WO2018070361A1 - Rewriteable paper and manufacturing method therefor, and method - Google Patents
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- WO2018070361A1 WO2018070361A1 PCT/JP2017/036574 JP2017036574W WO2018070361A1 WO 2018070361 A1 WO2018070361 A1 WO 2018070361A1 JP 2017036574 W JP2017036574 W JP 2017036574W WO 2018070361 A1 WO2018070361 A1 WO 2018070361A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
Definitions
- the present invention relates to a rewritable paper, a manufacturing method thereof, and a method.
- Photochromism is a phenomenon in which the color of a substance is reversibly changed by light including ultraviolet rays. HABI) compounds and the like are known.
- photochromic compounds are known to gradually return to their original structure in the presence of heat or visible light at room temperature, even when a color change due to structural change occurs due to ultraviolet light irradiation. As a paper application, the color could not be maintained for a long time.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide a rewritable paper that can suppress color fading for a long period of time and can be rewritten any number of times, a manufacturing method thereof, and a method thereof. .
- the rewritable paper which concerns on 1 aspect of this invention is equipped with the cellulose substrate and the hexaarylbisimidazole (HABI) represented by the following general formula (1) contained in a cellulose substrate.
- HABI hexaarylbisimidazole
- R 1 to R 30 each independently represents a hydrogen atom or a substituent.
- the manufacturing method of the rewritable paper which concerns on 1 aspect of this invention includes the process of making the cellulose substrate impregnate the hexaarylbisimidazole (HABI) represented by the said General formula (1), and the process of drying a cellulose substrate. .
- HABI hexaarylbisimidazole
- the method according to an embodiment of the present invention includes a step of irradiating at least a part of the rewritable paper with an electromagnetic wave to develop a color at a portion irradiated with the electromagnetic wave, and a step of heating the rewritable paper to decolorize. Including the step of color development and the step of decolorization.
- a rewritable paper that can suppress color fading for a long period of time and can be rewritten any number of times, a manufacturing method thereof, and a method thereof.
- the rewritable paper according to the present embodiment includes a cellulose substrate and hexaarylbisimidazole (HABI) represented by the general formula (1) included in the cellulose substrate.
- HABI hexaarylbisimidazole
- R 1 to R 30 each independently represents a hydrogen atom or a substituent.
- the cellulose substrate is a substrate containing cellulose, and preferably a substrate such as paper mainly composed of cellulose.
- the cellulose content in the substrate is 80% or more, preferably 90% or more.
- Hexaarylbisimidazole is represented by the above general formula (1), and in the general formula (1), R 1 to R 30 each independently represents a hydrogen atom or a substituent.
- HABI shows a photochromism in which a CN bond connecting two imidazole rings is equally cleaved by irradiation with an electromagnetic wave such as ultraviolet light to generate a triphenylimidazolyl radical (TPIR: lophyll radical) as a color former.
- TPIR triphenylimidazolyl radical
- the reaction (radical recombination) from TPIR to HABI is a thermal reaction, a film formed by simply applying a solution of HABI gradually undergoes the reaction by irradiation with ultraviolet light.
- the color retention period can be extended by impregnating and dispersing HABI in a cellulose substrate.
- TPIR generated by the irradiation of electromagnetic waves binds to cellulose and hardly causes a return reaction. For this reason, it is suppressed that it returns to the original structure gradually in the presence of heat at room temperature or visible light, and fading.
- TPIR binds to cellulose by heating at 50 ° C. or higher and quickly discolors.
- At least one of R 1 to R 30 is a substituent selected from a fluorine atom, a fluorinated alkyl group, or a cyano group.
- a substituent selected from a fluorine atom, a fluorinated alkyl group, or a cyano group By introducing such an electron-withdrawing substituent, it is possible to suppress the return (radical recombination) reaction from TPIR to HABI.
- rewritable papers using HABI rewritable papers with improved color retention period, stability, and repeated durability can be provided.
- At least one of R 1 to R 5 and R 16 to R 20 is a substituent selected from a fluorine atom, a fluorinated alkyl group, or a cyano group.
- the method for producing a rewritable paper according to this embodiment includes a step of impregnating a cellulose substrate with hexaarylbisimidazole (HABI) represented by the general formula (1) and a step of drying the cellulose substrate.
- HABI hexaarylbisimidazole
- HABI hydroxyastyrene-maleic anhydride
- a cellulose substrate is impregnated with a solution in which HABI is dissolved in an organic solvent.
- the cellulose substrate may be immersed in a solution containing HABI, or a solution containing HABI may be applied to the cellulose substrate.
- the cellulose substrate impregnated with HABI is dried to produce a rewritable paper.
- FIG. 1 is a diagram for explaining a method of using a rewritable paper according to the present embodiment.
- electromagnetic waves such as ultraviolet light are irradiated to at least a part of rewritable paper 1 impregnated with HABI by electromagnetic wave irradiation means 2.
- the electromagnetic wave irradiation means 2 is, for example, a pen type ultraviolet irradiator.
- a pen-shaped ultraviolet irradiator is operated to display a desired character 1a.
- An image may be displayed instead of the character 1a.
- the electromagnetic wave irradiation means 2 may be operated by a control device to display a desired character instead of being held and operated by a person.
- the rewritable paper 1 When erasing characters displayed on the rewritable paper 1, the rewritable paper 1 may be heated to 50 ° C. or higher. For example, the whole rewritable paper 1 is heated to 50 ° C. or higher by a heater. As a result, the TPIR in the rewritable paper 1 returns to HABI and is decolored.
- the rewritable paper 1 can be used repeatedly by color development by irradiation with ultraviolet light and decoloration by heating.
- HABI compound A-1 was manufactured by Tokyo Chemical Industry. Lophine and HABI compounds A-2 to A-9 were synthesized by referring to a known method (Japanese Patent Laid-Open No. 62-149668). Compounds A-10 to A-13 were synthesized with reference to a known method (Bull. Chem. Soc. Japan, (1960), 33, 566). Compounds A-10 to A-13 each represent a mixture of isomers having different bonding positions.
- Example 1 (Production of HABI-containing cellulose substrate) A filter paper (manufactured by Advantec, No. 1 185 mm) is cut into a size of 4 cm ⁇ 2 cm using a scissors, and the whole is immersed in the solution A-1 prepared earlier, then taken out and dried at room temperature. The sample of Example 1 was prepared. Samples of Examples 2 to 13 were prepared in the same manner as the sample of Example 1, except that Compound A-1 in the sample of Example 1 was changed to A-2 to A-13, respectively.
- Example 1 (exposure) The produced sample of Example 1 was exposed for 1 minute using a UV lamp (UVGL-25 Compact UV Lamp, manufactured by Funakoshi Co., Ltd.) to obtain a colored sample of Example 1. In the same manner as the colored sample of Example 1, colored samples of Examples 2 to 13 were obtained.
- a UV lamp UVGL-25 Compact UV Lamp, manufactured by Funakoshi Co., Ltd.
- Comparative example One drop of each of solutions A-3, A-7, and A-13 was dropped on a glass substrate and dried at room temperature to prepare samples of Comparative Examples 1 to 3. The samples of these comparative examples were also evaluated for color retention period, stability, and repeated durability.
- Table 1 shows the evaluation results of the samples of the examples and comparative examples.
- the color retention period is prolonged by including HABI on the filter paper substrate, and further, not only the color retention period but also the stability is maintained by using HABI having an electron withdrawing substituent. It can be seen that the durability and repeated durability are improved.
- the rewritable paper according to the present embodiment includes a cellulose substrate and hexaarylbisimidazole (HABI) represented by the general formula (1) included in the cellulose substrate.
- HABI hexaarylbisimidazole
- At least one of R 1 to R 30 is a substituent selected from a fluorine atom, a fluorinated alkyl group, or a cyano group.
- At least one of R 1 to R 5 and R 16 to R 20 is a substituent selected from a fluorine atom, a fluorinated alkyl group, or a cyano group.
- the method for producing a rewritable paper according to this embodiment includes a step of impregnating a cellulose substrate with hexaarylbisimidazole (HABI) represented by the above general formula (1) and a step of drying the cellulose substrate.
- HABI hexaarylbisimidazole
- the rewritable paper having the above-described performance can be manufactured at low cost.
- the method according to this embodiment includes a step of irradiating at least a part of the above-described rewritable paper with an electromagnetic wave to develop a color of a portion irradiated with the electromagnetic wave, and a step of heating and decoloring the rewritable paper, The color developing step and the color erasing step are repeated.
- the usage method of the rewritable paper which improved the color retention period, stability, and repetition durability can be provided.
Abstract
Provided are a rewriteable paper and a manufacturing method therefor, and a method, wherein fading of colors is suppressed for a long time, and rewriting is possible any number of times. A rewriteable paper according to one aspect of the present invention comprises a cellulose substrate, and a hexaarylbisimidazole (HABI) that is expressed by general formula (1) and is included in the cellulose substrate. (In general formula (1), R1-R30 each independently express a hydrogen atom or a substituent group.)
Description
本発明は、リライタブルペーパー及びその製造方法、並びに方法に関する。
The present invention relates to a rewritable paper, a manufacturing method thereof, and a method.
フォトクロミズムとは、物質の色が紫外線を含む光によって可逆的に変化する現象であるが、このような現象を生じるフォトクロミック材料としてはアゾベンゼン化合物、ジアリールエテン化合物、スピロピラン化合物、フルギド化合物、ヘキサアリールビスイミダゾール(ＨＡＢＩ)化合物などが知られている。
Photochromism is a phenomenon in which the color of a substance is reversibly changed by light including ultraviolet rays. HABI) compounds and the like are known.
近年、このようなフォトクロミック材料の用途の一つとして、サングラス用の調光ガラスが考えられ、ＨＡＢＩ化合物を用いて紫外線により発色し、屋内に戻ると速やかに退色する技術の検討がなされている（特許文献１、特許文献２）。
In recent years, dimming glass for sunglasses has been considered as one of the applications of such photochromic materials, and a technique for developing color by ultraviolet rays using a HABI compound and fading quickly when returning indoors has been studied ( Patent Document 1 and Patent Document 2).
これらのフォトクロミック化合物は、紫外光照射で構造変化による色変化が起こっても、室温程度の熱あるいは可視光の存在下で徐々に元の構造へ戻ってしまい退色することが知られており、リライタブルペーパー用途として、色を長期間維持することができなかった。
These photochromic compounds are known to gradually return to their original structure in the presence of heat or visible light at room temperature, even when a color change due to structural change occurs due to ultraviolet light irradiation. As a paper application, the color could not be maintained for a long time.
本発明はこのような事情に鑑みてなされたものであり、長期間、色の退色が抑制され、かつ何度でも書き換え可能なリライタブルペーパー及びその製造方法、並びに方法を提供することを目的とする。
The present invention has been made in view of such circumstances, and an object of the present invention is to provide a rewritable paper that can suppress color fading for a long period of time and can be rewritten any number of times, a manufacturing method thereof, and a method thereof. .
本発明の一態様に係るリライタブルペーパーは、セルロース基板と、セルロース基板に含まれる、下記一般式（１）で表されるヘキサアリールビスイミダゾール（ＨＡＢＩ）と、を備える。
The rewritable paper which concerns on 1 aspect of this invention is equipped with the cellulose substrate and the hexaarylbisimidazole (HABI) represented by the following general formula (1) contained in a cellulose substrate.
一般式（１）中、Ｒ１～Ｒ３０はそれぞれ独立に、水素原子又は置換基を表す。
In general formula (1), R 1 to R 30 each independently represents a hydrogen atom or a substituent.
本発明の一態様に係るリライタブルペーパーの製造方法は、セルロース基板に上記一般式（１）で表されるヘキサアリールビスイミダゾール（ＨＡＢＩ）を含浸させる工程と、セルロース基板を乾燥させる工程と、を含む。
The manufacturing method of the rewritable paper which concerns on 1 aspect of this invention includes the process of making the cellulose substrate impregnate the hexaarylbisimidazole (HABI) represented by the said General formula (1), and the process of drying a cellulose substrate. .
本発明の一態様に係る方法は、上述したリライタブルペーパーの少なくとも一部に電磁波を照射して、電磁波が照射された部位を発色させる工程と、リライタブルペーパーを加熱して消色させる工程と、を含み、発色させる工程及び消色させる工程を繰り返し行うものである。
The method according to an embodiment of the present invention includes a step of irradiating at least a part of the rewritable paper with an electromagnetic wave to develop a color at a portion irradiated with the electromagnetic wave, and a step of heating the rewritable paper to decolorize. Including the step of color development and the step of decolorization.
本発明によれば、長期間、色の退色が抑制され、かつ何度でも書き換え可能なリライタブルペーパー及びその製造方法、並びに方法を提供することができる。
According to the present invention, it is possible to provide a rewritable paper that can suppress color fading for a long period of time and can be rewritten any number of times, a manufacturing method thereof, and a method thereof.
添付図面を参照して、本発明の好適な実施形態について説明する。（なお、各図において、同一の符号を付したものは、同一又は同様の構成を有する。）
A preferred embodiment of the present invention will be described with reference to the accompanying drawings. (In addition, in each figure, what attached | subjected the same code | symbol has the same or similar structure.)
本実施形態に係るリライタブルペーパーは、セルロース基板と、セルロース基板に含まれる、一般式（１）で表されるヘキサアリールビスイミダゾール（ＨＡＢＩ）と、を備える。
The rewritable paper according to the present embodiment includes a cellulose substrate and hexaarylbisimidazole (HABI) represented by the general formula (1) included in the cellulose substrate.
一般式（１）中、Ｒ１～Ｒ３０はそれぞれ独立に、水素原子又は置換基を表す。
In general formula (1), R 1 to R 30 each independently represents a hydrogen atom or a substituent.
セルロース基板とは、セルロースを含む基板であり、好ましくはセルロースを主成分とする紙などの基板である。基板におけるセルロースの含有率は８０％以上であり、好ましくは９０％以上である。
The cellulose substrate is a substrate containing cellulose, and preferably a substrate such as paper mainly composed of cellulose. The cellulose content in the substrate is 80% or more, preferably 90% or more.
ヘキサアリールビスイミダゾール（ＨＡＢＩ）は、上記一般式（１）で表されるものであり、一般式（１）中、Ｒ１～Ｒ３０はそれぞれ独立に、水素原子、置換基を表す。
Hexaarylbisimidazole (HABI) is represented by the above general formula (1), and in the general formula (1), R 1 to R 30 each independently represents a hydrogen atom or a substituent.
ＨＡＢＩは、紫外光などの電磁波の照射により、二つのイミダゾール環を結ぶＣ－Ｎ結合が均等開裂し、発色体であるトリフェニルイミダゾリルラジカル（ＴＰＩＲ：ロフィルラジカル）を生成するフォトクロミズムを示す。ＴＰＩＲからＨＡＢＩへの戻り（ラジカル再結合）反応は熱反応であるが、ＨＡＢＩの溶液を単に塗布して形成した膜は紫外光照射によっても徐々に戻り反応が起こる。
HABI shows a photochromism in which a CN bond connecting two imidazole rings is equally cleaved by irradiation with an electromagnetic wave such as ultraviolet light to generate a triphenylimidazolyl radical (TPIR: lophyll radical) as a color former. Although the reaction (radical recombination) from TPIR to HABI is a thermal reaction, a film formed by simply applying a solution of HABI gradually undergoes the reaction by irradiation with ultraviolet light.
本実施形態では、セルロース基板にＨＡＢＩを含浸させ分散させることにより、色保持期間を長くすることができることが見出された。これは、電磁波の照射により生成されたＴＰＩＲがセルロースと結合し、戻り反応を起こし難くなるものと推定される。このため、室温程度の熱あるいは可視光の存在下で徐々に元の構造へ戻ってしまい退色することが抑制される。一方、５０℃以上の加熱によりＴＰＩＲがセルロースと結合し、速やかに消色することが見出された。
In this embodiment, it has been found that the color retention period can be extended by impregnating and dispersing HABI in a cellulose substrate. This is presumed that TPIR generated by the irradiation of electromagnetic waves binds to cellulose and hardly causes a return reaction. For this reason, it is suppressed that it returns to the original structure gradually in the presence of heat at room temperature or visible light, and fading. On the other hand, it has been found that TPIR binds to cellulose by heating at 50 ° C. or higher and quickly discolors.
好ましくは、一般式（１）中、Ｒ１～Ｒ３０のいずれか少なくとも一つが、フッ素原子、フッ素化アルキル基又はシアノ基から選択される置換基である。このような電子吸引性置換基を導入することにより、ＴＰＩＲからＨＡＢＩへの戻り（ラジカル再結合）反応を抑制することができる。これにより、ＨＡＢＩを利用したリライタブルペーパーの中でも、色保持期間、安定性、繰り返し耐久性を向上させたリライタブルペーパーを提供できる。
Preferably, in general formula (1), at least one of R 1 to R 30 is a substituent selected from a fluorine atom, a fluorinated alkyl group, or a cyano group. By introducing such an electron-withdrawing substituent, it is possible to suppress the return (radical recombination) reaction from TPIR to HABI. Thereby, among the rewritable papers using HABI, rewritable papers with improved color retention period, stability, and repeated durability can be provided.
さらに好ましくは、一般式（１）中、Ｒ１～Ｒ５、Ｒ１６～Ｒ２０のいずれか少なくとも一つが、フッ素原子、フッ素化アルキル基又はシアノ基から選択される置換基である。このような電子吸引性置換基を特定の位置に導入することにより、ＴＰＩＲからＨＡＢＩへの戻り（ラジカル再結合）反応を効果的に抑制することができる。これにより、ＨＡＢＩを利用したリライタブルペーパーの中でも、色保持期間、安定性、繰り返し耐久性を向上させたリライタブルペーパーを提供できる。
More preferably, in the general formula (1), at least one of R 1 to R 5 and R 16 to R 20 is a substituent selected from a fluorine atom, a fluorinated alkyl group, or a cyano group. By introducing such an electron-withdrawing substituent at a specific position, the return (radical recombination) reaction from TPIR to HABI can be effectively suppressed. Thereby, among the rewritable papers using HABI, rewritable papers with improved color retention period, stability, and repeated durability can be provided.
本実施形態に係るリライタブルペーパーの製造方法は、セルロース基板に上記一般式（１）で表されるヘキサアリールビスイミダゾール（ＨＡＢＩ）を含浸させる工程と、前記セルロース基板を乾燥させる工程と、を含む。
The method for producing a rewritable paper according to this embodiment includes a step of impregnating a cellulose substrate with hexaarylbisimidazole (HABI) represented by the general formula (1) and a step of drying the cellulose substrate.
具体的には、市販のＨＡＢＩを用いるか、公知の方法によりＨＡＢＩを合成する。そして、有機溶媒にＨＡＢＩを溶解させた溶液をセルロース基板に含浸させる。含浸方法としては、ＨＡＢＩを含有する溶液にセルロース基板を浸漬しても、セルロース基板にＨＡＢＩを含む溶液を塗布してもよい。最後にＨＡＢＩを含浸させたセルロース基板を乾燥させることにより、リライタブルペーパーが製造される。
Specifically, commercially available HABI is used, or HABI is synthesized by a known method. Then, a cellulose substrate is impregnated with a solution in which HABI is dissolved in an organic solvent. As the impregnation method, the cellulose substrate may be immersed in a solution containing HABI, or a solution containing HABI may be applied to the cellulose substrate. Finally, the cellulose substrate impregnated with HABI is dried to produce a rewritable paper.
図１は、本実施形態に係るリライタブルペーパーの使用方法を説明するための図である。
図１に示すように、ＨＡＢＩを含浸させたリライタブルペーパー１の少なくとも一部に電磁波照射手段２により紫外光などの電磁波を照射する。これにより、紫外光が照射された部位のＨＡＢＩが開裂してＴＰＩＲとなり発色することにより、文字１ａが表示される。電磁波照射手段２は、例えば、ペン型の紫外線照射器である。ペン型の紫外線照射器を操作して、所望の文字１ａを表示させる。なお、文字１ａの代わりに画を表示させてもよい。また、電磁波照射手段２は、人が把持して操作されるものではなく、制御装置により動作され、所望の文字を表示させるものであってもよい。 FIG. 1 is a diagram for explaining a method of using a rewritable paper according to the present embodiment.
As shown in FIG. 1, electromagnetic waves such as ultraviolet light are irradiated to at least a part ofrewritable paper 1 impregnated with HABI by electromagnetic wave irradiation means 2. As a result, the HABI at the site irradiated with the ultraviolet light is cleaved to become TPIR and develop color, whereby the character 1a is displayed. The electromagnetic wave irradiation means 2 is, for example, a pen type ultraviolet irradiator. A pen-shaped ultraviolet irradiator is operated to display a desired character 1a. An image may be displayed instead of the character 1a. Further, the electromagnetic wave irradiation means 2 may be operated by a control device to display a desired character instead of being held and operated by a person.
図１に示すように、ＨＡＢＩを含浸させたリライタブルペーパー１の少なくとも一部に電磁波照射手段２により紫外光などの電磁波を照射する。これにより、紫外光が照射された部位のＨＡＢＩが開裂してＴＰＩＲとなり発色することにより、文字１ａが表示される。電磁波照射手段２は、例えば、ペン型の紫外線照射器である。ペン型の紫外線照射器を操作して、所望の文字１ａを表示させる。なお、文字１ａの代わりに画を表示させてもよい。また、電磁波照射手段２は、人が把持して操作されるものではなく、制御装置により動作され、所望の文字を表示させるものであってもよい。 FIG. 1 is a diagram for explaining a method of using a rewritable paper according to the present embodiment.
As shown in FIG. 1, electromagnetic waves such as ultraviolet light are irradiated to at least a part of
リライタブルペーパー１に表示させた文字を消去する際には、リライタブルペーパー１を５０℃以上に加熱すればよい。例えば、リライタブルペーパー１の全体をヒーターにより５０℃以上に加熱する。これにより、リライタブルペーパー１におけるＴＰＩＲがＨＡＢＩへ戻り、消色する。リライタブルペーパー１は、紫外光の照射による発色と、加熱による消色により、繰り返し使用可能である。
When erasing characters displayed on the rewritable paper 1, the rewritable paper 1 may be heated to 50 ° C. or higher. For example, the whole rewritable paper 1 is heated to 50 ° C. or higher by a heater. As a result, the TPIR in the rewritable paper 1 returns to HABI and is decolored. The rewritable paper 1 can be used repeatedly by color development by irradiation with ultraviolet light and decoloration by heating.
（実施例）
以下、本発明を実施例および比較例によってさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 (Example)
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples.
以下、本発明を実施例および比較例によってさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 (Example)
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples.
（ＨＡＢＩ化合物の合成）
ＨＡＢＩ化合物Ａ－１は、東京化成工業製のものを使用した。ロフィン及びＨＡＢＩ化合物Ａ－２～Ａ－９は、公知の方法（特開昭６２－１４９６６８号公報）を参考に合成した。化合物Ａ－１０～Ａ－１３は、公知の方法（Ｂｕｌｌ． Ｃｈｅｍ． Ｓｏｃ． Ｊａｐａｎ， （１９６０）， ３３， ５６６）を参考に合成した。化合物Ａ－１０～Ａ－１３は、それぞれ、結合位置が異なる異性体の混合物を表す。 (Synthesis of HABI compound)
The HABI compound A-1 was manufactured by Tokyo Chemical Industry. Lophine and HABI compounds A-2 to A-9 were synthesized by referring to a known method (Japanese Patent Laid-Open No. 62-149668). Compounds A-10 to A-13 were synthesized with reference to a known method (Bull. Chem. Soc. Japan, (1960), 33, 566). Compounds A-10 to A-13 each represent a mixture of isomers having different bonding positions.
ＨＡＢＩ化合物Ａ－１は、東京化成工業製のものを使用した。ロフィン及びＨＡＢＩ化合物Ａ－２～Ａ－９は、公知の方法（特開昭６２－１４９６６８号公報）を参考に合成した。化合物Ａ－１０～Ａ－１３は、公知の方法（Ｂｕｌｌ． Ｃｈｅｍ． Ｓｏｃ． Ｊａｐａｎ， （１９６０）， ３３， ５６６）を参考に合成した。化合物Ａ－１０～Ａ－１３は、それぞれ、結合位置が異なる異性体の混合物を表す。 (Synthesis of HABI compound)
The HABI compound A-1 was manufactured by Tokyo Chemical Industry. Lophine and HABI compounds A-2 to A-9 were synthesized by referring to a known method (Japanese Patent Laid-Open No. 62-149668). Compounds A-10 to A-13 were synthesized with reference to a known method (Bull. Chem. Soc. Japan, (1960), 33, 566). Compounds A-10 to A-13 each represent a mixture of isomers having different bonding positions.
（ヘキサアリールビスイミダゾール溶液の調製）
化合物Ａ－１（５０ｍｇ）に塩化メチレン（１．５ｍＬ）を加え、完溶させ、溶液Ａ－１を調製した。溶液Ａ－１における化合物Ａ－１を、Ａ－２～Ａ－１３に、それぞれ変更した以外は溶液１と同様にして、溶液Ａ－２～Ａ－１３を調製した。 (Preparation of hexaarylbisimidazole solution)
Methylene chloride (1.5 mL) was added to compound A-1 (50 mg) and dissolved completely to prepare solution A-1. Solutions A-2 to A-13 were prepared in the same manner asSolution 1, except that Compound A-1 in Solution A-1 was changed to A-2 to A-13, respectively.
化合物Ａ－１（５０ｍｇ）に塩化メチレン（１．５ｍＬ）を加え、完溶させ、溶液Ａ－１を調製した。溶液Ａ－１における化合物Ａ－１を、Ａ－２～Ａ－１３に、それぞれ変更した以外は溶液１と同様にして、溶液Ａ－２～Ａ－１３を調製した。 (Preparation of hexaarylbisimidazole solution)
Methylene chloride (1.5 mL) was added to compound A-1 (50 mg) and dissolved completely to prepare solution A-1. Solutions A-2 to A-13 were prepared in the same manner as
（ＨＡＢＩ含有セルロース基板の作製）
ろ紙（Ａｄｖａｎｔｅｃ社製、Ｎｏ．１ １８５ｍｍ）を、鋏を用いて４ｃｍ×２ｃｍの大きさに切り、これを先ほど調製した溶液Ａ－１に全体を浸し、その後、取り出し、室温で乾燥させ、実施例１のサンプルを作製した。実施例１のサンプルにおける化合物Ａ－１を、Ａ－２～Ａ－１３に、それぞれ変更した以外は実施例１のサンプルと同様にして、実施例２～１３のサンプルを調製した。 (Production of HABI-containing cellulose substrate)
A filter paper (manufactured by Advantec, No. 1 185 mm) is cut into a size of 4 cm × 2 cm using a scissors, and the whole is immersed in the solution A-1 prepared earlier, then taken out and dried at room temperature. The sample of Example 1 was prepared. Samples of Examples 2 to 13 were prepared in the same manner as the sample of Example 1, except that Compound A-1 in the sample of Example 1 was changed to A-2 to A-13, respectively.
ろ紙（Ａｄｖａｎｔｅｃ社製、Ｎｏ．１ １８５ｍｍ）を、鋏を用いて４ｃｍ×２ｃｍの大きさに切り、これを先ほど調製した溶液Ａ－１に全体を浸し、その後、取り出し、室温で乾燥させ、実施例１のサンプルを作製した。実施例１のサンプルにおける化合物Ａ－１を、Ａ－２～Ａ－１３に、それぞれ変更した以外は実施例１のサンプルと同様にして、実施例２～１３のサンプルを調製した。 (Production of HABI-containing cellulose substrate)
A filter paper (manufactured by Advantec, No. 1 185 mm) is cut into a size of 4 cm × 2 cm using a scissors, and the whole is immersed in the solution A-1 prepared earlier, then taken out and dried at room temperature. The sample of Example 1 was prepared. Samples of Examples 2 to 13 were prepared in the same manner as the sample of Example 1, except that Compound A-1 in the sample of Example 1 was changed to A-2 to A-13, respectively.
（露光）
作製した実施例１のサンプルをＵＶランプ（ＵＶＧＬ－２５ Ｃｏｍｐａｃｔ ＵＶ Ｌａｍｐ、フナコシ社製）を用いて、１分間露光し、実施例１の着色サンプルを得た。実施例１の着色サンプルと同様にして、実施例２～１３の着色サンプルを得た。 (exposure)
The produced sample of Example 1 was exposed for 1 minute using a UV lamp (UVGL-25 Compact UV Lamp, manufactured by Funakoshi Co., Ltd.) to obtain a colored sample of Example 1. In the same manner as the colored sample of Example 1, colored samples of Examples 2 to 13 were obtained.
作製した実施例１のサンプルをＵＶランプ（ＵＶＧＬ－２５ Ｃｏｍｐａｃｔ ＵＶ Ｌａｍｐ、フナコシ社製）を用いて、１分間露光し、実施例１の着色サンプルを得た。実施例１の着色サンプルと同様にして、実施例２～１３の着色サンプルを得た。 (exposure)
The produced sample of Example 1 was exposed for 1 minute using a UV lamp (UVGL-25 Compact UV Lamp, manufactured by Funakoshi Co., Ltd.) to obtain a colored sample of Example 1. In the same manner as the colored sample of Example 1, colored samples of Examples 2 to 13 were obtained.
（色保持期間評価）
それぞれの着色サンプルについて、色が完全に消色するまでに要した期間（日）を記録した。１日以内に消色した場合は、×、２～６日で消色した場合は△、７日後でも消色していないものは○とする。 (Evaluation of color retention period)
For each colored sample, the period (days) required for the color to completely disappear was recorded. If the color is erased within 1 day, ×: if the color is erased after 2 to 6 days, Δ: if it is not erased after 7 days
それぞれの着色サンプルについて、色が完全に消色するまでに要した期間（日）を記録した。１日以内に消色した場合は、×、２～６日で消色した場合は△、７日後でも消色していないものは○とする。 (Evaluation of color retention period)
For each colored sample, the period (days) required for the color to completely disappear was recorded. If the color is erased within 1 day, ×: if the color is erased after 2 to 6 days, Δ: if it is not erased after 7 days
（安定性評価）
着色サンプルを１日放置した後、ホットプレート上で１２０℃に加熱し、消色させた際に、着色前の色と比較して大きく変化している場合は×、僅かに変化している場合は△、全く変化していない場合は○とする。 (Stability evaluation)
When the colored sample is left for one day and then heated to 120 ° C. on a hot plate and decolored, the color changes significantly compared to the color before coloring. △, and ◯ when there is no change.
着色サンプルを１日放置した後、ホットプレート上で１２０℃に加熱し、消色させた際に、着色前の色と比較して大きく変化している場合は×、僅かに変化している場合は△、全く変化していない場合は○とする。 (Stability evaluation)
When the colored sample is left for one day and then heated to 120 ° C. on a hot plate and decolored, the color changes significantly compared to the color before coloring. △, and ◯ when there is no change.
（繰り返し耐久性）
ＵＶランプを用いて１分間露光して着色させ、ホットプレート上で１２０℃に加熱し、消色させるという操作を２０回繰り返した後の色が、初期状態と比較して大きく変化している場合は×、僅かに変化している場合は△、全く変化していない場合は○とする。 (Repeated durability)
When the color after exposure and coloring for 1 minute using a UV lamp, heating to 120 ° C. on a hot plate and erasing 20 times has changed significantly compared to the initial state Is ×, Δ when slightly changing, and ○ when not changing at all.
ＵＶランプを用いて１分間露光して着色させ、ホットプレート上で１２０℃に加熱し、消色させるという操作を２０回繰り返した後の色が、初期状態と比較して大きく変化している場合は×、僅かに変化している場合は△、全く変化していない場合は○とする。 (Repeated durability)
When the color after exposure and coloring for 1 minute using a UV lamp, heating to 120 ° C. on a hot plate and erasing 20 times has changed significantly compared to the initial state Is ×, Δ when slightly changing, and ○ when not changing at all.
（比較例）
溶液Ａ－３、Ａ－７、Ａ－１３をそれぞれガラス基板上へ１滴落とし、室温下で乾燥させ、比較例１～３のサンプルを作製した。これら比較例のサンプルについても、色保持期間、安定性、繰り返し耐久性を評価した。 (Comparative example)
One drop of each of solutions A-3, A-7, and A-13 was dropped on a glass substrate and dried at room temperature to prepare samples of Comparative Examples 1 to 3. The samples of these comparative examples were also evaluated for color retention period, stability, and repeated durability.
溶液Ａ－３、Ａ－７、Ａ－１３をそれぞれガラス基板上へ１滴落とし、室温下で乾燥させ、比較例１～３のサンプルを作製した。これら比較例のサンプルについても、色保持期間、安定性、繰り返し耐久性を評価した。 (Comparative example)
One drop of each of solutions A-3, A-7, and A-13 was dropped on a glass substrate and dried at room temperature to prepare samples of Comparative Examples 1 to 3. The samples of these comparative examples were also evaluated for color retention period, stability, and repeated durability.
表１に、実施例及び比較例のサンプルの評価結果を示す。
Table 1 shows the evaluation results of the samples of the examples and comparative examples.
表１の結果から、ＨＡＢＩをろ紙基板上へ含有させることで、色保持期間が長期化しており、さらに、電子求引性置換基を持つＨＡＢＩを用いることで、色保持期間だけでなく、安定性、繰り返し耐久性が向上していることが分かる。
From the results of Table 1, the color retention period is prolonged by including HABI on the filter paper substrate, and further, not only the color retention period but also the stability is maintained by using HABI having an electron withdrawing substituent. It can be seen that the durability and repeated durability are improved.
以上、本発明の例示的な実施形態および実施例について説明した。
The exemplary embodiments and examples of the present invention have been described above.
本実施形態に係るリライタブルペーパーは、セルロース基板と、セルロース基板に含まれる、上記一般式（１）で表されるヘキサアリールビスイミダゾール（ＨＡＢＩ）と、を備える。これにより、セルロース基板内にＨＡＢＩを分散させることで、固体状態としても色保持期間を長くすることができる。
The rewritable paper according to the present embodiment includes a cellulose substrate and hexaarylbisimidazole (HABI) represented by the general formula (1) included in the cellulose substrate. Thus, by dispersing HABI in the cellulose substrate, the color retention period can be extended even in a solid state.
好ましくは、一般式（１）中、Ｒ１～Ｒ３０のいずれか少なくとも一つが、フッ素原子、フッ素化アルキル基又はシアノ基から選択される置換基である。これにより、ＨＡＢＩを利用したリライタブルペーパーの中でも、色保持期間、安定性、繰り返し耐久性を向上させたリライタブルペーパーを提供できる。
Preferably, in general formula (1), at least one of R 1 to R 30 is a substituent selected from a fluorine atom, a fluorinated alkyl group, or a cyano group. Thereby, among the rewritable papers using HABI, rewritable papers with improved color retention period, stability, and repeated durability can be provided.
さらに好ましくは、一般式（１）中、Ｒ１～Ｒ５、Ｒ１６～Ｒ２０のいずれか少なくとも一つが、フッ素原子、フッ素化アルキル基又はシアノ基から選択される置換基である。この場所に置換基を導入することにより、容易かつ効果的に、色保持期間、安定性、繰り返し耐久性を向上させることができる。
More preferably, in the general formula (1), at least one of R 1 to R 5 and R 16 to R 20 is a substituent selected from a fluorine atom, a fluorinated alkyl group, or a cyano group. By introducing a substituent in this place, the color retention period, stability, and repetition durability can be improved easily and effectively.
本実施形態に係るリライタブルペーパーの製造方法は、セルロース基板に上記一般式（１）で表されるヘキサアリールビスイミダゾール（ＨＡＢＩ）を含浸させる工程と、セルロース基板を乾燥させる工程とを含む。本実施形態によれば、上述した性能をもつリライタブルペーパーを安価に製造できる。
The method for producing a rewritable paper according to this embodiment includes a step of impregnating a cellulose substrate with hexaarylbisimidazole (HABI) represented by the above general formula (1) and a step of drying the cellulose substrate. According to this embodiment, the rewritable paper having the above-described performance can be manufactured at low cost.
本実施形態に係る方法は、上述したリライタブルペーパーの少なくとも一部に電磁波を照射して、電磁波が照射された部位を発色させる工程と、リライタブルペーパーを加熱して消色させる工程と、を含み、発色させる工程及び消色させる工程を繰り返し行うものである。これにより、色保持期間、安定性、繰り返し耐久性を向上させたリライタブルペーパーの使用方法を提供できる。
The method according to this embodiment includes a step of irradiating at least a part of the above-described rewritable paper with an electromagnetic wave to develop a color of a portion irradiated with the electromagnetic wave, and a step of heating and decoloring the rewritable paper, The color developing step and the color erasing step are repeated. Thereby, the usage method of the rewritable paper which improved the color retention period, stability, and repetition durability can be provided.
以上説明した実施形態は、本発明の理解を容易にするためのものであり、本発明を限定して解釈するためのものではない。実施形態が備える各要素並びにその配置、材料、条件、形状及びサイズ等は、例示したものに限定されるわけではなく適宜変更することができる。また、異なる実施形態で示した構成同士を部分的に置換し又は組み合わせることが可能である。
The embodiment described above is for facilitating the understanding of the present invention, and is not intended to limit the present invention. Each element included in the embodiment and its arrangement, material, condition, shape, size, and the like are not limited to those illustrated, and can be changed as appropriate. In addition, the structures shown in different embodiments can be partially replaced or combined.
１…リライタブルペーパー、１ａ…文字、２…電磁波照射手段
DESCRIPTION OF SYMBOLS 1 ... Rewritable paper, 1a ... Letter, 2 ... Electromagnetic wave irradiation means
Claims (5)
- セルロース基板と、
前記セルロース基板に含まれる、下記一般式（１）で表されるヘキサアリールビスイミダゾールと、
を備える、リライタブルペーパー。
A hexaarylbisimidazole represented by the following general formula (1), contained in the cellulose substrate;
A rewritable paper.
- 前記一般式（１）中、Ｒ１～Ｒ３０のいずれか少なくとも一つが、フッ素原子、フッ素化アルキル基又はシアノ基から選択される置換基である、
請求項１に記載のリライタブルペーパー。 In the general formula (1), at least one of R 1 to R 30 is a substituent selected from a fluorine atom, a fluorinated alkyl group, or a cyano group.
The rewritable paper according to claim 1. - 前記一般式（１）中、Ｒ１～Ｒ５、Ｒ１６～Ｒ２０のいずれか少なくとも一つが、フッ素原子、フッ素化アルキル基又はシアノ基から選択される置換基である、
請求項１又は２に記載のリライタブルペーパー。 In the general formula (1), at least one of R 1 to R 5 and R 16 to R 20 is a substituent selected from a fluorine atom, a fluorinated alkyl group, or a cyano group.
The rewritable paper according to claim 1 or 2. - セルロース基板に下記一般式（１）で表されるヘキサアリールビスイミダゾールを含浸させる工程と、
前記セルロース基板を乾燥させる工程と、
を含む、リライタブルペーパーの製造方法。
Drying the cellulose substrate;
A method for producing a rewritable paper.
- 請求項１から３のいずれか一項に記載のリライタブルペーパーの少なくとも一部に電磁波を照射して、前記電磁波が照射された部位を発色させる工程と、
前記リライタブルペーパーを加熱して消色させる工程と、
を含み、
前記発色させる工程及び前記消色させる工程を繰り返し行う、
方法。
Irradiating at least a part of the rewritable paper according to any one of claims 1 to 3 with an electromagnetic wave, and coloring the portion irradiated with the electromagnetic wave;
Heating and erasing the rewritable paper; and
Including
Repeatedly performing the color developing step and the decoloring step,
Method.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3909328A (en) * | 1973-04-10 | 1975-09-30 | Du Pont | Decoration of substrates by thermal transfer of photosensitive, thermoplastic, dye-imaged film |
| JPS5265425A (en) * | 1975-11-24 | 1977-05-30 | Minnesota Mining & Mfg | Image forming composition |
| JPS55151638A (en) * | 1979-05-11 | 1980-11-26 | Du Pont | Photosensistive system |
| US20020146649A1 (en) * | 2000-03-08 | 2002-10-10 | Mooney William Frank | Elements for forming print-out images |
| JP2005316483A (en) * | 2004-04-29 | 2005-11-10 | Xerox Corp | Reimageable medium |
-
2017
- 2017-10-10 WO PCT/JP2017/036574 patent/WO2018070361A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3909328A (en) * | 1973-04-10 | 1975-09-30 | Du Pont | Decoration of substrates by thermal transfer of photosensitive, thermoplastic, dye-imaged film |
| JPS5265425A (en) * | 1975-11-24 | 1977-05-30 | Minnesota Mining & Mfg | Image forming composition |
| JPS55151638A (en) * | 1979-05-11 | 1980-11-26 | Du Pont | Photosensistive system |
| US20020146649A1 (en) * | 2000-03-08 | 2002-10-10 | Mooney William Frank | Elements for forming print-out images |
| JP2005316483A (en) * | 2004-04-29 | 2005-11-10 | Xerox Corp | Reimageable medium |
Non-Patent Citations (2)
| Title |
|---|
| CASPAR, V. J. ET AL.: "ESR study of lophyl free radicals in dry films", MACROMOLECULES, vol. 28, pages 636 - 641, XP055499253 * |
| TAKEDA, GO ET AL.: "Photochromic properties of HABI-doped SiO2 glass", POLYMER PREPRINTS , JAPAN, vol. 56, no. 2, 4 September 2007 (2007-09-04) * |
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