JPH05346563A - Material for optical modulation element - Google Patents
Material for optical modulation elementInfo
- Publication number
- JPH05346563A JPH05346563A JP4177775A JP17777592A JPH05346563A JP H05346563 A JPH05346563 A JP H05346563A JP 4177775 A JP4177775 A JP 4177775A JP 17777592 A JP17777592 A JP 17777592A JP H05346563 A JPH05346563 A JP H05346563A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- group
- modulation element
- alkyl group
- light
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 32
- 230000003287 optical effect Effects 0.000 title abstract description 28
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 32
- 239000005264 High molar mass liquid crystal Substances 0.000 claims description 21
- 239000004973 liquid crystal related substance Substances 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 239000005266 side chain polymer Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 4
- 229910052799 carbon Inorganic materials 0.000 abstract 4
- 239000010408 film Substances 0.000 description 26
- 238000002834 transmittance Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 8
- 230000010287 polarization Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000007699 photoisomerization reaction Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- SLZQXATXJXFJPG-UHFFFAOYSA-N (2-cyanophenyl) 4-phenylbenzoate Chemical group C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)OC1=CC=CC=C1C#N SLZQXATXJXFJPG-UHFFFAOYSA-N 0.000 description 1
- NOQZCQDCKJPQDE-UHFFFAOYSA-N (2-cyanophenyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1C#N NOQZCQDCKJPQDE-UHFFFAOYSA-N 0.000 description 1
- CFWGZPGPNMCLMA-UHFFFAOYSA-N (2-methoxyphenyl) 4-phenylbenzoate Chemical group COC1=CC=CC=C1OC(=O)C1=CC=C(C=2C=CC=CC=2)C=C1 CFWGZPGPNMCLMA-UHFFFAOYSA-N 0.000 description 1
- NLWCWEGVNJVLAX-UHFFFAOYSA-N 1-methoxy-2-phenylbenzene Chemical group COC1=CC=CC=C1C1=CC=CC=C1 NLWCWEGVNJVLAX-UHFFFAOYSA-N 0.000 description 1
- YXBOJYCLFCVTLS-UHFFFAOYSA-N 2-(2-methoxy-6-phenylphenyl)benzoic acid Chemical compound COC1=CC=CC(=C1C2=CC=CC=C2C(=O)O)C3=CC=CC=C3 YXBOJYCLFCVTLS-UHFFFAOYSA-N 0.000 description 1
- WLPATYNQCGVFFH-UHFFFAOYSA-N 2-phenylbenzonitrile Chemical group N#CC1=CC=CC=C1C1=CC=CC=C1 WLPATYNQCGVFFH-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- RAFZSIJNOAREMW-UHFFFAOYSA-N benzoic acid;2-phenylbenzonitrile Chemical compound OC(=O)C1=CC=CC=C1.N#CC1=CC=CC=C1C1=CC=CC=C1 RAFZSIJNOAREMW-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004428 fluoroalkoxy group Chemical group 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- IZYQCDNLUPLXOO-UHFFFAOYSA-N guaiacol benzoate Chemical compound COC1=CC=CC=C1OC(=O)C1=CC=CC=C1 IZYQCDNLUPLXOO-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- -1 polysiloxane Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規な光変調素子用材
料に関し、詳しくは、フォトクロミック化合物を用いた
安定で高感度な光演算素子、光シャッターおよび光メモ
リーに応用可能な光変調素子用材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel material for a light modulation device, and more particularly, to a stable and highly sensitive optical operation device using a photochromic compound, an optical modulation device applicable to an optical shutter and an optical memory. Regarding materials.
【０００２】[0002]
【従来の技術】従来から、フォトクロミック材料を光メ
モリーや光変調素子として応用することが提案されてい
る。しかしながら、その実用化には、材料の化学安定性
の向上、非破壊読み出し性の改善や変調光による変調感
度の向上等、解決すべき問題があった。これらの解決方
法の一つとして、フォトクロミック材料を液晶と複合化
する技術等、従来から種々の技術が提案されている（特
開平１−２５１３４４号、同２−１９０８２７号および
同１−２４６５３８号公報等）。これらの技術では、フ
ォトクロミック化合物の構造変化を液晶に伝達するか或
いは増幅することによって、液晶の光学特性の変化とし
て利用することを意図したものである。2. Description of the Related Art Conventionally, it has been proposed to apply a photochromic material as an optical memory or an optical modulator. However, there are problems to be solved for practical use, such as improvement of chemical stability of materials, improvement of nondestructive readability, and improvement of modulation sensitivity by modulated light. As one of these solutions, various techniques such as a technique of combining a photochromic material with a liquid crystal have been proposed in the past (Japanese Patent Laid-Open Nos. 1-251344, 2-190827 and 1-246538). etc). These techniques are intended to be used as a change in the optical characteristics of the liquid crystal by transmitting or amplifying the structural change of the photochromic compound to the liquid crystal.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記の
技術においても、未だ変調感度や記録感度は小さいため
に、実用化が困難であった。例えば、フォトクロミック
化合物を液晶材料と組み合わせた場合、時間の経過と共
に液晶が流動し、記録が不明確になり、さらに記録の熱
安定性および繰り返し耐久性等に問題があった。以上の
ように、従来のフォトクロミック化合物を用いた光変調
素子や光メモリー材料では、解決すべき多くの問題があ
り、未だ実用化には至っていない。本発明は、従来の技
術における上記のような問題点に鑑みてなされたもので
ある。本発明の目的は、従来技術の課題であった耐久
性、安定性、非破壊的な読み出し性等に優れ、かつ大き
な変調効果をもつ光変調素子用材料を提供することにあ
る。However, even in the above technique, the modulation sensitivity and the recording sensitivity are still small, so that it is difficult to put them into practical use. For example, when a photochromic compound is combined with a liquid crystal material, the liquid crystal flows with the passage of time, the recording becomes unclear, and there are problems in the thermal stability of recording and repeated durability. As described above, the conventional optical modulator and optical memory material using the photochromic compound have many problems to be solved and have not yet been put into practical use. The present invention has been made in view of the above problems in the conventional technique. An object of the present invention is to provide a material for an optical modulation element, which has excellent durability, stability, non-destructive readability, and the like, which have been problems of the prior art, and has a large modulation effect.
【０００４】[0004]
【課題を解決するための手段】本発明者等は、鋭意研究
を進めた結果、側鎖型高分子液晶と特定構造のフォトク
ロミック化合物を組み合わせた複合膜において、フォト
クロミック反応によって引き起こされる高分子液晶媒体
の屈折率異方性の変化が、フォトクロミック化合物の吸
収をもたない波長領域に大きな変化として可逆的に現れ
ることを見出し、本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies by the present inventors, a polymer liquid crystal medium caused by a photochromic reaction in a composite film in which a side chain type polymer liquid crystal and a photochromic compound having a specific structure are combined. The inventors have found that the change in the refractive index anisotropy of 1 appears reversibly as a large change in the wavelength region that does not have the absorption of the photochromic compound, and have completed the present invention.
【０００５】本発明の光変調素子用材料は、側鎖型高分
子液晶および下記一般式（Ｉ）または（II）で示される
熱安定性フォトクロミック化合物の少なくとも二成分か
らなる複合膜よりなることを特徴とする。The material for a light modulation element of the present invention comprises a composite film comprising a side chain type polymer liquid crystal and at least two components of a thermostable photochromic compound represented by the following general formula (I) or (II). Characterize.
【化３】 〔式中、Ｒ1 〜Ｒ8 は、同一または異なるものであっ
て、水素原子、ハロゲン原子、炭素数１〜１０のアルキ
ル基を表わし、Ａは酸素原子、硫黄原子、または−ＮＲ
9 （ただしＲ9 は水素原子、炭素数１〜１０のアルキル
基または置換されていてもよいフェニル基を表わす。）
を表わし、Ｂは炭素数２〜３０のアルキル基または下記
一般式（III ）または（IV）で示される基[Chemical 3] [In the formula, R 1 to R 8 are the same or different and represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms, and A is an oxygen atom, a sulfur atom, or -NR
9 (wherein R 9 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an optionally substituted phenyl group)
B is an alkyl group having 2 to 30 carbon atoms or a group represented by the following general formula (III) or (IV)
【化４】 （ただし、Ｘは単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ
−、−ＣＨ2 Ｏ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−または−
Ｎ＝ＣＨ−を表わし、Ｒ10は炭素数１〜３０のアルキル
基、アルコキシ基、ハロゲン原子またはシアノ基を表わ
し、ｎは１〜５の整数を表わす。）を表わす。〕[Chemical 4] (However, X is a single bond, -O-, -COO-, -OCO.
-, - CH 2 O -, - N = N -, - CH = N- or -
N = CH-, R 10 represents an alkyl group having 1 to 30 carbon atoms, an alkoxy group, a halogen atom or a cyano group, and n represents an integer of 1 to 5. ) Is represented. ]
【０００６】本発明によれば、高感度な光変調が実現さ
れると共に、光メモリー素子として応用した場合には、
非破壊的な記録の読み出し性、優れた記録感度や耐久性
が実現可能になる。According to the present invention, a highly sensitive optical modulation is realized and, when applied as an optical memory device,
Non-destructive readability of recording, excellent recording sensitivity and durability can be realized.
【０００７】本発明の光変調素子用材料を構成する必須
の成分の一つである側鎖型高分子液晶とは、液晶性を示
すメソゲン分子を、適当なアルキルスペーサを介して側
鎖にペンダント分子として有する高分子を意味し、低分
子液晶と同様に、ネマチック相、スメクチック相或いは
コレステリック相等の種々の液晶相を形成することが知
られている。その構造は、Ｍｏｌ．Ｃｒｙｓｔ．Ｌｉ
ｑ．Ｃｒｙｓｔ．，１６７，１６９（１９８９）等に開
示されている。例えば、誘電率異方性が正のシアノビフ
ェニル、シアノフェニルベンゾエート、シアノビフェニ
ルベンゾエート、シアノフェニル（４−フェニルベンゾ
エート）構造、或いは誘電率異方性が負のメトキシビフ
ェニル、メトキシフェニルベンゾエート、メトキシビフ
ェニルベンゾエート、メトキシフェニル（４−フェニル
ベンゾエート）構造をもち、主鎖構造がポリアクリレー
ト系、ポリメタクリル系、ポリエーテル系、ポリエステ
ル系、ポリシロキサン系であるもの等が一般的なもので
ある。本発明において使用可能な側鎖型高分子液晶につ
いて、その具体例を以下に単量体単位で示すが、本発明
は、これ等に限定されるものではない。The side-chain type polymer liquid crystal which is one of the essential components constituting the material for the light modulation element of the present invention is a mesogen molecule exhibiting liquid crystallinity pendant to the side chain via an appropriate alkyl spacer. It means a polymer having a molecule, and is known to form various liquid crystal phases such as a nematic phase, a smectic phase, a cholesteric phase, and the like, similar to a low-molecular liquid crystal. Its structure is described in Mol. Cryst. Li
q. Cryst. , 167, 169 (1989) and the like. For example, cyanobiphenyl, cyanophenylbenzoate, cyanobiphenylbenzoate, cyanophenyl (4-phenylbenzoate) structure having a positive dielectric anisotropy, or methoxybiphenyl, methoxyphenylbenzoate, methoxybiphenylbenzoate having a negative dielectric anisotropy. In general, those having a methoxyphenyl (4-phenylbenzoate) structure and having a main chain structure of polyacrylate type, polymethacrylic type, polyether type, polyester type, polysiloxane type, and the like. Specific examples of the side chain type polymer liquid crystal usable in the present invention are shown below in the form of a monomer unit, but the present invention is not limited thereto.
【０００８】[0008]
【化５】 〔式中、Ｒ11は水素原子またはメチル基を表わし、ｒは
１〜２０の整数を意味し、Ｘ1 及びＹ1 は、それぞれ単
結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝Ｎ−
または−Ｎ＝ＣＨ−を表わし、Ｒ12はアルキル基、アル
コキシ基、カルボン酸基、フロロアルキル基、フロロア
ルコキシ基、シアノ基、ハロゲン原子、水素原子または
水酸基を表わし、Φ1 およびΦ2 は、それぞれ下記の基
を表わす。[Chemical 5] Wherein, R11 represents a hydrogen atom or a methyl group, r means an integer of 1 to 20, X 1 and Y 1 each represent a single bond, -O -, - COO -, - OCO -, - CH = N-
Or -N = CH-, R 12 represents an alkyl group, an alkoxy group, a carboxylic acid group, a fluoroalkyl group, a fluoroalkoxy group, a cyano group, a halogen atom, a hydrogen atom or a hydroxyl group, and Φ 1 and Φ 2 are The following groups are respectively represented.
【０００９】[0009]
【化６】 （式中、Ｑは水素原子、フッ素原子、塩素原子または臭
素原子を表わし、ｍは０〜４の整数を表わす。）〕[Chemical 6] (In the formula, Q represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, and m represents an integer of 0 to 4.)
【００１０】上記側鎖型高分子液晶の分子量は特に限定
されるものではないが、重量平均分子量１０００ないし
１００万の範囲が好ましく、さらに好ましくは１０００
ないし５万の範囲である。また、ガラス転移点（Ｔｇ）
については、５０℃以下である場合に高い変調特性を示
すので、Ｔｇ５０℃以下のものが好ましい。The molecular weight of the side chain type polymer liquid crystal is not particularly limited, but the weight average molecular weight is preferably in the range of 1,000 to 1,000,000, more preferably 1,000.
To 50,000. Also, the glass transition point (Tg)
With respect to the above, since a high modulation characteristic is exhibited when the temperature is 50 ° C. or lower, Tg of 50 ° C. or lower is preferable.
【００１１】次に、他の必須の成分であるフォトクロミ
ック化合物について説明する。本発明において使用され
るフォトクロミック化合物は、上記側鎖型高分子液晶と
の相溶性が高く、化学的に安定なフルギド系化合物であ
って、上記一般式（Ｉ）または（II）で示される。光変
調素子用材料中に含有されるフォトクロミック化合物の
量は、目的とする諸物性によって変更し得るが、０．１
〜５０重量％の範囲が好ましく、特に０．１〜２０重量
％の範囲が好ましい。フォトクロミック化合物の量が
０．１重量％よりも低くなると、目的とする光異方性に
伴う物性変化を得ることができず、また、５０重量％よ
りも高くなると液晶性が著しく低下し、目的とする光変
調特性を得ることができなくなる。Next, the photochromic compound which is another essential component will be described. The photochromic compound used in the present invention is a chemically stable fulgide compound having a high compatibility with the side chain type polymer liquid crystal and is represented by the general formula (I) or (II). The amount of the photochromic compound contained in the material for the light modulation element may be changed depending on the desired physical properties, but is 0.1
The range of ˜50 wt% is preferable, and the range of 0.1-20 wt% is particularly preferable. If the amount of the photochromic compound is lower than 0.1% by weight, the desired change in physical properties due to the optical anisotropy cannot be obtained, and if it is higher than 50% by weight, the liquid crystallinity is remarkably deteriorated. It becomes impossible to obtain the light modulation characteristic.
【００１２】本発明の光変調素子用材料は、側鎖型高分
子液晶および上記フォトクロミック化合物を必須の構成
要素とするが、さらに耐久性等の向上を目的として、ヒ
ンダードアミンやヒンダードフェノールに代表される酸
化防止剤等、各種耐候性安定剤を添加することが可能で
ある。その添加量は、高分子液晶＋フォトクロミック化
合物に対して、０．０１〜５重量％の範囲が好ましい。
さらに光異性化に伴う物性変化を増大させる目的で、公
知の種々の低分子液晶化合物或いは組成物を添加混合す
ることもでき、それにより粘度の低下や屈折率異方性の
向上効果が生じる。これらの添加量は、高分子液晶に対
して１〜５０重量％の範囲で好ましく選択される。The material for a light modulation element of the present invention comprises a side chain type polymer liquid crystal and the above photochromic compound as essential constituent elements, but is typified by hindered amine and hindered phenol for the purpose of further improving durability and the like. It is possible to add various weather resistance stabilizers such as antioxidants. The addition amount thereof is preferably in the range of 0.01 to 5% by weight with respect to the polymer liquid crystal + photochromic compound.
Further, various known low molecular weight liquid crystal compounds or compositions can be added and mixed for the purpose of increasing the change in physical properties due to photoisomerization, which results in the effect of lowering the viscosity and improving the anisotropy of refractive index. The addition amount of these is preferably selected in the range of 1 to 50% by weight with respect to the polymer liquid crystal.
【００１３】本発明の光変調素子用材料は、その中に含
まれる少なくとも側鎖型高分子液晶の液晶分子が一軸方
向に配向された形態をとるのが好ましく、それにより変
調特性の向上効果が生じる。その際、他の一成分である
フォトクロミック化合物が、液晶分子と同様に配向して
いてもよい。配向方法としては、低分子液晶を配向させ
る公知の方法と同様な配向方法が適用可能である。例え
ば、ポリビニルアルコールやポリイミド等の薄膜を施し
てラビング処理した公知の配向膜を用いる方法が適用可
能である。その際、この配向膜が液晶相を示す温度範囲
で熱アニーリング処理したり、軟化点まで加熱した後徐
冷する方法によって、効果的に配向をさせることができ
る。また、配向膜を使用せずに、延伸処理等の外的応力
によって配向させる高分子液晶特有の方法を適用するこ
とも可能である。The material for a light modulation element of the present invention preferably has a configuration in which at least liquid crystal molecules of the side chain type polymer liquid crystal contained therein are oriented in a uniaxial direction, whereby the effect of improving modulation characteristics is obtained. Occurs. In that case, the photochromic compound which is another component may be aligned similarly to the liquid crystal molecules. As the alignment method, the same alignment method as a known method for aligning a low-molecular liquid crystal can be applied. For example, a method of using a known alignment film that has been subjected to a rubbing treatment by applying a thin film of polyvinyl alcohol, polyimide or the like can be applied. At this time, the alignment film can be effectively aligned by a thermal annealing treatment in a temperature range in which the alignment film shows a liquid crystal phase, or a method of heating to a softening point and then gradually cooling. It is also possible to apply a method peculiar to polymer liquid crystals in which orientation is performed by external stress such as stretching treatment without using an orientation film.
【００１４】次に、本発明の光変調素子用材料を光変調
素子において使用した具体例について説明する。本発明
の光変調素子用材料を使用する場合、素子の構成として
は少なくとも二枚の基板間に複合膜層を挾持した構造の
ものが好ましい。もちろん複合膜層と基板との間に配向
膜を設けてもよく、また、一方の基板の表面に光反射層
を設けてもよい。さらに、最表面に反射を防止するため
の反射防止膜や、入射するレーザー光の効率を向上させ
る干渉層を設けてもよい。フォトクロミック化合物を含
む側鎖型高分子液晶からなる複合膜層の厚みは、０．１
〜１００μｍの範囲が好ましく、特に好ましい範囲は、
１〜３０μｍである。また、配向膜を設ける場合、その
膜厚は０．００１〜１０μｍの範囲が好ましい。ここで
使用可能な基板の材料としては、ガラス、ポリカーボネ
ート、ポリメチルメタクリレート、オレフィン系樹脂
等、光学素子として使用されている種々のものがあげら
れる。特に、透過光型光変調を行う構成のものでは、光
学的に透明であることが好ましい。Next, a specific example in which the material for an optical modulator of the present invention is used in an optical modulator will be described. When the material for a light modulation device of the present invention is used, the device preferably has a structure in which a composite film layer is sandwiched between at least two substrates. Of course, an alignment film may be provided between the composite film layer and the substrate, and a light reflection layer may be provided on the surface of one substrate. Furthermore, an antireflection film for preventing reflection or an interference layer for improving the efficiency of incident laser light may be provided on the outermost surface. The thickness of the composite film layer made of the side chain type polymer liquid crystal containing the photochromic compound is 0.1.
To 100 μm is preferable, and a particularly preferable range is
It is 1 to 30 μm. When an alignment film is provided, its thickness is preferably in the range of 0.001-10 μm. Examples of the material of the substrate that can be used here include glass, polycarbonate, polymethylmethacrylate, olefin resin, and various other materials used as optical elements. In particular, in the case of a structure for performing transmitted light type light modulation, it is preferably optically transparent.
【００１５】次に、代表的なセルの作製方法について説
明する。まず、基板上に、スピンコート法、バーコート
法或いはドクターブレード法等によって配向膜材料を含
む溶液を塗布し、乾燥して配向膜を形成する。形成され
た配向膜を布や紙を用いて一方向に擦ってラビング処理
する。次に、フォトクロミック化合物／側鎖型高分子液
晶組成物を溶媒に溶解して、または加熱溶融して上記配
向膜上に塗布し、所定の膜厚の複合膜層を設ける。次
に、この複合膜層の上に、他の一枚の配向膜を設けた基
板を重ね、減圧下での圧着や加熱圧着を行って、セルを
作製する。この際、ガラスや樹脂の微粒子またはフィル
ム等のスペーサーを用いて、正確な膜厚を得ることもで
きる。最後に所定の温度に加熱してアニーリング処理す
るか、徐冷することにより、一軸方向に液晶分子を配向
させる。一軸方向に配向したセルは、透明な形態を示す
が、偏光顕微鏡で観察すると、クロスニコル下で回転角
４５°ごとに暗状態と明状態が繰り返し現れることが確
認される。Next, a method of manufacturing a typical cell will be described. First, a solution containing an alignment film material is applied onto a substrate by a spin coating method, a bar coating method, a doctor blade method or the like, and dried to form an alignment film. The formed alignment film is rubbed in one direction with a cloth or paper for rubbing. Next, the photochromic compound / side-chain type polymer liquid crystal composition is dissolved in a solvent or heated and melted to be applied on the alignment film to form a composite film layer having a predetermined film thickness. Next, on this composite film layer, a substrate provided with another alignment film is placed, and pressure bonding under reduced pressure or thermocompression bonding is performed to fabricate a cell. At this time, an accurate film thickness can be obtained by using a spacer such as fine particles of glass or resin or a film. Finally, the liquid crystal molecules are aligned uniaxially by heating to a predetermined temperature for annealing treatment or by gradually cooling. The uniaxially oriented cell has a transparent morphology, but it is confirmed by observation with a polarizing microscope that a dark state and a bright state repeatedly appear under a crossed Nicol at every rotation angle of 45 °.
【００１６】次に、光変調素子の変調方法について説明
する。フォトクロミック化合物の構造を、光により変化
する前の状態と変化した後の状態を構造Ａおよび構造Ｂ
とした場合、光変調は、フォトクロミック化合物の構造
Ａが吸収を有する波長：λAと構造Ｂが吸収する波長：
λB の光によって行われ、構造ＡおよびＢが吸収を有し
ない波長：λC の直線偏光を変調する。すなわち、この
直線偏光がセルを透過またはセルで反射した後、検光子
を透過する光の強度が変調される。Next, the modulation method of the light modulator will be described. The structure of the photochromic compound is shown as structure A and structure B before and after being changed by light.
In this case, the light modulation is as follows: the wavelength that the structure A of the photochromic compound has absorption: λA and the wavelength that the structure B absorbs:
The light of wavelength .lambda.B modulates the linearly polarized light of wavelength .lambda.C where structures A and B have no absorption. That is, after the linearly polarized light is transmitted through the cell or reflected by the cell, the intensity of the light transmitted through the analyzer is modulated.
【００１７】本発明の光変調素子用材料を使用した光変
調素子による光変調原理は明らかではないが、以下のよ
うに想定される。光変調素子を、その配向方向がいずれ
かの偏光面に対して３０〜６０°の範囲、より好ましく
は４５°の角度になるようにクロスニコルまたはパラレ
ルニコルの間に配置する。このとき複屈折媒体中に直線
偏光λが入射すると、正常光と異常光の光路差により光
は偏光方向が螺旋を巻くように伝搬する。その場合、入
射光の偏光方向と屈折率の異方性Δｎの方向が４５°の
角度をとると、正常光と異常光の強度は等しくなる。厚
さｄの複屈折媒体を２枚の偏光板で挾み、入射側の偏光
板の偏光方向とΔｎの方向が４５°の角度をとる場合を
考える。１枚目の偏光板の透過光強度を１とすると、２
枚の偏光板の配置がクロスニコルの場合の透過率ＴC は
（１）式で与えられる。 ＴC ＝ｓｉｎ2 （πΔｎｄ／λ） （１） また、２枚の偏光板の配置がパラニコルの場合の透過率
ＴP は（２）式で与えられる。 ＴP ＝ｃｏｓ2 （πΔｎｄ／λ） （２）The principle of light modulation by the light modulation element using the material for the light modulation element of the present invention is not clear, but it is assumed as follows. The light modulation element is arranged between crossed Nicols or parallel Nicols so that the orientation direction thereof is in the range of 30 to 60 °, and more preferably 45 ° with respect to any polarization plane. At this time, when linearly polarized light λ is incident on the birefringent medium, the light propagates so that the polarization direction spirals due to the optical path difference between the normal light and the extraordinary light. In that case, if the polarization direction of the incident light and the direction of the anisotropy Δn of the refractive index form an angle of 45 °, the intensities of the normal light and the extraordinary light become equal. Consider a case where a birefringent medium having a thickness d is sandwiched between two polarizing plates and the polarization direction of the polarizing plate on the incident side and the direction of Δn form an angle of 45 °. If the transmitted light intensity of the first polarizing plate is 1, then 2
When the arrangement of the polarizing plates is crossed Nicol, the transmittance TC is given by the equation (1). TC = sin 2 (πΔnd / λ) (1) Further, the transmittance TP when the two polarizing plates are arranged in the para-Nicol is given by the equation (2). TP = cos 2 (πΔnd / λ) (2)
【００１８】すなわち、クロスニコル下では、Δｎｄ／
λ＝０，１，２・・・・のとき、透過率が最大になり、
Δｎｄ／λ＝１／２，３／２・・・・のとき、透過率が
最小になる。また、パラレルニロル下では、Δｎｄ／λ
＝１／２，３／２・・・・のとき、透過率が最大にな
り、Δｎｄ／λ＝０，１，２・・・・のとき、透過率が
最小になる。ここで適当なΔｎｄを選べば、初期状態で
の変調波長光における透過率を最大または最小に設定す
ることができる。光変調材料として、フォトクロミック
化合物を少なくとも１種類含む側鎖型高分子液晶を一軸
配向して用いた場合、波長λA の光を照射した部分は、
光異性化により液晶分子の配向が変化するためにΔｎが
変化し、透過率の最大または最小を示す波長が変化す
る。図１はその状態を示すグラフであり、光異性化前と
光異性化後の波長が変化していることを示す。初期状態
における透過率が最大になるように膜厚ｄを設定した場
合は、透過率が減少し、一方、初期状態における透過率
が最小になるように膜厚ｄを設定した場合は、光異性化
に伴い透過率が増加するため、透過光の変調を行うこと
ができる。なお、上記の説明においては、初期状態が透
過率最大或いは透過率最小の場合を例にして述べたが、
光異性化前後で透過光の変化が観測されれば、初期状態
はこれに限定されるものではない。以上のように、本発
明の光変調素子材料を用いた場合、所定の波長の光を用
いて光変調を行なうことが可能になる。また本発明の光
変調素子材料は、光メモリーに応用することも好まし
い。その場合、記録を読み出す場合に、フォトクロミッ
ク化合物が吸収を持たない波長光を使用することによっ
て、非破壊的な読み出しが可能になる。That is, under crossed Nicols, Δnd /
When λ = 0, 1, 2 ..., the transmittance becomes maximum,
When Δnd / λ = 1/2, 3/2 ..., The transmittance becomes minimum. Also, under parallel Nirol, Δnd / λ
= 1 / 2,3 / 2 ..., the transmittance becomes maximum, and Δnd / λ = 0,1,2 ..., the transmittance becomes minimum. If an appropriate Δnd is selected here, the transmittance of the modulated wavelength light in the initial state can be set to the maximum or the minimum. When a side chain type polymer liquid crystal containing at least one type of photochromic compound is uniaxially aligned and used as the light modulation material, the portion irradiated with light of wavelength λA is
Since the orientation of the liquid crystal molecules is changed by photoisomerization, Δn is changed, and the wavelength at which the transmittance is maximum or minimum is changed. FIG. 1 is a graph showing that state, and shows that the wavelength before and after photoisomerization changes. When the film thickness d is set so as to maximize the transmittance in the initial state, the transmittance decreases, while when the film thickness d is set so that the transmittance in the initial state is minimized, Since the transmittance increases with the increase in the number, the transmitted light can be modulated. In the above description, the case where the initial state is the maximum transmittance or the minimum transmittance is described as an example.
If a change in transmitted light is observed before and after photoisomerization, the initial state is not limited to this. As described above, when the light modulation element material of the present invention is used, light modulation can be performed using light having a predetermined wavelength. Further, the light modulation element material of the present invention is also preferably applied to an optical memory. In that case, non-destructive read-out becomes possible by using the wavelength light that the photochromic compound does not absorb when reading the record.
【００１９】[0019]
【実施例】側鎖型高分子液晶として、下記構造式（１）
で示される単量体単位より構成されるものを使用した。
この側鎖型高分子液晶は、重量平均分子量：約２万、液
晶相を示す温度範囲：３５〜１２２℃を有していた。フ
ォトクロミック化合物としては、下記構造式（２）で示
されるｐ−ｎ−オクチルフェニレン基を有するフルギイ
ミド誘導体を合成して使用した。Example As a side chain type polymer liquid crystal, the following structural formula (1)
What was comprised by the monomer unit shown by was used.
This side-chain polymer liquid crystal had a weight average molecular weight of about 20,000 and a temperature range showing a liquid crystal phase: 35 to 122 ° C. As the photochromic compound, a fulgiimide derivative having a pn-octylphenylene group represented by the following structural formula (2) was synthesized and used.
【化７】 [Chemical 7]
【００２０】試料としてセルを作製した。まず、ラビン
グ処理したポリイミド配向膜を形成したガラス基板上
に、上記フォトクロミック化合物を１、３、５または７
重量％の濃度で含有する側鎖型高分子液晶の４０重量％
テトラヒドロフラン溶液をバーコーターにより塗布し
た。乾燥した後、粒径１０μｍの樹脂スペーサーを散布
し、他の一方のガラス基板を重ね、１４０℃まで昇温し
て圧着した。セルは、圧着後、１２０℃から室温まで２
℃／分の速度で徐冷して一軸配向させた。このようにし
て作製した試料の外観は透明であり、偏光顕微鏡で観察
すると、良好な配向状態を有していることが確認でき
た。A cell was prepared as a sample. First, 1, 3, 5 or 7 of the photochromic compound was placed on a glass substrate having a rubbing-treated polyimide alignment film formed thereon.
40% by weight of side-chain polymer liquid crystal contained at a concentration of% by weight
The tetrahydrofuran solution was applied with a bar coater. After drying, a resin spacer having a particle size of 10 μm was dispersed, another glass substrate was overlaid, the temperature was raised to 140 ° C., and pressure was applied. The cell should be heated from 120 ℃ to room temperature after pressure bonding.
Uniaxially oriented by slow cooling at a rate of ° C / min. The sample thus produced had a transparent appearance, and it was confirmed by observation with a polarizing microscope that it had a good alignment state.
【００２１】この試料に紫外線（λ＝３６５ｎｍ）を照
射すると、直ちに赤色に変化した。図２に、この際の吸
収スペクトル変化を示す。図に示されるように、紫外線
照射後、λ＝５２０ｎｍに最大吸収を示し、吸収端は６
２０ｎｍであった。変調特性を調べるため、クロスニコ
ル下に試料の配向軸を偏光子の偏光面に対して４５°の
角度で設置し、紫外線照射前後の透過光スペクトルの変
化を測定した（測定温度２５℃）。図３に透過光スペク
トル変化の測定結果の一例を示す。紫外線を照射するこ
とによって、フォトクロミック化合物の吸収波長変化に
伴う透過光の変化が現れるとともに、それに関係しない
６２０〜８２０ｎｍの波長領域に大きな変化が生じてい
ることが確認できた。各試料の透過光（透過率）の変化
量（ΔＴmax ）を表１に示す。When this sample was irradiated with ultraviolet rays (λ = 365 nm), it immediately turned red. FIG. 2 shows the change in absorption spectrum at this time. As shown in the figure, after the ultraviolet irradiation, the maximum absorption was observed at λ = 520 nm, and the absorption edge was 6
It was 20 nm. In order to examine the modulation characteristics, the orientation axis of the sample was set under a crossed Nicol at an angle of 45 ° with respect to the polarization plane of the polarizer, and the change in the transmitted light spectrum before and after irradiation with ultraviolet rays was measured (measurement temperature 25 ° C). FIG. 3 shows an example of the measurement result of the transmitted light spectrum change. It was confirmed that by irradiating with ultraviolet rays, a change in the transmitted light due to a change in the absorption wavelength of the photochromic compound appears, and a large change in the wavelength region of 620 to 820 nm unrelated to the change occurs. Table 1 shows the amount of change (ΔTmax) in the transmitted light (transmittance) of each sample.
【００２２】[0022]
【表１】 [Table 1]
【００２３】表１から明らかなように、フォトクロミッ
ク化合物の含有量が増えるに従い、その変化量は大きく
なる傾向があり、最大２１％もの変化量を示した。これ
らの変化は、紫外線と可視光の照射によって可逆的に発
現可能で、何度も繰り返し実行可能であり、変化率の減
少等の劣化は認められなかった。As is clear from Table 1, as the content of the photochromic compound increases, the amount of change tends to increase, showing a maximum change of 21%. These changes can be reversibly expressed by irradiation with ultraviolet rays and visible light, can be repeatedly executed many times, and deterioration such as decrease in change rate was not observed.
【００２４】実施例２ 側鎖型高分子液晶として、下記構造式（３）で示される
単量体単位より構成されるものを使用した。この側鎖型
高分子液晶は、重量平均分子量：約６千、液晶相を示す
温度範囲：１２．５〜９８℃を有していた。Example 2 As the side chain type polymer liquid crystal, one composed of a monomer unit represented by the following structural formula (3) was used. This side chain type polymer liquid crystal had a weight average molecular weight of about 6,000 and a temperature range showing a liquid crystal phase: 12.5 to 98 ° C.
【化８】 フォトクロミック化合物として、実施例１と同様に、上
記構造式（２）で示されるフルギイミド誘導体を使用し
（１、３または５重量％）、実施例１と同様な方法で一
軸配向させた試料を作製した。[Chemical 8] As the photochromic compound, the fulgiimide derivative represented by the above structural formula (2) was used as in the case of Example 1 (1, 3 or 5% by weight), and a uniaxially oriented sample was prepared in the same manner as in Example 1. did.
【００２５】この試料は、紫外線の照射により赤色に着
色し、λ＝５２０ｎｍに最大吸収を示し、吸収端は６２
０ｎｍであった。実施例１と同様に測定した各試料の透
過光（透過率）の変化量（ΔＴmax ）を表２に示す。This sample was colored red by irradiation with ultraviolet rays, showed maximum absorption at λ = 520 nm, and had an absorption edge of 62%.
It was 0 nm. Table 2 shows the amount of change (ΔTmax) in transmitted light (transmittance) of each sample measured in the same manner as in Example 1.
【表２】 表２から明らかなように、フォトクロミック化合物の含
有量が増えるに従い、その変化量は大きくなる傾向があ
り、最大１０％もの変化量を示した。これらの変化は、
紫外線と可視光の照射によって可逆的に発現可能で、何
度も繰り返し実行可能であり、変化率の減少等の劣化は
認められなかった。[Table 2] As is clear from Table 2, as the content of the photochromic compound increases, the amount of change tends to increase, and the maximum amount of change is 10%. These changes are
It can be reversibly expressed by irradiation with ultraviolet rays and visible light, can be repeatedly executed many times, and deterioration such as decrease in change rate was not observed.
【００２６】実施例３ 下記構造式（４）で示されるバルキーな置換基を持つフ
ルギド誘導体（１、３または５重量％）と、実施例１に
おける上記構造式（１）で示される単量体単位より構成
され、重量平均分子量：約５５００、液晶相を示す温度
範囲：２７〜１０６℃を有するものを使用し、実施例１
と同様な方法で一軸配向させた試料を作製した。Example 3 A fulgide derivative having a bulky substituent represented by the following structural formula (4) (1, 3 or 5% by weight) and a monomer represented by the above structural formula (1) in Example 1. Example 1 using a unit having a weight average molecular weight of about 5500 and a liquid crystal phase temperature range of 27 to 106 ° C.
A uniaxially oriented sample was prepared in the same manner as in.
【化９】 [Chemical 9]
【００２７】この試料は、紫外線の照射により赤色に着
色し、λ＝５２０ｎｍに最大吸収を示し、吸収端は６２
０ｎｍであった。実施例１と同様に測定した各試料の透
過光（透過率）の変化量（ΔＴmax ）を表３に示す。This sample was colored red by irradiation with ultraviolet rays, showed maximum absorption at λ = 520 nm, and had an absorption edge of 62.
It was 0 nm. Table 3 shows the amount of change (ΔTmax) in transmitted light (transmittance) of each sample measured in the same manner as in Example 1.
【表３】 表３から明らかなように、フォトクロミック化合物の含
有量が増えるに従い、その変化量は大きくなる傾向があ
り、最大２４％もの変化量を示した。これらの変化は、
紫外線と可視光の照射によって可逆的に発現可能で、何
度も繰り返し実行可能であり、変化率の減少等の劣化は
認められなかった。[Table 3] As is clear from Table 3, as the content of the photochromic compound increases, the amount of change tends to increase, and the maximum amount of change is 24%. These changes are
It can be reversibly expressed by irradiation with ultraviolet rays and visible light, can be repeatedly executed many times, and deterioration such as decrease in change rate was not observed.
【００２８】[0028]
【発明の効果】本発明の光変調素子用材料は、上記のよ
うに、側鎖型高分子液晶と特定構造の熱安定性フォトク
ロミック化合物を組み合わせた複合膜よりなるから、耐
久性、安定性、非破壊的な読み出し性等に優れ、かつ大
きな変調効果を生じる。したがって、光−光変調素子や
フォトンモードの高密度記録が可能な優れたものであ
り、光演算素子、光コンピューター、光シャッター、セ
ンサー、光ディスク或いは光メモリーカード等に、幅広
く応用可能である。As described above, the material for a light modulation element of the present invention is composed of a composite film in which a side chain type polymer liquid crystal and a thermostable photochromic compound having a specific structure are combined, so that durability, stability, It has excellent nondestructive readability and produces a large modulation effect. Therefore, it is an excellent device capable of high-density recording in the light-light modulation device and the photon mode, and can be widely applied to optical operation devices, optical computers, optical shutters, sensors, optical disks, optical memory cards and the like.
【図面の簡単な説明】[Brief description of drawings]
【図１】 本発明の光変調素子用材料の異性化前後の波
長の変化を示すグラフ。FIG. 1 is a graph showing changes in wavelength before and after isomerization of a material for a light modulation element of the present invention.
【図２】 本発明の光変調素子用材料の紫外線照射によ
る吸収スペクトルの変化を示すグラフ。FIG. 2 is a graph showing changes in absorption spectrum of the material for a light modulation element of the present invention due to ultraviolet irradiation.
【図３】 本発明の光変調素子用材料の紫外線照射によ
る透過光の変化を示すグラフ。FIG. 3 is a graph showing changes in transmitted light of the material for a light modulation element of the present invention when irradiated with ultraviolet rays.
Claims (3)
（Ｉ）または（II）で示される熱安定性フォトクロミッ
ク化合物の少なくとも二成分からなる複合膜よりなるこ
とを特徴とする光変調素子用材料 【化１】 〔式中、Ｒ1 〜Ｒ8 は、同一または異なるものであっ
て、水素原子、ハロゲン原子または炭素数１〜１０のア
ルキル基を表わし、Ａは酸素原子、硫黄原子、または−
ＮＲ9 （ただしＲ9 は水素原子、炭素数１〜１０のアル
キル基または置換されていてもよいフェニル基を表わ
す。）を表わし、Ｂは炭素数２〜３０のアルキル基また
は下記一般式（III ）または（IV）で示される基 【化２】 （ただし、Ｘは単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ
−、−ＣＨ2 Ｏ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−または−
Ｎ＝ＣＨ−を表わし、Ｒ10は炭素数１〜３０のアルキル
基、アルコキシ基、ハロゲン原子またはシアノ基を表わ
し、ｎは１〜５の整数を表わす。）を表わす。〕1. A material for a light modulation element, comprising a composite film comprising a side chain type polymer liquid crystal and at least two components of a thermostable photochromic compound represented by the following general formula (I) or (II). [Chemical 1] [Wherein R 1 to R 8 are the same or different and represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms, and A is an oxygen atom, a sulfur atom, or-
NR 9 (wherein R 9 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an optionally substituted phenyl group), and B represents an alkyl group having 2 to 30 carbon atoms or the following general formula (III ) Or a group represented by (IV) (However, X is a single bond, -O-, -COO-, -OCO.
-, - CH 2 O -, - N = N -, - CH = N- or -
N = CH-, R 10 represents an alkyl group having 1 to 30 carbon atoms, an alkoxy group, a halogen atom or a cyano group, and n represents an integer of 1 to 5. ) Is represented. ]
が一軸方向に配向されていることを特徴とする請求項１
記載の光変調素子用材料。2. A liquid crystal molecule of at least a side chain type polymer liquid crystal is uniaxially aligned.
The material for a light modulation element described.
量が０．１〜２０重量％の範囲であることを特徴とする
請求項１記載の光変調素子用材料。3. The material for a light modulation element according to claim 1, wherein the content of the thermostable photochromic compound is in the range of 0.1 to 20% by weight.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4177775A JP2734456B2 (en) | 1992-06-12 | 1992-06-12 | Light modulation element materials |
| US07/981,866 US5644416A (en) | 1991-11-26 | 1992-11-25 | Light modulation device and method of light modulation using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4177775A JP2734456B2 (en) | 1992-06-12 | 1992-06-12 | Light modulation element materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05346563A true JPH05346563A (en) | 1993-12-27 |
| JP2734456B2 JP2734456B2 (en) | 1998-03-30 |
Family
ID=16036900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4177775A Expired - Fee Related JP2734456B2 (en) | 1991-11-26 | 1992-06-12 | Light modulation element materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2734456B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6368760B1 (en) | 1996-11-22 | 2002-04-09 | Sharp Kabushiki Kaisha | Phase sheet |
| JP2007248528A (en) * | 2006-03-13 | 2007-09-27 | Nissan Motor Co Ltd | Reflection dimming object and manufacturing method thereof |
-
1992
- 1992-06-12 JP JP4177775A patent/JP2734456B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6368760B1 (en) | 1996-11-22 | 2002-04-09 | Sharp Kabushiki Kaisha | Phase sheet |
| JP2007248528A (en) * | 2006-03-13 | 2007-09-27 | Nissan Motor Co Ltd | Reflection dimming object and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2734456B2 (en) | 1998-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5644416A (en) | Light modulation device and method of light modulation using the same | |
| Akiyama et al. | Synthesis and properties of azo dye aligning layers for liquid crystal cells | |
| US4974941A (en) | Process of aligning and realigning liquid crystal media | |
| KR101178438B1 (en) | Liquid crystal materials | |
| Hsu | The application of side-chain liquid-crystalline polymers | |
| JPWO2005080529A1 (en) | Liquid crystal material for optical element and light modulation element | |
| JPS6164493A (en) | Optical record medium | |
| JPH0336527A (en) | Optical element | |
| EP0302497B1 (en) | Data recording medium | |
| Katsis et al. | Vitrified chiral− nematic liquid crystalline films for selective reflection and circular polarization | |
| Rosenhauer et al. | Light-induced orientation of liquid crystalline terpolymers containing azobenzene and dye moieties | |
| Christianen et al. | Alignment of molecular materials in high magnetic fields | |
| Hattori et al. | Synthesis and properties of photochromic liquid‐crystalline copolymers containing both spironaphthoxazine and cholesteryl groups | |
| KR20040028988A (en) | Optical recording material | |
| JPH0741573A (en) | Homeotropically aligned liquid crystal polymer film containing dichroic dye | |
| JP2734456B2 (en) | Light modulation element materials | |
| JP2006348133A (en) | Liquid crystal/polymer composite and optical element | |
| JP2887051B2 (en) | Light modulation element | |
| Chigrinov et al. | New photo-aligning and photo-patterning technology: superthin internal polarizers, retarders, and aligning layers | |
| Bobrovsky et al. | Ordering phenomena and photoorientation processes in photochromic thin films of LC chiral azobenzene-containing polymer systems | |
| Cui et al. | Photo-driven liquid crystal cell with high sensitivity | |
| JP2002146353A (en) | Liquid crystal optical material utilizing polymer network formed from polymerizable disk monomer | |
| JP2001100171A (en) | Liquid crystal, optical material for thermal writing using side-chain liquid crystal copolymer | |
| Chigrinov et al. | Azo‐dye aligning layers for liquid‐crystal cells | |
| JPH06148608A (en) | Optical modulation element material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |