JP2015113312A - π-ELECTRON COMPOUND AND HARDENING REACTION VISUALIZING AGENT - Google Patents
π-ELECTRON COMPOUND AND HARDENING REACTION VISUALIZING AGENT Download PDFInfo
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本発明は、π電子化合物及びこれを含む硬化反応可視化剤に関する。 The present invention relates to a π-electron compound and a curing reaction visualization agent containing the same.
本発明者らは、既に、非特許文献１で、フレキシブルで非平面のπジョイントと２つの剛直で平面状のウイングとで構成されたπ共役系化合物を報告した。具体的には、πジョイントとしてシクロオクタテトラエン、ウイングとして発光性アントラセンイミドを持ち、両者を縮環させた構造のπ共役系化合物Ａ（Ｒ＝ｎ−Ｂｕ）を合成し、その性質を調べた。そうしたところ、化合物Ａは、ポリマーマトリクス中では青色、溶液中では緑色、結晶では赤色の発色を示すことを見いだした。化合物Ａは、ポリマーマトリクス中ではπジョイントを挟んで両ウイングがＶ字をなすＶ字型構造になり、溶液中ではπジョイントと両ウイングとが同一平面に並んだ平面型構造になり、結晶中ではＶ字型構造が積み重なったスタッキング構造になると考えられる。また、化合物Ａは、ＭＴＨＦ溶液（ＭＴＨＦは２−メチルテトラヒドロフラン）では温度に依存して発光色が変化した。すなわち、温度１６３ＫでＭＴＨＦ溶液が液体の場合には緑色に発光したのに対して、温度７７ＫでＭＴＨＦ溶液がガラス化した場合には青色に発光した。 The present inventors have already reported, in Non-Patent Document 1, a π-conjugated compound composed of a flexible, non-planar π joint and two rigid, planar wings. Specifically, we synthesized π-conjugated compound A (R = n-Bu) with cyclooctatetraene as the π joint and luminescent anthracene imide as the wing, and a condensed ring of both, and investigated its properties. It was. As a result, Compound A was found to show blue color in the polymer matrix, green color in solution, and red color in crystals. Compound A has a V-shaped structure in which both wings are V-shaped across the π joint in the polymer matrix, and a planar structure in which the π joint and both wings are aligned in the same plane in the solution. Then, it is thought that it becomes a stacking structure in which V-shaped structures are stacked. In addition, the emission color of Compound A in the MTHF solution (MTHF is 2-methyltetrahydrofuran) changed depending on the temperature. That is, when the MTHF solution was liquid at a temperature of 163K, it emitted green, whereas when the MTHF solution was vitrified at a temperature of 77K, it emitted blue.
こうした結果を踏まえて、本発明者らは、化合物Ａを用いれば、接着剤の硬化の過程をリアルタイムで可視化できるのではないかと考えた。即ち、接着剤の硬化前では液状のため緑色に発色し、接着剤の硬化後では固形のため青色に発色し、その色の変化を肉眼で観察して硬化の過程を把握できると考えた。接着剤は、硬化が完了したか否かの判断が難しい。接着剤の硬化が完了していないにもかかわらず硬化が完了したと判断してしまうと、次の工程において接着剤で接着されていた２つの部材が接着力不足により剥がれてしまうおそれがある。接着剤の硬化の過程をリアルタイムで可視化することは、こうしたおそれの発生を防止することができる。 Based on these results, the present inventors thought that if Compound A was used, the curing process of the adhesive could be visualized in real time. That is, it was thought that the color of the product was colored before the adhesive was cured, so that the color was green. After the adhesive was cured, the color was colored blue because of the solid, and the color change was observed with the naked eye. It is difficult to determine whether or not the adhesive has been cured. If it is determined that the curing has been completed even though the curing of the adhesive has not been completed, there is a risk that the two members bonded with the adhesive in the next step will be peeled off due to insufficient adhesive force. Visualizing the curing process of the adhesive in real time can prevent the occurrence of such a fear.
しかしながら、上述した化合物Ａを接着剤に添加しただけでは、接着剤の硬化の過程に応じて発色が変わる様子が見られなかった。 However, only by adding the above-mentioned compound A to the adhesive, it was not observed that the color development changed according to the curing process of the adhesive.
本発明は、このような課題を解決するためになされたものであり、接着剤などのように液状物から固形物へ変化する化学品が硬化する過程を肉眼で観察するのに適した新規なπ電子化合物を提供することを主目的とする。 The present invention has been made to solve such problems, and is a novel suitable for observing the process of curing a chemical product that changes from a liquid to a solid, such as an adhesive, with the naked eye. The main object is to provide a π-electron compound.
本発明者らは、化合物Ａを接着剤に添加しただけでは接着剤の硬化の過程に応じて発色が変わる様子が見られなかった原因を追究した。そうしたところ、化合物Ａと接着剤との相溶性に問題があることに気づいた。化合物Ａは０．１質量％程度を添加するに過ぎないため、当初は相溶性に問題があるとは考えていなかった。しかし、詳しく調べたところ、化合物Ａと接着剤との相溶性が問題になって発色しなかったのに気づいた。そこで、化合物Ａの窒素上の置換基Ｒを種々検討したところ、接着剤の硬化の過程を肉眼で観察可能な新規なπ電子化合物を見いだし、本発明を完成するに至った。 The present inventors have investigated the reason why the color change did not change depending on the curing process of the adhesive only by adding the compound A to the adhesive. As a result, it was found that there was a problem in the compatibility between Compound A and the adhesive. Since only about 0.1% by mass of Compound A was added, it was not initially considered that there was a problem in compatibility. However, as a result of detailed examination, it was found that the compatibility between the compound A and the adhesive became a problem and no color was developed. Thus, various studies were made on the substituent R on the nitrogen of the compound A, and as a result, a novel π-electron compound capable of observing the curing process of the adhesive with the naked eye was found, and the present invention was completed.
即ち、本発明の新規なπ電子化合物は、下記式（１）で表されるものである。式（１）中、Ｒは、分岐を有するアルキル基か、少なくとも２位と６位に同じか互いに異なるアルキル基を備えたフェニル基である。 That is, the novel π-electron compound of the present invention is represented by the following formula (1). In the formula (1), R is a branched alkyl group or a phenyl group having the same or different alkyl groups at least at the 2-position and the 6-position.
また、本発明の硬化反応可視化剤は、溶剤としてケトン類、酢酸エステル類、アルコール類及びシクロアルカン類の１種又は２種以上を含む液状物が硬化する過程を肉眼で観察するための硬化反応可視化剤であって、上記式（１）で表されるπ電子化合物を主成分とするものである。 Further, the curing reaction visualizing agent of the present invention is a curing reaction for observing with the naked eye a process of curing a liquid material containing one or more of ketones, acetates, alcohols and cycloalkanes as a solvent. It is a visualizing agent and contains a π electron compound represented by the above formula (1) as a main component.
本発明のπ電子化合物は、溶剤としてケトン類、酢酸エステル類、アルコール類及びシクロアルカン類の１種又は２種以上を含む液状物が硬化する過程を肉眼で観察するための硬化反応可視化剤の成分として用いるのに適している。 The π-electron compound of the present invention is a curing reaction visualizing agent for visually observing the process of curing a liquid material containing one or more of ketones, acetates, alcohols and cycloalkanes as a solvent. Suitable for use as an ingredient.
本発明の新規なπ電子化合物は、上記式（１）で表されるものである。式（１）中、Ｒは、分岐を有するアルキル基か、少なくとも２位と６位に同じか互いに異なるアルキル基を備えたフェニル基である。 The novel π-electron compound of the present invention is represented by the above formula (1). In the formula (1), R is a branched alkyl group or a phenyl group having the same or different alkyl groups at least at the 2-position and the 6-position.
分岐を有するアルキル基としては、イソプロピル基やイソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、イソペンチル基などでもよいが、イソブチル基の２つのメチル基の一方又は両方にアルキル基が結合した置換基すなわちＲ1ＣＨ2（Ｒ2ＣＨ2）ＣＨＣＨ2−（但し、Ｒ1は水素原子又はアルキル基であり、Ｒ2はアルキル基である）が好ましい。Ｒ1ＣＨ2（Ｒ2ＣＨ2）ＣＨＣＨ2−としては、２−メチルブチル基、２−エチルブチル基、２−ｎ−プロピルブチル基、２−イソプロピルブチル基、２−メチルペンチル基、２−エチルペンチル基、２−ｎ−プロピルペンチル基、２−イソプロピルペンチル基、２−メチルヘキシル基、２−エチルヘキシル基、２−ｎ−プロピルヘキシル基、２−イソプロピルヘキシル基、２−メチルヘプチル基、２−エチルヘプチル基、２−ｎ−プロピルヘプチル基、２−イソプロピルヘプチル基などが挙げられる。 The branched alkyl group may be an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, or the like, but a substituent in which an alkyl group is bonded to one or both of two methyl groups of the isobutyl group. That is, R 1 CH 2 (R 2 CH 2 ) CHCH 2 — (where R 1 is a hydrogen atom or an alkyl group, and R 2 is an alkyl group) is preferable. R 1 CH 2 (R 2 CH 2 ) CHCH 2 — includes 2-methylbutyl group, 2-ethylbutyl group, 2-n-propylbutyl group, 2-isopropylbutyl group, 2-methylpentyl group, and 2-ethylpentyl. Group, 2-n-propylpentyl group, 2-isopropylpentyl group, 2-methylhexyl group, 2-ethylhexyl group, 2-n-propylhexyl group, 2-isopropylhexyl group, 2-methylheptyl group, 2-ethyl A heptyl group, 2-n-propyl heptyl group, 2-isopropyl heptyl group, etc. are mentioned.
少なくとも２位と６位に同じか互いに異なるアルキル基を備えたフェニル基としては、２，４，６−トリアルキルフェニル基や２，６−ジアルキルフェニル基などが挙げられる。２，４，６−トリアルキルフェニル基としては、２，４，６−トリメチルフェニル基（メシチル基）、２，４，６−トリエチルフェニル基、２，４，６−トリ−ｎ−プロピルフェニル基、２，４，６−トリイソプロピルフェニル基などが挙げられる。なお、「トリアルキル」は３つのアルキルがすべて同じでもよいし、２つのアルキルが同じで１つのアルキルが異なっていてもよいし、３つのアルキルがすべて異なっていてもよい。２，６−ジアルキルフェニル基としては、２，６−ジメチルフェニル基、２，６−ジエチルフェニル基、２，６−ジ−ｎ−プロピルフェニル基、２，６−ジイソプロピルフェニル基などが挙げられる。なお、「ジアルキル」は２つのアルキルが同じでもよいし異なっていてもよい。 Examples of the phenyl group having the same or different alkyl groups at least at the 2-position and the 6-position include 2,4,6-trialkylphenyl group and 2,6-dialkylphenyl group. As 2,4,6-trialkylphenyl group, 2,4,6-trimethylphenyl group (mesityl group), 2,4,6-triethylphenyl group, 2,4,6-tri-n-propylphenyl group 2,4,6-triisopropylphenyl group and the like. In “trialkyl”, all three alkyls may be the same, two alkyls may be the same and one alkyl may be different, or all three alkyls may be different. Examples of the 2,6-dialkylphenyl group include a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a 2,6-di-n-propylphenyl group, and a 2,6-diisopropylphenyl group. In “dialkyl”, two alkyls may be the same or different.
本発明のπ電子化合物は、溶剤としてケトン類、酢酸エステル類、アルコール類及びシクロアルカン類の１種又は２種以上を含む液状物が硬化する過程を肉眼で観察するための硬化反応可視化剤の主成分に使用することが適している。こうした液状物としては、例えば接着剤や塗料、保冷剤などが挙げられる。ケトン類としては、例えば、アセトン、メチルエチルケトン、メチルビニルケトンなどが挙げられる。酢酸エステル類としては、例えば、酢酸メチル、酢酸エチル、酢酸ｎ−プロピル、酢酸イソプロピル、酢酸ｎ−ブチルなどが挙げられる。アルコール類としては、メタノール、エタノール、イソプロパノール、ｎ−プロパノールなどが挙げられる。シクロアルカンとしては、シクロプロパン、シクロペンタンなどが挙げられる。溶剤として、ケトン類や酢酸エステル類を含むことが好ましい。 The π-electron compound of the present invention is a curing reaction visualizing agent for visually observing the process of curing a liquid material containing one or more of ketones, acetates, alcohols and cycloalkanes as a solvent. Suitable for use as the main component. Examples of such a liquid material include an adhesive, a paint, and a cooling agent. Examples of ketones include acetone, methyl ethyl ketone, and methyl vinyl ketone. Examples of acetates include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate. Examples of alcohols include methanol, ethanol, isopropanol, and n-propanol. Examples of the cycloalkane include cyclopropane and cyclopentane. As a solvent, it is preferable to contain ketones and acetates.
本発明のπ電子化合物は、こうした液状物（溶液）中ではＶ字構造をとっているが、光を当てると励起状態になり、その励起状態で安定な平面構造へと構造変化を起こす。この平面構造から光を放出すると、発色は緑色になる。一方、液状物が硬化した後は、光を当てて励起状態になっても構造変化を起こすことができず、Ｖ字形の構造のままである。このＶ字構造から光を放出すると、発色は青色になる。したがって、本発明のπ電子化合物を液状物に添加し、硬化していない状態で光を当てると緑色に発色し、硬化した状態で光を当てると青色に発色する。また、一部硬化した状態で光を当てると、硬化していない部分は緑色、硬化した部分は青色に発色する。このように肉眼で液状物が硬化する過程を観察することができる。 The π-electron compound of the present invention has a V-shaped structure in such a liquid material (solution). However, when it is exposed to light, it is in an excited state and undergoes a structural change to a stable planar structure in the excited state. When light is emitted from this planar structure, the color becomes green. On the other hand, after the liquid material is cured, the structure cannot be changed even if it is irradiated with light to be in an excited state, and remains in a V-shaped structure. When light is emitted from this V-shaped structure, the color becomes blue. Accordingly, when the π-electron compound of the present invention is added to a liquid and irradiated with light in an uncured state, it develops green, and when exposed to light in a cured state, it develops blue. When light is applied in a partially cured state, the uncured portion is colored green, and the cured portion is colored blue. In this way, the process of curing the liquid material can be observed with the naked eye.
上記式（１）のＲが直鎖状のアルキル基（例えばｎ−ブチル基）であるπ電子化合物の場合には、こうした液状物との相溶性が悪く、溶け残ってしまう。そのため、硬化の前後で発色の変化は見られない。Ｒが直鎖状のアルキル基の場合には、Ｒが嵩高くないため、π電子化合物が積み重なりやすくなり、相溶性が悪くなったと考えられる。一方、Ｒが分岐を有するアルキル基や２位と６位にアルキル基を備えたフェニル基の場合には、Ｒが嵩高いため、π電子化合物が積み重なりにくくなり、相溶性が良好になったと考えられる。そのため、硬化の前後で発色の変化が見られたと考えられる。 In the case of a π-electron compound in which R in the above formula (1) is a linear alkyl group (for example, n-butyl group), the compatibility with such a liquid material is poor and it remains undissolved. Therefore, there is no change in color development before and after curing. When R is a linear alkyl group, R is not bulky. Therefore, it is considered that the π-electron compound is easily stacked and the compatibility is deteriorated. On the other hand, in the case where R is a branched alkyl group or a phenyl group having an alkyl group at the 2nd and 6th positions, the R is bulky, so that the π-electron compound is difficult to stack and the compatibility is considered to be good. It is done. Therefore, it is considered that a color change was observed before and after curing.
次に、本発明のπ電子化合物の合成方法について説明する。本発明のπ電子化合物は、下記スキームに示すように、エステル基を持つジベンゾバレレン骨格から光異性化によってジベンゾ縮環シクロオクタテトラエン骨格へと導いた後、アセン類の伸長反応を利用してπ共役系を拡張し、最後に末端をイミド部位へ変換することにより合成することができる。また、中央のπジョイントであるシクロオクタテトラエンでＶ字型に折れ曲がった分子構造をとることは、Ｘ線結晶構造解析から確認することができる。 Next, a method for synthesizing the π-electron compound of the present invention will be described. As shown in the following scheme, the π-electron compound of the present invention is derived from a dibenzovalerene skeleton having an ester group to a dibenzo-condensed cyclooctatetraene skeleton by photoisomerization, and then utilizes the elongation reaction of acenes. Then, the π-conjugated system can be expanded and finally the terminal can be converted to an imide moiety. Moreover, it can confirm from X-ray crystal structure analysis that it takes the molecular structure bent into the V shape by cyclooctatetraene which is a center (pi) joint.
［実験例１〜５］
・合成手順
下記表１に示す実験例１〜５のπ電子化合物を合成した。実験例１〜４のπ電子化合物の合成手順を以下に説明する。実験例１〜４のπ電子化合物を化合物１ａ〜１ｄと称するものとする。実験例５のπ電子化合物は、非特許文献１に記載された既知化合物である。なお、実験例１〜４が本発明の実施例に相当し、実験例５が比較例に相当する。
[Experimental Examples 1-5]
Synthesis procedure The π-electron compounds of Experimental Examples 1 to 5 shown in Table 1 below were synthesized. A procedure for synthesizing the π electron compounds of Experimental Examples 1 to 4 will be described below. The π-electron compounds of Experimental Examples 1 to 4 are referred to as compounds 1a to 1d. The π-electron compound of Experimental Example 5 is a known compound described in Non-Patent Document 1. Experimental examples 1 to 4 correspond to examples of the present invention, and experimental example 5 corresponds to a comparative example.
［実験例１］
下記式に示すように、化合物１ａは、Ｎ−（２，６−ジイソプロピルフェニル）マレイミドとトリブチルホスフィンを反応させた後に、つづけて塩基存在下で化合物２を反応させることで合成した。化合物２は、非特許文献１に記載された方法により合成した。まず、Ｎ−（２，６-ジイソプロピルフェニル）マレイミド（１．２ｍｍｏｌ，３０８ｍｇ）の塩化メチレン溶液を、窒素雰囲気下０℃に冷やしたトリブチルホスフィン（１．３ｍｍｏｌ，０．３２ｍＬ）に滴下し、室温で３０分間撹拌した。その後、反応溶液を窒素雰囲気下０℃に冷やした化合物２（０．５００ｍｍｏｌ，２０８ｍｇ）の塩化メチレン懸濁液（１００ｍＬ）に滴下し、塩基であるジアザビシクロウンデセン（ＤＢＵ，０．０５ｍｍｏｌ，７．５μＬ）を滴下した。室温で７２時間撹拌した後、反応溶液に水を加えて反応をクエンチし、塩化メチレンで３回抽出した。抽出後の有機層を無水硫酸ナトリウムで脱水した後、溶媒を留去した。黄色の残留物をヘキサン−塩化メチレン混合溶媒（混合比１：３，Ｒｆ＝０．３８）を用いてシリカゲルカラムクロマトグラフィーにより分離精製することで，黄色固体として化合物１ａ（０．１５ｍｍｏｌ，１２５ｍｇ，２９％）を得た。化合物１ａのスペクトルデータは以下のとおり。mp:220.3℃(decomposed);1H NMR(400 MHz, CDCl3):δ 8.56 (s, 4H), 8.55 (s, 4H), 7.95 (s, 4H), 7.47 (t, J = 7.6 Hz, 2H), 7.30 (d, J = 7.6 Hz, 4H), 7.24 (s, 4H), 2.722.79 (m, 4H), 1.17 (d, J = 6.8 Hz, 24H); 13C NMR (100 MHz, CDCl3):δ 167.79, 147.13, 136.71, 133.43, 132.46, 132.29, 130.36, 129.91, 128.55, 127.45, 126.75, 126.66, 124.14, 29.53, 24.13; HR-MS (APCI, positive): [(M+H)+] calcd for C60H51N2O4, 863.3843; found 863.3847.
[Experimental Example 1]
As shown in the following formula, Compound 1a was synthesized by reacting N- (2,6-diisopropylphenyl) maleimide and tributylphosphine, and then reacting Compound 2 in the presence of a base. Compound 2 was synthesized by the method described in Non-Patent Document 1. First, a methylene chloride solution of N- (2,6-diisopropylphenyl) maleimide (1.2 mmol, 308 mg) was added dropwise to tributylphosphine (1.3 mmol, 0.32 mL) cooled to 0 ° C. under a nitrogen atmosphere. For 30 minutes. Thereafter, the reaction solution was added dropwise to a methylene chloride suspension (100 mL) of Compound 2 (0.500 mmol, 208 mg) cooled to 0 ° C. under a nitrogen atmosphere, and the diazabicycloundecene (DBU, 0.05 mmol, 7.5 μL) was added dropwise. After stirring at room temperature for 72 hours, the reaction solution was quenched with water and extracted three times with methylene chloride. The organic layer after extraction was dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off. The yellow residue was separated and purified by silica gel column chromatography using a mixed solvent of hexane-methylene chloride (mixing ratio 1: 3, R f = 0.38) to give Compound 1a (0.15 mmol, 125 mg as a yellow solid). 29%). The spectrum data of Compound 1a are as follows. mp: 220.3 ° C (decomposed); 1 H NMR (400 MHz, CDCl 3 ): δ 8.56 (s, 4H), 8.55 (s, 4H), 7.95 (s, 4H), 7.47 (t, J = 7.6 Hz, 2H), 7.30 (d, J = 7.6 Hz, 4H), 7.24 (s, 4H), 2.722.79 (m, 4H), 1.17 (d, J = 6.8 Hz, 24H); 13 C NMR (100 MHz, CDCl 3 ): δ 167.79, 147.13, 136.71, 133.43, 132.46, 132.29, 130.36, 129.91, 128.55, 127.45, 126.75, 126.66, 124.14, 29.53, 24.13; HR-MS (APCI, positive): ((M + H) + ] calcd for C 60 H 51 N 2 O 4 , 863.3843; found 863.3847.
［実験例２］
下記式に示すように、マレイミドとしてＮ−（メシチル）マレイミドを用いた以外は、実験例１と同様にして化合物１ｂを合成した。化合物１ｂのスペクトルデータは以下のとおり。mp:223.2℃(decomposed);1H NMR (400 MHz, CDCl3):δ 8.54 (s, 8H), 7.93 (s, 4H), 7.24 (s, 4H), 7.01 (s, 4H), 2.33 (s, 6H), 2.14 (s, 12H); 13C NMR (100 MHz, CDCl3): δ 166.96, 139.54, 136.72, 136.35, 133.44, 132.43, 132.29, 129.90, 129.47, 128.50, 127.61, 126.78, 126.58, 21.30, 18.16; HR-MS (APCI, positive): [(M)+] calcd for C54H38N2O4,; 778.2826; found 778.2799.
[Experiment 2]
As shown in the following formula, Compound 1b was synthesized in the same manner as in Experimental Example 1 except that N- (mesityl) maleimide was used as the maleimide. The spectral data of Compound 1b is as follows. mp: 223.2 ° C (decomposed); 1 H NMR (400 MHz, CDCl 3 ): δ 8.54 (s, 8H), 7.93 (s, 4H), 7.24 (s, 4H), 7.01 (s, 4H), 2.33 ( s, 6H), 2.14 (s, 12H); 13 C NMR (100 MHz, CDCl 3 ): δ 166.96, 139.54, 136.72, 136.35, 133.44, 132.43, 132.29, 129.90, 129.47, 128.50, 127.61, 126.78, 126.58, 21.30, 18.16; HR-MS (APCI, positive): [(M) + ] calcd for C 54 H 38 N 2 O 4 ,; 778.2826; found 778.2799.
［実験例３］
下記式に示すように、マレイミドとしてＮ−２−エチルヘキシルマレイミドを用いたこと、及び、ＤＢＵ滴下後の反応時間を１２時間にしたこと以外は、実験例１と同様にして化合物１ｃを合成した。化合物１ｃのスペクトルデータは以下のとおり。mp:215.0℃(decomposed);1H NMR (400 MHz, CDCl3):δ 8.47 (s, 4H), 8.39 (s, 4H), 7.88 (s, 4H), 7.20 (s, 4H), 3.64 (d, J = 7.2 Hz, 4H), 1.88 (m, 2H), 1.291.34 (m, 16H), 0.850.93 (m, 12H); 13C NMR (100 MHz, CDCl3): δ 168.20, 136.55, 133.38, 132.34, 132.14, 129.70, 128.38, 126.94, 125.72, 42.46, 38.44, 30.78, 28.69, 24.11, 23.14, 14.17, 10.60; HR-MS (APCI, positive): [(M+H)+] calcd for C52H51N2O4, 767.3843; found 767.3848.
[Experiment 3]
As shown in the following formula, Compound 1c was synthesized in the same manner as in Experimental Example 1 except that N-2-ethylhexylmaleimide was used as the maleimide and the reaction time after dropping the DBU was 12 hours. The spectral data of Compound 1c is as follows. mp: 215.0 ° C (decomposed); 1 H NMR (400 MHz, CDCl 3 ): δ 8.47 (s, 4H), 8.39 (s, 4H), 7.88 (s, 4H), 7.20 (s, 4H), 3.64 ( d, J = 7.2 Hz, 4H), 1.88 (m, 2H), 1.291.34 (m, 16H), 0.850.93 (m, 12H); 13 C NMR (100 MHz, CDCl 3 ): δ 168.20, 136.55 , 133.38, 132.34, 132.14, 129.70, 128.38, 126.94, 125.72, 42.46, 38.44, 30.78, 28.69, 24.11, 23.14, 14.17, 10.60; HR-MS (APCI, positive): [(M + H) + ] calcd for C 52 H 51 N 2 O 4 , 767.3843; found 767.3848.
［実験例４］
下記式に示すように、マレイミドとしてＮ−イソブチルマレイミドを用いたこと、ＤＢＵ滴下後の反応時間を１２時間にしたこと、及び、分離精製時の溶出液を塩化メチレン−酢酸エチル混合溶媒(混合比１０：１）を用いたこと以外は、実験例１と同様にして化合物１ｄを合成した。化合物１ｄのスペクトルデータは以下のとおり。mp:224.8℃(decomposed);1H NMR (400 MHz, o-dichlorobenzene-d4, 170 ℃): δ 8.22 (s, 4H), 8.19 (s, 4H), 7.73 (s, 4H), 7.11 (s, 4H), 3.55 (d, J = 6.8 Hz, 4H), 2.162.23 (m, 2H), 0.92 (d, J = 6.8 Hz, 12H);13C NMRスペクトルは、有機溶媒への溶解性が低いため測定できなかった; HR-MS (APCI, positive): [M+] calcd for C44H34N2O4, 654.2513; found 654.2536.
[Experimental Example 4]
As shown in the following formula, N-isobutylmaleimide was used as maleimide, the reaction time after dropping DBU was 12 hours, and the eluate during separation and purification was mixed with methylene chloride-ethyl acetate mixed solvent (mixing ratio). Compound 1d was synthesized in the same manner as in Experimental Example 1 except that 10: 1) was used. The spectral data of Compound 1d is as follows. mp: 224.8 ℃ (decomposed); 1 H NMR (400 MHz, o-dichlorobenzene-d 4 , 170 ℃): δ 8.22 (s, 4H), 8.19 (s, 4H), 7.73 (s, 4H), 7.11 ( s, 4H), 3.55 (d, J = 6.8 Hz, 4H), 2.162.23 (m, 2H), 0.92 (d, J = 6.8 Hz, 12H); 13 C NMR spectra are soluble in organic solvents HR-MS (APCI, positive): [M + ] calcd for C 44 H 34 N 2 O 4 , 654.2513; found 654.2536.
・評価
接着剤として、一成分溶剤形であり、セルロース２０質量％、酢酸ビニル樹脂５質量％、有機溶剤７５質量％を含むもの（接着剤Ａという）を使用した。有機溶剤の内訳は、アセトン、エタノール、イソプロパノール、酢酸ブチルであった。この接着剤Ａに、実験例１のπ電子化合物を濃度が約０．１質量％となるように添加した。また、実験例２〜５のπ電子化合物についても、同様にして接着剤Ａに添加した。添加後、π電子化合物の接着剤Ａに対する相溶性を肉眼で観察した。その結果を表１に示した。相溶性の評価は、極めて良好、良好、やや良好、やや不良、不良の５段階とした。また、各π電子化合物を添加した接着剤Ａにつき、硬化する前に３６５ｎｍの光を照射したときの発光と、硬化した後に同じ波長の光を照射したときの発光とを肉眼で観察した。その結果を表１に示した。
Evaluation As the adhesive, a one-component solvent type containing 20% by mass of cellulose, 5% by mass of vinyl acetate resin, and 75% by mass of organic solvent (referred to as adhesive A) was used. The breakdown of organic solvents was acetone, ethanol, isopropanol, and butyl acetate. To this adhesive A, the π-electron compound of Experimental Example 1 was added so as to have a concentration of about 0.1% by mass. Further, the π electron compounds of Experimental Examples 2 to 5 were added to the adhesive A in the same manner. After the addition, the compatibility of the π-electron compound with the adhesive A was observed with the naked eye. The results are shown in Table 1. The evaluation of compatibility was made into 5 levels of extremely good, good, slightly good, slightly bad and bad. Further, regarding the adhesive A to which each π-electron compound was added, light emission when irradiated with 365 nm light before curing and light emission when irradiated with light of the same wavelength after curing were observed with the naked eye. The results are shown in Table 1.
表１に示すように、Ｒがｎ−ブチル基の場合（実験例５）、π電子化合物と接着剤Ａとの相溶性が不良だったため、硬化前後の発光を評価できなかった。これに対して、Ｒがイソブチル基の場合（実験例４）、接着剤Ａに何とか溶けたため、硬化前後で発光色の変化が認められたものの、発光が弱く、色の変化はやや明確性に欠けた。一方、Ｒがｎ−エチルヘキシル基の場合（実験例３）、相溶性が良好であり、硬化前後で発光色の変化が認められた。また、発光が強かったため、色の変化も明確に把握できた。更に、Ｒが２，６−ジイソプロピルフェニル基やメシチル基の場合（実験例１，２）、相溶性はきわめて良好で、硬化前後で発光色の変化が認められた。また、発光が非常に強かったため、色の変化も一層明確に把握できた。 As shown in Table 1, when R is an n-butyl group (Experimental Example 5), since the compatibility between the π-electron compound and the adhesive A was poor, the light emission before and after curing could not be evaluated. On the other hand, when R is an isobutyl group (Experimental Example 4), since it was somehow dissolved in the adhesive A, a change in the emission color was observed before and after curing, but the emission was weak and the color change was somewhat clear. Chipped. On the other hand, when R is an n-ethylhexyl group (Experimental Example 3), the compatibility was good, and a change in emission color was observed before and after curing. Moreover, since the luminescence was strong, the change in color was clearly grasped. Furthermore, when R is a 2,6-diisopropylphenyl group or a mesityl group (Experimental Examples 1 and 2), the compatibility is very good, and a change in emission color is observed before and after curing. Moreover, since the luminescence was very strong, the color change could be grasped more clearly.
以上のことから、Ｒが分岐を有するアルキル基であれば、接着剤Ａの硬化前後で発光色の変化が認められることがわかった。但し、Ｒがイソブチル基の場合には、発光色の変化の明確性に問題があったが、Ｒが２−エチルヘキシル基（イソブチル基の２つのメチル基の一方にｎ−プロピル基、もう一方にメチル基が結合した置換基）の場合には、発光色の変化は明確であった。こうしたことから、Ｒとして、イソブチル基の２つのメチル基の少なくとも一方にアルキル基が結合した置換基を用いれば、発光色の変化は明確になるものと予測される。また、Ｒがメシチル基や２，６−ジイソプロピルフェニル基のように少なくとも２，６位にアルキル基を有するフェニル基の場合には、発光色の変化は極めて明確であった。 From the above, it was found that when R is a branched alkyl group, a change in emission color is recognized before and after the adhesive A is cured. However, when R is an isobutyl group, there was a problem in the clarity of the change in emission color, but R was a 2-ethylhexyl group (one of the two methyl groups of the isobutyl group was an n-propyl group and the other was In the case of a substituent having a methyl group attached thereto, the change in emission color was clear. For these reasons, it is expected that the change in emission color will be clear if a substituent having an alkyl group bonded to at least one of the two methyl groups of the isobutyl group is used as R. In addition, when R is a phenyl group having an alkyl group at least at the 2,6-position, such as a mesityl group or a 2,6-diisopropylphenyl group, the change in emission color was very clear.
［実験例６〜８］
実験例３のπ電子化合物（Ｒは２−エチルヘキシル基）について、接着剤Ｂ〜Ｄとの相溶性および硬化前後の発光色の変化を観察した。接着剤Ｂ〜Ｄの種類及び成分を表２に示した。表２には、接着剤Ａの種類及び成分も併せて示した。また、観察結果を表３に示した。表３には、実験例３の結果も併せて示した。なお、実験例６が本発明の実施例に相当し、実験例７，８が比較例に相当する。
[Experimental Examples 6 to 8]
Regarding the π-electron compound of Experimental Example 3 (R is 2-ethylhexyl group), the compatibility with the adhesives B to D and the change in emission color before and after curing were observed. Table 2 shows the types and components of the adhesives B to D. Table 2 also shows the types and components of the adhesive A. The observation results are shown in Table 3. Table 3 also shows the results of Experimental Example 3. Experimental example 6 corresponds to an example of the present invention, and experimental examples 7 and 8 correspond to comparative examples.
表３に示すように、接着剤Ａ，Ｂのように有機溶剤としてケトン類や酢酸エステル類、アルコール類、シクロアルカン類を含む接着剤の場合、π電子化合物（Ｒは２−エチルヘキシル基）と接着剤との相溶性が良好であり、硬化前後で発光色の変化が認められ、発光が強かったためその色の変化も明確に把握できた。これに対して、接着剤Ｃ，Ｄのように上述した有機溶剤を含まない接着剤の場合、π電子化合物（Ｒは２−エチルヘキシル基）と接着剤との相溶性がやや不良あるいは不良であったため、硬化前後の発光を評価できなかった。以上のことから、硬化前後の発光色の変化を観察可能な接着剤としては、有機溶剤としてケトン類やアルコール類、酢酸エステル類、シクロアルカン類を含む接着剤、特に、ケトン類や酢酸エステル類を含む接着剤が適しているといえる。ただし、接着剤自体が発光を示さないことを前提とする。 As shown in Table 3, in the case of an adhesive containing ketones, acetates, alcohols, and cycloalkanes as an organic solvent such as adhesives A and B, a π-electron compound (R is a 2-ethylhexyl group) and The compatibility with the adhesive was good, a change in emission color was observed before and after curing, and the change in color could be clearly grasped because the emission was strong. On the other hand, in the case of an adhesive that does not contain the organic solvent described above, such as adhesives C and D, the compatibility between the π-electron compound (R is 2-ethylhexyl group) and the adhesive is slightly poor or poor. Therefore, the luminescence before and after curing could not be evaluated. From the above, adhesives that can observe changes in emission color before and after curing include adhesives containing ketones, alcohols, acetates, and cycloalkanes as organic solvents, especially ketones and acetates. It can be said that an adhesive containing is suitable. However, it is assumed that the adhesive itself does not emit light.
なお、実施例としては、本発明のπ電子化合物を接着剤に添加した場合を例示したが、接着剤の代わりに塗料や保冷剤に添加しても同様の効果が得られると予測される。 In addition, although the case where the π-electron compound of the present invention was added to the adhesive was illustrated as an example, it is expected that the same effect can be obtained even if it is added to a paint or a cooling agent instead of the adhesive.
Claims (5)
請求項１に記載のπ電子化合物。 The phenyl group is a 2,4,6-trialkylphenyl group or a 2,6-dialkylphenyl group.
The π-electron compound according to claim 1.
請求項１〜３のいずれか１項に記載のπ電子化合物を主成分とする硬化反応可視化剤。 A curing reaction visualizing agent for visually observing a process of curing a liquid material containing one or more of ketones, acetates, alcohols and cycloalkanes as a solvent,
The hardening reaction visualization agent which has the pi electron compound of any one of Claims 1-3 as a main component.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016080358A1 (en) * | 2014-11-18 | 2016-05-26 | 国立研究開発法人科学技術振興機構 | Mechanochromic luminescent material, mechanochromic resin obtained by crosslinking mechanochromic luminescent material, method for producing mechanochromic luminescent material, and method for producing mechanochromic resin |
| WO2019172200A1 (en) | 2018-03-05 | 2019-09-12 | 国立研究開発法人科学技術振興機構 | Compound and polymeric compound including said compound |
| JP2021031456A (en) * | 2019-08-27 | 2021-03-01 | デンカ株式会社 | Triphenylene type liquid crystal compound, and adhesive and adhesive body using triphenylene type liquid crystal compound |
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2013
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016080358A1 (en) * | 2014-11-18 | 2016-05-26 | 国立研究開発法人科学技術振興機構 | Mechanochromic luminescent material, mechanochromic resin obtained by crosslinking mechanochromic luminescent material, method for producing mechanochromic luminescent material, and method for producing mechanochromic resin |
| WO2019172200A1 (en) | 2018-03-05 | 2019-09-12 | 国立研究開発法人科学技術振興機構 | Compound and polymeric compound including said compound |
| JPWO2019172200A1 (en) * | 2018-03-05 | 2021-03-04 | 国立研究開発法人科学技術振興機構 | Compounds and polymer compounds containing the compounds |
| US11560383B2 (en) | 2018-03-05 | 2023-01-24 | Japan Science And Technology Agency | Compound and polymer compound containing the compound |
| JP7387175B2 (en) | 2018-03-05 | 2023-11-28 | 国立研究開発法人科学技術振興機構 | Compound and polymer compound containing the compound |
| JP2021031456A (en) * | 2019-08-27 | 2021-03-01 | デンカ株式会社 | Triphenylene type liquid crystal compound, and adhesive and adhesive body using triphenylene type liquid crystal compound |
| JP7240671B2 (en) | 2019-08-27 | 2023-03-16 | デンカ株式会社 | Triphenylene-type liquid crystalline compound and adhesive and adhesive body using triphenylene-type liquid crystalline compound |
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