JPS5872924A - Liquid crystal display element - Google Patents
Liquid crystal display elementInfo
- Publication number
- JPS5872924A JPS5872924A JP56171418A JP17141881A JPS5872924A JP S5872924 A JPS5872924 A JP S5872924A JP 56171418 A JP56171418 A JP 56171418A JP 17141881 A JP17141881 A JP 17141881A JP S5872924 A JPS5872924 A JP S5872924A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- liquid crystal
- polyamic acid
- diamine
- 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
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
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- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、ホモジニアス配向を利用した液晶表示素子に
係り、特に液晶表示素子の配向膜に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a liquid crystal display element using homogeneous alignment, and particularly to an alignment film of a liquid crystal display element.
液晶表示素子は、基本的には２枚のガラス基板が一定の
間隔をおいて平行に配置され、またこれら２枚の基板の
対向する面上にはそれぞれ透明導電膜が選択的に配置さ
れていて、しかもこれら導電膜およびガラス面はいずれ
も一定方向に液晶を配向させる配向膜で完全に被覆され
ており、更にこれら配向膜間には液晶が充填されていて
、上記基板の全周は液晶がもれないように密封されてお
り、また上記基板の配向膜の形成されていない面上には
偏光板が配置された構造になっている。A liquid crystal display element basically consists of two glass substrates arranged in parallel at a certain distance, and a transparent conductive film is selectively arranged on each of the opposing surfaces of these two substrates. Moreover, both the conductive film and the glass surface are completely covered with an alignment film that orients the liquid crystal in a certain direction, and the space between these alignment films is filled with liquid crystal, so that the entire circumference of the substrate is covered with liquid crystal. The substrate is sealed to prevent leakage, and a polarizing plate is disposed on the surface of the substrate on which the alignment film is not formed.
このような基本構成の液晶表示素子の表示方式にば二
（ａ） ツイステッドネマクィック電界効果型表示方
式、
（ｂ） 誘起複屈折電界効果型表示方式、（Ｃ）
動的散乱型表示方式、
（ｄ） ゲストホスト型二色表示方式、（ｅｌ 配
向振動型表示方式、
などがあり、（ａ）の方式が広く実用化され【いる。The display methods of a liquid crystal display element with such a basic configuration are as follows: (a) Twisted nematic field effect display method, (b) Induced birefringence field effect display method, (C)
There are dynamic scattering display methods, (d) guest-host two-color display methods, (el) orientation vibration display methods, etc., and method (a) is widely put into practical use.
そして、液晶表示素子の配向膜には従来、ｌａ） 酸
化ケイ素などの斜方蒸着膜、（′ｂ）表面処理膜、直鎖
状高分子やエポキシ樹脂などの熱硬化高分子膜をラビン
グ処理したもの、
（Ｃ） 耐熱性良好なポリイｉド等の膜をラビング処
理したもの、
などが採用されている。Conventionally, the alignment film of a liquid crystal display element is made of la) an oblique vapor deposition film such as silicon oxide, ('b) a surface treatment film, and a thermosetting polymer film such as a linear polymer or epoxy resin that is rubbed. (C) A film coated with a film made of poly-iide or the like with good heat resistance and subjected to a rubbing treatment.
しかし、上記の配向膜は、いずれも以下に述べる欠点を
有していた。However, all of the above alignment films had the following drawbacks.
（ｉ） 酸化ケイ素などの斜方蒸着膜は使用する液晶
によって配向能に差があり、液晶によっては配向性が悪
いものもある。このため、液晶の温度特性、電気光学特
性を改善するため各種液晶を混合して使用できない。(i) The alignment ability of an obliquely vapor deposited film such as silicon oxide differs depending on the liquid crystal used, and some liquid crystals have poor alignment properties. For this reason, various liquid crystals cannot be mixed and used to improve the temperature characteristics and electro-optical characteristics of the liquid crystal.
また、視角骨性がやや劣る。また、屈折率＜１６５であ
るため、適正膜厚で塗布しても電極反射を防止できない
。さらに、原価低減と６５点からも不適当である。In addition, visual angular bone properties are slightly inferior. Furthermore, since the refractive index is <165, electrode reflection cannot be prevented even if the film is coated with an appropriate thickness. Furthermore, it is inappropriate in terms of cost reduction and 65 points.
（ｂ） 表面処理膜、直鎖状高分子やエポキシ樹脂な
どの熱硬化高分子膜は、封着剤、封止剤を加熱して封着
や封止作業を行う際に配向能が低下する。(b) The orientation ability of surface treatment films, thermosetting polymer films such as linear polymers and epoxy resins decreases when sealing agents or sealants are heated to perform sealing or sealing work. .
（ｃ） ポリイミド膜（例えばジアミノジフェニルエ
ーテルと酸無水物とからなる縮合物は透明電極の反射が
なく、配向性も良好であるが、加熱閉環時に着色が目立
ち、素子としての外観を損う。更に耐湿信頼性向上方法
としてシラン：カップリング剤を添加する場合があるが
液の安定性の点から添加量が制限され、素子寿命として
は７０℃９５％ＲＨで５００ｈ程度が限界である。(c) A polyimide film (for example, a condensate of diaminodiphenyl ether and an acid anhydride has no reflection from a transparent electrode and has good orientation, but coloration becomes noticeable during ring closure by heating, impairing the appearance of the device. Silane: A coupling agent may be added as a method of improving moisture resistance reliability, but the amount added is limited from the viewpoint of liquid stability, and the device life is limited to about 500 hours at 70° C. and 95% RH.
また、ビス（アミノフェノキシ）ジフェニル化合物をジ
アミン成分に用いたポリイｉドの例が、あるが、この場
合加熱時の膜の着色は防止できてもｉ板に対する耐湿接
着性が悪いため、信頼性を向上できない。In addition, there is an example of a poly-iide using a bis(aminophenoxy)diphenyl compound as a diamine component, but in this case, although coloring of the film during heating can be prevented, the moisture-resistant adhesion to the i-plate is poor, resulting in poor reliability. cannot be improved.
また、芳香族ジヒドラジドと酸無水物を配向膜とする例
があるが、この場合、加勢時の膜の着色は防止できるが
、ヒドラジド結合は加水分解を受けやすく、その結果液
の析出。In addition, there is an example in which an aromatic dihydrazide and an acid anhydride are used as an alignment film, but in this case, coloring of the film during application can be prevented, but the hydrazide bonds are susceptible to hydrolysis, resulting in liquid precipitation.
配向不良が問題となる。Poor orientation becomes a problem.
また、カップリング剤によっては液がゲル化し、素子の
耐湿信頼性を向上させるためにも不利である。更に膜が
もろく、ラビング時ゝ・１、
の作業マージンが小さい。高温高湿下では、素子内部を
流れる微小電流の増加が大きく、消費電力が大きい。ポ
リイミド膜に比べて膜の絶縁性も悪い。Further, depending on the coupling agent, the liquid may turn into a gel, which is disadvantageous for improving the moisture resistance reliability of the device. Furthermore, the film is brittle and the working margin for rubbing is small. Under high temperature and high humidity conditions, the small current flowing inside the device increases significantly, resulting in large power consumption. The insulation properties of the film are also poorer than polyimide films.
本発明の目的は、上記した従来技術の欠点を無くし、
（ａ） 耐湿信頼性の高い、
（ｂ） 耐ラビング性が良い、
（ａ 膜がキ凰ア時に着色しにくい、ｌｄ） 電極
パターンの浮き出て見えない、（ｅ） ポリマ溶液と
して液安定性のすぐれた、配向膜を有する液晶表示素子
を提供することにある。The purpose of the present invention is to eliminate the above-mentioned drawbacks of the prior art, and to provide (a) high moisture resistance reliability; (b) good rubbing resistance; An object of the present invention is to provide a liquid crystal display element having an alignment film that does not appear to stand out and (e) has excellent liquid stability as a polymer solution.
本発明は、かかる点に関しなされたもので透明電極の形
成された一対の基板間に挟持された液晶層を有する液晶
表示素子において、前記基板の対向面上に配向膜材とし
て一般式＋ＨＮ−Ｒ−れるものでｎとしてはジメチルス
ルホキシドを溶媒としてす℃で測定したポリマの還元粘
度で０．１〜ｔＯｄＬ／を程度の値）で示されるポリア
ミド酸を加熱したものを用いる場合、本発明の特徴は上
記ポリアミド酸（Ｉ）が加熱時に着色しＫくぃような原
料ジアミンにＮ−Ｒ−Ｎにとして、一般式−テル結合を
有する芳香族ジアミンを３０〜９蝕ル嘱用い、かつ基板
との耐湿接着性を良くしてＲ，−ＮＨ，で示されるシア
ζノシロキサンを２〜２０モル％の範囲で共重合させ、
更に膜強度、成膜性など目的によりＨ，！’（−Ｑ−〜
−Ｑ−ＮＨ，で示される芳香族シア２ンを０〜５０モル
％以下の範囲で共重合させることである。ただし上記式
中、Ｒ１ｃ７゜
鳥は水素原子、低級アルキル基、鳥は２価の炭化水素基
、へは１価の炭化水素基、鳥は一〇−１−ＣＨ，−、−
ＣＯ−、−０＜Σｏ−、−ｏＱｏＱｏ−などである。The present invention has been made in this regard, and provides a liquid crystal display element having a liquid crystal layer sandwiched between a pair of substrates on which transparent electrodes are formed. - When using a heated polyamic acid having a reduced viscosity of 0.1 to tOdL/, where n is a reduced viscosity of the polymer measured at ℃ using dimethyl sulfoxide as a solvent, the characteristics of the present invention are as follows. The above-mentioned polyamic acid (I) is colored when heated, and the raw material diamine is converted into N-R-N, and an aromatic diamine having a general formula -ter bond is used for 30 to 9 times, and the substrate and Copolymerizing cyanosiloxane represented by R, -NH in a range of 2 to 20 mol% to improve moisture-resistant adhesion,
Furthermore, depending on the purpose such as film strength and film formability, H,! '(-Q-~
The purpose is to copolymerize aromatic cyanide represented by -Q-NH in a range of 0 to 50 mol%. However, in the above formula, R1c7゜bird is a hydrogen atom, a lower alkyl group, a bird is a divalent hydrocarbon group, 〇 is a monovalent hydrocarbon group, and a bird is 10-1-CH, -, -
CO-, -0<Σo-, -oQoQo-, etc.
膜の着色を防止するための上記ジアミンＨ，Ｎ２．２−
ヒｘ（４−（４−アミノフェノキシ）フェニル〕プロパ
ン、２，２−芦ス〔３−メチル−４−（４−アはノフエ
ノキシ）フェニル〕グロパン、２，２−ビス〔３−エチ
ル−４−（４−７２ノフエノキシ）フェニル〕プロパン
、２，２−ビス〔５−プロピル−４−（４−アミノフェ
ノキシ）フェニル〕プロパ７．２．２−ビス〔５−イソ
プロピル−４−（Ａ−アミノフェノキシ）フェニル〕プ
ロパン、２，２７ビス〔３，５−ジメチル−４−（４−
アミノフェノキシ）フェニル〕プロパン、１．１−ビス
（ａ−（ａ−アミノフェノキシ）フェニル〕エタン、２
．２−ビス〔４−（アミノフェノキシ）フェニル〕へキ
サフルオロプロパンなどがあり、このように要分子のジ
アミンを用いることにより、ポリイミドの着色の主な原
因であるイミド環のポリマに対する比率を小さくし、膜
の着色を防止できる。この中でも特に好ましいのは、２
，２−ビス（４−（４−アミノフェノキシ）フェニル〕
プロパン、’２．２−ビス〔３，５−ジメチル−４−（
４−アミノフェノキシ）フェニル〕プロパン、２，２−
ビス〔４−（４−アミノフェノキシ）フェニル〕ヘキサ
ンルオロプロパンである。これらのジアミンの共重合比
としては、ジアミン全体の３０モル゛襲上であれば、実
用上無着色の膜が得られる。The above diamine H,N2.2- for preventing coloring of the film
Hyx(4-(4-aminophenoxy)phenyl)propane, 2,2-Asu[3-methyl-4-(4-a is nophenoxy)phenyl]glopane, 2,2-bis[3-ethyl-4 -(4-72nophenoxy)phenyl]propane, 2,2-bis[5-propyl-4-(4-aminophenoxy)phenyl]propa7.2.2-bis[5-isopropyl-4-(A-amino phenoxy)phenyl]propane, 2,27bis[3,5-dimethyl-4-(4-
Aminophenoxy)phenyl]propane, 1,1-bis(a-(a-aminophenoxy)phenyl)ethane, 2
．． Examples include 2-bis[4-(aminophenoxy)phenyl]hexafluoropropane, and by using diamines as key molecules, the ratio of imide rings to polymer, which is the main cause of polyimide coloration, can be reduced. , coloring of the film can be prevented. Among these, 2 is particularly preferable.
,2-bis(4-(4-aminophenoxy)phenyl)
Propane, '2,2-bis[3,5-dimethyl-4-(
4-aminophenoxy)phenyl]propane, 2,2-
Bis[4-(4-aminophenoxy)phenyl]hexanefluoropropane. As for the copolymerization ratio of these diamines, if the copolymerization ratio is 30 moles or more of the total amount of diamines, a practically uncolored film can be obtained.
ガラスに対する接着性を良くするために共重釆的である
。Copolymerized to improve adhesion to glass.
上記シロキサンジアミンの共重合比として）１、ジアミ
ン全体の２〜２０モル幅が望ましくＳ０２モル−未満で
はシロキサンジアミンによるガラスに対する接着効果が
あまりなく、２０モル％をこえるとポリアミド酸溶液と
しての液装置安定性が悪くなる。また、脂肪族シロキサ
ンジアミンの場合に２０モル％をこえると配向性が悪く
なる場合がある。特に好ましくは５〜１０モル襲の範囲
で使用すればよい。As for the copolymerization ratio of the above siloxane diamine), it is desirable that the total diamine has a 2 to 20 mole width.If it is less than 2 moles, the siloxane diamine will not have much of an adhesion effect on glass, and if it exceeds 20 mole%, the liquid device as a polyamic acid solution. Stability deteriorates. Furthermore, in the case of aliphatic siloxane diamine, if the content exceeds 20 mol %, the orientation may deteriorate. Particularly preferably, it is used in a range of 5 to 10 moles.
膜強度を更に太きくシ、成膜性を良くするたにＮＱＯＱ
ＯＱＮＨ，、などがあるが、耐ラビング性の点からはＨ
，Ｎ−＠＞モー０−Ｎ鴇が特に好ましい。これらはジア
ミン全体の５０モル％をこえるとジアミンによっては着
色が目立つものもあるので０〜５０襲で使用する。NQOQ to further increase film strength and improve film formability.
There are OQNH,, etc., but from the point of view of rubbing resistance, H
, N-@>Mo0-N is particularly preferred. If these exceed 50 mol% of the total diamine, some diamines may show noticeable coloring, so they are used in amounts of 0 to 50.
ポリアミド酸（Ｉ）の原料酸無水物
以上のようなジアミン、酸無水物からポリアミド酸（耳
）が合成されるわけであるが、更に素子の耐湿信頼性を
高める方法として、上記ポリアミド酸にシランカップリ
ング剤を添加すると効果的である。Raw material acid anhydride for polyamic acid (I) Polyamic acid (synthesis) is synthesized from the above-mentioned diamines and acid anhydrides, but as a method to further improve the moisture resistance reliability of the device, silane is added to the polyamic acid (I). It is effective to add a coupling agent.
カップリング剤としては、Ｃ残、、−ＣＨ−８ｉ （Ｏ
Ｃル）、。As a coupling agent, C residue, -CH-8i (O
C Le),.
ＣＨ，＝ ＣＨＳ ｉ （ＯＣ−Ｈｅ ） ＊ −Ｃ八
−ＣＨ−ＣＨｌｏ Ｃ−ｋｌａ ８ ｔ （ＯＣＨｓ
） ＠ −＼ １
が挙げられ、このうちガラス基板と９接着効果を上げる
ためにはアミノシランカップリング剤が特に好ましい。CH,=CHS i (OC-He) * -C8-CH-CHlo C-kla8t (OCHs
) ＠ -＼ 1 Among these, aminosilane coupling agents are particularly preferred in order to improve the adhesion effect with glass substrates.
カップリング剤の添加量は、その種類によって異なるが
、液の安定−性まで考直に入れると、例えばにＮ−（Ｃ
几）ｓ Ｓ ｉ（ＯＣ−）（ｓ ）−の場合、ポリアミ
ド酸（Ｉ）に対して５〜１０ｗｔ％、本発明に用いる反
応溶媒としてはＮ、Ｎ−ジメチルホルムアミド、Ｎ、Ｎ
−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン
、Ｎ−エチル−２−ピロリドン、Ｎ−シクロヘキシル−
２−ピロリドン、Ｎ−ベンジル−２−ピロリドン、Ｎτ
アセチル−ε−カプロラクタム等である。これらは、単
独もしくは
本発明の反応縮合溶液を透明電極の形成されたガラス基
板上に塗布する方法としては、浸漬法１回転塗布法、ス
プレー法、印刷法等があり。The amount of coupling agent added varies depending on the type of coupling agent, but when considering the stability of the liquid, for example, N-(C
几)s In the case of Si(OC-)(s)-, 5 to 10 wt% based on polyamic acid (I), and the reaction solvent used in the present invention is N,N-dimethylformamide, N,N
-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-
2-pyrrolidone, N-benzyl-2-pyrrolidone, Nτ
Acetyl-ε-caprolactam and the like. Methods for applying these alone or the reaction condensation solution of the present invention onto a glass substrate on which a transparent electrode is formed include a dipping method, a one-turn coating method, a spray method, and a printing method.
塗布後１５０〜３５０℃で加熱し分子内閉環させてから
ラビング処理をする。ラビング方法は、ガーゼ１．。After coating, it is heated at 150 to 350°C to cause intramolecular ring closure, and then rubbed. The rubbing method is 1. with gauze. .
パフ研磨が一般に使用できる。Puff polishing can generally be used.
本発明の配向膜と組合わせて使用できる液晶は、シック
塩基型液晶、フェニルシクロヘキサン型液晶、アゾキシ
型液晶、アゾ型液晶、ビフェニル型液晶、エステル型液
晶、フェニルピリジジン型液晶等のネマティック液晶に
旋光性物質コレステロール化合物、光学活性な置換基を
有するビフェニル誘導体、フェニルベンゾエート等の光
学活性化合物を添加したコレステリック型液晶などが挙
げられる。Liquid crystals that can be used in combination with the alignment film of the present invention include nematic liquid crystals such as thick base type liquid crystals, phenylcyclohexane type liquid crystals, azoxy type liquid crystals, azo type liquid crystals, biphenyl type liquid crystals, ester type liquid crystals, and phenylpyridine type liquid crystals. Examples include cholesteric liquid crystals to which optically active compounds such as optically active substance cholesterol compounds, biphenyl derivatives having optically active substituents, and phenylbenzoate are added.
また本発明の配向膜と組合わせて使用できる封着剤は、
エポキシ系樹脂等の有機物である。Furthermore, the sealing agent that can be used in combination with the alignment film of the present invention is as follows:
It is an organic substance such as epoxy resin.
本発明の配向膜と組合せて使用する基板は、ガラス製ま
たはガラス表面に８ｉ０．コーティングをほどこしたも
のである。The substrate used in combination with the alignment film of the present invention is made of glass or has a glass surface of 8i0. It is coated.
実施例ｔ
モル（４１３モル％）、
ル（５，０モル−）を、１７８ｔのＮ−メチル−２−ピ
ロリドンに四クロフラスコ中でかくはんし溶解させた。Example t mol (413 mol %), mol (5.0 mol) were dissolved in 178 t of N-methyl-2-pyrrolidone with stirring in a four-neck flask.
次に氷で０〜５℃に保ちながら６時間かくはんを続けた
。その後５０〜６０℃で２時間さらにかくはんし、Ｎメ
チル２ピロリドンで固形分を６０ｗｔ％に希釈したとこ
ろ約５５０ｍｐａｓ（２５℃）の粘度の淡黄色のフェス
が得られた。Next, stirring was continued for 6 hours while maintaining the temperature at 0 to 5°C with ice. Thereafter, the mixture was further stirred at 50 to 60°C for 2 hours, and the solid content was diluted to 60 wt % with N-methyl 2-pyrrolidone to obtain a pale yellow festival with a viscosity of about 550 mpas (25°C).
これに、日本ユニカ製シランカップリング剤Ａ−１１０
０を固形分に対して７．０ｗｔ％加え、これを第１図に
示す透明電極１．８ｉ０．コート付のガラス基板２上に
印刷し、２５０℃で０．５時間加熱して溶媒を除去し、
閉環させ、６ｏｏＸ、 ｉ ｏｏｏＸ、 １４ｏｏＸの
膜厚で配向膜５を形成した。これを、パフ布によって一
方向にラビングし、この配向膜面を平行に対向させ、液
晶注入口を除いてエポキシ系樹脂で封着し、１８０℃で
２ｈｒ加熱し、封着部４を形成した（上下基板間のギャ
ップを１０μｍｌ（なるようにスペーサを入れている）
。その後、液晶５を封入した。封入した液晶はアゾキシ
型混合物ステル系混合物（Ｃ４Ｈ＠吾Ｃｏｏ＠−ＣＮ
＋ ｃ、）ｌ、、Ｆ （ｙｃｏｏ−ＱｃＮ＋ｃ、Ｈ，、
−Ｑ−ｃｏｏ−ＱｃＮ） 、 ヒ−ｙ ｚ ＝ ｓ。To this, silane coupling agent A-110 manufactured by Nippon Unica
0 was added to the solid content in an amount of 7.0 wt%, and this was added to the transparent electrode 1.8i0.0 shown in FIG. Printed on a coated glass substrate 2, heated at 250°C for 0.5 hours to remove the solvent,
The rings were closed to form alignment films 5 with film thicknesses of 6ooX, iooooX, and 14ooX. This was rubbed in one direction with a puff cloth, the alignment film surfaces were placed parallel to each other, and sealed with epoxy resin except for the liquid crystal injection port, and heated at 180° C. for 2 hours to form a sealed portion 4. (Spacers are inserted to ensure that the gap between the upper and lower substrates is 10μml)
. After that, liquid crystal 5 was sealed. The sealed liquid crystal is an azoxy type mixture and a ster type mixture (C4H@GoCoo@-CN
+c,)l,,F (ycoo-QcN+c,H,,
-Q-coo-QcN), He-y z = s.
型液晶混合物（Ｃ，Ｈｌ、−ｏ−ｏｃＮ＋Ｃ１Ｈ１ｓ−
ｏ−ｏ−ｃＮ＋Ｃ５Ｈ−ｖｏｏｏ−ｃＮ ） 、シ／
ａ ヘ＃ サｙ ７ ｚ ＝ ルＩＩ ＆容物＜ Ｃｓ
ｈ？Ｎ ＋ ＣＩＨ１１４にンＮ ＋ Ｃ，ｒＨ，バ）
（ンＣＮ） 、シッフ 塩基ｍ−ａ合物（Ｃ４Ｈｅ−Ｇ
−ＣＨ＝Ｎ＋ｏｃに＋ ｃ、５ｏ−ｏ−ｃＨ＝Ｎ−＠ａ
Ｎ＋ ｃ、Ｈ，、ｃｏｏ＠−ｃＨ＝Ｎ−ｏｃＮ）の５種
類である。封入口の封止は、ＮｌＣｒＡｕ蒸着後半田で
行なった。更に、配向膜のラビング方向に合わせて偏光
板６をはりつけた。type liquid crystal mixture (C, Hl, -o-ocN+C1H1s-
o-o-cN+C5H-vooo-cN), C/
a F # Sai 7 z = Le II & container < Cs
h? N + CIH114 N + C, rH, B)
(CN), Schiff base m-a compound (C4He-G
-CH=N+oc+c, 5o-o-cH=N-@a
There are five types: N+c, H, coo@-cH=N-ocN). The sealing port was sealed with NlCrAu vapor-deposited solder. Furthermore, a polarizing plate 6 was attached in accordance with the rubbing direction of the alignment film.
配向性は極めて良好であり、しかも配向膜厚６００〜１
４００Ｘの範囲内では透明電極の反射は完全に防止され
ていた。The orientation is extremely good, and the orientation film thickness is 600~1
Reflection from the transparent electrode was completely prevented within the range of 400X.
膜の着色については、各配向膜厚について波長４ＱＯｎ
ｍと６００ｎｍでの透過率の比で評価した。Regarding the coloring of the film, the wavelength 4QOn is used for each orientation film thickness.
Evaluation was made based on the ratio of transmittance at 600 nm and m.
Ｔ１４００ｎｍ／Ｔ６ｏｏｎｍ＜α８５では目視で着色
がわかる。本実施例では、第２図の７に示すように配向
膜厚６００〜１４００Ａの範囲内でＴ４００ｎｍ／Ｔｓ
ＯＯｎｆｆｌ＞α８５であり、実用上無色であった。ま
た、表には膜厚１ｏｏｏＸでのＴ Ａ ００ ｎ ｍ／
Ｔ ６００ ｎｍ値を示した。When T1400nm/T6oonm<α85, coloring can be seen visually. In this example, as shown in 7 in FIG.
OOnffl>α85, and it was practically colorless. The table also shows T A 00 nm/at a film thickness of 1oooX.
The T 600 nm value was shown.
印刷液の放置安定性は一２０℃で６０日後粘度変化はな
く、−５℃で６０日後粘度低下は２５弧である。Regarding the storage stability of the printing liquid, there is no change in viscosity after 60 days at -20°C, and the viscosity decreases by 25 arcs after 60 days at -5°C.
液のゲル化、析出物等はない。There is no gelation of the liquid, no precipitates, etc.
耐ラビング性については、表に示すように実用上十分マ
ージンがあり、けずりくずかのこったり、膜が傷ついた
りすることはなかった。Regarding the rubbing resistance, as shown in the table, there was a sufficient margin for practical use, and there were no shavings or scratches on the film.
信頼性試験は、まず７０℃９５％ＲＨ１０００時間後の
素子の点灯状態を見たが、表に示すように全数不良はな
かった。また、表に示すように、４０℃直流１０Ｖで５
００時間後も不良はなかった。In the reliability test, we first looked at the lighting state of the device after 1000 hours at 70° C., 95% RH, and as shown in the table, there were no defects in all of the devices. In addition, as shown in the table, at 40℃ DC 10V
There were no defects even after 00 hours.
実施例２゜
Ｎ−メチル−２−ピロリドン中で実施１と同様の方法で
ボリナ２ド酸を合成した。このときの粘度は、６ｗｔ％
ＮＭＰ溶液で約８００ｍｐａ−ｓ （２５℃）であっ
た。実施例１と同様の方法で素子を作った。Example 2 Borina diacid was synthesized in the same manner as in Example 1 in N-methyl-2-pyrrolidone. The viscosity at this time is 6wt%
It was about 800 mpa-s (25°C) in NMP solution. A device was made in the same manner as in Example 1.
測定結果を表の５２と第２図の８に示した。The measurement results are shown in 52 in the table and 8 in FIG.
ジメチルホルムアミドを溶媒として１８重景襲溶液中、
０℃で６時間かくはんし、２５℃で２０００ｍｐａ−ｓ
の粘度の淡黄色ボリアεド酸を得た。In a 18-fold solution using dimethylformamide as a solvent,
Stir at 0°C for 6 hours, then at 25°C and 2000 mpa-s.
A pale yellow boria epsilon acid with a viscosity of .
・これを４重量−に希釈し、日本ユニカ製シランカップ
リング剤Ａ−１１００を固形分に対して７０ｗｔ％加え
たものを回転塗布、により基板上に塗布し、後は実施例
１と同様の方法で素子を作った。・This was diluted to 4% by weight and 70% by weight of silane coupling agent A-1100 manufactured by Nippon Unica was added to the solid content, and the mixture was coated on the substrate by spin coating, and the rest was carried out in the same manner as in Example 1. The device was made using this method.
測定結果を表のＡ３と第２図の９に示した。The measurement results are shown in A3 of the table and 9 of FIG.
六
屁
片
１′
此
上記実施例１〜１２は、液の放置安定性すべて良好、透
明電極の反射は目視で判別できない程度に良好（膜厚６
００〜１４００Ｘのもの）。Six pieces 1' In Examples 1 to 12 above, the storage stability of the liquid was all good, and the reflection of the transparent electrode was so good that it could not be visually discerned (the film thickness was 6
00-1400X).
ＣＨ。CH.
Ｈ，Ｎ（＞ｏ（）ｒｑに４８８モル％酸無水物として５
００モル％実施例１と同様の方法でＮＭＰ中で反応させ
、６ｗｔ％で８５０ｍｐｍ・５（２５℃）の粘度のポリ
アミド酸が得られた。これを用いて実施例１と同様の方
法で素子を作った。測定結果を表の／ｌ＆４と図の１０
に示した。5 as 488 mol% acid anhydride in H,N(>o()rq)
The reaction was carried out in NMP in the same manner as in Example 1 to obtain a polyamic acid having a viscosity of 850 mpm·5 (25°C) at 6 wt%. Using this, a device was made in the same manner as in Example 1. The measurement results are /l&4 in the table and 10 in the figure.
It was shown to.
を用いてポリアミド酸を合成しく ８ｗｔ５ ＮＭＰ溶
液２５℃で２５００ｍｐａ−ｓ入信越化学製シランカッ
プリング剤Ｘ−１２−５７５Ｄを固形分に対し１０ｗｔ
％添加して、実施例１と同様の方法で素子を作った。測
定結果を表のＡ５と第２図の１１に示した。Synthesize polyamic acid using 8wt5 NMP solution at 25℃ and 2500mpa-s.
%, and a device was fabricated in the same manner as in Example 1. The measurement results are shown in A5 of the table and 11 of FIG.
実施例＆
方法でポリアミド酸を合成した。（６ｗｔ％ＮＭＰ溶液
２５℃で約１５００ｍｐｍ・＄）これに信越化学製シラ
ンカップリング剤Ｘ−１２−５７５−Ｄを固形分に対し
て１０ｗｔ％添加し、これを用いて実施例１と同様にし
て、素子を作りだ。測定結果を表のＡ６と第２図の１２
に示した。Polyamic acid was synthesized according to Example & Method. (6 wt% NMP solution at 25°C, approximately 1500 mpm/$) To this was added 10 wt% of the solid content of Shin-Etsu Chemical's silane coupling agent Then, I made an element. The measurement results are shown in A6 of the table and 12 of Figure 2.
It was shown to.
実施例２
品）５モル−１酸無水物としてｏ＞ＱΩ〉′。カα３３
〕
５００モル％ｏ ｏ ｓｏモル％を用いてゝ
ＣＯ
実施例１と同様の方法でポリアミド酸を合成しく ６ｗ
ｔ５ ＮＭＰ溶液２５℃で約１０００ｍｐ１００Ｏ、こ
れに日本ユニカ製シランカップリング剤Ａ−１８７を固
形分に対し８ｗｔ％添加し、これを用いて素子を作った
。測定結果を表のＡ７と第２図の１３に示した。Example 2 Product) o>QΩ〉′ as 5 mol-1 acid anhydride. Kaα33
] Polyamic acid was synthesized in the same manner as in Example 1 using 500 mol% of CO.
t5 A NMP solution of about 1000 mp100O at 25° C. was added with 8 wt % of silane coupling agent A-187 manufactured by Nippon Unica based on the solid content, and an element was made using this. The measurement results are shown in A7 of the table and 13 of FIG.
実施例８゜
モル襲、Ｈ，Ｎ逢傾心羽Ｈ，４７，５モル％、例１と同
様の方法でポリアミド酸を合成しく６ｗｔ％ ＮＭＰ溶
液２５℃で約２０００ｍｐａ−ｓ ）これに日本ユニカ
製シランカップリング剤Ａ−１８９を固形分に対し８ｗ
ｔ％添加したものを用いて、素子を作った。測定結果を
表のＡ８と第２図の１４に示した。Example 8 Polyamic acid was synthesized using the same method as in Example 1, using a 6 wt % NMP solution containing 47.5 mol % of H, N, 6 wt % NMP solution (approximately 2000 mpa-s at 25°C), and Nippon Unica Co., Ltd. 8w of silane coupling agent A-189 based on solid content
An element was made using the material to which t% was added. The measurement results are shown in A8 of the table and 14 of FIG.
実施例９
施例１と同様の方法でボリア２ド酸を合成し、シランカ
ップリング剤として、日本二二カ製Ａ−１１００を固形
分に対し７ｗｔ−添加したものを用いて、実施例１と同
様の方法で素子を作った。測定結果を表のＡ９と第２図
の１５に示した。Example 9 Boria diacid was synthesized in the same manner as in Example 1, and as a silane coupling agent, 7 wt of A-1100 manufactured by Nippon Nijika was added to the solid content. The device was made using the same method. The measurement results are shown in A9 of the table and 15 of FIG.
は以下の方法で合成した。一般式内で示される二価フェ
ノールを水酸化ナトリウムなどのアルカリで処理して、
一般式■で示される二価フェノールのアルカリ金属塩を
形成する。これに、（０式のＰ−ニトロクロロベンゼン
を作用させて、一般式ので示されるジニトロ化合物を合
成する。was synthesized by the following method. By treating the dihydric phenol shown in the general formula with an alkali such as sodium hydroxide,
Forms an alkali metal salt of a dihydric phenol represented by the general formula (2). This is treated with P-nitrochlorobenzene of the formula (0) to synthesize a dinitro compound represented by the general formula.
次に０式で示されるジニトロ化合物を、鉄−塩酸、パラ
ジウム、ラネーニッケルなどを触媒とした水素添加反応
により還元して、０式で示されるエーテル結合を有する
芳香族シア２ンを製造する。Next, the dinitro compound represented by the formula 0 is reduced by a hydrogenation reaction using iron-hydrochloric acid, palladium, Raney nickel, or the like as a catalyst to produce an aromatic cyanide having an ether bond represented by the formula 0.
ＣＡ） （ａ（Ｑ
（Ｉ）［Ｆ］
実施例１０゜
１と同様の方法で素子を作った。測定結果を表のＡ１０
と第２図の１６に示した。CA) (a(Q
(I) [F] A device was made in the same manner as in Example 10.1. The measurement results are shown in A10 of the table.
16 in Figure 2.
ａｏモｈ％、Ｈ，灰引又殆０．−０−ＯｅＮＨ，２０％
Ａ／ ＜、１と同様の方法で素子を作った。測定結果
を表のＡ１１と第２図の１７に示した。aomoh%, H, Ashikimata almost 0. -0-OeNH, 20%
A/<, an element was made in the same manner as in 1. The measurement results are shown in A11 of the table and 17 of FIG.
を用いて実施例１と同様の方法で素子を作った。A device was made in the same manner as in Example 1 using the following.
測定結果を表の４１２と第２図の１８に示した。The measurement results are shown in 412 in the table and 18 in FIG.
比較例１
実施例１と同様の方法で素子を作りた。測定結果は表の
比較例１に示したように、封着剤付近の配向規制力が弱
かった。Comparative Example 1 A device was made in the same manner as in Example 1. As shown in Comparative Example 1 in the table, the measurement results showed that the orientation regulating force near the sealant was weak.
比較例２゜
の方法で素子を作った。測定結果は表の比較例２と第２
図の１９に示したように、１４００Ｘの膜厚のもので透
過率比”ｏａ”ｍ／ｒ、ｓｏｏｎｍ ＝ ｏ、ｓ１トｔ
ｘ リ、。A device was made by the method of Comparative Example 2. The measurement results are shown in Comparative Example 2 and Comparative Example 2 in the table.
As shown in Figure 19, with a film thickness of 1400X, the transmittance ratio "oa" m/r, soonm = o, s1 to t
x Ri,.
素子の着色がやや目立った。The coloring of the element was somewhat noticeable.
比較例＆
モル弧、Ｈ，Ｎ＠−ｏ＠−ｓ３ ｓｏモル％、酸無水
物合成し、シランカップリング剤を加えないで素子を作
った。測定結果は表の比較例乙に示したように、１℃９
５％ＲＨ中、１００時間後で点灯時に不良が発生した。Comparative Example & Molar arc, H, N@-o@-s3 so mol %, acid anhydride was synthesized, and a device was made without adding a silane coupling agent. The measurement results are as shown in Comparative Example B of the table at 1℃9.
A defect occurred during lighting at 5% RH after 100 hours.
比較例４゜
比較例３と同じボリア２ド酸を合成し、日本ユニカ製シ
ランカップリング剤Ａ−１１００ポリマに対し５．０ｗ
ｔ％添加したものを用いて素子を作った。Comparative Example 4゜The same boria dihydric acid as in Comparative Example 3 was synthesized, and 5.0w was applied to the silane coupling agent A-1100 polymer made by Nippon Unica.
An element was made using the material to which t% was added.
測定結果は表の比較例４に示したよ５に、７０℃９５％
ＲＨ中２５０ｈで一部点灯時に不良が発生した。The measurement results are shown in Comparative Example 4 in the table.
A defect occurred when some lights were turned on after 250 hours during RH.
以上述べたように、本発明によれば、液晶表示素子の配
向膜は配向性にすぐれ、着色しにく＜ （１ｏｏｏＸ膜
厚でＴ４００ｎｍ／Ｔ６ｏｏｎｍ＞ｏ、８５）、基板と
の接着性にすぐれ、耐湿信頼性の高いものとなる。（７
０℃９５％ＲＨで１０００ｈｒ以上良好）。As described above, according to the present invention, the alignment film of a liquid crystal display element has excellent alignment, is resistant to coloring (T400 nm/T6 oonm in 1 oooX film thickness, 85), and has excellent adhesion to the substrate. , it has high moisture resistance and reliability. (7
Good for 1000 hours or more at 0°C and 95%RH).
更に、透明電極の反射もなく、絶縁性も非常ニＪ： ＜
（４０’ｅＤｃ１０ｖで５ｏＯｈｒ以上良好）、ラビ
ング作業に対するマージンも十分である。Furthermore, there is no reflection from the transparent electrode, and the insulation is very good.
(5oOhr or better at 40'eDc10v), and the margin for rubbing work is also sufficient.
第１図は液晶表示素子の断面図（液晶封入口は省略）、
第２図は、各配向膜の膜厚と、透過率比Ｔ４００ｎｒｎ
／Ｔ６ｏｏｎｍ（Ｔ４００ｎｒｎ／Ｔ６ｏｏｎｍ〉α８
５であれば実用上無色）との関係を示す図である。
５・・・・・・・・・配向膜
代理人弁理士 薄 １）利 幸
６で定−Figure 1 is a cross-sectional view of a liquid crystal display element (liquid crystal filling port is omitted).
Figure 2 shows the film thickness of each alignment film and the transmittance ratio T400nrn.
/T6oonm (T400nrn/T6oonm>α8
If it is 5, it is practically colorless). 5・・・・・・・・・Alignment film agent Patent attorney Usui 1) Toshiyuki Determined by 6-
Claims (1)
晶層を有する液晶表示素子において前記基板間の対向面
上の配向膜材として、で示されるシア電ン化合物（但し
、式中のら選ばれた一種類の基であり、＾〜鳥は水素原
子もしくは低級アルキル基である）のうちから遺はれた
少なくとも一種類の化合場 場 れるシロキサンシア電ン化合物（但し、式中の島は２価
の炭化水素基であり、馬は１価の炭化水素基である）の
うちから選ばれた少なくとも一種類の化合吻２〜２０モ
ル襲−般式Ｈ，Ｎ −Ｑ−Ｒ，−Ｑ−ＮＨ，テ示すレル
芳香族ジアンン化合物（但し、式中の−は−ｏ−、−Ｃ
Ｈ，−、−ＣＯ−、→（紳−１−ｏ−ｏ−ｏ−ｏ−ｏの
うちから選はれた一種類の基である）のうちから選ばれ
た少なくとも一種類の化合物５０〜０モル襲からなりか
つジアミン成分が１００モル襲となるよう混合されたも
のと、９ 、ｃｏ、 、ｃｏ、 一般式ＯＢ、 ０で示される酸無 ＼ＣＯ〆 ＼ＣＯ／ 水物（但し、式中の鳥は：ＣＸ、Ｘχｏにｘズ−℃Ｌ為
。４のうちから選はれた一種類の基ら選ばれた一種類の
基である）のうちから選ばれた一種類の化合物とを等モ
ル反応させて得られたボリアイド酸（イ目し、ポリアミ
ド酸の重合度（ｎ）は、ジメチルスルホキシドを溶媒と
して３０℃で測定した時の還元粘度が０．１〜ｔ Ｏｄ
Ｌ／ｌの範囲にある）と、（ロ） シランカップリング
剤がエポキシ基を有するアルコキシシラン、ビニル基を
有するアルコキシシラン、モルフォリノ基ヲ有スるアル
コキシシラン、メルカプト基を有スるアルコキシシラン
、脂肪族アミノシランのうちから選ばれた少なくとも一
種類の化合物の場合は、上記（イ）項のポリアミド酸９
０〜９７ｗｔ％に対して１０〜５ｗｔ％、シランカップ
リング剤が芳香族アミノシランの場合は、上記（イ）項
のポリアミド酸８０〜９５ｗｔ％に対して２０〜５ｗｔ
襲配合されており、 （ハ）少なくとも上記（イ）項のポリアミド酸を溶解せ
しめる溶媒が塗布に適する粘度とするに必要な量配合さ
れているポリアミド酸組成物を、 加熱して得られたものであることを４！徴とすであり、 るシロキサンジアミン化合物中の鳥が−（ＣＨ，）−で
あり、＆がｍ−であ゛す、 一般式ＨｓＮＱ＆＜＞ＮＨ＊ テ示すｈル芳香′族ジア
ミン化合物中の鳥が一〇−であり、を特徴とする特許請
求の範囲第１項記載の液晶表示素子。[Claims] t In a liquid crystal display element having a liquid crystal layer sandwiched between a pair of substrates on which transparent electrodes are formed, a cyanide compound ( However, at least one type of compound remaining from among the groups in the formula (where ``(a)'' is one type of group selected from the group ^~ is a hydrogen atom or a lower alkyl group) is a siloxane siane compound ( However, 2 to 20 moles of at least one compound selected from the group consisting of 2 to 20 moles of at least one compound selected from the group consisting of 2 to 20 mols of the general formula H,N-Q; -R, -Q-NH, is an aromatic diane compound (in the formula, - is -o-, -C
At least one type of compound selected from H, -, -CO-, → (one type of group selected from Gen-1-o-o-o-o-o) 50~ 0 moles and a diamine component mixed so as to have 100 moles, 9, co, , co, acid-free \CO〆 \CO / hydrate represented by the general formula OB, 0 (however, the formula The bird inside is: CX, The degree of polymerization (n) of polyamic acid obtained by reacting equimolar amounts of polyamic acid is 0.1 to t Od
(L/l) and (b) the silane coupling agent is an alkoxysilane having an epoxy group, an alkoxysilane having a vinyl group, an alkoxysilane having a morpholino group, an alkoxysilane having a mercapto group, In the case of at least one compound selected from aliphatic aminosilanes, polyamic acid 9 of item (a) above
10 to 5 wt% relative to 0 to 97 wt%, and when the silane coupling agent is an aromatic aminosilane, 20 to 5 wt% relative to 80 to 95 wt% of the polyamic acid in item (a) above.
(c) A polyamic acid composition obtained by heating a polyamic acid composition containing at least the solvent for dissolving the polyamic acid described in item (a) above in an amount necessary to achieve a viscosity suitable for coating. 4 to be! In the siloxane diamine compound, the symbol is -(CH,)-, and & is m-, and the general formula HsNQ&<>NH* indicates that in the aromatic diamine compound, The liquid crystal display element according to claim 1, wherein the bird is 10-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56171418A JPS5872924A (en) | 1981-10-28 | 1981-10-28 | Liquid crystal display element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56171418A JPS5872924A (en) | 1981-10-28 | 1981-10-28 | Liquid crystal display element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5872924A true JPS5872924A (en) | 1983-05-02 |
Family
ID=15922762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56171418A Pending JPS5872924A (en) | 1981-10-28 | 1981-10-28 | Liquid crystal display element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5872924A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62129935A (en) * | 1985-11-29 | 1987-06-12 | Hitachi Chem Co Ltd | Binder curable by radiation for magnetic recording medium |
| JPS63130633A (en) * | 1986-11-20 | 1988-06-02 | Kanegafuchi Chem Ind Co Ltd | Novel polyamic acid and production of polyimide |
| JPH03195730A (en) * | 1989-12-25 | 1991-08-27 | Hitachi Chem Co Ltd | Siloxane modified polyimide and precursor thereof |
| US5194579A (en) * | 1983-04-11 | 1993-03-16 | Hitachi, Ltd. | Fluorine-containing polyamide acid and polyamide |
| US5332603A (en) * | 1992-03-31 | 1994-07-26 | Hoechst Aktiengesellschaft | Liquid crystal display device |
| US5721299A (en) * | 1989-05-26 | 1998-02-24 | International Business Machines Corporation | Electrically conductive and abrasion/scratch resistant polymeric materials, method of fabrication thereof and uses thereof |
| US7906214B2 (en) | 2007-01-26 | 2011-03-15 | Transitions Optical, Inc. | Optical elements comprising compatiblizing coatings and methods of making the same |
| WO2018051956A1 (en) * | 2016-09-13 | 2018-03-22 | 日産化学工業株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| WO2019106952A1 (en) * | 2017-11-30 | 2019-06-06 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal device |
-
1981
- 1981-10-28 JP JP56171418A patent/JPS5872924A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194579A (en) * | 1983-04-11 | 1993-03-16 | Hitachi, Ltd. | Fluorine-containing polyamide acid and polyamide |
| JPS62129935A (en) * | 1985-11-29 | 1987-06-12 | Hitachi Chem Co Ltd | Binder curable by radiation for magnetic recording medium |
| JPS63130633A (en) * | 1986-11-20 | 1988-06-02 | Kanegafuchi Chem Ind Co Ltd | Novel polyamic acid and production of polyimide |
| US5721299A (en) * | 1989-05-26 | 1998-02-24 | International Business Machines Corporation | Electrically conductive and abrasion/scratch resistant polymeric materials, method of fabrication thereof and uses thereof |
| JPH03195730A (en) * | 1989-12-25 | 1991-08-27 | Hitachi Chem Co Ltd | Siloxane modified polyimide and precursor thereof |
| US5332603A (en) * | 1992-03-31 | 1994-07-26 | Hoechst Aktiengesellschaft | Liquid crystal display device |
| US7906214B2 (en) | 2007-01-26 | 2011-03-15 | Transitions Optical, Inc. | Optical elements comprising compatiblizing coatings and methods of making the same |
| WO2018051956A1 (en) * | 2016-09-13 | 2018-03-22 | 日産化学工業株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| KR20190052052A (en) * | 2016-09-13 | 2019-05-15 | 닛산 가가쿠 가부시키가이샤 | A liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element |
| JPWO2018051956A1 (en) * | 2016-09-13 | 2019-06-27 | 日産化学株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display device |
| WO2019106952A1 (en) * | 2017-11-30 | 2019-06-06 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal device |
| CN111164501A (en) * | 2017-11-30 | 2020-05-15 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal element |
| JPWO2019106952A1 (en) * | 2017-11-30 | 2020-07-30 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal element |
| CN111164501B (en) * | 2017-11-30 | 2022-10-04 | Jsr株式会社 | Liquid crystal aligning agent, method for producing liquid crystal element, liquid crystal alignment film, and liquid crystal element |
| TWI786195B (en) * | 2017-11-30 | 2022-12-11 | 日商Ｊｓｒ股份有限公司 | Liquid crystal alignment agent, method for manufacturing liquid crystal element, liquid crystal alignment film, and liquid crystal element |
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