JPH0339934A - Composition for liquid crystal oriented film, liquid crystal oriented film, liquid crystal holding substrate and liquid crystal display element - Google Patents
Composition for liquid crystal oriented film, liquid crystal oriented film, liquid crystal holding substrate and liquid crystal display elementInfo
- Publication number
- JPH0339934A JPH0339934A JP32435789A JP32435789A JPH0339934A JP H0339934 A JPH0339934 A JP H0339934A JP 32435789 A JP32435789 A JP 32435789A JP 32435789 A JP32435789 A JP 32435789A JP H0339934 A JPH0339934 A JP H0339934A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- alignment film
- composition
- crystal alignment
- oriented 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.)
- Granted
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 97
- 239000000758 substrate Substances 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title claims description 18
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims abstract description 27
- 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 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- 229920005575 poly(amic acid) Polymers 0.000 claims description 24
- -1 diamine compound Chemical class 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 150000004985 diamines Chemical class 0.000 abstract description 2
- 239000004952 Polyamide Substances 0.000 abstract 2
- 229920002647 polyamide Polymers 0.000 abstract 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 26
- 239000004642 Polyimide Substances 0.000 description 12
- 229920001721 polyimide Polymers 0.000 description 12
- 210000002858 crystal cell Anatomy 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-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
- UWCWUCKPEYNDNV-LBPRGKRZSA-N 2,6-dimethyl-n-[[(2s)-pyrrolidin-2-yl]methyl]aniline Chemical compound CC1=CC=CC(C)=C1NC[C@H]1NCCC1 UWCWUCKPEYNDNV-LBPRGKRZSA-N 0.000 description 2
- IFECJVCGOCKABU-UHFFFAOYSA-N 4-[(3,4-dicarboxybenzoyl)oxy-diphenylsilyl]oxycarbonylphthalic acid Chemical compound C(=O)(O)C=1C=C(C(=O)O[Si](C2=CC=CC=C2)(C2=CC=CC=C2)OC(C2=CC(=C(C=C2)C(=O)O)C(=O)O)=O)C=CC1C(=O)O IFECJVCGOCKABU-UHFFFAOYSA-N 0.000 description 2
- XZOQPRNOAGCWNT-UHFFFAOYSA-N 4-[[(3,4-dicarboxyphenyl)-dimethylsilyl]oxy-dimethylsilyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1[Si](C)(C)O[Si](C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 XZOQPRNOAGCWNT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- HNHQPIBXQALMMN-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)-dimethylsilyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1[Si](C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 HNHQPIBXQALMMN-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- NOGAGTWFYUBTQF-UHFFFAOYSA-N 4-[[(3,4-dicarboxyphenyl)-diphenylsilyl]oxy-diphenylsilyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[Si](C=1C=C(C(C(O)=O)=CC=1)C(O)=O)(C=1C=CC=CC=1)C1=CC=CC=C1 NOGAGTWFYUBTQF-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing 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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (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用組成物、これを用いた液晶配向膜
。液晶挾持基板および液晶表示素子に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a composition for a liquid crystal alignment film, and a liquid crystal alignment film using the same. The present invention relates to a liquid crystal holding substrate and a liquid crystal display element.
（従来の技術） 従来９大型デイスプレィ用液晶表示素子には。(Conventional technology) Conventional 9 liquid crystal display elements for large displays.
視覚特性をよくするために５ＴＮ（スーパーツィステッ
ドネマチック）方式が用いられている。これはセル内で
の液晶分子の長軸方向が２６０〜２７０°ねじれた方式
（２６０〜２７０°ツイスト・）である。これらの８Ｔ
Ｎ方式素子の配向膜には、液晶分子と、配向膜が形成さ
れているガラス基板のなす角度（プレチルト角）が、７
°以上となる材料が必要６６る。しかし、従来のポリイ
ミド系配向膜では前記プレチルト角を７°以上とする仁
とができなかった。A 5TN (super twisted nematic) system is used to improve visual characteristics. This is a method in which the long axis direction of the liquid crystal molecules within the cell is twisted by 260 to 270 degrees (260 to 270 degrees twist). These 8T
In the alignment film of the N-type element, the angle (pretilt angle) between the liquid crystal molecules and the glass substrate on which the alignment film is formed is 7.
A material with a temperature of at least 66° is required. However, with conventional polyimide alignment films, it has not been possible to achieve a pretilt angle of 7° or more.
（発明が解決しようとする課題） 本発明の目的は、前記従来技術の問題を解決し。(Problem to be solved by the invention) The object of the present invention is to solve the problems of the prior art.
プレチルト角を７°以上とすることができる液晶配向膜
用組成物、これを用いた液晶配向膜、液晶挾持基板およ
び液晶表示素子を提供することにある。It is an object of the present invention to provide a composition for a liquid crystal alignment film that can have a pretilt angle of 7° or more, a liquid crystal alignment film using the composition, a liquid crystal holding substrate, and a liquid crystal display element.
（課題を解決するための手段）
本発明者らは、前記従来技術の問題に鑑み、鋭意研究し
た結果、ポリアミド酸溶液中にテトラカルボン酸を含ん
でなる組成物を用いて液晶配向膜を形成するとプレチル
ト角が７°以上となることを見出し１本発明に到達した
、
すなわち１本発明は、ジアミン化合物１よびテトラカル
ボン酸二無水物を溶媒中で反応させで得られるポリアミ
ド酸溶液中に一般式＋１）（式中、Ｉ（、￥ｉ４価の炭
化水素基筐ｆｒ、、はシリコンおよび／もしくはシロキ
サン結合を含む炭化水素基を意味する）で表されるテト
ラカルボン酸を含せせてなる液晶配向膜用組成物ならび
に該液晶配向膜用組成物から形成された液晶配向膜、こ
の液晶配向膜の形成された液晶挾持基板および該液晶挟
持基板を有する液晶表示素子に関するものである。(Means for Solving the Problems) In view of the problems of the prior art described above, the present inventors have conducted extensive research, and as a result, formed a liquid crystal alignment film using a composition containing a tetracarboxylic acid in a polyamic acid solution. Then, they discovered that the pretilt angle was 7° or more, and arrived at the present invention. That is, the present invention is a method for producing a polyamic acid solution obtained by reacting a diamine compound 1 and a tetracarboxylic dianhydride in a solvent. A liquid crystal containing a tetracarboxylic acid represented by formula +1) (in the formula, I (, ¥i tetravalent hydrocarbon group fr,, means a hydrocarbon group containing silicon and/or siloxane bond) The present invention relates to a composition for an alignment film, a liquid crystal alignment film formed from the composition for a liquid crystal alignment film, a liquid crystal holding substrate on which the liquid crystal alignment film is formed, and a liquid crystal display element having the liquid crystal holding substrate.
本発明に用いられる前記一般式ｍで表されるテトラカル
ボン酸としては、ビロメリント酸、３．３：４゜４’
−ジフェニルテトラカルボン酸、３，３：４，４゛−ベ
ンゾフェノンテトラカルボン酸、ａ、３：ｔ４′−ジシ
クロ−＼キシルテトラカルボン酸、１．３−ビス（３，
４−ジカルボキシフェニル） −ｉ、 ｉ、 ３． ａ
−テトラメチルジシロキサン、ビス（３，４−ジカルボ
キシフェニル）−ジメチルシラン、下記の一般式ｔｕｔ
で表されるテトラカルボン酸などが挙げられ、これらＦ
ｉ１種唸たは２種以上併用して使用することができる。The tetracarboxylic acid represented by the general formula m used in the present invention includes biromellitic acid, 3.3:4°4'
-diphenyltetracarboxylic acid, 3,3:4,4'-benzophenonetetracarboxylic acid, a,3:t4'-dicyclo-\xyltetracarboxylic acid, 1,3-bis(3,
4-dicarboxyphenyl) -i, i, 3. a
-tetramethyldisiloxane, bis(3,4-dicarboxyphenyl)-dimethylsilane, the following general formula tut
These F
One type can be used or two or more types can be used in combination.
−紋穴ｔＵ）
（式中、 ＡｒｌおよびＡｒｃは芳香族基、 Ｒｌｔ
Ｒ１，Ｒ３しよびＲ４け炭素数１〜ｉ−Ｏｆでのアルキ
ル基、炭素数１〜１０−？での置換アルキル基！たは芳
香族基、Ｘｌおよびｘ、Ｆｉ −ｃ−ｏ−筐たば１
筐での整数を示すＬ’ｓ Ｃは０または１．ｂは０″
またＨｌから５″＆での整数を示す）で表されるテトラ
カルボン酸を用いることが好オしい。- Monana tU) (wherein, Arl and Arc are aromatic groups, Rlt
R1, R3 and R4 are an alkyl group having 1 to 1 carbon atoms and 1 to 10 carbon atoms? Substituted alkyl group with! or aromatic group, b is 0''
Further, it is preferable to use a tetracarboxylic acid represented by 5''& representing an integer from H1.
本発明に用いられる前記−紋穴（ＩＩ）で表されるテト
ラカルボン酸としては、１．３−ビス（よ４−ジカルボ
キシフェニル）−１，１，３，３−テトラメチルジシロ
キサン、１．３−ビス（３，４−ジカルボキシフェニル
） −１，Ｌ ３．３−テトラエチルジシロキサン、１
．３−ビス（３，４−ジカルボキシフェニル）−１，１
，３，３−テトラフエニルジシロキサン）、１゜３−ビ
ス（３−（３，４−ジカルボキシベンゾイルオキシ）プ
ロピルｌ −１，１，３，３−テトラメチルジシロキサ
ン、１，３−ビス（２−（３，４−ジカルポキシベンゾ
イルオキシ）エチルｌ−１，１，３，３−テトラメチル
ジシロキサン、１．３−ビス（５−（３゜４−ジカルボ
キシベンゾイルオキシ）ペンチル）−１，１，：％ ３
−テトラメチルジシロキサン、１．３−ビス（３−（ａ
４−ジカルボキシベンゾイルオキシ）プロピル） −１
，１，３，３−テトラフエニルジシロキサン、ビス（３
，４−ジカルボキシベンゾイルオキシ）ジフェニルシラ
ン、ビス（ａ４−ジカルボキシベンゾイルオキシ）ジメ
チルシラン、ビス（３，４−ジカルボキシベンゾイルオ
キシ）エチルメチルシラン、ｌｌ３−ビス（３，４−ジ
カルボキシフェニル）−１，３−ジメチル−１，３−ジ
エチルジシロキサン、１，３−ビス（３，４−ジカルボ
キシフェニル ） −１゜１．３． ＆ ５．５−ヘキ
サメチルトリシロキサン、１．３−ビス（３，４−ジカ
ルボキシフェニル） −Ｌ Ｌ ”＋ ”’＋ ５＋
５＋ ７＋ ７ ＃クタメチルテトラシロキサン、１
．３−ビス（３，４−ジカルボキシフェニル） −１，
１，３，ａ ５．５．７．７．９．９−デカメチルペン
タシロキサン、１．３−ビス（ａ４−ジカルボキシ７ｘ
二ｈ ） −１，１，３，：％５，５，７，７，９．９
＋ １１．１１−ドデカメチルヘキサシロキサンなどが
挙げられ、これらは１種または２種以上併用して使用す
ることができる。Examples of the tetracarboxylic acid represented by the above-mentioned -Momona (II) used in the present invention include 1,3-bis(yo4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane, 1 .3-bis(3,4-dicarboxyphenyl)-1,L 3.3-tetraethyldisiloxane, 1
．． 3-bis(3,4-dicarboxyphenyl)-1,1
, 3,3-tetraphenyldisiloxane), 1゜3-bis(3-(3,4-dicarboxybenzoyloxy)propyl l-1,1,3,3-tetramethyldisiloxane, 1,3- Bis(2-(3,4-dicarpoxybenzoyloxy)ethyl l-1,1,3,3-tetramethyldisiloxane, 1,3-bis(5-(3゜4-dicarboxybenzoyloxy)pentyl) -1,1,:%3
-tetramethyldisiloxane, 1,3-bis(3-(a
4-dicarboxybenzoyloxy)propyl) -1
, 1,3,3-tetraphenyldisiloxane, bis(3
,4-dicarboxybenzoyloxy)diphenylsilane, bis(a4-dicarboxybenzoyloxy)dimethylsilane, bis(3,4-dicarboxybenzoyloxy)ethylmethylsilane, ll3-bis(3,4-dicarboxyphenyl) -1,3-dimethyl-1,3-diethyldisiloxane, 1,3-bis(3,4-dicarboxyphenyl) -1゜1.3. & 5.5-hexamethyltrisiloxane, 1.3-bis(3,4-dicarboxyphenyl) -LL ”+ ”'+ 5+
5+ 7+ 7 #cutamethyltetrasiloxane, 1
．． 3-bis(3,4-dicarboxyphenyl) -1,
1,3,a 5.5.7.7.9.9-decamethylpentasiloxane, 1,3-bis(a4-dicarboxy7x
2h) -1,1,3,:%5,5,7,7,9.9
+11.11-Dodecamethylhexasiloxane and the like can be mentioned, and these can be used alone or in combination of two or more.
本発明に用いられるポリアミド酸は、ジアミン化合物お
よびテトラカルボン酸二無水物を溶媒中で反応させて得
られるものであれば特に制限はない。The polyamic acid used in the present invention is not particularly limited as long as it can be obtained by reacting a diamine compound and a tetracarboxylic dianhydride in a solvent.
ジアミン化合物としては２例えばｍ−フェニレンジアミ
ン、ｐ−フェニレンジアミン、４．４′−ジアミノジフ
ェニルエーテル、４．４’−ジアミノジフェニル・メタ
ン＊３＋３’−ジメチルー４．４′−ジアミノジフェニ
ルメタン、３．３’５．５’−テトラメチル４，４′な
一ジアミノジフェニルメタン、２．２−ビス（４−アミ
ノフェニル）プロパン、４．４’−ジアミノジフェニル
スルフィド、４．４’−ジアミノジフェニルスルホン、
１．５−ジアミノナフタレン、２．６−ジアミノナフタ
レン、２．２−ビス（４−アミノフェノキシフェニル）
フロパン、 ２．２−ビス（４−アミノフェノキシフ
ェニル） −１，１，１，３，３，３，−ヘキサフルオ
ロプロパン、１．３−ビスアミノプロピル−１，１，３
，３−テトラメチルジシロキサン、ビス（４−（３−７
ミノフエノキシ）フェニル）スルホン、１，３−ジアミ
ノ−２，３，５，６−チトラメチルベンゼン、９．９−
ビス（４−アミノフェニル）フルオレン、９．９−ビス
（４−アミノフェニル）アントラセン（Ｉ０）、＆３’
−ジアミノジフェニルスルホン、４．４′−ジアミノジ
フェニルエーテル−３−カルボンアミド、１．４−ジア
ミノシクロヘキサン、１．６−ジアミノヘキサン、１，
７−ジアミノへブタン、１，８−ジアミノオクタン、１
．９−ジアミノノナン、１．１０−ジアミノデカン、１
．１１−ジアミノウンデカン、１．１２−ジアミノドデ
カンなどが挙げられ、これらは２種以上を併用すること
もできる。Examples of diamine compounds include m-phenylenediamine, p-phenylenediamine, 4.4'-diaminodiphenyl ether, 4.4'-diaminodiphenyl methane*3+3'-dimethyl-4.4'-diaminodiphenylmethane, 3.3'5.5'-tetramethyl4,4' monodiaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone,
1.5-diaminonaphthalene, 2.6-diaminonaphthalene, 2.2-bis(4-aminophenoxyphenyl)
Furopane, 2.2-bis(4-aminophenoxyphenyl)-1,1,1,3,3,3,-hexafluoropropane, 1.3-bisaminopropyl-1,1,3
, 3-tetramethyldisiloxane, bis(4-(3-7
Minophenoxy)phenyl)sulfone, 1,3-diamino-2,3,5,6-titramethylbenzene, 9.9-
Bis(4-aminophenyl)fluorene, 9.9-bis(4-aminophenyl)anthracene (I0), &3'
-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether-3-carbonamide, 1,4-diaminocyclohexane, 1,6-diaminohexane, 1,
7-Diaminohebutane, 1,8-diaminooctane, 1
．． 9-diaminononane, 1.10-diaminodecane, 1
．． Examples include 11-diaminoundecane and 1,12-diaminododecane, and two or more of these can also be used in combination.
またテトラカルボン酸二無水物としては６例えばピロメ
リット酸二無水物、３．３’、４．４’−ジフェニルテ
トラカルボン酸二無水物、３，３Ｓ４．４′−ベンゾフ
ェノ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、１，２，５．６−
ナフタレンテトラカルボン酸二無水物、２．２Ｓ＆３′
−ジフェニル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、ビス（ａ４
−ジカルボキシフェニル）エーテル二無水物。３．３′
、４４′−ジシクロへキシルテトラカルボン酸二無水物
などが挙げられ、これらは２種以上を併用することもで
きる。Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 3.3',4.4'-diphenyltetracarboxylic dianhydride, and 3,3S4.4'-benzophenonetetracarboxylic dianhydride. , 2,3,6.7-naphthalenetetracarboxylic dianhydride, 1,2,5.6-
Naphthalenetetracarboxylic dianhydride, 2.2S &3'
-diphenyltetracarboxylic dianhydride, 3,4°9.
10-perylenetetracarboxylic dianhydride, bis(a4
-dicarboxyphenyl)ether dianhydride. 3.3'
, 44'-dicyclohexyltetracarboxylic dianhydride, etc., and two or more of these can also be used in combination.
また前記反応溶媒には１例えばＮ−メチル−２−ピロリ
ドン、Ｎ、Ｎ−ジメチルホルムアミドＩ ＮｌＮ−ジエ
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、テトラメチルスルホン、１，４−ジ
オキサンなどが用いられる。Examples of the reaction solvent used include N-methyl-2-pyrrolidone, N,N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, tetramethylsulfone, and 1,4-dioxane. .
本発明の液晶配向膜用組成物は、前記反応によって得ら
れたポリアミド酸溶液に前記−紋穴ｆ１．）で表される
テトラカルボン酸、好渣しくは前記一般式（ＩＩＩで表
されるテトラカルボン酸を添加し、充分混合することに
よって得られる。該一般式（Ｉ）で表されるテトラカル
ボン酸、好１しくは前記−紋穴＋Ｉｌｌで表されるテト
ラカルボン酸の添加量は、液晶配向膜の成膜性の点から
、全ポリアミド酸に対して０．０５〜４０重量優が好１
しく、よジ好１しくは０．５〜２０重量係である。The composition for a liquid crystal alignment film of the present invention is prepared by adding the -patterned hole f1 to the polyamic acid solution obtained by the reaction. ), preferably by adding the tetracarboxylic acid represented by the general formula (III) and mixing thoroughly.Tetracarboxylic acid represented by the general formula (I) , Preferably, the added amount of the tetracarboxylic acid represented by the above-mentioned -Moonhole+Ill is preferably 0.05 to 40% by weight based on the total polyamic acid from the viewpoint of film formability of the liquid crystal alignment film.
It is preferably 0.5 to 20% by weight.
液晶配向膜用組成物は、加熱（例えば１００〜４００℃
）および／または化学的処理（例えば無水酢酸処理）に
よってポリアミド酸が脱水閉環され、テトラカルボン酸
を自んだポリイミドとなる。The composition for liquid crystal alignment film is heated (for example, 100 to 400°C
) and/or chemical treatment (for example, acetic anhydride treatment), the polyamic acid is dehydrated and ring-closed to become a polyimide containing tetracarboxylic acid.
本発明のテトラカルボン酸を含む液晶配向膜用組成物は
６例、（ば２あらかじめＩ ＴＯ（Ｉｎｄｉ、ｕｍＴｉ
ｎ Ｑｘｉｄｅ ）等の透明電極が形成されたガラス基
板上に塗布され、ポリアミド酸を乾燥、脱水閉環させ、
ラビングされてテトラカルボン酸を含んだポリイミド系
配向膜とされる。Six examples of the composition for liquid crystal alignment film containing the tetracarboxylic acid of the present invention were prepared using ITO (Indi, umTi) in advance.
The polyamic acid is dried, dehydrated, and ring-closed.
It is rubbed to form a polyimide alignment film containing tetracarboxylic acid.
塗布方法としては、浸ａ：法、印刷法、吹付は法等の方
法が用いられる。脱水閉環温度は１５０〜４００℃、好
ましくは１５０〜３００℃の範囲で任意に選択すること
ができる。普た加熱時間は１分〜６時間、好１しくは】
９〜３時間とされる。As a coating method, methods such as a dipping method, a printing method, and a spraying method are used. The dehydration ring closure temperature can be arbitrarily selected within the range of 150 to 400°C, preferably 150 to 300°C. The heating time is 1 minute to 6 hours, preferably]
It is said to be 9 to 3 hours.
該ポリイミド系配向膜の形成にＦｉ９ ガラス基板とポ
リイミド層との密着性をよくするために、こ０間にシラ
ンカップリング剤、チタンカンプリング剤等の接着助剤
を用いてもよい。In order to improve the adhesion between the Fi9 glass substrate and the polyimide layer in forming the polyimide alignment film, an adhesion aid such as a silane coupling agent or a titanium compacting agent may be used between the layers.
このようにして形成されたテトラカルボン酸ヲ含むポリ
イミド層は９表面をラビングすることによって液晶配向
膜として用いられる。該液晶配向膜を有する液晶挟持基
板を用いて公知の方法によう液晶表示素子を得ることが
できる。The thus formed polyimide layer containing tetracarboxylic acid is used as a liquid crystal aligning film by rubbing the surface thereof. A liquid crystal display element can be obtained by a known method using the liquid crystal sandwiching substrate having the liquid crystal alignment film.
本発明の液晶配向膜用組成物を用いて得られる液晶妃向
膜＃ｔ、２６０〜２７０°のツイスト角を有するＳ Ｔ
Ｎ方式の液晶表示表子に特に適している。Liquid crystal alignment film #t obtained using the composition for liquid crystal alignment film of the present invention, ST having a twist angle of 260 to 270°
It is particularly suitable for N-type liquid crystal display panels.
（実施例） 以下９本発明を実施例によシ説明する。な釦。(Example) The present invention will be explained below using nine examples. A button.
−２−ピロリドン（以下ＮＭＰと略称する。）溶液ＬＱ
−１＆ＯＯ（日立化成工業社製商品名）１５０、！９９
に、１．３− ビス（３，４−ジカルボキシフェニル）
−１，１，３，３−テトラメチルジシロキサン３．７
５９を添加し、充分攪拌してテトラカルボン酸を含んだ
ポリアミド酸溶液を調製した。-2-pyrrolidone (hereinafter abbreviated as NMP) solution LQ
-1&OO (product name manufactured by Hitachi Chemical Co., Ltd.) 150,! 99
, 1,3-bis(3,4-dicarboxyphenyl)
-1,1,3,3-tetramethyldisiloxane 3.7
59 was added and thoroughly stirred to prepare a polyamic acid solution containing tetracarboxylic acid.
この溶液をＮＭＰによりｉ固形分を５％に希釈した後、
２枚のＩＴＯ透明電極付ガラス基板上にスピンナー塗布
し、２５０℃で１時間加熱し、溶媒の除去卦よびポリア
ミド酸の脱水閉環を行い。After diluting this solution with NMP to a solid content of 5%,
It was applied with a spinner onto two glass substrates with ITO transparent electrodes and heated at 250°C for 1 hour to remove the solvent and dehydrate and ring-close the polyamic acid.
厚さ５ｏａｋのテトラカルボン酸を含んだポリイミド層
を形成した。２枚のガラス基板上のこの層の表面をラビ
ング処理して液晶配向膜として液晶挾持基板を得、これ
をラビング方向がアンチパラレルになるように２枚のポ
リイミド層を対向させて組合わせ１周りをエポキシ系シ
ール剤Ｅ Ｎ −１０００（日立化成工業社製商品名）
で封止し。A polyimide layer containing tetracarboxylic acid having a thickness of 5 oak was formed. The surfaces of this layer on the two glass substrates are rubbed to obtain a liquid crystal holding substrate as a liquid crystal alignment film, and the two polyimide layers are placed facing each other so that the rubbing directions are antiparallel, and then the combination 1 is assembled. Epoxy sealant E N-1000 (trade name manufactured by Hitachi Chemical Co., Ltd.)
Seal it with.
１８０℃で２時間の加熱硬化後室温で内部に液晶ＺＬＩ
−１１３２（メルク社製商品名）を封入し。After heating and curing at 180℃ for 2 hours, the liquid crystal ZLI is placed inside at room temperature.
-1132 (trade name manufactured by Merck & Co.) is enclosed.
液晶セルを形成した。この液晶セルを液晶ＺＬＩ−１１
３２のＴＮＩ （７１℃）以上の温度である１００℃で
１時間加熱した後、該セルのプレチルト角をレーザー光
を用いて測定したところ、プレチルト角は９．０°であ
り、２７０’ツイストの液晶表示素子用配向膜の必要条
件を満たしていた。A liquid crystal cell was formed. This liquid crystal cell is liquid crystal ZLI-11
After heating for 1 hour at 100°C, which is a temperature higher than the TNI of 32 (71°C), the pretilt angle of the cell was measured using a laser beam, and the pretilt angle was 9.0°, which was 270' It met the requirements for alignment films for liquid crystal display devices.
次に前記溶液を用いて前記と同様の方法で６４０Ｘ２０
０ドツトになるようにＩＴＯ透明電極が形成された基板
上にテトラカルボン酸を含んだポリイミド層を形成し、
この層の表面をラビング処理し、上記と同様にして２７
００ツイストになるようにセルを組み立てて室温で上記
液晶にカイラル剤８−８１１（メルク社製）を添加し調
整した液晶を封入し、１００℃で１時間加熱して液晶表
示表子を形成した。Next, using the above solution, 640×20
A polyimide layer containing tetracarboxylic acid is formed on a substrate on which an ITO transparent electrode is formed so that there are no dots,
The surface of this layer was rubbed and treated in the same manner as above.
A cell was assembled to have a 0.00 twist, and a liquid crystal prepared by adding chiral agent 8-811 (manufactured by Merck & Co., Ltd.) to the above liquid crystal was sealed at room temperature, and heated at 100°C for 1 hour to form a liquid crystal display panel. .
該液晶表示素子は、６４０Ｘ２００ドツトで駆動でき、
ドメイン等の配向不良が発生せず高表示品質であった。The liquid crystal display element can be driven with 640 x 200 dots,
High display quality was achieved with no alignment defects such as domains.
実施例２
芳香族ポリアミド酸樹脂の１４．９％ＮＭＰ溶液ＬＱ−
１８００（日立化成工業社製商品名）１５０．１１９に
１，３−ビス（３，４−ジカルボキシフェニル） −１
，１，３，３−テトラメチルジシロキサン５．４６９を
添加し、充分攪拌してテトラカルボン酸を含んだポリア
ミド酸酢液を調製した。Example 2 14.9% NMP solution of aromatic polyamic acid resin LQ-
1800 (trade name manufactured by Hitachi Chemical Co., Ltd.) 150.119 to 1,3-bis(3,4-dicarboxyphenyl) -1
, 1,3,3-tetramethyldisiloxane (5.469 g) was added thereto and thoroughly stirred to prepare a polyamic acid-acetic acid solution containing tetracarboxylic acid.
この溶液を用いて実施例１と同様な方法で処理して液晶
セルを形成し、１００℃で１時間加熱した後、プレチル
ト角を測定したところ、プレチルト角は９．０°であっ
た。Using this solution, a liquid crystal cell was formed by processing in the same manner as in Example 1, and after heating at 100° C. for 1 hour, the pretilt angle was measured, and the pretilt angle was 9.0°.
さらにこの溶液を用いて実施例１と同様にして液晶表示
素子を形成したが、配向不良は発生せず高表示品質であ
った。Furthermore, a liquid crystal display element was formed using this solution in the same manner as in Example 1, but no alignment defects occurred and the display quality was high.
実施例３
芳香族ポリアミド酸樹脂の１４．９％Ｎ−メチル−２−
ピロリドン（以下ＮＭＰと略称する。）溶液ＬＱ−１８
００（日立化成工業社製商品名）１５０．１５ｓに、１
，３−ビス（３，４−ジカルボキシフェニル）−１，１
，３，３−テトラメチルジシロキサン１．１２９を添加
し、充分攪拌してテトラカルボン酸を含んだポリアミド
酸溶液を調製した。Example 3 14.9% N-methyl-2- of aromatic polyamic acid resin
Pyrrolidone (hereinafter abbreviated as NMP) solution LQ-18
00 (trade name manufactured by Hitachi Chemical Co., Ltd.) 150.15s, 1
,3-bis(3,4-dicarboxyphenyl)-1,1
, 1.129 of 3,3-tetramethyldisiloxane were added thereto and thoroughly stirred to prepare a polyamic acid solution containing tetracarboxylic acid.
この溶液をＮＭＰによシ総固形分を５ｅＩｂに希釈した
後、２枚のＩＴＯ透明透明付極付ラス基板上にスピンナ
ー塗布し、２５０℃で１時間加熱し。This solution was diluted with NMP to a total solid content of 5 eIb, and then applied with a spinner onto two transparent ITO lath substrates with polarized electrodes, and heated at 250° C. for 1 hour.
溶媒の除去によびポリアミド酸の脱水閉環を行い。Dehydration and ring closure of the polyamic acid is performed by removing the solvent.
厚さ５ｏｏＡのテトラカルボン酸を含んだポリイミド層
を形成した。２枚のガラス基板上のこの層の表面をラビ
ング処理し、これをラビング方向がアンチパラレルにな
るように２枚のポリイミド層を対向させて組み合わせ９
周シをエポキシ系シール剤ＥＮ−１０００（日立化成工
業株式会社製商品名）で封止し、内部に液晶ＺＬＩ−１
１３２（メルク社製商品名）を封入し、液晶セルを形成
した。次にこの液晶セルを安定させるためエージング処
理として液晶ＺＬＩ−１１３２のＴＮＩ（７１℃）以上
の温度である１２０℃で１時間加熱した後、プレチルト
角をレーザー光を用いて測定したところ、プレチルト角
は９．５°であＬ ２７０’ツイストの液晶表示素子
用配向膜の必要条件を満たしていた。A polyimide layer containing tetracarboxylic acid having a thickness of 5 ooA was formed. The surfaces of these layers on the two glass substrates are rubbed, and then the two polyimide layers are placed facing each other so that the rubbing directions are antiparallel and combined 9
The periphery is sealed with epoxy sealant EN-1000 (trade name manufactured by Hitachi Chemical Co., Ltd.), and a liquid crystal ZLI-1 is placed inside.
132 (trade name, manufactured by Merck & Co., Ltd.) was sealed to form a liquid crystal cell. Next, in order to stabilize this liquid crystal cell, after heating it for 1 hour at 120°C, which is a temperature higher than the TNI (71°C) of liquid crystal ZLI-1132, as an aging treatment, the pretilt angle was measured using a laser beam. The angle was 9.5°, which satisfied the requirements for an alignment film for a liquid crystal display element with L 270' twist.
次に前記溶液を用いて前記と同様の方法で６４０×２０
０ドツトになるようにＩＴＯ透明電極が形成された基板
上にポリイミド層を形成し、この層の表面を２７０°ツ
イストになるようにラビング処理し、上記と同様にして
２７０°ツイストになるようにセルを組み立てて、室温
で上記液晶にカイラル剤８−８１１（メルク社製）を添
加し調整した液晶を封入し、エージング処理を行って液
晶表示素子を作成した。Next, using the above solution, 640 x 20
A polyimide layer was formed on the substrate on which the ITO transparent electrode was formed so that there were no dots, and the surface of this layer was rubbed so as to have a 270° twist. A cell was assembled, and a liquid crystal prepared by adding chiral agent 8-811 (manufactured by Merck & Co., Ltd.) to the above liquid crystal was sealed at room temperature, and an aging treatment was performed to prepare a liquid crystal display element.
該液晶表示素子は、６４０Ｘ２００ドツトで駆動でき、
ドメイン等の配向不良が発生せずコントラスト良好で高
表示品質であった。The liquid crystal display element can be driven with 640 x 200 dots,
The display quality was high with good contrast and no defective alignment of domains, etc.
実施例４
芳香族ポリアミド酸樹脂の１４゜９％ＮＭＰ溶液ＬＱ−
１８００（日立化成工業社製商品名）１５０．１８９に
、１．３−ビス（３−（よ４−ジカルボキシベンゾイル
オキシ）プロピル） −１，１，３゜３−テトラメチル
ジシロキサン３．３６ｇを添加し。Example 4 14°9% NMP solution of aromatic polyamic acid resin LQ-
1800 (trade name manufactured by Hitachi Chemical Co., Ltd.) 150.189, 3.36 g of 1,3-bis(3-(yo4-dicarboxybenzoyloxy)propyl)-1,1,3°3-tetramethyldisiloxane Add.
充分攪拌してテトラカルボン酸を含んだポリアミド酸溶
液を調製した。A polyamic acid solution containing tetracarboxylic acid was prepared by thorough stirring.
この溶液を用いて実施例３と同様な方法で処理して液晶
セルを形成し、１２０℃で１時間加熱することによυエ
ージング処理した後、プレチルト角を測定したところ、
プレチルト角は８．５°であり２７０°ツイストの液晶
表示素子用配向膜の必要条件を満たしていた。Using this solution, a liquid crystal cell was formed by processing in the same manner as in Example 3, and after aging treatment by heating at 120°C for 1 hour, the pretilt angle was measured.
The pretilt angle was 8.5°, which satisfied the requirements for an alignment film for a 270° twist liquid crystal display element.
さらにこの溶液を用いて実施例３と同様の方法で液晶表
示素子を形成したが、該液晶表示素子は。Furthermore, a liquid crystal display element was formed using this solution in the same manner as in Example 3, but the liquid crystal display element was as follows.
６４０Ｘ２００ドツトで駆動でき、ドメイン等の配向不
良が発生せずコントラスト良好で高表示品質であった。It was possible to drive with 640 x 200 dots, and the display quality was high with good contrast and no alignment defects such as domains.
実施例５
芳香族ポリアミド酸樹脂の１４．９％ＮＭＰ溶液ＬＱ−
１８００（日立化成工業社製商品名）１５０．１９９に
、ビス（３，４−ジカルボキシベンゾイルオキシ）ジフ
ェニルシラン１．１２９℃ｍ加し、充分攪拌してテトラ
カルボン酸を含んだポリアミド酸溶液を調製した。Example 5 14.9% NMP solution of aromatic polyamic acid resin LQ-
To 1800 (trade name manufactured by Hitachi Chemical Co., Ltd.) 150.199, 1.129°C of bis(3,4-dicarboxybenzoyloxy)diphenylsilane was added and stirred thoroughly to form a polyamic acid solution containing tetracarboxylic acid. Prepared.
この溶液を用いて実施例３と同様な方法で処理して液晶
セルを形成し、１２０℃で１時間加熱することにようエ
ージング処理した後、プレチルト角を測定したところ、
プレチルト角Ｆｉ９．３°であり２７０°ツイストの液
晶表示素子用配向膜の必要条件を満たしていた。Using this solution, a liquid crystal cell was formed by processing in the same manner as in Example 3, and after aging treatment by heating at 120°C for 1 hour, the pretilt angle was measured.
The pretilt angle Fi was 9.3°, which satisfied the requirements for an alignment film for a 270° twist liquid crystal display element.
さらにこの溶液を用いて実施例３と同様の方法で液晶表
示素子を形成したが、該液晶表示素子は。Furthermore, a liquid crystal display element was formed using this solution in the same manner as in Example 3, but the liquid crystal display element was as follows.
６４０Ｘ２００ドツトで駆動でき、ドメイン等の配向不
良が発生せずコントラスト良好で高表示品質でめった。It was possible to drive with 640 x 200 dots, and the display quality was high with good contrast and no alignment defects such as domains.
実施例６
芳香族ポリアミド酸樹脂の１４．９％ＮＭＰ溶液ＬＱ−
１８００（日立化成工業社製商品名）１５０．１６ｇグ
、１．３−ビス（３，４−ジカルボキシフェニル）−１
，１，３，３−テトラフエニルジシロキサン２．２４９
を添加し、充分攪拌してテトラカルボン酸を含んだポリ
アミド酸溶液を調製した。Example 6 14.9% NMP solution of aromatic polyamic acid resin LQ-
1800 (trade name manufactured by Hitachi Chemical Co., Ltd.) 150.16 g, 1,3-bis(3,4-dicarboxyphenyl)-1
, 1,3,3-tetraphenyldisiloxane 2.249
was added and sufficiently stirred to prepare a polyamic acid solution containing tetracarboxylic acid.
この溶液を用いて実施ｆ！ｉＩＪ ３と同様な方法で処
理して液晶セルを形成し、１２０℃で１時間加熱するこ
とによりエージング処理し７た後、プレチルト角を測定
したところ、ブＬノチルト角は９．１°テｈ９２７０°
ツイストの液晶表示素子用配向膜の必登条件を満たして
いた。Perform f! using this solution! A liquid crystal cell was formed by processing in the same manner as IJ3, and after aging treatment by heating at 120°C for 1 hour, the pretilt angle was measured and found to be 9.1°. °
It met the requirements for twist alignment films for liquid crystal display devices.
さらにこの溶液を用いて実施例３と同様の方法で液晶表
示素子を形成したが９該液晶表示素子は９６４０Ｘ２０
０ドツトで駆動でき、ドメイン等の配向不良が発生せｆ
′二Ｉントラスト良好で高表示品質であった。Furthermore, using this solution, a liquid crystal display element was formed in the same manner as in Example 3.9 The liquid crystal display element was 9640×20
It can be driven with 0 dots, and alignment defects such as domains do not occur.
The contrast was good and the display quality was high.
比較例１
野香族ポリアミド酸樹脂の１４．９％ＮＭＰ溶液Ｌｑ−
ｔｓｏｏｃｓ立化成工業社製商品名）ｆ：ＮＭＰによシ
総固形分を５多に希釈後、ＩＴＯ透８Ａ電極付ガラス基
板上にスピンナー塗布し１以上！！施例１と同様な方法
で処理して液晶セルを形成し、１００℃で１時間加熱し
ｆｃ後、プレチルト角をし・−ジー光を・用いて測定し
だところ、プレチルト角は５゜５°でめった。Comparative Example 1 14.9% NMP solution of Noko group polyamic acid resin Lq-
tsoocs (manufactured by Rikkasei Kogyo Co., Ltd., product name) f: After diluting the total solid content with NMP to 50%, apply it with a spinner onto a glass substrate with an ITO transparent 8A electrode to 1 or more! ! A liquid crystal cell was formed by processing in the same manner as in Example 1, heated at 100°C for 1 hour, fc, and then measured using a pretilt angle.The pretilt angle was 5°5. It was rare at °.
さらにこの溶液を・用いて実施例１と同様にして液晶表
示素子を形成したが、ドメインが発生した。Furthermore, a liquid crystal display element was formed using this solution in the same manner as in Example 1, but domains were generated.
比較例２
芳香族ポリアミド酸樹脂の１４９％ＮＭＰ溶液ＬＱ−１
８００（日立化成工業社製商品名）をＮＭＰにより総固
形分を５優に希釈した後、２枚のＩＴＯ透明電極付ガラ
ス基板上にスピンナー塗布ｉｙ １以下実施例３と同様
な方法で処理して液晶セルを形成し、１２０℃で１時間
加熱することによりエージング処理した後、プレチルト
角をレーザー光を用いて測定したところ、プレチルト角
は６．０°でめった。Comparative Example 2 149% NMP solution of aromatic polyamic acid resin LQ-1
800 (trade name, manufactured by Hitachi Chemical Co., Ltd.) was diluted to a total solid content of 5% with NMP, and then coated with a spinner on two glass substrates with transparent ITO electrodes in the same manner as in Example 3. A liquid crystal cell was formed, and after aging treatment by heating at 120° C. for 1 hour, the pretilt angle was measured using a laser beam, and the pretilt angle was found to be 6.0°.
さらにこの溶液を用（へ’７：実施例３と同様にして液
晶表示素子を形成したが、ドメインが発生した。Furthermore, using this solution, a liquid crystal display element was formed in the same manner as in Example 3, but domains were generated.
（発明の効果）
本発明の液晶配向膜組成物によれば、プレチルト角が７
°以上となる液晶配向膜を形成することができる。また
この液晶配向膜を有する液晶挾持基板を１史用して２６
０〜２７００ツイストさせた液晶表示素子はドメイン等
の配向不良が発生せず尚い表示品質を有する。(Effect of the invention) According to the liquid crystal alignment film composition of the present invention, the pretilt angle is 7.
It is possible to form a liquid crystal alignment film having a temperature of at least . In addition, the liquid crystal holding substrate having this liquid crystal alignment film was used for 26 days.
A liquid crystal display element twisted by 0 to 2,700 degrees has good display quality without causing alignment defects such as domains.
’Ｈ'H
Claims (1)
溶媒中で反応させて得られるポリアミド酸溶液中に一般
式（ I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒは４価の炭化水素基またはシリコンおよび／
もしくはシロキサン結合を含む炭化水素基を意味する）
で表されるテトラカルボン酸を含ませてなる液晶配向膜
用組成物。２、テトラカルボン酸が一般式（II） ▲数式、化学式、表等があります▼ （式中、Ａｒ＿１およびＡｒ＿２は芳香族基、Ｒ＿１，
Ｒ＿３，Ｒ＿３およびＲ＿４は炭素数１〜１０までのア
ルキル基、炭素数１〜１０までの置換アルキル基または
芳香族基、Ｘ＿１およびＸ＿２は▲数式、化学式、表等
があります▼または ▲数式、化学式、表等があります▼を示し（ｎは１から
１０ま での整数を示す）、ａ，ｃは０または１、ｂは０または
１から５までの整数を示す）で表されるテトラカルボン
酸である請求項１記載の液晶配向膜用組成物。 ３、一般式（ I ）で表されるテトラカルボン酸または
一般式（II）で表されるテトラカルボン酸を全ポリアミ
ド酸に対して０．０５〜４０重量％含ませてなる請求項
１記載の液晶配向膜用組成物。 ４、請求項１，２または３記載の液晶配向膜用組成物か
ら形成された液晶配向膜。 ５、請求項１，２または３記載の液晶配向膜用組成物か
ら形成された液晶配向膜を有する液晶挾持基板。 ６、液晶に面して電極が設けられた液晶挾持基板上に、
請求項１，２または３記載の液晶配向膜用組成物から得
られる液晶配向膜を有する液晶表示素子。[Claims] 1. General formula (I) ▲Mathematical formula, chemical formula, table, etc. are present in the polyamic acid solution obtained by reacting a diamine compound and tetracarboxylic dianhydride in a solvent▼(I) ( In the formula, R is a tetravalent hydrocarbon group or silicon and/or
or a hydrocarbon group containing a siloxane bond)
A composition for a liquid crystal alignment film comprising a tetracarboxylic acid represented by: 2. Tetracarboxylic acid has the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar_1 and Ar_2 are aromatic groups, R_1,
R_3, R_3 and R_4 are alkyl groups with 1 to 10 carbon atoms, substituted alkyl groups or aromatic groups with 1 to 10 carbon atoms, , tables, etc. ▼ (n is an integer from 1 to 10, a, c is 0 or 1, b is 0 or an integer from 1 to 5) A composition for a liquid crystal alignment film according to claim 1. 3. The polyamic acid according to claim 1, which contains 0.05 to 40% by weight of the tetracarboxylic acid represented by the general formula (I) or the tetracarboxylic acid represented by the general formula (II) based on the total polyamic acid. Composition for liquid crystal alignment film. 4. A liquid crystal alignment film formed from the composition for liquid crystal alignment film according to claim 1, 2 or 3. 5. A liquid crystal holding substrate having a liquid crystal alignment film formed from the composition for liquid crystal alignment film according to claim 1, 2 or 3. 6. On the liquid crystal holding substrate with electrodes facing the liquid crystal,
A liquid crystal display element having a liquid crystal alignment film obtained from the composition for liquid crystal alignment film according to claim 1, 2 or 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32435789A JP2943190B2 (en) | 1989-04-14 | 1989-12-14 | Liquid crystal alignment film composition, liquid crystal alignment film, liquid crystal sandwiching substrate and liquid crystal display device |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-95897 | 1989-04-14 | ||
| JP9589789 | 1989-04-14 | ||
| JP32435789A JP2943190B2 (en) | 1989-04-14 | 1989-12-14 | Liquid crystal alignment film composition, liquid crystal alignment film, liquid crystal sandwiching substrate and liquid crystal display device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0339934A true JPH0339934A (en) | 1991-02-20 |
| JP2943190B2 JP2943190B2 (en) | 1999-08-30 |
Family
ID=26437061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32435789A Expired - Lifetime JP2943190B2 (en) | 1989-04-14 | 1989-12-14 | Liquid crystal alignment film composition, liquid crystal alignment film, liquid crystal sandwiching substrate and liquid crystal display device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2943190B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5308525A (en) * | 1991-11-20 | 1994-05-03 | Dow Corning Toray Silicone Co., Ltd. | Electroviscous fluid comprising a base neutralized carboxyaryl group-containing organopolysiloxane polyelectrolyte |
| JP2012254962A (en) * | 2011-05-17 | 2012-12-27 | Shin-Etsu Chemical Co Ltd | Carboxylic acid silyl ester compound having bulky substituent, and method for producing the same |
-
1989
- 1989-12-14 JP JP32435789A patent/JP2943190B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5308525A (en) * | 1991-11-20 | 1994-05-03 | Dow Corning Toray Silicone Co., Ltd. | Electroviscous fluid comprising a base neutralized carboxyaryl group-containing organopolysiloxane polyelectrolyte |
| JP2012254962A (en) * | 2011-05-17 | 2012-12-27 | Shin-Etsu Chemical Co Ltd | Carboxylic acid silyl ester compound having bulky substituent, and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2943190B2 (en) | 1999-08-30 |
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