JPS5817416A - Liquid crystal display element - Google Patents
Liquid crystal display elementInfo
- Publication number
- JPS5817416A JPS5817416A JP56115242A JP11524281A JPS5817416A JP S5817416 A JPS5817416 A JP S5817416A JP 56115242 A JP56115242 A JP 56115242A JP 11524281 A JP11524281 A JP 11524281A JP S5817416 A JPS5817416 A JP S5817416A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- group
- crystal display
- display element
- polyimide
- 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
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 32
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 14
- 229920001721 polyimide Polymers 0.000 abstract description 19
- 239000004642 Polyimide Substances 0.000 abstract description 17
- 238000010438 heat treatment Methods 0.000 abstract description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract description 4
- 125000006267 biphenyl group Chemical group 0.000 abstract description 4
- 125000004427 diamine group Chemical group 0.000 abstract description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 abstract description 4
- 239000012965 benzophenone Substances 0.000 abstract description 3
- 235000010290 biphenyl Nutrition 0.000 abstract description 3
- 239000004305 biphenyl Substances 0.000 abstract description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 238000004040 coloring Methods 0.000 abstract description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 abstract description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 abstract description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract 2
- 239000013078 crystal Substances 0.000 abstract 1
- 238000004299 exfoliation Methods 0.000 abstract 1
- 150000002430 hydrocarbons Chemical group 0.000 abstract 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 14
- 239000011521 glass Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 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 4
- 230000000740 bleeding effect Effects 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol 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
- 230000002411 adverse Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 125000006840 diphenylmethane group Chemical group 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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)
- Liquid Crystal (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は液晶表示素子ＫｒｊＪＪＩＡ七〈に、透明性の
すぐれた液晶表示素子に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a liquid crystal display element KrjJJIA7 with excellent transparency.
一般に、液晶表示素子は第１図に示すような構造會有μ
ガラス基板り、１′上に酸化インジウムＣｒｓ＊ｏ、）
などの透明導電膜から成るセグメント電極２．２’ ＝
ｉ設け、その上に配向膜（または、絶縁膜）３．３’會
形成ＬＡ これ會もって液晶４ｔサンドイッテム周辺部
【シーＪＩｙｓｆｃよって封止している。さらに、その
両側に偏光板６，６′が配置されている。Generally, a liquid crystal display element has a structure as shown in Figure 1.
Glass substrate, indium oxide Crs*o on 1')
A segment electrode 2.2' made of a transparent conductive film such as
An alignment film (or insulating film) 3.3' is formed thereon, and the surrounding area of the liquid crystal 4t is sealed by LA. Further, polarizing plates 6, 6' are arranged on both sides thereof.
従来、液晶表示素子、とくに、電界の作用に１〕動作す
る電気光学効果を利用したネマチック液晶表示素子にお
いては、配向膜としてＳのの蒸着膜など無機質材料が主
として用いられていた。その理由は、これら無機膜は液
晶と接しても液晶に悪影響ｔ−４える因子を持たず、ま
た、ガラスフリットシールを行なっても液晶を均一に配
向できる利点があるためでｂゐ。Conventionally, in liquid crystal display elements, particularly in nematic liquid crystal display elements that operate under the action of an electric field and utilize an electro-optic effect, inorganic materials such as evaporated S films have been mainly used as alignment films. The reason for this is that these inorganic films do not have a factor that adversely affects the liquid crystal even when they come into contact with the liquid crystal, and also have the advantage of being able to align the liquid crystal uniformly even when glass frit sealing is performed.
一方へ配向膜として各種有機高分子材料を用いた液晶表
示素子も提案されている。この場合、高分子ａｔ布等で
一方向擦過して配向処理した後、擦過方向が互に直交す
るＬうにして用いるのが一般的である。フッ素樹脂、ポ
リビニル アルコール、ポリエステル、ケイ素樹脂、ポ
リアミド、ポリエステルイミド、ポリカーボネートやそ
の他の多くの有機高分子化合物からなる膜が液晶表示素
子用配向膜として提案されている。従来知られたこれら
の高分子膜扛液晶配向の均一性が十分とは言えず、また
長期に亘る通電試験及び劣化試験によって、無機絶縁膜
に比較して配向の不均一性が増加しやすく、個々の液晶
表示素子にかなりのバラツキが発生する欠点がある。ま
た、ガラスフリットシールは約４００℃に加熱されるが
、従来知られ友高分子膜の多くは、耐熱性が不十分なた
め、配向膜が破壊されて液晶が配向しないという欠点が
ある。On the other hand, liquid crystal display devices using various organic polymer materials as alignment films have also been proposed. In this case, it is common to perform orientation treatment by rubbing in one direction with a polymeric AT cloth or the like, and then use it in a manner that the rubbing directions are perpendicular to each other. Films made of fluororesin, polyvinyl alcohol, polyester, silicone resin, polyamide, polyesterimide, polycarbonate, and many other organic polymer compounds have been proposed as alignment films for liquid crystal display devices. The uniformity of the liquid crystal alignment of these conventionally known polymer films is not sufficient, and the non-uniformity of the alignment tends to increase due to long-term current tests and deterioration tests compared to inorganic insulating films. There is a drawback that considerable variation occurs among individual liquid crystal display elements. Furthermore, glass frit seals are heated to about 400° C., but many of the conventionally known polymer films have insufficient heat resistance, resulting in the disadvantage that the alignment film is destroyed and the liquid crystal is not aligned.
これまでの有機高分子材料の中で比較的配向性にすぐれ
た配向Ｈ＊影形成る材料としてポリインドを挙げること
ができる。例えに特開昭５１−６５９６０号公報に１載
されているピロメリット酸二無水物と４，４′−ジアミ
ノジフェニルエーテルとの縮合に工夛得られるポリイミ
ド前駆体であるポリアミド酸を塗布後加熱閉環して得ら
れるポリインドは配向の均一性ならびに劣化試験による
耐久性の点ではかな９良好である。しかム ピロメリッ
ト酸二無水物とジアミノジフェニルエーテルから得られ
るポリイミドで代表されるポリイミドの多くのものは、
３００℃〜３５０℃のイミド閉環温度や４００℃位のガ
ラスフリットシールの温度で加熱すると著しく着色する
。Among conventional organic polymer materials, polyindo can be cited as a material that forms an oriented H* shadow with relatively excellent orientation. For example, after coating polyamic acid, which is a polyimide precursor obtained by condensing pyromellitic dianhydride and 4,4'-diaminodiphenyl ether, as described in JP-A No. 51-65960, the ring is closed by heating. The polyind obtained in this manner has a score of 9 in terms of uniformity of orientation and durability in a deterioration test. However, many polyimides, typified by polyimides obtained from pyromellitic dianhydride and diaminodiphenyl ether, are
When heated at the imide ring-closing temperature of 300°C to 350°C or the glass frit seal temperature of about 400°C, it will be significantly colored.
このため、液晶を封入した後の液晶表示素子が着色を帯
び、同時に視野が暗くな九更にはコントラストが低下μ
表示素子としての機能、とくに高品位の表示の要求愛情
さないという問題が６つ’ｆＣ。For this reason, the liquid crystal display element becomes colored after being filled with liquid crystal, and at the same time, the field of view becomes dark, and furthermore, the contrast decreases.
There are six problems in terms of function as a display element, especially in not meeting the requirements for high-quality display.
また、ポリイミドを配向膜として用ｉた場合、ポリイミ
ドが基板に対して非常に接着性が悪Ｉ／％ため、配向膜
のはがれｔ生じて配向不良になった広液晶表示素子内へ
浸透した水分が基板上に凝集して水滴となり文字などに
Ｋじみを生ずるという問題が起りやすい。In addition, when polyimide is used as an alignment film, since polyimide has very poor adhesion to the substrate, the alignment film peels off and moisture permeates into the wide liquid crystal display element, resulting in poor alignment. This tends to cause problems such as water droplets condensing on the substrate and causing K smudges on letters and the like.
したがって、従来のポリイミドでは透明性にすぐれた液
晶表示素子を得ることは困難である。そζで、加熱閉環
及びガラスフリットによるシール時の加熱によっても着
色が少表く透明性にすぐれた配向膜の開発が望まれてい
る。Therefore, it is difficult to obtain a liquid crystal display element with excellent transparency using conventional polyimide. Therefore, there is a desire to develop an alignment film that exhibits little coloring even when heated during ring closure and sealing with a glass frit, and has excellent transparency.
本発明＃ｉこのよう表現状に＃ｌみてなされ−ＩＦ、、
ものでちゃ、その目的は、加熱によ多着色せず透明性の
すぐれた液晶表示素−−−−−−−−−
子ｔ−提供することである。The present invention #i is made in this way #l-IF,,
The purpose is to provide a liquid crystal display element which does not become colored by heating and has excellent transparency.
（式中、Ｒ□はテトラカルボン酸の有機残基である）で
示される繰シ返し単位ｉ有するポリイミドから攻ること
ｔ−特徴としている。(In the formula, R□ is an organic residue of a tetracarboxylic acid.) It is characterized by starting from a polyimide having a repeating unit i represented by the formula:
上記式中、Ｒ１＃：ｌ：テトラカルボン酸の有機残基で
ある。Ｒ□としてはフェニル基、ナフタレ７基、ペリレ
ン基、ジフェニル基、ベンゾフェノン基などの芳香族基
が好ましいが、とくに好ｔし込のは、フェニル豚ベンゾ
フェノン基及びジフェニル基である。In the above formula, R1#:l: is an organic residue of tetracarboxylic acid. R□ is preferably an aromatic group such as a phenyl group, a naphthalene group, a perylene group, a diphenyl group, or a benzophenone group, and particularly preferred are phenyl, benzophenone, and diphenyl groups.
本発明で配向膜として用いるポリイミドはテトラカルボ
ン酸二無水物と３．３′−ジアミノジフェニルスルホン
との縮重合反応で得られるが、通常両者を溶媒中で反応
させてポリイミド前駆体であるポリアミド酸溶液上つく
り、次いでこれｔ液晶表示素子用ガラス基板に塗布、転
弧熱処理することにより、目的とする上記繰９返し単位
を有する配向膜管形成することができる。The polyimide used as the alignment film in the present invention is obtained by a polycondensation reaction of tetracarboxylic dianhydride and 3,3'-diaminodiphenylsulfone, but usually the two are reacted in a solvent to form polyamic acid, which is a polyimide precursor. By preparing the solution as a solution, then coating it on a glass substrate for a liquid crystal display element, and subjecting it to arc rolling heat treatment, it is possible to form an alignment film tube having the above-mentioned nine repeating units.
本発明におり°るポリイミド前駆体の合成社、３．３’
−ジアミノジフェニルスルホンと、ピロメリット酸二無
水物、ベンゾフェノンテトラカルボン酸二無水物又祉ビ
フエエルテトラカルポン酸二無水物等のテトラカルボン
酸二無水物とを有機溶剤中で１５℃〜５０℃程度の温度
で数時間攪拌することにニジ好ましく行なわれる。生成
重合体の重合度は塗膜形成能があれば１く、％に制限さ
れない。生成した重合体の溶液を濃度５重量−程度に稀
釈１．、１００ＯＡ前後の希望の膜厚になるように塗布
した後、２００〜３５０℃程度の温度で３０〜６０分程
度加熱することにｌ希望のポリイミド膜全形成すること
ができる。この反応に用いられる有機溶剤の例として、
Ｎ−メチル−２−ピロリドン、Ｎ、Ｎ−ジメチルアセド
アミド等の極性有機溶剤１１＃けることができる。ポリ
イミド前駆体溶液の塗布方法としては回転塗布法、浸漬
塗布法、ロール塗布法、印刷ム刷毛塗シ法などが例とし
て挙げられる。Synthesis of polyimide precursor according to the present invention, 3.3'
- Diaminodiphenyl sulfone and a tetracarboxylic dianhydride such as pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, or bifertetracarboxylic dianhydride in an organic solvent at 15°C to 50°C. This is preferably carried out by stirring for several hours at a temperature of about °C. The polymerization degree of the produced polymer is 1 as long as it has the ability to form a coating film, and is not limited to %. Dilute the resulting polymer solution to a concentration of about 5% by weight.1. After coating to a desired film thickness of about 100 OA, the entire desired polyimide film can be formed by heating at a temperature of about 200 to 350° C. for about 30 to 60 minutes. Examples of organic solvents used in this reaction are:
Polar organic solvents such as N-methyl-2-pyrrolidone and N,N-dimethylacedeamide can be used. Examples of the method for applying the polyimide precursor solution include a spin coating method, a dip coating method, a roll coating method, a printing method and a brush coating method.
本発明のポリイミドは、目的とする特性を大きくそこな
わない範囲内で、ジアミン残基のジフェニにスルホン基
の一部會他のジアミン残基で置きかえたものでもよい。In the polyimide of the present invention, some of the sulfone groups may be replaced with diphenyl diamine residues by other diamine residues as long as the desired properties are not significantly impaired.
ジフェニルスルホン基の一部を置きかえうるジアミン残
基の例として、ジフェニルエーテル基、ジフェニルメタ
ン基、カルバモイルジフェニルエーテル基、ビスフェノ
キシジフェニルスルホン基、ビスフェノキシジフェニル
エーテル基などが例として挙げられるが、勿論これらに
限定されるものでは表い。Examples of diamine residues that can replace part of the diphenyl sulfone group include diphenyl ether group, diphenylmethane group, carbamoyl diphenyl ether group, bisphenoxy diphenyl sulfone group, bisphenoxy diphenyl ether group, etc., but are of course limited to these. It's not a thing.
本発明における前記のポリイミドからなる配向膜は導電
層を設けた基板上に直接形成することができるが、導電
層の下層又は上層に無機絶縁膜を設けた基板を用いるこ
とによシ、さらにすぐれた液晶表示素子會得ることがで
きる。これは、導電層を有するガラス基板上Ｋ［壁形成
した配向膜の方ハソーダガラス中のナトリウムイオン等
による熱劣化が加速され難いことによる。このような効
果會示す無機絶縁膜としてＦｉｓｔｏ、が適当でめる。Although the alignment film made of polyimide according to the present invention can be formed directly on a substrate provided with a conductive layer, it is even more advantageous to use a substrate provided with an inorganic insulating film below or above the conductive layer. A liquid crystal display element assembly can be obtained. This is because thermal deterioration due to sodium ions in the soda glass is less likely to be accelerated in an alignment film formed on a glass substrate having a conductive layer. Fisto is a suitable inorganic insulating film that exhibits such effects.
又、本発明において、いっ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ッグリング剤のｉ
ｓ以上を併用する仁とができる。シランカップリング剤
の例として、ｒ−アミノプロピルトリエトキシシラン、
ｒ−グリシドキシグロビルトリメトキシシランが挙げら
れる。適用に当っては、前記ポリイミドの前駆体溶液に
添加してもよく、又、ガラス基板上にシランカップリン
グ剤の膜を形成した上に配向膜を形成してもよい。In addition, in the present invention, in order to obtain an even stronger alignment film, the i
It can be used in combination with s or more. Examples of silane coupling agents include r-aminopropyltriethoxysilane,
Examples include r-glycidoxyglobyltrimethoxysilane. In application, it may be added to the polyimide precursor solution, or an alignment film may be formed on a silane coupling agent film formed on a glass substrate.
液晶表示素子に封入する液晶としては公知のもの會適宜
選択して用いて工い〇
本発明の液晶表示素子は重合体の加熱閉ｌＩｔ行なって
も黄褐色に着色せず、透明性を保持Ｕコントラストがす
ぐれているという利点を有する。As the liquid crystal to be sealed in the liquid crystal display element, a well-known liquid crystal may be appropriately selected and used. The liquid crystal display element of the present invention does not turn yellowish brown even when the polymer is heated and closed, and maintains transparency. It has the advantage of excellent contrast.
さらに、本発明で使用するポリイミドのジアミン残基で
らるジフェニルスルホン基の一部を１
（ことで、Ｒ２は２価の有機基、Ｒ３は１価の炭化水素
基−５は１以上の整数管、各々表わしている）で示され
るシロキサン基で置きかえる仁とにニジ、透明性を向上
できるだけでなく、配向膜のはがれやにじみの問題を回
避することも可能となムシロキサン基としては、
（Ｊ３ ｃＨｓ
Ｃ６Ｈ６Ｃ，ｌへ
が典型的な例として挙げられるが、これらに限定されな
いことハ勿論である。シロキサン基と３．３′−ジフェ
ニルスルホ７基の比は前者が１〜１０モル−１後者が９
９〜９０モル−の範囲から選択することが望ましい。Furthermore, a part of the diphenylsulfone group formed by the diamine residue of the polyimide used in the present invention is 1 (so that R2 is a divalent organic group, R3 is a monovalent hydrocarbon group, and 5 is an integer of 1 or more. In contrast to the siloxane groups that can be replaced with the siloxane groups shown by (represented by tubes, respectively), the musiloxane groups that can not only improve transparency but also avoid problems with peeling and bleeding of the alignment film are: ( J3 cHs C6H6C,l is given as a typical example, but it goes without saying that it is not limited to these.The ratio of the siloxane group to the 3,3'-diphenylsulfo7 group is 1 to 10 mol-1 for the former. is 9
It is desirable to select from the range of 9 to 90 mol.
以下実施例に基づいて本発明鵞説明する。The present invention will be explained below based on examples.
実施例 １゜
３．３’−ジアミノジフェニルスルホン（１００モル−
）トベンゾフェノンテト２カルボン酸二無水物（１００
モルチ）及びＮ−メチル−２−ピロリドンｔ−フラスコ
に入れ、５０℃で３時間攪拌した。３０℃での粘度が１
０．５ポアズの２３％溶液を得た。この溶液管Ｎ−メチ
ルー２−ピロリドンで稀釈ＬＡ５チの塗布溶液ｖ、ｔた
。Example 1゜3.3'-diaminodiphenylsulfone (100 mol-
) Tobenzophenoneteto dicarboxylic dianhydride (100
Morti) and N-methyl-2-pyrrolidone were placed in a T-flask and stirred at 50°C for 3 hours. Viscosity at 30℃ is 1
A 23% solution of 0.5 poise was obtained. This solution tube was filled with a coating solution of LA5 diluted with N-methyl-2-pyrrolidone.
Ｉｎ、Ｏ，透明電極付ガラス基板にあらかじめｒ−アミ
ノプロピルトリエトキシシランの塗膜音形成１ついで、
前記塗布溶液ｔスピンナで塗布１．、３００℃、１時間
加熱して、膜厚的１００ＯＡのポリイミド膜を形成した
。綿布で一定方向にこすって配向膜を形成した。こうし
て得た２枚のガラス基板のシール部をグッズマ・エツチ
ングで除去した後組合せて、エポキシ樹脂を用いてシー
ルしセルを作成した。ついで、シッフ型のネマチック液
晶會注入し％液晶表示素子を完成した。After forming a coating film of r-aminopropyltriethoxysilane on a glass substrate with In, O, and transparent electrodes,
Coating the above coating solution using a t-spinner 1. , and was heated at 300° C. for 1 hour to form a polyimide film having a thickness of 100 OA. An alignment film was formed by rubbing in a certain direction with a cotton cloth. The sealed portions of the two glass substrates thus obtained were removed by Goodsma etching, and then combined and sealed using epoxy resin to create a cell. Next, a Schiff-type nematic liquid crystal was injected to complete a liquid crystal display element.
上記液晶表示素子の４但ｈｏｐの透過率は７７チであっ
た。The 4-hop transmittance of the liquid crystal display element was 77 cm.
又〜７０℃、９５ＳＲＨの芥日気中Ｋ１００時間放置後
、点灯しにじみを調べた力ζ全く発生しなかった。Also, after being left in the air at 70° C. and 95 SRH for 100 hours, it was turned on and checked for bleeding, and no force ζ was generated.
実施例 ２゜
３．３′−ジアミノジフェニルスルホン（９５モルｑｋ
）、弐〇Ｈ，ＣＨｓ
で示される化合物（５モル−）、ピロメリット酸二無水
物（１００−Ｅ−ルＬｓ）及びＮ−メチル−２−ピロリ
ドンをフラスコに入れ、５０℃で３時間攪拌した。３０
℃での粘度が１１ポアズの２５−溶液をえた。この溶液
１ｒＮ−メチル−２−ピロリドンで稀釈し３．０ｓの塗
布溶液をえた、。Example 2゜3.3'-diaminodiphenylsulfone (95 mol qk
), 2〇H, CHs (5 moles), pyromellitic dianhydride (100-E-Ls), and N-methyl-2-pyrrolidone were placed in a flask and stirred at 50°C for 3 hours. did. 30
A 25-solution with a viscosity of 11 poise at °C was obtained. This solution was diluted with 1rN-methyl-2-pyrrolidone to obtain a 3.0 s coating solution.
シランカップリング剤の塗膜を形成していな％／−ｈＩ
％２０．透明電極付ガラス基板を用いて、実施例１と同
様にして液晶表示素子を形成した。Does not form a coating film of silane coupling agent%/-hI
%20. A liquid crystal display element was formed in the same manner as in Example 1 using a glass substrate with transparent electrodes.
実施例１と同様な評価を行なったとζろ、４０−一の透
過率は’１６％で、耐湿テスト後のにじみは観察されな
かった。When the same evaluation as in Example 1 was performed, the transmittance of 40-1 was 16%, and no bleeding was observed after the moisture resistance test.
比較実施例 １゜
ジアミノジフェニルエーテル（１００モル％）、ピロメ
リット酸二無水物（１００モルチ）及びＮ−メチル−２
−ピロリドンｔ−フラスコに入れ、５０℃で３時間攪拌
した。３０℃での粘度が１０ポアズの１７％溶液τ得た
。この溶液ｔ−Ｎ−メチル−２−ピロリドンで稀釈して
２．．５−の塗布浴１１［を得た。Comparative Example 1° Diaminodiphenyl ether (100 mol%), pyromellitic dianhydride (100 mol%) and N-methyl-2
-Pyrrolidone was placed in a T-flask and stirred at 50°C for 3 hours. A 17% solution τ having a viscosity of 10 poise at 30°C was obtained. This solution was diluted with t-N-methyl-2-pyrrolidone and 2. ．． 5- coating bath 11[ was obtained.
シランカップリング剤の塗膜を形成していないＩｎ、Ｏ
，透明電極付ガラス基板を用いて、実施例１と同様にし
て液晶表示素子を形成した。In, O without forming a coating film of silane coupling agent
A liquid crystal display element was formed in the same manner as in Example 1 using a glass substrate with transparent electrodes.
実施例１と同様な評価を行なったところ、４０−の透過
率ａ６５ｓで、耐湿テスト後に、にじみが観察された。When the same evaluation as in Example 1 was performed, bleeding was observed after the moisture resistance test at a transmittance of 40-65s.
第１図は液晶表示素子の断面図である。
Ｊ 、 １’−・・・・・ガラス基板、２．２’・・・
・・・透明導電膜、３．３′・・・・・・配向Ｋ
４ ・−−−一液晶、 ５・−・・・シール寿ムロ
、 ６’ −−−−−偏光札FIG. 1 is a sectional view of a liquid crystal display element. J, 1'-...Glass substrate, 2.2'...
...Transparent conductive film, 3.3'...Orientation K
4 ・---1 liquid crystal, 5 ・--- Seal Kotobuki
, 6' --------Polarized tag
Claims (1)
−有する（式中、Ｒはテトラカルボン酸の有機残基であ
る）て示される繰シ返し単位Ｙｒｖするポリインドから
なることｔ特徴とする液晶表示素子。(1) Liquid crystal alignment film 1 on a substrate on which transparent electrodes are formed!
- A liquid crystal display element comprising polyindo having repeating units Yrv (wherein R is an organic residue of tetracarboxylic acid).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56115242A JPS5817416A (en) | 1981-07-24 | 1981-07-24 | Liquid crystal display element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56115242A JPS5817416A (en) | 1981-07-24 | 1981-07-24 | Liquid crystal display element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5817416A true JPS5817416A (en) | 1983-02-01 |
Family
ID=14657861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56115242A Pending JPS5817416A (en) | 1981-07-24 | 1981-07-24 | Liquid crystal display element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5817416A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60184202A (en) * | 1984-03-02 | 1985-09-19 | Toray Ind Inc | Heat resistant coloring paste for color filter |
| JPS61254905A (en) * | 1985-05-08 | 1986-11-12 | Toray Ind Inc | Color filter |
| JPH02130528A (en) * | 1988-11-11 | 1990-05-18 | Nippon I B M Kk | Color liquid crystal display device and production thereof |
| JPH0711132A (en) * | 1993-07-16 | 1995-01-13 | Toray Ind Inc | Heat-resistant color paste for color filter |
-
1981
- 1981-07-24 JP JP56115242A patent/JPS5817416A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60184202A (en) * | 1984-03-02 | 1985-09-19 | Toray Ind Inc | Heat resistant coloring paste for color filter |
| JPS61254905A (en) * | 1985-05-08 | 1986-11-12 | Toray Ind Inc | Color filter |
| JPH02130528A (en) * | 1988-11-11 | 1990-05-18 | Nippon I B M Kk | Color liquid crystal display device and production thereof |
| JPH0711132A (en) * | 1993-07-16 | 1995-01-13 | Toray Ind Inc | Heat-resistant color paste for color filter |
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