JPH046926B2 - - Google Patents
Info
- Publication number
- JPH046926B2 JPH046926B2 JP18917581A JP18917581A JPH046926B2 JP H046926 B2 JPH046926 B2 JP H046926B2 JP 18917581 A JP18917581 A JP 18917581A JP 18917581 A JP18917581 A JP 18917581A JP H046926 B2 JPH046926 B2 JP H046926B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- formula
- crystal display
- display element
- alignment film
- 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.)
- Expired - Lifetime
Links
- 239000004973 liquid crystal related substance Substances 0.000 claims description 36
- 229920001721 polyimide Polymers 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 8
- 239000004642 Polyimide Substances 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 8
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 210000002858 crystal cell Anatomy 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 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
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- -1 aminophenoxy Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- JRDBISOHUUQXHE-UHFFFAOYSA-N pyridine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)N=C1C(O)=O JRDBISOHUUQXHE-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
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
Landscapes
- 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)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Liquid Crystal (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
本発明は液晶表示素子に関する。
従来、液晶セル、特に電界の作用により動作す
る電気光学的効果を利用したネマチツク液晶表示
素子においては、配向膜として二酸化珪素の斜め
蒸着膜等の無機質材料が主に用いられていた。そ
の理由は、これらの無機膜は液晶と接しても液晶
に溶解しないので悪影響を与える要因を持たず、
シツフ型液晶及びビフエニル型液晶等を均一に配
向できる利点があるためである。しかし、二酸化
珪素の斜め蒸着膜は、透明性には優れているが、
ネサパターンが見えると云う欠点がある。一方、
配向膜に有機高分子材料を用いて布等で一方向に
こすつて配向処理した液晶表示素子が開発されて
いる。
しかし有機高分子材料の大部分のものは、これ
らを配向膜として用いた場合、液晶配向の均一性
が十分なものが得難く、また長期に亘る通電劣化
によつて、配向の不均一性が増加し易い欠点があ
る。
これまでの有機高分子材料の中で比較的配向性
に優れた配向膜を形成する材料としてポリイミド
を挙げることができ、例えば特開昭51−65960号
公報に記載されている４，4′−ジアミノジフエニ
ルエーテルとピロメリツト酸二無水物との縮合に
より得られるポリイミドは、配向の均一性ならび
に劣化試験による耐久性の点でかなり良好であ
る。しかし、このようなポリイミド系膜は溶剤の
除去並びに脱水閉環する際の加熱により著しく褐
色化が進むため、液晶を封入した後の液晶表示素
子が褐色味を帯び、同時に視野が暗くなり、更に
はコントラストが低下し、表示素子としての機
能、特に高品質の表示の要求を満たさないという
問題があつた。
また近年液晶層が透明な基板を介して二層以上
積層された構造の多層構造液晶セルの需要が増大
する中で、これまでのポリイミド配向膜ではその
着色が問題となつている。
本発明はこのような現状に鑑みて成されたもの
で、その目的は、溶剤の除去並びに脱水閉環の加
熱によつても着色せず透明性に優れ且つネサパタ
ーンの目立たない配向膜を有する液晶表示素子を
提供することである。
本発明は、電極が形成された基板上に液晶配向
膜を有する液晶表示素子において、該配向膜が次
式
〔但し、式中、Ｒはトリフルオロメチル基を示
し、Ar方向は芳香族テトラカルボン酸残基を示
す。〕で表されるくり返し単位を有する芳香族ポ
リイミド重合体からなることを特徴とする液晶表
示素子を提供することにある。
本発明者等は、従来のポリイミド膜の欠点であ
つた着色を低減し透明性を向上させるため、着色
の原因及びその解決方法につき種々検討を重ね
た。その結果、従来のポリイミド膜が着色する大
きな原因がポリイミドの合成に用いられる原料、
特にジアミン化合物にあることをつきとめ、着色
の少ない特殊なジアミンを用いることにより、閉
環時の加熱によつても着色が少なく、透明性に優
れ、ネサパターンが目立たず十分な液晶配向性を
有する配向膜を形成しうることを見出し本発明を
完成するに至つた。
本発明の配向膜は、透明度が高いので多層構造
の液晶表示素子用としても優れている。
本発明で用いられる芳香族ポリイミド重合体
は、式
〔但し、式中、Ｒはトリフルオロメチル基を示
す。〕で表されるジアミンと芳香族テトラカルボ
ン酸二無水物との反応によつて得られる。
前記ジアミンとしては、１，１，１，３，３，
３−ヘキサフルオロ−２，２−ビス〔４−（４−
アミノフエノキシ）フエニル〕プロパンがある。
次に芳香族テトラカルボン酸二無水物の具体例
をあげると、ピロメリツト酸二無水物、３，3′，
４，4′−ベンゾフエノンテトラカルボン酸二無水
物、３，3′，４，4′−ジフエニルテトラカルボン
酸二無水物、シクロペンタンテトラカルボン酸二
無水物、１，２，５，６−ナフタレンテトラカル
ボン酸二無水物、２，３，６，７−ナフタレンテ
トラカルボン酸二無水物、２，３，５，６−ピリ
ジンテトラカルボン酸二無水物、１，４，５，８
−ナフタレンテトラカルボン酸二無水物、３，
４，９，10−ペリレンテトラカルボン酸二無水
物、４，4′−ジスルホニルジフタル酸二無水物な
どが挙げられ、１種もしくは２種以上用いられ
る。
本発明における重合体の合成は、前記ジアミン
化合物、及びテトラカルボン酸二無水物を、通常
有機溶媒中、10℃程度の温度で数時間撹拌して縮
合させることにより行なわれる。生成した重合体
溶液を濃度５〜10重量％程度に希釈し、150〜300
℃の温度に加熱して溶媒除去並びに閉環すること
により得られる。
この反応における有機溶剤としては、Ｎ−メチ
ル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトア
ミド、Ｎ，Ｎ−ジメチルホルムアミド、ジメチル
スルホキシド、ヘキサメチルホスホルアミド等が
適している。なお配向膜の形成に当つて、上記に
より調製した重合体溶液の取扱いは特別の配慮は
不要であり、刷毛塗り、浸漬、回転塗布、印刷そ
の他慣用の手段により行なうことができる。
本発明の配向膜は、導電層を設けた基板上に直
接形成することができるが、導電層の下層または
上層に無機絶縁膜を設けたものを用いることによ
り、更に優れた液晶表示素子を得ることができ
る。これは、導電層を有するガラス基板上に直接
形成するよりも無機絶縁膜上に形成した方が、ソ
ーダガラス中のナトリウムイオン等による硬化時
の熱劣化が防止できることが実験により確認され
た。このような効果を示す無機絶縁膜としては、
SiO2，Al2O3及びTiO2の膜が適当である。
また、本発明においては、いつそう強固な配向
膜を得るために、エポキシ系及びアミノ系シラン
カツプリング剤の１種以上を併用することができ
る。シランカツプリング剤としては、例えば、γ
−アミノプロピルトリエトキシシラン及びγ−グ
リシドキシプロピルトリメトキシシラン等を挙げ
ることができる。適用に当つては、上記重合体溶
液中に滴下添加しても良く、また、シランカツプ
リング剤の膜を形成した上に更に配向膜を形成し
ても良い。
本発明の液晶表示素子に封入する液晶の一例と
しては、次のものを挙げることができる。これら
は通常二成分以上の混合物として適用される。(1)
ビフエニル型液晶として
The present invention relates to a liquid crystal display element. Conventionally, in liquid crystal cells, particularly in nematic liquid crystal display elements that operate under the action of an electric field and utilize electro-optical effects, inorganic materials such as obliquely deposited silicon dioxide films have been mainly used as alignment films. The reason is that these inorganic films do not dissolve in liquid crystals even when they come into contact with liquid crystals, so they do not have any negative effects.
This is because it has the advantage that Schiff-type liquid crystals, biphenyl-type liquid crystals, etc. can be aligned uniformly. However, although the obliquely deposited silicon dioxide film has excellent transparency,
There is a drawback that the Nesa pattern is visible. on the other hand,
A liquid crystal display element has been developed in which an organic polymer material is used as an alignment film and alignment treatment is performed by rubbing it in one direction with a cloth or the like. However, when most organic polymer materials are used as alignment films, it is difficult to obtain sufficient uniformity of liquid crystal alignment, and long-term deterioration due to electricity supply causes non-uniform alignment. There is a drawback that it is easy to increase. Among conventional organic polymer materials, polyimide can be mentioned as a material that forms an alignment film with relatively excellent alignment properties. The polyimide obtained by condensation of diaminodiphenyl ether and pyromellitic dianhydride has fairly good orientation uniformity and durability in deterioration tests. However, such a polyimide film undergoes significant browning due to solvent removal and heating during dehydration and ring closure, so the liquid crystal display element after encapsulating the liquid crystal becomes brownish, and at the same time, the field of view becomes dark, and furthermore, There was a problem in that the contrast deteriorated and the function as a display element, especially the requirement for high quality display, was not met. Furthermore, as demand for multilayer liquid crystal cells having a structure in which two or more liquid crystal layers are laminated via a transparent substrate has increased in recent years, coloring has become a problem with conventional polyimide alignment films. The present invention has been made in view of the current situation, and its purpose is to provide a liquid crystal display having an alignment film that does not become colored even when the solvent is removed or heated for dehydration and ring closure, has excellent transparency, and has an inconspicuous Nesa pattern. The purpose is to provide an element. The present invention provides a liquid crystal display element having a liquid crystal alignment film on a substrate on which electrodes are formed, wherein the alignment film has the following formula: [However, in the formula, R represents a trifluoromethyl group, and the Ar direction represents an aromatic tetracarboxylic acid residue. An object of the present invention is to provide a liquid crystal display element characterized by being made of an aromatic polyimide polymer having repeating units represented by the following formula. The inventors of the present invention have repeatedly investigated the causes of coloring and methods for solving the problem in order to reduce coloring, which was a drawback of conventional polyimide films, and improve transparency. As a result, the major cause of coloring of conventional polyimide films is the raw materials used for polyimide synthesis.
In particular, by using a special diamine that has little coloration, we have found that it has less coloration even when heated during ring-closing, has excellent transparency, and has an alignment film that has sufficient liquid crystal orientation without noticeable Nesa patterns. The present invention was completed based on the discovery that it is possible to form the following. Since the alignment film of the present invention has high transparency, it is also excellent for use in multilayer liquid crystal display elements. The aromatic polyimide polymer used in the present invention has the formula [However, in the formula, R represents a trifluoromethyl group. ] It is obtained by the reaction of the diamine represented by the following formula with an aromatic tetracarboxylic dianhydride. The diamines include 1,1,1,3,3,
3-hexafluoro-2,2-bis[4-(4-
There is aminophenoxy)phenyl]propane. Next, specific examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',
4,4'-Benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,2,5,6 -Naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8
-naphthalenetetracarboxylic dianhydride, 3,
Examples include 4,9,10-perylenetetracarboxylic dianhydride, 4,4'-disulfonyldiphthalic dianhydride, and one or more of them may be used. Synthesis of the polymer in the present invention is carried out by stirring and condensing the diamine compound and tetracarboxylic dianhydride, usually in an organic solvent, at a temperature of about 10° C. for several hours. The resulting polymer solution was diluted to a concentration of 5 to 10% by weight, and 150 to 300%
It is obtained by heating to a temperature of .degree. C. to remove the solvent and close the ring. Suitable organic solvents for this reaction include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, and the like. In forming the alignment film, no special consideration is required in handling the polymer solution prepared as described above, and it can be carried out by brush coating, dipping, spin coating, printing, or other conventional means. The alignment film of the present invention can be formed directly on a substrate provided with a conductive layer, but an even more excellent liquid crystal display element can be obtained by using one in which an inorganic insulating film is provided below or above the conductive layer. be able to. It has been confirmed through experiments that thermal deterioration caused by sodium ions in soda glass during curing can be better prevented by forming it on an inorganic insulating film rather than directly forming it on a glass substrate having a conductive layer. Inorganic insulating films that exhibit such effects include:
Films of SiO 2 , Al 2 O 3 and TiO 2 are suitable. Furthermore, in the present invention, one or more types of epoxy-based and amino-based silane coupling agents can be used in combination in order to obtain a strong alignment film. Examples of the silane coupling agent include γ
Examples include -aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane. In application, it may be added dropwise into the above polymer solution, or an alignment film may be formed on top of the silane coupling agent film. As an example of the liquid crystal sealed in the liquid crystal display element of the present invention, the following can be mentioned. These are usually applied as a mixture of two or more components. (1)
As a biphenyl type liquid crystal
【式】【formula】
【式】【formula】
【式】【formula】
【式】の混合物、 (2)エステル型液晶としては A mixture of [Formula], (2) As an ester type liquid crystal,
【式】の混合
物、(3)シクロヘキサン型液晶としては
As a mixture of [Formula], (3) cyclohexane type liquid crystal,
【式】【formula】
の混合物がある。
次に、本発明を実施例により説明する。
実施例 １
１，１，１，３，３，３−ヘキサフルオロ−
２，２−ビス〔４−（４−アミノフエノキシ）フ
エニル〕プロパン0.1モル、ピロメリツト酸二無
水物0.1モル及びＮ−メチル−２−ピロリドンを
フラスコに入れ、５℃で３時間撹拌し、25℃にお
ける粘度が10000cp、濃度12重量％の重合体溶液
を得た。これにプロピルトリエトキシシラン0.1
重量％を添加し７重量％に希釈した該溶液を、液
晶セル基板上にオフセツト印刷機を用いて印刷
し、さらに200℃、１時間加熱して溶剤除去並び
に閉環を行つて500、1000、1500Åの厚さの配向
膜を形成した。その後、綿布で一定方向にこすり
操作を行ない、該基板の２枚をスペーサを介し
て、ガラスフリツトシールを施し液晶セルを形成
した。該セルに前記の(1)ビフエニル型液晶、(2)エ
ステル型液晶、(3)シクロヘキサン型液晶をそれぞ
れ別個に注入した後、各注入口をエポキシ樹脂で
封止し、液晶表示素子を作製してその透明性並び
にネサパターン有無を調べた。
いずれも非常に透明性に優れ、かつネサパター
ンの目立たない高品質の素子を得ることができ
た。なお、前記素子の配向膜の厚さが1000Åのも
のについて、波長400nｍと500nｍの光透過率を
測定した結果、前者が86％、後者が92％であり、
両透過率の比は0.93であり、ほとんど無色の液晶
表示素子が得られた。
実施例 ２
１，１，１，３，３，３−ヘキサフルオロ−
２，２−ビス〔４−（４−アミノフエノキシ）フ
エニル）プロパン0.1モル、ピロメリツト酸二無
水物0.05モル、３，3′，４，4′−ベンゾフエノン
テトラカルボン酸二無水物0.05モル及びＮ，Ｎ−
ジメチルアセトアミドをフラスコ容器に入れ、10
℃で５時間反応させて、25℃における粘度
12500cp、濃度14重量％の重合体溶液を得た。こ
の溶液を５重量％に希釈し、予めSiO2の無機絶
縁膜を1200Åの厚さに形成し、更にIn2O3を主成
分とする透明電極を形成した基板上に、この重合
体溶液を用いてオフセツト印刷機で500、1000、
1500Åの配向膜を形成した。いずれも非常に透明
性に優れ、且つネサパターンの目立たない高品質
の素子を得ることができた。なお、実施例１と同
様に測定した波長400nｍと500nｍの光透過率の
比は、0.90であり、ほとんど無色の液晶表示素子
が得られた。 There is a mixture of Next, the present invention will be explained by examples. Example 1 1,1,1,3,3,3-hexafluoro-
0.1 mol of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 0.1 mol of pyromellitic dianhydride, and N-methyl-2-pyrrolidone were placed in a flask, stirred at 5°C for 3 hours, and then stirred at 25°C. A polymer solution with a viscosity of 10,000 cp and a concentration of 12% by weight was obtained. Add this to propyltriethoxysilane 0.1
The solution diluted to 7% by weight was printed on a liquid crystal cell substrate using an offset printer, and further heated at 200°C for 1 hour to remove the solvent and close the ring. An alignment film with a thickness of . Thereafter, a rubbing operation was performed in a certain direction with a cotton cloth, and a glass frit seal was applied to the two substrates via a spacer to form a liquid crystal cell. After separately injecting the above-mentioned (1) biphenyl type liquid crystal, (2) ester type liquid crystal, and (3) cyclohexane type liquid crystal into the cell, each injection port was sealed with epoxy resin to produce a liquid crystal display element. The transparency and presence or absence of the Nesa pattern were investigated. In both cases, high-quality elements with very excellent transparency and inconspicuous Nesa patterns could be obtained. In addition, as a result of measuring the light transmittance at wavelengths of 400 nm and 500 nm for the element with an alignment film thickness of 1000 Å, the former was 86% and the latter was 92%,
The ratio of both transmittances was 0.93, and an almost colorless liquid crystal display element was obtained. Example 2 1,1,1,3,3,3-hexafluoro-
2,2-bis[4-(4-aminophenoxy)phenyl)propane 0.1 mol, pyromellitic dianhydride 0.05 mol, 3,3',4,4'-benzophenonetetracarboxylic dianhydride 0.05 mol and N ,N-
Pour dimethylacetamide into a flask container and add 10
Viscosity at 25℃ after 5 hours reaction at ℃
A polymer solution of 12,500 cp and a concentration of 14% by weight was obtained. This solution was diluted to 5% by weight, and this polymer solution was placed on a substrate on which an inorganic insulating film of SiO 2 was previously formed to a thickness of 1200 Å, and a transparent electrode mainly composed of In 2 O 3 was formed. 500, 1000, with offset printing machine using
A 1500 Å alignment film was formed. In either case, high-quality elements with very excellent transparency and inconspicuous Nesa patterns could be obtained. The ratio of light transmittance at wavelengths of 400 nm and 500 nm measured in the same manner as in Example 1 was 0.90, and an almost colorless liquid crystal display element was obtained.
Claims (1)
る液晶表示素子において、該配向膜が次式 〔但し、式中、Ｒはトリフルオロメチル基を示
し、Arは芳香族テトラカルボン酸残基を示す。〕
で表されるくり返し単位を有する芳香族ポリイミ
ド重合体からなることを特徴とする液晶表示素
子。 ２ 前記Arが【式】または 【式】であることを特徴 とする特許請求の範囲第１項記載の液晶表示素
子。[Claims] 1. In a liquid crystal display element having a liquid crystal alignment film on a substrate on which electrodes are formed, the alignment film has the following formula: [However, in the formula, R represents a trifluoromethyl group, and Ar represents an aromatic tetracarboxylic acid residue. ]
A liquid crystal display element comprising an aromatic polyimide polymer having repeating units represented by: 2. The liquid crystal display element according to claim 1, wherein the Ar is [Formula] or [Formula].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56189175A JPS5891430A (en) | 1981-11-27 | 1981-11-27 | Liquid crystal display element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56189175A JPS5891430A (en) | 1981-11-27 | 1981-11-27 | Liquid crystal display element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5891430A JPS5891430A (en) | 1983-05-31 |
| JPH046926B2 true JPH046926B2 (en) | 1992-02-07 |
Family
ID=16236734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56189175A Granted JPS5891430A (en) | 1981-11-27 | 1981-11-27 | Liquid crystal display element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5891430A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5215677A (en) * | 1985-09-27 | 1993-06-01 | Sanyo Electric Co., Ltd. | Liquid crystal display device |
| JPS6326630A (en) * | 1986-07-21 | 1988-02-04 | Seiko Epson Corp | Liquid crystal display device |
| JPS63130633A (en) * | 1986-11-20 | 1988-06-02 | Kanegafuchi Chem Ind Co Ltd | Novel polyamic acid and production of polyimide |
| DE3881726T2 (en) * | 1987-03-09 | 1994-01-13 | Chisso Corp | Diamino compounds and films for the orientation of liquid crystals. |
| AU610606B2 (en) * | 1987-07-15 | 1991-05-23 | Government of the United States of America as represented by the Administrator of the National Aeronautics and Space Administration (NASA), The | Process for preparing low dielectric polyimides |
| US4831977A (en) * | 1987-07-17 | 1989-05-23 | Ethyl Corporation | Pistons with wear resistant solid film lubricant coatings |
| US4803147A (en) * | 1987-11-24 | 1989-02-07 | Hoechst Celanese Corporation | Photosensitive polyimide polymer compositions |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55163513A (en) * | 1979-06-06 | 1980-12-19 | Hitachi Ltd | Liquid crystal display element |
-
1981
- 1981-11-27 JP JP56189175A patent/JPS5891430A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55163513A (en) * | 1979-06-06 | 1980-12-19 | Hitachi Ltd | Liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5891430A (en) | 1983-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS5911884B2 (en) | liquid crystal display element | |
| JPS62231222A (en) | Solution for forming orientation film of liquid crystal | |
| EP1276003A1 (en) | Liquid-crystal display | |
| JPH0433010B2 (en) | ||
| JPH0560566B2 (en) | ||
| JPH046926B2 (en) | ||
| JPS5950043B2 (en) | liquid crystal display element | |
| JPH02176631A (en) | Composition for liquid crystal oriented film liquid crystal oriented film and liquid crystal display element | |
| JP2000143985A (en) | Black coating composition, resin black matrix, color filter and liquid crystal display | |
| JPS61267030A (en) | Liquid crystal display element | |
| JPS5821244B2 (en) | liquid crystal display element | |
| JPS5817418A (en) | Liquid crystal display element | |
| TW202037714A (en) | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal element | |
| JP2573824B2 (en) | Liquid crystal cell and method of manufacturing the same | |
| JPS6040607B2 (en) | liquid crystal display element | |
| JPS5817417A (en) | Liquid crystal display element | |
| JPS6262326B2 (en) | ||
| JPS5944604B2 (en) | liquid crystal display element | |
| JPS61226732A (en) | Liquid crystal display element | |
| JPS5949563B2 (en) | Liquid crystal display element and its manufacturing method | |
| KR101464541B1 (en) | Liquid crystal display device | |
| JPH0830167B2 (en) | Curable composition | |
| JPS5817416A (en) | Liquid crystal display element | |
| JPS62231223A (en) | Solution for forming orientation film of liquid crystal | |
| JPH09279026A (en) | Resin solution composition for color filter, method for applying the same, color filter, and liquid crystal display |