JPH05341433A - Spiropyran carrier and its production - Google Patents
Spiropyran carrier and its productionInfo
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- JPH05341433A JPH05341433A JP14929792A JP14929792A JPH05341433A JP H05341433 A JPH05341433 A JP H05341433A JP 14929792 A JP14929792 A JP 14929792A JP 14929792 A JP14929792 A JP 14929792A JP H05341433 A JPH05341433 A JP H05341433A
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- Prior art keywords
- spiropyran
- carrier
- coloring
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- time
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はスピロピラン担持体とそ
の製造方法に関する。FIELD OF THE INVENTION The present invention relates to a spiropyran carrier and a method for producing the same.
【０００２】[0002]
【従来の技術】従来、スピロピランは光照射により変色
をするフォトクロミック化合物として良く知られている
が、その担持法としては、高分子等をマトリックスとし
た担持法が主流であった。光照射により着消色を起こす
ため、装飾材料や表示材料、記録材料としての利用があ
るが、着消色の繰り返し耐久性が良くないため実用化に
至っているものは少ない。2. Description of the Related Art Conventionally, spiropyran is well known as a photochromic compound which is discolored by irradiation with light, but as a supporting method thereof, a supporting method using a polymer or the like as a matrix has been mainstream. It is used as a decorative material, a display material, and a recording material because it causes coloration / decoloration by light irradiation, but few of them have been put to practical use because of poor durability against repeated coloration / coloration.
【０００３】また、スピロピランは一般に以下のような
操作で着消色を行う。長波長に吸収を有する異性体（開
環した状態で可視域に吸収を持ち着色している。以後着
色体と呼ぶ。）に、その着色体の吸収する可視光を照射
し、消色させる。この時、着色体は、光反応により短波
長に吸収を有する異性体（閉環した状態で可視域に吸収
を持たず無色である。以後、無色体と呼ぶ。）に変換さ
れる。また、紫外光を照射し、閉環した無色体を開環さ
せて着色体に戻すことで着色させる。Further, spiropyran is generally colored and erased by the following operation. An isomer having absorption at a long wavelength (which is colored by absorbing light in the visible region in a ring-opened state; hereinafter referred to as a colored body) is irradiated with visible light absorbed by the colored body to be erased. At this time, the colored body is converted into an isomer having absorption at a short wavelength by a photoreaction (colorless without absorption in the visible region in the closed state, hereinafter referred to as colorless body). Further, it is colored by irradiating it with ultraviolet light to open the ring-closed colorless body and return it to the colored body.
【０００４】高分子に担持させる以外に、スピロピラン
を直接無機マトリックスであるシリカゲルに化学結合で
固定する方法（特開平３−９３８９１号公報）や、オキ
サジンを有機包接化合物でるシクロデキストリンに包接
して薄膜化する方法（特開平３−１８５０９０号公報）
がある。これらの担時法により、物理的強度の向上や紫
外線に対する耐性が向上し、着消色の耐久性も改善され
る。In addition to being supported on a polymer, a method of directly fixing spiropyran to silica gel, which is an inorganic matrix, by a chemical bond (JP-A-3-93891), or encapsulating oxazine in cyclodextrin, which is an organic inclusion compound. Thinning method (JP-A-3-185090)
There is. By these carrying methods, the physical strength and the resistance to ultraviolet rays are improved, and the durability of coloring and decoloring is also improved.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、従来の
方法は、着消色の繰り返し耐久性向上は不十分であっ
た。すなわち、従来のスピロピラン担持体は光照射時に
起こる劣化反応のために、着消色の繰り返し耐久性が低
いという課題があった。また、従来の着消色の繰り返し
耐久性の良いフォトクロミック化合物を得るには、特殊
な化合物を合成する必要があり、簡便迅速に繰り返し耐
久性に優れたもの担持体が得られないという課題があっ
た。However, the conventional methods have not been sufficiently improved in the durability against repeated coloring / decoloring. That is, the conventional spiropyran support has a problem of low durability against repeated color fading due to a deterioration reaction that occurs upon light irradiation. Further, in order to obtain a conventional photochromic compound having good durability against repeated coloring / decoloring, it is necessary to synthesize a special compound, and there is a problem that a carrier having excellent durability against repeated durability cannot be obtained easily and quickly. It was
【０００６】本発明は、前記従来技術の課題を解決する
ため、着消色の繰返し特性に優れたスピロピラン担持体
とその簡便で迅速な製造方法とを提供することを目的と
する。In order to solve the above-mentioned problems of the prior art, it is an object of the present invention to provide a spiropyran support having excellent repeating characteristics of coloration and decoloration, and a simple and rapid production method thereof.
【０００７】[0007]
【課題を解決するための手段】前記目的を達成するた
め、本発明のスピロピラン担持体は、表面にシラノール
基を有する多孔質体に、開環したスピロピランを吸着さ
せてなるという構成からなる。To achieve the above object, the spiropyran-supporting material of the present invention has a structure in which a ring-opened spiropyran is adsorbed on a porous material having silanol groups on its surface.
【０００８】前記構成においては、光照射に対して可逆
的な異性化反応を示し、変色することが好ましい。また
前記構成においては、スピロピラン担持体の着色時の色
が黄色または橙色であることが好ましい。In the above-mentioned constitution, it is preferable that a reversible isomerization reaction is caused by light irradiation and the color is changed. Further, in the above-mentioned constitution, it is preferable that the color of the spiropyran-supporting body at the time of coloring is yellow or orange.
【０００９】また前記構成においては、スピロピランを
担持させた表面にシラノ−ル基を有する多孔質体の微小
体を高分子中に分散してなることが好ましい。また前記
構成においては、スピロピランが前記式（化１）の構造
を有するスピロピランであることが好ましい。ここでＲ
1 ，Ｒ2 はＨまたは有機基であり、好ましくはアルキル
基、アルコキシ基、アリール基、シクロアルキル基、ア
ルキルエステル基及びこれらの誘導体である。In the above structure, it is preferable that fine particles of a porous material having a silanol group are dispersed in a polymer on the surface supporting spiropyran. Further, in the above structure, it is preferable that the spiropyran is a spiropyran having the structure of the above formula (Formula 1). Where R
1 and R 2 are H or an organic group, preferably an alkyl group, an alkoxy group, an aryl group, a cycloalkyl group, an alkyl ester group and derivatives thereof.
【００１０】また前記構成においては、スピロピランが
前記式（化２）（化３）または（化４）のいずれかの構
造を有するスピロピランであることが好ましい。次に本
発明のスピロピラン担持体の第１の製造方法は、表面に
シラノール基を有する多孔質体にスピロピランを吸着さ
せる際に、スピロピランの溶液に紫外光を照射するとい
う構成からなる。Further, in the above constitution, it is preferable that the spiropyran is a spiropyran having a structure of any one of the above formulas (Formula 2) (Formula 3) or (Formula 4). Next, the first method for producing a spiropyran-supported material of the present invention comprises irradiating a solution of spiropyran with ultraviolet light when adsorbing spiropyran on a porous material having a silanol group on the surface.
【００１１】次に本発明のスピロピラン担持体の第２の
製造方法は、スピロピランと非極性溶媒とのスピロピラ
ン溶液から、表面にシラノール基を有する多孔質体に前
記溶液中の開環したスピロピランを吸着させて製造する
ことを特徴とする。Next, the second method for producing a spiropyran-supported material of the present invention is to adsorb the ring-opened spiropyran in the above solution from a spiropyran solution of spiropyran and a nonpolar solvent onto a porous material having silanol groups on the surface. It is characterized by being manufactured.
【００１２】前記構成においては、スピロピランと非極
性溶媒とのスピロピラン溶液から、表面にシラノール基
を有する多孔質体に前記溶液中の開環したスピロピラン
を吸着させたあと、極性溶媒に浸す処理を行うことが好
ましい。In the above-mentioned constitution, from the spiropyran solution of spiropyran and a non-polar solvent, the ring-opened spiropyran in the solution is adsorbed to the porous body having a silanol group on the surface, and then the solution is immersed in a polar solvent. It is preferable.
【００１３】[0013]
【作用】前記した本発明スピロピラン担持体の構成によ
れば、シラノール基を有する多孔質体表面に吸着する
と、シラノール基の極性の高さのために、スピロピラン
と多孔質体表面の間には特別な吸着状態が生じ、このた
めに着色した状態の吸収波長も短波長にシフトする。そ
の結果、得られたスピロピラン担持体の着消色の繰り返
し耐久性も大幅に改善される。According to the above-mentioned structure of the spiropyran-supported material of the present invention, when it is adsorbed on the surface of the porous body having a silanol group, the spiropyran and the surface of the porous body have a special property due to the high polarity of the silanol group. A different adsorption state occurs, and as a result, the absorption wavelength in the colored state also shifts to a shorter wavelength. As a result, the durability of the resulting spiropyran-supported material against repeated coloring and decoloring is also greatly improved.
【００１４】また、本発明のスピロピラン担持体は、紫
外線を照射してスピロピランを着色体にして吸着させる
製造方法を用いれば、短時間で簡便に得られる。これ
は、特別な化合物の合成をする必要がないのに加えて、
多孔質体表面の極性が高く、無色体と着色体のうちの極
性の高い着色体の吸着速度が高いためである。Further, the spiropyran-supported material of the present invention can be easily obtained in a short time by using a production method of irradiating ultraviolet rays to adsorb spiropyran as a colored material. This is in addition to the need to synthesize special compounds,
This is because the surface of the porous body has a high polarity, and the colored body having a high polarity among the colorless body and the colored body has a high adsorption rate.
【００１５】また、本発明のスピロピラン担持体の製造
は、非極性溶媒からの吸着によると、短時間で可能にな
る。吸着する着色体の極性が高いために非極性溶媒中に
溶解しているよりは、極性の高い多孔質体表面に吸着し
ようするからである。この時得られる担持体の色相は、
極性溶媒のときとは異なる。使用時の色相を変えたいと
きは極性の異なる溶媒に浸すことで異なった色相のスピ
ロピラン担持体の製造が可能になる。これは、極性の異
なる溶媒に浸すことで吸着状態が微妙に変化するためで
ある。The production of the spiropyran-supported material of the present invention can be carried out in a short time by adsorption from a nonpolar solvent. This is because the colorant to be adsorbed has a high polarity, and thus the colorant tends to be adsorbed on the surface of the porous body having a high polarity rather than being dissolved in the nonpolar solvent. The hue of the carrier obtained at this time is
Different from polar solvents. When it is desired to change the hue at the time of use, it can be prepared by immersing it in a solvent having a different polarity to produce a spiropyran carrier having a different hue. This is because the adsorption state is slightly changed by immersing in a solvent having different polarities.
【００１６】[0016]
【実施例】以下実施例を用いて本発明をさらに具体的に
説明する。本発明のスピロピラン担持体の特徴はスピロ
ピランを表面にシラノール基を有する多孔質体に担持さ
せてなることである。多孔質体の孔径や多孔度について
は市販されているシラノール基を表面に有する多孔質体
である多孔質ガラスはほとんどが平均４０オングストロ
ーム（Ａ）程度であり、孔の占める体積が全体の２〜３
割前後でこの程度であれば問題ない。また以後の実施例
では多孔質体として多孔質ガラス板を主に用いている
が、形状については、球体や繊維状のもの、ウィスカー
等でもよく、特にその形状等にはとらわれない。特に多
孔質ガラスが微小体であるときには、微小体に溶液中か
らスピロピランを吸着させておき、さらにこれを高分子
材料などに担持させることが可能である。微小体の大き
さがサブμｍ以下の大きさの場合は透明度の良い担持体
が得られる。The present invention will be described in more detail with reference to the following examples. A feature of the spiropyran-supported material of the present invention is that spiropyran is supported on a porous material having a silanol group on its surface. Regarding the pore size and the porosity of the porous body, most of the commercially available porous glass which is a porous body having a silanol group on the surface has an average of about 40 angstrom (A), and the volume occupied by the pores is 2 to Three
There is no problem if it is around this level. Further, in the following examples, a porous glass plate is mainly used as the porous body, but the shape may be a sphere, a fibrous shape, a whisker, or the like, and is not particularly limited to the shape or the like. In particular, when the porous glass is a microscopic body, it is possible to adsorb spiropyran from the solution to the microscopic body and further to support it on a polymer material or the like. When the size of the fine particles is sub-μm or less, a carrier having good transparency can be obtained.
【００１７】以後で述べる実施例ではスピロピラン原料
の一例として下記式（化５、スピロピラン１）（化６、
スピロピラン２）（化７、スピロピラン３）の構造を有
する化合物を用いたが、スピロピランであれば特に制限
を受けない。なお下記式化合物は、閉環時のものを示し
ているが、表面にシラノール基を有する多孔質体に担持
させることにより開環させる。In the examples described below, as an example of a spiropyran raw material, the following formula (formula 5, spiropyran 1) (formula 6,
A compound having a structure of spiropyran 2) (Chemical formula 7, spiropyran 3) was used, but spiropyran is not particularly limited. The compound of the following formula, which is shown at the time of ring closure, is opened by supporting it on a porous body having a silanol group on the surface.
【００１８】[0018]
【化５】 [Chemical 5]
【００１９】[0019]
【化６】 [Chemical 6]
【００２０】[0020]
【化７】 [Chemical 7]
【００２１】また、本発明の担持体の着色体の色は、高
分子中に分散された場合よりも、浅くなる（すなわち、
吸収帯が短波長にシフトする）が、着消色の繰り返し耐
久性の観点からは色の浅いもの、特に黄色から橙色（吸
収帯が４５０ｎｍ程度以下）のものが効果的である。Further, the color of the colored body of the carrier of the present invention becomes lighter than that when dispersed in a polymer (that is,
Although the absorption band shifts to a short wavelength), from the viewpoint of repeated durability of coloration and decoloration, a light color, particularly a yellow to orange color (absorption band of about 450 nm or less) is effective.
【００２２】また、製造時には、非極性溶媒のスピロピ
ラン溶液から吸着を行なうと吸着が速くなる。さらに、
色相を浅くしたい時には極性溶媒に浸すことにより目的
の担持体が得られる。この時使用する非極性溶媒は、ト
ルエン等のベンゼン置換体等が有効であるがヘキサン、
オクタン等の不飽和炭化水素が特に効果的である。極性
溶媒としては、エタノール等のアルコールが有効である
が、特にアセトニトリルが好ましい。Further, at the time of production, if adsorption is carried out from a spiropyran solution of a nonpolar solvent, the adsorption will be accelerated. further,
When it is desired to make the hue shallow, the target carrier can be obtained by immersing it in a polar solvent. As the non-polar solvent used at this time, benzene substitution products such as toluene are effective, but hexane,
Unsaturated hydrocarbons such as octane are especially effective. Alcohol such as ethanol is effective as the polar solvent, and acetonitrile is particularly preferable.
【００２３】また、本発明の担持体は加熱により着色す
るため、紫外線を用いる必要がなくなる。さらに、担持
体の一部を加熱して全面に可視光を照射すると、加熱し
た部分に着色パターンを形成でき、可視光を遮るとパタ
ーンの消去ができる。すなはち、周囲の明るさに依存し
てパターンを表示できる。また、通常のスピロピラン担
持体は一つの色相しか表せないが、本発明の担持体は、
着色状態で気体あるいは液体、特に水が付着すると色相
が深くなり、天候や特定の気体等の有無により２種以上
の色相をだすことができる。Since the carrier of the present invention is colored by heating, it is not necessary to use ultraviolet rays. Furthermore, when a part of the carrier is heated and the entire surface is irradiated with visible light, a colored pattern can be formed on the heated part, and the pattern can be erased by blocking visible light. That is, the pattern can be displayed depending on the ambient brightness. Further, the usual spiropyran carrier can represent only one hue, but the carrier of the present invention is
When a gas or liquid, especially water, adheres in a colored state, the hue becomes deep, and two or more kinds of hues can be produced depending on the weather or the presence or absence of a specific gas.
【００２４】実施例１ スピロピラン２（日本感光色素社製）のアセトニトリル
溶液に紫外線ランプで紫外線（３６６ｎｍ）を照射し溶
液を着色させたあと、多孔質ガラス（コ−ニング社製、
７９３０）を９時間この溶液に浸してスピロピラン担持
体を作成した。これを、１Torrの減圧下室温で２４時間
乾燥した。得られた担持体は黄色であり乾燥前後で変化
はなかった。この時の吸収スペクトルを図１のＡ線に示
す。Example 1 Acetonitrile solution of spiropyran 2 (manufactured by Nihon Senshi Dye Co., Ltd.) was irradiated with ultraviolet rays (366 nm) by an ultraviolet lamp to color the solution, and then porous glass (manufactured by Corning Co.,
7930) was immersed in this solution for 9 hours to prepare a spiropyran carrier. This was dried at room temperature under reduced pressure of 1 Torr for 24 hours. The obtained carrier was yellow and did not change before and after drying. The absorption spectrum at this time is shown by line A in FIG.
【００２５】この担持体に、ハロゲンランプと分光器を
組み合わせて、４４０ｎｍの可視光を２０ｍＪ／ｃｍ2
照射すると、初期の黄色はほぼ無色になった。この時の
吸収スペクトルを図１のＢ線に示す。これに、紫外線ラ
ンプで３６６ｎｍの紫外光を４ｍＪ／ｃｍ2 照射すると
再び黄色に戻った。１０００回繰り返しを行なったが、
着色時の吸光度は初期の８割以上であった。A halogen lamp and a spectroscope were combined with this carrier, and visible light of 440 nm was emitted at 20 mJ / cm 2.
Upon irradiation, the initial yellow color became almost colorless. The absorption spectrum at this time is shown by the line B in FIG. When this was irradiated with 4 mJ / cm 2 of 366 nm ultraviolet light from an ultraviolet lamp, it returned to yellow again. Repeated 1000 times,
The absorbance at the time of coloring was 80% or more of the initial value.
【００２６】比較例１ スピロピラン２をポリビニルブチラ−ル（ポリビニルブ
チラ−ルＢＬ−Ｓ、セキスイ社製）と重量比で１対１０
０の割合でトルエンに溶解させた溶液からスピンコ−テ
ィングによりポリエチレンテレフタレートフィルム
（“テトロン”（登録商標）フィルム、帝人社製）上に
薄膜化した。これを１Ｔｏｒｒの減圧下室温で２４時間
乾燥した。得られた担持体は無色であった。これに紫外
線ランプで３６６ｎｍの紫外光を３０ｍＪ／ｃｍ2 照射
すると赤色に着色した。さらにハロゲンランプと分光器
を組み合わせて、５６０ｎｍの可視光を１１００ｍＪ／
ｃｍ2照射すると初期の赤色はほぼ無色になった。この
繰り返しを１２回くり返すと着色時の吸光度は初期の８
割に低下した。Comparative Example 1 Spiropyran 2 was mixed with polyvinyl butyral (polyvinyl butyral BL-S, manufactured by Sekisui) in a weight ratio of 1:10.
The solution was dissolved in toluene at a ratio of 0 to form a thin film on a polyethylene terephthalate film (“Tetron” (registered trademark) film, manufactured by Teijin Ltd.) by spin coating. This was dried under reduced pressure of 1 Torr at room temperature for 24 hours. The resulting carrier was colorless. When this was irradiated with 30 mJ / cm 2 of 366 nm ultraviolet light from an ultraviolet lamp, it was colored red. Furthermore, by combining a halogen lamp and a spectroscope, visible light of 560 nm is 1100 mJ /
Upon irradiation with cm 2 , the initial red color became almost colorless. When this repetition is repeated 12 times, the absorbance at the time of coloring is 8
It fell relatively.
【００２７】比較例２ 多孔質体でないガラス板（石英ガラス、大興製作所社
製）を重クロム酸カリウム、硫酸混液で親水性処理して
シラノール基を表面に出させたものに、スピロピラン２
を１層、ＬＢ法によって吸着させた。これを、１Torrの
減圧下室温で２４時間乾燥した。最初無色で紫外線照射
で赤色に発色した。これについて、比較例１と同じ条件
で着消色の繰り返しを行なったが、９回後には着色時の
吸光度が初期の８割以下になった。Comparative Example 2 Spiropyran 2 was prepared by subjecting a glass plate (quartz glass, manufactured by Daiko Seisakusho Co., Ltd.) which is not a porous body to hydrophilic treatment with a mixed solution of potassium dichromate and sulfuric acid to expose silanol groups on the surface.
Was adsorbed by the LB method. This was dried at room temperature under reduced pressure of 1 Torr for 24 hours. It was initially colorless and developed a red color upon irradiation with ultraviolet light. About this, the coloring and decoloring was repeated under the same conditions as in Comparative Example 1, but after 9 times, the absorbance during coloring was 80% or less of the initial value.
【００２８】比較例３ スピロピラン２のアセトニトリル溶液に、多孔質ガラス
を３０時間この溶液に浸して、スピロピラン担持体を作
製した。これを、１Ｔｏｒｒの減圧下室温で２４時間乾
燥した。このスピロピラン担持体は最初黄色に着色して
おり、その着色の度合は実施例１と同等であった。ま
た、着消色の特性も実施例１に述べた担持体と同等であ
った。Comparative Example 3 Porous glass was immersed in an acetonitrile solution of spiropyran 2 for 30 hours to prepare a spiropyran-supported body. This was dried at room temperature under reduced pressure of 1 Torr for 24 hours. The spiropyran-loaded material was initially colored yellow, and the degree of coloring was the same as in Example 1. In addition, the characteristics of color fading and decoloring were similar to those of the carrier described in Example 1.
【００２９】比較例４ 実施例１と同じ条件で、スピロピラン以外のフォトクロ
ミック化合物である下記式（化８）で示すオキサジン１
及び下記式（化９）で示すフルギド１を用いて各々スピ
ロピラン担持体を作製した。両スピロピラン担持体とも
光照射による比較例１の条件で光照射を行なったが着消
色が起こらなかった。Comparative Example 4 Under the same conditions as in Example 1, Oxazine 1 represented by the following formula (Formula 8) which is a photochromic compound other than spiropyran.
Further, fulgide 1 represented by the following formula (Formula 9) was used to prepare spiropyran-supported bodies. Both spiropyran-supported materials were irradiated with light under the conditions of Comparative Example 1, but no discoloration occurred.
【００３０】[0030]
【化８】 [Chemical 8]
【００３１】[0031]
【化９】 [Chemical 9]
【００３２】表１に実施例１と比較例１〜４の吸着時
間、着色時の吸光度が初期の８割になる繰り返し回数、
着色時の色、消色時の照射エネルギをまとめる。この様
に、シラノール基を有する多孔質体にスピロピランを担
持せたときのみ、繰り返し特性が向上した。また、弱い
照射エネルギで着消色を起こすことが可能になった。ま
た、紫外線照射してスピロピランを吸着させることでス
ピロピラン担持体の製造時間が短縮された。Table 1 shows the adsorption times of Example 1 and Comparative Examples 1 to 4, the number of repetitions when the absorbance during coloring was 80% of the initial value,
Summarize the colors when coloring and the irradiation energy when erasing. Thus, the repeating property was improved only when the spiropyran was supported on the porous body having a silanol group. In addition, it is possible to cause coloration and decoloring with weak irradiation energy. In addition, the production time of the spiropyran-supported body was shortened by irradiating it with ultraviolet rays to adsorb spiropyran.
【００３３】[0033]
【表１】 [Table 1]
【００３４】実施例２ スピロピラン２のｎ−オクタン溶液を作成し、多孔質ガ
ラスを１．５時間この溶液に浸してスピロピラン担持体
を作成した。これを、１Ｔｏｒｒの減圧下室温で２４時
間乾燥した。得られた担持体は赤色で乾燥前後で変化は
なかった。Example 2 An n-octane solution of spiropyran 2 was prepared, and porous glass was immersed in this solution for 1.5 hours to prepare a spiropyran-supported body. This was dried at room temperature under reduced pressure of 1 Torr for 24 hours. The resulting carrier was red and did not change before and after drying.
【００３５】この担持体に、ハロゲンランプと分光器を
組み合わせて、４８０ｎｍの可視光を２００ｍＪ／ｃｍ
2 照射すると初期の赤色はほぼ無色になった。これに、
紫外線ランプで３６６ｎｍの紫外光を１２ｍＪ／ｃｍ2
照射すると再び赤色に戻った。このようなサイクルを２
００回繰り返したが、着色時の吸光度は初期の８割以上
であった。A halogen lamp and a spectroscope were combined with this carrier, and visible light of 480 nm was 200 mJ / cm 2.
After irradiation, the initial red color became almost colorless. to this,
12mJ / cm 2 of 366nm UV light with UV lamp
Upon irradiation, it returned to red again. 2 such cycles
Repeated 00 times, the absorbance at the time of coloring was 80% or more of the initial value.
【００３６】表２に実施例２の吸着時間、着色時の吸光
度が初期の８割になる繰り返し回数、着色時の色、消色
時の照射エネルギをまとめる。このように、吸着時の溶
媒を変えることで吸着時間を短くでき、着色時の色相も
変えることがでた。この時着消色の繰り返しや感度特性
も良好であった。Table 2 summarizes the adsorption time, the number of repetitions when the absorbance at the time of coloring is 80% of the initial value, the color at the time of coloring, and the irradiation energy at the time of erasing in Table 2. Thus, the adsorption time can be shortened by changing the solvent at the time of adsorption, and the hue at the time of coloring can also be changed. At this time, the repetition of coloration and decoloring and the sensitivity characteristics were good.
【００３７】[0037]
【表２】 [Table 2]
【００３８】実施例３ スピロピラン２のシクロヘキサン溶液を作成し、多孔質
ガラスを１．８時間この溶液に浸してスピロピラン担持
体を作成した。この担持体の色は赤色であった。これ
を、１Torrの減圧下室温で２４時間乾燥した。さらに１
０分間超音波洗浄器中でアセトニトリルに浸して超音波
処理を行なうことで、黄色に着色した担持体が得られ
た。Example 3 A cyclohexane solution of spiropyran 2 was prepared, and porous glass was immersed in this solution for 1.8 hours to prepare a spiropyran-supported body. The color of this carrier was red. This was dried at room temperature under reduced pressure of 1 Torr for 24 hours. 1 more
By immersing it in acetonitrile in an ultrasonic cleaner for 0 minutes and performing ultrasonic treatment, a yellow colored carrier was obtained.
【００３９】これに実施例１と同じ条件で着消色の繰り
返しを行なったところ、同様に黄色と無色状態の間を１
０００回往復しても着色状態の吸光度は初期の８割以上
であった。When the coloration and decoloration were repeated under the same conditions as in Example 1, the color between the yellow and colorless states was 1
Even after reciprocating 000 times, the absorbance in the colored state was 80% or more of the initial value.
【００４０】表３に実施例３の吸着時間、着色時の吸光
度が初期の８割になる繰り返し回数、着色時の色、消色
時の照射エネルギをまとめる。この様に、非極性溶媒中
からスピロピランを吸着させた後、極性溶媒に浸すこと
で、短時間の内に、好みの色に着色して繰り返し特性、
感度に優れたスピロピラン担持体を製造することができ
た。Table 3 summarizes the adsorption time of Example 3, the number of repetitions when the absorbance at the time of coloring becomes 80% of the initial value, the color at the time of coloring, and the irradiation energy at the time of erasing. In this way, after adsorbing spiropyran from a non-polar solvent, by immersing it in a polar solvent, within a short time, it is colored to a desired color and repeated characteristics,
It was possible to produce a spiropyran carrier having excellent sensitivity.
【００４１】[0041]
【表３】 [Table 3]
【００４２】実施例４ スピロピラン２のアセトニトリル溶液に紫外線ランプで
紫外線を照射し溶液を着色させて、実施例１の多孔質ガ
ラスを平均粒径３μｍに粉砕したものを、９時間この溶
液に浸した。これをポリビニルブチラール中に分散させ
てアルミ板上に製膜した。製膜はスピンコート法を採用
し、溶媒はトルエンを用いた。この膜を、１Ｔｏｒｒの
減圧下室温で２４時間乾燥した。得られたスピロピラン
担持体は赤色であった。Example 4 An acetonitrile solution of spiropyran 2 was irradiated with ultraviolet rays from an ultraviolet lamp to color the solution, and the porous glass of Example 1 was crushed to have an average particle size of 3 μm, and immersed in this solution for 9 hours. . This was dispersed in polyvinyl butyral to form a film on an aluminum plate. The film was formed by the spin coating method and the solvent was toluene. The film was dried under reduced pressure of 1 Torr at room temperature for 24 hours. The resulting spiropyran-loaded material was red.
【００４３】これに実施例２と同じ条件で、着消色の繰
り返しを行なった。このようなサイクルを３００回繰り
返したが、着色時の吸光度は初期の８割以上であった。
表４に実施例４の吸着時間、着色時の吸光度が初期の８
割になる繰り返し回数、着色時の色、消色時の照射エネ
ルギをまとめる。Under the same conditions as in Example 2, the coloring and decoloring were repeated. Such a cycle was repeated 300 times, but the absorbance at the time of coloring was 80% or more of the initial value.
In Table 4, the adsorption time of Example 4 and the absorbance at the time of coloring were 8
Summarize the number of repeated repetitions, the color when coloring, and the irradiation energy when erasing.
【００４４】[0044]
【表４】 [Table 4]
【００４５】このように、多孔質体の微粒子を高分子に
分散する方法でも、着消色の繰り返し特性も良好なスピ
ロピラン担持体を形成することが可能になり、任意の形
の表面にスピロピラン担持体を形成できるようになる。As described above, even by the method of dispersing fine particles of a porous material in a polymer, it is possible to form a spiropyran carrier having good repeating characteristics of coloration and decoloration, and spiropyran-supported on a surface of any shape. Be able to form the body.
【００４６】実施例５ 実施例１、２で得られたスピロピラン担持体にハロゲン
ランプを照射して消色させた後、５０℃に加熱すること
により再着色した。この様な繰り返しを１０００回行な
ったが、着色時の吸光度は初期の８割以上あった。Example 5 The spiropyran-supporting bodies obtained in Examples 1 and 2 were irradiated with a halogen lamp to be decolored and then recolored by heating at 50 ° C. Such repetition was repeated 1000 times, and the absorbance at the time of coloring was 80% or more of the initial value.
【００４７】また、日中通常の明るさの下、担持体の一
部をヒータで５０℃に加熱することで、加熱された部分
が着色し、その他の部分は無色になった。夜間、暗所で
全体が着色してきて、加熱している部分とそれ以外の部
分は判別がつかなくなった。これは周囲の明るさの変化
に応じて繰り返した。By heating a part of the carrier to 50 ° C. with a heater under normal brightness during the daytime, the heated part became colored and the other part became colorless. At night, the whole was colored in the dark, and the heated part and the other part were indistinguishable. This was repeated according to changes in ambient brightness.
【００４８】本発明のスピロピラン担持体を用いること
で、紫外光源なしで着色が可能になり、さらに部分的に
加熱して５０℃に昇温させることで、担持体の置かれた
場所の明るさに応じて異なった着色パターンを表示する
ことが可能になる。By using the spiropyran carrier of the present invention, coloring can be carried out without an ultraviolet light source, and by further partially heating to raise the temperature to 50 ° C., the brightness of the place where the carrier is placed can be improved. It is possible to display different coloring patterns depending on the.
【００４９】実施例６ 実施例１、２で得られたスピロピラン担持体には黄色で
あったが、これにアンモニアガスを触れさせると赤色に
着色した、さらに塩化水素ガスに触れさせると再び黄色
に戻った。また、初期の黄色の状態に水滴を滴下する
と、その部分のみが青く変色したが、時間経過にともな
い水が蒸発すると再び黄色に戻った。後は実施例１、３
の着消色特性を示した。この様に、一つのフォトクロミ
ック化合物を用いても、液体、気体、特に水との接触を
利用することで、多様な色相のパターンを形成すること
が可能になった。Example 6 The spiropyran-supporting bodies obtained in Examples 1 and 2 were yellow, but when they were contacted with ammonia gas, they were colored red, and when they were contacted with hydrogen chloride gas, they became yellow again. I'm back. Also, when a water drop was dropped in the initial yellow state, only that part turned blue, but when the water evaporated over time, it returned to yellow again. After that, Examples 1 and 3
The coloration and decoloring characteristics of As described above, even if one photochromic compound is used, it is possible to form patterns of various hues by utilizing contact with liquid, gas, especially water.
【００５０】実施例７ スピロピラン１のエタノ−ル溶液に紫外線ランプを照射
して、多孔質ガラスを６時間浸してスピロピラン担持体
を作成した。これを、１Ｔｏｒｒの減圧下室温で２４時
間乾燥した。得られた、担持体は橙色でり乾燥前後で変
化はなかった。Example 7 An ethanol solution of spiropyran 1 was irradiated with an ultraviolet lamp and the porous glass was immersed for 6 hours to prepare a spiropyran carrier. This was dried at room temperature under reduced pressure of 1 Torr for 24 hours. The obtained carrier was orange and did not change before and after drying.
【００５１】この担持体に、実施例１同様にハロゲンラ
ンプと分光器を組み合わせて、４２０ｎｍの可視光を１
８ｍＪ／ｃｍ2 照射すると初期の橙色はほぼ無色になっ
た。これに、紫外線ランプで３６６ｎｍの紫外光を５ｍ
Ｊ／ｃｍ2 照射すると再び橙色に戻った。このようなサ
イクルを６００回繰り返したが、着色時の吸光度は初期
の８割以上であった。A halogen lamp and a spectroscope were combined with this carrier in the same manner as in Example 1 to emit visible light of 420 nm.
Upon irradiation with 8 mJ / cm 2 , the initial orange color became almost colorless. In addition to this, ultraviolet light of 366 nm is emitted for 5 m with an ultraviolet lamp.
When it was irradiated with J / cm 2, it returned to orange again. Such a cycle was repeated 600 times, but the absorbance at the time of coloring was 80% or more of the initial value.
【００５２】また、この繰り返しで紫外線の代わり５０
度に加熱することによっても再着色をし、同様に６００
回のサイクル後、着色時の吸光度は初期の８割以上であ
った。By repeating this process, instead of using ultraviolet rays, 50
It is also recolored by heating it to 600
After cycling, the absorbance at the time of coloring was 80% or more of the initial value.
【００５３】また、水蒸気に接しさせることで暗青色に
変色した 比較例５ スピロピラン１をポリビニルブチラ−ルと重量比で１対
１００の割合でトルエンに溶解させた溶液からスピンコ
−ティングによりポリエチレンテレフタレ−ト上に薄膜
化した。これを、１Ｔｏｒｒの減圧下室温で２４時間乾
燥した。得られた担持体は無色であった。これに紫外線
ランプで３６６ｎｍの紫外光を３０ｍＪ／ｃｍ2 照射す
ると赤色に着色した。さらに、ハロゲンランプと分光器
を組み合わせて、５６０ｎｍの可視光を８００ｍＪ／ｃ
ｍ2 照射すると初期の赤色はほぼ無色になった。この繰
り返しを８回繰り返すと、着色時の吸光度は初期の８割
以下になっていた。Comparative Example 5 Spiropyran 1, which turned dark blue by contact with water vapor, was dissolved in polyvinyl butyral in toluene at a ratio of 1: 100 by weight. It was made into a thin film on a sauce. This was dried at room temperature under reduced pressure of 1 Torr for 24 hours. The resulting carrier was colorless. When this was irradiated with 30 mJ / cm 2 of 366 nm ultraviolet light from an ultraviolet lamp, it was colored red. Furthermore, by combining a halogen lamp and a spectroscope, visible light of 560 nm is 800 mJ / c.
Upon irradiation with m 2 , the initial red color became almost colorless. When this repetition was repeated 8 times, the absorbance at the time of coloring was 80% or less of the initial value.
【００５４】また、５０℃に加熱することによって着色
は起こらなず、水蒸気との接触による色相の変化もなか
った。表５に実施例５の吸着時間、着色時の吸光度が初
期の８割になる繰り返し回数、着色時の色、消色時の照
射エネルギをまとめる。このように、長鎖を有しないス
ピロピラン１を用いた本発明のスピロピラン担持体も二
本の長鎖を有するスピロピラン２を用いた担持体と同様
の着消色特性を示した。When heated to 50 ° C., coloring did not occur, and there was no change in hue due to contact with water vapor. Table 5 summarizes the adsorption time, the number of repetitions when the absorbance at the time of coloring is 80% of the initial value, the color at the time of coloring, and the irradiation energy at the time of erasing in Table 5. As described above, the spiropyran carrier of the present invention using spiropyran 1 having no long chain also exhibited the same coloration and decoloring characteristics as the carrier using spiropyran 2 having two long chains.
【００５５】[0055]
【表５】 [Table 5]
【００５６】実施例８ スピロピラン３のアセトニトリル溶液に紫外線ランプを
照射して、この溶液に多孔質ガラスを８時間浸してスピ
ロピラン担持体を作成した。これを、１Ｔｏｒｒの減圧
下室温で２４時間乾燥した。得られた、担持体は橙色で
乾燥前後で変化はなかった。Example 8 An acetonitrile solution of spiropyran 3 was irradiated with an ultraviolet lamp, and porous glass was immersed in this solution for 8 hours to prepare a spiropyran-supported body. This was dried at room temperature under reduced pressure of 1 Torr for 24 hours. The obtained carrier was orange and did not change before and after drying.
【００５７】この担持体に、実施例１同様にハロゲンラ
ンプと分光器を組み合わせて、４４０ｎｍの可視光を２
１ｍＪ／ｃｍ2 照射すると初期の橙色はほぼ無色になっ
た。これに、紫外線ランプで３６６ｎｍの紫外光を３ｍ
Ｊ／ｃｍ2 照射すると再び橙色に戻った。このようなサ
イクルを１０００回繰り返したが、着色時の吸光度は初
期の８割以上であった。A halogen lamp and a spectroscope were combined with this carrier in the same manner as in Example 1 to emit visible light of 440 nm.
Upon irradiation with 1 mJ / cm 2 , the initial orange color became almost colorless. In addition to this, ultraviolet light of 366 nm was emitted for 3 m with an ultraviolet lamp.
When it was irradiated with J / cm 2, it returned to orange again. Such a cycle was repeated 1000 times, but the absorbance at the time of coloring was 80% or more of the initial value.
【００５８】また、この繰り返しで紫外線の代わり５０
度に加熱することによっても再着色をし、同様に１００
０回のサイクルを再現よく行えた。また、水蒸気に接し
させることで暗青色に変色した 比較例６ スピロピラン３をポリビニルブチラ−ルと重量比で１／
４０の割合でトルエンに溶解させた溶液からスピンコ−
テエイングによりポリエチレンテレフタレ−ト上に薄膜
化した。これを、１Ｔｏｒｒの減圧下室温で２４時間乾
燥した。得られた担持体は無色であった。これに紫外線
ランプで３６６ｎｍの紫外光を３００ｍＪ／ｃｍ2 照射
すると赤色に着色した。さらに、ハロゲンランプと分光
器を組み合わせて、５６０ｎｍの可視光を１２００ｍＪ
／ｃｍ2 照射すると初期の赤色はほぼ無色になった。こ
の繰り返しを９０回行なうと、着色時の吸光度は初期の
８割以下に低下した。By repeating this process, instead of using ultraviolet rays, 50
It can be recolored by heating it to 100
The cycle of 0 times was reproducibly performed. In addition, Comparative Example 6 Spiropyran 3 which changed its color to dark blue by contacting with water vapor was mixed with polyvinyl butyral in a weight ratio of 1 /.
Spin-coupling from a solution of 40 in toluene
A thin film was formed on the polyethylene terephthalate by the taing. This was dried at room temperature under reduced pressure of 1 Torr for 24 hours. The resulting carrier was colorless. When this was irradiated with 300 mJ / cm 2 of 366 nm ultraviolet light from an ultraviolet lamp, it was colored red. Furthermore, by combining a halogen lamp and a spectroscope, the visible light of 560 nm is 1200 mJ.
When irradiated with / cm 2 , the initial red color became almost colorless. When this repetition was repeated 90 times, the absorbance at the time of coloring decreased to 80% or less of the initial value.
【００５９】また、５０℃に加熱することによって着色
は起こらなず、水蒸気との接触による色相の変化もなか
った。表６に実施例６の吸着時間、着色時の吸光度が初
期の８割になる繰り返し回数、着色時の色、消色時の照
射エネルギをまとめる。このように、スピロピラン２と
異なる官能基を有するスピロピラン３も、シラノール基
を表面に有する多孔質体に吸着させることでスピロピラ
ン２同様良好な着消色特性を示した。Further, when heated to 50 ° C., coloring did not occur, and there was no change in hue due to contact with water vapor. Table 6 summarizes the adsorption time of Example 6, the number of repetitions when the absorbance at coloring is 80% of the initial value, the color at coloring, and the irradiation energy at decoloring. As described above, spiropyran 3 having a functional group different from that of spiropyran 2 also showed good coloration / decoloration characteristics similar to spiropyran 2 by being adsorbed on the porous body having a silanol group on the surface.
【００６０】[0060]
【表６】 [Table 6]
【００６１】[0061]
【発明の効果】本発明のスピロピラン担持体は、開環し
たスピロピランを、表面にシラノール基を有した多孔質
体に担持してなることを特徴としている。表面への特別
な吸着状態のために、着色異性体が安定化され、スピロ
ピラン担持体の着消色の繰り返し特性が向上し、小さな
光エネルギーで着消色が可能になる効果がある。とくに
着色時の色が黄色から橙色のものの繰り返し特性向上の
効果が大きい。また、着色、消色のうち、消色に要する
エネルギが小さくなる効果が大きい。さらに、紫外光源
なしでも、加熱により着色が可能になる効果もある。The spiropyran-supporting material of the present invention is characterized in that the ring-opened spiropyran is carried on a porous material having silanol groups on the surface. Due to the special adsorption state on the surface, the colored isomers are stabilized, the repeating characteristics of the coloring and decoloring of the spiropyran carrier are improved, and the coloring and decoloring can be performed with a small light energy. In particular, the effect of improving the repeating characteristics is large when the coloring is yellow to orange. Further, of the coloring and erasing, the effect of reducing the energy required for erasing is great. Further, there is an effect that coloring can be performed by heating even without using an ultraviolet light source.
【００６２】本発明のスピロピラン担持体の製造は、ス
ピロピランの多孔質体への吸着を、溶液に紫外線照射し
て行なうか、非極性溶媒の溶液中から行なうことで行な
う。、簡便に短時間でスピロピラン担持体が製造できる
効果がある。また、選択的に開環した着色体が吸着され
るために最初から着色した担持体が得られる効果があ
る。The spiropyran-supported material of the present invention is produced by adsorbing spiropyran to the porous material by irradiating the solution with ultraviolet rays or in a solution of a nonpolar solvent. There is an effect that a spiropyran-supported body can be easily produced in a short time. In addition, since the colored body that is selectively opened is adsorbed, there is an effect that a colored carrier can be obtained from the beginning.
【００６３】また、本発明のスピロピラン担持体の製造
は、非極性溶媒の溶液中からスピロピランの吸着を行な
ったあと、極性の異なる溶媒に浸すことが特徴である。
こうすることで、多様な色相の担持体を短時間で製造で
きるという効果がある。The production of the spiropyran-supported material of the present invention is characterized in that the spiropyran is adsorbed from a solution of a nonpolar solvent and then immersed in a solvent having a different polarity.
By doing so, there is an effect that a carrier having various hues can be manufactured in a short time.
【００６４】本発明のスピロピラン担持体は、紫外光、
可視光の照射に加熱、水等との接触等を組み合わせて行
なえるため、光、熱、水等の多様な刺激に対して多様な
色相で着消色が可能になる効果ある。The spiropyran-supporting material of the present invention is
Since irradiation with visible light can be combined with heating, contact with water, etc., it is possible to change colors with various hues against various stimuli such as light, heat and water.
【００６５】以上のように、本発明は繰り返し耐久性に
感度に優れ、多様な発色が可能になるスピロピラン担持
体とその簡便な製造方法とすることができる。As described above, the present invention can provide a spiropyran support having excellent repeated durability and sensitivity and capable of producing various colors, and a simple method for producing the same.
【図１】本発明の実施例１のスピロピランの可視光線照
射前（Ａ）と可視光線照射後（Ｂ）の吸収スペクトル
図。FIG. 1 is an absorption spectrum diagram of spiropyran of Example 1 of the present invention before visible light irradiation (A) and after visible light irradiation (B).
Claims (9)
に、開環したスピロピランを吸着させてなるスピロピラ
ン担持体。1. A spiropyran-supporting body obtained by adsorbing a ring-opened spiropyran on a porous body having a silanol group on its surface.
し、変色する請求項１に記載のスピロピラン担持体。2. The spiropyran-supported material according to claim 1, which exhibits a reversible isomerization reaction upon light irradiation and changes color.
または橙色である請求項２に記載のスピロピラン担持
体。3. The spiropyran-supporting body according to claim 2, wherein the color of the spiropyran-supporting body when colored is yellow or orange.
−ル基を有する多孔質体の微小体を高分子中に分散して
なる請求項１または２に記載のスピロピラン担持体。4. The spiropyran-supporting body according to claim 1, wherein fine particles of a porous body having a silanol group are dispersed in a polymer on the surface on which spiropyran is supported.
有するスピロピラン（ただしＲ1 ，Ｒ2 はＨまたは有機
基）である請求項１または２に記載のスピロピラン担持
体。 【化１】 5. The spiropyran-supporting body according to claim 1 , wherein the spiropyran is a spiropyran having a structure of the following formula (Formula 1) (wherein R 1 and R 2 are H or an organic group). [Chemical 1]
または（化４）のいずれかの構造を有するスピロピラン
である請求項１または２に記載のスピロピラン担持体。 【化２】 【化３】 【化４】 6. Spiropyran is represented by the following formula (formula 2) (formula 3):
The spiropyran-supporting material according to claim 1 or 2, which is spiropyran having the structure of (Chemical Formula 4). [Chemical 2] [Chemical 3] [Chemical 4]
スピロピランを吸着させる際に、スピロピランの溶液に
紫外光を照射するスピロピラン担持体の製造方法。7. A method for producing a spiropyran-supporting body, which comprises irradiating a solution of spiropyran with ultraviolet light when adsorbing spiropyran on a porous body having a silanol group on its surface.
ラン溶液から、表面にシラノール基を有する多孔質体に
前記溶液中の開環したスピロピランを吸着させて製造す
ることを特徴とするスピロピラン担持体の製造方法。8. A method for producing a spiropyran-supported material, which is prepared by adsorbing a ring-opened spiropyran in a solution from a spiropyran solution of spiropyran and a nonpolar solvent onto a porous body having a silanol group on the surface. Method.
ラン溶液から、表面にシラノール基を有する多孔質体に
前記溶液中の開環したスピロピランを吸着させたあと、
極性溶媒に浸す処理を行う請求項８に記載のスピロピラ
ン担持体の製造方法。9. From a spiropyran solution of spiropyran and a nonpolar solvent, after adsorbing the ring-opened spiropyran in the solution to a porous body having a silanol group on the surface,
The method for producing a spiropyran-supported body according to claim 8, wherein the treatment is carried out by immersing in a polar solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4149297A JP2975768B2 (en) | 1992-06-09 | 1992-06-09 | Spiropyran carrier and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4149297A JP2975768B2 (en) | 1992-06-09 | 1992-06-09 | Spiropyran carrier and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05341433A true JPH05341433A (en) | 1993-12-24 |
| JP2975768B2 JP2975768B2 (en) | 1999-11-10 |
Family
ID=15472088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4149297A Expired - Fee Related JP2975768B2 (en) | 1992-06-09 | 1992-06-09 | Spiropyran carrier and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2975768B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6362005B1 (en) | 1997-08-29 | 2002-03-26 | Nippon Telegraph And Telephone Corporation | Nitrogen dioxide gas sensing method, nitrogen dioxide gas sensor element, and nitrogen dioxide gas sensor using the same |
| JP2006096027A (en) * | 2004-07-27 | 2006-04-13 | Fuji Photo Film Co Ltd | Lithographic printing original plate and the lithographic printing method |
| JP2010059289A (en) * | 2008-09-02 | 2010-03-18 | Ricoh Co Ltd | Photochromic composition, image display medium, and image forming device |
| JP2010059288A (en) * | 2008-09-02 | 2010-03-18 | Ricoh Co Ltd | Photochromic composition, image display medium and image forming device |
| KR20180055081A (en) * | 2016-11-16 | 2018-05-25 | 한국과학기술연구원 | Composite comprising spiropyran sensor molecules and process of analyzing strain |
-
1992
- 1992-06-09 JP JP4149297A patent/JP2975768B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6362005B1 (en) | 1997-08-29 | 2002-03-26 | Nippon Telegraph And Telephone Corporation | Nitrogen dioxide gas sensing method, nitrogen dioxide gas sensor element, and nitrogen dioxide gas sensor using the same |
| JP2006096027A (en) * | 2004-07-27 | 2006-04-13 | Fuji Photo Film Co Ltd | Lithographic printing original plate and the lithographic printing method |
| JP4705817B2 (en) * | 2004-07-27 | 2011-06-22 | 富士フイルム株式会社 | Planographic printing plate precursor and planographic printing method |
| JP2010059289A (en) * | 2008-09-02 | 2010-03-18 | Ricoh Co Ltd | Photochromic composition, image display medium, and image forming device |
| JP2010059288A (en) * | 2008-09-02 | 2010-03-18 | Ricoh Co Ltd | Photochromic composition, image display medium and image forming device |
| KR20180055081A (en) * | 2016-11-16 | 2018-05-25 | 한국과학기술연구원 | Composite comprising spiropyran sensor molecules and process of analyzing strain |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2975768B2 (en) | 1999-11-10 |
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