agent such as EDTA (citric acid, lactic, tartaric, malic acid or gluconic acid). or other hydroxycarboxylic acid. The chelating agent is a complex with metal selected from manganese, iron, cobalt, nickel, chromium, copper or vanadium.

The metal chelate is preferably an iron citrate, preferably in the form of a.monium iron (III) citrate, which is soluble in water.

According to a preferred embodiment of this first aspect of the invention, the density of the composition, when liquid, is from 1.1 to 1.4 g / cm ³ . It is preferable for the composition to contain potassium chlorate from 40 to 60% dry weight and red amorphous phosphorus in an amount up to 9% dry weight in burning matches and up to

2% dry weight in safe matches. Gelatin may be a suitable binder if it is from 3 to 18% dry weight, or alternatively, the binder may be in the form of a live animal. It is preferred that the sealant is starch included in an amount of up to 5% dry weight, whereas feldspar or other silicate materials may be selected as fillers. The composition may also contain an ash enhancer, a pigment and a decolorizing agent. Arylan PWS, an aminosol of alkylarylsulfonic acid, up to 0.2% dry weight, may be used as a foaming agent. The mixture may also contain an ash enhancer as an infusional soil in an amount of up to 6% dry weight or pulp, for example olive kernel flour, up to 7%, and pigment as ferric oxide in a ratio of 3 to 10% by weight.

The composition may also include ferrophosphorus (a mixture of iron and phosphides containing typically 18 to 25% phosphorus).

According to a preferred embodiment of the invention, iron citrate is in the form of ammonium iron (III) citrate. Alternatively, iron citrate may also be added as iron (III) citrate or may be in the form of ferrocitrate monohydrate.

According to one preferred embodiment, the amount of iron citrate in the formulation for the match heads is 0.01-2.14% dry weight, according to another preferred embodiment is 0.15% -1.5% dry weight, and in one preferred embodiment the amount of iron citrate is 0.4-0.9% dry weight.

According to a preferred embodiment of the invention, the amount of phosphorus in the formulation is from 0.01 to 9% dry weight.

Examples of carrying out the invention

Some examples of formulations suitable for the production of safe and combustible matches are described.

In the past, comb formulations suitable for the production of combustible matches from everywhere contained phosphorus sesquisulfide compounds as an active ingredient. Alternatively, phosphorous sesquisulfide may be replaced by red amorphous phosphorus.

Example 1. Composition for comb heads, suitable for the production of burning matches from everywhere, was prepared by mixing 48.34% dry weight of potassium chlorate with 12.43% dry weight of gelatin, 2.76% dry weight of starch, 20.72% dry weight feldspar, 0.35% dry weight eosin, 2.76% dry weight titanium dioxide, 6.90% dry weight limestone and 0.21% dry weight sodium dithionite. All components are wetted and mixed well, followed by the addition of 5% dry weight amorphous phosphorus as an aqueous suspension and 0.57% dry weight iron citrate in the form of ammonium iron (III) citrate.

This composition has a satisfactory sensitivity and burning rate and there is no danger of separating burning particles or droplets of hot ash. It has economic advantages over known compositions. Sensitivity is significantly increased compared to formulations that do not contain iron citrate.

The water content of the composition may be 40 to 50 g per 100 g solids, but is usually 45.6 / 100 g solids.

The density of the composition, when liquid, may be 1.1-1.4 g / cm ³ but is generally 1.2-1.35 g / cm ³ . The value is lower than usual for matched head compositions of this type as a result of the higher aeration, which improves sensitivity and speeds up drying. Thus, the mixture can dry even during periods of unusually high atmospheric humidity.

The amount of potassium chlorate available can be in the range of 40 to 60% dry weight, while the red amorphous phosphorus can be from 1 to 9% dry weight in the composition to improve the properties. Iron citrate can be 0.01-2.5% dry weight.

Table 1 shows the change in sensitivity, measured in grams, with an increase in the amount of iron citrate.

Table 1:

Composition for burning is a match with 5% red phosphorus everywhere

Iron citrate (%) 0.00 0.15 0.43 0.87 1.43 2.14 Sensitivity (g) 212 197 160 164 153 163

The amount of red phosphorus may vary to achieve an optimal level of iron citrate.

Table 2:

Composition for burning everywhere matches with 0.6% ferric citrate

Red phosphorus (%) 0.00 1.0 2.0 3.0 4.0 Sensitivity (g) don't turn on don't turn on 272 201 163

In these experiments, iron citrate was added in the form of ammonium iron (III) citrate. Alternatively, iron citrate may also be administered in the form of iron (III) citrate or ferrocitrate monohydrate.

The term "iron citrate" will be used throughout the description to describe chelate complexes containing iron and citrate, which may also be undefined compounds. Iron content can vary greatly from 15 to 28% depending on what form of iron citrate is used. Water-soluble complexes, for example, also contain ammonia. The effectiveness of a particular compound depends on and is proportional to the iron content. The same applies if different other metals are used.

The iron citrate complex may also be formed in citu by the addition of any citrate, for example potassium, to the composition, and an iron salt, for example iron () sulfate. These two compounds will interact to form a soluble iron citrate complex. Many other alternative compounds can be used to give the desired complex with the appropriate reaction. This also applies to the other complexes considered in the invention formed by any of the metals: manganese, cobalt, nickel, chromium, copper or vanadium, with a chelating agent, lactic, tartaric, malic acid, gluconic or other hydroxycarboxylic acid or EDTA.

Gelatin is present as a binder, the content of the agent being less than usual, which increases the sensitivity of the composition and the drying rate. Gelatin can be added in an amount of 8 to 18% dry weight. Animal gelatin can also be used in place of gelatin, which also gives satisfactory results.

Starch is added as a sealant to improve head formation upon immersion and may be present in an amount of 1 to 4% dry weight and still satisfactorily perform its function.

The use of amorphous phosphorus makes it difficult to achieve clear light colors characteristic of the phosphorus sesquisulfide-matched comb heads. The muddy color of the amorphous phosphorus in the above mixtures is particularly difficult to mask in the orange-yellow spectrum and therefore a colorant such as eosin will need to be added in an amount up to 7% dry weight. An alternative colorant, such as rhodamine, may not need to be administered in such a quantity in order to obtain a cymbal head composition in the blue-red region of the spectrum. Sodium dithionite and titanium dioxide can be used as a masking agent to aid in coloring and decolourising gelatin, which can be added in an amount of up to 7% by weight.

A limestone of 3 to 14% dry weight may be used to control the pH of the mixture while the feldspar is used as a filler and serves to fill the composition.

It should be noted that said composition lacks phosphorus sesquisulfide, zinc oxide and dichromates. The absence of sulfur in the mixture reduces the odor of burning matches covered with it. The absence of phosphorous sesquisulfide is an advantage as it is difficult to handle in manufacturing. It is possible for these compounds to be incorporated into the mixture in smaller amounts than usual using 0.01-2.5% iron citrate in order to improve sensitivity control.

In the past, the combinatorial compositions for the production of safe matches contained chromium compounds, sulfur compounds and zinc oxide, and in particular potassium dichromate, sulfur powder and zinc oxide. In the second example, they are all absent from the composition and are replaced in the composition according to the invention with red amorphous phosphorus and iron citrate.

Experiments were repeated using different combinations of metal chelate complexes and ferric citrate as indicated by citric, lactic, tartaric, malic acid or EDTA (ethylenediaminetetraacetic acid) as well as gluconic acid (other α-hydroxycarboxylic acids may be used) acids) complexed with manganese, cobalt, nickel, chromium, copper and vanadium, yielding similar results.

Example 2. Composition for matched heads suitable for a safe match obtained by mixing 54.18% dry weight potassium chlorate with 4.06% dry weight gelatin, 4.06% dry weight starch, 20.32% dry weight feldspar, 2.71% dry weight of infuser soil, 6.77% dry weight of iron oxide, 0.09% dry weight of Arylan PWS and 6.77% dry weight of limestone, which are wetted and dispersed well before adding 0, 5% dry weight amorphous phosphorus as an aqueous suspension and 0.5% dry weight iron (III) citrate in the form of ammonium iron (III) citrate.

The water content of this mixture may be in the range of 40 to 55 g per 100 g solids, but is usually 48.8 g / l00 g solids.

The density of the mixture in the form of a liquid composition may be 1.0-1.4 g / cm ³ . As in Example 1, this value is lower than is usual for mixtures of matches of this type, which results from the higher aeration and increases the sensitivity and speeds up drying.

It has been found that the amount of potassium chlorate available can be from 40 to 60% dry weight, and that of amorphous phosphorus is in the order of 0.01-2.0% dry weight, in order to maintain satisfactory properties. The amount of iron citrate can be from 0.01% to 2.5% dry weight.

Example 3. Composition for matched heads suitable for safe match was obtained by mixing 57.98% dry weight of potassium chlorate with 9.28% dry weight of tukkala, 30.97% dry weight of a non-colored premix of inert materials including silicon dioxide, aluminosilicates and alkaline earth carbonates, 0.09% dry weight Arylan PMS and 0.14% dry weight eosin dye, before adding 1.1% dry weight amorphous phosphorus and 0.43% dry weight ammonium iron (III) citrate. A safe match of red color is obtained.

EXAMPLE 4 Composition for Matched Heads Suitable for Safe Matches was prepared by mixing 55.93% dry weight of potassium chlorate with 8.95% dry weight of tukkala, 33.56% dry weight of a brown premix of aggregates including silica, aluminum silicates, alkaline earth carbonates and iron oxides (iron oxides give brown color to the heads), 0.08% dry weight Arylan PWS before adding 1.06% dry weight amorphous phosphorus, and 0.42% dry weight ammonium iron (III) citrate. The safe match is brown in color.

Table 3 shows the change in sensitivity, measured in grams, with increasing amounts of iron citrate.

Table 3.

Composition for safe match with 5% red phosphorus

Iron citrate (% ' 0.00 0.15 0.43 0.87 1.43 2.14 Sensitivity (g) 134 117 99 84 104 94

The red phosphorus ratio can be varied to achieve an optimum level of iron citrate.

Table 4.

Safe match with 0.6% iron citrate

Red phosphorus (%) 0.00 0.29 0.86 Sensitivity (g) TG5 ^- 135 86

In the above experiments, ferric citrate was added in the form of ferrocitrate monohydrate. Alternatively, iron citrate may also be added as iron (III) citrate or in the form of ammonium iron (III) citrate.

Gelatin is used as a binder whose content, as in Example 1, is less than usual and therefore increases the sensitivity of the mixture and the drying rate. Gelatin may be from 3 to 12% dry weight. Animal gelatin can be used instead of gelatin, which also gives satisfactory results.

The presence of amorphous phosphorus makes it difficult to achieve a clear bright color but does not interfere with the production of standard brown blends. In this case, the iron oxide is used as a pigment and can be added in an amount of 3 to 10% dry weight.

This mixture is free of potassium dichromate, sulfur and zinc oxide. The absence of sulfur from it reduces the odor produced by the ignition of the stick covered with the mixture. The advantage is the absence of potassium dichromate, as it is difficult to work with in manufacturing. However, according to the invention, it is possible to incorporate any of these components in the place of red phosphorus, but with the addition of ferric citrate a smaller amount of them is required. This will reduce the environmental impact and increase the sensitivity. It will be appreciated by one of ordinary skill in the art that the amount of ferric nitrate used can vary according to the components in the rest of the composition and also at its desired final cost.

Such safe match formulations can be prepared according to the above example by combining satisfactory sensitivity and burning rate without the match separating burning particles or dripping hot ash. The composition meets all the requirements of BS 3795 and has better economic performance than known such compositions.

Example 5. In order to obtain brighter mixtures of matches for comb heads for the production of safe matches, having properties similar to those described in Example 2, 55.52% dry weight of potassium chlorate is mixed with 4.16% dry weight of gelatin, 4.16% dry weight starch, 13.88% dry weight feldspar, 5.55% dry weight infuser soil, 0.09% dry weight Arylan PWS, 6.04% dry weight limestone, 6.94% dry weight flour from olive stone, up to 7.0% dry weight of selected pigment and 1.39% dry weight of titanium dioxide. All ingredients are wetted and dispersed well before the addition of 0.5% dry weight amorphous phosphorus as an aqueous suspension and 0.5% dry weight iron citrate in the form of ammonium iron (III) citrate.

Table 5 shows the change in sensitivity, measured in grams, with an increase in the amount of iron citrate.

Table 5.

Composition for safe match with 0.86% red phosphorus

Iron citrate (%) 0.00 0.15 0.43 0.87 1.43 2.14 Sensitivity (g) 129 118 99 88 105 94

The red phosphorus ratio can be varied to achieve the optimum level of iron citrate.

Table 6.

Safe match with 0.6% iron citrate

Red phosphorus (%) 0.00 0.29 0.86 Sensitivity (k) 416 135 86

In these experiments, ferric citrate was added in the form of ferrocitrate monohydrate. Alternatively, iron citrate may also be added as iron (III) citrate or in the form of ammonium iron (III) citrate.

This mixture is similar to that described in Example 2 and only differs in that it can be brightly colored. Therefore, the amounts of chlorine, amorphous phosphorus, gelatin, starch, infusional soil, Arylan PWS, limestone and feldspar can vary practically within the same limits as described in Example 2. Of the ingredients not found in this example, olive shell flour acts as an improver ash and may be present in an amount up to 7% dry weight, while titanium dioxide may also be present in an amount up to 7% dry weight to act as a masking agent as described in Example 1. Olive shell flour may replaced with other cellulose flours.

EXAMPLE 6 The amorphous phosphorus of the mixtures described in Examples 2 and 3 can be replaced by ferrophosphorus, a mixture of iron phosphides containing typically 18 to 25% phosphorus. Ferrophosphorus is relatively inexpensive and easy to handle, but it is a thick black powder and therefore limits the ability to produce different colors.

A mixture of match heads of this type, suitable for the production of safe match, is obtained by mixing 53.63% dry weight of potassium chlorate with 3.95% dry weight of gelatin, 3.95% dry weight of starch, 19.73% dry feldspar weight, 6.57% dry weight iron oxide, 12.66% dry weight ferrophosphorus and 0.5% dry weight iron citrate.

Table 7 shows the change in sensitivity, measured in grams, with an increase in the amount of iron citrate.

Table 7.

Composition for safe matches with 12% ferrophosphorus

Iron citrate (%) 0.00 0.15 0.43 0.87 1.43 2.14 Sensitivity (g) 128 115 97 84 101 93

In these experiments, ferric citrate was added in the form of ferrocitrate monohydrate. Alternatively, iron citrate may also be added as iron (III) citrate or ammonium iron (III) citrate.

Tests were repeated using different combinations of citric, lactic, tartaric, malic, malic, or EDTA (ethylenediaminetetraacetic acid) metal chelate complexes, as well as gluconic acid (other c /.-Hydroxycarboxylic acids would also be appropriate) complexed with manganese , iron, cobalt, nickel, chromium, copper and vanadium, yielding similar results.

Preferably, the ferrophosphorus is ground to a particle size of 100 μ. The preferred size for the composition given in Example 6 is less than 5 μ. With a particle size of 20 to 65 μ, it is possible to obtain a composition which is not black in color when using dyes. With this particle size, ferrophosphorus has been found to be suitable for various pyrotechnic applications.

It has been found that in order to maintain satisfactory qualities, the amount of potassium chlorate should be from 40 to 60% dry weight, while the amount of ferrophosphorus is greater than 5% dry weight.

The amount of gelatin in the mixture should be from 3 to 12% dry weight, while the starch may be present in an amount up to 10% dry weight. As in the previous examples, the feldspar is used as a filler and serves to supplement the mixture.

If a brighter formulation is required despite the nature of the ferrophosphorus, iron oxide can be avoided and replaced with titanium dioxide and suitable pigment, each in an amount of up to 7% dry weight.

It should be understood that in each of these attempts it may be possible to include greater amounts of ferric citrate or the corresponding metal chelate, which may not improve the sensitivity or in any way adversely affect the properties of the composition but would increase the cost of the composition.

Of all metal chelate complexes, iron citrate has proven to be effective in controlling the sensitivity of the composition to the cymbal head, and is also the most environmentally friendly and economically viable.

Claims (9)

Claims CLAIMS 1. Composition for comb heads suitable for the production of flamboyant everywhere or safe matches, which formulation is a chelating agent such as EDTA, citric, lactic, tartaric, malic or gluconic acid, or other α-hydroxycarboxylic acids, such as hexa. the agent is complexed with metal that can be selected from manganese, iron, cobalt, nickel, chromium, copper or vanadium. Composition for matched heads according to claim 1, characterized in that 5 The metal chelate complex is iron citrate. 3. A combination head composition according to claim 1, characterized in that it contains potassium chlorate and red amorphous phosphorus, which are supplemented with a binder, 10 sealant, filler and foaming agent, except for phosphorus sesquisulfide. Matching head composition according to any one of claims 2 and 3, characterized in that the iron citrate is in the form 15 of ferrocitrate monohydrate. Matching head composition according to any one of claims 2 and 3, characterized in that the iron citrate is in the form of iron (III) citrate. Matching head composition according to 20, any one of claims 2 and 3, characterized in that the iron citrate is in the form of ammonium iron (III) citrate. Composition for comb heads according to any one of claims 2 to 5, characterized in that the metal chelate complex is formed in situ by the addition of a chelate compound such as potassium citrate, with a metal salt such as ferric (III) sulfate, wherein the chelate compound and the metal salt inter- 30 act upon adding them to the formulation to form the desired metal chelate. Composition for head matches according to claim 1, characterized in that the amount of the metal complex is 0.01- 35 2.14% by weight. Matching head composition according to claim 1, characterized in that the amount of the metal complex is 0,151,5% in terms of dry weight. 10. A match head composition according to claim 1, characterized in that the amount of the metal complex is 0.4-0.9% in terms of dry weight.