KR20050004778A - Formable, porous, chemiluminescent reactant composition and device therefor - Google Patents

Abstract

A moldable porous chemiluminescent reactant composition, apparatus 11 thereof, and a method of making the same are disclosed. The flowable solid mixture 12 of the present invention can be cured to a somewhat rigid form regardless of the use of a mold. Cured solids are useful as chemiluminescent reactant components and can be used in a variety of environments.

Description

Formable porous chemiluminescent reactant composition and device {FORMABLE, POROUS, CHEMILUMINESCENT REACTANT COMPOSITION AND DEVICE THEREFOR}

"Chemiluminescent reactant", "chemiluminescent reactive" or "chemiluminescent reactant composition" means a mixture or component thereof that, when reacted with other essential reactants in the processes disclosed herein, generates chemiluminescent light.

"Fluorescent compound" means a compound that fluoresces in a chemiluminescent reaction.

"Chemical luminescent composition" means a mixture that generates chemiluminescence.

"Deagglomerate" means breaking or breaking up a dense part of a cluster or mass.

"Fluidable solid mixture" means a non-fluid mixture that behaves as a pseudo fluid during stirring but has the properties of a solid when stable.

In general, a two-component system for chemically generating light is used to generate chemiluminescent light. Chemiluminescent light is produced by combining two components, which are present in the form of a chemical solution referred to as an "oxalate" component and an "activator" component. All suitable oxalate and activator compositions can be used in the present invention, including various other fluorescent agents, catalysts, and the like, which have proven useful in the prior art.

These two components physically sequester prior to activation by various means. Frequently, sealed and brittle glass vials containing one component are housed in an external flexible container containing the other component. The outer container is sealed to hold both the second component and the filled and brittle vial. For example, the force generated by intimate contact with the internal vial by flexing destroys the vial, releasing the first component, thus mixing the first and second components and generating light. Since devices of this type are intended for usable light generation, generally the outer container is made of a transparent or translucent material such as polyethylene or polypropylene that allows light generated by the chemiluminescent system to propagate through the container walls. It is composed. These devices can be designed to propagate a variety of colors to one or both of the chemiluminescent reactant compositions, or by addition of dyes or fluorescent compounds to the container. Furthermore, these devices may be modified to propagate only light derived from certain selected portions.

Examples of such chemiluminescent systems are described in U.S. Pat. 5,043,851 (Kaplan). Kaplan discloses a polygonal chemiluminescent photogenerator that focuses light at the corners of the device, enhancing the visibility of the light emitted from the light stick portion of the device and optimizing the amount and distribution of the light emitted.

U.S. Patent 4,626,383 (Richter et al.) Discloses a chemiluminescent catalyst in a method for generating light for a short period of time; High strength system; Initiate a low temperature system. The invention relates to a catalyst for a two component chemiluminescent system, wherein one component is a hydrogen peroxide component and the other component is an oxalate ester-phosphor component. Lithium carboxylic acid salt catalysts such as lithium salicylate are taught which lower the activation energy of the reaction and reduce the temperature dependence of the light emission process.

U.S. Patent 5,121,302 (Bay et al.) Discloses a thin chemiluminescent solid state device that generates light in one direction. The apparatus comprises a back sheet of laminated metal foil heat sealed at an edge; Two-component front sheet; It consists of temporary containment means arranged to divide the interior region into two compartments. The two-component has a first component of the laminated metal foil and a second component of the transparent or translucent polyolefin sheet. Two-component copper foils have thermal stability; Increased half-life; It provides relative impermeability to the volatile components of the activator solution. The metal foil stack for activator solution storage allows the activator solution to maintain viability due to the impermeability of the foil.

U.S. Patent 6,062,380 (Dorney) discloses an afterglow cup system having a light emitting capability. The device is generally a cylindrical container consisting of a semi-rigid material, preferably a semi-transparent plastic material, which has limited flexibility in the outer layer of the cup so that upon application of pressure on the sides it can be temporarily deformed. There is a cavity in the side wall of the cup. The cavity has a plurality of breakable ampoules containing a chemiluminescent fluid. The chemiluminescent fluid in the ampoule is oxalate. The second chemiluminescent fluid is present in the cavity, and when the ampoule breaks, these two fluids come into contact and emit light. The ampoule is destroyed when the user applies pressure to the common point in the outer layer of the cup. The bottom of the cup has a plug that is removed or non-removable, which seals the second chemiluminescent component in the cavity space.

In addition, it is desirable to generate chemiluminescent light from objects of various shapes or shapes. U.S. Pat. 4,814,949 to Elliott discloses means for making two-dimensional chemiluminescent objects. Light is generated by combining traditional liquid chemiluminescent reactants.

Absorbent non-woven articles of the desired shape absorb the chemiluminescent reactants after mixing and activation and generate light from the desired shape. Although this shape may be simple or complex if desired, it is inevitably limited to two dimensions and also has the limitation of generating only monochromatic light per device.

Examples of making chemiluminescent systems capable of generating light from an expandable polymerizable composition are described in U.S. Pat. Pat. 3,816,325 to Lauhut et al. Two primary means can be used to produce a solid chemiluminescent system. The first system is based on the diffusion of chemiluminescent oxalate solution into a solid polymer substrate such as long flexible vinyl tubing. The diffusion process proceeds when long vinyl perfusion is immersed in a suitable chemiluminescent reactant for a long time. After removal of the perfusion from the oxalate solution, the liquid activator is applied to the surface of the perfusion to generate light in the perfusion. It is difficult to activate oxalate quickly and completely in perfusion in that the solid polymer is relatively non-porous because the activator solution reaches the chemiluminescent reactant diffused into the polymer before light is generated. This is because the phase depends on the relatively slow diffusion process.

U.S. In another embodiment of Patent 3,816,325, the chemiluminescent oxalate solution is mixed with polyvinyl chloride (PVC) resin powder to form a paste, which is then developed on a substrate and dried at high temperature in an oven to form a flexible and flexible film. do. Although the above embodiments are practiced, the polyvinyl chloride sheets described above exhibit weaknesses in uniformity, strength, flexibility and most importantly porosity. In addition, the process described above is suitable for producing relatively thin objects.

U.S. Pat. 5,173,218 to Cohen et al. Discloses a combination of PVC polymer resins for making porous, flexible chemiluminescent structures from liquid slurries. Although there are improvements over the prior art, the resulting products also have various drawbacks, especially in the case of solids, which produce chemiluminescent objects rather than relatively flat and thin objects. The thin "pad" is made from a mixture of polymerizable resins that are strong and flexible and exhibit satisfactory absorption properties of the activator fluid. However, the process taught herein concentrates on a production pad made by pouring a liquid slurry mixture into a mold. Thus, the slurry and the resulting pad shape is limited to the shape of the mold into which the slurry is poured and gathered. In addition, chemiluminescent pads having relatively rough and impermeable "surfaces" are made with the formulas and processes used in the prior art, which surfaces are created by contact of the slurry with the mold during the high temperature drying process. The surface is easily perceived as a darker and more transparent area of the pad and is highly impermeable. As a result, it is impossible to absorb the liquid activator solution quickly, and thus contributes little to the light generation of the device. Although the thickness of these surfaces depends on the time and temperature of the hot drying process, these surfaces represent useless materials with little generation of available light. The surface is known to occur because the slurry does not attract air (or other gases) during the hot drying process. In order to achieve significant porosity products, air must be introduced into the slurry mixture from the exposed surface of the slurry pool during the hot drying process. During the curing process, air is generally replaced by the volume that is attracted to the pad and occupied by the solvent absorbed in the PVC resin. Since the upper region of the pad is cured first and the lower region of the pad is then cured, this process continues until air is drawn to a deeper portion within the pad. This ingress of air into the pad during the hot drying process primarily determines the proportion of open pore space and the absorbency of the pad. At some point during the above-described high temperature drying process, the bottom of the mold reaches a temperature at which the slurry mixture in contact with the region of the mold starts to harden and harden, but there is an air passage from the exposed surface of the slurry to the lower region. You may not. Due to the lack of air available in the solidifying slurry, this "bottom up" curing process results in a pad that is rough and dense in the area adjacent to the mold bottom and is substantially non-porous and slightly less in the mold edge area. Side effects of this bottom-up process can be minimized by placing the bottom of the mold in a cold thermal mass in a curing oven to provide heating and curing of the slurry lower portion after the slurry remains. Nevertheless, unwanted production of the rough and impermeable surface layer is still not solved.

U.S. During the high temperature drying process as described in Patent 5,173,218, when air is attracted to the polymer matrix, the slurry expands, which adds to the volume of the matrix. As a result, significant problems arise when trying to cure a relatively large amount of slurry. For example, pouring a liquid slurry mixture into a test tube and drying it for an appropriate time to cure, as taught in the 218 patent, results in a coarse and dense mass that exhibits very poor porosity, poor absorption in the entire mass. This is partly due to the "bottom-up" curing process described above, where insufficient air is attracted to the slurry during the curing process due to the presence of an air tight liquid layer on the slurry that hardens around the mold bottom. It has also been found that if the slurry does not expand during the curing process, the slurry material does not attract essential air. In the case of the test tubes exemplified above, the side walls of the test tubes inhibit the expansion of the slurry and allow the air required to produce a cured matrix with high porosity and absorbance to enable activation of the product with liquid activators. Inhibits attraction. The slurry expands freely and vertically in the test tube during the curing process, but lateral compression on the slurry by the walls of the test tube is sufficient to inhibit the air expansion into the mass and optimum expansion of the slurry during the curing process. Thus, the cured mass exhibits low porosity and poor light generation, which are disadvantages of the prior art.

Frequently, it is desirable to provide chemiluminescent devices capable of generating light as well as light of various colors. U.S. Patent 5,508,893 (Nowak et al.) Relates to multicolor chemiluminescent photogeneration devices and methods of producing such products. The device comprises a flexible tube at least partially filled with activator solution; A plurality of ampoules containing an oxalate solution located in the tube; It consists of at least one barrier element between the ampoules to prevent color mixing. The device can deliver different chemiluminescent colors after activation.

U.S. Patent 5,705, 103 (Chopdekar et al.) Describes a composition that generates chemiluminescent light with adjustable duration. The composition comprises an oxalate component (including oxalate ester) dissolved in a solvent; Activator elements (peroxides and catalysts) dissolved in a solvent; It consists of a fluorescent agent. By appropriately selecting the molecular weight of the homopolymer for the oxalate component, it is possible to change the control of the overall afterglow time and the timing at which light generation is started. Although such devices provide an adjustable duration or light safety, no proposals have been made with respect to compositions that control the generation of a gas, or a composition independent of the container, that is to say a non-molded or porous composition.

Thus, there is no means in the prior art in the art for producing a three-dimensional material that is self-luminescing by chemiluminescence and producing a highly porous composition that exhibits rapid activation and excellent light generation. In addition, no prior art has predicted a product that is independent of the container, minimizes dark areas due to gas generation and can simultaneously generate chemiluminescent light of multiple spatially isolated colors or wavelengths.

Summary of the invention

The present invention teaches a means for producing a three-dimensional object that is self-emitting. The object can be simple or complex if desired. These objects are made by methods using moldable chemiluminescent reactant compositions. The composition is easily disposed in containers of various shapes and then has the property of being cured in the container, where the composition solidifies and has a shape that exactly matches the container. Once molded, the composition is semi-rigid and can be transferred from the container if desired. In addition, the present invention provides chemiluminescent reactant compositions that are exceptionally porous and are not limited to relatively flat strip materials as in the prior art. In addition, the object made with the present invention is hollow so that a minimum amount of material is used to make a three-dimensional object that emits light. In addition, these objects are multicolored, meaning that a single object can be created that can simultaneously produce chemiluminescent light of spatially isolated color or wavelength.

The primary object of the present invention is to allow a significant portion of the gap space to be made prior to curing in the solid product required for rapid and reliable activation by liquid activators. Thus, such a system does not primarily rely on porosity generated during the curing process, which must introduce air from the outside into the matrix. Since the final porosity of the product according to the invention is primarily a function of the level of compression densification prior to curing, the final porosity of the product can be precisely and advantageously controlled.

Typically, it is desirable to provide a product that is activated as quickly as possible. To this end, the activator solution must react quickly and completely with the oxalate portion of the chemiluminescent system. However, in some cases, it may be desirable to delay the reaction rate, or at least slow the rate at which the activator reaches and reacts with the oxalate component. Since the product of the present invention can be compressively strengthened to a substantially desirable level, the gap space available for the activator to communicate with the solid product is reduced if necessary, thereby the mobility of the activator and the ability to react with the solid oxalate containing component. Decreases. In addition, since the porosity of chemiluminescent solids is primarily determined by the level of compression strengthening prior to curing, the product of the present invention can be cured in a relatively limited space, for example an inspection tube, where the resulting product is highly porous and Sensitivity to activator solution is sensitive.

It is therefore an object of the present invention to provide a means for producing a three-dimensional object capable of self-luminescing through fluorescence, which can simultaneously generate a plurality of spatially isolated colors or wavelengths.

Another object of the present invention is to produce a highly porous three-dimensional chemiluminescent object.

Another object of the present invention is to provide a three-dimensional chemiluminescent object that can easily and accurately control the porosity.

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

Another object of the present invention is to provide a three-dimensional chemiluminescent object in which there are few dark areas due to the "surface" effect caused by improper curing.

It is yet another object of the present invention to provide a three-dimensional chemiluminescent object that is shaped in a way that the object is hollowed out.

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

It is a further object of the present invention to provide a formulation for a chemiluminescent reactant composition which is moldable and thus easily molded into the desired shape with or without a mold.

Other objects of the present invention are apparent from the following detailed description, taken in conjunction with the accompanying drawings which illustrate embodiments and specific embodiments of the invention. The drawings constitute part of the specification and include typical embodiments of the invention and illustrate various objects and features thereof.

The present invention relates to chemiluminescent compositions, especially devices for generating light from immobilized immunoluminescent materials.

Figure 1 shows the light generation vs. different bulk density of solid oxalate. A chart showing activation time;

2 is a pictorial view of a typical embodiment of the present invention.

3 is a cross-sectional view of the exemplary embodiment of FIG. 2 showing the placement of the chemiluminescent reactant composition.

4 is a cross-sectional view of FIG. 3 showing compression strengthening of the chemiluminescent reactant composition using a tamping tool.

5 is a cross-sectional view of a typical embodiment after compression strengthening showing second chemiluminescent reactant component ampoule placement and spacing in the flowable solid mixture.

6 is a cross-sectional view of another exemplary embodiment of the present invention showing the placement of a chemiluminescent reactant composition.

7 is a cross-sectional view of the embodiment of FIG. 6 showing the location of the compression tool within the chemiluminescent reactant composition.

8 is a cross-sectional view of an embodiment of the present invention showing compression strengthening of the chemiluminescent reactant composition by the compression tool of FIG. 7.

9 is a cross-sectional view of an embodiment of the present invention showing a compression enhanced chemiluminescent reactant composition.

The present invention relates to formulations, manufacturing processes, and apparatus associated with chemiluminescent reactant compositions that can be used to produce moldable and multidimensional objects. Such compositions overcome the weaknesses of the prior art and are used to apply chemiluminescent materials to novel molding processes to provide chemiluminescent objects molded into a unique, highly porous shape. The process of the present invention is not limited to conventional casting processes that produce relatively thin and flat objects as described in the prior art.

Moldable porous powders of the present invention can be densely packed to various levels and form a relatively strong, flexible and highly porous mass immediately after heat curing. The apparent density of the material is easily controlled through the degree of compaction or compression strengthening. For this reason, objects of desired apparent density can be made. Since apparent density directly affects the rate of activator absorption, the rate of chemiluminescence activation is advantageously controlled.

As described above, FIG. 1 is a chart showing how the adjustment of bulk product density is utilized to change activation time. Two devices were made and tested, each containing a chemiluminescent reactant composition in the form of a solid oxalate-containing composition (hereafter solid oxalate). The first device had a bulk density of approximately 0.54 g / cc and reached maximum light generation approximately 10 minutes after activation. The second device had a bulk density of approximately 0.72 g / cc and reached maximum light generation approximately 37 minutes after activation. These data suggest that activation time is affected by bulk density, and that more compacted objects require longer activation periods. The ability to adjust the light generation curve enables the manufacture of chemiluminescent devices that can meet a variety of market demands.

For example, in the production of large chemiluminescent objects, the hollow chemiluminescent shape is preferred over the solid form, because the light generated within the solid form does not reach the surface inadequately and is not generated as a useful light return effect. ) Decreases. In addition, the hollow chemiluminescent shape provides a simple and precise means of introducing the second reactant component into the product. The ampoule or vessel holding the second reactant component may be placed in a hollow, empty space. In the event of an ampoule or vessel breakage, the second component is readily absorbed at the hollow surface and quickly transferred to the capillary action through the porous chemiluminescent matrix until the entire mass is moistened and generates light through chemiluminescence. . In addition, disposing the second component in the empty space may produce a more satisfactory product externally.

An example of a form that can be made according to the teachings of the present invention is a chemiluminescent candle. These candles provide a safe and reliable alternative to real candles. Flames from real candles can ignite other objects. Unlike traditional candles, chemiluminescent candles are wind resistant and water resistant and can be made to generate light in any color or any combination of colors or wavelengths desired from a single device by using the present invention.

Previous attempts to make "candles" using chemiluminescent systems as light sources have had drawbacks. Typically, chemiluminescent photogeneration devices, such as light sticks, that use liquids have a head-space that occupies approximately 30% of the container volume in the device. Light cannot be generated in this upper space. Japanese Patent Application No. 10-170263 discloses a bubble capturing means in which a gaseous upper space (or bubble) present on a liquid chemiluminescent fluid in a sealed chemiluminescent device is captured in an area other than the uppermost part in the device. When bubbles are removed from the sealed chemiluminescent device, for example the top portion of the candle, the entire portion of the candle flame tip appears to emit light during the chemiluminescence reaction. If the bubble remains at the tip of the flame, dark areas appear around the top of the flame because no light is generated in the bubble region. This dark area reduces the overall visual acceptability of the device. Carbon dioxide, carbon monoxide and oxygen are the gases commonly generated in peroxide luminescence systems. These gases rise to the top of the liquid chemiluminescent system and form bubbles on top of the device. Therefore, although the device described in Japanese Patent Application No. 10-170263 effectively solves the bubble problem first contained in the upper portion of the chemiluminescent device, it does not present a method for removing the bubble generated during the chemiluminescence process. The method of the present invention allows the production of candles or other desired chemiluminescent objects, which eliminates the visible visible increase in bubbles in the apparatus as the initial head-space bubbles and chemiluminescent processes proceed in the apparatus. In addition, the present invention does not require any type of trap, channel or valve in the device to realize this advantage. Since the moldable mass of the chemiluminescent system according to the invention is a solid, there is no space for the bubbles to aggregate and bind. Although gases generated during the chemiluminescence process are still produced, these gases are inhibited from rising in the moldable solid mass and are evenly distributed throughout the solid, resulting in the complete generation of the surface area of light.

2 shows a preferred embodiment of the present invention as a chemiluminescent candle 10 comprising a blow-molded lid in a candlestick shape. When the device is activated, the flame portion of the candle emits light.

As shown in FIG. 3, the candle cover 11 may be made of blow-molding or other suitable molding means from a material, for example polyethylene or polypropylene. Suitably, the distal end of the candle cover opposite the flame shape remains open. The candle cover 11 is arranged so that the open end is positioned above. The moldable chemiluminescent reactant composition 12 of the present invention is placed in the candle lid 11 so that the lid is partially filled. The flowable solid mixture, although fluid, exhibits a certain level of stickiness and yields a packable, moldable and moist powder. Accordingly, auxiliary feeding means, such as vibration feeders, are useful for assisting the feeding of the moldable chemiluminescent reactant composition 12. Once the moldable chemiluminescent reactant composition 12 has entered the candle lid 11, the composition is slightly compressed with a tamping tool 13 designed for this purpose as shown in FIG. 4. This compression process not only assists the composition to fit the shape of the candle lid 11, but also compressively strengthens and compresses the composition so that the composition does not flow or move further in the candle lid 11 even if the lid orientation changes. . However, the composition may be transferred from the lid with the application of sufficient vibratory force, in order to induce liquefaction of the compressed chemiluminescent reactant composition 15 if necessary. The tamping tool 13 is designed with a tapered tip 14 to compress the composition as well as to generate a cavity 16 in the resulting compressed composition as shown in FIG. 5. The cavity 16 provides a convenient means, for example, to facilitate dispersion of the second chemiluminescent reactant component in the ampoule 1 and to facilitate rapid and even activation of the device. Once the second chemiluminescent reactant component is positioned, the plug 19 is heat sealed at the distal end of the candle lid 11. In addition, the cavity 16 provides space for the composition to expand during the curing process, allowing exceptional porous products to be produced. Cavities are not required to produce highly porous products but are used to produce exceptionally porous products in certain cases. Such cavitation is not possible with the processes taught in the prior art.

As shown in FIG. 6, the chemiluminescent rose-shaped cover 21 is made by blow-molding the cover from polyethylene, for example, into a rose-shaped rose bud shape. The diameter of the bag is usually significantly smaller than the diameter of the bud. In this embodiment, it is desirable to make a rose bud in which the entire surface of the bud is illuminated via chemiluminescence. It is also desirable to make the article with the lowest possible chemiluminescent material to achieve the desired effect. The rose-shaped lid 21 is filled with a small amount of moldable chemiluminescent reactant composition 12.

As shown in FIG. 7, a compression tool 22 consisting of a hollow needle 23 with an expandable air bag 24 in a rose-shaped cover 21 holding a chemiluminescent reactant composition 12. ) Is inserted into which the tool is positioned by at least one anchoring ring (25). The distal end of the hollow needle 23 is plugged and a hole below the expandable air bag 24 on the side of the needle allows air pressure inside the needle to fill and expand the expandable air bag 24. The air bag is inflated as shown in FIG. 8 using air pressure for inflation purposes, wherein the moldable chemiluminescent reactant composition 12 surrounding the inflated air bag 24 is densely packed on the inner wall of the rose bud cover. . 9 shows the dense chemiluminescent reactant composition 15 in a semi-solid state. After this compression process, the air bag contracts and the needle probe is removed to leave the cavity 16. The dense chemiluminescent reactant composition is then cured by hot drying in a rosebud cover for 10 minutes at 95 ° C. in a preferred embodiment. After cooling the composition, a sealed ampoule holding the second chemiluminescent reactant component solution is inserted into the rose-shaped lid 21 and the plug is fitted into a bag and heat sealed to seal as previously described in the candle embodiment. Form a hermetic seal. The resulting product is an object that appears to be a real rose bud that, when activated, emits light from the entire surface of the bud. Activation can be accomplished, for example, by breaking the ampoule by simply bending the stem of the rose and releasing a second component, which is absorbed into the chemiluminescent reactant composition or the moldable solid mixture. Since the dense chemiluminescent reactant composition is very suitable for the inner wall of the cover, a thin paper leaf such as a rose petal is obtained by the process of the present invention.

In connection with the candle and rose embodiments described herein, it is assumed that the cured solid product is present in the polymer sheath, which material is readily molded and cured in the mold and then transferred. Solid chemiluminescent objects can be made with the present invention using, for example, compression or centrifugal molding. Individually shaped articles made by the process of the present invention may be included as free-flowing objects that emit light when placed in a container holding a second chemiluminescent reactant component solution. Such a system can, for example, create a "snow globe" that holds luminescent snow particles. Since the moldable mass of the chemiluminescent reactant composition in the present invention is in solid form, multiple positionable and spatially fixed colors may be used in a single device. For example, you can make a rose bud that shows red with orange stripes.

A particular advantage of the present invention compared to the fully liquid chemiluminescent system found in conventional light sticks is that it can emit the entire surface of the object if desired.

Since the product of the present invention is a solid chemiluminescent material, it can be used even in situations where a liquid chemiluminescent system that depends on the container is not available.

The following examples describe experimental processes that support the novelty of the present invention.

A series of experiments were designed to identify the optimal materials and formulas needed to make moldable porous chemiluminescent reactant compositions. As taught in the prior art, approximately 2 parts of PVC resin (Geon Corp. # 121) are dissolved with 98 parts of chemiluminescent reactant solution, illustrated herein as oxalate solution, to prepare pre-slurry. In addition, according to '218, 59 fractions of the oxalate pre-slurry was prepared by mixing 31 fractions of medium particle size PVC powder resin (Geon # 218) and 9 fractions of large particle size PVC resin (Geon # 30). The resulting material is a flowable liquid slurry.

Example 1-6

Six tests were conducted to determine the effect of varying curing times and temperatures as well as slurry thickness on porosity. In each test, approximately 7 g of liquid slurry was placed in a small aluminum pan, and then the pan was placed in a spacer to tilt the pan bottom slightly to make a slurry having a depth of 0.015 "to 0.180". During each inspection, the pan was placed on a wire shelf in a circulating air oven. After curing for a certain time, each sample article was transferred from the pan, cut and tested for proper curing and porosity. Properly cured samples are defined as samples in which all oxalate solutions are absorbed into the PVC matrix and show no signs of over-curing. In a properly cured matrix, lesser molecular weight PVC particles fuse with each other. However, more molecular weight PVC particles absorb liquid oxalate solutions but do not significantly fuse. If the curing time and temperature are excessive, more molecular weight PVC particles fuse with each other and produce an over-cured matrix, which is confirmed by the presence of dark and / or shiny areas called pads in the cured sample. This over-cured matrix shows very low porosity.

Table 1 shows the results obtained using various slurry curing conditions.

Inspection article Curing time (minutes) Curing temperature (℃) Results / observation One 3 95 Under-curing / shuttering in thick parts 2 5 95 Possibly over-curing; Non-porous at the point of contact with the fan 3 8 95 Non-porous up to approximately one-third the thickness of the pad in contact with the fan 4 10 95 congestion; Non-porous at bottom 1/3 thickness of pad 5 20 95 congestion; Non-porous at bottom 1/3 thickness of pad 6 8 82 Less dense; Dark and dense in contact with the fan

In Test Article 1, the PVC particles did not fully absorb the oxalate solution because the material was soft and contained a significant amount of free liquid. In Test Article 2-5, it was found that only the exposed surface of each cured sample was porous, although the material was less soft.

Each of Test Articles 1-5 was activated with a chemiluminescent activator reactant. Article 2-5 emitted light from the surface but did not generate light from the dark non-porous region. Article 1 generated little light at most surfaces because a liquid oxalate solution that was not absorbed into the PVC matrix during the curing process acts as a barrier, preventing the activator solution from reaching the liquid oxalate below the surface. It seems to be because. Some luminescence appeared in the boundary layer where the activator and oxalate solution bound around the surface of the matrix. Article 6 cured at lower temperatures because article 1-5 was found to be over-cured and the high molecular weight PVC particles fuse with each other due to the application of excessive heat. However, the test results from Item 6 contradicted this hypothesis. Even at the lower times and at lower temperatures used to cure article 6, there was still a dark, dense area in the contact with the pan.

Example 7

Chemiluminescent candles were made using the same liquid slurry formulation in Test 1-6 above. To make this candle, approximately 3.2 g liquid slurry was injected into the polyethylene candle cover using a syringe. A glass ampoule containing chemiluminescent activator was inserted into the slurry so that the bottom of the apple was in contact with the inner bottom of the candle lid. This assembly was placed in a circulating air oven set at 82 ° C. and cured for 12 minutes. After that, the assembly was cooled to room temperature, and then the candle cover and cured slurry were cut for observation. The PVC matrix (cured slurry) appeared to be fully cured but dark and dense. The PVC matrix portion was removed from the cover and placed in an aluminum pan. Chemiluminescent activator reactants were added to these portions where the cured slurry dimly emitted. The activator was observed to react with the outermost surface of the cured slurry and not reach inside the cured slurry. This absorbent member of the activator solution with the cured slurry was found not to be due to over- or under-curing of the slurry, but due to the very low porosity exhibited by the pads. The porosity or cavity space in the matrix is derived from two sources. A small part of the porosity is due to the porous PVC particles in the matrix. A more important factor in determining the porosity of the cured slurry is the ability of air to enter the entire slurry volume during the curing process. Using the liquid slurry formulation taught in '218, it was observed that when the heat reached the inner region sufficient to cure the slurry before the outer region was fully cured to porous, the inner region was cured to low porosity. This effect occurs because air cannot pass through the surrounding liquid region and move inside.

Example 8

With these results in mind, the amount of slurry was supported on a 10 cm x 10 cm section of an air permeable substrate, for example a 2 mm thick nonwoven polyester felt, placed in a circulating air oven and held at 82 ° C. for 8 minutes. . It was expected that the felt would provide a uniform inflow of air into the slurry, and the slurry would be heat cured from the outside in such a way that no dark non-porous regions were formed as in the case of the slurry cured in an impermeable aluminum pan. Each continuous layer of slurry is porous because it is cured from the outside and allows air to reach the subsequent layer. The sample is transferred from the oven and cooled. In the examination, the pads were free of dark or dense parts and were extremely porous. The sample was activated with the chemiluminescent activator reactant, which was bright and uniformly luminescent throughout.

A model describing the formation of gap spaces in PVC particles / solvent slurries is that large coarse spherical PVC particles are joined together by smaller, lower molecular weight PVC particles to form a matrix. These PVC particles absorb the solvent that initially filled the gap space between the particles. As air enters the matrix during curing, the solvent-absorbing PVC particles expand and expand.

Example 9

New slurry formulations were made and tested to see if increased air inflow through the slurry could be achieved by using more weight percent larger particle PVC. The slurry contained 56 parts of pre-slurry, 29 parts of medium size particle resin (Geon # 218), and 15 parts of large particle size resin (Geon # 30). Approximately 2.5 ml of liquid slurry was placed in a polyethylene candle cover, to which a free activator ampoule was added. The slurry was cured and cooled at 75 ° C. for 12 minutes. In closer inspection, the slurry was found to cure but still retain dark non-porous regions.

For this reason, we have established and validated the hypothesis that formulations of PVC resins and liquid oxalates can be produced in a way that results in materials that allow air to pass through these formulations prior to and during cure.

Example 10

A new formulation was made with the pre-slurry described above prepared by dissolving approximately 2 parts of PVC resin (Geon Corp. # 121) in 98 parts of oxalate solution. The liquid oxalate solution in this example is based on propylene glycol dibenzoate, but any base compound known in the art is available. In this new formulation, higher weight percent single PVC particles replaced the medium and large particle PVC resins used in the slurry described above. Approximately 40 parts of pre-slurry was added to 60 parts of resin (Geon # 466). The resulting composition was a wet, packageable and moldable powder characterized by a flowable solid mixture rather than a liquid slurry. The resin is chosen to have sufficient particle size or range to provide a flowable solid mixture. In a typical unlimited embodiment, the resin is a PVC resin having an average particle size distribution of approximately 125 microns.

Various polymers can be used in the polymerizable composition: polyethylene, polypropylene, poly (vinyl chloride), poly (methyl methacrylate), poly (vinyl benzoate), poly (vinyl acetate), cellulose poly (vinyl pyrrolidone ), Polyacrylamide, epoxy, silicone, poly (vinyl butyral), polyurethane, nylon, polyacetyl, polycarbonate, polyester, polyether. Crosslinked polymers may also be used: polystyrene-poly (divinyl benzene), polyacrylamide-poly (methylenebisacrylamide), polybutadiene-copolymers and the like. In most cases the polymer is selected to be soluble, expandable or permeable to the activated hydrogen peroxide liquid. Suitably, this permeability allows for effective contact between the activating liquid, chemiluminescent material, and fluorescent agent (if needed). Frequently, it is desirable to select polymers and activating liquids that can provide a specific diffusion rate and control the intensity and duration of light emission. Such 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). Permeability of polymers to solvents is well known in the art, and it is not difficult to select useful polymer / solvent combinations. Particularly useful are solvents used as plasticizers. The chemiluminescent material or fluorescent agent need not be dissolved in the polymer itself, but the activating liquid should provide at least partial solubility if the polymer itself does not provide solubility for both components. Alternatively, the polymer may be plasticized into soluble plasticizers.

The moist powder of the resulting chemiluminescent reactant composition has a similar consistency as the light brown sugar. Due to the stickiness of the flowable solid mixture, it is advantageous to deaggregate or decompose the compressed part in such a way as to sift through the screen mesh or stir with a whisk to ensure that the moist powder is not dense prior to use. To assist in material placement, vibration supply systems may also be used. Although the method described above is typical for decomposing dense parts, it is also possible to use means for deagglomerating the flowable solid mixture. With the discovery that the gap space present in the material is important for the curing process, the novel formulations of the present invention resulted in an immediate and significant improvement in the time required for complete chemiluminescent activator reactant absorption and corresponding light emission.

Thus, the moldable chemiluminescent reactant composition comprises a first chemiluminescent reactive component with an amount of the first polymerizable resin particles effective to yield a uniform dispersion, and is embodied as a liquid slurry. Thereafter, the second polymerizable resin particles are mixed with the uniform dispersion in an amount effective to yield a flowable solid mixture. The flowable solid mixture can be shaped into a specific shape. It provides a means for deagglomerating the flowable solid mixture to decompose the dense mass portions during manufacture. It also provides a means of curing the flowable solid mixture with or without a mold. In a preferred embodiment, the first polymerizable resin particles and the second polymerizable resin particles are each polyvinyl chloride resins. Generally, an activator solution is added to the composition to initiate light emission, but in the present invention oxalate and activator may be interchanged. In this case, the first chemiluminescent reactive component consists of oxalate and the second chemiluminescent reactive component consists of activator. Alternatively, the first chemiluminescent reactive component consists of an activator and the second chemiluminescent reactive component consists of oxalate.

In order to provide a chemiluminescent system, a second component must be included. For this reason, the chemiluminescent composition of the present invention produces a first chemiluminescent reactant and a flowable solid mixture comprising a first chemiluminescent reactive component with an amount of the first polymerizable resin particles effective to yield a uniform dispersion. It contains the second polymerizable resin particles mixed with the uniform dispersion in an effective content. A second chemiluminescent reactant component is included, wherein contact between the first and second chemiluminescent reactant components generates light. Generation of light involves at least one unique wavelength in the visible spectrum or the invisible spectrum. Provided are means for controllably activating the flowable solid mixture.

And a uniform dispersion in an amount effective to yield at least one first chemiluminescent reactant and a flowable solid mixture comprising a first chemiluminescent reactive component with an amount of first polymerizable resin particles effective in producing a homogeneous dispersion. Also disclosed is a multidimensional chemiluminescent device comprising second polymerizable resin particles to be mixed. At least one flowable solid mixture is dispersed in a multidimensional vessel wherein compression strengthening the flowable solid mixture results in a multidimensional chemiluminescent device. Chemiluminescence occurs upon contact of the device with the second chemiluminescent reactant component. As noted above, the emission of light involves one or more unique wavelengths or colors. Thus, the means for compression or compression strengthening of the flowable solid mixture provide a means for controllably activating the flowable solid mixture, which can be achieved with the various techniques envisioned herein. For example, compressive strengthening of the flowable solid mixture is accomplished with molding techniques, in which a moldable or hollow object is formed having a controlled compressive strengthening portion. This change in density represents a control parameter for the light emission response and results in an object that can control activation.

The process for producing a chemiluminescent reactant according to the present invention comprises the steps of providing a first polymerizable resin, and then mainly combining the first chemiluminescent reactive component in solution form with an effective amount of the first polymerizable resin to form a slurry. do. A second polymerizable resin is provided that is combined with the slurry in an amount effective to make a flowable solid mixture. Also included are means for providing controllable activation of the inducible solid mixture achieved by compacting the mixture to a desired level. As shown in FIG. 1, the denser the mass, the longer the time to reach maximum light emission.

These flowable solid mixtures are not liquid and do not require their own level in that U.S. Pat. Significantly different from the liquid slurry taught in 5,173,218. In addition, the flowable solid mixture is flowable but neither flows nor stagnates. Pat. Significantly different from the pastes described in 3,816,325. Most importantly, the powder compositions of the present invention have essentially high porosity and interconnected air spaces. In addition, such flowable solid mixtures retain the cohesive properties that are molded into a constant solid shape by simply pressing the moist powder with a gentle force. For example, such material can be touched by hand or placed between two plates to form a thin sheet. Furthermore, the adhesion seen in the moist powder is sufficient to maintain the desired shape after pressing. For example, the flowable solid mixture can be cured by pressing into small masses and drying in an oven with or without molding, in which the individual particles in the powder are bonded to each other in a single porous mass. In other embodiments, the flowable solid mixture may be placed in a mold and hot dried (cured) to form a solid object having a shape that exactly matches the formation of the mold. Since the lightly compressed moist powders lose flowability as in dry powders or liquid slurries, the flowable solid mixtures of the present invention can be formed, processed or processed in such a way that hollow objects are produced. Such hollow chemiluminescent objects are of high value in that the external light-emitting surface can be shaped into any desired shape while maintaining the hollow interior. This hollow interior allows for the preservation of chemiluminescent materials, which not only saves cost but also enables the production of relatively large chemiluminescent objects with high surface brightness at minimal cost.

Although PVC is the preferred polymerizable resin, the polymerizable composition is not limited thereto.

Various molding and / or processing methods can be applied to the chemiluminescent reactant composition of the present invention. Examples of such methods include molding, extrusion, compression molding, cast molding, powder molding, electrostatic deposition, eg xerography. ), But are not limited to these. Powder molding consists of dry mixing the moist powder and the curable additive to form a moldable composition.

In addition, the flowable solid mixture may be electrostatically deposited through a process such as zeroography, wherein electrical charge is provided to the surface of the vessel holding the chemiluminescent reactant composition. Adhesion between the chemiluminescent reactant composition and the container surface proceeds only at the charged portion, which allows for specific placement of the chemiluminescent reactant composition in the vessel.

All patents and publications described herein are incorporated by reference in their entirety.

Although certain forms are illustrated in the present invention, they are not limited to such specific forms. It will be apparent to those skilled in the art that various modifications may be made without departing from the scope of the invention and that the invention is not limited to the details shown and described in the specification and drawings. As will be appreciated by those skilled in the art, the present invention may be adapted to carry out the objects described or realized herein and to achieve advantages. The embodiments, methods, processes, and techniques described herein are representative of preferred and exemplary embodiments, but are not limited to these. Changes and other uses encompassed within the spirit of the invention and defined by the appended claims fall within the ordinary skill of those skilled in the art. Although the present invention has been described in connection with specific preferred embodiments, the invention is not limited to this specific embodiment. Indeed, various modifications of the above-described form for practicing the present invention will be apparent to those skilled in the art and fall within the scope of the following claims.

Claims (50)

Chemiluminescent reactant composition consisting of: A chemiluminescent reactant solution that produces a slurry when mixed with an effective amount of the first particulate polymerizable resin; A second particulate polymerizable resin, when mixed with the slurry in an effective amount to produce a flowable solid mixture. 2. The chemiluminescent reactant composition of claim 1, wherein the flowable solid mixture is deaggregated. The chemiluminescent reactant composition of claim 1 wherein the flowable solid mixture is cured. The chemiluminescent reactant composition of claim 1 wherein the flowable solid mixture is shaped into a specific shape. The chemiluminescent reactant composition of claim 1, wherein the first particulate polymerizable resin is polyvinyl chloride. The chemiluminescent reactant composition of claim 1, wherein the second particulate polymerizable resin is polyvinyl chloride. The chemiluminescent reactant composition according to claim 6, wherein the second particulate polymerizable resin is porous. 7. The chemiluminescent reactant composition of claim 6, wherein the second particulate polymerizable resin has an average particle size distribution sufficient to provide a flowable solid mixture. The chemiluminescent reactant composition of claim 8 wherein the second particulate polymerizable resin has an average particle size of 125 microns. The chemiluminescent reactant composition of claim 1, wherein the slurry is uniformly dispersed. The chemiluminescent reactant composition of claim 1 wherein the chemiluminescent reactant solution contains oxalate. The chemiluminescent reactant composition of claim 1, wherein the chemiluminescent reactant solution contains an activator. Chemiluminescent composition, consisting of: First chemiluminescence containing a chemiluminescent reactant solution that yields a slurry when mixed with an effective amount of a first particulate polymerizable resin and a second particulate polymerizable resin that when mixed with the slurry in an effective amount produces a flowable solid mixture Reactant components; A second chemiluminescent reactant component; Here, chemiluminescence occurs when the first chemiluminescence reactant component contacts. 14. The chemiluminescent composition of claim 13, wherein the flowable solid mixture is deaggregated. The chemiluminescent composition of claim 13, wherein the flowable solid mixture is cured. The chemiluminescent reactant composition of claim 13, wherein the flowable solid mixture is shaped into a specific shape. The chemiluminescent composition according to claim 13, wherein the first particulate polymerizable resin is polyvinyl chloride. 13. The chemiluminescent composition of claim 12, wherein the second particulate polymerizable resin is polyvinyl chloride. 19. The chemiluminescent composition of claim 18, wherein the second particulate polymerizable resin is porous polyvinyl chloride. 19. The chemiluminescent composition of claim 18, wherein the second particulate polymerizable resin has an average particle size distribution sufficient to provide a flowable solid mixture. The chemiluminescent composition of claim 13, wherein the slurry is uniformly dispersed. 14. The chemiluminescent composition of claim 13, wherein the first chemiluminescent reactant component contains oxalate and the second chemiluminescent reactant component contains an activator. The chemiluminescent composition of claim 13, wherein the first chemiluminescent reactant component contains an activator and the second chemiluminescent reactant component contains oxalate. The chemiluminescent composition of claim 13, wherein the generation of light involves at least one unique wavelength or color. The chemiluminescent composition of claim 13, wherein the flowable solid mixture is controllably activated. Method for producing a chemiluminescent reactant composition consisting of the following steps: Mixing a chemiluminescent reactant component with an effective amount of the first particulate polymerizable resin to yield a slurry; The slurry and the effective amount of the second particulate polymerizable resin are mixed to yield a flowable solid mixture. 27. The method of claim 26, wherein the first particulate polymerizable resin is polyvinyl chloride. 27. The method of claim 26, wherein the second particulate polymerizable resin is polyvinyl chloride. 29. The method of claim 28, wherein the second particulate polyvinyl chloride is porous. 29. The method of claim 28, wherein the second particulate polyvinyl chloride has an average particle size distribution sufficient to provide a flowable solid mixture. 27. The method of claim 26, wherein the slurry is uniformly dispersed. 27. The method of claim 26, wherein the flowable solid mixture is cured. 27. The method of claim 26, wherein the first chemiluminescent reactant element contains oxalate. 27. The method of claim 26, wherein the first chemiluminescent reactant element contains an activator. 27. The method of claim 26, wherein the flowable solid mixture is deagglomerated. 27. The method of claim 26, wherein the flowable solid mixture is shaped into a specific shape. Multi-dimensional chemiluminescent device composed as follows: A first chemiluminescent reactant component containing an effective amount of the first particulate polymerizable resin yielding the slurry and a second particulate polymerizable resin mixed with the slurry in an effective amount yielding the at least one flowable solid mixture At least one first chemiluminescent reactant composition, wherein At least one flowable solid mixture is dispersed in a multidimensional vessel, Compression densification of the flowable solid mixture results in a multidimensional chemiluminescent device; Chemiluminescence occurs when the device contacts the second chemiluminescent reactant component. 38. The multi-dimensional chemiluminescent device of claim 37, wherein the flowable solid mixture is deaggregated. 38. The multidimensional chemiluminescent device of claim 37, wherein the flowable solid mixture is cured. 38. The multidimensional chemiluminescent device of claim 37, wherein the flowable solid mixture is shaped into a specific shape. 38. The multidimensional chemiluminescent device according to claim 37, wherein the first particulate polymerizable resin is polyvinyl chloride. 38. The multidimensional chemiluminescent device according to claim 37, wherein the second particulate polymerizable resin is polyvinyl chloride. 43. The multi-dimensional chemiluminescent device of claim 42, wherein the second particulate polyvinyl chloride is porous. 43. The multi-dimensional chemiluminescent device of claim 42, wherein said second particulate polyvinyl chloride resin has an average particle size distribution sufficient to provide a flowable solid mixture. 38. The multi-dimensional chemiluminescent device according to claim 37, wherein the slurry is uniformly dispersed. 38. The multidimensional chemiluminescent device according to claim 37, wherein the first chemiluminescent reactant component contains oxalate and the second chemiluminescent reactant component contains an activator. 38. The multidimensional chemiluminescent device according to claim 37, wherein the first chemiluminescent reactant component contains an activator and the second chemiluminescent reactant component contains oxalate. 38. The multi-dimensional chemiluminescent device of claim 37, wherein the generation of light involves at least one unique wavelength or color. 38. The multi-dimensional chemiluminescent device according to claim 37, wherein the compression strengthening provides a means by which the flowable solid mixture is controllably activated. 38. The multi-dimensional chemiluminescent device according to claim 37, wherein the compression strengthening of the flowable solid mixture is achieved by molding techniques, wherein hollow objects are formed.