JP2007204443A - Organic solid fluorescent substance - Google Patents
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- JP2007204443A JP2007204443A JP2006026875A JP2006026875A JP2007204443A JP 2007204443 A JP2007204443 A JP 2007204443A JP 2006026875 A JP2006026875 A JP 2006026875A JP 2006026875 A JP2006026875 A JP 2006026875A JP 2007204443 A JP2007204443 A JP 2007204443A
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本発明は、化粧品、塗料、印刷インキ、文具、建材、皮革などを着色する分野、及びエレクトロニクス分野での波長変換デバイスとしての用途分野において用いられる有機固体蛍光顔料や、その成分である固体状態において非常に明るいＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２,５−ジアミノ−３,６−ピラジンカルボニトリルの結晶や、該結晶の製造法に関する。 The present invention is an organic solid fluorescent pigment used in the field of coloring cosmetic products, paints, printing inks, stationery, building materials, leather, etc., and as a wavelength conversion device in the electronics field, and in the solid state that is a component thereof The present invention relates to very bright N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile crystals and a method for producing the crystals.
蛍光物質は、樹脂着色、塗料、印刷インキ、波長変換材料など幅広く利用されているが、有機物で固体状態において蛍光を持つものは非常に珍しい。無機物で固体状態において蛍光を持つものは知られているが、無機物は樹脂と混ぜにくく利用しにくいという欠点がある。また、固体蛍光物質は、液状蛍光物質よりも耐光性が良いことから、固体状態で蛍光を持つ有機蛍光物質の開発が望まれている。また、固体として明るいものほど少量でも鮮やかに発色することから、より広い用途が期待でき、より明るい有機固体蛍光物質の開発が望まれている。 Fluorescent substances are widely used for resin coloring, paints, printing inks, wavelength conversion materials, etc., but organic substances having fluorescence in a solid state are very rare. Inorganic substances that are fluorescent in the solid state are known, but inorganic substances have the drawback of being difficult to mix with resins and difficult to use. Further, since the solid fluorescent material has better light resistance than the liquid fluorescent material, it is desired to develop an organic fluorescent material having fluorescence in the solid state. In addition, since brighter solids produce more vivid colors even in smaller amounts, they can be expected to be used in a wider range and development of brighter organic solid fluorescent materials is desired.
一方、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリルは公知であり、特許文献１ではカラー複写機によって複写した場合、複写したことが一目瞭然に分かり、偽造することを防止出来る印刷物あるいは複写画像に使用するインキ又はトナーに用いる波長変換色素として記載されている。また、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリルの構造は、特許文献２における一般式［１］で示されるシアノピラジン誘導体に含まれているが、それ自体の合成実施例は記載されておらず物性値も示されていない。また、そこに開示されている合成法と同様の手法では本発明である非常に明るい結晶は得られない。 On the other hand, N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile is known, and in Patent Document 1, when copied by a color copying machine, It is described as a wavelength conversion dye used for an ink or a toner used for a printed matter or a copy image that can be clearly recognized at a glance and can be prevented from forgery. The structure of N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile is a cyano represented by the general formula [1] in Patent Document 2. Although it is contained in the pyrazine derivative, its own synthesis example is not described and physical property values are not shown. Moreover, the very bright crystal | crystallization which is this invention is not obtained by the method similar to the synthesis method currently disclosed there.
蛍光物質は蛍光顔料としても使用されている。従来の無機蛍光顔料は、蛍光染料を樹脂中に均一に溶解し、固溶体にして粉砕使用している例が多い。この場合、いろいろな処方で他成分と混合して使用するときに濃度の調整が困難である。また、有機蛍光顔料の多くは液体状態において蛍光を有している。液体状態では樹脂と相溶性が良い反面、耐光性が悪いという欠点を持つことが多い。固体蛍光物質は、液状蛍光物質よりも耐光性が良いことから、固体状態で蛍光を持つ有機蛍光物質の開発が望まれている。また、固体として明るいものほど少量でも鮮やかに発色することから、より広い用途が期待でき、より明るい有機固体蛍光物質の開発が望まれている。本発明の課題は、固体状態において非常に明るい高輝度の有機固体蛍光物質を提供することにある。 Fluorescent materials are also used as fluorescent pigments. In many conventional inorganic fluorescent pigments, a fluorescent dye is uniformly dissolved in a resin and then used as a solid solution for pulverization. In this case, it is difficult to adjust the concentration when mixed with other components in various formulations. Many organic fluorescent pigments have fluorescence in a liquid state. In the liquid state, it is compatible with the resin, but often has the disadvantage of poor light resistance. Since solid fluorescent materials have better light resistance than liquid fluorescent materials, development of organic fluorescent materials having fluorescence in the solid state is desired. In addition, since brighter solids produce more vivid colors even in smaller amounts, they can be expected to be used in a wider range and development of brighter organic solid fluorescent materials is desired. An object of the present invention is to provide an organic solid fluorescent material having a very bright and high brightness in a solid state.
本発明者らは、従来、Ｎ，Ｎ’−ジメチルアセトアミド中に、２，５−ジアミノ−３，６−ジシアノピラジン及び２−メチルベンジルブロマイドを加え、撹拌しながら０℃以上にならないようにＮａＯＨ水溶液又は固体のＮａＯＨを徐々に加えて攪拌・反応させ、反応物をＮａＣｌ水溶液に分散させ濾過し、得られた固形状のＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリルの粗結晶を、モノクロルベンゼンに加熱溶解し、冷却して再結晶させ、析出した暗赤色の固体を濾取して加熱乾燥し、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリルを９８％の純度で暗赤色の結晶として得ていた。モノクロルベンゼンで再結晶を行うと９８％という高純度のものが得られ、再結晶操作に使用する量も少なくて済む反面、モノクロルベンゼンの除去が困難であるという欠点があるため、再結晶溶媒及び後処理法の検討を行った。 The present inventors have conventionally added 2,5-diamino-3,6-dicyanopyrazine and 2-methylbenzyl bromide in N, N′-dimethylacetamide and added NaOH with stirring so that the temperature does not exceed 0 ° C. Aqueous solution or solid NaOH is gradually added to stir and react, the reaction product is dispersed in NaCl aqueous solution and filtered, and the resulting solid N, N, N ′, N′-tetrakis (2-methylbenzyl)- The crude crystals of 2,5-diamino-3,6-pyrazinecarbonitrile are dissolved in monochlorobenzene by heating, cooled and recrystallized. The precipitated dark red solid is collected by filtration, dried by heating, and N, N , N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile was obtained as dark red crystals with a purity of 98%. Recrystallization with monochlorobenzene yields a high purity of 98%, and the amount used for the recrystallization operation is small, but there is a disadvantage that it is difficult to remove monochlorobenzene. The post-processing method was examined.
シアノピラジン誘導体は対称形であるため一般に各種溶媒への溶解度が低い。Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２,５−ジアミノ−３,６−ピラジンカルボニトリルも各種溶媒に対する溶解度が低く、塩化メチレン、イソプロパノール、エタノール及びメタノール溶媒では溶けにくく上手く再結晶ができない。上記従来の工程におけるモノクロルベンゼンに代わる条件について種々検討を行ったところ、メチルイソブチルケトンを用いると、結晶の溶解性、再結晶の析出量及び溶媒除去の容易さの面で再結晶溶媒として好適であることがわかった。さらに予想していなかったこととして、モノクロルベンゼンからの再結晶で得られた暗赤色の結晶は高純度であることから固有の色であると考えられていたが、メチルイソブチルケトンからの再結晶で得られた結晶のほうが、固体状態で少し明るい赤色蛍光を持つことがわかった。 Since cyanopyrazine derivatives are symmetrical, they generally have low solubility in various solvents. N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile is also poorly soluble in various solvents and is soluble in methylene chloride, isopropanol, ethanol and methanol solvents. It is difficult to recrystallize well. As a result of various investigations on the conditions in place of monochlorobenzene in the conventional process, methyl isobutyl ketone is suitable as a recrystallization solvent in terms of crystal solubility, recrystallization precipitation amount and ease of solvent removal. I found out. In addition, unexpectedly, the dark red crystals obtained by recrystallization from monochlorobenzene were considered to have a unique color because of their high purity, but were recrystallized from methyl isobutyl ketone. The obtained crystal was found to have a slightly brighter red fluorescence in the solid state.
結晶形が異なると、異なる色を示す例は多々あるが、モノクロルベンゼンとメチルイソブチルケトン溶媒による再結晶で得られた結晶をＮＭＲ及び粉末Ｘ線結晶回折を測定したところ、元の暗赤色の結晶と同一構造、同一結晶形であるというデータが得られ、結晶多形による色の違いではないと判断された。 There are many examples that show different colors depending on the crystal form, but when the crystals obtained by recrystallization with monochlorobenzene and methyl isobutyl ketone solvent were measured by NMR and powder X-ray crystal diffraction, the original dark red crystals It was judged that it was not the color difference due to the crystal polymorphism.
そこで、メチルイソブチルケトン以外の多くの他の溶媒を用いる再結晶につき検討したところ、モノクロルベンゼンに代えてクロロホルムを用いた場合、前記粗結晶はクロロホルムに加熱溶解し難いことがわかった。念のため、モノクロルベンゼンで再結晶させた暗赤色の結晶をクロロホルムに加熱溶解し、冷却により再結晶したところ、明るい赤色蛍光を持つＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリルの結晶が得られた。この明るい赤色蛍光を持つ結晶についても、粉末Ｘ線解析を行ったところ、前記暗赤色の結晶とほぼ同じデータが得られた（図１参照）。そこで、暗赤色の結晶と明るい赤色蛍光を持つ結晶について顕微鏡で１０００倍に拡大して観察したところ、明るい赤色蛍光を持つ結晶の粒子径は少し小さく表面が平滑であったのに対し、暗赤色の結晶の粒子径は少し大きく更に表面に小さな結晶が付着していることが認められた（図２参照）。表面状態をも含め、なぜ明るい赤色蛍光を持つ結晶に変わったのか理由は明らかになっていないが、表面状態及び単結晶の集合状態の違いが明るさの違いの原因となっている可能性があると考えられる。 Then, when recrystallization using many other solvents other than methyl isobutyl ketone was examined, it was found that when chloroform was used instead of monochlorobenzene, the crude crystals were difficult to dissolve in chloroform by heating. As a precaution, dark red crystals recrystallized with monochlorobenzene were dissolved in chloroform with heating and recrystallized by cooling. As a result, N, N, N ′, N′-tetrakis (2-methylbenzyl) having bright red fluorescence was obtained. ) -2,5-diamino-3,6-pyrazinecarbonitrile crystals were obtained. When the powder X-ray analysis was performed on the crystal having bright red fluorescence, almost the same data as the dark red crystal was obtained (see FIG. 1). Therefore, when a dark red crystal and a crystal having bright red fluorescence were magnified 1000 times with a microscope, the particle size of the crystal having bright red fluorescence was slightly small and the surface was smooth, whereas the dark red crystal was dark red. It was recognized that the particle diameter of the crystals was slightly larger and further small crystals adhered to the surface (see FIG. 2). The reason why it changed to a crystal with bright red fluorescence, including the surface state, is not clear, but the difference in the surface state and the aggregate state of single crystals may cause the difference in brightness. It is believed that there is.
その後、晶析のための冷却条件等を検討することにより、明るさが増したＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリルの結晶が得られることを見い出した。その他、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリルはクロロホルムに加熱溶解し難い上に、加熱溶解した後に冷却しても析出しがたいことがわかったので、前記暗赤色の結晶をクロロホルムに加熱溶解し、イソプロパノールを加えて、冷却により再結晶することにより、明るさの点で多少低下するが、収率が向上することを見い出した。 Then, N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazine whose brightness was increased by examining cooling conditions for crystallization It has been found that crystals of carbonitrile are obtained. In addition, N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile is difficult to heat and dissolve in chloroform. However, it was found that the dark red crystals were dissolved by heating in chloroform, and isopropanol was added and recrystallized by cooling. I found something to do.
赤色蛍光を持つ結晶の明るさを、定量的に評価するため、安息角、スパチュウラ角、表面形状及び粒度分布も定量的指標となり得ないが、後分光方式の反射率測定による固体における可視光領域の最大反射率が最適であることを確認し、本発明を完成するに至った。 Since the brightness of crystals with red fluorescence is quantitatively evaluated, the angle of repose, spatula angle, surface shape, and particle size distribution cannot be quantitative indicators, but the visible light region in solids by reflectivity measurement in the post-spectral method As a result, it was confirmed that the maximum reflectance was optimal, and the present invention was completed.
すなわち本発明は、（１）後分光方式の反射率測定による固体における可視光領域の最大反射率が１００％以上であることを特徴とする構造式［Ｉ］：
で表されるＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２,５−ジアミノ−３,６−ピラジンカルボニトリル結晶や、（２）波長６００〜７００ｎｍの領域において、最大反射率を有することを特徴とする上記（１）記載のＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２,５−ジアミノ−３,６−ピラジンカルボニトリル結晶や、（３）後分光方式の反射率測定による固体における可視光領域の最大反射率が、１２０％以上であることを特徴とする上記（１）又は（２）記載のＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２,５−ジアミノ−３,６−ピラジンカルボニトリル結晶や、（４）後分光方式の反射率測定による固体における可視光領域の最大反射率が、１５０％以上であることを特徴とする上記（３）記載のＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２,５−ジアミノ−３,６−ピラジンカルボニトリル結晶や、（５）後分光方式の反射率測定による固体における可視光領域の最大反射率が１００％未満であるＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリルを、クロロホルム又はメチルイソブチルケトンに加熱溶解し、冷却することで再結晶することにより得られることを特徴とする上記（１）〜（４）のいずれか記載のＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリル結晶に関する。
That is, according to the present invention, (1) the structural formula [I] is characterized in that the maximum reflectance in the visible light region of a solid by post-spectral reflectance measurement is 100% or more:
N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile crystal represented by: (2) Maximum in the region of wavelength 600 to 700 nm N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile crystal according to the above (1), which has a reflectance, 3) N, N, N ′, N ′ according to the above (1) or (2), wherein the maximum reflectance in the visible light region in the solid by the reflectance measurement of the post-spectral method is 120% or more. -The maximum reflectivity in the visible light region of a tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile crystal or (4) solid spectroscopy by post-spectral reflectance measurement is 150% or more (3) above, characterized in that N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile crystals as described above, and (5) visible in solids by post-spectral reflectance measurement. N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile having a maximum reflectance in the light region of less than 100%, chloroform or methyl isobutyl ketone N, N, N ′, N′-tetrakis (2-methylbenzyl) according to any one of (1) to (4) above, wherein the N, N, N ′, N′-tetrakis (2-methylbenzyl) is obtained by recrystallization by heating and dissolving ) -2,5-diamino-3,6-pyrazinecarbonitrile crystals.
また本発明は、（６）Ｎ，Ｎ’−ジメチルアセトアミド中に、２，５−ジアミノ−３，６−ジシアノピラジン及び２−メチルベンジルブロマイドを加え、撹拌しながら０℃以上にならないようにＮａＯＨ水溶液又は固体のＮａＯＨを徐々に加えて反応させ、反応物をＮａＣｌ水溶液に分散させ濾過し、得られた濾過物をメチルイソブチルケトンに加熱溶解し、冷却により再結晶することを特徴とする上記（１）〜（３）のいずれか記載のＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリル結晶の製造法や、（７）Ｎ，Ｎ’−ジメチルアセトアミド中に、２，５−ジアミノ−３，６−ジシアノピラジン及び２−メチルベンジルブロマイドを加え、撹拌しながら０℃以上にならないようにＮａＯＨ水溶液又は固体のＮａＯＨを徐々に加えて反応させ、反応物をＮａＣｌ水溶液に分散させ濾過し、得られた濾過物をモノクロルベンゼンに加熱溶解し、冷却することにより得られる暗赤色の固体をクロロホルムに加熱溶解し、冷却により再結晶することを特徴とする上記（１）〜（４）のいずれか記載のＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリル結晶の製造法や、（８）Ｎ，Ｎ’−ジメチルアセトアミド中に、２，５−ジアミノ−３，６−ジシアノピラジン及び２−メチルベンジルブロマイドを加え、撹拌しながら０℃以上にならないようにＮａＯＨ水溶液又は固体のＮａＯＨを徐々に加えて反応させ、反応物をＮａＣｌ水溶液に分散させ濾過し、得られた濾過物をモノクロルベンゼンに加熱溶解し、冷却することにより得られる暗赤色の固体をクロロホルムに加熱溶解し、イソプロパノールを加えて、冷却により再結晶することを特徴とする上記（１）〜（３）のいずれか記載のＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリル結晶の製造法や、（９）後分光方式の反射率測定による固体における可視光領域の最大反射率が１００％未満であるＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリルを、クロロホルム又はメチルイソブチルケトンで再結晶することにより、後分光方式の反射率測定による固体における可視光領域の最大反射率を１００％以上にすることを特徴とする上記（１）〜（４）のいずれか記載のＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリル結晶の製造方法に関する。 In the present invention, (6) 2,5-diamino-3,6-dicyanopyrazine and 2-methylbenzyl bromide are added to N, N′-dimethylacetamide, and NaOH is added so that the temperature does not exceed 0 ° C. with stirring. An aqueous solution or solid NaOH is gradually added to cause a reaction, the reaction product is dispersed in an aqueous NaCl solution and filtered, and the obtained filtrate is heated and dissolved in methyl isobutyl ketone, and recrystallized by cooling. 1) to (3), a method for producing an N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile crystal, ) Add 2,5-diamino-3,6-dicyanopyrazine and 2-methylbenzyl bromide to N, N'-dimethylacetamide, and it will not rise above 0 ° C with stirring. To the reaction mixture, an aqueous NaOH solution or solid NaOH is gradually added, and the reaction product is dispersed in an aqueous NaCl solution and filtered. The obtained filtrate is heated and dissolved in monochlorobenzene, and cooled to obtain a dark red solid. N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5 according to any one of (1) to (4) above, which is dissolved by heating in chloroform and recrystallized by cooling. -Diamino-3,6-pyrazinecarbonitrile crystal production method, (8) 2,5-diamino-3,6-dicyanopyrazine and 2-methylbenzyl bromide are added to N, N'-dimethylacetamide, While stirring, an aqueous NaOH solution or solid NaOH was gradually added so as not to exceed 0 ° C. and reacted, and the reaction product was dispersed in an aqueous NaCl solution and filtered. The above (1) to (3), wherein the dark red solid obtained by heating and dissolving the excess in monochlorobenzene and cooling is heated and dissolved in chloroform, isopropanol is added, and recrystallization is performed by cooling. N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile crystal production method according to any one of (1) and (9) post-spectral reflection N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile having a maximum reflectance in the visible light region of a solid of less than 100% by a rate measurement By recrystallizing with chloroform or methyl isobutyl ketone, the maximum reflectance in the visible light region in solids by post-spectral reflectance measurement is 100% or more. The method for producing N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile crystal according to any one of (1) to (4) above About.
さらに本発明は、（１０）上記（１）〜（５）のいずれか記載のＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリル結晶を含有することを特徴とする有機固体蛍光顔料に関する。 Furthermore, the present invention provides (10) the N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazine described in any one of (1) to (5) above. The present invention relates to an organic solid fluorescent pigment characterized by containing carbonitrile crystals.
本発明によると、有機固体蛍光顔料として有用な、明るい赤色蛍光を持つＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２,５−ジアミノ−３,６−ピラジンカルボニトリルの結晶を提供することができる。 According to the present invention, N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile having bright red fluorescence, which is useful as an organic solid fluorescent pigment, is used. Crystals can be provided.
本発明のＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２,５−ジアミノ−３,６−ピラジンカルボニトリル結晶（以下、「本発明の結晶」ということがある）としては、後分光方式の反射率測定による固体における可視光領域の最大反射率が１００％以上である前記構造式［Ｉ］で表されるＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２,５−ジアミノ−３,６−ピラジンカルボニトリルの結晶であれば特に制限されず、３８０ｎｍ以上かつ７８０ｎｍ未満の可視光領域、例えば波長６００〜７００ｎｍの領域において、好ましくは最大反射率が１２０％以上、より好ましくは１５０％以上の明るい赤色蛍光を持つ結晶や、後分光方式の反射率測定による固体における可視光領域の最大反射率が１００％未満であるＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリルを、クロロホルム又はメチルイソブチルケトンに加熱溶解し、冷却することで再結晶することにより得られる結晶を好適に例示することができる。 As N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile crystal of the present invention (hereinafter sometimes referred to as “crystal of the present invention”) Is N, N, N ′, N′-tetrakis (2-methyl) represented by the structural formula [I], in which the maximum reflectance in the visible light region in the solid is 100% or more as measured by reflectance measurement using a post-spectral method Benzyl) -2,5-diamino-3,6-pyrazinecarbonitrile is not particularly limited, and is preferably a maximum reflectance in a visible light region of 380 nm or more and less than 780 nm, for example, a wavelength region of 600 to 700 nm. Is a crystal having bright red fluorescence of 120% or more, more preferably 150% or more, or N having a maximum reflectance of less than 100% in the visible light region in a solid by a reflectance measurement of a post-spectral method , N, N ′, N′-Tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile is heated and dissolved in chloroform or methyl isobutyl ketone and cooled to recrystallize. The crystals obtained by the above can be suitably exemplified.
本特許において「後分光方式の反射率測定による固体における可視光領域の最大反射率」とは、ＪＩＳ Ｚ−８７２２に準拠する０−４５°後分光方式に基づく分光式色差計である日本電色工業株式会社ＳＥ−２０００を用いて分光反射率を測定し、その可視光領域内で示した最も高い反射率のことをいい、日本電色工業株式会社ＳＥ−２０００を用いての測定は、粉体サンプルを口径３０ｍｍのガラス製シャーレに均一に敷き詰めて、ＳＥ−２０００の取扱説明書記載の通りに行い、光源には標準イルミナントＡを用いるものの、標準イルミナントＣを用いての測定値に計算されている反射率で示されている。Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２,５−ジアミノ−３,６−ピラジンカルボニトリルの反射率では、物質固有の色に同じ波長の蛍光が加わった値が測定されることになる。 In this patent, “maximum reflectance in the visible light region in a solid by reflectance measurement of the post-spectral method” means Nippon Denshoku, which is a spectral color difference meter based on a 0-45 ° post-spectral method in accordance with JIS Z-8722. Spectral reflectance was measured using SE-2000, Inc., and the highest reflectance shown in the visible light region was measured, and measurement using Nippon Denshoku Industries Co., Ltd., SE-2000, A body sample is uniformly spread on a glass petri dish with a diameter of 30 mm, and is performed as described in the instruction manual for SE-2000. It is indicated by the reflectance. In the reflectance of N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile, the value obtained by adding fluorescence of the same wavelength to the color unique to the substance Will be measured.
本発明の結晶の製造方法としては、後分光方式の反射率測定による固体における可視光領域の最大反射率が１００％未満であるＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２，５−ジアミノ−３，６−ピラジンカルボニトリルを、クロロホルム又はメチルイソブチルケトンで再結晶することにより、後分光方式の反射率測定による固体における可視光領域の最大反射率を１００％以上にする方法を挙げることができ、より具体的には、Ｎ，Ｎ’−ジメチルアセトアミド中に、２，５−ジアミノ−３，６−ジシアノピラジン及び２−メチルベンジルブロマイドを加え、撹拌しながら０℃以上にならないようにＮａＯＨ水溶液又は固体のＮａＯＨを徐々に加え反応させ、反応物をＮａＣｌ水溶液に分散させ濾過し、得られた濾過物（粗結晶）をメチルイソブチルケトンに加熱溶解し、冷却により再結晶する方法（以下「製法１」ということがある）や、Ｎ，Ｎ’−ジメチルアセトアミド中に、２，５−ジアミノ−３，６−ジシアノピラジン及び２−メチルベンジルブロマイドを加え、撹拌しながら０℃以上にならないようにＮａＯＨ水溶液又は固体のＮａＯＨを徐々に加え反応させ、反応物をＮａＣｌ水溶液に分散させ濾過し、得られた濾過物をモノクロルベンゼンに加熱溶解し、冷却することにより得られる暗赤色の固体をクロロホルムに加熱溶解し、冷却により再結晶する方法（以下「製法２」ということがある）や、Ｎ，Ｎ’−ジメチルアセトアミド中に、２，５−ジアミノ−３，６−ジシアノピラジン及び２−メチルベンジルブロマイドを加え、撹拌しながら０℃以上にならないようにＮａＯＨ水溶液又は固体のＮａＯＨを徐々に加え反応させ、反応物をＮａＣｌ水溶液に分散させ濾過し、得られた濾過物をモノクロルベンゼンに加熱溶解し、冷却することにより得られる暗赤色の固体をクロロホルムに加熱溶解し、イソプロパノールを加えて、冷却により再結晶する方法（以下「製法３」ということがある）を好適に例示することができる。 As a method for producing the crystal of the present invention, N, N, N ′, N′-tetrakis (2-methylbenzyl) whose maximum reflectance in a visible light region in a solid by a reflectance measurement by a post-spectral method is less than 100%. By recrystallizing -2,5-diamino-3,6-pyrazinecarbonitrile with chloroform or methyl isobutyl ketone, the maximum reflectivity in the visible light region in solids by post-spectral reflectivity measurement is 100% or more. More specifically, 2,5-diamino-3,6-dicyanopyrazine and 2-methylbenzyl bromide are added to N, N′-dimethylacetamide and stirred at 0 ° C. In order not to become above, NaOH aqueous solution or solid NaOH is gradually added and reacted, the reaction product is dispersed in NaCl aqueous solution and filtered, and the obtained filtrate (Crude crystals) are dissolved in methyl isobutyl ketone by heating and recrystallized by cooling (hereinafter sometimes referred to as “Production Method 1”), or 2,5-diamino-3,6 in N, N′-dimethylacetamide. -Dicyanopyrazine and 2-methylbenzyl bromide are added, NaOH aqueous solution or solid NaOH is gradually added and reacted so that the temperature does not exceed 0 ° C while stirring, the reaction product is dispersed in NaCl aqueous solution and filtered, and the obtained filtration A method in which a dark red solid obtained by heating and dissolving a product in monochlorobenzene and cooling is dissolved in chloroform and recrystallized by cooling (hereinafter sometimes referred to as “Production Method 2”), or N, N′— 2,5-diamino-3,6-dicyanopyrazine and 2-methylbenzyl bromide are added to dimethylacetamide, and the mixture is stirred with stirring. In order to avoid this, an aqueous NaOH solution or solid NaOH is gradually added and reacted, the reaction product is dispersed in an aqueous NaCl solution and filtered, and the resulting filtrate is dissolved in monochlorobenzene by heating and cooled, and then obtained by cooling. A method in which the solid is dissolved in chloroform by heating, isopropanol is added, and recrystallization is performed by cooling (hereinafter sometimes referred to as “Production Method 3”) can be suitably exemplified.
上記製法１によると、波長６００〜７００ｎｍの領域において、後分光方式の反射率測定による固体における最大反射率が１２０％以上の本発明の結晶を得ることができ、上記製法２によると、波長６００〜７００ｎｍの領域において、後分光方式の反射率測定による固体における最大反射率が１５０％以上の本発明の結晶を得ることができる。また、上記製法３によると、波長６００〜７００ｎｍの領域において、後分光方式の反射率測定による固体における最大反射率が１２０％以上の本発明の結晶を得ることができ、上記製法２よりも本発明の結晶を高収率で得ることができる。 According to the said manufacturing method 1, the crystal | crystallization of this invention with the maximum reflectance in the solid of 120% or more by the reflectance measurement of a post-spectral system can be obtained in the wavelength 600-700 nm area | region, According to the said manufacturing method 2, the wavelength 600 In the region of ˜700 nm, it is possible to obtain the crystal of the present invention having a maximum reflectance of 150% or more in the solid according to the reflectance measurement by the post-spectral method. Moreover, according to the said manufacturing method 3, the crystal | crystallization of this invention in which the maximum reflectance in the solid by the reflectance measurement of a post-spectral system is 120% or more can be obtained in the wavelength range of 600-700 nm. The crystals of the invention can be obtained in high yield.
本発明の有機固体蛍光顔料は、上記本発明の結晶を含有するものであれば特に制限されず、化粧品、塗料、印刷インキ、文具、建材、皮革などを着色する分野、エレクトロニクス分野での波長変換デバイスとしての用途分野等、高輝度の着色が要求される用途分野において有利に用いることができる。 The organic solid fluorescent pigment of the present invention is not particularly limited as long as it contains the crystal of the present invention. Wavelength conversion in the field of coloring cosmetics, paints, printing inks, stationery, building materials, leather, etc., electronics field It can be advantageously used in application fields that require high-luminance coloring, such as application fields as devices.
以下、実施例等により本発明をさらに詳しく説明するが、本発明の技術的範囲はこれら実施例等により制限されるものではない。なお、実施例等における後分光方式の反射率測定による固体における可視光領域の分光反射率は、ＪＩＳ Ｚ−８７２２に準拠する０−４５°後分光方式に基づく分光式色差計である日本電色工業株式会社ＳＥ−２０００を用い、粉体サンプルを口径３０ｍｍのガラス製シャーレに均一に敷き詰めて、ＳＥ−２０００の取扱説明書記載の通りに行い、光源には標準イルミナントＡを用いるものの、標準イルミナントＣを用いての測定値で表されている。
［実施例］
EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further in detail, the technical scope of this invention is not restrict | limited by these Examples. In addition, the spectral reflectance of the visible light region in the solid by the reflectance measurement of the post-spectral method in Examples and the like is Nippon Denshoku, which is a spectral color difference meter based on the 0-45 ° post-spectral method in accordance with JIS Z-8722. Using SE-2000 Kogyo Co., Ltd., spread the powder sample uniformly on a glass petri dish with a diameter of 30 mm, and perform as described in the instruction manual of SE-2000. The standard illuminant A is used as the light source. It is represented by the measured value using C.
[Example]
［参考例１］
Ｎ，Ｎ’−ジメチルアセトアミド４８０ｍＬ中に２，５−ジアミノ−３，６−ジシアノピラジン１９．２ｇ、２−メチルベンジルブロマイド９７．６ｇを入れ，撹拌しながら、０℃以上にならないように２５％ＮａＯＨ水溶液８０．８ｇを徐々に加えた。添加後１時間０℃で撹拌し、更に常温で１時間撹拌した後、ＮａＣＬ１２０ｇを９６０ｍＬの水に溶かした溶液に分散してろ過した。得られた固形物（粗結晶）を６５０ｍＬのモノクロルベンゼンに加熱溶解し、室温下１昼夜かけて緩慢に冷却すると暗赤色の固体が析出し、濾取して加熱乾燥すると４２．５ｇの化合物１（融点２０３℃）が得られた。後分光方式の反射率測定による固体における可視光領域の分光反射率を図３に示す。
[Reference Example 1]
Into 480 mL of N, N′-dimethylacetamide, 19.2 g of 2,5-diamino-3,6-dicyanopyrazine and 97.6 g of 2-methylbenzyl bromide were added, and 25% so as not to exceed 0 ° C. with stirring. 80.8 g of NaOH aqueous solution was gradually added. After the addition, the mixture was stirred at 0 ° C. for 1 hour and further stirred at room temperature for 1 hour, and then dispersed in a solution of 120 g of NaCL in 960 mL of water and filtered. The obtained solid (crude crystals) was dissolved in 650 mL of monochlorobenzene by heating and slowly cooled at room temperature over 1 day to precipitate a dark red solid, which was collected by filtration and dried by heating to 42.5 g of compound 1 (Melting point 203 ° C.) was obtained. FIG. 3 shows the spectral reflectance in the visible light region of the solid by the post-spectral reflectance measurement.
参考例１のモノクロルベンゼンの代わりに１２５０ｍＬのメチルイソブチルケトンを用いて、参考例１の粉体よりも明るい本発明の結晶４３．２ｇを得た（融点２０３℃）。後分光方式の反射率測定による固体における可視光領域の分光反射率を図３に示す。 Using 1250 mL of methyl isobutyl ketone instead of the monochlorobenzene of Reference Example 1, 43.2 g of crystals of the present invention brighter than the powder of Reference Example 1 were obtained (melting point: 203 ° C.). FIG. 3 shows the spectral reflectance in the visible light region of the solid by the post-spectral reflectance measurement.
参考例１で得られた暗赤色の固体６０．０ｇをクロロホルム５００ｍＬに加熱溶解し、室温下１昼夜かけて緩慢に冷却し、種結晶を入れて、さらに１昼夜室温放置すると、本発明のきわめて明るい赤色の結晶４０ｇを収率６７％で得た（融点２０３℃）。後分光方式の反射率測定による固体における可視光領域の分光反射率を図３に示す。 When 60.0 g of the dark red solid obtained in Reference Example 1 was dissolved in 500 mL of chloroform by heating, slowly cooled at room temperature for 1 day and night, seed crystals were added, and the mixture was allowed to stand at room temperature for 1 day and night. 40 g of bright red crystals were obtained with a yield of 67% (melting point 203 ° C.). FIG. 3 shows the spectral reflectance in the visible light region of the solid obtained by the reflectance measurement using the post-spectral method.
参考例１で得られた暗赤色の固体３６．０ｇをクロロホルム５００ｍＬに加熱溶解し、イソプロパノール（ＩＰＡ）５００ｍＬを加えて、室温下１昼夜かけて緩慢に冷却し、種結晶を入れて、さらに１昼夜室温放置すると、本発明のきわめて明るい赤色の結晶３２ｇを収率８９％で得た（融点２０３℃）。後分光方式の反射率測定による固体における可視光領域の分光反射率を図３に示す。 36.0 g of the dark red solid obtained in Reference Example 1 was dissolved by heating in 500 mL of chloroform, 500 mL of isopropanol (IPA) was added, and the mixture was slowly cooled at room temperature for one day and night. After standing at room temperature for 24 hours, 32 g of extremely bright red crystals of the present invention were obtained with a yield of 89% (melting point 203 ° C.). FIG. 3 shows the spectral reflectance in the visible light region of the solid obtained by the reflectance measurement using the post-spectral method.
Claims (10)
で表されるＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−メチルベンジル）−２,５−ジアミノ−３,６−ピラジンカルボニトリル結晶。 Structural formula [I], characterized in that the maximum reflectance in the visible light region in a solid by a reflectance measurement by a post-spectral method is 100% or more:
N, N, N ′, N′-tetrakis (2-methylbenzyl) -2,5-diamino-3,6-pyrazinecarbonitrile crystal represented by
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Cited By (2)
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|---|---|---|---|---|
| WO2017082246A1 (en) * | 2015-11-10 | 2017-05-18 | 国立大学法人九州大学 | Dicyanopyrazine compound, luminescent material, light transmitter using same, and production method for 2,5-dicyano-3,6-dihalogenopyrazine |
| KR20190085138A (en) | 2017-01-13 | 2019-07-17 | 고쿠리쓰다이가쿠호진 규슈다이가쿠 | Dicyano N-heterocyclic compound, luminescent material and luminescent element using the same |
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2006
- 2006-02-03 JP JP2006026875A patent/JP2007204443A/en active Pending
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| WO2017082246A1 (en) * | 2015-11-10 | 2017-05-18 | 国立大学法人九州大学 | Dicyanopyrazine compound, luminescent material, light transmitter using same, and production method for 2,5-dicyano-3,6-dihalogenopyrazine |
| KR20180080197A (en) | 2015-11-10 | 2018-07-11 | 고쿠리쓰다이가쿠호진 규슈다이가쿠 | Dicyanopyrazine compound, luminescent material, luminescent device using the same, and production method of 2,5-dicyano-3,6-dihalogenopyrazine |
| JPWO2017082246A1 (en) * | 2015-11-10 | 2018-08-30 | 国立大学法人九州大学 | Dicyanopyrazine compound, light emitting material, light emitting device using the same, and method for producing 2,5-dicyano-3,6-dihalogenopyrazine |
| US10399960B2 (en) | 2015-11-10 | 2019-09-03 | Kyushu University, National University Corporation | Dicyanopyrazine compound, luminescent material, luminescence device using the same, and method for producing 2,5-dicyano-3,6-dihalogenopyrazine |
| US10497878B2 (en) | 2015-11-10 | 2019-12-03 | Kyushu University, National University Corporation | Dicyanopyrazine compound, luminescent material, luminescence device using the same, and method for producing 2,5-dicyano-3,6-dihalogenopyrazine |
| US10522763B2 (en) | 2015-11-10 | 2019-12-31 | Kyushu University, National Universit Corporation | Dicyanopyrazine compound, luminescent material, luminescence device using the same, and method for producing 2,5-dicyano-3,6-dihalogenopyrazine |
| EP3882236A1 (en) | 2015-11-10 | 2021-09-22 | Kyushu University National University Corporation | Production method for 2,5-dicyano-3,6-dihalogenopyrazine |
| EP3882243A1 (en) | 2015-11-10 | 2021-09-22 | Kyushu University National University Corporation | Dicyanopyrazine compound, luminescent material and light transmitter using same |
| KR20230093541A (en) | 2015-11-10 | 2023-06-27 | 고쿠리쓰다이가쿠호진 규슈다이가쿠 | Dicyanopyrazine compound, luminescent material, light transmitter using same, and production method for 2,5-dicyano-3,6-dihalogenopyrazine |
| KR20190085138A (en) | 2017-01-13 | 2019-07-17 | 고쿠리쓰다이가쿠호진 규슈다이가쿠 | Dicyano N-heterocyclic compound, luminescent material and luminescent element using the same |
| US11279680B2 (en) | 2017-01-13 | 2022-03-22 | Kyushu University, National University Corporation | Dicyano N-heterocyclic compound, light-emitting material, and light-emitting element in which same is used |
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