US3441456A - Striker compositions - Google Patents

Description

No Drawing. Filed Oct. 31, 1966, Ser. No. 590,483 Int. Cl. COM 3/ 08 US. Cl. 149-49 Unite 10 Claims ABSTRACT OF THE DISCLOSURE Waterproof match-striker compositions and manufacturing processes therefor are disclosed. These compositions have increased pot-life at elevated temperatures and comprise as the binder therefor: (A) a proteinaceous adhesive material and (B) a hydrolyzed interpolymer of an alkyl vinyl ether and maleic anhydride which are cross-linked in situ to a water-insoluble state, preferably in the presence of an accelerator, at elevated temperatures.

This invention relates to match striker compositions in general and, more particularly, to novel water-proof match-striker compositions, to processes for their production and to methods for their application in the match industry.

The common variety of safety matches which are sold either in boxes or in cardboard folders must be struck against a friction element in order to initiate the burning process which elements are usually referred to as striker compositions. Compositions for the formation of match strikers form an essential part of the safety match industry, and intense efforts have been extended to provide satisfactory striker surfaces.

In general, safety match production and use comprise two basic components:

(1) a striking friction surface containing a readily ignitable compound, and

(2) a pyrotechnic match which is capable of ignition. The striker assembly generally comprises an igniting agent, a friction agent, and a binder material to cement the friction agent or abrasive and the igniting agent into a coherent mass and to adhere this mass to a base substrate, such as a cardboard or wooden matchbox. The pyrotechnic match usually comprises a paper or wood sliver, the tip of which is coated with a composition containing a material which can yield free oxygen to support combustion, such as potassium chlorate, readily combustible fillers, such as rosin or sulfur, inert fillers for body, a binder and a colloidal agent.

Heretofore, the compositions employed in forming the match-striker surfaces have been characterized by the lack of resistance to water, non-uniformity in the striking surface, poor pot-life of the composition and poor sensitivity to the action of the match in achieving the desired aims. Various attempts, however, have been made to overcome these several previous disadvantages and enhance the scope of the commercial applications available to the match-striker composition. In the main, these prior attempts have involved the use of various types of binder ingredients, such as synthetic materials of various types, the water-proofing of the compositions by various methods and the use of sundry physical manipulations of the binder compositions in order to overcome the several disadvantages enumerated hereinabove. However, none of these prior methods and materials have operated to produce a satisfactory striker composition, especially as to the problems involving water resistance and stability.

Of the several binders which have been employed in these match-striker compositions heretofore, there may be mentioned such materials as casein, synthetic mateatent O 3,441,456 Patented Apr. 29, 1969 rials and materials derived from proteinaceous origin, such as animal glue, pitch glue and the like. Casein, for example, has not been satisfactory as a binder as this material tends to gel on standing and, in addition, has a strong tendency to putrefy when employed as a striker composition binder. Also, the films formed from casein bases are not generally considered sufiiciently water resistant, a factor which is of the utmost priority in achieving a satisfactory match-striker composition. Moreover, much of the casein used in the United States match industry must be imported and, therefore, is subject to wide fluctuation in market price.

As mentioned, various synthetic lattices have also been suggested as binders, such as polystyrene, for example. However, the lattices of these materials are similarly not truly water resistant, particularly when the coatings containing these materials are subjected to long-term immersion in water.

A particularly desirable binder for use in match-striker compositions would be materials formed from a proteinaceous origin, such as animal glues and fish glues and the like, as these materials are economical and readily available. However, these materials have been found to be particularly poor in their resistance to water and, thus, are easily solubilized when contacted with an aqueuos environment. Moreover, the lack of uniformity as to quality is a characteristic of the available supply of these proteinaceous materials because of the natural origin of the material and their ready susceptibility to bacterial attack under a variety of conditions. The first-mentioned drawback, namely, lack of water resistance, has proven particularly objectionable since this reduces considerably the scope of commercial applications available for this type of match-striker composition material.

Various procedures have been resorted to heretofore in an effort to overcome or otherwise mitigate this poor resistance to water solubilization and thereby render materials of protein origin satisfactory binders in the formation of match-striker composition. In the main these procedures 'have involved primarily the utilization of an insolubilization or tanning" technique whereby the protein material is converted to a substantially water-resistant form. Insolubilization of the protein material has heretofore been attempted, for example, by the use of one or more tanning agents as formaldehyde, substances which yield formaldehyde under the conditions of the tanning treatment, chrome alum, bichromate, ferric salts, and the like. Of the materials mentioned, perhaps formaldehyde has thus far proven to be the most effective from a commercial standpoint since its use does not impart spurious coloration to the glue product. However, tanning processes based on the use of formaldehyde are not without one or more attendant disadvantages. For example, the addition of formaldehyde to the glue solution is accompanied by an almost instantaneous insolubilization reaction with the result that substantial immobilization of the glue product occurs thereby presenting serious obstacles for handling of the insolubilized glue product. Furthermore, it has been found that the glue product so immobilized cannot be satisfactorily coated onto the particular substrate, in this case, the base to which the match-striker composition is to be applied. Moreover, when the protein material is tanned or hardened such compositions tend to be softened when wet by water and thus will not generate the adequate friction required for the ignition of matches. A further and probably more important disadvantage occurring with the employment of tanning procedures with formaldehyde or formaldehyde donors is that there is thus created noxious fumes during processing, and, hence, the commercial aspects of such a product would be considerably retarded.

A still further disadvantage of a glue-based striker composition insolubilized by the use of tanning procedures now known to the art is that it shortens the pot-life of the composition and thus renders it practically inoperative for use in match-striker compositions.

Various other techniques have also been attempted in order to place a binder of protein origin in a state whereby it may be used satisfactorily as a match-striker binder composition. One of these techniques has been by the use of hot melt application. By this technique, the binder is coated on the substrate and, while still hot, is powdered with the abrasive material to be included in the striker composition. However, this method requires removal of the excess abrasive which did not stick to the, binder and thus an untidy extra processing step is generally necessary. Another technique which has been suggested for water proofing the striker composition is by the application of a water-resistant overlay to the striker film. However, these coatings are often impaired after repeated strikings with matches and thus form sites which are readily penetrated by water. Moreover, this second coat is obviously an extra operation and will serve to add processing costs and thereby increase ultimate costs of the striker product.

It is accordingly one object of this invention to provide novel match-striker compositions employing a novel binder in formation of the compositions.

It is a further object of this invention to provide novel match-striker compositions which are water-proof, have excellent pot-life, and otherwise mitigate the disadvantages attendant to striker compositions of the prior art.

A still further object of this invention is to provide novel, water-resistant match-striker compositions, methods for preparing the same and their application, wherein a novel binder of protein origin is employed.

A still further object of the invention is to provide novel water-resistant match-striker compositions having increased pot-life at elevated temperatures which utilize adhesive binder compositions of proteinaceous origin and methods for preparing the same, as well as processes for their application in the match industry.

Other objects and advantages of the present invention will become apparent as the description thereof proceeds.

In accordance with this invention and in satisfaction of the foregoing objects and advantages, there are provided in its broader aspects novel matchstriker compositions comprising an igniting agent, a friction agent, and a binder material to cement the igniting agent and friction agents into a coherent mass, the binder material comprising: (1) a proteinaceous adhesive material, and (Q) a hydrolyzed interpolymer of an alkyl vinyl ether and maleic anhydride. In addition, there may also be included within the binder composition, an accelerator material which aids in insolubilization of the porteinaceous material.

According to this invention, it has been found that use of the novel binder composition of this invention permits the use of an economical readily available binder, namely, a glue material, without the need for noxious tanning agents and Without the'undesirable limited pot-life of glue-formaldehyde compositions such as are ordinarily employed in insolubil-izing adhesives of protein origin. Moreover, the utilization of the binder compositions of this invention permits the use of low-grade, inexpensive glues, particularly those of low gel strength, by upgrading them through cross-linking action with the hydrolyzed interpolymers of alkyl vinyl ethers and maleic anhydrides. Under the conditions employed in forming these binder compositions, the interpolymer serves to insolubilize the proteinaceous material and thereby renders the mixture particularly suitable in match-striker compositions.

The striker compositions formed employing the novel binders described hereinbelow, which are obtained from proteinaceous materials, have been found to exhibit the excellent high water resistance of striker materials which referred to herein,

are based on glues formed by conventional tanning procedures. However, the insolubilization of the glues employed herein by the use of hydrolyzed interpolymers of alkyl vinyl ethers and maleic anhydride have been found to eliminate the tendencies for the glue to putrefy and thus overcomes one of the primary disadvantages of the glue compositions employed heretofore.

In general, the novel striker compositions of this invention are formed by intimately admixing an aqueous solution of the proteinaceous adhesive, an aqueous solution of the hydrolyzed interpolymer of an alkyl vinyl ether and maleic anhydride and optionally an insolubilization ac celerator at temperatures ranging from about room temperature to elevated temperatures on the order of the liquifaction point of the proteinaceous adhesive and then adding thereto the igniting agent and the friction agent. A convenient method for the addition of the igniting agent and the friction agent is by the use of an aqueous slurry. Thickeners and inert fillers can be added as desired to achieve the required consistency.

The proteinaceous adhesives which are employed in formation of the novel binders of this invention are of proteinaceous origin and are commonly described as animal glues, fish glues, and the like. The various glues, as are generally described as organic colloids of protein derivation. They are generally obtained by boiling animal matter, such as skin and bone, in water and then drying the extract. Chemically, these materials are known as polypeptide chains terminated at one end of the molecule by an amino group and at the other end by a carboxyl group. A pure form of proteinaceous material which has been found to be particularly suitable in the process of this invention is gelatin.

Any grade of animal glue and/ or fish glue may be employed to advantage in the present invention, the only requirements with respect thereto being that they conform to the usual commercial standards as regards quality, purity, and the like. Any of the glue materials commonly employed in the production of animal and/or fish glue adhesives are quite satisfactory. The animal or fish glue is employed in the form of an aqueous solution which can be readily prepared by stirring the glue in question into cold water preferably containing a preservative, until thoroughly wet-out and allowing the resultant slurry to swell. The slurry is then heated to a temperature of from to F. during which time the mixture is maintained under agitation. In this manner, solution of the glue is readily achieved.

The vinyl alkyl ether/maleic anhydride interpolymers which are found to be eminently suitable for use in producing the hydrolysates utilizable to advantage in the present invention are readily available commercially. Particularly good results are obtained with products available under the trade name designation Gantrez-an sold by the General Aniline & Film Corporation. These products are water soluble, linear, resinous interpolymers of methyl vinyl ether and maleic anhydride having molecular weights ranging from about 156,000 to about 4,000,000.

Structurally, these interpolymers can be represented by the following formula:

wherein n has a value of from about 1,000 to about 25,000. Accordingly, such products are usually designated in terms of specific viscosity, this being considered a more accurate indicia for polymer identification. Thus, expressed in terms of specific viscosity, the products encompassed by the above formula possess an nsp value as measured at a one gram concentration in methyl ethyl ketone at 25 C. within the range of from about 0.1 to about 3.5, with a range of 1.5 to 3.5 being preferred.

Hydrolysis of the foregoing polymeric materials can be readily accomplished by merely adding the interpolymer to an aqueous medium and allowing the solution thus obtained to stand from approximately 24 to 48 hours in a closed container at room temperature. Occasional stirring can be employed if desired. The hydrolysis reaction can be accelerated by employing elevated temperatures on the order of 90l00 C., with temperatures of 95-99 C. being preferred.

In carrying out the hydrolysis reaction, the aqueous medium is preferably pro-heated to the previously indicated temperature range and maintained under stirring sufficient to produce a rapidly whirling vortex. The interpolymer is then introduced directly into the vortex in order to expedite polymer Wet-out and dispersion. Stirring is maintained under the elevated temperature conditions 'until complete solution of the interpolymer material iS achieved, during which time the slurry exhibits an increase in viscosity. Completion of the polymer dissolution is indicated by a decrease in solution viscosity and by an almost instantaneous change in appearance from milky white to transparent. Since the adhesive compositions modified in accordance with the present invention are in most instances provided in aqueous media, it will be readily understood that hydrolysis of the interpolymer may be carried out either in the presence or absence of the adhesive substance, e.g., animal glue. The former, which can be termed for convenience an in situ hydrolysis is, however, a less preferred method for carrying out the hydrolysis reaction, since in many instances, it can result in a significant shortening in the pot-life of the glue composition.

In explanation of the foregoing, it has been postulated that, if hydrolysis is effected in the glue solution at room temperature, the several days time required for all anhydride rings to open would correspondingly reduce pot-life. This conclusion is borne out in experimental data and observations which establish that insolubilization of the glue composition inherently occurs during the period required for complete hydrolysis. Moreover, it will be readily apparent that the use of elevated temperatures to accelerate hydrolysis of the interpolymer will exert a like accelerating effect upon the insolubilization reaction, with the obvious result that the pot-life is severely diminished. Accordingly, the realization of optimum results is further assured by conducting at least a substantial portion of the hydrolysis reaction, e.g., 6575%, in the absence of the glue product.

The interpolymer material may be fully hydrolyzed or partially hydrolized as desired. Additionally, the alkyl vinyl ether/maleic anhydride interpolymer may also be partially esterified, the only criticality relative to a partial esterification being that a sufficient number of carboxylic groups must remain available for cross-linking with the glue or gelatin material.

Other interpolymer materials which have been found satisfactory for use in forming the binder compositions of this invention include such materials as Acrysol A3, a polyacrylic acid composition sold under that trade name designated by Rohm and Haas Company, which polymer must be subjected to hydrolysis under the conditions set forth hereinabove. Of these interpolymer compositions, however, the Gantrez-an materials sold by General Aniline & Film Corporation represent preferred compositions for use in the invention.

The proportions of hydrolyzed interpolymer employed in the present binder compositions range from about 1 to about 100 parts per 100 parts of animal or fish glue or gelatin. However, particularly advantageous glue insolubilization systems are obtained with proportions of hydrolyzed interpolymers ranging from about 5 to about 25 parts per 100 parts of glue on a dry-weight basis.

The binder compositions of the present invention may be prepared in any desired manner and the components added in any desired order. Preferably, however, the

aqueous solution of hydrolyzed or partially hydrolyzed interpolymer is added to a pre-formed aqueous solution of the animal and/ or fish glue which has been heated to its liquefaction temperature. Stirring may be employed, if desired, to promote inter-dispersion of the respective glue and polymer solutions. At this stage, any other ingredients, such as an accelerator, filler, etc., desired o be included in the binder composition, may be added. The said other ingredients may, of course, also be included in either of the polymer or glue solutions instead of adding the same separately to the aqueous, hydrolyzed intermixture.

As indicated hereinbefore, the insolubilization of the glue to form the binders will occur at room temperature although it is advisable from an economic standpoint to maintain the composition under an elevated temperature, in order to. accelerate gel formation. However, .it should be understood that other means may be employed to ad vantage to effect the rate of insolubilization, pot-life, and the like.

In this respect, it has been determined that advantageous results are obtained if means are employed to accelerate the degree and rate of the insolubilization reaction. In particular, it has been discovered, through the use of laboratory experimentation, that the use of the hereinafter enumerated accelerating means or materials serve to synergistically modify the binder compositions by exerting a catalytic effect on the rate of insolubilization. Increasing the rate of insolubilization has been found to result in a significant increase in the rub resistance of the striker compositions while simultaneously increasing the pot-life of the compositions.

Several methods are available for acceleration of the insolubilization process in satisfaction of the abovedefined advantages. The foremost methods comprise the use of higher molecular weight grades of hydrolyzed interpolymer and the addition of various chemical materials. Of the chemical materials which have been found useful in accelerating the insolubilization reaction, synthetic organic resin materials which contain a plurality of groups reactive towards the glue molecule have been found to be particularly benefical. Of the several materials encompassed by this definition, there may be mentioned the methylated methylol melamine resins. Of these several materials, a methylated methylol melamine resin sold commercially by the Monsanto Chemical Company under the trade name designation Resloom M-75 has been found to be particularly outstanding as an accelerator. In addition to these resins, a number of other materials, such as the alkali metal bichromates, (e.g., sodium bichromate, potassium bichromate, etc.), polyamines, polyepoxides, polyisocyanates, etc., have been found to be particularly suitable accelerator materials for the compositions.

Other accelerating additives which have been found satisfactory for use in the compositions of this invention include such materials as urea, Kymene 557, a cationic, water-soluble resin sold commercially under that name by Hercules Powder Company, ammonium zirconyl carbonate and Vinol-125, a polyvinyl alcohol composition sold commercially by Airco Chemical. However, it is to be understood that the use of the alkali metal bichromates and Resloom M75 as accelerators represent preferred aspects of the invention.

Compositions found to be particularly advantageous in the sense of providing improved pot-life and excellent water-resistant properties comprise as essential ingredients a hydrolyzed methyl vinyl ether/maleic acid interpolymer with low gel strength bone glue and, as the accelerator, an alkylated alkylol melamine resin.

The proportions of the accelerator materials employed in formulating the glue compositions are not particularly critical as depending primarily on the requirements of the processor as Well as the molecular weight of the hydrolyzed interpolymer, the type of glue, etc. However, it has been found that optimum results are obtained when the above-mentioned materials are employed in concentrations ranging from about 0.05 to about 50 parts per 100 parts of the glue material.

In forming the binder compositions for use in the striker compositions of the invention, it has been observed that variations in the composition ingredients will affect the properties of the resultant product and/or the rate at which insolubilization occurs. For example, it has been observed that, as the molecular weight of the hydrolyzed alkyl vinyl ether/maleic anhydride interpolymer increases, the pot-life of the glue compositions containing it decreases, whereas the rate and degree of the insolubilization reaction increases. Moreover, it has been observed that the degree and rate of insolubilization of glue containing an identical percentage of the same molecular weight grade of hydrolyzed interpolymer appears to be greater for high gel strength high glue as opposed to low gel strength bone glue.

As a general proposition, it has been discovered that satisfactory binder compositions for use in the matchstriker compositions of this invention may be represented by the following general formula with parts given by weight.

Ingredient: Parts by weight Glue or gelatin 100 Hydrolyzed interpolymer 1-100 Accelerator 0.05- 50 The resulting mixture may be brought to the desired solids content and viscosity by the addition of water and/ or an organic solvent.

An even more specific and preferred mixture of components would include 5-25 parts of the hydrolyzed alkyl vinyl ether/maleic anhydride interpolymer and 0.25-12.5 parts of accelerator based on 100 parts of glue.

The striker compositions of the present invention, as pointed out hereinabove, are formed by admixture of the above-described binder composition with a suitable igniting agent and a friction agent.

A generalized match-striker composition according to this invention may be as follows, the parts being given by weight.

Ingredient: Parts by weight Binder Igniting agent 60 Friction agent The binder ingredient is, of course, the composition described in detail hereinabove.

The igniting agents which are employed in the compositions of this invention include such well-known materials as red phosphorous, red antimony sulfide, and the like. However, it should be understood that other igniting agents, such as are commonly used in the match-striker art, may be included in the compositions of this invention.

A preferred friction agent for use in forming the striker compositions of this invention is powdered or ground glass which is commonly employed in compositions of this type. However, other friction agents, such as silica sand, for example, which are adapted to provide the necessary friction may be employed as desired. A particularly desirable friction agent is Ground Glass No. 80 sold commercially under that name by The Bassichis Company.

It is to be understood that the striker composition may also contain additional ingredients which are generally well known in the art for the attainment of the required consistency, etc. For example, inert ingredients, such as whiting, clay, zinc oxide, and carbon black, viscosity control agents, liquid diluents, dispersing agents, and ignitable substances, such as paraflin, gums, rosin, etc., may be employed as desired in the compositions. Also, other materials, such as inert fillers, coloring pigments, and the like may be added as desired. All of these materials are well known in the art.

Preparation of a match-striker composition according to this invention may be carried out generally as follows:

Dried powdered glue of any gel strength, but preferably from 200 to 400 grams gel strength (by Bloom Gelometer rating) is stirred into cold water until the particles are wet and then is allowed to swell. The swollen glue is then solvated at about 38 to 60 C. (100 to 140 F.) as described above. It should be noted here that direct solution of the glue in hot water is possible but use of this technique often causes entrapment of unwetted glue particles. Therefore, direct stirring of the dried, powered glue into cold water represents a preferred aspect of the matchstriker composition preparation.

To this glue solution maintained at about 38 C. to about 60 C. under mechanical agitation is added the aqueous hydrolyzed solution of the alkyl vinyl ether/ maleic anhydride interpolymer or its partial ester.

It should be noted that low gel strength glue solutions are often liquid at room temperature whereas high solids, high gel strength glue solutions must necessarily be maintained at about 60 C. to insure their fluidity. Obviously then, the glue solution should be fluid enough to accept the addition of the compounding materials.

The addition of the hydrolyzed interpolymer or its partial ester is then followed by the addition of the accelerator material either in dry form or as a liquid dispersion. After addition of the accelerator, the igniting agents and friction agents may be added. Preferably, these materials are added to the blend as aqueous slurries as this has been found to be the most convenient and satisfactory method of perfecting the addition of these materials. However, it is also within the scope of this inventoin to add these materials by other means, such as by sifting the solids into the binder mixture.

After the addition of each of the above ingredients, the resulting mixture is in the form of an aqueous slurry and may be applied directly to the desirable substrate. The preferred substrates for application are the cellulosic substrates, such as ordinarily used in forming match-striker compositions.

The match-striker composition can be applied to the substrates, such as paper or wood, by any means known to the trade. Such means include the ordinary use of such apparatus as transfer rolls, doctor blades, air knives, intaglio printing, and the like.

After application of the aqueous slurry to the substrate, it is necessary to effect curing of the coated composition in view of the fact that the applied film generally contains water and/or organic solvents, depending on the solvent employed, which are necessary to be evaporated. Although these volatiles will evaporate from the coating at room temperature, this method is too slow for use in mass production techniques. It has, therefore, been found that evaporation of the volatiles and cure of the coating can be effected in one step by subjecting the coated substrate to an elevated temperature. According to a preferred embodiment of this invention, a drying temperature of from about 50 C. to about C., preferably about 60 C., has been found to be particularly suitable to effect the curing and drying steps where suitable equipment is employed. Such equipment may include circulating hotair ovens, infra-red heaters, high-frequency heating coils, and the like. The only limitations to be encountered in carrying out these heating and curing steps is to insure that combustion does not occur. It has been found that coatings which are cured for about 3 minutes at 60 C. and then aged at room temperature for about hours are quite water resistant and, therfore, the use of this curing technique represents a preferred aspect of the present invention.

The compositions of the following examples are given for the purpose of illustrating various embodiments of the present invention and are not to be regarded in any Way as being limitative thereof. All parts are given by weight on wet basis and solid concentrations are as indicated.

Representative glue stocks were initially prepared for use as binders by solvating animal (hide) glue in distilled water containing a preservative (phenol) at 60 C. according to the following formula with parts being by weight.

Ingredient: Parts by weight Cold distilled water 49.5 Phenol 0.5 Animal (hide) glue 50.0

for the various periods set forth in the following table. Thereafter, the applied striker composition was dried at 60 C. for 3 minutes and the card containing it immersed in tap water for 2 minutes. Then, after removing from the water, a Kleenex tissue was rubbed across the still wet card. The tissue should not pick up any of the red phosphorous from the applied composition.

The results of this test, which demonstrates both rub resistance and resistance to water, are set forth in the tabular form in Table I hereinbelow. In the tests, the degree of red phosphorous pick-up was rated as from minusone (l) to plus-seven (+7). Minus-one (1) indicated no pick-up whereas plus-seven (+7) indicated the heaviest pick-up.

RUB RESISTANCE OF STRIKER COMPOSITIONS 30 Min. at 3 Min. at 3 Min. at 3 Min. at 60 C. 2 3 Min. at 30 Min. at 60 C. 24 60 C. 100 60 C. 2 months a 60 C. 60 C. hrs. at RT. hrs. at RT. \vks.at RT. RT

(1) 379 g. Hide Glue, 10% Hyd. Gantrez AN-119 6 2 (2) 379 g. Hide Glue, 20% Hyd. Gantrez AN-1l9. 7 4 (3) 120 g. Bone Glue, 20% Hyd. Gantrez AN-l19.. 7 6 (4) 379 g. Hide Glue, 20% Acrysol A-3 7 +4 to 6 (5) 379 g. Hide Glue, 20% Hyd. Gantrez AN-119, 5% Urea r. 7 5 (6) 379 g. Hide Glue, 20% Hyd. Gantrez AN-119, 5% Kymene 557,. 6 +3 (7) 379 g. Hide Glue, 20% Hyd. Gantrez AN-1l9, 25% Kymene 557. 7 (8) 379 g. Hide Glue, 20% Hyd. Gantrez AN-llt), 5% Ammonium Zirconyl Carbonate. 7 6 (9) 379 g. Hide Glue,

B ichromate 7 +3 (10) 379 g. Hide Glue, 20% Hyd. Gantrez AN-139, 10% Vinol 125. 7 4 (11) 379 g. Hide Glue, 20% Hyd. Gantrez AN-139 7 3 to 4 (12) 379 g. Hide Glue, Hyd. Gantrez ANY-139, 5% Acrysol A3 7 (13A) 379 g. Hide Glue, 10% Hyd. Gantrez AN-139, 10% Acrysol 7 5 (14) 379 g. Hide Glue, Hyd. Gantrez AN-139, 5% Resloorn M- 7 +1 07 2 t07 1 to +1 -1t01 +1 to -2 (15) 379 g. Hide Glue, Hyd. Gantrez AN-139, 5% Resloom M-75 6 3 +1 1 1 to +1 (ltliv)I 1;;9 g. Hide Glue, 20% Hyd. Gantrez AN-l 50% Resloom 6 1 1 1 (17) 379 g e ue, 10% Hyd. G a Rcsloom 75 7 4 4 4 +2 (18) 379 g e, 10% Dry Resloorn M-75 on Dry Weight of Glue Gelled immediately In all cases hydrolyzed Gantrez AN percent is the percent dry weight based on the dry weight of glue, the same being true for the Acrysol .A-3

and Vinol.

Percent of urea, Kymene 557, Ammonium Zireonyl Carbonate, Sodium Bichromate, and Resloom M-75 are their percent dry weight based on the dry weight of Hyd. Gantrez An. Kymene 557-Cationic, water soluble resin from Hercules Powder Company. Aerysol A-3-Polyacrylic acid irom Rohm and Haas. Vinol 125P0lyvinyl alcohol from Aireo Chemical. Resloom M75-Methylated methylol melamine resin from Monsanto Chemical Company.

Rub Resistance Ratings: Excellent to Poor, 1 to +7.

Material Parts by weight Red phosphorous 29.75 Ground Glass No. 80 12.75 Cold distilled water 42.50

The basic striker formula set forth hereinabove was employed in forming striker compositions for testing which includes 15 parts by weight of binder, 60 parts by weight igniting agent and 25 parts by weight friction agent.

After preparation of each of the required starting compositions, the striker compositions were prepared employing this basic formula. To the aqueous glue binders maintained at 60 C. with agitation, was added the appropriate amount of striker slurry which had been preheated to 60 C.

After formation of the several representative striker compositions, as delineated in the following table, they were subjected to a standard test to determine their rub resistance as follows:

By means of a glass rod, buttons of each striker composition lwere applied to cigarette carton kraft and cured It is to be noted from the results of the rub resistance test set forth in the above examples that particularly advantageous and desirable match-striker compositions are obtained where the compositions are accelerator cured. See, for instance, Examples 9 and 13-16.

It is also to be noted from the above results that Examples 1 and 2 show the difference in performance of the compositions as a function of the hydrolyzed polyvinyl methyl/rnaleic anhydride interpolymer concentration, whereas Examples 2 and 3 show the difference in performance of the compositions as a function of glue gel rating.

It should be understood that various other ingredients may be included in the compositions provided by the present invention in addition to those specifically enumerated hereinbefore. For example, the physical characteristics of the interpolymer-glue blend may be modified in degree by the incorporation of various compatible materials as desired in order to modify or adjust the physical or other characteristics of a given formula. As examples of such ingredients, there may be mentioned plasticizers, humectants, diluents, fillers, and the like.

The invention has been disclosed with respect to certain preferred embodiments thereof, and there will become obvious to persons skilled in the art various modifications, equivalents or variations thereof which are intended to be included within the spirit and scope of the invention.

What is claimed is:

1. A water-proof match-striker composition comprising an igniting agent, a friction agent, and a water-dispersed binder material to cement the igniting agent and friction agent into a coherent mass, the binder material comprising (1) a proteinaceous adhesive material and (2) a hydrolyzed interpolymer of an alkyl vinyl ether and maleic anhydride, said proteinaceous adhesive material and said hydrolyzed interpolymer being cross-linked by heat to a water-insoluble state.

2. A match-striker composition according to claim 1 wherein the proteinaceous material is selected from the group consisting of animal glue, fish glue, and gelatin.

3. A match-striker composition according to claim 1 wherein the alkyl vinyl ether comprises methyl vinyl ether.

4. A match-striker composition according to claim 1 which further contains a compound which accelerates insolubilization of the said binder material.

5. A match-striker composition according to claim 4 wherein the accelerator material is selected from the group consisting of (1) an alkylated alkylol melamine resin containing a plurality of pendant alkylol groups and (2) an alkali metal bichromate.

6. A match-striker composition according to claim 5 wherein the accelerator material comprises methylated methylol melamine resins.

7. A match-striker composition according to claim 1 which comprises 1 to 100 parts of hydrolyzed interpolymer of an alkyl vinyl ether and maleic anhydride per 100 parts of proteinaceous material on a dry basis and from .05 to parts of accelerator material per parts of proteinaceous material.

8. A composition according to claim 7 wherein the proteinaceous material is selected from the group consisting of animal glue, fish glue and gelatin.

9. A composition according to claim 8 wherein the alkyl vinyl ether comprises methyl vinyl ether.

10. A match-striker composition according to claim 9 wherein the accelerator material is selected from the group consisting of an alkylated alkylol melamine resin containing a plurality of dependent alkylol groups and an alkali metal dichromate.

References Cited UNITED STATES PATENTS 660,366 10/1900 Craveri 4448 2,589,607 3/1952 Ellern 44-48 X 2,683,098 7/1954 Sinks 44-48 X 3,202,539 8/1965 Holt et al 260- 8 X 3,313,749 4/1967 Ready 260-8 DANIEL F. WYMA-N, Primary Examiner. C. F. DEES, Assistant Examiner.

US. 01. X.R. 44 4s