JP4844721B2 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
- Publication number
- JP4844721B2 JP4844721B2 JP2006079088A JP2006079088A JP4844721B2 JP 4844721 B2 JP4844721 B2 JP 4844721B2 JP 2006079088 A JP2006079088 A JP 2006079088A JP 2006079088 A JP2006079088 A JP 2006079088A JP 4844721 B2 JP4844721 B2 JP 4844721B2
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- JP
- Japan
- Prior art keywords
- liquid crystal
- dianhydride
- bis
- aligning agent
- crystal aligning
- 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.)
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 141
- 239000003795 chemical substances by application Substances 0.000 title claims description 52
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- 229920005575 poly(amic acid) Polymers 0.000 claims description 47
- -1 diamine compound Chemical class 0.000 claims description 39
- 239000011248 coating agent Substances 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 21
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 17
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical group O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 12
- LVYXPOCADCXMLP-UHFFFAOYSA-N 3-butoxy-n,n-dimethylpropanamide Chemical group CCCCOCCC(=O)N(C)C LVYXPOCADCXMLP-UHFFFAOYSA-N 0.000 claims description 8
- LBVMWHCOFMFPEG-UHFFFAOYSA-N 3-methoxy-n,n-dimethylpropanamide Chemical compound COCCC(=O)N(C)C LBVMWHCOFMFPEG-UHFFFAOYSA-N 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
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- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 4
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- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 claims description 3
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- 239000000203 mixture Substances 0.000 claims description 3
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- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims 1
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Landscapes
- Liquid Crystal (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明は、液晶配向剤に関する。さらに詳しくは、液晶配向性が良好で、かつ高プレチルト角を安定に保つことのできる液晶配向膜を形成することのできる液晶配向剤に関する。 The present invention relates to a liquid crystal aligning agent. More specifically, the present invention relates to a liquid crystal aligning agent that can form a liquid crystal alignment film that has good liquid crystal alignment and can stably maintain a high pretilt angle.
従来、透明導電膜を介して液晶配向膜が表面に形成されている２枚の基板の間に、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、上記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ＴＮ（Ｔｗｉｓｔｅｄ Ｎｅｍａｔｉｃ）型液晶セルを有するＴＮ型液晶表示素子が知られている。このＴＮ型液晶表示素子などの液晶表示素子における液晶の配向は、通常、ラビング処理により液晶分子の配向能が付与された液晶配向膜により実現される。ここに、液晶表示素子を構成する液晶配向膜の材料としては、従来より、ポリイミド、ポリアミドおよびポリエステルなどの樹脂が知られている。特にポリイミドは、耐熱性、液晶との親和性、機械的強度などに優れているため多くの液晶表示素子に使用されている。
しかしながら、従来知られているポリアミック酸やその脱水閉環したイミド化重合体を含有する液晶配向剤を塗布して得られる液晶配向膜を用いて液晶表示素子を作製した場合、印刷時の環境温度などの変化によって膜厚ムラが生じ、液晶表示素子の表示特性に悪影響を与えるという問題を有している。また、溶剤のポリイミドに対する溶解性が悪い場合には、印刷時にハジキを起こし部分的な液晶配向不良を生じてしまうという問題を有している。
Conventionally, a nematic liquid crystal layer having a positive dielectric anisotropy is formed between two substrates having a liquid crystal alignment film formed on the surface via a transparent conductive film to form a sandwich-structured cell. There is known a TN liquid crystal display element having a TN (Twisted Nematic) type liquid crystal cell in which the major axis of liquid crystal molecules is continuously twisted by 90 degrees from one substrate toward the other substrate. The alignment of the liquid crystal in the liquid crystal display element such as the TN liquid crystal display element is usually realized by a liquid crystal alignment film provided with the alignment ability of liquid crystal molecules by rubbing treatment. Here, as materials for the liquid crystal alignment film constituting the liquid crystal display element, resins such as polyimide, polyamide, and polyester are conventionally known. In particular, polyimide is used in many liquid crystal display elements because of its excellent heat resistance, affinity with liquid crystals, mechanical strength, and the like.
However, when a liquid crystal display element is produced using a liquid crystal alignment film obtained by applying a liquid crystal alignment agent containing a polyamic acid known in the art or an imidized polymer that has been dehydrated and closed, the environmental temperature during printing, etc. The film thickness unevenness is caused by this change, which has the problem of adversely affecting the display characteristics of the liquid crystal display element. Moreover, when the solubility with respect to the polyimide of a solvent is bad, it has the problem that it causes repelling at the time of printing and produces the partial liquid crystal orientation defect.
本発明は、以上のような事情に基づいてなされたものであって、本発明の第１の目的は、ラビング処理などの配向処理によって液晶分子の配向能が確実に付与され、優れた液晶配向性を有する液晶表示素子を構成することができる液晶配向剤を提供することにある。 The present invention has been made based on the circumstances as described above, and the first object of the present invention is to provide liquid crystal molecules with an alignment ability reliably by an alignment treatment such as a rubbing treatment, and an excellent liquid crystal alignment. An object of the present invention is to provide a liquid crystal aligning agent capable of constituting a liquid crystal display element having a property.
本発明の第２の目的は、印刷時の環境温度が変化した場合でも良好な塗膜均一性を与える液晶配向剤を提供することにある。本発明の第３の目的は、印刷時のハジキを減らし良好な塗布均一性を与える液晶配向剤を提供することにある。 A second object of the present invention is to provide a liquid crystal aligning agent that provides good coating uniformity even when the environmental temperature during printing changes. A third object of the present invention is to provide a liquid crystal aligning agent that reduces repelling during printing and gives good coating uniformity.
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、本発明によれば、テトラカルボン酸二無水物とジアミン化合物とを反応させて得られるポリアミック酸、ポリアミック酸を脱水閉環して得られる構造を有するイミド化重合体またはポリアミック酸とイミド化重合体の混合物が有機溶媒中に溶解含有されて構成される液晶配向剤であって、上記有機溶媒が３−ブトキシ−Ｎ，Ｎ−ジメチルプロパンアミド、３−メトキシ−Ｎ，Ｎ−ジメチルプロパンアミドまたは３−ヘキシルオキシ−Ｎ，Ｎ−ジメチルプロパンアミドを含有することを特徴とする液晶配向剤によって達成される。
上記テトラカルボン酸二無水物は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、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、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および１，４，５，８−ナフタレンテトラカルボン酸二無水物よりなる群から選ばれ、そして上記ジアミン化合物は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’−（ｍ−フェニレンイソプロピリデン）ビスアニリン、４，４’−メチレンビス（シクロヘキシルアミン）および１，４−ビス（４−アミノフェノキシ）ベンゼンよりなる群から選ばれることが好ましい。
According to the present invention, the above-mentioned objects and advantages of the present invention are, according to the present invention, a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine compound, a structure obtained by dehydrating and cyclizing a polyamic acid. A liquid crystal aligning agent constituted by dissolving and containing a mixture of polyamic acid and imidized polymer in an organic solvent, wherein the organic solvent is 3-butoxy-N, N-dimethylpropanamide And 3-methoxy-N, N-dimethylpropanamide or 3-hexyloxy-N, N-dimethylpropanamide .
The tetracarboxylic dianhydride is butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Dianhydride, 1,2,3,4-cyclopentanetetracarboxylic 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-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, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, 3 , 3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride and 1,4,5,8-naphthalenetetracarboxylic dianhydride And the diamine compound is 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 '-(m-phenyleneisopropylidene) bisaniline, 4,4'-methylenebis (cyclohexylamine) and It is preferably selected from the group consisting of 1,4-bis (4-aminophenoxy) benzene.
本発明の液晶配向剤によれば、印刷時の環境温度が変化した場合でも膜厚の均一性の高い塗膜を形成することができて、良好な液晶配向性を有する液晶配向膜を形成することができる。このため、配向不良がない液晶表示素子を得ることができる。
本発明の液晶配向剤を用いて形成した液晶配向膜を有する液晶表示素子は、ＴＮ型液晶表示素子に好適に使用できる以外に、使用する液晶を選択することにより、ＳＴＮ（Ｓｕｐｅｒ Ｔｗｉｓｔｅｄ Ｎｅｍａｔｉｃ）型、ＳＨ（Ｓｕｐｅｒ Ｈｏｍｅｏｔｒｏｐｉｃ）型、強誘電性および反強誘電性の液晶表示素子などにも好適に使用することができる。
さらに、本発明の液晶配向剤を用いて形成した液晶配向膜を有する液晶表示素子は、種々の装置に有効に使用でき、例えば卓上計算機、腕時計、置時計、係数表示板、ワードプロセッサ、パーソナルコンピューター、液晶テレビなどの表示装置に用いられる。
According to the liquid crystal aligning agent of the present invention, a coating film with high film thickness uniformity can be formed even when the environmental temperature during printing changes, and a liquid crystal aligning film having good liquid crystal alignment is formed. be able to. For this reason, the liquid crystal display element without an orientation defect can be obtained.
The liquid crystal display element having the liquid crystal alignment film formed by using the liquid crystal aligning agent of the present invention can be suitably used for a TN type liquid crystal display element, and by selecting a liquid crystal to be used, an STN (Super Twisted Nematic) type is used. , SH (Super Homeotropic) type, ferroelectric and antiferroelectric liquid crystal display elements can also be suitably used.
Furthermore, the liquid crystal display element having the liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention can be effectively used in various devices, such as a desk calculator, a wristwatch, a table clock, a coefficient display board, a word processor, a personal computer, and a liquid crystal. Used for display devices such as televisions.
以下、本発明についてその詳細を説明する。 Hereinafter, the details of the present invention will be described.
＜ポリアミック酸＞
本発明の液晶配向剤を構成するポリアミック酸は、テトラカルボン酸二無水物とジアミン化合物とを反応させることにより得られる。
<Polyamic acid>
The polyamic acid constituting the liquid crystal aligning agent of the present invention is obtained by reacting a tetracarboxylic dianhydride and a diamine compound.
＜テトラカルボン酸二無水物＞
かかるポリアミック酸の合成反応に用いられるテトラカルボン酸二無水物としては、上記の如く、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、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、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および１，４，５，８−ナフタレンテトラカルボン酸二無水物が用いられる。これらは単独でまたは２種以上を組み合わせて使用できる。これらのテトラカルボン酸二無水物を用いると、特に良好な液晶配向性を示す液晶配向剤が得られる。
<Tetracarboxylic dianhydride>
Examples of the tetracarboxylic dianhydride used in the polyamic acid synthesis reaction include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic 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- (teto Hydro-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, bicyclo [2,2,2] -oct-7-ene-2,3 5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic Acid dianhydride and 1,4,5,8-naphthalene tetracarboxylic dianhydride are used. These can be used alone or in combination of two or more. When these tetracarboxylic dianhydrides are used, a liquid crystal aligning agent exhibiting particularly good liquid crystal alignment can be obtained.
本発明では、上記テトラカルボン酸二無水物とともに、必要により、その他のテトラカルボン酸二無水物を併用することができる。かかる他のテトラカルボン酸二無水物としては、例えば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、１，２，４，５−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、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−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−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、下記式（Ｉ）および（ＩＩ）で示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； In the present invention, other tetracarboxylic dianhydrides can be used in combination with the tetracarboxylic dianhydride as necessary. Examples of such other tetracarboxylic dianhydrides include 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-dichloro-1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride 1,3,3a, 4,5,9b-Hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione , , 3,3a, 4,5,9b-Hexahydro-5-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, , 3,3a, 4,5,9b-Hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, , 3,3a, 4,5,9b-Hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, , 3,3a, 4,5,9b-Hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, Aliphatics such as compounds of formula (I) and (II) and Alicyclic tetracarboxylic acid dianhydride;
（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。）
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’−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、２，３，４，５−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、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。これらの他のテトラカルボン酸二無水物は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.)
2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetra Carboxylic dianhydride, 2,3,4,5-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis ( 3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene -Bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-dipheny Ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4 -Butanediol-bis (anhydro trimellitate), 1,6-hexanediol-bis (anhydro trimellitate), 1,8-octanediol-bis (anhydro trimellitate), 2,2-bis Aromatic tetracarboxylic dianhydrides such as (4-hydroxyphenyl) propane-bis (anhydrotrimellitate) and compounds represented by the following formulas (1) to (4) can be mentioned. These other tetracarboxylic dianhydrides may be used alone or in combination of two or more.
これら他のテトラカルボン酸二無水物のうち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、１，２，４，５−シクロヘキサ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−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−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−ジオンが良好な液晶配向性を示す点から好ましい。
かかる他のテトラカルボン酸二無水物は、前記した本発明の必須テトラカルボン酸二無水物１モルに対し、好ましくは０〜１モル％で用いられる。
Of these other tetracarboxylic dianhydrides, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic Acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 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-hexahydride -7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [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-Ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione is preferred because it exhibits good liquid crystal alignment.
Such other tetracarboxylic dianhydrides are preferably used in an amount of 0 to 1 mol% based on 1 mol of the essential tetracarboxylic dianhydride of the present invention.
＜ジアミン化合物＞
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、上記の如く、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’−ジメチル−４，４’−ジアミノビフェニル、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’−（ｍ−フェニレンイソプロピリデン）ビスアニリン、４，４’−メチレンビス（シクロヘキシルアミン）および１，４−ビス（４−アミノフェノキシ）ベンゼンが用いられる。これは単独でまたは２種以上組合せて用いられる。
本発明では、上記ジアミン化合物とともに、必要により、その他のジアミン化合物を併用することができる。
<Diamine compound>
As described above, diamine compounds used for the synthesis of polyamic acid include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, and 2,7-diamino. Fluorene, 4,4′-diaminodiphenyl ether, 2,2′-dimethyl-4,4′-diaminobiphenyl, 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 '-(m-phenylene Isopropylidene) bisaniline, 4,4′-methylenebis (cyclohexylamine) and 1,4-bis (4-Aminophenoxy) benzene is used. These may be used alone or in combination of two or more.
In the present invention, other diamine compounds can be used in combination with the diamine compound as necessary.
かかる他のジアミン化合物としては、例えばｍ−フェニレンジアミン、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、３，３−ジメチル−４，４’−ジアミノビフェニル、５−アミノ−１−（４’ーアミノフェニル）−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］スルホン、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、４，４’−メチレン−ビス（２−クロロアニリン）、２，２’−ジトリルフルオロメチル−４，４’−ジアミノジフェニル、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、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'−トリフルオロメトキシベンゾイロキシ)シクロヘキシル−３，５−ジアミノベンゾエートなどの芳香族ジアミン；
１，３−ビス（アミノメチル）シクロヘキサン、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などの脂肪族および脂環式ジアミン；
下記式（ＩＩＩ）で示されるモノ置換フェニレンジアミン類；下記式（ＩＶ）で示されるジアミノオルガノシロキサン；
Examples of such other diamine compounds include m-phenylenediamine, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenylsulfone, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4 '-Diaminobenzanilide, 3,3-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, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2- Bis [4- (4-aminophenoxy) phenyl] sulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3 Aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 4,4′-methylene-bis (2-chloroaniline), 2,2′-ditolylfluoromethyl-4,4 '-Diaminodiphenyl, 2,2', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3, 3′-dimethoxy-4,4′-diaminobiphenyl, 1,4,4 ′-(p-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, aromatic diamines such as 4- (4'-trifluoromethoxy acetoxyphenyl) cyclohexyl-3,5-aminobenzoate;
1,3-bis (aminomethyl) cyclohexane, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoin danylene dimethylene diamine, tricyclo [6,2,1,0 2.7 ] -undecylenedimethyl diamine Aliphatic and cycloaliphatic diamines such as;
Mono-substituted phenylenediamines represented by the following formula (III); diaminoorganosiloxanes represented by the following formula (IV);
（式中、Ｘ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、Ｒ５は、ステロイド骨格またはトリフルオロメチル基を有する１価の有機基を示す。Ｒ６は炭素数１〜１２の炭化水素基を示し、複数存在するＲ６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（５）〜（８）で示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。
(Wherein X represents a divalent organic group selected from —O—, —COO—, —OCO—, —NHCO—, —CONH— and —CO—, and R 5 represents a steroid skeleton or trifluoro A monovalent organic group having a methyl group, R 6 represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R 6 may be the same or different, and p is an integer of 1 to 3 And q is an integer from 1 to 20.)
Examples include compounds represented by the following formulas (5) to (8). 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。）
これら他のジアミン化合物のうちｍ−フェニレンジアミン、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、３，３−ジメチル−４，４’−ジアミノビフェニル、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、４，４’−（ｐ−フェニレンイソプロピリデン）ビスアニリン、１，４−ジアミノシクロヘキサン、４−(４'−トリフルオロメトキシベンゾイロキシ)シクロヘキシル−３，５−ジアミノベンゾエート、１，３−ビス（アミノメチル）シクロヘキサン、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が良好な液晶配向性を示す点から好ましい。
これらの他のジアミン化合物は、前記した本発明の必須ジアミン化合物１モルに対し、好ましくは０〜５モル％で用いられる。
(In the formula, y is an integer of 2 to 12, and z is an integer of 1 to 5.)
Among these other diamine compounds, m-phenylenediamine, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenylsulfone, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′- Diaminobenzanilide, 3,3-dimethyl-4,4′-diaminobiphenyl, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 4,4 ′-(p- Phenylene isopropylidene) bisaniline, 1,4-diaminocyclohexane, 4- (4′-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,3-bis (aminomethyl) cyclohexane, 1,3- Propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine Is preferable from the viewpoint of good liquid crystal alignment.
These other diamine compounds are preferably used at 0 to 5 mol% with respect to 1 mol of the essential diamine compound of the present invention described above.
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との使用割合は、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に含まれる酸無水物基が０.２〜２当量となる割合が好ましく、さらに好ましくは０.３〜１.４当量となる割合である。テトラカルボン酸二無水物に含まれる酸無水物基の割合が０.２当量未満の場合および２当量を超える場合のいずれにおいても、得られる重合体の分子量が小さくなりすぎ、液晶配向剤の塗布性が劣るものとなる場合がある。
本発明における液晶配向剤を構成するポリアミック酸は、テトラカルボン酸二無水物とジアミン化合物との反応により合成される。ポリアミック酸の合成反応は、有機溶媒中で、好ましくは０〜１５０℃、より好ましくは０〜１００℃の温度条件下で行われる。反応温度が０℃以下であると化合物の溶剤に対する溶解性が劣る場合があり、１５０℃を超えると得られる重合体の分子量が低下する場合がある。
The ratio of the tetracarboxylic dianhydride and the diamine compound used in the polyamic acid synthesis reaction is such that the acid anhydride group contained in the tetracarboxylic dianhydride is equivalent to 1 equivalent of the amino group contained in the diamine compound. Is preferably a ratio of 0.2 to 2 equivalents, more preferably 0.3 to 1.4 equivalents. In both cases where the ratio of the acid anhydride group contained in the tetracarboxylic dianhydride is less than 0.2 equivalent or more than 2 equivalent, the molecular weight of the resulting polymer becomes too small, and the liquid crystal aligning agent is applied. May be inferior.
The polyamic acid constituting the liquid crystal aligning agent in the present invention is synthesized by a reaction of tetracarboxylic dianhydride and a diamine compound. The synthetic reaction of polyamic acid is carried out in an organic solvent under a temperature condition of preferably 0 to 150 ° C, more preferably 0 to 100 ° C. If the reaction temperature is 0 ° C. or lower, the solubility of the compound in the solvent may be inferior, and if it exceeds 150 ° C., the molecular weight of the resulting polymer may be reduced.
ポリアミック酸の合成に用いられる有機溶媒としては、テトラカルボン酸二無水物、ジアミン化合物および反応で生成するポリアミック酸を溶解し得るものであれば特に制限はなく、例えばγ−ブチロラクトン、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、テトラメチル尿素、ヘキサメチルホスホリルトリアミド、１，３−ジメチル−２−イミダゾリジノン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、３−メトキシ−Ｎ，Ｎ−ジメチルプロパンアミド、３−ブトキシ−Ｎ，Ｎ−ジメチルプロパンアミド、３−ヘキシルオキシ−Ｎ，Ｎ−ジメチルプロパンアミドなどのアミド系溶剤を挙げることができる。
有機溶媒の使用量（Ａ）は、反応原料であるテトラカルボン酸二無水物とジアミン化合物との総量（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 organic solvent used for the synthesis of the polyamic acid is not particularly limited as long as it can dissolve the tetracarboxylic dianhydride, the diamine compound, and the polyamic acid generated by the reaction. For example, γ-butyrolactone, N-methyl- Aprotic polar solvents such as 2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoryltriamide, 1,3-dimethyl-2-imidazolidinone; Phenolic solvents such as m-cresol, xylenol, phenol, halogenated phenol, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N- Amide solvents such as dimethylpropanamide It can gel.
The amount (A) of the organic solvent used is such that the total amount (B) of the tetracarboxylic dianhydride as the reaction raw material and the diamine compound is 0.1 to 30% by weight based on the total amount (A + B) of the reaction solution. It is preferable that the amount is small.
なお、上記有機溶媒には、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、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、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モノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、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、エチレングリコールメチルエーテルアセテート、プロピレングリコールメチルエーテル、プロピレングリコールエチルエーテル、プレピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、ジプロピレングリコールメチルエーテル、ジプロピレングリコールエチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテル、エチレングリコールエチルエーテルアセテート、４−ヒドロキシ−４−メチル−２−ペンタノン、２−ヒドロキシプロピオン酸エチル、乳酸エチル、乳酸メチル、乳酸ブチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２−ヒドロキシ−３−メチルブタン酸メチル、３−メトキシプロピオン酸メチル、３−メトキシプロピオン酸エチル、３−エトキシプロピオン酸メチル、３−メチル−３−メトキシブタノール、３−エチル−３−メトキシブタノール、２−メチル−２−メトキシブタノール、２−エチル−２−メトキシブタノール、３−メチル−３−エトキシブタノール、３−エチル−３−エトキシブタノール、２−メチル−２−エトキシブタノール、２−エチル−２−エトキシブタノール、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。これらは１種単独でまたは２種以上組み合わせて用いることができる。 In addition, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are poor solvents for polyamic acid, are used in combination with the organic solvent as long as the resulting polyamic acid does not precipitate. be able to. Specific examples of such poor solvents include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetic acid. Methyl, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, 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, ethylene glycol methyl ether acetate, propylene glycol methyl ether, propylene glycol ethyl ether, prepylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol dimethyl ether , Dipropylene glycol diethyl ether, ethylene glycol ethyl ether acetate, 4-hydroxy-4-methyl-2-pentanone, ethyl 2-hydroxypropionate, ethyl lactate, methyl lactate, butyl lactate, ethyl ethoxy acetate, ethyl hydroxy acetate, 2 -Methyl hydroxy-3-methylbutanoate, 3-methyl Methyl xylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-methyl-3-methoxybutanol, 3-ethyl-3-methoxybutanol, 2-methyl-2-methoxybutanol, 2-ethyl- 2-methoxybutanol, 3-methyl-3-ethoxybutanol, 3-ethyl-3-ethoxybutanol, 2-methyl-2-ethoxybutanol, 2-ethyl-2-ethoxybutanol, tetrahydrofuran, dichloromethane, 1,2-dichloroethane 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like. These can be used alone or in combination of two or more.
以上の合成反応によって、ポリアミック酸を溶解してなる重合体溶液が得られる。そして、この重合体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する工程を１回または数回行うことにより、ポリアミック酸の精製を行うことができる。 By the above synthesis reaction, a polymer solution obtained by dissolving polyamic acid is obtained. And a polyamic acid can be obtained by pouring this polymer solution in a lot of poor solvents, obtaining a deposit, and drying this deposit under reduced pressure. Further, the polyamic acid can be purified by dissolving the polyamic acid again in an organic solvent and then performing the step of precipitation with a poor solvent once or several times.
＜イミド化重合体＞
本発明の液晶配向剤を構成するイミド化重合体は、下記方法（１）〜（２）により調整することができる。また、ポリアミック酸の繰り返し単位の一部が脱水閉環された、いわゆるイミド化率が１００％未満である重合体も、本発明の液晶配向剤に好適に用いられる。
<Imidized polymer>
The imidized polymer constituting the liquid crystal aligning agent of the present invention can be adjusted by the following methods (1) to (2). A polymer having a so-called imidation ratio of less than 100% in which a part of the repeating unit of polyamic acid is dehydrated and cyclized is also suitably used for the liquid crystal aligning agent of the present invention.
方法（１）：ポリアミック酸を加熱して脱水閉環する方法。
この方法における反応温度は、好ましくは、６０〜３００℃であり、より好ましくは１２０〜２５０℃である。反応温度が６０℃未満ではイミド化反応が十分に進行せず、反応温度が３００℃を超えると得られるポリイミドの分子量が小さくなることがある。
Method (1): A method in which polyamic acid is heated to perform dehydration ring closure.
The reaction temperature in this method is preferably 60 to 300 ° C, more preferably 120 to 250 ° C. If the reaction temperature is less than 60 ° C., the imidization reaction does not proceed sufficiently, and if the reaction temperature exceeds 300 ° C., the molecular weight of the resulting polyimide may be small.
方法（２）：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イミド化触媒を添加し、必要に応じて加熱する方法。
この方法において、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１．６〜２０モルとするのが好ましい。また、イミド化触媒としては、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が、これらに限定されるものではない。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０．５〜１０モルとするのが好ましい。なお、イミド化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ものを挙げることができる。そして、イミド化反応の反応温度は、好ましくは、０〜１８０℃であり、より好ましくは６０〜１５０℃である。
Method (2): A method in which polyamic acid is dissolved in an organic solvent, a dehydrating agent and an imidization catalyst are added to the solution, and heating is performed as necessary.
In this method, as the dehydrating agent, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. It is preferable that the usage-amount of a dehydrating agent shall be 1.6-20 mol with respect to 1 mol of repeating units of a polyamic acid. Moreover, as an imidation 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 imidization catalyst used is preferably 0.5 to 10 mol with respect to 1 mol of the dehydrating agent to be used. In addition, as an organic solvent used for imidation reaction, the same thing 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 imidation reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 60-150 degreeC.
＜ポリアミック酸およびイミド化重合体の固有粘度＞
以上のようにして得られるポリアミック酸およびイミド化重合体の固有粘度（３０℃、Ｎ−メチル−２−ピロリドン中で測定。以下において同じ。）は、好ましくは０．０５〜１０ｄｌ／ｇであり、より好ましくは０．０５〜５ｄｌ／ｇである。
<Intrinsic viscosity of polyamic acid and imidized polymer>
The intrinsic viscosity (measured in N-methyl-2-pyrrolidone at 30 ° C., the same hereinafter) of the polyamic acid and imidized polymer obtained as described above is preferably 0.05 to 10 dl / g. More preferably, it is 0.05-5 dl / g.
＜末端修飾型の重合体＞
本発明の液晶配向膜を形成する液晶配向剤に用いられるポリアミック酸およびイミド化重合体は、末端修飾型の重合体であってもよい。この末端修飾型の重合体は、分子量が調節され、本発明の効果を損なうことなく、液晶配向剤の塗布特性などを改善することができる。末端修飾型の重合体は、ポリアミック酸を合成する際に、酸無水物、モノアミン化合物、またはモノイソシアネート化合物を反応系に添加することにより合成することができる。
<End-modified polymer>
The polyamic acid and imidized polymer used for the liquid crystal aligning agent for forming the liquid crystal aligning film of the present invention may be a terminal-modified polymer. The terminal-modified polymer has an adjusted molecular weight, and can improve the coating properties of the liquid crystal aligning agent without impairing the effects of the present invention. The terminal-modified polymer can be synthesized by adding an acid anhydride, a monoamine compound, or a monoisocyanate compound to the reaction system when synthesizing the polyamic acid.
末端修飾型の重合体を得るためポリアミック酸を合成する際の反応系に添加される酸無水物としては、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、反応系に添加されるモノアミンとしては、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のアルキルアミン類；３−アミノプロピルメチルジエトキシシラン、３−［Ｎ−アリル−Ｎ−（２−アミノエチル）］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、Ｎ−［（３−トリメトキシシリル）プロピル］ジエチレントリアミン、４−アミノフェニルオクタデシルエーテル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。 Examples of the acid anhydride added to the reaction system for synthesizing the polyamic acid in order to obtain a terminal-modified polymer include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, Examples thereof include n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, and the like. Examples of the monoamine added to the reaction system include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosyl Alkylamines such as amine; 3-aminopropylmethyldiethoxysilane, 3- [N-allyl-N- (2-aminoethyl)] aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-amino Propylmethyldimethoxysilane, N-[(3-trimethoxysilyl) propyl Propyl] diethylenetriamine and 4-aminophenyl octadecyl ether. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
＜液晶配向剤＞
本発明の液晶配向剤は、上記アミック酸および／またはイミド化重合体を、有機溶媒中に溶解含有されて構成される液晶配向剤より形成される。
本発明の液晶配向剤を構成する有機溶媒は、３−ブトキシ−Ｎ，Ｎ−ジメチルプロパンアミド、３−メトキシ−Ｎ，Ｎ−ジメチルプロパンアミドまたは３−ヘキシルオキシ−Ｎ，Ｎ−ジメチルプロパンアミドを含有することが良好な印刷性を示すことから必須であるが、印刷性以外の他の配向特性又は粘性、揮発性などを考慮して他の溶媒を含有することが好ましい。これらの有機溶媒は単独であるいは２種以上一緒に用いることができる。とりわけ、γ−ブチロラクトンとブチルセロソルブと３−ブトキシ−Ｎ，Ｎ−ジメチルプロパンアミドの混合溶媒が好ましい。さらに好ましくは、全混合溶媒に対してγ−ブチロラクトンを７５〜９０重量％、ブチルセロソルブを５〜１５重量％、３−ブトキシ−Ｎ，Ｎ−ジメチルプロパンアミドを１〜１５重量％の割合で混合して使用することが好ましい。
<Liquid crystal aligning agent>
The liquid crystal aligning agent of this invention is formed from the liquid crystal aligning agent comprised by melt | dissolving and containing the said amic acid and / or imidized polymer in the organic solvent.
The organic solvent medium constituting the liquid crystal aligning agent of the present invention, 3-butoxy -N, N-dimethylpropanamide, 3-methoxy -N, N-dimethylpropanamide or 3-hexyloxy -N, N-dimethylpropanamide It is essential to contain good printability, but it is preferable to contain other solvents in consideration of other orientation characteristics other than printability, viscosity, volatility, and the like. These organic solvents can be used alone or in combination of two or more. In particular, a mixed solvent of γ-butyrolactone, butyl cellosolve, and 3-butoxy-N, N-dimethylpropanamide is preferable. More preferably, γ-butyrolactone is mixed at a ratio of 75 to 90% by weight, butyl cellosolve at 5 to 15% by weight, and 3-butoxy-N, N-dimethylpropanamide at a ratio of 1 to 15% by weight with respect to the total mixed solvent. Are preferably used.
本発明の液晶配向膜を与える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。すなわち、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が形成されるが、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い。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。また、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℃、より好ましくは２０℃〜６０℃である。 The solid content concentration in the liquid crystal aligning agent that gives the liquid crystal alignment film of the present invention is selected in consideration of viscosity, volatility, etc., but is preferably in the range of 1 to 10% by weight. That is, 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 alignment film. When the solid content concentration is less than 1% by weight, the coating film thickness is It is too small to obtain a good liquid crystal alignment film. 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 increased, so that the coating properties tend to be inferior. Moreover, the temperature at the time of preparing the liquid crystal aligning agent of this invention, Preferably, it is 0 to 200 degreeC, More preferably, it is 20 to 60 degreeC.
本発明の液晶配向膜を形成する液晶配向剤は、必要により、分子内に少なくとも１つのエポキシ基を有する化合物を含有することができる。分子内に少なくとの一つのエポキシ基を有するエポキシ化合物としては、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。
The liquid crystal aligning agent which forms the liquid crystal aligning film of this invention can contain the compound which has an at least 1 epoxy group in a molecule | numerator as needed. Examples of the epoxy compound having at least one epoxy group in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl 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- xylene diamine, 1,3-bis (N, N-diglycidyl aminomethyl) cyclohexane, N, N, N ', N '- may be mentioned as being preferred and tetraglycidyl-4,4'-diaminodiphenylmethane.
本発明の液晶配向膜を形成する液晶配向剤には、基板表面に対する接着性を向上させる観点から、さらに、官能性シラン含有化合物が含有されていてもよい。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。 The liquid crystal aligning agent that forms the liquid crystal alignment film of the present invention may further contain a functional silane-containing compound from the viewpoint of improving the adhesion to the substrate surface. 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。
<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）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、本発明の液晶配向膜を形成する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。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。なお、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。 (1) A liquid crystal aligning agent for forming the liquid crystal alignment film of the present invention is applied to one surface of a substrate provided with a patterned transparent conductive film by a method such as a roll coater method, a spinner method, or a printing method, and then A coating film is formed by heating the coated surface. 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. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane-containing compound, a functional titanium-containing compound, or the like is previously applied to the surface of the substrate. You can also The heating temperature after application of the liquid crystal aligning agent is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. In addition, 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, but further proceeds with dehydration ring closure by further heating, and is further imidized. It can also be set as a coating film. The film thickness of the formed coating film is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.
（２）液晶配向剤によって形成された被膜表面を、例えばナイロン、レーヨン、コットンなどの繊維からなる布を巻き付けたロールで一定方向に擦るラビング処理を行う。これにより、液晶分子の配向能が被膜に付与されて液晶配向膜となる。また、ラビング処理による方法以外に、樹脂膜表面に偏光紫外線、イオンビーム、電子ビーム等を照射して配向能を付与する方法や、一軸延伸法、ラングミュア・ブロジェット法などで被膜を得る方法などにより、液晶配向膜を形成することもできる。なお、ラビング処理時に発生する微粉体（異物）を除去して表面を清浄な状態とするために、形成された液晶配向膜をイソプロピルアルコールなどによって洗浄することが好ましい。また、形成された液晶配向膜の表面に紫外線、イオンビーム、電子ビーム等を部分的に照射することによりプレチルト角を変化させる処理（例えば特開平６−２２２３６６号公報、特開平６−２８１９３７号公報、特開平７−１６８１８７号公報、特開平８−２３４２０７号公報参照）、形成された液晶配向膜の表面にレジスト膜を部分的に形成し、先行のラビング処理とは異なる方向にラビング処理を行った後、前記レジスト膜を除去して、液晶配向膜の配向能を変化させるような処理（例えば特開平５−１０７５４４号公報参照）を行うことによって、作製される液晶表示素子の視野角特性を改善することもできる。 (2) A rubbing process is performed in which the surface of the coating formed by the liquid crystal aligning agent is rubbed in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. In addition to the rubbing method, the surface of the resin film is irradiated with polarized ultraviolet rays, ion beams, electron beams, etc., and alignment ability is imparted, and the film is obtained by the uniaxial stretching method, the Langmuir / Blodgett method, etc. Thus, a liquid crystal alignment film can also be formed. Note that the formed liquid crystal alignment film is preferably washed with isopropyl alcohol or the like in order to remove the fine powder (foreign matter) generated during the rubbing process and make the surface clean. Further, a treatment for changing the pretilt angle by partially irradiating the surface of the formed liquid crystal alignment film with an ultraviolet ray, an ion beam, an electron beam or the like (for example, JP-A-6-222366 and JP-A-6-281937). , Japanese Patent Laid-Open Nos. 7-168187 and 8-234207), a resist film is partially formed on the surface of the formed liquid crystal alignment film, and a rubbing process is performed in a direction different from the previous rubbing process. Then, the viewing angle characteristics of the manufactured liquid crystal display element can be improved by removing the resist film and changing the alignment ability of the liquid crystal alignment film (see, for example, JP-A-5-107544). It can also be improved.
（３）上記のようにして液晶配向膜が形成された基板を２枚作製し、それぞれの液晶配向膜における配向処理方向、すなわちラビング方向が直交または逆平行となるように、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それぞれの基板の他面側に、偏光板を、その偏光方向が当該基板の一面に形成された液晶配向膜のラビング方向と一致または直交するように貼り合わせることにより、液晶表示素子が得られる。 (3) Two substrates on which the liquid crystal alignment film is formed as described above are manufactured, and the two substrates are formed so that the alignment treatment direction in each liquid crystal alignment film, that is, the rubbing direction is orthogonal or antiparallel. , Facing each other through a gap (cell gap), the peripheral portions of two substrates are bonded together using a sealant, and liquid crystal is injected and filled into the cell gap defined by the substrate surface and the sealant, Is sealed to form a liquid crystal cell. A polarizing plate is disposed on the outer surface of the liquid crystal cell, that is, on the other surface side of each substrate constituting the liquid crystal cell, and the polarization direction thereof coincides with or is orthogonal to the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate. A liquid crystal display element is obtained by pasting together.
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。
液晶としては、ネマティック型液晶を挙げることができ、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。
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。
Here, as the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
Examples of liquid crystals include nematic liquid crystals, such as Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenyl cyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenyl cyclohexane liquid crystals, pyrimidine liquid crystals, dioxanes. Type liquid crystal, 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.
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。なお、以下の実施例および比較例において調製された液晶配向剤の評価項目および評価方法を下記に示す。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the evaluation item and evaluation method of the liquid crystal aligning agent prepared in the following Examples and Comparative Examples are shown below.
［液晶の配向性］
当該配向膜を塗布した基板にて液晶セルを作成し、そのセルに液晶を真空注入した際に流動配向が生じるか否かを確認することにより配向性の評価とした。
[Orientation of liquid crystal]
A liquid crystal cell was prepared with the substrate coated with the alignment film, and the orientation was evaluated by checking whether or not fluid alignment occurred when the liquid crystal was vacuum injected into the cell.
［液晶配向剤を用いて印刷した塗膜の均一性］
２５℃および３５℃の環境で印刷した塗膜に関して、触針式膜厚計を用いて、塗膜の平均膜厚および最大膜厚と最小膜厚との差（バラツキ）を測定した。
[Uniformity of coating film printed using liquid crystal aligning agent]
Regarding the coating film printed in an environment of 25 ° C. and 35 ° C., the average film thickness of the coating film and the difference (variation) between the maximum film thickness and the minimum film thickness were measured using a stylus-type film thickness meter.
［液晶配向剤を用いて印刷した塗膜の表面状態］
当該配向膜を印刷した塗膜に関して、表面を顕微鏡で観察し、塗膜のハジキ個数を評価した。
[Surface condition of coating film printed with liquid crystal aligning agent]
Regarding the coating film on which the alignment film was printed, the surface was observed with a microscope, and the number of repellency of the coating film was evaluated.
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１１２．０９ｇ（０．５モル）、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１５７．１４ｇ（０．５モル）、ジアミン化合物としてｐ−フェニレンジアミン９４．６２ｇ（０．８７５モル）、ビスアミノプロピルテトラメチルジシロキサン２４．８５ｇ（０．１モル）、３，６−ビス（４−アミノベンゾイルオキシ）コレスタン６．４３ｇ（０．０１モル）、４−アミノフェニルオクタデシルエーテル４．０４ｇ（０．０３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０．８２ｄｌ／ｇ、イミド化率０％のポリアミック酸３７０ｇ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２３．４ｇおよび無水酢酸１８．１ｇ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０．７７ｄｌ／ｇ、イミド化率１００％のポリイミド（これを「ポリイミド（Ａ−１）」とする。）１８．５ｇを得た。
Synthesis example 1
2,3,5-tricarboxycyclopentyl acetic acid dianhydride 112.09 g (0.5 mol), 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 as tetracarboxylic dianhydride (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 157.14 g (0.5 mol), p-phenylenediamine 94.62 g as the diamine compound (0.875 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane, 6.43 g (0.01 mol) of 3,6-bis (4-aminobenzoyloxy) cholestane, 4-amino 4.04 g (0.03 mol) of phenyl octadecyl ether 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. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 370 g of polyamic acid having a logarithmic viscosity of 0.82 dl / g and an imidization rate of 0%. 30 g of the resulting polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 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 18.5 g of polyimide having a logarithmic viscosity of 0.77 dl / g and an imidization rate of 100% (hereinafter referred to as “polyimide (A-1)”).
合成例２
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１１２．０９ｇ（０．５モル）および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１５７．１５ｇ（０．５モル）、ジアミン化合物としてｐ−フェニレンジアミン９０．０３ｇ（０．８３２５モル）、ビスアミノプロピルテトラメチルジシロキサン２４．８５ｇ（０．１モル）および４−(４'−トリフルオロメトキシベンゾイロキシ)シクロヘキシル−３，５−ジアミノベンゾエート２６．３ｇ（０．０６モル）、モノアミンとしてアニリン１．３９６ｇ（０．０１５モル）をＮ−メチル−２−ピロリドン４５００ｇ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０．８１ｄｌ／ｇ、イミド化率０％のポリアミック酸４００ｇ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２３．４ｇおよび無水酢酸１８．１ｇ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０．７５ｄｌ／ｇのポリイミド（これを「ポリイミド（Ａ−２）」とする）１８．０１ｇを得た。
Synthesis example 2
2,3,5-tricarboxycyclopentylacetic acid dianhydride 112.09 g (0.5 mol) and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 as tetracarboxylic dianhydride (Tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione 157.15 g (0.5 mol), p-phenylenediamine as a diamine compound 90.03 g (0 8325 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane and 26.3 g (0.06) of 4- (4′-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate. Mol), 1.396 g (0.015 mol) of aniline as a monoamine was dissolved in 4500 g of N-methyl-2-pyrrolidone, and 6 ℃ In the reaction was allowed to proceed for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 400 g of polyamic acid having a logarithmic viscosity of 0.81 dl / g and an imidization rate of 0%. 30 g of the resulting polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 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 18.01 g of polyimide having a logarithmic viscosity of 0.75 dl / g (referred to as “polyimide (A-2)”).
合成例３
テトラカルボン酸二無水物として１，２，３，４−シクロブタンテトラカルボン酸１９６．１２ｇ（１．０モル）、ジアミン化合物として４，４’−ジアミノジフェニルエーテル２００．２４ｇ（１．０モル）をＮ−メチル−２−ピロリドン４，５００ｇに溶解させ、４０℃で３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０．８９ｄｌ／ｇのポリアミック酸（これを「ポリアミック酸（Ｂ−１）」とする）３６９．１２ｇを得た。
Synthesis example 3
As a tetracarboxylic dianhydride, 196.12 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic acid and 200.24 g (1.0 mol) of 4,4′-diaminodiphenyl ether as a diamine compound were added. -Methyl-2-pyrrolidone was dissolved in 4,500 g and reacted at 40 ° C. for 3 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 369.12 g of a polyamic acid having a logarithmic viscosity of 0.89 dl / g (referred to as “polyamic acid (B-1)”). It was.
合成例４
テトラカルボン酸二無水物として１，２，３，４−シクロブタンテトラカルボン酸二無水物１９６．１２ｇ（１．０モル）、ジアミン化合物として２，２'−ジメチル−４，４'−ジアミノビフェニル２１２．３ｇ（１．０モル）をＮ−メチル−２−ピロリドン４，５００ｇに溶解させ、４０℃で３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０.９１ｄｌ／ｇのポリアミック酸（これを「ポリアミック酸（Ｂ−２）」とする）３９０ｇを得た。
Synthesis example 4
196.12 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 2,2′-dimethyl-4,4′-diaminobiphenyl 212 as diamine compound .3 g (1.0 mol) was dissolved in 4,500 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 390 g of a polyamic acid having a logarithmic viscosity of 0.91 dl / g (referred to as “polyamic acid (B-2)”).
合成例５
テトラカルボン酸二無水物としてピロメリット酸二無水物１０９．０６ｇ（０．５モル）および１，２，３，４−シクロブタンテトラカルボン酸二無水物９８．０６ｇ（０．５モル）、ジアミン化合物として４，４’−ジアミノジフェニルメタン１９８．２７ｇ（１．０モル）をＮ−メチル−２−ピロリドン４，５００ｇに溶解させ、４０℃で３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０．９３ｄｌ／ｇのポリアミック酸（これを「ポリアミック酸（Ｂ−３）」とする）４１１．２１ｇを得た。
Synthesis example 5
Pyromellitic dianhydride 109.06 g (0.5 mol) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride 98.06 g (0.5 mol) as a tetracarboxylic dianhydride, a diamine compound As a result, 198.27 g (1.0 mol) of 4,4′-diaminodiphenylmethane was dissolved in 4,500 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 411.21 g of polyamic acid having a logarithmic viscosity of 0.93 dl / g (referred to as “polyamic acid (B-3)”). It was.
実施例１
（１）合成例１で得られたポリイミド（Ａ−１）、合成例３で得られたポリアミック酸（Ｂ−１）およびエポキシ基含有化合物とを、γ−ブチロラクトン／３−ブトキシ−Ｎ，Ｎ−ジメチルプロパンアミド／ブチルセロソルブ混合溶剤（重量比７３／１５／１２）に溶解させて固形分濃度４重量％の溶液とし、この溶液を孔径１μｍのフィルターを用いて濾過し、液晶配向剤を調製した。なお、ポリイミドとポリアミック酸は、ポリイミド：ポリアミック酸＝１：４（重量比）となるような割合で用い、エポキシ基含有化合物は、重合体１００重量部に対し、２重量部含むように調製した。
（２）上記液晶配向剤を、液晶配向膜塗布用印刷機を用いてＩＴＯ膜からなる透明電極付きガラス基板の透明電極面に塗布し、２００℃のホットプレート上で１０分間乾燥することにより、被膜を形成した。この塗膜の膜厚の状態は、２５℃の環境下では平均膜厚が５１０オングストローム、最大較差の値が１１オングストローム、３５℃の環境下では平均膜厚が４９８オングストローム、最大較差の値が１３オングストロームであった。ハジキの個数は１０平方センチメートルあたり２個であった。
（３）液晶配向剤が形成された被膜にレーヨン製の布を巻き付けたロールを有するラビングマシーンにより、ロールの回転数４００ｒｐｍ、ステージの移動速度３ｃｍ／秒、毛足押し込み長さ０.４ｍｍでラビング処理を行った。上記液晶配向膜塗布基板を、水中に１分間浸漬した後、１００℃のホットプレート上で１０分間乾燥した。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５．５μｍ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、ネマティック型液晶（メルク社製、ＭＬＣ−６２２１）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た。流動配向は見られず、コントラストムラ、表示欠損は見られなかった。
Example 1
(1) Polyimide (A-1) obtained in Synthesis Example 1, polyamic acid (B-1) obtained in Synthesis Example 3 and an epoxy group-containing compound were converted to γ-butyrolactone / 3-butoxy-N, N -A liquid crystal aligning agent was prepared by dissolving in a dimethylpropanamide / butyl cellosolve mixed solvent (weight ratio 73/15/12) to obtain a solution having a solid content of 4% by weight, and filtering this solution using a filter having a pore size of 1 μm. . The polyimide and polyamic acid were used in such a ratio that polyimide: polyamic acid = 1: 4 (weight ratio), and the epoxy group-containing compound was prepared to contain 2 parts by weight with respect to 100 parts by weight of the polymer. .
(2) By applying the liquid crystal aligning agent to the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film using a printing machine for applying a liquid crystal alignment film, and drying on a hot plate at 200 ° C. for 10 minutes, A film was formed. As for the state of film thickness of this coating film, the average film thickness is 510 angstroms and the maximum difference value is 11 angstroms at 25 ° C., and the average film thickness is 498 angstroms and the maximum difference value is 13 at 35 ° C. It was Angstrom. The number of repellants was 2 per 10 square centimeters.
(3) By a rubbing machine having a roll in which a rayon cloth is wound around a film on which a liquid crystal aligning agent is formed, the rubbing is performed at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.4 mm. Processed. The liquid crystal alignment film-coated substrate was immersed in water for 1 minute and then dried on a hot plate at 100 ° C. for 10 minutes. Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 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 nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) is filled between the substrates through 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. Were laminated to prepare a liquid crystal display element. No fluid orientation was observed, and no contrast unevenness or display defect was observed.
実施例２〜８および比較例１
表１、表２に示す処方に従い、合成例１〜２で得られたポリイミドおよび合成例３〜５で得られたポリアミック酸を用い、実施例１と同様にして液晶配向剤を調製した。次いで、このようにして得られた液晶配向剤の各々を用い、実施例１と同様にして液晶表示素子を作製した。得られた液晶配向剤の各々について、形成される塗膜の膜厚の状態、液晶表示素子の配向性および保存安定性について評価した。結果を表１、表２に示す。
Examples 2 to 8 and Comparative Example 1
According to the formulations shown in Tables 1 and 2, a liquid crystal aligning agent was prepared in the same manner as in Example 1 using the polyimides obtained in Synthesis Examples 1 and 2 and the polyamic acid obtained in Synthesis Examples 3 to 5. Next, a liquid crystal display element was produced in the same manner as in Example 1 using each of the liquid crystal aligning agents thus obtained. About each of the obtained liquid crystal aligning agent, the state of the film thickness of the coating film formed, the orientation of a liquid crystal display element, and storage stability were evaluated. The results are shown in Tables 1 and 2.
表１、表２における溶剤の種類は次のとおりである。
（ａ）γ−ブチロラクトン（ｂ）Ｎ−メチル−２−ピロリドン（ｃ）３−ブトキシ−Ｎ，Ｎ−ジメチルプロパンアミド（ｄ）３−メトキシ−Ｎ，Ｎ−ジメチルプロパンアミド（ｅ）３−ヘキシルオキシ−Ｎ，Ｎ−ジメチルプロパンアミド（ｆ）ブチルセロソルブ
The types of solvents in Tables 1 and 2 are as follows.
(A) γ-butyrolactone (b) N-methyl-2-pyrrolidone (c) 3-butoxy-N, N-dimethylpropanamide (d) 3-methoxy-N, N-dimethylpropanamide (e) 3-hexyl Oxy-N, N-dimethylpropanamide (f) butyl cellosolve
Claims (4)
Applying the liquid crystal aligning agent according to any one of claims 1 to 3 to one surface of a substrate, then heating the coating surface to form a coating film, and performing a rubbing treatment on the coating film surface A method for forming a liquid crystal alignment film.
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| JP4336922B2 (en) * | 2000-04-12 | 2009-09-30 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| JP5142450B2 (en) * | 2003-12-25 | 2013-02-13 | 徹也 西尾 | Diamino compound, vinyl compound, polymer compound, alignment film, organic semiconductor device using alignment film, conductive polymer, electroluminescence element using the conductive polymer, liquid crystal alignment film, and liquid crystal alignment film Optical element used |
| TWI359189B (en) * | 2004-01-27 | 2012-03-01 | Jsr Corp | Liquid crystal alignment agent, liquid crystal ali |
| JP4620438B2 (en) * | 2004-02-27 | 2011-01-26 | チッソ株式会社 | Liquid crystal alignment film, liquid crystal alignment agent, and liquid crystal display element |
| JP4513950B2 (en) * | 2004-03-05 | 2010-07-28 | Ｊｓｒ株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
-
2006
- 2006-03-22 JP JP2006079088A patent/JP4844721B2/en active Active
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2007
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| Publication number | Publication date |
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| JP2007256485A (en) | 2007-10-04 |
| CN101042504B (en) | 2011-02-09 |
| CN101042504A (en) | 2007-09-26 |
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