JPS6315223A - Coating liquid for liquid crystal orientation film and liquid crystal orientation film formed by heating - Google Patents
Coating liquid for liquid crystal orientation film and liquid crystal orientation film formed by heatingInfo
- Publication number
- JPS6315223A JPS6315223A JP16012586A JP16012586A JPS6315223A JP S6315223 A JPS6315223 A JP S6315223A JP 16012586 A JP16012586 A JP 16012586A JP 16012586 A JP16012586 A JP 16012586A JP S6315223 A JPS6315223 A JP S6315223A
- Authority
- JP
- Japan
- Prior art keywords
- group
- formulas
- formula
- tables
- liquid crystal
- 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
- 239000011248 coating agent Substances 0.000 title claims abstract description 39
- 238000000576 coating method Methods 0.000 title claims abstract description 39
- 239000007788 liquid Substances 0.000 title claims abstract description 17
- 238000010438 heat treatment Methods 0.000 title claims abstract description 10
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000011521 glass Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 229920001721 polyimide Polymers 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 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 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 150000004985 diamines Chemical class 0.000 claims abstract description 11
- 239000004642 Polyimide Substances 0.000 claims abstract description 9
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- -1 aminosilicon compound Chemical class 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 7
- 150000003377 silicon compounds Chemical class 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 12
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 4
- 229920001296 polysiloxane Polymers 0.000 abstract description 3
- 229920013822 aminosilicone Polymers 0.000 abstract 2
- 125000002837 carbocyclic group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 19
- 210000004027 cell Anatomy 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 9
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229920000620 organic polymer Polymers 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 5
- 229960003493 octyltriethoxysilane Drugs 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 239000004988 Nematic liquid crystal Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- OBFQBDOLCADBTP-UHFFFAOYSA-N aminosilicon Chemical class [Si]N OBFQBDOLCADBTP-UHFFFAOYSA-N 0.000 description 3
- 210000002858 crystal cell Anatomy 0.000 description 3
- 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
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- TUGAQVRNALIPHY-UHFFFAOYSA-N 2,2-dimethylpentane-1,5-diamine Chemical compound NCC(C)(C)CCCN TUGAQVRNALIPHY-UHFFFAOYSA-N 0.000 description 1
- DDHUNHGZUHZNKB-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diamine Chemical compound NCC(C)(C)CN DDHUNHGZUHZNKB-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-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
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- RWDKFLHJOYBXFV-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCCC(CN)(CN)CCCCCCCCCCCCCCCCCC Chemical compound CCCCCCCCCCCCCCCCCCC(CN)(CN)CCCCCCCCCCCCCCCCCC RWDKFLHJOYBXFV-UHFFFAOYSA-N 0.000 description 1
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 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
- 239000012456 homogeneous solution Substances 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (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〕
本発明はスーパー・ツイスト複屈折効果型の液晶配向膜
用塗布液及びそれを加熱することによ多形成されたスー
パー・ツイスト複屈折効果型の液晶配向膜に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a super twist birefringence effect type liquid crystal alignment film coating solution and a super twist birefringence effect type coating solution formed by heating the same. The present invention relates to a liquid crystal alignment film.
（以後、ＴＮ方式と呼ぶことがある）が主流の為、水平
配向用の膜が主として用いられている。(hereinafter sometimes referred to as the TN method) is the mainstream, so a film for horizontal alignment is mainly used.
その水平配向膜は初期の頃のＳｔＯなどを真空蒸着など
でガラス基板上につけた無機配向膜からポリビニルアル
コールやテフロン等をガラス基板上にコーティングして
、その形成された膜を布などによりラピングすることに
より液晶を配向させる有機高分子膜へと変わってきた。The horizontal alignment film is created by coating the glass substrate with polyvinyl alcohol, Teflon, etc. from the initial inorganic alignment film made of StO, etc., on a glass substrate by vacuum evaporation, and wrapping the formed film with cloth, etc. This has led to the transition to organic polymer films that orient liquid crystals.
その理由は、第１に作業性の面で、無機配向膜の場合は
どうしても真空槽内で、ごく限られた数のガラス基板し
か処理できないのに対し、有機配向膜の場合には、１回
に処理できる数が無機配向膜の場合と比べれば数十倍に
もなるからである。The first reason for this is workability.In the case of an inorganic alignment film, only a limited number of glass substrates can be processed in a vacuum chamber, whereas in the case of an organic alignment film, it is possible to process only a limited number of glass substrates in a vacuum chamber. This is because the number of films that can be processed is several tens of times larger than that of an inorganic alignment film.
第２に、無機配向膜は真空槽内の真空度や蒸着する時の
条件等を厳密にコントロールして品質を一定に保つこと
は極めて難しいが、有機高分子膜では比較的条件がコン
トロールしやすい為、品質が一定に保たれやすいからで
ある。Second, with inorganic alignment films, it is extremely difficult to maintain constant quality by strictly controlling the degree of vacuum in the vacuum chamber and the conditions during vapor deposition, but with organic polymer films, it is relatively easy to control the conditions. This is because the quality is easily kept constant.
現在、有機高分子膜としては耐吸湿性などで秀れている
ポリイミド膜が主として使われている。しかし、現在使
われているポリイミドは、ガラス基板との接着性が悪い
為、シランカップリング剤でガラス基板を処理した後に
塗布しないと、十分な接着性が得られなかった。Currently, polyimide films, which are excellent in moisture absorption resistance, are mainly used as organic polymer films. However, the currently used polyimide has poor adhesion to glass substrates, so sufficient adhesion cannot be obtained unless the polyimide is applied after treating the glass substrate with a silane coupling agent.
ここでＴＮ方式用の配向膜にとってＨ９なものの１つに
、プレ・チルト角というものがある。Here, one of the H9 factors for the alignment film for the TN system is the pre-tilt angle.
これは、セルにネマチック液晶を注入して、電圧を印加
していない状態で、液晶分子がガラス基板となす角度の
ことである。このプレ・チルト角が小さい程、大画面化
に適していると言える。現在液晶表示素子は大画面化の
方向へ急速に進歩しているが、従来のＴＮ方式では大画
面化はもう限界に達してしまい、その解決策として、新
しい方式がいくつか考え出されている。This is the angle that the liquid crystal molecules make with the glass substrate when nematic liquid crystal is injected into the cell and no voltage is applied. It can be said that the smaller this pre-tilt angle is, the more suitable it is for making the screen larger. Currently, liquid crystal display elements are rapidly progressing toward larger screens, but the conventional TN method has already reached its limit for larger screens, and several new methods have been devised as a solution. .
その１つがスーパー・ツイスト複屈折効果方式（以後Ｓ
ＢＥ方式と呼ぶことがある）である。One of them is the super twist birefringence effect method (hereinafter S
(sometimes called the BE method).
これはＴＮ方式がセル内で液晶分子を９０度ねじって配
列させているのに対して、２００〜２７０度ものねじシ
を与えて配列させており、表示のコントラスト比（＊ｌ
）や視角依存性（＊２）が大きく改善される。This is because, while the TN system twists the liquid crystal molecules 90 degrees and arranges them within the cell, the liquid crystal molecules are arranged with a twist of 200 to 270 degrees.
) and viewing angle dependence (*2) are greatly improved.
（＊１）電圧を印加した黒い表示の部分と背景の白い部
分との明るさの比で、この比が大きい程表示かくつきシ
と見える。(*1) The brightness ratio between the black display part to which voltage is applied and the white part of the background. The larger this ratio is, the more the display appears to be distorted.
（＊２）！示を見る時に１見る方向によりコントラスト
比が変化することで、依存性が小さい程、良い。(*2)! The contrast ratio changes depending on the direction in which the image is viewed, so the smaller the dependence, the better.
ところが、このＳＢＥ方式では安定な２００〜２７０４
＆Ｌのねじりを得る為に１ｊＴＮ方式とは異なりプレ・
チルト角が６度〜３０度であることが望ましい。この場
合に傾斜配向という言葉が使われている。傾斜配向とは
プレ・チルト角が０度よりある程度以上大きく、９０度
よ勺ある程度以下小さいことを言う。強いて言えば約５
〜８０度であることをいう。この傾斜配向を得る為には
、無機配向膜が使われている。真空蒸着をする角度を変
えることにより、プレ・チルト角を望みの角度にコント
ロールできるからである。However, with this SBE method, the stable 200-2704
In order to obtain the &L twist, unlike the 1jTN method, pre-
It is desirable that the tilt angle is 6 degrees to 30 degrees. In this case, the term tilted orientation is used. Tilted orientation means that the pre-tilt angle is larger than 0 degrees to a certain extent and smaller than 90 degrees to a certain extent. If I had to say it, it would be about 5.
~80 degrees. An inorganic alignment film is used to obtain this tilted alignment. This is because by changing the angle of vacuum deposition, the pre-tilt angle can be controlled to a desired angle.
従来、傾斜配向を得るのに無機配向膜が使われているが
、作業性や品質の均一性の面からは、有機高分子膜の方
が秀れているから、有機高分子膜で傾斜配向が得られた
方が好ましい。ところが、今まで有機高分子膜では完全
な当直配向かほとんど０度に近いプレ・チルト角しか得
られていなかった。更に、従来の有機高分子膜はガラス
基板との接着性が悪いために、シランカップリング剤に
よる前処理が必要であった。Conventionally, inorganic alignment films have been used to obtain tilted alignment, but organic polymer films are superior in terms of workability and uniformity of quality. It is preferable that . However, until now, organic polymer membranes have only been able to achieve complete duty alignment or a pre-tilt angle close to 0 degrees. Furthermore, since conventional organic polymer films have poor adhesion to glass substrates, pretreatment with a silane coupling agent is required.
本発明は上記従来技術の問題点を解決して上記要望を満
たすための手段であって、第１Ｋ。The present invention is a means for solving the problems of the prior art described above and satisfying the above needs.
下記の式（１）で表わされるテトラカルボン酸二無水物
、式（２）で表わされるジアミン及び式（３）で表わさ
れるアミノシリコン化合物を溶媒中で混合し、反応を行
ない、必要により式（４）で表わされるシリコン化合物
を添加し、場合により加熱反応を行なうことにより得ら
れる可溶性ポリイミドノロキサン前駆体を含有すること
を特徴とする液晶配向膜用塗布液である。A tetracarboxylic dianhydride represented by the following formula (1), a diamine represented by the formula (2), and an aminosilicon compound represented by the formula (3) are mixed in a solvent and reacted, and if necessary, the formula ( This is a coating liquid for a liquid crystal aligning film characterized by containing a soluble polyimidonoroxane precursor obtained by adding the silicon compound represented by 4) and optionally performing a heating reaction.
Ｎｌ２− Ｒ２−Ｎｌ２ ・・・・・・・・・・
・・（２）Ｎｌ２−Ｒ３−３ｉＲ４３，Ｘ−・・・・・
・・・・（３）ｓｉ（Ｒ５）３ｘ２ ・・・・
・・・・・・・・（４）〔式（１）〜（４）において
Ｈｌは４価の炭素環式芳香るいは分枝状の脂肪族基、炭
素数６〜５０個のここに８は１〜４の整数を表わす。）
、Ｒ４は独立に炭素数１〜２０個のアルキル基、フェニ
ル基、若しくはアルキル置換フェニル基を表わし、Ｘｌ
及びＸ２は独立にアルコキシ基、アセトキシ基、ハロゲ
／ｉたけ水酸基を表わし、Ｒ５は独立にＲ４、Ｘ２また
は次式（６）を表わしくここにｌはｌ≦ｌ≦１００の値
をとる。）Ｒ５の全てが同時にＲ４になることはなく、
ｍは１≦ｍ ＜、 ３の値をとる。Nl2- R2-Nl2 ・・・・・・・・・
...(2) Nl2-R3-3iR43,X-...
...(3) si(R5)3x2 ...
・・・・・・・・・(4) [In formulas (1) to (4)
Hl represents a tetravalent carbocyclic aromatic or branched aliphatic group having 6 to 50 carbon atoms, where 8 represents an integer of 1 to 4; )
, R4 independently represents an alkyl group having 1 to 20 carbon atoms, a phenyl group, or an alkyl-substituted phenyl group,
and X2 independently represent an alkoxy group, an acetoxy group, or a halogen/i hydroxyl group, and R5 independently represents R4, X2 or the following formula (6), where l takes a value of l≦l≦100. ) All of R5 will not become R4 at the same time,
m takes a value of 1≦m<3.
Ｈ４ｎ ４
なお同一記号の基又は英文字はそれを含む一般式が異な
っても独立に所定の範囲の基または数を表わす。以下同
様。〕
第２に前記溶液をガラス基板上に塗布し１００〜３００
℃に加熱することにより溶媒を蒸発させるとともに該前
駆体を架橋させ、硬化させることにより形成される液晶
配向膜である。H4n 4 Note that groups or alphabetic characters with the same symbol independently represent groups or numbers within a predetermined range even if the general formulas containing them are different. Same below. ] Second, apply the solution on a glass substrate and apply it to
It is a liquid crystal aligning film formed by evaporating the solvent by heating to °C, crosslinking the precursor, and curing it.
本発明の原料について説明する。The raw materials of the present invention will be explained.
式（１）で表わされるテトラカルボン酸二無水物として
次の化合物を挙げることができる。Examples of the tetracarboxylic dianhydride represented by formula (1) include the following compounds.
ピロメリット酸二無水物、３．３’、４．４’−ビフェ
ニルテトラカルボン酸二無水物、２．２’、 ３．３’
−ビフェニルテトラカルボン酸二無水物、２，３．３
’。Pyromellitic dianhydride, 3.3', 4.4'-biphenyltetracarboxylic dianhydride, 2.2', 3.3'
-Biphenyltetracarboxylic dianhydride, 2,3.3
'.
４′−ビフェニルテトラカルボン酸二ｍ水物、３゜３’
、４．４’−ベンゾフェノンテトラカルボン酸二無水物
、２，３．３’、４’−ベンゾフェノンテトラカルボン
酸二無水物、２．２’、３．３−ベンゾフェノンテトラ
カルボン酸二無水物、ビス（３，４−ジカルボキシフェ
ニル）−エーテルニ無水物、ヒス（３，４−ジカルボキ
シフェニル）−スルホンニ無水物、１，２，５．６−ナ
フタリンテトラカルボン酸二無水物、２，３，６．７−
ナフタリンテトラカルボン酸二無水物等。4'-biphenyltetracarboxylic acid dimhydrate, 3°3'
, 4.4'-benzophenonetetracarboxylic dianhydride, 2,3.3',4'-benzophenonetetracarboxylic dianhydride, 2.2',3.3-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl)-ether dianhydride, his(3,4-dicarboxyphenyl)-sulfone dianhydride, 1,2,5.6-naphthalenetetracarboxylic dianhydride, 2,3,6 .7-
Naphthalene tetracarboxylic dianhydride, etc.
また式（２）で表わされるジアミンの具体例としては次
の化合物を挙げることができる。Moreover, the following compounds can be mentioned as specific examples of the diamine represented by formula (2).
１．３−ジアミノプロパン、２．２−ジメチル−１゜３
−ジアミノプロパン、２．２−シヘキシル−１゜３−ジ
アミノプロパン、２，２−ジオクタデシル−１，３−ジ
アミノプロパン、１．４−ジアミノブタン、１．５−ジ
アミノブタンタン、１，６−ジアミツヘキサン等の脂肪
族ジアミン、２．２− （４，４’−ジアミノジフエニ
ル）プロパン等の芳香脂肪族ジアミンあるいは下式で表
わされるポリシロキサンのジアミン類等である。1,3-diaminopropane, 2,2-dimethyl-1゜3
-Diaminopropane, 2,2-cyhexyl-1°3-diaminopropane, 2,2-dioctadecyl-1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminobutantane, 1,6- These include aliphatic diamines such as diamithexane, aromatic aliphatic diamines such as 2,2-(4,4'-diaminodiphenyl)propane, and diamines of polysiloxanes represented by the following formulas.
ＣＨ３０Ｈ。CH30H.
Ｃ６”１３ ０６Ｈ１３
Ｈ３ＣＨ３
次に式（３）で表わされるアミノシリコン化合物として
は次の化合物を挙けることができる。C6''13 06H13 H3CH3 Next, the following compounds can be mentioned as aminosilicon compounds represented by formula (3).
ＮＦ２ （ＣＨ２）３ Ｓｉ （ＯＣＨ３）３、Ｎ
Ｆ２−（ｃ）Ｉ２）３− ｓｉ （ＯＣ２Ｈ５）３、Ｎ
Ｆ２ （ＣＨ２）３ ５ｉ（ＣＨｓ）（ＯＣＨ３）ｚ
、ＮＦ２ （ＣＨ２）３ ８１ （ＣＨ３） （ＯＣ
２Ｈ５）２、ＮＦ２ （ＣＨ２）３ ５ｌ（Ｃ２Ｈ５
）（Ｏｎ Ｃ３１１７）２、ＮＦ２ （ＣＨ２）４−
８ｉ（ＯＣＨ３）３、ＮＦ２ （ＣＨ２）４ ８１（
ＯＣ２Ｈ５）３、ＮＦ２ （ＣＨ２）４ ５ｔ（ＣＨ
３）（ＯＣ２Ｈｓ）ｚ、ＮＦ２−○−８ｉ （ＯＣ２Ｈ
５）３、また式（４）で表わされるシリコン化合物とし
ては次の化合物を挙げることができる。NF2 (CH2)3 Si (OCH3)3, N
F2-(c)I2)3-si(OC2H5)3,N
F2 (CH2)3 5i (CHs) (OCH3)z
, NF2 (CH2)3 81 (CH3) (OC
2H5)2, NF2 (CH2)3 5l(C2H5
)(On C3117)2, NF2 (CH2)4-
8i (OCH3)3, NF2 (CH2)4 81(
OC2H5)3, NF2 (CH2)4 5t(CH
3) (OC2Hs)z, NF2-○-8i (OC2H
5) As the silicon compound represented by 3 and formula (4), the following compounds can be mentioned.
Ｓ ｉ （ＯＣＨ３）４ 、Ｓ ｉ （ＣＨ３） （Ｏ
ＣＨ３）３、”’（Ｃ６Ｈ１３）（ＯＣＨ３）３、Ｓ
１ （ＣｔｓＨ３７） （ＯＣＨ３）３．５ｔ（ＣＨ３
）２（ＯＣＨ３）２、 Ｓｔ（ＣＨ３）（Ｃ１ｇＨ３−
、）（ＯＣＨ３）２．５ｉ（ＯＣ２Ｈ５人、３１（ＣＩ
（３）（ＯＣ２Ｈ５） 、５ｉ（Ｃ６Ｈ１３）（ＯＣ２
Ｈ５）３．５ｉ（Ｃ１ａＨ３７）（ＯＣ２Ｈ５）３．５
ｌ（ＣＨｓ）ｚ （ＯＣ２”５）２、ＣＨ５ＣＨ３ＣＨ
３
ＣＨＣＨ，ＣＨ３
ＣＭ３ＣＨ，ＣＨ３
本発明方法において上記の原料化合物をＩ！８媒中で反
応させるだめの好ましい溶媒（以下反応溶媒と言うこと
がある）として、Ｎ−メチル−２−ピロリドン、Ｎ、Ｎ
−ジメチルアセトアミド、Ｎ、Ｎ−ジメチルホルムアミ
ド、ジメチルスルホキシド、テトラメチル尿素、ピリジ
ノ、ジメチルスルホン、ヘキサメチルホスホルアミド、
メチルホルムアミド、Ｎ−アセテルー２−ピロリドン、
トルエン、キシレン、エチレンクリコールモノメチルエ
ーテル、エチレングリコールモノエチルエーテル、エチ
レングリコールモツプチルエーテル、ジエチレングリコ
ールモノメチルエーテル、ジエチレングリコールジメチ
ルエーテル、シクロペンタノン、シクロヘキサノン等の
１植または２ｓ以上を使用でき、また上記溶媒を３０重
′！にチ以上含有する他の溶媒との混合溶媒としても用
いることができる。S i (OCH3)4 , S i (CH3) (O
CH3)3,"'(C6H13)(OCH3)3,S
1 (CtsH37) (OCH3) 3.5t (CH3
)2(OCH3)2, St(CH3)(C1gH3-
) (OCH3) 2.5i (OC2H5 people, 31 (CI
(3) (OC2H5), 5i (C6H13) (OC2
H5) 3.5i (C1aH37) (OC2H5) 3.5
l(CHs)z (OC2”5)2, CH5CH3CH
3 CHCH,CH3 CM3CH,CH3 In the method of the present invention, the above raw material compound is I! N-methyl-2-pyrrolidone, N,N
-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, pyridino, dimethylsulfone, hexamethylphosphoramide,
Methylformamide, N-acetel-2-pyrrolidone,
One or more of toluene, xylene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol motsubutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, etc. can be used. Heavy! It can also be used as a mixed solvent with other solvents containing at least 100% of the solvent.
次に反応方法について説明する。式（１）で示されるテ
トラカルボン酸二無水物、式（２）で示されるジアミン
及び式（３）で示されるアミノシリコン化合物とを反応
溶媒中で反応させる。Next, the reaction method will be explained. A tetracarboxylic dianhydride represented by formula (1), a diamine represented by formula (2), and an aminosilicon compound represented by formula (3) are reacted in a reaction solvent.
反応溶媒はこれと添加した原料との合計蓋基準で４０重
量％以上使用するのが良い。これ以下では撹拌操作が困
難である場合がある。The reaction solvent is preferably used in an amount of 40% by weight or more based on the total weight of the reaction solvent and the added raw materials. If it is less than this, the stirring operation may be difficult.
この第１段階の反応は０℃以上２００℃以下で行うのが
よい。This first stage reaction is preferably carried out at a temperature of 0°C or higher and 200°C or lower.
反応時間ａ Ｏ，２〜２０時間反応せしめるのがよい。Reaction time a O, preferably 2 to 20 hours.
反応温度が比較的高い温度、例えば６０〜２００℃の場
合では後述するようにイミド化反応と同時にシロキサン
組合反応が進行し液はゲル化反応により流動性を失なう
場合がある。When the reaction temperature is relatively high, for example 60 to 200°C, the siloxane combination reaction proceeds simultaneously with the imidization reaction, as will be described later, and the liquid may lose fluidity due to the gelation reaction.
この様な現象を避けるため少量の（ＣＨ３）３Ｓｔ （
ＯＣＨ３）、（ＣＨ３）３Ｓｉ（’Ｃ２Ｈ３）等のシリ
ル化剤を添加して反応を行なうこともできる。To avoid this phenomenon, a small amount of (CH3)3St (
The reaction can also be carried out by adding a silylating agent such as OCH3) or (CH3)3Si('C2H3).
酸とアミンの混合比は、式（１）で表わされる酸無水物
の量をλモル式（２）で表わされるジアミンの量をＢモ
ル、式（３）で表わされるアミノシリコン化合物の量を
Ｃモルとすれば２Ａ＝２Ｂ＋Ｃから両辺のずれが±２０
％以内が特に好ましい。The mixing ratio of acid and amine is as follows: the amount of acid anhydride represented by formula (1) is λ mole, the amount of diamine represented by formula (2) is B mole, and the amount of aminosilicon compound represented by formula (3) is If it is C mole, the deviation on both sides is ±20 from 2A=2B+C
% or less is particularly preferable.
式（２）で示されるジアミンがシリコンを含まない場合
には、それに対する式（３）で示されるアミノシリコン
化合物の比率は式（７）の範囲が特に好ましい。When the diamine represented by formula (2) does not contain silicon, the ratio of the amino silicon compound represented by formula (3) to it is particularly preferably within the range of formula (7).
□≧０．１ ・・・・・・・・・（７）Ｂ＋Ｃ
反応原料の反応系への添加層厚に関しては、テトラカル
ボン酸二無水物、ジアミン及びアミノシリコン化合物の
全部を同時に反応溶媒に加えて反応せしめてもよく、前
二者をあらかじめ反応せしめた後、その反応生成物にア
ミノシリコン化合物を反応せしめることもできる。アミ
ノシリコン化合物の添加を最後にした場合にはよシ高分
子量のポリマーが得られやすい。□≧0.1 (7) B+C Regarding the layer thickness of the reaction raw materials added to the reaction system, all of the tetracarboxylic dianhydride, diamine, and aminosilicon compound are added to the reaction solvent at the same time. They may be reacted in addition, or the former two may be reacted in advance and then the reaction product may be reacted with the aminosilicon compound. If the amino silicon compound is added last, it is easier to obtain a polymer with a higher molecular weight.
さらに必要により第１段階の反応液に式（４）で示され
るシリコン化合物を添加したままでも使用可能であり、
またこの混合６０−２２．００３ ；Ｏ時間反応を行な
うこともできる。この場合にも反応液のゲル化を防ぐた
めにシリル化剤を添加することも可能でありまたシロキ
サン縮合反応を進行させる丸めトリエチルアミン等の３
級アミンあるいは酢酸等の酸触媒を添加することもでき
るし、少量の水を添加することも反応促進に寄与する場
合がある。Furthermore, if necessary, the silicon compound represented by formula (4) can be used as it is added to the first stage reaction solution,
It is also possible to carry out this mixing reaction for 60-22.003;0 hours. In this case, it is also possible to add a silylating agent to prevent gelation of the reaction solution, and a silylating agent such as rounded triethylamine to advance the siloxane condensation reaction.
It is also possible to add a grade amine or an acid catalyst such as acetic acid, and addition of a small amount of water may also contribute to promoting the reaction.
式（４）の化合物の添加の効果は、本発明塗布液をガラ
ス基板に塗布し、焼成したときの接着効果を増加させる
ほか、その添加量の増減により、式（１）、（２Ｌ （
３）の化合物から形成されるポリイミドによる配向膜の
プレ・チルト角を増減させることが可能であシ、これに
より所望のプレ・チルト角を得ることができることであ
る。The effect of adding the compound of formula (4) is to increase the adhesive effect when the coating solution of the present invention is applied to a glass substrate and fired, and also to increase or decrease the amount of addition of the compound of formula (1), (2L (
It is possible to increase or decrease the pre-tilt angle of the polyimide alignment film formed from the compound of 3), thereby making it possible to obtain a desired pre-tilt angle.
上述したように第１段階の反応液、これと式（４）のシ
リコン化合物の混合物またはこの混合物の反応を行なっ
た第２段階の反応液のいづれも本発明の塗布液として使
用することは可能であるが、これらのいづれかのものと
他の化合物、例えば通常の全芳香族のポリアミド酸（プ
レチルト角の調整のために加える）との混合物の溶液と
して使用することもできる。As mentioned above, any of the first-stage reaction solution, a mixture of this and the silicon compound of formula (4), or a second-stage reaction solution obtained by reacting this mixture can be used as the coating solution of the present invention. However, it is also possible to use a solution of a mixture of any of these with other compounds, such as a conventional wholly aromatic polyamic acid (added to adjust the pretilt angle).
このようにして得られた可溶性ポリイミドシロキチン前
駆体を含有する塗布液は塗布対称にスピンナー、ディッ
プ、印刷等の公知の方法で塗布し、１００〜３００℃に
加熱することにより溶媒を蒸発させるとともに該前駆体
を架橋させ、硬化させることができる。The coating solution containing the soluble polyimidosilochitin precursor thus obtained is applied by a known method such as spinner, dipping, printing, etc., and the solvent is evaporated by heating to 100 to 300°C. The precursor can be crosslinked and cured.
本発明の方法によって製造した可溶性ポリイミドシロキ
サン前駆体を含む塗布液は適当な方法によりガラス基板
上に塗布後焼成することによりイミド化反応の完結とと
もにシロキサン結合の形成が進行し、硬くて強靭な被膜
を形成するとともにガラス基板とは強固に接着する。The coating solution containing the soluble polyimide siloxane precursor produced by the method of the present invention is coated onto a glass substrate by an appropriate method and then baked to complete the imidization reaction and progress the formation of siloxane bonds, resulting in a hard and tough coating. It forms a strong bond to the glass substrate.
その為、従来のポリイミド膜では必要であったシランカ
ップリング剤によるガラス基板の前処が。Therefore, the glass substrate must be pre-treated with a silane coupling agent, which was necessary with conventional polyimide films.
理が不要となった。更に安定な傾斜配Ｒ囁膜をラビング
することにより容易に得られる。Reasoning is no longer necessary. Furthermore, it can be easily obtained by rubbing a stable R-shaped film.
以下、実施例、比較例及び使用試験によって本発明を更
に具体的に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples, Comparative Examples, and Usage Tests.
実施例１
かくはん装置、滴下ロート、温度計、コンデンサーおよ
び窒素置換装置を付した１１のフラスコを恒温槽内に固
定した。フラスコ内を窒素ガスによジ置換した後、脱水
精製した５００ｊｄＤ２−ブトキシェタノール、１６．
９８ Ｆ （６０１６６モル）の数平均分子量１０２０
（式（５）の７＝１１．４）の両末端（３−アミノプロ
ピル）ポリジメチルシロキサ／を投入した後フラスコ内
の温度を１０〜１５℃に保ちつつ４．８４ｆ（０，０２
２２モル）のピロメリット酸二無水物を投入しこの温度
で３時間反応を行なった後、１．９０ｆ（０，００９８
モル）の３−７ミノプロビルジエトキシシランを添加し
さらに２５〜３０℃で３時間反応を行ない透明液（フェ
ノ）を得た。得られた本発明の塗布液の２５℃での回転
粘度は２５センチポイズであった。Example 1 Eleven flasks equipped with a stirring device, a dropping funnel, a thermometer, a condenser, and a nitrogen purging device were fixed in a constant temperature bath. After purging the inside of the flask with nitrogen gas, 500jdD2-butoxyshetanol was dehydrated and purified, 16.
Number average molecular weight of 98 F (60166 mol) 1020
After adding (3-aminopropyl)polydimethylsiloxa/ (7=11.4 in formula (5)) at both ends, 4.84f (0,02
After adding 22 mol) of pyromellitic dianhydride and carrying out the reaction at this temperature for 3 hours, 1.90 f (0,0098
mol) of 3-7 minopropyldethoxysilane was added, and the reaction was further carried out at 25 to 30°C for 3 hours to obtain a transparent liquid (pheno). The rotational viscosity of the obtained coating liquid of the present invention at 25° C. was 25 centipoise.
前記回転粘度は東京計器＠製にＥＷ粘度計を使用し、温
度２５±０．１℃で測定した。The rotational viscosity was measured at a temperature of 25±0.1° C. using an EW viscometer manufactured by Tokyo Keiki@.
以下同様。Same below.
この塗布液を０．２μのフィルターを通してろ過するこ
とによりａ製した後、ガラス基板上にスピンナーで均一
に塗布した。これをオープン中２００℃で加熱すること
により溶媒を蒸発させるとともに硬化させた。得られた
塗膜の表面は滑らかで、ガラス基板上に強く接着してお
シ、下記接着テストでｄ塗膜のはがれはなかった。This coating solution was filtered through a 0.2μ filter to prepare a sample, and then coated uniformly onto a glass substrate using a spinner. This was heated at 200° C. while open to evaporate the solvent and harden it. The surface of the resulting coating film was smooth and adhered strongly to the glass substrate, and no peeling of the coating film occurred in the following adhesion test.
前記接着テストは次のようにして行なったニーガラス基
板上の１１１膜に切目を入れて、−辺２ｎの正方形１０
０個の小片に細分し、その表面にセロ・・／テープを貼
シ付けて直ちＫはがした。The adhesion test was carried out as follows: A cut was made in the 111 film on the knee glass substrate, and a square 10 with side 2n was cut.
It was divided into 0 small pieces, and cello tape was applied to the surface of the piece and immediately removed.
そのときのはがれた枚数を数えることにより接着性の評
価を行なった。Adhesion was evaluated by counting the number of peeled sheets.
実施例２
実施例１で得られたフェノの一部をと）これにオクチル
トリエトキシシラン及び溶媒である２−ブトキシェタノ
ールを添加し、フェス中の固形分とオクチルトリエトキ
シシランの合計量に対するオクチルトリエトキシシラン
の割合を３０重量パーセントとしかつフェス中の固形分
とオクチルトリエトキシシランの合計量が全混合液に対
して５重量パーセントになるように調製し九。この混合
液を１００℃３時間反応させるととくより本発明の塗布
液を得た。この塗布液の２５℃での回転粘度は３１セン
チポイズであつ九。Example 2 Octyltriethoxysilane and 2-butoxyshetanol, which is a solvent, were added to a part of the pheno obtained in Example 1, and the total amount of solid content and octyltriethoxysilane in the pheno was added. The ratio of octyltriethoxysilane was adjusted to 30% by weight, and the total amount of solid content in the face and octyltriethoxysilane was adjusted to 5% by weight based on the total mixed liquid. This mixed solution was reacted at 100° C. for 3 hours to obtain a coating solution of the present invention. The rotational viscosity of this coating liquid at 25°C is 31 centipoise.
これを実施例１と同様に精製、塗布硬化させた。得られ
た塗膜の表面は滑らかで、前記接着テストで塗膜のはが
れはなかった・
実施例３〜６
実施例１と同様の装置及び方法により５００ ｊｊの２
−メトキシエタノール、５．９６ ｆ （０，０５８４
モル）の２．２−ジメチル−１，３−ジアミノプロパン
、４．０３Ｆ（０，０２１１モル）の３−アミノプロピ
ルメチルジェトキシシラン及び１５，２９２（００７０
モル）のビロメリツ）Ｉｌｆｆ二無水物を投入し２０〜
２５℃で３時間、さらに５５〜６０℃で１時間反応を行
ないポリイミドシロキサン前駆体を含有する均−液を得
た。この反応生成液の一部をとってオクタデシルトリエ
トキシシラン及び２−メトキシエタノールを添加し第１
表に示すような組成物に調合し各溶液を１２０℃８時間
反応を行ない本発明の塗布液を得た。This was purified, coated and cured in the same manner as in Example 1. The surface of the obtained coating film was smooth, and there was no peeling of the coating film in the adhesion test mentioned above.
-methoxyethanol, 5.96 f (0,0584
mol) of 2,2-dimethyl-1,3-diaminopropane, 4.03F (0.0211 mol) of 3-aminopropylmethyljethoxysilane and 15,292 (0.070 mol) of 3-aminopropylmethyljethoxysilane.
mol) of Ilff dianhydride was added and the
The reaction was carried out at 25°C for 3 hours and then at 55-60°C for 1 hour to obtain a homogeneous liquid containing a polyimidosiloxane precursor. A portion of this reaction product solution was taken and octadecyltriethoxysilane and 2-methoxyethanol were added to it.
The compositions shown in the table were prepared and each solution was reacted at 120° C. for 8 hours to obtain a coating solution of the present invention.
各塗布液を実施例１と同様の方法でｆ＃製した後スピン
ナーによりガラス基板上に塗布し、２００℃で１時間焼
成し硬化させた。Each coating solution was prepared into f# in the same manner as in Example 1, and then applied onto a glass substrate using a spinner, and baked at 200° C. for 1 hour to harden.
何れの塗膜の表面も滑らかで、ガラス基板上に強く接着
しており、前記接着テストでは塗膜のはがれはなかった
。The surface of each coating film was smooth and adhered strongly to the glass substrate, and no peeling of the coating film occurred in the adhesion test.
第 １ 表
ただし、０ＤＳＥはオクタデシルトリエトキシシランで
あり固形分とは前段階のポリイミドシロキチン前駆体溶
液を２００’Ｃ焼成したときに固体であるものを言う。Table 1 However, 0DSE is octadecyltriethoxysilane, and the solid content refers to what is solid when the polyimide silochitin precursor solution in the previous step is fired at 200'C.
以下同様。Same below.
実施例７
実施例１と同様の装置及び方法により５００ＩＩｌの２
−メトキシエタノール、２，４５１’（０，０２００モ
ル）の２，２−ジメチル−１，５−ジアミノペンタン、
６．７８ｙ（０，０１３３モル）の両末端（３−アミノ
プロピル）ポリジメチルシロキサン（式（ｓ）。Example 7 2 of 500IIl was prepared using the same apparatus and method as in Example 1.
-methoxyethanol, 2,451' (0,0200 mol) of 2,2-dimethyl-1,5-diaminopentane,
6.78y (0,0133 mol) at both ends (3-aminopropyl)polydimethylsiloxane (formula (s)).
ｌ ＝ ４．５０）及び１２．９ｏｒ （０，０４００
モル）の３．３’。l = 4.50) and 12.9or (0,0400
3.3' of mole).
４．４′−べ／シフエノンテトラカルボン酸二無水物を
投入し、２５〜３０℃で２時間反応を行なった後、２．
９４ｆ（０，０１３３モル）の３−アミノプロピルトリ
エトキシンランを添加し、５５〜６０℃で１時間反応を
行ない均−液を得た。この反応生成液の一部Ｋｎ−オク
チルトリエトキシシラン及び２−メトキシエタノールを
混合し、前段階の反応液中の固形分の１貸とｎ−オクチ
ルトリエトキシシランの重量が等量になり、かつこの両
方の合計量が全溶液の５１！に％である本発明の塗布液
を調合した。この塗布液の２５℃での回転粘度Ｆｉ４．
３七ンチボインチボイズ。4. After adding 4'-be/siphenotetracarboxylic dianhydride and carrying out a reaction at 25 to 30°C for 2 hours, 2.
94f (0,0133 mol) of 3-aminopropyltriethoxine was added, and the reaction was carried out at 55 to 60°C for 1 hour to obtain a homogeneous solution. Part of this reaction product liquid was mixed with Kn-octyltriethoxysilane and 2-methoxyethanol, so that the weight of the solid content in the reaction liquid in the previous step was equal to the weight of n-octyltriethoxysilane, and The total amount of both is 51 of the total solution! A coating solution of the present invention was prepared in a proportion of . The rotational viscosity of this coating liquid at 25°C is Fi4.
37 inches bois.
この塗布液をスピンナーによりガラス基板上に塗布した
後、２００℃１時間焼成し硬化させた。この塗膜の表面
は滑らかで、ガラス基板上に＠固に接着しており、前記
接着テストでは塗膜のはがれはなかった。This coating liquid was applied onto a glass substrate using a spinner, and then baked at 200° C. for 1 hour to harden it. The surface of this coating film was smooth and firmly adhered to the glass substrate, and no peeling of the coating film occurred in the adhesion test.
比較例１
実施例１と同様の装置及び方法で５００ｄのＮ−メチル
−２−ピロリドン及び１２．９７ Ｆ（０，０ｆ５４８
モル）の４．４′−ジアミノジフェニルエーテル及び１
４．１４ ｒ （０，０６４８モル）のピロメリット酸
二無水物を投入し、１５〜２０℃で８時間反応を行なう
ことにより透明液を得た。Comparative Example 1 500d N-methyl-2-pyrrolidone and 12.97F (0,0f548
mol) of 4,4'-diaminodiphenyl ether and 1
A transparent liquid was obtained by adding 4.14 r (0,0648 mol) of pyromellitic dianhydride and carrying out the reaction at 15 to 20°C for 8 hours.
この反応生成液の２５℃での回転粘度は４７七ンチボイ
ズであった。The rotational viscosity of this reaction product liquid at 25° C. was 477 inch voids.
この反応生成液を実施例１と同様の方法で精製した後、
ガラス基板上にスピンナーで塗布し、オーブン中３００
℃で１時間加熱することＫよ。After purifying this reaction product solution in the same manner as in Example 1,
Coated on a glass substrate with a spinner and placed in an oven for 300 min.
Heat it at ℃ for 1 hour.
り硬化させた。得られた塗膜の表面は滑らかであったが
前記接着テストでは１００％はがれた。hardened. Although the surface of the resulting coating film was smooth, it peeled off 100% in the adhesion test.
使用試験１
実施例１及び２に示した方法で得られた塗膜をレンズク
リーン・ペーパーで３０回ラビングし、セル厚が約１０
μｍになるように調整し９０夏ねじシのＴＮセルに組立
てた。Use test 1 The coating film obtained by the method shown in Examples 1 and 2 was rubbed 30 times with lens clean paper, and the cell thickness was approximately 10
It was adjusted to have a diameter of μm and assembled into a TN cell with a 90 mm screw.
このＴＮセルにチッソ■製のＰ型ネマチック（以下ｒ
Ｎ ｐ ｆｊｌ Ｊと略記する。）液晶材料ＬＩＸＯＮ
（登録商標）ＧＲ−６３を注入して、プレ・チルト角
θを測定した。結果を第２表に示す。In this TN cell, P-type nematic (hereinafter referred to as r) manufactured by Chisso ■
It is abbreviated as N p fjl J. )Liquid crystal material LIXON
(registered trademark) GR-63 was injected and the pre-tilt angle θ was measured. The results are shown in Table 2.
プレ・チルト角の測定原理は以下に示す通りである。（
第１図（、）〜（ｃ）参照）液晶分子をプレ・チルト角
０度で配列させてその時にしきい値電圧ｖｔｈ以下の印
加電圧ＶをかけてａＩＩｔ率を測定すると、液晶分子は
動かない為に１観測される誘電率ε。ｂＢｌｉｌユに対
応する。（第１図（ａ））
しきい値電圧を超える印加電圧をかけると液晶分子はだ
んだん立ち上がってきて、十分に高い印加電圧ではＣ０
ｂ８はりと等しくなる。（第１図（ｂ））
その中間の印加電圧ではＣ０ｂ、はＣ５と８上のベクト
ル和で（１）式の様に表わされる。その時０は液晶分子
の傾きを示す。The principle of measuring the pre-tilt angle is as shown below. (
(See Figure 1 (,) to (c)) When liquid crystal molecules are aligned at a pre-tilt angle of 0 degrees and an applied voltage V below the threshold voltage vth is applied to measure the aIIt rate, the liquid crystal molecules do not move. Therefore, the dielectric constant ε observed is 1. Corresponds to bBlilyu. (Figure 1 (a)) When an applied voltage exceeding the threshold voltage is applied, the liquid crystal molecules gradually rise, and at a sufficiently high applied voltage, C0
It becomes equal to the b8 beam. (FIG. 1(b)) At an intermediate applied voltage, C0b is expressed as the sum of vectors on C5 and 8 as shown in equation (1). At that time, 0 indicates the tilt of the liquid crystal molecules.
εｏｂｓ＝’ｚ ｓｉｎθ＋ｅ、Ｌｃｏ８θ （１）
ところで、初めから、液晶分子がプレ・チルト角θを持
って傾斜配向していたら、しきい値電圧ｖｔｈよ）十分
低い印加電圧をかけてｇ。ｂ、を測定すると、’ｏｂｓ
はやはシ（１）式で表わされることは・」らかである。εobs='z sinθ+e, Lco8θ (1)
By the way, if the liquid crystal molecules are oriented obliquely with a pre-tilt angle θ from the beginning, apply a sufficiently low applied voltage (threshold voltage vth) to g. When we measure b, 'obs
It is obvious that it can be expressed by equation (1).
そこで、今回のプレ・チルト角の測定では、あらかじめ
セルに注入するネマチック液晶材料のε、とＣ上を測定
しておき、θとＣ０ｂｓ”関係を示すグラフを（１）式
を用いて書いておき、測定されたＩ。ｂ、からグラフよ
シプレ・チルト角θを決めた。尚、誘電率’ｏｂｓ＋は
Ｉ ＫＨｚのｓｉｎ波で０．５ｖ印加して、セルに液晶
材料を注入する前と後の容量比から求めた。Therefore, in this pre-tilt angle measurement, we first measured ε and C of the nematic liquid crystal material injected into the cell, and then drew a graph showing the relationship between θ and C0bs'' using equation (1). The Sipre tilt angle θ was determined from the graph from the measured I.b.The dielectric constant 'obs+ was determined by applying 0.5V with a sine wave of I KHz and before injecting the liquid crystal material into the cell. It was determined from the subsequent capacity ratio.
比較例１で示した塗布液をシランカップリング剤で処理
したガラス基板上に比較例１で示した方法で塗布し、加
熱して得られた塗膜（以後「比較例１の塗膜」と呼ぶこ
とがある。）をレンズクリーン・ペーパーで２５回ラビ
ングし、セル厚が約１０μｍになる様にｖ４整し、９０
ＩＩｔねじシのＴＮセルに組立てた。このＴＮセルに同
じネマチック液晶ＬＩＸＯＮ （登録商標）ＧＲ−６３
を注入して、前述の方法でプレ・チルト角０を測定した
。結果を第２表に示す。The coating solution shown in Comparative Example 1 was applied onto a glass substrate treated with a silane coupling agent by the method shown in Comparative Example 1, and the resulting coating film was heated (hereinafter referred to as "the coating film of Comparative Example 1"). ) was rubbed 25 times with lens clean paper, adjusted to v4 so that the cell thickness was approximately 10 μm, and then
It was assembled into a TN cell with an IIt screw. The same nematic liquid crystal LIXON (registered trademark) GR-63 as this TN cell
was injected, and the pre-tilt angle 0 was measured using the method described above. The results are shown in Table 2.
第２！ｌ！
従来のポリイミド膜では水平配向になってしまうが、本
発明の膜では傾斜配向が得られることがわかる。Second! l! It can be seen that while the conventional polyimide film results in horizontal orientation, the film of the present invention provides oblique orientation.
使用試験２
実施例３〜６及び比較例１の塗膜をレンズ・クリーン・
ペーパーで３０回ラビングし、セル厚が約１０μｍにな
る様に調整し、９０度ねじシのＴＮセルに組立てた。こ
のＴＮセルにチッソ四のＮｐ型液晶材料ＬＩＸＯＮ（登
録商標）３０４６−１５を注入し、前述の方法でプレ・
チルト角０を測定した。結果を第３表に示す。Use test 2 The coating films of Examples 3 to 6 and Comparative example 1 were applied to Lens Clean.
The cell was rubbed 30 times with paper, adjusted to have a cell thickness of about 10 μm, and assembled into a TN cell with a 90 degree screw. Chisso Shishi's Np type liquid crystal material LIXON (registered trademark) 3046-15 was injected into this TN cell, and pre-injected using the method described above.
A tilt angle of 0 was measured. The results are shown in Table 3.
第３表
従来のポリイミド膜では、やはシ水平配向になってしま
うが、本発明による塗膜はどれも傾斜配向することがわ
かる。更に原料組成のＯＤＳＥ比が大きくなるに従いプ
レ・チルト角θも大きくなっていく。Table 3 It can be seen that conventional polyimide films tend to have a horizontal orientation, but all the coating films according to the present invention have an oblique orientation. Furthermore, as the ODSE ratio of the raw material composition increases, the pre-tilt angle θ also increases.
０ＤＳＥ比を変えることによりプレ・チルト角を自由に
コントロールできることがわかる。It can be seen that the pre-tilt angle can be freely controlled by changing the 0DSE ratio.
使用試験３
実施例７及び比較例１の塗膜をレンズ・クリーン・ペー
パーで３０回ラうングシ、セル厚カ約１０μｍＫなる様
ＫｖＩ！整し、９０度ねじりのＴＮセルに組立てた。こ
のＴＮセルにチッソ■（ＤＮｐｆｆｌＱ晶材料ＬＩＸＯ
Ｎ （登録商ｇ ） ３０４６−１５を注入し、前述の
方法でブレ・チルト角を測定した。Usage Test 3 The coating films of Example 7 and Comparative Example 1 were rubbed with lens clean paper 30 times until the cell thickness was approximately 10 μmK. It was then assembled into a TN cell with a 90 degree twist. In this TN cell, Chisso ■ (DNpfflQ crystal material LIXO
N (Registered Trademark G) 3046-15 was injected, and the shake and tilt angles were measured using the method described above.
結果を第４！２に示す。The results are shown in Section 4!2.
第４表
従来のポリイミドでは水平配向になってしまうが、本発
明による塗膜では、傾斜配向することがわかる。Table 4 It can be seen that conventional polyimide has a horizontal orientation, but the coating film according to the present invention has an oblique orientation.
先回面の簡単な説明
第１図（ａ）ＩｉＮｐｍ液晶を注入した液晶セルのブレ
・チルト角が０度のときに、Ｌきい値を圧よシ低い印加
電圧を印加して観察される誘ｆｉｔ率εｏｂａを示す図
、同（ｂ）はＮｐＷ液晶を注入した液晶セルにしきい値
電圧より十分に高い電圧を印加して観察されるε。ｂｓ
を示す図、同（Ｃ）はＮｐ型液晶を注入した液晶セル内
で液晶分子が０度傾斜した状態にあるときに、観察され
るｔ。ｂ、を示す図である。Brief explanation of the previous issue Figure 1 (a) When the shake/tilt angle of a liquid crystal cell injected with IiNpm liquid crystal is 0 degrees, the induced voltage observed by applying a lower voltage than the L threshold Figure 2 (b) shows the fit rate εoba observed when a voltage sufficiently higher than the threshold voltage is applied to a liquid crystal cell injected with NpW liquid crystal. bs
(C) shows the t observed when the liquid crystal molecules are tilted at 0 degrees in a liquid crystal cell injected with Np type liquid crystal. It is a figure showing b.
以上 特許出鵬人 チッソ株式会社 代理人 弁理士 佐々井 彌太部 同 上 野 中 克 Ｊthat's all Patent issuer Chisso Co., Ltd. Agent: Patent Attorney Yatabe Sasai Same as above Katsu No Naka J
Claims (2)
無水物、式（２）で表わされるジアミン及び式（３）で
表わされるアミノシリコン化合物を溶媒中で混合し、反
応を行ない、必要により式（４）で表わされるシリコン
化合物を添加し、場合により加熱反応を行なうことによ
り得られる可溶性ポリイミドシロキサン前駆体を含有す
るスーパー・ツイスト複屈折効果型の液晶配向膜用塗布
液。 ▲数式、化学式、表等があります▼……………（１） ＮＨ＿２−Ｒ＾２−ＮＨ＿２……………（２） ＮＨ＿２−Ｒ＾３−ＳｉＲ＾４＿３＿−＿ｍＸ＾４＿ｍ
………（３） Ｓｉ（Ｒ＾５）＿３Ｘ＾２……………（４） 〔式（１）〜（４）において、Ｒ＾１は４価の炭素環式
芳香族基を表わし、Ｒ＾２は炭素数２〜５０個直鎖状ま
たは分岐状の脂肪族基、炭素数６〜５０個の芳香脂肪族
基、次式（５）で表わされるポリシロキサン基であり、
Ｒ＾３は−（ＣＨ＿２）＿■−、▲数式、化学式、表等
があります▼、▲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▼であり（ただし、
ここに■は１〜４の整数を表わす。）、Ｒ＾４は独立に
炭素数１〜２０個のアルキル基、フェニル基、若しくは
炭素数１〜２０個のアルキル置換フエニル基を表わし、
Ｘ＾１及びＸ＾２は独立にアルコキシ基、アセトキシ基
、ハロゲンまたは水酸基を表わし、Ｒ＾５は独立にＲ＾
４、Ｘ＾２または次式（６）を表わし、 ▲数式、化学式、表等があります▼…………（６） （ここにｌは１≦１≦１００の値をとる。）Ｒ＾５の全
てが同時にＲ＾４になることはなく、ｍは１≦ｍ≦３の
値をとる。 ▲数式、化学式、表等があります▼………（５） なお同一記号の基又は英文字はそれを含む一般式が異な
つても独立に所定の範囲の基または数を表わす。以下同
様。〕(1) A tetracarboxylic dianhydride represented by the following formula (1), a diamine represented by the formula (2), and an aminosilicon compound represented by the formula (3) are mixed in a solvent, a reaction is performed, and the necessary A coating liquid for a super twist birefringence effect type liquid crystal alignment film, which contains a soluble polyimidosiloxane precursor obtained by adding a silicon compound represented by formula (4) and optionally performing a heating reaction. ▲There are mathematical formulas, chemical formulas, tables, etc.▼……………(1) NH_2-R^2-NH_2………(2) NH_2-R^3-SiR^4_3_-_mX^4_m
………(3) Si(R^5)_3X^2………(4) [In formulas (1) to (4), R^1 represents a tetravalent carbocyclic aromatic group, R^2 is a linear or branched aliphatic group having 2 to 50 carbon atoms, an aromatic aliphatic group having 6 to 50 carbon atoms, or a polysiloxane group represented by the following formula (5),
R^3 is -(CH_2)＿■-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However,
Here, ■ represents an integer from 1 to 4. ), R^4 independently represents an alkyl group having 1 to 20 carbon atoms, a phenyl group, or an alkyl-substituted phenyl group having 1 to 20 carbon atoms,
X^1 and X^2 independently represent an alkoxy group, acetoxy group, halogen or hydroxyl group, and R^5 independently represents R^
4. Represents X^2 or the following formula (6), ▲There are mathematical formulas, chemical formulas, tables, etc.▼…………(6) (Here l takes a value of 1≦1≦100.)R＾5 are not all R^4 at the same time, and m takes a value of 1≦m≦3. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (5) Groups or alphabetic characters with the same symbol independently represent groups or numbers within a given range even if the general formulas containing them are different. Same below. ]
無水物、式（２）で表わされるジアミン及び式（３）で
表わされるアミノシリコン化合物を溶媒中で混合し、反
応を行ない、必要により式（４）で表わされるシリコン
化合物を添加し、場合により加熱反応を行なうことによ
り得られる可溶性ポリイミドシロキサン前駆体を含有す
る液晶配向膜用塗布液をガラス基板上に塗布し１００〜
３００℃に加熱することにより溶媒を蒸発させるととも
に該前駆体を架橋させ、硬化させることにより形成され
るスーパー・ツイスト複屈折効果型の液晶配向膜。 ▲数式、化学式、表等があります▼…………（１） ＮＨ＿２−Ｒ＾２−ＮＨ＿２…………（２） ＮＨ＿２−Ｒ＾３−ＳｉＲ＾４＿３＿−＿ｍＸ＾１＿ｍ
…………（３） Ｓｉ（Ｒ＾５）＿３Ｘ＾２…………（４） 〔式（１）〜（４）において、Ｒ＾１は４価の炭素環式
芳香族基を表わし、Ｒ＾２は炭素数２〜５０個の直鎖状
または分岐状の脂肪族基、炭素数６〜５０個の芳香脂肪
族基、次式（５）で表わされるポリシロキサン基であり
、Ｒ＾３は−（ＣＨ＿２）■−、▲数式、化学式、表等
があります▼、▲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▼であり（ただし、
ここに＿■は１〜４の整数を表わす。）、Ｒ＾４は独立
に炭素数１〜２０個のアルキル基、フェニル基若しくは
アルキル置換フェニル基を表わし、Ｘ＾１及びＸ＾２は
独立にアルコキシ基、アセトキシ基、ハロゲンまたは水
酸基を表わし、Ｒ＾５は独立にＲ＾４、Ｘ＾２または次
式（６）を表わし ▲数式、化学式、表等があります▼…………（６） （ここにｌは１≦ｌ≦１００の値をとる。）Ｒ＾５の全
てが同時にＲ＾４になることはなく、ｍは１≦ｍ≦３の
値をとる。 ▲数式、化学式、表等があります▼………（５）〕(2) A tetracarboxylic dianhydride represented by the following formula (1), a diamine represented by the formula (2), and an aminosilicon compound represented by the formula (3) are mixed in a solvent, a reaction is performed, and the necessary A coating liquid for a liquid crystal alignment film containing a soluble polyimide siloxane precursor obtained by adding a silicon compound represented by formula (4) and optionally performing a heating reaction is applied onto a glass substrate.
A super twist birefringence effect type liquid crystal alignment film formed by heating to 300° C. to evaporate the solvent, crosslink the precursor, and harden the precursor. ▲There are mathematical formulas, chemical formulas, tables, etc.▼…………(1) NH_2-R^2-NH_2…………(2) NH_2-R^3-SiR^4_3_-_mX^1_m
………(3) Si(R^5)_3X^2…………(4) [In formulas (1) to (4), R^1 represents a tetravalent carbocyclic aromatic group, R^2 is a linear or branched aliphatic group having 2 to 50 carbon atoms, an aromatic aliphatic group having 6 to 50 carbon atoms, or a polysiloxane group represented by the following formula (5); 3 is -(CH_2)■-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However,
Here, _■ represents an integer from 1 to 4. ), R^4 independently represents an alkyl group having 1 to 20 carbon atoms, a phenyl group or an alkyl-substituted phenyl group, X^1 and X^2 independently represent an alkoxy group, an acetoxy group, a halogen or a hydroxyl group, R^5 independently represents R^4, X^2 or the following formula (6) ▲There are mathematical formulas, chemical formulas, tables, etc.▼…………(6) (Here l is a value of 1≦l≦100 ) All of R^5 do not become R^4 at the same time, and m takes a value of 1≦m≦3. ▲There are mathematical formulas, chemical formulas, tables, etc.▼……(5)]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16012586A JPS6315223A (en) | 1986-07-08 | 1986-07-08 | Coating liquid for liquid crystal orientation film and liquid crystal orientation film formed by heating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16012586A JPS6315223A (en) | 1986-07-08 | 1986-07-08 | Coating liquid for liquid crystal orientation film and liquid crystal orientation film formed by heating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6315223A true JPS6315223A (en) | 1988-01-22 |
Family
ID=15708407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16012586A Pending JPS6315223A (en) | 1986-07-08 | 1986-07-08 | Coating liquid for liquid crystal orientation film and liquid crystal orientation film formed by heating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6315223A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4970283A (en) * | 1987-10-11 | 1990-11-13 | Chisso Corporation | Silicon-containing soluble polyimide precursor, its cured material, and method for preparing them |
| JPH03275722A (en) * | 1990-03-23 | 1991-12-06 | Shin Etsu Chem Co Ltd | Curable resin, production thereof and protecting film for electronic part |
| JPH05158046A (en) * | 1991-12-04 | 1993-06-25 | Sumitomo Bakelite Co Ltd | Production of polyamic acid for liquid crystal oriented film and liquid crystal oriented film using the acid |
| JPH10310639A (en) * | 1997-05-09 | 1998-11-24 | Ube Ind Ltd | Colorless transparent polyimide and production thereof |
| US6244594B1 (en) | 1998-03-02 | 2001-06-12 | Tohoku Ricoh Co., Ltd. | Apparatus for storing sheets driven out of an image forming apparatus |
-
1986
- 1986-07-08 JP JP16012586A patent/JPS6315223A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4970283A (en) * | 1987-10-11 | 1990-11-13 | Chisso Corporation | Silicon-containing soluble polyimide precursor, its cured material, and method for preparing them |
| JPH03275722A (en) * | 1990-03-23 | 1991-12-06 | Shin Etsu Chem Co Ltd | Curable resin, production thereof and protecting film for electronic part |
| JPH05158046A (en) * | 1991-12-04 | 1993-06-25 | Sumitomo Bakelite Co Ltd | Production of polyamic acid for liquid crystal oriented film and liquid crystal oriented film using the acid |
| JPH10310639A (en) * | 1997-05-09 | 1998-11-24 | Ube Ind Ltd | Colorless transparent polyimide and production thereof |
| US6244594B1 (en) | 1998-03-02 | 2001-06-12 | Tohoku Ricoh Co., Ltd. | Apparatus for storing sheets driven out of an image forming apparatus |
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