WO2012101848A1 - Oxidizing liquid for chemiluminescent element and chemiluminescent system containing same - Google Patents
Oxidizing liquid for chemiluminescent element and chemiluminescent system containing same Download PDFInfo
- Publication number
- WO2012101848A1 WO2012101848A1 PCT/JP2011/067485 JP2011067485W WO2012101848A1 WO 2012101848 A1 WO2012101848 A1 WO 2012101848A1 JP 2011067485 W JP2011067485 W JP 2011067485W WO 2012101848 A1 WO2012101848 A1 WO 2012101848A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ether
- glycol
- chemiluminescent
- diethylene glycol
- solution
- Prior art date
Links
Classifications
-
- 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
Definitions
- the present invention relates to a chemiluminescent system comprising a chemiluminescent oxidizing solution and the chemiluminescent oxidizing solution. More specifically, the present invention relates to an oxidation solution for chemiluminescent materials using a specific solvent, and a chemiluminescence system comprising the oxidation solution for chemiluminescent materials and a fluorescent solution for chemiluminescent materials.
- chemiluminescence is caused at any time by mixing with a solution (oxidation solution) contained therein 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.
- Patent Document 2 discloses that citrate esters are used as a solvent for a fluorescent solution and an oxidizing solution using such a non-aromatic solvent.
- a safer solvent is also required from the viewpoint of fire prevention.
- a solvent composition of a fluorescent solution a mixed solution of tributyl acetylcitrate (ATBC), benzyl benzoate (BeB), and dipropylene glycol dimethyl ether (DMM) has been widely used.
- ATBC tributyl acetylcitrate
- BeB benzyl benzoate
- DDM dipropylene glycol dimethyl ether
- solvents have a flash point. It is high and has a flash point of 100 ° C. or higher even in a mixed state.
- conventional solutions used as oxidizing solutions include alcohols such as ethanol, which have a low flash point, in both phthalic acid and non-phthalic acid systems, so they have a low flash point of about 20 ° C to 40 ° C. Was showing.
- Patent Document 3 discloses that at least one of ethylene glycol monoalkyl air acetate or diethylene glycol monoalkyl air acetate is used as a solvent for the oxidizing solution.
- these solvents are difficult to dissolve a salicylate salt such as sodium salicylate unless an alcohol such as t-butanol coexists, so that it is difficult to produce a luminescent solution having a high flash point.
- t-butanol flash point: 11 ° C.
- the conventional chemiluminescent composition oxidizing solution has a low flash point, so that it is difficult to handle as a dangerous substance and has a problem of being restricted as an air cargo.
- the present invention aims to provide an oxidation liquid for a chemiluminescent material that does not contain phthalic acid compounds and has improved fire safety safety than before without deteriorating luminous performance. To do.
- the present invention relates to the following inventions (1) to (5).
- a chemiluminescent oxidation solution 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 oxidation solution is
- the solvent contained in the oxidizing solution is 60 ° C.
- the solvent contained in the oxidizing solution is triethyl citrate, acetyl tributyl citrate, benzyl benzoate, trimethyl trimellitic acid, tri-n-butyl trimellitic acid, tris trimellitic acid (2-ethylhexyl), Diethyl adipate, diisopropyl adipate, diisobutyl adipate, diethyl sebacate, bis (2-ethylhexyl) azelate, 3-methoxy-3-methylbutanol, hexylene glycol, propylene glycol, butyrolactone, triethylene glycol, triacetin, diethylene glycol Diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, ethylene
- the solvent contained in the oxidizing solution is triethyl citrate, acetyl tributyl citrate, benzyl benzoate, trimethyl trimellitic acid, tri-n-butyl trimellitic acid, tris trimellitic acid (2-ethylhexyl), At least one selected from diethyl adipate, diisopropyl adipate, diisobutyl adipate, diethyl sebacate and bis (2-ethylhexyl) azelate, 3-methoxy-3-methylbutanol, hexylene glycol, propylene glycol, Butyrolactone, Triethylene glycol, Triacetin, Diethylene glycol diethyl ether, Diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, Triethylene glycol dimethyl ether, Ethylene Recall isopropyl ether, diethylene glycol dibutyl ether, chemiluminescence-body
- oxidizing solution for chemiluminescent materials according to any one of (1) to (4), wherein the solvent contained in the oxidizing solution further contains polyethylene glycol and / or polypropylene glycol.
- a chemiluminescent system comprising the chemiluminescent oxidizing solution according to any one of (1) to (6) above and a fluorescent solution containing an oxalate ester and a fluorescent substance.
- the chemiluminescent oxidizing solution of the present invention has a high flash point compared to conventional oxidizing solutions, as well as the chemiluminescent fluorescent solution, and has excellent safety while maintaining the chemiluminescent performance. I will provide a.
- the present invention relates to an oxidation 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, the flash point of the oxidation solution
- the present invention relates to an oxidizing solution for chemiluminescent materials, characterized in that the temperature is 60 ° C. or higher.
- the chemiluminescent oxidizing solution of the present invention is a chemiluminescent fluorescent solution (hereinafter simply referred to as “oxidizing solution”) containing an oxalate ester and a fluorescent substance (luminescent agent). It has a function of causing a chemiluminescence phenomenon when mixed with a fluorescent solution.
- the oxidizing solution contains hydrogen peroxide, which is an oxidant, as an essential component, and the concentration of this hydrogen peroxide is adjusted to improve compatibility (mixing property) with the luminescent agent in the fluorescent solution described below, and to improve luminous efficiency. It contains a solvent for improving the solubility of salicylate and the like added to improve the solubility.
- an oxidizing liquid having a flash point of 60 ° C. or higher, preferably 70 ° C., particularly preferably 100 ° C. or higher is used.
- the flash point refers to a value measured by a rapid equilibrium sealing method defined in JISK 2265-2.
- 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.
- the flash point in the oxidizing solution of the present invention is 70 ° C.
- the safety rank is further increased because the designation of dangerous materials No. 3 petroleum class 70 to 200 ° C. is applied. 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 is not a phthalic acid compound.
- phthalic acid-based compounds are being suspected as environmental hormone substances, and are excluded from the construction of a safer oxidizing solution, and thus a luminescent system.
- the solvent contained in the oxidizing solution of the present invention is a mixture containing at least two or more selected from the following compounds.
- specific examples of the solvent contained in the oxidizing solution in the present invention include triethyl citrate (flash point: 151 ° C.), tributyl acetyl citrate (flash point: 204 ° C.), benzyl benzoate (flash point: 148 ° C.).
- these solvents 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 used as a mixture of at least two or more, 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 triethyl citrate, acetyl tributyl citrate, benzyl benzoate, tri-n-butyl trimellitic acid, tris (2-ethylhexyl) trimellitic acid, diethyl adipate, diisobutyl adipate, azelain A mixture of at least two selected from bis (2-ethylhexyl) acid, 3-methoxy-3-methylbutanol, hexylene glycol, propylene glycol, butyrolactone, triacetin, diethylene glycol diethyl ether and diethylene glycol monomethyl ether.
- the oxidation solution is triethyl citrate, tributyl acetyl citrate, benzyl benzoate, trimethyl trimellitic acid, tri-n-butyl trimellitic acid, tris (2-ethylhexyl) trimellitic acid, diethyl adipate, diisopropyl adipate
- solvent A selected from diisobutyl adipate, diethyl sebacate and bis (2-ethylhexyl) azelate, and 3-methoxy-3-methylbutanol, hexylene glycol, propylene glycol, butyrolactone , Triethylene glycol, triacetin, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, ethylene group Call isopropyl ether, diethylene glycol dibutyl ether, is preferably a mixture
- the oxidizing solution is triethyl citrate, acetyl tributyl citrate, benzyl benzoate, tri-n-butyl trimellitic acid, tris (2-ethylhexyl) trimellitic acid, diethyl adipate, diisobutyl adipate and azelaic acid.
- the solvent A triethyl citrate and benzyl benzoate are particularly preferable, and as the solvent B, triacetin, 3-methoxy-3-methylbutanol and hexylene glycol are particularly preferably used.
- the mixing ratio of the solvent is appropriately determined depending on the use of the final product, required safety, and the like.
- the ratio (volume%) of the solvent A and the solvent B is generally 1 to 99:99 to 1, preferably 10 to 90:90 to 10, More preferably, it is 20 to 80:80 to 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 (average molecular weight 400, flash point: 240 ° C.) or polypropylene glycol (average molecular weight 400, flash point: 226 ° C.). 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.
- polypropylene glycol is preferably used from the viewpoints of miscibility, chemical stability, and luminance.
- 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.
- the chemiluminescent oxidation solution usually contains a small amount of salicylic acid and its derivatives such as lithium salicylate, lithium t-butylsalicylate, sodium salicylate, tetraalkylammonium salicylate, etc. as a catalyst component (usually relative to the oxidation solution). It is desirable to contain 0.1 mM to 10 mM).
- 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 used in the present invention
- oxalic acid derivatives such as oxalic acid halide, oxalic acid ester and oxalic oxamide
- typical oxalate 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.
- the fluorescent liquid 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.
- ATBC acetyl tributyl citrate
- BeB benzyl benzoate
- DDM dipropylene glycol dimethyl ether
- phthalic acid esters such as dimethyl phthalate and dibutyl phthalate are not used not only as a solvent for an oxidizing solution but also as a solvent for a fluorescent solution.
- 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 the concentration of the oxalate ester is usually 0.01 to 0.5 mol / liter, preferably 0.05 to 0.3. An amount of solvent that will be in moles / liter 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.
- Luminance measurement method (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, 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 device and the sample were allowed to stand, and the emission luminance was measured again after 5 minutes.
- Flash point measurement method (unit: ° C) The flash point was measured by a setter sealing method using a flash point tester (33000-0JIS type) (manufactured by Tanaka Scientific Instruments) according to K 2265-2 (rapid equilibrium sealing method).
- Example 1 Preparation of fluorescent solution used for examination of oxidation solution (Comparison test of emission luminance) (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, 2 mM equivalent of bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate (CPPO) was added to dissolve the entire amount.
- CPPO dipropylene glycol dimethyl ether
- Examples 2 to 10 As shown in Table 1, the experiment was performed in the same manner as in Example except that the solvent constituting the oxidizing solution and the composition ratio were changed, and the light emission luminance was measured. The results are also shown in Table 1.
- Example 1 Comparative Example 1 In Example 1, an experiment was performed in the same manner as in Example 1 except that only TEC was used as the solvent of the oxidizing solution, and the light emission luminance and the flash point were measured. The results are also shown in Table 1.
- Example 2 Comparative Example 2 In Example 1, an experiment was performed in the same manner as in Example 1 except that TEC and ethanol (EtOH) were used as shown in Table 1 as solvents constituting the oxidizing solution, and the emission luminance and flash point were measured. The results are also shown in Table 1.
- TEC and ethanol EtOH
- each of the oxidizing solutions of Examples 1 to 10 has an emission luminance equal to or higher than that obtained when an oxidizing solution using a mixed solution of TEC and ethanol as a solvent, and further has a flash point of 60 ° C. or higher. Indicated.
- Examples 11-15 As shown in Table 2, the experiment was performed in the same manner as in Example 1 except that the solvent constituting the oxidizing solution and the composition ratio were changed, and the light emission luminance and the flash point were measured. The results are also shown in Table 2.
- Example 16-18 As shown in Table 3, the experiment was performed in the same manner as in Example 1 except that the solvent constituting the oxidizing solution and the composition ratio were changed, and the light emission luminance and the flash point were measured. The results are also shown in Table 3.
- the chemiluminescent oxidizing solution of the present invention has a higher flash point than conventional oxidizing solutions, and provides a chemiluminescent system with excellent safety while maintaining chemiluminescent performance.
Abstract
Provided is an oxidizing liquid for chemiluminescent elements which has a higher flash point than conventional oxidizing liquids and which has excellent safety while maintaining chemiluminescent performance. Also provided is a chemiluminescent system.
The oxidizing liquid for chemiluminescent elements causes a chemiluminescent phenomenon when mixed with a fluorescent liquid comprising an oxalic acid ester and a fluorescent substance, and comprises hydrogen peroxide and solvents. The oxidizing liquid has a flash point of 60ºC or higher. The solvents contained in the oxidizing liquid are a mixture comprising two or more solvents selected from triethyl citrate, tributyl acetylcitrate, benzyl benzoate, tri-n-butyl trimellitate, tris(2-ethylhexyl) trimellitate, diethyl adipate, diisobutyl adipate, bis(2-ethylhexyl) azelate, 3-methoxy-3-methyl butanol, hexylene glycol, triacetin, diethylene glycol diethyl ether, etc. Polyethylene glycol and/or polypropylene glycol can be further added to the oxidizing liquid.
Description
本発明は、化学発光体用酸化液および当該化学発光体用酸化液を含んでなる化学発光システムに関する。より詳しくは、特定の溶媒を使用する化学発光体用酸化液、およびその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 a chemiluminescent system comprising a chemiluminescent oxidizing solution and the chemiluminescent oxidizing solution. More specifically, the present invention relates to an oxidation solution for chemiluminescent materials using a specific solvent, and a chemiluminescence system comprising the oxidation solution for chemiluminescent materials and a fluorescent solution for chemiluminescent materials.
既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 that use chemiluminescence are already on the market. A solution (fluorescent solution) containing an oxalate ester and a fluorescent substance (pigment), an oxidizing agent (mainly hydrogen peroxide), and a catalyst component (for example, salicylate) In general, chemiluminescence is caused at any time by mixing with a solution (oxidation solution) contained therein 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.
しかしながら、近年、これらの芳香族系溶媒の安全性に問題があることが指摘されており、特にフタル酸系の溶媒は環境ホルモン物質としての疑いがあることから、欧州等で規制の動きが見られている。化学発光体は、子供が玩具として使用する機会が多いことから、安全性の高い非芳香族系溶媒を使用した化学発光体用蛍光液および化学発光体用酸化液が望まれている。特許文献２には、このような非芳香族系溶媒を使用した蛍光液、酸化液の溶媒として、クエン酸エステル類を使用することが開示されている。
However, in recent years, it has been pointed out that there is a problem with the safety of these aromatic solvents, and in particular, phthalic acid solvents are suspected as environmental hormone substances, so regulatory movements have been seen in Europe and other countries. It has been. Since chemiluminescent materials have many opportunities for children to use as toys, a fluorescent solution for chemiluminescent materials and an oxidizing solution for chemiluminescent materials using non-aromatic solvents with high safety are desired. Patent Document 2 discloses that citrate esters are used as a solvent for a fluorescent solution and an oxidizing solution using such a non-aromatic 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（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）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１００℃以上の引火点を有するものである。
しかし、従来、酸化液として使用されている溶液はフタル酸系、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。例えば、特許文献３には、エチレングリコールモノアルキルエーエルアセテート又はジエチレングリコールモノアルキルエーエルアセテートの少なくとも一つを酸化液の溶媒とし使用することが開示されている。しかしながらこれらの溶媒は、t-ブタノールなどのアルコールが共在しないとサリチル酸ナトリウムなどのサリチル酸塩が溶解しにくいため、引火点の高い発光液を作製するのが困難である。因みに、特許文献３では、実施例を含め好ましい態様にはｔ－ブタノール（引火点:１１℃）が共溶媒として使用されている。
このように従来の化学発光組成物の酸化液は、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。 On the other hand, in recent years, a safer solvent is also required from the viewpoint of fire prevention. Conventionally, as a solvent composition of a fluorescent solution, a mixed solution of tributyl acetylcitrate (ATBC), benzyl benzoate (BeB), and dipropylene glycol dimethyl ether (DMM) has been widely used. These solvents have a flash point. It is high and has a flash point of 100 ° C. or higher even in a mixed state.
However, conventional solutions used as oxidizing solutions include alcohols such as ethanol, which have a low flash point, in both phthalic acid and non-phthalic acid systems, so they have a low flash point of about 20 ° C to 40 ° C. Was showing. For example, Patent Document 3 discloses that at least one of ethylene glycol monoalkyl air acetate or diethylene glycol monoalkyl air acetate is used as a solvent for the oxidizing solution. However, these solvents are difficult to dissolve a salicylate salt such as sodium salicylate unless an alcohol such as t-butanol coexists, so that it is difficult to produce a luminescent solution having a high flash point. Incidentally, in Patent Document 3, t-butanol (flash point: 11 ° C.) is used as a cosolvent in preferred embodiments including Examples.
As described above, the conventional chemiluminescent composition oxidizing solution has a low flash point, so that it is difficult to handle as a dangerous substance and has a problem of being restricted as an air cargo.
しかし、従来、酸化液として使用されている溶液はフタル酸系、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。例えば、特許文献３には、エチレングリコールモノアルキルエーエルアセテート又はジエチレングリコールモノアルキルエーエルアセテートの少なくとも一つを酸化液の溶媒とし使用することが開示されている。しかしながらこれらの溶媒は、t-ブタノールなどのアルコールが共在しないとサリチル酸ナトリウムなどのサリチル酸塩が溶解しにくいため、引火点の高い発光液を作製するのが困難である。因みに、特許文献３では、実施例を含め好ましい態様にはｔ－ブタノール（引火点:１１℃）が共溶媒として使用されている。
このように従来の化学発光組成物の酸化液は、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。 On the other hand, in recent years, a safer solvent is also required from the viewpoint of fire prevention. Conventionally, as a solvent composition of a fluorescent solution, a mixed solution of tributyl acetylcitrate (ATBC), benzyl benzoate (BeB), and dipropylene glycol dimethyl ether (DMM) has been widely used. These solvents have a flash point. It is high and has a flash point of 100 ° C. or higher even in a mixed state.
However, conventional solutions used as oxidizing solutions include alcohols such as ethanol, which have a low flash point, in both phthalic acid and non-phthalic acid systems, so they have a low flash point of about 20 ° C to 40 ° C. Was showing. For example, Patent Document 3 discloses that at least one of ethylene glycol monoalkyl air acetate or diethylene glycol monoalkyl air acetate is used as a solvent for the oxidizing solution. However, these solvents are difficult to dissolve a salicylate salt such as sodium salicylate unless an alcohol such as t-butanol coexists, so that it is difficult to produce a luminescent solution having a high flash point. Incidentally, in Patent Document 3, t-butanol (flash point: 11 ° C.) is used as a cosolvent in preferred embodiments including Examples.
As described above, the conventional chemiluminescent composition oxidizing solution has a low flash point, so that it is difficult to handle as a dangerous substance and has a problem of being restricted as an air cargo.
これらの状況を鑑みて、本発明は、発光性能を低下させることなく、従来よりも防火安全性を向上させた、フタル酸系化合物を含まない化学発光体用酸化液を提供することを目的とする。
In view of these circumstances, the present invention aims to provide an oxidation liquid for a chemiluminescent material that does not contain phthalic acid compounds and has improved fire safety safety than before without deteriorating luminous performance. To do.
本発明者らは、発光輝度等の発光性能と防火性能の両面から、酸化液として適切な溶媒について鋭意検討した結果、特定の溶媒を２種以上混合することにより、これらの要求を満たす酸化液が得られることを見出し、本発明に到達した。
As a result of intensive studies on a suitable solvent as an oxidizing solution from the viewpoints of light emitting performance such as luminance and fire prevention performance, the present inventors have obtained an oxidizing solution that satisfies these requirements by mixing two or more specific solvents. And the present invention has been achieved.
即ち、本発明は次の（１）から（５）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、該酸化液の引火点が６０℃以上であり、酸化液に含有される溶媒が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）、アジピン酸ジメチル、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、アジピン酸ジイソノニル、セバシン酸ジエチル、セバシン酸ジブチル、アゼライン酸ビス（２－エチルヘキシル）、３-メトキシ-３-メチルブタノール、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、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２種以上を含む混合物である化学発光体用酸化液。
（２）前記酸化液の引火点が７０℃以上である前記（１）に記載の化学発光体用酸化液。
（３）前記酸化液に含有される溶媒が、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メチル、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）、３-メトキシ-３-メチルブタノール、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、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２種以上を含む混合物である前記（１）又は（２）に記載の化学発光体用酸化液。
（４）前記酸化液に含有される溶媒が、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メチル、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種以上と、３-メトキシ-３-メチルブタノール、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、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種以上との混合物である前記（１）から（３）のいずれかに記載の化学発光体用酸化液。
（５）前記酸化液に含有される溶媒が、更に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を含む前記（１）から（４）のいずれかに記載の化学発光体用酸化液。
（６）前記酸化液に含有される溶媒が、ポリプロピレングリコールである前記（５）に記載の化学発光体用酸化液。
（７）前記（１）から（６）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化学発光システム。 That is, the present invention relates to the following inventions (1) to (5).
(1) A chemiluminescent oxidation solution 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 oxidation solution is The solvent contained in the oxidizing solution is 60 ° C. or higher, and triethyl citrate, acetyl tributyl citrate, benzyl benzoate, butyl benzoate, trimethyl trimellitic acid, tripropyl trimellitic acid, tri-n-butyl trimellitic acid , Trimellitic acid tris (2-ethylhexyl), dimethyl adipate, diethyl adipate, diisopropyl adipate, diisobutyl adipate, diisononyl adipate, diethyl sebacate, dibutyl sebacate, bis (2-ethylhexyl) azelate, 3- Methoxy-3-methylbutanol, hexylene glycol, At least selected from propylene glycol, butyrolactone, triethylene glycol, triacetin, 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 dimethyl ether and dipropylene glycol dimethyl ether An oxidation solution for a chemiluminescent material, which is a mixture containing two or more types.
(2) The oxidizing solution for chemiluminescent materials according to (1), wherein the flash point of the oxidizing solution is 70 ° C. or higher.
(3) The solvent contained in the oxidizing solution is triethyl citrate, acetyl tributyl citrate, benzyl benzoate, trimethyl trimellitic acid, tri-n-butyl trimellitic acid, tris trimellitic acid (2-ethylhexyl), Diethyl adipate, diisopropyl adipate, diisobutyl adipate, diethyl sebacate, bis (2-ethylhexyl) azelate, 3-methoxy-3-methylbutanol, hexylene glycol, propylene glycol, butyrolactone, triethylene glycol, triacetin, diethylene glycol Diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, ethylene glycol isopropyl ether, die Chemiluminescence-body oxidation liquid according to glycol dibutyl ether, wherein a mixture comprising at least two or more selected from diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether (1) or (2).
(4) The solvent contained in the oxidizing solution is triethyl citrate, acetyl tributyl citrate, benzyl benzoate, trimethyl trimellitic acid, tri-n-butyl trimellitic acid, tris trimellitic acid (2-ethylhexyl), At least one selected from diethyl adipate, diisopropyl adipate, diisobutyl adipate, diethyl sebacate and bis (2-ethylhexyl) azelate, 3-methoxy-3-methylbutanol, hexylene glycol, propylene glycol, Butyrolactone, Triethylene glycol, Triacetin, Diethylene glycol diethyl ether, Diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, Triethylene glycol dimethyl ether, Ethylene Recall isopropyl ether, diethylene glycol dibutyl ether, chemiluminescence-body oxidation solution according to any one of the is a mixture of at least one kind selected from diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether (1) (3).
(5) The oxidizing solution for chemiluminescent materials according to any one of (1) to (4), wherein the solvent contained in the oxidizing solution further contains polyethylene glycol and / or polypropylene glycol.
(6) The oxidizing solution for chemiluminescent materials according to (5), wherein the solvent contained in the oxidizing solution is polypropylene glycol.
(7) A chemiluminescent system comprising the chemiluminescent oxidizing solution according to any one of (1) to (6) above and a fluorescent solution containing an oxalate ester and a fluorescent substance.
（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、該酸化液の引火点が６０℃以上であり、酸化液に含有される溶媒が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）、アジピン酸ジメチル、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、アジピン酸ジイソノニル、セバシン酸ジエチル、セバシン酸ジブチル、アゼライン酸ビス（２－エチルヘキシル）、３-メトキシ-３-メチルブタノール、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、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２種以上を含む混合物である化学発光体用酸化液。
（２）前記酸化液の引火点が７０℃以上である前記（１）に記載の化学発光体用酸化液。
（３）前記酸化液に含有される溶媒が、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メチル、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）、３-メトキシ-３-メチルブタノール、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、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２種以上を含む混合物である前記（１）又は（２）に記載の化学発光体用酸化液。
（４）前記酸化液に含有される溶媒が、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メチル、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種以上と、３-メトキシ-３-メチルブタノール、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、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種以上との混合物である前記（１）から（３）のいずれかに記載の化学発光体用酸化液。
（５）前記酸化液に含有される溶媒が、更に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を含む前記（１）から（４）のいずれかに記載の化学発光体用酸化液。
（６）前記酸化液に含有される溶媒が、ポリプロピレングリコールである前記（５）に記載の化学発光体用酸化液。
（７）前記（１）から（６）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化学発光システム。 That is, the present invention relates to the following inventions (1) to (5).
(1) A chemiluminescent oxidation solution 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 oxidation solution is The solvent contained in the oxidizing solution is 60 ° C. or higher, and triethyl citrate, acetyl tributyl citrate, benzyl benzoate, butyl benzoate, trimethyl trimellitic acid, tripropyl trimellitic acid, tri-n-butyl trimellitic acid , Trimellitic acid tris (2-ethylhexyl), dimethyl adipate, diethyl adipate, diisopropyl adipate, diisobutyl adipate, diisononyl adipate, diethyl sebacate, dibutyl sebacate, bis (2-ethylhexyl) azelate, 3- Methoxy-3-methylbutanol, hexylene glycol, At least selected from propylene glycol, butyrolactone, triethylene glycol, triacetin, 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 dimethyl ether and dipropylene glycol dimethyl ether An oxidation solution for a chemiluminescent material, which is a mixture containing two or more types.
(2) The oxidizing solution for chemiluminescent materials according to (1), wherein the flash point of the oxidizing solution is 70 ° C. or higher.
(3) The solvent contained in the oxidizing solution is triethyl citrate, acetyl tributyl citrate, benzyl benzoate, trimethyl trimellitic acid, tri-n-butyl trimellitic acid, tris trimellitic acid (2-ethylhexyl), Diethyl adipate, diisopropyl adipate, diisobutyl adipate, diethyl sebacate, bis (2-ethylhexyl) azelate, 3-methoxy-3-methylbutanol, hexylene glycol, propylene glycol, butyrolactone, triethylene glycol, triacetin, diethylene glycol Diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, ethylene glycol isopropyl ether, die Chemiluminescence-body oxidation liquid according to glycol dibutyl ether, wherein a mixture comprising at least two or more selected from diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether (1) or (2).
(4) The solvent contained in the oxidizing solution is triethyl citrate, acetyl tributyl citrate, benzyl benzoate, trimethyl trimellitic acid, tri-n-butyl trimellitic acid, tris trimellitic acid (2-ethylhexyl), At least one selected from diethyl adipate, diisopropyl adipate, diisobutyl adipate, diethyl sebacate and bis (2-ethylhexyl) azelate, 3-methoxy-3-methylbutanol, hexylene glycol, propylene glycol, Butyrolactone, Triethylene glycol, Triacetin, Diethylene glycol diethyl ether, Diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, Triethylene glycol dimethyl ether, Ethylene Recall isopropyl ether, diethylene glycol dibutyl ether, chemiluminescence-body oxidation solution according to any one of the is a mixture of at least one kind selected from diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether (1) (3).
(5) The oxidizing solution for chemiluminescent materials according to any one of (1) to (4), wherein the solvent contained in the oxidizing solution further contains polyethylene glycol and / or polypropylene glycol.
(6) The oxidizing solution for chemiluminescent materials according to (5), wherein the solvent contained in the oxidizing solution is polypropylene glycol.
(7) A chemiluminescent system comprising the chemiluminescent oxidizing solution according to any one of (1) to (6) above and a fluorescent solution containing an oxalate ester and a fluorescent substance.
本発明の化学発光体用酸化液は、化学発光体用蛍光液同様、従来の酸化液に比べ高い引火点を有しており、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。
The chemiluminescent oxidizing solution of the present invention has a high flash point compared to conventional oxidizing solutions, as well as the chemiluminescent fluorescent solution, and has excellent safety while maintaining the chemiluminescent performance. I will provide a.
以下、本発明を詳細に説明する。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、該酸化液の引火点が６０℃以上であることを特徴とする化学発光体用酸化液に係るものである。
Hereinafter, the present invention will be described in detail. The present invention relates to an oxidation 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, the flash point of the oxidation solution The present invention relates to an oxidizing solution for chemiluminescent materials, characterized in that the temperature is 60 ° C. or higher.
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（発光剤）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発光剤との相溶性（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 (hereinafter simply referred to as “oxidizing solution”) containing an oxalate ester and a fluorescent substance (luminescent agent). It has a function of causing a chemiluminescence phenomenon when mixed with a fluorescent solution. The oxidizing solution contains hydrogen peroxide, which is an oxidant, as an essential component, and the concentration of this hydrogen peroxide is adjusted to improve compatibility (mixing property) with the luminescent agent in the fluorescent solution described below, and to improve luminous efficiency. 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℃、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、ＪＩＳＫ ２２６５－２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 an oxidizing liquid having a flash point of 60 ° C. or higher, preferably 70 ° C., particularly preferably 100 ° C. or higher is used.
Here, the flash point refers to a value measured by a rapid equilibrium sealing method defined in JISK 2265-2.
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.
Furthermore, when the flash point in the oxidizing solution of the present invention is 70 ° C. or higher, the safety rank is further increased because the designation of dangerous materials No. 3 petroleum class 70 to 200 ° C. is applied.
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.
ここで、引火点とは、ＪＩＳＫ ２２６５－２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 an oxidizing liquid having a flash point of 60 ° C. or higher, preferably 70 ° C., particularly preferably 100 ° C. or higher is used.
Here, the flash point refers to a value measured by a rapid equilibrium sealing method defined in JISK 2265-2.
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.
Furthermore, when the flash point in the oxidizing solution of the present invention is 70 ° C. or higher, the safety rank is further increased because the designation of dangerous materials No. 3 petroleum class 70 to 200 ° C. is applied.
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.
更に、この酸化液に含まれる溶媒が、フタル酸系化合物ではないことが特徴である。フタル酸系化合物は、前述の如く環境ホルモン物質としての疑いが議論されており、より安全な酸化液、ひいては発光用システム構築上からこれを除外したものである。
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た少なくとも２種以上を含む混合物であることが特徴である。 Further, the solvent contained in the oxidizing solution is not a phthalic acid compound. As mentioned above, phthalic acid-based compounds are being suspected as environmental hormone substances, and are excluded from the construction of a safer oxidizing solution, and thus a luminescent system.
In addition, the solvent contained in the oxidizing solution of the present invention is a mixture containing at least two or more selected from the following compounds.
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た少なくとも２種以上を含む混合物であることが特徴である。 Further, the solvent contained in the oxidizing solution is not a phthalic acid compound. As mentioned above, phthalic acid-based compounds are being suspected as environmental hormone substances, and are excluded from the construction of a safer oxidizing solution, and thus a luminescent system.
In addition, the solvent contained in the oxidizing solution of the present invention is a mixture containing at least two or more selected from the following compounds.
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℃）、安息香酸ベンジル（引火点：１４８℃）、安息香酸ブチル（引火点：１２２℃）、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℃）、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℃）、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℃）、アゼライン酸ビス（２－エチルヘキシル）（引火点：２１１℃）、３-メトキシ-３-メチルブタノール（引火点：６７℃）、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℃）、ブチロラクトン（引火点：９８℃）、トリエチレングリコール（引火点：１７７℃）、トリアセチン（引火点：１４８℃）、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℃）、ジエチレングリコールジブチルエーテル（引火点：１１８℃）、ジエチレングリコールジメチルエーテル（引火点：５８℃）またはジプロピレングリコールジメチルエーテル（引火点：６０℃）である。
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。
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、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。 That is, specific examples of the solvent contained in the oxidizing solution in the present invention include triethyl citrate (flash point: 151 ° C.), tributyl acetyl citrate (flash point: 204 ° C.), benzyl benzoate (flash point: 148 ° C.). ), Butyl benzoate (flash point: 122 ° C.), trimethyl trimellitic acid (flash point: 182 ° C.), tripropyl trimellitic acid (no flash point), tri-n-butyl trimellitic acid (flash point: 215 ° C.) ), Tris (2-ethylhexyl) trimellitic acid (flash point: 262 ° C.), 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.), diethyl sebacate (flash point: 20 ° C), dibutyl sebacate (flash point: 190 ° C), bis (2-ethylhexyl) azelate (flash point: 211 ° C), 3-methoxy-3-methylbutanol (flash point: 67 ° C), hexylene glycol (Flash point: 96 ° C.), propylene glycol (flash point: 99 ° C.), butyrolactone (flash point: 98 ° C.), triethylene glycol (flash point: 177 ° C.), triacetin (flash point: 148 ° C.), diethylene glycol diethyl ether (Flash point: 71 ° C.), diethylene glycol monomethyl ether (flash point: 93 ° C.), diethylene glycol monoethyl ether (flash point: 96 ° C.), triethylene glycol dimethyl ether (flash point: 113 ° C.), ethylene glycol isopropyl ether (flash point) : 44 ° C), diethylene glycol dibu It is chill ether (flash point: 118 ° C.), diethylene glycol dimethyl ether (flash point: 58 ° C.) or dipropylene glycol dimethyl ether (flash point: 60 ° 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 used as a mixture of at least two or more, 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.
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。
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、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。 That is, specific examples of the solvent contained in the oxidizing solution in the present invention include triethyl citrate (flash point: 151 ° C.), tributyl acetyl citrate (flash point: 204 ° C.), benzyl benzoate (flash point: 148 ° C.). ), Butyl benzoate (flash point: 122 ° C.), trimethyl trimellitic acid (flash point: 182 ° C.), tripropyl trimellitic acid (no flash point), tri-n-butyl trimellitic acid (flash point: 215 ° C.) ), Tris (2-ethylhexyl) trimellitic acid (flash point: 262 ° C.), 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.), diethyl sebacate (flash point: 20 ° C), dibutyl sebacate (flash point: 190 ° C), bis (2-ethylhexyl) azelate (flash point: 211 ° C), 3-methoxy-3-methylbutanol (flash point: 67 ° C), hexylene glycol (Flash point: 96 ° C.), propylene glycol (flash point: 99 ° C.), butyrolactone (flash point: 98 ° C.), triethylene glycol (flash point: 177 ° C.), triacetin (flash point: 148 ° C.), diethylene glycol diethyl ether (Flash point: 71 ° C.), diethylene glycol monomethyl ether (flash point: 93 ° C.), diethylene glycol monoethyl ether (flash point: 96 ° C.), triethylene glycol dimethyl ether (flash point: 113 ° C.), ethylene glycol isopropyl ether (flash point) : 44 ° C), diethylene glycol dibu It is chill ether (flash point: 118 ° C.), diethylene glycol dimethyl ether (flash point: 58 ° C.) or dipropylene glycol dimethyl ether (flash point: 60 ° 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 used as a mixture of at least two or more, 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、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メチル、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）、３-メトキシ-３-メチルブタノール、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、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２種以上の混合物であることが好ましい。
Among the above solvents, triethyl citrate, tributyl acetyl citrate, benzyl benzoate, trimethyl trimellitic acid, tri-n-butyl trimellitic acid, tris (2-ethylhexyl) trimellitic acid, diethyl adipate, diisopropyl adipate, Diisobutyl adipate, diethyl sebacate, bis (2-ethylhexyl) azelate, 3-methoxy-3-methylbutanol, hexylene glycol, propylene glycol, butyrolactone, triethylene glycol, triacetin, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, triethylene glycol dimethyl ether, ethylene glycol isopropyl ether, diethylene glycol Ether is preferably a mixture of at least two or more species selected from diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether.
更に、好ましくは、上記溶媒が、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）、３-メトキシ-３-メチルブタノール、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、トリアセチン、ジエチレングリコールジエチルエーテルおよびジエチ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 triethyl citrate, acetyl tributyl citrate, benzyl benzoate, tri-n-butyl trimellitic acid, tris (2-ethylhexyl) trimellitic acid, diethyl adipate, diisobutyl adipate, azelain A mixture of at least two selected from bis (2-ethylhexyl) acid, 3-methoxy-3-methylbutanol, hexylene glycol, propylene glycol, butyrolactone, triacetin, diethylene glycol diethyl ether and diethylene glycol monomethyl ether.
特に、酸化液が、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メチル、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、３-メトキシ-３-メチルブタノール、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、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 oxidation solution is triethyl citrate, tributyl acetyl citrate, benzyl benzoate, trimethyl trimellitic acid, tri-n-butyl trimellitic acid, tris (2-ethylhexyl) trimellitic acid, diethyl adipate, diisopropyl adipate At least one solvent (solvent A) selected from diisobutyl adipate, diethyl sebacate and bis (2-ethylhexyl) azelate, and 3-methoxy-3-methylbutanol, hexylene glycol, propylene glycol, butyrolactone , Triethylene glycol, triacetin, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, ethylene group Call isopropyl ether, diethylene glycol dibutyl ether, is preferably a mixture of at least one or more solvents selected from diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether (solvent B).
更に好ましくは、酸化液が、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、３-メトキシ-３-メチルブタノール、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、トリアセチン、ジエチレングリコールジエチルエーテルおよびジエチ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１種以上の溶媒（溶媒Ｂ）との混合物である。
More preferably, the oxidizing solution is triethyl citrate, acetyl tributyl citrate, benzyl benzoate, tri-n-butyl trimellitic acid, tris (2-ethylhexyl) trimellitic acid, diethyl adipate, diisobutyl adipate and azelaic acid. At least one solvent selected from bis (2-ethylhexyl) (solvent A) and 3-methoxy-3-methylbutanol, hexylene glycol, propylene glycol, butyrolactone, triacetin, diethylene glycol diethyl ether and diethylene glycol monomethyl ether It is a mixture with at least one selected solvent (solvent B).
溶媒Ａとしては、特に、クエン酸トリエチル、安息香酸ベンジルが好ましく、溶媒Ｂとしては、特に、トリアセチン、３-メトキシ-３-メチルブタノール、ヘキシレングリコールが好ましく使用される。
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％）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。 As the solvent A, triethyl citrate and benzyl benzoate are particularly preferable, and as the solvent B, triacetin, 3-methoxy-3-methylbutanol and hexylene glycol are particularly preferably used.
The mixing ratio of the solvent is appropriately determined depending on the use of the final product, required safety, and the like. When the solvent is a mixed solvent of the solvent A and the solvent B, the ratio (volume%) of the solvent A and the solvent B is generally 1 to 99:99 to 1, preferably 10 to 90:90 to 10, More preferably, it is 20 to 80:80 to 20.
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％）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。 As the solvent A, triethyl citrate and benzyl benzoate are particularly preferable, and as the solvent B, triacetin, 3-methoxy-3-methylbutanol and hexylene glycol are particularly preferably used.
The mixing ratio of the solvent is appropriately determined depending on the use of the final product, required safety, and the like. When the solvent is a mixed solvent of the solvent A and the solvent B, the ratio (volume%) of the solvent A and the solvent B is generally 1 to 99:99 to 1, preferably 10 to 90:90 to 10, More preferably, it is 20 to 80:80 to 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、前記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。
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 is difficult to make an oxidizing solution equivalent to or higher than the lower alcohol.
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.
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 is difficult to make an oxidizing solution equivalent to or higher than the lower alcohol.
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（平均分子量４００、引火点：２４０℃）又はポリプロピレングリコール（平均分子量４００、引火点：２２６℃）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 (average molecular weight 400, flash point: 240 ° C.) or polypropylene glycol (average molecular weight 400, flash point: 226 ° C.). 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.
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.
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 (average molecular weight 400, flash point: 240 ° C.) or polypropylene glycol (average molecular weight 400, flash point: 226 ° C.). 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.
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、ｔ－ブチルサリチル酸リチウム、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０．１ｍＭから１０ｍＭ）含有することが望ましい。
In addition, the chemiluminescent oxidation solution usually contains a small amount of salicylic acid and its derivatives such as lithium salicylate, lithium t-butylsalicylate, sodium salicylate, tetraalkylammonium salicylate, etc. as a catalyst component (usually relative to the oxidation solution). It is desirable to contain 0.1 mM to 10 mM).
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（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 (oxalate) used in the present invention, oxalic acid derivatives such as oxalic acid halide, oxalic acid ester and oxalic oxamide can be used. As typical oxalate, 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。
なお、本発明では、フタル酸ジメチル、フタル酸ジブチル等のフタル酸エステル類を、酸化液の溶媒のみならず蛍光液の溶媒としても使用しない。 In the fluorescent liquid 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.
In the present invention, phthalic acid esters such as dimethyl phthalate and dibutyl phthalate are not used not only as a solvent for an oxidizing solution but also as a solvent for a fluorescent solution.
なお、本発明では、フタル酸ジメチル、フタル酸ジブチル等のフタル酸エステル類を、酸化液の溶媒のみならず蛍光液の溶媒としても使用しない。 In the fluorescent liquid 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.
In the present invention, phthalic acid esters such as dimethyl phthalate and dibutyl phthalate are not used not only as a solvent for an oxidizing solution but also as a solvent for a fluorescent solution.
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０．０１～０．５モル／リットル、好ましくは０．０５～０．３モル／リットル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 the concentration of the oxalate ester is usually 0.01 to 0.5 mol / liter, preferably 0.05 to 0.3. An amount of solvent that will be in moles / liter 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。 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.
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。 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.
以下、本発明を実施例により詳しく説明するが、本発明はこれらの実施例に限定されるものではない。
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
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）、安息香酸ベンジル（ＢｅＢ）、３－メトキシ－３－メチルブタノール（ＭＭＢ）、ヘキシレングリコール（ＨＧ）、アセチルクエン酸トリブチル（ＡＴＢＣ）、プロピレングリコール（ＰＧ）、ブチロラクトン（ＢＬ）、ジエチレングリコールモノメチルエーテル（ＥＤＧ）、トリアセチン（ＴＡ）、ジエチレングリコールジエチルエーテル（ＥＧＤＥＥ）、トリメリット酸トリ-n-ブチル（ＴＢＴＭ）、トリメリット酸トリス(2-エチルヘキシル）（ＴＯＴＭ）、アジピン酸ジエチル（ＤＥＡＤ）、アジピン酸ジイソブチル（ＤＩＢＡＤ）、アゼライン酸ビス（2-エチルヘキシル）（ＤＯＡＺ），ポリエチレングリコール（ＰＥＧ）、ポリプロピレングリコール（ＰＰＧ）
なお、共通組成として、酸化液には過酸化水素（３重量％）、サリチル酸ナトリウム（２．０ｍＭ）を含む。 The solvent used and the abbreviation of each solvent in Table 1 below are as follows.
Triethyl citrate (TEC), benzyl benzoate (BeB), 3-methoxy-3-methylbutanol (MMB), hexylene glycol (HG), tributyl acetyl citrate (ATBC), propylene glycol (PG), butyrolactone (BL ), Diethylene glycol monomethyl ether (EDG), triacetin (TA), diethylene glycol diethyl ether (EGDEE), tri-n-butyl trimellitic acid (TBTM), tris (2-ethylhexyl) trimellitic acid (TOTM), diethyl adipate (TOTM) DEAD), diisobutyl adipate (DIBAD), bis (2-ethylhexyl) azelate (DOAZ), polyethylene glycol (PEG), polypropylene glycol (PPG)
As a common composition, the oxidizing solution contains hydrogen peroxide (3% by weight) and sodium salicylate (2.0 mM).
クエン酸トリエチル（ＴＥＣ）、安息香酸ベンジル（ＢｅＢ）、３－メトキシ－３－メチルブタノール（ＭＭＢ）、ヘキシレングリコール（ＨＧ）、アセチルクエン酸トリブチル（ＡＴＢＣ）、プロピレングリコール（ＰＧ）、ブチロラクトン（ＢＬ）、ジエチレングリコールモノメチルエーテル（ＥＤＧ）、トリアセチン（ＴＡ）、ジエチレングリコールジエチルエーテル（ＥＧＤＥＥ）、トリメリット酸トリ-n-ブチル（ＴＢＴＭ）、トリメリット酸トリス(2-エチルヘキシル）（ＴＯＴＭ）、アジピン酸ジエチル（ＤＥＡＤ）、アジピン酸ジイソブチル（ＤＩＢＡＤ）、アゼライン酸ビス（2-エチルヘキシル）（ＤＯＡＺ），ポリエチレングリコール（ＰＥＧ）、ポリプロピレングリコール（ＰＰＧ）
なお、共通組成として、酸化液には過酸化水素（３重量％）、サリチル酸ナトリウム（２．０ｍＭ）を含む。 The solvent used and the abbreviation of each solvent in Table 1 below are as follows.
Triethyl citrate (TEC), benzyl benzoate (BeB), 3-methoxy-3-methylbutanol (MMB), hexylene glycol (HG), tributyl acetyl citrate (ATBC), propylene glycol (PG), butyrolactone (BL ), Diethylene glycol monomethyl ether (EDG), triacetin (TA), diethylene glycol diethyl ether (EGDEE), tri-n-butyl trimellitic acid (TBTM), tris (2-ethylhexyl) trimellitic acid (TOTM), diethyl adipate (TOTM) DEAD), diisobutyl adipate (DIBAD), bis (2-ethylhexyl) azelate (DOAZ), polyethylene glycol (PEG), polypropylene glycol (PPG)
As a common composition, the oxidizing solution contains hydrogen peroxide (3% by weight) and sodium salicylate (2.0 mM).
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装置し、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、装置と試料を静置し５分後に再度発光輝度を計測した。 Luminance measurement method (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, 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 device and the sample were allowed to stand, and the emission luminance was measured again after 5 minutes.
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装置し、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、装置と試料を静置し５分後に再度発光輝度を計測した。 Luminance measurement method (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, 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 device 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（３３０００－０ＪＩＳ形）（田中科学機器製作所製）を使用し、 Ｋ ２２６５－２（迅速平衡密閉法）に準じセタ密閉式により測定した。 Flash point measurement method (unit: ° C)
The flash point was measured by a setter sealing method using a flash point tester (33000-0JIS type) (manufactured by Tanaka Scientific Instruments) according to K 2265-2 (rapid equilibrium sealing method).
引火点は、引火点試験器（３３０００－０ＪＩＳ形）（田中科学機器製作所製）を使用し、 Ｋ ２２６５－２（迅速平衡密閉法）に準じセタ密閉式により測定した。 Flash point measurement method (unit: ° C)
The flash point was measured by a setter sealing method using a flash point tester (33000-0JIS type) (manufactured by Tanaka Scientific Instruments) according to K 2265-2 (rapid equilibrium sealing method).
実施例１
（１）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）２ｍＭ相当量を添加し全量を溶解した。更に、発光色素として９，１０－ビス（フェニルエチニル）アントラセン（ＢＰＥＡ）を１０ｍＭ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。
（２）酸化液（ＴＥＣ（７０），ＥＧＤＥＥ（３０））の作製
クエン酸トリエチル（ＴＥＣ）：７０容量％にジエチレングリコールジエチルエーテル（ＥＧＤＥＥ）：３０容量％を加え、これにサリチル酸ナトリウム２．０ｍＭ添加し全量を溶解した。これに更に過酸化水素水を過酸化水素として、酸化液１００重量％に対し３重量％となるように添加し撹拌し、酸化液を得た。酸化液の配合組成およびその引火点を表１に示した。
（３）発光輝度の測定
上記蛍光液（１）と酸化液（２）を攪拌混合し、前記発光輝度の測定方法に従い、反応開始後と５分経過後の発光輝度を測定した。結果を表１に併せて示した。 Example 1
(1) Preparation of fluorescent solution used for examination of oxidation solution (Comparison test of emission luminance) (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, 2 mM equivalent of bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate (CPPO) was added to dissolve the entire amount. Furthermore, 10 mM 9,10-bis (phenylethynyl) anthracene (BPEA) was added as a luminescent dye, and the whole amount was dissolved. 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).
(2) Preparation of oxidizing solution (TEC (70), EGDEE (30)) Triethyl citrate (TEC): 70% by volume diethylene glycol diethyl ether (EGDEE): 30% by volume, to which 2.0mM sodium salicylate was added The entire amount was dissolved. Further, hydrogen peroxide water was added as hydrogen peroxide so as to be 3% by weight with respect to 100% by weight of the oxidizing solution and stirred to obtain an oxidizing solution. Table 1 shows the composition of the oxidizing solution and its flash point.
(3) Measurement of emission luminance The fluorescent solution (1) and the oxidizing solution (2) were stirred and mixed, and the emission luminance after the start of the reaction and after 5 minutes was measured according to the measurement method of the emission luminance. The results are also shown in Table 1.
（１）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）２ｍＭ相当量を添加し全量を溶解した。更に、発光色素として９，１０－ビス（フェニルエチニル）アントラセン（ＢＰＥＡ）を１０ｍＭ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。
（２）酸化液（ＴＥＣ（７０），ＥＧＤＥＥ（３０））の作製
クエン酸トリエチル（ＴＥＣ）：７０容量％にジエチレングリコールジエチルエーテル（ＥＧＤＥＥ）：３０容量％を加え、これにサリチル酸ナトリウム２．０ｍＭ添加し全量を溶解した。これに更に過酸化水素水を過酸化水素として、酸化液１００重量％に対し３重量％となるように添加し撹拌し、酸化液を得た。酸化液の配合組成およびその引火点を表１に示した。
（３）発光輝度の測定
上記蛍光液（１）と酸化液（２）を攪拌混合し、前記発光輝度の測定方法に従い、反応開始後と５分経過後の発光輝度を測定した。結果を表１に併せて示した。 Example 1
(1) Preparation of fluorescent solution used for examination of oxidation solution (Comparison test of emission luminance) (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, 2 mM equivalent of bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate (CPPO) was added to dissolve the entire amount. Furthermore, 10 mM 9,10-bis (phenylethynyl) anthracene (BPEA) was added as a luminescent dye, and the whole amount was dissolved. 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).
(2) Preparation of oxidizing solution (TEC (70), EGDEE (30)) Triethyl citrate (TEC): 70% by volume diethylene glycol diethyl ether (EGDEE): 30% by volume, to which 2.0mM sodium salicylate was added The entire amount was dissolved. Further, hydrogen peroxide water was added as hydrogen peroxide so as to be 3% by weight with respect to 100% by weight of the oxidizing solution and stirred to obtain an oxidizing solution. Table 1 shows the composition of the oxidizing solution and its flash point.
(3) Measurement of emission luminance The fluorescent solution (1) and the oxidizing solution (2) were stirred and mixed, and the emission luminance after the start of the reaction and after 5 minutes was measured according to the measurement method of the emission luminance. The results are also shown in Table 1.
実施例２～１０
表１に示すように酸化液を構成する溶媒および組成比を変更した以外は実施例と同様に実験を行い、発光輝度を測定した。結果を併せて表１に示した。 Examples 2 to 10
As shown in Table 1, the experiment was performed in the same manner as in Example except that the solvent constituting the oxidizing solution and the composition ratio were changed, and the light emission luminance was measured. The results are also shown in Table 1.
表１に示すように酸化液を構成する溶媒および組成比を変更した以外は実施例と同様に実験を行い、発光輝度を測定した。結果を併せて表１に示した。 Examples 2 to 10
As shown in Table 1, the experiment was performed in the same manner as in Example except that the solvent constituting the oxidizing solution and the composition ratio were changed, and the light emission luminance was measured. The results are also shown in Table 1.
比較例１
実施例１において、酸化液の溶媒としてＴＥＣのみを使用した以外は実施例１と同様に実験を行い、発光輝度および引火点を測定した。結果を併せて表１に示した。 Comparative Example 1
In Example 1, an experiment was performed in the same manner as in Example 1 except that only TEC was used as the solvent of the oxidizing solution, and the light emission luminance and the flash point were measured. The results are also shown in Table 1.
実施例１において、酸化液の溶媒としてＴＥＣのみを使用した以外は実施例１と同様に実験を行い、発光輝度および引火点を測定した。結果を併せて表１に示した。 Comparative Example 1
In Example 1, an experiment was performed in the same manner as in Example 1 except that only TEC was used as the solvent of the oxidizing solution, and the light emission luminance and the flash point were measured. The results are also shown in Table 1.
比較例２
実施例１において、酸化液を構成する溶媒を表１に示すようにＴＥＣとエタノール（ＥｔＯＨ）を使用した以外は実施例１と同様に実験を行い、発光輝度および引火点を測定した。結果を併せて表１に示した。 Comparative Example 2
In Example 1, an experiment was performed in the same manner as in Example 1 except that TEC and ethanol (EtOH) were used as shown in Table 1 as solvents constituting the oxidizing solution, and the emission luminance and flash point were measured. The results are also shown in Table 1.
実施例１において、酸化液を構成する溶媒を表１に示すようにＴＥＣとエタノール（ＥｔＯＨ）を使用した以外は実施例１と同様に実験を行い、発光輝度および引火点を測定した。結果を併せて表１に示した。 Comparative Example 2
In Example 1, an experiment was performed in the same manner as in Example 1 except that TEC and ethanol (EtOH) were used as shown in Table 1 as solvents constituting the oxidizing solution, and the emission luminance and flash point were measured. The results are also shown in Table 1.
上記結果から明らかなように、ＴＥＣのみを溶媒とした場合は、触媒であるサリチル酸ナトリウムの溶解度が低いため、発光開始直後の発光輝度とその５分後の発光輝度のいずれにおいても発光輝度が低いことが確認された。
また、比較例２のＴＥＣとエタノールの混合溶液の場合は、発光輝度は十分であるが酸化液の引火点が３７℃と低かった。
一方、実施例１～１０の酸化液は、いずれもＴＥＣとエタノールの混合溶液を溶媒とする酸化液を使用した場合と同等かそれ以上の発光輝度が確認され、更に引火点も６０℃以上を示した。 As is clear from the above results, when only TEC is used as the solvent, the solubility of sodium salicylate, which is the catalyst, is low, so the emission luminance is low in both the emission luminance immediately after the start of light emission and the emission luminance after 5 minutes. It was confirmed.
Further, in the case of the mixed solution of TEC and ethanol of Comparative Example 2, the emission luminance was sufficient, but the flash point of the oxidizing solution was as low as 37 ° C.
On the other hand, each of the oxidizing solutions of Examples 1 to 10 has an emission luminance equal to or higher than that obtained when an oxidizing solution using a mixed solution of TEC and ethanol as a solvent, and further has a flash point of 60 ° C. or higher. Indicated.
また、比較例２のＴＥＣとエタノールの混合溶液の場合は、発光輝度は十分であるが酸化液の引火点が３７℃と低かった。
一方、実施例１～１０の酸化液は、いずれもＴＥＣとエタノールの混合溶液を溶媒とする酸化液を使用した場合と同等かそれ以上の発光輝度が確認され、更に引火点も６０℃以上を示した。 As is clear from the above results, when only TEC is used as the solvent, the solubility of sodium salicylate, which is the catalyst, is low, so the emission luminance is low in both the emission luminance immediately after the start of light emission and the emission luminance after 5 minutes. It was confirmed.
Further, in the case of the mixed solution of TEC and ethanol of Comparative Example 2, the emission luminance was sufficient, but the flash point of the oxidizing solution was as low as 37 ° C.
On the other hand, each of the oxidizing solutions of Examples 1 to 10 has an emission luminance equal to or higher than that obtained when an oxidizing solution using a mixed solution of TEC and ethanol as a solvent, and further has a flash point of 60 ° C. or higher. Indicated.
実施例１１～１５
表２に示すように酸化液を構成する溶媒および組成比を変更した以外は実施例１と同様に実験を行い、発光輝度および引火点を測定した。結果を併せて表２に示した。
Examples 11-15
As shown in Table 2, the experiment was performed in the same manner as in Example 1 except that the solvent constituting the oxidizing solution and the composition ratio were changed, and the light emission luminance and the flash point were measured. The results are also shown in Table 2.
表２に示すように酸化液を構成する溶媒および組成比を変更した以外は実施例１と同様に実験を行い、発光輝度および引火点を測定した。結果を併せて表２に示した。
Examples 11-15
As shown in Table 2, the experiment was performed in the same manner as in Example 1 except that the solvent constituting the oxidizing solution and the composition ratio were changed, and the light emission luminance and the flash point were measured. The results are also shown in Table 2.
実施例１６～１８
表３に示すように酸化液を構成する溶媒および組成比を変更した以外は実施例１と同様に実験を行い、発光輝度および引火点を測定した。結果を併せて表３に示した。 Examples 16-18
As shown in Table 3, the experiment was performed in the same manner as in Example 1 except that the solvent constituting the oxidizing solution and the composition ratio were changed, and the light emission luminance and the flash point were measured. The results are also shown in Table 3.
表３に示すように酸化液を構成する溶媒および組成比を変更した以外は実施例１と同様に実験を行い、発光輝度および引火点を測定した。結果を併せて表３に示した。 Examples 16-18
As shown in Table 3, the experiment was performed in the same manner as in Example 1 except that the solvent constituting the oxidizing solution and the composition ratio were changed, and the light emission luminance and the flash point were measured. The results are also shown in Table 3.
ＰＥＧ、ＰＰＧを添加することにより、蛍光液との混和性が向上した。なお、ＰＥＧに比較してＰＰＧの方が、混和性が良好で特に発光輝度も高かった。
By adding PEG and PPG, the miscibility with the fluorescent solution was improved. Note that PPG had better miscibility and particularly higher luminance than PEG.
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、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。
The chemiluminescent oxidizing solution of the present invention has a higher flash point than conventional oxidizing solutions, and provides a chemiluminescent system with excellent safety while maintaining chemiluminescent performance.
Claims (7)
- 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、該酸化液の引火点が６０℃以上であり、酸化液に含有される溶媒が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）、アジピン酸ジメチル、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、アジピン酸ジイソノニル、セバシン酸ジエチル、セバシン酸ジブチル、アゼライン酸ビス（２－エチルヘキシル）、３-メトキシ-３-メチルブタノール、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、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２種以上を含む混合物であ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 that produces a chemiluminescence phenomenon when mixed with an oxalate ester and a fluorescent solution containing a fluorescent substance, the flash point of the oxidation solution being 60 ° C. or higher The solvent contained in the oxidation solution is triethyl citrate, acetyl tributyl citrate, benzyl benzoate, butyl benzoate, trimethyl trimellitic acid, tripropyl trimellitic acid, tri-n-butyl trimellitic acid, trimellitic Acid tris (2-ethylhexyl), dimethyl adipate, diethyl adipate, diisopropyl adipate, diisobutyl adipate, diisononyl adipate, diethyl sebacate, dibutyl sebacate, bis (2-ethylhexyl) azelate, 3-methoxy-3 -Methylbutanol, hexylene glycol, pro At least selected from lenglycol, butyrolactone, triethylene glycol, triacetin, 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 dimethyl ether and dipropylene glycol dimethyl ether An oxidation solution for a chemiluminescent material, which is a mixture containing two or more types.
- 前記酸化液の引火点が７０℃以上であることを特徴とする請求項１記載の化学発光体用酸化液。 The oxidizing solution for chemiluminescent materials according to claim 1, wherein the flash point of the oxidizing solution is 70 ° C or higher.
- 前記酸化液に含有される溶媒が、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メチル、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）、３-メトキシ-３-メチルブタノール、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、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２種以上を含む混合物であることを特徴とする請求項１又は２に記載の化学発光体用酸化液。 Solvents contained in the oxidizing solution are triethyl citrate, acetyl tributyl citrate, benzyl benzoate, trimethyl trimellitic acid, tri-n-butyl trimellitic acid, tris (2-ethylhexyl) trimellitic acid, diethyl adipate Diisopropyl adipate, diisobutyl adipate, diethyl sebacate, bis (2-ethylhexyl) azelate, 3-methoxy-3-methylbutanol, hexylene glycol, propylene glycol, butyrolactone, triethylene glycol, triacetin, diethylene glycol diethyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, ethylene glycol isopropyl ether, diethylene Recall dibutyl ether, chemiluminescence-body oxidation liquid according to claim 1 or 2, characterized in that a mixture comprising at least two or more selected from diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether.
- 前記酸化液に含有される溶媒が、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メチル、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種以上と、３-メトキシ-３-メチルブタノール、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、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種以上との混合物であることを特徴とする請求項１から３のいずれかの項に記載の化学発光体用酸化液。 Solvents contained in the oxidizing solution are triethyl citrate, acetyl tributyl citrate, benzyl benzoate, trimethyl trimellitic acid, tri-n-butyl trimellitic acid, tris (2-ethylhexyl) trimellitic acid, diethyl adipate At least one selected from diisopropyl adipate, diisobutyl adipate, diethyl sebacate and bis (2-ethylhexyl) azelate, 3-methoxy-3-methylbutanol, hexylene glycol, propylene glycol, butyrolactone, Ethylene glycol, triacetin, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, ethylene glycol The chemiluminescent material according to any one of claims 1 to 3, which is a mixture with at least one selected from allyl isopropyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether. Oxidizing solution.
- 前記酸化液に含有される溶媒が、更に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を含むことを特徴とする請求項１から４のいずれかの項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 4, wherein the solvent contained in the oxidizing solution further contains polyethylene glycol and / or polypropylene glycol.
- 前記酸化液に含有される溶媒が、ポリプロピレングリコールであることを特徴とする請求項５に記載の化学発光体用酸化液。 6. The oxidizing solution for chemiluminescent materials according to claim 5, wherein the solvent contained in the oxidizing solution is polypropylene glycol.
- 請求項１から６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 phosphor oxidizing solution according to any one of claims 1 to 6 and a fluorescent solution containing an oxalate ester and a fluorescent substance.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2011/051641 WO2011099375A1 (en) | 2010-02-09 | 2011-01-27 | Oxidizing liquid for chemiluminescence and chemiluminescence system using same |
| JPPCT/JP2011/051641 | 2011-01-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2012101848A1 true WO2012101848A1 (en) | 2012-08-02 |
Family
ID=46582427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2011/067485 WO2012101848A1 (en) | 2011-01-27 | 2011-07-29 | Oxidizing liquid for chemiluminescent element and chemiluminescent system containing same |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2012101848A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014194332A1 (en) | 2013-06-01 | 2014-12-04 | Cyalume Technologies | Broad temperature performance chemiluminescent systems and methods |
| CN106479488A (en) * | 2016-09-26 | 2017-03-08 | 宁波美乐雅荧光科技股份有限公司 | A kind of chemical luminous composite of environmental protection |
| CN107955181A (en) * | 2017-07-06 | 2018-04-24 | 同济大学 | A kind of high stability two dimension cationic halogenation lead material and its preparation and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3994820A (en) * | 1972-06-19 | 1976-11-30 | American Cyanamid Company | Polymers in oxalate chemiluminescent systems |
| WO1994019421A1 (en) * | 1993-02-22 | 1994-09-01 | Omniglow Corporation | Phthalate free chemiluminescent activator |
| JPH11502553A (en) * | 1995-03-31 | 1999-03-02 | ケミカル ライト テクノロジーズ インク． | Improved chemiluminescence solution |
| JP2004331947A (en) * | 2003-04-14 | 2004-11-25 | Lumica Corp | Chemiluminescent composition |
| JP2006104266A (en) * | 2004-10-01 | 2006-04-20 | Omniglow Japan Co Ltd | Fluorescent liquid for chemiluminescence, oxidizing liquid for chemiluminescence, and chemiluminescent system |
| JP4702653B1 (en) * | 2009-12-04 | 2011-06-15 | シーエルテクノロジー株式会社 | Chemiluminescent composition |
-
2011
- 2011-07-29 WO PCT/JP2011/067485 patent/WO2012101848A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3994820A (en) * | 1972-06-19 | 1976-11-30 | American Cyanamid Company | Polymers in oxalate chemiluminescent systems |
| WO1994019421A1 (en) * | 1993-02-22 | 1994-09-01 | Omniglow Corporation | Phthalate free chemiluminescent activator |
| JPH11502553A (en) * | 1995-03-31 | 1999-03-02 | ケミカル ライト テクノロジーズ インク． | Improved chemiluminescence solution |
| JP2004331947A (en) * | 2003-04-14 | 2004-11-25 | Lumica Corp | Chemiluminescent composition |
| JP2006104266A (en) * | 2004-10-01 | 2006-04-20 | Omniglow Japan Co Ltd | Fluorescent liquid for chemiluminescence, oxidizing liquid for chemiluminescence, and chemiluminescent system |
| JP4702653B1 (en) * | 2009-12-04 | 2011-06-15 | シーエルテクノロジー株式会社 | Chemiluminescent composition |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014194332A1 (en) | 2013-06-01 | 2014-12-04 | Cyalume Technologies | Broad temperature performance chemiluminescent systems and methods |
| EP3004286A1 (en) * | 2013-06-01 | 2016-04-13 | Cyalume Technologies, Inc | Broad temperature performance chemiluminescent systems and methods |
| EP3004286A4 (en) * | 2013-06-01 | 2017-04-05 | Cyalume Technologies, Inc | Broad temperature performance chemiluminescent systems and methods |
| AU2014273869B2 (en) * | 2013-06-01 | 2018-04-05 | Cyalume Technologies | Broad temperature performance chemiluminescent systems and methods |
| CN106479488A (en) * | 2016-09-26 | 2017-03-08 | 宁波美乐雅荧光科技股份有限公司 | A kind of chemical luminous composite of environmental protection |
| CN106479488B (en) * | 2016-09-26 | 2019-05-24 | 宁波美乐雅荧光科技股份有限公司 | A kind of environmentally protective chemical luminous composite |
| CN107955181A (en) * | 2017-07-06 | 2018-04-24 | 同济大学 | A kind of high stability two dimension cationic halogenation lead material and its preparation and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5305310B2 (en) | Oxidizing solution for chemiluminescence and chemiluminescence system comprising the same | |
| CN101240165B (en) | Excellent oxalic ester chemoluminescence system | |
| JP4702653B1 (en) | Chemiluminescent composition | |
| US20080308776A1 (en) | Chemiluminescent compositions and methods of making and using thereof | |
| WO2012101848A1 (en) | Oxidizing liquid for chemiluminescent element and chemiluminescent system containing same | |
| JP6495169B2 (en) | Oxidizing solution for chemiluminescent body and chemiluminescent system comprising the same | |
| CN106479488B (en) | A kind of environmentally protective chemical luminous composite | |
| US20090166595A1 (en) | Enhanced chemiluminescent lighting formulation and element | |
| US20120126188A1 (en) | Phthalate-free chemiluminescent formulations | |
| KR102156615B1 (en) | Chemiluminescent body and chemiluminescent system, and fragile container for chemiluminescent body, chemiluminescent oxidizing liquid | |
| EP1477545A1 (en) | Chemiluminescent compositions | |
| AU2014273869B2 (en) | Broad temperature performance chemiluminescent systems and methods | |
| JP2003183641A (en) | Chemiluminescent composition emitting red chemiluminecence and chemiluminescent material using the same | |
| JP2006104266A (en) | Fluorescent liquid for chemiluminescence, oxidizing liquid for chemiluminescence, and chemiluminescent system | |
| CN100549119C (en) | A kind of chemical infrared radiation agent | |
| CN101486897A (en) | Chemical luminophor | |
| JP4048372B2 (en) | Chemiluminescence method and chemiluminescence display device | |
| JPH0453894A (en) | Red chemiluminesent material | |
| JP4634054B2 (en) | Chemiluminescent composition | |
| JP2012031336A (en) | Oxidization liquid for chemiluminescence | |
| CN112646569A (en) | Chemiluminescent composition and preparation method thereof | |
| CN112852411A (en) | Chemiluminescent composition | |
| JP3176558U (en) | Chemiluminescence learning materials | |
| JP2008013777A (en) | Composition for chemiluminescence and method of chemiluminescence | |
| CN102775983A (en) | Solid chemiluminescent composition with organic matter as filler |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11856901 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 11856901 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: JP |