JPH0414020A - Composition for liquid crystal oriented film - Google Patents
Composition for liquid crystal oriented filmInfo
- Publication number
- JPH0414020A JPH0414020A JP11847590A JP11847590A JPH0414020A JP H0414020 A JPH0414020 A JP H0414020A JP 11847590 A JP11847590 A JP 11847590A JP 11847590 A JP11847590 A JP 11847590A JP H0414020 A JPH0414020 A JP H0414020A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- formula
- group
- composition
- alkyl group
- 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.)
- Granted
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 35
- 239000000203 mixture Substances 0.000 title claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical group C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract 2
- 229920005575 poly(amic acid) Polymers 0.000 claims description 16
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 5
- 239000004952 Polyamide Substances 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 2
- 229920002647 polyamide Polymers 0.000 abstract 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 230000035807 sensation Effects 0.000 abstract 1
- 229920001721 polyimide Polymers 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 150000004985 diamines Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 150000004984 aromatic diamines Chemical class 0.000 description 4
- -1 cyclopentanetetracarboxylic anhydride Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- YVHAIVPPUIZFBA-UHFFFAOYSA-N Cyclopentylacetic acid Chemical compound OC(=O)CC1CCCC1 YVHAIVPPUIZFBA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 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
- BZUNJUAMQZRJIP-UHFFFAOYSA-N CPDA Natural products OCCCCCCCCCCCCCCC(O)=O BZUNJUAMQZRJIP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- GISJHCLTIVIGLX-UHFFFAOYSA-N n-[4-[(4-chlorophenyl)methoxy]pyridin-2-yl]-2-(2,6-difluorophenyl)acetamide Chemical compound FC1=CC=CC(F)=C1CC(=O)NC1=CC(OCC=2C=CC(Cl)=CC=2)=CC=N1 GISJHCLTIVIGLX-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007921 spray Substances 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は液晶配向膜を形成しうる液晶配向膜用組成物に
関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a composition for a liquid crystal alignment film that can form a liquid crystal alignment film.
液晶表示装置に用いられる液晶素子には、一般に所定の
間隙を有するように対向させて配した透明基板の内側面
の透明電極の表面に液晶配向膜か形成されている。この
液晶配向膜には、従来のＴＮ方式の液晶装置の場合、ポ
リイミド膜がよく使用される。ポリイミド膜は、その前
駆体のポリアミド酸を有機溶剤に溶解した液晶配向膜用
組成物を透明電極上に塗布し、加熱脱水閉環して形成す
る。In a liquid crystal element used in a liquid crystal display device, a liquid crystal alignment film is generally formed on the surface of transparent electrodes on the inner surfaces of transparent substrates that are arranged to face each other with a predetermined gap. In the case of a conventional TN type liquid crystal device, a polyimide film is often used as the liquid crystal alignment film. The polyimide film is formed by applying a composition for a liquid crystal alignment film in which a polyamic acid precursor thereof is dissolved in an organic solvent onto a transparent electrode, and subjecting the composition to thermal dehydration and ring closure.
従来、液晶配向膜のポリイミドには全芳香族系ジアミン
を原料とするポリイミド膜が使用されてきた。例えば、
無水ピロメリト酸と４，４° −ジアミノジフェニルエ
ーテルの反応より得られるポリアミド酸からなる液晶配
向膜用組成物を脱水閉環し得られるポリイミド膜があげ
られる。この種のポリイミドは配向性が優れているなど
の長所があるか、最近注目されている超ねじれ複屈折効
果（Ｓｕｐｅｒ Ｔｗｉｓｔｅｄ Ｂｊｒｅｆｒｉｎｇ
ｅｎｃｅ Ｅｆｆｅｃｔ：Ｓ Ｔ Ｂ Ｅと略す）を利
用した液晶表示装置には対応できない。この表示装置は
従来のＴＮ型に比較して、コントラスト、視覚特性がき
わめて優れているという特徴がある。これに用いる配向
膜はプレチルト角を高くする必要かあるが、従来のポリ
イミドではプレチルト角が２°以下で、ドメインができ
ディスクリネーションと呼ばれる線欠陥が発生する等良
好な表示特性が得られない。従って、５ＴＢＥ型表示装
置で満足のいく表示特性が得られる配向膜として現状で
は酸化珪素等の無機斜方蒸着膜等か主に用いられていた
。Conventionally, polyimide films made from wholly aromatic diamines have been used as polyimide films for liquid crystal alignment films. for example,
A polyimide film obtained by dehydrating and ring-closing a composition for a liquid crystal aligning film consisting of a polyamic acid obtained by the reaction of pyromellitic anhydride and 4,4°-diaminodiphenyl ether is mentioned. This type of polyimide has advantages such as excellent orientation, and it also has the super twisted birefringence effect that has been attracting attention recently.
It is not compatible with liquid crystal display devices that utilize the ence effect (abbreviated as STBE). This display device is characterized by extremely superior contrast and visual characteristics compared to the conventional TN type. The alignment film used for this needs to have a high pretilt angle, but with conventional polyimide, if the pretilt angle is less than 2 degrees, good display characteristics cannot be obtained, such as domains and line defects called disclinations. . Therefore, at present, inorganic obliquely vapor deposited films such as silicon oxide are mainly used as alignment films that can provide satisfactory display characteristics in 5TBE display devices.
しかし、無機斜方蒸着膜は、液晶に対して選択性があり
、全ての液晶組成物の配向を良好に行うことは困難であ
る。また、組立て時の高温加熱処理により配向にムラが
生し歩留りが低下して生産性が悪くなる欠点を有し、配
向膜に必要なコントラストおよび視覚特性を満足するこ
とができなかった。However, the inorganic obliquely deposited film has selectivity to liquid crystal, and it is difficult to achieve good alignment of all liquid crystal compositions. In addition, the high temperature heat treatment during assembly causes uneven alignment, lowering the yield and resulting in poor productivity, and the contrast and visual characteristics required for an alignment film cannot be satisfied.
本発明者等は上記の様な種々の問題がある無機斜方蒸着
膜にかわる、比較的高いプレチルト角を有するポリイミ
ド膜の開発を検討した。従来のポリイミド膜は平面構造
のため、プレチルト角か低いと考え、平面から構成分子
の一部が立っている様なポリイミド膜を試作すべく、液
晶配向膜用組成物について検討した。The present inventors have studied the development of a polyimide film having a relatively high pretilt angle to replace the inorganic obliquely deposited film, which has the various problems described above. Since conventional polyimide films have a planar structure, we assumed that the pretilt angle would be low, so we investigated compositions for liquid crystal alignment films in order to create a prototype polyimide film in which some of the constituent molecules were erected from a plane.
その結果、従来品に比較して、プレチルト角が高く、斜
方配向が可能であるポリイミド配向膜を形成することの
できる優れた液晶配向膜用組成物を発明するに至った。As a result, we have invented an excellent composition for a liquid crystal alignment film that can form a polyimide alignment film that has a higher pretilt angle and is capable of oblique alignment than conventional products.
すなわち、本発明は一般式（１）
（式中、Ｒ１は芳香環又は脂環てあり、Ｒ２は置換また
は無置換のアゾベンゼン基てあり、Ｒ３はアルキル基、
アルコキシ基、またはハロゲン原子てあり、Ｘはアルキ
ル基、０、ｓＸｃ、ｃ−ｏ、Ｓ、５−Ｏ１ＮＲ４（Ｒ４
は水素原子又はアルキＯＯ
ル基） 、Ｃ−ＮＲ４，５−ＮＲ４の１種または２種以
上よりなる鎖状置換基てあり、ｎは正の整数を示す。）
で表わされるポリアミド酸を含有することを特徴とする
液晶配向膜用組成物。That is, the present invention is based on the general formula (1) (wherein R1 is an aromatic ring or alicyclic ring, R2 is a substituted or unsubstituted azobenzene group, R3 is an alkyl group,
It is an alkoxy group or a halogen atom, and X is an alkyl group, 0, sXc, c-o, S, 5-O1NR4 (R4
is a hydrogen atom or a chain substituent consisting of one or more types of alkyl group), C-NR4,5-NR4, and n represents a positive integer. )
A composition for a liquid crystal alignment film, characterized by containing a polyamic acid represented by:
本発明の液晶配向膜用組成物は、主に一般式（Ｉ）のポ
リアミド酸およびこれを溶解し得る有機溶媒からなり、
これを脱水閉環と同時に有機溶媒を揮散させてポリイミ
ド膜とする。The composition for a liquid crystal alignment film of the present invention mainly consists of a polyamic acid of general formula (I) and an organic solvent capable of dissolving this,
This is dehydrated and ring-closed, and at the same time, the organic solvent is volatilized to form a polyimide film.
ここで、−紋穴（１）のポリアミド酸について詳しく述
べる。このポリアミド酸は酸無水物と鎖状置換基を有す
る芳香族ジアミンとの反応により得られるが、酸無水物
としては、例えば無水ピロメリト酸、無水３，３°、４
，４“−ビフェニルテトラカルボン酸、無水３． ３’
、 ４．４’ −ベンゾフェノンテトラカルボン酸
、無水シクロペンタンテトラカルボン酸、無水２，３．
５４リカルボキンシクロペンチル酢酸、無水５− （２
，５−ジオキソテトラヒドロ−３−フラニル）−３シク
ロヘキセン−１、］−ジカルボン酸等があげられる。鎖
状置換基を有する芳香族ジアミンは、−紋穴（ｎ）
（式中のＲ２、Ｒ３及びＸは前記と同じ）で示される化
合物で、例えば下記のものがあげられる。Here, the polyamic acid of Monana (1) will be described in detail. This polyamic acid is obtained by the reaction of an acid anhydride with an aromatic diamine having a chain substituent. Examples of the acid anhydride include pyromellitic anhydride, 3,3°, 4
, 4"-biphenyltetracarboxylic acid, anhydride 3. 3'
, 4.4'-benzophenonetetracarboxylic acid, cyclopentanetetracarboxylic anhydride, 2,3.
54 Ricarboquine cyclopentyl acetic acid, anhydrous 5- (2
, 5-dioxotetrahydro-3-furanyl)-3cyclohexene-1,]-dicarboxylic acid and the like. The aromatic diamine having a chain substituent is a compound represented by -Mokken (n) (in the formula, R2, R3 and X are the same as above), and examples thereof include the following.
なお、化合物Ｎｏ、は実施例においても共通に用いる。Note that compound No. is also commonly used in Examples.
化合物Ｎｏ。Compound no.
構 辺 式 ％式％ 式 Ｈ２ Ｈ２ ２Ｎ ２Ｎ ８゜ Ｈ２ ２Ｎ ２Ｎ ２Ｎ ■２ ＣＨ。Structure Side Formula %formula% formula H2 H2 2N 2N 8゜ H2 2N 2N 2N ■2 CH.
２Ｎ ２Ｎ ２Ｎ 化合物Ｎｏ。2N 2N 2N Compound no.
構
造
式
上記の酸無水物および鎖状置換基を有する芳香族ジアミ
ンをそれぞれ１種または２種以上を有機溶媒中、無水条
件下、好ましくは５０℃以下の温度で反応させ、ポリア
ミド酸の溶液とする。One or more of the acid anhydride and aromatic diamine having a chain substituent having the above structural formula are reacted in an organic solvent under anhydrous conditions, preferably at a temperature of 50° C. or lower, and a solution of polyamic acid is prepared. do.
ここで用いる有機溶媒には、比較的揮散しやすく、生成
するポリアミド酸を溶解し得る極性溶媒、例えば、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、ジメチルスルホキ
シド等を用いる。The organic solvent used here includes a polar solvent that volatilizes relatively easily and can dissolve the polyamic acid produced, such as N,
N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, etc. are used.
また、ガラス基板、金属類等との接着性の向上を目的と
して、反応成分にシランカップリング剤やジアミノシロ
キサンを併用することも何らさしつかえがない。シラン
カップリング剤としてはγアミノプロピルトリエトキシ
シラン、Ｎ−（β−アミノエチル）−γ−アミノプロピ
ルトリエトキシシラン、γ−グリシドキシプロピルトリ
メトキシシラン、γ−メルカプトプロピルトリメトキシ
シラン、γ−メタクリロキシプロピルトリメトキシシラ
ン等があげられる。Further, for the purpose of improving adhesion to glass substrates, metals, etc., there is no problem in using a silane coupling agent or diaminosiloxane as a reaction component. Silane coupling agents include γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ- Examples include methacryloxypropyltrimethoxysilane.
ジアミノシロキサンには１，３−ビス（３−アミノプロ
ピル） −１，１，３； ３−テトラメチルジシロキ
サン、α、ω−ビス（３−アミノプロピルジメチルシリ
ル）ベンゼン等があげられる。Diaminosiloxanes include 1,3-bis(3-aminopropyl)-1,1,3; 3-tetramethyldisiloxane, α,ω-bis(3-aminopropyldimethylsilyl)benzene, and the like.
上記のようにして得られた本発明のポリアミド酸を含有
する液晶配向膜用組成物を使用して配向膜を形成する方
法は、下記のとおりである。The method for forming an alignment film using the composition for liquid crystal alignment film containing the polyamic acid of the present invention obtained as described above is as follows.
つまり、前記ポリアミド酸を有機溶媒中０．１〜２０重
量％溶液として、これをデイツプ法、スピナー法、スプ
レー法、印刷法等により、液晶を構成する電極上に塗布
する。塗布後、１００〜４００℃、好ましくは１５０〜
２５０℃で加熱処理して、上記ポリアミド酸を脱水閉環
してボリイミド被膜が得られる。この被膜をラビング処
理して、液晶配向膜とされる。液晶配向膜と液晶間のプ
レチルト角は従来のポリイミド膜では２°以下であった
が、本発明の組成物より得られる液晶配向膜では、プレ
チルト角が高くなり、４０°位まで可能となった。本発
明のポリアミド酸を含有する液晶配向膜用組成物は５Ｔ
ＢＥ方式の液晶表示装置に適している。That is, the polyamic acid is made into a 0.1 to 20% by weight solution in an organic solvent, and this is applied onto the electrodes constituting the liquid crystal by a dip method, a spinner method, a spray method, a printing method, or the like. After coating, the temperature is 100-400℃, preferably 150-400℃.
Heat treatment is performed at 250° C. to dehydrate and ring-close the polyamic acid to obtain a polyimide film. This film is subjected to a rubbing treatment to obtain a liquid crystal alignment film. The pretilt angle between the liquid crystal alignment film and the liquid crystal was 2° or less in the conventional polyimide film, but in the liquid crystal alignment film obtained from the composition of the present invention, the pretilt angle was increased to about 40°. . The composition for liquid crystal alignment film containing polyamic acid of the present invention is 5T
Suitable for BE type liquid crystal display devices.
以下、実施例により本発明の詳細な説明する。 Hereinafter, the present invention will be explained in detail with reference to Examples.
なお、実施例中の部とは重量部を表わす。In addition, parts in the examples represent parts by weight.
実施例Ｉ
Ｎ、Ｎ−ジメチルアセトアミド６４部に化合物Ｎｏ、２
のジアミン４．１９部を溶解し、窒素雰囲気下、等モル
の無水３，３°、４．４° −ビフェニルテトラカルボ
ン酸２．９４部を加え２０〜３０℃で２４時間反応させ
た。得られたポリアミド酸の溶液にＮ、Ｎ−ジメチルア
セトアミドを加え５重量％の溶液を調製して液晶配向膜
用組成物とした。これをスピンコータを用いて、ＩＴＯ
の透明ガラス基板（３ｃｍＸ３ｃｍ厚さ１ｍｍ）上に塗
布した。塗布後２５０℃で１時間加熱して脱水閉環させ
、わずかに黄味を帯びたポリイミド被膜を形成した。Example I Compound No. 2 was added to 64 parts of N,N-dimethylacetamide.
4.19 parts of diamine were dissolved, and 2.94 parts of equimolar anhydrous 3.3°, 4.4°-biphenyltetracarboxylic acid were added under a nitrogen atmosphere, and the mixture was reacted at 20 to 30°C for 24 hours. N,N-dimethylacetamide was added to the obtained polyamic acid solution to prepare a 5% by weight solution to prepare a composition for a liquid crystal alignment film. This was coated with ITO using a spin coater.
It was coated on a transparent glass substrate (3 cm x 3 cm, thickness 1 mm). After coating, it was heated at 250° C. for 1 hour to cause dehydration and ring closure, forming a slightly yellowish polyimide film.
次にこの被膜をラビング処理した基板の一対を用いて、
液晶ＺＬＩ−２２１４（メルク社製）を封入して液晶表
示装置（厚み６μ）を作成した。Next, using a pair of substrates with this film rubbed,
A liquid crystal display device (thickness: 6 μm) was prepared by enclosing liquid crystal ZLI-2214 (manufactured by Merck & Co., Ltd.).
プレチルト角を測定したところ８°であった。本装置に
電圧を印加して、立ち上がり特性及びコントラストを観
察したところ極めて良好であった。The pretilt angle was measured to be 8°. When voltage was applied to this device and the rise characteristics and contrast were observed, they were extremely good.
実施例２〜５
実施例１において使用した化合物Ｎｏ、２のジアミンお
よび酸無水物の代わりに表１に示した物を用いて実施例
１と同様の操作を行いプレチルト角を測定した。その結
果を表１に示す。Examples 2 to 5 The same operations as in Example 1 were carried out using the compounds shown in Table 1 in place of the diamines and acid anhydrides of Compounds No. 2 and 2 used in Example 1, and the pretilt angles were measured. The results are shown in Table 1.
表１
またいずれの場合においても実施例１と同様良好な立ち
上がりとコントラストが観察された。Table 1 Also, in both cases, good rise and contrast were observed as in Example 1.
なお、表１におけるＰＭＤＡは無水ピロメリト酸、ＢＰ
ＤＡは無水３．３’ 、４．４’ −ビフェニルテト
ラカルボン酸、ＢＺＤＡは無水３３゜４．４°−ベンゾ
フェノンテトラカルボン酸、ＣＰＤＡは無水シクロペン
タンテトラカルボン酸を示す。In addition, PMDA in Table 1 is pyromellitic anhydride, BP
DA represents 3.3',4.4'-biphenyltetracarboxylic anhydride, BZDA represents 33°4.4°-benzophenone tetracarboxylic anhydride, and CPDA represents cyclopentanetetracarboxylic anhydride.
実施例６
Ｎ、Ｎ−ジメチルアセトアミド５７部に化合物ＮＯ１２
のジアミン４．１５部および１，３〜ビス（３−アミノ
プロピル）−１，１，３，３−テトラメチルジシロキサ
ン０．０２５部（ジアミン全体の１ｍｏ１％）を溶解し
、窒素雰囲気下、無水ピロメリト酸２．１８部を加え２
０〜３０℃で２４時間反応させた。得られたポリアミド
酸の溶液にＮ、Ｎ−ジメチルアセトアミドを加え５重量
％の溶液を調製して液晶配向膜用組成物とした。Example 6 Compound NO12 was added to 57 parts of N,N-dimethylacetamide.
4.15 parts of diamine and 0.025 parts of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (1 mo 1% of the total diamine) were dissolved, and under a nitrogen atmosphere, Add 2.18 parts of pyromellitic anhydride and
The reaction was carried out at 0 to 30°C for 24 hours. N,N-dimethylacetamide was added to the obtained polyamic acid solution to prepare a 5% by weight solution to prepare a composition for a liquid crystal alignment film.
この組成物を用いて実施例１と同様にして、ポリイミド
被膜を得て、さらに液晶表示装置を作成し、プレチルト
角を測定したところ、９°であった。Using this composition, a polyimide film was obtained in the same manner as in Example 1, and a liquid crystal display device was prepared.The pretilt angle was measured and found to be 9°.
また、実施例１と同様良好な立ち上かりとコントラスト
が観察された。Further, as in Example 1, good rise and contrast were observed.
実施例７
実施例２において実施例１と同様にして得た反応液にジ
アミンに対して１ｍｏ１％のγ−アミノプロピルトリエ
トキシシランを添加して実施例１と同様の操作を行いプ
レチルト角を測定したところ、１５°てあった。また、
実施例１と同様良好、な立ち上がりとコントラストが観
察された。Example 7 In Example 2, 1 mo 1% of γ-aminopropyltriethoxysilane was added to the diamine to the reaction solution obtained in the same manner as in Example 1, and the same operation as in Example 1 was performed to measure the pretilt angle. When I did that, it was 15 degrees. Also,
As in Example 1, good rise and contrast were observed.
実施例８
Ｎ、Ｎ−ジメチルアセトアミド５９部に化合物Ｎｏ、１
３のジアミン９．５２部および４４′ジアミノジフエニ
ルエーテル０．８部を溶解し、窒素雰囲気下、無水ピロ
メリト酸４，３６部を加え２０〜３０℃で２４時間反応
させた。得られたポリアミド酸の溶液にＮ、Ｎ−ジメチ
ルアセトアミドを加え５重量％の溶液を調製して液晶配
向膜用組成物とした。この組成物を用いて実施例１と同
様にして、ポリイミド被膜を得て、さらに液晶表示装置
を作成し、プレチルト角を測定したところ、２５６であ
った。また、実施例１と同様良好な立ち上がりとコント
ラストが観察された。Example 8 Compound No. 1 was added to 59 parts of N,N-dimethylacetamide.
9.52 parts of the diamine No. 3 and 0.8 parts of 44' diaminodiphenyl ether were dissolved, and 4.36 parts of pyromellitic anhydride was added under a nitrogen atmosphere, followed by reaction at 20 to 30°C for 24 hours. N,N-dimethylacetamide was added to the obtained polyamic acid solution to prepare a 5% by weight solution to prepare a composition for a liquid crystal alignment film. Using this composition, a polyimide film was obtained in the same manner as in Example 1, and a liquid crystal display device was prepared.The pretilt angle was measured and found to be 256. Also, similar to Example 1, good rise and contrast were observed.
実施例２において、化合物２のジアミンのかわりに、４
．４’ −ジアミノジフェニルエーテルを用いて、実施
例２と同様の操作を行いプレチルト角を測定したところ
、２°であった。In Example 2, instead of the diamine of compound 2, 4
．． The same operation as in Example 2 was carried out using 4'-diaminodiphenyl ether, and the pretilt angle was measured to be 2°.
本発明の液晶配向膜用組成物を配向制御に用いることに
より、コントラストおよび視覚特性の優れた表示装置を
得ることができる。By using the composition for a liquid crystal alignment film of the present invention for alignment control, a display device with excellent contrast and visual characteristics can be obtained.
以上that's all
Claims (1)
または無置換のアゾベンゼン基であり、Ｒ＿３はアルキ
ル基、アルコキシ基、またはハロゲン原子であり、Ｘは
アルキル基、Ｏ、Ｓ、▲数式、化学式、表等があります
▼、▲数式、化学式、表等があります▼、▲数式、化学
式、表等があります▼、▲数式、化学式、表等がありま
す▼、ＮＲ＿４（Ｒ＿４は水素原子又はアルキル基）、
▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼の１種または２種以上よりなる鎖状置
換基であり、ｎは正の整数を示す。）で表わされるポリ
アミド酸を含有することを特徴とする液晶配向膜用組成
物。[Claims] General formula (I) ▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R_1 is an aromatic ring or alicyclic ring, R_2 is a substituted or unsubstituted azobenzene group, and R_3 is an alkyl group, alkoxy group, or halogen atom, and X is an alkyl group, O, S, ▲ There are mathematical formulas, chemical formulas, tables, etc. There are ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, NR_4 (R_4 is a hydrogen atom or an alkyl group),
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
It is a chain substituent consisting of one or more types of ▼, and n represents a positive integer. ) A composition for a liquid crystal alignment film, characterized by containing a polyamic acid represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11847590A JP2852789B2 (en) | 1990-05-08 | 1990-05-08 | Composition for liquid crystal alignment film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11847590A JP2852789B2 (en) | 1990-05-08 | 1990-05-08 | Composition for liquid crystal alignment film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0414020A true JPH0414020A (en) | 1992-01-20 |
| JP2852789B2 JP2852789B2 (en) | 1999-02-03 |
Family
ID=14737596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11847590A Expired - Lifetime JP2852789B2 (en) | 1990-05-08 | 1990-05-08 | Composition for liquid crystal alignment film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2852789B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0679633A1 (en) * | 1994-04-28 | 1995-11-02 | Nissan Chemical Industries Ltd. | Diaminobenzene derivatives and polyimides prepared therefrom |
| WO2001014457A1 (en) * | 1999-08-24 | 2001-03-01 | Chisso Corporation | Polyamide compounds and liquid crystal aligning agents containing the same |
| CN115197420A (en) * | 2022-05-10 | 2022-10-18 | 复旦大学 | Non-oriented non-bias positive light control photo-deformation azobenzene polyimide film material and preparation method thereof |
-
1990
- 1990-05-08 JP JP11847590A patent/JP2852789B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0679633A1 (en) * | 1994-04-28 | 1995-11-02 | Nissan Chemical Industries Ltd. | Diaminobenzene derivatives and polyimides prepared therefrom |
| CN1077580C (en) * | 1994-04-28 | 2002-01-09 | 日产化学工业株式会社 | Diaminobenzene derivatives and polyimides prepared therefrom |
| WO2001014457A1 (en) * | 1999-08-24 | 2001-03-01 | Chisso Corporation | Polyamide compounds and liquid crystal aligning agents containing the same |
| CN115197420A (en) * | 2022-05-10 | 2022-10-18 | 复旦大学 | Non-oriented non-bias positive light control photo-deformation azobenzene polyimide film material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2852789B2 (en) | 1999-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2857779B2 (en) | Composition for liquid crystal alignment film and liquid crystal device | |
| KR101026662B1 (en) | Material for liquid crystal alignment and liquid crystal displays made by using the same | |
| KR101877826B1 (en) | Producing method of liquid crystal aligning agent | |
| KR100940471B1 (en) | Aligning agent for liquid crystal and liquid-crystal display element | |
| JP5751171B2 (en) | Liquid crystal alignment treatment agent and liquid crystal display element using the same | |
| WO2009084665A1 (en) | Liquid crystal aligning agent and liquid crystal display device using the same | |
| JPH02176631A (en) | Composition for liquid crystal oriented film liquid crystal oriented film and liquid crystal display element | |
| WO2021177080A1 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
| JP2841095B2 (en) | Liquid crystal alignment film and liquid crystal display device | |
| JPH0414020A (en) | Composition for liquid crystal oriented film | |
| JPH07109438A (en) | Polyimide varnish | |
| JP2916786B2 (en) | Composition for liquid crystal alignment film and liquid crystal device | |
| JP5298398B2 (en) | Liquid crystal aligning agent and liquid crystal display device using the same | |
| JP2729618B2 (en) | Liquid crystal element | |
| JP2893790B2 (en) | Liquid crystal alignment film composition, liquid crystal alignment film, method of manufacturing liquid crystal alignment film, liquid crystal sandwiching substrate and liquid crystal display device | |
| JPS6228713A (en) | Ferroelectric liquid crystal element | |
| JPH03164714A (en) | Composition for liquid crystal oriented film, production of the film, the film and liquid crystal display element | |
| JPH075472A (en) | Production of liquid crystal oriented film composition therefor liquid crystal holding substrate, liquid crystal oriented film, and liquid crystal display element | |
| JPH01219719A (en) | Liquid crystal orientation film and liquid crystal display element | |
| JPH0339934A (en) | Composition for liquid crystal oriented film, liquid crystal oriented film, liquid crystal holding substrate and liquid crystal display element | |
| JP2722403B2 (en) | Electro-optic electrode substrate | |
| JP2722234B2 (en) | Liquid crystal alignment film and liquid crystal display device | |
| JPH05249474A (en) | Controlling method for pretilt angle of liquid crystal display element, composition for liquid crystal oriented film, liquid crystal oriented film, supporting substrate for liquid crystal, and liquid crystal display element | |
| JPH0284620A (en) | Composition for liquid crystal oriented film, liquid crystal oriented film and liquid crystal display element | |
| JPH06337424A (en) | Composition for liquid crystal oriented film, manufacture of liquid crystal oriented film, liquid crystal oriented film, liquid crystal sandwiching substrate and liquid crystal display element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081120 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081120 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091120 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091120 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101120 Year of fee payment: 12 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101120 Year of fee payment: 12 |