WO2004013249A1 - Compositions reactives chimioluminescentes poreuses, formables, et dispositif pour ces compositions - Google Patents

Compositions reactives chimioluminescentes poreuses, formables, et dispositif pour ces compositions Download PDF

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Publication number
WO2004013249A1
WO2004013249A1 PCT/US2003/002035 US0302035W WO2004013249A1 WO 2004013249 A1 WO2004013249 A1 WO 2004013249A1 US 0302035 W US0302035 W US 0302035W WO 2004013249 A1 WO2004013249 A1 WO 2004013249A1
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Prior art keywords
composition
chemiluminescent
slurry
polymeric resin
fluidizable solid
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PCT/US2003/002035
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English (en)
Inventor
William R. Palmer
Stephen L. Palmer
Earl Cranor
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Omniglow Corporation
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Application filed by Omniglow Corporation filed Critical Omniglow Corporation
Priority to MXPA04007835A priority Critical patent/MXPA04007835A/es
Priority to AU2003214881A priority patent/AU2003214881A1/en
Priority to CA2476317A priority patent/CA2476317C/fr
Priority to KR1020047012445A priority patent/KR100945094B1/ko
Priority to JP2004525960A priority patent/JP3996165B2/ja
Priority to EP03710724A priority patent/EP1481034A4/fr
Publication of WO2004013249A1 publication Critical patent/WO2004013249A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C09K11/07—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials having chemically interreactive components, e.g. reactive chemiluminescent compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds

Definitions

  • This invention is directed toward the field of chemiluminescent compositions and more particularly, to devices which produce light from an immobilized chemiluminescent material .
  • chemiluminescent reactant chemiluminescently reactive
  • chemiluminescent reactant composition is interpreted to mean a mixture or component thereof which will result in chemiluminescent light production when reacted with other necessary reactants in the processes as disclosed herein.
  • fluorescent compound is interpreted to mean a compound which fluoresces in a chemiluminescent reaction, or a compound which fluoresces in a chemiluminescent reaction.
  • chemiluminescent composition is interpreted to mean a mixture which will result in chemiluminescence .
  • deagglomerate is interpreted to mean to break up or loosen a compacted portion of a cluster or a mass.
  • fluidizable solid admixture is interpreted to mean a non-liquid admixture which behaves as a pseudo fluid when agitated, but has properties of a solid when at rest .
  • Chemiluminescent light production generally utilizes a two-component system to chemically generate light. Chemiluminescent light is produced by combining the two components, which are usually in the form of chemical solutions referred to as the "oxalate” component and the "activator" component.
  • oxalate and activator compositions inclusive of the various additional fluorescers, catalysts and the like, known to be useful in the prior art, are contemplated for use within the present invention.
  • the two components are kept physically separated prior to activation by a variety of means.
  • a sealed, frangible, glass vial containing one component is housed within an outer flexible container containing the other component .
  • This outer container is sealed to contain both the second component and the filled, frangible vial. Forces created by intimate contact with the internal vial, e.g. by flexing, cause the vial to rupture, thereby releasing the first component, allowing the first and second components to mix and produce light.
  • the outer vessel is usually composed of a clear or translucent material, such as polyethylene or polypropylene, which permits the light produced by the chemiluminescent system to be transmitted through the vessel walls.
  • a clear or translucent material such as polyethylene or polypropylene
  • These devices may be designed so as to transmit a variety of colors by either the addition of a dye or fluorescent compound to one or both of the chemiluminescent reactant compositions or to the vessel .
  • the device may be modified so as to only transmit light from particularly chosen portions thereof. Examples of such a chemiluminescent system include: U.S. Pat. No. 5,043,851 issued to Kaplan.
  • Kaplan discloses a polygonal, chemiluminescent lighting device which concentrates light in the corners of the device, thus enhancing visibility of light emanating from the light stick portion of the device and optimizing the amount and distribution of light radiated.
  • U.S. Patent No. 4,626,383 to Richter et al discloses chemiluminescent catalysts in a method for producing light in short duration, high intensity systems, and low temperature systems. This invention relates to catalysts for two component chemiluminescent systems wherein one component is a hydrogen peroxide component and the other component is an oxalate ester-fluorescer component.
  • Lithium carboxylic acid salt catalysts such as lithium salicylate, which lower the activation energy of the reaction and also reduce the temperature dependence of the light emission process are taught.
  • U.S. Patent No. 5,121,302 to Bay et al . describes a solid, thin, chemiluminescent device emitting light in one direction.
  • the device is comprised of a back sheet of a laminated metal foil having heat sealed thereto at its edges a bi-component front sheet and a temporary separation means positioned to divide the interior area into two compartments.
  • the bi-component includes a first component of which is a laminated metal foil and a second component of which is a transparent or translucent polyolefin sheet.
  • the metal foil of the bi-component offers heat stability, increased shelf life, and relative impermeability to volatile components of the activator solution.
  • the metal foil laminate for activator solution storage enables the activator solution to retain its viability due to the impermeability of the metal foil.
  • U.S. Patent No. 6,062,380 to Dorney discloses a glow cup system with illumination capabilities.
  • the apparatus is a generally cylindrically-shaped container made out of a semi-rigid material, with a preferred embodiment comprised of a translucent plastic material, to allow limited flexibility at the outer layer of the cup as its form can be somewhat altered temporarily by applying pressure to the sides.
  • Within the side wall of the cup is a cavity.
  • the cavity contains a plurality of rupturable ampoules containing a chemiluminescent fluid.
  • the chemiluminescent fluid within the ampoule is an oxalate.
  • a second chemiluminescent fluid resides within the cavity so that when the ampoule breaks open, the two fluids make contact and provide illumination.
  • the ampoule is broken by applying pressure by the user on the outer layer of the cup at the cavity point.
  • the bottom of the cup contains a plug, which may or may not be removable, which seals the second chemiluminescent component within the cavity spacing. Additionally, it is desirable to produce chemiluminescent light from objects of various shapes or forms.
  • U.S. Pat. No. 4,814,949 issued to Elliott discloses a means of making shaped, two-dimensional, chemiluminescent objects.
  • a non-woven, absorbent article in the desired shape is permitted to absorb the chemiluminescent reagents after mixing and activation so that the article emits light from the shape desired.
  • the shape may be as simple or as complex as desired, it is essentially limited to a two- dimensional surface and is additionally limited to producing a single color of light per device.
  • An example of creating a chemiluminescent system capable of producing light from a swellable polymeric composition is disclosed in U.S. Pat. No. 3,816,325 issued to Rauhut et al . Two primary means are employed to produce solid chemiluminescent systems.
  • the first system relies on diffusion of a chemiluminescent oxalate solution into a solid polymer substrate such as a length of flexible vinyl tubing.
  • the diffusion process occurs when a length of the vinyl tubing is immersed in a suitable chemiluminescent reagent for an extended period of time.
  • a suitable chemiluminescent reagent for an extended period of time.
  • application of liquid activator to the surface of the tubing causes the tubing to emit light. Since the solid polymer is relatively non-porous, it is difficult to rapidly and completely activate the oxalate in the tubing because the relatively slow process of diffusion must also be relied upon to permit the activator solution to reach the chemiluminescent reagent diffused into the polymer before light can be generated.
  • the chemiluminescent oxalate solution is mixed with a polyvinyl chloride (PVC) resin powder to form a paste, which is then spread on a substrate and baked in an oven to form a flexible, elastic film.
  • PVC polyvinyl chloride
  • the polyvinyl chloride sheet described exhibits weaknesses in uniformity, strength, flexibility, and most importantly, porosity. Additionally, the processes described are primarily suitable for producing relatively thin objects only.
  • U.S. Pat. No. 5,173,218 to Cohen et al . discloses a combination of PVC polymer resins to produce a porous, flexible, chemiluminescent structure from liquid slurries.
  • a thin "pad” is produced from a mixture of polymer resins, which is strong and flexible, and exhibits satisfactory 1 absorptive properties of the activator fluid.
  • the bottom of the mold may reach a temperature at which the slurry mixture in contact with this region of the mold begins to jell and cure, even though an air path from the exposed surfaces of the slurry to this lower region may not have been created. Due to a lack of air available to this jelling slurry, this "bottom up" curing process results in a pad which is tough, dense, and virtually non-porous in the region of the pad proximal to the mold bottom and to a lesser extent, the mold edges.
  • the side walls of the test tube constrain the slurry from expanding and drawing in the air required to produce a cured matrix with the high degree of porosity and absorbency required to permit activation of the product with liquid activator.
  • the slurry is free to expand vertically in the test tube during the curing process, the lateral constraint on the slurry by the walls of the test tube is sufficient to prevent optimal expansion of the slurry and air induction into the mass during the curing process.
  • the cured mass will exhibit low porosity and yield poor light output which is a limitation of the art. It is often desirable to provide a chemiluminescent device which is not only capable of producing light, but producing light in a variety of colors.
  • 5,508,893 issued to Nowak et al . is directed toward a multi-color chemiluminescent lighting device and method of producing the product.
  • This device is comprised of a flexible tube filled at least partially with an activator solution, a plurality of ampoules containing oxalate solutions located within the tube, and at least one barrier element between ampoules to prevent color mixing.
  • This device is capable of imparting different chemiluminescent colors following activation.
  • U.S. Patent No. 5,705,103 issued to Chopdekar et al . describes a composition for producing chemiluminescent light of controllable duration.
  • the composition is comprised of an oxalate component (including an oxalate ester) in a solvent, an activator component (a peroxide compound and a catalyst) in a solvent, and a fluorescer.
  • an oxalate component including an oxalate ester
  • an activator component a peroxide compound and a catalyst
  • a fluorescer a fluorescer
  • the instant invention teaches a means to produce three-dimensional objects which are self-illuminated.
  • the objects may be as simple or as complex as desired.
  • the objects are produced by a method employing a formable, chemiluminescent reactant composition.
  • This composition is of such a nature that it may be readily placed in variously shaped containers and then cured in said containers whereupon the composition becomes solid and is of a shape that precisely matches the container in which it was formed. Once formed, the composition is semi-rigid and may be removed from the container if desired.
  • the instant invention provides for a chemiluminescent reactant composition which ' is exceptionally porous and is not limited to relatively flat strips of material, as is the case in prior art.
  • objects produced by means of the instant invention may be hollow so that a minimal amount of material may be used to produce glowing, three-dimensional objects. Further, these objects may be multi-colored, that is, a single object can be created which is capable of simultaneously generating a plurality of spatially separated colors or wavelengths of chemiluminescent light .
  • a fundamental objective of the instant invention is that a significant portion of the interstitial spaces in the solid product necessary for quick and reliable activation by a liquid activator is created prior to curing. As such, the system does not rely primarily on porosity created during the curing process in which the air must enter the matrix from outside.
  • the final porosity of the product of the instant invention is primarily a function of the degree of densification prior to curing, the final porosity of the product may be precisely and advantageously controlled.
  • the product of the instant invention may be densified to practically any desirable degree, the interstitial space available through which the activator communicates with the solid product may be reduced as desired, thereby reducing the mobility of the activator and its ability to react with the solid oxalate containing component. Additionally, because most of the porosity of the chemiluminescent solid is determined by the degree of densification prior to curing, the product of the instant invention can be cured in a relatively confined space, such as a test tube, and the resulting product will be highly porous and receptive to activator solution.
  • FIG. 1 is a chart depicting light output versus activation time for differing bulk densities of solid oxalate
  • FIG. 2 is a pictorial view of an example embodiment of the instant invention
  • FIG. 3 is a cross sectional view of the example embodiment of Figure 2 illustrating placement of the chemiluminescent reactant composition
  • FIG. 4 is a cross sectional view of Figure 3 illustrating densification of the chemiluminescent reactant composition using a tamping tool
  • FIG. 5 is a cross sectional view of the example embodiment following densification, illustrating second chemiluminescent reactant component ampoule placement and a void in the fluidizable solid admixture
  • FIG. 1 is a chart depicting light output versus activation time for differing bulk densities of solid oxalate
  • FIG. 2 is a pictorial view of an example embodiment of the instant invention
  • FIG. 3 is a cross sectional view of the example embodiment of Figure 2 illustrating placement of the chemil
  • FIG. 6 is a cross sectional view of another example embodiment of the instant invention illustrating placement of the chemiluminescent reactant composition
  • FIG. 7 is a cross sectional view of the embodiment of Figure 6 illustrating positioning of a compression tool within the chemiluminescent reactant composition
  • FIG. 8 is a cross sectional view of an embodiment of the instant invention illustrating densification of the chemiluminescent reactant composition by the compression tool of Figure 7
  • FIG. 9 is a cross sectional view of an embodiment of the instant invention illustrating the densified chemiluminescent reactant composition.
  • the present invention is directed toward a formulation, process of making, and device for use regarding a chemiluminescent reactant composition which is formable, and may be used to produce a multi-dimensional object.
  • This composition overcomes weaknesses of the prior art and implements the use of a novel forming process to be applied to a chemiluminescent material, thereby furnishing a highly porous, uniquely shaped, chemiluminescent object.
  • the process of the instant invention is not limited to the conventional casting process producing relatively thin, flat objects described in the prior art .
  • the formable and porous powder of the instant invention may be readily compacted to various degrees, and upon heat curing, may form a relatively strong, flexible, and highly porous mass.
  • Figure 1 is a chart depicting how the control of bulk product density may be used to vary activation time.
  • Two devices were produced and tested, each comprising a chemiluminescent reactant composition which is in the form of a solid oxalate containing composition, hereinafter referred to as a solid oxalate.
  • the first device had a bulk density of approximately of 0.54 g/cc and reached maximum light output at approximately 10 minutes after activation.
  • the second device with a bulk density of about 0.72 g/cc, reached its peak light output at approximately 37 minutes after activation. This data indicated that activation time is affected by bulk density with more compacted objects requiring a longer period to activate.
  • the ability to control the light output curve enables the production of chemiluminescent devices to meet a wide array of market needs .
  • a hollow chemiluminescent shape may be preferred to a solid one, since there is a diminishing return effect as light produced from deep within the solid shape reaches the surface inefficiently and may not be emitted as useful light.
  • a hollow chemiluminescent shape provides for a convenient and elegant means to introduce a second reactant component to the product .
  • An ampoule or vessel containing a second reactant component may be placed inside the void in a hollow shape. When the ampoule or vessel is ruptured, the second component is readily absorbed by the interior surface of the hollow shape and is quickly transferred by capillary action through the porous, chemiluminescent matrix until the entire mass is wetted and producing light through chemiluminescence . Placing the second component means inside the void also hides it from view and permits production of a more aesthetically pleasing product.
  • An example of a form which may be produced using the teaching of the instant invention is that of a chemiluminescent candle.
  • Such candles provide a safe, reliable alternative to real candles.
  • the flame from real candles can ignite other objects.
  • chemiluminescent candles are wind resistant and waterproof ⁇ and by employing the instant invention,, can be produced to emit light in any color desired or in any combination of colors or wavelengths from a single device.
  • Previous attempts at producing these "candles" which use chemiluminescent systems as light sources have met with drawbacks.
  • a chemiluminescent lighting device such as a light stick, which employs liquids, has a head-space in the device which represents approximately 30% of the container volume. Light cannot be produced in this head-space area.
  • 10- 170263 discloses an air bubble capture means in which the gaseous head-space (or bubble) which is above the liquid chemiluminescent fluid in a sealed chemiluminescent device is trapped in a region of the device other than the uppermost portion.
  • a sealed chemiluminescent device such as a candle for example
  • the entire portion of the candle flame tip will appear to glow during the chemiluminescent reaction.
  • the bubble had been permitted to remain at the flame tip, it would create a dark region near the top of the flame since the area of the bubble will not produce any light. Such a dark region would detract from the overall visual acceptability of the device.
  • Carbon dioxide, carbon monoxide, and oxygen are common gases liberated in peroxyluminescent systems. These gases rise to the top of any liquid chemiluminescent system and form bubbles at the top of the device.
  • a method is not provided to displace bubbles which are generated during the chemiluminescent process.
  • the instant invention permits a candle or any other chemiluminescent object desired to be produced in which an initial head-space bubble in the device and any significant visible build up of bubbles in the device as the chemiluminescent process progresses is eliminated.
  • the instant invention does not require any specially formed traps, channels, or valves in the device to realize this benefit. Since the formable mass of the chemiluminescent system of the instant invention is a solid, there is no space for bubbles to aggregate and combine. While gasses generated during the chemiluminescent process are still produced, these gasses are constrained from rising in the solid formable mass and are evenly distributed throughout the solid, which subsequently result in a seemingly flawless output of light.
  • Figure 2 sets forth a preferred embodiment of the present invention as a chemiluminescent candle 10 which comprises a blow-molded envelope in the shape of a candlestick. When the device is activated, the flame portion of the candle glows .
  • a candle envelope 11, as illustrated in Figure 3, may be created by blow-molding or other suitable forming means from materials such as, but not limited to, polyethylene or polypropylene.
  • the distal end of the candle envelope opposite the flame shape is left open.
  • the candle envelope 11 is positioned so that the open end is up.
  • a formable chemiluminescent reactant composition 12 of the instant invention is placed into a candle envelope 11 so that the envelope is partially full. While the fluidizable solid admixture is flowable, it also exhibits a degree of cohesiveness, and yields a packable, formable, moist powder. Therefore, an auxiliary feeding means, such as a vibratory feeder, may be useful to aid in feeding the formable chemiluminescent reactant composition 12.
  • the formable chemiluminescent reactant composition 12 may be compacted slightly with a tamping tool 13, as illustrated in Figure 4, designed for this purpose.
  • This compression process not only serves to assist the composition in conforming to the shape of candle envelope 11, but also densifies the composition and compresses it so that it will not flow or be further displaced in the candle envelope 11 should the envelope orientation be altered.
  • the composition may however, be removed from the envelope, if desired, by application of sufficient vibratory forces so as to cause liquefaction of the compacted chemiluminescent reactant composition 15.
  • a tamping tool 13 may be designed with a tapered tip 14 such that it will not only compact the composition but also produce a cavity 16, as illustrated in Figure 5, in the resultant compacted composition.
  • the cavity 16 provides a convenient means to facilitate distribution of a second chemiluminescent reactant component 18, such as within an ampoule 17 and promotes quick, even activation of the device. Once the second chemiluminescent reactant component is in place, a plug 19 at the distal end of the candle envelope 11 may be heat sealed. Additionally, the cavity 16 provides a space into which the composition may expand during the curing process so that an exceptionally porous product may be produced.
  • the cavity is not required to produce products which are highly porous but may be employed in certain cases to produce products with exceptional porosity.
  • a chemiluminescent rose- shaped envelope 21 is produced by first blow-molding an envelope, from polyethylene by way of example, into the shape of a rose bud with a stem attached.
  • the diameter of the stem is considerably smaller than that of the bud.
  • the rose-shaped envelope 21 is filled with a small quantity of formable chemiluminescent reactant composition 12.
  • a compression tool 22 comprising a hollow needle 23 equipped with an expandable bladder 24, which for purposes of illustration is depicted as being held in place by at least one retainer ring 25.
  • the distal end of the hollow needle 23 is plugged and a hole in the side of the needle beneath the expandable bladder 24 permits air pressure from within the needle to fill and inflate the expandable bladder 24.
  • the bladder expands, as illustrated in Figure 8, by using air pressure for inflation purposes, whereby the formable chemiluminescent reactant composition 12 surrounding the inflated bladder 24 compacts against the interior wall of the rose bud envelope.
  • Figure 9 illustrates the compacted chemiluminescent reactant composition 15 in a semi-solid state. Following this compression process, the bladder deflates and the needle probe is removed, leaving a cavity 16.
  • the compacted chemiluminescent reactant composition may subsequently be cured by baking while in place inside the rose bud envelope, in a preferred embodiment, at 95°C for 10 minutes. After the composition cools, a sealed ampoule containing a solution of second chemiluminescent reactant component is inserted into the rose-shaped envelope 21 and a plug may be fitted to the stem and heat sealed to form a hermetic seal as previously described for the candle embodiment.
  • the resulting product is an object appearing as a realistic rose bud which, when activated, emits light from the entire surface of the bud. Activation is accomplished, by way of example, by simply flexing the stem of the rose to fracture the ampoule and release the second component which is then absorbed into the chemiluminescent reactant composition, or formable solid admixture. Since the compacted chemiluminescent reactant composition highly conforms with the interior wall of the envelope, even fine details such as petals of the rose are captured by the process of the instant invention. Concerning the candle and rose embodiments as discussed, it is assumed that the cured solid product will remain in the polymer envelope, however, the material may just as easily be cast and cured in a mold and then removed.
  • Solid chemiluminescent objects may be produced employing the instant invention using, by way of example, compression or centrifugal molding. Individually shaped items produced by the process of the instant invention could be included as free-floating objects which would glow if placed in a vessel containing a second chemiluminescent reactant component solution. Such a system could produce, by way of example, a "snow globe" which contains glowing snow particles. Since the formable mass of the chemiluminescent reactant composition in the instant invention is in solid form, a plurality of positionable and spatially fixed colors may be employed in a single device. For example, a rose bud may be produced in which the bud is red with orange stripes .
  • the following examples describe the experimental process performed to reach the novelties of the present invention.
  • a series of experiments were devised to identify optimal materials and formulas necessary to produce a formable, porous, chemiluminescent reactant composition. As taught in the prior art, a pre-slurry may be prepared by dissolving approximately 2 parts PVC resin (Geon Corp.
  • oxalate solution a chemiluminescent reactant solution which is exemplified herein as an oxalate solution.
  • a slurry was prepared, also according to '218, by mixing 59 parts oxalate pre-slurry (from above) with 31 parts medium particle size PVC powder resin (Geon #218) and 9 parts large particle size PVC resin (Geon #30) .
  • the resultant material is a pourable, liquid slurry. Examples 1-6 Six tests were conducted to determine the effects of varying cure times and temperatures as well as slurry thickness on porosity.
  • test item 1 it was apparent that the PVC particles had not completely absorbed the oxalate solution as the material was doughy and contained significant amounts of free liquid.
  • tests 2-5 the material was found to be less doughy, but only the exposed surface of each cured sample was determined to be porous .
  • test items 1-5 were activated with chemiluminescent activator reagent. Items 2-5 glowed from the surface, but did not produce significant light from the dark, non-porous areas. Item 1 produced very little light over most of its surface, presumably because the liquid oxalate solution that was not absorbed into the PVC matrix during the curing process presented a barrier, preventing the activator solution from reaching the balance of the liquid oxalate below the surface. Some glow was evident near the surface of the matrix at the boundary layer where the activator and oxalate solutions combined. Item 6 was cured at a lower temperature since items 1-5 appeared to be over-cured by application of excessive heat, causing the high molecular weight PVC particles to fuse together.
  • Example 7 A chemiluminescent candle was produced using the same liquid slurry formation as that used in tests 1-6 above. To make this candle, approximately 3.2 grams of liquid slurry, was injected into a polyethylene candle envelope using a syringe. A glass ampoule containing chemiluminescent activator was inserted into tthis slurry such that the lower end of the ampoule contacted the inside bottom of the candle envelope. The assembly was
  • Example 8 With these results in mind, an aliquot of slurry was supported upon an air permeable substrate, e.g. a 10 cm by 10 cm section of 2 mm thick non-woven polyester felt and
  • a model which explains the formation of interstitial spaces in PVC particle/solvent slurries is that in which large, roughly spherical, PVC particles are joined together by smaller, lower molecular weight, PVC particles to form a matrix.
  • the PVC particles absorb the solvent that had initially filled the interstitial spaces between these particles. If air is permitted to enter the matrix during this curing process, the PVC particles will swell and expand as the solvent is absorbed into the particles.
  • Example 9 To determine if increased air access through the slurry could be achieved by using a greater weight percent of larger particle PVC, a new preparation of slurry was created and tested.
  • This new slurry contained 56 parts pre-slurry, 29 parts medium size particle resin (Geon #218) and 15 parts large particle size resin (Geon #30) . Approximately 2.5 ml of this liquid slurry was placed in a polyethylene candle envelope to which a glass activator
  • ampoule was added.
  • the item was cured at 75°C for 12
  • Example 10 A new formulation was created which utilized the pre- slurry described above by dissolving approximately 2 parts PVC resin (Geon Corp. #121) with 98 parts of an oxalate solution. Although in this example the liquid oxalate solution was propylene glycol dibenzoate based, any base compound in the art is contemplated. In this new formulation, a higher weight percent of a single PVC particle was used in place of the medium and large particle PVC resins employed in the slurries previously described. Approximately 40 parts of pre-slurry were added to 60 parts of resin (Geon #466) .
  • the resulting composition was not a liquid slurry, but rather a moist, packable and formable powder characterized as a fluidizable solid admixture.
  • the resin should be selected so as to contain a particle size or range thereof sufficient to provide said fluidizable solid admixture. In an illustrative, albeit not limiting embodiment, this resin is a PVC resin having an average particle size distribution of about 125 microns.
  • polymers may be employed in the polymeric composition: polyethylene, polypropylene, poly(vinyl Chloride), Poly (methyl methacrylate) , poly (vinyl benzoate) , pol (vinyl acetate), cellulose poly(vinyl pyrrolidone) , polyacrylamide, epoxies, silicones, poly (vinyl butyral), polyurethane, nylons, poly acetyl, polycarbonate', polyesters and polyethers are non- limiting examples.
  • Cross-linked polymers may also be employed, such as polystyrene-poly (divinyl benzene), p o lya c ry 1 ami de - p o 1 y ( me t hy 1 eneb i s a c ry 1 ami de ) , polybutadiene-copolymers, and the like.
  • the polymer should be selected in conjunction with the activating hydrogen peroxide liquid so as to be dissolvable, swellable, or otherwise permeable to said activating liquid. Such permeability is normally desired to permit efficient contact between the activating liquid, the chemiluminescent material, and (when desired or necessary) the fluorescer.
  • Some useful polymer- solvent combinations are: 1) poly (vinyl pyrrolidone) - water, 2) poly (vinyl styrene-polydivinyl benzene) copolymer-ethylbenzene, 3) poly (vinyl chloride-ethyl benzoate), 4) poly(methyl methacrylate dimethyl phthalate) .
  • the permeability of polymers to solvents is, of course, well known to the art and it is a straightforward matter to select useful polymer/solvent combinations. Solvents used as plasticizers are particularly advantageous.
  • the activating liquid should provide at least partial solubility.
  • the polymer could be plasticized with a solubilizing plasticizer.
  • the moist powder of the resulting chemiluminescent reactant composition has a consistency similar to light brown sugar. Due to the cohesive nature of the fluidizable solid admixture, it has been found to be beneficial to deagglomerate or loosen any compressed portions by a method such as by being sifted through a screen mesh or stirred with a whisking tool to insure that the moist powder would not become compacted prior to use. To aid in material placement, a vibratory feed system may be used as well. Although the above serve as examples for loosening compacted portions, any means for deagglomerating the fluidizable solid admixture may be
  • the formable, chemiluminescent reactant composition thus comprises a first chemilu inescently reactive component in combination with an amount of first polymeric resin particles effective to yield a uniform dispersion, visualized as a liquid slurry.
  • An amount of second polymeric resin particles in combination with the uniform dispersion in an amount effective to yield a fluidizable solid admixture is then provided. This fluidizable solid admixture may be molded to form a specific shape.
  • a means for deagglomerating the fluidizable solid admixture may be provided in order to loosen any portions of the mass which may have been compacted during preparation.
  • a means to cure the fluidizable solid admixture may also be provided either with or without the use of a mold.
  • the first polymeric resin particles and second polymeric resin particles are each a polyvinyl chloride resin.
  • an activator solution is commonly added to a composition to commence the emission of light, the oxalate and activator of the instant invention may be interchangeable. In such a case the first chemiluminescently reactive component might comprise an oxalate, and the ⁇ second chemiluminescently reactive component might then comprise an activator.
  • a chemiluminescent composition of the present invention comprises a first chemiluminescent reactant including a first chemiluminescently reactive component in combination with an amount of first polymeric resin particles effective to yield a uniform dispersion and an amount of second polymeric resin particles in combination with the uniform dispersion in an amount effective to yield a fluidizable solid admixture.
  • a second chemiluminescent reactant component is included, wherein contact between the first and second chemiluminescent reactant components will result in the generation of light.
  • the generation of light includes at least one distinct wavelength, within the visible or invisible spectrum.
  • a means may be provided to controllably activate the fluidizable solid admixture .
  • a multi-dimensional chemiluminescent device is also disclosed comprising at least one first chemiluminescent reactant including a first chemiluminescently reactive component in combination with an amount of first polymeric resin particles effective to yield a uniform dispersion and an amount of second polymeric resin particles in combination with the uniform dispersion in an amount effective to yield a fluidizable solid admixture.
  • At least one fluidizable solid admixture is dispersed within a multi-dimensional container, whereby densification of the fluidizable solid admixture causes the formation of the multi-dimensional chemiluminescent device.
  • Contacting the device with a second chemiluminescent reactant component will result in generation of chemiluminescent light.
  • the resulting emission of light may be of more than one distinct wavelength or color.
  • Means for compacting or densification of the fluidizable solid admixture thereby provide a means to controllably activate the fluidizable solid admixture and may be accomplished by a variety of techniques all contemplated by the instant invention.
  • the densification of the fluidizable solid admixture is by a molding technique, wherein a moldable object is formed or a hollow object is formed having areas of controlled densification.
  • a process for the production of a chemiluminescent reactant composition of the instant invention comprises providing a first polymeric resin, then combining a first chemiluminescently reactive component, typically in solution form, with an effective amount of the first polymeric resin to create a slurry.
  • a second polymeric resin is provided which is combined with the slurry in an amount effective to create a fluidizable solid admixture.
  • a means for providing controllable activation of the fluidizable solid admixture is also included which may be accomplished by compacting the admixture to a desired degree. As illustrated in Figure 1, the more compact the mass, the longer it takes to reach a peak light output.
  • This fluidizable solid admixture is significantly different than the liquid slurry taught in U.S. Pat. No. 5,173,218 in that it is not a liquid and will not seek its own level.
  • the fluidizable solid admixture is also significantly different from the paste described in U.S. Pat. No. 3,816,325 in that it is flowable, but will neither sag nor slump. Most significantly, this powder composition has an intrinsically high degree of porosity and interconnecting, interstitial air spaces.
  • the fluidizable solid admixture has a cohesive nature which permits it to be formed into definite, solid shapes by simply pressing the moist powder together with a gentle force.
  • the material may be manipulated with a human hand, or placed between two plates to create a thin sheet.
  • the cohesion exhibited by the moist powder is sufficient to retain a desired shape after pressing.
  • the fluidizable solid admixture may be pressed into small cakes either with or without the use of forms and simply cured by baking in an oven whereupon the individual particles in the powder bond together into a single porous mass.
  • the fluidizable solid admixture may be placed into a mold and baked (cured) to form a solid object which has a shape precisely matching that of the mold. Since the moist powder, once slightly compacted, is not flowable such as a dry powder or liquid slurry would be, the fluidizable solid admixture of the instant invention may be shaped, processed, or otherwise manipulated in such a manner that a hollow object is produced. Such hollow chemiluminescent objects have great value in that the outer, light-emitting surface of the object may be formed into any desired shape while maintaining a hollow interior.
  • This hollow interior not only permits conservation of chemiluminescent material and thereby reduces cost, but also allows relatively large chemiluminescent objects to be produced which exhibit a high surface brightness at minimal cost .
  • PVC is the preferred polymeric resin
  • the polymeric composition is not limited thereto.
  • Various methods for shaping and/ ⁇ r processing are applicable to the chemiluminescent reactant composition of the present invention. Examples of such methods include, but are not limited to, injection molding, extrusion, compression molding, cast molding, powder molding, or electrostatic deposition, such as xerography.
  • Powder molding comprises dry blending the moist powder and a curable additive to form a moldable composition.
  • the fluidizable solid admixture may be deposited electrostatically through a process such as xerography, wherein the surface of a container retaining the chemiluminescent reactant composition is given an electric charge. Adhesion between the chemiluminescent reactant composition and the container surface occurs only at the charged areas to enable particular placement of a chemiluminescent reactant composition within a container.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Luminescent Compositions (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

L'invention concerne une composition réactive chimioluminescente poreuse, formable (11). Cette composition comprend un mélange solide fluidifiable (12) qui peut être traité de manière à prendre une forme plus ou moins rigide, avec ou sans utilisation d'un moule. Ce solide traité peut être utilisé en tant que composant réactif chimioluminescent dans des environnements variés.
PCT/US2003/002035 2002-02-12 2003-01-23 Compositions reactives chimioluminescentes poreuses, formables, et dispositif pour ces compositions WO2004013249A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
MXPA04007835A MXPA04007835A (es) 2002-02-12 2003-01-23 Composiciones reactivas que se pueden formar porosas, quimioluminescentes y aparato para las mismas.
AU2003214881A AU2003214881A1 (en) 2002-02-12 2003-01-23 Formable, porous, chemiluminescent reactant compositions and device therefor
CA2476317A CA2476317C (fr) 2002-02-12 2003-01-23 Compositions reactives chimioluminescentes poreuses, formables, et dispositif pour ces compositions
KR1020047012445A KR100945094B1 (ko) 2002-02-12 2003-01-23 성형가능한 다공성 화학발광 반응체 조성물 및 그 장치
JP2004525960A JP3996165B2 (ja) 2002-02-12 2003-01-23 形状化が可能な多孔性の化学発光反応体組成物及びその装置
EP03710724A EP1481034A4 (fr) 2002-02-12 2003-01-23 Compositions reactives chimioluminescentes poreuses, formables, et dispositif pour ces compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7606102A 2002-02-12 2002-02-12
US10/076,061 2002-02-12

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WO2004013249A1 true WO2004013249A1 (fr) 2004-02-12

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EP (1) EP1481034A4 (fr)
JP (1) JP3996165B2 (fr)
KR (1) KR100945094B1 (fr)
CN (1) CN1643103A (fr)
AU (1) AU2003214881A1 (fr)
CA (1) CA2476317C (fr)
MX (1) MXPA04007835A (fr)
WO (1) WO2004013249A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2005202648B2 (en) * 2004-08-13 2008-04-24 Glowstix Australia Pty Limited A chemiluminescent article

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3808414A (en) * 1972-12-21 1974-04-30 American Cyanamid Co Device for the packaging of a three or more component chemiluminescent system
US3994820A (en) * 1972-06-19 1976-11-30 American Cyanamid Company Polymers in oxalate chemiluminescent systems
US5158349A (en) * 1991-07-03 1992-10-27 Lexington & Associates, Inc. Multi-color chemical lighting device
US5173218A (en) * 1990-12-24 1992-12-22 American Cyanamid Company Preparation of chemiluminescent vinyl halide or vinylidene halide polymer structures

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3774022A (en) * 1965-06-30 1973-11-20 Trw Inc Packaged chemiluminescent material
TWI285671B (en) * 1998-10-13 2007-08-21 Orion 21 A D Pty Ltd Luminescent gel coats and moldable resins
US6207077B1 (en) * 2000-02-18 2001-03-27 Orion 21 A.D. Pty Ltd Luminescent gel coats and moldable resins
DE60301883T2 (de) * 2002-06-03 2006-07-27 Urs Tanner Kurbel mit freilauf
US20050158349A1 (en) * 2004-01-20 2005-07-21 Jampani Hanuman B. Two-phase compositions containing alcohol

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3994820A (en) * 1972-06-19 1976-11-30 American Cyanamid Company Polymers in oxalate chemiluminescent systems
US3808414A (en) * 1972-12-21 1974-04-30 American Cyanamid Co Device for the packaging of a three or more component chemiluminescent system
US5173218A (en) * 1990-12-24 1992-12-22 American Cyanamid Company Preparation of chemiluminescent vinyl halide or vinylidene halide polymer structures
US5158349A (en) * 1991-07-03 1992-10-27 Lexington & Associates, Inc. Multi-color chemical lighting device

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1481034A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2005202648B2 (en) * 2004-08-13 2008-04-24 Glowstix Australia Pty Limited A chemiluminescent article

Also Published As

Publication number Publication date
KR20050004778A (ko) 2005-01-12
CN1643103A (zh) 2005-07-20
EP1481034A1 (fr) 2004-12-01
JP3996165B2 (ja) 2007-10-24
EP1481034A4 (fr) 2009-04-29
CA2476317C (fr) 2014-03-11
MXPA04007835A (es) 2005-09-30
KR100945094B1 (ko) 2010-03-02
JP2005534768A (ja) 2005-11-17
AU2003214881A1 (en) 2004-02-23
CA2476317A1 (fr) 2004-02-12

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