JPH0423832A - Fluorine-containing polyamide compound and fluorine-containing polyimide compound - Google Patents
Fluorine-containing polyamide compound and fluorine-containing polyimide compoundInfo
- Publication number
- JPH0423832A JPH0423832A JP12961590A JP12961590A JPH0423832A JP H0423832 A JPH0423832 A JP H0423832A JP 12961590 A JP12961590 A JP 12961590A JP 12961590 A JP12961590 A JP 12961590A JP H0423832 A JPH0423832 A JP H0423832A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- group
- liquid crystal
- compound
- polyamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 23
- 239000011737 fluorine Substances 0.000 title claims abstract description 23
- 229920001721 polyimide Polymers 0.000 title claims description 31
- 239000004952 Polyamide Substances 0.000 title claims description 26
- 229920002647 polyamide Polymers 0.000 title claims description 26
- 239000004642 Polyimide Substances 0.000 title claims description 18
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 2
- 125000000962 organic group Chemical group 0.000 claims 1
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 abstract description 19
- 150000000000 tetracarboxylic acids Chemical class 0.000 abstract description 16
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 15
- 150000004985 diamines Chemical class 0.000 abstract description 8
- 239000003960 organic solvent Substances 0.000 abstract description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- 239000000758 substrate Substances 0.000 description 13
- 238000000862 absorption spectrum Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000003949 imides Chemical group 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 229920006122 polyamide resin Polymers 0.000 description 6
- -1 alicyclic tetracarboxylic acids Chemical class 0.000 description 5
- 210000002858 crystal cell Anatomy 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000009719 polyimide resin Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000004988 Nematic liquid crystal Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 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 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- FWOLORXQTIGHFX-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluoroaniline Chemical group FC1=C(F)C(N)=C(F)C(F)=C1C1=C(F)C(F)=C(N)C(F)=C1F FWOLORXQTIGHFX-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- KJLPSBMDOIVXSN-UHFFFAOYSA-N 4-[4-[2-[4-(3,4-dicarboxyphenoxy)phenyl]propan-2-yl]phenoxy]phthalic acid Chemical compound C=1C=C(OC=2C=C(C(C(O)=O)=CC=2)C(O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 KJLPSBMDOIVXSN-UHFFFAOYSA-N 0.000 description 1
- 235000003385 Diospyros ebenum Nutrition 0.000 description 1
- 241000792913 Ebenaceae Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 101100074988 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) nmp-1 gene Proteins 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 108091006629 SLC13A2 Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- GHWVXCQZPNWFRO-UHFFFAOYSA-N butane-2,3-diamine Chemical compound CC(N)C(C)N GHWVXCQZPNWFRO-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- CURBACXRQKTCKZ-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C1C(O)=O CURBACXRQKTCKZ-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- OWEZJUPKTBEISC-UHFFFAOYSA-N decane-1,1-diamine Chemical compound CCCCCCCCCC(N)N OWEZJUPKTBEISC-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- DDLUSQPEQUJVOY-UHFFFAOYSA-N nonane-1,1-diamine Chemical compound CCCCCCCCC(N)N DDLUSQPEQUJVOY-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- GPCKFIWBUTWTDH-UHFFFAOYSA-N pentane-3,3-diamine Chemical compound CCC(N)(N)CC GPCKFIWBUTWTDH-UHFFFAOYSA-N 0.000 description 1
- RNWSXEXIJDAZOJ-UHFFFAOYSA-N phenyl tris(phenoxycarbonyl)silylformate Chemical compound C=1C=CC=CC=1OC(=O)[Si](C(=O)OC=1C=CC=CC=1)(C(=O)OC=1C=CC=CC=1)C(=O)OC1=CC=CC=C1 RNWSXEXIJDAZOJ-UHFFFAOYSA-N 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 238000001907 polarising light microscopy Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- JWHOQZUREKYPBY-UHFFFAOYSA-N rubonic acid Natural products CC1(C)CCC2(CCC3(C)C(=CCC4C5(C)CCC(=O)C(C)(C)C5CC(=O)C34C)C2C1)C(=O)O JWHOQZUREKYPBY-UHFFFAOYSA-N 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Liquid Crystal (AREA)
- Liquid Crystal Substances (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、液晶配向膜として有用な含フツ素ポリアミド
化合物２含フツ素ポリイミド化合物に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a fluorine-containing polyamide compound (2) useful as a liquid crystal aligning film.
従来の技術
液晶表示素子の構成は、液晶を液晶配向膜を塗布した透
明電極で挟持するものが一般的である。BACKGROUND OF THE INVENTION Conventional liquid crystal display devices generally have a structure in which a liquid crystal is sandwiched between transparent electrodes coated with a liquid crystal alignment film.
この場合、液晶の分子長軸を一定方向へ配列させる必要
がある。この液晶の配向状態を実現するために配向膜を
合成繊維からなる布で一方向にこすっている（ラビング
している）、また、一般にポリイミド樹脂は液晶配向膜
として工業的に広く用いられている。In this case, it is necessary to align the long axes of molecules of the liquid crystal in a certain direction. In order to achieve this alignment of liquid crystals, the alignment film is rubbed in one direction with a cloth made of synthetic fibers, and polyimide resin is generally widely used industrially as a liquid crystal alignment film. .
ネマティック液晶の分子長軸を上下の基板間で９０度連
続的にねしるものをＴＮ方式とよび、この方式を用いて
液晶テレビが市販されている。最近では、さらに高速応
答・大画面化をめざして液晶自体が強い自発分極をもつ
強誘電性液晶を用いた表示素子の開発が盛んである。A system in which the molecular long axis of a nematic liquid crystal is continuously twisted by 90 degrees between upper and lower substrates is called a TN system, and liquid crystal televisions using this system are commercially available. Recently, with the aim of achieving even faster response and larger screens, there has been active development of display elements using ferroelectric liquid crystals, in which the liquid crystal itself has strong spontaneous polarization.
この強誘電性液晶を一定方向に配列させるのに適した配
向膜は、液晶と基板平面とのなす角（プレチルト角）が
ゼロではない材料である。液晶を基板平面から傾斜配向
させることによって、ジグザグ欠陥とよばれる配向不良
はなくなる。An alignment film suitable for aligning this ferroelectric liquid crystal in a certain direction is a material in which the angle (pretilt angle) between the liquid crystal and the plane of the substrate is not zero. By aligning the liquid crystal obliquely from the plane of the substrate, alignment defects called zigzag defects are eliminated.
プレチルト角を高めるためのポリイミド材料（ハイプレ
チルトポリイミド材料）は、ポリイミド骨格にトロフロ
ロメチル基を有するものが知られている（「液晶デバイ
スハンドブック」２５５ページ 日本学術振興協会第１
４２委員会編・日刊工業新聞社、１９８９年９月発行、
参照）、シかし、トリフロロメチル基を有するノλイブ
レチルトポリイミド材料では大きなプレチルト角が得ら
れるものの、強誘電性液晶がツイスト配向しやすい。Polyimide materials for increasing the pretilt angle (high pretilt polyimide materials) are known to have a trophofluoromethyl group in the polyimide skeleton ("Liquid Crystal Device Handbook" page 255, Japan Society for the Promotion of Science Vol. 1)
42 Committee, Nikkan Kogyo Shimbun, published September 1989,
However, although a large pretilt angle can be obtained with a non-lambda bretilt polyimide material having trifluoromethyl groups, the ferroelectric liquid crystal tends to be twisted in orientation.
発明が解決しようとする課題
強誘電性液晶を基板上で一定方向に配列させるのに、プ
レチルト角の大きな、ポリイミド骨格にトリフロロメチ
ル基を有する化合物が知られていた。しかしこのような
従来のトリフロロメチル基を有するハイプレチルトポリ
イミド材料を配向膜に用いると、大きなプレチルト角が
得られるものの、強誘電性液晶がツイスト配向するとい
う問題があった。Problems to be Solved by the Invention Compounds having a trifluoromethyl group in a polyimide skeleton and having a large pretilt angle are known for aligning ferroelectric liquid crystals in a fixed direction on a substrate. However, when such a conventional high pretilt polyimide material having a trifluoromethyl group is used for an alignment film, although a large pretilt angle can be obtained, there is a problem in that the ferroelectric liquid crystal is twistedly aligned.
本発明はこのような問題を解決するもので、強誘電性液
晶がツイスト配向せずに大きなプレチルト角が得られる
強誘電性液晶配向膜材料を提供することを目的とするも
のである。The present invention is intended to solve these problems, and aims to provide a ferroelectric liquid crystal alignment film material that can obtain a large pretilt angle without twisting the ferroelectric liquid crystal.
課題を解決するための手段
この課題を解決するために本発明は、
一般式［Ｉ）
（式中Ｒ１は炭素数２以上の脂肪族基、環式脂肪族基、
単環式芳香族基、縮合多環式芳香族基より選ばれた４価
の基、Ｒ２は水素あるいは１価の有Ｓ基、ｎは１または
２を表わす。）で表わされる繰り返し単位を含む含フツ
素ポリアミド化合物を強誘電性液晶の配向膜として用い
るものである。Means for Solving the Problem In order to solve this problem, the present invention has the following features: General formula [I] (wherein R1 is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
A tetravalent group selected from a monocyclic aromatic group and a fused polycyclic aromatic group, R2 represents hydrogen or a monovalent S-containing group, and n represents 1 or 2. ) is used as an alignment film for ferroelectric liquid crystal.
また、一般式（ＩＩ）
（式中Ｒ１は炭素数２以上の脂肪族基、環式脂肪族基、
単環式芳香族基、縮合多環式芳香族基より選ばれた４価
の基、ｎは１または２を表わす、）で表わされる繰り返
し単位を含む含フツ素ポリイミド化合物を強誘電性液晶
の配向膜として用いるものである。Further, general formula (II) (wherein R1 is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
A fluorine-containing polyimide compound containing a repeating unit represented by a tetravalent group selected from a monocyclic aromatic group and a fused polycyclic aromatic group, where n represents 1 or 2 is used as a ferroelectric liquid crystal. It is used as an alignment film.
作用
本発明の含フツ素ポリイミド化合物およびポリイミド化
合物は、従来の含フツ素ポリアミド化合物やポリイミド
化合物と異なり、フッ素がｓｐ３炭素ではなく ｓｐ２
炭素に結合している。フ・ン素はｓｐ３戻素と結合した
場合は、−Ｉ効果で強く分極するが、フッ素がｓｐ２炭
素に結合した場合は４−Ｒ効果により相殺され分極が弱
くなる。従来のフッ素化した配向膜ではフッ素が強くマ
イナス分極している。この配向膜表面における強誘電性
液晶の自発分極は配向膜表面にプラス分極を向けて安定
化する。よって、上下基板間の強誘電性液晶は配向膜表
面から連続的にねしれてしまい、ツイスト配向しやすい
。Effect The fluorine-containing polyimide compound and polyimide compound of the present invention differ from conventional fluorine-containing polyamide compounds and polyimide compounds in that fluorine is not an sp3 carbon but an sp2 carbon.
Bonded to carbon. When fluorine is combined with sp3 return element, it is strongly polarized due to the -I effect, but when fluorine is combined with sp2 carbon, it is offset by the 4-R effect and the polarization becomes weak. In conventional fluorinated alignment films, fluorine is strongly negatively polarized. The spontaneous polarization of the ferroelectric liquid crystal on the surface of the alignment film is stabilized by directing positive polarization toward the surface of the alignment film. Therefore, the ferroelectric liquid crystal between the upper and lower substrates is continuously twisted from the surface of the alignment film, and tends to be twisted in alignment.
一方、分極が弱い本発明のポリアミドまたはポリイミド
化合物では配向膜表面の極性はあまり大きくない。した
がって強誘電性液晶の自発分極の向きは一方向に規定さ
れることがないため上下基板間にねしれをもたないユニ
フォーム配向しやすくなり、ツイストせずに配向するこ
ととなる。On the other hand, in the case of the polyamide or polyimide compound of the present invention which has weak polarization, the polarity of the surface of the alignment film is not so large. Therefore, since the direction of spontaneous polarization of the ferroelectric liquid crystal is not defined in one direction, uniform alignment without waviness between the upper and lower substrates is easily achieved, and alignment is achieved without twisting.
実施例
本発明の含フツ素ポリイミド化合物は一般式％式％）
〔■〕
（式中Ｒ１は炭素数２以上の脂肪族基、環式脂肪族基、
単環式芳香族基、縮合多環式芳香族基より選ばれた４価
の基、ｎは１または２を表わす。）で表わされる繰り返
し単位を含む含フツ素ポリイミド化合物は、一般式［１
）
（式中Ｒ１は炭素数２以上の脂肪族基、環式脂肪族基、
単環式芳香族基、縮合多環式芳香族基より選ばれた４価
の基、Ｒ２は水素あるいは１価の有Ｉ９基、ｎは１また
は２を表わす。）で表わされる繰り返し単位を含む含フ
ツ素ポリアミド化合物を前駆体とし、これに加熱などの
処理をすることにより製造する。Examples The fluorine-containing polyimide compound of the present invention has the general formula %) [■] (wherein R1 is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
A tetravalent group selected from a monocyclic aromatic group and a fused polycyclic aromatic group, and n represents 1 or 2. ) The fluorine-containing polyimide compound containing the repeating unit represented by the general formula [1
) (wherein R1 is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
A tetravalent group selected from a monocyclic aromatic group and a fused polycyclic aromatic group, R2 represents hydrogen or a monovalent I9 group, and n represents 1 or 2. ) A fluorine-containing polyamide compound containing a repeating unit represented by the following formula is used as a precursor, and it is produced by subjecting the precursor to a treatment such as heating.
本発明の一般式ＣＩ）で表わされる含フツ素ボッアミド
樹脂組成物は、以下に記述する方法によって製造する。The fluorine-containing boamide resin composition of the present invention represented by general formula CI) is produced by the method described below.
本発明のポリアミドは通常下記一般式ＣＩＩＩＪ（ｎは
１または２）で表わされる含フツ素ジアミンとテトラカ
ルボン酸類とを有機溶媒中で縮合反応させることにより
製造される。ここでテトラカルボン酸類とは、テトラカ
ルボン酸、テトラカルボン酸−無水物、テトラカルボン
酸二無水物、テトラカルボン酸モノアルキルエステル、
テトラカルボン酸ジアルキルアステル１テトラカルボン
酸トリアルキルエステルおよびテトラカルボン酸テトラ
アルキルエステルを表わすものである。The polyamide of the present invention is usually produced by subjecting a fluorine-containing diamine represented by the following general formula CIIIJ (n is 1 or 2) to a condensation reaction with a tetracarboxylic acid in an organic solvent. Here, the tetracarboxylic acids include tetracarboxylic acid, tetracarboxylic acid anhydride, tetracarboxylic dianhydride, tetracarboxylic acid monoalkyl ester,
Tetracarboxylic acid dialkyl ester 1 represents a tetracarboxylic acid trialkyl ester and a tetracarboxylic acid tetraalkyl ester.
本発明に使用できるテトラカルボン酸類としてはピロメ
リット酸、３．３’、４．４°−ビフェニルテトラカル
ボン酸、２．３ ３’ ４’ −テトラカルボキシ
ビフェニル、３．３′、４．４’テトラカルボキシビフ
エニルエーテル、２．３３．４“−テトラカルボキシビ
フェニルエーテル、３．３’ 、４．４“ −テトラカ
ルボキシヘンシフエノン、２．３．３°、４′−テトラ
カルボキシヘンシフエノン ２．３．６．７−チトラカ
ルポキシナフタレン、ｌ、４．５．７−チトラカルポキ
シナフタレン、１．２．５．６−チトラカルポキシナフ
タレン、３．３“、４，４“−テトラカルボキシジフェ
ニルメタン、２，２°−ビス（３，４−ジカルボキシフ
ェニル）プロパン、３゜３．４．４°−テトラカルボキ
シビフェニルス）Ｌホン、Ｌ ２，７．８−テトラカ
ルボキノペリレン、２，２−ビス（４−（３，４−ジカ
ルボキシフェノキシ）フェニル）プロパン、３３４．４
゛ −ジメチルジフェニルシランテトラカルボン酸、３
，３°、４，４°−テトラフェニルシランテトラカルボ
ン酸などの芳香族テトラカルボン酸、ブタンテトラカル
ボン酸、１．２，３４シクロブタンテトラカルボン酸、
１．２．３４−シクロペンタンテトラカルボン酸、１．
２゜３．４−フランテトラカルボン酸などの脂肪族また
は脂環族テトラカルボン酸をあげることができる。Tetracarboxylic acids that can be used in the present invention include pyromellitic acid, 3.3', 4.4°-biphenyltetracarboxylic acid, 2.3 3'4' -tetracarboxybiphenyl, 3.3', 4.4' Tetracarboxybiphenyl ether, 2.33.4"-tetracarboxybiphenyl ether, 3.3', 4.4"-tetracarboxyhensiphenone, 2.3.3°,4'-tetracarboxyhensiphenone 2 .3.6.7-Titracarpoxynaphthalene, 1, 4.5.7-Titracarpoxynaphthalene, 1.2.5.6-Titracarpoxynaphthalene, 3.3", 4,4"-Tetracarboxy diphenylmethane, 2,2°-bis(3,4-dicarboxyphenyl)propane, 3°3.4.4°-tetracarboxybiphenyls)L phone, L2,7.8-tetracarboquinoperylene, 2, 2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane, 334.4
-dimethyldiphenylsilanetetracarboxylic acid, 3
, 3°, 4,4°-Aromatic tetracarboxylic acids such as tetraphenylsilanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,34 cyclobutanetetracarboxylic acid,
1.2.34-cyclopentanetetracarboxylic acid, 1.
Examples include aliphatic or alicyclic tetracarboxylic acids such as 2°3.4-furantetracarboxylic acid.
これらのテトラカルボン酸類のうち好ましくは芳香族テ
トラカルボン酸類、特に好ましいものとして：ま、ピロ
メリット酸、３．３’、４．４テトラカルボキシヘンシ
フエノン、２．３．３’４−テトラカルボキシヘンシフ
エノン、２．３゜３．４°−テトラカルボキシビフェニ
ルエーテル、３．３’ 、４．４”−ビフェニルテトラ
カルボン酸である。Among these tetracarboxylic acids, aromatic tetracarboxylic acids are preferred, and particularly preferred are: pyromellitic acid, 3.3',4.4tetracarboxyhensiphenone, 2.3.3'4-tetracarboxylic acid. Hensifhenone, 2.3°3.4°-tetracarboxybiphenyl ether, 3.3',4.4''-biphenyltetracarboxylic acid.
また前記テトラカルボン酸類と反応させるジアミンとし
ては一般式ＣＩ［Ｉ）で表わされるジアミン単独または
以下に示すジアミノ類と組み合わせて用いることができ
る。バラフェニレンジアミン、メタフェニレンジアミン
４．４′−ジアミノジフェニルメタン、４．４゛−ジア
ミノジフェニルエタン、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、４
．４〜ジアミノジフエニルエーテル、４，４゛−ジアミ
ノビフェニル、１，５−ジアミノナフタレン、３．３゛
−ジアミノベンゾフェノン、３，４゜ジアミノベンゾフ
ェノン、４，４° −ジアミノベンゾフェノン、３，４
° −ジアミノジフェニルエーテル、１．４−ビス（４
−アミノフェノキシ）ベンゼン、１．３−ビス（４−ア
ミノフェノキシ）ベンゼン、３．３°−ジメトキシ−４
，４″−ジアミノビフェニルなどの芳香族ジアミン、１
．３ジアミノプロパン、ジアミノブタン、ジアミノペン
タン、ジアミノヘキサン、ジアミノへブタン、ジアミノ
オクタン、ジアミノノナン、ジアミノデカン、ジアミノ
ドデカン、１．４−ジアミノシクロヘキサンなどの脂肪
族または脂環族ジアミンを挙げることができる。Further, as the diamine to be reacted with the tetracarboxylic acids, the diamine represented by the general formula CI[I] can be used alone or in combination with the diamino shown below. Rose phenylene diamine, metaphenylene diamine 4.4'-diaminodiphenylmethane, 4.4'-diaminodiphenyl ethane, 4,4-diaminodiphenylsulfide, 4.4'-diaminodiphenyl sulfone, 4
．． 4-diaminodiphenyl ether, 4,4゛-diaminobiphenyl, 1,5-diaminonaphthalene, 3,3゛-diaminobenzophenone, 3,4゜diaminobenzophenone, 4,4゛-diaminobenzophenone, 3,4
° -Diaminodiphenyl ether, 1,4-bis(4
-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 3.3°-dimethoxy-4
, 4″-diaminobiphenyl and other aromatic diamines, 1
．． Mention may be made of aliphatic or cycloaliphatic diamines such as 3-diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminohbutane, diaminooctane, diaminononane, diaminodecane, diaminododecane, 1,4-diaminocyclohexane.
なお基板との接着性向上のためにシリコーン系ジアミン
を用いることができる。たとえば（ここでｍ＝１〜３の
整数、ｎ＝１〜２０の整数、Ｒ３は脂肪族炭化水素基、
脂環族炭化水素基、芳香族基を表わす。）が挙げられる
。Note that silicone diamine can be used to improve adhesion to the substrate. For example, (where m = an integer of 1 to 3, n = an integer of 1 to 20, R3 is an aliphatic hydrocarbon group,
Represents an alicyclic hydrocarbon group or an aromatic group. ).
本発明においてジアミン類とテトラカルボン酸類との反
応における配合割合はジアミノｉｔモルに対してテトラ
カルボン酸類１モル〜１．１モルの場合に最も高い分子
量でしかも保存安定性の高いポリアミド樹脂が得られる
０反応条件は通常はＮＮ−ジメチルホルムアミド、Ｎ、
Ｎ−ジメチルアセトアミド、Ｎ、Ｎ−ジエチルホルムア
ミド、ＮＮ−ジエチルアセトアミド、ジメチルスルホキ
シド、Ｎ−メチル−２−ピロリドンなどの有ｍ溶媒中に
ジアミン類を溶解し、溶液を攪拌しながらテトラカルボ
ン酸を加えることで合成できる。反応溶媒は単一でも２
種類以上を混合して用いてもよい。また高分子量の樹脂
を得るためには溶媒を脱水して用いるべきである。In the present invention, when the mixing ratio in the reaction between diamines and tetracarboxylic acids is 1 mol to 1.1 mol of tetracarboxylic acids per mol of diamino, a polyamide resin with the highest molecular weight and high storage stability can be obtained. 0 reaction conditions are usually NN-dimethylformamide, N,
Dissolve diamines in a solvent such as N-dimethylacetamide, N,N-diethylformamide, NN-diethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, etc., and add tetracarboxylic acid while stirring the solution. It can be synthesized by The reaction solvent may be single or two.
More than one type may be mixed and used. Further, in order to obtain a high molecular weight resin, the solvent should be dehydrated before use.
反応温度としてはテトラカルボン酸類として酸無水物を
用いる場合はＯ″Ｃ〜５０℃Ｃ〜５０℃程度ルボン酸や
エステルを用いる場合は４０〜１８０ ”Ｃの温度範囲
が望ましい。The reaction temperature is desirably within the range of O''C to 50C to 50C when an acid anhydride is used as the tetracarboxylic acid, and 40 to 180C when a rubonic acid or ester is used.
以上のような方法でポリアミド樹脂を得ることができる
。この樹脂はＮ、Ｎ−ジメチルホルムアミド、ＮＮ−ジ
メチルアセトアミド、ＮＮジエチルホルムアミド、Ｎ、
Ｎ−ジエチルアセトアミド、ジメチルスルホキシド、Ｎ
−メチル−２−ピロリドンなどの溶媒に室温で容易に溶
解するので溶液の状態で基板上に塗布したのちに乾燥さ
せて使用できる。A polyamide resin can be obtained by the method described above. This resin is N,N-dimethylformamide, NN-dimethylacetamide, NNdiethylformamide, N,
N-diethylacetamide, dimethyl sulfoxide, N
Since it is easily dissolved in a solvent such as -methyl-2-pyrrolidone at room temperature, it can be used by coating it on a substrate in a solution state and then drying it.
上記ポリアミド樹脂は２５０°Ｃ程度の温度で加熱する
ことにより閉環反応がおこりポリイミド樹脂を得ること
ができる。したがってポリアミド樹脂を基板上に塗布し
たのち加熱してポリイミド樹脂にすることも可能である
。また加熱温度を調節することによりイミド化率を適切
に選ぶことができる。したがってポリアミド樹脂内にポ
リイミド樹脂を含むフィルムを作成することも可能であ
る。When the above-mentioned polyamide resin is heated at a temperature of about 250°C, a ring-closing reaction occurs and a polyimide resin can be obtained. Therefore, it is also possible to apply a polyamide resin onto a substrate and then heat it to form a polyimide resin. Moreover, the imidization rate can be appropriately selected by adjusting the heating temperature. It is therefore also possible to create films containing polyimide resin within polyamide resin.
またポリアミド樹脂をピリジンと無水酢酸の混合溶媒中
で化学的に閉環させてポリイミド樹脂とすることも可能
である。It is also possible to chemically ring-close a polyamide resin in a mixed solvent of pyridine and acetic anhydride to obtain a polyimide resin.
以下により具体的な実施例を示す。More specific examples will be shown below.
（実施例１）
容量２００ ｍｌの丸底フラスコに４，４°−ジアミノ
オクタフロロビフェニル（４，９ｇ ）をいれ、そこへ
Ｎ−メチル−２−ピロリドン（ＮＭＰ）１００１ｄｌを
加えて溶解した。溶液を撹拌しながら昇華精製した無水
ピロメリント酸３．６ｇを約１５分かけて加えた。さら
に室温で２時間撹拌して反応させた。この溶液を０．２
μｍのメンブレンフィルタでろ過後ガラス板上のＮａＣ
１上にスビンコ−４してのち１００ ”Ｃで溶媒を除去
してポリアミドフィルムを作成した。さらにこのフィル
ムを２００“Ｃで２時間熱処理し淡黄色透明なポリイミ
ドフィルムを得た。上記ポリアミドおよびポリイミド化
合物のフィルムの赤外吸収スペクトルを第１回および第
２図に示した。第１図ではアミドのＮＨ伸縮およびカル
ボン酸のＯＨ伸縮に基づく吸収が３２００ｃｍ”にみら
れた。またＣＯ伸縮に基づく吸収が１６７０Ｃ１１（と
１７ＤＯＣ１１４にみられた。第２図では、イミドカル
ボニルのＣＯ伸縮に基づく吸収が１７４０ＣＩ”と１７
９０Ｃ１１４にみられた。(Example 1) 4,4°-diaminooctafluorobiphenyl (4.9 g) was placed in a 200 ml round bottom flask, and 1001 dl of N-methyl-2-pyrrolidone (NMP) was added thereto and dissolved. While stirring the solution, 3.6 g of pyromellitic anhydride purified by sublimation was added over about 15 minutes. The mixture was further stirred at room temperature for 2 hours to react. Add this solution to 0.2
NaC on a glass plate after filtration with a μm membrane filter
A polyamide film was prepared by carrying out Svinco-4 on 1 and removing the solvent at 100"C. This film was further heat-treated at 200"C for 2 hours to obtain a pale yellow transparent polyimide film. The infrared absorption spectra of the polyamide and polyimide compound films are shown in Figures 1 and 2. In Figure 1, absorption due to NH stretching of amide and OH stretching of carboxylic acid was observed at 3200 cm. Absorption due to CO stretching was also observed at 1670C11 (and 17DOC114). Absorption based on expansion and contraction is 1740 CI” and 17
Found in 90C114.
（実施例２）
実施例１と同様な方法で４，４−ジアミノオクタフロロ
ビフェニル４．９ｇと３．３’ 、４．４’ビフエニル
テトラカルボン酸二無水物４．９ｇをＮＭＰ １００ｄ
中で反応させポリアミドを合成した。実施例１と同様に
ポリアミドフィルムを作成し熱処理してポリイミドフィ
ルムを作成した。赤外吸収スペクトルでイミド環の生成
を確認した。(Example 2) In the same manner as in Example 1, 4.9 g of 4,4-diaminooctafluorobiphenyl and 4.9 g of 3.3',4.4'biphenyltetracarboxylic dianhydride were mixed with NMP 100d.
Polyamide was synthesized by reacting in A polyamide film was prepared in the same manner as in Example 1 and heat treated to produce a polyimide film. Formation of an imide ring was confirmed by infrared absorption spectrum.
（実施例３）
実施例１と同様な方法で４．４′−ジアミノオクタフロ
ロビフェニル４．９ｇと２．３．３’ 、４’ペンシラ
エノンテトラカルボン酸二無水物５．３ｇをＮＭＰ １
００ｄ中で反応させポリアミドを合成した。実施例１と
同様にポリアミドフィルムを作成し熱処理してポリイミ
ドフィルムを作成した。赤外吸収スペクトルでイミド環
の生成を確認した。(Example 3) In the same manner as in Example 1, 4.9 g of 4.4'-diaminooctafluorobiphenyl and 5.3 g of 2.3.3',4'pensilaenonetetracarboxylic dianhydride were mixed with NMP1.
Polyamide was synthesized by reaction in 00d. A polyamide film was prepared in the same manner as in Example 1 and heat treated to produce a polyimide film. Formation of an imide ring was confirmed by infrared absorption spectrum.
（実施例４）
実施例１と同様な方法で４．４゛−ジアミノテトラフロ
ロベンゼン２．７ｇと無水ピロメリット酸３．６ｇをＮ
ＭＰ １００ａｅ中で反応させポリアミドを合成した。(Example 4) In the same manner as in Example 1, 2.7 g of 4.4'-diaminotetrafluorobenzene and 3.6 g of pyromellitic anhydride were mixed with N
Polyamide was synthesized by reaction in MP 100ae.
得られたポリアミド溶液をＮａＣ１上に塗布したのち１
００℃で加熱してポリアミドフィルムを作成した。さら
に２５０℃で２時間加熱してポリイミドフィルムとした
。赤外吸収スペクトルでイミド環の生成をｉ！認した。After coating the obtained polyamide solution on NaC1,
A polyamide film was prepared by heating at 00°C. It was further heated at 250° C. for 2 hours to form a polyimide film. i! The formation of imide rings using infrared absorption spectra! Approved.
（実施例５）
実施例１と同様な方法で４．４′−ジアミノテトラフロ
ロベンゼン２．７ｇと３．３°、４．４゜ビフェニルテ
トラカルボン酸二無水物４．９ｇをＮＭＰ １００ｄ中
で反応させポリアミドを合成した。実施例１と同様にポ
リアミドフィルムを作成し熱処理してポリイミドフィル
ムを作成した。赤外吸収スペクトルでイミド環の生成を
確認した。(Example 5) In the same manner as in Example 1, 2.7 g of 4,4'-diaminotetrafluorobenzene and 4.9 g of 3.3° and 4.4° biphenyltetracarboxylic dianhydride were added in NMP 100d. The reaction was carried out to synthesize polyamide. A polyamide film was prepared in the same manner as in Example 1 and heat treated to produce a polyimide film. Formation of an imide ring was confirmed by infrared absorption spectrum.
（実施例６）
実施例１と同様な方法で４．４“−ジアミノテトラフロ
ロベンゼン２．７ｇと２．３．３’ 、４’ベンゾフエ
ノンテトラカルボン酸二無水物５．３ｇをＮＭＰ １０
０ｄ中で反応させポリアミドを合成した。実施例１と同
様にポリアミドフィルムを作成し熱処理してポリイミド
フィルムを作成した。赤外吸収スペクトルでイミド環の
生成を確認した。(Example 6) In the same manner as in Example 1, 2.7 g of 4.4"-diaminotetrafluorobenzene and 5.3 g of 2.3.3', 4'benzophenone tetracarboxylic dianhydride were mixed with NMP 10.
A polyamide was synthesized by reacting in 0d. A polyamide film was prepared in the same manner as in Example 1 and heat treated to produce a polyimide film. Formation of an imide ring was confirmed by infrared absorption spectrum.
（比較例）
実施例１と同様な方法で４．４゛−ビスアミノフェニル
へキサフルオロプロパン３．１ｇと無水ピロメリット酸
２．２ｇをＮＭＰ １００ｄ中で反応させポリアミドを
合成した。得られたポリアミド溶液をＮａ （１！上に
塗布したのち１００°Ｃで加熱してポリアミドフィルム
を作成した。さらに２５０°Ｃで２時間加熱してポリイ
ミドフィルムとした。(Comparative Example) In the same manner as in Example 1, 3.1 g of 4.4'-bisaminophenyl hexafluoropropane and 2.2 g of pyromellitic anhydride were reacted in NMP 100d to synthesize a polyamide. The obtained polyamide solution was coated on Na(1!) and heated at 100°C to create a polyamide film. It was further heated at 250°C for 2 hours to form a polyimide film.
赤外吸収スペクトルでイミド環の生成をＷＬ認した。Formation of imide rings was confirmed by infrared absorption spectrum.
（プレチルト角測定および強誘電性液晶セル評価）
液晶セルを作成しプレチルト角測定および強誘電性液晶
セル評価をおこなった。液晶セルは縦４０■、横３０−
２厚さ１．１鴎のガラス表面に酸化インジウムすず（Ｉ
ＴＯ）の透明導電膜を形成した基板上に実施例１〜６お
よび比較例のポリアミド溶液を塗布したのち２００°Ｃ
で２時間硬化して配向膜を作成した。この膜表面をナイ
ロン不織布で一定方向にこすったのち、２枚の基板をポ
リイミド膜が向き合うようにしてラビング方向が上下の
基板で逆方向になるように配置してエボ夫シ接着剤で固
定した。上下基板の間隔は１６μｍあるいは２μｍとし
た。１６μｍのセルにはネマティック液晶リクソン９１
５０（チッソ石油化学製）を、２μｍのセルには強誘電
性液晶ＣＳ −１０１４（チッソ石油化学製）を注入し
た。ネマティック液晶を封入したセルでは磁場容量法に
よりプレチルト角を、強誘電性液晶セルでは偏光顕微鏡
観察をおこなった。偏光顕微鏡でツイスト状態かユニフ
ォーム状態かを観察するためにはクロスニコル下で観察
するとともに片側の偏光板を回転させて判断した（大向
・竹添・幅用、ジャパニーズ ジャーナル・オブ・アプ
ライドフィジックスＪａｐａｎｅｓｅ Ｊｏｕｒｎａｌ
ｏｆ Ａｐｐｌｉｅｄ Ｐｈｙｓｉｃｓ ２６＋ （
１）＋１−１４ （１９８７）参照）。(Pretilt angle measurement and ferroelectric liquid crystal cell evaluation) A liquid crystal cell was prepared, and pretilt angle measurement and ferroelectric liquid crystal cell evaluation were performed. The liquid crystal cell is 40 cm tall and 30 cm wide.
2 Thickness 1.1 Indium tin oxide (I) is applied to the surface of the glass.
After coating the polyamide solutions of Examples 1 to 6 and comparative examples on the substrate on which the transparent conductive film of TO) was formed, the solution was heated at 200°C.
The film was cured for 2 hours to form an alignment film. After rubbing the surface of this film in a certain direction with a nylon non-woven cloth, the two substrates were placed so that the polyimide films faced each other, the rubbing direction was opposite for the upper and lower substrates, and they were fixed with Ebony adhesive. . The interval between the upper and lower substrates was 16 μm or 2 μm. Nematic liquid crystal Rixon 91 for 16μm cell
50 (manufactured by Chisso Petrochemicals), and ferroelectric liquid crystal CS-1014 (manufactured by Chisso Petrochemicals) was injected into the 2 μm cell. For cells filled with nematic liquid crystals, pretilt angles were observed using the magnetic field capacitance method, and for ferroelectric liquid crystal cells, polarized light microscopy was observed. In order to observe whether it is in a twisted state or a uniform state with a polarizing microscope, it was determined by observing under crossed nicols and rotating the polarizing plate on one side (Omukai, Takezoe, Haba, Japanese Journal of Applied Physics, Japanese Journal
of Applied Physics 26+ (
1)+1-14 (1987)).
測定結果を第１表に示す。The measurement results are shown in Table 1.
第１表
実施例１〜６も比較例もプレチルト角は１０度以下のも
のもあったが、配向に間しては、比較例がツイスト配向
だったのに比べ本発明の実施例はいずれもジグザグ欠陥
をもたず全面ユニフォーム配向を示した。In Examples 1 to 6 of Table 1 and the comparative examples, some of the pretilt angles were less than 10 degrees, but in terms of orientation, the comparative examples had a twisted orientation, whereas the examples of the present invention all had a twisted orientation. The entire surface exhibited uniform orientation without any zigzag defects.
なお、本発明の含フツ素ポリアミド化合物およびポリイ
ミド化合物の用途は、実施例であげた強誘電性液晶デイ
スプレィ用配向膜に限定されるわけではなく、ＳＴＮ用
ハイプレチルト配向膜や低温硬化特性を往かして光ファ
イバのコーテイング材などにも用いることができる。Note that the use of the fluorine-containing polyamide compound and polyimide compound of the present invention is not limited to the alignment film for ferroelectric liquid crystal displays mentioned in the examples, but also for high pretilt alignment films for STN and those with low-temperature curing properties. It can also be used as a coating material for optical fibers.
発明の効果
以上の実施例の説明からも明らかなように、本発明の含
フツ素ポリアミド化合物および含フ、素ボリイ逃ド化合
物を配向膜として用いることにより、強誘電性液晶がプ
レチルト角が小さくてもユニフォーム配向するという効
果が得られる。Effects of the Invention As is clear from the description of the examples above, by using the fluorine-containing polyamide compound and the fluorine-containing polyamide escape compound of the present invention as an alignment film, the ferroelectric liquid crystal can have a small pretilt angle. However, the effect of uniform orientation can be obtained.
第１図は本発明の含フツ素ポリアミド化合物の赤外吸収
スペクトル図、第２回は同含フツ素ポリイミド化合物の
赤外吸収スペクトル図である。
代理人の氏名 弁理士 粟野重孝 はか１名区
＠ 頓 １１−３Figure 1 is an infrared absorption spectrum diagram of the fluorine-containing polyamide compound of the present invention, and Figure 2 is an infrared absorption spectrum diagram of the same fluorine-containing polyimide compound. Name of agent: Patent attorney Shigetaka Awano 1 name Ward @ Ton 11-3
Claims (2)
単環式芳香族基、縮合多環式芳香族基より選ばれた４価
の基、Ｒ２は水素あるいは１価の有機基、ｎは１または
２を表わす。）で表わされる繰り返し単位を含む含フッ
素ポリアミド化合物。(1) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R1 is an aliphatic group with 2 or more carbon atoms, a cycloaliphatic group,
A tetravalent group selected from a monocyclic aromatic group and a fused polycyclic aromatic group, R2 represents hydrogen or a monovalent organic group, and n represents 1 or 2. ) A fluorine-containing polyamide compound containing a repeating unit represented by:
単環式芳香族基、縮合多環式芳香族基より選ばれた４価
の基、ｎは１または２を表わす。）で表わされる繰り返
し単位を含む含フッ素ポリイミド化合物。(2) General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (In the formula, R1 is an aliphatic group with 2 or more carbon atoms, a cycloaliphatic group,
A tetravalent group selected from a monocyclic aromatic group and a fused polycyclic aromatic group, and n represents 1 or 2. ) A fluorine-containing polyimide compound containing a repeating unit represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12961590A JPH0423832A (en) | 1990-05-18 | 1990-05-18 | Fluorine-containing polyamide compound and fluorine-containing polyimide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12961590A JPH0423832A (en) | 1990-05-18 | 1990-05-18 | Fluorine-containing polyamide compound and fluorine-containing polyimide compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0423832A true JPH0423832A (en) | 1992-01-28 |
Family
ID=15013848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12961590A Pending JPH0423832A (en) | 1990-05-18 | 1990-05-18 | Fluorine-containing polyamide compound and fluorine-containing polyimide compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0423832A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0911680A4 (en) * | 1996-07-11 | 1999-09-15 | Nissan Chemical Ind Ltd | Aligning agent for liquid-crystal cells |
| US6080832A (en) * | 1998-09-10 | 2000-06-27 | Industrial Technology Research Institute | Low-pretilt alignment layer material |
-
1990
- 1990-05-18 JP JP12961590A patent/JPH0423832A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0911680A4 (en) * | 1996-07-11 | 1999-09-15 | Nissan Chemical Ind Ltd | Aligning agent for liquid-crystal cells |
| US6120702A (en) * | 1996-07-11 | 2000-09-19 | Nissan Chemical Industries, Ltd. | Aligning agent for liquid-crystal cells |
| US6080832A (en) * | 1998-09-10 | 2000-06-27 | Industrial Technology Research Institute | Low-pretilt alignment layer material |
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