Combination Of Polyvinyl Alcohol And Gelling Agent As A Binder In Match Formulations

Abstract

A binder for use in a match formulation is revealed which comprises a mixture of a gelling agent and a polyvinyl alcohol wherein the gelling agent-polyvinyl alcohol binder serves as a replacement for the animal glue binder conventionally used in the formulation of matches.

Description

This invention is concerned with an improved binder for the manufacture of matches which is less expensive than the animal glue usually employed as a binder in match formulations and which further produces match heads which are less hygroscopic than match heads made utilizing animal glue binder.

Stike-anywhere matches have been an article of commerce since about 1780 and safety matches since about 1855. At present, somewhat over 400,000,000,000 matches are manufactured per year in the United States alone. The most common type of match made is the cardboard safety match or book match.

Matches are formulated by making a mixture of inflammable ingredients, fillers, coloring agents, neutralizers, catalysts, dyes, and a binder and then drying this mixture upon the end of a rigid cellulosic material such as a stick of wood or a rigid stick of cardboard. The most common binder used is animal glue. The use of animal glue as a binder suffers due to the relatively high cost of the glue and due to the relatively high hygroscopicity of the matches made using this binder.

Accordingly, it would be an advantage if a replacement binder for animal glue could be developed which was less costly than animal glue and which, in addition, would produce matches which were less hygroscopic than matches made with animal glue.

In view of the above, it becomes an object of this invention to provide a binder for use in match formulation which is less costly than animal glue.

Another object of the invention is to provide a binder for use in matches as a replacement for animal glue which leads to the formation of matches which are less hygroscopic than matches formulated using an animal glue binder.

A further object of the invention is to provide a binder for use in safety match formulations which comprises a mixture of a gelling agent and a polyvinyl alcohol.

A yet further object of the invention is to provide a safety match formulation utilizing a binder comprising a mixture of a gelling agent and a polyvinyl alcohol.

A still further object of the invention is to provide a method for making a strike-anywhere match utilizing as a binder a mixture of a gelling agent and a polyvinyl alcohol.

Other objects will appear hereinafter and will be self-evident.

DETAILED DESCRIPTION OF THE INVENTION

Broadly speaking, the invention reveals a binder for use in match formulation which comprises a mixture of a gelling agent and a polyvinyl alcohol. The revealed binder may be used to formulate both safety matches and strike-anywhere matches. It may also be used in conjunction with other binder materials such as animal glue.

The production of safety matches is a relatively simple industrial operation. A mixture is made containing starch, sulfur, potassium chlorate, a neutralizer such as zinc oxide or calcium carbonate, diatomaceous earth and other siliceous fillers, such as powdered glass, fine silica, sand, quartz, etc., a burning rate catalyst, such as potassium dichromate or lead thiosulfate, and a water soluble dye. The mixture described above is then blended with a water solution of animal (hide) glue to form a complete safety match formulation. The formulation generally contains enough water so that it is thick but smoothly fluid. The formulation is then coated on the ends of cellulosic sticks such as wood sticks or rigid cardboard sticks and dried.

The resulting safety match may be struck upon a safety match striker formulation. Safety match striker formulations generally consist of dried mixtures of animal glue or casein insolubilized with formaldehyde, red phosphorus, calcium carbonate, powdered glass, and carbon black.

The starch used in the match formulations set out herein may be derived from any source, such as, for example, corn, wheat, potato, tapioca, rice, sago, and grain sorghum. Waxy starch may also be used. Crude starch sources such as ground cereals, macerated tubers, or the partially purified starches therefrom are additionally usable. The term "starch" is used broadly herein and encompasses unmodified starch and tailings and, as well, starch that has been modified with acids, alkalies, enzymes, heat, etc. Soluble or partially soluble modified starches, dextrins, pregelatinized products, and starch derivatives of different types are also suitable in the process. Generally, starches that are easily solubilized, such as dextrins and preswollen starches, are used in the match formulations.

A typical commercial safety match formulation will contain about 9 to 11 percent animal glue, 2 to 3 percent starch, 3 to 5 percent sulfur, 45 to 55 percent potassium chlorate, 2 to 4 percent of a neutralizer, 5 to 6 percent diatomaceous earth, 15 to 32 percent siliceous fillers, sufficient burning rate catalyst to obtain the desired rate of burning and a sufficient amount of a water soluble dye to obtain the desired color. The above percent figures are weight percent.

Commercial strike-anywhere matches are formulated by first formulating a base composition and coating it upon a rigid cellulosic stick and then formulating a tip composition and coating it upon the tip of the base composition.

Typically, base compositions for strike-anywhere matches are made by formulating a mixture of an extender, a paraffin, potassium chlorate, phosphorus sesquisulfide, sulfur, rosin, dammar gum, infusorial earth, powdered glass and other fillers, potassium dichromate and zinc oxide. This mixture is then blended with a solution of animal glue to form a thick but smoothly fluid suspension and the suspension is coated upon rigid cellulosic sticks in the same manner that safety match formulations are coated upon sticks.

A typical base composition will contain from about 11 to 13 percent animal glue, 4 to 6 percent extender, 11/2 to 21/2 percent paraffin, 35 to 40 percent potassium chlorate, 2 to 4 percent phosphorus sesquisulfide, 5 to 7 percent sulfur, 5 to 7 percent rosin, 2 to 4 percent dammar gum, 2 to 4 percent infusorial earth, 20 to 23 percent powdered glass and other filler, 0.2 to 1 percent potassium dichromate, and 0.5 to 1.5 percent zinc oxide, the percent figures being percent by weight.

Tip compositions for strike-anywhere matches are formulated by making a mixture of an extender, potassium chlorate, phosphorus sesquisulfide, rosin, powdered glass and other fillers, and zinc oxide. This mixture is then blended with a solution of animal glue to form a suspension which is thick but smoothly fluid. The suspension is then coated upon the tip of a base composition which has previously been deposited upon a rigid cellulosic stick.

This invention provides an alternative and superior binder which can be used in the above formulation in place of animal glue.

The binder comprises a mixture of a gelling agent and a polyvinyl alcohol.

Preferably, the gelling agent is an aromatic organic compound that contains at least two active hydrogens bonded to oxygen, nitrogen or sulfur atoms. The oxygen, nitrogen, or sulfur atoms are bonded to an aromatic ring. Examples of preferred gelling agents include resorcinol, .beta.-resorcylic acid, gallic acid, catechol, phloroglucinol, salicylanilide, and azo colors of the Congo Red family such as sodium diphenyldiazo-bis-.alpha.-naphthylaminesulfonate.

The structures of usable gelling agents may be represented by the formula:

where r and t are zero or positive integers, the sum, r + t, is at least two, s is 0 or 1, D, when present, is an organic divalent radical, Ar is an aromatic ring, and X is selected from the group consisting of sulfur, nitrogen, and oxygen atoms.

Since the polyvinyl alcohol and the gelling agent must be formulated into a binder solution it is essential that both be water soluble.

Preferably, the polyvinyl alcohol will be a polyvinyl alcohol which has a degree of polymerization in the range from about 150 to about 3,000. Most preferably, the polyvinyl alcohol will have a degree of polymerization that falls in the range from about 400 to about 700.

A suitable polyvinyl alcohol will be further characterized in that a 4 percent aqueous solution of the polyvinyl alcohol will have a Hoeppler viscosity in centipoise that falls in the range from about 3 to about 80 and more preferably in the range from about 4 to about 8, said Hoeppler viscosity being measured at 20.degree. C. on a Hoeppler Precision Viscometer, Model HV 303.

The measurement of viscosity with a Hoeppler Precision Viscometer, Model HV303 consists of determining the time required for a standard ball to traverse a set distance down a tube filled with liquid under the influence of gravitic force. The instrument is calibrated to obtain a ball constant using a liquid of known viscosity. The absolute viscosity in centipoise is then calculated by the equation:

V = ( Sp. Gr. B. - Sp. Gr. L. ) .times.(t) .times. (k)

where

Sp. Gr. B. = specific gravity of the standard ball,

Sp. Gr. L. = specific gravity of the liquid in the tube,

t = time in second in which the ball traverses a set distance, in the tube, and

k = ball constant determined using a liquid of known viscosity.

A further description of the Hoeppler Viscometer is available in the brochure,Hoeppler Viscometer, Description and Instructions for Using It, Gebrueder Haake, Medingen near Dresden, Germany 1936.

The preferred binder produced in accordance with this invention contains a ratio of polyvinyl alcohol to gelling agent which falls in the range from about 1:1 to about 7:1 . The most preferred binder contains polyvinyl alcohol and resorcinol.

The preferred binder solution generally contains from about 2 to about 30 percent by weight of solids dissolved in water. The preferred binder solution is further characterized in that it will form a gel on standing at 25.degree. C. with a gel strength of at least 30 grams as measured on a Bloom gelometer. Preferably, the gel will form in less than 6 hours. Most preferably, the gel will form in about 2 hours.

A liquid formulation suitable for making a safety match comprises a mixture of a gelling agent, a polyvinyl alcohol, starch, diatomaceous earth, a siliceous filler, sulfur, a neutralizer, potassium chlorate, a burning rate catalyst, a pigment, and water. The preferred gelling agent and polyvinyl alcohol for use in forming this liquid formulation are the same preferred gelling agent and polyvinyl alcohol as described above. The preferred siliceous filler is selected from the group consisting of sand and quartz, the preferred neutralizer is selected from the group consisting of zinc oxide and calcium carbonate, and the preferred burning rate catalyst is selected from the group consisting of potassium dichromate and lead thiosulfate.

Preferably, the liquid safety match formulation contains an amount of polyvinyl alcohol falling within the range from about 0.2 to about 15 percent, an amount of a gelling agent falling within the range from about 0.2 to about 10 percent, and an amount of total solids falling within the range from about 47 to about 87 percent the percent figures being percent by weight. Most preferably, the liquid safety match formulation contains an amount of polyvinyl alcohol falling within the range from about 3 to about 6 percent, an amount of resorcinol falling within the range from about 0.5 to about 2.0 percent, and an amount of total solids falling within the range from about 60 to about 70 percent.

A liquid base formulation suitable for making a strike-anywhere match comprises a mixture of a gelling agent and a polyvinyl alcohol, an extender, a paraffin, potassium chlorate, phosphorus sesquisulfide, sulfur, rosin, dammar gum, infusorial earth, siliceous filler, potassium dichromate, a neutralizer, and water.

The preferred polyvinyl alcohol and gelling agent are as described above.

Preferably, the liquid base formulation filler is selected from the group consisting of quartz and sand, the neutralizer is selected from the group consisting of zinc oxide and calcium carbonate and the extender is starch. More preferably, the liquid base formulation contains an amount of polyvinyl alcohol falling within the range from about 0.2 to about 15 percent, an amount of gelling agent falling within the range from about 0.2 to about 10 percent, and an amount of total solids falling within the range from about 47 to about 87 percent the percent figures being percent by weight. Most preferably, the liquid base formulation contains an amount of polyvinyl alcohol falling within the range from about 3 to about 6 percent, an amount of resorcinol falling within the range from about 0.5 to about 2.0 percent, and an amount of total solids falling within the range from about 60 to about 70 percent.

A liquid tip formulation suitable for making a strike-anywhere match tip comprises a mixture of a gelling agent, a polyvinyl alcohol, an extender, potassium chlorate, phosphorus sesquisulfide, rosin, a siliceous filler, a neutralizer, and water.

The preferred polyvinyl alcohol and gelling agents are as described above.

A preferred liquid tip formulation contains starch as the extender, a siliceous filler selected from the group consisting of sand and quartz, and a neutralizer selected from the group consisting of zinc oxide and calcium carbonate.

More preferably, the liquid tip formulation contains an amount of polyvinyl alcohol falling within the range from about 0.2 to about 15 percent, an amount of gelling agent falling within the range from about 0.2 to about 10 percent, and an amount of total solids falling within the range from about 47 to about 87 percent, the percent figures being percent by weight. Most preferably, the liquid tip formulation contains an amount of polyvinyl alcohol falling within the range from about 3 to about 6 percent, an amount of resorcinol falling within the range from about 0.5 to about 2.0 percent, and an amount of solids falling within the range from about 60 to about 70 percent.

Matches may be manufactured from the above formulations in the same manner as matches are now manufactured when animal glue is used as the binder.

Matches manufactured utilizing the binder composition of this invention have been found to be far less hygroscopic than matches manufactured using animal glue as the binder.

The following examples illustrate typical modes of carrying out the aims of the invention. It is understood, of course, that the examples are merely illustrative and the invention is not to be limited thereto. All parts and percentages are in terms of weight unless otherwise specifically indicated .

EXAMPLE 1

Three safety match formulations were synthesized utilizing polyvinyl alcohol-resorcinol mixtures as binders. A fourth safety match formulation was synthesized utilizing hide glue as the binder. The formulations synthesized are shown in TABLE I. --------------------------------------------------------------------------- TABLE I

Component Composition, % __________________________________________________________________________ Control Sample 1 Sample 2 Sample 3 __________________________________________________________________________ Polyvinyl alcohol* 0 4.55 5.20 5.20 Resorcinol 1.13 1.10 1.10 Hide glue 6.5 0 0 0 Starch** 2.5 2.5 2.5 0 Diatomaceous earth 4.53 4.60 4.55 4.74 Sand 8.68 8.80 8.73 9.07 Sulfur 3.98 4.04 4.00 4.16 Zinc oxide 1.23 1.27 1.24 1.30 Wood rosin 0.65 0.66 0.64 0.67 Toludine-red pigment 0.65 0.66 0.64 0.67 Potassium chlorate 36.28 36.79 36.40 38.00 Water 35.0 35.0 35.0 35.0 __________________________________________________________________________ * COVOL 9800 (Trademark of a polyvinyl alcohol distributed by Corn Products Company, Englewood Cliffs, New Jersey.): degree of polymerization, 500 to 600; Hoeppler viscosity of 4% aqueous solution, centipoise, 5.2 to 6.0; 98 to 99 percent hydrolyzed. ** MOGUL B242 (Trade name of a partially solubilized corn starch-dextrin mixture distributed by Corn Products Company, Englewood Cliffs, New Jersey.)

The formulations were made by grinding together all of the dry components except for the starch and potassium chlorate. The starch was added and dispersed in a liquid binder composition, comprising either polyvinyl alcohol and resorcinol or hide glue dissolved in water, at 40.degree. C. The dry components, excluding the potassium chlorate, were then dispersed in the liquid binder solution and the chlorate was added last. After all the ingredients were added, the system was dispersed for 10 minutes. The mixture was then placed in a 40.degree. C. bath and held at this temperature for viscosity stability measurements for one day. Both the initial Brookfield viscosity and the Brookfield viscosity after one day at 40.degree. C. were determined for the control and each of the three samples. The results are presented in Table II. --------------------------------------------------------------------------- TABLE II

Time at 40.degree. C., Composition Brookfield Viscosity, hour Centipoise (Spindle Number) __________________________________________________________________________ Control Sample 1 Sample 2 Sample 3 __________________________________________________________________________ 0 2,600(4) 11,000(5) 10,400(5) 2,500(4) 24 3,000(4) 10,400(5) -- 3,100(4) __________________________________________________________________________

Three 5 to 8 gram samples of each match formulation were placed in separate small petri dishes and dried in a 80.degree. C. vacuum oven for 3 hours. A dried sample of each formulation was placed into moisture chambers with relative humidities of 50 percent, 75 percent, and 93 percent. The dishes were left in the chambers for 72 hours and reweighed to determine the percent moisture pickup. The results of this test are set out in Table III. --------------------------------------------------------------------------- TABLE III

Relative Humidity, % Moisture Pickup,% __________________________________________________________________________ Control Sample 1 Sample 2 Sample 3 __________________________________________________________________________ 50 1.40 0.59 0.59 0.48 75 4.73 1.51 1.50 1.30 93 9.64 3.37 3.69 .cndot. 2.90 __________________________________________________________________________

To determine if the final formulations would be usable in producing matches, match heads were prepared from the formulations upon 5-inch by 1/4-inch by 1/16-inch wooden sticks. The match heads were prepared as follows: The stick was dipped into the formulation and hand turned several times at room temperature until sufficient cooling had taken place to gel the head. All matches made with polyvinyl alcohol-resorcinol mixtures as the binder composition ignited when struck on a standard match book striking surface.

Two liquid binder solutions comprising a polyvinyl alcohol, resorcinol, and water were formulated and their viscosities were determined immediately upon formulation and also after 24 hours of aging at 40.degree. C. An animal glue liquid binder formulation consisting of hide glue dissolved in water was also formulated and its viscosity was determined both immediately upon formulation and after 24 hours aging at 40.degree. C. Each solution composition and viscosity is reported in Table IV. --------------------------------------------------------------------------- TABLE IV

Time at Composition Brookfield 40.degree. C. Viscosity Centipoise hour (No. 2 Spindle) __________________________________________________________________________ 11.1% Polyvinyl 12.6% Polyvinyl 15.6% Alcohol Alcohol* Hide Glue 2.8% Resorcinol 2.7% Resorcinol __________________________________________________________________________ 0 50 38 56 24 48 40 56 __________________________________________________________________________ * COVOL 9800: degree of polymerization, 500 to 600; Hoeppler viscosity of 4% aqueous solution, centipoise, 5.2 to 6.0; 98 to 99 percent hydrolyzed.

Samples of each of the three liquid binder solutions just described were stored at 25.degree. C. for 2 hours to determine if the systems would gel upon cooling. Gelling did occur and the gel strength of each of the gelled binder compositions was measured on a Bloom gelometer. Basically, a Bloom gelometer measures the amount of weight which must be added to a plumb bob resting upon the surface of the gel to cause the plumb bob to penetrate the surface. The results of this test are listed in Table V.

TABLE V

Composition Gel Strength, g., after 2 Hours at 25.degree. C. __________________________________________________________________________ 11.1% Polyvinyl 12.6% Polyvinyl Alcohol* Alcohol* 15.6% Hide Glue 2.8% Resorcinol 2.7% Resorcinol __________________________________________________________________________ 51 88 86 __________________________________________________________________________ * COVOL 9800: degree of polymerization, 500 to 600; Hoeppler viscosity of 4 percent aqueous solution, centipoise, 5.2 to 6.0; 98 to 99 percent hydrolyzed.

The data clearly indicate that liquid binder solutions made utilizing a mixture of a polyvinyl alcohol and resorcinol as binding ingredients will have similar viscosity properties to a liquid binder solution made utilizing hide glue as the binder ingredient. In addition, stronger gels are formed when mixtures of polyvinyl alcohol and resorcinol are used as the binder components in the liquid binder solution than when hide glue is used in a like manner.

EXAMPLE 2

Two polyvinyl alcohols having widely differing structures and properties were tested as binder constituents. Binder solutions made using the two alcohols in conjunction with resorcinol were stored at 25.degree. C. to determine if the systems would gel at this temperature. Gelling of both binder solutions occurred. The two binder solutions were constituted as follows:

1. 15 percent, COVOL 9700 (Trademark of a polyvinyl alcohol distributed by Corn Products Company, Englewood Cliffs, New Jersey): degree of polymerization, 500 to 600; Hoeppler viscosity of 4 percent aqueous solution, centipoise, 4.7 to 5.4; 87 to 89 percent hydrolyzed, and

7.5 percent, resorcinol.

2. 3 percent, COVOL 9840 (Trademark of a polyvinyl alcohol distributed by Corn Products Company, Englewood Cliffs, New Jersey): degree of polymerization, 1700 to 1800; Hoeppler viscosity of 4 percent aqueous solution, centipoise, 25 to 35; at least 99.3 percent hydrolyzed, and

3 percent, resorcinol.

EXAMPLE 3

Two polyvinyl alcohols having different structures and properties were dissolved in water along with resorcinol to form binder solutions. The binder solutions were constituted as follows:

1. 3 percent, COVOL 9840, and 3 percent, resorcinol.

2. 1.4 percent, COVOL 9860 (Trademark of a polyvinyl alcohol distributed by Corn Products Company, Englewood Cliffs, New Jersey): degree of polymerization, 2,400 to 2,500; Hoeppler viscosity of 4 percent aqueous solution, centipoise, 55 to 67; 98 to 99 percent hydrolyzed, and

1.4 percent, resorcinol.

Safety matches were made using the above binder solutions. The safety match formulations were constituted as follows:

1. 1 percent COVOL 9840, 1 percent resorcinol, 35 percent water, 39.2 percent potassium chlorate, 2.7 percent starch, other ingredients proportionately as in Example 1, Table I.

2. 0.5 percent COVOL 9860, 0.5 percent resorcinol, 35 percent water, 39.8 percent potassium chlorate, 2.7 percent starch, other ingredients proportionately as in Example 1, Table I.

The safety matches lighted readily when struck on a standard safety match book striking surface.

While the invention has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modification, and this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice in the art to which the invention pertains and as may be applied to the essential features hereinbefore set forth, and as fall within the scope of the invention.

Claims

That which is claimed is:

1. A liquid formulation suitable for making a safety match comprising polyvinyl alcohol; a gelling agent selected from the group consisting of resorcinol, beta-resorcylic acid, gallic acid, catechol, phloroglucinol, salicylanilide and sodium diphenyl -diazo-bis-alpha-naphthylaminesulfonate; starch; diatomaceous earth; a siliceous filler selected from the group consisting of powdered glass, silica, sand and quartz; sulfur; a neutralizer selected from the group consisting of zinc oxide and calcium carbonate; potassium chlorate; a burning rate catalyst selected from the group consisting of potassium dichromate and lead thiosulfate; and water.

2. The liquid formulation of claim 1, wherein the polyvinyl alcohol has a degree of polymerization of from about 150 to about 3,000.

3. The liquid formulation of claim 1, wherein the gelling agent is resorcinol.

4. The liquid formulation of claim 1, wherein the polyvinyl alcohol is present in an amount of from about 3 percent to about 6 percent by weight, the gelling agent is present in an amount of from about 0.5 percent to about 2.0 percent by weight, and having a solids content of from about 60 percent to about 70 percent by weight.

5. A liquid base formulation for making a strike-anywhere match base comprising a polyvinyl alcohol; a gelling agent selected from the group consisting of resorcinol, beta-resorcylic acid, gallic acid, catechol, phloroglucinol, salicylanilide and sodium diphenyldiazo-bis-alpha-naphthylaminesulfonate; starch; a paraffin; potassium chlorate; phosphorous sesquisulfide; sulfur; rosin; dammar gum; infusorial earth; a siliceous filler selected from the group consisting of powdered glass, silica, sand and quartz; potassium dichromate; a neturalizer selected from the group consisting of zinc oxide and calcium carbonate; and water.

6. The base formulation of claim 4, wherein the polyvinyl alcohol has a degree of polymerization of from about 150 to about 3,000.

7. The base formulation of claim 4, wherein the gelling agent is resorcinol.

8. The base formulation of claim 4, wherein the polyvinyl alcohol is present in an amount of from about 3 percent to about 6 percent by weight, the gelling agent is present in an amount from about 0.5 percent to about 2.0 percent by weight, and having a solids content of from about 60 percent to about 70 percent by weight.

9. A liquid tip formulation suitable for making a strike-anywhere match tip comprising polyvinyl alcohol; a gelling agent selected from the group consisting of resorcinol, beta-resorcylic acid, gallic acid, catechol, phloroglucinol, salicylanilide and sodium diphenyldiazo-bis-alpha-naphthylaminesulfonate; starch; potassium chlorate; phosphorous sesquisulfide; rosin; a siliceous filler selected from the group consisting of powdered glass, silica, sand and quartz; a neutralizer selected from the group consisting of zinc oxide and calcium carbonate; and water.

10. The tip formulation of claim 8, wherein the gelling agent is resorcinol.

11. The tip formulation of claim 8, wherein the polyvinyl alcohol is present in an amount from about 0.5 percent to about 2.0 percent by weight, and having a solids content of from about 60 percent to about 70 percent by weight.

12. A safety match having, as the ignition composition, a dried formulation of claim 1.

13. A strike-anywhere match having, as the ignition composition upon the tip of a strike-anywhere match base, a dried formulation of claim 8.