JPS591587A - Increasing of luminance of chemical emission - Google Patents

Abstract

PURPOSE:To increase luminance of chemical emission effectively, by adding glass fibers, asbestos, etc. to a chemical illuminant system. CONSTITUTION:Glass fiber, silica glass fiber, superfine artificial fiber, asbestos, zeolite or diatomaceous earth is added to a chemical illuminant system which emits light by contact of a solution of a chemical illuminant such as bis-9,10- phenylethyl anthracene with a solution of an oxidizing substance such as hydrogen peroxide and the system is made to undergo luminescence reaction in the presence thereof. Preferred additives are superfine fibers with a diameter of about 1-2mu and paper, cloth, etc. made thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for increasing brightness in known chemiluminescent phenomena.

Chemiluminescence is a chemical reaction that generates an excited state in the constituent molecules of a substance, and when this transitions to the ground state, it generates visible light. Mu (made in the United States); Kemihotaru, Starlit (made in Japan), etc., are commercially available as ◆.
For example, a solution of bis-9゜10-phenyl ethynyl anthracene dissolved in dibutyl phthalate and a solution of hydrogen peroxide dissolved in dimethyl phthalate are prepared in an isolated state, and the two solutions are mixed to emit light. This is the type of thing. These commercially available Cyreem and Starlit are both of the type that mix a considerable amount of two liquids in a cylindrical body with a certain diameter, and the chemiluminescent properties are achieved by the action of a dispersant added to the liquid. The chemical agent and its oxidizing agent are mixed in an emulsion and a luminescent phenomenon occurs at the interface of countless finely dispersed particles, so it can produce a certain degree of practical brightness, and there is less liquid to participate in the reaction. That is, it has been experimentally confirmed that when the thickness of the liquid in the direction viewed by the observer is thin, the brightness is very weak. In other words, after mixing the two liquids used in the Starlit product currently on the market to cause a luminescent phenomenon, the mixed solution is placed in a transparent plastic envelope-like bag and the thickness of the liquid in the direction of observation is approx. At 0.5%, almost no luminance could be obtained, and only by increasing the liquid thickness to 2X or more could a certain degree of luminance be obtained.

Therefore, although rod-shaped luminescent bodies can be produced using currently commercially available products that apply chemiluminescence, it is practically difficult to apply them to planar luminescent bodies that are large in area and thin.

The present invention relates to a method for eliminating the above-mentioned drawbacks and increasing luminescence brightness, and the gist thereof is to use a drug having chemiluminescent properties,
When the drug is brought into contact with an oxidizing substance that causes it to oxidize and emit light, a chemiluminescent reaction proceeds.

This method of increasing chemiluminescence brightness is characterized by interposing one or more selected from glass fibers, silica glass fibers, asbestos, zeolites, and diatoms into the reaction system either beforehand or after the start of the reaction.

As a result of intervening various substances in the chemiluminescent reaction system in carrying out the present invention, the above-mentioned glass fibers, silica glass fibers, asbestos, zeolite (using an artificial zeolite with the trade name Molecuilar Sieves), and diatomaceous earth have luminescent luminance. It was found that fibrous (paper, cloth, string-like), porous, or powdery forms of these substances have a greater effect. In particular, the brightness enhancement effect is strong in ultrafine fibers of 1 to 2 microns (diameter) or less, as well as paper, cloth, etc. made using such fibers. (Japan Inorganic MM■ product FM paper, etc.) The effect of glass fibers, paper, cloth, string, etc. with a diameter of 5 to 8 microns is slightly weaker than that of 1 to 2 shiba kuron.

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

In addition to the above substances, almost no increase in brightness was observed for naturally produced paper pulp fibers and their products, nylon, saran, rayon, wool, cotton, and silk fibers.

However, for chemiluminescent reactions using air or other gases as the oxidizing agent, as will be described later, the porosity of paper or cloth increases the area where the liquid chemiluminescent agent comes into contact with air or other gases, resulting in a decrease in luminescence brightness. Since there is an increase in brightness, the above-mentioned natural m fibers were also recognized to have a brightness increasing effect compared to the liquid:reaction.

For porous materials such as natural sponges, synthetic sponges, and expanded polystyrene, a slight upward trend was observed, but it was not significant. However, Filton, a commercially available pumice stone with water-repellent properties for waste oil treatment, was highly effective even with liquid:liquid chemiluminescence, but it was not as effective as glass sinter.

In the case of confectionery liquids using air as the oxidizing agent, a slight increase was observed in all porous bodies, regardless of the material, compared to liquids, but in this case as well, 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> Take one stick of commercially available chemiluminescent product name Chemifirefly (9I diameter 45 x length 38~), bend it slightly from approximately the center of the stick to break the glass tube sealed inside, and shake well. When both solutions are mixed, chemiluminescence starts immediately. Now immediately cut off the top of the external rod-shaped plastic container,
The luminescent liquid substance is aspirated using a micro cylinder and 0.15 CC is immediately injected into a flat bottom transparent 10% height cylindrical plastic spring with an inner diameter of 11.0X. Then, it takes 120 minutes to bend the luminescent body and start chemiluminescence.
When 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. do). The results are shown in Table 1.

Here, as a reference for the relative intensity of luminescence luminance, the reading on the scale of a luminance meter 60 seconds after the start of luminescence of a bent firefly in its original state was set as 300.

This luminance was 260 after 5 minutes, and 260 after 20 minutes. After 60 minutes, it was 170.

As shown in the table, if a luminescent liquid is placed in a transparent plastic container (11% inner diameter) and no materials are inserted, the luminance will be 60 after 120 seconds have elapsed from the start of the luminescent reaction. Ta.

Table 1 As can be seen from this table, the luminance of glass fibers and asbestos m-fibers reached 4 to 5 times that of the case without them. (If nothing is added, the brightness is 600, and the brightness of the commercial rod-shaped light emitter as it is is 600.) Even if the principle of the brightness increasing effect of glass fibers will have to be clarified in the future, the phenomenon itself is considered to be unique.

Silica fibers have little brightness increasing effect (especially QR80,
A considerable increase in brightness is observed for QR200) and QR100*, but this is thought to be because QR80 and 200 use an alumina binder to form paper, but QR1oo* does not contain alumina at all.

Even with delicate glass paper, there are slight differences in luminescent properties 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, G
BlooR and GC-50 have a small diameter of approximately 0.6 microns, while GC-90 and G5-25 contain a small amount of organic binder.

<Example 2> Carefully cut the outer container of commercially available Kemifirefly, Sailyum 4-inch, 6-inch, etc. luminescent material with a knife to avoid touching the inner tube with tin [7. Organic! #Take out the chemiluminescent agent, which is a colored liquid, and add it to 05-6% hydrogen peroxide (H
When contacted with zO* (no other components), these two
Do not mix the liquids (H, 02 water on dry side, luminescent agent on top)
separate into phases. In the dark, weak chemiluminescence is observed only at this boundary r&+. In other words, it is clear that commercially available chemiluminescent agents and hydrogen peroxide solutions cannot provide practical luminescence brightness.

Here, we present the results of Jin's investigation of the chemiluminescence brightness when glass fiber #i trade paper or cloth and other materials were impregnated with a commercially available chemiluminescent agent and then immersed in a hydrogen peroxide aqueous solution. It is shown in Table 2. The measurement container was the same plastic cylindrical transparent flat bottom container as in Example 1, and 0.50C H2O was added to it.
2 Water was added in advance, and a luminescent agent impregnated with glass fiber P paper or the like 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 reported when a glass m-fiber filter paper impregnated with hydrogen peroxide solution was inserted and immersed in a commercially available luminescent liquid.

Table 2 (Example 6) Tetraxy-N-dimethyl-amino-ethylene (TeLrakis
-N-dimeLhyl-amino-eLbyla
ne), and the glass fibers shown in Table 3 were used as materials to be impregnated with this drug.

Izuwamo/22%, thickness 05-0. <i% and the material was pre-plated flat on the bottom of a 25% clear flat-bottomed plastic container. Then, place it in an atmosphere surrounded by nitrous gas,
In this, the chemiluminescent agent 015ω, which had been collected in advance in a nitrogen stream, was dropped onto a material such as a glass Im paper ring and the like. Next, this container was placed in the air and the chemiluminescence brightness at the bottom was measured. The meter was read as the sample was placed in the air, and the maximum E reading of the chemiluminescence brightness, which reached the maximum value after 60 to 60 seconds, was used as data. This is because the time required to reach the maximum fi differs slightly depending on the material.

As in Example 1.2, the standard for the reading of the photometer meter was set at 600, which was the brightness after the chemiluminescence initiation surface of the commercially available Chemifirefly. Also, for reference and comparison purposes, 0.150C 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 6 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 Nihon Chuko Kasei Seisakusho An envelope-shaped bag with inner dimensions of 10% and 880%.

In one bag, put GB-10OR glass fiber F paper with a width of 8~ and a length of 509. 0 for this. It is impregnated with a leprosy chemiluminescent agent (same as in Example 5), then encapsulated and sealed.

The other one is 0' in a Teflon bag for comparison! iL chemiluminescent agent was added alone and sealed.

All these operations were performed in a nitrogen stream. At the same time, we exposed the two Teflon bags to the air and measured the chemiluminescence brightness of both after 2 hours. The results showed that the brightness with the glass m-fiber filter paper was 25 times that of the case with the luminescent agent alone. showed that.

Table 3 (Example 4) Commercially available glass wide-mouth bottle Actual internal volume approximately 260cc (inner diameter 58, inner purity 98X, inner surface and inner bottom surface all covered with 1 piece of silica fiber GB-10 paper) Using a R-all 9J cutting clip and stainless steel wire, first cut 19 to the inside surface.
A piece of paper with a size of 0 x 90 was set so that it was in close contact with the inner surface, and then a piece of paper with a diameter of 55% was set at the bottom.

After the bottom and sides were lined with a piece of silica fiber paper, the air in the P paper was completely expelled through nitrogen gas, and then 10 cc of the chemiluminescent agent used in Example 31ζ was injected. After uniformly impregnating the silica fiber P paper, store it tightly. 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 bottom side of the wide-mouth bottle emitted strong light.

<Example 5> GB-100R%GS, -25/22 on a glass flat plate
~ 1 paper and Zeorum 6A powder to a thickness of 05~1. (22
% is prepared, and after it is placed in a nitrogen gas stream until the oxygen is completely eliminated, it is impregnated with the same chemiluminescent agent as in Example 3 by 02ω. After confirming that the skewer did not emit light by placing it in a dark place, a gas containing oxygen from a nitrogen gas outlet was passed through the skewer. As a result, the above 3-dotted flat plate showed luminescence in the dark using the white eyes. Place it in a separate plastic cylinder @ container.
No luminescence was observed only with the chemiluminescent agent.

<Example 6> Cut off the top of a rod-shaped container of commercially available Chemifirefly (outer diameter: 459, length: 689), pour 4 milligrams of Molekiller Sieves and commercially available Zeolum-4A powder into the opening, and mix well. After mixing with the luminescent liquid, the upper part was tightly capped, and the glass tube was broken by slightly bending the center as usual, to generate chemiluminescence. The initial brightness for one minute after the start of this light emission is 68
It reached 0.

By the way, the basic comparison is based on the initial light emission brightness of Kemifirefly of 300. Of course, this brightness intensity with the addition of Zeorum 4A is 5 to 10
It diminishes rapidly, disappearing within minutes.

<Example 7> A 4J cylindrical (width: 60 to 70%) flat container is manufactured using transparent polyethylene foil (thickness: 0.2%).

Then, a sheet of Toyo P Paper G8-25, which is glass fiber paper, is taken and cut into a size of 50XXX50X. As the chemiluminescent liquid, a commercially available product from Cyreem was used.

Contents tacc above G5-25.5 cm x 5
When the tube was impregnated with AN and inserted into an envelope-shaped polyethylene bag (flat plate), and then the oxide in the glass tube in Cyreum was added, the entire flat surface was immediately observed to emit strong light. The brightness reached 310-320 (initial scale).

By the way, for comparison, when 5A P paper was used instead of glass fiber paper, and when only 3Q light emitter was used in the polyethylene bag.
When C was added to emit light, almost no noticeable planar light emission was observed indoors.

Practical planar light emission was also obtained by using hydrogen peroxide solution instead of the oxidizing agent in the commercially available luminescent material.

In this case) i202 is preferably 1 to 2% or more. 05%
In the H20° solution, the luminance was weaker, but the luminescence time was extremely long, and luminescence could be seen with the naked eye in the dark even after 10 days. In order to achieve planar luminescence with glass fiber paper using a commercially available luminescent agent, the glass fiber paper only needs to be present during the reaction, and even if the glass fiber paper is first emitted and then inserted into the liquid, Alternatively, similar brightness can be obtained by impregnating glass fiber paper with an oxidizing liquid in advance.

The same applies when H2O2 is used as the oxidizing agent.

The luminescence characteristics of Cyryumuroinchi differ from Cyryumuroinchi, Starlit 75, and Kemihotaru in that the initial brightness is strong, but in this case, as in the case of Kemifirefly, the luminescence brightness (malt) of the liquid itself in the flat bag is Although it is weak, use a skewer to insert glass fiber paper (1 piece of GB-10OR) 3
The brightness was 90 (initial brightness).

When the regular luminescence of Cyreum Roinch was transferred to a Chemifirefly container and the brightness was measured, it was found that according to the present invention, the currently commercially available liquid:
In either case, a liquid-based chemiluminescent agent or a liquid: air-based chemiluminescent agent can be used to greatly increase the luminance, and can be put to practical use even when the thickness of the liquid participating in the chemical reaction is thin. In addition, in the present invention, the substances intervening in the chemiluminescent reaction include glass am, silica glass, asbestos, and zeolite!・Since it is a solid such as diatomaceous earth, by using it in a shadow picture of a wide planar object, it is possible to obtain a wide planar luminous object that was not possible in the past.

Patent Applicant Yanagase ← Law Department Attorney Noriyoshi Ariyoshi Written amendment to the sentinel procedure (voluntary) 1. Indication of the case 1982 Patent Application No. 110391 2 Title of the invention Method for increasing chemiluminescence brightness 3 Person making the amendment Relationship to the case Patent Applicant address il+ The scope of the claims is amended as follows.

1. When bringing a chemical with chemiluminescent properties into contact with an oxidizing substance that causes the chemical to oxidize and emit light to proceed with the chemiluminescent reaction, in advance or after the start of the reaction, it is necessary to , zeolite,
A method for increasing chemiluminescence brightness, characterized by intervening one or more types selected from diatoms in the reaction system.

2. The method for increasing chemiluminescence brightness according to claim 1, wherein the oxidizing substance is a liquid such as hydrogen peroxide.

8. The method for increasing chemiluminescence brightness according to claim 1, wherein the oxidizing substance is air or a gas containing oxygen. (2) On page 4, line 1 of the specification, add ``ultra-fine man-made fiber'' before ``asbestos.''

(3) Add "Ultra-fine man-made fibers," in front of "asbestos" on page 4, line 6.

+11 (4) On page 4, lines 11 and 12, [The brightness enhancement effect makes the fibers thinner” is corrected to “The brightness enhancement effect makes the fiber diameters of glass and artificial fibers thinner.”

(5) Delete “some” on page 4, line 16.

(6) After ``Not recognized.'' on page 5, line 5 [However, as a result of testing the latest products, especially among man-made fibers, the following was revealed.

That is, (a) Regarding fibers such as polyester and nylon, when the fiber diameter was 45 to 55 microns or larger, almost no brightness increasing effect was observed compared to commercially available natural and artificial fibers.

(Example) A paper-like molded product with an average fiber diameter of 06 microns made of polyester pulp as ultra-fine W4 fibers was found to have almost the same brightness increasing effect as glass P paper. ” to join.

(Add [, ultra-fine man-made fibers] after ``glass fibers'' on page 6, line 2).

(8) On page 9, line 12, after ``not having things'', add ``and having a small diameter''.

(9) "Silica fiber P paper" in the following parts of the specification
Correct to "glass m, mF paper".

■Page 17, line 4■Page 17, line 9■Page 17, line 12 (5 places above)Ql Page 22, line 8 of the song “Asbestos”
Added ``Slim and delicate.''

Claims (1)

[Scope of Claims] 1. When a chemical having chemiluminescent properties is brought into contact with an oxidizing substance that causes the chemical to oxidize and emit light to cause a chemiluminescent reaction, glass fibers, silica glass fibers, asbestos, etc. are used in advance or after the start of the reaction. A method for increasing chemiluminescence brightness, characterized by interposing one or more selected from among , zeolite, and silica frozen earth in the reaction system. 2. The method for increasing chemiluminescence brightness according to claim 1, wherein the oxidizing substance is a liquid such as hydrogen peroxide. 8. The method for increasing chemiluminescence brightness according to claim 1, wherein the oxidizing substance is air or a gas containing oxygen.