JP4634054B2 - Chemiluminescent composition - Google Patents
Chemiluminescent composition Download PDFInfo
- Publication number
- JP4634054B2 JP4634054B2 JP2004060652A JP2004060652A JP4634054B2 JP 4634054 B2 JP4634054 B2 JP 4634054B2 JP 2004060652 A JP2004060652 A JP 2004060652A JP 2004060652 A JP2004060652 A JP 2004060652A JP 4634054 B2 JP4634054 B2 JP 4634054B2
- Authority
- JP
- Japan
- Prior art keywords
- composition
- fluorescent substance
- chemiluminescent
- solvent
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 95
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 claims description 38
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 37
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 25
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 claims description 22
- 229960002903 benzyl benzoate Drugs 0.000 claims description 19
- 150000002148 esters Chemical class 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 11
- -1 acetyl citrate ester Chemical class 0.000 claims description 6
- WWXUGNUFCNYMFK-UHFFFAOYSA-N Acetyl citrate Chemical compound CC(=O)OC(=O)CC(O)(C(O)=O)CC(O)=O WWXUGNUFCNYMFK-UHFFFAOYSA-N 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 230000001747 exhibiting effect Effects 0.000 claims 3
- 239000005711 Benzoic acid Substances 0.000 claims 2
- 235000010233 benzoic acid Nutrition 0.000 claims 2
- 238000009472 formulation Methods 0.000 description 23
- 230000001590 oxidative effect Effects 0.000 description 23
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 14
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 14
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 7
- 229960001826 dimethylphthalate Drugs 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229960004025 sodium salicylate Drugs 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000003901 oxalic acid esters Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 2
- WRRWIFOOAXCBNU-UHFFFAOYSA-N 1-chloro-2,3-bis(2-phenylethynyl)anthracene Chemical compound C=1C=CC=CC=1C#CC1=CC2=CC3=CC=CC=C3C=C2C(Cl)=C1C#CC1=CC=CC=C1 WRRWIFOOAXCBNU-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- MCJCREGWRMCHIM-UHFFFAOYSA-N bis(2-butoxycarbonyl-3,4,6-trichlorophenyl) oxalate Chemical compound CCCCOC(=O)C1=C(Cl)C(Cl)=CC(Cl)=C1OC(=O)C(=O)OC1=C(Cl)C=C(Cl)C(Cl)=C1C(=O)OCCCC MCJCREGWRMCHIM-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- RVRCFVVLDHTFFA-UHFFFAOYSA-N heptasodium;tungsten;nonatriacontahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W] RVRCFVVLDHTFFA-UHFFFAOYSA-N 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Description
本発明は、化学発光の有機溶媒として使用されている、フタル酸ジブチルやフタル酸ジメチルに代る新規な溶媒を使った化学発光組成物に関する。 The present invention relates to a chemiluminescent composition using a novel solvent in place of dibutyl phthalate or dimethyl phthalate, which is used as an organic solvent for chemiluminescence.
化学発光組成物に関する発明は特公昭５３−４７７９８号をはじめ、多数なされている。これらの発明に使用されている有機溶媒の代表例がフタル酸ジブチルやフタル酸ジメチルであり、実際市場に出回っている棒状化学発光体の溶媒も上記のものである。種々の溶媒の中で、過酸化水素を含んだ組成物（酸化液）の溶媒としてフタル酸ジメチルが選ばれた理由は、この溶媒は発光性能が良好であり且つ貯蔵安定性も良い為である。しかし、近年フタル酸エステルは環境ホルモンの疑いがある為、国によっては使用禁止又は禁止の方向へむかっている。
本発明は、フタル酸ジブチル及びフタル酸ジメチルに代わる有機溶媒であって、貯蔵性に優れ、発光性能の良好な化学発光組成物を提供することを目的とする。 An object of the present invention is to provide a chemiluminescent composition which is an organic solvent in place of dibutyl phthalate and dimethyl phthalate, which has excellent storability and good luminescent performance.
化学発光組成物中の１成分である、修酸エステルは例えば、ビス（２，４，５−トリクロロ−６−カルボブトキシフェニル）オキザレートやビス（２，４，５−トリクロロ−カルボペントキシフェニル）オキザレート（以下ＣＰＰＯと略す）等が代表例である。化学発光組成物中の有機溶媒は、人体に対する安全性と共に,このＣＰＰＯが希望する濃度まで、溶解することが必要である。種々の実験の結果、アセチルクエン酸エステルが良好な溶媒として見出された。アセチルクエン酸エステルの代表例であるアセチルクエン酸トリブチルＣＨ3ＣＯＯ−ＣＨ（ＣＨ2ＣＯＯＣ4Ｈ9）2−ＣＯＯＣ4Ｈ9の安全性を下記に示す。 アセチルクエン酸トリブチル（以下ＡＴＢＣと略す）の製法はクエン酸とブタノールのエステル化反応でクエン酸トリブチルを作り、次にクエン酸のＯＨ基を封じる為、無水酢酸でアセチル化する。 Oxalic acid esters which are one component in the chemiluminescent composition are, for example, bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate and bis (2,4,5-trichloro-carbopentoxyphenyl). A typical example is oxalate (hereinafter abbreviated as CPPO). The organic solvent in the chemiluminescent composition must be dissolved to the desired concentration of this CPPO along with safety to the human body. As a result of various experiments, acetyl citrate was found as a good solvent. The safety of tributyl acetyl citrate CH 3 COO—CH (CH 2 COOC 4 H 9 ) 2 —COOC 4 H 9 , which is a representative example of acetyl citrate, is shown below. In the production method of tributyl acetyl citrate (hereinafter abbreviated as ATBC), tributyl citrate is produced by esterification reaction of citric acid and butanol, and then acetylated with acetic anhydride to seal off the OH group of citric acid.
この物質は古くから食品関係溶可塑剤として定評があった。反応に使用する原料のクエン酸は食物からの分離であり（現在はトウモロコシから）、ブタノールはアルコール、酢酸は酢である。従って、安全性は高い。イギリスＢ．Ｐ．ＦＳＥＣＯＮＤ ＲＥＰＯＲＴでは毒性係数Ｔ＝１００で安全係数はもっとも高い。米国・ＦＤＡでも安全性を広く認めている（ＦＤＡ.Ｎｏ１７５．１０５ １７５．３００ １７５．３２０ １７８．３９１０ １８１．２７）。因みに塩ビ食品衛生協議会のＰＬ承認Ｎｏ．はＢ−４−（３）である。
ＣＰＰＯはアセチルクエン酸トリブチルに約０．０８３モル／Ｌ溶解し、アセチルクエン酸トリエチルは０．０４１モル／Ｌ溶解する。この溶媒を用いた発光性能は充分満足するものであった。
This substance has long been recognized as a food-related plasticizer. The raw material citric acid used for the reaction is separation from food (currently from corn), butanol is alcohol and acetic acid is vinegar. Therefore, safety is high. UK B. P. FSECOND REPORT has the highest safety factor with a toxicity factor T = 100. Safety is widely recognized in the US and FDA (FDA. No. 175.105 175.300 175.320 178.3910 181.27). Incidentally, the PL approval No. of the PVC Food Sanitation Council. Is B-4- (3).
CPPO is dissolved in tributyl acetyl citrate at about 0.083 mol / L, and triethyl acetyl citrate is dissolved in 0.041 mol / L. The luminous performance using this solvent was sufficiently satisfactory.
下記にフタル酸ジブチルとＡＴＢＣを溶媒として使用した発光データを示す。
調合Ｘ．フタル酸ジブチル１Ｌに１−クロロビスフェニルエチニルアントラセン（以下１−ｃＢＰＥＡと略す）０．００７モルとＣＰＰＯ ０．０８３モルを加え加熱溶解する。
The luminescence data using dibutyl phthalate and ATBC as solvents are shown below.
Formulation X. To 1 L of dibutyl phthalate, 0.007 mol of 1-chlorobisphenylethynylanthracene (hereinafter abbreviated as 1-cBPEA) and 0.083 mol of CPPO are added and dissolved by heating.
調合Ｙ．アセチルクエン酸トリブチルＡＴＢＣ １Ｌに上記と同様１−ｃＢＰＥＡ ０．００７モル、ＣＰＰＯ ０．０８３モルを加え加熱溶解する。
上記の調合Ｘの溶液０．８４ｃｃに酸化液０．４２ｃｃを加え、混合し発光させる。
調合Ｙの溶液０．８４ｃｃに酸化液０．４２ｃｃを加え、混合し発光させる。
Formulation Y. In the same manner as above, 0.007 mol of 1-cBPEA and 0.083 mol of CPPO are added to 1 L of tributyl acetyl citrate and dissolved by heating.
Add 0.42 cc of the oxidizing solution to 0.84 cc of the above Formulation X solution, mix and emit light.
Add 0.42 cc of the oxidizing solution to 0.84 cc of the solution of Formulation Y, mix and emit light.
なお、この時の酸化液は下記の組成のものである。
調合Ｚ．エチレングリコールモノブチルエーテルアセテート４００ｃｃにｔ−ブタノール１００ｃｃを加え、これに８５％の過酸化水素水を３５g加え、さらにサリチル酸ナトリウム０．０００８モル／Ｌ加え溶解したものである。
測定結果、数値としては、多少の差があるが、肉眼では差は感じられない。
この酸化液中のエチレングリコールモノブチルエーテルアセテートをフタル酸ジメチルに替えても、ほぼ同様の輝度データが得られた。
The oxidizing solution at this time has the following composition.
Formulation Z. 100 cc of t-butanol was added to 400 cc of ethylene glycol monobutyl ether acetate, 35 g of 85% aqueous hydrogen peroxide was added thereto, and 0.0008 mol / L of sodium salicylate was added and dissolved.
As a result of the measurement, there are some differences in numerical values, but no difference is felt with the naked eye.
Even if the ethylene glycol monobutyl ether acetate in the oxidizing solution was replaced with dimethyl phthalate, almost the same luminance data was obtained.
過酸化水素を含んだ組成物中の溶媒として一般的に使用されているのが、フタル酸ジメチルとｔ−ブタノールの混合物である。これに代わるものそしてアセチルクエン酸トリエチルとｔ−ブタノールの組み合わせも可能であるが、必ずしも保存性が良いとは言えなかった。というのも６０℃で２週間ガラス容器に入れて保存した加速試験では、触媒として使用したサリチル酸ナトリウムの濃度が当初の半分以下に低下していたからである。しかし半年以内など比較的早期に使用する場合は問題ない。 A commonly used solvent in compositions containing hydrogen peroxide is a mixture of dimethyl phthalate and t-butanol. An alternative and a combination of triethyl acetyl citrate and t-butanol are possible, but the storage stability is not always good. This is because the concentration of sodium salicylate used as a catalyst in the accelerated test stored in a glass container at 60 ° C. for 2 weeks was reduced to less than half of the initial value. However, there is no problem if it is used relatively early, such as within half a year.
酸化液の溶媒として発光性能、長期保存性の良いものを研究した結果、エチレングリコールモノアルキルエーテルアセテート及びジエチレングリコールモノアルキルエーテルアセテートが良好という実験結果を得た。このエステルの代表的なものとして、エチレングリコールモノブチルエーテルアセテート（Ethylene glycol monobutyl ether acetate）(ＣＨ3ＣＯＯ ＣＨ2-ＣＨ2ＯＣ4Ｈ9)やジエチレングリコールモノブチルエーテルアセテート(Dietylene glycol monobutyl ether acetate)(ＣＨ3ＣＯＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ2ＯＣ4Ｈ9)があり、以下前者をＥＧＭＢＡと略し、後者をＤＥＧＭＢＡと略す。 As a result of investigating those having good light emission performance and long-term storage stability as the solvent of the oxidizing solution, experimental results were obtained that ethylene glycol monoalkyl ether acetate and diethylene glycol monoalkyl ether acetate were good. Typical esters include ethylene glycol monobutyl ether acetate (CH 3 COO CH 2 —CH 2 OC 4 H 9 ) and diethylene glycol monobutyl ether acetate (CH 3 COOCH 2 CH 2 OCH 2 CH 2 OC 4 H 9 ), hereinafter the former is abbreviated as EGMBA and the latter is abbreviated as DEGMBA.
以下過酸化水素を含んだ組成物を酸化液と呼び修酸エステル、蛍光物質を含んだ組成物を蛍光液と呼ぶ。 Hereinafter, a composition containing hydrogen peroxide is referred to as an oxidizing solution, and a oxalic acid ester, and a composition containing a fluorescent substance is referred to as a fluorescent solution.
本発明によると、フタル酸エステルを使用しなくても貯蔵性に優れ、発光性能の良好な化学発光組成物を提供することができる。 According to the present invention, a chemiluminescent composition having excellent storability and good luminescent performance can be provided without using a phthalate ester.
以下、本発明の実施の形態を従来の化学発光組成物と対比しながら詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail in comparison with conventional chemiluminescent compositions.
ｔ−ブタノールが入っていない酸化液の発光データを下記にしめす。
調合１、ＥＧＭＢＡ ５００ｃｃに８５％の過酸化水素水を３５ｇ加え、さらにさらにサリチル酸ナトリウム０．０００８モル／Ｌ加え溶解したものである。
調合２、ＡＴＢＣに安息香酸ベンジルを３０％（容量割合）加えたもの１Ｌに１−ｃＢＰＥＡ ０．００７４モルとＣＰＰＯ ０．１６４モルを加え加熱溶解する。
The luminescence data of the oxidizing solution containing no t-butanol is shown below.
Formulation 1, EGMBA 500 cc, 35 g of 85% aqueous hydrogen peroxide was added, and further sodium salicylate 0.0008 mol / L was added and dissolved.
Add 1-cBPEA (0.0074 mol) and CPPO (0.164 mol) to 1 L of Formulation 2, ATBC with 30% (volume ratio) of benzyl benzoate.
このデータは調合１の酸化液０．４２ｃｃに調合２の蛍光液０．８４ｃｃ加え混合し発光させた。単位はｍｃｄ/ｍ2、測定温度２３℃、以下の表において別段の定めのないかぎりこの条件である。 This data was obtained by adding 0.84 cc of the fluorescent solution of Formula 2 to 0.42 cc of the oxidizing solution of Formula 1 and mixing them to emit light. The unit is mcd / m 2 , the measurement temperature is 23 ° C., and the conditions are unless otherwise specified in the following table.
次に従来の発光組成物と本発明の組成物の発光を比較する。
調合３．フタル酸ジブチル１Ｌに１−ｃＢＰＥＡ ０．００７４モルとＣＰＰＯ ０．１６４モルを加え加熱溶解する。
Next, the light emission of the conventional light emitting composition and the composition of the present invention will be compared.
Formulation 3. Add 1-cBPEA 0.0074 mol and CPPO 0.164 mol to 1 L dibutyl phthalate and dissolve with heating.
調合４．フタル酸ジメチル４００ｃｃにｔ−ブタノール１００ｃｃを加え、これに８５％の過酸化水素水を３５ｇ加え、さらにサリチル酸ナトリウム０．０００８モル加え溶解する。 Formulation 4. 100 cc of t-butanol is added to 400 cc of dimethyl phthalate, 35 g of 85% hydrogen peroxide is added thereto, and 0.0008 mol of sodium salicylate is added and dissolved.
調合５．ＤＥＧＭＢＡ ４００ｃｃにｔ−ブタノール１００ｃｃ加え、これに８５％の過酸化水素水を３５ｇ加え、さらにさらにサリチル酸ナトリウム０．０００８モル／Ｌ加え溶解したものである。 Formulation 5. 100 g of t-butanol was added to 400 cc of DEGMBA, 35 g of 85% hydrogen peroxide was added thereto, and 0.0008 mol / L of sodium salicylate was further added and dissolved.
調合６．ＥＧＭＢＡ４００ｃｃにｔ−ブタノール１００ｃｃ加え、これに８５％の過酸化水素水を３５ｇ加え、さらにさらにサリチル酸ナトリウム０．０００８モル／Ｌ加え溶解したものである。 Formulation 6. 100cc of t-butanol was added to 400cc of EGMBA, 35g of 85% hydrogen peroxide was added thereto, and 0.0008mol / L of sodium salicylate was further added and dissolved.
従来の発光組成物
上記の調合３の蛍光液０．８４ｃｃに調合４の酸化液０．４２ｃｃを加え混合し発光させた。
本発明の組成物
上記調合２の蛍光液０．８４ｃｃに調合５の酸化液０．４２ｃｃ加え混合し発光させた。
調合２の蛍光液０．８４ｃｃに調合６の酸化液０．４２ｃｃ加え混合し発光させた。
この表から調合３調合４の組み合わせより調合２調合５、調合２調合６の組み合わせの方が２分後の発光が強い。
Conventional Luminescent Composition 0.42 cc of the oxidizing solution of Formula 4 was added to 0.84 cc of the fluorescent solution of Formula 3 and mixed to emit light.
Composition of the Invention 0.42 cc of the oxidizing solution of Formula 5 was added to 0.84 cc of the fluorescent solution of Formula 2 and mixed to emit light.
0.42 cc of the oxidizing solution of Preparation 6 was added to 0.84 cc of the fluorescent solution of Preparation 2 and mixed to emit light.
From this table, the combination of Formulation 2 Formulation 5 and Formulation 2 Formulation 6 has stronger emission after 2 minutes than the combination of Formulation 3 Formulation 4.
従来使用されているフタル酸ジブチル溶媒に溶解しているＣＰＰＯ濃度は約０．１６モル／Ｌである。アセチルクエン酸トリブチルにＣＰＰＯを同じ濃度まで加熱溶解は可能であるが、製品化した後の長期貯蔵時の気温等により結晶が析出する場合がある。そこでトルエン、キシレン等の芳香族化合物、アセトン等のケトン類,安息香酸エステル等の有機溶媒を加える事により充分な溶解度が得られるようにしたのである。例えばアセチルクエン酸トリブチリルに安息香酸エステル中の安息香酸ベンジルを加えると、ＣＰＰＯが充分に溶解することを見出した。例えばＡＴＢＣ８０％安息香酸ベンジル２０％（容量割合で）の場合は、ＣＰＰＯが約０．１８８モル／Ｌ溶解する。またＡＴＢＣ７０％安息香酸ベンジル３０％の場合はＣＰＰＯが約０．２２６モル／Ｌ溶解する。上記の安息香酸ベンジルのかわりに安息香酸ブチルを使用しても溶解度はほぼ同じ傾向を示す。 The concentration of CPPO dissolved in the conventionally used dibutyl phthalate solvent is about 0.16 mol / L. Although CPPO can be dissolved by heating in tributyl acetyl citrate to the same concentration, crystals may precipitate depending on the temperature during long-term storage after commercialization. Therefore, sufficient solubility can be obtained by adding aromatic compounds such as toluene and xylene, ketones such as acetone, and organic solvents such as benzoic acid esters. For example, it has been found that when benzyl benzoate in a benzoate is added to tributyryl acetyl citrate, CPPO is sufficiently dissolved. For example, in the case of 20% ATBC 80% benzyl benzoate (by volume ratio), CPPO is dissolved at about 0.188 mol / L. In the case of ATBC 70% benzyl benzoate 30%, CPPO is dissolved at about 0.226 mol / L. Even if butyl benzoate is used in place of the above-mentioned benzyl benzoate, the solubility tends to be almost the same.
次にＡＴＢＣに安息香酸ベンジルの添加量を増やしていった時の発光特性を下記に示す。溶媒ＡＴＢＣのみのものを組成Ａとする。
ＡＴＢＣに安息香酸ベンジルを１０％（容量割合）加えたものを組成Ｂ
ＡＴＢＣに安息香酸ベンジルを２０％（容量割合）加えたものを組成Ｃ
ＡＴＢＣに安息香酸ベンジルを３０％（容量割合）加えたものを組成Ｄ
ＡＴＢＣに安息香酸ベンジルを４０％（容量割合）加えたものを組成Ｅ
ＡＴＢＣに安息香酸ベンジルを５０％（容量割合）加えたものを組成Ｆ
ＡＴＢＣに安息香酸ベンジルを６０％（容量割合）加えたものを組成Ｇ
Next, the emission characteristics when the amount of benzyl benzoate added to ATBC is increased are shown below. A solvent ATBC alone is designated as composition A.
Composition of B with 10% (volume ratio) of benzyl benzoate added to ATBC
Composition obtained by adding 20% (volume ratio) of benzyl benzoate to ATBC
Composition of ATBC plus 30% benzyl benzoate (volume ratio)
Composition E with 40% (volume ratio) of benzyl benzoate added to ATBC
Composition F with 50% (volume ratio) of benzyl benzoate added to ATBC
Composition G with 60% (volume ratio) of benzyl benzoate added to ATBC
上記表４のＡＴＢＣのみの各時間毎の輝度値を１００として他の組成の割合を下記表５に示す。 Table 5 below shows the ratio of other compositions with the luminance value for each time of only ATBC in Table 4 being 100.
なお、上記データは各溶媒に、ＣＰＰＯ ０．１６４モル／Ｌ、１−ｃＢＰＥＡ ０．００７４モル／Ｌ加えたものであり、この溶液０．８４ｃｃに酸化液０．４２ｃｃを加える。酸化液は調合６を使用した。 The above data is obtained by adding 0.164 mol / L of CPPO and 0.0074 mol / L of 1-cBPEA to each solvent, and adding 0.42 cc of the oxidizing solution to 0.84 cc of this solution. Formula 6 was used as the oxidizing solution.
次にＡＴＢＣに安息香酸ブチルの添加量を増やしていった時の発光特性を下記に示す。溶媒ＡＴＢＣのみのものを組成Ｈとする。
ＡＴＢＣに安息香酸ブチルを１０％（容量割合）加えたものを組成Ｉ
ＡＴＢＣに安息香酸ブチルを２０％（容量割合）加えたものを組成Ｊ
ＡＴＢＣに安息香酸ブチルを３０％（容量割合）加えたものを組成Ｋ
ＡＴＢＣに安息香酸ブチルを４０％（容量割合）加えたものを組成Ｌ
ＡＴＢＣに安息香酸ブチルを５０％（容量割合）加えたものを組成Ｍ
ＡＴＢＣに安息香酸ブチルを６０％（容量割合）加えたものを組成Ｎ
Next, the emission characteristics when increasing the amount of butyl benzoate added to ATBC are shown below. The solvent H only is ATBC.
Composition obtained by adding 10% (volume ratio) of butyl benzoate to ATBC
Composition of ATBC with 20% butyl benzoate (volume ratio)
Composition K with 30% (volume ratio) of butyl benzoate added to ATBC
Composition L with 40% (volume ratio) of butyl benzoate added to ATBC
Composition with 50% (volume ratio) of butyl benzoate added to ATBC
Composition N with 60% (volume ratio) of butyl benzoate added to ATBC
上記表６のＡＴＢＣのみの各時間毎の輝度値を１００として他の組成の割合を下記表７に示す。 Table 7 below shows the ratio of other compositions with the luminance value for each time of ATBC alone in Table 6 as 100.
なお、上記データは各溶媒に、ＣＰＰＯ ０．１６４モル／Ｌ、１−ｃＢＰＥＡ ０．００７４モル／Ｌ加えたものであり、この溶液０．８４ｃｃに酸化液０．４２ｃｃを加える。酸化液は調合６を使用した。この酸化液の溶媒にＤＥＧＭＢＡを使用しても、ほぼ同様の数値が得られた。上記したように、安息香酸ベンジル、安息香酸ブチルの添加量の増加と共に、発光輝度が少しづつ低下する傾向にある。本発明は、安全性の高い溶媒を発明することが主目的であるから、ＡＴＢＣのみ又は１０〜３０％他の例えば安息香酸ベンジル等を添加するのが望ましい。ＣＰＰＯ濃度０．１３モルの溶液を調合する時は安息香酸ベンジルを１０〜２０％（容量）加え、ＣＰＰＯ濃度０．１６モルの溶液を調合する時は、安息香酸ベンジルを２０〜３０％加えるのが効果的である。 The above data is obtained by adding 0.164 mol / L of CPPO and 0.0074 mol / L of 1-cBPEA to each solvent, and adding 0.42 cc of the oxidizing solution to 0.84 cc of this solution. Formula 6 was used as the oxidizing solution. Even when DEGGMA was used as the solvent of the oxidizing solution, almost the same numerical value was obtained. As described above, the emission luminance tends to decrease little by little as the addition amount of benzyl benzoate and butyl benzoate increases. Since the main object of the present invention is to invent a highly safe solvent, it is desirable to add only ATBC or 10-30% of other solvents such as benzyl benzoate. When preparing a solution with a CPPO concentration of 0.13 mol, add 10-20% (volume) of benzyl benzoate. When preparing a solution with a CPPO concentration of 0.16 mol, add 20-30% of benzyl benzoate. Is effective.
ＡＴＢＣに安息香酸ベンジル３０％加えた組成Ｃ及び調合６の酸化液の長期保存テストの結果を下記に示す。
イ． 組成Ｃ調合後、その０．８４ｃｃに酸化液を０．４２ｃｃ加え測定。
ロ． 組成Ｃを６０℃で２週間ガラス容器に密閉保存した後、常温保存している酸化液を加えて測定。
ハ． 酸化液を６０℃で２週間ガラス容器に密閉保存した後、常温保存している組成Cに加えて測定。
ニ． 組成Ｃ及び酸化液をそれぞれ６０℃で２週間ガラス容器に密閉保存したものを測定。
The results of a long-term storage test of the oxidation solution of Composition C and Preparation 6 in which 30% of benzyl benzoate was added to ATBC are shown below.
I. After composition C was prepared, 0.42 cc of the oxidizing solution was added to 0.84 cc and measured.
B. The composition C was hermetically stored in a glass container at 60 ° C. for 2 weeks, and then measured by adding an oxidizing solution stored at room temperature.
C. Measured in addition to composition C stored at room temperature after the oxidizing solution was hermetically stored in a glass container at 60 ° C. for 2 weeks.
D. The composition C and the oxidizing solution were each sealed and stored in a glass container at 60 ° C. for 2 weeks.
上記表８のイの各時間毎の輝度値を１００として他の組成の割合を下記表９に示す。 Table 9 below shows the ratio of other compositions, with the luminance value for each time of A in Table 8 set to 100.
次に従来の発光組成物である調合３、調合４の長期保存テストの結果を下記に示す。
ホ、調合３の蛍光液０．８４ｃｃ、調合４の酸化液０．４２ｃｃ加え測定
ヘ、調合３の蛍光液及び調合４の酸化液をそれぞれ６０℃で２週間ガラス容器に密閉保存した後、蛍光液０．８４ｃｃに酸化液を０．４２ｃｃ加えて測定。
Next, the results of long-term storage tests of Formulation 3 and Formulation 4, which are conventional luminescent compositions, are shown below.
E, 0.84 cc of the phosphor solution of formulation 3 and 0.42 cc of the oxide solution of formulation 4 were added to the measurement, and after storing the phosphor solution of formulation 3 and the oxide solution of formulation 4 in a glass container at 60 ° C. for 2 weeks, Measured by adding 0.42cc of oxidizing solution to 0.84cc of solution.
上記表１０のホの各時間毎の輝度値を１００としてヘの組成の割合を下記表１１に示す。 Table 11 below shows the ratio of the composition with the luminance value for each hour of E in Table 10 as 100.
表９のロとハの蛍光液と酸化液の貯蔵安定性（ガラス容器の場合）を比較するとはるかに蛍光液の方が安定である。
蛍光液と酸化液を６０℃で２週間保存した場合で従来の組成物（ヘ）では３時間後は１１％落ちているのに対し本発明のものは（ニ）１7％落ちているが、その差は6％であり実用上問題はない。
Comparing the storage stability (in the case of a glass container) of the fluorescent solutions and oxidizing solutions in Tables 9 and 9, the fluorescent solution is much more stable.
When the fluorescent solution and the oxidizing solution were stored at 60 ° C. for 2 weeks, the conventional composition (f) dropped 11% after 3 hours, while that of the present invention (d) dropped 17%. The difference is 6% and there is no practical problem.
Claims (7)
学発光を呈する系において、前記修酸エステル及び蛍光物質を含んだ組成物の溶媒として、アセチルクエン酸エステル又はアセチルクエン酸エステルを含む有機溶媒を使用したことを特徴とする化学発光組成物。 Compositions containing hydrogen peroxide and oxalic ester, by mixing the composition comprising a fluorescent substance, in a system exhibiting chemiluminescence, as a solvent of a composition containing the oxalic ester and a fluorescent substance, acetyl citrate A chemiluminescent composition using an organic solvent containing an ester or an acetyl citrate ester.
用したことを特徴とする化学発光組成物。 Compositions containing hydrogen peroxide and oxalic ester, by mixing the composition comprising a fluorescent substance, in a system which exhibits chemiluminescent, oxalic esters, acetyl tributyl citrate as a solvent of the composition containing the fluorescent substance chemiluminescent composition characterized in that use the organic solvent was added to benzoic acid ester up to about 30% by volume ratio <br/>.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004060652A JP4634054B2 (en) | 2003-04-14 | 2004-03-04 | Chemiluminescent composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003108501 | 2003-04-14 | ||
| JP2004060652A JP4634054B2 (en) | 2003-04-14 | 2004-03-04 | Chemiluminescent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004331947A JP2004331947A (en) | 2004-11-25 |
| JP4634054B2 true JP4634054B2 (en) | 2011-02-16 |
Family
ID=33513104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004060652A Expired - Lifetime JP4634054B2 (en) | 2003-04-14 | 2004-03-04 | Chemiluminescent composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4634054B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011099375A1 (en) * | 2010-02-09 | 2011-08-18 | 株式会社ルミカ | Oxidizing liquid for chemiluminescence and chemiluminescence system using same |
| WO2012101848A1 (en) * | 2011-01-27 | 2012-08-02 | 株式会社ルミカ | Oxidizing liquid for chemiluminescent element and chemiluminescent system containing same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994019421A1 (en) * | 1993-02-22 | 1994-09-01 | Omniglow Corporation | Phthalate free chemiluminescent activator |
| JP2000509096A (en) * | 1996-04-30 | 2000-07-18 | ジェーム ファイン ケミカルズ，インク． | Two-component chemiluminescent composition |
| US6126871A (en) * | 1999-03-17 | 2000-10-03 | Omniglow Corporation | High output chemiluminescent light formulations |
-
2004
- 2004-03-04 JP JP2004060652A patent/JP4634054B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994019421A1 (en) * | 1993-02-22 | 1994-09-01 | Omniglow Corporation | Phthalate free chemiluminescent activator |
| JP2000509096A (en) * | 1996-04-30 | 2000-07-18 | ジェーム ファイン ケミカルズ，インク． | Two-component chemiluminescent composition |
| US6126871A (en) * | 1999-03-17 | 2000-10-03 | Omniglow Corporation | High output chemiluminescent light formulations |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004331947A (en) | 2004-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5597517A (en) | Two-component chemiluminescent composition | |
| US4717511A (en) | Chemiluminescent composition | |
| US6126871A (en) | High output chemiluminescent light formulations | |
| CN101240165B (en) | Excellent oxalic ester chemoluminescence system | |
| JPS61254688A (en) | Chemoluminescent composition | |
| KR100893034B1 (en) | Chemiluminescent compositions | |
| JP5305310B2 (en) | Oxidizing solution for chemiluminescence and chemiluminescence system comprising the same | |
| JP4702653B1 (en) | Chemiluminescent composition | |
| JP4634054B2 (en) | Chemiluminescent composition | |
| US7416689B2 (en) | Chemiluminescent composition | |
| US3974086A (en) | Stabilization of hydrogen peroxide solutions | |
| JP2016210950A (en) | Fluoride phosphor and production method thereof, and semiconductor light-emitting device | |
| JP3604017B2 (en) | Chemiluminescent composition for producing red chemiluminescence and chemiluminescent body using the same | |
| US3948797A (en) | Process for restoration of performance of a chemical light system | |
| WO2012101848A1 (en) | Oxidizing liquid for chemiluminescent element and chemiluminescent system containing same | |
| EP3004286B1 (en) | Broad temperature performance chemiluminescent systems and methods | |
| JP2003137824A (en) | Anthracene compound and chemiluminescence composition comprising the same | |
| JPWO2007034609A1 (en) | Ultraviolet emission afterglow phosphor | |
| WO2015005246A1 (en) | Oxidizing fluid for chemiluminescent body and chemiluminescent system containing same | |
| CN101486897A (en) | Chemical luminophor | |
| JP2006104266A (en) | Fluorescent liquid for chemiluminescence, oxidizing liquid for chemiluminescence, and chemiluminescent system | |
| US3450643A (en) | Alkaline earth yttrate luminescent materials | |
| CN112852411A (en) | Chemiluminescent composition | |
| CN112877056A (en) | Chemiluminescent composition | |
| JPH07278538A (en) | Double structure ampule type chemical luminous material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040824 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20051207 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20051207 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070302 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100727 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100927 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20101019 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20101118 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4634054 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131126 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |