JPS61117524A

JPS61117524A - Liquid crystal display element

Info

Publication number: JPS61117524A
Application number: JP23904084A
Authority: JP
Inventors: Eisuke Tomita; 富田　英介
Original assignee: Seiko Instruments Inc
Current assignee: Seiko Instruments Inc
Priority date: 1984-11-13
Filing date: 1984-11-13
Publication date: 1986-06-04

Abstract

PURPOSE:To obtain the titled element having good heat-resistance and reproducibility properties for a vertical orientation and an extended life time by forming an undercoating film contg. an organometal compd. on an electrode substrate, a vertically oriented film contg. an org. silane compd. thereon and a liquid crystal layer thereon in regular order. CONSTITUTION:The titled element is prepared by forming the undercoating films 5, 6 contg. the org. metal compd. on a surface contacting with the liquid crystal 11 which is interposed between two electrode substrates 1, 2 and by forming the vertically oriented film 7, 8 contg. the organosilane compd. on the films 5, 6. The org. metal compd. comprises for example, compds. shown by formula I or II wherein R<1> is 1-10 C an alkyl group, (n) is 0-40, Me is Ti, Zr, and Si. The organosilane compd. comprises the compds. shown by formula III or IV wherein R<2> is 10-30 C a straight chain alkyl group, R<3> is 1-4 C an alkyl group, R<4> is 1-4 C an alkyl or an aryl group. By applying the orgnometal compd. to the undercoating films 5, 6, the adhesive property of the films 5, 6 against the substrates 1, 2 is improved whereby the titled element is improved in he heat - resistance and the life time, and the vertical orientation of the orgnosilane compd. is stabilized.

Description

【発明の詳細な説明】〔産業上の利用分野〕この発明は、液晶表示素子に関するもので、特に、液晶
分、子を電極基板面に垂直屹配向させて用いる液晶表示
素子に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a liquid crystal display element, and more particularly to a liquid crystal display element in which liquid crystal molecules are aligned perpendicularly to the surface of an electrode substrate.

[Conventional technology]

従来、液晶分子を垂直に配向させる方式としては、第２
図に示すような垂直配向膜７として、（１）レシチンあ
るいは界面活性剤等を基板に塗布するか、あるいは液晶
材料に混合する方法、（２）有機クロム錯体等を基板に
塗布する方法、（８）フッ化カルシウム蒸着膜や酸化セ
リウム蒸着膜を用いる方法。Conventionally, the second method of vertically aligning liquid crystal molecules is
The vertical alignment film 7 as shown in the figure can be formed by (1) coating lecithin or a surfactant on the substrate or mixing it with the liquid crystal material, (2) coating the substrate with an organic chromium complex, etc. 8) A method using a calcium fluoride vapor-deposited film or a cerium oxide vapor-deposited film.

（４）シランカップリング剤を基板に塗布する方法、（
５）シランカップリング剤にテトラアルコキシシランを
添加する方法、が知られている。(4) Method of applying a silane coupling agent to a substrate, (
5) A method of adding tetraalkoxysilane to a silane coupling agent is known.

[Problem that the invention seeks to solve]

しかし従来の垂直配向方式は、次のような欠点があった
。However, the conventional vertical alignment method has the following drawbacks.

（１）の方式では、耐熱性および素子の寿命の面で問題
があった。The method (1) had problems in terms of heat resistance and element life.

（２）の方式では、公害面の問題が残されている。With method (2), there are still problems with pollution.

（８）の方式では、量産性の悪さに問題がある。The method (8) has a problem of poor mass productivity.

（４）の方式では、垂直配向性の再現性が悪い。In the method (4), the reproducibility of vertical alignment is poor.

（ωΦ方式は、（４）の問題の解決策として提示された
ものであるが、この方式を用いても再現性は良好ではな
い。(The ωΦ method was proposed as a solution to problem (4), but even if this method is used, the reproducibility is not good.

[Failure to solve the problem]

上記問題点を解決するためこの発明は、液晶層を挾む２
枚の電極基板のうち少なくとも一方の電極基板の液晶と
接する面に、有機金属化合物からなる下地膜と、その上
にオをガノシラン化合物からなる垂直配向膜を形成して
、垂直配向の再現性を高めた。本発明に用いる有機金属
化合物としては、例えば、一般式（１）または（２）で
示される構造のようなものである。In order to solve the above problems, the present invention provides two
A base film made of an organometallic compound is formed on the surface of at least one of the electrode substrates in contact with the liquid crystal, and a vertical alignment film made of a ganosilane compound is formed on the base film to improve the reproducibility of vertical alignment. I raised it. Examples of the organometallic compound used in the present invention include those having a structure represented by general formula (1) or (2).

Ｍ　、　−（ＯＲ＋）、　　　・・・α）・　拳　・　
（２）（ここに、Ｒ＋は炭素原子数が１〜１０のアルキル基、
？ｌは０〜４０の正の整数、Ｍ、はＴｊ、Ｚ。M, -(OR+), ...α)・Fist・
(2) (Here, R+ is an alkyl group having 1 to 10 carbon atoms,
? l is a positive integer from 0 to 40, M is Tj, Z.

、Ｓｚ、Ｇ６．Ｓｆｉのうちから選ばれた少なくとも１
種類の金属原子）また、本発明におけるオルガノシラン化合物は、例えば
、一般式（８）または（４）に示すような構造のもので
ある。, Sz, G6. At least one selected from Sfi
Furthermore, the organosilane compound in the present invention has a structure as shown in general formula (8) or (4), for example.

Ｒ１，Ｓ　ｚ−（ＯＲ”）　３　　　・・・（８）（こ
とｌこ、Ｒ１は炭素原子数がｌＯ〜３０の直鎖のアルキ
ル基％Ｒ”Ｆｉ戻紫原子数が１〜４のアルキル基、Ｒ４
は炭素原子数が１〜４のアルキル基またはアリール基）上記の有機金属化合物からなる下地膜と、オルガノシラ
ン化合物からなる垂直配向膜の形成方法については、従
来から用いられているスピンナー塗布法、ハケ塗り法、
浸漬法、オフセット印刷法、凸版印刷法、スプレー塗布
法などによって行なう。R1, S z-(OR") 3 ... (8) (R1 is a straight-chain alkyl group having 10 to 30 carbon atoms. R"Fi is a straight-chain alkyl group having 1 to 4 carbon atoms. group, R4
is an alkyl group or an aryl group having 1 to 4 carbon atoms) The method for forming the base film made of the above-mentioned organometallic compound and the vertical alignment film made of the organosilane compound includes the conventionally used spinner coating method, brush painting method,
This is done by dipping, offset printing, letterpress printing, spray coating, etc.

[Effect]

有機金属化合物を下地膜として用いることにより、基板
との接着性を高め、耐熱性向上と、素子寿命が長くなる
。′ｔた、有機金属化合物の下地膜は、オルガノシラン
化合物の垂直配向性の安定性向上に効果があり、本発明
の垂直配向膜は、再現性が良好な垂直配向性をもつ、。By using an organometallic compound as a base film, adhesion to the substrate is improved, heat resistance is improved, and device life is extended. Furthermore, the base film of an organometallic compound is effective in improving the stability of the vertical alignment of the organosilane compound, and the vertical alignment film of the present invention has vertical alignment with good reproducibility.

Ｃ実施例）以下にこの発明の実施例を図面にもとづいて説明する。Example C) Embodiments of the present invention will be described below based on the drawings.

第１図において、基板１に、透明電極８を形成する。そ
の上に、有機金属化合物溶液をシール部以外に印刷、加
熱硬化して、下地膜６を形成する。さらにその上に、オ
ルガノシラン化合物溶液をシール部以外に印刷、加熱硬
化して、垂直配向膜７を形成する。In FIG. 1, a transparent electrode 8 is formed on a substrate 1. Thereon, an organometallic compound solution is printed on areas other than the seal portion and cured by heating to form a base film 6. Furthermore, an organosilane compound solution is printed on the area other than the seal portion and cured by heating to form the vertical alignment film 7.

上記の有機金属化合物は、−例として、一般式（１）ま
たは伐）で示される構造のものを用へた。As the above-mentioned organometallic compound, one having a structure represented by the general formula (1) or (1) was used.

Ｍ　６−（ＯＲ＋）　４　　　　・　・　・（１）・　
・　・（２）（ここに、Ｒ＋は炭素原子数が１〜１０のアルキル基、
答はθ〜４０の正の整数、Ｍ、はＴｉ、Ｚｔ−、Ｒ４、
ｃｚ、、８′ｎのうちから選ばれた少なくとも１種類の
金属原子）上記の化合物（１）および（２）の−例として、特に、
チタン化合物であるテトラブトキシチタネートを用いた
。M 6-(OR+) 4 ・・・(1)・
・・(2) (Here, R+ is an alkyl group having 1 to 10 carbon atoms,
The answer is a positive integer between θ and 40, M is Ti, Zt-, R4,
At least one metal atom selected from cz, , 8'n) As an example of the above compounds (1) and (2), in particular,
Tetrabutoxytitanate, a titanium compound, was used.

また、上記のオルガノシラン化合物は、−例として、一
般式（８）または（４）で示される構造のものを用いた
。Moreover, as the above-mentioned organosilane compound, one having a structure represented by general formula (8) or (4) was used as an example.

Ｒ宜−８７−（ＯＲＪ’）３　　　・・・（８）（ここ
に　’ｆｌＮは炭素原子数がｌＯ〜加の直鎖のアルキル
基　Ｒ１は炭素原子数が１〜４のアルキル基、Ｒ’ｔｄ
炭素原子数が１〜４のアルキル基または了り−ル基）上記の化合物（１）および（２）の−例として、特に、
オクタデシルトリエトキシシランを用いた。R-87-(ORJ')3 ... (8) (here, 'flN is a straight-chain alkyl group having 10 to 4 carbon atoms, R1 is an alkyl group having 1 to 4 carbon atoms, R' td
Examples of the above compounds (1) and (2) include, in particular,
Octadecyltriethoxysilane was used.

〔Effect of the invention〕

この発明は、有機金属化合物からなる下地膜と、オルガ
ノシラン化合物からなる垂直配向膜を形成することによ
り、耐熱性良好で、再現性良好な垂直配向性をもち、寿
命の長い液晶表示素子の作成を可能にする効果があるゆThis invention creates a liquid crystal display element with good heat resistance, vertical alignment with good reproducibility, and long life by forming a base film made of an organometallic compound and a vertical alignment film made of an organosilane compound. It has the effect of enabling

[Brief explanation of the drawing]

第１図は、との発明にかかる液晶表示素子の断面図、第
２図は、従来の液晶表示素子の断面図である。１．２・・・基板８．４・・・透明電極５＃６・・・下地膜７．８・・・垂直配向膜９、川・・・シール材１１−・・・・液晶以　　　上FIG. 1 is a sectional view of a liquid crystal display element according to the invention, and FIG. 2 is a sectional view of a conventional liquid crystal display element. 1.2...Substrate 8.4...Transparent electrode 5#6...Underlying film 7.8...Vertical alignment film 9, River...Sealing material 11-...Liquid crystal and above

Claims

[Claims] 1. At least one of the two electrode substrates sandwiching the liquid crystal layer has a base film made of an organometallic compound on the surface in contact with the liquid crystal, and a vertical film made of an organosilane compound on the base film. A liquid crystal display element characterized by forming an alignment film. 2. The above organometallic compound has the following general formula (1) or (2) Me-(DR^1)_4...(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) ( Here, R^1 is an alkyl group having 1 to 10 carbon atoms, n is a positive integer of 0 to 40, and Me is Ti, Zr, Si,
At least one metal atom selected from Ge and Sn) The organosilane compound has the following general formula (3) or (4) R^2-Si-(OR^ 3)_3...(3)▲Numerical formula,
There are chemical formulas, tables, etc.▼...(4) (Here, R^2 is a linear alkyl group with 10 to 30 carbon atoms, R^3 is an alkyl group with 1 to 4 carbon atoms,
2. The liquid crystal display element according to claim 1, wherein R^4 is an alkyl group or an aryl group having 1 to 4 carbon atoms.