JP2008013777A - Composition for chemiluminescence and method of chemiluminescence - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new composition for chemiluminescence, facilitating the utilization as a display, and having excellent long-term storage stability and large chemiluminescent effects, and to provide a method of chemiluminescence by using the composition. <P>SOLUTION: The composition for chemiluminescence contains an oxalic acid ester, a fluorescent material, hydrogen peroxide and an organic strong acid, and has pH 3.6-4.2, wherein the reaction of the oxalic acid with the hydrogen peroxide is inhibited. The composition for chemiluminescence contains the oxalic acid ester, the hydrogen peroxide and the organic strong acid, and has pH 3.6-4.2, wherein the reaction of the oxalic acid with the hydrogen peroxide is inhibited. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a chemiluminescent composition and a chemiluminescent method.

  Conventionally, A liquid (fluorescent liquid) containing an oxalate ester and a fluorescent substance contained in one container and B liquid (oxidizing liquid) containing hydrogen peroxide and a catalyst component contained in the other container Systems that cause chemiluminescence by mixing are known.

  In the conventional chemiluminescence system, as described above, chemiluminescence is caused by mixing the A liquid (fluorescent liquid) and the B liquid (oxidizing liquid), but there are various limitations when used as a display device. receive.

  In order to solve the above problem, there is a method of performing chemiluminescence by bringing a solution containing a oxalate ester, a fluorescent substance, and hydrogen peroxide prepared in advance into contact with a light-emitting substrate carrying a catalyst component. It is known (see, for example, Patent Document 1). However, when a solution containing an oxalate ester, a fluorescent substance, and hydrogen peroxide is prepared, the oxalate ester and hydrogen peroxide react slightly to emit light weakly. Therefore, the lifetime of a solution is short and long-term storage stability is lacking. In addition, since a weakly luminescent solution is used in advance, there is a problem that impact is weak when used at an event or the like.

JP 2002-138278 A

  The present invention has been made in view of the above circumstances, and its purpose is to provide a novel chemiluminescent composition that can be easily used as a display device, has excellent long-term storage stability, and has a large chemiluminescent effect. It is to provide a chemiluminescent method used.

  As a result of intensive investigations in view of the above problems, the present inventor can suppress the reaction between the oxalate ester and hydrogen peroxide by adding a strong organic acid to the mixture of the oxalate ester and hydrogen peroxide. The inventors have found that the activity can be maintained even when stored for a long time, and have completed the present invention.

  That is, the first gist of the present invention resides in a chemiluminescent composition containing an oxalate ester, a fluorescent substance, hydrogen peroxide and a strong organic acid.

  The second gist of the present invention resides in a chemiluminescent composition containing an oxalate ester, hydrogen peroxide and a strong organic acid.

  The third gist of the present invention is a chemiluminescence characterized in that a composition containing an oxalate ester, a fluorescent substance, hydrogen peroxide and a strong organic acid is brought into contact with a light-emitting substrate on which a catalyst component is supported. Lies in the way.

  The fourth gist of the present invention is a chemiluminescence characterized in that a composition containing an oxalate ester, hydrogen peroxide and a strong organic acid is brought into contact with a light-emitting substrate carrying a catalyst component and a fluorescent material. Lies in the way.

  The composition for chemiluminescence of the present invention can be easily used as a display device, is excellent in long-term storage, and has a large chemiluminescence effect. Therefore, the chemiluminescent method using the chemiluminescent composition of the present invention can be applied to various display devices, and the industrial value of the present invention is high.

  Hereinafter, the present invention will be described in detail. The composition described in the first aspect of the present invention (hereinafter referred to as the chemiluminescent composition (1)) comprises an oxalate, a fluorescent substance, hydrogen peroxide, and a strong organic acid. The composition described (hereinafter referred to as chemiluminescent composition (2)) comprises an oxalate ester, hydrogen peroxide and a strong organic acid.

  The luminescence principle in the chemiluminescence of the present invention is considered to be the same as that of a conventionally known chemiluminescence system, and is based on a chemical reaction based on each component constituting the conventional A liquid (fluorescent liquid) and B liquid (oxidizing liquid). (Peroxalate chemiluminescence).

  That is, the reaction of oxalate and hydrogen peroxide generates a light emitting intermediate (peroxide), and the fluorescent material emits strong light by the light emitting intermediate. Specifically, a chemiluminescence reaction (peroxalate chemiluminescence) with oxalate and hydrogen peroxide produces 1,2-dioxetanedione or substituted 1,2-dioxetanedione from the peroxide, which is combined with a phosphor. A charge transfer complex is formed between them, and then decomposes into excited phosphors and carbon dioxide. Such a reaction is promoted by the action of the catalyst. Therefore, in this invention, each component which comprises the conventional A liquid (fluorescent liquid) and B liquid (oxidizing liquid) can be used.

  Examples of the oxalate ester (oxalate) include bis (2,4,5-trichloro-6-carbobutoxyphenyl oxalate) and bis (2,4,5-trichloro-6-carbopentoxyphenyl oxalate). And the like.

  The fluorescent material is not particularly limited as long as it has spectral emission at 300 to 1200 nm and is at least partially soluble in the diluent. Examples of these fluorescent substances include anthracene, substituted anthracene, benzoanthracene, phenanthrene, substituted anthracene, benzoanthracene, phenanthrene, substituted phenanthrene, naphthacene, substituted naphthacene, pentacene, substituted pentacene, perylene, substituted perylene, violanthrone, substituted violanthrone, and the like. And conjugated polycyclic aromatic compounds having at least three condensed rings. Examples of the substituent of the above compound include a phenyl group, a lower alkyl group (C1 to C16), a chloro group, a bromo group, a cyano group, and an alkoxy group (C1 to C16).

  Suitable fluorescent materials include 9,10-bis (phenylethynyl) anthracene, 1-methoxy-9,10-bis (phenylethynyl) anthracene, perylene, 1,5-dichloro-9,10-bis (phenylethynyl) Anthracene, 1,8-dichloro-9,10-bis (phenylethynyl) anthracene, rubrene, monochloro and dichloro-substituted 9,10-bis (phenylethynyl) anthracene, 5,12-bis (phenylethynyl) tetracene, 9,10 -Diphenylanthracene, 16,17-dihexyloxyviolanthrone, 2-methyl-9,10-bis- (phenylethynyl) anthracene, 9,10-bis- (4-methoxyphenyl) -2-chloroanthracene, 9, 10-bis- (4-ethoxyphenyl) -2-chloroa Tracene, 16,17-didecycloxyviolanthrone, “Lumogen Red” (“LUMOGEN RED”, perylenedicarboxyimide fluorescent agent emitting red), (“LUMOGEN YELLOW”, perylenedicarboximide fluorescent agent emitting yellow ), ("LUMOGEN ORANGE", perylene dicarboxyimide fluorescent agent emitting orange), 5,12-bis- (phenylethynyl) naphthacene, 5,6,11,12-tetraphenylnaphthacene and mixtures thereof. It is done.

  As hydrogen peroxide, commercially available products can be used.

  In the chemiluminescent compositions (1) and (2) of the present invention, the proportions of the above components can be arbitrarily selected according to conventionally known chemiluminescent materials. In general, the amount ratio (molar ratio) of oxalate to fluorescent material is sufficient to cause chemiluminescence, but is preferably 20 to 40: 1.

The organic strong acid used in the present invention has a function of adjusting the pH of the chemiluminescent composition and suppressing the reaction between the oxalate ester and hydrogen peroxide, and is not particularly limited as long as it has this function. . The pka of the strong organic acid is usually 2 or less, preferably -2 to 2, although it depends on the amount of strong organic acid used. As the organic strong acid, an aromatic strong acid or an aliphatic strong acid having a sulfonic acid group, a phosphoric acid group, or a carboxylic acid group is preferable. As aromatic sulfonic acids, benzene sulfonic acid, o-toluene sulfonic acid, m-toluene sulfonic acid, p-toluene sulfonic acid, o-xylene-3-sulfonic acid, o-xylene-4-sulfonic acid, o-xylene -5-sulfonic acid, p-xylenesulfonic acid, o-benzenesulfonic acid, m-benzenesulfonic acid, p-benzenesulfonic acid, 1,3,5-benzenetrisulfonic acid, o-chlorobenzenesulfonic acid
, M-chlorobenzenesulfonic acid, p-chlorobenzenesulfonic acid, o-bromobenzenesulfonic acid, m-bromobenzenesulfonic acid, p-bromobenzenesulfonic acid, o-phenolsulfonic acid, m-phenolsulfonic acid, p-phenolsulfone Examples include acids, phenol-2,4-disulfonic acid, catechol-3,5-disulfonic acid, nitrobenzenesulfonic acid, 4-chloro-3-methyl-5-nitrozenzensulfonic acid, 4-hydroxy-3-nitrobenzenesulfonic acid, etc. Is done.

  Examples of the aliphatic sulfonic acid include methanesulfonic acid, ethanesulfonic acid, methanedisulfonic acid, 1,2-ethanedisulfonic acid, 2-hydroxyethanesulfonic acid, sulfoacetic acid and the like.

  Examples of the organic strong acid having a phosphoric acid group or a carboxylic acid group include organic phosphoric acids such as 2-glycerin phosphoric acid, p-glucose-1-phosphoric acid, nitroacetic acid, and picolinic acid, and carboxylic acids.

  The above strong organic acids may be used in combination of two or more. Among the above strong organic acids, p-toluenesulfonic acid and nitroacetic acid are preferable, and p-toluenesulfonic acid is more preferable from the viewpoint of low cost and easy availability.

  In the present invention, a strong organic acid is used to suppress the reaction between the oxalate ester and hydrogen peroxide. However, when a carboxylic acid or the like, which is a weak acid, is used, the above reaction suppression cannot be achieved and is stronger. When mineral acids (hydrochloric acid, sulfuric acid, etc.) are used, oxalic acid esters and hydrogen peroxide are decomposed. Further, it is conceivable to dilute and use the mineral acid, but the addition of the diluted acid reduces the concentration of the oxalate ester and hydrogen peroxide, thereby reducing the reactivity.

The amount of the strong organic acid to be added varies depending on the pka of the strong organic acid to be used. Usually, it is added in an amount of 0.1 mmol times or more, preferably 10 mmol times or more, per mol of hydrogen peroxide. If the amount added is too small, the reaction between the oxalate ester and hydrogen peroxide may not be suppressed. If the amount added is too large, the acidity becomes too strong, and chemiluminescence may not occur even when contacted with the catalyst.

The pH of the chemiluminescent compositions (1) and (2) is usually 3.0 to 4.5, preferably 3.6.
~ 4.2. If the pH is lower than 3.0, there is a possibility that chemiluminescence does not occur even when contacted with the catalyst. If the pH is higher than 4.5, the reaction between the oxalate and hydrogen peroxide may not be suppressed. There is sex.

  In the chemiluminescent compositions (1) and (2) of the present invention, a solvent may be used as necessary. Examples of the solvent include esters, alcohols, and the like. As the esters, phthalic esters such as dimethyl phthalate and dibutyl phthalate are preferable. As alcohols, tertiary alcohols are preferable, and t-butanol is more preferable.

  The chemiluminescent composition (1) emits chemiluminescence when brought into contact with the catalyst, and the chemiluminescent composition (2) emits chemiluminescence when brought into contact with the mixture of the catalyst and the fluorescent material. Examples of the catalyst (activator) include salicylic acid and derivatives thereof such as lithium salicylate, lithium 5-t-butylsalicylate, sodium salicylate, tetraalkylammonium salicylate, lithium 2-chlorobenzoate, rubidium acetate, and the like. Examples thereof include metal salts or ammonium salts of derivatives or acetic acid.

  The method for preparing the chemiluminescent compositions (1) and (2) of the present invention is not particularly limited. In the case of the chemiluminescent composition (1), oxalate ester, fluorescent substance, hydrogen peroxide and strong organic acid In the case of the chemiluminescent composition (2), oxalic acid ester, hydrogen peroxide and strong organic acid can be mixed and prepared by any method. From the viewpoint of long-term storage stability, it is preferable to prepare by the following method so as not to start the reaction.

  That is, in the case of the chemiluminescent composition (1), a solution (referred to as solution A) comprising an oxalate ester, a fluorescent substance and, if necessary, a solvent is prepared. Separately, hydrogen peroxide, strong organic acid If necessary, a solution comprising a solvent is prepared (referred to as solution B), and the solution A and the solution B are mixed to prepare the chemiluminescent composition (1) of the present invention. In the case of the chemiluminescent composition (2), a solution (referred to as solution A ′) comprising an oxalate ester and, if necessary, a solvent is prepared. Separately, hydrogen peroxide, a strong organic acid, and if necessary Then, a solution composed of a solvent is prepared (referred to as solution B), and the solution A ′ and the solution B are mixed to prepare the chemiluminescent composition (2) of the present invention. In the above preparation method, the pH of hydrogen peroxide is adjusted to be weakly acidic with an organic strong acid and then mixed with the oxalate, so that the reaction between hydrogen peroxide and the oxalate can be minimized.

  The chemiluminescent composition (1) of the present invention contains a fluorescent substance, but no chemiluminescent phenomenon is observed in the chemiluminescent composition (1) prepared as described above. This is because the pH of the chemiluminescent composition (1) is adjusted to a region where the reaction between the oxalate ester and hydrogen peroxide is suppressed by adding a strong organic acid. Similarly, in the chemiluminescent composition (2) of the present invention, the reaction of the oxalate ester with hydrogen peroxide is suppressed by adding a strong organic acid to the pH of the chemiluminescent composition (2). Is adjusted to the area. Therefore, the chemiluminescent compositions (1) and (2) of the present invention can be stored stably for a long period of time. Further, since no chemiluminescence phenomenon is observed, the effect of chemiluminescence when brought into contact with the catalyst is very large.

  On the other hand, the pH of a chemiluminescent composition composed of an oxalate ester, a fluorescent substance and hydrogen peroxide without the addition of a strong organic acid is higher than the region where the reaction between the oxalate ester and hydrogen peroxide is suppressed. The reaction between the oxalate ester and hydrogen peroxide occurs slightly and weak chemiluminescence occurs, so that it cannot be stored for a long time. Moreover, since it has emitted light weakly in advance when used in an event or the like, the effect of chemiluminescence upon contact with the catalyst is weak.

  In the chemiluminescent method of the present invention, in the case of the chemiluminescent composition (1), the catalyst is supported on the light emitting substrate, and in the chemiluminescent composition (2), the catalyst and A fluorescent material is supported. And chemiluminescence is performed by making the solution containing the composition (1) or (2) for chemiluminescence of this invention corresponding to such a light emitting base material contact, respectively.

  The type of the light-emitting substrate is not particularly limited as long as it can carry a catalyst component or a fluorescent substance, and examples thereof include a glass fiber sheet, paper (filter paper), a glass sheet, a plastic sheet, and a metal sheet. The catalyst or the composition comprising the catalyst and the fluorescent material is supported on the surface of the light emitting substrate by a kneading method or a solution spraying method.

  Since the chemiluminescent method of the present invention uses the light-emitting substrate as described above, it can be easily used as a display device. For example, a display (for example, an arrow) is provided on the surface of the sheet by carrying a catalyst or a composition composed of a catalyst and a fluorescent material to form a display portion, and the chemiluminescent composition of the present invention can be supplied and provided with a window. The above-mentioned display part is attached to the inside of the window of the container, and the chemiluminescent composition is supplied when light emission is necessary. As a result, the composition comprising the catalyst component or the catalyst and the fluorescent material supported on the display (for example, the arrow) and the chemiluminescent composition come into contact with each other, and the display (for example, the arrow) emits light.

  The chemiluminescence method of the present invention can be suitably used for a display device. In this case, the light-emitting substrate constitutes the display unit as described above. And the display part, such as a character, a figure, a symbol, is formed by carrying | supporting the composition which consists of a catalyst or a catalyst, and a fluorescent substance. The chemiluminescence method of the present invention is particularly useful as an emergency display during a power failure. In this case, the composition for chemiluminescence is supplied by a battery or a method using a head.

  For example, it can be suitably used as a display line for evacuation guidance. That is, in an evacuation guide light that continuously displays an evacuation route to an emergency exit in a line with a pipe or the like, a catalyst or a composition comprising a catalyst and a fluorescent material is carried in the pipe, and the present invention is used at the time of use. When the composition for chemiluminescence (1) or (2) is circulated in the pipe, it can be used as an evacuation guide light by linear and continuous chemiluminescence. In the conventional method of causing chemiluminescence by mixing A liquid (fluorescent liquid) and B liquid (oxidizing liquid), mixing preparation takes time, and the chemiluminescence ability is lost before reaching the end of the pipe. There was a possibility. In addition, the method described in JP-A No. 2002-138278 has a problem that the solution has a short life and lacks long-term storage stability. By using the chemiluminescent method using the chemiluminescent composition of the present invention, an excellent chemiluminescent display device can be provided.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded.

Example 1:
10% by weight of bis (2,4,5-trichloro-6-carbobutoxyphenyl oxalate) as an oxalate ester and 9,10-bis- (4-methoxyphenyl) -2-chloroanthracene as a blue fluorescent substance A solution consisting of .12% by weight and 89.88% by weight of dimethyl phthalate as a solvent was prepared (referred to as solution a). Meanwhile, a solution comprising 3% by weight of hydrogen peroxide, 0.01% by weight of p-toluenesulfonic acid as a strong organic acid, 89.99% by weight of dibutyl phthalate and 7% by weight of tertiary butanol as a solvent was prepared ( Referred to as solution b). Next, when the solution a and the solution b were mixed, a transparent solution was obtained (referred to as a solution ab), and no light emission phenomenon was observed. The pH of the solution ab was 4.0.

Next, a 1% by weight aqueous solution containing sodium salicylate as a catalyst was prepared, applied to a white cloth and dried to prepare a white cloth unchanged from that before drying. Next, when the solution ab was applied to the brush and the letters were written on the white cloth, the letters that emitted blue light emerged. In addition, when the same operation was performed using the solution ab after storage at room temperature for 10 days, a blue light-emitting character emerged in the same manner. Therefore, it was found that the long-term storage stability of the solution ab was excellent.

Example 2:
A solution consisting of 10% by weight of bis (2,4,5-trichloro-6-carbobutoxyphenyl oxalate) as an oxalate and 90% by weight of dimethyl phthalate as a solvent was prepared (referred to as solution c). Meanwhile, a solution comprising 3% by weight of hydrogen peroxide, 0.01% by weight of p-toluenesulfonic acid as a strong organic acid, 89.99% by weight of dibutyl phthalate and 7% by weight of tertiary butanol as a solvent was prepared ( Referred to as solution d). Next, when the solution c and the solution d were mixed, a transparent solution was obtained (referred to as solution cd). The pH of the solution cd was 4.0.

  Next, a methanol solution containing 1% by weight of sodium salicylate as a catalyst and 0.12% by weight of 9,10-bis- (4-methoxyphenyl) -2-chloroanthracene as a blue fluorescent material was prepared, and a white cloth was prepared. A white cloth that was the same as before drying was prepared. Next, when the solution cd was applied to the brush and the letters were written on the white cloth, the letters that emitted blue light emerged. In addition, when the same operation was performed using the solution cd after storage at room temperature for 10 days, a blue light-emitting character similarly emerged. Therefore, it was found that the long-term storage stability of the solution cd was excellent.

Comparative Example 1:
Solutions a and b ′ were prepared in the same manner as in Example 1 except that p-toluenesulfonic acid was not added and 90% by weight of dimethyl phthalate was used in Solution B of Example 1. Next, when the solution a and the solution b were mixed, a transparent solution was obtained (referred to as solution ab ′), but a light blue luminescence phenomenon was observed. The pH of the solution ab ′ was 5.0. When solution ab ′ was stored at room temperature for 3 days, blue light was not emitted. As in Example 1, a white cloth coated with an aqueous solution of sodium salicylate and dried was written with a solution ab ′ that stopped emitting light on the brush, but the characters that emitted blue light did not emerge, and the solution ab ′ Was dead.

Claims (4)

  A chemiluminescent composition containing an oxalate, a fluorescent substance, hydrogen peroxide and a strong organic acid, having a pH of 3.6 to 4.2, and a reaction between the oxalate and hydrogen peroxide being suppressed. .   A chemiluminescent composition containing an oxalate ester, hydrogen peroxide, and a strong organic acid, having a pH of 3.6 to 4.2, and suppressing a reaction between the oxalate ester and hydrogen peroxide.   The composition for chemiluminescence according to claim 1 or 2, wherein the pka of the strong organic acid is 2 or less.   The chemiluminescent composition according to any one of claims 1 to 3, wherein the strong organic acid is p-toluenesulfonic acid.