JP2005534768A - Porous chemiluminescent reactant composition capable of shaping and apparatus therefor - Google Patents

Abstract

Disclosed is a porous chemiluminescent reactant composition, device (11), and method of manufacture thereof that can be shaped. The flowable solid mixture (12) of the present invention can be cured to a generally rigid shape with or without the use of a mold. The cured solid is useful as a chemiluminescent reactant component and is useful in a variety of environments.

Description

  The present invention is directed to the field of chemiluminescent compositions, and more particularly to an apparatus for generating light from a fixed chemiluminescent material.

  The terms “chemiluminescent reactant”, “chemiluminescently reactive”, or “chemiluminescent reactant composition” are used in the methods disclosed herein. And is taken to mean a mixture or component thereof that produces chemiluminescent light when reacted with other necessary reactants.

  The term “fluorescent compound” is taken to mean a compound that fluoresces in a chemiluminescent reaction.

  The term “chemiluminescent composition” is taken to mean a mixture resulting from chemiluminescence.

  The term “deagglomerate” is taken to mean crushing or loosening the compressed part of the cluster or agglomerate.

  The term “fluidizable solid admixture” is taken to mean a mixture that, when stirred, behaves as a pseudo-fluid but is not a liquid having a solid character in the stationary state.

  In general, the generation of chemiluminescent light utilizes a two-component system to chemically generate light. Chemiluminescent light is generated by mixing the two components, and it is usually present in the form of a chemical solution called the “oxalate” component and the “activator” component. . All suitable oxalate and activator compositions containing various additives such as fluorescent agents, catalysts, etc. known to be beneficial in the prior art are contemplated for use in the present invention.

  The two components are physically separated and stored prior to activation by various means. In many cases, a sealed fragile glass bottle containing one component is housed in a container having outer flexibility containing the other component. This outer container is sealed to contain both the second component and a full fragile glass bottle. For example, the force generated by the close contact with the internal glass bottle breaks the glass bottle by bending, thereby releasing the first component and mixing the first and second components to generate light. Make it possible to do. Since the purpose of this type of device is to obtain a usable light output, the outer container is usually composed of a transparent or translucent material such as polyethylene or polypropylene. This in turn allows light generated by the chemiluminescent system to be transmitted through the container wall. These devices can also be designed to transmit various colors by adding either dyes or fluorescent compounds to one or both of the chemiluminescent reactant compositions or to the container. Furthermore, the device could be modified to transmit only certain selected light.

  An example of such a chemiluminescent system is Kaplan US Pat. No. 5,048,851. Kaplan discloses a polygonal chemiluminescent lighting device that concentrates light at the corners of the device, which improves the visibility of the light emitted from the light bar portion of the device, and the amount of light and light emitted. The distribution is optimized.

  US Pat. No. 4,626,383 to Richter et al. Discloses a chemiluminescent catalyst in a method for producing light at high intensity and low temperature in a short time. The present invention relates to a catalyst for a two-component chemiluminescent system, one component being a hydrogen peroxide component and the other being an oxalate-phosphor component. Teaches lithium carboxylate catalysts such as lithium salicyl salts that reduce the activation energy of the reaction and also reduce the temperature dependence of the light emission process.

  US Pat. No. 5,121,302 to Bay et al. Describes a solid, thin chemiluminescent device that emits light in one direction. This apparatus is composed of a back sheet and two front sheets made of a thin film metal foil that seals heat at its end, and temporary separation means arranged to divide the internal region into two chambers. ing. The two front sheets include a first part made of a thin film metal foil and a second part made of a transparent or translucent polyolefin sheet. These two metal foils provide thermal stability, increased shelf life, and relative impermeability to the volatile components of the activator solution. Metal foil thin films for active agent solution storage make it possible to retain the ability of the active agent solution due to the impermeability of the metal foil.

  Dorney US Pat. No. 6,062,380 discloses a glow cup system with illumination function. This device is generally a cylindrical container made of a semi-rigid material, and in a preferred embodiment, the device is made of a translucent synthetic resin material, and its shape is somewhat temporary by applying pressure from the side. Limited flexibility is given to the outer wall of the cup so that it can be changed. The inside of the cup sidewall is hollow. The cavity contains a plurality of rupturable ampoules containing a chemiluminescent fluid. The chemiluminescent fluid in the ampoule is oxalate. The second chemiluminescent fluid is located in the cavity such that when the ampoule breaks open, the two fluids come into contact to provide illumination. The ampoule is ruptured by the user pressure on the outer layer of the cup at the tip of the cavity. A plug is provided at the bottom of the cup. The plug may or may not be removable, but in any event the plug seals the second chemiluminescent component in the cavity space.

  Furthermore, it is desirable to generate chemiluminescent light from objects of various shapes or forms. Elliott U.S. Pat. No. 4,814,949 discloses a means for producing formed two-dimensional chemiluminescent objects. Conventional liquid chemiluminescent reagents are added to generate light. The nonwoven absorbent material of the desired shape can absorb the chemiluminescent reagent after mixing and activation so that the absorbent emits light from the desired shape. The shape may be simple or complex as desired, but is substantially limited to a two-dimensional surface, and is further limited to the generation of monochromatic light per device.

  An example of a chemiluminescent system that can produce light from a swellable polymer composition is disclosed in US Pat. No. 3,816,325 to Lowhat et al. Two main means have been used to form solid state chemiluminescent systems. The first system relies on the diffusion of the chemiluminescent oxalate solution onto a solid polymer surface such as a flexible length of vinyl tubing. A diffusion process occurs when a length of vinyl tube is immersed in a suitable chemiluminescent reagent for a long period of time. After removing the vinyl tube from the oxalate solution, the vinyl tube emits light by the attachment of the liquid activator to the vinyl tube surface. Since solid polymers are not relatively porous, it is difficult to rapidly and fully activate the oxalate in the vinyl tube. This is because a relatively slow diffusion process must be relied upon to enable the activator solution to reach the chemiluminescent reagent diffused in the polymer before it can generate light. is there.

  In a further embodiment of U.S. Pat. No. 3,816,325, a chemiluminescent oxalate solution is mixed with polyvinyl chloride (PVC) resin powder to produce a paste, which is applied to the surface and baked in an oven; A thin film having flexibility and elasticity is formed. While this embodiment is effective, the polyvinyl chloride sheet exhibits weaknesses in uniformity, strength, flexibility, and most importantly porosity. In addition, the method is mainly suitable for producing only relatively thin objects.

  US Pat. No. 5,173,218 to Cohen et al. Discloses the bonding of PVC polymeric resins to produce porous and flexible chemiluminescent structures from liquid slurries. Despite improvements over the prior art, the manufactured products still have various drawbacks. In particular, in the case of solids, the chemiluminescent object is relatively flat and produces something other than a thin object. The thin “pad” is produced from a mixture of strong and flexible polymeric resins and exhibits satisfactory absorption characteristics of the activator fluid. However, the method taught concentrates on the manufacture of pads made by injecting a mixture of liquid slurry into the mold. The shape of such a slurry and the resulting pad is limited to the shape of the mold in which the slurry is poured and stays. In addition, the formulations and methods utilized in the prior art provide a chemiluminescent pad that has a relatively tough and impermeable “skin”, whenever the slurry is in contact with the mold during the firing process. It is well known to those skilled in the art that it will produce. This coating is easily recognized as a darker and more transparent pad area and is highly impervious. As a result, it is impossible to rapidly absorb the liquid activator solution, resulting in a drastic decrease in the light output of the device. Although the thickness of this coating varies with the firing time and temperature, anyway, this coating is a wasteful part that can hardly produce usable light. It is clear that this film is formed because of the inability to draw air (or other gas) into the slurry during the firing process. In order to obtain a sufficiently porous product, air must enter the slurry mixture from the exposed surface of the slurry pool (the part where the slurry is stored) during the firing process. During the curing process, air is typically drawn into the pad to replace the capacity occupied by the solvent absorbed by the PVC resin. This process continues with air traveling in the depth direction within the pad so that the upper region of the pad is first cured and then the lower region of the pad is continuously cured. First, air enters the pad during the firing process which determines the porosity of the small holes and then determines the absorbency of the pad. At some point during the firing process described above, the bottom of the mold will contain a mixture of slurries in contact with the mold area, even though no air flow path is formed from the exposed surface of the slurry to the lower area. The temperature will begin to harden and harden. This “bottom up” cure is tough and dense at the bottom of the mold, locally in the region closest to the end of the mold, due to the lack of air available for the solidified slurry. Producing a pad that is substantially non-porous. If the mold bottom is placed on the thermally cool agglomerate of the curing device, the adverse effects of this bottom-up curing process can be minimized, thereby heating and curing the slurry bottom following the remainder of the slurry. Can provide. Nevertheless, the undesired formation of a tough and impermeable coating remains unresolved.

  As disclosed in US Pat. No. 5,173,218, during the firing process, the slurry expands as air is drawn into the polymer matrix, and the air increases the volume of the polymer matrix. As a result, significant problems arise when trying to cure this relatively large amount of slurry. For example, as taught in US Pat. No. 5,173,218, when a mixture of liquid slurries is poured into a test tube and fired for an appropriate time for curing, a dense and tough agglomerate is very poor. Produced with a good porosity, and therefore most of the agglomerates are produced with insufficient absorbency. This is somewhat due to the “bottom-up” curing process described above, and the presence of a liquid-impermeable liquid layer on the slurry cured near the mold bottom reduces the amount of air drawn into the slurry during the curing process. This is enough. Furthermore, it has been surprisingly found that if the slurry is prevented from diffusing during the curing process, the slurry material will not be drawn into the required amount of air. In the case of the test tube described above, the slurry is contained in the required amount of air in order to produce a cured matrix with the high degree of porosity and absorbency necessary to enable activation of the product containing the liquid activator. The side wall of the test tube is restrained from being diffused and drawn in. Even if the slurry diffuses freely vertically in the test tube during the curing process, the lateral constraints on the slurry by the test tube walls prevent optimal diffusion of the slurry and air introduction into the agglomerates. Enough. Aggregates thus cured exhibit low porosity, which is a limitation of the prior art, and cannot produce sufficient light output.

  It is often desirable to provide chemiluminescent devices that generate light of various colors, not just light. U.S. Pat. No. 5,508,893 to Norwork et al. Is directed to a multicolor chemiluminescent lighting device and method for manufacturing the product. The apparatus includes at least one barrier between a flexible tube at least partially filled with an active agent solution, a plurality of ampoules containing an oxalate solution disposed in the tube, and an ampoule to prevent color mixing. It consists of elements. This device can impart different chemiluminescent colors following activation.

  US Pat. No. 5,705,103 to Chopdeker et al. Describes a composition for generating chemiluminescent light over a controllable period. This composition is composed of an oxalate component (including an oxalate ester) in a solvent, an activator component (peroxide compound and catalyst) in the solvent, and a phosphor. By appropriate selection of the molecular weight of the homopolymer for the oxalate component, the total emission time and emission point control can be varied within the time that the onset of photogeneration occurs. This device provides a controllable time or stability of the light, but does not suggest any composition that controls the generation of the gas produced or a container-independent composition and can be shaped It is not porous.

  Thus, what is lacking in the prior art is to produce a highly porous composition for producing self-luminous three-dimensional objects by means of chemiluminescence and exhibiting rapid activation and excellent light output. Means. In addition, the prior art provides a product that is independent of the container, minimizes dark areas due to gas generation, and can simultaneously generate multiple spatially separated colors or wavelengths of chemiluminescent light. It is failing to predict.

US Pat. No. 5,048,851 US Pat. No. 4,626,383 US Pat. No. 5,121,302 US Pat. No. 6,062,380 U.S. Pat. No. 4,814,949 U.S. Pat. No. 3,816,325 US Pat. No. 5,173,218 US Pat. No. 5,508,893 US Pat. No. 5,705,103

Summary of invention

  The present invention teaches means for producing a self-luminous three-dimensional object. This three-dimensional object can be as simple or complex as desired. This three-dimensional object is manufactured by a method of obtaining a formable chemiluminescent reactant composition. This composition is of a type that can be easily placed in containers of various shapes and that cures in the container in which the composition solidifies, and has a shape that exactly matches the container formed. doing. Once formed, the composition is semi-rigid and can be removed from the container if desired. Further, the present invention provides a chemiluminescent reactant composition having a high degree of porosity and is not limited to a relatively flat and elongated piece of material as in the prior art. Also, the object produced according to the present invention may be hollow to produce a three-dimensional object that emits light with minimal material. Furthermore, these objects may be multicolored. That is, multiple spatially separated colors or wavelengths of chemiluminescent light can be generated simultaneously from a single object.

  The basic object of the present invention is that a large part of the interstitial space of the solid product required for rapid and reliable activation by the liquid activator is formed before curing. As such, chemiluminescent systems are less likely to create porosity during the curing process where air must be supplied externally into the matrix. Since the final porosity of the inventive product is primarily a function of the degree of densification prior to curing, the final porosity of the product is accurately and effectively controlled.

  In general, it is desirable to provide a product that activates as quickly as possible. In order for this to occur, the activator solution needs to react rapidly and completely with the oxalate of the chemiluminescent system. However, it may be desirable to slow the reaction rate, or perhaps at least the rate at which the active agent reaches the oxalate component and reacts with the oxalate component. Since the product of the present invention can be densified to any desired degree in practice, the available interstitial space where the active agent is in communication with the solid product can be reduced as desired, and as a result, The mobility of the active agent and the ability of the active agent to react with the solid oxalate component will be reduced. Furthermore, since most of the porosity of the chemiluminescent solid is determined by the degree of densification before curing, the product of the present invention can be cured in a relatively narrow space such as a test tube. The resulting product has a high porosity and is receptive to the activator solution.

  Accordingly, it is an object of the present invention to provide a means for producing a three-dimensional object that can self-emit via chemiluminescence and that generates multiple spatially separated colors or wavelengths simultaneously.

  A further object of the present invention is to produce a three-dimensional chemiluminescent material having a high degree of porosity.

  It is a further object of the present invention to provide a three-dimensional chemiluminescent material whose porosity can be easily and accurately controlled.

  It is a further object of the present invention to provide a three-dimensional chemiluminescent material produced by molding in a mold that does not cause significant expansion of the chemiluminescent reactant composition during the curing process.

  Another object of the present invention is to provide a three-dimensional chemiluminescent that has little or no dark regions due to the “film” effect caused by insufficient curing.

  A further object of the present invention is to provide a three-dimensional chemiluminescent material formed in such a manner that the object is hollow.

  It is a further object of the present invention to provide a three-dimensional chemiluminescent object in which a substantial portion of porosity is generated prior to the curing process.

  Yet another object of the present invention is to provide a formulation of a chemiluminescent reaction composition that can be shaped and as such can be easily shaped into the desired shape, regardless of the use of a mold. It is to be.

  Other objects and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, illustrated by way of example, of embodiments of the invention and embodiments. The drawings form part of the present specification and include exemplary embodiments of the present invention to illustrate various objects and features thereof.

  The present invention is directed to formulations, manufacturing methods and apparatus used in connection with a shapeable chemiluminescent reactant composition and can also be used to manufacture multidimensional objects. This composition overcomes the weaknesses of the prior art and meets the use of new forming methods applied to chemiluminescent materials, thereby providing chemiluminescent objects with high porosity and unique morphology. . The method of the present invention is not limited to conventional molding methods for producing relatively thin and flat objects as described in the prior art.

  The porous powder that can be shaped according to the present invention can be easily compressed to various degrees, and can form relatively strong, flexible, and highly porous aggregates during heat curing. The apparent density of the material can be easily controlled by the degree of compression or densification. Thus, any desired apparent density object can be produced. Since the apparent density directly affects the absorption rate of the active agent, the activation rate of chemiluminescence will be effectively controlled.

  Now, with respect to the drawings, FIG. 1 is a diagram showing how the bulk density control is used varying with activation time. Two devices were manufactured and tested. These two devices both consist of a chemiluminescent reactant composition in the form of a solid oxalate containing components called solid oxalate below. The first device had a bulk density of about 0.54 g / cc and reached maximum light output in about 10 minutes after activation. The second device had a bulk density of about 0.72 g / cc, and the light output peaked about 37 minutes after activation. This data shows that more compressed objects take longer to activate and therefore activation time is affected by bulk density. The ability to control the light output curve enables the production of chemiluminescent devices to meet the great demands of the market.

  As an example, in the production of large chemiluminescent objects, there is a diminishing return effect so that light generated from deep within the solid form does not reach the surface sufficiently and is not emitted as useful light. Thus, a hollow chemiluminescent shape would be preferred over a solid chemiluminescent shape. Further, the hollow chemiluminescent feature provides a convenient and accurate means for supplying the product with the second reactant component. An ampoule or container containing the second reactant component will be placed in the hollow space. When the ampoule or container is cracked, the second reactant component is easily absorbed by the inner surface of the hollow portion until the entire wetted chemiluminescence produces light, and the capillary through the porous chemiluminescent matrix Move quickly depending on the phenomenon. Arranging the second reactant component in the void means hiding it from view, enabling the production of a more aesthetic and satisfying product.

  Among the forms produced using the teachings of the present invention are chemiluminescent candles. Such candles provide a safe and reliable alternative to real candles. Flames from real candles can ignite other objects. Unlike traditional candles, chemiluminescent candles are windproof and waterproof, and by using the present invention, emit any light of any color, or any combination of colors and wavelengths, from a single device. Can be manufactured as follows.

  In making these “candles” using a chemiluminescent system as a light source, previous attempts have been weak. Usually, in a chemiluminescent lighting device such as a light rod using liquid, a space is provided at the tip portion of the device occupying about 30% of the container volume. Light cannot be generated in the space region at the tip. Japanese Patent Application No. 10-170263 (Japanese Patent Laid-Open No. 2000-11701) discloses that a gas tip space (or bubble) above a liquid chemiluminescent fluid in a sealed chemiluminescent device is placed in a region other than the top. Disclosed is a bubble trapping means for confinement. For example, by moving the bubble from the top of a sealed chemiluminescent device such as a candle, the entire tip of the candle flame will appear to emit light during the chemiluminescent reaction. Since no light is generated in the area where the bubbles are present, if the bubbles remain at the tip of the flame, a dark area is formed near the tip of the flame. Such dark areas will impair the overall visual acceptability of the device. Carbon dioxide, carbon monoxide, and oxygen are common gases that are liberated in the peroxide luminescence system. These gases rise to the tip of the liquid chemiluminescence system and form bubbles at the tip of the device. Therefore, the device disclosed in Japanese Patent Application No. 10-170263 can effectively eliminate the problem of bubbles formed at the tip of the chemiluminescent device at the beginning, but it occurs in the process of chemiluminescence. No method is provided to replace the bubbles. The present invention makes it possible to produce a candle or chemiluminescent object that eliminates the tip space bubbles in the device at the initial stage and the significant increase in bubbles in the device where the chemiluminescent process is in progress. And Furthermore, the present invention does not require any specially shaped traps, channels, or valves in the device to realize this advantage. Since the agglomerates that can be shaped into the chemiluminescent system of the present invention are solid, there is no space for bubbles to collect and bind. Gases generated during the chemiluminescence process are still produced, but these gases are evenly distributed in the solid, with the rise inside the agglomerates that can be shaped into a solid being suppressed. This in turn makes it possible to continuously produce a perfect light output.

  FIG. 2 shows a preferred embodiment of the present invention as a chemiluminescent candle 10 with an envelope blow molded into the shape of a candlestick. When the device is activated, the candle flame shines.

  As shown in FIG. 3, the candle envelope 11 may be manufactured from materials such as, but not limited to, polyethylene or polypropylene by blow molding or other suitable forming means. Preferably, the end of the candle envelope opposite the flame shape is open. The candle envelope 11 is formed with the open end on top. The formable chemiluminescent reactant composition 12 of the present invention is placed in a candle envelope 11 so as to partially fill the envelope. The fluidized solid mixture may overflow, but also forms a wet powder that is sticky and can be filled and shaped. Thus, auxiliary supply means such as a vibratory feeder may help to facilitate the supply of the shapeable chemiluminescent reactant composition 12. The shapeable chemiluminescent reaction composition 12, once placed in the candle envelope 11, will be slightly compressed by the filler 13 for this purpose, as shown in FIG. This compression process not only helps to support the composition to conform to the shape of the candle envelope 11, but also densifies and compresses so that it does not flow through the candle envelope 11, or the orientation of the envelope has been altered. If so, it is densified and compressed to move further. However, if desired, the composition could be removed from the envelope by applying sufficient vibrational force to cause liquefaction of the compressed chemiluminescent reactant composition 15. In addition to compressing the composition, the filler 13 may have a tapered tip 14 so as to form a cavity 16 in the resulting compressed composition, as shown in FIG. . The cavity 16 provides a convenient means for facilitating the distribution of the second chemiluminescent reactant component 18, as shown in the ampule 17, and facilitates rapid and even activation of the device. Once the second chemiluminescent reactant component is in place, the open end of the candle envelope 11 is heat sealed with a plug 19. Furthermore, the cavities 16 provide a space for the composition to diffuse during the curing process so that an exceptionally porous product is obtained. The cavities are not only necessary to produce a product with a high degree of porosity, but may be used in certain cases such as producing products with exceptional exceptional porosity. Such a cavity is not possible with the methods taught in the prior art.

  As shown in FIG. 6, the chemiluminescent rose-shaped envelope 21 is first manufactured by blow molding, for example, into a rose bud shape having a stem from polyethylene. The stem diameter is much smaller than the bud diameter. In this preferred embodiment, it is desirable to produce rose buds whose entire surface is illuminated with chemiluminescence. It is also desirable to produce items that use the least chemiluminescent material capable of producing the desired effect. The rose-shaped envelope 21 is filled with a small amount of the chemiluminescent reactant composition 12 that can be shaped.

  Referring to FIG. 7, a compression tool 23 having a hollow needle 23 with an inflatable bladder 24 is inserted into a rose-shaped envelope 21 having a chemiluminescent reactant composition 12 therein, and by way of example. The bladder 24 is depicted as being held by at least one retaining ring 25. The end of the hollow needle 23 is plugged, and the hole on the side of the needle below the inflatable bladder 24 fills the hollow needle with air pressure and allows the inflatable bladder 24 to be inflated. Yes. As shown in FIG. 8, the bladder is inflated by using air pressure for inflating purposes, so that the chemiluminescent reactant composition 12 that can be shaped to enclose a full bladder 24 has a rose bud portion. Press the inner wall of the envelope. FIG. 9 shows the chemiluminescent reactant composition 15 compressed into a semi-solid form. After this compression treatment, the air bag is removed with the cavity 16 left, and the needle is removed. Next, while the rose bud is placed in the envelope, the compressed chemiluminescent reactant composition is cured, preferably by baking at 95 ° C. for 10 minutes. After cooling the composition, a sealed ampoule containing a solution of the second chemiluminescent reactant component is inserted into the rose-shaped envelope 21 and the plug is attached to the stem, similar to the candle embodiment described above. And will be heat sealed to form a seal. The resulting product looks like a real rose bud that, when activated, emits light from the entire surface of the bud. By way of example, activation simply crushes the ampoule and flexes the stem of the rose to release the second chemiluminescent component that is absorbed into the chemiluminescent reactant composition or formable solid mixture. Is executed by. Because the compressed chemiluminescent reactant composition is highly compatible with the inner wall of the envelope, even details such as rose petals can be obtained by the method of the present invention.

  With the candle and rose embodiments described above, the solid product that is cured will remain in the polymeric envelope, but the material can be easily cast and cured in a mold and then removed. . Solid chemiluminescent materials will be manufactured using the present invention by utilizing, for example, compression or centrifugal casting. Individual shaped items produced by the method of the present invention can include unconstrained objects that will glow if placed in a container containing a solution of the second chemiluminescent reactant component. By way of example, such a system could generate a “snow globe” containing shining snow particles. Because the agglomerates that can be shaped into the chemiluminescent reactant composition of the present invention are in solid form, multiple colors that are fixed in position and in space may be used in a single device. For example, a red rose bud can be generated with bud portions having orange stripes.

  An important advantage of the present invention over a complete liquid chemiluminescent system such as found in conventional light bars is that the entire surface of the object shines as desired.

  Since the resulting product of the present invention is a solid state chemiluminescent material, the product could be used in situations where it is impractical or impossible to use a container-dependent liquid chemiluminescent system.

  The following examples describe experimental procedures that were performed to give the novelty of the present invention.

  A series of experiments were devised to identify the optimal materials and formulations necessary to produce a chemiluminescent reactant composition that can be shaped and has porosity. As taught in the prior art, the pre-slurry is about 2 parts by weight PVC resin (Geon # 121) to 98 parts by weight of the chemiluminescent reactant solution exemplified here as the oxalate solution. ) Can be dissolved. Also, according to US Pat. No. 5,173,218, 31 parts by weight of a PVC powder resin (Geon # 218) having a medium particle size and 9 parts by weight of a PVC resin (Geon # 30) having a large particle size, Is mixed with 59 parts by weight of the oxalate pre-slurry to prepare a slurry. The resulting material is an injectable liquid slurry.

Example 1-6
Six tests were performed to determine the effect of varying the slurry thickness, cure time and temperature on the porous. In each test, a small aluminum weighing pan placed on a spacer with the bottom of the weighing pan tilted slightly so that a slurry having a depth in the range of 0.015 inch to 0.180 inch is obtained. About 7 g of liquid slurry was placed on top. During each test, the weighing pan was placed on a wire rack of a circulating air oven. After curing for a predetermined time, each sample item was removed from the weighing pan and cut to investigate whether it had proper curing and porosity. It is clear that properly cured samples are those in which the entire oxalate solution is absorbed into the PVC matrix and does not show any signs of overcuring. With a properly cured matrix, smaller molecular weight PVC particles will melt. However, larger molecular weight PVC particles absorb liquid oxalate solutions while not melting much. If the curing time is excessively long and the temperature is excessively high, the PVC particles with higher molecular weights melt and are manifested by the presence of dark and / or bright areas in the cured sample called the pad. The result is an overcured matrix. This overcured matrix will exhibit very low porosity.

テスト項目１では、材料が生焼け状態であり、かなりの量の自由液体を含有しているので、ＰＶＣ粒子はシュウ酸塩溶液に完全に吸収されていないことは明らかである。テスト項目２〜５では、材料の生焼け状態は低下することが分かったが、各々硬化サンプルの露出表面だけが多孔性を有することが明らかとなった。 Table 1 shows the results obtained using various slurry cure conditions.

In Test Item 1, it is clear that the PVC particles are not completely absorbed by the oxalate solution because the material is in the burned state and contains a significant amount of free liquid. In test items 2 to 5, it was found that the burnt state of the material was lowered, but it was revealed that only the exposed surface of each cured sample had porosity.

  Each of test items 1-5 was activated using a chemiluminescent activator reagent. Test items 2-5 emitted light from the surface, but no significant light was generated from dark and non-porous areas. Test item 1 produced little light on most of its surface. This is probably because the liquid oxalate solution that was not absorbed into the PVC matrix during the curing process formed a barrier as if the activator solution prevented the subsurface liquid oxalate from reaching equilibrium. Conceivable. Some light was revealed near the surface of the matrix in the boundary layer where the activator and oxalate solution were combined. Test item 6 was cured at low temperature because test items 1-5 seemed to be in an overcured state due to the use of excessive heat causing melting of the high molecular weight PVC particles. However, the test result of test item 6 contradicted this assumption. The presence of a dark dense area where the pad touches the weighing pan was evident even at shorter times and at lower temperatures than used for the curing process in Test Item 6.

Example 7
Chemiluminescent candles were made using liquid slurry formulations similar to those used in tests 1-6 above. To make this candle, about 3.2 g of the liquid slurry was poured into a polyethylene candle envelope using a dropper. A glass ampoule containing a chemiluminescent activator was inserted into the slurry so that the lower end of the ampoule was in contact with the inner surface of the bottom of the candle envelope. The assembly was placed in a circulating air oven set set at 82 ° C. and cured for 12 minutes. After the assembly was removed from the oven set, the assembly was cooled to room temperature and the candle envelope and cured slurry were cut for observation. The PVC matrix (cured slurry) appeared to be fully cured but was dark and dense. The PVC matrix portion was removed from the envelope and placed on an aluminum weighing pan. A chemiluminescent activator reagent was added to those portions where the cured slurry was dim and emitting light. It was observed that the activator reacts only on the outermost surface of the cured slurry and cannot reach the interior of the cured slurry. It is determined that the lack of absorption of the active agent solution into the cured slurry is due to the very low porosity exhibited by the pad, not as a result of slurry overcuring or undercuring. The porous or small pore space within the matrix draws two sources. This less porous part is attributed to PVC particles already having small pores in the matrix. A more prominent factor determining the porosity due to the cured slurry is the aerodynamic capacity introduced into the entire slurry volume during the curing process. When utilizing the formation of a liquid slurry taught in US Pat. No. 5,173,218, if sufficient heat reaches the inner region to cure the slurry before the outer region is fully cured and porous For example, it was observed that the inner region was sufficiently cured even with low porosity. This effect is due to the inability of air to move in through the surrounding liquid region.

Example 8
In view of these results, the slurry sample was supported on an air permeable substrate, for example, a 10 cm × 10 cm, 2 mm thick nonwoven polyester felt, and placed in a circulating air oven to hold at 82 ° C. for 8 minutes. . This felt provides a uniform access of air to the slurry, and a non-dark and non-porous region is formed as a case in the pre-cured slurry in an impervious aluminum dish It was speculated that heat would cure the slurry from the outside as it was done. Each successive layer of slurry cured from the outside forms a small hole, which allows air to reach the subsequent layers. The sample is removed from the oven and cooled. It was noted that the pad did not have dark dense areas and had a large number of small holes in the inspection. The sample was activated with a chemiluminescent activator reagent that emitted light generally and evenly.

  A model that describes the interstitial space formulation in PVC particles / solvent slurry is that large, generally spherical PVC particles combine with smaller, low molecular weight PVC particles to form a matrix. The PVC particles first absorb the solvent that fills the interstitial space between these particles. If air enters the matrix during this curing process, the PVC particles swell and expand as the solvent is absorbed into the particles.

Example 9
A new slurry was made and tested to see if using larger particle size PVC particles with higher weight content could increase the amount of air passing through the slurry. . This new slurry contains 56 parts by weight pre-slurry, 29 parts by weight of a medium particle size resin (Geon # 218), and 15 parts by weight of a large particle size resin (Geon # 30). Yes. About 2.5 ml of this liquid slurry was added into a polyethylene candle envelope containing a glass activator ampoule. The sample was cured at 75 ° C. for 12 minutes and cooled. Detailed analysis revealed that the slurry had hardened but contained dark areas that were not yet porous.

  The speculation that PVC resin and liquid oxalate will be made has been developed and tested in a manner that results in a material that allows air to move through the formulation before and during curing.

Example 10
A new formulation was made using the pre-slurry in which about 2 parts by weight PVC resin (Geon # 121) was dissolved in 98 parts by weight oxalate solution. In this example, the liquid oxalate solution was propylene glycol dibenzoate, but any base compound of the prior art can be taken into account. In this new formulation, single PVC particles with higher weight content were used in place of the medium and large particle size PVC resins formulated in the slurry described above. About 40 parts by weight of the pre-slurry was added to 60 parts by weight of resin (Geon # 466). The resulting composition was not a liquid slurry, but rather a wet fillable shapeable powder characterized as a flowable solid mixture. The resin is selected to include a particle size and range sufficient to provide the flowable solid mixture. Although not limited to the examples, in this example, the resin is a PVC resin having a particle size distribution with an average particle size of about 125 μm.

  A wide variety of polymers could be used for the polymer component. Polyethylene, polypropylene, poly (vinyl chloride), poly (methyl methacrylate), poly (vinyl benzoate), poly (vinyl acetate), cellulose poly (vinyl pyrrolidone), polyacrylamide, epoxy resin, silicone resin, poly (vinyl butyral), Polyurethane, nylon, polyacetyl, polycarbonate, polyester, and polyether are non-limiting examples. Cross-linked polymers such as polystyrene-poly (divinylbenzene), polyacrylamide-poly (methylenebisacrylamide), polybutadiene copolymers and the like may be used. For most applications, the polymer should be selected in conjunction with the activated hydrogen peroxide liquid to be soluble, swellable, or otherwise permeable to the activated liquid. Such penetrability is usually desirable to allow effective contact between the activating liquid, the chemiluminescent material, and the fluorescent agent (as desired or required). In many cases, it is desirable to select polymers and activating liquids that provide a specific diffusion rate and thus control the intensity and duration of light emission. Useful polymer-solvent combinations are as follows. 1) Poly (vinylpyrrolidone) -water, 2) Poly (vinylstyrene-polydivinylbenzene) copolymer-ethylbenzene, 3) Poly (vinyl chloride-ethylbenzoate), 4) Poly (methyl methacrylate-dimethylphthalate) is there. The permeability of the polymer to the solvent is of course well known and selecting a useful polymer / solvent combination is a simple matter. Solvents used as plasticizers have particular advantages. If the polymer does not provide solubility in both the chemiluminescent material and the fluorescent agent, the activation liquid will provide at least partial solubility, but being soluble in the polymer is It is not necessary for either chemiluminescent materials or fluorescent agents. Instead, the polymer will be plasticized with a soluble plasticizer.

  The resulting wet powder of chemiluminescent reactant composition has a viscosity similar to light brown sugar. Due to the stickiness of the flowable solid mixture, it can be crushed to ensure that the wet powder is not compressed before use, or it can be stirred through a sieve such as a sieve or brush. It has been found beneficial to loosen the compression part by such a method. A vibration supply system could also be used to facilitate material placement. While the method described above serves as an example for loosening the compressed portion, any means for disrupting the flowable solid mixture could be used. Newly prepared formulations with the knowledge that pre-existing interstitial spaces in the material are important for the curing process are required for perfect chemiluminescent activator reagent absorption and corresponding light output. Within a certain amount of time, an immediate improvement was obtained.

  The chemiluminescent reaction composition that can be shaped in this way has a first chemiluminescent reaction component combined with the first polymeric resin particles in an amount effective to obtain a uniform dispersion visualized as a liquid slurry. have. A second polymeric resin particle amount is then provided that is uniformly dispersed and bound in an amount effective to obtain a flowable solid mixture. This flowable solid mixture can be molded to form a specific shape. Means for crushing the flowable solid mixture will be provided to loosen any portion of the agglomerates that were compressed in the preparatory stage. A means for curing the flowable solid mixture can also be provided with or without the use of a mold. In a preferred embodiment, each of the first polymer resin particles and the second polymer resin particles is a polyvinyl chloride resin. The activator solution is usually added to the ingredients to initiate light emission, but the oxalate and activator of the present invention can be interchangeable. In such a case, the first chemiluminescently reactive component may contain oxalate and the second chemiluminescently reactive component may comprise an activator. A component that selectively reacts in a first chemiluminescent manner may be constituted by an activator, and the component that reacts in a second chemiluminescent reaction may contain oxalate.

  In order to obtain a chemiluminescent system, a second chemiluminescently reactive component must be included. The chemiluminescent composition of the present invention comprises a first chemiluminescent reacting component combined with an effective amount of the first polymer resin particles to obtain a uniform dispersion, and a flowable solid mixture. A first chemiluminescent reactant containing second polymeric resin particles bonded in an effective amount to obtain a uniform dispersion. The second chemiluminescent reactant component is contained such that contact between the first chemiluminescent reactant component and the second chemiluminescent reactant component generates light. The light generation has at least one distinct wavelength in the visible or invisible spectrum. One means is provided for controllably activating the flowable solid mixture.

  The multidimensional chemiluminescent device also provides a flowable solid mixture with a first chemiluminescently reactive component combined with an amount of the first polymeric resin particles effective to obtain a uniform dispersion. And at least one first chemiluminescent reactant containing second polymer resin particles bonded in an effective amount with a uniform dispersion. At least one flowable solid mixture is dispersed within the multidimensional container, whereby densification of the flowable solid mixture causes formation of a multidimensional chemiluminescent device. Contact between the second chemiluminescent reaction component and the multidimensional chemiluminescent device will result in the generation of chemiluminescent light. As already mentioned, the resulting light emission will be one or more distinct wavelengths or colors. Thereby, the means for compression or densification of the flowable solid mixture provides a means to controllably activate the flowable solid mixture and is achieved by all the various techniques considered by the present invention. Will be done. As an example, densification of the flowable solid mixture is done by molding techniques, where a moldable object is formed or a hollow object is formed with a controlled densified region. . Density variation is an example of a control parameter for a photoluminescent reaction, resulting in a controllably activated object.

  The method for producing the chemiluminescent reaction composition of the present invention comprises preparing a first polymer resin and then using an amount of the first polymer resin effective to produce a slurry, usually in the form of a solution. To the chemiluminescent reacting component. The second polymeric resin is combined with the slurry in an amount effective to produce a flowable solid mixture. A means of obtaining a controllable activation of the flowable solid mixture will be achieved by compressing the mixture to the required extent. As shown in FIG. 1, the greater the degree of compression of the agglomerates, the longer it takes to reach the peak of light output.

  This flowable solid mixture differs significantly from the liquid slurry taught in US Pat. No. 5,173,218 in that it is not liquid and is not flat per se. Also, the flowable solid mixture is significantly different from the paste described in US Pat. No. 3,816,325 in that it is fluid but does not sag or fall. Most importantly, the powder composition has essentially high porosity and interstitial spaces that are interconnected. Furthermore, the flowable solid mixture has a tackiness that can be reliably formed into a solid form by simply pressing the wet powder with a gentle force. For example, the material is processed by human hands or placed between two plates to make a thin film sheet. Furthermore, the agglomeration exhibited by the wet powder is sufficient to maintain the desired shape after pressing. For example, a flowable solid mixture is pressed into small solids with or without the use of a formwork, and by simply baking in an oven, the individual particles in the powder combine into a single It becomes an agglomerate having porosity. In a variation, the flowable solid mixture may be placed in a mold and fired (cured) to form a solid object having a shape that exactly matches the shape of the mold. Because the wet powder once slightly compressed does not flow like a dry powder or liquid slurry, the flowable solid mixture of the present invention is formed and processed in such a way that a hollow body is produced, or It will be manufactured in another way. Such hollow chemiluminescent materials are of great value in that the hollow interior is maintained while the light emitting surface outside the object could be formed in any desired shape. This hollow interior allows for the protection of chemiluminescent materials, thus not only reducing costs, but also enabling the production of relatively large chemiluminescent materials that exhibit high surface brightness at a minimum cost.

  Although PVC is a preferred polymer resin, the polymer composition is not limited to this.

  Various formation and / or processing methods can be applied to the chemiluminescent reactant composition of the present invention. Such methods include, but are not limited to, electrostatic deposition methods such as injection molding, extrusion molding, compression molding, mold molding, powder molding, or xerography. Powder molding consists of a dry product in which a wet powder and a curable additive for forming a molding composition are mixed.

  Furthermore, the flowable solid mixture could be electrostatically deposited via a method such as xerography where a charge is applied to the surface of the container holding the chemiluminescent reactant composition. Adhesion between the chemiluminescent reactant composition and the container surface occurs only in the charged region that allows for special placement of the chemiluminescent reaction composition within the container.

  All patents and publications are incorporated by reference to the same extent as if each individual publication was clearly and individually shown to be incorporated by reference.

  While an embodiment of the invention is shown, it should be understood that the invention is not limited to the specific forms or methods described or shown herein. It will be apparent to those skilled in the art that various modifications may be made without departing from the scope of the invention, which is limited only as shown and described in the specification and drawings. is not. Those skilled in the art will readily recognize that the present invention is well suited to accomplishing its objectives and that in addition to these inherent ones, the present invention achieves the stated objects and advantages. The embodiments, methods, procedures and techniques described herein are representative of presently preferred embodiments and are intended to be exemplary and are not intended to limit the scope of the invention. . Variations and other uses of the present specification will fall within the spirit of the invention and will occur to those skilled in the art as defined by the appended claims. Although the invention has been described in terms of certain preferred embodiments, it is to be understood that the claimed invention should not be unnecessarily limited to such particular embodiments. . Indeed, various modifications of the above-described aspects for carrying out the invention which are obvious to those skilled in the art are intended to be within the scope of the following claims.

FIG. 4 is a diagram representing light output and activation time for different bulk densities of solid oxalate. 1 is a perspective view of an exemplary embodiment of the present invention. FIG. 3 is a cross-sectional view of the exemplary embodiment of FIG. 2 with a chemiluminescent reactant composition disposed thereon. FIG. 4 is a cross-sectional view of FIG. 3 illustrating densification of the chemiluminescent reactant composition by using a filler. FIG. 6 is a cross-sectional view of an exemplary embodiment after densification showing the ampule location of the second chemiluminescent reaction component and voids in the flowable solid mixture. FIG. 6 is a cross-sectional view of another exemplary embodiment of the present invention showing the location of the chemiluminescent reactant composition. FIG. 7 is a cross-sectional view of the embodiment of FIG. 6 showing the position of the compression tool in the chemiluminescent reactant composition. FIG. 8 is a cross-sectional view of an embodiment of the present invention in which the chemiluminescent reactant composition is densified by the compression tool of FIG. 7. 1 is a cross-sectional view of an embodiment of the present invention showing a densified chemiluminescent reactant composition.

Claims (50)

An effective amount of the chemiluminescent reactant solution and the first granular polymer resin to produce a slurry in a mixed state;
A chemiluminescent reactant composition comprising a second particulate polymeric resin mixed with the slurry in an amount effective to produce a flowable solid mixture.   The composition according to claim 1, wherein the flowable solid mixture is crushed.   The composition of claim 1, wherein the flowable solid mixture is cured.   The composition according to claim 1, wherein the composition is shaped to form the flowable solid mixture into a specific shape.   The composition of claim 1, wherein the first granular polymer resin is polyvinyl chloride.   The composition according to claim 1, wherein the second granular polymer resin is polyvinyl chloride.   The composition according to claim 6, wherein the second granular polymer resin is porous.   The composition of claim 6, wherein the second particulate polymeric resin has an average particle size distribution sufficient to provide the flowable solid mixture.   9. The composition of claim 8, wherein the second granular polymer resin has an average particle size of about 125 [mu] m.   The composition of claim 1, wherein the slurry comprises a uniform dispersion.   The composition of claim 1, wherein the chemiluminescent reactant solution comprises oxalate.   The composition of claim 1, wherein the chemiluminescent reactant solution comprises an activator. An amount of the chemiluminescent reactant solution and the first particulate polymer resin effective to produce a slurry in a mixed state, and a first amount mixed with the slurry in an amount effective to produce a flowable solid mixture. A first chemiluminescent reactant component containing two particulate polymer resins;
A second chemiluminescent reactant component;
A chemiluminescent composition wherein the contact between the first chemiluminescent reaction component and the second chemiluminescent reaction component causes the second chemiluminescent component to generate chemiluminescent light.   14. The composition of claim 13, wherein the flowable solid mixture is crushed.   14. The composition of claim 13, wherein the flowable solid mixture is cured.   14. The composition of claim 13, wherein the flowable solid mixture is shaped to form a specific shape.   The composition according to claim 13, wherein the first granular polymer resin is polyvinyl chloride.   The composition according to claim 13, wherein the second granular polymer resin is polyvinyl chloride.   The composition of claim 18, wherein the second granular polymer resin is porous polyvinyl chloride.   19. The composition of claim 18, wherein the second particulate polymeric resin has an average particle size distribution sufficient to supply the flowable solid mixture.   The composition of claim 13, wherein the slurry comprises a uniform dispersion.   14. The composition of claim 13, wherein the first chemiluminescent reactant component contains oxalate and the second chemiluminescent reactant component contains an activator.   14. The composition of claim 13, wherein the first chemiluminescent reactant component contains an activator and the second chemiluminescent reactant component contains oxalate.   14. The composition of claim 13, wherein the light generation includes at least one distinct wavelength or color.   14. The composition of claim 13, wherein the flowable solid mixture is controllably activated. Mixing the chemiluminescent reactant component with the first particulate polymeric resin in an effective amount to produce a slurry;
And a step of mixing the second granular polymer resin with the slurry in an amount effective to produce a solid mixture capable of flowing.   27. The method of claim 26, wherein the first particulate polymeric resin is polyvinyl chloride.   27. The method of claim 26, wherein the second particulate polymeric resin is polyvinyl chloride.   30. The method of claim 28, wherein the second granular polyvinyl chloride is porous.   30. The method of claim 28, wherein the second particulate polyvinyl chloride has an average particle size distribution sufficient to provide the flowable solid mixture.   27. The method of claim 26, wherein the slurry comprises a uniform dispersion.   27. The method of claim 26, wherein the flowable solid mixture is cured.   27. The method of claim 26, wherein the first chemiluminescent reactant component comprises oxalate.   27. The method of claim 26, wherein the first chemiluminescent reactant component contains an activator.   27. The method of claim 26, wherein the flowable solid mixture is disintegrated.   27. The method of claim 26, wherein the flowable solid mixture is formed into a specific shape. A first chemiluminescent reactant component having a first particulate polymeric resin in an effective amount to produce a slurry and mixed with the slurry in an effective amount to produce at least one flowable solid mixture. A multidimensional chemiluminescent device comprising at least one first chemiluminescent reactant composition containing the second granular polymer resin produced,
The at least one flowable solid mixture is dispersed in a multidimensional container, whereby densification of the flowable solid mixture results in a formulation of the multidimensional chemiluminescent device;
A multi-dimensional chemiluminescent device wherein the contact between the second chemiluminescent reactant component and the device generates chemiluminescent light.   38. The apparatus of claim 37, wherein the flowable solid mixture is crushed.   38. The apparatus of claim 37, wherein the flowable solid mixture is cured.   38. The apparatus of claim 37, wherein the flowable solid mixture is formed into a specific shape.   38. The apparatus of claim 37, wherein the first granular polymer resin is polyvinyl chloride.   38. The apparatus of claim 37, wherein the second granular polymer resin is polyvinyl chloride.   43. The apparatus of claim 42, wherein the second granular polyvinyl chloride is porous.   43. The apparatus of claim 42, wherein the second granular polyvinyl chloride has an average particle size distribution sufficient to obtain the flowable solid mixture.   38. The apparatus of claim 37, wherein the slurry comprises a uniform dispersion.   38. The apparatus of claim 37, wherein the first chemiluminescent reactant component contains oxalate and the second chemiluminescent reactant component contains an activator.   38. The apparatus of claim 37, wherein the first chemiluminescent reactant component contains an activator and the second chemiluminescent reactant component contains oxalate.   38. The apparatus of claim 37, wherein the light generation includes at least one distinct wavelength or color.   38. The apparatus of claim 37, wherein the densification is a means for controllably activating the flowable solid mixture.   38. The apparatus of claim 37, wherein the densification of the flowable solid mixture is accomplished by a molding technique that forms a hollow body.

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