JP2006030961A - Vertical liquid crystal orientation agent and vertical liquid crystal display element - Google Patents
Vertical liquid crystal orientation agent and vertical liquid crystal display element Download PDFInfo
- Publication number
- JP2006030961A JP2006030961A JP2005123440A JP2005123440A JP2006030961A JP 2006030961 A JP2006030961 A JP 2006030961A JP 2005123440 A JP2005123440 A JP 2005123440A JP 2005123440 A JP2005123440 A JP 2005123440A JP 2006030961 A JP2006030961 A JP 2006030961A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- organic solvent
- ether
- vertical liquid
- aligning agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 148
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 54
- 239000003960 organic solvent Substances 0.000 claims abstract description 55
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 44
- 239000004642 Polyimide Substances 0.000 claims abstract description 31
- 229920001721 polyimide Polymers 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 239000012046 mixed solvent Substances 0.000 claims abstract description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 18
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- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical group COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
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- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
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- 230000002194 synthesizing effect Effects 0.000 description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 4
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- 239000004988 Nematic liquid crystal Substances 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
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- SBHHKGFHJWTZJN-UHFFFAOYSA-N 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1(C)C(C(O)=O)C(C)(C(O)=O)C1C(O)=O SBHHKGFHJWTZJN-UHFFFAOYSA-N 0.000 description 3
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Landscapes
- Liquid Crystal (AREA)
Abstract
Description
本発明は、垂直液晶配向剤および垂直液晶表示素子に関する。さらに詳しくは、大型の基板を用いて作製される液晶表示素子のための、塗布ムラやピンホールなどの欠陥の無い垂直液晶配向膜を安定的に与えることのできる垂直液晶配向剤、および当該液晶配向剤から得られる垂直液晶配向膜を具備する液晶表示素子に関する。 The present invention relates to a vertical liquid crystal aligning agent and a vertical liquid crystal display element. More specifically, a vertical liquid crystal aligning agent capable of stably providing a vertical liquid crystal alignment film free from defects such as coating unevenness and pinholes for a liquid crystal display device manufactured using a large substrate, and the liquid crystal The present invention relates to a liquid crystal display element including a vertical liquid crystal alignment film obtained from an alignment agent.
現在、液晶表示素子としては、透明導電膜が設けられている基板表面にポリアミック酸、ポリイミドなどからなる液晶配向膜を形成して液晶表示素子用基板とし、その2枚を対向配置してその間隙内に正の誘電異方性を有するネマチック型液晶の層を形成してサンドイッチ構造のセルとし、液晶分子の長軸が一方の基板から他方の基板に向かって連続的に90度捻れるようにした、いわゆるTN型(Twisted Nematic)液晶セルを有するTN型液晶表示素子が知られている。
また、TN型液晶表示素子に比してコントラストが高くて、その視角依存性の少ないSTN(Super Twisted Nematic)型液晶表示素子が開発されている。このSTN型液晶表示素子は、ネマチック型液晶に光学活性物質であるカイラル剤をブレンドしたものを液晶として用い、液晶分子の長軸が基板間で180度以上にわたって連続的に捻れる状態となることにより生じる複屈折効果を利用するものである。
Currently, as a liquid crystal display element, a liquid crystal alignment film made of polyamic acid, polyimide, or the like is formed on the surface of a substrate on which a transparent conductive film is provided to form a liquid crystal display element substrate. A nematic liquid crystal layer having positive dielectric anisotropy is formed in a cell having a sandwich structure so that the major axis of the liquid crystal molecules is continuously twisted 90 degrees from one substrate to the other. A TN type liquid crystal display element having a so-called TN type (Twisted Nematic) liquid crystal cell is known.
Further, STN (Super Twisted Nematic) type liquid crystal display elements have been developed that have higher contrast than TN type liquid crystal display elements and have less viewing angle dependency. This STN type liquid crystal display element uses nematic liquid crystal blended with a chiral agent which is an optically active substance as liquid crystal, and the major axis of liquid crystal molecules is continuously twisted over 180 degrees between substrates. The birefringence effect generated by the above is utilized.
また、液晶を駆動するための2つの電極を片側の基盤に櫛歯状に配置し、基板面に平行な電界を発生させ、液晶分子をコントロールする横電界方式液晶表示素子が知られている。これらの液晶表示素子における液晶の配向は、通常、ラビング処理が施された液晶配向膜により発現される。
上記とは別の液晶表示素子として、負の誘電異方性を有する液晶分子を基板に垂直に配向させてなる垂直配向(Vertical Alignment)型液晶セルを有する液晶表示素子が知られている。このような液晶表示素子においても、液晶の配向制御は、通常、ポリアミック酸、ポリイミドなどの重合体を含有する液晶配向剤により形成された液晶配向膜によりなされている。
Also known is a lateral electric field type liquid crystal display element in which two electrodes for driving a liquid crystal are arranged in a comb-like shape on one side of the base, an electric field parallel to the substrate surface is generated, and liquid crystal molecules are controlled. The alignment of the liquid crystal in these liquid crystal display elements is usually expressed by a liquid crystal alignment film subjected to a rubbing treatment.
As a liquid crystal display element different from the above, a liquid crystal display element having a vertical alignment type liquid crystal cell in which liquid crystal molecules having negative dielectric anisotropy are aligned perpendicular to a substrate is known. In such a liquid crystal display element, the alignment control of the liquid crystal is usually performed by a liquid crystal alignment film formed of a liquid crystal alignment agent containing a polymer such as polyamic acid or polyimide.
液晶配向膜は、液晶配向剤をロールコーター法やスピンコート法、印刷法などの方法を用いて、カラーフィルターや半導体が形成された、電極付き基板上に塗布し、焼成により溶剤を蒸発させることで形成されるが、用いる液晶配向剤の塗布性が十分でない場合には、液晶配向膜の膜厚が均一では無いために生じる塗布ムラやピンホールなどの欠陥が発生する。この欠陥は液晶配向に大きな影響を与えるために、欠陥を有する液晶配向膜を含有する液晶表示素子は、美しい画像を得ることができないことがあった。
そこで、塗布性に優れた液晶配向剤を得るために、特許文献1、特許文献2および特許文献3に開示されているような技術を用いることによって塗布ムラを改善しようとする検討が実施され、従来の液晶表示素子の製造工程においては十分な効果を発揮することができていたが、これは当時の液晶表示素子のサイズが小さいものであったことの寄与も加味された結果である。
The liquid crystal alignment film is formed by applying a liquid crystal aligning agent on a substrate with an electrode on which a color filter or a semiconductor is formed using a roll coater method, a spin coat method, a printing method, or the like, and evaporating the solvent by baking. However, when the coating property of the liquid crystal aligning agent to be used is not sufficient, defects such as coating unevenness and pinholes occur because the liquid crystal aligning film is not uniform. Since this defect has a great influence on the liquid crystal alignment, a liquid crystal display element containing a liquid crystal alignment film having a defect sometimes cannot obtain a beautiful image.
Therefore, in order to obtain a liquid crystal aligning agent having excellent coating properties, studies have been carried out to improve coating unevenness by using techniques such as those disclosed in Patent Document 1, Patent Document 2, and Patent Document 3, In the conventional manufacturing process of the liquid crystal display element, a sufficient effect could be exhibited, which is a result of taking into account the contribution of the small size of the liquid crystal display element at that time.
液晶表示素子は、配向膜を形成した一対の母基板を貼り合わせてセルを組み、液晶を注入した後に分割する多面取り法が一般的に行われる。
従来は、製造する液晶表示素子のサイズが基板に対して十分に小さかったために、一対の母基板から数枚から数十枚の液晶表示素子を得ることができ、母基板上の配向膜の一部分に塗布ムラなどの欠陥があっても、その部分を含まない液晶表示素子が多数得られるために高い製造効率を実現することができた。
ところが、近年では液晶表示素子は大型化の傾向にあり、最近では40インチクラスのものまで製造されるようになっている。
液晶表示素子の大型化が進む一方で、母基板の大型化の程度は、その製造や搬送の制約のために小さく留まり、一対の母基板から得ることのできる液晶表示素子の数は従来よりも低下する状況にある。
このため、母基板に形成された液晶配向膜に欠陥があった場合に製造効率に与える影響は従来よりも格段に大きくなり、従って、従来よりも塗布性が著しく向上し、欠陥の無い液晶配向膜を安定的に与えることのできる液晶配向剤の開発が待ち望まれていた。
Conventionally, since the size of the liquid crystal display element to be manufactured was sufficiently small relative to the substrate, several to several tens of liquid crystal display elements can be obtained from a pair of mother substrates, and a part of the alignment film on the mother substrate Even if there is a defect such as coating unevenness, a large number of liquid crystal display elements not including that portion can be obtained, so that high production efficiency can be realized.
However, in recent years, liquid crystal display elements have been increasing in size, and recently, even 40-inch class devices have been manufactured.
While the size of the liquid crystal display element is increasing, the size of the mother substrate is small because of restrictions on manufacturing and transportation, and the number of liquid crystal display elements that can be obtained from a pair of mother substrates is larger than the conventional one. The situation is in decline.
For this reason, when there is a defect in the liquid crystal alignment film formed on the mother substrate, the effect on the production efficiency is significantly greater than in the prior art. Development of a liquid crystal aligning agent that can stably provide a film has been awaited.
本発明の目的は、塗布性に優れ、塗布ムラなどの欠陥のない垂直液晶配向膜を安定的に得ることのできる垂直液晶配向剤を提供することにある。 An object of the present invention is to provide a vertical liquid crystal aligning agent which is excellent in coating properties and can stably obtain a vertical liquid crystal alignment film free from defects such as coating unevenness.
本発明の他の目的は、本発明の液晶配向剤から得られる垂直液晶配向膜を具備してなる垂直液晶表示素子を提供することにある。 Another object of the present invention is to provide a vertical liquid crystal display device comprising a vertical liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention.
本発明の他の目的および利点は、以下の説明から明らかになろう。 Other objects and advantages of the present invention will become apparent from the following description.
本発明によれば、本発明の上記目的および利点は、第1に、表面張力が39dyne/cm以上の、分子内に窒素原子を含有する第1有機溶剤、表面張力が39dyne/cm以上の、分子内に窒素原子を含有しない第2有機溶剤および表面張力が32dyne/cm以下の第3有機溶剤からなる混合溶剤ならびに該混合溶剤に溶解されているポリアミック酸の部分イミド化重合体および/またはポリイミドを含有することを特徴とする垂直液晶配向剤によって達成される。 According to the present invention, the above objects and advantages of the present invention are as follows. First, the surface tension is 39 dyne / cm or more, the first organic solvent containing a nitrogen atom in the molecule, the surface tension is 39 dyne / cm or more, A mixed solvent comprising a second organic solvent containing no nitrogen atom in the molecule and a third organic solvent having a surface tension of 32 dyne / cm or less, and a partially imidized polymer of polyamic acid and / or polyimide dissolved in the mixed solvent It is achieved by a vertical liquid crystal aligning agent characterized by containing
本発明によれば、本発明の上記目的および利点は、第2に、本発明の垂直液晶配向剤から形成される液晶配向膜を具備することを特徴とする垂直液晶表示素子によって達成される。 According to the present invention, the above objects and advantages of the present invention are secondly achieved by a vertical liquid crystal display element comprising a liquid crystal alignment film formed from the vertical liquid crystal aligning agent of the present invention.
本発明の液晶配向剤は、大型基板を用いた場合でも塗布ムラなどの欠陥の無い垂直液晶配向膜を安定的に与えることができ、特に大型の液晶表示素子を製造するために好適に使用することができる。
本発明の液晶表示素子は、種々の装置に有効に使用することができ、例えば、卓上計算機、腕時計、置時計、携帯電話、計数表示板、ワードプロセッサ、パーソナルコンピュータ、液晶テレビなどの表示装置として好適に用いることができる。
The liquid crystal aligning agent of the present invention can stably provide a vertical liquid crystal alignment film free from defects such as coating unevenness even when a large substrate is used, and is particularly preferably used for producing a large liquid crystal display element. be able to.
The liquid crystal display element of the present invention can be effectively used in various devices, and is suitable for display devices such as desk calculators, watches, table clocks, mobile phones, counting display boards, word processors, personal computers, and liquid crystal televisions. Can be used.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明における液晶配向剤は、上記のとおり、ポリアミック酸の部分イミド化重合体および/またはポリイミドを、第1有機溶剤、第2有機溶剤および第3有機溶剤からなる混合溶剤に溶解した溶液からなる。
上記ポリイミドは、通常、テトラカルボン酸二無水物とジアミン化合物とを開環重付加させて得られたポリアミック酸を脱水閉環させて得られる。部分イミド化重合体は、通常、ポリアミック酸を部分的に脱水閉環させる方法か、アミック酸プレポリマーとイミドプレポリマーとを結合させてブロック共重合体を合成する方法により、得ることができる。
The liquid crystal aligning agent in this invention consists of the solution which melt | dissolved the partial imidation polymer and / or polyimide of polyamic acid in the mixed solvent which consists of a 1st organic solvent, a 2nd organic solvent, and a 3rd organic solvent as above-mentioned. .
The polyimide is usually obtained by dehydrating and ring-closing polyamic acid obtained by ring-opening polyaddition of tetracarboxylic dianhydride and a diamine compound. The partially imidized polymer can be usually obtained by a method of partially dehydrating and ring-closing polyamic acid or a method of synthesizing a block copolymer by combining an amic acid prepolymer and an imide prepolymer.
<ポリアミック酸>
[テトラカルボン酸二無水物]
テトラカルボン酸二無水物としては、例えば、ブタンテトラカルボン酸二無水物、1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,2−ジメチル−1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,3−ジメチル−1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,3−ジクロロ−1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,2,3,4−テトラメチル−1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,2,3,4−シクロペンタンテトラカルボン酸二無水物、1,2,4,5−シクロヘキサンテトラカルボン酸二無水物、3,3’,4,4’−ジシクロヘキシルテトラカルボン酸二無水物、2,3,5−トリカルボキシシクロペンチル酢酸二無水物、3,5,6−トリカルボキシノルボルナン−2−酢酸二無水物、2,3,4,5−テトラヒドロフランテトラカルボン酸二無水物、1,3,3a,4,5,9b−ヘキサヒドロ−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−5−メチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−5−エチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−7−メチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−7−エチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−8−メチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−8−エチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−5,8−ジメチル−5(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、5−(2,5−ジオキソテトラヒドロフラル)−3−メチル−3−シクロヘキセン−1,2−ジカルボン酸二無水物、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、3−オキサビシクロ[3.2.1]オクタン−2,4−ジオン−6−スピロ−3’−(テトラヒドロフラン−2’,5’−ジオン)、下記式(I)および(II)で表される化合物などの脂肪族および脂環式テトラカルボン酸二無水物;
<Polyamic acid>
[Tetracarboxylic dianhydride]
Examples of tetracarboxylic dianhydride include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4 , 5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6- Recarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro-2, 5-Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2 , 5-Dioxo-3-furanyl) -naphth [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-) 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- 2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6 -Tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), the following formula (I ) And aliphatic and alicyclic tetracarboxylic dianhydrides such as compounds represented by (II);
(式中、R1およびR3は、芳香環を有する2価の有機基を示し、R2およびR4は、水素原子またはアルキル基を示し、複数存在するR2およびR4は、それぞれ同一でも異なっていてもよい。)
ピロメリット酸二無水物、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物、3,3’,4,4’−ビフェニルスルホンテトラカルボン酸二無水物、1,4,5,8−ナフタレンテトラカルボン酸二無水物、2,3,6,7−ナフタレンテトラカルボン酸二無水物、3,3’,4,4’−ビフェニルエーテルテトラカルボン酸二無水物、3,3’,4,4’−ジメチルジフェニルシランテトラカルボン酸二無水物、3,3’,4,4’−テトラフェニルシランテトラカルボン酸二無水物、1,2,3,4−フランテトラカルボン酸二無水物、4,4’−ビス(3,4−ジカルボキシフェノキシ)ジフェニルスルフィド二無水物、4,4’−ビス(3,4−ジカルボキシフェノキシ)ジフェニルスルホン二無水物、4,4’−ビス(3,4−ジカルボキシフェノキシ)ジフェニルプロパン二無水物、3,3’,4,4’−パーフルオロイソプロピリデンジフタル酸二無水物、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、ビス(フタル酸)フェニルホスフィンオキサイド二無水物、p−フェニレン−ビス(トリフェニルフタル酸)二無水物、m−フェニレン−ビス(トリフェニルフタル酸)二無水物、ビス(トリフェニルフタル酸)−4,4’−ジフェニルエーテル二無水物、ビス(トリフェニルフタル酸)−4,4’−ジフェニルメタン二無水物、エチレングリコール−ビス(アンヒドロトリメリテート)、プロピレングリコール−ビス(アンヒドロトリメリテート)、1,4−ブタンジオール−ビス(アンヒドロトリメリテート)、1,6−ヘキサンジオール−ビス(アンヒドロトリメリテート)、1,8−オクタンジオール−ビス(アンヒドロトリメリテート)、2,2−ビス(4−ヒドロキシフェニル)プロパン−ビス(アンヒドロトリメリテート)、下記式(1)〜(4)で表される化合物などの芳香族テトラカルボン酸二無水物を挙げることができる。これらは1種単独でまたは2種以上組み合わせて用いられる。
(Wherein R 1 and R 3 represent a divalent organic group having an aromatic ring, R 2 and R 4 represent a hydrogen atom or an alkyl group, and a plurality of R 2 and R 4 are the same. But it may be different.)
Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis ( 3,4-dicar Boxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (Phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4 , 4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, ethylene glycol-bis (anhydro trimellitate), propylene glycol-bis (anhydro trimellitate) 1,4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydride) Trimetrate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), the following formulas (1) to (4) An aromatic tetracarboxylic dianhydride such as a compound represented by These may be used alone or in combination of two or more.
これらのうち、ブタンテトラカルボン酸二無水物、1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,3−ジメチル−1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,2,3,4−シクロペンタンテトラカルボン酸二無水物、1,2,4,5−シクロヘキサンテトラカルボン酸二無水物、2,3,5−トリカルボキシシクロペンチル酢酸二無水物、5−(2,5−ジオキソテトラヒドロフラル)−3−メチル−3−シクロヘキセン−1,2−ジカルボン酸二無水物、1,3,3a,4,5,9b−ヘキサヒドロ−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−8−メチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−5,8−ジメチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]フラン−1,3−ジオン、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、3−オキサビシクロ[3.2.1]オクタン−2,4−ジオン−6−スピロ−3’−(テトラヒドロフラン−2’,5’−ジオン)、ピロメリット酸二無水物、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物、3,3’,4,4’−ビフェニルスルホンテトラカルボン酸二無水物、1,4,5,8−ナフタレンテトラカルボン酸二無水物、上記式(I)で表される化合物のうち下記式(5)〜(7)で表される化合物および上記式(II)で表される化合物のうち下記式(8)で表される化合物が、良好な液晶配向性を発現させることができる観点から好ましい。特に好ましいものとして、1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,3−ジメチル−1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,2,4,5−シクロヘキサンテトラカルボン酸二無水物、2,3,5−トリカルボキシシクロペンチル酢酸二無水物、1,3,3a,4,5,9b−ヘキサヒドロ−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−8−メチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]フラン−1,3−ジオン、3−オキサビシクロ[3.2.1]オクタン−2,4−ジオン−6−スピロ−3’−(テトラヒドロフラン−2’,5’−ジオン)、ピロメリット酸二無水物および下記式(5)で表される化合物を挙げることができる。 Of these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- ( 2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5 − Oxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2, 5-Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic Acid dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride Of the anhydrides, compounds represented by the above formula (I) Among the compounds represented by the formulas (5) to (7) and the compound represented by the above formula (II), the compound represented by the following formula (8) can exhibit good liquid crystal alignment. It is preferable from the viewpoint. Particularly preferred are 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5 Cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′) , 5'-Geo ), It may be mentioned compounds represented by pyromellitic dianhydride and the following formula (5).
特に、式(I−1)で表される繰り返し単位(アミック酸単位)と式(I−2)で表される繰り返し単位(イミド単位)が共に存在する場合、(I−1)におけるP1で表される4価の有機基と、(I−2)で表される繰り返し単位(イミド単位)P2で表される4価の有機基は、それぞれ同一であっても異なっていてもよいが、P1の好ましいものとしては下記式(i)および(i’)および(ii)のそれぞれで表される基が挙げられる。P2の好ましいものとしては、脂環骨格を有する基が挙げられ、特に好ましくは下記式(ii)および(ii’)のそれぞれで表される基が挙げられる。 In particular, when both the repeating unit represented by formula (I-1) (amic acid unit) and the repeating unit represented by formula (I-2) (imide unit) are present, P 1 in (I-1) and tetravalent organic group represented in a tetravalent organic group represented by the repeating unit (imide units) P 2 represented by (I-2), may each be the same or different However, preferred examples of P 1 include groups represented by the following formulas (i) and (i ′) and (ii). P 2 is preferably a group having an alicyclic skeleton, particularly preferably a group represented by each of the following formulas (ii) and (ii ′).
(式中、P1およびP2は互に独立に4価の有機基であり、Q1およびQ2は互に独立に2価の有機基であり、Rはハロゲン原子、メチル基またはエチル基であり、aは0または1の整数であり、bは0〜5の整数であり、cおよびdは0〜4の整数である。)
各繰返し単位における好ましいテトラカルボン酸二無水物の具体例としては、アミック酸単位を構成するテトラカルボン酸二無水物としては、1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,3−ジメチル−1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,2,4,5−シクロヘキサンテトラカルボン酸二無水物、2,3,5−トリカルボキシシクロペンチル酢酸二無水物、ピロメリット酸二無水物、式(5)で表される化合物等が挙げられ、また、イミド単位を構成するテトラカルボン酸二無水物としては脂環式テトラカルボン酸二無水物、特に、2,3,5−トリカルボキシシクロペンチル酢酸二無水物、1,3,3a,4,5,9b−ヘキサヒドロ−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−8−メチル−5(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、3−オキサビシクロ[3.2.1]オクタン−2,4−ジオン−6−スピロ−3’−(テトラヒドロフラン−2’,5’−ジオン)等が挙げられる。
Wherein P 1 and P 2 are independently a tetravalent organic group, Q 1 and Q 2 are each independently a divalent organic group, and R is a halogen atom, a methyl group or an ethyl group A is an integer of 0 or 1, b is an integer of 0 to 5, and c and d are integers of 0 to 4.)
Specific examples of the preferred tetracarboxylic dianhydride in each repeating unit include 1,2,3,4-cyclobutanetetracarboxylic dianhydride as the tetracarboxylic dianhydride constituting the amic acid unit, 3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, Pyromellitic dianhydride, a compound represented by the formula (5), and the like, and examples of the tetracarboxylic dianhydride constituting the imide unit include alicyclic tetracarboxylic dianhydrides, 3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furani ) -Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) ) -Naphtho [1,2-c] -furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′) , 5′-dione) and the like.
[ジアミン化合物]
上記ポリアミック酸の合成に用いられるジアミン化合物としては、例えばp−フェニレンジアミン、m−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、3,3’−ジメチル−4,4’−ジアミノビフェニル、4,4’−ジアミノベンズアニリド、4,4’−ジアミノジフェニルエーテル、1,5−ジアミノナフタレン、2,2’−ジメチル−4,4’−ジアミノビフェニル、5−アミノ−1−(4’−アミノフェニル)−1,3,3−トリメチルインダン、6−アミノ−1−(4’−アミノフェニル)−1,3,3−トリメチルインダン、3,4’−ジアミノジフェニルエーテル、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、2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]ヘキサフルオロプロパン、2,2−ビス(4−アミノフェニル)ヘキサフルオロプロパン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]スルホン、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、1,3−ビス(3−アミノフェノキシ)ベンゼン、9,9−ビス(4−アミノフェニル)−10−ヒドロアントラセン、2,7−ジアミノフルオレン、9,9−ビス(4−アミノフェニル)フルオレン、4,4’−メチレン−ビス(2−クロロアニリン)、2,2’,5,5’−テトラクロロ−4,4’−ジアミノビフェニル、2,2’−ジクロロ−4,4’−ジアミノ−5,5’−ジメトキシビフェニル、3,3’−ジメトキシ−4,4’−ジアミノビフェニル、1,4,4’−(p−フェニレンイソプロピリデン)ビスアニリン、4,4’−(m−フェニレンイソプロピリデン)ビスアニリン、2,2’−ビス[4−(4−アミノ−2−トリフルオロメチルフェノキシ)フェニル]ヘキサフルオロプロパン、4,4’−ジアミノ−2,2’−ビス(トリフルオロメチル)ビフェニル、4,4’−ビス[(4−アミノ−2−トリフルオロメチル)フェノキシ]−オクタフルオロビフェニル、4−(4−n−ヘプチルシクロヘキシル)フェノキシ−2,4−ジアミノベンゼンなどの芳香族ジアミン;
1,1−メタキシリレンジアミン、1,3−プロパンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、4,4−ジアミノヘプタメチレンジアミン、1,4−ジアミノシクロヘキサン、イソホロンジアミン、テトラヒドロジシクロペンタジエニレンジアミン、ヘキサヒドロ−4,7−メタノインダニレンジメチレンジアミン、トリシクロ[6.2.1.02,7]−ウンデシレンジメチルジアミン、4,4’−メチレンビス(シクロヘキシルアミン)などの脂肪族および脂環式ジアミン;
2,3−ジアミノピリジン、2,6−ジアミノピリジン、3,4−ジアミノピリジン、2,4−ジアミノピリミジン、5,6−ジアミノ−2,3−ジシアノピラジン、5,6−ジアミノ−2,4−ジヒドロキシピリミジン、2,4−ジアミノ−6−ジメチルアミノ−1,3,5−トリアジン、1,4−ビス(3−アミノプロピル)ピペラジン、2,4−ジアミノ−6−イソプロポキシ−1,3,5−トリアジン、2,4−ジアミノ−6−メトキシ−1,3,5−トリアジン、2,4−ジアミノ−6−フェニル−1,3,5−トリアジン、2,4−ジアミノ−6−メチル−s−トリアジン、2,4−ジアミノ−1,3,5−トリアジン、4,6−ジアミノ−2−ビニル−s−トリアジン、2,4−ジアミノ−5−フェニルチアゾール、2,6−ジアミノプリン、5,6−ジアミノ−1,3−ジメチルウラシル、3,5−ジアミノ−1,2,4−トリアゾール、6,9−ジアミノ−2−エトキシアクリジンラクテート、3,8−ジアミノ−6−フェニルフェナントリジン、1,4−ジアミノピペラジン、3,6−ジアミノアクリジン、ビス(4−アミノフェニル)フェニルアミンおよび下記式(III)〜(IV)で表される化合物などの、分子内に2つの1級アミノ基および該1級アミノ基以外の窒素原子を有するジアミン;
[Diamine compound]
Examples of the diamine compound used for the synthesis of the polyamic acid include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2, 2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl)- 1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, , 4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexa Fluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1 , 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9 , 9-bis (4-aminophenyl) fluorene, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5,5′-tetra Loro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 1,4 , 4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] Hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 4 -Aromatic diamines such as (4-n-heptylcyclohexyl) phenoxy-2,4-diaminobenzene;
1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1 , 4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylene methylenediamine, tricyclo [6.2.1.0 2,7 ] -undecylenedimethyldiamine, 4 Aliphatic and cycloaliphatic diamines such as 4,4'-methylenebis (cyclohexylamine);
2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4 -Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3 , 5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl -S-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6- Aminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6 2 in the molecule such as phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine and compounds represented by the following formulas (III) to (IV) A diamine having one primary amino group and a nitrogen atom other than the primary amino group;
(式中、R5は、ピリジン、ピリミジン、トリアジン、ピペリジンおよびピペラジンから選ばれる窒素原子を含む環構造を有する1価の有機基を示し、Xは2価の有機基を示す。) (In the formula, R 5 represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X represents a divalent organic group.)
(式中、Xは、ピリジン、ピリミジン、トリアジン、ピペリジンおよびピペラジンから選ばれる窒素原子を含む環構造を有する2価の有機基を示し、R6は2価の有機基を示し、複数存在するXは、同一でも異なっていてもよい。)
下記式(V)で表されるモノ置換フェニレンジアミン類;下記式(VI)で表されるジアミノオルガノシロキサン;
(Wherein X represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, R 6 represents a divalent organic group, and a plurality of X May be the same or different.)
Mono-substituted phenylenediamines represented by the following formula (V); diaminoorganosiloxanes represented by the following formula (VI);
(式中、R7は、−O−、−COO−、−OCO−、−NHCO−、−CONH−および−CO−から選ばれる2価の有機基を示し、R8は、ステロイド骨格、トリフルオロメチル基およびフルオロ基から選ばれる基を有する1価の有機基または炭素数6〜30のアルキル基を示す。) (Wherein R 7 represents a divalent organic group selected from —O—, —COO—, —OCO—, —NHCO—, —CONH— and —CO—, and R 8 represents a steroid skeleton, A monovalent organic group having a group selected from a fluoromethyl group and a fluoro group or an alkyl group having 6 to 30 carbon atoms is shown.)
(式中、R9は炭素数1〜12の炭化水素基を示し、複数存在するR9は、それぞれ同一でも異なっていてもよく、pは1〜3の整数であり、qは1〜20の整数である。)
下記式(9)〜(13)で表される化合物などを挙げることができる。これらのジアミン化合物は、単独でまたは2種以上組み合わせて用いることができる。
(In the formula, R 9 represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R 9 may be the same or different, p is an integer of 1 to 3, and q is 1 to 20) Is an integer.)
Examples include compounds represented by the following formulas (9) to (13). These diamine compounds can be used alone or in combination of two or more.
(式中、yは2〜12の整数であり、zは1〜5の整数である。)
これらのうち、p−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スルフィド、1,5−ジアミノナフタレン、2,7−ジアミノフルオレン、4,4’−ジアミノジフェニルエーテル、2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパン、9,9−ビス(4−アミノフェニル)フルオレン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]ヘキサフルオロプロパン、2,2−ビス(4−アミノフェニル)ヘキサフルオロプロパン、4,4’−(p−フェニレンジイソプロピリデン)ビスアニリン、4,4’−(m−フェニレンジイソプロピリデン)ビスアニリン、1,4−シクロヘキサンジアミン、4,4’−メチレンビス(シクロヘキシルアミン)、1,4−ビス(4−アミノフェノキシ)ベンゼン、4,4’−ビス(4−アミノフェノキシ)ビフェニル、上記式(9)〜(13)で表される化合物、2,6−ジアミノピリジン、3,4−ジアミノピリジン、2,4−ジアミノピリミジン、3,6−ジアミノアクリジン、上記式(III)で表される化合物のうち下記式(14)で表される化合物、上記式(IV)で表される化合物のうち下記式(15)で表される化合物および上記式(V)で表される化合物のうち下記式(16)〜(21)で表される化合物が好ましい。
(In the formula, y is an integer of 2 to 12, and z is an integer of 1 to 5.)
Among these, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2, 2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2 , 2-bis (4-aminophenyl) hexafluoropropane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine 4,4′-methylenebis (cyclohexylamine), 1,4-bis (4-amino) Enoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, compounds represented by the above formulas (9) to (13), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4 -Diaminopyrimidine, 3,6-diaminoacridine, the compound represented by the following formula (14) among the compounds represented by the above formula (III), and the following formula (15) among the compounds represented by the above formula (IV) ) And compounds represented by the following formulas (16) to (21) are preferred among the compounds represented by the formula (V).
[ポリアミック酸の合成反応]
ポリアミック酸の合成反応に供されるテトラカルボン酸二無水物とジアミン化合物の使用割合は、ジアミン化合物に含まれるアミノ基1当量に対して、テトラカルボン酸二無水物の酸無水物基が0.2〜2当量となる割合が好ましく、さらに好ましくは0.3〜1.2当量となる割合である。
[Synthetic reaction of polyamic acid]
The ratio of the tetracarboxylic dianhydride and the diamine compound used for the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.1 relative to 1 equivalent of the amino group contained in the diamine compound. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.
ポリアミック酸の合成反応は、有機溶媒中において、好ましくは−20〜150℃、より好ましくは0〜100℃の温度条件下で行われる。ここで、有機溶媒としては、合成されるポリアミック酸を溶解できるものであれば特に制限はなく、例えば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、γ−ブチロラクトン、テトラメチル尿素、ヘキサメチルホスホルトリアミドなどの非プロトン系極性溶媒;m−クレゾール、キシレノール、フェノール、ハロゲン化フェノールなどのフェノール系溶媒を例示することができる。また、有機溶媒の使用量(a)は、テトラカルボン酸二無水物およびジアミン化合物の総量(b)が、反応溶液の全量(a+b)に対して0.1〜30重量%になるような量であることが好ましい。 The synthetic reaction of polyamic acid is preferably carried out in an organic solvent under a temperature condition of -20 to 150 ° C, more preferably 0 to 100 ° C. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide And aprotic polar solvents such as γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. The amount of the organic solvent used (a) is such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 30% by weight with respect to the total amount (a + b) of the reaction solution. It is preferable that
[貧溶媒]
前記有機溶媒には、ポリアミック酸の貧溶媒であるアルコール類、ケトン類、エステル類、エーテル類、ハロゲン化炭化水素類、炭化水素類などを、生成するポリアミック酸が析出しない範囲で併用することができる。かかる貧溶媒の具体例としては、例えばメチルアルコール、エチルアルコール、イソプロピルアルコール、シクロヘキサノール、エチレングリコール、プロピレングリコール、1,4−ブタンジオール、トリエチレングリコール、エチレングリコールモノメチルエーテル、乳酸エチル、乳酸ブチル、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、酢酸メチル、酢酸エチル、酢酸ブチル、メチルメトキシプロピオネ−ト、エチルエトキシプロピオネ−ト、シュウ酸ジエチル、マロン酸ジエチル、ジエチルエーテル、エチレングリコールメチルエーテル、エチレングリコールエチルエーテル、エチレングリコール−n−プロピルエーテル、エチレングリコール−i−プロピルエーテル、エチレングリコール−n−ブチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールエチルエーテルアセテート、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、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モノエチルエーテル、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、テトラヒドロフラン、ジクロロメタン、1,2−ジクロロエタン、1,4−ジクロロブタン、トリクロロエタン、クロルベンゼン、o−ジクロルベンゼン、ヘキサン、ヘプタン、オクタン、ベンゼン、トルエン、キシレンなどを挙げることができる。
[Poor solvent]
Alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are poor solvents for polyamic acid, may be used in combination with the organic solvent as long as the resulting polyamic acid does not precipitate. it can. Specific examples of the poor solvent include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene Glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n- Chill ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1 , 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like.
以上のようにして、ポリアミック酸を溶解してなる反応溶液が得られる。そして、この反応溶液を大量の貧溶媒中に注いで析出物を得、この析出物を減圧下乾燥することによりポリアミック酸を得ることができる。また、このポリアミック酸を再び有機溶媒に溶解させ、次いで貧溶媒で析出させる工程を1回または数回行うことにより、ポリアミック酸を精製することができる。 As described above, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain a polyamic acid. The polyamic acid can be purified by dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent once or several times.
<ポリイミド>
本発明の液晶配向剤を構成するポリイミドは、上記ポリアミック酸を脱水閉環することにより調製することができる。ポリアミック酸の脱水閉環は、例えば(i)ポリアミック酸を加熱する方法により、または(ii)ポリアミック酸を有機溶媒に溶解し、この溶液中に脱水剤および脱水閉環触媒を添加し必要に応じて加熱する方法により有利に行われる。
上記(i)のポリアミック酸を加熱する方法における反応温度は、好ましくは50〜200℃であり、より好ましくは60〜170℃である。反応温度が50℃未満では脱水閉環反応が十分に進行し難く、反応温度が200℃を超えると得られるイミド化重合体の分子量が低下することがある。
<Polyimide>
The polyimide constituting the liquid crystal aligning agent of the present invention can be prepared by dehydrating and ring-closing the polyamic acid. The dehydration and ring closure of the polyamic acid can be performed, for example, by (i) a method of heating the polyamic acid or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to this solution, and heating as necessary. This method is advantageously performed.
The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. If the reaction temperature is less than 50 ° C., the dehydration ring-closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 ° C., the molecular weight of the imidized polymer obtained may decrease.
一方、上記(ii)のポリアミック酸の溶液中に脱水剤および脱水閉環触媒を添加する方法において、脱水剤としては、例えば無水酢酸、無水プロピオン酸、無水トリフルオロ酢酸などの酸無水物を用いることができる。脱水剤の使用量は、ポリアミック酸の繰り返し単位1モルに対して0.01〜20モルとするのが好ましい。また、脱水閉環触媒としては、例えばピリジン、コリジン、ルチジン、トリエチルアミンなどの3級アミンを用いることができる。しかし、これらに限定されるものではない。脱水閉環触媒の使用量は、使用する脱水剤1モルに対して0.01〜10モルとするのが好ましい。なお、脱水閉環反応に用いられる有機溶媒としては、ポリアミック酸の合成に用いられるものとして例示した有機溶媒と同じ有機溶媒を挙げることができる。そして、脱水閉環反応の反応温度は、好ましくは0〜180℃、より好ましくは10〜150℃である。また、このようにして得られる反応溶液に対し、ポリアミック酸の精製方法と同様の操作を行うことにより、ポリイミドを精製することができる。 On the other hand, in the method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can do. The amount of the dehydrating agent used is preferably 0.01 to 20 mol relative to 1 mol of the polyamic acid repeating unit. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. In addition, as an organic solvent used for dehydration ring closure reaction, the same organic solvent as the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. And the reaction temperature of dehydration ring closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC. Moreover, a polyimide can be refine | purified by performing operation similar to the purification method of polyamic acid with respect to the reaction solution obtained in this way.
<部分イミド化重合体>
本発明に用いられる部分イミド化重合体は、上記ポリアミック酸を部分的にイミド化して得られる構造を有する。本発明に用いられる部分イミド化重合体におけるイミド化率は、好ましくは10〜90%、さらに好ましくは30〜70%である。ここで、「イミド化率」とは、重合体における繰り返し単位の総数に対する、イミド環を形成してなる繰り返し単位の数の割合を%で表したものとする。このとき、イミド環の一部がイソイミド環であってもよい。
<Partially imidized polymer>
The partially imidized polymer used in the present invention has a structure obtained by partially imidizing the polyamic acid. The imidation ratio in the partially imidized polymer used in the present invention is preferably 10 to 90%, more preferably 30 to 70%. Here, the “imidation ratio” is the percentage of the number of repeating units that form an imide ring with respect to the total number of repeating units in the polymer. At this time, a part of the imide ring may be an isoimide ring.
部分イミド化重合体を合成する方法としては、例えば(i)上記ポリアミック酸を加熱することにより部分的に脱水閉環させて合成する方法、(ii)上記ポリアミック酸を有機溶媒に溶解し、この溶液中に脱水剤および脱水閉環触媒を添加し必要に応じて加熱することにより、部分的に脱水閉環させて合成する方法、または(iii)テトラカルボン酸二無水物、ジアミン化合物およびジイソシアネート化合物とを混合し、必要に応じて加熱することにより、縮合させて合成する方法が用いられる。
上記(i)の方法において、反応温度は、好ましくは300℃以下であり、より好ましくは100〜250℃である。反応温度が300℃を超えると得られる部分イミド化重合体の分子量が低下することがある。
As a method for synthesizing a partially imidized polymer, for example, (i) a method of synthesizing by partially dehydrating and cyclizing the polyamic acid by heating, and (ii) dissolving the polyamic acid in an organic solvent, this solution A method in which a dehydrating agent and a dehydrating ring-closing catalyst are added and heated as necessary to partially dehydrate and cyclize, or (iii) tetracarboxylic dianhydride, diamine compound and diisocyanate compound are mixed And the method of condensing and synthesizing by heating as needed is used.
In the method (i), the reaction temperature is preferably 300 ° C. or less, more preferably 100 to 250 ° C. When the reaction temperature exceeds 300 ° C., the molecular weight of the partially imidized polymer obtained may decrease.
一方、上記(ii)の方法において用いられる脱水剤としては、例えば無水酢酸、無水プロピオン酸、無水トリフルオロ酢酸などの酸無水物を挙げることができる。脱水剤の使用量は、ポリアミック酸の繰り返し単位1モルに対して0.2〜20モルとするのが好ましい。また、脱水閉環触媒としては、例えばピリジン、コリジン、ルチジン、トリエチルアミンなどの第3級アミンを用いることができる。これらに限定されるものではない。また、イミド化触媒の使用量は、使用する脱水剤1モルに対して0.1〜10モルとするのが好ましい。なお、脱水閉環の反応に用いられる有機溶媒としては、ポリアミック酸の合成に用いられるものとして例示した有機溶媒と同じ有機溶媒を挙げることができる。そして、脱水閉環の反応温度は、好ましくは0〜180℃、より好ましくは60〜150℃である。また、このようにして得られる反応溶液に対し、ポリアミック酸の精製方法と同様の操作を行うことにより、部分イミド化重合体を精製することができる。 On the other hand, examples of the dehydrating agent used in the method (ii) include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. The amount of the dehydrating agent used is preferably 0.2 to 20 mol with respect to 1 mol of the polyamic acid repeating unit. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. It is not limited to these. Moreover, it is preferable that the usage-amount of an imidation catalyst shall be 0.1-10 mol with respect to 1 mol of dehydrating agents to be used. In addition, as an organic solvent used for reaction of dehydration ring closure, the same organic solvent as the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. And the reaction temperature of dehydration ring closure becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 60-150 degreeC. Further, the partially imidized polymer can be purified by performing the same operation as the polyamic acid purification method on the reaction solution thus obtained.
上記(iii)の反応において用いられるジイソシアネート化合物の具体例としては、ヘキサメチレンジイソシアネートなどの脂肪族ジイソシアネート;シクロヘキサン−1,2−ジイソシアネート、1−メチルシクロヘキサン−2,4−ジイソシアネート、1,2−ジメチルシクロヘキサン−ω,ω’−ジイソシアネート、1,4−ジメチルシクロヘキサン−ω,ω’−ジイソシアネート、イソホロンジイソシアネート、1,3,5−トリメチル−2−プロピルシクロヘキサン−1ω,2ω−ジイソシアネート、ジシクロヘキシルメタン−4,4’−ジイソシアネートなどの脂環式ジイソシアネート;ジフェニルメタン−4,4’−ジイソシアネート、1,3−フェニレンジイソシアネート、1,4−フェニレンジイソシアネート、1−メチル−2,4−フェニレンジイソシアネート、1−メチル−2,6−フェニレンジイソシアネート、下記式(22)〜(26)で表されるジイソシアネ−トなどの芳香族ジイソシアネートが挙げられる。 Specific examples of the diisocyanate compound used in the reaction (iii) include aliphatic diisocyanates such as hexamethylene diisocyanate; cyclohexane-1,2-diisocyanate, 1-methylcyclohexane-2,4-diisocyanate, 1,2-dimethyl. Cyclohexane-ω, ω′-diisocyanate, 1,4-dimethylcyclohexane-ω, ω′-diisocyanate, isophorone diisocyanate, 1,3,5-trimethyl-2-propylcyclohexane-1ω, 2ω-diisocyanate, dicyclohexylmethane-4, Cycloaliphatic diisocyanates such as 4′-diisocyanate; diphenylmethane-4,4′-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methyl And aromatic diisocyanates such as bets - 2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, diisocyanates represented by the following formula (22) to (26).
これらのうち、ジシクロヘキシルメタン−4,4’−ジイソシアネート、ジフェニルメタン−4,4’−ジイソシアネート、1−メチル−2,4−フェニレンジイソシアネート、1−メチル−2,6−フェニレンジイソシアネートが好ましいものとして挙げられる。これらは単独でまたは2種以上組み合わせて用いることができる。なお、上記(iii)の反応には特に触媒は必要とされず、反応温度は、好ましくは50〜200℃、より好ましくは100〜160℃である。 Of these, preferred are dicyclohexylmethane-4,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate, 1-methyl-2,4-phenylene diisocyanate, and 1-methyl-2,6-phenylene diisocyanate. . These can be used alone or in combination of two or more. In addition, a catalyst is not particularly required for the reaction (iii), and the reaction temperature is preferably 50 to 200 ° C, more preferably 100 to 160 ° C.
[末端修飾]
<末端修飾型の重合体>
上記ポリアミック酸および部分イミド化重合体は、分子量が調節された末端修飾型のものであってもよい。この末端修飾型の重合体を用いることにより、本発明の効果が損われることなく液晶配向剤の塗布特性などを改善することができる。このような末端修飾型のものは、ポリアミック酸を合成する際に、酸一無水物、モノアミン化合物、モノイソシアネート化合物などを反応系に添加することにより合成することができる。ここで、酸一無水物としては、例えば無水マレイン酸、無水フタル酸、無水イタコン酸、n−デシルサクシニック酸無水物、n−ドデシルサクシニック酸無水物、n−テトラデシルサクシニック酸無水物、n−ヘキサデシルサクシニック酸無水物などを挙げることができる。また、モノアミン化合物としては、例えばアニリン、シクロヘキシルアミン、n−ブチルアミン、n−ペンチルアミン、n−ヘキシルアミン、n−ヘプチルアミン、n−オクチルアミン、n−ノニルアミン、n−デシルアミン、n−ウンデシルアミン、n−ドデシルアミン、n−トリデシルアミン、n−テトラデシルアミン、n−ペンタデシルアミン、n−ヘキサデシルアミン、n−ヘプタデシルアミン、n−オクタデシルアミン、n−エイコシルアミンなどを挙げることができる。また、モノイソシアネート化合物としては、例えばフェニルイソシアネート、ナフチルイソシアネートなどを挙げることができる。
[Terminal modification]
<End-modified polymer>
The polyamic acid and the partially imidized polymer may be of a terminal modified type with a controlled molecular weight. By using this terminal-modified polymer, the coating characteristics of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. Such a terminal-modified type can be synthesized by adding an acid monoanhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system when synthesizing the polyamic acid. Here, examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride. , N-hexadecyl succinic anhydride and the like. Examples of monoamine compounds include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, and n-undecylamine. N-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine, etc. Can do. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
[対数粘度]
<重合体の対数粘度>
以上のようにして得られるポリアミック酸および部分イミド化重合体の対数粘度(ηln)の値は好ましくは0.05〜10dl/g、より好ましくは0.05〜5dl/gである。
本発明における対数粘度(ηln)の値は、N−メチル−2−ピロリドンを溶媒として用い、濃度が0.5g/100ミリリットルである溶液について30℃で粘度の測定を行い、下記式(A)によって求められるものである。
[Logarithmic viscosity]
<Logarithmic viscosity of polymer>
The logarithmic viscosity (η ln ) of the polyamic acid and the partially imidized polymer obtained as described above is preferably 0.05 to 10 dl / g, more preferably 0.05 to 5 dl / g.
The value of the logarithmic viscosity (η ln ) in the present invention is determined by measuring the viscosity at 30 ° C. for a solution having a concentration of 0.5 g / 100 ml using N-methyl-2-pyrrolidone as a solvent. ).
<液晶配向剤>
本発明の液晶配向剤は、ポリイミドおよび/または部分イミド化重合体が、有機溶媒中に溶解含有されて構成される。
本発明の液晶配向剤を構成する有機溶媒としては、表面張力が39dyne/cm以上の、分子内に窒素原子を含有する第1有機溶剤、表面張力が39dyne/cm以上の、分子内に窒素原子を含有しない第2有機溶剤および表面張力が32dyne/cm以下の第3有機溶剤からなる混合溶剤が用いられる。
第1有機溶剤、第2有機溶剤および第3有機溶剤の混合割合が、下記式
(A×B×C)×10−3 ≧12
ここで、A、BおよびCは、第1有機溶剤、第2有機溶剤および第3有機溶剤の合計重量を基準にする、それぞれ、第1有機溶剤の重量%、第2有機溶剤の重量%および第3有機溶剤の重量%である、
を満足するのが好ましく、14以上であることがさらに好ましい。
<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention is constituted by dissolving and containing a polyimide and / or a partially imidized polymer in an organic solvent.
The organic solvent constituting the liquid crystal aligning agent of the present invention includes a first organic solvent having a surface tension of 39 dyne / cm or more and containing nitrogen atoms in the molecule, and a nitrogen atom in the molecule having a surface tension of 39 dyne / cm or more. A mixed solvent composed of a second organic solvent not containing selenium and a third organic solvent having a surface tension of 32 dyne / cm or less is used.
The mixing ratio of the first organic solvent, the second organic solvent, and the third organic solvent is the following formula (A × B × C) × 10 −3 ≧ 12
Here, A, B, and C are based on the total weight of the first organic solvent, the second organic solvent, and the third organic solvent, respectively, wt% of the first organic solvent, wt% of the second organic solvent, and % By weight of the third organic solvent,
Is preferably satisfied, more preferably 14 or more.
第1有機溶剤の具体例としては、例えばN−メチル−2−ピロリドンおよび N,N−ジメチル−2−イミダゾリジノンなどを挙げることができる。
この溶剤の含有量は、重合体の溶解性の点から、5〜75重量%が望ましく、15〜70重量%がさらに望ましい。
Specific examples of the first organic solvent include N-methyl-2-pyrrolidone and N, N-dimethyl-2-imidazolidinone.
The content of this solvent is preferably from 5 to 75% by weight, more preferably from 15 to 70% by weight, from the viewpoint of the solubility of the polymer.
第2有機溶剤の具体例としては、例えばγ−ブチロラクトンやプロピレンカーボネートなどが挙げられる。この溶剤の含有量は、配向剤の吸湿性の点から、5〜75重量%が望ましく、10〜65重量%がさらに望ましい。 Specific examples of the second organic solvent include γ-butyrolactone and propylene carbonate. The content of the solvent is preferably 5 to 75% by weight and more preferably 10 to 65% by weight from the viewpoint of the hygroscopicity of the alignment agent.
第3有機溶剤の具体例としては、例えばエチレングリコールメチルエーテル、エチレングリコールエチルエーテル、エチレングリコール−n−プロピルエーテル、エチレングリコール−i−プロピルエーテル、エチレングリコール−n−ブチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールエチルエーテルアセテート、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、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モノエチルエーテル、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールジメチルエーテルおよび4−ヒドロキシ−4−メチル−2−ペンタノンなどが挙げられる。
この溶剤の含有量は、印刷時のレベリング性の点から、5〜70重量%が望ましく、15〜60重量%がさらに望ましい。
Specific examples of the third organic solvent include, for example, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol. Ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol Bruno methyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol dimethyl ether and 4-hydroxy-4-methyl-2-pentanone and the like.
The content of the solvent is preferably 5 to 70% by weight and more preferably 15 to 60% by weight from the viewpoint of leveling properties during printing.
本発明の液晶配向剤における固形分濃度は、粘性、揮発性などを考慮して選択されるが、好ましくは1〜10重量%の範囲である。本発明の液晶配向剤は、基板表面に塗布され、液晶配向膜となる塗膜を形成するが、固形分濃度が1重量%未満である場合には、この塗膜の膜厚が過小となって良好な液晶配向膜を得難く、固形分濃度が10重量%を超える場合には、塗膜の膜厚が過大となって良好な液晶配向膜を得難く、また、液晶配向剤の粘性が増大して塗布特性が劣り易くなる。本発明の液晶配向剤を調製する際の温度は、好ましくは0℃〜200℃であり、より好ましくは20℃〜60℃である。
本発明の液晶配向剤は、必要に応じ配向膜の強靭性を向上させるために、分子内にエポキシ基を有する化合物を含有することができる。
The solid content concentration in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, etc., but is preferably in the range of 1 to 10% by weight. The liquid crystal aligning agent of the present invention is applied to the substrate surface to form a coating film that becomes a liquid crystal aligning film. When the solid content concentration is less than 1% by weight, the film thickness of this coating film becomes too small. It is difficult to obtain a good liquid crystal alignment film, and when the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film because the film thickness is excessive, and the viscosity of the liquid crystal aligning agent is It increases and the coating properties tend to be inferior. The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 0 to 200 degreeC, More preferably, it is 20 to 60 degreeC.
The liquid crystal aligning agent of this invention can contain the compound which has an epoxy group in a molecule | numerator, in order to improve the toughness of an alignment film as needed.
かかるエポキシ基含有化合物としては、例えばエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,6−ヘキサンジオールジグリシジルエーテル、グリセリンジグリシジルエーテル、2,2−ジブロモネオペンチルグリコールジグリシジルエーテル、1,3,5,6−テトラグリシジル−2,4−ヘキサンジオール、N,N,N’,N’−テトラグリシジル−m−キシレンジアミン、1,3−ビス(N,N−ジグリシジルアミノメチル)シクロヘキサン、N,N,N’,N’−テトラグリシジル−4、4’−ジアミノジフェニルメタンなどを好ましいものとして挙げることができる。 Examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 -Hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N '-Tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N', N'-tetraglycidyl-4 , And the like as preferred 4'-diaminodiphenylmethane.
また、本発明の液晶配向剤には必要に応じ、配向膜と基板との密着性を向上させるために、官能性シラン含有化合物を含有させてもよい。かかる官能性シラン含有化合物としては、例えば3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、2−アミノプロピルトリメトキシシラン、2−アミノプロピルトリエトキシシラン、N−(2−アミノエチル)−3−アミノプロピルトリメトキシシラン、N−(2−アミノエチル)−3−アミノプロピルメチルジメトキシシラン、3−ウレイドプロピルトリメトキシシラン、3−ウレイドプロピルトリエトキシシラン、N−エトキシカルボニル−3−アミノプロピルトリメトキシシラン、N−エトキシカルボニル−3−アミノプロピルトリエトキシシラン、N−トリエトキシシリルプロピルトリエチレントリアミン、N−トリメトキシシリルプロピルトリエチレントリアミン、10−トリメトキシシリル−1,4,7−トリアザデカン、10−トリエトキシシリル−1,4,7−トリアザデカン、9−トリメトキシシリル−3,6−ジアザノニルアセテート、9−トリエトキシシリル−3,6−ジアザノニルアセテート、N−ベンジル−3−アミノプロピルトリメトキシシラン、N−ベンジル−3−アミノプロピルトリエトキシシラン、N−フェニル−3−アミノプロピルトリメトキシシラン、N−フェニル−3−アミノプロピルトリエトキシシラン、N−ビス(オキシエチレン)−3−アミノプロピルトリメトキシシラン、N−ビス(オキシエチレン)−3−アミノプロピルトリエトキシシランなどを挙げることができる。 Further, the liquid crystal aligning agent of the present invention may contain a functional silane-containing compound as necessary in order to improve the adhesion between the alignment film and the substrate. Examples of such functional silane-containing compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl). -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-amino Propyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl- , 4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N -Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc. can be mentioned.
<液晶表示素子>
本発明の液晶配向剤を用いて得られる液晶表示素子は、例えば次の方法によって製造することができる。
(1)パターニングされた透明導電膜が設けられている基板の一面に、本発明の液晶配向剤を例えばロールコーター法、スピンナー法、印刷法、インクジェット法などの方法によって塗布し、次いで、塗布面を加熱することにより塗膜を形成する。ここに、基板としては、例えばフロートガラス、ソーダガラスなどのガラス;ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエーテルスルホン、ポリカーボネートなどのプラスチックからなる透明基板を用いることができる。基板の一面に設けられる透明導電膜としては、酸化スズ(SnO2)からなるNESA膜(米国PPG社登録商標)、酸化インジウム−酸化スズ(In2O3−SnO2)からなるITO膜などを用いることができる。これらの透明導電膜のパターニングには、フォト・エッチング法や予めマスクを用いる方法が用いられる。反射電極にはAlやAgなどの金属、あるいは、これらの金属を含有する合金などを用いることができる。十分な反射率を有してさえいればこれらに限定されるものではない。液晶配向剤の塗布に際しては、基板表面および透明導電膜や反射電極と塗膜との接着性をさらに良好にするために、基板の該表面に、官能性シラン含有化合物、官能性チタン含有化合物などを予め塗布することもできる。液晶配向剤塗布後の加熱温度は、好ましくは80〜300℃であり、より好ましくは120〜250℃である。ポリアミック酸を含有する本発明の液晶配向剤は、塗布後に有機溶媒を除去することによって配向膜となる塗膜を形成するが、さらに加熱することによって脱水閉環を進行させ、よりイミド化された塗膜とすることもできる。形成される塗膜の膜厚は、好ましくは0.001〜1μmであり、より好ましくは0.005〜0.5μmである。
(2)形成された塗膜面を、特開2002−327058号公報に示されているように、基板上に感光性樹脂を用いて構造物を形成し、その上に垂直液晶配向膜を形成する。
(3)上記のようにして垂直液晶配向膜が形成された基板を2枚作製し、2枚の基板を、間隙(セルギャップ)を介して対向配置し、2枚の基板の周辺部をシール剤を用いて貼り合わせ、基板表面およびシール剤により区画されたセルギャップ内に液晶を注入充填し、注入孔を封止して液晶セルを構成する。そして、液晶セルの外表面、すなわち、液晶セルを構成する透明基板側に、偏光板を配することにより、液晶表示素子が得られる。
ここに、シール剤としては、例えば硬化剤およびスペーサーとしての酸化アルミニウム球を含有するエポキシ樹脂などを用いることができる。
<Liquid crystal display element>
The liquid crystal display element obtained using the liquid crystal aligning agent of this invention can be manufactured, for example with the following method.
(1) The liquid crystal aligning agent of the present invention is applied to one surface of a substrate on which a patterned transparent conductive film is provided by a method such as a roll coater method, a spinner method, a printing method, an ink jet method, etc. Is heated to form a coating film. Here, as the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used. As a transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO 2 ), an ITO film made of indium oxide-tin oxide (In 2 O 3 —SnO 2 ), etc. Can be used. For patterning these transparent conductive films, a photo-etching method or a method using a mask in advance is used. A metal such as Al or Ag or an alloy containing these metals can be used for the reflective electrode. As long as it has sufficient reflectivity, it is not limited to these. When applying the liquid crystal aligning agent, a functional silane-containing compound, a functional titanium-containing compound, or the like is provided on the surface of the substrate in order to further improve the adhesion between the substrate surface and the transparent conductive film or reflective electrode and the coating film. Can also be applied in advance. The heating temperature after application of the liquid crystal aligning agent is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The liquid crystal aligning agent of the present invention containing a polyamic acid forms a coating film that becomes an alignment film by removing the organic solvent after coating. It can also be a membrane. The film thickness of the formed coating film is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.
(2) As shown in Japanese Patent Application Laid-Open No. 2002-327058, a structure is formed on a substrate using a photosensitive resin, and a vertical liquid crystal alignment film is formed thereon. To do.
(3) Two substrates on which the vertical liquid crystal alignment film is formed as described above are manufactured, the two substrates are arranged to face each other with a gap (cell gap) therebetween, and the peripheral portions of the two substrates are sealed. A liquid crystal cell is formed by laminating using an agent, injecting and filling liquid crystal into the cell gap defined by the substrate surface and the sealing agent, and sealing the injection hole. And a liquid crystal display element is obtained by arrange | positioning a polarizing plate to the outer surface of a liquid crystal cell, ie, the transparent substrate side which comprises a liquid crystal cell.
Here, as the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
液晶としては、ネマティック型液晶およびスメクティック型液晶を挙げることができる。その中でもネマティック型液晶が好ましく、例えばシッフベース系液晶、アゾキシ系液晶、ビフェニル系液晶、フェニルシクロヘキサン系液晶、エステル系液晶、ターフェニル系液晶、ビフェニルシクロヘキサン系液晶、ピリミジン系液晶、ジオキサン系液晶、ビシクロオクタン系液晶、キュバン系液晶などを用いることができる。また、これらの液晶に、例えばコレスチルクロライド、コレステリルノナエート、コレステリルカーボネートなどのコレステリック型液晶や商品名「C−15」「CB−15」(メルク社製)として販売されているようなカイラル剤などを添加して使用することもできる。さらに、p−デシロキシベンジリデン−p−アミノ−2−メチルブチルシンナメートなどの強誘電性液晶も使用することができる。
また、液晶セルの外表面に貼り合わされる偏光板としては、ポリビニルアルコールを延伸配向させながら、ヨウ素を吸収させたH膜と称される偏光膜を酢酸セルロース保護膜で挟んだ偏光板またはH膜そのものからなる偏光板を挙げることができる。
Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable, for example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, and bicyclooctane. Type liquid crystal, cubane type liquid crystal and the like can be used. Further, for these liquid crystals, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate, and chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck). Etc. can also be used. Furthermore, a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.
Further, as a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film in which a polarizing film called an H film that absorbs iodine while sandwiching and stretching polyvinyl alcohol is sandwiched between cellulose acetate protective films. The polarizing plate which consists of itself can be mentioned.
以下、本発明を実施例によりさらに具体的に説明するが、本発明はこれらの実施例に制限されるものではない。実施例および比較例における印刷性、垂直配向性は以下の方法により評価した。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The printability and vertical alignment in the examples and comparative examples were evaluated by the following methods.
[液晶配向剤の印刷性試験]
本発明の液晶配向剤を、液晶配向膜印刷機(日本写真印刷機(株)製)を用いてITO膜からなる透明電極付きガラス基板(300mm X 400mm X 0.7mm)の透明電極面に塗布し、焼成によって液晶配向膜を形成した後、この液晶配向膜の周辺部、中央部を倍率20倍の顕微鏡にて観察し、塗布ムラの無い場合を「良好」、塗布ムラの有る場合を「不良」と判定した。
[Printability test of liquid crystal alignment agent]
The liquid crystal aligning agent of this invention is apply | coated to the transparent electrode surface of the glass substrate with a transparent electrode (300mmX400mmX0.7mm) which consists of an ITO film | membrane using a liquid crystal aligning film printer (Nissha Printing Co., Ltd. product). Then, after forming the liquid crystal alignment film by firing, the peripheral part and the center part of the liquid crystal alignment film are observed with a microscope with a magnification of 20 times, and the case where there is no coating unevenness is “good”, and the case where there is coating unevenness is “ It was determined as “bad”.
[垂直配向性]
電圧OFF時および交流12V(ピーク−ピーク)での液晶表示素子をクロスニコル下で観察し、異常ドメインの有無を偏光顕微鏡で観察し、異常ドメインのない場合を「良好」、異常ドメインのある場合を「不良」と判定した。
[Vertical alignment]
When the voltage is OFF and the liquid crystal display element is at 12V AC (peak-peak) under crossed Nicols, the presence or absence of an abnormal domain is observed with a polarizing microscope. Was judged as “bad”.
合成例1
テトラカルボン酸二無水物として2,3,5−トリカルボキシシクロペンチル酢酸二無水物224.17g(1.0モル)、ジアミン化合物としてp−フェニレンジアミン68.13g(0.63モル)、上記式(16)で表されるジアミン化合物193.44g(0.37モル)をN−メチル−2−ピロリドン4,500gに溶解させ、60℃で6時間反応させた。次いで、反応溶液を大過剰のメチルアルコール中に注いで反応生成物を沈澱させた。その後、メチルアルコールで洗浄し、減圧下40℃で15時間乾燥させることにより、対数粘度0.57dl/gのポリアミック酸520gを得た。
得られたポリアミック酸30gをN−メチル−2−ピロリドン570gに溶解させ、ピリジン5.7gおよび無水酢酸7.4gを添加し110℃で4時間脱水閉環させ、上記と同様にして沈殿、洗浄、減圧を行い、対数粘度0.50dl/gのポリイミド(これを「ポリイミド(PI−1)」とする)19.0gを得た。
Synthesis example 1
224.17 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 68.13 g (0.63 mol) of p-phenylenediamine as a diamine compound, The diamine compound 193.44 g (0.37 mol) represented by 16) was dissolved in 4,500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Then, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 520 g of polyamic acid having a logarithmic viscosity of 0.57 dl / g.
30 g of the resulting polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 5.7 g of pyridine and 7.4 g of acetic anhydride were added, and dehydration was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, The pressure was reduced to obtain 19.0 g of polyimide having a logarithmic viscosity of 0.50 dl / g (referred to as “polyimide (PI-1)”).
合成例2
合成例1において、ジアミン化合物としてp−フェニレンジアミン77.86g(0.72モル)、上記式(16)で表されるジアミン化合物146.38g(0.28モル)を用いた以外は合成例1と同様にして、対数粘度0.45dl/gのポリアミック酸390gを得た。得られたポリアミック酸30gを用いた以外は合成例1と同様にイミド化を行い、対数粘度0.56dl/gのポリイミド(これを「ポリイミド(PI−2)」とする)18.9gを得た。
Synthesis example 2
In Synthesis Example 1, Synthesis Example 1 except that 77.86 g (0.72 mol) of p-phenylenediamine and 146.38 g (0.28 mol) of the diamine compound represented by the above formula (16) were used as the diamine compound. In the same manner as above, 390 g of polyamic acid having a logarithmic viscosity of 0.45 dl / g was obtained. Except for using 30 g of the obtained polyamic acid, imidization was performed in the same manner as in Synthesis Example 1 to obtain 18.9 g of a polyimide having a logarithmic viscosity of 0.56 dl / g (hereinafter referred to as “polyimide (PI-2)”). It was.
合成例3
合成例2において、ジアミン化合物としてp−フェニレンジアミン95.16g(0.88モル)、上記式(16)で表されるジアミン化合物62.74g(0.12モル)を用いた以外は合成例2と同様にして、対数粘度0.38dl/gのポリアミック酸450gを得た。その後、ピリジン4.8gおよび無水酢酸6.1gを用いた以外は合成例2と同様にして、対数粘度0.40dl/gのポリイミド(これを「ポリイミド(PI−3)」とする)20.3gを得た。
Synthesis example 3
In Synthesis Example 2, Synthesis Example 2 except that 95.16 g (0.88 mol) of p-phenylenediamine and 62.74 g (0.12 mol) of the diamine compound represented by the above formula (16) were used as the diamine compound. In the same manner, 450 g of polyamic acid having a logarithmic viscosity of 0.38 dl / g was obtained. Thereafter, a polyimide having a logarithmic viscosity of 0.40 dl / g (referred to as “polyimide (PI-3)”) in the same manner as in Synthesis Example 2 except that 4.8 g of pyridine and 6.1 g of acetic anhydride were used. 3 g was obtained.
合成例4
合成例3において、ジアミン化合物としてp−フェニレンジアミン97.33g(0.88モル)、2,4−ジアミノ−1−オクタデシルオキシベンゼン37.66g(0.1モル)を用いた以外は合成例1と同様にして、対数粘度0.42dl/gのポリイミド(これを「ポリイミド(PI−4)」とする)24.3gを得た。
Synthesis example 4
In Synthesis Example 3, Synthesis Example 1 except that 97.33 g (0.88 mol) of p-phenylenediamine and 37.66 g (0.1 mol) of 2,4-diamino-1-octadecyloxybenzene were used as the diamine compound. In the same manner as above, 24.3 g of polyimide having a logarithmic viscosity of 0.42 dl / g (referred to as “polyimide (PI-4)”) was obtained.
合成例5
合成例1において、ジアミン化合物としてp−フェニレンジアミン64.88g(0.88モル)、4−(4−n−ヘプチルシクロヘキシル)フェノキシ−2,4−ジアミノベンゼン36.65g(0.1モル)を用いた以外は合成例1と同様にして、対数粘度0.49dl/gのポリイミド(これを「ポリイミド(PI−5)」とする)24.3gを得た。
Synthesis example 5
In Synthesis Example 1, 64.88 g (0.88 mol) of p-phenylenediamine and 36.65 g (0.1 mol) of 4- (4-n-heptylcyclohexyl) phenoxy-2,4-diaminobenzene were used as diamine compounds. Except having used, it carried out similarly to the synthesis example 1, and obtained 24.3g of polyimides (this is set to "polyimide (PI-5)") with a logarithmic viscosity of 0.49 dl / g.
合成例6
合成例1においてジアミン化合物としてp−フェニレンジアミン86.51g(0.80モル)、上記式(16)で表されるジアミン化合物104.56g(0.20モル)を用いた以外は合成例1と同様にして、対数粘度0.42dl/gのポリイミド(これを「ポリイミド(PI−6)」とする)18.0gを得た。
Synthesis Example 6
Synthesis Example 1 except that 86.51 g (0.80 mol) of p-phenylenediamine and 104.56 g (0.20 mol) of the diamine compound represented by the above formula (16) were used as the diamine compound in Synthesis Example 1. Similarly, 18.0 g of polyimide having a logarithmic viscosity of 0.42 dl / g (referred to as “polyimide (PI-6)”) was obtained.
合成例7
合成例1において、ジアミン化合物としてp−フェニレンジアミン75.70g(0.70モル)、ジアミノジフェニルメタン39.65g(0.20モル)、上記式(16)で表されるジアミン化合物52.28g(0.10モル)を用いた以外は合成例1と同様にして、対数粘度0.50dl/gのポリイミド(これを「ポリイミド(PI−7)」とする)17.5gを得た。
Synthesis example 7
In Synthesis Example 1, 75.70 g (0.70 mol) of p-phenylenediamine, 39.65 g (0.20 mol) of diaminodiphenylmethane as a diamine compound, 52.28 g (0 of diamine compound represented by the above formula (16)) .1 mol) was obtained in the same manner as in Synthesis Example 1 except that 10 mol) was used, and a polyimide having a logarithmic viscosity of 0.50 dl / g (referred to as “polyimide (PI-7)”) was obtained.
実施例1
(印刷性試験)
合成例1で得られた部分イミド化重合体(PI−1)を、N−メチル−2−ピロリドン/γ−ブチロラクトン/エチレングリコール モノブチルエーテル混合溶剤(重量比70/10/20)に溶解させて固形分濃度5重量%の溶液とし、十分な攪拌後、この溶液を孔径1μmのフィルターを用いて濾過し、本発明の液晶配向剤を調製した。上記液晶配向剤を、ガラス基板の一面に設けられたITO膜からなる透明導電膜上に、液晶配向膜印刷機(日本写真印刷機(株)製)を用いて塗布し、ホットプレート上で、80℃で1分の仮乾燥を行い、次いでクリーンオーブンで、200℃で1時間乾燥することにより、液晶配向膜を形成した。この液晶配向膜は塗布ムラが観察されず、従って、実施例1で調製した液晶配向剤の印刷性を「良好」と判定した。
Example 1
(Printability test)
The partially imidized polymer (PI-1) obtained in Synthesis Example 1 was dissolved in a mixed solvent of N-methyl-2-pyrrolidone / γ-butyrolactone / ethylene glycol monobutyl ether (weight ratio 70/10/20). A solution having a solid content concentration of 5% by weight was prepared, and after sufficient stirring, the solution was filtered using a filter having a pore size of 1 μm to prepare the liquid crystal aligning agent of the present invention. The liquid crystal aligning agent is applied onto a transparent conductive film made of an ITO film provided on one surface of a glass substrate using a liquid crystal aligning film printer (Nissha Printing Co., Ltd.), on a hot plate, A liquid crystal alignment film was formed by performing temporary drying at 80 ° C. for 1 minute and then drying at 200 ° C. for 1 hour in a clean oven. No coating unevenness was observed in this liquid crystal alignment film. Therefore, the printability of the liquid crystal aligning agent prepared in Example 1 was determined as “good”.
(垂直配向性試験)
合成例1で得られた部分イミド化重合体(PI−1)を、N−メチル−2−ピロリドン/γ−ブチロラクトン/エチレングリコール モノブチルエーテル混合溶剤(重量比70/10/20)に溶解させて固形分濃度3.5重量%の溶液とし、十分な攪拌後、この溶液を孔径1μmのフィルターを用いて濾過した後、ガラス基板の一面に設けられたITO膜からなる透明導電膜上にスピンナーを用いて塗布し、ホットプレート上で、80℃で1分の仮乾燥を行い、次いでクリーンオーブンで、200℃で1時間乾燥することにより、液晶配向膜を有する透明電極基板を作成した。次に、一対の透明電極/透明電極基板の上記液晶配向膜塗布基板の液晶配向膜を有するそれぞれの外縁に、直径3.5μmの酸化アルミニウム球入りエポキシ樹脂接着剤を塗布した後、液晶配向膜面が相対するように重ね合わせて圧着し、接着剤を硬化させた。次いで、液晶注入口より基板間に、ネガ型液晶(メルク社製、MLC−6608)を充填した後、アクリル系光硬化接着剤で液晶注入口を封止し、基板の外側の両面に偏光板を張り合わせ、液晶表示素子を作製し、得られた液晶表示素子の垂直配向性を評価したところ、異常ドメインは発生せず、「良好」であると判定した。結果を表2に示す。
(Vertical orientation test)
The partially imidized polymer (PI-1) obtained in Synthesis Example 1 was dissolved in a mixed solvent of N-methyl-2-pyrrolidone / γ-butyrolactone / ethylene glycol monobutyl ether (weight ratio 70/10/20). After a solid solution having a solid concentration of 3.5% by weight and sufficient stirring, the solution was filtered using a filter having a pore size of 1 μm, and then a spinner was placed on the transparent conductive film made of an ITO film provided on one surface of the glass substrate. The transparent electrode substrate having a liquid crystal alignment film was prepared by performing temporary drying at 80 ° C. for 1 minute on a hot plate and then drying at 200 ° C. for 1 hour in a clean oven. Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 μm to the outer edges of the pair of transparent electrodes / transparent electrode substrates having the liquid crystal alignment film of the liquid crystal alignment film coated substrate, the liquid crystal alignment film The adhesive was cured by overlapping and pressing so that the surfaces were opposed. Next, a negative type liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) is filled between the substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, and polarizing plates are formed on both sides of the substrate. The liquid crystal display element was manufactured and the vertical alignment property of the obtained liquid crystal display element was evaluated. As a result, no abnormal domain was generated, and it was determined that the liquid crystal display element was “good”. The results are shown in Table 2.
実施例2〜18
下記表1に示す処方に従って、合成例2〜5で得られた部分イミド化重合体(PI−2)〜(PI−5)を混合溶剤に溶解させた以外は実施例1と同様に行って、本発明の液晶配向剤を調製した。このようにして調製された液晶配向剤の各々を用い、実施例1と同様にして、印刷性、垂直配向性を評価した。結果を表1に示す。
Examples 2-18
According to the formulation shown in Table 1 below, the same procedure as in Example 1 was performed except that the partially imidized polymers (PI-2) to (PI-5) obtained in Synthesis Examples 2 to 5 were dissolved in a mixed solvent. The liquid crystal aligning agent of this invention was prepared. Using each of the liquid crystal aligning agents thus prepared, printability and vertical alignment were evaluated in the same manner as in Example 1. The results are shown in Table 1.
比較例1〜3
下記表1に示す処方に従って、実施例と同様に液晶配向剤を作製し、印刷性と垂直配向性を評価した。結果を表2に示す。
Comparative Examples 1-3
According to the prescription shown in Table 1 below, a liquid crystal aligning agent was prepared in the same manner as in the Examples, and the printability and vertical alignment were evaluated. The results are shown in Table 2.
表1注:各溶剤種において、括弧内の数字は含有割合を示す。
記号の意味は下記の通りである。
溶剤群
A−1 N−メチル−2−ピロリドン
A−2 N,N’−ジメチル−1−イミダゾリジノン
B−1 γ−ブチロラクトン
B−2 プロピレンカーボネート
C−1 エチレングリコールモノブチルエーテル
C−2 ジエチレングリコールモノエチルエーテル
C−3 ジプロピレングリコールモノメチルエーテル
C−4 4−ヒドロキシ−4−メチル−2−ペンタノン
Table 1 Note: In each solvent type, the number in parentheses indicates the content ratio.
The meanings of the symbols are as follows.
Solvent group A-1 N-methyl-2-pyrrolidone A-2 N, N′-dimethyl-1-imidazolidinone B-1 γ-butyrolactone B-2 propylene carbonate C-1 ethylene glycol monobutyl ether C-2 diethylene glycol mono Ethyl ether C-3 Dipropylene glycol monomethyl ether C-4 4-hydroxy-4-methyl-2-pentanone
Claims (6)
(A×B×C)×10−3 ≧12
ここで、A、BおよびCは、第1有機溶剤、第2有機溶剤および第3有機溶剤の合計重量を基準にする、それぞれ、第1有機溶剤の重量%、第2有機溶剤の重量%および第3有機溶剤の重量%である、
を満足する、請求項1に記載の垂直液晶配向剤。 The mixing ratio of the first organic solvent, the second organic solvent, and the third organic solvent is the following formula (A × B × C) × 10 −3 ≧ 12
Here, A, B, and C are based on the total weight of the first organic solvent, the second organic solvent, and the third organic solvent, respectively, wt% of the first organic solvent, wt% of the second organic solvent, and % By weight of the third organic solvent,
The vertical liquid crystal aligning agent according to claim 1, wherein:
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