JP2002348374A - Polyamic acid or polyimide and liquid crystalline orientating agent - Google Patents
Polyamic acid or polyimide and liquid crystalline orientating agentInfo
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- JP2002348374A JP2002348374A JP2001156431A JP2001156431A JP2002348374A JP 2002348374 A JP2002348374 A JP 2002348374A JP 2001156431 A JP2001156431 A JP 2001156431A JP 2001156431 A JP2001156431 A JP 2001156431A JP 2002348374 A JP2002348374 A JP 2002348374A
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- polyimide
- liquid crystal
- image embedded
- polyamic acid
- Prior art date
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリアミック酸又
はポリイミド及びこれらの何れか一方又は双方を主成分
として含む液晶配向剤に関し、特に、ポリアミック酸又
はポリイミドの反応成分として特定のジアミンを用いた
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamic acid or a polyimide and a liquid crystal aligning agent containing one or both of them as a main component, and more particularly to a liquid crystal aligning agent using a specific diamine as a reaction component of the polyamic acid or the polyimide. It is.
【０００２】[0002]
【従来の技術】液晶表示素子としては、透明電極が設け
られている基板上に液晶配向膜を形成して液晶表示素子
用基板とし、この基板２枚を対向配置し、生じた空隙に
液晶層を注入してサンドイッチ構造としたものが知られ
ている。液晶配向膜は、液晶表示素子用基板上に形成さ
れた液晶配向剤被膜の表面にラビング処理を施すことに
より形成され、液晶表示素子における液晶分子へ配向性
を付与している。この液晶配向剤被膜は、従来よりポリ
アミック酸又はポリイミド溶液を主成分として含有する
組成物（液晶配向剤）が用いられている。2. Description of the Related Art As a liquid crystal display device, a liquid crystal alignment film is formed on a substrate on which a transparent electrode is provided to form a substrate for a liquid crystal display device. Is known to have a sandwich structure. The liquid crystal alignment film is formed by performing a rubbing treatment on the surface of a liquid crystal alignment agent film formed on a liquid crystal display element substrate, and imparts alignment properties to liquid crystal molecules in the liquid crystal display element. For this liquid crystal aligning agent film, a composition (liquid crystal aligning agent) containing a polyamic acid or a polyimide solution as a main component has been conventionally used.
【０００３】また、液晶配向膜は、表示部材としての高
い品質を求めるために、液晶が配向膜に接するときにな
す角（プレチルト角）を高めに設定する必要があり、従
来の液晶配向剤は、高いプレチルト角を得るために、ふ
っ素あるいは長鎖アルキル基を導入した芳香族系のジア
ミンからポリアミド酸又はポリイミド樹脂溶液を得てい
る。In addition, in order to obtain a high quality as a display member, it is necessary to set the angle (pretilt angle) of the liquid crystal when the liquid crystal contacts the alignment film at a high angle. In order to obtain a high pretilt angle, a polyamic acid or a polyimide resin solution is obtained from fluorine or an aromatic diamine into which a long-chain alkyl group is introduced.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、芳香族
系のジアミンを反応させて得たポリアミド酸又はポリイ
ミドは、分子内に存在する方向環のために高い透明性を
付与することが困難であるという問題がある。However, polyamic acids or polyimides obtained by reacting aromatic diamines are difficult to impart high transparency due to directional rings present in the molecule. There's a problem.
【０００５】本発明は、前記した従来技術の問題点を解
決するためになされたものであり、高いプレチルト角を
付与することができ、しかも高い透明性を有するポリア
ミド酸又はポリイミドの提供を目的とするものである。
また、本発明は、高いプレチルト角と高い透明性を有す
る液晶配向膜を形成することができる液晶配向剤の提供
を目的とするものである。The present invention has been made to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a polyamic acid or polyimide which can provide a high pretilt angle and has high transparency. Is what you do.
Another object of the present invention is to provide a liquid crystal alignment agent capable of forming a liquid crystal alignment film having a high pretilt angle and high transparency.
【０００６】[0006]
【課題を解決するための手段】前記目的を達成するた
め、本発明は、ジアミンから選ばれる少なくとも１種の
化合物と酸二無水物から選ばれる少なくとも１種の化合
物を有機溶媒中で反応させてなる生成物であり、前記ジ
アミンの必須成分として炭化水素側鎖を有する脂肪族環
構造ジアミンが反応に供せられてなるポリアミック酸又
はポリイミドを提供する。また、本発明は、ジアミンか
ら選ばれる少なくとも１種の化合物と酸二無水物から選
ばれる少なくとも１種の化合物を有機溶媒中で反応させ
てなる生成物であり、前記ジアミンの必須成分として炭
化水素側鎖を有する脂肪族環構造ジアミンが反応に供せ
られてなるポリアミック酸又はポリイミドを主成分とし
て含有する液晶配向剤を提供する。In order to achieve the above object, the present invention provides a method comprising reacting at least one compound selected from diamines with at least one compound selected from acid dianhydrides in an organic solvent. A polyamic acid or polyimide obtained by subjecting an aliphatic cyclic diamine having a hydrocarbon side chain to a reaction as an essential component of the diamine. Further, the present invention is a product obtained by reacting at least one compound selected from diamines and at least one compound selected from acid dianhydrides in an organic solvent, wherein hydrocarbon is an essential component of the diamine. Provided is a liquid crystal aligning agent containing, as a main component, a polyamic acid or a polyimide obtained by subjecting an aliphatic cyclic diamine having a side chain to a reaction.
【０００７】[0007]
【発明の実施の形態】本発明において、炭化水素側鎖を
有する脂肪族環構造ジアミンの炭化水素鎖としては、メ
チル基、エチル基、プロピル基、イソプロピル基等であ
り、炭化水素鎖がメチル基のときの脂肪族環構造ジアミ
ンは、化学式BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the hydrocarbon chain of an aliphatic ring structure diamine having a hydrocarbon side chain includes a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like. The diamine of the aliphatic ring structure at the time of the chemical formula
【化２１】 で表わされる。Embedded image Is represented by
【０００８】炭化水素側鎖を有する脂肪族環構造ジアミ
ン以外のジアミンとしては、化学式The diamine other than the diamine having an aliphatic ring structure having a hydrocarbon side chain is represented by the following chemical formula:
【化２２】 Embedded image
【化２３】 Embedded image
【化２４】 Embedded image
【化２５】 Embedded image
【化２６】 Embedded image
【化２７】 Embedded image
【化２８】 Embedded image
【化２９】 Embedded image
【化３０】 Embedded image
【化３１】 Embedded image
【化３２】 Embedded image
【化３３】 Embedded image
【化３４】 Embedded image
【化３５】 Embedded image
【化３６】 Embedded image
【化３７】 Embedded image
【化３８】 Embedded image
【化３９】 Embedded image
【化４０】 Embedded image
【化４１】 Embedded image
【化４２】 Embedded image
【化４３】 Embedded image
【化４４】 Embedded image
【化４５】 Embedded image
【化４６】 Embedded image
【化４７】 Embedded image
【化４８】 及びEmbedded image as well as
【化４９】 で表わされる化合物から選ばれる少なくとも１種を使用
することが好ましい。Embedded image It is preferable to use at least one selected from the compounds represented by
【０００９】酸二無水物としては、化学式The acid dianhydride has the chemical formula
【化５０】 Embedded image
【化５１】 Embedded image
【化５２】 Embedded image
【化５３】 Embedded image
【化５４】 Embedded image
【化５５】 及びEmbedded image as well as
【化５６】 で表わされる化合物から選ばれる少なくとも１種を使用
することが好ましい。Embedded image It is preferable to use at least one selected from the compounds represented by
【００１０】本発明において、高いプレチルト角を実現
できるのは化学式（１）で表わされる化合物で代表され
る炭化水素側鎖を有する脂肪族環構造ジアミンを反応成
分として使用ためである。又、炭化水素側鎖を有する脂
肪族環構造ジアミンは、高い透明性を実現する上でも有
用であり、この炭化水素側鎖を有する脂肪族環構造ジア
ミンに加えて、ジアミン成分として化学式（２）〜（１
０）で表わされる化合物の少なくとも１種と、酸二無水
物成分として化学式（３０）、（３１）、（３４）、
（３６）で表わされる化合物の少なくとも１種を反応成
分としてなるポリアミック酸又はポリイミドは、より高
い透明性の実現を可能とする。In the present invention, a high pretilt angle can be realized because an aliphatic cyclic diamine having a hydrocarbon side chain represented by the compound represented by the chemical formula (1) is used as a reaction component. Further, an aliphatic ring structure diamine having a hydrocarbon side chain is also useful for realizing high transparency, and in addition to the aliphatic ring structure diamine having a hydrocarbon side chain, a diamine component represented by the chemical formula (2) ~ (1
0) and at least one compound represented by chemical formulas (30), (31), (34), and
A polyamic acid or polyimide containing at least one of the compounds represented by (36) as a reaction component enables higher transparency to be realized.
【００１１】ジアミンと酸二無水物を有機溶媒中で反応
させることにより、ポリアミック酸が生成され、更にポ
リアミック酸を熱処理あるいは無水酢酸を添加すること
等により脱水閉環させることによりポリイミドを調整す
ることができ、本発明の液晶配向剤はこれらポリアミッ
ク酸及びポリイミドのいずれか一方又は双方を主成分と
して含有するものである。A polyamic acid is produced by reacting a diamine and an acid dianhydride in an organic solvent, and a polyimide can be prepared by subjecting the polyamic acid to dehydration and ring closure by heat treatment or addition of acetic anhydride. The liquid crystal aligning agent of the present invention contains one or both of the polyamic acid and the polyimide as a main component.
【００１２】又、ジアミンと酸二無水物を有機溶媒に溶
解させて直接イミド化することによってポリイミドを得
ることもでき、更にはジアミンと酸二無水物を有機溶媒
中で溶解反応させ、続いてジアミン及び酸二無水物の少
なくとも一方を添加してイミド化することによりポリイ
ミドを得ることができる。ジアミンと酸二無水物との混
合比は、酸二無水物の合計量１モル％に対して、ジアミ
ンの合計量０．９５〜１．０５モル％とするのが好まし
い。A polyimide can also be obtained by dissolving a diamine and an acid dianhydride in an organic solvent and directly imidizing the same. Further, a diamine and an acid dianhydride are dissolved and reacted in an organic solvent. A polyimide can be obtained by adding at least one of a diamine and an acid dianhydride and imidizing the same. The mixing ratio of the diamine and the acid dianhydride is preferably 0.95 to 1.05 mol% of the total amount of the diamine with respect to 1 mol% of the total amount of the acid dianhydride.
【００１３】有機溶媒としては、Ｎ−メチル−２−ピロ
リドン、ジメチルホルムアミド、ジメチルアセトアミ
ド、スルホラン、アニソール、ジオキソラン、ブチルセ
ルソルブアセテート、ラクトン系等が挙げられ、これら
単独で使用することができるが、２種以上を混合して使
用してもよい。ラクトン系としては、γ−カプロラクト
ン、γ−バレロラクトン、γ−ブチロラクトン、γ−テ
トロン酸、γ−フタリド、γ−フタリド酸、γ−クマリ
ン等が挙げられ、ラクトン系とピリジン、キノリン、Ｎ
−メチルモルフォリン等の塩基化合物との混合物も使用
可能である。Examples of the organic solvent include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, sulfolane, anisole, dioxolan, butylcellosolve acetate, lactone and the like, and these can be used alone. Two or more kinds may be used as a mixture. Examples of lactones include γ-caprolactone, γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ-phthalidic acid, γ-coumarin and the like.Lactones and pyridine, quinoline, N
Mixtures with basic compounds such as -methylmorpholine can also be used.
【００１４】ジアミン及び酸二無水物を有機溶媒中で反
応させて得られたポリアミック酸及び／又はポリイミド
を有機溶媒で希釈することにより、液晶配向剤が得られ
る。液晶配向剤には基板との接着性を向上させるために
シランカップリング剤やチタネートカップリング剤を少
量添加しても良い。A liquid crystal aligning agent can be obtained by diluting a polyamic acid and / or polyimide obtained by reacting a diamine and an acid dianhydride in an organic solvent with an organic solvent. A small amount of a silane coupling agent or a titanate coupling agent may be added to the liquid crystal alignment agent in order to improve the adhesion to the substrate.
【００１５】[0015]
【実施例】以下、本発明の実施例を比較例と共に説明す
る。Hereinafter, examples of the present invention will be described together with comparative examples.
【００１６】（実施例１） ［工程１］攪拌器を取りつけた１０００ｍｌのセパラブ
ル四つ口フラスコに、水分分離トラップを備えた玉付冷
却管を取りつけ、１，２，３，４−シクロペンタンテト
ラカルボン酸二無水物（化学式（３０））２１．０ｇ、
４，４′−ジアミノ−３，３′−ジメチルジシクロヘキ
シルメタン（ＤＭＨＭ、化学式（１））２３．８ｇ、γ
−カプロラクトン１．１ｇ、ピリジン２．０ｇ、Ｎ−メ
チル−２−ピロリドン（ＮＭＰ）２００．０ｇ、トルエ
ン４０．０ｇを加え、常温で窒素雰囲気下で１０分間攪
拌した後、反応槽の内容物を１８０℃に昇温し、攪拌機
の回転数を１８０ｒｐｍに設定して３時間攪拌し、攪拌
終了後真空乾燥を行い反応液（ワニス）を得た。なお留
出成分は反応中に水分分離トラップより適時取り除い
た。 ［工程２］［工程１］で得たワニスをメタノール中に投
入することによって、生成した沈殿を分離し、粉砕、ろ
過、洗浄および減圧乾燥させる工程を経ることによりポ
リイミド粉末を得た。このポリイミド粉末を赤外線吸収
スペクトルを測定したところ、１７１５cm-1及び１７８
５cm-1にイミド環の特性吸収が認められた。 ［工程３］その後ＮＭＰ９．５ｇにポリイミド粉末０．
５ｇを溶解して液晶配向剤を得た。Example 1 [Step 1] A ball-cooled condenser equipped with a water separation trap was attached to a 1000 ml separable four-necked flask equipped with a stirrer, and 1,2,3,4-cyclopentanetetra 21.0 g of carboxylic dianhydride (chemical formula (30)),
2,3.8 g of 4,4'-diamino-3,3'-dimethyldicyclohexylmethane (DMHM, chemical formula (1)), γ
-1.1 g of caprolactone, 2.0 g of pyridine, 200.0 g of N-methyl-2-pyrrolidone (NMP) and 40.0 g of toluene were added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 10 minutes. The temperature was raised to 180 ° C., the mixture was stirred for 3 hours with the rotation speed of the stirrer set at 180 rpm, and after the stirring was completed, vacuum drying was performed to obtain a reaction liquid (varnish). Distilled components were removed from the water separation trap during the reaction as appropriate. [Step 2] The varnish obtained in [Step 1] was poured into methanol to separate a generated precipitate, followed by pulverization, filtration, washing and drying under reduced pressure to obtain a polyimide powder. The infrared absorption spectrum of this polyimide powder was measured to be 1715 cm -1 and 178 cm -1.
Characteristic absorption of the imide ring was observed at 5 cm -1 . [Step 3] Then, add 9.5 g of NMP to polyimide powder.
5 g was dissolved to obtain a liquid crystal aligning agent.
【００１７】（実施例２） ［工程１］実施例１と同様の装置に、ビシクロ（２，
２，２）オクト−７−エン−２，３，５，６−テトラカ
ルボン酸二無水物（ＢＣＤ、化学式（３１））２４．８
ｇ、ＤＭＨＭ２３．８ｇ、γ−カプロラクトン１．１
ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０ｇ、トルエン
４０．０を加え、実施例１の［工程１］と同様にして反
応液（ワニス）を得た。 ［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。このポリ
イミド粉末を赤外線吸収スペクトルを測定したところ、
１７１５cm-1及び１７８５cm-1にイミド環の特性吸収が
認められた。 ［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理して液晶配向剤を得た。(Example 2) [Step 1] Bicyclo (2,2) was added to the same apparatus as in Example 1.
2,2) Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD, chemical formula (31)) 24.8
g, 23.8 g of DMHM, γ-caprolactone 1.1
g, pyridine 2.0 g, NMP 200.0 g, and toluene 40.0 were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 1. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. When measuring the infrared absorption spectrum of this polyimide powder,
Characteristic absorption of the imide ring was observed at 1715 cm -1 and 1785 cm -1 . [Step 3] Using the polyimide powder obtained in [Step 2] in Example 1
[Step 3] to obtain a liquid crystal aligning agent.
【００１８】（実施例３） ［工程１］実施例１と同様の装置に、４，４′−オキシ
ジフタル酸無水物（ＯＤＰＡ、化学式（３４））３１．
０ｇ、ＤＭＨＭ２３．８ｇ、γ−カプロラクトン１．１
ｇ、ピリジン２．０ｇ、ＮＭＰ２００ｇ、トルエン４
０．０ｇを加え、実施例１の［工程１］と同様にして反
応液（ワニス）を得た。 ［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。このポリ
イミド粉末を赤外線吸収スペクトルを測定したところ、
１７１５cm-1及び１７８５cm-1にイミド環の特性吸収が
認められた。 ［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理して液晶配向剤を得た。(Example 3) [Step 1] In the same apparatus as in Example 1, 4,4'-oxydiphthalic anhydride (ODPA, chemical formula (34)).
0 g, 23.8 g of DMHM, γ-caprolactone 1.1
g, pyridine 2.0 g, NMP 200 g, toluene 4
0.0 g was added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 1. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. When measuring the infrared absorption spectrum of this polyimide powder,
Characteristic absorption of the imide ring was observed at 1715 cm -1 and 1785 cm -1 . [Step 3] Using the polyimide powder obtained in [Step 2] in Example 1
[Step 3] to obtain a liquid crystal aligning agent.
【００１９】（実施例４） ［工程１］実施例１と同様の装置に、ＢＣＤ１２．４
ｇ、３，３′，４，４′−ビフェニルテトラカルボン酸
二無水物（ＢＰＤＡ、化学式（３３））１４．７ｇ、Ｄ
ＭＨＭ１１．９ｇ、３，５−ジアミノ安息香酸（ＤＡＢ
ｚ、化学式（１３））７．６ｇ、γ−カプロラクトン
１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０ｇ、ト
ルエン４０．０ｇを加え、実施例１の［工程１］と同様
にして反応液（ワニス）を得た。 ［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。このポリ
イミド粉末を赤外線吸収スペクトルを測定したところ、
１７１５cm-1及び１７８５cm-1にイミド環の特性吸収が
認められた。 ［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理して液晶配向剤を得た。Example 4 [Step 1] The same apparatus as in Example 1 was used,
g, 14.7 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA, chemical formula (33)), D
MHM 11.9 g, 3,5-diaminobenzoic acid (DAB
z, chemical formula (13)), 7.6 g, γ-caprolactone 1.1 g, pyridine 2.0 g, NMP 200.0 g, toluene 40.0 g were added, and the reaction solution (varnish) was prepared in the same manner as in [Step 1] of Example 1. ) Got. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. When measuring the infrared absorption spectrum of this polyimide powder,
Characteristic absorption of the imide ring was observed at 1715 cm -1 and 1785 cm -1 . [Step 3] Using the polyimide powder obtained in [Step 2] in Example 1
[Step 3] to obtain a liquid crystal aligning agent.
【００２０】（実施例５） ［工程１］実施例１と同様の装置に、ＯＤＰＡ１５．５
ｇ、ピロメリット酸二無水物（化学式（３２））１０．
９ｇ、ＤＭＨＭ１１．９ｇ、ＤＡＢｚ７．６ｇ、γ−カ
プロラクトン１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２０
０．０ｇ、トルエン４０．０ｇを加え、実施例１の［工
程１］と同様にして反応液（ワニス）を得た。 ［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。このポリ
イミド粉末を赤外線吸収スペクトルを測定したところ、
１７１５cm-1及び１７８５cm-1にイミド環の特性吸収が
認められた。 ［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理して液晶配向剤を得た。(Example 5) [Step 1] ODPA15.5 was applied to the same apparatus as in Example 1.
g, pyromellitic dianhydride (chemical formula (32))
9 g, DMHM 11.9 g, DABz 7.6 g, γ-caprolactone 1.1 g, pyridine 2.0 g, NMP20
0.0 g and 40.0 g of toluene were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 1. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. When measuring the infrared absorption spectrum of this polyimide powder,
Characteristic absorption of the imide ring was observed at 1715 cm -1 and 1785 cm -1 . [Step 3] Using the polyimide powder obtained in [Step 2] in Example 1
[Step 3] to obtain a liquid crystal aligning agent.
【００２１】（比較例１）実施例1と同様の装置に、Ｂ
ＣＤ２４．８ｇ、３，９−ビス（３−アミノプロピル）
−２，４，８，１０−テトラオキサスピロ−５，５−ウ
ンデカン（ＡＴＵ）２７．４ｇ、γ−カプロラクトン
１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０ｇ、ト
ルエン４０．０ｇを加え、実施例１の［工程１］と同様
にして反応液（ワニス）を得た。 ［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。このポリ
イミド粉末を赤外線吸収スペクトルを測定したところ、
１７１５cm-1及び１７８５cm-1にイミド環の特性吸収が
認められた。 ［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理して液晶配向剤を得た。(Comparative Example 1) In the same apparatus as in Example 1, B
CD 24.8 g, 3,9-bis (3-aminopropyl)
Example 2-27.4 g of -2,4,8,10-tetraoxaspiro-5,5-undecane (ATU), 1.1 g of γ-caprolactone, 2.0 g of pyridine, 200.0 g of NMP and 40.0 g of toluene were added. A reaction liquid (varnish) was obtained in the same manner as in [Step 1] of No. 1. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. When measuring the infrared absorption spectrum of this polyimide powder,
Characteristic absorption of the imide ring was observed at 1715 cm -1 and 1785 cm -1 . [Step 3] Using the polyimide powder obtained in [Step 2] in Example 1
[Step 3] to obtain a liquid crystal aligning agent.
【００２２】（比較例２） ［工程１］実施例1と同様の装置に、ＯＰＤＡ３１．０
ｇ、ＡＴＵ２７．４ｇ、γ−カプロラクトン １．１
ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０ｇ 、トルエ
ン４０．０ｇを加え、実施例１の［工程１］と同様にし
て反応液（ワニス）を得た。 ［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。このポリ
イミド粉末を赤外線吸収スペクトルを測定したところ、
１７１５cm-1及び１７８５cm-1にイミド環の特性吸収が
認められた。 ［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理して液晶配向剤を得た。(Comparative Example 2) [Step 1] OPDA 31.0 was added to the same apparatus as in Example 1.
g, ATU 27.4 g, γ-caprolactone 1.1
g, pyridine 2.0 g, NMP 200.0 g, and toluene 40.0 g, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 1. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. When measuring the infrared absorption spectrum of this polyimide powder,
Characteristic absorption of the imide ring was observed at 1715 cm -1 and 1785 cm -1 . [Step 3] Using the polyimide powder obtained in [Step 2] in Example 1
[Step 3] to obtain a liquid crystal aligning agent.
【００２３】実施例１〜５及び比較例１、２の液晶配向
剤についてプレチルト角及びの光透過率を評価し、その
結果を表１に示した。The liquid crystal aligning agents of Examples 1 to 5 and Comparative Examples 1 and 2 were evaluated for pretilt angle and light transmittance, and the results are shown in Table 1.
【００２４】プレチルト角評価セルの作成とプレチルト
角の評価：ＩＴＯ付きガラス基板上に液晶配向剤をスピ
ンコート法により塗布、焼成した後、ラビング処理を施
すことで液晶表示素子用基板とした。得られた液晶表示
素子用基板をセルギャップ５０μｍで対向配置し、接着
剤で固定し、その後真空注入法により液晶を注入し、液
晶注入口をUV硬化樹脂により封止することで、プレチル
ト角評価セルを得た。また、得られたプレチルト角評価
セルを、波長６３３ｎｍの光源を用いてプレチルト角を
測定した。Preparation of Pretilt Angle Evaluation Cell and Evaluation of Pretilt Angle: A liquid crystal aligning agent was applied on a glass substrate with ITO by spin coating, baked, and then subjected to a rubbing treatment to obtain a liquid crystal display element substrate. The obtained substrate for a liquid crystal display element was placed facing the cell gap of 50 μm, fixed with an adhesive, and then liquid crystal was injected by a vacuum injection method, and the liquid crystal injection port was sealed with a UV curable resin to evaluate the pretilt angle. I got a cell. The pretilt angle of the obtained pretilt angle evaluation cell was measured using a light source having a wavelength of 633 nm.
【００２５】光透過率評価基板の作成及び光透過率の測
定：ガラス基板上に液晶配向剤をスピンコート法により
塗布、焼成した後、ＵＶ−可視分光光度計を用いて３８
０ｎｍの光透過率を測定した。Preparation of Light Transmittance Evaluation Substrate and Measurement of Light Transmittance: A liquid crystal aligning agent is applied on a glass substrate by a spin coating method, baked, and then subjected to UV-visible spectrophotometry.
The light transmittance at 0 nm was measured.
【００２６】[0026]
【表１】 [Table 1]
【００２７】（実施例６） ［工程１］実施例１と同様の装置に、ＢＣＤ７．４５
ｇ、ＢＰＤＡ１７．６５ｇ、ＤＭＨＭ１０．７３ｇ、Ｄ
ＡＢｚ６．８５ｇ、γ−バレロラクトン０．９ｇ、メチ
ルモルフォリン１．８ｇ、ＮＭＰ２２４．０ｇ、トルエ
ン４５．０ｇを加え、実施例１の［工程１］と同様にし
て反応液（ワニス）を得た。 ［工程２］［工程１］で得たワニスの一部を２００℃で
２時間加熱することによって固形分（樹脂分）の濃度を
測定したところ、１５．１重量％であった。また、ワニ
スより固形分を取り出し、赤外線吸収スペクトルを測定
したところ、１７１５cm-1及び１７８５cm-1にイミド環
の特性吸収が認められた。 ［工程３］［工程１］で得たワニスにγ−バレロラクト
ンを添加することにより液を希釈し、固形分の濃度が
５．０重量％となるように調整して液晶配向剤を得た。(Example 6) [Step 1] The same apparatus as in Example 1 was used except that BCD 7.45 was used.
g, BPDA 17.65 g, DMHM 10.73 g, D
6.85 g of ABz, 0.9 g of γ-valerolactone, 1.8 g of methylmorpholine, 224.0 g of NMP, and 45.0 g of toluene were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 1. . [Step 2] A portion of the varnish obtained in [Step 1] was heated at 200 ° C. for 2 hours to measure the solid content (resin content) concentration, which was 15.1% by weight. Further, the solid content was taken out from the varnish, and the infrared absorption spectrum was measured. As a result, characteristic absorption of an imide ring was observed at 1715 cm -1 and 1785 cm -1 . [Step 3] The liquid was diluted by adding γ-valerolactone to the varnish obtained in [Step 1], and adjusted to have a solid content of 5.0% by weight to obtain a liquid crystal aligning agent. .
【００２８】（実施例７） ［工程１］実施例１と同様の装置に、ＢＣＤ７．４５
ｇ、ＢＰＤＡ１７．６５ｇ、ＤＭＨＭ１０．７３ｇ、Ｄ
ＡＢｚ６．８５ｇ、γ−ブチロラクトン０．７７ｇ、メ
チルモルフォリン１．８ｇ、ＮＭＰ２２４．０ｇ、トル
エン４５．０ｇを加え、実施例１の［工程１］と同様に
して反応液（ワニス）を得た。 ［工程２］［工程１］で得たワニスを実施例６の［工程
２］と同様にして処理して固形分（樹脂分）の濃度を測
定したところ、１５．２重量％であった。また、ワニス
より固形分を取り出し、赤外線吸収スペクトルを測定し
たところ、１７１５cm-1及び１７８５cm-1にイミド環の
特性吸収が認められた。 ［工程３］［工程１］で得たワニスを実施例６の［工程
３］と同様に調整して液晶配向剤を得た。(Example 7) [Step 1] In the same apparatus as in Example 1, BCD 7.45 was used.
g, BPDA 17.65 g, DMHM 10.73 g, D
6.85 g of ABz, 0.77 g of γ-butyrolactone, 1.8 g of methylmorpholine, 224.0 g of NMP, and 45.0 g of toluene were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 1. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 6, and the concentration of solids (resin) was measured. As a result, it was 15.2% by weight. Further, the solid content was taken out from the varnish, and the infrared absorption spectrum was measured. As a result, characteristic absorption of an imide ring was observed at 1715 cm -1 and 1785 cm -1 . [Step 3] The varnish obtained in [Step 1] was adjusted in the same manner as in [Step 3] of Example 6 to obtain a liquid crystal aligning agent.
【００２９】（実施例８） ［工程１］実施例１と同様の装置に、ＢＣＤ７．４５
ｇ、ＢＰＤＡ１７．６５ｇ、ＤＭＨＭ１０．７３ｇ、Ｄ
ＡＢｚ６．８５ｇ、γ−カプロラクトン１．０３ｇ、メ
チルモルフォリン１．８ｇ、ＮＭＰ２２４．０ｇ、トル
エン４５．０ｇを加え、実施例１の［工程１］と同様に
して反応液（ワニス）を得た。 ［工程２］［工程１］で得たワニスを実施例６の［工程
２］と同様にして処理して固形分（樹脂分）の濃度を測
定したところ、１５．０重量％であった。また、ワニス
より固形分を取り出し、赤外線吸収スペクトルを測定し
たところ、１７１５cm-1及び１７８５cm-1にイミド環の
特性吸収が認められた。 ［工程３］［工程１］で得たワニスを実施例６の［工程
３］と同様に調整して液晶配向剤を得た。(Embodiment 8) [Step 1] A BCD of 7.45 was set in the same apparatus as in Embodiment 1.
g, BPDA 17.65 g, DMHM 10.73 g, D
6.85 g of ABz, 1.03 g of γ-caprolactone, 1.8 g of methylmorpholine, 224.0 g of NMP, and 45.0 g of toluene were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 1. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 6, and the concentration of solids (resin) was measured. As a result, it was 15.0% by weight. Further, the solid content was taken out from the varnish, and the infrared absorption spectrum was measured. As a result, characteristic absorption of an imide ring was observed at 1715 cm -1 and 1785 cm -1 . [Step 3] The varnish obtained in [Step 1] was adjusted in the same manner as in [Step 3] of Example 6 to obtain a liquid crystal aligning agent.
【００３０】（実施例９） ［工程１］実施例１と同様の装置に、ＢＣＤ７．４５
ｇ、ＤＡＢｚ６．８５ｇγ−カプロラクトン１．０３
ｇ、メチルモルフォリン１．８ｇ、ＮＭＰ１１４．０
ｇ、トルエン２３．０ｇを加え、常温下に窒素ガス雰囲
気中で１０分間攪拌した後、攪拌機の回転数を１８０ｒ
ｐｍに設定して１時間攪拌して反応させた。(Example 9) [Step 1] The same apparatus as in Example 1 was used except that BCD 7.45 was used.
g, DABz 6.85 g γ-caprolactone 1.03
g, 1.8 g of methylmorpholine, 114.0 NMP
g, and 23.0 g of toluene, and the mixture was stirred at room temperature in a nitrogen gas atmosphere for 10 minutes.
The reaction was carried out by stirring at 1 pm for 1 hour.
【００３１】反応液を一昼夜空冷し、これに、ＢＰＤＡ
１７．６５ｇ、ＤＭＨＭ１０．７３ｇ、ＮＭＰ１１０
ｇ、トルエン２２ｇを加え、反応槽の内容物を１８０℃
に昇温し、攪拌機の回転数を１８０ｒｐｍに設定して４
時間攪拌し反応液（ワニス）を得た。なお留出成分は反
応中に水分分離トラップより適時取り除いた。 ［工程２］［工程１］で得たワニスを実施例６の［工程
２］と同様にして処理して固形分（樹脂分）の濃度を測
定したところ、１５．３重量％であった。また、ワニス
より固形分を取り出し、赤外線吸収スペクトルを測定し
たところ、１７１５cm-1及び１７８５cm-1にイミド環の
特性吸収が認められた。 ［工程３］［工程１］で得たワニスを実施例６の［工程
３］と同様に調整して液晶配向剤を得た。The reaction solution was air-cooled all day and night.
17.65 g, 10.73 g of DMHM, NMP110
g and toluene 22 g, and the contents of the reaction
And the rotation speed of the stirrer was set to 180 rpm to 4
After stirring for an hour, a reaction liquid (varnish) was obtained. Distilled components were removed from the water separation trap during the reaction as appropriate. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 6, and the concentration of solids (resin) was measured. As a result, it was 15.3% by weight. Further, the solid content was taken out from the varnish and the infrared absorption spectrum was measured. As a result, characteristic absorption of an imide ring was observed at 1715 cm -1 and 1785 cm -1 . [Step 3] The varnish obtained in [Step 1] was adjusted in the same manner as in [Step 3] of Example 6 to obtain a liquid crystal aligning agent.
【００３２】実施例６〜９の液晶配向剤についてプレチ
ルト角評価し、その結果を表２に示した。The pretilt angles of the liquid crystal aligning agents of Examples 6 to 9 were evaluated, and the results are shown in Table 2.
【００３３】[0033]
【表２】 [Table 2]
【００３４】[0034]
【発明の効果】本発明によれば、高いプレチルト角を有
し、且つ高い透明性を有する液晶配向膜を透明電極が設
けられている基板上に形成することができる。またこの
液晶配向剤を適応した液晶表示素子は液晶プロジェクタ
ー、液晶テレビ、コンピューターディスプレイ、計算
機、時計、各種装置表示板等の表示装置として用いるこ
とができる。According to the present invention, a liquid crystal alignment film having a high pretilt angle and high transparency can be formed on a substrate provided with a transparent electrode. The liquid crystal display element to which the liquid crystal aligning agent is applied can be used as a display device such as a liquid crystal projector, a liquid crystal television, a computer display, a computer, a clock, and various device display panels.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 本田 祐樹 茨城県日立市日高町５丁目１番１号 日立 電線株式会社総合技術研究所内 (72)発明者 安藤 好幸 茨城県日立市日高町５丁目１番１号 日立 電線株式会社総合技術研究所内 (72)発明者 浅野 健次 茨城県日立市日高町５丁目１番１号 日立 電線株式会社総合技術研究所内 (72)発明者 伊藤 雄三 茨城県日立市日高町５丁目１番１号 日立 電線株式会社総合技術研究所内 (72)発明者 近藤 克己 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 (72)発明者 冨岡 安 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 (72)発明者 阿部 英俊 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 Ｆターム(参考） 2H090 HB08Y HB09Y JB02 MA10 MB01 4J043 PA04 PC01 PC02 PC06 PC13 QB26 RA02 RA34 SA06 TA21 TA22 TA47 UA03 UA04 UA05 UA13 WA07 XA11 XA13 YA06 YA07 ZB23 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yuki Honda 5-1-1, Hidaka-cho, Hitachi City, Ibaraki Prefecture Within Hitachi Cable Engineering Co., Ltd. (72) Inventor Yoshiyuki Ando Hidaka-cho, Hitachi City, Ibaraki Prefecture 5-1-1, Hitachi Cable, Ltd., Research Institute of Technology (72) Inventor Kenji Asano 5-1-1, Hidaka-cho, Hitachi City, Ibaraki Prefecture Hitachi Cable, Ltd. Research Institute of Technology (72) Inventor Yuzo Ito Ibaraki Hitachi Cable, Ltd. 5-1-1, Hidaka-cho, Hitachi City, Japan (72) Inventor Katsumi Kondo 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Within Hitachi Research Laboratory, Hitachi, Ltd. (72) Inventor Yasushi Tomioka 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Inside Hitachi Research Laboratory, Hitachi, Ltd. (72) Inventor Hidetoshi Abe Hitachi City University, Ibaraki Prefecture 7-1-1 Mikamachi F-term in Hitachi Research Laboratory, Hitachi, Ltd. F-term (reference) 2H090 HB08Y HB09Y JB02 MA10 MB01 4J043 PA04 PC01 PC02 PC06 PC13 QB26 RA02 RA34 SA06 TA21 TA22 TA47 UA03 UA04 UA05 UA13 WA07 XA11 YA06 YA06
Claims (5)
合物と酸二無水物から選ばれる少なくとも１種の化合物
を有機溶媒中で反応させてなる生成物であり、前記ジア
ミンの必須成分として炭化水素側鎖を有する脂肪族環構
造ジアミンが反応に供せられてなることを特徴とするポ
リアミック酸又はポリイミド。1. A product obtained by reacting at least one compound selected from diamines and at least one compound selected from acid dianhydrides in an organic solvent. A polyamic acid or polyimide obtained by subjecting an aliphatic diamine having a chain to a reaction.
ンは、化学式 【化１】 で表わされる化合物である請求項１記載のポリアミック
酸又はポリイミド。2. An aliphatic cyclic diamine having a hydrocarbon side chain is represented by the following chemical formula: The polyamic acid or polyimide according to claim 1, which is a compound represented by the formula:
に供せられてなる請求項１記載のポリアミック酸又はポ
リイミド。3. A compound of the formula: ## STR2 ## Is converted to an acid dianhydride Embedded image Embedded image And The polyamic acid or polyimide according to claim 1, wherein at least one selected from the compounds represented by the following formulas is subjected to the reaction.
二無水物として 【化１７】 【化１８】 【化１９】 及び 【化２０】 から選ばれる少なくとも１種が反応に供せられてなる請
求項１記載のポリアミック酸又はポリイミド。4. The chemical formula as a diamine: And a compound represented by the formula Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image And At least one compound selected from the compounds represented by the formula is used as an acid dianhydride. Embedded image Embedded image And The polyamic acid or polyimide according to claim 1, wherein at least one selected from the group consisting of:
ポリアミック酸又はポリイミドを含有することを特徴と
する液晶配向剤。5. A liquid crystal aligning agent comprising the polyamic acid or polyimide according to claim 1.
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| JP2001156431A JP2002348374A (en) | 2001-05-25 | 2001-05-25 | Polyamic acid or polyimide and liquid crystalline orientating agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001156431A JP2002348374A (en) | 2001-05-25 | 2001-05-25 | Polyamic acid or polyimide and liquid crystalline orientating agent |
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