WO2018131421A1 - Corps chimioluminescent et système chimioluminescent, récipient cassable pour corps chimioluminescent, et solution d'oxydation pour corps chimioluminescent - Google Patents

Corps chimioluminescent et système chimioluminescent, récipient cassable pour corps chimioluminescent, et solution d'oxydation pour corps chimioluminescent Download PDF

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WO2018131421A1
WO2018131421A1 PCT/JP2017/045977 JP2017045977W WO2018131421A1 WO 2018131421 A1 WO2018131421 A1 WO 2018131421A1 JP 2017045977 W JP2017045977 W JP 2017045977W WO 2018131421 A1 WO2018131421 A1 WO 2018131421A1
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composition
chemiluminescent
container
fluorescent
fluorescent substance
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PCT/JP2017/045977
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English (en)
Japanese (ja)
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士郎 原田
昭憲 有吉
哲郎 山手
竜一 永利
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株式会社ルミカ
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Priority to JP2018561897A priority Critical patent/JP6621120B2/ja
Priority to CN201780037862.3A priority patent/CN109415626B/zh
Priority to KR1020187036872A priority patent/KR102156615B1/ko
Publication of WO2018131421A1 publication Critical patent/WO2018131421A1/fr

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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
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen

Definitions

  • the present invention relates to a chemiluminescent body and a chemiluminescent system, a chemiluminescent breakable container, and a chemiluminescent oxidizing solution.
  • the concentration of the contents is adjusted in the fluorescent solution and the oxidizing solution, and a solvent is used so that the reaction species in both solutions are mixed and reacted to make a relatively low viscosity solution.
  • a solvent is used so that the reaction species in both solutions are mixed and reacted to make a relatively low viscosity solution.
  • aromatic solvents such as phthalates and benzoates are used as the solvent.
  • Patent Document 2 discloses a chemiluminescent composition in which a oxalate ester is present in a solid state. Has been.
  • JP 2002-138278 A Japanese Patent No. 4726237
  • a chemiluminescent material emits light when an oxide generated by the reaction of an oxalate with hydrogen peroxide in the presence of a catalyst excites a fluorescent substance (fluorescent dye). Therefore, it is essential to separate oxalates and hydrogen peroxide when not in use.
  • the design is generally called “fluorescent solution” and “oxidizing solution”. That is, the “fluorescent solution” is a basic composition obtained by mixing an oxalate ester and a fluorescent substance together with a solvent. The concentration of oxalates in this fluorescent solution is about 5 to 30% by mass when designed as a general fluorescent solution.
  • the “oxidizing solution” is a basic composition in which hydrogen peroxide, a solvent for the oxidizing solution and a catalyst are mixed. This is because hydrogen peroxide itself is highly reactive, so it is considered better to separate it from other components directly involved in chemiluminescence.
  • the fluorescent solution When considering the change of the concentration of each component from such a design, the fluorescent solution inevitably reduces the solvent concentration from the composition of the fluorescent solution.
  • Patent Document 2 by increasing the concentration of oxalate esters (oxalate esters), it is possible to reduce the solvent concentration of the entire chemiluminescent body, thereby increasing the brightness, It is expected that the light emission performance will be enhanced, such as maintaining the light emission time for a long time.
  • a phosphor product having such a composition that realizes longer light emission has become mainstream only in a part such as yellow.
  • most emission colors cannot be realized for the following reasons.
  • the concentration of the fluorescent material is increased by lowering the solvent concentration, the fluorescent material in the fluorescent solution (or fluorescent solution composition) is likely to be deposited.
  • the precipitated solid fluorescent material hardly contributes to light emission, and the fluorescent material with low solubility cannot be easily dissolved even after contact with the oxidizing solution solvent, so that the original initial light emitting performance cannot be satisfied.
  • the present invention aims to enhance the chemiluminescence performance of such chemiluminescence, and provide a chemiluminescent material and chemiluminescent system excellent in stable luminescence brightness and luminescence time, and the fracture used in them. It is an object to provide a conductive container, an oxidizing solution, and the like.
  • the present invention relates to the following inventions.
  • a chemiluminescent material that emits light by mixing the first composition and the second composition wherein the first composition is a composition containing oxalate esters, A chemiluminescent material, wherein the second composition is a composition containing hydrogen peroxide, an oxidizing solution solvent, and a fluorescent material.
  • It has a splittable inner container and a chemiluminescent container containing the splittable inner container, and either the first composition or the second composition is splittable inside.
  • the chemiluminescent material according to ⁇ 1> wherein the chemiluminescent material is contained in a container, and the other composition is contained between the splittable inner container and the chemiluminescent material container.
  • ⁇ 3> The chemiluminescent material according to ⁇ 2>, wherein the composition contained in the splittable inner container is a first composition.
  • ⁇ 4> The chemiluminescent material according to any one of ⁇ 1> to ⁇ 3>, wherein the concentration of the oxalate ester in the first composition is 50% by mass or more.
  • ⁇ 5> The chemiluminescent material according to any one of ⁇ 1> to ⁇ 4>, wherein the fluorescent substance contained in the second composition is a perylene fluorescent substance and / or a naphthalimide fluorescent substance.
  • ⁇ 6> The chemiluminescent material according to any one of ⁇ 1> to ⁇ 5>, wherein the first composition is solid.
  • a first composition enclosed in a breakable container and a second composition enclosed separately from the first composition in a chemiluminescent container containing the breakable container A breakable container encapsulating a first composition used for a chemiluminescent material that emits light by mixing with an object,
  • the breakable container whose said 1st composition is a composition containing 50 mass% or more of oxalic acid esters.
  • a chemiluminescence system that emits light by mixing the first composition and the second composition, wherein the first composition is a composition containing oxalate esters, A chemiluminescence system, wherein the second composition is a composition containing hydrogen peroxide, an oxidizing solution solvent, and a fluorescent material.
  • a chemiluminescent body and a chemiluminescent system which are stable and excellent in emission luminance and emission time, and compositions and ampoules used for them.
  • the present invention is a chemiluminescent material that emits light by mixing the first composition and the second composition, wherein the first composition is a composition containing oxalic acid esters,
  • the second composition relates to a chemiluminescent material that is a composition containing hydrogen peroxide, an oxidizing solution solvent, a catalyst, and a fluorescent material.
  • a chemiluminescent body By setting it as such a chemiluminescent body, stable light emission arises by mixing a composition within a chemiluminescent body.
  • the composition for chemiluminescent materials is mixed in the chemiluminescent container by breaking or hitting the chemiluminescent material and breaking the breakable inner container in the chemiluminescent container. When this is done, the concentration of the oxalate ester in the first composition is high and the precipitation of the fluorescent material can be prevented, so that the emission luminance is high and the emission time can be extended.
  • this invention is a chemiluminescent system light-emitted by mixing a 1st composition and a 2nd composition
  • Said 1st composition is a composition containing oxalate ester.
  • the present invention relates to a chemiluminescence system in which the second composition is a composition containing hydrogen peroxide, an oxidizing solution solvent, a catalyst, and a fluorescent material.
  • the second composition is a composition containing hydrogen peroxide, an oxidizing solution solvent, a catalyst, and a fluorescent material.
  • the concentration of the oxalate ester in the first composition is high and the fluorescent material is contained in the second composition, precipitation in the first composition can be prevented, so that stable light emission is achieved. Arise.
  • the inventors changed the composition of the fluorescent liquid (fluorescent composition) and left the fluorescent substance solid in the liquid, or mixed the fluorescent composition into a powder form and mixed as a chemiluminescent material.
  • the cause of the formation of difficult lumps was examined.
  • it has been found that the influence of precipitation of the fluorescent material contained in the fluorescent composition is large.
  • FIG. 1 is a diagram showing the structure of a typical chemiluminescent material relating to the present invention.
  • the present invention can be an embodiment of the chemiluminescent body 10 shown in FIG.
  • the first composition 1 enclosed in the splittable inner container 3 is separated from the first composition 1 in the chemiluminescent container 4 enclosing the splittable inner container 3.
  • the present invention relates to a chemiluminescent body 10 having an encapsulated second composition 2.
  • the splittable inner container 3 is broken in the chemiluminescent container 4, and the first composition 1 and the second composition 2 are mixed to chemistry. Emits light.
  • oxalate (CIPO) is encapsulated alone as a first composition 1 and oxidized as a second composition 2. It was prepared using a mixture of liquid solvent (mixed solvent of DMP and t-BuOH), hydrogen peroxide, catalyst (SS) and fluorescent substance (Lumogen® F Red). The chemiluminescent material was bent to break the breakable inner container 3 and shaken lightly. As a result, the fluorescent substance was not precipitated, and was quickly mixed to produce stable light emission.
  • this invention can be made into embodiment of the chemiluminescent body 11 shown in FIG.1 (b).
  • the second composition 2 enclosed in the splittable inner container 3 is separated from the second composition 2 in the chemiluminescent container 4 containing the splittable inner container 3.
  • the present invention relates to a chemiluminescent body 11 having an encapsulated first composition 1.
  • This chemiluminescent body 11 is a modified version of the chemiluminescent body 10 in which the first composition and the second composition are contained.
  • the chemiluminescent body 11 breaks the splittable inner container 3 in the chemiluminescent body container 4 during use, and the first composition 1 and the second composition Chemiluminescence is produced by mixing the product 2.
  • the present invention may be an embodiment of the chemiluminescence system shown in FIG.
  • the nonwoven fabric 5 impregnated with the first composition 6 was prepared in FIG.
  • the first composition can be composed of substantially only oxalic acid esters or substantially composed of only oxalic acid esters and a solvent
  • the first composition is colorless and where the first composition is. It is in a state where it is difficult to visually recognize whether an object is arranged (portion indicated by a dotted line in FIG. 2A).
  • the second composition 7 is brought into contact with the nonwoven fabric 5 from the container 71.
  • the chemiluminescence system of the present invention is such that in a non-contact (mixed) state, the colorless first composition is arranged in a hidden character-like form, and chemiluminescence is generated during use. It can be.
  • the first composition used in the present invention is a composition containing oxalic acid esters. Since such a composition contains oxalate esters, chemiluminescence occurs when mixed with the second composition described in detail later.
  • the first composition used in the present invention contains oxalates as main components contributing to the chemiluminescence.
  • oxalate esters used here those capable of starting chemiluminescence when the first composition containing the oxalate ester and the second composition are mixed can be appropriately used.
  • Specific examples of oxalate esters include bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate, bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate, and the like. Can be mentioned.
  • the first composition used in the present invention preferably contains oxalates at a higher concentration than ordinary fluorescent solutions. With such a configuration, it is possible to improve light emission characteristics during chemiluminescence. Basically, the higher the concentration of oxalates, the better the chemiluminescent emission characteristics.
  • This first composition contains a high concentration of oxalates, so that the first composition becomes a solid, paste, or slurry composition.
  • concentration of oxalates when the concentration of oxalates is low, it is designed to contain a large amount of other solvents, etc., so that the precipitation of the fluorescent material is less likely to occur and the composition of the conventional fluorescent solution has the effect of hydrogen peroxide on the fluorescent material.
  • the conventional idea is that it is easy to design without consideration.
  • the concentration of oxalates in the first composition is preferably 50% by mass or more, and more preferably 80% by mass or more. More preferably, it is more preferably 90% by mass or more.
  • the concentration of the oxalate is 80% by mass or more, the property is substantially excellent in that it can be handled as being equivalent to the oxalate alone.
  • the first composition may be substantially oxalic acid esters alone, or expressed as the first composition as a concept including the case of oxalic acid esters alone.
  • the first composition used in the present invention is preferably solid.
  • the first composition used in the present invention in addition to the oxalate esters, those added as optional components described later are also solid at room temperature, and the entire first composition is a powder or It can also be a solid mixture such as a granule.
  • a chemiluminescence is produced by using a powdery body or a granule, it is considered that the liquid second composition is likely to enter the gap between the powdery body or the granule. The characteristics are improved.
  • the first composition is generally often enclosed in a fractureable inner container inside the chemiluminescent body. Since this breakable inner container has an extremely thin diameter depending on the size of the chemiluminescent material, it is preferable to use a powdery material or a granular material with relatively high fluidity so that it can be easily enclosed therein.
  • the first composition of the present invention can be substantially oxalate esters alone, but other components may be mixed.
  • a catalyst that is preferably contained on the second composition side may also be contained on the first composition side.
  • a chemiluminescent reaction occurs more stably.
  • an anthracene-based fluorescent material has high solubility and is unlikely to precipitate, so it may be used on the first composition side.
  • fluorescent substance is 1-chloro-9,10-bis (phenylethynyl) anthracene (2-Et-BPEA), a yellow fluorescent substance that has already been put to practical use to some extent.
  • an antioxidant, a stabilizer, a solvent, and the like may be appropriately contained.
  • the first composition used in the present invention can be mainly made of oxalate esters in a solid form.
  • a solvent may be contained.
  • the solvent generally, tributyl acetyl citrate (ATBC), benzyl benzoate (BeB), dipropylene glycol dimethyl ether (DMM) and the like are used alone or Used as a mixture.
  • the first composition used in the present invention preferably reduces components having low solubility in the solution of the first composition.
  • a typical example of such a component is a fluorescent material.
  • a perylene fluorescent material, a naphthalimide fluorescent material, and the like are contained in the first composition having a low solvent and low fluidity. Precipitation is likely to occur, and chemiluminescence characteristics are likely to deteriorate. Therefore, the content of the perylene fluorescent material and the naphthalimide fluorescent material in the first composition is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, and More preferably, the content is 1% by mass or less. It is particularly preferable that these contents are not used (0% by mass) without being used as a raw material of the composition.
  • the breakable inner container containing the first composition used in the chemiluminescent material of the present invention is a chemiluminescent chemiluminescent container, and only the breakable inner container preferentially breaks.
  • the first composition contained therein is dispersed.
  • a glass or resin ampule shape, an aluminum or PP bag shape, or the like can be given.
  • the present invention provides a first composition sealed in a splittable container and a second composition sealed and separated from the first composition in a chemiluminescent container containing the splittable container.
  • a chemiluminescent breakable container encapsulating a first composition used for a chemiluminescent substance that emits light by mixing with the composition, wherein the first composition is an oxalate ester It is possible to make a chemiluminescent breakable container that is a composition containing 50% by mass or more.
  • the chemiluminescent breakable container can be configured to correspond to the above-described breakable inner container containing the first composition. This chemiluminescent breakable container is used for reacting with the second composition so as to be mixed with excellent mixing properties as a chemiluminescent and exhibit excellent luminescent properties.
  • the chemiluminescent breakable container is contained in the chemiluminescent container as a whole of the chemiluminescent body, it is relatively small and the diameter thereof is often an elongated tubular ampule. .
  • the first composition as its contents does not contain a fluorescent substance that predominantly determines the color of chemiluminescence and can be widely used as a chemiluminescent material. It can also be a standardized ampoule.
  • This ampoule has a little influence on the color adjustment of the light emission characteristics, and it is practically a yellow fluorescent substance (for example, 1-chloro-9,10- Bis (phenylethynyl) anthracene (2-Et-BPEA)) may also be included.
  • a yellow fluorescent substance for example, 1-chloro-9,10- Bis (phenylethynyl) anthracene (2-Et-BPEA)
  • the second composition used in the present invention is a composition containing hydrogen peroxide, an oxidizing solution solvent, and a fluorescent material.
  • a second composition by preparing and using a liquid composition, when used as a chemiluminescent material, it is mixed with excellent mixing properties with the first composition described above, and stable chemiluminescence is obtained. Arise. This is because the fluorescent material is contained on the second composition side, thereby causing problems due to the mixing and solubility problems between the first composition such as solid or slurry and the oxidizing solution. It is because it becomes difficult to do.
  • the second composition used in the present invention contains hydrogen peroxide.
  • the second composition contains hydrogen peroxide, which is an oxidant, as an essential component, and adjusts the concentration of this hydrogen peroxide to improve compatibility (mixability) with the first composition, and further, luminous efficiency. It contains a solvent for improving the solubility of salicylate and the like added to improve the solubility.
  • a standard for the concentration of hydrogen peroxide in the second composition is about 1 to 10% by mass.
  • the second composition used in the present invention contains an oxidizing solution solvent.
  • the solvent contained in the oxidizing solution in the present invention include citric acid esters, phthalic acid esters, benzoic acid esters, trimellitic acid esters, adipic acid esters, sebacic acid esters, azelaic acid esters.
  • Solvents containing organic solvents such as glycerin esters, lactones, glycols and alkyl glycol ethers are preferably used. From these solvents, from the viewpoint of stability, it is preferable to use a solvent having a flash point of 60 ° C. or higher as the main solvent and to set the flash point as a whole to 70 ° C. or higher.
  • 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.
  • the amount of the oxidizing solution solvent in the second composition is the remainder of the other components such as hydrogen peroxide, catalyst, and fluorescent material contained in the second composition.
  • At least one of the first composition and the second composition used in the present invention contains a catalyst.
  • This catalyst is preferably contained in the second composition using a solvent.
  • the catalyst may be contained only in the first composition.
  • it can contribute to quick light emission as mentioned above partially, or stable light emission.
  • a catalyst component for example, a small amount of salicylic acid such as lithium salicylate, ammonium salicylate, sodium salicylate, tetraalkylammonium salicylate and its derivatives (usually 0.1 mmol / L to 10 mmol / L with respect to the oxidizing solution) Is desirable.
  • the second composition used in the present invention contains a fluorescent substance.
  • this fluorescent substance By including this fluorescent substance on the second composition side using a solvent, the problem of mixing that occurs when the oxalic acid ester concentration in the first composition is increased and the fluorescent substance is conventionally contained. Does not occur. Therefore, the first composition and the second composition are quickly mixed, and a reaction place where components essential for chemiluminescence such as oxalate ester, hydrogen peroxide, catalyst, and fluorescent substance are in an appropriate presence state. Is stably obtained in the chemiluminescent body. Thereby, effects such as improvement of initial light emission intensity and light emission time can be obtained.
  • the standard of the concentration of the fluorescent substance in the second composition is about 0.01 to 5% by mass, and is set according to the light emitting performance such as color, intensity, time, and the mixing property. From the viewpoint of solubility (precipitation prevention, etc.), this concentration is preferably set to the above range as a standard of concentration as a total amount when a plurality of fluorescent substances are used.
  • the lower limit of the concentration of the fluorescent substance is more preferably 0.05% by mass or more in order to improve the color developability during light emission.
  • the upper limit of the concentration of the fluorescent substance is that even if the fluorescent substance is mixed excessively, the color developability may be saturated, the concentration of the component contributing to chemiluminescence is relatively easily raised, and the precipitation of the fluorescent substance occurs. In order to make it hard to do, it is more preferable to set it as 2 mass% or less.
  • 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 the oxidizing solution solvent.
  • These fluorescent compounds include anthracene, substituted anthracene, benzoanthracene, phenanthrene, substituted phenanthrene, naphthacene, substituted naphthacene, pentacene, substituted pentacene, perylene, substituted perylene, violanthrone, substituted violanthrone, naphthalimide, substituted naphthalimide, etc.
  • the conjugated polycyclic aromatic compound which has is illustrated.
  • 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.
  • perylene fluorescent substances such as perylene and substituted perylene
  • naphthalimide fluorescent substances such as naphthalimide and substituted naphthalimide are deposited in the first composition mainly composed of oxalate ester. This is likely to occur and the light emission characteristics are likely to be unstable.
  • the fluorescent material contained in the second composition is preferably a perylene fluorescent material and / or a naphthalimide fluorescent material. These perylene fluorescent material and naphthalimide fluorescent material fluorescent material are also preferable because they are stable for a long time even in the second composition.
  • fluorescent substance described above examples include 2-chloro-9,10-bis (4-methylethynyl) anthracene, 9,10-bis (phenylethynyl) anthracene, 1-methoxy-9,10-bis ( Phenylethynyl) anthracene, 1,5-dichloro-9,10-bis (phenylethynyl) anthracene, 1,8-dichloro-9,10-bis (phenylethynyl) anthracene, monochloro and dichloro-substituted 9,10-bis (phenyl) Ethynyl) anthracene, 5,12-bis (phenylethynyl) tetracene, 9,10-diphenylanthracene, 16,17-dihexyloxyviolanthrone, 2-methyl-9,10-bis- (phenylethynyl) anthracene, 9, 10-bis- (4-methoxypheny
  • the fluorescent substance contained in the second composition of the present invention is preferably a perylene fluorescent substance.
  • the perylene fluorescent material is a fluorescent material having a skeleton of perylene or substituted perylene.
  • Perylene has a structure represented by the following formula (1), and a perylene fluorescent material has this structure as a skeleton.
  • Such a perylene-based fluorescent material is stable for a long time even when it is contained in the second composition that is a so-called oxidation solution, and is excellent in long-term storage.
  • perylene dicarboxyimide fluorescent substances are particularly preferable.
  • Specific products of this perylenedicarboxyimide-based fluorescent material include, for example, lumogen red (LUMOGEN RED, red-emitting perylenedicarboxyimide fluorescent agent, BASF, trade name), lumogen yellow (LUMOGEN YELLOW, yellow) Perylene dicarboxylimide fluorescing agent, BASF, trade name), and Lumogen Orange (LUMOGEN ORANGE, perylene dicarboxylimide fluorescing agent, BASF, trade name).
  • the fluorescent substance contained in the second composition of the present invention is preferably a naphthalimide fluorescent substance.
  • the compound used as the naphthalimide-based fluorescent material is a compound having a naphthalimide skeleton, and one that can be used as a fluorescent material in chemiluminescence is used.
  • the naphthalimide skeleton may have a substituent.
  • the naphthalimide skeleton is represented by the following formula (2).
  • the nitrogen atom in the above formula can be bonded to, for example, a hydrogen atom; a hydrocarbon group that may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • the hydrocarbon group is as defined above.
  • Examples of commercially available compounds having a naphthalimide skeleton include Lumogen F Violet 570 (BASF).
  • the second composition used in the present invention may contain other components as long as the object of the present invention is not impaired.
  • an antioxidant can be added to stabilize hydrogen peroxide or the like in the second composition during storage.
  • the present invention relates to a first composition sealed in a splittable inner container and an oxidation sealed separately from the first composition in a chemiluminescent container containing the splittable inner container.
  • This oxidizing solution corresponds to the second composition used in the present invention described above.
  • This oxidizing solution is used, for example, enclosed outside of the splittable inner container. Moreover, it is easy to change the color as a chemiluminescent body by changing the fluorescent substance of this oxidizing solution.
  • the ampule used for the splittable inner container has a smaller diameter and is less likely to be filled with the contents.
  • the chemiluminescent container filled with the oxidizing solution is designed with a wider diameter. Therefore, it is easy to fill the liquid.
  • chemiluminescence that shows any color development just by changing the color of the fluorescent material in the oxidizing solution The body can be manufactured efficiently.
  • any shape used as a chemiluminescent can be adopted.
  • the combination with a splittable inner container or the like containing the color, size, emission intensity, time, etc. is appropriately adjusted.
  • it may be a small chemiluminescent body for fishing gear, a light stick-like concert light, a warning light, or an emergency light.
  • a mask-like container may be used as a light emitter for an event that emits light, or a toy shape such as a star shape or a heart shape may be used.
  • the chemiluminescence system according to the present invention is a system in which the first composition and the second composition are brought into contact with each other and reacted. For this reason, it can be set as the chemiluminescent set of a 1st composition and a 2nd composition.
  • this invention is a chemiluminescent method light-emitted by mixing a 1st composition and a 2nd composition, Said 1st composition is a composition containing oxalate ester.
  • the chemiluminescent method may be a method in which the second composition is a composition containing hydrogen peroxide, an oxidizing solution solvent, and a fluorescent material.
  • the other composition when one composition is placed (impregnated) in advance, the other composition is contacted separately, and the shape, impregnated characters, figures, etc.
  • the light emission may be generated.
  • the first composition according to the chemiluminescence system of the present invention can be configured so that the content of the fluorescent substance exhibiting coloration is extremely small or substantially not contained, so One composition can be made colorless before the second composition comes into contact.
  • positioned at the time of use emits light utilization like a hidden character is possible.
  • composition such as a ceremony
  • one composition may be placed in an arbitrary container, and light may be emitted while adding the other composition from an opening or the like during use.
  • light can be emitted in a configuration corresponding to a hidden character, or each composition can be provided in different colors and mixed to emit light as a new color.
  • the concentration of the oxalate ester of the first composition can be reduced. Specifically, the concentration of oxalic acid esters can be 3% by mass or more. Further, for hidden characters, the first composition should be free of coloring of the fluorescent material, so its content is reduced to 0.1% by mass or less, more preferably 0.05% by mass or less. It is preferable to do. At this time, the lower limit of the content of the fluorescent substance is 0% by mass without being used as a raw material.
  • the second composition contains a perylene-based fluorescent substance and / or a sodium.
  • a phthalimide-based fluorescent material can be contained, and the first composition can contain other fluorescent materials exemplified above.
  • the first composition and the second composition can be colored, and in use, the mixed color can be developed.
  • Test method 1 Experiment in which fluorescent substance is contained in first composition (powder) side (in powder)”
  • An oxidizing solution (composition outline: DMP 81.6% by mass, t-BuOH 13.4% by mass, H 2 O 2 5% by mass, SS 0.04% by mass) was prepared.
  • (2) 9.85 g of CIPO and 0.15 g of the fluorescent substance (a) were weighed and mixed using a mortar.
  • (3) 0.14 g of the mixed powder of (1) was weighed into a 4 mL sample tube bottle.
  • (4) 0.43 mL of the oxidizing solution of (1) was added to the sample tube bottle of (3) to emit light.
  • the mixture was stirred for 10 seconds with a homogenizer (25M hand mixer + 215A type micro homogenizer) (the bottom of the container was stirred to allow the powder to diffuse into the oxidizing solution).
  • a homogenizer 25M hand mixer + 215A type micro homogenizer
  • the light emission luminance was measured from the upper part of the Marem container every predetermined measurement time described below, with the end of stirring as a reference zero point (initial). Measurement time: 30 seconds, 1 minute, 5 minutes, 15 minutes
  • the mixture was stirred with a homogenizer for 10 seconds (the bottom of the container was stirred to diffuse the powder into the oxidizing solution).
  • the light emission luminance was measured from the upper part of the Marem container every predetermined measurement time described below, with the end of stirring as a reference zero point (initial). Measurement time: 30 seconds, 1 minute, 5 minutes, 15 minutes
  • FIG. 3 and Table 1 show the emission luminance curve and the emission luminance for each time when the fluorescent substance (a) is contained in the powder and in the oxidizing solution, respectively. The test was performed twice under each condition.
  • Example 2 The stability of the fluorescent material in the oxidizing solution composition was tested.
  • test sample An oxidizing solution (composition outline: DMP 81.6 mass%, t-BuOH 13.4 mass%, H 2 O 2 5 mass%, SS 0.04 mass%) was prepared. (2) 100 g of the oxidizing solution (1) was weighed, 0.15 g (about 0.15% by mass) of a fluorescent substance was added thereto, and stirred at room temperature to dissolve. (3) The oxidizing solution of (2) was subdivided into screw tubes, and an accelerated treatment test was performed in a thermostatic chamber at 60 ° C. (4) The thing which is performing the acceleration process test in a 60 degreeC thermostat was taken out after one week. (5) For samples before and after the accelerated treatment test, the samples in which the fluorescent substance (pigment) was deposited were all dissolved using an ultrasonic cleaner and then measured.
  • HPLC measurement The stability of the fluorescent substance in the oxidizing solution prepared in the step of preparing the test sample was evaluated by the test by HPLC measurement under the following conditions. Measurement condition dilution operation: Detection wavelength: 254 nm with 4 mL of acetonitrile added to 10 ⁇ L of sample Mobile phase: 100% acetonitrile, column oven: 40 ° C Flow rate: 0.7 mL / min, injection volume: 5 ⁇ L Detection time: 20 minutes
  • Luminance measurement (1) 2.0 mL of a blank liquid (solute: CPPO, solvent: ATBC, BeB), which is an oxalate ester-containing composition, was added to a Marem container. (2) 1.0 mL of an oxidizing solution containing each fluorescent substance was weighed and added to the above (1) to start light emission. (3) The mixture was stirred with a homogenizer for 10 seconds. (4) Luminance was measured with 0 seconds as the end of stirring.
  • CPPO blank liquid
  • solvent ATBC, BeB
  • a chemiluminescent body and a chemiluminescent system that are stable and excellent in emission luminance and emission time are provided.
  • this chemiluminescent material can be used for various purposes such as events such as concert lights, light emitters used for fishing gear, disaster prevention simple lights, beacon lights, and warning lights, and is industrially useful. is there.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
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Abstract

L'objectif de la présente invention est de fournir un corps chimioluminescent tel que la réduction, etc., des propriétés luminescentes du matériau fluorescent dues à la précipitation sont supprimées et tel que que les propriétés luminescentes comprenant la luminosité d'émission de lumière et le temps d'émission de lumière sont excellentes. La présente invention concerne un corps chimioluminescent (10) qui mélange une première composition (1) et une seconde composition (2) pour émettre de la lumière, la première composition (1) étant une composition comprenant des oxalates, et la seconde composition (2) étant une composition comprenant un peroxyde d'hydrogène, un solvant pour une solution d'oxydation, un catalyseur et un matériau fluorescent. Ce corps chimioluminescent (10) peut être configuré pour comprendre un récipient interne cassable (1) et un récipient de corps chimioluminescent (4) qui contient le récipient interne cassable (3) à l'intérieur de celui-ci, la première composition (1) étant contenue dans le récipient interne cassable (3), et la seconde composition (2) étant contenue entre le récipient interne cassable (3) et le récipient de corps chimioluminescent (4).
PCT/JP2017/045977 2017-01-16 2017-12-21 Corps chimioluminescent et système chimioluminescent, récipient cassable pour corps chimioluminescent, et solution d'oxydation pour corps chimioluminescent WO2018131421A1 (fr)

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JP2018561897A JP6621120B2 (ja) 2017-01-16 2017-12-21 化学発光体および化学発光システム、ならびに化学発光体用破割性容器、化学発光用酸化液
CN201780037862.3A CN109415626B (zh) 2017-01-16 2017-12-21 化学发光体和化学发光系统以及化学发光体用易碎性容器、化学发光用氧化液
KR1020187036872A KR102156615B1 (ko) 2017-01-16 2017-12-21 화학 발광체 및 화학 발광 시스템, 및 화학 발광체용 깨짐성 용기, 화학 발광용 산화액

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5491982A (en) * 1977-12-19 1979-07-20 American Cyanamid Co Barrlike illumination lamp
JPS5653500U (fr) * 1979-03-30 1981-05-11
JPS56154506U (fr) * 1980-04-21 1981-11-18
JPS59146394A (ja) * 1983-02-09 1984-08-22 樽井　常一 緊急用位置報知方法
JP2011529124A (ja) * 2008-07-23 2011-12-01 キャルメ テクノロジーズ、インコーポレイテッド 秘密裏の侵入検知に有用な圧力起動可能な化学発光システム
US20130001485A1 (en) * 2011-06-28 2013-01-03 Weiwei Li Chemiluminescent Compositions and Methods of Making and Using Thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4726237Y1 (fr) 1968-07-20 1972-08-12
US4186426A (en) * 1977-12-19 1980-01-29 American Cyanamid Company Emergency lighting device
JPS5666258U (fr) * 1979-02-14 1981-06-02
US5597517A (en) * 1996-04-30 1997-01-28 Jame Fine Chemicals, Inc. Two-component chemiluminescent composition
JP2002138278A (ja) 2000-11-06 2002-05-14 Omniglow Japan Co Ltd 化学発光システム
CN103429699A (zh) * 2010-12-17 2013-12-04 克禄美科技股份有限公司 粘性化学发光组分和分配装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5491982A (en) * 1977-12-19 1979-07-20 American Cyanamid Co Barrlike illumination lamp
JPS5653500U (fr) * 1979-03-30 1981-05-11
JPS56154506U (fr) * 1980-04-21 1981-11-18
JPS59146394A (ja) * 1983-02-09 1984-08-22 樽井　常一 緊急用位置報知方法
JP2011529124A (ja) * 2008-07-23 2011-12-01 キャルメ テクノロジーズ、インコーポレイテッド 秘密裏の侵入検知に有用な圧力起動可能な化学発光システム
US20130001485A1 (en) * 2011-06-28 2013-01-03 Weiwei Li Chemiluminescent Compositions and Methods of Making and Using Thereof

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CN109415626A (zh) 2019-03-01
TW201831654A (zh) 2018-09-01
KR20190009789A (ko) 2019-01-29
JPWO2018131421A1 (ja) 2019-11-07
TWI751259B (zh) 2022-01-01
CN109415626B (zh) 2021-12-17
KR102156615B1 (ko) 2020-09-16

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