JPS6059270B2 - Planar chemiluminescent material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a luminescent material capable of actively causing a chemiluminescent phenomenon on a planar sheet.

Chemiluminescence is a chemical reaction that produces an excited state in the constituent molecules of a substance, and when this transitions to the ground state, it generates light in the visible region.For example, bis-9, 10-
Liquid-liquid solutions such as a solution of phenylethylene anthracene in dibutyl phthalate and a solution of peroxide-hydrogen in dimethyl phthalate, and liquid-gas solutions such as tetraxin-N-dimethyl-amino-ethylene and oxygen. A variety of devices have been developed that use .

Practical versions of these products are commercially available, such as Sirium made in the United States, Kemihotaru, and Starlit made in Japan.

However, all of these commercially available products mix two liquids in a cylindrical body with a fairly large diameter, and the amount of liquid participating in the reaction is small, i.e., the thickness of the liquid in the direction viewed by the observer is small. It was experimentally confirmed that when the light is thin, the brightness is very weak. In other words, the two liquids used in the Starrit product currently on the market were mixed to create a luminescent phenomenon, and then placed in a transparent plastic envelope-like bag to change the thickness in the viewing direction. However, its thickness is O, 5wgn/w
If you become a gn, you can almost get the luminance, 2Wr! n/
A certain level of luminance could only be obtained at Twt or higher.

Therefore, although it is possible to use these currently commercially available rod-shaped light emitters (which also have a somewhat large volume), it is practically difficult to apply them to planar light emitters that have a large area and are thin. I can say that. The present invention aims to eliminate the above-mentioned drawbacks and provide a planar chemiluminescent material that can obtain sufficient brightness and uniform brightness even in a thin planar shape. A surface characterized by a porous body made of a substance having the function of increasing luminance, or a planar sheet of a porous body to which a substance that increases chemiluminescence luminance is attached, sealed in a light-transmitting airtight container. In some cases, this planar sheet is impregnated in advance with one of the liquids that exhibit chemiluminescence.

The planar chemiluminescent material of the present invention, for example, as shown in FIG.
A transparent or semi-transparent translucent plastic container 1 is made of one or more of the above-mentioned substances having an effect of increasing chemiluminescence brightness, such as glass fiber, or has one or more of these substances having an effect of increasing chemiluminescence brightness attached thereto. A planar sheet 2 is enclosed, and the planar sheet 2 is impregnated with one of the liquids in the case of liquid-liquid chemiluminescence, or with the liquid in the case of liquid-gas chemiluminescence. In some cases.

A stopper 3 is attached to the translucent plastic container 1, and from the stopper 3 a liquid that has been mixed elsewhere and is already causing chemiluminescence, or one of the liquids that are to exhibit chemiluminescence is passed through the stopper 3. If the sheet is pre-impregnated, the other liquid or gas such as air may be allowed to flow into the container 1, or if there is no such stopper and the sheet is injected into the container 1 with a syringe, etc. As shown in the figure, a planar sheet 2 impregnated with one liquid and a breakable ampoule 4, such as glass, filled with the other liquid or oxygen, etc. are assembled in a container 1, and when used, the ampoule 4 is There are cases where the container 1 is broken from the outside and the liquid or oxygen inside the ampoule 4 is made to flow out. When two liquids or a liquid and a gas that are to exhibit chemiluminescence are brought into contact with each other on the surface of the planar sheet 2 by any of the methods described above, a chemiluminescence phenomenon occurs there.

Furthermore, the planar sheet of the present invention is not limited to those shown in FIGS. 1 and 2, but may also be wire-shaped. For example, as shown in FIG. ,
Various configurations are conceivable, such as one in which a wire-like planar sheet 2 is placed inside. Regarding substances that increase the brightness of chemiluminescence, the above-mentioned glass fibers, silica glass fibers, asbestos, and zeolite (using artificial zeolite with the trade name Molecular Sieves) greatly increase the brightness of chemiluminescence, but others Almost no increase in brightness was observed for naturally produced paper bulb fibers and their products, nylon, saran, rayon, wool, cotton, and silk fibers, which were experimentally confirmed.

However, in the case of chemiluminescent reactions in which air or other gases are used as oxidizing agents, as will be explained later, the porosity of paper or cloth increases the area where the infiltrated liquid chemiluminescent agent comes into contact with air or other gases, resulting in a decrease in luminance. Because of the increase in brightness, the above-mentioned natural fibers were also recognized to have a brightness increasing effect compared to the liquid:liquid reaction. The brightness enhancement effect is particularly strong in ultrafine fibers of 1 to 2 microns (diameter) or less, as well as paper, cloth, etc. made using such fibers.

Glass fibers, paper, cloth, strings, etc. with a diameter of 5 to 8 microns (manufactured by Tamoto Inorganic Fibers Co., Ltd., FM paper, etc.) have a slightly weaker effect than those with a diameter of 1 to 2 microns.

Silica fibers (based on SiO2) having a diameter of 6 to 7 microns are less effective than those of 1 to 2 microns.

For porous materials such as natural sponges, synthetic sponges, and expanded polystyrene, a slight upward trend was observed, but it was not significant. However, the product name Filton, a commercially available pumice stone with water-repelling properties for waste oil treatment, was highly effective even with liquid:liquid chemiluminescence, but it was not as effective as glass fibers. In the case of chemical liquids using air as the oxidizing agent, a slight increase was observed in all porous bodies, regardless of the material, compared to liquid:liquid, but in this case too, the effect of glass fibers was remarkable.

Manganese dioxide, silica gel, alumina desiccant, etc. have almost no effect.

Examples of the present invention will be shown below.

<Example 1> Commercially available chemiluminescent substance, trade name: Kemifirefly (outer diameter 4.5?/order,
Take one rod of length (length), bend it slightly from approximately the center of the rod, and break the glass tube sealed inside.
Shake well to mix both solutions and chemiluminescence will start immediately.

Immediately, the upper part of the external rod-shaped plastic container was cut off, and the luminescent liquid substance was sucked in using a micro cylinder. -/Flat bottom transparent height 1-/Front Pour 0.15 cc into a cylindrical plastic container. Then, it takes 1 time to bend the luminescent body and start chemiluminescence.
When 20 seconds have elapsed, quickly insert the materials listed in Table 1 into the container, immerse them in the luminescent liquid, and immediately measure the luminescence from the bottom plane (measure the light by placing a photoelectric photometer on the bottom plane). do). The results are shown in Table 1.
Here, as a reference for the relative intensity of the luminescence brightness, the reading on the scale of the luminance meter after 3 elapses after the firefly started to emit light was set at 300 while the firefly was bent.

The brightness increased to 26 after 5 minutes and to 230 after 2α. After the 6th conflict, the number rose to 170.

As shown in the table, plastic (Fllm/Wm inner diameter)
If you put a luminescent liquid in a transparent container and do not insert any materials, it will remain as a luminescent liquid until 1208 days after the luminescence reaction starts.
After a while, the brightness was 60.

As can be seen from this table, it was found that the luminance of glass fiber and asbestos fiber reached 4 to 5 times that of the case without glass fiber and asbestos fiber. (If nothing is added, the brightness is 60, and the brightness of the commercially available rod-shaped light emitter as it is is 300.) Even if the principle of the brightness increasing effect of glass fibers has to be clarified in the future, the phenomenon itself is considered to be unique. Silica fibers have little brightness increasing effect (especially QR8O, .QR2OO), QRlOO
A considerable increase in brightness is observed after engraving, but the reason is that QR8 and 200 are made of paper using an alumina binder, but Q
This is thought to be due to the fact that RlOO water does not contain any alumina.

There are slight differences in the luminescent properties of glass and fiber paper depending on the product, but this is thought to be related to the diameter of the glass fiber itself and the presence or absence of a binder.

By the way, GBlOOR. ．． GC-50 has a small diameter of about 0.3 microns, and GC-90 and GS-25 contain a small amount of organic binder. Example 2: Carefully cut the outer container of a commercially available Chemifirefly, Sailyum 4-inch, 6-inch, etc. luminescent body with a knife so as not to damage the internal encapsulation tube, take out the chemiluminescent agent, which is an organic colored liquid, and with 0.5-6% hydrogen peroxide (H2
When brought into contact with O2 (only O2 and no other components), these two liquids separate into two phases, with H2O2 water on the bottom and the luminescent agent on top, without mixing.

A weak chemiluminescence can be observed only at this interface in the dark. In other words, it is clear that commercially available chemiluminescent agents and hydrogen peroxide solutions cannot provide practical luminescence brightness.
Table 2 shows the results of examining the chemiluminescence brightness when glass fiber paper or cloth or other materials were impregnated with a commercially available chemiluminescent agent and then immersed in an aqueous hydrogen peroxide solution. show.

The measurement container used was the same plastic cylindrical transparent flat bottom container as in Example 1, and 0.5 cc of H2O was added thereto. Water was filled in advance, and a luminescent agent impregnated with glass fiber door paper was inserted into the water. As can be seen from Table 2, the effect of glass fiber is remarkable here as well.

A similar increase in brightness was also observed when glass fiber paper impregnated with hydrogen peroxide solution was inserted and immersed in a commercially available luminescent liquid.

Example 3 Tetraxy N-dimethyl-aminoethylene (Tetrakis
-N-Dimethyl-AmirlO-Ethyle
ne), and the glass fibers shown in Table 3 were used as materials to be impregnated with this drug.

Both F22m/7n1 thickness 0.5~0.67n,/
m, and the material was previously placed flat on the bottom of a F25m/TrL transparent flat-bottomed plastic container.

Then, this was placed in a nitrogen gas atmosphere, in which 0.15 cc of the chemiluminescent agent previously collected in a nitrogen stream was
was dropped onto a material such as glass fiber paper and allowed to stand. Next, this container was placed in the air and the chemiluminescence brightness at the bottom was measured. While placing it in the air, the meter was read, and the maximum value of the chemiluminescence brightness, which reached the maximum value after 30 seconds, was taken as data. This is because the time required to reach the maximum value differs slightly depending on the material. Note that, as in Examples 1 and 2, the standard for reading the photometer meter was the luminance of 300 immediately after the start of chemiluminescence of the commercially available Chemifirefly.

Also, for reference and comparison, 0.15 cc of the drug was placed in a plastic container without any paper or the like placed therein, and the container was then brought into the air and the luminescence was measured. The results obtained are shown in Table 3. Note that the Teflon thin film has the property of allowing oxygen in the air to pass through it, so if one side of the Teflon thin film is brought into contact with the chemiluminescent agent of Example 3 and the other side is placed in the air, oxygen will pass through the Teflon film and cause the chemiluminescent agent to pass through. It moves toward the direction and emits chemiluminescence.

In this application, the following effects of the present invention were recognized. Teflon membrane used: 6 microns thick Teflon manufactured by Nippon Chukoh Kasei Internal dimensions 107n/Wl. ×807n/7T1, envelope-shaped bag.

One bag has a width of 87TL/Trl. , length 507n/7
Insert GB-100R glass fiber door paper. 0 for this
．． It is impregnated with 3 cc of chemiluminescent agent (same as in Example 5), then sealed and sealed. In the other bag for comparison, 0.3 cc of chemiluminescent agent was placed alone in a Teflon bag and sealed.

All these operations were performed in a nitrogen stream.

At the same time, leave these two Teflon bags in the air.
As a result of measuring the chemiluminescence brightness of both after a period of time, it was found that the brightness with the glass fiber door paper was 25 times that of the case with the luminescent agent alone. <Example 4> A commercially available glass wide-mouth pin, with an actual internal volume of 260 cc (inner diameter 57 m/m, inner surface height 98 wL/m), was coated with glass fiber p paper GB-100R on the inner bottom surface. Using cutting clips and stainless steel wire, first set a piece of 190W1,/7n x 907n,/m on the inside surface so that it adheres tightly to the inside surface, then set a piece with a diameter of 55mm on the bottom.
W1. /Trl, was set.

After the bottom and sides were lined with glass fiber door paper in this way, nitrogen gas was passed through the door to completely drive out the air in the paper, and then 10 cc of the chemiluminescent agent used in Example 3 was injected almost uniformly. Glass fiber? Impregnate the paper and store in a tightly capped container. Since it was carried out in a nitrogen stream, no light was emitted. After 10 days, open the bottle, blow enough air into the internal space, and then close the bottle again.

After 3 to 5 minutes, the side and bottom surfaces of the wide-mouthed pins emitted strong light.

<Example 5> GB-100R. ．． GS-
A molded product of F22m/m(7)P paper and zeolani-containing powder with a thickness of 0.5m/7TL1f227n/ml was prepared, and this was placed in a nitrogen gas stream and after the oxygen was completely removed, Example 3 Impregnate 0.2 cc of the same chemiluminescent agent as above.

After placing these in a dark place and confirming that no light was emitted, a gas containing 0.1% volume of oxygen in nitrogen gas was passed through. As a result, luminescence was observed in the inner eye of the three types of plates mentioned above in the dark. Separately, no luminescence was observed for the chemiluminescent agent placed in a plastic cylindrical container. Example 6〉 Transparent polyethylene foil (thickness 0.27TL/7TL) was used to make an envelope shape (dimensions: width 607TL/m x 707T1,/T
rL) Make a flat container.

Then, take a sheet of Toyo Togashi GS-25, which is glass fiber paper, and wrap it with 50W1. Cut into dimensions of /7TL x 50TrL/m. The contents of commercially available psyllium were used as the chemiluminescent liquid. 1.8cc of the contents was transferred to the above GS-25.
It was observed that if the glass tube was impregnated with 5CrR and inserted into an envelope-shaped polyethylene bag (flat plate), and then the oxide in the glass tube in Cylium was added, the entire flat surface immediately emitted strong light.

The brightness reached 310-320 (initial brightness). By the way, for comparison purposes, when we used Ninomashi paper instead of glass fiber paper, and when we placed only 3cc of the luminous material in a polyethylene bag and caused it to emit light, there was almost no noticeable planar luminescence in the room. . In addition, practical planar light emission was obtained even when hydrogen peroxide solution was used instead of the oxidizing agent in the commercially available light emitter. In this case, H2O2 is desirably 1 to 2% or more. 0.
Although the luminance of the 5% H2O2 liquid was weak, the luminescence time was extremely long, and luminescence could be seen with the naked eye in the dark even after 10 days had passed.

In order to perform plane luminescence with glass fiber paper using a commercially available luminescent agent, it is only necessary that the glass fiber paper be present during the reaction, and even if it is inserted into the liquid after emitting light, Alternatively, similar brightness can be obtained by impregnating glass fiber paper with an oxidizing liquid in advance. The same applies to the case where H2O2 is used as an oxidizing agent.

The luminescence characteristics of the Sylium 6 inch differ from the Sairium 4 inch and the Starlit 7 Airy Firefly, and the initial brightness is strong, but in this case as well, the luminance of the liquid itself contained in the flat bag (thin layer) is weak, as in the case of the Sylium 6 inch. By inserting glass fiber paper (1 piece of GB-100R) 39
It became 0 (initial brightness). It was a Chemifirefly 300, and when I transferred the regular luminescence of a 6-inch psyllium into a Chemifirefly container and measured the brightness, the initial brightness was 380. As described above, according to the present invention, it is possible to significantly increase the luminescence brightness using currently commercially available chemiluminescent agents, and since the chemiluminescence occurs on a planar sheet, If the planar sheet is made into various shapes, it is possible to obtain a light emitting body of any shape, whether it is a wide sheet or a long and narrow sheet (wire shape). This has the effect that a planar sheet of any desired form can be made to emit light uniformly regardless of its properties such as flexibility.

[Brief explanation of drawings]

FIGS. 1 to 3 are explanatory views showing various forms of the light-emitting body of the present invention, respectively. In the figure, 1: airtight container, 2: planar sheet.

Claims (1)

[Scope of Claims] 1. A porous body of a substance having the function of increasing chemiluminescence brightness, which is made of one or more selected from glass fiber, silica glass fiber, asbestos, and zeolite, or increasing the chemiluminescence brightness. A planar chemiluminescent material characterized in that a planar sheet of a porous material to which a substance is attached is sealed in a translucent airtight container. 2. Claim 1, characterized in that the planar sheet is impregnated in advance with one of the liquids when the chemiluminescent substance is liquid-liquid, or with that liquid when it is liquid-gas. The planar chemiluminescent material described in . 3. The planar chemiluminescent material according to claim 2, characterized in that when the substance exhibiting chemiluminescence is liquid oxygen, a non-oxidizing atmosphere is provided in the closed container.