JP2010006712A - Anthracene derivative, its dimer, optical information-recording material using them, and method for recording optical information - Google Patents

Anthracene derivative, its dimer, optical information-recording material using them, and method for recording optical information Download PDF

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JP2010006712A
JP2010006712A JP2008164722A JP2008164722A JP2010006712A JP 2010006712 A JP2010006712 A JP 2010006712A JP 2008164722 A JP2008164722 A JP 2008164722A JP 2008164722 A JP2008164722 A JP 2008164722A JP 2010006712 A JP2010006712 A JP 2010006712A
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anthracene derivative
dimer
optical information
anthracene
information recording
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JP5083980B2 (en
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Hidemoto Kihara
秀元 木原
Shohyaku Ri
鍾百 李
Nobuyuki Tamaoki
信之 玉置
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National Institute of Advanced Industrial Science and Technology AIST
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound usable for a display or a recording material, a re-writable optical information-recording medium by using the same, and a method for recording or erasing the optical information. <P>SOLUTION: This anthracene derivative is expressed by general formula [wherein, (n) is an integer of 1 to 20], and its dimer is also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、表示・記録材料などに用いることができるアントラセン誘導体及びその二量体、並びにこれらを用いた書き換え可能な光情報記録体、光情報記録方法に関する。   The present invention relates to an anthracene derivative that can be used for display / recording materials and the like, a dimer thereof, a rewritable optical information recording body using the same, and an optical information recording method.

基板となるポリマーそのものの形状変化（ポリマーに添加した色素などの化学変化ではなく）を利用して情報を記録する例として液晶ポリマーを用いた情報記録が報告されている。例えば、均一で透明なホメオトロピック配向の液晶ポリマー薄膜にレーザー光を照射して一部分を熱により等方相に転移させ、その後急冷すると、光照射部分がポリドメインの液晶相となり白濁する（非特許文献１参照）。あるいは、アゾベンゼンを有する液晶ポリマーに紫外光を照射すると照射部分のアゾベンゼンが異性化して液晶→等方相転移が誘起され、その後同様に白濁する（非特許文献２参照）。しかし、この場合いずれも、透明な初期状態であるホメオトロピック配向を実現するために、加熱と電場印加（あるいは磁場印加）という操作が必要であり、さらに書き込んだ記録を消去する場合もこの操作を毎回必要とする。
またアントラセンのように光化学反応の前後で蛍光を出したり、出さなかったりする分子を用いて光記録材料とする試みもされている。この場合記録の読み出しは、ある特定の波長の励起光を照射して出てくる蛍光を測定しなければならない。しかし、読み出しの励起光はしばしば書き込み光と近い波長を有するので記録を破壊してしまうという問題を抱えている。これを解決するために2種類の光反応性部位を1分子中に組み込むことにより、書き込み光と読み出し光の波長を大きく変える方法も提示されている（非特許文献３参照）。 Information recording using a liquid crystal polymer has been reported as an example of recording information using a change in shape of a polymer itself as a substrate (not a chemical change such as a dye added to the polymer). For example, when a uniform and transparent liquid crystal polymer thin film with homeotropic alignment is irradiated with laser light, a part of it is transformed into an isotropic phase by heat, and then rapidly cooled, the light irradiated part becomes a liquid crystal phase of a polydomain and becomes cloudy (non-patented) Reference 1). Alternatively, when the liquid crystal polymer having azobenzene is irradiated with ultraviolet light, the azobenzene in the irradiated portion is isomerized to induce a liquid crystal → isotropic phase transition and then become cloudy in the same manner (see Non-Patent Document 2). However, in this case, in order to realize the homeotropic alignment which is a transparent initial state, operations of heating and electric field application (or magnetic field application) are necessary, and this operation is also performed when erasing a written record. I need it every time.
Attempts have also been made to produce optical recording materials using molecules such as anthracene that emit or do not emit fluorescence before and after the photochemical reaction. In this case, in order to read out the record, it is necessary to measure fluorescence emitted by irradiating excitation light having a specific wavelength. However, since the readout excitation light often has a wavelength close to that of the write light, there is a problem that the recording is destroyed. In order to solve this problem, a method for greatly changing the wavelengths of the writing light and the reading light by incorporating two types of photoreactive sites in one molecule has been proposed (see Non-Patent Document 3).

本発明者は、波長365nmのみで重合させる主鎖型液晶ポリマーをすでに特許出願している（特許文献１参照）。また、さらに、当該ポリマーの一部には液晶性を示さないジアントラセンのアモルファスポリマーが存在していることを見出し、これを用いた光情報記録材料をすでに特許出願している（特許文献２参照）。
しかし、これらはポリマーであることから融点が比較的高く、このポリマーから作製した薄膜において、フォトマスクを通して紫外光を照射しながら加熱すると、照射部分はアモルファスポリマーのままで透明であり、一方加熱によりモノマーに戻った部分が結晶となって白濁することによりパターンを形成することが出来るが、このポリマーの系では一旦モノマーに戻った部位を再び光照射によってポリマー化してアモルファスにすることは困難である。つまり情報の書き換えは今のところ実現できていないなど、画像解析精度等の点において光情報記録材料として改良すべき点があった。
本発明者は、CR-RWやDVD-RWのような書き換え可能な光記録メディアに用いることができる光情報記録材料を提供する。 The inventor has already filed a patent application for a main-chain liquid crystal polymer that is polymerized only at a wavelength of 365 nm (see Patent Document 1). Furthermore, it was found that a dianthracene amorphous polymer that does not exhibit liquid crystallinity exists in a part of the polymer, and an optical information recording material using the same has already been filed for a patent (see Patent Document 2). ).
However, since these are polymers, their melting points are relatively high. When a thin film made from this polymer is heated while being irradiated with ultraviolet light through a photomask, the irradiated part remains transparent as an amorphous polymer, while heating causes Patterns can be formed when the part that has returned to the monomer becomes crystallized and becomes cloudy, but in this polymer system, it is difficult to polymerize the part that has returned to the monomer once again by light irradiation to make it amorphous. . That is, there has been a point to be improved as an optical information recording material in terms of image analysis accuracy and the like, such as information rewriting has not been realized so far.
The present inventor provides an optical information recording material that can be used for rewritable optical recording media such as CR-RW and DVD-RW.

特願2007-104629Japanese Patent Application No. 2007-104629 特願2008-108072Japanese Patent Application No. 2008-108072 V. P. Shibaev, et al., Polymer Commun. 1983, 24, 364.V. P. Shibaev, et al., Polymer Commun. 1983, 24, 364. T. Ikeda and O. Tsutsumi, Nature 1995, 268, 1873.T. Ikeda and O. Tsutsumi, Nature 1995, 268, 1873. M. Irie, et al., Science2002, 420, 759.M. Irie, et al., Science 2002, 420, 759. R. G. Weiss, et al., Liquid Crystals,1989, 4, 367.R. G. Weiss, et al., Liquid Crystals, 1989, 4, 367.

本発明は、アントラセン誘導体及びその二量体並びにこれらを用いた書き換え可能な光記録メディアに用いることができる光情報記録材料、光情報記録体を提供する。
本発明の光情報記録材料に用いる化合物は、光化学反応前の単量体では室温で結晶性であるが、一旦光照射により二量化すると室温において結晶化せずにアモルファス相を示すような有機化合物を見出すこと、さらに得られた二量体を熱あるいは光により再び単量体に戻せることができる化合物を提供する。 The present invention provides an anthracene derivative, a dimer thereof, an optical information recording material that can be used for a rewritable optical recording medium using the same, and an optical information recording body.
The compound used for the optical information recording material of the present invention is an organic compound that is crystalline at room temperature in the monomer before photochemical reaction, but shows an amorphous phase without being crystallized at room temperature once dimerized by light irradiation. And a compound capable of returning the obtained dimer to a monomer again by heat or light.

すなわち、本発明は、一般式

Figure 2010006712
（式中、ｎは１〜２０の整数である）で示されるアントラセン誘導体である。
また、本発明は、
化学式
Figure 2010006712
 で示されるアントラセン誘導体である。
さらに、本発明は、
化学式
Figure 2010006712
 （式中、ｎは１〜２０の整数である）
で示されるアントラセン誘導体の二量体である。 That is, the present invention has the general formula
Figure 2010006712
 (Wherein n is an integer of 1 to 20).
The present invention also provides:
Chemical formula
Figure 2010006712
 It is an anthracene derivative shown by.
Furthermore, the present invention provides
Chemical formula
Figure 2010006712
 (Where n is an integer from 1 to 20)
It is a dimer of the anthracene derivative shown by.

また、本発明は、本発明に係るアントラセン誘導体の薄膜を加熱溶融させて透明基板に塗布した光情報記録媒体である。
さらに、本発明は、本発明に係る光情報記録媒体において、所望の箇所に紫外線を照射することにより、紫外線照射部を透明化して情報の記録を行い、該紫外線照射部を熱による白濁化を利用して情報の消去を行うことを特徴とする光情報記録媒体を利用した情報の記録・消去方法である。
また、本発明は、紫外線照射部の透明化が、本発明に係るアントラセン誘導体の二量体への紫外線照射による二量化反応によるものであることを特徴とするものである。
さらに、本発明は、紫外線照射部の熱による白濁化が、本発明に係るアントラセン誘導体の二量体の単量体アントラセン誘導体への単量体化反応によるものであることを特徴とするものである。 The present invention is also an optical information recording medium in which a thin film of an anthracene derivative according to the present invention is heated and melted and applied to a transparent substrate.
Furthermore, the present invention provides an optical information recording medium according to the present invention by irradiating ultraviolet rays to a desired location, thereby making the ultraviolet irradiation part transparent and recording information, and making the ultraviolet irradiation part turbid by heat. An information recording / erasing method using an optical information recording medium, wherein the information is erased by using the optical information recording medium.
Further, the present invention is characterized in that the transparency of the ultraviolet irradiation part is due to a dimerization reaction by ultraviolet irradiation to the dimer of the anthracene derivative according to the present invention.
Further, the present invention is characterized in that the white turbidity due to heat in the ultraviolet irradiation part is due to the monomerization reaction of the dimer of the anthracene derivative according to the present invention to the monomer anthracene derivative. is there.

本発明のアントラセン誘導体及びアントラセン誘導体の二量体は、情報の書き込みには波長の短い（254 nmなど）紫外光を用いることができ、書き換え可能な記録媒体であるCD-RWやDVD-RWに利用することができる。光情報記録体の作成に関して、キャスト法やスピンコート法を用いることができるために、製造コストや製造時間の削減ができる。 The anthracene derivative and dimer of the anthracene derivative of the present invention can use ultraviolet light having a short wavelength (eg, 254 nm) for writing information, and can be used for rewritable recording media such as CD-RW and DVD-RW. Can be used. Since the casting method and the spin coating method can be used for producing the optical information recording body, the manufacturing cost and the manufacturing time can be reduced.

本発明のアントラセン誘導体及びアントラセン誘導体の二量体は、情報の書き込みには波長の短い（254 nmなど）紫外光を用いることができが、書き換え可能な記録媒体として働くために、以下の創意をした。
本発明のアントラセン誘導体及びアントラセン誘導体の二量体の光・熱記録の原理は、従来知られているアントラセンはある紫外光（例えば波長365nm）を照射すると二量化し、逆にこの二量体に別の紫外光（例えば波長254nm）を照射するかまたは加熱することによりアントラセン単量体に戻ることが知られている原理を利用する。
アントラセン誘導体のうち、どのような化学構造を有するものがもっとも効率が良いかどうかを勘案した。アントラセン誘導体の末端には液晶に良く用いられる剛直な構造であるシアノビフェニルを導入した。この2つの化学構造であるアントラセンとシアノビフェニルをアルキル鎖などにより直線的に結合させることにより単量体の結晶性を向上させることを考えた。そのためにアントラセンの１位や９位の位置ではなく、２位に置換基が導入された2-アントラセンカルボン酸を原料として用いた。 The anthracene derivative and dimer of the anthracene derivative of the present invention can use ultraviolet light having a short wavelength (such as 254 nm) for writing information. However, in order to work as a rewritable recording medium, did.
The principle of optical and thermal recording of the anthracene derivative and dimer of the anthracene derivative of the present invention is that the anthracene known in the art dimerizes when irradiated with certain ultraviolet light (for example, wavelength 365 nm). The principle is known to return to the anthracene monomer by irradiation with another ultraviolet light (eg, wavelength 254 nm) or by heating.
The chemical structure of anthracene derivatives was considered to be most efficient. Cyanobiphenyl, a rigid structure often used for liquid crystals, was introduced at the end of the anthracene derivative. We thought to improve the crystallinity of the monomer by linearly bonding these two chemical structures, anthracene and cyanobiphenyl, with alkyl chains. Therefore, 2-anthracenecarboxylic acid having a substituent introduced at the 2-position instead of the 1-position or 9-position of anthracene was used as a raw material.

この考え方により合成した化合物が本件発明のアントラセン誘導体1である（図１）。アントラセン誘導体1は狙い通り結晶性が良く、融点が144℃であった。この分子1を融点以上で熱しておいて紫外光365 nmを照射するとアントラセン部位が付加環化反応を起こして二量体分子が生成するが、この二量体分子は室温においてアモルファス相つまり透明であることがわかった。
二量体は図２のような構造であるが、図に示したように立体異性体が多数存在する。このことが室温において結晶化することを妨げてアモルファス相になる原因と考えられる。次にこの二量体を高温（約220℃）に加熱するとアントラセンの熱戻り反応が起こり、結晶性の良い分子1が再生できる。光記録材料として用いるときは、分子1を溶融させてガラス基板上に広げて薄膜状にし、ここに一部だけ紫外光365 nmを照射すれば、室温において照射された部分のみ透明になり、照射されていない部分が結晶化して白濁することになる。この操作により情報の書き込みが出来る。情報を消去するときは膜全体を加熱し、全体を白濁させればよい。この書き込み・消去の操作は繰り返し行うことが出来た。 A compound synthesized by this concept is the anthracene derivative 1 of the present invention (FIG. 1). Anthracene derivative 1 had good crystallinity as intended and had a melting point of 144 ° C. When this molecule 1 is heated above the melting point and irradiated with 365 nm ultraviolet light, the anthracene site undergoes a cycloaddition reaction to form a dimer molecule. This dimer molecule is in an amorphous phase or transparent at room temperature. I found out.
The dimer has a structure as shown in FIG. 2, but there are many stereoisomers as shown in the figure. This is considered to be a cause of preventing crystallization at room temperature and becoming an amorphous phase. Next, when this dimer is heated to a high temperature (about 220 ° C.), a heat return reaction of anthracene occurs, and molecule 1 having good crystallinity can be regenerated. When used as an optical recording material, the molecule 1 is melted and spread on a glass substrate to form a thin film, and if only a part of it is irradiated with 365 nm ultraviolet light, only the irradiated part becomes transparent and irradiated. The part which is not crystallized and becomes cloudy. Information can be written by this operation. When erasing information, the whole film may be heated to make the whole cloudy. This write / erase operation could be repeated.

同様の働きをする結晶性のアントラセン誘導体としては以下のようなものがある。

Figure 2010006712
（式中、ｎは１〜２０で表される整数） Examples of crystalline anthracene derivatives that function similarly include the following.
Figure 2010006712
 (Wherein n is an integer represented by 1 to 20)

（アントラセン誘導体１と他のアントラセン誘導体との比較）
本発明者は、アントラセン誘導体１において、このような置換基が有効であることを示すために、アントラセン誘導体1と類似の化合物aとbを合成した。aはメソゲンを持たないでアントラセンにアルキル鎖のみが結合している。

Figure 2010006712
一方、bはメソゲンとしてシアノビフェニルではなくフェニルシクロヘキサンを持っている。a、ｂ両方とも結晶性を示した。このa、bにそれぞれ紫外光を照射したところ1と同じようにダイマーが得られたが、そのダイマーはアモルファスではなく結晶性であった。また、R. G. Weissらはやはり1と類似の構造を持つ化合物cを合成し、さらにその光二量体について報告している（非特許文献４参照）。cはコレステリル基をメソゲンとして有するために結晶相および液晶相を示すが、そのダイマーの相については報告されていない。このようにモノマーが結晶かつダイマーがアモルファスという系を実現するためにはシアノビフェルニ基の効果が大きいことが示唆される。
(Comparison of anthracene derivative 1 with other anthracene derivatives)
In order to show that such a substituent is effective in the anthracene derivative 1, the present inventor synthesized compounds a and b similar to the anthracene derivative 1. a has no mesogen and only an alkyl chain is bonded to anthracene.
Figure 2010006712
 On the other hand, b has phenylcyclohexane as mesogen instead of cyanobiphenyl. Both a and b showed crystallinity. When a and b were each irradiated with ultraviolet light, a dimer was obtained as in 1, but the dimer was not amorphous but crystalline. In addition, RG Weiss et al. Synthesized a compound c having a structure similar to 1 and reported a photodimer thereof (see Non-Patent Document 4). Although c has a cholesteryl group as a mesogen, it exhibits a crystal phase and a liquid crystal phase, but the dimer phase has not been reported. Thus, in order to realize a system in which the monomer is crystalline and the dimer is amorphous, it is suggested that the effect of the cyanobiferni group is large.

（アントラセン誘導体1の合成）
アントラセン誘導体1の合成スキームを図3に示した。

＜4-シアノ-4’-(6-ブロモヘキシルオキシ)ビフェニル(2)の合成＞
500 mL3つ口フラスコに4-シアノ-4’-ヒドロキシビフェニル5 g(25.6 mmol)、1,6-ジブロモヘキサン31.2 g(128 mmol)、炭酸カリウム5.3gおよびアセトン200
mLを加え、18時間加熱還流した。この反応混合物を冷却後ろ過して、得られたろ液からロータリーエバポレーターを用いてアセトンを減圧留去した。残渣をシリカゲルカラムクロマトグラフィー（展開液：ヘキサン／塩化メチレン＝１／１）および再結晶（溶媒：エタノール）により精製して化合物(2)6.7 g（18.7 mmol、収率73%）を得た。
＜4-シアノ-4’-(6-(2-アントラセンカルボニルオキシ)ヘキシルオキシ)ビフェニル(1)の合成＞
200mL3つ口フラスコに2-アントラセンカルボン酸0.5
g( 2.25 mmol)と脱水DMSO（ジメチルスルホキシド）45
mL加えた。さらにここにDBU(1,8-ジアザビシクロ[5.4.0]ウンデカ-7-エン)0.37 mL加え、50 ℃で30分間攪拌した。その後、4-シアノ-4-(6-ブロモヘキシルオキシ)ビフェニル0.73 g(2.0 mmol)加え、さらに50℃で４時間加熱した。冷却後、反応溶液を塩化メチレン200 mLと共に分液ロートに移し変え、飽和食塩水で2回洗浄した。その後、有機層を無水硫酸マグネシウムで乾燥、ろ過し、溶媒をロータリーエバポレーターで減圧留去した。残渣をシリカゲルカラムクロマトグラフィー（展開液：塩化メチレン）および再結晶（溶媒：エタノールとトルエンの混合溶媒）により精製して化合物(1)0.81 g(1.6 mmol、収率80%)を得た。
化合物1の構造は1H NMRおよびMSにより確認した。
1H NMR (CDCl3), d 1.62 (m, 4H), 1.89 (m, 4H), 6.97 (d, 2H), 7.47 (d, 2H), 7.54 (m, 2H),
7.58 (d, 2H), 7.63 (d, 2H), 8.01 (m, 4H), 8.44 (s, 1H), 8.55 (s, 1H), 8.80 (s,
1H). MS (MALDI-TOFMS)
m/z = Found (Calcd.): 499.7 [M+H]+ (500.2). (Synthesis of anthracene derivative 1)
A synthesis scheme of the anthracene derivative 1 is shown in FIG.

<Synthesis of 4-cyano-4 '-(6-bromohexyloxy) biphenyl (2)>
In a 500 mL three-neck flask, 4-cyano-4'-hydroxybiphenyl 5 g (25.6 mmol), 1,6-dibromohexane 31.2 g (128 mmol), potassium carbonate 5.3 g and acetone 200
mL was added and heated to reflux for 18 hours. The reaction mixture was cooled and then filtered, and acetone was distilled off from the obtained filtrate under reduced pressure using a rotary evaporator. The residue was purified by silica gel column chromatography (developing solution: hexane / methylene chloride = 1/1) and recrystallization (solvent: ethanol) to obtain 6.7 g (18.7 mmol, yield 73%) of compound (2).
<Synthesis of 4-cyano-4 '-(6- (2-anthracenecarbonyloxy) hexyloxy) biphenyl (1)>
2-Anthracenecarboxylic acid 0.5 in a 200 mL 3-neck flask
g (2.25 mmol) and dehydrated DMSO (dimethyl sulfoxide) 45
mL was added. Furthermore, 0.37 mL of DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) was added here, and it stirred at 50 degreeC for 30 minutes. Thereafter, 0.73 g (2.0 mmol) of 4-cyano-4- (6-bromohexyloxy) biphenyl was added, and the mixture was further heated at 50 ° C. for 4 hours. After cooling, the reaction solution was transferred to a separatory funnel with 200 mL of methylene chloride and washed twice with saturated brine. Thereafter, the organic layer was dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure using a rotary evaporator. The residue was purified by silica gel column chromatography (developing solution: methylene chloride) and recrystallization (solvent: mixed solvent of ethanol and toluene) to obtain 0.81 g (1.6 mmol, yield 80%) of compound (1).
The structure of Compound 1 was confirmed by 1 H NMR and MS.
1 H NMR (CDCl 3 ), d 1.62 (m, 4H), 1.89 (m, 4H), 6.97 (d, 2H), 7.47 (d, 2H), 7.54 (m, 2H),
7.58 (d, 2H), 7.63 (d, 2H), 8.01 (m, 4H), 8.44 (s, 1H), 8.55 (s, 1H), 8.80 (s,
1H). MS (MALDI-TOFMS)
m / z = Found (Calcd.): 499.7 [M + H] + (500.2).

（紫外光（波長：365 nm）照射による二量体の生成）
化合物1の2 mgを2枚のカバーグラスに挟み込み、ホットステージで150℃に加熱しながら、高圧水銀ランプと光学フィルターを用いて紫外光（波長：365 nm、強度：5 mW/cm2）の照射を一定時間行った。得られたサンプルをTHF溶媒に溶かしてGPC測定を行った。その結果を図4に示した。紫外光照射前は化合物1に由来するピーク（溶出時間：12.8分）のみが見られたが、照射時間が長くなるにつれ二量体に由来するピーク（溶出時間：12.1分）が現れ、20分間の照射では約90％の1が二量体に転化しているのが分かった。
化合物1を一旦150℃に加熱して紫外光を照射せずに室温に急冷したサンプルと、150℃で20分間紫外光を照射してから急冷したサンプルの写真を図5に示す。紫外光を照射していないサンプルは結晶化して光を散乱し白濁しているが、照射したサンプルは室温で固化しても透明であった。これは二量体がアモルファスであることを示している。 (Generation of dimers by irradiation with ultraviolet light (wavelength: 365 nm))
2 mg of Compound 1 is sandwiched between two cover glasses, heated to 150 ° C on a hot stage, and irradiated with ultraviolet light (wavelength: 365 nm, intensity: 5 mW / cm 2 ) using a high-pressure mercury lamp and optical filter. Irradiation was performed for a certain time. The obtained sample was dissolved in a THF solvent and GPC measurement was performed. The results are shown in FIG. Before the UV irradiation, only the peak derived from Compound 1 (elution time: 12.8 minutes) was observed, but as the irradiation time increased, the peak derived from the dimer (elution time: 12.1 minutes) appeared, 20 minutes It was found that about 90% of 1 was converted to dimer by irradiation.
FIG. 5 shows photographs of a sample in which Compound 1 was once heated to 150 ° C. and rapidly cooled to room temperature without being irradiated with ultraviolet light, and a sample that was rapidly cooled after being irradiated with ultraviolet light at 150 ° C. for 20 minutes. The sample not irradiated with ultraviolet light crystallized and scattered light and became cloudy, but the irradiated sample was transparent even when solidified at room temperature. This indicates that the dimer is amorphous.

＜アントラセン誘導体１の二量体の加熱によるアントラセン誘導体1の再生＞
前述の要領で20分間紫外光を照射して二量体にしておいたサンプルをある一定温度で5分間加熱した。得られたサンプルをTHF溶媒に溶かしGPC測定を行った。その結果を図6に示す。加熱することによってアントラセン誘導体1のピークが現れているのがわかる。また加熱温度が上昇するにつれアントラセン誘導体1の割合が増え、２２０℃ではほぼ全てのアントラセン誘導体１の二量体が、アントラセン誘導体1に戻っている。
紫外光照射前の化合物1、150℃で20分紫外光を照射したサンプル、さらにそのサンプルを220℃で5分間加熱したサンプルの1H NMRスペクトルを併せて図7に示す。
紫外光を照射したサンプルではアントラセン由来のピーク（8.81, 8.57, 8.45 ppm等）が消失し、代わりにアントラセン二量体に特徴的なピーク（4.62 ppm付近）が現れている。次にこれを220℃で加熱したサンプルでは、アントラセンの二量体のピークが消え、アントラセンのピークが復活しているのが分かる。この結果からも紫外光照射によりアントラセン誘導体1は二量体を形成し、その二量体は加熱することによりアントラセン誘導体1に戻ることが確認できた。 <Regeneration of Anthracene Derivative 1 by Heating Dimer of Anthracene Derivative 1>
The sample which had been irradiated with ultraviolet light for 20 minutes as described above to form a dimer was heated at a certain temperature for 5 minutes. The obtained sample was dissolved in a THF solvent and GPC measurement was performed. The results are shown in FIG. It can be seen that the peak of anthracene derivative 1 appears by heating. Further, as the heating temperature increases, the ratio of the anthracene derivative 1 increases. At 220 ° C., almost all dimers of the anthracene derivative 1 return to the anthracene derivative 1.
FIG. 7 shows the 1 H NMR spectrum of Compound 1 before irradiation with ultraviolet light, a sample irradiated with ultraviolet light at 150 ° C. for 20 minutes, and a sample obtained by heating the sample at 220 ° C. for 5 minutes.
In the sample irradiated with ultraviolet light, the anthracene-derived peak (8.81, 8.57, 8.45 ppm, etc.) disappears, and a peak characteristic of anthracene dimer (around 4.62 ppm) appears instead. Next, in the sample heated at 220 ° C., the anthracene dimer peak disappears and the anthracene peak is restored. Also from this result, it was confirmed that the anthracene derivative 1 formed a dimer by irradiation with ultraviolet light, and the dimer returned to the anthracene derivative 1 by heating.

（光によるパターン（情報）の書き込み・熱による消去・光による再書き込み）
化合物1を2 mg挟み込んだカバーグラスをホットステージにより150℃に加熱しながら、フォトマスク（金属製のしおり）を通して紫外光（365 nm、5 mW/cm2）を照射した。5分間照射して室温まで急冷したサンプルと用いたフォトマスクの写真を図８に示した。
紫外光が照射されていた部分は透明になり一方照射されていなかった部分は白濁してパターンが形成されている。このサンプルを220℃で5分加熱した後の写真を図９に示す。サンプル全体が結晶化したために、全体が白濁している。
さらにこのサンプルを用いて、150℃に加熱しながら初めとは異なるフォトマスクを用いて紫外光を５分間照射して急冷した。
得られたサンプルと用いたフォトマスクの写真を図10に示す。新たなパターンが形成されていることが確認できた。前述したとおり５分間の紫外光照射では化合物1の全てが二量化しているわけではないと考えられるが、系をアモルファス相にするにはこのように化合物1と二量体の混合物の状態でも可能であった。
(Light pattern (information) writing, heat erasing, light rewriting)
A cover glass sandwiched with 2 mg of Compound 1 was irradiated with ultraviolet light (365 nm, 5 mW / cm 2 ) through a photomask (metal bookmark) while being heated to 150 ° C. by a hot stage. A photograph of the photomask used and a sample that was irradiated for 5 minutes and rapidly cooled to room temperature is shown in FIG.
The portion irradiated with the ultraviolet light is transparent, while the portion not irradiated is clouded to form a pattern. A photograph after heating this sample at 220 ° C. for 5 minutes is shown in FIG. Since the whole sample crystallized, the whole is cloudy.
Furthermore, this sample was rapidly cooled by being irradiated with ultraviolet light for 5 minutes using a photomask different from the original while being heated to 150 ° C.
A photograph of the obtained sample and the photomask used is shown in FIG. It was confirmed that a new pattern was formed. As mentioned above, it is thought that not all of Compound 1 is dimerized by ultraviolet light irradiation for 5 minutes, but in order to make the system amorphous, the mixture of Compound 1 and dimer is also in this way. It was possible.

本発明のアントラセン誘導体及びアントラセン誘導体の二量体は、情報の書き込みには波長の短い（例えば254 nmなど）紫外光を用いることができ、書き換え可能な記録媒体であるCD-RWやDVD-RWに利用することができ、光情報媒体として産業上利用可能性が高いものである。   The anthracene derivative and dimer of the anthracene derivative of the present invention can use ultraviolet light having a short wavelength (for example, 254 nm) for writing information, and are rewritable recording media such as CD-RW and DVD-RW. The optical information medium is highly industrially applicable.

アントラセン誘導体１の構造Structure of anthracene derivative 1 誘導体１の光照射により得られる二量体の構造Structure of dimer obtained by light irradiation of derivative 1 化合物１の合成スキームSynthesis scheme of compound 1 化合物１に紫外光を一定時間照射したときのGPCチャートGPC chart when compound 1 is irradiated with ultraviolet light for a certain period of time 化合物1を150℃に加熱してそのまま急冷したサンプル（a）と紫外光を照射してから急冷したサンプル（b）の写真Photograph of sample (a) in which compound 1 was heated to 150 ° C and rapidly cooled as it was, and sample (b) in which sample 1 was rapidly cooled after being irradiated with ultraviolet light 化合物１の二量体を一定温度で５分間加熱したときのGPCチャートGPC chart when the dimer of Compound 1 is heated at a constant temperature for 5 minutes 1H NMRスペクトル：(a)化合物１、(b)化合物１に150℃で紫外光を20分間照射したサンプル、(c)さらにそのサンプルを220℃で5分間加熱したサンプル1H NMR spectrum: (a) Compound 1, (b) Sample irradiated with ultraviolet light at 150 ° C. for 20 minutes, (c) Sample heated further at 220 ° C. for 5 minutes フォトマスクに使用した金属製のしおり（左）と化合物１上に形成したパターン（右）Metal bookmark used for photomask (left) and pattern formed on compound 1 (right) 化合物1上に形成したパターンを加熱することにより消去したサンプルの写真Photo of the sample erased by heating the pattern formed on Compound 1 一度パターンを消去したサンプルに別のフォトマスク（左）を用いて書き込んだ新たなパターン（右）A new pattern (right) written using a different photomask (left) on the sample once erased

Claims (7)

一般式
Figure 2010006712
 （式中、ｎは１〜２０の整数である）で示されるアントラセン誘導体。 General formula
Figure 2010006712
 (Wherein n is an integer of 1 to 20). 化学式
Figure 2010006712
 で示されるアントラセン誘導体。
Chemical formula
Figure 2010006712
 Anthracene derivatives represented by
化学式
Figure 2010006712
 （式中、ｎは１〜２０の整数である）
で示されるアントラセン誘導体の二量体。 Chemical formula
Figure 2010006712
 (Where n is an integer from 1 to 20)
A dimer of an anthracene derivative represented by 請求項１または２に記載のアントラセン誘導体の薄膜を加熱溶融させて透明基板に塗布した光情報記録媒体。
An optical information recording medium, wherein the thin film of the anthracene derivative according to claim 1 or 2 is heated and melted and applied to a transparent substrate.
請求項４に記載の光情報記録媒体において、所望の箇所に紫外線を照射することにより、紫外線照射部を透明化して情報の記録を行い、該紫外線照射部を熱による白濁化を利用して情報の消去を行うことを特徴とする光情報記録媒体を利用した情報の記録・消去方法。   5. The optical information recording medium according to claim 4, wherein information is recorded by irradiating a desired portion with ultraviolet rays to make the ultraviolet irradiation portion transparent, and the ultraviolet irradiation portion is used to make information utilizing heat turbidity. A method for recording and erasing information using an optical information recording medium, wherein the information is erased. 紫外線照射部の透明化が、請求項３に記載のアントラセン誘導体の二量体への紫外線照射による二量化反応によるものであることを特徴とする請求項５に記載の情報記録・消去法。   6. The information recording / erasing method according to claim 5, wherein the ultraviolet irradiation part is made transparent by a dimerization reaction of the anthracene derivative dimer according to claim 3 by ultraviolet irradiation. 紫外線照射部の熱による白濁化が、請求項３に記載のアントラセン誘導体の二量体の単量体アントラセン誘導体への単量体化反応によるものである請求項５に記載の情報の記録・消去法。
6. The information recording and erasure according to claim 5, wherein the white turbidity due to heat in the ultraviolet irradiation part is due to a monomerization reaction of the dimer of the anthracene derivative according to claim 3 to the monomer anthracene derivative. Law.
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JP2012045864A (en) * 2010-08-27 2012-03-08 National Institute Of Advanced Industrial Science & Technology Optical information recording medium using liquid crystal polymer, optical information recording method, and method for manufacturing optical information recording medium
JP2012055814A (en) * 2010-09-07 2012-03-22 Chiba Univ Functional solubilizing agent
JP2014037496A (en) * 2012-08-17 2014-02-27 National Institute Of Advanced Industrial & Technology Resin composition capable of phase separation, writable resin composition for optical recording and optical recording medium using the same, method of recording information using the optical recording medium
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JP2008260846A (en) * 2007-04-12 2008-10-30 National Institute Of Advanced Industrial & Technology Photoreactive liquid crystal monomer and production method of main chain type liquid crystal polymer using the same
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012045864A (en) * 2010-08-27 2012-03-08 National Institute Of Advanced Industrial Science & Technology Optical information recording medium using liquid crystal polymer, optical information recording method, and method for manufacturing optical information recording medium
JP2012055814A (en) * 2010-09-07 2012-03-22 Chiba Univ Functional solubilizing agent
JP2014037496A (en) * 2012-08-17 2014-02-27 National Institute Of Advanced Industrial & Technology Resin composition capable of phase separation, writable resin composition for optical recording and optical recording medium using the same, method of recording information using the optical recording medium
US10465040B2 (en) 2014-10-31 2019-11-05 National Institute Of Advanced Industrial Science And Technology Photocurable composition and anthracene derivative used with the same

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