JPH0416914A - Method for controlling orientation of liquid crystalline high polymer - Google Patents
Method for controlling orientation of liquid crystalline high polymerInfo
- Publication number
- JPH0416914A JPH0416914A JP12228090A JP12228090A JPH0416914A JP H0416914 A JPH0416914 A JP H0416914A JP 12228090 A JP12228090 A JP 12228090A JP 12228090 A JP12228090 A JP 12228090A JP H0416914 A JPH0416914 A JP H0416914A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystalline
- orientation
- liquid crystal
- substrates
- crystalline polymer
- 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
- 238000000034 method Methods 0.000 title claims description 28
- 239000007788 liquid Substances 0.000 title abstract description 10
- 229920000642 polymer Polymers 0.000 title abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 238000011282 treatment Methods 0.000 claims abstract description 18
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 88
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 26
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 22
- 229920006254 polymer film Polymers 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 description 11
- 238000000576 coating method Methods 0.000 description 8
- 239000013543 active substance Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000370 acceptor Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- -1 polysiloxane Polymers 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 239000005264 High molar mass liquid crystal Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011306 natural pitch Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は液晶表示素子用補償板、光メモリー媒体等にお
ける液晶性高分子の配向制御方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for controlling the alignment of liquid crystal polymers in compensating plates for liquid crystal display elements, optical memory media, and the like.
〔従来の技術及び発明が解決しようとする課題〕液晶は
、電場や磁場、せん断力などの外場によって配向状態が
変化し、これに伴う光学的性質の変化を利用することに
より各種光エレクトロニクスの分野で利用されている。[Prior art and problems to be solved by the invention] The alignment state of liquid crystals changes depending on external fields such as electric fields, magnetic fields, and shear forces, and by utilizing the accompanying changes in optical properties, various optoelectronic devices can be used. used in the field.
このうち液晶性高分子は低分子液晶に較べて液晶状態で
高粘性であるため、液晶状態で配向させたのち、ガラス
転移点以下に冷却することによって液晶の配向状態を固
定化することができるという低分子液晶に見られない特
徴を有している。これを利用して、熱書き込みの光メモ
リーや光学フィルターなどの光エレクトロニクス分野で
の応用が試みられている。これらを実現するためには所
望の分子配′向を高度に制御する必要がある。たとえば
一種の光学位相子であるスーパーツ不ステッドネマティ
ック（ＳＴＮ）型液晶表示素子用の色補償板は、ＳＴＮ
型液晶表示素子の液晶セルと偏光板の間に挿入され、液
晶セルによって楕円偏光となった光を直線偏光に戻すよ
うに機能する必要があるが、この様な機能は液晶性高分
子を水平に、かつ、一定の方向に高い秩序度と均一性を
持って配向させることによって初めて発現させることが
できる。Among these, liquid crystal polymers have higher viscosity in the liquid crystal state than low-molecular liquid crystals, so after being oriented in the liquid crystal state, the liquid crystal orientation state can be fixed by cooling to below the glass transition point. It has characteristics not found in low-molecular liquid crystals. Utilizing this, attempts are being made to apply it to optical electronics fields such as thermal writing optical memory and optical filters. In order to realize these, it is necessary to highly control the desired molecular orientation. For example, a color compensation plate for a supertsunstead nematic (STN) type liquid crystal display element, which is a type of optical retarder, is a type of optical retarder.
It is inserted between the liquid crystal cell and the polarizing plate of a type liquid crystal display element, and it must function to return the light that has become elliptically polarized by the liquid crystal cell to linearly polarized light. Moreover, it can only be realized by orienting it in a certain direction with a high degree of order and uniformity.
低分子液晶の場合、配向制御方法はほぼ確立されている
が、液晶性高分子（高分子液晶）の場合、十分には確立
されていない。液晶性高分子の配向制御の例としては、
ずり応力のような外力を加える方法、磁場や電場のよう
な外場を与える方法等が知られているが、これらは大面
積の配向制御が不可能であったり、均一性の点で十分と
は言えない。配向処理を施した基板間の空隙に低分子液
晶を注入する方法をそのまま液晶性高分子に適用した場
合には、液晶性高分子の高粘性のため、注入時の流れに
沿って液晶性高分子が配向してしまい。In the case of low-molecular liquid crystals, alignment control methods are almost established, but in the case of liquid crystalline polymers (polymer liquid crystals), they are not fully established. Examples of orientation control of liquid crystalline polymers include:
Methods of applying an external force such as shear stress, and methods of applying an external field such as a magnetic field or an electric field are known, but these methods either make it impossible to control the orientation over a large area, or are insufficient in terms of uniformity. I can't say that. If the method of injecting low-molecular-weight liquid crystal into the gap between substrates that has been subjected to alignment treatment is applied directly to liquid crystalline polymers, the liquid crystalline polymer will flow along the injection flow due to the high viscosity of liquid crystalline polymers. The molecules become oriented.
所望の配向が得られなかったり、大きな面積になると注
入すら困難となる。If the desired orientation is not obtained or if the area becomes large, even implantation becomes difficult.
本発明者らは、配向処理した基板に液晶性高分子を塗布
し、片面が空気に接したままで液晶温度に加温すること
によって良好な配向を、大面積にわたって実現できるこ
とを見いだしたが、この方法では液晶性高分子にねじれ
構造がある場合には、厚さの不均一性がそのままねじれ
角の不均一となってしまう。また前述の液晶表示素子用
補償板などではねじれ角を制御するためにきわめて厳密
に液晶性高分子膜の厚さを制御する必要があった。The present inventors have discovered that good alignment can be achieved over a large area by coating a liquid crystalline polymer on an alignment-treated substrate and heating it to the liquid crystal temperature with one side in contact with air. In this method, if the liquid crystalline polymer has a twisted structure, non-uniformity in thickness directly results in non-uniformity in twist angle. Furthermore, in the above-mentioned compensating plate for a liquid crystal display element, etc., it is necessary to control the thickness of the liquid crystal polymer film very strictly in order to control the twist angle.
本発明は以上のｌうな従来技術の問題点に鑑みてなされ
たものであり、その目的は、液晶性高分子を大面積にわ
たって均一で、高度に配向させることのできる液晶性高
分子の配向制御方法を提供することにある。The present invention has been made in view of the problems of the prior art as described above, and its purpose is to control the alignment of liquid crystalline polymers that can uniformly and highly align the liquid crystalline polymers over a large area. The purpose is to provide a method.
〔課題を解決するための手段及び作用〕上記目的を達成
するため１本発明によれば、液晶性高分子を配向させう
る配向処理の施された二枚の基板上にそれぞれ液晶性高
分子膜を形成し。[Means and effects for solving the problems] In order to achieve the above object, according to the present invention, a liquid crystal polymer film is formed on each of two substrates which have been subjected to an alignment treatment capable of aligning liquid crystal polymers. form.
液晶性高分子を配向させた後、該二枚の基板を、該液晶
性高分子どうしが密着するように重ね合わせることを特
徴とする液晶性高分子の配向制御方法が提供される。A method for controlling the alignment of a liquid crystalline polymer is provided, which comprises aligning the liquid crystalline polymer and then superimposing the two substrates so that the liquid crystalline polymers are in close contact with each other.
また、上述の方法で得た液晶性高分子膜を加熱によって
再配向させることによって、更に高度な配向制御を可能
とする方法が提供される。Furthermore, a method is provided that enables even more sophisticated alignment control by reorienting the liquid crystalline polymer film obtained by the above method by heating.
次に本発明を図面を用いて詳細に説明する。Next, the present invention will be explained in detail using the drawings.
第１図及び第２図は本発明による液晶性高分子の配向制
御方法を説明するための模式的断面図である。FIGS. 1 and 2 are schematic cross-sectional views for explaining the method for controlling the alignment of liquid crystalline polymers according to the present invention.
まず、ガラス、プラスチック等の基板ｌに配向処理層２
を形成する。配向処理の方法としてはポリイミド、ポリ
エーテルイミド、ポリアミドイミド、ポリエステルイミ
ド、ポリアミド、ポリエステル、ポリビニルアルコール
、ポリアクリロニトリル等の高分子被膜を形成後、ラビ
ング処理をする方法、アルコキシシラン、有機チタネー
トなどの有機金属化合物などの塗膜またはその熱処理膜
をラビング処理する方法、酸化珪素などの斜め蒸着法な
どを例示することができる。またプラスチック基板を直
接ラビング処理することによって配向処理することも可
能で、この場合、配向処理層２は不要となる。First, an alignment treatment layer 2 is placed on a substrate l made of glass, plastic, etc.
form. Orientation treatment methods include forming a polymer film of polyimide, polyetherimide, polyamideimide, polyesterimide, polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, etc., and then rubbing it; organic film such as alkoxysilane, organic titanate, etc. Examples include a method of rubbing a coating film of a metal compound or the like or a heat-treated film thereof, and an oblique vapor deposition method of silicon oxide or the like. It is also possible to carry out the alignment treatment by directly rubbing the plastic substrate; in this case, the alignment treatment layer 2 becomes unnecessary.
ついで、配向処理面に液晶性高分子を塗布し液晶性高分
子層３を形成する。Next, a liquid crystal polymer layer 3 is formed by applying a liquid crystal polymer to the alignment-treated surface.
用いることのできる液晶性高分子はサーモトロピックな
液晶性高分子であり、構造は特に限定されないが、例え
ばポリエステル、ポリエステルアミド、ポリカーボネー
ト、ポリエーテル等で主鎖に液晶性残基を有する下記構
造の主鎖型液晶性高分子ニ
一０ｆ１−Ｘ’）−＋Ａ１−Ｘ２ｈ
ｘ１．ｘ２： −ｃｏｏ−、−ＣＯＮＨ−、−０ＣＯ−
、−０−等−Ｎ＝！Ｉｔ−であり、本は不斉炭素原子、
ｎは０−１８の↓
整数を表わす。）
あるいはビニル系高分子、ポリシロキサンなどで側鎖に
液晶性残基を有する下記構造の側鎖型液晶性高分子：
Ｍ２： −Ｐｈ−Ｐｈ−Ｒ’ 、−０−Ｐｈ−Ｐｈ−Ｒ
３，−Ｐｈ−Ｃｏｏ−Ｐｈ−Ｒ’ 、−０−Ｐｈ−ＣＯ
［）−Ｐｈ−Ｒ’（但し、Ｒ３はアルキル基、アルコキ
シ基、ハロゲン原子、ニトロ基又はシアノ基であり、ｎ
は０−１８の整数を表わす。）
などを例示することができる。液晶性高分子は単独でま
たは混合して用いられる。液晶性高分子中に光学活性基
を導入したり、光学活性な化合物を添加することもでき
る。The liquid crystalline polymer that can be used is a thermotropic liquid crystalline polymer, and the structure thereof is not particularly limited. Main chain liquid crystalline polymer 20f1-X')-+A1-X2h x1. x2: -coo-, -CONH-, -0CO-
, -0-etc.-N=! It-, and the book is an asymmetric carbon atom,
n represents an integer from 0 to 18. ) Or a side chain type liquid crystalline polymer such as a vinyl polymer or polysiloxane having a liquid crystalline residue in the side chain and having the following structure: M2: -Ph-Ph-R', -0-Ph-Ph-R
3,-Ph-Coo-Ph-R', -0-Ph-CO
[)-Ph-R' (where R3 is an alkyl group, an alkoxy group, a halogen atom, a nitro group or a cyano group, and n
represents an integer from 0 to 18. ) can be exemplified. Liquid crystalline polymers may be used alone or in combination. It is also possible to introduce an optically active group into the liquid crystalline polymer or add an optically active compound.
塗布法としては液晶性高分子が流動性を有するガラス転
移点以上の温度で直接塗布する方性、または液晶性高分
子を溶媒に溶解させ、溶液として塗布または印刷する方
法を用いることができる。As a coating method, there can be used a method in which the liquid crystalline polymer is directly coated at a temperature equal to or higher than the glass transition point at which it has fluidity, or a method in which the liquid crystalline polymer is dissolved in a solvent and coated or printed as a solution.
膜厚の均一性と制御のしやすさの点で後者を特に好まし
く用いる。液晶性高分子の溶媒としては、用いる液晶性
高分子の種類、重合度等によって異なるが１通常下記の
物より選ばれる。The latter is particularly preferably used in terms of uniformity of film thickness and ease of control. The solvent for the liquid crystalline polymer varies depending on the type of liquid crystalline polymer used, degree of polymerization, etc., but is usually selected from the following.
クロロホルム、ジクロロエタン、テトラクロロエタン、
トリクロロエチレン、テトラクロロエチレン、オルソジ
クロロベンゼンなどのハロゲン系炭化水素、フェノール
、０−クロロフェノール、クレゾールなどのフェノール
系溶媒、ジメチルホルムアミド、ジメチルアセトアミド
、ジメチルスルホキシドなどの非プロトン性極性溶媒、
テトラヒドロフラン、ジオキサン等のエーテル系溶媒お
よびこれらの混合溶媒。Chloroform, dichloroethane, tetrachloroethane,
Halogenated hydrocarbons such as trichlorethylene, tetrachlorethylene, and orthodichlorobenzene; phenolic solvents such as phenol, 0-chlorophenol, and cresol; aprotic polar solvents such as dimethylformamide, dimethylacetamide, and dimethylsulfoxide;
Ether solvents such as tetrahydrofuran and dioxane, and mixed solvents thereof.
溶液濃度は塗布法、高分子の粘性、目的とする膜厚等に
より異なるが、液晶表示素子用の補償板を例にすると、
要求される膜厚は２〜１０声程度であるので、通常は２
〜５０ｗｔ％の範囲で使用され、好ましくは５−３０ｗ
ｔ％の範囲で使用される。塗布法としてはスピンコード
法、ロールコート法、グラビアコート法、ディッピング
法、スクリーン印刷法などを採用できる。液晶性高分子
を塗布後、溶媒を乾燥して除去し、液晶性高分子が液晶
性を示す温度で熱処理して液晶性高分子を配向させる。The solution concentration varies depending on the coating method, the viscosity of the polymer, the desired film thickness, etc., but taking a compensation plate for a liquid crystal display element as an example,
The required film thickness is about 2 to 10 tones, so usually 2 to 10 tones are required.
Used in the range of ~50wt%, preferably 5-30w
It is used in the range of t%. As a coating method, a spin code method, a roll coating method, a gravure coating method, a dipping method, a screen printing method, etc. can be adopted. After coating the liquid crystalline polymer, the solvent is removed by drying, and the liquid crystalline polymer is aligned by heat treatment at a temperature at which the liquid crystalline polymer exhibits liquid crystallinity.
液晶性高分子を配向させるときの温度は、液晶性高分子
のガラス転移点以上で、かつ、液晶性高分子の等方性液
体への転移温度より低いことが必要である。配向膜の界
面効果による配向を助ける意味でポリマーの粘性は低い
方がよく、シたがって温度は高い方がよいが、あまり高
いとコストの増大と作業性の悪化を招き好ましくない。The temperature when orienting the liquid crystalline polymer needs to be higher than the glass transition point of the liquid crystalline polymer and lower than the transition temperature of the liquid crystalline polymer to an isotropic liquid. The lower the viscosity of the polymer, the better, in order to assist the alignment due to the interfacial effect of the alignment film, and therefore the higher the temperature, but if it is too high, it is not preferable as it increases cost and deteriorates workability.
一般的には５０°Ｃ〜３００℃の範囲が好ましい。Generally, a range of 50°C to 300°C is preferred.
以上のようにして得られた液晶性高分子膜はモノドメイ
ン配向した優れた配向性を有しているが、塗布法である
ため厚さ分布は避けられず、所望の厚みに対して０．５
％以下の面精度を得ることは困難である。この値は用途
によっては十分な値であるが、液晶表示素子用補償板の
ように液晶性高分子がねしれ構造を持ち、ねじれ角をも
制御する必要がある場合には、膜厚の分布がねしれ角の
分布にもなってしまい好ましくない。本発明の液晶性高
分子にねしれ構造を導入するには、液晶性高分子として
コレステリック液晶相を呈するものを用いればよい。コ
レステリック液晶相を呈する液晶性高分子は前述のよう
にネマティック相を呈する液晶性高分子中に光学活性基
を導入するか、光学活性な物質を添加すればよい。この
場合、液晶性高分子は配向処理膜面では配向処理の方向
に配列し、厚み方向に自然ピッチに相当するねじれ角、
すなわち自然ピンチをＰＯ１膜厚をｄ、ねじれ角をωと
したときにω＝３６０Ｘｄ／Ｐｏ（°）なるねじれ角を
形成する。The liquid crystalline polymer film obtained as described above has excellent monodomain orientation, but since it is a coating method, thickness distribution is unavoidable, and the desired thickness is 0.5%. 5
It is difficult to obtain a surface accuracy of less than %. This value is sufficient for some applications, but if the liquid crystal polymer has a twisted structure, such as a compensation plate for liquid crystal display elements, and the twist angle also needs to be controlled, the thickness distribution This also results in a distribution of torsion angles, which is undesirable. In order to introduce a twisted structure into the liquid crystalline polymer of the present invention, a liquid crystalline polymer exhibiting a cholesteric liquid crystal phase may be used. A liquid crystalline polymer exhibiting a cholesteric liquid crystal phase may be obtained by introducing an optically active group into a liquid crystalline polymer exhibiting a nematic phase as described above, or by adding an optically active substance to the liquid crystalline polymer exhibiting a nematic phase. In this case, the liquid crystalline polymer is aligned in the direction of the alignment treatment on the alignment treatment film surface, and has a twist angle corresponding to the natural pitch in the thickness direction.
That is, when the natural pinch is defined as PO1 film thickness d and twist angle as ω, a twist angle of ω=360Xd/Po (°) is formed.
本発明では、以上のようにして配向させた液晶性高分子
膜を二層、第２図に示したように重ねあわせる。二層の
液晶性高分子層３，３′を一つの層とみなすと、この層
に入射する光は、入射時と出射時の両方において、配向
処理層２，２′と液晶性高分子層３，３′の界面を通過
する。この界面での液晶性高分子の配向方向は配向処理
層２，２′によって各々の面内で均一になっている。従
って、二枚の基板１．１′上で液晶性高分子を配向させ
たときに、配向処理層２，２′に接していない面上での
配向方向にムラがあったとしても、このムラは部分的に
キャンセルすることができる。また、請求項２に示した
方法では、加熱する前の液晶性高分子層３，３′の界面
近傍での該液晶性高分子層３，３′の各々の配向方向が
ほぼ平行となるように重ねた場合、二枚の基板１，１′
上で液晶性高分子を別々に配向させたときに、配向処理
層２，２′に接していない面上に生じてしまった配向ム
ラが加熱−再配向させる際に解消され、高度に配向制御
された液晶性高分子層を得ることができる。In the present invention, two layers of liquid crystalline polymer films oriented as described above are superimposed as shown in FIG. When the two liquid crystal polymer layers 3 and 3' are considered as one layer, the light incident on this layer is transmitted to the alignment treatment layers 2 and 2' and the liquid crystal polymer layer both at the time of incidence and at the time of output. It passes through the interface of 3 and 3'. The alignment direction of the liquid crystalline polymer at this interface is made uniform within each plane by the alignment treatment layers 2 and 2'. Therefore, when the liquid crystal polymer is aligned on the two substrates 1.1', even if there is unevenness in the alignment direction on the surfaces that are not in contact with the alignment treatment layers 2, 2', this unevenness can be partially canceled. Further, in the method according to claim 2, the orientation directions of each of the liquid crystalline polymer layers 3 and 3' in the vicinity of the interface of the liquid crystalline polymer layers 3 and 3' before heating are approximately parallel to each other. When stacked on top of each other, two substrates 1, 1'
When the liquid crystalline polymers are oriented separately above, the alignment unevenness that occurs on the surfaces that are not in contact with the alignment treatment layers 2 and 2' is eliminated during heating and reorientation, and the alignment can be highly controlled. A liquid crystalline polymer layer can be obtained.
液晶性高分子層３，３′の構成材料は、同一のものであ
る必要はなく、ねじれ構造をとらせた場合も、ねじれの
向きやピッチを異らせることができる。The constituent materials of the liquid crystalline polymer layers 3 and 3' do not need to be the same, and even if they have a twisted structure, the direction and pitch of the twist can be different.
また、配向処理層２，２′も水平配向、傾斜配向、垂直
配向の任意の組み合わせが可能である。例として層２に
水平配向性を持たせるとともに層を２′に垂直配向性を
持たせ、請求項２の配向方法を用いると、いわゆるＨＡ
・Ｎ（ｈｙｂｒｉｄ ａｌｉｇｎｅｄ ｎｅｍａｔｉｃ
）型液晶表示素子と同様の構造を作ることができる。Furthermore, the alignment treatment layers 2 and 2' can also have any combination of horizontal alignment, oblique alignment, and vertical alignment. For example, if layer 2 is made to have horizontal orientation and layer 2' is made to have vertical orientation and the alignment method of claim 2 is used, the so-called HA
・N (hybrid aligned nematic
) type liquid crystal display element can be created.
また、液晶性高分子層３，３′に屈折率異方性へ〇の異
った材料を用い、それぞれに光学活性物質を添加するこ
とによって異ったねじれピッチを持たせ、ＳＴＮ型液晶
表示素子に対する、高性能な色補償板、視角補償板が作
製可能となる。In addition, materials with different refractive index anisotropy are used for the liquid crystal polymer layers 3 and 3', and optically active substances are added to each material to give them different twist pitches. It becomes possible to produce high-performance color compensation plates and viewing angle compensation plates for elements.
液晶性高分子層３，３′の構成材料として、異った波長
域の光を吸収するような材料を用いるか、または異なっ
た波長域の光を吸収するような色素を液晶性高分子層３
，３′のそれぞれに添加することにより、記録容量が倍
増した、光記録媒体用の液晶性高分子層が得られる。As the constituent material of the liquid crystal polymer layers 3 and 3', materials that absorb light in different wavelength ranges are used, or dyes that absorb light in different wavelength ranges are used in the liquid crystal polymer layers. 3
, 3', a liquid crystalline polymer layer for optical recording media with double the recording capacity can be obtained.
請求項１の方法で得られる液晶性高分子層３，３′では
密着した面における各々の液晶性高分子層３゜３′の配
向方向の成す角度を自由に調節することができる。従っ
て、液晶性高分子層３，３′のそれぞれに液晶性高分子
とともに配向するような電子供与性物質と受容物質やエ
ネルギー供与性物質と受容物質などを添加し、最も効率
良く電子移動反応やエネルギー移動反応が起こるような
、界面における配向方向の相対角度をさがすことができ
る。In the liquid crystalline polymer layers 3, 3' obtained by the method of claim 1, the angle formed by the alignment direction of each liquid crystalline polymer layer 3°3' on the closely contacted surfaces can be freely adjusted. Therefore, an electron donating substance and an acceptor substance, an energy donating substance and an acceptor substance, etc. that are aligned together with the liquid crystal polymer are added to each of the liquid crystal polymer layers 3 and 3' to achieve the most efficient electron transfer reaction. It is possible to search for the relative angle of orientation at the interface at which an energy transfer reaction occurs.
次に本発明を実施例により更に詳細に説明するが、本発
明はこれら実施例に限定されるものではない。EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
（実施例１）
ガラス基板上にポリイミド系樹脂を主成分とするサンエ
バー１５０（日産化学社製）を専用シンナーで２ｗｔ％
まで希釈した溶液を塗布した。１００°Ｃのオーブンで
３０分間乾燥後、２５０℃に昇温し１時間焼成した。放
冷後、ナイロン植毛布でラビングを行い、その上に下記
の繰返し単位を持つ液晶性高分子の溶液をスピンナー塗
布した。(Example 1) 2wt% of Sunever 150 (manufactured by Nissan Chemical Co., Ltd.) whose main component is polyimide resin was applied on a glass substrate using a special thinner.
A diluted solution was applied. After drying in an oven at 100°C for 30 minutes, the temperature was raised to 250°C and baked for 1 hour. After cooling, rubbing was performed with a nylon flocked cloth, and a solution of a liquid crystalline polymer having the following repeating units was applied thereon using a spinner.
ついで、これを９０°Ｃのオーブンで１時間乾燥し、そ
の後オーブンの温度を上げて１１０℃に５分間保ち、基
板をオーブンから取り出し、放冷することにより、液晶
性高分子膜付き基板を得た。これをクロスニコルにした
偏光板ではさんで複屈折色を観察したところ、はぼ−様
な色が見られたが、所々に厚みムラによる色ムラが認め
られた。触針式の膜厚計で測定したところ、液晶性高分
子膜の厚さは約３戸で、最大で０．５μｍ程度の厚みム
ラがあった。Next, this was dried in an oven at 90°C for 1 hour, and then the temperature of the oven was raised to 110°C for 5 minutes, and the substrate was taken out of the oven and allowed to cool, thereby obtaining a substrate with a liquid crystal polymer film. Ta. When the birefringent color was observed by sandwiching this between crossed nicol polarizing plates, a hazy color was observed, but color unevenness due to thickness unevenness was observed in some places. When measured with a stylus-type film thickness meter, the thickness of the liquid crystalline polymer film was approximately 3 mm, and there was a maximum thickness unevenness of approximately 0.5 μm.
液晶性高分子には光学活性物質を添加しており、偏光解
析の結果、液晶性高分子の配向方向は、厚み方向で約１
２０°ねしれていることがわかった。このようにして作
成した液晶性高分子膜付きの基板２枚を、界面での分子
配向がほぼ平行となるよう密着させ、補償板とした。該
補償板を二枚の偏光板の間にはさんで複屈折色をｍ察し
たところ、わずかに色ムラが誌められた。ついで該補償
板をＩＩ０℃のオーブンに入れ、１０分間後に取り出し
、放冷した。この処理の後では、二枚の偏光板の間には
さんで観察しても色ムラは認められなかった。An optically active substance is added to the liquid crystal polymer, and as a result of polarization analysis, the orientation direction of the liquid crystal polymer is approximately 1 in the thickness direction.
It was found that it was bent by 20 degrees. Two substrates with liquid crystalline polymer films prepared in this manner were brought into close contact with each other so that the molecular orientations at the interface were substantially parallel, thereby forming a compensating plate. When the compensating plate was sandwiched between two polarizing plates and the birefringence color was observed, slight color unevenness was observed. The compensator plate was then placed in an oven at II0°C, taken out after 10 minutes, and allowed to cool. After this treatment, no color unevenness was observed even when observed between two polarizing plates.
また、液晶性高分子を再配向させた補償板をＳＴＮ型液
晶表示素子と偏光板の間にはさむと、ＳＴＮ型液晶表示
素子に特有の複屈折色はほぼ消え、白黒表示に近い画質
が得られた。Furthermore, when a compensating plate with re-oriented liquid crystal polymers was sandwiched between an STN liquid crystal display element and a polarizing plate, the birefringent color characteristic of STN liquid crystal display elements almost disappeared, resulting in an image quality close to that of black and white display. .
（実施例２）
液晶性高分子として下記の繰返し単位を持つものを用い
、
光学活性体の８体と８体を添加した２種類の溶液を別々
の基板に塗布し、１１０℃のオーブンで１時間乾燥した
。次に、オーブンの温度を１３０°Ｃに上げ、１０分間
保った後でオーブンから取り出し、放冷した。光学活性
体の濃度は、液晶性高分子の配向ねじれ角が１８０°に
なるように調整した。８体と８体のねしれの向きは逆に
なっていた。ねじれの向きが逆となっている一対の基板
を、膜面が密着するように重ね、補償板とした。該補償
板をＤＡＰ型液晶表示素子と偏光板の間にはさんだとこ
ろ、視角補償効果が得られ、表示の視認角度が広くなっ
た。(Example 2) Using a liquid crystalline polymer having the following repeating unit, two types of solutions containing optically active substances 8 and 8 were applied to separate substrates, and the mixture was heated in an oven at 110°C for 1 hour. Dry for an hour. Next, the temperature of the oven was increased to 130° C., kept at that temperature for 10 minutes, and then removed from the oven and allowed to cool. The concentration of the optically active substance was adjusted so that the orientation twist angle of the liquid crystalline polymer was 180°. The directions of the twists of the 8th and 8th bodies were opposite. A pair of substrates with opposite twist directions were stacked so that the film surfaces were in close contact with each other to form a compensation plate. When the compensation plate was sandwiched between the DAP type liquid crystal display element and the polarizing plate, a viewing angle compensation effect was obtained, and the viewing angle of the display was widened.
〔発明の効果〕
請求項１の方法によれば、二枚の基板上で別々に配向さ
せた液晶性高分子膜を膜面が密着するように重ねあわせ
るので、別々に配向させたときに生じた、配向処理層に
接していない面での配向ムラによる特性ムラが部分的に
キャンセルされる。[Effects of the Invention] According to the method of claim 1, liquid crystalline polymer films that have been separately oriented on two substrates are overlapped so that the film surfaces are in close contact with each other, so that the liquid crystalline polymer films that are oriented separately on two substrates are overlapped so that the film surfaces are in close contact with each other. In addition, characteristic unevenness due to alignment unevenness on the surface not in contact with the alignment treatment layer is partially canceled.
また、各々の基板に塗布する液晶性高分子材料に異った
光学活性体や異った波長帯の光を吸収する色素、または
電子供与物質と電子受容体、あるいはエネルギー供与体
とエネルギー受容体を別々に添加することにより、多様
な光学補償板、光記録媒体などの高機能性素材を提供で
きる。In addition, different optically active substances, dyes that absorb light in different wavelength bands, electron donor substances and electron acceptors, or energy donors and energy acceptors are added to the liquid crystalline polymer material applied to each substrate. By adding these separately, highly functional materials such as various optical compensators and optical recording media can be provided.
請求項２の方法では、二枚の基板上で別々に配向させた
液晶性高分子膜を膜面が密着するように重ねあわせた後
、加熱することにより液晶性高分子を再配向させるので
、非常に均一な配向が得られ、光学特性の優れた液晶性
高分子膜を提供できる。In the method of claim 2, the liquid crystal polymer films that have been separately oriented on two substrates are superimposed so that the film surfaces are in close contact with each other, and then the liquid crystal polymers are reorientated by heating. Very uniform alignment can be obtained and a liquid crystalline polymer film with excellent optical properties can be provided.
第１図及び第２図は本発明の詳細な説明するための液晶
性高分子膜付き基板の断面図である。
ｌ、１′・・・基板
２．２′・・配向処理層
３．３′・・・液晶性高分子層
第１図
特許出願人 株式会社 リ コ1 and 2 are cross-sectional views of a substrate with a liquid crystalline polymer film for explaining the present invention in detail. l, 1'...Substrate 2.2'...Alignment treatment layer 3.3'...Liquid crystal polymer layer Figure 1 Patent applicant Rico Co., Ltd.
Claims (2)
二枚の基板上にそれぞれ液晶性高分子膜を形成し、該液
晶性高分子を配向させた後、該二枚の基板を、該液晶性
高分子膜どうしが密着するように重ねあわせることを特
徴とする液晶性高分子の配向制御方法。(1) A liquid crystal polymer film is formed on each of two substrates that have been subjected to an alignment treatment that can orient the liquid crystal polymer, and after aligning the liquid crystal polymer, the two substrates are . A method for controlling the alignment of a liquid crystalline polymer, characterized in that the liquid crystalline polymer films are superimposed so as to be in close contact with each other.
高分子膜を該二枚の基板間にはさんだままで加熱するこ
とにより、該液晶性高分子を再配向させることを特徴と
する液晶性高分子の配向制御方法。(2) The liquid crystalline polymer film obtained by the method according to claim 1 is heated while being sandwiched between the two substrates to reorient the liquid crystalline polymer. A method for controlling the orientation of liquid crystalline polymers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12228090A JPH0416914A (en) | 1990-05-11 | 1990-05-11 | Method for controlling orientation of liquid crystalline high polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12228090A JPH0416914A (en) | 1990-05-11 | 1990-05-11 | Method for controlling orientation of liquid crystalline high polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0416914A true JPH0416914A (en) | 1992-01-21 |
Family
ID=14832054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12228090A Pending JPH0416914A (en) | 1990-05-11 | 1990-05-11 | Method for controlling orientation of liquid crystalline high polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0416914A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09211459A (en) * | 1996-02-05 | 1997-08-15 | Susumu Sato | Orientation treatment of liquid crystal substrate and production of liquid crystal cell |
| JP2003509725A (en) * | 1999-09-16 | 2003-03-11 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Optical compensator and liquid crystal display I |
| JP2011128417A (en) * | 2009-12-18 | 2011-06-30 | Dainippon Printing Co Ltd | Method for producing electromagnetic wave reflection member and method for recovering reflectance of electromagnetic wave reflection member |
-
1990
- 1990-05-11 JP JP12228090A patent/JPH0416914A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09211459A (en) * | 1996-02-05 | 1997-08-15 | Susumu Sato | Orientation treatment of liquid crystal substrate and production of liquid crystal cell |
| JP2003509725A (en) * | 1999-09-16 | 2003-03-11 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Optical compensator and liquid crystal display I |
| JP2011128417A (en) * | 2009-12-18 | 2011-06-30 | Dainippon Printing Co Ltd | Method for producing electromagnetic wave reflection member and method for recovering reflectance of electromagnetic wave reflection member |
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