JPH0453894A - Red chemiluminesent material - Google Patents
Red chemiluminesent materialInfo
- Publication number
- JPH0453894A JPH0453894A JP16380090A JP16380090A JPH0453894A JP H0453894 A JPH0453894 A JP H0453894A JP 16380090 A JP16380090 A JP 16380090A JP 16380090 A JP16380090 A JP 16380090A JP H0453894 A JPH0453894 A JP H0453894A
- Authority
- JP
- Japan
- Prior art keywords
- chemiluminescent
- chemiluminescence
- formula
- fluorescent substance
- luminescence
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 4
- PONZBUKBFVIXOD-UHFFFAOYSA-N 9,10-dicarbamoylperylene-3,4-dicarboxylic acid Chemical class C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=N)C2=C1C3=CC=C2C(=N)O PONZBUKBFVIXOD-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000007539 photo-oxidation reaction Methods 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 description 10
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000005562 fading Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 3
- 229910000071 diazene Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- TZZLVFUOAYMTHA-UHFFFAOYSA-N bis-(2,4,5-trichloro-6-(pentyloxycarbonyl)phenyl)oxalate Chemical compound CCCCCOC(=O)C1=C(Cl)C(Cl)=CC(Cl)=C1OC(=O)C(=O)OC1=C(Cl)C=C(Cl)C(Cl)=C1C(=O)OCCCCC TZZLVFUOAYMTHA-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
有用な赤色発光体を実用化することにより、防災・標識
灯等の分野での利用が期待できる。[Detailed Description of the Invention] (Industrial Application Field) By putting a useful red light emitting material into practical use, it can be expected to be used in fields such as disaster prevention and marker lights.
（従来の技術）
シュウ酸型エステルと蛍光物質および有機溶媒からなる
組成液を過酸化水素と反応させ化学発光を得る方法は、
従来から知られているが、化学発光に有用な蛍光物質は
限られており、主に４７０−５４０ｎｍの波長を持つ化
学発光が主でいわゆる赤色、６２０ｎｍ前後の発光波長
を持つ化学発光体は実用化されていなかった。５．１２
−ビスフェニルエチニルナフタセンを塩素置換した１、
４−ジクロロ−５，１２−ビスフェニルエチニルナ
フタセ：／ （ＤＣＢＰＥＮと略す）は６１５ｎｍの化
学発光波長を持つことが知られているが、発光収車が低
く発光強度も低く、また構造上非常に酸化を受けやすい
ため、化学発光反応中の退色および保存中の酸化劣化が
起こり、実用的ではなかった。また、有機溶媒に対する
溶解度も低く、その点からも充分な発光を得ることが困
難であった。(Prior art) A method for obtaining chemiluminescence by reacting a liquid composition consisting of an oxalic acid ester, a fluorescent substance, and an organic solvent with hydrogen peroxide is as follows.
Although it has been known for a long time, there are only a limited number of fluorescent substances useful for chemiluminescence, and chemiluminescence mainly has a wavelength of 470-540 nm, and so-called red chemiluminescent substances with an emission wavelength of around 620 nm are not practical. It had not been standardized. 5.12
-bisphenylethynylnaphthacene substituted with chlorine 1,
4-dichloro-5,12-bisphenylethynylnaphtase:/ (abbreviated as DCBPEN) is known to have a chemiluminescent wavelength of 615 nm, but its luminescence collection is low, the luminescence intensity is low, and it is structurally very difficult. Because it is susceptible to oxidation, color fading during chemiluminescence reactions and oxidative deterioration during storage occur, making it impractical. Furthermore, the solubility in organic solvents is low, which also makes it difficult to obtain sufficient luminescence.
（目的）
上記の間開点を解決すべく、酸化に強く、保存性にも優
れ、化学発光収車の高い赤色の化学発光体を実用化する
ここを目的とする。(Purpose) In order to solve the above-mentioned problem, the purpose is to put into practical use a red chemiluminescent material that is resistant to oxidation, has excellent storage stability, and has high chemiluminescence absorption.
（構成）
アリールオキシ置換ペリレン−３，４，９，１０−テト
ラカルボン酸ジイミドは、特開昭６２−１４８５７１号
明細書に記載されているものであるが、それにはその化
合物を合成樹脂中に混合させ、可視光線を吸収させ、こ
れを蛍光として発光させることを目的としている。(Structure) Aryloxy-substituted perylene-3,4,9,10-tetracarboxylic acid diimide is described in JP-A-62-148571, in which the compound is incorporated into a synthetic resin. The purpose is to mix them together, absorb visible light, and emit it as fluorescence.
この化合物の中で、式１のものを本発明では化学発光組
成液中の蛍光物質として用いる。Among these compounds, the compound of formula 1 is used as a fluorescent substance in the chemiluminescent composition solution in the present invention.
具体的に記載すれば、混合したときに化学発光を生じる
２種の化学発光組成液Ａ、 Ｂのうち、Ａを蛍光液、
Ｂを酸化液と称したとき、Ａには、（１）下図のような
シュウ酸ビスエステル誘導体Ｒ−ＯＱ−Ｒ
（２）式１で表されるアリールオキシ置換ペリレン−３
，４，９，１０−テトラカルボン酸ジイミド（３）有機
溶媒が含まれ、Ｂには（１）過酸化水！ （２）有機塩
基触媒（３）有機溶媒が含まれる。必要時にＡ、 Ｂ
を混合させることにより、鮮やかな赤色発光を得ること
が出来る。Specifically, among the two chemiluminescent composition liquids A and B that produce chemiluminescence when mixed, A is a fluorescent liquid,
When B is referred to as an oxidizing liquid, A includes (1) an oxalic acid bisester derivative R-OQ-R as shown in the figure below (2) an aryloxy-substituted perylene-3 represented by formula 1.
, 4,9,10-tetracarboxylic acid diimide (3) organic solvent is included, and B contains (1) peroxide water! (2) Organic base catalyst (3) Organic solvent is included. A, B when necessary
By mixing these, it is possible to obtain bright red light emission.
（効果）
本発明により、今までになかった鮮やかな赤色発光を得
ることが出来る。また、酸化、特に光酸化に強いため、
従来のように光を遮断して保存する必要もなくなり、発
光中の発光色の退色もない。(Effects) According to the present invention, it is possible to obtain bright red light emission that has never been seen before. In addition, it is resistant to oxidation, especially photo-oxidation, so
There is no longer a need to block light for storage as in the past, and there is no fading of the luminescent color during luminescence.
また、発光（麦の化学発光体の色は発光前の色と殆ど変
化がないため、化学発光体として商品化した際、商品と
してのイメージが良い。In addition, the color of wheat's chemiluminescent material is almost unchanged from the color before luminescence, so when it is commercialized as a chemiluminescent material, it has a good image as a product.
（実施例）
■ビス（２，４，５−トリクロロ−６−カルボペントキ
シフェニル）オキザレート（以下ｃｐｐ。(Example) (1) Bis(2,4,5-trichloro-6-carbopentoxyphenyl)oxalate (hereinafter referred to as cpp).
と略す）Ｏ，１７Ｍ、アリールオキシ１換ペリレン−３
，４，９，ｉｏ−テトラカルボン酸ジイミド ３Ｘ１０
−’Ｍ、をフタル酸ジブチルに溶解。) O, 17M, aryloxy 1-substituted perylene-3
,4,9,io-tetracarboxylic acid diimide 3X10
-'M, dissolved in dibutyl phthalate.
■ＣＰＰ０ ０．１７Ｍ、ＤＣＢＰＥＮ ３ｘｌＯ−
３Ｍ、をフタル酸ジブチルに溶解。■CPP0 0.17M, DCBPEN 3xlO-
3M, dissolved in dibutyl phthalate.
■過酸化水素 ＩＭ、サリチル酸ナトリウム ０゜００
０８Ｍ、をフタル酸ジブチルに溶解、６■と■、■と■
を混合させて化学発光をおこさせ、その発光特性、発光
波長を測定し、また、■■の光酸化テスト及び保存テス
トを行った。■Hydrogen peroxide IM, sodium salicylate 0゜00
08M, dissolved in dibutyl phthalate, 6■ and ■, ■ and ■
were mixed to cause chemiluminescence, and the luminescent properties and wavelength of the luminescence were measured. In addition, the photooxidation test and storage test described in (■■) were conducted.
（ア）発光特性 表１の通り （イ）発光波長 ■・・・最大発光波長 ６１３ｎｍ ■・・・最大発光波長 ６１５ｎｍ （つ）光酸化テスト 日光に１週間！ｌＩＮさせ、退色、発光を調べた。(a) Luminescence characteristics As per Table 1 (a) Emission wavelength ■...Maximum emission wavelength 613nm ■...Maximum emission wavelength 615nm (1) Photooxidation test A week in Nikko! The cells were incubated for 1 IN, and their color fading and luminescence were examined.
■・・・退色もなく、発光も曝露前と変化なかった。■...There was no fading and the luminescence was unchanged from before exposure.
■・・・２−３日で退色し、殆ど発光しなかった。■...The color faded in 2-3 days, and almost no light was emitted.
（１）保存テスト
■■を４０°Ｃの恒温槽に１ケ月間保存し、発光を調べ
た。(1) Storage test ■■ was stored in a constant temperature bath at 40°C for one month, and the luminescence was examined.
■・・・保存前と殆ど変化なかった。■... There was almost no change from before storage.
■・・・酸化が起こり、半分はどの発光強度になってい
た。■...Oxidation occurred, and half of the light emission intensity was at what level.
Claims (1)
として式１の化合物（アリールオキシ置換ペリレン−３
，４，９，１０−テトラカルボン酸ジイミド）を単体又
は他の蛍光物質と合わせて使用した化学発光体 ▲数式、化学式、表等があります▼[Claims] The compound of formula 1 (aryloxy-substituted perylene-3
, 4,9,10-tetracarboxylic acid diimide) alone or in combination with other fluorescent substances▲There are mathematical formulas, chemical formulas, tables, etc.▼
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16380090A JPH0453894A (en) | 1990-06-20 | 1990-06-20 | Red chemiluminesent material |
| US08/091,925 US5321587A (en) | 1990-06-20 | 1993-07-16 | Chemiluminescence device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16380090A JPH0453894A (en) | 1990-06-20 | 1990-06-20 | Red chemiluminesent material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0453894A true JPH0453894A (en) | 1992-02-21 |
Family
ID=15780943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16380090A Pending JPH0453894A (en) | 1990-06-20 | 1990-06-20 | Red chemiluminesent material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0453894A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994025504A1 (en) * | 1993-05-04 | 1994-11-10 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Tetraaroxyperylene-3,4,9,10-tetracarboxylic acid polyimides |
| JP2011529631A (en) * | 2008-07-29 | 2011-12-08 | ソルヴェイ（ソシエテ アノニム） | Perylenetetracarboximide derivatives for photovoltaic devices |
| JP2013542595A (en) * | 2010-09-28 | 2013-11-21 | コーニンクレッカ フィリップス エヌ ヴェ | Light emitting device with organic phosphor |
| JP2014503981A (en) * | 2010-10-06 | 2014-02-13 | コーニンクレッカ フィリップス エヌ ヴェ | Light emitting device with organic phosphor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62148571A (en) * | 1985-12-19 | 1987-07-02 | バスフ アクチェン ゲゼルシャフト | Fluorescent aryloxy substituted perylene-3, 4, 9, 10-tetracarboxylic diimide |
| JPH03178942A (en) * | 1989-11-28 | 1991-08-02 | American Cyanamid Co | Chemically luminous solution based on substituted anthracene |
-
1990
- 1990-06-20 JP JP16380090A patent/JPH0453894A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62148571A (en) * | 1985-12-19 | 1987-07-02 | バスフ アクチェン ゲゼルシャフト | Fluorescent aryloxy substituted perylene-3, 4, 9, 10-tetracarboxylic diimide |
| JPH03178942A (en) * | 1989-11-28 | 1991-08-02 | American Cyanamid Co | Chemically luminous solution based on substituted anthracene |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994025504A1 (en) * | 1993-05-04 | 1994-11-10 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Tetraaroxyperylene-3,4,9,10-tetracarboxylic acid polyimides |
| JP2011529631A (en) * | 2008-07-29 | 2011-12-08 | ソルヴェイ（ソシエテ アノニム） | Perylenetetracarboximide derivatives for photovoltaic devices |
| TWI473804B (en) * | 2008-07-29 | 2015-02-21 | Solvay | Perylene tetracarboximide derivatives for photovoltaic devices |
| JP2013542595A (en) * | 2010-09-28 | 2013-11-21 | コーニンクレッカ フィリップス エヌ ヴェ | Light emitting device with organic phosphor |
| JP2014503981A (en) * | 2010-10-06 | 2014-02-13 | コーニンクレッカ フィリップス エヌ ヴェ | Light emitting device with organic phosphor |
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