US 3808414 A
A device for providing chemiluminescent light from a chemical reaction of suitable compounds in the presence of a fluorescent compound. The device comprises a self-contained light transmitting package having a number of reactants stored in separate compartments, all sealed with a single sealing clip. The reactants in the separate compartments are combined in a single compartment by removal of the single sealing clip.
Description (OCR text may contain errors)
United States Patent [191 Roberts [451 Apr. 30, 1974 DEVICE FOR THE PACKAGING OF A THREE OR MORE COMPONENT CHEMILUMINESCENT SYSTEM  Inventor: Bernard George Roberts, Rowayton,
 Assignee: American Cyanamid Company,
 Filed: Dec. 21, 172
21 App]. No.: 317,459
 U.S. Cl. 240/225  Int. Cl. F2lv 9/16  Field of Search 240/225  References Cited UNITED STATES PATENTS 3,539,794 11/1970 Rauhut etal. ..240/2.25
Primary Examiner-Richard M. Sheer Attorney, Agent, or Firm-Charles J. Fickey ABSTRACT A device for providing chemiluminescent light from a chemical reaction of suitable compounds in the presence of a fluorescent compound. The device comprises a self-contained'light transmitting package having a number of reactants stored in separate compartments, all sealed with a single sealing clip. The reactants in the separate compartments are combined in a single compartment by removal of the single sealing clip.
4 Claims, 3 Drawing Figures DEVICE FOR THE PACKAGING OF A THREE OR MORE COMPONENT CHEMILUMINESCE SYSTEM This invention relates to systems and devices for providing chemiluminescent light incorporating chemical components which react chemically and provide excitation for a fluorescent compound. The invention more particularly relates to systems and devices whereby the reactive components are maintained in a non-reactive condition until light is desired, the systems incorporating means to bring said components into a reactive condition and means to display the resultant light.
Under certain circumstances, it is desirable to have a source of visible light which is not electrically activated. Light can be provided by chemical systems, wherein the luminosity is solely the result of chemical reaction without provision of any electrical energy. Such light is known as chemiluminescent light.
Chemiluminescent light may be useful where there is no source of electricity. For example, in emergencies where sources of electrical power have failed, a chemiluminescent system could provide light. Since the system requires no externally generated source of energy, devices can be made small and highly portable. Moreover, chemiluminescent light is cold light and can be used where the heat of conventional illumination is not desired. It is also useful where electrical means could cause a tire hazard, such as in the presence of inflammable agents. Chemiluminescent light is also effective under water since there are no electrical connections to short out. Thus it may be seen that chemiluminescent light can have many useful applications.
A principal object of the present invention is to provide systems and devices incorporating chemiluminescent components for the provision of chemiluminescent light.
A further object of this invention is to provide means for containing chemically reactive chemiluminescent components in a non-reactive condition and means to combine said components when desired to provide chemiluminescent light.
A further object is to provide .a self-contained, highly portable chemiluminescent lighting device having all chemical components therein and in which the light is displayed.
Another object is to providea chemiluminescent lighting device which is inexpensive to make, easy to activate and highly effective.
Another object of the invention is to provide an illuminated package having a chemiluminescent lighting system.
A further object is to provide a chemiluminescent lighting package capable of containing different reaction materials, in separated compartments which may be readily and easily-combined 'by removal of asingle seal and the products of the reaction without leakage.
These and other objects of the invention will-become apparent as the description thereof proceeds.
A chemical lighting system may require the separate packaging of three or more non-compatible components. This present'device has as many compartments for component storage as required, but still uses only one clip for removal during mixing and reacting. An added advantage is the ability'to fill eachcomponent from the sameside of the package.
The device consists of a package separated into two sections by a removable clip placed horizontally across the package. One section of this device is partitioned vertically (at to the clip) into the number of components required in the chemiluminescent system be either heat sealing or some other permanent or semipermanent manner. (One of the components can also be stored in the second section below the clip partitioning.) By removing the single clip all components can be mixed to form the chemiluminescent system.
Three or more non-compatible components may be packaged separately within one device. Only one removable clip is required to allow the mixing of all the components. All the components can be filled into the device from one end thus facilitating its production.
Chemical lighting systems e.g., thixotropic systems may require the addition to a regular chemiluminescent system of a non-storage-compatible thickening agent. This device permits the packing of the agent in a separate compartment.
The chemiluminescent system of this invention thus comprises the device as described accomodating the admixture of at a number of chemiluminescent reactants and providing for the admixture in the device of at the chemiluminescent reactants comprising either (a) one component containing a chemiluminescent compound, another component containing a hydroperoxide compound, a'component containing a fluorescer fluid or solid, and the like. Any other necessary ingredients for the production of chemiluminescent light, .or for lifetime control, or for intensity improvement, or for storage stabilization may be included in one of the components with which they are compatible, or included as additional components. In particular with the preferred oxalic-type chemiluminescent compounds of this invention, a fluororescent compound must be included in the system.
The preferred chemiluminescent light is obtained in this invention by .the reaction of a hydroperoxide with a chemiluminescent composition which, in combination, comprises a chemiluminescent compound selected from the group consisting of (l) an oxalic-type anhydride of the type disclosed and claimed in the copending application, 485,920 now U.S. Pat. No. 3,399,137, which is hereby incorporated by reference, (2) an oxalic-type amide of the type disclosed and claimed in copending applications, Ser. No. 520,052 now U.S. Pat. No. 3,442,815 and 547,782 now abandoned, which are hereby incorporated by refernence, 3) an oxalic-type O-acylhydroxylamine of the type disclosed and claimed in copending application, Ser. No.
547,761 now abandoned, and (4) an oxalic-type ester disclosed and claimed in application, Ser. No. 491,896 now abandoned, in the presence of a fluorescer com- .pound and a-solvent. Other suitable chemiluminescent compounds are 3-aminophthalhydrazine, 3,4,5- triphenylimidazole, l0, l0 '-diall yl-9,9 'biacrdinium salts, and 9-chlorocarbonyl- 1 O-methylacridinium chloride. The latter is disclosedand claimed in copend- :ing application, Ser. No. 427,459 now U.S. Pat. No.-
3,352,791. All of the foregoing provide chemiluminescence when reacted with a hydroperoxide .com-
pound in the presence of a base. Other chemiluminescent materials are described by K. D. Gunderrnan,
Angew. Chemie, Int. -Ed., 4, 566/1965.
The preferred chemiluminescent compound of this invention'is an oxalic-type ester selected from the group consisting of (a) an ester of an oxalic-type acid and an alcohol characterized by acid ionization constant in water greater than 1.3 X and (b) a vinyl ester of an oxalic-type ester. Similarly, in a preferred embodiment thereof, the alcohol would be an aromatic U8. Pat. No. 3,749,679 and 886,406, now abandoned,
filed Mar. 15, 1971, and Dec. 18, 1969, respectively. These applications disclose bisphenyl esters of oxalic acid as discussed above, and which are further substituted with alkoxyphenyl and carbalkoxy groups. These applications are incorporated herein by reference.
The peroxides employed in the components of this invention may be any hydroperoxide compound. Typical hydroperoxides include t-buty-lhydroperoxide, peroxybenzoic acid, and hydrogen peroxide. Hydrogen peroxide is the preferred hydroperoxide and may be employed as a solution of hydrogen peroxide in a sol vent or as an anhydrous hydrogen peroxide compound such as perhydrate of urea (urea peroxide), perhydrate of pyrophosphate (sodium pyrophosphate peroxide), perhydrate of 'histidine (histidine peroxide), sodium perhydrate of pyro'phosphate (sodium pyrophosphate peroxide), perhydrate of histidine (histidine peroxide), sodium perborate, sodium peroxide, and the like. Whenever hydrogen peroxide is contemplated to be employed, anysuitable compound may be substituted which will produce hydrogen peroxide.
The peroxide concentration may range from'about l5 molar down to about 10' preferably about 2 molar down to about l0 molar. The ester of this invention may be added as a solid or in admixture with a suitable solid peroxide reactant or in a suitable diluent, or alternatively dissolved directly in a solution containing the peroxide reactant.
Typical diluents, which additionally may be'used inconjunction with the necessary diluent of this invention, are those which do not readily react with a peroxide such as hydrogen peroxide, and which do not react with an ester of oxalic acid.
ole, tetralin, and, polychlorobiphenyls, providing said solvent combination accommodates hydroperoxide solubility. However, when oxalic-type chemiluminescent materials are used, strong electron donor solvents such as dimethyl formamide, dimethyl sulfonide, and hexamethylphosphoramide should not, in general, be used as a major solvent component.
Where a solvent is employed with a component containing the chemiluminescent material any fluid can be used providing said fluid solubilizes at least 0.01 M concentration of the chemiluminescent material and is unreactive toward the chemiluminescent material. Typical solvents include ethers, esters, aromatic hydrocarbons, chlorinated aliphatic and aromatic hydrocarbons, such as those cited in the preceding paragraph. For oxalic-type chemiluminescent compounds, hydroxylic solvents such as water or alcohols and basic solvents such as pyridine should not be employed since such solvents used in general, react with and destroy oxalic-type chemiluminescent compounds. Solvent combinations may, of course, be used but such combinations when used with oxalic-type chemiluminescent compounds should not include strong electron donor solvents.
When a component comprising a solid chemiluminescent compound and a solid hydroperoxide is used, the solvent or solvent composition comprising the second component may vary broadly. Said solvent, however, should preferably dissolve at least 0.02 M concentrations of both, the hydroperoxide and the chemiluminescent compound, and for oxalic-type chemiluminescent compounds, strong electron donor solvents should be avoided as major solvent components.
The fluorescent compounds contemplated herein are numerous; and they may be defined broadlyas those which do not readily react on contact with the peroxide employed in this invention, such as hydrogen peroxide, likewise, they do not readily react on contact with the chemiluminescent compound.
A fluorescent compound is required for light emission when the prepared oxalic-type chemiluminescent compound of the invention is employed. For other types of chemiluminescent compounds a fluorescer is not required but may be used to shift, the wavelength-of emitted light toward the red region of the spectrum so as to change the color of emitted light. Fluorescent compounds for use with oxalic-type chemiluminescent compounds should be soluble in the reactive solvent at least to the extent of 0.0001 moles per liter.
Typical suitable fluorescent compounds for use in the present invention are those which have a spectral emission falling between 330 millimicrons and 1000 millimicrons and which are at least partially soluble in any of the above diluents, if such diluent is employed.
Among these are the conjugated polycyclic aromatic compounds having at least 3 fused rings, such as anthracene, substituted anthracene, benzanthracene, phenanthrene, substituted phenanthrene, naphthacene, substituted naphthacene, pentacene, substituted pentacene, and the like. Typical substituents for all of these are phenyl, lower alkyl, chlorine, bromine, cyano, alkoxy (C -C and other like substituents which 'do not interfere with the light-generating reaction contemplated herein.
Numerous other fluorescent compounds having the properties given hereinabove are well known in the art.
Many of these are fully described in Fluorescence and Phosphorescence, by Peter Pringsheim, lnterscience Publishers, Inc., New York, NY. 1949. Other fluorescers are described in The Colour Index," Second Edition, Volume 2, The American Association of Textile Chemists and Colorists, 1956, pp. 2907-2923. While only typical fluorescent compounds are listed hereinabove, the person skilled in the art is fully aware of the fact that this invention is not so restricted and that numerous other fluorescent compounds having similar properties are contemplated for use herein.
A fluorescent oxalic-type ester, such as the oxalic acid ester of 2-naphthol-3,6,8-trisulfonic acid, does not require a separate fluorescent compound to obtain light. Other typical fluorescent oxalic acid esters include esters of oxalic acid (1) 2-carboxyphenol, (2) 2-carboxy-6-hydroxyphenol, (3) l,4-dihydroxy-9,ldiphenylanthracene, and (4) 2-naphthol. Thus, a reactant including a fluorescent oxalic-type ester would thereby include at least one fluorescent compound.
It has been found that the molar (moles per liter of diluent) concentrations of the major components of the novel composition herein described may vary considerably. It is only necessary that components be in sufficient concentration to obtain chemiluminescence. The ester of oxalic acid molar concentration normally is in the range of at least about 10 to molar, preferably in the range of at least about 10- to about 1 molar; the l p'res sn c ma un is p es in, range o about 10 to 5, preferably lO to 10' molar; and the diluent must be present in a sufficient amount to form at least a partial solution of the reactants involved in the chemiluminescent reaction. If the ester is liquid, it
may serve as either the sole diluent or a partial diluent.
The wavelength of the light emitted by chemiluminescence of the compositions of this invention, i.e., the color of the light emitted, may be varied by the addition of any one or more energy transfer agents (fluorescers) such as the known fluorescent compounds discussed at length above.
The wavelength of the light emitted by the composition of this invention will vary, depending upon the particular fluorescent component employed in the reaction.
Additionally, it hasbeen found that the superior intensity of chemiluminescence is obtained when the final mixture producing the luminescence is maintained at a temperature of between about 40C. and 75C., preferably between about C. and 50C. However, temperature is not critical and the luminescence of Applicants process is not limited to these ranges.
The lifetime and the intensity of the chemiluminescent light obtained with the preferred oxalic-type chemiluminescent compounds of this invention can be regulated by the use of certain regulators such as:
(1) By the addition of base to the chemiluminescent composition. Both the strength and the concentration of the base are critical for purposes of regulation.
(2) By the variation of hydroperoxide. Both the type and the concentration of hydroperoxide are critical for the purposes of regulation.
(3) By the addition of water.
(4) By the addition of a catalyst which changes the rate of reaction of hydroperoxide with the oxalic-type ester. Catalysts which accomplish that objective include those described in M. L. Bender, Chem. Revs, Vol. 60, p. 53 (1960). Also, catalysts which alter the rate of reaction or the rate of chemiluminescence include those accelerators of copending application, Ser. No. 577,595, now abandoned, and decelerators of copending application, Ser. No. 577,615, now abandoned.
While acids are not in general accelerators for oxalictype chemiluminescent reactions it should be noted specifically that acids are accelerators for the oxalic amide chemiluminescent compounds of copending application, Ser. No. 547,782, now abandoned.
More specifically, the advantages obtained by the incorporation of a catalyst of Ser. vNo. 577,595 may be obtained in conjunction with the objects of this present invention, by employing, according to the copending application, an ionized salt having a cation selected from (a) an organic quaternary cation selected from the group consisting of ammonium, arsenic, and phosphorous, and (b) alkali metal having an atomic weight above 22, the salt of said cation preferably being soluble in an organic solvent and preferably being characterized by a property of forming cation-aggregates when reacted with the oxalic-type ester and a hydroperoxide. One of the' advantages is the fact that an excessive amount of the chemiluminescent agent may be employed whereby a higher quantum yield may be obtained when the ionized salt is employed, in contrast to systems not employing the accelerator whereby such systems would be limited to a much lower maximum concentration of chemiluminescent agent which would continue to increase rather than decrease the total quantum yield of chemiluminescent light.
Similarly, within the scope of thepresent invention is the concurrent employment of one or more decelera tors either alone in the composition of this invention, or in conjunction with one or more of the accelerators discussed in the preceding paragraphs. By employing one of the accelerators of the preceding paragraph, it would be possible to employ a greater total concentration of the chemiluminescent agent while concurrently would be possible to employ a decelerator which would prolong the period during which the light of high intensity is obtained from the chemiluminescent reaction. Such decelerators set forth in the copending application, Ser. No. 577,6l5, include for example a compound such as oxalic acid.
When oxalate-type chemiluminescent compounds are used in a solution component it may be desirable to include a stabilizing agent such as those described in copending application, Ser. No. 614,397, now abandoned.
The chemical compounds, components and their reactions for providing chemiluminescent light are described in copending, commonly assigned applications,
Ser. Nos. 442,802 now U.S. .Pat. No. 3,329,621;
442,818 now U.S. Pat. No. 3,425,949, and those previously mentioned, and as such they do not form a part of the present invention.
If a gelled chemiluminescent composition is desired, a thix'otropic or gelling agent may be included in one of the compartments. Suitable agents are disclosed in U.S. Pat. No. 3,671,450, and are for example, alkali and alkaline earth metal soaps; bentonite; polyaryl ureas; silica; saccharides; indanthrene blue (less desirable because of intense color); natural plant hydrocolloids such as guar, tragacanth, algin and the pectins; starches and starch derivatives; cellulose and synthetic cellulose derivatives such as nitrocellulose; polyvinyl compounds such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylates, and ethylene oxide polymers; hevea latex.
In this invention, the reactive components are stored in a multiple compartment container device having a plurality of compartments, wherein the separate components may be brought into contact to produce the reaction which provides chemiluminescent light to be displayed in said container. When either the chemiluminescent compounds, hydroperoxide, or both are fluid, they must be in separate compartments. The diluent and fluorescent compounds can be in either of these two compartments. If the chemiluminescent compounds, hydroperoxide and fluorescent compounds are dry powdered solids, they may be kept together in one compartment with the diluent in the other compartment. The reactive components are brought together to provide chemiluminescent light.
The invention may be better understood by reference to the drawings in which FIG. 1 shows a plan view of a flexible package as one embodiment of the chemiluminescent light device,
FIG. 2 shows a view of the same device as in FIG. 1,
showing reactants in the various package compart ments.
Referring to FIGS. 1 and 2 an elongated rectangular package A is composed of two sheets and 6 of flexible material, sealed around the outside edges. The seal may be by any suitable means, such as heat sealing, or suitable adhesive. One portion B of package A is divided into a plurality of compartments, as shown compartments 1,2,3 and 4 by means of heat sealing (or otherwise sealing) sheets 5 and 6 at points 7, 8, and 9, from package edge 10 towards the opposite end 1 1. Thus the compartment 1, 2, 3 and 4 are open at their ends facing edge 11 and open into a larger single compartment 12 in portion C of package. A clamp D is provided which reaches across all open ends of compartments 1, 2, 3 and 4 to close them from single compartment 12. Thus each of the four'compartments may contain separate, non-compatible ingredients for chemiluminescent light production which are kept separate from each other. When clip D is removed the ingredients from compartments will be admixed in compartment 12 and reach chemically to provide chemiluminescent light as shown in FIG. 3. Thus at least one of the sheets Sand 6 should be light transmitting i.e., transparent or translucent. The other sheet may be reflective, o'pague or likewise transparent as desired. 7 The sheets may be plastic, flexible aluminum foil, or the like, so long as they are impervious to the fluids contained and inert to the reactants. Polyethylene, polypropylene, teflon or the like have been found suitable as plastics.
Clip D may be of any suitable design, many of which are known in the art. One type is shown in FIG. 2 which consists of a rod 13 around which pavkage A is wrapped and an outer clamp 14 conforming to the rod shape..This type of clip may be easily removed by pull- I ing on package edges 10 and 11.
The package A is moreover easily prepared. For this, it may be held with edge 11 upward and unsealed, while the other three edges are sealed. Ingredients are placed in compartments 1, 2, 3, 4 at the open ends and clip D is attached which effectively closes the open ends of compartments 1, 2, 3, and 4. Edge 11 is then heat sealed to form compartment 12, and finish the light package.
The color of the light emission will depend on the type of fluorescent compound and its spectral response. However, the visible color could be varied by using a colored plastic for sheets 5 or 6.
It will be obvious that the construction of the inventive device may be varied so long as the basic requirements are maintained.
The invention provides a device for providing visible light whenever and whereever desired, independent of conventional electrical lighting methods and without the hazards and limitations of electrical lighting. The chemiluminescentlighting systems can be especially useful in emergency situations where all other forms of lighting have failed. The systems do not have the tire of ignitable lighting devices such as candles, gas, or oil lights.
It will be readilyapparent that the chemiluminescent device is not confined to emergency lighting, however. It can be used at any time where a cold, safe illuminating means is desired. It is also useful to'provide illumination where electrical illumination is unavailable. The device is highly portable and can be hand held for signalling. In addition, by use of a magnetic attachment, the package could ne made to adhere to metal surfaces.
While certain specific embodiments and preferred modes of practice of the invention have been described, it will be understood that this is solely for illustration, and that various changes and modifications of the invention may be made without departing from the spirit of the disclosure or the scope of the appended claims.
1. A chemiluminescent light comprising a package having two coextensive, flexible sheets, sealed together at the outer edges, a plurality of parallel elongated compartments formed by sealing said sheets together along spaced apart lines parallel to one edge of the package, said lines extending a portion of the distance along said one edge, a removable clamp means adapted to clamp across said package transverse to said elongated compartments and close said compartments from the remainder of the package, to form a larger single compartment in the remaining area of thepackage, at least one of said sheets being light transmitting, and a reactive chemiluminescent ingredient in each elongated compartment.
2. The chemiluminescent light of claim 1 wherein said sheet material is a plastic of the group polyethylene, polypropylene or teflon.
3. The chemiluminescent light of. claim 1 wherein one of said flexible sheets is reflective.
4. The chemiluminescent light of claim 1 having four elongated compartments and wherein each elongated compartment contains one of the ingredients, a bisfor said ingredients.