JPH03248127A - Composition for liquid crystal oriented film - Google Patents
Composition for liquid crystal oriented filmInfo
- Publication number
- JPH03248127A JPH03248127A JP4636490A JP4636490A JPH03248127A JP H03248127 A JPH03248127 A JP H03248127A JP 4636490 A JP4636490 A JP 4636490A JP 4636490 A JP4636490 A JP 4636490A JP H03248127 A JPH03248127 A JP H03248127A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- ring
- composition
- film
- formula
- 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 34
- 239000000203 mixture Substances 0.000 title claims description 21
- 125000001424 substituent group Chemical group 0.000 claims abstract description 12
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 229920005575 poly(amic acid) Polymers 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims 1
- 229920001721 polyimide Polymers 0.000 abstract description 18
- 230000000007 visual effect Effects 0.000 abstract description 5
- 230000018044 dehydration Effects 0.000 abstract description 3
- 238000006297 dehydration reaction Methods 0.000 abstract description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 3
- 239000004952 Polyamide Substances 0.000 abstract 2
- 229920002647 polyamide Polymers 0.000 abstract 2
- 230000035807 sensation Effects 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 9
- 150000004985 diamines Chemical class 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- -1 cyclopentanetetracarboxylic anhydride Chemical class 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 150000004984 aromatic diamines Chemical class 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 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
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur 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
Landscapes
- Liquid Crystal (AREA)
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つ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 forming 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が形成されている。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
所があるが、最近注目されている超ねじれ複屈折効果（
Ｓｕｐｅｒ Ｔｗｉｓｔｅｄ Ｂｉｒｅｒｒｌｎｇｅｎ
ｃｅ Ｅｆｆ’ｅｃｔ： 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かある。これに用いる配向
膜はプレチルト角を高くする必要があるが、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が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,
Examples include polyimide films obtained by dehydrating and ring-closing a liquid crystal alignment film composition comprising a polyamic acid obtained from a reaction of pyromellitic anhydride and 4,4'-diaminodiphenyl ether. This type of polyimide has advantages such as excellent orientation, but has recently attracted attention due to its supertwisted birefringence effect (
Super Twisted Birerrlngen
It is not compatible with liquid crystal display devices that use ce 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 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
生じ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 reducing productivity, making it impossible to satisfy the contrast and visual characteristics required for an alignment film.
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、プレチルト角が低いと考え、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. Considering that conventional polyimide films have a low pretilt angle because they have a planar structure, we investigated compositions for liquid crystal alignment films in order to create a prototype polyimide film in which some of the constituent molecules are 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（Ｉ）
（式中、Ｒ１は芳香環または脂環であり、Ｒ２は側鎖に
１個以上の鎖状置換基を有する芳香環または側鎖に１個
以上の鎖状置換基と、ハロゲン原子とを有する芳香環で
あり、ｎは正の整数を示す。）で表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である
。That is, the present invention is based on the general formula (I) (wherein R1 is an aromatic ring or alicyclic ring, and R2 is an aromatic ring having one or more chain substituents in the side chain or one or more chains in the side chain). A composition for a liquid crystal aligning film, characterized in that it contains a polyamic acid represented by the following: an aromatic ring having a halogen atom and a halogen atom, and n represents a positive integer.
本発明の液晶配向膜組成物は、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 liquid crystal alignment film composition of the present invention mainly consists of the polyamic acid of general formula (I) and an organic solvent capable of dissolving it, and is made into a polyimide film by simultaneously dehydrating and ring-closing the organic solvent and volatilizing the organic solvent.
ここで、一般式（Ｉ）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
．５−トリカルボキシ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−１，１−ジカルボン酸等があげられる。Here, the polyamic acid of general formula (I) will be described in detail. This polyamic acid is obtained by a reaction between an acid anhydride and an aromatic diamine having a chain substituent. Examples of the acid anhydride include pyromellitic anhydride, 3.3' anhydride,
4.4'-biphenyltetracarboxylic acid, anhydride3.
3', 4.4'-benzophenonetetracarboxylic acid, cyclopentanetetracarboxylic anhydride, anhydride 2.3
．． 5-Tricarboxycyclopentyl acetic acid, anhydrous 5-(
Examples include 2,5 dioxotetrahydro-3-furanyl)-3-cyclohexene-1,1-dicarboxylic acid.
鎖状置換基を有する芳香族ジアミンは、一般式（ｎ）
（Ｘ−Ｒ４） Ｎ
／
Ｈ２Ｎ ＲＩ ＮＢ２
（ＩＩ）（式中、Ｒ３は芳香環であり、Ｒ４は鎖状置換
基、Ｘは結合のみか、あるいは炭素、酸素、窒素、イオ
ウの各々またはその組合せからなる官能基であり、１は
１．２．３または４を示す。）で表される化合物である
。The aromatic diamine having a chain substituent has the general formula (n) (X-R4) N/H2N RI NB2
(II) (In the formula, R3 is an aromatic ring, R4 is a chain substituent, X is a bond or a functional group consisting of each of carbon, oxygen, nitrogen, sulfur, or a combination thereof, and 1 is a .2.3 or 4).
一般式（ＩＩ）で表されるジアミンについてさらに詳し
く説明する。Ｒ３の芳香環には他の置換基（アルキル基
、アルコキシ基、ハロゲン原子等）があってもよいベン
ゼン環、ナフタリン環、ビフェニル環等があげられる。The diamine represented by general formula (II) will be explained in more detail. The aromatic ring of R3 includes a benzene ring, a naphthalene ring, a biphenyl ring, etc., which may have other substituents (alkyl group, alkoxy group, halogen atom, etc.).
Ｒ４の鎖状置換基には置換していてもよい直鎖状または
分岐状のアルキル基、アルケニル基、アルキニル基等が
あげられる。これらの置換基としてはアルコキシ基、ハ
ロゲン原子、ヒドロキシ基、アシル基、カルボキシ基、
オキシカルボニル基、アモノ基、アミド基、シアノ基、
ニトロ基、スルホニル基、スルホニルオキシ基、芳香族
基等があげられる。Ｘには、０、Ｓ、ＮＲ５（Ｒ５は水
素原子、アルキル基、アシル基を示す。） 、Ｃ，Ｃ−
０、Ｃ−ＮＲ１０ ０ ０
れ、また芳香環と鎖状置換基が直接結合した結合のみを
も表わす。Examples of the chain substituent for R4 include optionally substituted linear or branched alkyl groups, alkenyl groups, and alkynyl groups. These substituents include alkoxy groups, halogen atoms, hydroxy groups, acyl groups, carboxy groups,
Oxycarbonyl group, amono group, amide group, cyano group,
Examples include nitro group, sulfonyl group, sulfonyloxy group, and aromatic group. X is 0, S, NR5 (R5 represents a hydrogen atom, an alkyl group, or an acyl group), C, C-
0, C-NR10 0 0 and also represents only a bond in which an aromatic ring and a chain substituent are directly bonded.
一般式（ＩＩ）で示される化合物の具体例を下記にあげ
る。なお、化合物Ｎｏ、は実施例においても共通に用い
る。Specific examples of the compound represented by general formula (II) are listed below. Note that compound No. is also commonly used in Examples.
化合物隠 構 造 式 ０式％１３ ） 化合物Ｎへ 構 にミ。Compound hidden structure formula 0 formula%13 ) to compound N Structure Nimi.
式 ％式％） 式 ２ 化合物Ｎｏ。formula %formula%) formula 2 Compound no.
構
埠
式
（
）
化合物磁
構
シミ
式
％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’Ｃ以下の温度で反応させ、ポリ
アミド酸の溶液とする。Shimibo formula ( ) Compound magnetic structure Shimi formula % Formula % One or more of the above acid anhydrides and aromatic diamines having a chain substituent are added in an organic solvent under anhydrous conditions, preferably at 50'C. The reaction is carried out at the following temperature to form a solution of polyamic acid.
ここで用いる有機溶媒には、比較的揮散しゃすく、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 is relatively volatile 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−グリシドキシプロビルトリメ
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. Examples of silane coupling agents include γ-aminopropyltriethoxysilane, N-(βaminoethyl)-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。Diaminosiloxane includes 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane,
Examples include α,ω-bis(3-aminopropyldimethylsilyl)benzene.
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 liquid crystal alignment film composition 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、液晶素子を構成する電極上に
塗布する。塗布後、１００〜４００℃、好ましくは１５
０〜２５０℃で加熱処理して、上記ポリアミド酸を脱水
閉環してポ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、はぼ垂直まで可能となった。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 element by a dip method, a spinner method, a spray method, a printing method, or the like. After coating, 100-400℃, preferably 15
A heat treatment is performed at 0 to 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 pre-tilt angle has been increased, making it possible to go almost vertical.
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
５ＴＢＥ方式の液晶表示装置に適している。The composition for a liquid crystal alignment film containing a polyamic acid of the present invention is suitable for a 5TBE type liquid crystal display device.
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、１
のジアミン３．７７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、Ｉ
ＴＯの透明ガラス電極（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. 1 was added to 64 parts of N,N-dimethylacetamide.
In a nitrogen atmosphere, 2.94 parts of anhydrous 3.3', 4.4'-biphenyltetracarboxylic acid was added thereto in 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 using a spin coater.
It was applied onto a TO transparent glass electrode (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１５６てあった。When the pretilt angle was measured, it was 156.
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。When voltage was applied to this device and the rise characteristics and contrast were observed, they were extremely good.
実施例２〜１９
実施例１において使用した化合物Ｎｏ、１のジアミン、
酸無水物および溶媒の代わりに表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。Examples 2 to 19 Compound No. 1 diamine used in Example 1,
The same operation as in Example 1 was carried out using the substances shown in Table 1 instead of the acid anhydride and solvent, and the pretilt angle was measured.
その結果を表１に示す。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。The results are shown in 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３，３′４．４′−ベンゾ
フェノンテトラカルポン酸、ＣＰＤＡは無水シクロペン
タンテトラカルボン酸、ＤＭＡはＮ、Ｎ−ジメチルアセ
トアミド、ＮＭＰはＮ−メチルピロリドンを示す。In addition, PMDA in Table 1 is pyromellitic anhydride, BP
DA is 3.3',4.4'-biphenyltetracarboxylic anhydride, BZDA is 3,3'4,4'-benzophenonetetracarboxylic anhydride, CPDA is cyclopentanetetracarboxylic anhydride, DMA is N,N -dimethylacetamide, NMP indicates N-methylpyrrolidone.
表１
実施例２Ｏ
Ｎ、 Ｎ−ジメチルアセトアミド６４部に化合物Ｎｏ、
１のジアミン３．７３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１ｍｏ １％）を溶
解し、窒素雰囲気下、無水ピロメリト酸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。Table 1 Example 2O N, Compound No. 64 parts of N-dimethylacetamide,
3.73 parts of diamine No. 1 and 0.025 parts of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (1 mo 1% of the total diamine) were dissolved in a nitrogen atmosphere. Then, 2.94 parts of pyromellitic anhydride was added and reacted at 20 to 30°C for 24 hours. Add N,N-dimethylacetamide to the obtained polyamic acid solution.
A solution of % by weight was prepared and used as a composition for 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、１７＠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 17@.
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。Also, similar to Example 1, good rise and contrast were observed.
実施例２１
実施例１９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１ｍｏ １％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、２０°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 21 In Example 19, 1 mo of 1% γ-aminopropyltriethoxysilane with respect to the diamine was added to the reaction solution obtained in the same manner as in Example 1, and the same operation as in Example 1 was performed to adjust the pretilt angle. When measured, it was 20°. Also, similar to Example 1, good rise and contrast were observed.
実施例２２
Ｎ、 Ｎ−ジメチルアセトアミド４３部に化合物Ｎｏ、
２０のジアミン５．７部および４．４−ジアミノジフェ
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、１５’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 22 Compound No. 43 parts of N,N-dimethylacetamide,
5.7 parts of diamine No. 20 and 0.8 parts of 4,4-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 coating was obtained in the same manner as in Example 1, and a liquid crystal display device was also produced.The pretilt angle was measured and found to be 15'. 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で、実棒ｊＮ、
ニニ司項、二擾ｉ＝を・２□、−二４”シト角を測定し
たところ、２″であった。In Example 2, instead of the diamine of compound 2, 4
．． Using 4-diaminodiphenyl ether, the actual rod jN,
When the angle was measured, it was 2''.
Ｃ発明の効果〕
、本発明の液晶配向膜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。C Effects of the Invention] By using the liquid crystal alignment film composition 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)
鎖に１個以上の鎖状置換基を有する芳香環または側鎖に
１個以上の鎖状置換基と、ハロゲン原子とを有する芳香
環であり、ｎは正の整数を示す。）で表されるポリアミ
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) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 is an aromatic ring or alicyclic ring, and R_2 has one or more chain substitutions in the side chain. An aromatic ring having a group or an aromatic ring having one or more chain substituents and a halogen atom in the side chain, and n is a positive integer) characterized by containing a polyamic acid represented by A composition for a liquid crystal alignment film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4636490A JP2916786B2 (en) | 1990-02-27 | 1990-02-27 | Composition for liquid crystal alignment film and liquid crystal device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4636490A JP2916786B2 (en) | 1990-02-27 | 1990-02-27 | Composition for liquid crystal alignment film and liquid crystal device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03248127A true JPH03248127A (en) | 1991-11-06 |
| JP2916786B2 JP2916786B2 (en) | 1999-07-05 |
Family
ID=12745102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4636490A Expired - Lifetime JP2916786B2 (en) | 1990-02-27 | 1990-02-27 | Composition for liquid crystal alignment film and liquid crystal device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2916786B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008013501A (en) * | 2006-07-06 | 2008-01-24 | Jsr Corp | Novel diamine compound and method for preparing the same |
| JP2009265538A (en) * | 2008-04-30 | 2009-11-12 | Jsr Corp | Liquid crystal aligning agent and liquid crystal display element |
| CN115947663A (en) * | 2022-12-21 | 2023-04-11 | 中国科学院长春应用化学研究所 | Diamine monomer, polyimide material, preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5048742B2 (en) * | 2009-11-06 | 2012-10-17 | 株式会社ジャパンディスプレイイースト | Liquid crystal display |
-
1990
- 1990-02-27 JP JP4636490A patent/JP2916786B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008013501A (en) * | 2006-07-06 | 2008-01-24 | Jsr Corp | Novel diamine compound and method for preparing the same |
| JP2009265538A (en) * | 2008-04-30 | 2009-11-12 | Jsr Corp | Liquid crystal aligning agent and liquid crystal display element |
| CN115947663A (en) * | 2022-12-21 | 2023-04-11 | 中国科学院长春应用化学研究所 | Diamine monomer, polyimide material, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2916786B2 (en) | 1999-07-05 |
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