WO2015005246A1 - Oxidizing fluid for chemiluminescent body and chemiluminescent system containing same - Google Patents

Oxidizing fluid for chemiluminescent body and chemiluminescent system containing same Download PDF

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WO2015005246A1
WO2015005246A1 PCT/JP2014/067965 JP2014067965W WO2015005246A1 WO 2015005246 A1 WO2015005246 A1 WO 2015005246A1 JP 2014067965 W JP2014067965 W JP 2014067965W WO 2015005246 A1 WO2015005246 A1 WO 2015005246A1
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chemiluminescent
solution
solvent
flash point
oxidizing solution
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PCT/JP2014/067965
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French (fr)
Japanese (ja)
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裕之 佐野
正隆 小林
英幸 岡
智一 下川
沙織 下郡
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株式会社ルミカ
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Priority to JP2015526311A priority Critical patent/JP6495169B2/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C09K11/07—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials having chemically interreactive components, e.g. reactive chemiluminescent compositions
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21K—NON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
    • F21K2/00—Non-electric light sources using luminescence; Light sources using electrochemiluminescence
    • F21K2/06—Non-electric light sources using luminescence; Light sources using electrochemiluminescence using chemiluminescence

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  • the present invention relates to an oxidation solution for chemiluminescent bodies and a chemiluminescent system comprising the same. More specifically, the present invention relates to a chemiluminescent system comprising a chemiluminescent oxidizing solution obtained by adding an antioxidant to a chemiluminescent oxidizing solution and a chemiluminescent fluorescent solution.
  • chemiluminescence is generated at any time by mixing with a solution (oxidizing solution) containing a salt) and used for the purpose.
  • a solvent is used so that the concentration of the content is adjusted and the reaction species in both solutions are mixed and reacted uniformly.
  • aromatic solvents such as phthalates and benzoates are used as the solvent.
  • the solvent used as an oxidizing solution in the past includes alcohols such as ethanol, which has a low flash point, both phthalic acid and non-phthalic acid, and therefore has a low flash point of about 20 ° C to 40 ° C. Was showing.
  • alcohols such as ethanol
  • Patent Documents 2 to 5 propose techniques for using a specific solvent as a solvent for the oxidizing liquid.
  • the flash point can be increased by changing to the solvent design of the oxidizing solution for chemiluminescent materials as disclosed in the above-mentioned patent document.
  • the inventors of the present invention have a possibility that the high flash point solvent oxidizing solution may change over time when the high flash point solvent oxidizing solution is stored for a long period of several years at room temperature in the process of further evaluation. I found.
  • An object of the present invention is to provide a method for suppressing the change over time of the oxidation solution for chemiluminescent bodies and an oxidation solution for suppressing the change over time.
  • the present invention relates to the following inventions.
  • the antioxidant is a phenol-based antioxidant.
  • the phenolic antioxidant is at least one antioxidant selected from hydroquinone, catechol, resorcinol, tert-butylhydroquinone, butylhydroxyanisole, hydroquinone monomethyl ether and di-t-butyl-p-cresol.
  • the oxidizing solution for chemiluminescent materials according to ⁇ 2> which is an agent.
  • ⁇ 4> The oxidation for chemiluminescent materials according to any one of ⁇ 1> to ⁇ 3>, wherein the concentration of the antioxidant is 0.05 mmol / L or more and 10 mmol / L or less with respect to the entire oxidizing solution. liquid.
  • the solvent is phthalic acid esters, citric acid esters, benzoic acid esters, trimellitic acid esters, adipic acid esters, sebacic acid esters, azelaic acid esters, glycerin esters, lactones,
  • the oxidizing solution for chemiluminescent materials according to any one of ⁇ 1> to ⁇ 4>, wherein the oxidizing solution is a mixture of at least two selected from glycols and alkyl glycol ethers.
  • a chemiluminescence system comprising the chemiluminescent substance oxidizing solution according to any one of ⁇ 1> to ⁇ 5>, and a fluorescent solution containing an oxalate ester and a fluorescent substance .
  • the oxidizing solution for chemiluminescent materials according to the present invention can be an oxidizing solution for chemiluminescent materials that has little reduction in flash point when a long time has passed and little reduction in luminous luminance. This makes it possible to provide a chemiluminescent material that can be used for a long period of time and stored for a long period of time and is more reliable even in an environment where the temperature tends to be high.
  • the present invention relates to an oxidizing solution for a chemiluminescent body containing hydrogen peroxide and a solvent, which generates a chemiluminescence phenomenon when mixed with a fluorescent solution containing an oxalate ester and a fluorescent substance, and the flash point of the oxidizing solution Is 60 ° C. or higher and relates to the chemiluminescent oxidizing solution containing an antioxidant in the oxidizing solution.
  • the chemiluminescent oxidizing solution of the present invention is a chemiluminescent fluorescent solution containing oxalic acid ester and a fluorescent substance (hereinafter simply referred to as “fluorescent solution”). And have the effect of causing a chemiluminescence phenomenon when mixed with.
  • the oxidizing solution contains hydrogen peroxide, which is an oxidizing agent, as an essential component, and adjusts the concentration of this hydrogen peroxide to improve the compatibility (mixing property) with the fluorescent substance in the fluorescent solution described later. It contains a solvent for improving the solubility of salicylate and the like added to improve the solubility.
  • this oxidizing solution has a flash point of 60 ° C. or higher, preferably 70 ° C. or higher, particularly preferably 100 ° C. or higher.
  • the flash point is a value measured by a rapid equilibrium sealing method defined in JIS K2265-2.
  • the dangerous rank in the Fire Service Act is designated as the third petroleum class (70 to 200 ° C.), and the safety rank is further increased. Furthermore, when the flash point in the oxidizing solution of the present invention is 100 ° C. or higher, the safety of the fireproof surface is remarkably increased.
  • the solvent contained in the oxidizing solution of the present invention is characterized by containing an antioxidant.
  • the oxidizing solution of the present invention contains a hydrogen peroxide solution and is a solvent intended to be oxidized. Therefore, the inclusion of an antioxidant in the solvent tends to be avoided.
  • the present inventors have found that the flash point and emission luminance of the oxidizing solution are stabilized for a long period of time by containing an antioxidant in the oxidizing solution, and have reached the present invention.
  • the antioxidant means a substance that suppresses decomposition of hydrogen peroxide, solvent, etc. of the oxidizing solution by reacting with free radicals and peroxides to change into a stable substance.
  • hydrogen peroxide contained in the oxidizing solution may be decomposed and may no longer function as the oxidizing solution.
  • an ester solvent is often used as the solvent of the high flash point oxidizing solution in consideration of odor, stability, compatibility with the fluorescent solution, and the like.
  • ester-based solvents change to low flash point substances when decomposed. This decomposition is caused by a reaction with the surrounding environment, oxygen in the air, etc.
  • an organic antioxidant is preferably used from the viewpoint of compatibility with an oxidizing solution.
  • phenolic antioxidants are particularly preferably used.
  • Phenol-based antioxidants are highly compatible with the solvent contained in the oxidizing solution and are uniformly dissolved and dispersed, and generate acids and alkalis so that they do not react excessively with other components in the oxidizing solution.
  • the oxidation of the present invention has advantages such as being difficult, and reducing the oxidizing function of the oxidizing solution, which may reduce the light-emitting property when mixed with the fluorescent solution, so that the reducing property is not too high. Suitable as an inhibitor.
  • the phenolic antioxidant refers to an antioxidant having a phenol group in the molecule, and a monophenolic antioxidant, a bisphenolic antioxidant, a high-molecular phenolic antioxidant, etc. having a phenol derivative are used. be able to.
  • the phenolic antioxidant preferably used in the present invention include hydroquinone (1,4-benzenediol), catechol (1,2-benzenediol), resorcinol (1,3-benzenediol), and tert-butylhydroquinone. Butylhydroxyanisole, hydroquinone monomethyl ether (4-methoxyphenol), di-t-butyl-p-cresol (DBPC) and the like.
  • antioxidants may be used alone, or two or more kinds of antioxidants may be appropriately used.
  • phenolic antioxidants hydroquinone and di-t-butyl-p-cresol are more preferably used.
  • the antioxidant selected as this preferred antioxidant is not only excellent in the long-term stability of the flash point and emission luminance when mixed with the oxidizing solution of the present invention, but also has almost no coloring of the oxidizing solution or the like. Further, it is further excellent in that precipitates are hardly generated.
  • the concentration of the antioxidant depends on the type of phenolic antioxidant to be added, the concentration of each component in the oxidizing solution, the assumed storage period, etc., but preferably 0.05 mmol / L with respect to the entire oxidizing solution. As mentioned above, More preferably, it is 0.3 mmol / L or more.
  • the concentration of the antioxidant is too low, there is a possibility that the flash point lowering suppressing ability and the hydrogen peroxide decomposition inhibiting function may not be exhibited for a sufficient period.
  • the upper limit becomes like this.
  • it is 10 mmol / L or less, More preferably, it is 5 mmol / L or less, More preferably, it is 3 mmol / L or less.
  • the oxidation function of oxidation liquid may be inhibited and the emitted light brightness when mixed with fluorescent liquid may fall.
  • the emission color of the illuminant may be different due to the coloring of the antioxidant.
  • a solvent selected from the following compounds or a mixture thereof can be used as the solvent contained in the oxidizing solution of the present invention.
  • the solvent contained in the oxidizing solution in the present invention include citrate esters, phthalate esters, benzoate esters, trimellitic acid esters, adipic acid esters, sebacic acid esters, azelain.
  • a solvent containing an organic solvent such as acid esters, glycerin esters, lactones, glycols, alkyl glycol ethers is preferably used. From these solvents, those having a flash point of 60 ° C. or higher are used as the main solvents, and the flash point as a whole becomes 70 ° C. or higher, and a solvent that can achieve the object of the present invention can be selected and used. .
  • the main solvent is designed from the high flash point and the high blending ratio when adjusting the blending amount so that the flash point can achieve the target temperature of the present invention. It refers to the solvent that is the center of time.
  • the solvent may be a main solvent alone.
  • triethyl citrate flash point: 151 ° C.
  • tributyl acetyl citrate flash point: 204 ° C.
  • solvents for phthalates dimethyl phthalate (flash point: 146 ° C.), diethyl phthalate (flash point: 166 ° C.), and dibutyl phthalate (flash point: 157 ° C.) are used.
  • benzyl benzoate flash point: 148 ° C.
  • butyl benzoate flash point: 122 ° C.
  • Trimellitic acid trimethyl (flash point: 182 ° C), trimellitic acid tripropyl (no flash point), trimellitic acid tri-n-butyl (flash point: 215 ° C) Trimellitic acid tris (2-ethylhexyl) (flash point: 262 ° C.) is used.
  • dimethyl adipate flash point: 122 ° C.
  • diethyl adipate flash point: 127 ° C.
  • diisopropyl adipate flash point: 136 ° C.
  • diisobutyl adipate flash point: 156 ° C.
  • diisononyl adipate flash point: 232 ° C.
  • sebacic acid esters diethyl sebacate (flash point: 220 ° C.) and dibutyl sebacate (flash point: 190 ° C.) are used.
  • azelaic acid esters bis (2-ethylhexyl) azelate (flash point: 211 ° C.) can also be used.
  • a solvent for glycerin esters triacetin (glycerin triacetate) (flash point: 148 ° C.) or the like is used.
  • the lactone solvent ⁇ -butyrolactone (flash point: 98 ° C.) or the like is used.
  • glycol solvents include hexylene glycol (flash point: 96 ° C.), propylene glycol (flash point: 99 ° C.), and triethylene glycol (flash point: 177 ° C.).
  • These are easily soluble in hydrogen peroxide as an oxidizing agent and salicylate as a catalyst, and are excellent in compatibility with a fluorescent solution containing a fluorescent substance.
  • These solvents are preferably used in a mixture of at least two kinds, and the flash point of the mixed solvent (oxidizing solution) is 60 ° C. or higher. From the viewpoint of fire resistance, the flash point of these solvents alone is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and particularly preferably 100 ° C. or higher.
  • the solvent is dimethyl phthalate, diethyl phthalate, triethyl citrate, tributyl acetyl citrate, benzyl benzoate, tri-n-butyl trimellitic acid, tris (2-ethylhexyl) trimellitic acid, adipine Diethyl acetate, diisobutyl adipate, bis (2-ethylhexyl) azelate, hexylene glycol, propylene glycol, ⁇ -butyrolactone, triacetin (glycerol triacetate), 3-methoxy-3-methylbutanol, diethylene glycol dimethyl ether, diethylene glycol monoethyl A mixture of at least two selected from ether, diethylene glycol monomethyl ether and tripropylene glycol monomethyl ether.
  • the oxidizing solution is dimethyl phthalate, diethyl phthalate, triethyl citrate, tributyl acetyl citrate, benzyl benzoate, butyl benzoate, trimethyl trimellitic acid, tripropyl trimellitic acid, tri-n-butyl trimellitic acid
  • solvent A selected from tris (2-ethylhexyl) trimellitic acid, diethyl adipate, diisopropyl adipate, diisobutyl adipate, diethyl sebacate and bis (2-ethylhexyl) azelate , Hexylene glycol, propylene glycol, butyrolactone, triethylene glycol, triacetin (glycerin triacetate), diethylene glycol dimethyl ether, 3-methoxy-3-methylbutanol, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono
  • the mixing ratio of the solvent is appropriately determined depending on the use of the final product and the required safety.
  • the ratio (volume ratio) of solvent A to solvent B is generally 1:99 to 99: 1, preferably 10:90 to 90:10, More preferably, it is 20:80 to 80:20.
  • the solvent A such as triethyl citrate and benzyl benzoate is the main solvent of the oxidizing solution
  • the solvent B such as 3-methoxy-3-methylbutanol and hexylene glycol is used as the auxiliary solvent.
  • the oxidizing solution of the present invention preferably further contains polyethylene glycol or polypropylene glycol.
  • polypropylene glycol is preferably used from the viewpoints of miscibility, chemical stability, and luminance.
  • Polyethylene glycol and polypropylene glycol are preferably those having a low molecular weight to a medium molecular weight from the viewpoint of compatibility with the oxidizing solution.
  • the addition amount of polyethylene glycol and / or polypropylene glycol is 1 to 50% by volume, preferably 2 to 25% by volume, based on 100% by volume of the entire solvent.
  • the concentration of hydrogen peroxide in the oxidizing solution can be appropriately selected depending on the purpose of use, but is usually 0.5 to 10% by weight, preferably 3 to 6% by weight.
  • salicylic acid and its derivatives such as lithium salicylate, ammonium salicylate, sodium salicylate, tetraalkylammonium salicylate and the like as a usual catalyst component (usually 0.1 mmol with respect to the oxidation solution) / L to 10 mmol / L).
  • the fluorescent solution contains an oxalate ester, a fluorescent substance, and a solvent, and generates a chemiluminescence phenomenon when mixed with an oxidizing solution containing hydrogen peroxide.
  • oxalate esters (oxalate) used in the present invention oxalic acid derivatives such as oxalic acid halides, oxalic acid esters and oxalic acid oxamides can be used.
  • Typical oxalates include, for example, bis (2, 4, 5-trichloro-6-carbobutoxyphenyl) oxalate, bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate and the like.
  • the fluorescent substance is not particularly limited as long as it is a fluorescent compound having spectral emission at 300 to 1200 nm and at least partially soluble in a solvent.
  • These fluorescent compounds include conjugated polycyclic aromatics having condensed rings such as anthracene, substituted anthracene, benzoanthracene, phenanthrene, substituted phenanthrene, naphthacene, substituted naphthacene, pentacene, substituted pentacene, perylene, substituted perylene, violanthrone, substituted violanthrone, etc. Examples are compounds.
  • the substituent of the above compound is not particularly limited as long as it does not hinder the luminescence reaction, and examples thereof include a phenyl group, a lower alkyl group, a chloro group, a bromo group, a cyano group, an alkoxy group, and a phenylnaphthyl group.
  • Specific fluorescent materials include 2-chloro-9,10-bis (4-methylethynyl) anthracene, 9,10-bis (phenylethynyl) anthracene, 1-methoxy-9,10-bis (phenylethynyl) anthracene.
  • Examples of products of these fluorescent substances include Lumogen Red (LUMOGEN RED, perylene dicarboxyimide fluorescent agent emitting red, BASF, trade name), Lumogen Yellow (LUMOGEN YELLOW, perylene dicarboximide fluorescent emitting yellow).
  • Agent, BASF, trade name Lumogen Orange (LUMOGEN ORANGE, perylenedicarboxyimide fluorescent agent that emits orange, BASF, trade name) is preferably used.
  • acetyl tributyl citrate ATBC
  • BeB benzyl benzoate
  • DDM dipropylene glycol dimethyl ether
  • the flash point of the fluorescent liquid is equal to or higher than the flash point (60 ° C.) required for the oxidizing liquid.
  • the composition ratio of each component in the fluorescent solution can be arbitrarily selected according to the purpose to be used.
  • the amount ratio (molar ratio) between the oxalate ester and the fluorescent material is an amount sufficient to generate chemiluminescence, but is preferably 20: 1 to 40: 1.
  • the amount ratio of the solvent to the oxalate ester can also be appropriately selected depending on the purpose of use, but usually the concentration of the oxalate ester is 0.01 to 0.5 mol / L, preferably 0.05 to 0.3 mol / L. An amount of solvent that is L is used.
  • an additive such as a surfactant can be added to the oxidizing solution and the fluorescent solution as needed within a range not impairing the gist of the present invention.
  • the oxidizing solution and the fluorescent solution can be used by being supported on a light-emitting base material such as a nonwoven fabric, a woven fabric, glass or plastic.
  • the chemiluminescent oxidation solution of the present invention produces a chemiluminescent phenomenon when mixed with a chemiluminescent phosphor containing an oxalate ester and a fluorescent substance. That is, the oxidation solution of the present invention constitutes a chemiluminescence system in combination with the above-described fluorescent solution.
  • a chemiluminescence system in which a catalyst component or a fluorescent substance is supported on these light-emitting substrates and other solutions are brought into contact with each other can be obtained.
  • the oxidizing solution of the present invention and the chemiluminescence system using the same can provide a highly safe system having excellent chemiluminescence performance.
  • the period for maintaining the safety is very long, and it is suitable for long-term storage. Specific examples of this chemiluminescent system include those used in open systems such as ceremonies and events, and sealed chemiluminescent materials used for concerts and warning lights.
  • the oxidizing solution contains hydrogen peroxide (H 2 O 2 ) and sodium salicylate (SS).
  • Luminance was measured by the following method using a luminance meter (manufactured by Konica Minolta: LS-100). In a dark room, a transparent container is installed at a distance that satisfies the measurement field of the luminance meter, and 1 mL of the fluorescent solution and 1 mL of the oxidizing solution are mixed therein, and the mixture is vigorously stirred using a small stirring homogenizer. The value with the highest intensity at this time was defined as the emission luminance immediately after the start of the reaction. Thereafter, the transparent container and the sample were allowed to stand, and the emission luminance was measured again after 5 minutes.
  • Examples 1 to 4, Comparative Example 1 [Preparation of oxidizing solution (1)] 60 parts by weight of TEC and 40 parts by weight of EDG were mixed to prepare a solvent (1). This solvent (1) was mixed so that the concentration of H 2 O 2 was 5 wt% and the concentration of SS was 0.5 mmol / L to obtain an oxidizing solution (1). The flash point immediately after the preparation of the oxidizing solution (1) was 110 ° C.
  • oxide solution (1), Comparative Example 1, Example 1, the liquid of Example 3, using HPLC, and of H 2 O 2 the liquid in, to determine the amount of SS is a catalyst.
  • the result is shown in FIG.
  • the first peak observed near the elapsed time 4 min is an index of the amount of H 2 O 2
  • the second peak observed near the elapsed time 7 min is the index of the amount of SS.
  • oxidation solution immediately after mixing (1) H 2 O 2 , SS although both large peak observed in the liquid of Comparative Example 1 without the oxidizing agent added in the present invention, in particular reduction of H 2 O 2 It was remarkable and almost no peak was seen.
  • reduction of H 2 O 2 is observed in the liquid according to Example 1 and Example 3, which is sufficiently remained, it was to function as a fully oxidized solution.
  • Examples 5 and 6, Comparative Example 2 [Preparation of oxidizing solution (2)] 70 parts by weight of DMP and 30 parts by weight of MDG were mixed to prepare a solvent (2).
  • the solvent (2) was mixed with an H 2 O 2 concentration of 5 wt% and an SS concentration of 0.5 mmol / L to form an oxidizing solution (2).
  • the flash point immediately after the preparation of the oxidizing solution (2) was 114 ° C.
  • Examples 7 and 8, Comparative Example 3 [Preparation of oxidizing solution (3)] 70 parts by weight of DMP and 30 parts by weight of EDG were mixed to prepare a solvent (3). This solvent (3) was mixed so that the H 2 O 2 concentration was 3 wt% and the SS concentration was 0.5 mmol / L to obtain an oxidizing solution (3). The flash point immediately after preparation of the oxidizing solution (3) was 112 ° C.
  • BPEA 9,10-bis (phenylethynyl) anthracene
  • the chemiluminescent oxidizing solution of the present invention has a higher flash point than conventional oxidizing solutions, and the flash point of the oxidizing solution is stable for a very long time. It is another object of the present invention to provide a chemiluminescent system excellent in safety while maintaining chemiluminescent performance.

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Abstract

The purpose of the present invention is to provide: a method for inhibiting an oxidizing fluid for a chemiluminescent body from deteriorating with the passage of time; and an oxidizing fluid which is inhibited from deteriorating with the passage of time. This oxidizing fluid for a chemiluminescent body is an oxidizing fluid which contains both hydrogen peroxide and a solvent and causes a chemiluminescence phenomenon when mixed with a fluorescent fluid that contains both an oxalic acid ester and a fluorescent substance and which is characterized by: having a flash point of 60ºC or higher; and containing an antioxidant. Therefore, the oxidizing fluid for a chemiluminescent body is inhibited from deteriorating with the passage of time, so that the oxidizing fluid can minimize the decrease in the luminance of fluorescence and exhibits a suppressed lowering in flash point. Thus, the oxidizing fluid for a chemiluminescent body can stand up to long-period use and storage.

Description

化学発光体用酸化液およびそれを含んでなる化学発光システムOxidizing solution for chemiluminescent body and chemiluminescent system comprising the same
　本発明は、化学発光体用酸化液およびそれを含んでなる化学発光システムに関する。より詳しくは、化学発光体用酸化液に酸化防止剤を添加した化学発光体用酸化液と化学発光体用蛍光液とを含んでなる化学発光システムに関するものである。 The present invention relates to an oxidation solution for chemiluminescent bodies and a chemiluminescent system comprising the same. More specifically, the present invention relates to a chemiluminescent system comprising a chemiluminescent oxidizing solution obtained by adding an antioxidant to a chemiluminescent oxidizing solution and a chemiluminescent fluorescent solution.
　これまでに、化学発光を利用した製品が数多く上市されており、シュウ酸エステルおよび蛍光物質（色素）を含有する溶液（蛍光液）と、酸化剤（主として過酸化水素）および触媒成分（たとえばサリチル酸塩）を含有する溶液（酸化液）とを混合することにより、任意の時機に化学発光を起こさせ、目的に供することが一般に行われている。 Many products using chemiluminescence have been put on the market so far, including a solution (fluorescent liquid) containing an oxalate ester and a fluorescent substance (pigment), an oxidizing agent (mainly hydrogen peroxide), and a catalyst component (for example, salicylic acid). In general, chemiluminescence is generated at any time by mixing with a solution (oxidizing solution) containing a salt) and used for the purpose.
　そして、蛍光液や酸化液には、内容物の濃度を調節し、両液中の反応種が均一に混合して反応するように、溶媒が使用されている。たとえば、特許文献１にて開示された蛍光液には、溶媒としては、フタル酸エステル類、安息香酸エステル類などの芳香族系溶媒が使用されている。 In the fluorescent solution and the oxidizing solution, a solvent is used so that the concentration of the content is adjusted and the reaction species in both solutions are mixed and reacted uniformly. For example, in the fluorescent solution disclosed in Patent Document 1, aromatic solvents such as phthalates and benzoates are used as the solvent.
　一方、近年、防火面からもより安全な溶媒が求められている。従来、蛍光液の溶媒の組成としては、アセチルクエン酸トリブチル、安息香酸ベンジル、ジプロピレングリコールジメチルエーテルを混合した溶液が多用されており、これらの溶媒は引火点が高く、混合状態でも９４℃以上の引火点を有するものである。 On the other hand, in recent years, there is a demand for a safer solvent from the viewpoint of fire prevention. Conventionally, as a composition of a solvent of a fluorescent solution, a solution in which tributyl acetyl citrate, benzyl benzoate, and dipropylene glycol dimethyl ether are mixed is frequently used. These solvents have a high flash point and are 94 ° C. or higher even in a mixed state. It has a flash point.
　しかし、従来、酸化液として使用されている溶媒はフタル酸系、非フタル酸系のいずれも引火点の低いエタノールなどのアルコ－ルを含んでいるため２０℃～４０℃程度の低い引火点を示していた。このように化学発光組成物の酸化液の引火点が低いため、危険物としての取り扱いが厳しく、航空貨物としても制限を受ける等の課題があった。この酸化液の引火点を向上させる技術として、特許文献２～５には、特定の溶媒を酸化液の溶媒に用いる技術が提案されている。 However, the solvent used as an oxidizing solution in the past includes alcohols such as ethanol, which has a low flash point, both phthalic acid and non-phthalic acid, and therefore has a low flash point of about 20 ° C to 40 ° C. Was showing. As described above, since the flash point of the oxidizing solution of the chemiluminescent composition is low, handling as a dangerous substance is severe, and there are problems such as being restricted as air cargo. As techniques for improving the flash point of the oxidizing liquid, Patent Documents 2 to 5 propose techniques for using a specific solvent as a solvent for the oxidizing liquid.
特開２００２－１３８２７８号公報JP 2002-138278 A 特開２００６－１０４２６６号公報JP 2006-104266 A 特許４７０２６５３号公報Japanese Patent No. 4702653 国際公開２０１１／９９３７５号公報International Publication No. 2011/99375 国際公開２０１２／１０１８４８号公報International Publication 2012/101848
　前述した特許文献に開示されるような化学発光体用酸化液の溶媒設計に変更することで、高引火点とすることができる。しかし、本発明者等は、この高引火点溶媒酸化液をさらに評価を進める過程において、常温で数年間という長期間保管する場合に、高引火点溶媒酸化液が経時変化する可能性があることを見出した。また、この経時変化によって、発光輝度が低下したり、引火点が低下するものがあることがわかり、この経時変化は、化学発光体の使用期限や保管期限を限定せざるを得ない理由となることに着目した。 The flash point can be increased by changing to the solvent design of the oxidizing solution for chemiluminescent materials as disclosed in the above-mentioned patent document. However, the inventors of the present invention have a possibility that the high flash point solvent oxidizing solution may change over time when the high flash point solvent oxidizing solution is stored for a long period of several years at room temperature in the process of further evaluation. I found. In addition, it can be seen that there are those in which the luminance is lowered or the flash point is lowered due to this change with time, and this change with time is the reason why the expiration date or storage period of the chemiluminescent material must be limited. Focused on that.
　本発明は、これら化学発光体用酸化液の経時変化を抑制する方法および経時変化を抑制させた酸化液を提供することを目的とする。 An object of the present invention is to provide a method for suppressing the change over time of the oxidation solution for chemiluminescent bodies and an oxidation solution for suppressing the change over time.
　本発明者は、上記課題を解決すべく鋭意研究を重ねた結果、下記の発明が上記目的に合致することを見出し、本発明に至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the following inventions meet the above-mentioned object, and have reached the present invention.
　すなわち、本発明は、以下の発明に係るものである。
　＜１＞　シュウ酸エステルおよび蛍光物質を含有する蛍光液と混合した際に化学発光現象を生じる、過酸化水素および溶媒を含有する化学発光体用酸化液であって、前記酸化液の引火点が６０℃以上であり、前記酸化液に酸化防止剤が含有される化学発光体用酸化液。
　＜２＞　前記酸化防止剤が、フェノール系酸化防止剤である前記＜１＞記載の化学発光体用酸化液。
　＜３＞　前記フェノール系酸化防止剤が、ハイドロキノン、カテコール、レゾルシノール、ｔｅｒｔ－ブチルヒドロキノン、ブチルヒドロキシアニソール、ヒドロキノンモノメチルエーテルおよびジ－ｔ－ブチル－ｐ－クレゾールから選択される少なくとも１種以上の酸化防止剤である前記＜２＞記載の化学発光体用酸化液。
　＜４＞　前記酸化防止剤の濃度が、酸化液全体に対して、０．０５ｍｍｏｌ／Ｌ以上、１０ｍｍｏｌ／Ｌ以下である前記＜１＞～＜３＞のいずれかに記載の化学発光体用酸化液。
　＜５＞　前記溶媒が、フタル酸エステル類、クエン酸エステル類、安息香酸エステル類、トリメリット酸エステル類、アジピン酸エステル類、セバシン酸エステル類、アゼライン酸エステル類、グリセリンエステル類、ラクトン類、グリコール類、アルキルグリコールエーテル類から選ばれた少なくとも２種以上の混合物であることを特徴とする前記＜１＞～＜４＞のいずれかに記載の化学発光体用酸化液。
　＜６＞　前記＜１＞～＜５＞のいずれかの項に記載の化学発光体用酸化液とシュウ酸エステルおよび蛍光物質を含有する蛍光液とを含んでなることを特徴とする化学発光システム。 That is, the present invention relates to the following inventions.
<1> A chemiluminescent oxidizing solution containing hydrogen peroxide and a solvent that produces a chemiluminescent phenomenon when mixed with an oxalate ester and a fluorescent solution containing a fluorescent substance, wherein the flash point of the oxidizing solution is An oxidizing solution for chemiluminescent bodies that is 60 ° C. or higher and contains an antioxidant in the oxidizing solution.
<2> The oxidation solution for chemiluminescent materials according to <1>, wherein the antioxidant is a phenol-based antioxidant.
<3> The phenolic antioxidant is at least one antioxidant selected from hydroquinone, catechol, resorcinol, tert-butylhydroquinone, butylhydroxyanisole, hydroquinone monomethyl ether and di-t-butyl-p-cresol. The oxidizing solution for chemiluminescent materials according to <2>, which is an agent.
<4> The oxidation for chemiluminescent materials according to any one of <1> to <3>, wherein the concentration of the antioxidant is 0.05 mmol / L or more and 10 mmol / L or less with respect to the entire oxidizing solution. liquid.
<5> The solvent is phthalic acid esters, citric acid esters, benzoic acid esters, trimellitic acid esters, adipic acid esters, sebacic acid esters, azelaic acid esters, glycerin esters, lactones, The oxidizing solution for chemiluminescent materials according to any one of <1> to <4>, wherein the oxidizing solution is a mixture of at least two selected from glycols and alkyl glycol ethers.
<6> A chemiluminescence system comprising the chemiluminescent substance oxidizing solution according to any one of <1> to <5>, and a fluorescent solution containing an oxalate ester and a fluorescent substance .
　本発明による化学発光体用酸化液は、長時間経過したときの引火点の低下や、発光輝度の低下が少ない化学発光体用酸化液とすることができる。これによって、長期使用や長期保存ができ、高温となりやすい環境においても、より信頼性が高い化学発光体を提供することができる。 The oxidizing solution for chemiluminescent materials according to the present invention can be an oxidizing solution for chemiluminescent materials that has little reduction in flash point when a long time has passed and little reduction in luminous luminance. This makes it possible to provide a chemiluminescent material that can be used for a long period of time and stored for a long period of time and is more reliable even in an environment where the temperature tends to be high.
本発明にかかる酸化液の安定性をＨＰＬＣで評価した結果を示す図である。It is a figure which shows the result of having evaluated stability of the oxidation liquid concerning this invention by HPLC. 本発明にかかる酸化液を用いた発光輝度の変化を評価した結果を示す図である。It is a figure which shows the result of having evaluated the change of the light-emitting luminance using the oxidizing solution concerning this invention.
　以下に本発明の実施の形態を詳細に説明するが、以下に記載する構成要件の説明は、本発明の実施態様の一例（代表例）であり、本発明はその要旨を超えない限り、以下の内容に限定されない。 DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents.
　本発明は、シュウ酸エステルおよび蛍光物質を含有する蛍光液と混合した際に化学発光現象を生じる、過酸化水素および溶媒を含有する化学発光体用酸化液であって、前記酸化液の引火点が６０℃以上であり、前記酸化液に酸化防止剤を含有する化学発光体用酸化液に係るものである。このような構成とすることで、前記化学発光体用酸化液の引火点や発光輝度の長期安定性を向上させることができる。 The present invention relates to an oxidizing solution for a chemiluminescent body containing hydrogen peroxide and a solvent, which generates a chemiluminescence phenomenon when mixed with a fluorescent solution containing an oxalate ester and a fluorescent substance, and the flash point of the oxidizing solution Is 60 ° C. or higher and relates to the chemiluminescent oxidizing solution containing an antioxidant in the oxidizing solution. By setting it as such a structure, the flash point of the said chemiluminescent body oxidizing solution and the long-term stability of light-emitting luminance can be improved.
　ここに、本発明の化学発光体用酸化液（以下単に「酸化液」ということがある。）は、シュウ酸エステルおよび蛍光物質を含有する化学発光体用蛍光液（以下単に「蛍光液」ということがある。）と混合した際に化学発光現象を生じさせる作用を有するものである。酸化液は、酸化剤である過酸化水素を必須成分とし、この過酸化水素の濃度を調整し、後述する蛍光液中の蛍光物質との相溶性（混合性）を向上させ、更には発光効率を向上させるために添加されるサリチル酸塩等の溶解度を向上させるための溶媒を含有する。 Here, the chemiluminescent oxidizing solution of the present invention (hereinafter sometimes simply referred to as “oxidizing solution”) is a chemiluminescent fluorescent solution containing oxalic acid ester and a fluorescent substance (hereinafter simply referred to as “fluorescent solution”). And have the effect of causing a chemiluminescence phenomenon when mixed with. The oxidizing solution contains hydrogen peroxide, which is an oxidizing agent, as an essential component, and adjusts the concentration of this hydrogen peroxide to improve the compatibility (mixing property) with the fluorescent substance in the fluorescent solution described later. It contains a solvent for improving the solubility of salicylate and the like added to improve the solubility.
　本発明の特徴の一つは、この酸化液として、引火点が６０℃以上、好ましくは７０℃以上、特に好ましくは１００℃以上のものを使用することにある。ここで、引火点とは、ＪＩＳ　Ｋ２２６５－２に規定される迅速平衡密閉法により測定した値をいう。酸化液の引火点が６０℃未満である場合には、航空法における貨物規制に抵触し、国際郵便における危険物の扱いとなるが、本発明の酸化液は、引火点が６０℃以上であるため、前記航空法における貨物規制に抵触しないという利点がある。更に、本発明の酸化液における引火点が７０℃以上になると、消防法上の危険物　第３石油類指定（７０～２００℃）が適用されるため、安全性ランクが一段あがる。更に、本発明の酸化液における引火点が１００℃以上になると、防火面の安全性が格段に高まる。 One of the features of the present invention is that this oxidizing solution has a flash point of 60 ° C. or higher, preferably 70 ° C. or higher, particularly preferably 100 ° C. or higher. Here, the flash point is a value measured by a rapid equilibrium sealing method defined in JIS K2265-2. When the flash point of the oxidizing solution is less than 60 ° C., it conflicts with the cargo regulations in the Aviation Law and is handled as a dangerous material in international mail, but the oxidizing solution of the present invention has a flash point of 60 ° C. or more. Therefore, there is an advantage that it does not conflict with the cargo regulations in the Aviation Law. Further, when the flash point in the oxidizing solution of the present invention is 70 ° C. or higher, the dangerous rank in the Fire Service Act is designated as the third petroleum class (70 to 200 ° C.), and the safety rank is further increased. Furthermore, when the flash point in the oxidizing solution of the present invention is 100 ° C. or higher, the safety of the fireproof surface is remarkably increased.
　また、本発明の酸化液に含有される溶媒は、酸化防止剤を含有することを特徴とする。本発明の酸化液は前述のように過酸化水素水を含有するものであり、酸化させることを目的とする溶媒であることから、これに酸化防止剤を含有させることは忌避される方向にある。しかしながら、本発明者等は、この酸化液に酸化防止剤を含有させることで、酸化液の引火点や発光輝度が長期間安定することを見出し、本発明に達した。 The solvent contained in the oxidizing solution of the present invention is characterized by containing an antioxidant. As described above, the oxidizing solution of the present invention contains a hydrogen peroxide solution and is a solvent intended to be oxidized. Therefore, the inclusion of an antioxidant in the solvent tends to be avoided. . However, the present inventors have found that the flash point and emission luminance of the oxidizing solution are stabilized for a long period of time by containing an antioxidant in the oxidizing solution, and have reached the present invention.
　本発明において酸化防止剤とは、遊離基、過酸化物と反応して安定な物質に変えることにより、酸化液の過酸化水素や溶媒等の分解を抑制するものをいう。長期間経過したとき、酸化液に含まれる過酸化水素が分解し酸化液としての機能を果たさなくなる場合がある。また、高引火点の酸化液の溶媒には、臭気や安定性、蛍光液との相溶性等を考慮し、エステル系の溶媒が使用されることが多い。しかしながら、エステル系の溶媒は分解すると低引火点の物質に変わるものが多い。この分解は、長期間保管すると必然的に周辺環境や空気中の酸素等と反応することにより生じるものであり、高引火点酸化液溶媒の長期間安定性に関連するものである。また、酸化液中の過酸化水素の分解を抑制することで、蛍光液と混合された時の発光輝度が安定する。 In the present invention, the antioxidant means a substance that suppresses decomposition of hydrogen peroxide, solvent, etc. of the oxidizing solution by reacting with free radicals and peroxides to change into a stable substance. When a long time elapses, hydrogen peroxide contained in the oxidizing solution may be decomposed and may no longer function as the oxidizing solution. In addition, an ester solvent is often used as the solvent of the high flash point oxidizing solution in consideration of odor, stability, compatibility with the fluorescent solution, and the like. However, many ester-based solvents change to low flash point substances when decomposed. This decomposition is caused by a reaction with the surrounding environment, oxygen in the air, etc. when stored for a long period of time, and is related to the long-term stability of the high flash point oxidizing solution solvent. Further, by suppressing the decomposition of hydrogen peroxide in the oxidizing solution, the emission luminance when mixed with the fluorescent solution is stabilized.
　本発明に用いられる酸化防止剤としては、酸化液との相溶性等の観点から有機系の酸化防止剤が好ましく用いられる。有機系の酸化防止剤のなかでも、フェノール系酸化防止剤が特に好ましく用いられる。フェノール系酸化防止剤は、酸化液中に含まれる溶媒と相溶性が高く均一に溶解・分散するものであること、酸化液中で他の成分と反応しすぎないように酸やアルカリを生成しにくいものであること、酸化液の酸化機能が低下すると蛍光液と混合時の発光性が低下するおそれがあるため還元性が高すぎないものであることなどの利点を有するため、本発明の酸化防止剤に適している。 As the antioxidant used in the present invention, an organic antioxidant is preferably used from the viewpoint of compatibility with an oxidizing solution. Of the organic antioxidants, phenolic antioxidants are particularly preferably used. Phenol-based antioxidants are highly compatible with the solvent contained in the oxidizing solution and are uniformly dissolved and dispersed, and generate acids and alkalis so that they do not react excessively with other components in the oxidizing solution. The oxidation of the present invention has advantages such as being difficult, and reducing the oxidizing function of the oxidizing solution, which may reduce the light-emitting property when mixed with the fluorescent solution, so that the reducing property is not too high. Suitable as an inhibitor.
　本発明においてフェノール系酸化防止剤は分子内にフェノール基を有する酸化防止剤を指しフェノール誘導体を有するモノフェノール系酸化防止剤、ビスフェノール系酸化防止剤、及び高分子型フェノール系酸化防止剤等を用いることができる。本発明に好ましく用いられるフェノール系酸化防止剤としては、例えば、ハイドロキノン（１，４－ベンゼンジオール）、カテコール（１，２－ベンゼンジオール）、レゾルシノール（１，３－ベンゼンジオール）、ｔｅｒｔ－ブチルヒドロキノン、ブチルヒドロキシアニソール、ヒドロキノンモノメチルエーテル（４－メトキシフェノール）、ジ－ｔ－ブチル－ｐ－クレゾール（ＤＢＰＣ）等があげられる。これらの酸化防止剤のいずれかを単独で用いても良いし、適宜、２種類以上の酸化防止剤を用いてもよい。フェノール系の酸化防止剤のなかでも、さらに好ましくは、ハイドロキノンやジ－ｔ－ブチル－ｐ－クレゾールが用いられる。この好ましい酸化防止剤として選択される酸化防止剤は、本発明の酸化液に混合させたとき、引火点や発光輝度の長期安定性に優れているのみならず、酸化液等の着色がほとんどなく、析出物等も発生しにくいといった点でさらに優れている。 In the present invention, the phenolic antioxidant refers to an antioxidant having a phenol group in the molecule, and a monophenolic antioxidant, a bisphenolic antioxidant, a high-molecular phenolic antioxidant, etc. having a phenol derivative are used. be able to. Examples of the phenolic antioxidant preferably used in the present invention include hydroquinone (1,4-benzenediol), catechol (1,2-benzenediol), resorcinol (1,3-benzenediol), and tert-butylhydroquinone. Butylhydroxyanisole, hydroquinone monomethyl ether (4-methoxyphenol), di-t-butyl-p-cresol (DBPC) and the like. Any of these antioxidants may be used alone, or two or more kinds of antioxidants may be appropriately used. Of the phenolic antioxidants, hydroquinone and di-t-butyl-p-cresol are more preferably used. The antioxidant selected as this preferred antioxidant is not only excellent in the long-term stability of the flash point and emission luminance when mixed with the oxidizing solution of the present invention, but also has almost no coloring of the oxidizing solution or the like. Further, it is further excellent in that precipitates are hardly generated.
　前記酸化防止剤の濃度は、添加するフェノール系酸化防止剤の種類、酸化液中の各成分濃度、想定する保存期間等にもよるが、酸化液全体に対して、好ましくは０．０５ｍｍｏｌ／Ｌ以上、より好ましくは０．３ｍｍｏｌ／Ｌ以上である。酸化防止剤の濃度が低すぎる場合、十分な期間引火点低下抑制能や、過酸化水素分解抑制機能を発揮しないおそれがある。また、その上限は、好ましくは１０ｍｍｏｌ／Ｌ以下、より好ましくは５ｍｍｏｌ／Ｌ以下、さらに好ましくは３ｍｍｏｌ／Ｌ以下である。酸化防止剤の添加量が多すぎる場合、酸化液の酸化機能を阻害し、蛍光液と混合された時の発光輝度が低下する場合がある。また、酸化防止剤の着色が原因で、発光体の発光色が異なるものとなる場合がある。酸化防止剤の濃度がこれらの好ましい範囲のとき、長期間、安定して酸化液の機能を維持することができる。 The concentration of the antioxidant depends on the type of phenolic antioxidant to be added, the concentration of each component in the oxidizing solution, the assumed storage period, etc., but preferably 0.05 mmol / L with respect to the entire oxidizing solution. As mentioned above, More preferably, it is 0.3 mmol / L or more. When the concentration of the antioxidant is too low, there is a possibility that the flash point lowering suppressing ability and the hydrogen peroxide decomposition inhibiting function may not be exhibited for a sufficient period. Moreover, the upper limit becomes like this. Preferably it is 10 mmol / L or less, More preferably, it is 5 mmol / L or less, More preferably, it is 3 mmol / L or less. When there is too much addition amount of antioxidant, the oxidation function of oxidation liquid may be inhibited and the emitted light brightness when mixed with fluorescent liquid may fall. In addition, the emission color of the illuminant may be different due to the coloring of the antioxidant. When the concentration of the antioxidant is within these preferable ranges, the function of the oxidizing solution can be stably maintained for a long period of time.
　また、本発明の酸化液に含有される溶媒は、下記化合物から選ばれる溶媒やこれらの混合物を用いることができる。 Further, as the solvent contained in the oxidizing solution of the present invention, a solvent selected from the following compounds or a mixture thereof can be used.
　即ち、本発明における酸化液に含まれる溶媒の具体的例としては、クエン酸エステル類、フタル酸エステル類、安息香酸エステル類、トリメリット酸エステル類、アジピン酸エステル類、セバシン酸エステル類、アゼライン酸エステル類、グリセリンエステル類、ラクトン類、グリコール類、アルキルグリコールエーテル類等の有機系の溶媒を含む溶媒が好ましく用いられる。これらの溶媒から、引火点が６０℃以上のものを主たる溶媒として用いて、全体としての引火点が７０℃以上となり、本発明の目的を達成することができる溶媒を選択し使用することができる。なお、溶媒の選択において、主たる溶媒とは、引火点が本発明の目的とする温度を達成することができるように配合量を調整する際に、引火点の高さと配合比率の多さとから設計時の中心となる溶媒を指す。また、溶媒は、主たる溶媒単独の溶媒であってもよい。 That is, specific examples of the solvent contained in the oxidizing solution in the present invention include citrate esters, phthalate esters, benzoate esters, trimellitic acid esters, adipic acid esters, sebacic acid esters, azelain. A solvent containing an organic solvent such as acid esters, glycerin esters, lactones, glycols, alkyl glycol ethers is preferably used. From these solvents, those having a flash point of 60 ° C. or higher are used as the main solvents, and the flash point as a whole becomes 70 ° C. or higher, and a solvent that can achieve the object of the present invention can be selected and used. . In the selection of the solvent, the main solvent is designed from the high flash point and the high blending ratio when adjusting the blending amount so that the flash point can achieve the target temperature of the present invention. It refers to the solvent that is the center of time. The solvent may be a main solvent alone.
　これらの主たる溶媒としてより具体的には、クエン酸エステル類の溶媒として、クエン酸トリエチル（引火点：１５１℃）、アセチルクエン酸トリブチル（引火点：２０４℃）が用いられる。また、フタル酸エステル類の溶媒として、フタル酸ジメチル（引火点：１４６℃）、フタル酸ジエチル（引火点：１６６℃）、フタル酸ジブチル（引火点：１５７℃）が用いられる。また、安息香酸エステル類の溶媒としては、安息香酸ベンジル（引火点：１４８℃）、安息香酸ブチル（引火点：１２２℃）が用いられる。また、トリメリット酸エステル類の溶媒としては、トリメリット酸トリメチル（引火点：１８２℃）、トリメリット酸トリプロピル（引火点無し）、トリメリット酸トリ－ｎ－ブチル(引火点：２１５℃)、トリメリット酸トリス（２－エチルヘキシル）（引火点：２６２℃）が用いられる。 More specifically, triethyl citrate (flash point: 151 ° C.) and tributyl acetyl citrate (flash point: 204 ° C.) are used as the main solvent for these citrate esters. As solvents for phthalates, dimethyl phthalate (flash point: 146 ° C.), diethyl phthalate (flash point: 166 ° C.), and dibutyl phthalate (flash point: 157 ° C.) are used. Moreover, as a solvent of benzoic acid esters, benzyl benzoate (flash point: 148 ° C.) and butyl benzoate (flash point: 122 ° C.) are used. Trimellitic acid trimethyl (flash point: 182 ° C), trimellitic acid tripropyl (no flash point), trimellitic acid tri-n-butyl (flash point: 215 ° C) Trimellitic acid tris (2-ethylhexyl) (flash point: 262 ° C.) is used.
　また、アジピン酸エステル類の溶媒としては、アジピン酸ジメチル（引火点：１２２℃）、アジピン酸ジエチル（引火点：１２７℃）、アジピン酸ジイソプロピル（引火点：１３６℃）、アジピン酸ジイソブチル（引火点：１５６℃）、アジピン酸ジイソノニル（引火点：２３２℃）が用いられる。また、セバシン酸エステル類の溶媒としては、セバシン酸ジエチル（引火点：２２０℃）、セバシン酸ジブチル（引火点：１９０℃）が用いられる。アゼライン酸エステル類の溶媒としては、アゼライン酸ビス（２－エチルヘキシル）（引火点：２１１℃）も用いることができる。 As a solvent for adipates, dimethyl adipate (flash point: 122 ° C.), diethyl adipate (flash point: 127 ° C.), diisopropyl adipate (flash point: 136 ° C.), diisobutyl adipate (flash point) 156 ° C.), diisononyl adipate (flash point: 232 ° C.). Further, as a solvent for sebacic acid esters, diethyl sebacate (flash point: 220 ° C.) and dibutyl sebacate (flash point: 190 ° C.) are used. As a solvent for azelaic acid esters, bis (2-ethylhexyl) azelate (flash point: 211 ° C.) can also be used.
　さらには、グリセリンエステル類の溶媒としては、トリアセチン（グリセリントリアセタート）（引火点：１４８℃）などが用いられる。また、ラクトン類の溶媒としては、γ－ブチロラクトン（引火点：９８℃）などが用いられる。また、グリコール類の溶媒としては、ヘキシレングリコール（引火点：９６℃）、プロピレングリコール（引火点：９９℃）、トリエチレングリコール（引火点：１７７℃）。また、アルキルグリコールエーテル類の溶媒としては、３-メトキシ-３-メチルブタノール（引火点：６７℃）、ジエチレングリコールジメチルエーテル（引火点：５８℃）、ジエチレングリコールジエチルエーテル（引火点：７１℃）、ジエチレングリコールジブチルエーテル（引火点：１１８℃）、ジプロピレングリコールジメチルエーテル（引火点：６０℃）、ジエチレングリコールモノメチルエーテル（引火点：９３℃）、ジエチレングリコールモノエチルエーテル（引火点：９６℃）、トリエチレングリコールジメチルエーテル（引火点：１１３℃）、エチレングリコールイソプロピルエーテル（引火点：４４℃）を用いることができる。また、ジエチレングリコールモノイソプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノイソブチルエーテル、ジエチレングリコールモノベンジルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノイソプロピルエーテル、トリエチレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノイソプロピルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールジメチルエーテルおよびトリプロピレングリコールプロピルエーテルを用いることができる。 Furthermore, as a solvent for glycerin esters, triacetin (glycerin triacetate) (flash point: 148 ° C.) or the like is used. As the lactone solvent, γ-butyrolactone (flash point: 98 ° C.) or the like is used. Examples of glycol solvents include hexylene glycol (flash point: 96 ° C.), propylene glycol (flash point: 99 ° C.), and triethylene glycol (flash point: 177 ° C.). As solvents for alkyl glycol ethers, 3-methoxy-3-methylbutanol (flash point: 67 ° C.), diethylene glycol dimethyl ether (flash point: 58 ° C.), diethylene glycol diethyl ether (flash point: 71 ° C.), diethylene glycol diethylene glycol Butyl ether (flash point: 118 ° C), dipropylene glycol dimethyl ether (flash point: 60 ° C), diethylene glycol monomethyl ether (flash point: 93 ° C), diethylene glycol monoethyl ether (flash point: 96 ° C), triethylene glycol dimethyl ether (flash point) Point: 113 ° C.), ethylene glycol isopropyl ether (flash point: 44 ° C.) can be used. Diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monobenzyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoisopropyl ether, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether and tripropylene glycol propyl ether can be used.
　これらは、酸化剤である過酸化水素や触媒であるサリチル酸塩等の易溶解性、また蛍光物質を含有する蛍光液との相溶性に優れている。また、これらの溶媒は、少なくとも２種以上を混合して使用されることが好ましく、混合した溶媒(酸化液)の引火点は、６０℃以上となる。なお、防火性の観点からは、これらの溶媒単独での引火点が、６０℃以上が好ましく、７０℃以上がより好ましく、１００℃以上が特に好ましい。 These are easily soluble in hydrogen peroxide as an oxidizing agent and salicylate as a catalyst, and are excellent in compatibility with a fluorescent solution containing a fluorescent substance. These solvents are preferably used in a mixture of at least two kinds, and the flash point of the mixed solvent (oxidizing solution) is 60 ° C. or higher. From the viewpoint of fire resistance, the flash point of these solvents alone is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and particularly preferably 100 ° C. or higher.
　上記溶媒の中でも、フタル酸ジメチル、フタル酸ジエチル、クエン酸トリエチル、アセチルクエン酸トリブチル、安息香酸ベンジル、安息香酸ブチル、トリメリット酸トリメチル、トリメリット酸トリプロピル、トリメリット酸トリ－ｎ－ブチル、トリメリット酸トリス（２－エチルヘキシル）、アジピン酸ジエチル、アジピン酸ジイソプロピル、アジピン酸ジイソブチル、セバシン酸ジエチル、アゼライン酸ビス（２－エチルヘキシル）、ヘキシレングリコール、プロピレングリコール、γ―ブチロラクトン、トリエチレングリコール、トリアセチン（グリセリントリアセタート）、３-メトキシ-３-メチルブタノール、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、トリエチレングリコールジメチルエーテル、エチレングリコールイソプロピルエーテル、ジエチレングリコールジブチルエーテル、ジエチレングリコールモノイソプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノイソブチルエーテル、ジエチレングリコールモノベンジルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノイソプロピルエーテル、トリエチレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノイソプロピルエーテルジエチレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールジメチルエーテルおよびトリプロピレングリコールプロピルエーテルから選ばれた少なくとも２種以上の混合物であることが好ましい。 Among the above solvents, dimethyl phthalate, diethyl phthalate, triethyl citrate, tributyl acetyl citrate, benzyl benzoate, butyl benzoate, trimethyl trimellitic acid, tripropyl trimellitic acid, tri-n-butyl trimellitic acid, Trimellitic acid tris (2-ethylhexyl), diethyl adipate, diisopropyl adipate, diisobutyl adipate, diethyl sebacate, bis (2-ethylhexyl) azelate, hexylene glycol, propylene glycol, γ-butyrolactone, triethylene glycol, Triacetin (glycerin triacetate), 3-methoxy-3-methylbutanol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, ethylene glycol isopropyl ether, diethylene glycol dibutyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monobenzyl ether, triethylene glycol monomethyl ether, triethylene glycol mono Ethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoisopropyl ether diethylene glycol dimethyl ether A mixture of at least two selected from chill ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether and tripropylene glycol propyl ether is preferable.
　更に、好ましくは、上記溶媒が、フタル酸ジメチル、フタル酸ジエチル、クエン酸トリエチル、アセチルクエン酸トリブチル、安息香酸ベンジル、トリメリット酸トリ－ｎ－ブチル、トリメリット酸トリス（２－エチルヘキシル）、アジピン酸ジエチル、アジピン酸ジイソブチル、アゼライン酸ビス（２－エチルヘキシル）、ヘキシレングリコール、プロピレングリコール、γ－ブチロラクトン、トリアセチン（グリセリントリアセタート）、３-メトキシ-３-メチルブタノール、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテルおよびトリプロピレングリコールモノメチルエーテルから選ばれた少なくとも２種以上の混合物である。 More preferably, the solvent is dimethyl phthalate, diethyl phthalate, triethyl citrate, tributyl acetyl citrate, benzyl benzoate, tri-n-butyl trimellitic acid, tris (2-ethylhexyl) trimellitic acid, adipine Diethyl acetate, diisobutyl adipate, bis (2-ethylhexyl) azelate, hexylene glycol, propylene glycol, γ-butyrolactone, triacetin (glycerol triacetate), 3-methoxy-3-methylbutanol, diethylene glycol dimethyl ether, diethylene glycol monoethyl A mixture of at least two selected from ether, diethylene glycol monomethyl ether and tripropylene glycol monomethyl ether.
　特に、酸化液が、フタル酸ジメチル、フタル酸ジエチル、クエン酸トリエチル、アセチルクエン酸トリブチル、安息香酸ベンジル、安息香酸ブチル、トリメリット酸トリメチル、トリメリット酸トリプロピル、トリメリット酸トリ－ｎ－ブチル、トリメリット酸トリス（２－エチルヘキシル）、アジピン酸ジエチル、アジピン酸ジイソプロピル、アジピン酸ジイソブチル、セバシン酸ジエチルおよびアゼライン酸ビス（２－エチルヘキシル）から選ばれた少なくとも１種以上の溶媒（溶媒Ａ）と、
　ヘキシレングリコール、プロピレングリコール、ブチロラクトン、トリエチレングリコール、トリアセチン（グリセリントリアセタート）、ジエチレングリコールジメチルエーテル、３-メトキシ-３-メチルブタノール、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、トリエチレングリコールジメチルエーテル、ジエチレングリコールジブチルエーテル、ジエチレングリコールジメチルエーテルおよびジプロピレングリコールジメチルエーテルから選ばれた少なくとも１種以上の溶媒（溶媒Ｂ）との混合物であることが好ましい。 In particular, the oxidizing solution is dimethyl phthalate, diethyl phthalate, triethyl citrate, tributyl acetyl citrate, benzyl benzoate, butyl benzoate, trimethyl trimellitic acid, tripropyl trimellitic acid, tri-n-butyl trimellitic acid At least one solvent (solvent A) selected from tris (2-ethylhexyl) trimellitic acid, diethyl adipate, diisopropyl adipate, diisobutyl adipate, diethyl sebacate and bis (2-ethylhexyl) azelate ,
Hexylene glycol, propylene glycol, butyrolactone, triethylene glycol, triacetin (glycerin triacetate), diethylene glycol dimethyl ether, 3-methoxy-3-methylbutanol, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether , A mixture with at least one solvent (solvent B) selected from diethylene glycol dibutyl ether, diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether.
　上記溶媒の混合割合は、最終製品の用途や要求される安全性等により適宜決定される。溶媒が溶媒Ａと溶媒Ｂの混合溶媒の場合には、溶媒Ａと溶媒Ｂの比（容量比）が、一般には、１：９９～９９：１、好ましくは、１０：９０～９０：１０、より好ましくは、２０：８０～８０：２０である。 The mixing ratio of the solvent is appropriately determined depending on the use of the final product and the required safety. When the solvent is a mixed solvent of solvent A and solvent B, the ratio (volume ratio) of solvent A to solvent B is generally 1:99 to 99: 1, preferably 10:90 to 90:10, More preferably, it is 20:80 to 80:20.
　単独での使用は、従来使用されるエタノールやブタノール等の低級アルコールに比べ、酸化剤である過酸化水素や触媒であるサリチル酸塩等との相溶性、また蛍光物質を含有する蛍光液との相溶性において、従来の低級アルコールと同等あるいは同等以上の酸化液とすることが難しい場合がある。上記の溶媒の組み合わせにおいて、クエン酸トリエチル、安息香酸ベンジル等の溶媒Ａは、酸化液の主溶媒であり、３-メトキシ-３-メチルブタノール、ヘキシレングリコール等の溶媒Ｂは、補助溶媒としての機能を有し、両者が相俟って発光性能の良い酸化液が構成される。 When used alone, it is compatible with hydrogen peroxide as an oxidizing agent and salicylate as a catalyst, and compatible with a fluorescent solution containing a fluorescent substance, compared to conventional lower alcohols such as ethanol and butanol. In terms of solubility, it may be difficult to obtain an oxidizing solution equivalent to or higher than that of conventional lower alcohols. In the combination of the above solvents, the solvent A such as triethyl citrate and benzyl benzoate is the main solvent of the oxidizing solution, and the solvent B such as 3-methoxy-3-methylbutanol and hexylene glycol is used as the auxiliary solvent. An oxidizing solution having a function and a combination of both has a good light emission performance.
　本発明の酸化液には、上記溶媒に加え、更にポリエチレングリコール又はポリプロピレングリコールを含有することが望ましい。これらは分解特性に優れ、過酸化水素との相溶性に優れている。また、他の溶媒の混和性を促進する効果がある。中でも、ポリプロピレングリコールが混和性、化学的安定性、発光輝度の点から好適に使用される。ポリエチレングリコール、ポリプロピレングリコールは酸化液との相溶性の観点から低分子量～中分子量のものが好ましい。ポリエチレングリコール及び／又はポリプロピレングリコールの添加量は、溶媒全体を１００容量％として、１～５０容量％、好ましくは２～２５容量％である。 In addition to the above solvent, the oxidizing solution of the present invention preferably further contains polyethylene glycol or polypropylene glycol. These are excellent in decomposition characteristics and excellent in compatibility with hydrogen peroxide. In addition, there is an effect of promoting miscibility of other solvents. Among these, polypropylene glycol is preferably used from the viewpoints of miscibility, chemical stability, and luminance. Polyethylene glycol and polypropylene glycol are preferably those having a low molecular weight to a medium molecular weight from the viewpoint of compatibility with the oxidizing solution. The addition amount of polyethylene glycol and / or polypropylene glycol is 1 to 50% by volume, preferably 2 to 25% by volume, based on 100% by volume of the entire solvent.
　酸化液中の過酸化水素の濃度は、使用する目的により適宜選択することができるが、通常、０．５から１０重量％、好ましくは３から６重量％である。 The concentration of hydrogen peroxide in the oxidizing solution can be appropriately selected depending on the purpose of use, but is usually 0.5 to 10% by weight, preferably 3 to 6% by weight.
　なお、化学発光体用酸化液には、通常触媒成分として、例えば、サリチル酸リチウム、サリチル酸アンモニウム、サリチル酸ナトリウム、サリチル酸テトラアルキルアンモニウム塩等のサリチル酸およびその誘導体を少量（通常、酸化液に対し０．１ｍｍｏｌ／Ｌから１０ｍｍｏｌ／Ｌ）含有することが望ましい。 In addition, in the oxidation solution for chemiluminescent materials, a small amount of salicylic acid and its derivatives such as lithium salicylate, ammonium salicylate, sodium salicylate, tetraalkylammonium salicylate and the like as a usual catalyst component (usually 0.1 mmol with respect to the oxidation solution) / L to 10 mmol / L).
　次に本発明の化学発光体用蛍光液について説明する。蛍光液は、シュウ酸エステル、蛍光物質および溶媒を含有し、過酸化水素を含有する酸化液と混合した際に化学発光現象を生じるものである。 Next, the chemiluminescent phosphor solution of the present invention will be described. The fluorescent solution contains an oxalate ester, a fluorescent substance, and a solvent, and generates a chemiluminescence phenomenon when mixed with an oxidizing solution containing hydrogen peroxide.
　本発明で使用するシュウ酸エステル類（オキサレート）としては、シュウ酸ハライド、シュウ酸エステル、シュウ酸オキサミド等のシュウ酸誘導体が使用でき、代表的なオキサレートとしては、例えば、ビス（２，４，５－トリクロロ－６－カルボブトキシフェニル）オキサレート、ビス（２，４，５－トリクロロ－６－カルボペントキシフェニル）オキサレート等が挙げられる。 As the oxalate esters (oxalate) used in the present invention, oxalic acid derivatives such as oxalic acid halides, oxalic acid esters and oxalic acid oxamides can be used. Typical oxalates include, for example, bis (2, 4, 5-trichloro-6-carbobutoxyphenyl) oxalate, bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate and the like.
　蛍光物質としては、３００～１２００ｎｍにスペクトル発光を有し、且つ、溶媒に少なくとも部分的に可溶な蛍光化合物であれば特に制限はない。これらの蛍光化合物としては、アントラセン、置換アントラセン、ベンゾアントラセン、フェナントレン、置換フェナントレン、ナフタセン、置換ナフタセン、ペンタセン、置換ペンタセン、ペリレン、置換ペリレン、ビオラントロン、置換ビオラントロンなどの縮合環を有する共役多環芳香族化合物が例示される。上記化合物の置換基としては、発光反応を妨げない限りにおいて特に制限はなく、フェニル基、低級アルキル基、クロロ基、ブロモ基、シアノ基、アルコキシ基、フェニルナフチル基などが例示される。 The fluorescent substance is not particularly limited as long as it is a fluorescent compound having spectral emission at 300 to 1200 nm and at least partially soluble in a solvent. These fluorescent compounds include conjugated polycyclic aromatics having condensed rings such as anthracene, substituted anthracene, benzoanthracene, phenanthrene, substituted phenanthrene, naphthacene, substituted naphthacene, pentacene, substituted pentacene, perylene, substituted perylene, violanthrone, substituted violanthrone, etc. Examples are compounds. The substituent of the above compound is not particularly limited as long as it does not hinder the luminescence reaction, and examples thereof include a phenyl group, a lower alkyl group, a chloro group, a bromo group, a cyano group, an alkoxy group, and a phenylnaphthyl group.
　具体的な蛍光物質としては、２－クロロ-９，１０－ビス（４－メチルエチニル）アントラセン、９，１０－ビス（フェニルエチニル）アントラセン、１－メトキシ－９，１０－ビス（フェニルエチニル）アントラセン、ペリレン、１，５－ジクロロ－９，１０－ビス（フェニルエチニル）アントラセン、１，８－ジクロロ－９，１０－ビス（フェニルエチニル）アントラセン、モノクロロおよびジクロロ置換９，１０－ビス（フェニルエチニル）アントラセン、５，１２－ビス（フェニルエチニル）テトラセン、９，１０－ジフェニルアントラセン、１６，１７－ジヘキシルオキシビオラントロン、２－メチル－９，１０－ビス－（フェニルエチニル）アントラセン、９，１０－ビス－（４－メトキシフェニル）－２－クロロアントラセン、９，１０－ビス－（４－エトキシフェニル）－２－クロロアントラセン、５，１２－ビス－（フェニルエチニル）ナフタセン、５，６，１１，１２－テトラフェニルナフタセン（ルブレン）およびこれらの混合物が例示される。 Specific fluorescent materials include 2-chloro-9,10-bis (4-methylethynyl) anthracene, 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, 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-chloroanthracene, 5,12-bis- (phenylethynyl) naphthacene, 5,6,11,12-tetraphenylnaphthacene (rubrene) and mixtures thereof Is exemplified.
　これらの蛍光物質の製品としては、例えば、ルモゲン・レッド（ＬＵＭＯＧＥＮ　ＲＥＤ、赤色を発するペリレンジカルボキシイミド蛍光剤、ＢＡＳＦ社、商品名）、ルモゲン・イエロー（ＬＵＭＯＧＥＮ　ＹＥＬＬＯＷ、黄色を発するペリレンジカルボキシイミド蛍光剤、ＢＡＳＦ社、商品名）、ルモゲン・オレンジ（ＬＵＭＯＧＥＮ　ＯＲＡＮＧＥ、オレンジ色を発するペリレンジカルボキシイミド蛍光剤、ＢＡＳＦ社、商品名）が好適に使用される。 Examples of products of these fluorescent substances include Lumogen Red (LUMOGEN RED, perylene dicarboxyimide fluorescent agent emitting red, BASF, trade name), Lumogen Yellow (LUMOGEN YELLOW, perylene dicarboximide fluorescent emitting yellow). Agent, BASF, trade name), Lumogen Orange (LUMOGEN ORANGE, perylenedicarboxyimide fluorescent agent that emits orange, BASF, trade name) is preferably used.
　本発明の蛍光液において、溶媒としては、一般にアセチルクエン酸トリブチル（ＡＴＢＣ）、安息香酸ベンジル（ＢｅＢ）、ジプロピレングリコールジメチルエーテル（ＤＭＭ）等が単独であるいは混合して使用される。本発明においては、蛍光液の引火点が酸化液に要求される引火点（６０℃）以上であれば、特に限定されるものではない。 In the fluorescent solution of the present invention, as a solvent, acetyl tributyl citrate (ATBC), benzyl benzoate (BeB), dipropylene glycol dimethyl ether (DMM) or the like is generally used alone or in combination. In the present invention, there is no particular limitation as long as the flash point of the fluorescent liquid is equal to or higher than the flash point (60 ° C.) required for the oxidizing liquid.
　蛍光液における各成分の組成割合は、使用される目的に応じて任意に選択することが出来る。一般に、シュウ酸エステルと蛍光物質の量比（モル比）は、化学発光を生じるのに十分な量とされるが、好ましくは２０：１～４０：１である。溶媒とシュウ酸エステルとの量比も使用する目的により適宜選択することができるが、通常、シュウ酸エステルの濃度が０．０１～０．５ｍｏｌ／Ｌ、好ましくは０．０５～０．３ｍｏｌ／Ｌとなる量の溶媒を使用する。 The composition ratio of each component in the fluorescent solution can be arbitrarily selected according to the purpose to be used. In general, the amount ratio (molar ratio) between the oxalate ester and the fluorescent material is an amount sufficient to generate chemiluminescence, but is preferably 20: 1 to 40: 1. The amount ratio of the solvent to the oxalate ester can also be appropriately selected depending on the purpose of use, but usually the concentration of the oxalate ester is 0.01 to 0.5 mol / L, preferably 0.05 to 0.3 mol / L. An amount of solvent that is L is used.
　なお、酸化液、蛍光液には、必要に応じ界面活性剤等の添加剤を本発明の要旨を損なわない範囲で加えることができる。また、酸化液、蛍光液は不織布、織布、ガラスやプラスチック等の被発光基材に担持させて用いることもできる。 It should be noted that an additive such as a surfactant can be added to the oxidizing solution and the fluorescent solution as needed within a range not impairing the gist of the present invention. Further, the oxidizing solution and the fluorescent solution can be used by being supported on a light-emitting base material such as a nonwoven fabric, a woven fabric, glass or plastic.
　本発明の化学発光体用酸化液は、シュウ酸エステルおよび蛍光物質を含有する化学発光体用蛍光液と混合した際に化学発光現象を生じる。即ち、本発明の酸化液は、上記の蛍光液と組合せて化学発光システムを構成する。
　被発光基材を使用した場合は、触媒成分や蛍光物質をこれらの被発光基材に担持させ、それ以外の溶液を接触させる化学発光システムとすることができる。
　本発明の酸化液およびそれを使用した化学発光システムは、優れた化学発光性能を有し、安全性の高いシステムを提供することができる。また、その安全性を保持する期間が非常に長く、長期保管にも適している。この化学発光システムの具体的な態様としては、セレモニーやイベントのように開放系で用いられるものや、コンサート時や警告灯として用いられる密閉系の化学発光体などが挙げられる。 The chemiluminescent oxidation solution of the present invention produces a chemiluminescent phenomenon when mixed with a chemiluminescent phosphor containing an oxalate ester and a fluorescent substance. That is, the oxidation solution of the present invention constitutes a chemiluminescence system in combination with the above-described fluorescent solution.
When a light-emitting substrate is used, a chemiluminescence system in which a catalyst component or a fluorescent substance is supported on these light-emitting substrates and other solutions are brought into contact with each other can be obtained.
The oxidizing solution of the present invention and the chemiluminescence system using the same can provide a highly safe system having excellent chemiluminescence performance. In addition, the period for maintaining the safety is very long, and it is suitable for long-term storage. Specific examples of this chemiluminescent system include those used in open systems such as ceremonies and events, and sealed chemiluminescent materials used for concerts and warning lights.
　以下、実施例により本発明を更に詳細に説明するが、本発明は、その要旨を変更しない限り以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples unless the gist thereof is changed.
［酸化液の溶媒］
　使用した溶媒および下記の表１における各溶媒の略号は以下の通りである。
クエン酸トリエチル（ＴＥＣ）
フタル酸ジメチル（ＤＭＰ）
ジエチレングリコールモノエチルエーテル（別称エチルジグリコール：ＥＤＧ）
ジメチレングリコールモノエチルエーテル（別称メチルジグリコール：ＭＤＧ） [Solvent of oxidizing solution]
The solvent used and the abbreviation of each solvent in Table 1 below are as follows.
Triethyl citrate (TEC)
Dimethyl phthalate (DMP)
Diethylene glycol monoethyl ether (also known as ethyl diglycol: EDG)
Dimethylene glycol monoethyl ether (also known as methyl diglycol: MDG)
　なお、さらに、溶媒に用いた成分として、酸化液には過酸化水素（Ｈ2Ｏ2）、サリチル酸ナトリウム（ＳＳ）を含む。 Furthermore, as components used for the solvent, the oxidizing solution contains hydrogen peroxide (H 2 O 2 ) and sodium salicylate (SS).
［酸化液の酸化防止剤］
ジ－ｔ－ブチル－ｐ－クレゾール（ＤＢＰＣ）
ハイドロキノン（ＨＱ） [Antioxidant for oxidizing solution]
Di-t-butyl-p-cresol (DBPC)
Hydroquinone (HQ)
「測定方法」
［発光輝度の測定方法（単位：ｃｄ／ｍ2）］
　発光輝度の計測は、輝度計（コニカミノルタ社製：ＬＳ－１００）を使用し、次の方法により測定した。
　暗室内で、輝度計の計測視野を満たす距離に透明容器を設置し、これに蛍光液１ｍＬと酸化液１ｍＬを混合し、小型撹拌型ホモジナイザを使用して強撹拌する。このときの最も強度の高い値を反応開始直後の発光輝度とした。その後、透明容器と試料を静置し５分後に再度発光輝度を計測した。 "Measuring method"
[Measurement Method of Luminance (Unit: cd / m 2 )]
Luminance was measured by the following method using a luminance meter (manufactured by Konica Minolta: LS-100).
In a dark room, a transparent container is installed at a distance that satisfies the measurement field of the luminance meter, and 1 mL of the fluorescent solution and 1 mL of the oxidizing solution are mixed therein, and the mixture is vigorously stirred using a small stirring homogenizer. The value with the highest intensity at this time was defined as the emission luminance immediately after the start of the reaction. Thereafter, the transparent container and the sample were allowed to stand, and the emission luminance was measured again after 5 minutes.
［引火点の測定方法（単位：℃）］
　引火点は、引火点試験器（３３０００－０形）（田中科学機器製作所製）を使用し、ＪＩＳ　Ｋ２２６５－２（迅速平衡密閉法）に準じセタ密閉式により測定した。 [Measurement method of flash point (unit: ° C)]
The flash point was measured by a setter sealing method using a flash point tester (type 33000-0) (manufactured by Tanaka Scientific Instruments) according to JIS K2265-2 (rapid equilibrium sealing method).
［ＨＰＬＣ測定方法］
　過酸化水素の量を、以下の測定条件のＨＰＬＣを用いて測定した。
・測定条件
検出器：Ｗａｔｅｒｓ　２４８７
ポンプ：日立　６０００
オートサンプラー：日立　ＡＳ－２０００
カラムオーブン:ＪＡＳＣＯ　ＣＯ－９６５
カラム：ＯＤＳ　４．６×２５０ｍｍ＋ＯＤＳ　４．６×１５０ｍｍ
フロー：流量０．８ｍＬ/ｍｉｎ
移動相：ＭｅＯＨ:水:リン酸＝１５００：５００：０．８
検出法：ＵＶ（３１０ｎｍ）
注入量：５μＬ [HPLC measurement method]
The amount of hydrogen peroxide was measured using HPLC under the following measurement conditions.
Measurement condition detector: Waters 2487
Pump: Hitachi 6000
Autosampler: Hitachi AS-2000
Column oven: JASCO CO-965
Column: ODS 4.6 × 250 mm + ODS 4.6 × 150 mm
Flow: Flow rate 0.8mL / min
Mobile phase: MeOH: water: phosphoric acid = 1500: 500: 0.8
Detection method: UV (310 nm)
Injection volume: 5 μL
「実施例１～４、比較例１」
［酸化液（１）の調製］
　ＴＥＣ６０重量部とＥＤＧ４０重量部を混合し溶媒（１）を作成した。この溶媒（１）に、Ｈ2Ｏ2の濃度が５ｗｔ％、ＳＳの濃度が０．５ｍｍｏｌ／Ｌとなるようにそれぞれ混合し、酸化液（１）とした。この酸化液（１）の調製直後の引火点は、１１０℃であった。 “Examples 1 to 4, Comparative Example 1”
[Preparation of oxidizing solution (1)]
60 parts by weight of TEC and 40 parts by weight of EDG were mixed to prepare a solvent (1). This solvent (1) was mixed so that the concentration of H 2 O 2 was 5 wt% and the concentration of SS was 0.5 mmol / L to obtain an oxidizing solution (1). The flash point immediately after the preparation of the oxidizing solution (1) was 110 ° C.
　酸化液（１）に、酸化防止剤を添加し、６０℃のオーブンで８週間、加速試験を行った際の引火点の変化を評価した結果を、表１中の実施例１～４に示す。なお、酸化防止剤を添加しないときの加速試験の結果を表１中の比較例１に示す。ＤＢＰＣまたはＨＱといった酸化防止剤を混合した本願の酸化液は、加速試験後の引火点の低下が少なく、長期間安定したものであった。 The results of evaluating the change in flash point when an antioxidant was added to the oxidizing solution (1) and an accelerated test was conducted in an oven at 60 ° C. for 8 weeks are shown in Examples 1 to 4 in Table 1. . The results of the acceleration test when no antioxidant is added are shown in Comparative Example 1 in Table 1. The oxidation solution of the present application in which an antioxidant such as DBPC or HQ was mixed had a small decrease in flash point after the acceleration test and was stable for a long time.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　また、酸化液（１）、比較例１、実施例１、実施例３の液を、ＨＰＬＣを用いて、その液中のＨ2Ｏ2と、触媒であるＳＳの量を測定した。その結果を、図１に示す。図１において、経過時間４ｍｉｎ付近にみられる第一のピークは、Ｈ2Ｏ2の量の指標となるものであり、経過時間７ｍｉｎ付近にみられる第二のピークは、ＳＳの量の指標となる。
　混合直後のイニシャルにあたる酸化液（１）では、Ｈ2Ｏ2、ＳＳともに大きなピークがみられるが、本発明の酸化剤を添加しない比較例１にかかる液では、特にＨ2Ｏ2の減少が顕著であり、ピークがほとんど見られなくなった。また、実施例１および実施例３にかかる液ではＨ2Ｏ2の減少がみられるものの、十分に残存しているものであり、十分に酸化液として機能するものであった。 Further, oxide solution (1), Comparative Example 1, Example 1, the liquid of Example 3, using HPLC, and of H 2 O 2 the liquid in, to determine the amount of SS is a catalyst. The result is shown in FIG. In FIG. 1, the first peak observed near the elapsed time 4 min is an index of the amount of H 2 O 2 , and the second peak observed near the elapsed time 7 min is the index of the amount of SS. Become.
In initial falls oxidation solution immediately after mixing (1), H 2 O 2 , SS although both large peak observed in the liquid of Comparative Example 1 without the oxidizing agent added in the present invention, in particular reduction of H 2 O 2 It was remarkable and almost no peak was seen. Although reduction of H 2 O 2 is observed in the liquid according to Example 1 and Example 3, which is sufficiently remained, it was to function as a fully oxidized solution.
「実施例５、６、比較例２」
［酸化液（２）の調製］
　ＤＭＰ７０重量部とＭＤＧ３０重量部を混合し溶媒（２）を作成した。この溶媒（２）に、Ｈ2Ｏ2濃度が５ｗｔ％、ＳＳ濃度が０．５ｍｍｏｌ／Ｌとなるようにそれぞれ混合し、酸化液（２）とした。この酸化液（２）の調製直後の引火点は、１１４℃であった。 "Examples 5 and 6, Comparative Example 2"
[Preparation of oxidizing solution (2)]
70 parts by weight of DMP and 30 parts by weight of MDG were mixed to prepare a solvent (2). The solvent (2) was mixed with an H 2 O 2 concentration of 5 wt% and an SS concentration of 0.5 mmol / L to form an oxidizing solution (2). The flash point immediately after the preparation of the oxidizing solution (2) was 114 ° C.
　酸化液（２）に、酸化防止剤を添加し、６０℃のオーブンで８週間、加速試験を行った際の引火点の変化を評価した結果を、表２中の実施例５、６に示す。なお、酸化防止剤を添加しないときの加速試験の結果を表２中の比較例２に示す。ＤＢＰＣまたはＨＱといった酸化防止剤を混合した本願の酸化液は、加速試験後の引火点の低下が少なく、長期間安定したものであった。 The results of evaluating the change in flash point when an antioxidant was added to the oxidizing solution (2) and an accelerated test was conducted in an oven at 60 ° C. for 8 weeks are shown in Examples 5 and 6 in Table 2. . In addition, the result of the acceleration test when not adding an antioxidant is shown in Comparative Example 2 in Table 2. The oxidation solution of the present application in which an antioxidant such as DBPC or HQ was mixed had a small decrease in flash point after the acceleration test and was stable for a long time.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
「実施例７、８、比較例３」
［酸化液（３）の調製］
　ＤＭＰ７０重量部とＥＤＧ３０重量部を混合し溶媒（３）を作成した。この溶媒（３）に、Ｈ2Ｏ2濃度が３ｗｔ％、ＳＳ濃度が０．５ｍｍｏｌ／Ｌとなるように混合し、酸化液（３）とした。この酸化液（３）の調製直後の引火点は、１１２℃であった。 “Examples 7 and 8, Comparative Example 3”
[Preparation of oxidizing solution (3)]
70 parts by weight of DMP and 30 parts by weight of EDG were mixed to prepare a solvent (3). This solvent (3) was mixed so that the H 2 O 2 concentration was 3 wt% and the SS concentration was 0.5 mmol / L to obtain an oxidizing solution (3). The flash point immediately after preparation of the oxidizing solution (3) was 112 ° C.
　酸化液（３）に、酸化防止剤を添加し、６０℃のオーブンで４週間、加速試験を行った際の引火点の変化を評価した結果を、表３中の実施例７、８に示す。なお、酸化防止剤を添加しないときの加速試験の結果を表３中の比較例３に示す。ＤＢＰＣまたはＨＱといった酸化防止剤を混合した本願の酸化液は、加速試験後の引火点の低下が少なく、長期間安定したものであった。 The results of evaluating the change in flash point when an antioxidant was added to the oxidizing solution (3) and an accelerated test was conducted in an oven at 60 ° C. for 4 weeks are shown in Examples 7 and 8 in Table 3. . In addition, the result of the acceleration test when no antioxidant is added is shown in Comparative Example 3 in Table 3. The oxidation solution of the present application in which an antioxidant such as DBPC or HQ was mixed had a small decrease in flash point after the acceleration test and was stable for a long time.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
［酸化液の検討（発光輝度の比較試験）に使用する蛍光液の作製（発光色緑）］
　アセチルクエン酸トリブチル（ＡＴＢＣ）７０容量％に安息香酸ベンジル（ＢｅＢ）２０容量％と、ジプロピレングリコールジメチルエーテル（ＤＭＭ）１０容量％を加え、１００℃に加温しながらチッソ曝気を施し、更にこれを継続しながらビス（２，４，５－トリクロロ－６－カルボペントキシフェニル）オキサレート（ＣＰＰＯ）２ｍｍｏｌ／Ｌ相当量を添加し全量を溶解した。更に、蛍光物質として９，１０－ビス（フェニルエチニル）アントラセン（ＢＰＥＡ）を１０ｍｍｏｌ／Ｌ添加し全量を溶解した。これを放冷した後、カラムに充填したモレキュラーシーブに通液した。このようにして得られた溶液を蛍光液（緑色発光）とした。 [Preparation of fluorescent solution used for examination of oxidation solution (comparative test of emission luminance) (light emission color green)]
Add 70% by volume of tributyl acetyl citrate (ATBC) to 20% by volume of benzyl benzoate (BeB) and 10% by volume of dipropylene glycol dimethyl ether (DMM), and apply nitrogen aeration while heating to 100 ° C. While continuing, bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate (CPPO) equivalent to 2 mmol / L was added to dissolve the entire amount. Further, 9,10-bis (phenylethynyl) anthracene (BPEA) as a fluorescent substance was added at 10 mmol / L to dissolve the whole amount. After allowing to cool, the solution was passed through a molecular sieve packed in a column. The solution thus obtained was used as a fluorescent solution (green light emission).
［発光輝度の測定］
　上記蛍光液（緑色発光）と酸化液（３）を攪拌混合し、前記発光輝度の測定方法に従い、発光輝度の経時変化を測定した。また、比較例３、実施例７、実施例８にかかる加速試験を行った後の酸化液と上記蛍光液（緑色発光）とを攪拌混合し、前記発光輝度の測定方法に従い、発光輝度の経時変化を測定した。これらの発光輝度を測定した結果を表４および図２に示す。 [Measurement of luminance]
The fluorescent solution (green light emission) and the oxidizing solution (3) were mixed with stirring, and the change in light emission luminance with time was measured according to the method for measuring the light emission luminance. In addition, the oxidation solution after the acceleration test according to Comparative Example 3, Example 7, and Example 8 and the fluorescent solution (green light emission) were stirred and mixed, and the emission luminance was measured over time according to the method for measuring the emission luminance. Changes were measured. The results of measuring these emission luminances are shown in Table 4 and FIG.
　本発明の酸化防止剤を添加した酸化液である実施例７、実施例８にかかる溶媒は、加速試験後も酸化液として十分に機能し、発光輝度の低下も少なかった。一方、酸化防止剤を混合せず加速試験を行った比較例３にかかる溶媒は、発光輝度の低下がみられ、酸化液としての機能が低下していた。なお、同様の発光輝度の測定試験を比較例１の液を用いて行うと、ほとんど発光がみられなかった。一方、実施例１～４にかかる液を用いると、発光がみられた。 The solvents according to Examples 7 and 8, which are oxidizing solutions to which the antioxidant of the present invention was added, functioned satisfactorily as oxidizing solutions even after the acceleration test, and there was little decrease in light emission luminance. On the other hand, the solvent according to Comparative Example 3, which was subjected to the acceleration test without mixing the antioxidant, showed a decrease in emission luminance and a function as an oxidizing solution. Note that when the same emission luminance measurement test was performed using the liquid of Comparative Example 1, almost no light emission was observed. On the other hand, when the liquids according to Examples 1 to 4 were used, light emission was observed.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　本発明の化学発光体用酸化液は、従来の酸化液に比べ高い引火点を有しており、かつ、当前記酸化液の引火点は、非常に長期間安定するものである。また、化学発光性能を維持したままで安全性に優れた化学発光システムを提供するものである。 The chemiluminescent oxidizing solution of the present invention has a higher flash point than conventional oxidizing solutions, and the flash point of the oxidizing solution is stable for a very long time. It is another object of the present invention to provide a chemiluminescent system excellent in safety while maintaining chemiluminescent performance.

Claims (6)

  1. 　シュウ酸エステルおよび蛍光物質を含有する蛍光液と混合した際に化学発光現象を生じる、過酸化水素および溶媒を含有する化学発光体用酸化液であって、
    　前記酸化液の引火点が６０℃以上であり、
    　前記酸化液に酸化防止剤が含有されることを特徴とする化学発光体用酸化液。     A chemiluminescent oxidation solution containing hydrogen peroxide and a solvent, which produces a chemiluminescence phenomenon when mixed with an oxalate ester and a fluorescent solution containing a fluorescent substance,
    The flash point of the oxidizing solution is 60 ° C. or higher,
    An oxidation solution for a chemiluminescent material, wherein the oxidation solution contains an antioxidant.
  2. 　前記酸化防止剤が、フェノール系酸化防止剤である請求項１記載の化学発光体用酸化液。 2. The chemiluminescent oxidizing solution according to claim 1, wherein the antioxidant is a phenolic antioxidant.
  3. 　前記フェノール系酸化防止剤が、ハイドロキノン、カテコール、レゾルシノール、ｔｅｒｔ－ブチルヒドロキノン、ブチルヒドロキシアニソール、ヒドロキノンモノメチルエーテルおよびジ－ｔ－ブチル－ｐ－クレゾールから選択される少なくとも１種以上の酸化防止剤である請求項２記載の化学発光体用酸化液。 The phenolic antioxidant is at least one antioxidant selected from hydroquinone, catechol, resorcinol, tert-butylhydroquinone, butylhydroxyanisole, hydroquinone monomethyl ether and di-t-butyl-p-cresol. The oxidation liquid for chemiluminescent bodies according to claim 2.
  4. 　前記酸化防止剤の濃度が、酸化液全体に対して、０．０５ｍｍｏｌ／Ｌ以上、１０ｍｍｏｌ／Ｌ以下である請求項１～３のいずれかに記載の化学発光体用酸化液。 The oxidizing solution for chemiluminescent materials according to any one of claims 1 to 3, wherein the concentration of the antioxidant is 0.05 mmol / L or more and 10 mmol / L or less with respect to the whole oxidizing solution.
  5. 　前記溶媒が、フタル酸エステル類、クエン酸エステル類、安息香酸エステル類、トリメリット酸エステル類、アジピン酸エステル類、セバシン酸エステル類、アゼライン酸エステル類、グリセリンエステル類、ラクトン類、グリコール類、アルキルグリコールエーテル類から選ばれた少なくとも２種以上の混合物であることを特徴とする請求項１～４のいずれかに記載の化学発光体用酸化液。 The solvent is a phthalate ester, citrate ester, benzoate ester, trimellitic acid ester, adipic acid ester, sebacic acid ester, azelaic acid ester, glycerin ester, lactone, glycol, The oxidizing solution for chemiluminescent bodies according to any one of claims 1 to 4, which is a mixture of at least two selected from alkyl glycol ethers.
  6. 　請求項１～５のいずれかの項に記載の化学発光体用酸化液とシュウ酸エステルおよび蛍光物質を含有する蛍光液とを含んでなることを特徴とする化学発光システム。 A chemiluminescent system comprising the chemiluminescent oxide oxidizing solution according to any one of claims 1 to 5 and a fluorescent solution containing an oxalate ester and a fluorescent substance.
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JP2002265939A (en) * 2001-03-14 2002-09-18 Lumica Corp Chemiluminescent composition
JP2011137134A (en) * 2009-12-04 2011-07-14 Cl Technology Kk Chemiluminescent composition
WO2011099375A1 (en) * 2010-02-09 2011-08-18 株式会社ルミカ Oxidizing liquid for chemiluminescence and chemiluminescence system using same

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JP2006249012A (en) * 2005-03-11 2006-09-21 Shiseido Co Ltd Fluorescent cosmetic

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JP2000204362A (en) * 1999-01-13 2000-07-25 Kasei Optonix Co Ltd Pasty composition of fluorescent substances
JP2002265939A (en) * 2001-03-14 2002-09-18 Lumica Corp Chemiluminescent composition
JP2011137134A (en) * 2009-12-04 2011-07-14 Cl Technology Kk Chemiluminescent composition
WO2011099375A1 (en) * 2010-02-09 2011-08-18 株式会社ルミカ Oxidizing liquid for chemiluminescence and chemiluminescence system using same

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