JP2001311079A - Liquid crystal microcapsule and recording display medium - Google Patents
Liquid crystal microcapsule and recording display mediumInfo
- Publication number
- JP2001311079A JP2001311079A JP2000127174A JP2000127174A JP2001311079A JP 2001311079 A JP2001311079 A JP 2001311079A JP 2000127174 A JP2000127174 A JP 2000127174A JP 2000127174 A JP2000127174 A JP 2000127174A JP 2001311079 A JP2001311079 A JP 2001311079A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- compound
- microcapsule according
- group
- color
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 94
- 239000003094 microcapsule Substances 0.000 title claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 33
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol group Chemical group [C@@H]1(CC[C@H]2[C@@H]3CC=C4C[C@@H](O)CC[C@]4(C)[C@H]3CC[C@]12C)[C@H](C)CCCC(C)C HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 18
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 40
- -1 cholesteryl ester Chemical class 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 28
- 239000000463 material Substances 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000003098 cholesteric effect Effects 0.000 description 6
- 235000012000 cholesterol Nutrition 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 1
- QSGFWCJBAGSZKX-UHFFFAOYSA-N C(CCCCCCCCC#CC#CCCCCCCCCC)(C(=O)O)C(=O)O Chemical compound C(CCCCCCCCC#CC#CCCCCCCCCC)(C(=O)O)C(=O)O QSGFWCJBAGSZKX-UHFFFAOYSA-N 0.000 description 1
- BPHQFLFRXJVANR-UHFFFAOYSA-N C(CCCCCCCCCCC#CC#CCCCCCCCCCCC)(C(=O)O)C(=O)O Chemical compound C(CCCCCCCCCCC#CC#CCCCCCCCCCCC)(C(=O)O)C(=O)O BPHQFLFRXJVANR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 101001094026 Synechocystis sp. (strain PCC 6803 / Kazusa) Phasin PhaP Proteins 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、液晶マイクロカプ
セル及び記録表示媒体に関する。更に詳しくは、書き換
え可能な感熱式の特定の色又はフルカラーによる記録表
示が可能な液晶マイクロカプセル及び記録表示媒体に関
する。[0001] The present invention relates to a liquid crystal microcapsule and a recording and display medium. More specifically, the present invention relates to a liquid crystal microcapsule capable of recording and displaying a rewritable thermosensitive specific color or full color, and a recording display medium.
【０００２】[0002]
【従来の技術】フルカラーを記録することが可能で書き
換えが不可能な記録材料としてはカラー写真やカラーコ
ピーが知られている。書き換えが可能でフルカラーでは
ない記録材料としては、ベヘン酸等の長鎖アルキルカル
ボン酸誘導体を含む感熱記録材料やスピロピラン誘導体
等のフォトクロミック化合物を利用した光記録材料、そ
の他、磁気や光磁気等のメモリー材料が知られている。2. Description of the Related Art A color photograph and a color copy are known as recording materials capable of recording full color and not rewriting. Non-full-color rewritable recording materials include thermosensitive recording materials containing long-chain alkyl carboxylic acid derivatives such as behenic acid, optical recording materials using photochromic compounds such as spiropyran derivatives, and memories such as magnetism and magnetomagnetism. Materials are known.
【０００３】これまでの記録材料はフルカラーと書き換
え可能な特性を両立するものではなかった。確かに表示
材料の中にはテレビや液晶表示等のように表示が変化
し、かつフルカラーのものが存在するが財布の中に収ま
る程度の薄いカードとして用いたり電源なしにいつまで
も安定に画像を表示しておくことはできないため、記録
材料の代わりに使うことはできなかった。Conventional recording materials have not achieved both full color and rewritable characteristics. Certainly, some display materials change their display, such as televisions and liquid crystal displays, and there are full-color ones, but they can be used as a thin card that fits in a wallet or display images stably forever without a power supply It could not be used as a substitute for recording material.
【０００４】近年、液晶性化合物が示すコレステリック
相の干渉色を、０℃付近まで急冷することにより固定す
ることができる液晶性化合物を用いた、書き換え可能な
フルカラー記録が達成された（特開平１１−２４０２７
号公報、特許第２９４６０４２号公報、特開平１１−２
７７９１４号公報、特開平１１−２８１９４５号公
報）。しかし、上記従来の技術では、液晶性化合物その
ものを、直接ガラス板等の透明基板間に挟持させて記録
表示媒体として用いるため、液晶性化合物を多量に必要
とする、取扱いが困難である等の問題があった。In recent years, rewritable full-color recording has been achieved using a liquid crystal compound which can fix the interference color of the cholesteric phase exhibited by the liquid crystal compound by rapidly cooling it to around 0 ° C. -24027
Patent Publication, Japanese Patent No. 2946042, JP-A-11-2
No. 77914, JP-A-11-281945). However, in the above-mentioned conventional technology, the liquid crystal compound itself is directly sandwiched between transparent substrates such as a glass plate and used as a recording display medium, so that a large amount of the liquid crystal compound is required, handling is difficult, and the like. There was a problem.
【０００５】一方、特開平１０−６２７３７号公報、特
開平１０−３２９４５７号公報には、液晶マイクロカプ
セルが開示されているが、これらのマイクロカプセル
は、液晶化合物を内包する構造であるため、液晶の配向
を制御することが困難であり、特に上記コレステリック
相の干渉色を固定する液晶性化合物の場合には、コレス
テリック相を長期に保持することが困難であるという問
題があった。On the other hand, JP-A-10-62737 and JP-A-10-329457 disclose liquid crystal microcapsules. These microcapsules have a structure containing a liquid crystal compound. It is difficult to control the orientation of the cholesteric phase, and in particular, in the case of a liquid crystal compound that fixes the interference color of the cholesteric phase, there is a problem that it is difficult to maintain the cholesteric phase for a long time.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記従来の
問題に鑑み、液晶の使用量を低減でき、取扱いが容易
で、液晶の配向を容易に制御可能、かつ書き換え可能な
特定の色による記録又はフルカラー記録を達成できる液
晶マイクロカプセル及び記録表示媒体を提供することを
目的とする。SUMMARY OF THE INVENTION In view of the above-mentioned problems, the present invention can reduce the amount of liquid crystal used, is easy to handle, can easily control the orientation of liquid crystal, and uses a specific color that can be rewritten. It is an object of the present invention to provide a liquid crystal microcapsule and a recording display medium capable of achieving recording or full-color recording.
【０００７】[0007]
【課題を解決するための手段】即ち、本発明は、母粒子
の表面に液晶層を有することを特徴とする液晶マイクロ
カプセル及び、該液晶マイクロカプセルを透明樹脂中に
分散してなることを特徴とする記録表示媒体である。That is, the present invention is characterized in that a liquid crystal microcapsule characterized by having a liquid crystal layer on the surface of a base particle, and that the liquid crystal microcapsule is dispersed in a transparent resin. Is a recording and display medium.
【０００８】[0008]
【発明の実施の形態】以下、本発明を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
【０００９】本発明の液晶マイクロカプセルは、母粒子
の表面に液晶層を有する。The liquid crystal microcapsules of the present invention have a liquid crystal layer on the surface of the base particles.
【００１０】母粒子としては、例えば、アクリル樹脂、
ポリカーボネート、ポリオレフィン、ポリエステル、ポ
リアミド、ポリイミド、ポリエーテル、ポリスルフォン
等の樹脂粒子、カーボン粒子、ガラスビーズ等、有機
物、無機物のいずれでも使用しうる。また、液晶層が液
晶状態で、加熱温度に応じて発色し、該温度から急冷す
ることで該発色した状態を保持する液晶化合物よりなる
場合には、反射色を見やすくするために、着色粒子、特
に黒色系の粒子であることが好ましい。As the base particles, for example, acrylic resin,
Any of organic and inorganic substances such as resin particles such as polycarbonate, polyolefin, polyester, polyamide, polyimide, polyether, and polysulfone, carbon particles, and glass beads can be used. Further, when the liquid crystal layer is in a liquid crystal state, it is colored according to a heating temperature, and when the liquid crystal layer is formed of a liquid crystal compound which maintains the developed state by being rapidly cooled from the temperature, colored particles are used to make the reflected color easier to see. In particular, black particles are preferable.
【００１１】本発明の液晶層に用いる液晶化合物として
は、特に限定されないが、液晶状態で、加熱温度に応じ
て発色し、該温度から急冷することで該発色した状態を
保持する、即ち色を固定する液晶性化合物が好ましく、
例えば、二塩基酸ジコレステリルエステルが挙げられ、
具体的には下記一般式（１）で表される二塩基酸ジコレ
ステリルエステルが挙げられる。The liquid crystal compound used in the liquid crystal layer of the present invention is not particularly limited, but in the liquid crystal state, it develops a color in accordance with the heating temperature, and the color developed state is maintained by rapid cooling from the temperature, that is, the color is maintained. A liquid crystal compound to be fixed is preferred,
For example, dibasic acid cholesteryl ester,
Specific examples include dibasic acid cholesteryl ester represented by the following general formula (1).
【００１２】 ＹＯ−ＣＯ(ＣＨ2)n−Ｏ−Ｒ−Ｏ−(ＣＨ2)nＣＯ−ＯＹ・・・（１） （式中、Ｙはコレステリル基を示し、Ｒはｐ−フェニレ
ン又は４，４’−ビフェニレンを示し、ｎは１〜２０の
数を示す）YO—CO (CH 2 ) n —O—R—O— (CH 2 ) n CO—OY (1) (wherein, Y represents a cholesteryl group, and R represents p-phenylene or 4 , 4'-biphenylene, and n represents a number of 1 to 20)
【００１３】この二塩基酸ジコレステリルエステルは、
ジアルコキシベンゼン部又はジアルコキシビフェニル部
を含有する長鎖二塩基酸（以下、単に長鎖二塩基酸とも
言う）とコレステロールとを縮合反応させるか、又はω
−ブロモアルカン酸コレステリルエステルとハイドロキ
ノン又は４，４’−ジヒドロキシビフェニルを縮合反応
させることによって製造される。前記長鎖二塩基酸は、
下記一般式で表される。This dibasic acid cholesteryl ester is
A condensation reaction between a long-chain dibasic acid containing a dialkoxybenzene moiety or a dialkoxybiphenyl moiety (hereinafter, also simply referred to as a long-chain dibasic acid) and cholesterol, or
It is produced by a condensation reaction of cholesteryl bromoalkanoate and hydroquinone or 4,4'-dihydroxybiphenyl. The long-chain dibasic acid,
It is represented by the following general formula.
【００１４】 ＨＯＯＣ−(ＣＨ2)n−Ｏ−Ｒ−Ｏ−(ＣＨ2)n−ＣＯＯＨHOOC— (CH 2 ) n —O—R—O— (CH 2 ) n —COOH
【００１５】前記式中、Ｒは前記と同じ意味を有し、ｎ
は１〜２０、好ましくは３〜９の数を示す。前記長鎖二
塩基酸は、従来公知の化合物であり、例えば、相当する
ω−ブロモアルカン酸とハイドロキノン又は４，４’−
ビフェノールを水酸化ナトリウムの存在下、エタノール
中で７８℃で反応させることにより得ることができる。
ハイドロキノンを用いた場合の反応式を示すと、以下の
通りである。In the above formula, R has the same meaning as described above, and n
Represents a number of 1 to 20, preferably 3 to 9. The long-chain dibasic acid is a conventionally known compound, for example, a corresponding ω-bromoalkanoic acid and hydroquinone or 4,4′-
It can be obtained by reacting biphenol in ethanol in the presence of sodium hydroxide at 78 ° C.
The reaction formula when using hydroquinone is shown below.
【００１６】ＨＯＣ6Ｈ4ＯＨ ＋ ＨＯＯＣ(ＣＨ2)nＢ
ｒ→ ＨＯＯＣ(ＣＨ2)n−ＯＣ6Ｈ4Ｏ−(ＣＨ2)nＣＯＯ
ＨHOC 6 H 4 OH + HOOC (CH 2 ) n B
r → HOOC (CH 2 ) n -OC 6 H 4 O- (CH 2 ) n COO
H
【００１７】前記長鎖二塩基酸は、ω−ブロモアルカン
酸エチルとハイドロキノンとを反応させることによって
も得ることができる（Ｓ．Ｂｈａｔｔａｃｈａｒｙａ
ａｎｄ Ｓ．Ｄｅ，Ｃｈｅｍ．Ｃｏｍｍｕｎ．，１２８
３，１９９６）。The long-chain dibasic acid can also be obtained by reacting ethyl ω-bromoalkanoate with hydroquinone (S. Bhattacharya).
and S.M. De, Chem. Commun. , 128
3, 1996).
【００１８】前記した長鎖二塩基酸とコレステロールと
を縮合反応させる場合、コレステロールの使用割合は、
長鎖二塩基酸１モル当り、２〜４モル、好ましくは２〜
２．５モルの割合である。この反応は、塩化メチレン等
の反応溶媒を用い、ジシクロヘキシルカルボジイミド及
び４−ジメチルアミノピリジンの存在下、室温下で１２
時間程度撹拌することにより実施される。この場合、ジ
シクロヘキシルカルボジイミドは二塩基酸を活性化させ
る作用を示し、その使用量は、コレステロール１モル当
り、１〜２モルの割合である。一方、４−ジメチルアミ
ノピリジンは、縮合触媒として作用し、その使用量は、
コレステロール１モル当り、０．１〜０．２モルの割合
である。When the above-mentioned long-chain dibasic acid is subjected to a condensation reaction with cholesterol, the proportion of cholesterol used is as follows:
2 to 4 moles, preferably 2 to 4 moles per mole of the long-chain dibasic acid
2.5 moles. This reaction is carried out using a reaction solvent such as methylene chloride in the presence of dicyclohexylcarbodiimide and 4-dimethylaminopyridine at room temperature for 12 hours.
It is carried out by stirring for about an hour. In this case, dicyclohexylcarbodiimide has an effect of activating a dibasic acid, and the amount used is 1 to 2 mol per mol of cholesterol. On the other hand, 4-dimethylaminopyridine acts as a condensation catalyst, and its amount used is
The ratio is 0.1 to 0.2 mol per mol of cholesterol.
【００１９】また、分子量が２０００以下、好ましくは
５００〜１５００、更に好ましくは７００〜１２００で
ガラス転移温度が３５℃以上、好ましくは５０℃以上、
更に好ましくは７０〜１１０℃のコレステリック液晶性
化合物を挙げられる。Also, the molecular weight is 2,000 or less, preferably 500 to 1500, more preferably 700 to 1200 and the glass transition temperature is 35 ° C. or more, preferably 50 ° C. or more.
More preferably, a cholesteric liquid crystalline compound having a temperature of 70 to 110 ° C. can be used.
【００２０】これらのうちでも、特に好ましいコレステ
リック液晶性化合物として、下記一般式（２）で表され
る化合物が挙げられる。Of these, particularly preferred cholesteric liquid crystal compounds include compounds represented by the following general formula (2).
【００２１】 Ｚ−Ｏ−ＣＯ−Ｑ−ＣＯ−Ｏ−Ｘ・・・（２） （式中Ｘ及びＺは各々独立してコレステリル基、水素原
子又はアルキル基を、Ｑは炭素数２〜２０の２価の炭化
水素基を表し、Ｘ及びＺの少なくともいずれか一方はコ
レステリル基を表す）Z—O—CO—Q—CO—O—X (2) (wherein X and Z each independently represent a cholesteryl group, a hydrogen atom or an alkyl group, and Q represents 2 to 20 carbon atoms. Represents at least one of X and Z represents a cholesteryl group)
【００２２】前記２価の炭化水素基としては例えば下記
一般式（３）で表される基が挙げられる。The divalent hydrocarbon group includes, for example, a group represented by the following general formula (3).
【００２３】 −（ＣＨ2)l−Ｃ≡Ｃ−Ｃ≡Ｃ−（ＣＨ2)m−・・・（３） （式中ｌ及びｍは各々独立して１以上の整数であり、但
しｌとｍとの合計は３０を超えないものとする）-(CH 2 ) 1 -C≡CC−C- (CH 2 ) m- (3) (wherein l and m are each independently an integer of 1 or more, provided that l And the sum of m and m shall not exceed 30)
【００２４】コレステリック液晶性化合物の好ましい例
として、１０，１２−ドコサジインジカルボン酸ジコレ
ステリルエステル、エイコサンジカルボン酸ジコレステ
リルエステル、１０，１２−ペンタコサジインジカルボ
ン酸コレステリルエステル、ドデカジカルボン酸ジコレ
ステリルエステル、１２，１４−ヘキサコサジインジカ
ルボン酸ジコレステリルエステル等が挙げられる。Preferred examples of the cholesteric liquid crystalline compound include cholesteryl ester of 10,12-docosadiyne dicarboxylic acid, cholesteryl ester of eicosane dicarboxylic acid, and cholesteryl ester of 10,12-pentacosadiin dicarboxylic acid and dicholesteryl dodecadicarboxylate. Esters, 12,14-hexacosadiyne dicarboxylic acid dicholesteryl ester, and the like.
【００２５】上記液晶化合物は単独で用いてもよいし、
混合物として用いてもよい。混合物として用いることに
より、液晶化合物単体が示す液晶温度範囲とは異なる温
度範囲を示し、固定される反射波長の領域も異なるもの
となり、混合する化合物、混合割合を適宜設定すること
で、液晶温度範囲、固定される反射波長の領域を任意に
制御できる。その結果、化合物単体よりも低い温度での
色の固定も可能となる。この際、色を固定できない化合
物を混合してもよい。また、色を固定できない化合物同
士の混合物の場合にも、単体が示す液晶温度範囲とは異
なる温度範囲を示し、固定される反射波長の領域も異な
るものとなった結果、色を固定できるようになる。The above liquid crystal compound may be used alone,
It may be used as a mixture. When used as a mixture, the liquid crystal compound exhibits a temperature range different from the liquid crystal temperature range indicated by the liquid crystal compound alone, and the region of the fixed reflection wavelength is also different. By appropriately setting the compound to be mixed and the mixing ratio, the liquid crystal temperature range The region of the fixed reflection wavelength can be arbitrarily controlled. As a result, it is possible to fix the color at a temperature lower than that of the compound alone. At this time, a compound that cannot fix the color may be mixed. Also, even in the case of a mixture of compounds that cannot fix the color, the temperature range is different from the liquid crystal temperature range indicated by the simple substance, and the region of the reflection wavelength to be fixed is also different, so that the color can be fixed. Become.
【００２６】混合物としては、一般式（１）で表される
二塩基酸ジコレステリルエステル同士の混合物、、一般
式（１）で表される二塩基酸ジコレステリルエステルと
下記一般式（２）で表されるモノコレステリルエステル
との混合物が好ましい。As the mixture, a mixture of dibasic acid cholesteryl esters represented by the general formula (1), a dibasic acid cholesteryl ester represented by the general formula (1) and a dibasic acid cholesteryl ester represented by the following general formula (2) are used. Mixtures with the monocholesteryl esters represented are preferred.
【００２７】 ＹＯ−ＣＯ(ＣＨ2)n−Ｏ−Ｒ−ＯＨ・・・（２） （式中、Ｙはコレステリル基を示し、Ｒはｐ−フェニレ
ン又は４，４’−ビフェニレンを示し、ｎは１〜２０の
数を示す）YO—CO (CH 2 ) n —OR—OH (2) (wherein, Y represents a cholesteryl group, R represents p-phenylene or 4,4′-biphenylene, and n represents Represents the number of 1 to 20)
【００２８】混合割合としては特に限定されないが、２
種の化合物を混合する場合には、両者の重量比が１：
０．８〜１．２であることが好ましい。また、色を固定
できる化合物を２０重量％以上、より好ましくは４０重
量％〜６０重量％含有させることが好ましい。このよう
な混合割合とすることにより、液晶温度範囲、反射波長
域を広く取ることができる。The mixing ratio is not particularly limited.
When two kinds of compounds are mixed, the weight ratio between them is 1:
It is preferably 0.8 to 1.2. Further, it is preferable to contain a compound capable of fixing a color in an amount of 20% by weight or more, more preferably 40% by weight to 60% by weight. With such a mixing ratio, the liquid crystal temperature range and the reflection wavelength range can be widened.
【００２９】混合方法としては、従来公知の方法を使用
することでき、例えば混合しようとする化合物を、塩化
メチレン等のこれらを溶解する溶媒に溶解し、溶媒分を
留去した後に、真空乾燥することにより粉末状の混合物
を得ることができる。As a mixing method, conventionally known methods can be used. For example, a compound to be mixed is dissolved in a solvent in which these are dissolved, such as methylene chloride, and the solvent is distilled off, followed by vacuum drying. Thus, a powdery mixture can be obtained.
【００３０】また、本発明の液晶層には、色素、酸化防
止剤等の添加剤を含むことができる。この場合、上記液
晶化合物の量は９０重量％以上であることが好ましい。Further, the liquid crystal layer of the present invention may contain additives such as a dye and an antioxidant. In this case, the amount of the liquid crystal compound is preferably 90% by weight or more.
【００３１】液晶層の厚さは、特に限定されないが、
０．１μｍ〜１０μｍであることが好ましく、より好ま
しくは１μｍ〜５μｍである。Although the thickness of the liquid crystal layer is not particularly limited,
It is preferably from 0.1 μm to 10 μm, more preferably from 1 μm to 5 μm.
【００３２】本発明のマイクロカプセルは、液晶層の表
面に、透明性の高い樹脂、例えばアクリル樹脂（ＰＭＭ
Ａ）、ポリカーボネート、ポリスチレンなどよりなる透
明層を有してもよい。透明層を設けることにより、母粒
子と透明層で液晶層を挟み込み、液晶の配向性を均一に
し易くなる。透明層の厚さは、特に限定されないが、
０．０５μｍ〜５．０μｍであることが好ましく、より
好ましくは０．１μｍ〜２．０μｍである。The microcapsules according to the present invention have a high transparency resin such as an acrylic resin (PMM) on the surface of the liquid crystal layer.
A), and may have a transparent layer made of polycarbonate, polystyrene, or the like. By providing the transparent layer, the liquid crystal layer is sandwiched between the base particles and the transparent layer, and the orientation of the liquid crystal is easily made uniform. The thickness of the transparent layer is not particularly limited,
It is preferably from 0.05 μm to 5.0 μm, more preferably from 0.1 μm to 2.0 μm.
【００３３】本発明のマイクロカプセルの形状として
は、例えば、立方体状、直方体状等の方体状、球状、楕
円球等の球状、その他任意の形状が挙げられるが、球状
が好ましい。マイクロカプセルの大きさとしては、その
径が通常、１μｍ〜１００μｍが好ましく、５μｍ〜６
０μｍがより好ましい。The shape of the microcapsule of the present invention may be, for example, a cubic shape, a rectangular parallelepiped shape, or the like, a spherical shape, a spherical shape such as an elliptical sphere, or any other shape. A spherical shape is preferred. As the size of the microcapsules, the diameter is usually preferably 1 μm to 100 μm, and preferably 5 μm to 6 μm.
0 μm is more preferred.
【００３４】本発明のマイクロカプセルは、機械的方
法、即ち機械的エネルギーを利用して、母粒子表面に液
晶層を形成する方法により製造される。具体的には、母
粒子表面に、子粒子である液晶化合物の粉末をファンデ
ルワールス力や静電気力により付着させ、機械的力によ
り付着粉末の一部を母粒子中に固定化したり、或いは摩
擦熱により付着粉末を溶融させて薄膜状にする（メカノ
フュージョン）等の方法により製造される。The microcapsules of the present invention are manufactured by a mechanical method, that is, a method of forming a liquid crystal layer on the surface of the base particles using mechanical energy. Specifically, powder of the liquid crystal compound, which is a child particle, is adhered to the surface of the mother particle by van der Waals force or electrostatic force, and a part of the adhered powder is fixed in the mother particle by mechanical force, or friction is applied. It is manufactured by a method such as melting the attached powder by heat to form a thin film (mechanofusion).
【００３５】この際、母粒子の大きさは、子粒子である
液晶化合物粉末の１０倍以上であることが好ましく、具
体的には、母粒子の大きさは、０．５μｍ〜９０μｍで
あることが好ましく、子粒子である液晶化合物粉末の大
きさは、０．０５μｍ〜９μｍであることが好ましい。At this time, the size of the base particles is preferably at least 10 times the size of the liquid crystal compound powder as the child particles, and specifically, the size of the base particles is 0.5 μm to 90 μm. It is preferable that the size of the liquid crystal compound powder as the child particles is 0.05 μm to 9 μm.
【００３６】本発明のマイクロカプセルは、溶剤、透明
層を有さない場合には液晶層を溶解しない溶剤に分散さ
せて塗料として用いることができる。この塗料により形
成された塗膜は、樹脂中にマイクロカプセルを分散した
塗膜であり、記録表示媒体として使用し得る。即ち、透
明層を有す場合は、前述のように透明層と母粒子の間
で、透明層を有さない場合には、マイクロカプセルの周
りで固化した樹脂と母粒子との間で、液晶層を挟み込む
こととなり、液晶の配列を制御することができる。特
に、液晶層が、液晶状態で、加熱温度に応じて発色し、
該温度から急冷することで該発色した状態を保持する液
晶化合物を含有する場合には、固定された反射色又は透
過色を利用して、書換が可能なカラー記録表示が可能な
記録表示媒体として、例えば、カード、オーバーヘッド
プロジェクト用のシート、ラベル、チケット等として用
いることができる。The microcapsule of the present invention can be used as a coating material by dispersing it in a solvent or a solvent which does not dissolve the liquid crystal layer if it does not have a transparent layer. The coating film formed by this paint is a coating film in which microcapsules are dispersed in a resin, and can be used as a recording and display medium. That is, when the transparent layer is provided, the liquid crystal is formed between the transparent layer and the base particles as described above, and when the transparent layer is not provided, the liquid crystal is formed between the resin solidified around the microcapsules and the base particles. By sandwiching the layers, the alignment of the liquid crystal can be controlled. In particular, the liquid crystal layer develops color in the liquid crystal state according to the heating temperature,
When containing a liquid crystal compound that retains the colored state by being rapidly cooled from the temperature, using a fixed reflection color or transmission color, as a recording display medium capable of rewritable color recording display. For example, they can be used as cards, sheets, labels, tickets, etc. for overhead projects.
【００３７】この際、必要に応じ、保護層、裏面層等を
更に設けてもよい。例えば、ラベルの場合、記録表示媒
体の裏面に接着剤層を介して台紙が設けられる。磁気チ
ケットの場合、上記台紙に代えて、バインダーと強磁性
紛体からなる磁気記録層が設けられる。At this time, if necessary, a protective layer, a back surface layer and the like may be further provided. For example, in the case of a label, a backing paper is provided on the back surface of the recording display medium via an adhesive layer. In the case of a magnetic ticket, a magnetic recording layer made of a binder and a ferromagnetic powder is provided in place of the mount.
【００３８】[0038]
【実施例】（実施例１）母粒子となる平均粒径５０μｍ
のＰＭＭＡ（ポリメタクリル酸メチル）粒子３０ｇと、
子粒子となる微細粉末化（平均粒径１μｍ）した下記
（１’）式で表される液晶化合物３ｇを、ビニール袋に
入れてよく振り混ぜ、両者を均一に混合した。EXAMPLES (Example 1) Average particle size of 50 μm serving as base particles
30 g of PMMA (polymethyl methacrylate) particles,
3 g of a liquid crystal compound represented by the following formula (1 ′), which was made into fine powder (average particle size: 1 μm) as child particles, was placed in a plastic bag, shaken well, and both were uniformly mixed.
【００３９】 ＹＯ−ＣＯ(ＣＨ2)5−Ｏ−Ｒ−Ｏ−(ＣＨ2)5ＣＯ−ＯＹ・・・（１’） （式中、Ｙはコレステリル基を示し、Ｒはｐ−フェニレ
ンを示す）YO—CO (CH 2 ) 5 —O—R—O— (CH 2 ) 5 CO—OY (1 ′) (wherein Y represents a cholesteryl group, and R represents p-phenylene. Show)
【００４０】この混合粉末を、乾式マイクロカプセル製
造装置である「ハイブリダイザー」（株式会社奈良機械
製作所製）の材料投入口より材料導入部分へ投入したと
ころ、混合粉末は空気の流れによって成膜処理部分へ運
ばれた。成膜処理部分で、１１３００ｒｐｍで３分間処
理することにより、衝撃力を主体とする機械的熱エネル
ギーを与えられ、母粒子周囲に子粒子が溶融固化した状
態になり成膜処理された。この粒子を、捕集器によって
集め、母粒子の周辺に約２μｍの厚さの液晶層が成膜さ
れたマイクロカプセルを得た。The mixed powder was introduced into a material introduction portion through a material introduction port of "Hybridizer" (manufactured by Nara Machinery Co., Ltd.) which is a dry microcapsule manufacturing apparatus. Transported to the part. In the film formation processing portion, by performing the treatment at 11300 rpm for 3 minutes, mechanical thermal energy mainly including an impact force was given, and the child particles were melted and solidified around the base particles, and the film formation processing was performed. The particles were collected by a collector to obtain a microcapsule in which a liquid crystal layer having a thickness of about 2 μm was formed around the mother particles.
【００４１】このマイクロカプセル０．１ｇを、ポリビ
ニルアルコール（商品名「ゴーセノール」日本合成化学
工業株式会社製）２ｇを水１０ｍｌに溶解したものに加
えて撹拌し、懸濁状態として塗液を得た。0.1 g of the microcapsules was added to a solution of 2 g of polyvinyl alcohol (trade name "Gosenol", manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) in 10 ml of water, and the mixture was stirred to obtain a coating liquid in a suspended state. .
【００４２】この塗液を、厚さ０．５ｍｍのガラス基板
上に滴下し、スピンコーター（３００ｒｐｍ、３０秒
間）で均一な塗膜とした。その後、この基板を１５０℃
のホットプレート上で５分間ベークして、透明な膜とし
た。This coating solution was dropped on a glass substrate having a thickness of 0.5 mm, and a uniform coating film was formed with a spin coater (300 rpm, 30 seconds). Thereafter, the substrate is heated to 150 ° C.
Was baked on a hot plate for 5 minutes to form a transparent film.
【００４３】この膜を、ホットプレートを備えた顕微鏡
で観察したところ、室温では膜中にマイクロカプセルが
分散した状態が観察できた。温度を上昇させたところ、
液晶化合物が液晶状態になる温度に達すると、液晶層が
液晶状態になった。更に温度を上げると、透明点（液晶
から等方性液体になる温度）では、液晶状態から等方性
液体へと変化した。この状態から温度を下げると液晶状
態に戻り、更に温度を下げると液晶層の液晶化合物は結
晶化した。また、温度の上昇下降を繰り返したところ、
液晶層は状態の変化を繰り返した。When this film was observed with a microscope equipped with a hot plate, a state in which microcapsules were dispersed in the film could be observed at room temperature. After raising the temperature,
When the temperature at which the liquid crystal compound reached the liquid crystal state was reached, the liquid crystal layer was in the liquid crystal state. When the temperature was further increased, the liquid crystal changed from a liquid crystal state to an isotropic liquid at the clearing point (the temperature at which the liquid crystal changed to an isotropic liquid). When the temperature was lowered from this state, the state returned to the liquid crystal state. When the temperature was further lowered, the liquid crystal compound in the liquid crystal layer crystallized. Also, when the temperature rises and falls repeatedly,
The liquid crystal layer repeatedly changed its state.
【００４４】更に、ホットプレート上で基板を１８０℃
に加熱することにより液晶状態として、反射色が現れる
状態とし、その状態から、氷水へ投入することで急冷
し、青色の反射色を固定した。Further, the substrate is heated to 180 ° C. on a hot plate.
Then, the liquid was brought into a liquid crystal state by reflection, and a state in which a reflected color appeared was formed. From that state, the liquid was poured into ice water to be rapidly cooled to fix the blue reflected color.
【００４５】（実施例２）母粒子として平均粒径３０μ
ｍの黒色ポリスチレン粒子を用い、成膜処理部分での処
理を１２０００ｒｐｍで５分間とした以外は実施例１と
同様にしてマイクロカプセルを製造し、塗膜を形成し
て、実施例１と同様に観察したところ、実施例１と同様
の状態変化が見られ、また青色の固定もできた。Example 2 An average particle diameter of 30 μm was used as a base particle.
m, and microcapsules were produced in the same manner as in Example 1 except that the treatment in the film-forming treatment portion was performed at 12,000 rpm for 5 minutes, and a coating film was formed. Upon observation, the same state change as in Example 1 was observed, and blue fixation was also possible.
【００４６】[0046]
【発明の効果】以上説明のように、本発明によれば、液
晶層を表面に有するマイクロカプセルとすることによ
り、液晶の使用量を低減でき、取扱いを容易にでき、か
つ液晶の配向を容易に制御できる。また、液晶層に、液
晶状態で、加熱温度に応じて発色し、該温度から急冷す
ることで該発色した状態を保持する液晶化合物を含有さ
せることにより、書き換え可能な特定の色による記録又
はフルカラー記録を達成できる。As described above, according to the present invention, by using microcapsules having a liquid crystal layer on the surface, the amount of liquid crystal used can be reduced, handling can be facilitated, and alignment of the liquid crystal can be facilitated. Can be controlled. In addition, the liquid crystal layer contains a liquid crystal compound which develops a color in accordance with a heating temperature in a liquid crystal state and maintains the developed state by rapidly cooling from the temperature, thereby enabling recording in a rewritable specific color or full color. Achieve a record.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 2H088 EA62 GA02 GA03 GA13 MA16 MA20 2H089 HA06 HA09 JA05 UA09 4H027 BB07 BE07 DM03 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H088 EA62 GA02 GA03 GA13 MA16 MA20 2H089 HA06 HA09 JA05 UA09 4H027 BB07 BE07 DM03
Claims (10)
徴とする液晶マイクロカプセル。1. A liquid crystal microcapsule having a liquid crystal layer on the surface of a base particle.
とを特徴とする請求項１に記載の液晶マイクロカプセ
ル。2. The liquid crystal microcapsule according to claim 1, wherein a transparent layer is provided on a surface of the liquid crystal layer.
とする請求項１または２に記載の液晶マイクロカプセ
ル。3. The liquid crystal microcapsule according to claim 1, wherein the base particles are colored particles.
応じて発色し、該温度から急冷することで該発色した状
態を保持する液晶化合物を含有することを特徴とする請
求項１〜３に記載の液晶マイクロカプセル。4. The liquid crystal layer according to claim 1, wherein the liquid crystal layer contains a liquid crystal compound which develops a color in accordance with a heating temperature in a liquid crystal state and maintains the developed state by rapidly cooling from the temperature. 4. The liquid crystal microcapsule according to 3.
リルエステルであることを特徴とする請求項４に記載の
液晶マイクロカプセル。5. The liquid crystal microcapsule according to claim 4, wherein said liquid crystal compound is dibasic acid cholesteryl ester.
が、下記一般式（１）で表されることを特徴とする請求
項５に記載の液晶マイクロカプセル。 ＹＯ−ＣＯ(ＣＨ2)n−Ｏ−Ｒ−Ｏ−(ＣＨ2)nＣＯ−ＯＹ・・・（１） （式中、Ｙはコレステリル基を示し、Ｒはｐ−フェニレ
ン又は４，４’−ビフェニレンを示し、ｎは１〜２０の
数を示す）6. The liquid crystal microcapsule according to claim 5, wherein the dibasic acid cholesteryl ester is represented by the following general formula (1). YO—CO (CH 2 ) n —O—R—O— (CH 2 ) n CO—OY (1) (wherein, Y represents a cholesteryl group, and R represents p-phenylene or 4,4 ′) -Represents biphenylene, and n represents a number of 1 to 20)
下でガラス転移温度が３５℃以上のコレステリック液晶
性化合物であることを特徴とする請求項４に記載の液晶
マイクロカプセル。7. The liquid crystal microcapsule according to claim 4, wherein the liquid crystal compound is a cholesteric liquid crystal compound having a molecular weight of 2000 or less and a glass transition temperature of 35 ° C. or more.
記一般式（２）で表される化合物であることを特徴とす
る請求項７に記載の液晶マイクロカプセル。 Ｚ−Ｏ−ＣＯ−Ｑ−ＣＯ−Ｏ−Ｘ・・・（２） （式中Ｘ及びＺは各々独立してコレステリル基、水素原
子又はアルキル基を、Ｑは炭素数２〜２０の２価の炭化
水素基を表し、Ｘ及びＺの少なくともいずれか一方はコ
レステリル基を表す）8. The liquid crystal microcapsule according to claim 7, wherein the cholesteric liquid crystal compound is a compound represented by the following general formula (2). ZO-CO-Q-CO-OX (2) (wherein X and Z each independently represent a cholesteryl group, a hydrogen atom or an alkyl group, and Q represents a divalent group having 2 to 20 carbon atoms. Represents at least one of X and Z represents a cholesteryl group)
（３）で表される基であることを特徴とする請求項８に
記載の液晶マイクロカプセル。 −（ＣＨ2)l−Ｃ≡Ｃ−Ｃ≡Ｃ−（ＣＨ2)m−・・・（３） （式中ｌ及びｍは各々独立して１以上の整数であり、但
しｌとｍとの合計は３０を超えないものとする）9. The liquid crystal microcapsule according to claim 8, wherein the divalent hydrocarbon group is a group represented by the following general formula (3). -(CH 2 ) 1 -C≡CC−C- (CH 2 ) m- (3) (wherein l and m are each independently an integer of 1 or more, provided that l and m are Do not exceed 30)
プセルを透明樹脂中に分散してなることを特徴とする記
録表示媒体。10. A recording and display medium comprising the liquid crystal microcapsules according to claim 1 dispersed in a transparent resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000127174A JP2001311079A (en) | 2000-04-27 | 2000-04-27 | Liquid crystal microcapsule and recording display medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000127174A JP2001311079A (en) | 2000-04-27 | 2000-04-27 | Liquid crystal microcapsule and recording display medium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001311079A true JP2001311079A (en) | 2001-11-09 |
Family
ID=18636814
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000127174A Pending JP2001311079A (en) | 2000-04-27 | 2000-04-27 | Liquid crystal microcapsule and recording display medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001311079A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001354964A (en) * | 2000-06-14 | 2001-12-25 | Kyodo Printing Co Ltd | Recording display material and recording display medium |
| JP2002193994A (en) * | 2000-12-26 | 2002-07-10 | National Institute Of Advanced Industrial & Technology | Dicholesteryl ester compound and recording display material |
| JP2002193995A (en) * | 2000-12-26 | 2002-07-10 | National Institute Of Advanced Industrial & Technology | Dicholesteryl ester and recording display material |
| US8048335B2 (en) | 2008-10-06 | 2011-11-01 | Chisso Corporation | Cholesteric liquid crystal composition |
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| JPH1124027A (en) * | 1997-05-08 | 1999-01-29 | Agency Of Ind Science & Technol | Rewritable color image recording medium and image forming method using the medium |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH03197569A (en) * | 1989-02-13 | 1991-08-28 | Akzo Nv | Liquid crystal pigment, its manufacture, and its use in coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001354964A (en) * | 2000-06-14 | 2001-12-25 | Kyodo Printing Co Ltd | Recording display material and recording display medium |
| JP2002193994A (en) * | 2000-12-26 | 2002-07-10 | National Institute Of Advanced Industrial & Technology | Dicholesteryl ester compound and recording display material |
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| US8048335B2 (en) | 2008-10-06 | 2011-11-01 | Chisso Corporation | Cholesteric liquid crystal composition |
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