JP2009084178A

JP2009084178A - Polymerizable chiral compound

Info

Publication number: JP2009084178A
Application number: JP2007254124A
Authority: JP
Inventors: Masanao Hayashi; 正直林; Yutaka Nagashima; 豊長島; Tetsuo Kusumoto; 哲生楠本
Original assignee: DIC Corp; Dainippon Ink and Chemicals Co Ltd
Current assignee: DIC Corp
Priority date: 2007-09-28
Filing date: 2007-09-28
Publication date: 2009-04-23
Anticipated expiration: 2027-09-28
Also published as: JP5288156B2

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable chiral compound having high HTP (helical twisting power) and a low melting point. <P>SOLUTION: This polymerizable chiral compound is expressed by general formula (I). The compound has high HTP and a low melting point and also having excellent compatibility with another liquid crystalline compound by having the low melting point, and therefore it is useful as a constituting member of the liquid crystal composition. Also, an optical anisotropic material having excellent optical characteristics can be prepared by the polymerizable liquid crystal composition having the polymerizable chiral compound as its constituting member, since the content of the polymerizable chiral compound can be made as a large amount. The optically anisotropic material is useful for the uses such as a deflection plate, a retardation plate, etc. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は重合性キラル化合物、および当該化合物を含有する重合性液晶組成物、さらに当該重合性液晶組成物の硬化物である光学異方体に関する。 The present invention relates to a polymerizable chiral compound, a polymerizable liquid crystal composition containing the compound, and an optical anisotropic body which is a cured product of the polymerizable liquid crystal composition.

近年、情報化社会の進展に伴い液晶ディスプレイに必須な偏向板、位相差板などに用いられる光学異方体の重要性は益々高まっている。光学異方体に必要な光学特性は目的により異なるので目的にあった特性を有する化合物が必要である。また、光学特性だけでなく化合物の重合速度、溶解性、融点、ガラス転移点、重合物の透明性、重合物の機械的強度なども重要な因子となる。 In recent years, with the progress of the information society, the importance of optical anisotropic bodies used for deflecting plates, retardation plates and the like essential for liquid crystal displays has been increasing. Since the optical properties necessary for the optical anisotropic body vary depending on the purpose, a compound having the properties suitable for the purpose is required. In addition to the optical properties, the polymerization rate, solubility, melting point, glass transition point, transparency of the polymer, mechanical strength of the polymer, and the like are important factors.

近年、重合性コレステリック液晶を用いた円偏光分離機能素子が、輝度向上フィルムとして活用されている。コレステリック液晶は通常、ネマチック液晶に光学活性化合物（以下、キラル化合物）を添加することにより調整できる。液晶デバイスの光学補償フィルムとして、紫外線領域から可視光領域までの円偏光分離機能を得るためには、非常にピッチの短いらせん構造を必要とする。そのためにはＨＴＰ（らせんねじれ力）の強いキラル化合物を用いた液晶組成物が望ましい。ＨＴＰの小さなキラル化合物を用いた場合は、その添加量を増やさなければならず、液晶性、溶解性、重合物の透明性などが低下し、光学特性に悪影響を及ぼす。また光学活性部位を有する化合物は一般的に高価であり多量に使用することは得策でない。このような高いＨＴＰを示す化合物として環構造の光学活性部位を有するキラル化合物が提案されている（引用文献１および２参照）。これらの引用文献には１，４：３，６−ジアンヒドロ−Ｄ−マンニトール（イソマンニド）、ジアンヒドロ−Ｄ−グルシトール（イソソルビド）等の光学活性化合物に基づく高いＨＴＰを有する重合性キラル化合物が開示されている。しかしながら、これらの光学活性化合物は何れも融点が高い、溶解性が悪い、一部の液晶化合物との相溶性が低い等の問題があった。また、溶解性を向上させるために構造を非対称とした化合物は、溶解性の点ではある程度の改善が見られるものの、製造が煩雑であることから、光学異方性体の高価格化の要因となる問題があった。 In recent years, circularly polarized light separating functional elements using polymerizable cholesteric liquid crystals have been utilized as brightness enhancement films. A cholesteric liquid crystal can be usually adjusted by adding an optically active compound (hereinafter referred to as a chiral compound) to a nematic liquid crystal. In order to obtain a circularly polarized light separating function from the ultraviolet region to the visible light region as an optical compensation film of a liquid crystal device, a helical structure with a very short pitch is required. For this purpose, a liquid crystal composition using a chiral compound having a strong HTP (helical twisting power) is desirable. When a chiral compound having a small HTP is used, the amount added must be increased, and the liquid crystallinity, solubility, transparency of the polymer, and the like are lowered, which adversely affects optical properties. In addition, compounds having an optically active site are generally expensive and are not suitable for use in large quantities. As compounds exhibiting such high HTP, chiral compounds having an optically active site of a ring structure have been proposed (see References 1 and 2). These references disclose polymerizable chiral compounds having high HTP based on optically active compounds such as 1,4: 3,6-dianhydro-D-mannitol (isomannide), dianhydro-D-glucitol (isosorbide) and the like. Yes. However, all of these optically active compounds have problems such as high melting point, poor solubility, and low compatibility with some liquid crystal compounds. In addition, a compound having an asymmetric structure in order to improve the solubility can be improved to some extent in terms of solubility, but it is complicated to manufacture, which is a factor in increasing the cost of the optically anisotropic material. There was a problem.

特表平９−５０６０８８号公報JP 9-506088 gazette 特開２００３−１３７８８７号公報JP 2003-137877 A

本発明が解決しようとする課題は、高いＨＴＰと、低い融点を有する重合性キラル化合物を提供することである。 The problem to be solved by the present invention is to provide a polymerizable chiral compound having a high HTP and a low melting point.

本願発明者らは重合性化合物における種々の置換基の検討を行った結果、特定の構造を有する重合性化合物が前述の課題を解決できることを見出し本願発明を完成するに至った。
本願発明は、一般式（I） As a result of studying various substituents in the polymerizable compound, the present inventors have found that a polymerizable compound having a specific structure can solve the above-described problems, and have completed the present invention.
The present invention relates to the general formula (I)

（式中、Ｒ^１およびＲ^２はお互い独立して重合性基を表し、Ｓ^１およびＳ^２はお互い独立してスペーサー基又は単結合を表し、Ｙ^１およびＹ^２はお互い独立して−Ｏ−、−Ｓ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯ−、―ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＣＯ−ＮＲ^１１−、−ＮＲ^１１−ＣＯ−、−ＳＣＨ_２−、−ＣＨ_２Ｓ−、―ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＯＣ−ＣＨ＝ＣＨ−、―ＣＯＯＣ_２Ｈ_４−、−ＣＨ_２Ｈ_４ＣＯＯ−又は単結合を表し、Ｘ^１およびＸ^２はお互い独立して、−Ｏ−、−Ｓ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯ−、―ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＣＯ−ＮＲ^１１−、−ＮＲ^１１−ＣＯ−、−ＳＣＨ_２−、−ＣＨ_２Ｓ−、―ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＯＣ−ＣＨ＝ＣＨ−、−ＮＲ^１１−ＣＯ−、−ＣＯ−ＣＨ＝ＣＨ−、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−ＣＦ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２ＣＨ_２−、−ＣＨ_２ＣＦ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＨ−、−ＣＨ＝ＣＦ−、−Ｃ≡Ｃ−、―Ｃ_２Ｈ_４ＣＯＯ−、―ＣＯＯＣ_２Ｈ_４−又は単結合を表し、Ｂ^１およびＢ^２はお互い独立して、−Ｏ−、−Ｓ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯ−、―ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＣＯ−ＮＲ^１１−、−ＮＲ^１１−ＣＯ−、−ＳＣＨ_２−、−ＣＨ_２Ｓ−、―ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＯＣ−ＣＨ＝ＣＨ−、−ＮＲ^１１−ＣＯ−、−ＣＯ−ＣＨ＝ＣＨ−、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−ＣＦ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２ＣＨ_２−、−ＣＨ_２ＣＦ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＨ−、−ＣＨ＝ＣＦ−、−Ｃ≡Ｃ−、―Ｃ_２Ｈ_４ＣＯＯ−、―ＣＯＯＣ_２Ｈ_４−、―ＯＣ_２Ｈ_４Ｏ−、又は―ＯＣ_３Ｈ_６−、―Ｃ_３Ｈ_６Ｏ−又は単結合を表すが、Ｂ^１およびＢ^２の少なくとも一方は、―ＯＣ_２Ｈ_４Ｏ−、又は―ＯＣ_３Ｈ_６−、―Ｃ_３Ｈ_６Ｏ−を表し、（Ｙ^１、Ｙ^２、Ｂ^１、Ｂ^２、Ｘ^１およびＸ^２において、Ｒ^１１はお互い独立して炭素原子１〜４のアルキル基を表す。）、Ａ^１、Ａ^２、Ａ^３およびＡ^４はお互い独立して、１，４−シクロヘキシレン基、１，４−フェニレン基、ピリジン−２，５−ジイル基、ピリミジン−２，５−ジイル基、ナフタレン−２，６−ジイル基、テトラヒドロナフタレン−２，６−ジイル基、１，３−ジオキサン−２，５−ジイル基を表すが、Ａ^１、Ａ^２、Ａ^３およびＡ^４はお互い独立してアルキル基、ハロゲン化アルキル基、アルコキシ基、ハロゲン、シアノ基又はニトロ基により置換されていても良く、Ｚ^１は、−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯ−、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−ＣＦ_２−、−ＮＲ^１１−ＣＯ−又は単結合を表し、Ｚ^２は、−ＯＣ−、−ＯＣ−ＣＨ＝ＣＨ−、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−ＣＦ_２−、−ＣＯ−ＮＲ^１１−又は単結合を表し、ｍは１、２又は３を表し、ｎは０、１、２又は３を表す。）で表される重合性キラル化合物を提供し、当該化合物を構成部材とする液晶組成物、更に、当該液晶組成物を用いた光学異方体及び光学素子を提供する。 (Wherein R ¹ and R ² each independently represent a polymerizable group, S ¹ and S ² each independently represent a spacer group or a single bond, and Y ¹ and Y ² each independently represent —O _{_{-, - S -, - OCH}} 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - OCOO -, - CO-NR 11 -, - NR 11 -CO -, - SCH 2 _{-, - CH 2 S -,} - CH = CH-COO -, - OOC-CH = CH -, - COOC 2 H 4 -, - CH 2 H 4 COO- or a single bond, ^{X 1} and ^{X 2} Independently of each other, —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —OCOO—, —CO—NR ¹¹ —, —NR ¹¹ _{_{-CO -, - SCH 2 -,}} - CH 2 S -, - CH = CH-COO -, - OOC-CH ═CH—, —NR ¹¹ —CO—, —CO—CH═CH—, —CH ₂ —, —C ₂ H ₄ —, —CF ₂ —, —CF ₂ O—, —OCF ₂ —, —CF ₂ _{_{_{_{CH 2 -, - CH 2 CF}}}} 2 -, - CF 2 CF 2 -, - CH = N -, - N = CH -, - N = N -, - CH = CH -, - CF = CH -, - CH ═CF—, —C≡C—, —C ₂ H ₄ COO—, —COOC ₂ H ₄ — or a single bond, and B ¹ and B ² are independently of each other, —O—, —S—, — _{_{OCH 2 -, - CH 2 O}} -, - CO -, - COO -, - OCO -, - OCOO -, - CO-NR 11 -, - NR 11 -CO -, - SCH 2 -, - CH 2 S- , —CH═CH—COO—, —OOC—CH═CH—, —NR ¹¹ —CO—, —CO—CH═CH—, —CH ₂ —, —C ₂ H _{_{_{_{4 -, - CF 2 -,}}}} - CF 2 O -, - OCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, - CH = N -, - N = CH -, - N = N -, - CH = CH -, - CF = CH -, - CH = CF -, - C≡C -, - C 2 H 4 COO -, - COOC 2 H 4 -, - OC 2 H ₄ O—, or —OC ₃ H ₆ —, —C ₃ H ₆ O— or a single bond, but at least one of B ¹ and B ² is —OC ₂ H ₄ O— or —OC ₃ H _6- , -C ₃ H ₆ O-, (in Y ¹ , Y ² , B ¹ , B ² , X ¹ and X ² , R ¹¹ independently represents an alkyl group having 1 to 4 carbon atoms. . ), A ¹ , A ² , A ³ and A ⁴ are each independently 1,4-cyclohexylene group, 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl Group, naphthalene-2,6-diyl group, tetrahydronaphthalene-2,6-diyl group, 1,3-dioxane-2,5-diyl group, A ¹ , A ² , A ³ and A ⁴ represent each other Independently substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen, a cyano group, or a nitro group, and Z ¹ is —CO—, —CH═CH—CO—, —CH ₂ —, —C ₂ H ₄ —, —CF ₂ —, —NR ¹¹ —CO— or a single bond is represented, and Z ² represents —OC—, —OC—CH═CH—, —CH ₂ —, —C ₂ H _4. —, —CF ₂ —, —CO—NR ¹¹ — or a single bond M represents 1, 2 or 3, and n represents 0, 1, 2 or 3. And a liquid crystal composition comprising the compound as a constituent member, and an optical anisotropic body and an optical element using the liquid crystal composition.

本願発明の重合性キラル化合物は、高いＨＴＰ及び低い融点を有し、低融点であることから他の液晶化合物との優れた溶解性を有し重合性液晶組成物の構成部材として有用である。又、本願発明の重合性キラル化合物を構成部材とする重合性液晶組成物は、重合性キラル化合物の含有量を多くできることから優れた光学特性を有する光学異方体を作製することができる。本願発明の光学異方体は、偏向板、位相差板等の用途に有用である。 The polymerizable chiral compound of the present invention has a high HTP, a low melting point, and a low melting point, so that it has excellent solubility with other liquid crystal compounds and is useful as a constituent member of a polymerizable liquid crystal composition. Moreover, since the polymerizable liquid crystal composition having the polymerizable chiral compound of the present invention as a constituent member can increase the content of the polymerizable chiral compound, an optical anisotropic body having excellent optical characteristics can be produced. The optical anisotropic body of the present invention is useful for applications such as a deflection plate and a phase difference plate.

一般式（I）において、Ｒ^１およびＲ^２はお互い独立して重合性基を表すが、重合性基の具体的な例としては、下記に示す構造が挙げられる。 In the general formula (I), R ¹ and R ² each independently represent a polymerizable group, and specific examples of the polymerizable group include the structures shown below.

これらの重合基はラジカル重合、ラジカル付加重合、カチオン重合、およびアニオン重合により硬化する。特に重合方法として紫外線重合を行う場合には、式（Ｒ−１）、式（Ｒ−２）、式（Ｒ−４）、式（Ｒ−５）、式（Ｒ−７）、式（Ｒ−１１）、式（Ｒ−１３）又は式（Ｒ−１５）が好ましく、式（Ｒ−１）、式（Ｒ−２）、式（Ｒ−７）、式（Ｒ−１１）又は式（Ｒ−１３）がより好ましい。
Ｓ^１およびＳ^２はお互い独立してスペーサー基又は単結合を表すが、スペーサー基としては、炭素数２〜１０のアルキレン基が好ましく、該アルキレン基は酸素原子同士が直接結合しないものとして炭素原子が酸素原子に置き換えられても良く、液晶性および他の液晶化合物との相溶性の観点から炭素数３〜８のアルキレン基がより好ましい。
Ｙ^１およびＹ^２はお互い独立しては−Ｏ−、−ＣＯ−、―ＣＯＯ−、−ＯＣＯ−、―ＣＯＯＣ_２Ｈ_４−、−ＣＨ_２Ｈ_４ＣＯＯ−又は単結合が好ましい。 These polymerizable groups are cured by radical polymerization, radical addition polymerization, cationic polymerization, and anionic polymerization. In particular, when performing ultraviolet polymerization as a polymerization method, the formula (R-1), formula (R-2), formula (R-4), formula (R-5), formula (R-7), formula (R -11), formula (R-13) or formula (R-15) are preferred, and formula (R-1), formula (R-2), formula (R-7), formula (R-11) or formula ( R-13) is more preferred.
S ¹ and S ² each independently represent a spacer group or a single bond. The spacer group is preferably an alkylene group having 2 to 10 carbon atoms, and the alkylene group is a carbon atom on the assumption that oxygen atoms are not directly bonded to each other. May be replaced by an oxygen atom, and an alkylene group having 3 to 8 carbon atoms is more preferable from the viewpoint of liquid crystallinity and compatibility with other liquid crystal compounds.
Y ¹ and Y ² are each independently preferably —O—, —CO—, —COO—, —OCO—, —COOC ₂ H ₄ —, —CH ₂ H ₄ COO— or a single bond.

Ｘ^１およびＸ^２は結合基を表しお互い独立して、−Ｏ−、−Ｓ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、―ＣＯＯ−、−ＯＣＯ−、―Ｃ_２Ｈ_４ＣＯＯ−又は―ＣＯＯＣ_２Ｈ_４−が好ましく、液晶性の観点から１つ以上―ＣＯＯ−、又は−ＯＣＯ−であることがより好ましい。
Ｂ^１およびＢ^２はお互い独立して、−Ｏ−、−Ｓ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、―ＣＯＯ−、−ＯＣＯ−、―Ｃ_２Ｈ_４ＣＯＯ−又は―ＣＯＯＣ_２Ｈ_４−、―ＯＣ_２Ｈ_４Ｏ−、又は―ＯＣ_３Ｈ_６−、―Ｃ_３Ｈ_６Ｏ−が好ましく、溶解性、融点、液晶配向性の観点から―ＯＣ_２Ｈ_４Ｏ−、又は―ＯＣ_３Ｈ_６−、―Ｃ_３Ｈ_６Ｏ−がより好ましい。
Ｚ^１は、−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯ−又は−ＣＯ−が好ましく、Ｚ^２は、−ＯＣ−又は−ＯＣ−ＣＨ＝ＣＨ−が好ましい。
Ａ^１およびＡ^２は環構造を有する二価基であり、お互い独立して、1,4−シクロヘキシレン、1,4−フェニレン基、ナフタレン−2,6−ジイル基又は1,2,3,4−テトラヒドロナフタレン−2,6−ジイル基が好ましく1,4−シクロヘキシレン基又は1,4−フェニレン基がより好ましい。
ｍ及びｎは、液晶性の観点、耐熱性からｍ＋ｎが２〜５の整数であることが好ましく、３〜５の整数がより好ましい。 X ¹ and X ² represent a linking group and independently of each other, —O—, —S—, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —C ₂ H ₄ COO— or —COOC ₂ H ₄ — is preferable, and from the viewpoint of liquid crystallinity, one or more —COO— or —OCO— is more preferable.
B ¹ and B ² are independently of each other —O—, —S—, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —C ₂ H ₄ COO— or —COOC ₂ H. _{_{_{4 -, - OC 2 H 4}}} O-, or _{_{_{-OC 3 H 6 -, - C}}} 3 H 6 O- are preferable, solubility, melting point, crystal orientation of the viewpoint from _-OC 2 _H 4 O-, or - OC ₃ H ₆ — and —C ₃ H ₆ O— are more preferable.
Z ¹ is preferably —CO—, —CH═CH—CO— or —CO—, and Z ² is preferably —OC— or —OC—CH═CH—.
A ¹ and A ² are divalent groups having a ring structure, and independently of each other, 1,4-cyclohexylene, 1,4-phenylene group, naphthalene-2,6-diyl group or 1,2,3, A 4-tetrahydronaphthalene-2,6-diyl group is preferred, and a 1,4-cyclohexylene group or a 1,4-phenylene group is more preferred.
From the viewpoint of liquid crystallinity and m and n, m + n is preferably an integer of 2 to 5, and more preferably an integer of 3 to 5 from the viewpoint of heat resistance.

一般式（I）で表される化合物は、より具体的には、下記の一般式（I-1）〜一般式（I-11）で表される化合物が好ましい。 More specifically, the compound represented by the general formula (I) is preferably a compound represented by the following general formula (I-1) to general formula (I-11).

（式中、ｐおよびｑはお互い独立して２〜１８の整数を表す。）
本発明の化合物は以下に記載する合成方法で合成することができる。
（製法１）一般式（I-3）で表される化合物の製造
p-ヒドロキシ安息香酸4と塩化ベンジル6炭酸水素ナトリウムなど適当な塩基の存在下でエステル化させた後、エチレンカーボネートと反応させて4-(2-ヒドロキシエチル)オキシ安息香酸ベンジルエステル（S-3）を得る。 (In the formula, p and q independently represent an integer of 2 to 18.)
The compound of the present invention can be synthesized by the synthesis method described below.
(Production Method 1) Production of Compound Represented by General Formula (I-3)
After esterification in the presence of a suitable base such as p-hydroxybenzoic acid 4 and benzyl chloride 6 sodium hydrogen carbonate, it is reacted with ethylene carbonate to give 4- (2-hydroxyethyl) oxybenzoic acid benzyl ester (S-3 )

一方、p-ヒドロキシ安息香酸とベンジルクロリドとを水酸化ナトリウムなど適当な塩基の存在下でエーテル化させてフェノールに保護基を結合させた後、ジシクロヘキシルカルボジイミド等の脱水縮合剤を用いてエステル化反応させ、更に生成物をパラジウム触媒を用いた水素添加による還元反応によりフェノール保護基を脱離させイソソルビド誘導体（S-7）を得る。 On the other hand, p-hydroxybenzoic acid and benzyl chloride are etherified in the presence of a suitable base such as sodium hydroxide to bond a protecting group to phenol, and then esterified using a dehydrating condensing agent such as dicyclohexylcarbodiimide. Further, the phenol protecting group is eliminated from the product by a reduction reaction by hydrogenation using a palladium catalyst to obtain an isosorbide derivative (S-7).

次いで、得られた4-(2-ヒドロキシエチル)オキシ安息香酸ベンジルエステル（S-3）及びイソソルビド誘導体（S-7）とをトリフェニルホスフィン存在下でアゾジカルボン酸ジイソプロピルによりエーテル化反応させ、更にパラジウムカーボンによる水添反応によりベンジル基を脱保護させイソソルビド誘導体（S-8）を得る。 Next, the obtained 4- (2-hydroxyethyl) oxybenzoic acid benzyl ester (S-3) and isosorbide derivative (S-7) were etherified with diisopropyl azodicarboxylate in the presence of triphenylphosphine, and The benzyl group is deprotected by hydrogenation reaction with palladium carbon to obtain an isosorbide derivative (S-8).

得られたイソソルビド誘導体（S-8）とヒドロキシブチルアクリレートをジシクロヘキシルカルボジイミド等の脱水縮合剤を用いてエステル化反応させp=4の目的物化合物（I-3）を得ることができる。 The obtained isosorbide derivative (S-8) and hydroxybutyl acrylate can be esterified using a dehydration condensing agent such as dicyclohexylcarbodiimide to obtain the target compound (I-3) having p = 4.

（製法２）一般式（I-11）で表される化合物の製造
3-エチル-3-ヒドロキシメチルオキセタンと3-クロロ-1-プロパノールを水酸化ナトリウムなど適当な塩基の存在下でエーテル化させた後、ベンジルオキシフェノールと炭酸カリウム等の塩基によるエーテル化させ、更にパラジウムカーボンによる水添にて重合性基を有するフェノール誘導体（S-10）を得る。 (Production Method 2) Production of Compound Represented by General Formula (I-11)
3-ethyl-3-hydroxymethyloxetane and 3-chloro-1-propanol are etherified in the presence of a suitable base such as sodium hydroxide, and then etherified with a base such as benzyloxyphenol and potassium carbonate. A phenol derivative (S-10) having a polymerizable group is obtained by hydrogenation with palladium carbon.

得られたフェノール誘導体（S-10）とエチレンカーボネートとを反応させて重合性基を有する化合物（S-11）を得る。 The obtained phenol derivative (S-10) and ethylene carbonate are reacted to obtain a compound (S-11) having a polymerizable group.

及び得られた重合性基を有する化合物（S-11）とイソソルビド誘導体（S-7）をトリフェニルホスフィン存在下でアゾジカルボン酸ジイソプロピルによりエーテル化反応させP=3の目的物の一般式（I-11）で表される化合物を得ることができる。 And the resulting compound having a polymerizable group (S-11) and an isosorbide derivative (S-7) are etherified with diisopropyl azodicarboxylate in the presence of triphenylphosphine to give a general formula (I -11) can be obtained.

本願発明の化合物は、キラルネマチック、キラルスメクチック、およびコレステリック液晶組成物に好適に使用できる。本願発明の化合物を構成部材とする液晶組成物において、重合性キラル化合物の添加量は、０．１〜４０質量％が好ましく、５〜２５％がより好ましい。 The compound of the present invention can be suitably used for chiral nematic, chiral smectic, and cholesteric liquid crystal compositions. In the liquid crystal composition having the compound of the present invention as a constituent member, the addition amount of the polymerizable chiral compound is preferably 0.1 to 40% by mass, and more preferably 5 to 25%.

本願発明の重合性キラル化合物を含有する液晶組成物の構成としては、一般式（I）で表される化合物を含有する以外に制限はないが、組み合わせて使用する重合性液晶化合物としては、化合物中にアクリロイルオキシ基（R-1）又はメタアクリロイルオキシ基（R-2）を有するものが好ましく、重合性官能基を分子内に２つ以上持つものがより好ましい。 The composition of the liquid crystal composition containing the polymerizable chiral compound of the present invention is not limited except that it contains the compound represented by the general formula (I), but the polymerizable liquid crystal compound used in combination is a compound. Those having an acryloyloxy group (R-1) or methacryloyloxy group (R-2) are preferred, and those having two or more polymerizable functional groups in the molecule are more preferred.

組み合わせて使用する２官能性重合性液晶化合物として具体的には一般式（II） Specifically, the bifunctional polymerizable liquid crystal compound used in combination is represented by the general formula (II)

（式中、Ｗ¹及びＷ²はお互い独立して単結合、−Ｏ−、−ＣＯＯ−又は−ＯＣＯ−を表し、Ｙ³及びＹ⁴はお互い独立して−ＣＯＯ−又は−ＯＣＯ−を表し、ｒ及びｓはお互い独立して２〜１８の整数を表し、式中に存在する１，４−フェニレン基は炭素原子数１〜７のアルキル基、炭素原子数１〜７のアルコキシ基、炭素原子数１〜７のアルカノイル基、シアノ基又はハロゲン原子で一つ以上置換されていても良い。）で表される化合物が好ましい。 Wherein W ¹ and W ² each independently represent a single bond, —O—, —COO— or —OCO—, and Y ³ and Y ⁴ each independently represent —COO— or —OCO—. , R and s each independently represent an integer of 2 to 18, and the 1,4-phenylene group present in the formula is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, carbon One or more alkanoyl groups having 1 to 7 atoms, a cyano group, or a halogen atom may be substituted.

一般式（II）で表される化合物は、具体的には、一般式（II-1）〜一般式（II-8）で表される化合物が好ましい。 Specifically, the compound represented by the general formula (II) is preferably a compound represented by the general formula (II-1) to the general formula (II-8).

（式中、ｒ及びｓは一般式（II）と意味と同じ意味を表す。）
一般式（II-1）〜一般式（II-8）において、ｒ及びｓはお互い独立して３〜６の整数が好ましい。
組み合わせて使用する２官能性重合性液晶化合物として具体的には、一般式（III） (In the formula, r and s have the same meaning as in general formula (II).)
In the general formulas (II-1) to (II-8), r and s are preferably independently an integer of 3 to 6.
Specifically, the bifunctional polymerizable liquid crystal compound used in combination is represented by the general formula (III)

（式中、Ｗ^３およびＷ^４はお互い独立して単結合、−Ｏ−、−ＣＯＯ−又は−ＯＣＯ−を表し、Ｙ⁵は−ＣＯＯ−又は−ＯＣＯ−を表し、ｐおよびｑはお互い独立して２〜１８の整数を表し、式中に存在する３種の１，４−フェニレン基の水素原子はお互い独立して炭素原子数１〜７のアルキル基、アルコキシ基、アルカノイル基、シアノ基、又はハロゲン原子で一つ以上置換されていても良い。）で表される化合物も好ましい。
一般式（III）で表される化合物は、具体的には、一般式（III-1）〜一般式（III-8）で表される化合物が好ましい。 Wherein W ³ and W ⁴ each independently represent a single bond, —O—, —COO— or —OCO—, Y ⁵ represents —COO— or —OCO—, and p and q are independent of each other. And the hydrogen atoms of the three types of 1,4-phenylene groups present in the formula are independently of each other an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, or a cyano group. Or one or more halogen atoms may be substituted.) Is also preferred.
Specifically, the compound represented by general formula (III) is preferably a compound represented by general formula (III-1) to general formula (III-8).

（式中、ｐ及びｑは一般式（III）と意味と同じ意味を表す。）
このような化合物の中でも耐熱性や耐久性の点から、一般式（III-2）、一般式（III-5）、一般式（III-6）、一般式（III-9）、一般式(III-10）の化合物が好ましく、一般式（III-2）の化合物がより好ましい。
ホスト液晶となる重合性官能基を分子内に２つ以上持つ化合物としては、一般式（ａ−１）〜一般式（ａ―１０）で表される化合物を含有させることができる。 (Wherein p and q represent the same meaning as in general formula (III)).
Among these compounds, from the viewpoint of heat resistance and durability, general formula (III-2), general formula (III-5), general formula (III-6), general formula (III-9), general formula ( The compound of III-10) is preferable, and the compound of general formula (III-2) is more preferable.
As a compound having two or more polymerizable functional groups in the molecule serving as a host liquid crystal, compounds represented by general formulas (a-1) to (a-10) can be contained.

（式中、u及びvはお互い独立して２〜１８の整数を表す。）
これらの中でも、一般式（a-2）又は一般式(a-3）で表される化合物を添加が好ましい。ｕ及びｖは３〜１８が好ましく、４〜１６がより好ましく、６〜１２が特にに好ましい。
本願発明の液晶組成物に使用する重合性液晶化合物としては、液晶温度範囲や複屈折率の調節、粘度低減を目的として一般式（IV） (In the formula, u and v each independently represent an integer of 2 to 18.)
Among these, it is preferable to add the compound represented by the general formula (a-2) or the general formula (a-3). u and v are preferably 3 to 18, more preferably 4 to 16, and particularly preferably 6 to 12.
The polymerizable liquid crystal compound used in the liquid crystal composition of the present invention is represented by the general formula (IV) for the purpose of adjusting the liquid crystal temperature range, birefringence, and reducing viscosity.

（式中、ｅは０〜１８の整数を表し、ｅが０又は１のときｆは０を表し、ｅが２〜１８のとき、ｆは０又は１の整数を表し、ｉは０〜２の整数を表し、Ｃ、Ｄ及びＥはお互い独立して、1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、テトラヒドロチオピラン-2,5-ジイル基、1,4-ビシクロ(2,2,2)オクチレン基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基又はフルオレン2,7-ジイル基を表すが、該1,4-フェニレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基又はフルオレン2,7-ジイル基は非置換であるか又は置換基として１個又は２個以上のＦ、Ｃｌ、ＣＦ_３、ＯＣＦ_３又はＣＨ_３を有することができ、 (In the formula, e represents an integer of 0 to 18; when e is 0 or 1, f represents 0; when e is 2 to 18, f represents an integer of 0 or 1; i represents 0 to 2; C, D and E are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1 , 3-Dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine -2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group Phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group or fluorene 2 , 7-diyl group, Group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group or fluorene 2,7-diyl group is unsubstituted or substituted with one or more F , Cl, CF ₃ , OCF ₃ or CH ₃ ,

Ｙ^６及びＹ^７はお互い独立して、単結合、−ＣＯＯ−-、−ＯＣＯ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２ＣＨ_２Ｏ−、−ＯＣＨ_２ＣＨ_２ＣＨ_２−、-−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨＣＨ_２−、−ＣＨ＝ＣＨＣＯＯ−、−ＯＣＯＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２ＯＣＯ−又は−ＣＯＯＣＨ_２ＣＨ_２−を表し、Ｙ^８は単結合、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２ＣＯＯ−又は−ＣＨ_２ＯＣＯ−を表し、Ｚは炭素原子数１〜１８のアルキル基、炭素原子数２〜１８のアルケニル基、ハロゲン原子、シアノ基又はＮＣＳを表し、該アルキル基又はアルケニル基は非置換であるか又は置換基として1個又は2個以上のＦ、Ｃｌ、シアノ、ＣＨ_３又はＣＦ_３を有することができ、該アルキル基又はアルケニル基中に存在する１個又は２個以上のＣＨ_２基は、酸素原子が相互に直接結合しないものとして、Ｏ、ＣＯ又はＣＯＯで置換されていてもよい。）で表される単官能の重合性液晶化合物を添加することもできる。 Y ⁶ and Y ⁷ are each independently a single bond, —COO—, —OCO—, —CH═N—, —N═CH—, —C≡C—, —CH ₂ CH ₂ —, —CH. ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ O—, —OCH ₂ CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ — _{, -CH = N-N = CH} -, - CF = CF -, - CH = CH -, - CH 2 CH 2 CH = CH -, - CH = CHCH 2 -, - CH = CHCOO -, - OCOCH = CH —, —CH ₂ CH ₂ OCO— or —COOCH ₂ CH ₂ —, and Y ⁸ represents a single bond, —O—, —CO—, —COO—, —OCO—, —CH ₂ —, —OCH ₂ —. _{, -CH 2 O -, - CONH} -, - NHCO -, - CH 2 COO- or _-CH 2 OCO- Z represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a halogen atom, a cyano group, or NCS, and the alkyl group or alkenyl group is unsubstituted or substituted. 1 or 2 or more F, Cl, cyano, CH ₃ or CF ₃ may be present, and one or more CH ₂ groups present in the alkyl group or alkenyl group may have an oxygen atom It may be substituted with O, CO or COO as not directly bonded to It is also possible to add a monofunctional polymerizable liquid crystal compound represented by

一般式（IV）で表される化合物の添加量は５０質量％以下が好ましく、３０質量％以下がさらに好ましく、１５質量％以下が特に好ましい。一般式（IV）で表される化合物は具体的には、一般式（IV-1）〜一般式（IV-11）で表される化合物が好ましい。 The amount of the compound represented by the general formula (IV) is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 15% by mass or less. Specifically, the compound represented by the general formula (IV) is preferably a compound represented by the general formula (IV-1) to the general formula (IV-11).

（式中、e及びfは一般式（IV）と同じ意味を表し、Rは炭素原子数１〜１２のアルキル基又は炭素原子数２〜１２のアルケニル基を表す。）
さらに本発明の重合性液晶組成物には、重合性官能基を有する化合物であって、液晶性を示さない化合物を添加することもできる。このような化合物としては、通常、この技術分野で高分子形成性モノマーあるいは高分子形成性オリゴマーとして認識されるものであれば特に制限なく使用することができるが、その添加量は組成物として液晶性を呈するように調整する必要がある。
本発明の重合性液晶組成物中における本発明の光開始剤の濃度は、0.1〜10質量%が好ましく、0.2〜5質量%がさらに好ましく、0.4〜3質量%が特に好ましい。また、本発明の光開始剤の他に、他の光開始剤を添加することができる。光開始剤としては、ベンゾインエーテル類、ベンゾフェノン類、アセトフェノン類、ベンジルケタール類、アシルフォスフィンオキサイド等が挙げられる。 (In the formula, e and f represent the same meaning as in the general formula (IV), and R represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms.)
Furthermore, the polymerizable liquid crystal composition of the present invention may be added with a compound having a polymerizable functional group and not exhibiting liquid crystallinity. Such a compound can be used without particular limitation as long as it is generally recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field. It is necessary to adjust to exhibit sex.
The concentration of the photoinitiator of the present invention in the polymerizable liquid crystal composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and particularly preferably 0.4 to 3% by mass. In addition to the photoinitiator of the present invention, other photoinitiators can be added. Examples of the photoinitiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides.

また、本発明の重合性液晶組成物には、その保存安定性を向上させるために、安定剤を添加することもできる。使用できる安定剤としては、例えば、ヒドロキノン、ヒドロキノンモノアルキルエーテル類、第三ブチルカテコール類、ピロガロール類、チオフェノール類、ニトロ化合物類、β−ナフチルアミン類、β−ナフトール類、ニトロソ化合物等が挙げられる。安定剤を使用する場合の添加量は、液晶組成物に対して０．００５〜１質量％の範囲が好ましく、０．０２〜０．５質量％がさらに好ましく、０．０３〜０．１質量％が特に好ましい。 In addition, a stabilizer can be added to the polymerizable liquid crystal composition of the present invention in order to improve its storage stability. Examples of the stabilizer that can be used include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, and nitroso compounds. . When the stabilizer is used, the amount added is preferably 0.005 to 1% by mass, more preferably 0.02 to 0.5% by mass, and 0.03 to 0.1% by mass with respect to the liquid crystal composition. % Is particularly preferred.

また、本発明の重合性液晶組成物を偏光フィルムや配向膜の原料、又は印刷インキ及び塗料、保護膜等の用途に利用する場合には、その目的に応じて金属、金属錯体、染料、顔料、色素、蛍光材料、燐光材料、界面活性剤、レベリング剤、チキソ剤、ゲル化剤、多糖類、紫外線吸収剤、赤外線吸収剤、抗酸化剤、イオン交換樹脂、酸化チタン等の金属酸化物等を添加することもできる。 In addition, when the polymerizable liquid crystal composition of the present invention is used for a raw material of a polarizing film or an alignment film, a printing ink, a paint, a protective film or the like, a metal, a metal complex, a dye, or a pigment depending on the purpose. , Dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, metal oxides such as titanium oxide, etc. Can also be added.

次に本発明の光学異方体について説明する。本発明の重合性液晶組成物を重合させることによって製造される光学異方体は種々の用途に利用できる。例えば、本発明の重合性液晶組成物を、配向させない状態で重合させた場合、光散乱板、偏光解消板、モアレ縞防止板として利用可能である。また、本発明の重合性液晶組成物を配向させた状態において、重合させることにより製造された光学異方体は、物理的性質に光学異方性を有しており、有用である。このような光学異方体は、例えば、本発明の重合性液晶組成物表面を、布等でラビング処理した基板、もしくは有機薄膜を形成した基板表面を布等でラビング処理した基板、あるいはＳｉＯ_２を斜方蒸着した配向膜を有する基板上に担持させるか、基板間に挟持させた後、本発明の液晶を重合させることによって製造することができる。
重合性液晶組成物を基板上に担持させる際の方法としては、スピンコーティング、ダイコーティング、エクストルージョンコーティング、ロールコーティング、ワイヤーバーコーティング、グラビアコーティング、スプレーコーティング、ディッピング、プリント法等を挙げることができる。またコーティングの際、重合性液晶組成物に有機溶媒を添加しても良い。有機溶媒としては、酢酸エチル、テトラヒドロフラン、トルエン、ヘキサン、メタノール、エタノール、ジメチルホルムアミド、塩化メチレン、イソプロパノール、アセトン、メチルエチルケトン、アセトニトリル、セロソルブ類を挙げることができる。これらは単独でも、組み合わせて用いても良く、その蒸気圧と重合性液晶組成物の溶解性を考慮し、適宜選択すれば良い。また、その添加量は９０重量％以下が好ましい。添加した有機溶媒を揮発させる方法としては、自然乾燥、加熱乾燥、減圧乾燥、減圧加熱乾燥を用いることができる。重合性液晶材料の塗布性をさらに向上させるためには、基板上にポリイミド薄膜等の中間層を設けることや、重合性液晶材料にレベリング剤を添加するのも有効である。基板上にポリイミド薄膜等の中間層を設けるのは、重合性液晶材料を重合させて得られる光学異方体と基板の密着性が良くない場合に、密着性を向上させる手段としても有効である。 Next, the optical anisotropic body of the present invention will be described. The optical anisotropic body produced by polymerizing the polymerizable liquid crystal composition of the present invention can be used for various applications. For example, when the polymerizable liquid crystal composition of the present invention is polymerized without being oriented, it can be used as a light scattering plate, a depolarizing plate, or a moire fringe prevention plate. Moreover, the optically anisotropic body produced by polymerizing the polymerizable liquid crystal composition of the present invention in an aligned state has optical anisotropy in physical properties and is useful. Such an optical anisotropic body is, for example, a substrate obtained by rubbing the surface of the polymerizable liquid crystal composition of the present invention with a cloth or the like, a substrate obtained by rubbing a substrate surface on which an organic thin film is formed with a cloth, or SiO _2. Can be produced by polymerizing the liquid crystal of the present invention after it is supported on a substrate having an orientation film deposited obliquely or sandwiched between the substrates.
Examples of the method for supporting the polymerizable liquid crystal composition on the substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, and printing. . Further, an organic solvent may be added to the polymerizable liquid crystal composition during coating. Examples of the organic solvent include ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylformamide, methylene chloride, isopropanol, acetone, methyl ethyl ketone, acetonitrile, and cellosolves. These may be used alone or in combination, and may be appropriately selected in consideration of the vapor pressure and the solubility of the polymerizable liquid crystal composition. The amount added is preferably 90% by weight or less. As a method for volatilizing the added organic solvent, natural drying, heat drying, reduced pressure drying, or reduced pressure heat drying can be used. In order to further improve the applicability of the polymerizable liquid crystal material, it is also effective to provide an intermediate layer such as a polyimide thin film on the substrate or to add a leveling agent to the polymerizable liquid crystal material. Providing an intermediate layer such as a polyimide thin film on the substrate is also effective as a means for improving the adhesion when the adhesion between the optically anisotropic substance obtained by polymerizing the polymerizable liquid crystal material and the substrate is not good. .

重合性液晶組成物を基板間に挟持させる方法としては、毛細管現象を利用した注入法が挙げられる。基板間に形成された空間を減圧し、その後、重合性液晶材料を注入する手段も有効である。 Examples of a method for sandwiching the polymerizable liquid crystal composition between the substrates include an injection method using a capillary phenomenon. It is also effective to depressurize the space formed between the substrates and then inject a polymerizable liquid crystal material.

ラビング処理、あるいはＳｉＯ_２の斜方蒸着以外の配向処理としては、液晶材料の流動配向の利用や、電場又は磁場の利用を挙げることができる。これらの配向手段は単独で用いても、また組み合わせて用いても良い。さらに、ラビングに代わる配向処理方法として、光配向法を用いることもできる。この方法は、例えば、ポリビニルシンナメート等の分子内に光二量化反応する官能基を有する有機薄膜、光で異性化する官能基を有する有機薄膜又はポリイミド等の有機薄膜に、偏光した光、好ましくは偏光した紫外線を照射することによって、配向膜を形成するものである。この光配向法に光マスクを適用することにより配向のパターン化が容易に達成できるので、光学異方体内部の分子配向も精密に制御することが可能となる。 Examples of the alignment treatment other than the rubbing treatment or the oblique deposition of SiO ₂ include the use of flow alignment of a liquid crystal material and the use of an electric field or a magnetic field. These orientation means may be used alone or in combination. Furthermore, a photo-alignment method can be used as an alignment treatment method instead of rubbing. This method can be applied to, for example, an organic thin film having a functional group that undergoes photodimerization reaction in a molecule such as polyvinyl cinnamate, an organic thin film having a functional group that is isomerized by light, or an organic thin film such as polyimide. An alignment film is formed by irradiating polarized ultraviolet rays. By applying an optical mask to this photo-alignment method, patterning of the alignment can be easily achieved, so that the molecular orientation inside the optical anisotropic body can be precisely controlled.

基板の形状としては、平板の他に、曲面を構成部分として有していても良い。基板を構成する材料は、有機材料、無機材料を問わずに用いることができる。基板の材料となる有機材料としては、例えば、ポリエチレンテレフタレート、ポリカーボネート、ポリイミド、ポリアミド、ポリメタクリル酸メチル、ポリスチレン、ポリ塩化ビニル、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリアリレート、ポリスルホン、トリアセチルセルロース、セルロース、ポリエーテルエーテルケトン等が挙げられ、また、無機材料としては、例えば、シリコン、ガラス、方解石等が挙げられる。 As a shape of the substrate, in addition to a flat plate, a curved surface may be included as a constituent part. The material which comprises a board | substrate can be used regardless of an organic material and an inorganic material. Examples of the organic material used as the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, and triacetyl. Cellulose, cellulose, polyetheretherketone and the like can be mentioned, and examples of the inorganic material include silicon, glass and calcite.

これらの基板を布等でラビングすることによって適当な配向性を得られない場合、公知の方法に従ってポリイミド薄膜又はポリビニルアルコール薄膜等の有機薄膜を基板表面に形成し、これを布等でラビングしても良い。また、通常のツイステッド・ネマチック（ＴＮ）素子又はスーパー・ツイステッド・ネマチック（ＳＴＮ）素子で使用されているプレチルト角を与えるポリイミド薄膜は、光学異方体内部の分子配向構造を更に精密に制御することができることから、特に好ましい。 When appropriate orientation cannot be obtained by rubbing these substrates with a cloth or the like, an organic thin film such as a polyimide thin film or a polyvinyl alcohol thin film is formed on the substrate surface according to a known method, and this is rubbed with a cloth or the like. Also good. In addition, the polyimide thin film that gives the pretilt angle used in ordinary twisted nematic (TN) or super twisted nematic (STN) elements should control the molecular orientation structure inside the optical anisotropic body more precisely. Is particularly preferable.

また、電場によって配向状態を制御する場合には、電極層を有する基板を使用する。この場合、電極上に前述のポリイミド薄膜等の有機薄膜を形成するのが好ましい。
本発明の重合性キラル化合物を添加した組成物はらせん構造を示すので、これを配向させ液晶状態で重合することでらせん構造を有する位相差板を製造できる。らせんのピッチが光の波長の１／２程度〜同程度であれば、その波長を有する光をブラッグの法則に従い選択的に反射することができる。これは例えば、円偏光分離機能素子として使用できる。 In the case where the alignment state is controlled by an electric field, a substrate having an electrode layer is used. In this case, it is preferable to form an organic thin film such as the aforementioned polyimide thin film on the electrode.
Since the composition to which the polymerizable chiral compound of the present invention is added exhibits a helical structure, a retardation plate having a helical structure can be produced by aligning and polymerizing the composition in a liquid crystal state. If the pitch of the helix is about ½ to about the same as the wavelength of light, light having that wavelength can be selectively reflected according to Bragg's law. This can be used, for example, as a circularly polarized light separating functional element.

本発明の重合性液晶組成物を重合させる方法としては、迅速な重合の進行が望ましいので、紫外線又は電子線等の活性エネルギー線を照射することによって重合させる方法が好ましい。紫外線を使用する場合、偏光光源を用いても良いし、非偏光光源を用いても良い。また、液晶組成物を２枚の基板間に挟持させて状態で重合を行う場合には、少なくとも照射面側の基板は活性エネルギー線に対して適当な透明性が与えられていなければならない。また、光照射時にマスクを用いて特定の部分のみを重合させた後、電場や磁場又は温度等の条件を変化させることにより、未重合部分の配向状態を変化させて、さらに活性エネルギー線を照射して重合させるという手段を用いても良い。また、照射時の温度は、本発明の重合性液晶組成物の液晶状態が保持される温度範囲内であることが好ましい。特に、光重合によって光学異方体を製造しようとする場合には、意図しない熱重合の誘起を避ける意味からも可能な限り室温に近い温度、即ち、典型的には２５℃での温度で重合させることが好ましい。活性エネルギー線の強度は、０．１ｍＷ／ｃｍ^２〜２Ｗ／ｃｍ^２が好ましい。強度が０．１ｍＷ／ｃｍ^２以下の場合、光重合を完了させるのに多大な時間が必要になり生産性が悪化してしまい、２Ｗ／ｃｍ^２以上の場合、重合性液晶化合物又は重合性液晶組成物が劣化してしまう危険がある。 As a method of polymerizing the polymerizable liquid crystal composition of the present invention, since rapid progress of polymerization is desirable, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron beams is preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays. Moreover, after polymerizing only a specific part using a mask at the time of light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization. Moreover, it is preferable that the temperature at the time of irradiation is in the temperature range in which the liquid crystal state of the polymerizable liquid crystal composition of the present invention is maintained. In particular, when an optical anisotropic body is to be produced by photopolymerization, the polymerization is carried out at a temperature as close to room temperature as possible from the viewpoint of avoiding unintentional induction of thermal polymerization, that is, typically at a temperature of 25 ° C. It is preferable to make it. The intensity of the active energy ray is preferably 0.1 mW / cm ^{2 to 2} W / cm ² . When the intensity is 0.1 mW / cm ² or less, a great amount of time is required to complete the photopolymerization and the productivity is deteriorated. When the intensity is 2 W / cm ² or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal is used. There is a risk that the composition will deteriorate.

重合によって得られた本発明の光学異方体は、初期の特性変化を軽減し、安定的な特性発現を図ることを目的として熱処理を施すこともできる。熱処理の温度は５０〜２５０℃の範囲で、また熱処理時間は３０秒〜１２時間の範囲が好ましい。 The optical anisotropic body of the present invention obtained by polymerization can be subjected to heat treatment for the purpose of reducing initial characteristic changes and achieving stable characteristic expression. The heat treatment temperature is preferably in the range of 50 to 250 ° C., and the heat treatment time is preferably in the range of 30 seconds to 12 hours.

このような方法によって製造される本発明の光学異方体は、基板から剥離して単体で用いても、剥離せずに用いても良い。また、得られた光学異方体を積層しても、他の基板に貼り合わせて用いてもよい。 The optical anisotropic body of the present invention produced by such a method may be peeled off from the substrate and used alone or without peeling. Further, the obtained optical anisotropic bodies may be laminated or bonded to another substrate for use.

以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。また、以下の実施例及び比較例の組成物における「%」は『質量%』を意味する。
（実施例１）
撹拌装置、冷却器及び温度計を備えた反応容器に3-（p-ヒドロキシフェニル）プロピオン酸３３．２ｇ（２４０ミリモル）、ヨウ化カリウム４ｇ、テトラブチルアンモニウムブロミド１ｇ、エタノール４００ｍｌを仕込み室温で攪拌した。水酸化ナトリウム２４ｇの２５％水溶液をゆっくり滴下した。滴下終了後、反応容器を５０℃に保ち、ベンジルブロミド５０ｇ（２８８ミリモル）をゆっくり滴下した。滴下終了後、反応容器を更に７０℃に加温して更に３時間反応させた。反応終了後、１０％塩酸で中和して酢酸エチルで抽出を行い、硫酸ナトリウムで乾燥後、溶媒を濃縮して式（１）に示す化合物（中間体１）を３８ｇ合成した。 EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following examples and comparative examples means “mass%”.
Example 1
A reaction vessel equipped with a stirrer, a condenser and a thermometer was charged with 33.2 g (240 mmol) of 3- (p-hydroxyphenyl) propionic acid, 4 g of potassium iodide, 1 g of tetrabutylammonium bromide, and 400 ml of ethanol and stirred at room temperature. did. A 25% aqueous solution of 24 g of sodium hydroxide was slowly added dropwise. After completion of the dropping, the reaction vessel was kept at 50 ° C., and 50 g (288 mmol) of benzyl bromide was slowly added dropwise. After completion of the dropwise addition, the reaction vessel was further heated to 70 ° C. and further reacted for 3 hours. After completion of the reaction, the mixture was neutralized with 10% hydrochloric acid, extracted with ethyl acetate, dried over sodium sulfate, and the solvent was concentrated to synthesize 38 g of the compound represented by formula (1) (intermediate 1).

次いで、撹拌装置、冷却器及び温度計を備えた反応容器に、上記で合成した（中間体１）２８ｇ（１２３ミリモル）、イソソルビド７．７ｇ（５５ミリモル）、ジメチルアミノピリジン１．８ｇ、塩化メチレン５００ｍｌを仕込こみ、氷冷バスにて５℃以下に反応容器を保ち。窒素ガスの雰囲気下でジイソプロピルカルボジイミド１９ｇ（１５０ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液をろ過した後、ろ液に塩化メチレン２００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、５倍量（重量比）のシリカゲルカラムにより精製を行い式（２）に示す化合物（中間体２）２３ｇを得た。 Then, in a reaction vessel equipped with a stirrer, a condenser and a thermometer, 28 g (123 mmol) of the above synthesized (Intermediate 1), 7.7 g (55 mmol) of isosorbide, 1.8 g of dimethylaminopyridine, methylene chloride Charge 500 ml and keep the reaction vessel at 5 ° C or below with an ice-cooled bath. Under an atmosphere of nitrogen gas, 19 g (150 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction solution was filtered, 200 ml of methylene chloride was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was carried out with a 5-fold amount (weight ratio) silica gel column to obtain 23 g of a compound (intermediate 2) represented by the formula (2).

次いで、撹拌装置備えたオートクレーブ容器に、上記で合成した（中間体２）１１ｇ（１７．７ミリモル）、パラジウムカーボン１ｇ、エタノール１５０ｍｌを仕込み、1気圧の水素にて還元反応（反応温度５０℃、3時間）を行った。反応液をろ過した後、反応溶媒を留去して式（３）に示す化合物（中間体３）７．５ｇを得た。 Next, 11 g (17.7 mmol) of the above synthesized (intermediate 2), 1 g of palladium carbon, and 150 ml of ethanol were charged in an autoclave container equipped with a stirrer, and the reduction reaction (reaction temperature 50 ° C., 3 hours). After the reaction solution was filtered, the reaction solvent was distilled off to obtain 7.5 g of a compound (intermediate 3) represented by the formula (3).

また、撹拌装置、冷却器、及び温度計を備えた反応容器に4-ヒドロキシ安息香酸メチル１２．２ｇ（８０ミリモル）、炭酸エチレン７．８ｇ（９０ミリモル）、テトラブチルアンモニウムブロミド１．６ｇ（５ミリモル）、ジメチルホルムアミド５００ｍｌを仕込み１５時間還流した。反応終了後、塩化メチレン５００ｍｌ加え、純水および飽和食塩水で洗浄した。溶媒を濃縮し、トルエン／ヘキサンの混合溶媒で再結晶を行い、式（４）に示す化合物（中間体４）を１１ｇｇ合成した。 Further, in a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 12.4-g (80 mmol) of methyl 4-hydroxybenzoate, 7.8 g (90 mmol) of ethylene carbonate, 1.6 g of tetrabutylammonium bromide (5 Mmol) and 500 ml of dimethylformamide were charged and refluxed for 15 hours. After completion of the reaction, 500 ml of methylene chloride was added and washed with pure water and saturated brine. The solvent was concentrated and recrystallized with a mixed solvent of toluene / hexane to synthesize 11 mg of the compound represented by formula (4) (intermediate 4).

次いで、撹拌装置、冷却器及び滴下ロートを備えた反応容器に、上記で合成した（中間体４）を１１ｇｇ（５６ミリモル）、水酸化ナトリウム４．３ｇ（１０７ミリモル）、純水５０ｍｌ、エタノール１００ｍｌ仕込み、反応容器を６０℃に加温して２時間反応させた。反応終了後、反応液を酢酸エチル２００ｍｌで洗浄した後、水層に１０％塩酸水溶液を２００ｍｌ加えて結晶を析出させる。ろ過して得られた結晶をトルエンで再結晶を行い、式（５）に示す化合物（中間体５）９．５ｇを得た。 Next, 11 gg (56 mmol) of the above synthesized (intermediate 4), 4.3 g (107 mmol) of sodium hydroxide, 50 ml of pure water, and 100 ml of ethanol were added to a reaction vessel equipped with a stirrer, a cooler and a dropping funnel. The reaction vessel was charged to 60 ° C. and reacted for 2 hours. After completion of the reaction, the reaction solution is washed with 200 ml of ethyl acetate, and then 200 ml of 10% hydrochloric acid aqueous solution is added to the aqueous layer to precipitate crystals. The crystals obtained by filtration were recrystallized from toluene to obtain 9.5 g of a compound (intermediate 5) represented by the formula (5).

更に、撹拌装置、冷却器及び温度計を備えた反応容器に、上記で合成した（中間体５）９．５ｇ（５２ミリモル）、ベンジルブロミド９．７ｇ（５７ミリモル）、炭酸カリウム７．８ｇ（５７ミリモル）、ジメチルホルムアミド２００ｍｌを仕込み、窒素雰囲気下で５０℃で４時間反応させた。反応液をろ過した後、酢酸エチル３００ｍｌを加え、純粋で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させ式（６）に示す化合物（中間体６）１３ｇを得た。 Furthermore, in a reaction vessel equipped with a stirrer, a cooler and a thermometer, 9.5 g (52 mmol) of the above synthesized (intermediate 5), 9.7 g (57 mmol) of benzyl bromide, 7.8 g of potassium carbonate ( 57 mmol) and 200 ml of dimethylformamide were charged and reacted at 50 ° C. for 4 hours under a nitrogen atmosphere. After the reaction solution was filtered, 300 ml of ethyl acetate was added, washed with pure water, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate to obtain 13 g of a compound (intermediate 6) represented by the formula (6). It was.

次いで、撹拌装置、冷却器及び温度計を備えた反応容器に、上記で合成した（中間体６）１０．７ｇ（３９．４ミリモル）、上記中間体（３）７．５ｇ（１９．７ミリモル）、トリフェニルホスフィン１１．４ｇ（４３．３ミリモル）、ＴＨＦ２００ｍｌを仕込こみ、氷冷バスにて５℃以下に反応容器を保つ。窒素ガスの雰囲気下でジイソプロピルアゾジカルボキシレート７．９ｇ（３９．４ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液に酢酸エチル３００ｍｌを加え、純粋で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、ジクロロメタン／メタノールによる再結晶により式（７）に示す化合物（中間体７）を１７ｇ得た。 Subsequently, 10.7 g (39.4 mmol) of the above synthesized (intermediate 6) and 7.5 g (19.7 mmol) of the intermediate (3) were synthesized in a reaction vessel equipped with a stirrer, a cooler and a thermometer. ), 11.4 g (43.3 mmol) of triphenylphosphine and 200 ml of THF are charged, and the reaction vessel is kept at 5 ° C. or lower with an ice-cooled bath. Under an atmosphere of nitrogen gas, 7.9 g (39.4 mmol) of diisopropyl azodicarboxylate was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. To the reaction solution, 300 ml of ethyl acetate was added, washed purely, further washed with saturated saline, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, 17 g of the compound (intermediate 7) represented by the formula (7) was obtained by recrystallization from dichloromethane / methanol.

更に、撹拌装置備えたオートクレーブ容器に、上記で合成した（中間体７）１７ｇ（１８．９ミリモル）、パラジウムカーボン１．５ｇ、エタノール１５０ｍｌを仕込み、1気圧の水素にて還元反応（反応温度５０℃、3時間）を行った。反応液をろ過した後、反応溶媒を留去して式（８）に示す化合物（中間体８）１３．５ｇを得た。 Furthermore, 17 g (18.9 mmol) of the above synthesized (intermediate 7), 1.5 g of palladium carbon, and 150 ml of ethanol were charged in an autoclave container equipped with a stirrer, and the reduction reaction (reaction temperature 50) was performed with 1 atmosphere of hydrogen. C., 3 hours). After filtering the reaction solution, the reaction solvent was distilled off to obtain 13.5 g of a compound (intermediate 8) represented by the formula (8).

上記で合成した（中間体８）１３．５ｇ（１８．９ミリモル）を撹拌装置、冷却器及び温度計を備えた反応容器に仕込み、更にアクリル酸ヒドロキシブチル６．５ｇ（４５．３ミリモル）、ジメチルアミノピリジン５５３ｍｇ、塩化メチレン２００ｍｌを仕込こみ、氷冷バスにて５℃以下に反応容器を保ち。窒素ガスの雰囲気下でジイソプロピルカルボジイミド５．７ｇ（４５．３ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液をろ過した後、ろ液に塩化メチレン２００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、５倍量（重量比）のシリカゲルカラムにより精製を行い式（９）に示す目的の化合物１４ｇを得た。 13.5 g (18.9 mmol) of (Intermediate 8) synthesized above was charged into a reaction vessel equipped with a stirrer, a cooler and a thermometer, and further 6.5 g (45.3 mmol) of hydroxybutyl acrylate, Charge 553 mg of dimethylaminopyridine and 200 ml of methylene chloride and keep the reaction vessel at 5 ° C. or lower with an ice-cooled bath. Under an atmosphere of nitrogen gas, 5.7 g (45.3 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction solution was filtered, 200 ml of methylene chloride was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was performed with a 5-fold amount (weight ratio) silica gel column to obtain 14 g of the desired compound represented by the formula (9).

（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：８．０６−７．９７（ｍ，８Ｈ），７．００−６．９５（ｍ，８Ｈ），６．４７（ｄ，２Ｈ），６．１６（ｑ，２Ｈ），５．８７（ｄ，２Ｈ），５．４６（Ｓ，１Ｈ），５．３９（ｍ，１Ｈ），５．０５（ｔ，１Ｈ），４．５３（ｍ，１Ｈ），４．４０（ｓ，８Ｈ），４．３９（ｍ，４Ｈ）,４．２３（ｍ，４Ｈ），４．０９−４．０５（ｍ，４Ｈ）,１．８５−１．７０（ｍ，８Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１６５．９，１６５．８，１６５．３，１６４．９，１６２．３，１６２．０，１６１．９，１３６．０５，１３１．７６，１３１．６，１３１．４，１３０．６，１２８．４，１２８．０３，１２７．９，１２３．０９，１２２．９，１２２．２４，１１４．２，１１４．１，８６．１，８１．１，７８．２，７４．２，７３．５，７０．６，６６．４，６６．３，６４．２，６４．０，２５．５
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６０，１６５２−１６２２，８０９
（融点）１１１℃
式（９）で表される化合物は、融点が１１１℃と低く、他の液晶性化合物との溶解性に優れる。 (Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 8.06-7.97 (m, 8H), 7.00-6.95 (m, 8H), 6.47 (d, 2H), 6. 16 (q, 2H), 5.87 (d, 2H), 5.46 (S, 1H), 5.39 (m, 1H), 5.05 (t, 1H), 4.53 (m, 1H) ), 4.40 (s, 8H), 4.39 (m, 4H), 4.23 (m, 4H), 4.09-4.05 (m, 4H), 1.85-1.70 ( m, 8H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 165.9, 165.8, 165.3, 164.9, 162.3, 162.0, 161.9, 136.05, 131.76, 131 6, 131.4, 130.6, 128.4, 128.03, 127.9, 123.09, 122.9, 122.24, 114.2, 114.1, 86.1, 81.1 78.2, 74.2, 73.5, 70.6, 66.4, 66.3, 64.2, 64.0, 25.5.
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809
(Melting point) 111 ° C
The compound represented by the formula (9) has a low melting point of 111 ° C. and is excellent in solubility with other liquid crystal compounds.

（実施例２）
上記で合成した（中間体８）１３．５ｇ（１８．９ミリモル）を撹拌装置、冷却器及び温度計を備えた反応容器に仕込み、更にアクリル酸ヒドロキシエチル５．２ｇ（４５．３ミリモル）、ジメチルアミノピリジン５５３ｍｇ、塩化メチレン２００ｍｌを仕込こみ、氷冷バスにて５℃以下に反応容器を保ち。窒素ガスの雰囲気下でジイソプロピルカルボジイミド５．７ｇ（４５．３ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液をろ過した後、ろ液に塩化メチレン２００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、５倍量（重量比）のシリカゲルカラムにより精製を行い式（１０）に示す目的の化合物１１ｇを得た。 (Example 2)
13.5 g (18.9 mmol) synthesized above (Intermediate 8) was charged into a reaction vessel equipped with a stirrer, a condenser and a thermometer, and further 5.2 g (45.3 mmol) of hydroxyethyl acrylate, Charge 553 mg of dimethylaminopyridine and 200 ml of methylene chloride and keep the reaction vessel at 5 ° C. or lower with an ice-cooled bath. Under an atmosphere of nitrogen gas, 5.7 g (45.3 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction solution was filtered, 200 ml of methylene chloride was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was carried out with a 5 times amount (weight ratio) silica gel column to obtain 11 g of the objective compound represented by the formula (10).

（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：８．０６−７．９７（ｍ，８Ｈ），７．００−６．９５（ｍ，８Ｈ），６．４７（ｄ，２Ｈ），６．１６（ｑ，２Ｈ），５．８７（ｄ，２Ｈ），５．４６（Ｓ，１Ｈ），５．３９（ｍ，１Ｈ），５．０５（ｔ，１Ｈ），４．５３（ｍ，１Ｈ），４．４９（ｍ，８Ｈ），４．４０（ｓ，８Ｈ），４．０９−４．００（ｍ，４Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１６５．７，１６５．３，１６４．９，１６２．３，１６２．１，１３１．７，１３１．６，１３１．２，１２７．８，１２２．５，１２２．２，１２２．１，１１４．１，８６．０，８１．１，７８．２，７４．２，７３．５，７０．６，６６．４，６６．３，６２．４，６２．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６０，１６５２−１６２２，８０９
（融点）８６℃
式（１０）で表される化合物は、融点が８６℃と更に低く、他の液晶性化合物との溶解性に優れる。 (Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 8.06-7.97 (m, 8H), 7.00-6.95 (m, 8H), 6.47 (d, 2H), 6. 16 (q, 2H), 5.87 (d, 2H), 5.46 (S, 1H), 5.39 (m, 1H), 5.05 (t, 1H), 4.53 (m, 1H) ), 4.49 (m, 8H), 4.40 (s, 8H), 4.09-4.00 (m, 4H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 165.7, 165.3, 164.9, 162.3, 162.1, 131.7, 131.6, 131.2, 127.8, 122 5, 122.2, 122.1, 114.1, 86.0, 81.1, 78.2, 74.2, 73.5, 70.6, 66.4, 66.3, 62.4 , 62.3
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809
(Melting point) 86 ° C
The compound represented by the formula (10) has an even lower melting point of 86 ° C. and is excellent in solubility with other liquid crystal compounds.

（実施例３）
撹拌装置備えたオートクレーブ容器に、ｐ−ヨード安息香酸エチル３５ｇ（１３４ミリモル）、アクロレイン２０ｇ（３５７ミリモル）、酢酸パラジウム１．２ｇ、テトラブチルアンモニウムクロリド１５．８（１４４ミリモル）、トリエチルアミン３０ｍｌ、Ｎ，Ｎ−ジメチルホムルアミド１５０ｍｌを仕込み、窒素雰囲気下で室温２４時間反応させた。反応終了後、反応液を酢酸エチル５００ｍｌ、純水５００ｍｌで洗浄した後、硫酸ナトリウムで乾燥後、溶媒を濃縮して式（１１）に示す化合物（中間体９）を２３ｇ合成した。 (Example 3)
In an autoclave vessel equipped with a stirrer, 35 g (134 mmol) of ethyl p-iodobenzoate, 20 g (357 mmol) of acrolein, 1.2 g of palladium acetate, 15.8 (144 mmol) of tetrabutylammonium chloride, 30 ml of triethylamine, N, 150 ml of N-dimethylformulamide was charged and reacted at room temperature for 24 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was washed with 500 ml of ethyl acetate and 500 ml of pure water, then dried over sodium sulfate, and the solvent was concentrated to synthesize 23 g of the compound (intermediate 9) represented by the formula (11).

次いで、撹拌装置、冷却器及びを備えた反応容器に、上記で合成した（中間体９）を２３ｇ、ＴＨＦ２５０ｍｌを仕込み、反応容器を５℃以下に冷却後、水素化ホウ素ナトリウム５ｇのエタノール溶液１５０ｍｌを滴下した。滴下終了後、反応容器を室温に戻し、３時間反応させた。反応終了後、飽和塩化アンモニウム水溶液を３００ｍｌ加え、トルエン３００ｍｌで抽出した。純水５００ｍｌで洗浄した後、硫酸ナトリウムで乾燥後、溶媒を濃縮して得られた化合物を、撹拌装置備えたオートクレーブ容器に仕込み、更に、パラジウムカーボン１ｇ、プラチナカーボン１ｇ、メタノール５０ｍｌ、酢酸エチル３００ｍｌを加え、1気圧の水素にて還元反応（室温、５時間）を行った。反応液をろ過した後、反応溶媒を留去して式（１２）に示す化合物（中間体１０）２０．８ｇを得た。 Next, 23 g of the above-prepared (intermediate 9) and 250 ml of THF were charged into a reaction vessel equipped with a stirrer and a cooler, and the reaction vessel was cooled to 5 ° C. or lower, and then an ethanol solution of 5 g of sodium borohydride. 150 ml was added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 3 hours. After completion of the reaction, 300 ml of a saturated aqueous ammonium chloride solution was added and extracted with 300 ml of toluene. After washing with 500 ml of pure water, drying with sodium sulfate and concentrating the solvent, the compound obtained was charged into an autoclave container equipped with a stirrer, and further 1 g of palladium carbon, 1 g of platinum carbon, 50 ml of methanol, 300 ml of ethyl acetate. And a reduction reaction (room temperature, 5 hours) was carried out with 1 atm of hydrogen. After filtering the reaction solution, the reaction solvent was distilled off to obtain 20.8 g of a compound (intermediate 10) represented by the formula (12).

更に、撹拌装置、冷却器、及び温度計を備えた反応容器に上記で合成した（中間体１０）を２０．８ｇ、水酸化ナトリウム１２ｇ、エタノール２００ｍｌ、純水１００ｍｌを仕込み、５０℃で３時間攪拌した。反応終了後、１０％塩酸水溶液を３００ｍｌ加えて結晶を析出させた。ろ過して得られた結晶を真空乾燥させた後、得られた化合物を撹拌装置、冷却器、及び温度計を備えた反応容器に加え、更に、炭酸カリウム１２ｇ、Ｎ，Ｎ−ジメチルホムルアミド１５０ｍｌを仕込み、窒素雰囲気下で３０分攪拌した。次いで、塩化ベンジル１３ｇ（１０２ミリモル）を滴下し、反応容器を７０℃に加温して６時間反応させた。反応終了後、反応容器に純水４５０ｍｌ加え結晶を析出させた。ろ過して得られた結晶を真空乾燥させ、式（１３）に示す化合物（中間体１１）２５ｇを得た。 Furthermore, 20.8 g of the above synthesized (intermediate 10), 12 g of sodium hydroxide, 200 ml of ethanol, and 100 ml of pure water were charged into a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and the mixture was charged at 50 ° C. for 3 hours. Stir. After completion of the reaction, 300 ml of 10% aqueous hydrochloric acid solution was added to precipitate crystals. After the crystals obtained by filtration were vacuum dried, the obtained compound was added to a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and further 12 g of potassium carbonate, N, N-dimethylformulamide. 150 ml was charged and stirred for 30 minutes under a nitrogen atmosphere. Next, 13 g (102 mmol) of benzyl chloride was added dropwise, and the reaction vessel was heated to 70 ° C. and reacted for 6 hours. After completion of the reaction, 450 ml of pure water was added to the reaction vessel to precipitate crystals. The crystal obtained by filtration was vacuum-dried to obtain 25 g of a compound (intermediate 11) represented by the formula (13).

次いで、撹拌装置、冷却器及び温度計を備えた反応容器に、上記で合成した（中間体１１）１５．４ｇ（５７．０ミリモル）、上記中間体（３）１０ｇ（２５．８ミリモル）、トリフェニルホスフィン１６．４ｇ（６２．５ミリモル）、ＴＨＦ２００ｍｌを仕込こみ、氷冷バスにて５℃以下に反応容器を保つ。窒素ガスの雰囲気下でジイソプロピルアゾジカルボキシレート１１．４ｇ（５７．０ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液に純水５ｍｌ加え攪拌後、メタノール３００ｍｌ加え結晶を析出させた。ろ過して得られた結晶を酢酸エチル／メタノールで再結晶した後に真空乾燥させ、式（１４）に示す化合物（中間体１２）を２０ｇ得た。 Next, in a reaction vessel equipped with a stirrer, a cooler and a thermometer, 15.4 g (57.0 mmol) of the above synthesized (intermediate 11), 10 g (25.8 mmol) of the above intermediate (3), Charge 16.4 g (62.5 mmol) of triphenylphosphine and 200 ml of THF, and keep the reaction vessel at 5 ° C. or lower with an ice-cooled bath. In an atmosphere of nitrogen gas, 11.4 g (57.0 mmol) of diisopropyl azodicarboxylate was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After adding 5 ml of pure water to the reaction liquid and stirring, 300 ml of methanol was added to precipitate crystals. The crystals obtained by filtration were recrystallized from ethyl acetate / methanol and then vacuum-dried to obtain 20 g of a compound (intermediate 12) represented by the formula (14).

次いで、撹拌装置備えたオートクレーブ容器に仕込み、更に、パラジウムカーボン１ｇ、プラチナカーボン１ｇ、メタノール５０ｍｌ、酢酸エチル３００ｍｌを加え、1気圧の水素にて還元反応（室温、５時間）を行った。反応液をろ過した後、反応溶媒を留去して式（１２）に示す化合物（中間体１０）２０．８ｇを得た。 Next, the mixture was charged into an autoclave container equipped with a stirrer, and 1 g of palladium carbon, 1 g of platinum carbon, 50 ml of methanol, and 300 ml of ethyl acetate were added, and a reduction reaction (room temperature, 5 hours) was performed with 1 atmosphere of hydrogen. After filtering the reaction solution, the reaction solvent was distilled off to obtain 20.8 g of a compound (intermediate 10) represented by the formula (12).

上記で合成した（中間体８）１３．５ｇ（１８．９ミリモル）を撹拌装置、冷却器及び温度計を備えた反応容器に仕込み、更にアクリル酸ヒドロキシブチル６．５ｇ（４５．３ミリモル）、ジメチルアミノピリジン５５３ｍｇ、塩化メチレン２００ｍｌを仕込こみ、氷冷バスにて５℃以下に反応容器を保ち。窒素ガスの雰囲気下でジイソプロピルカルボジイミド５．７ｇ（４５．３ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液をろ過した後、ろ液に塩化メチレン２００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、５倍量（重量比）のシリカゲルカラムにより精製を行い式（１６）に示す目的の化合物１４ｇを得た。 13.5 g (18.9 mmol) of (Intermediate 8) synthesized above was charged into a reaction vessel equipped with a stirrer, a cooler and a thermometer, and further 6.5 g (45.3 mmol) of hydroxybutyl acrylate, Charge 553 mg of dimethylaminopyridine and 200 ml of methylene chloride and keep the reaction vessel at 5 ° C. or lower with an ice-cooled bath. Under an atmosphere of nitrogen gas, 5.7 g (45.3 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction solution was filtered, 200 ml of methylene chloride was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was performed with a 5-fold amount (weight ratio) silica gel column to obtain 14 g of the desired compound represented by the formula (16).

（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：７．９７（ｍ，８Ｈ），７．２９（ｍ，４Ｈ），６．９２（ｍ，４Ｈ），６．４７（ｄ，２Ｈ），６．１６（ｑ，２Ｈ），５．８７（ｄ，２Ｈ），５．４５（Ｓ，１Ｈ），５．３９（ｍ，１Ｈ），５．０５（ｔ，１Ｈ），４．５３（ｍ，１Ｈ），４．３６（ｍ，４Ｈ），４．２２（ｍ，４Ｈ）,４．１０−３．９８（ｍ，８Ｈ），２．８８（ｍ，４Ｈ），２．１４（ｍ，４Ｈ），１．８６−１．８５（ｍ，８Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１６６．１，１６５．８，１６５．３，１６４．９，１６２．７，１６２．７，１４６．５，１３１．６，１３０．５．１２９．６，１２８．３．１２７．９，１２１．６，１１３．９，８６．０，８１．０，７８．１，７７．３，１３０．６，１２８．４，１２８．０３，１２７．９，１２３．０９，１２２．９，１２２．２４，１１４．２，１１４．１，８６．１，８１．１，７８．２，７４．１，７３．４，７０．６，６６．７，６４．２，６３．９，３２．０，３０．２，２５．４
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６０，１６５２−１６２２，８０９
（融点）８２℃ (Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 7.97 (m, 8H), 7.29 (m, 4H), 6.92 (m, 4H), 6.47 (d, 2H), 6 .16 (q, 2H), 5.87 (d, 2H), 5.45 (S, 1H), 5.39 (m, 1H), 5.05 (t, 1H), 4.53 (m, 1H), 4.36 (m, 4H), 4.22 (m, 4H), 4.10-3.98 (m, 8H), 2.88 (m, 4H), 2.14 (m, 4H) ), 1.86-1.85 (m, 8H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 166.1, 165.8, 165.3, 164.9, 162.7, 162.7, 146.5, 131.6, 130.5.129 .6, 128.33.1127.9, 121.6, 113.9, 86.0, 81.0, 78.1, 77.3, 130.6, 128.4, 128.03, 127.9 , 123.09, 122.9, 122.24, 114.2, 114.1, 86.1, 81.1, 78.2, 74.1, 73.4, 70.6, 66.7, 64 .2, 63.9, 32.0, 30.2, 25.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809
(Melting point) 82 ° C

（比較例１）
撹拌装置、冷却器、及び温度計を備えた反応容器に4-（4-ヒドロキシフェニル）安息香酸２１．４ｇ（１００ミリモル）、ヨウ化カリウム２。５ｇ、テトラブチルアンモニウムブロミド０．７ｇ、エタノール４００ｍｌを仕込み室温で攪拌した。水酸化ナトリウム１２ｇの２５％水溶液をゆっくり滴下した。滴下終了後、反応容器を５０℃に保ち、6-クロロプロパノール２０ｇ（１５０ミリモル）をゆっくり滴下した。滴下終了後、反応容器を更に７０℃に加温して更に３時間反応させた。反応終了後、１０％塩酸で中和して酢酸エチルで抽出を行い、硫酸ナトリウムで乾燥後、溶媒を濃縮して式（１７）に示す化合物（中間体１７）を２２ｇ合成した。 (Comparative Example 1)
In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 21.4 g (100 mmol) of 4- (4-hydroxyphenyl) benzoic acid, 2.5 g of potassium iodide, 0.7 g of tetrabutylammonium bromide, 400 ml of ethanol Was stirred at room temperature. A 25% aqueous solution of 12 g of sodium hydroxide was slowly added dropwise. After completion of the dropping, the reaction vessel was kept at 50 ° C., and 20 g (150 mmol) of 6-chloropropanol was slowly added dropwise. After completion of the dropwise addition, the reaction vessel was further heated to 70 ° C. and further reacted for 3 hours. After completion of the reaction, the mixture was neutralized with 10% hydrochloric acid, extracted with ethyl acetate, dried over sodium sulfate, and the solvent was concentrated to synthesize 22 g of the compound represented by formula (17) (intermediate 17).

次いで、撹拌装置、冷却器及びディーンスタックを備えた反応容器に、上記で合成した中間体１７を２２ｇ（７１ミリモル）、アクリル酸１０ｇ（１４０ミリモル）、ｐ−トルエンスルホン酸１ｇ、トルエン１００ｍｌを仕込んだ。反応容器を加熱してトルエン還流させそのまま４時間反応させた。反応終了後、反応液を飽和炭酸水素ナトリウムで洗浄した後、１０％塩酸水溶液で中和、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去して、式（１８）に示す化合物（中間体１８）１９ｇを得た。 Next, 22 g (71 mmol) of the intermediate 17 synthesized above, 10 g (140 mmol) of acrylic acid, 1 g of p-toluenesulfonic acid, and 100 ml of toluene were charged into a reaction vessel equipped with a stirrer, a cooler, and a Dean stack. It is. The reaction vessel was heated to reflux with toluene and allowed to react for 4 hours. After completion of the reaction, the reaction solution was washed with saturated sodium hydrogen carbonate, neutralized with 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 19 g of a compound (intermediate 18) represented by the formula (18).

更に、撹拌装置、冷却器及び温度計を備えた反応容器に、上記で合成した中間体９１９ｇ（５１ミリモル）、イソソルビド３．８ｇ（２７ミリモル）、ジメチルアミノピリジン０．９ｇ、塩化メチレン２００ｍｌを仕込こみ、氷冷バスにて５℃以下に反応容器を保ち。窒素ガスの雰囲気下でジイソプロピルカルボジイミド９ｇ（６．３ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液をろ過した後、ろ液に塩化メチレン１００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、シリカゲルカラムおよび再結晶により精製を行い式（１９）に示す目的の化合物１４ｇを得た。この化合物の融点は１５０℃以上であり測定できなかった。 Furthermore, in a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 919 g (51 mmol) of the intermediate 909 synthesized above, 3.8 g (27 mmol) of isosorbide, 0.9 g of dimethylaminopyridine, and 200 ml of methylene chloride were added. Charge and keep the reaction vessel at 5 ° C or lower with an ice-cooled bath. Under an atmosphere of nitrogen gas, 9 g (6.3 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction solution was filtered, 100 ml of methylene chloride was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was performed by silica gel column and recrystallization to obtain 14 g of the desired compound represented by the formula (19). The melting point of this compound was 150 ° C. or higher and could not be measured.

（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：８．１３（ｄ，４Ｈ），８．１２（ｄ，４Ｈ），７．５０（ｍ，４Ｈ），７．１（ｄ，４Ｈ），６．５５（ｄ，２Ｈ），６．１５（ｑ，２Ｈ），５．８５（ｄ，２Ｈ），５．６５（ｄｄ，２Ｈ），５．３５（ｓ，２Ｈ），４．５０（ｔ，４Ｈ），４．３０（ｔ，４Ｈ），４．０３（ｓ，４Ｈ），３．９８（ｍ，２Ｈ），３．９３（ｍ，２Ｈ），２．９６（ｍ，４Ｈ），２．６６（ｍ，４Ｈ），１．８３（ｍ，４Ｈ），１．７１（ｍ，４Ｈ），１．５５−１．４５（ｍ，８Ｈ）
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６０，１６５２−１６２２，８０９
（融点）＞１５０℃
比較例１記載の式（１９）で表される化合物は、本願発明の化合物の特徴となるイソソルビド間から数えて一つめの環と二つめに環の間のエーテル結合を有する連結基を持たない。そのため、融点が高く他の化合物との溶解性にも問題があった。 (Physical property value)
¹ H-NMR (solvent: chloroform): δ: 8.13 (d, 4H), 8.12 (d, 4H), 7.50 (m, 4H), 7.1 (d, 4H), 6 .55 (d, 2H), 6.15 (q, 2H), 5.85 (d, 2H), 5.65 (dd, 2H), 5.35 (s, 2H), 4.50 (t, 4H), 4.30 (t, 4H), 4.03 (s, 4H), 3.98 (m, 2H), 3.93 (m, 2H), 2.96 (m, 4H), 2. 66 (m, 4H), 1.83 (m, 4H), 1.71 (m, 4H), 1.55-1.45 (m, 8H)
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809
(Melting point)> 150 ° C.
The compound represented by the formula (19) described in Comparative Example 1 does not have a linking group having an ether bond between the first ring and the second ring counted from the isosorbide characteristic of the compound of the present invention. . Therefore, the melting point is high, and there is a problem in solubility with other compounds.

（実施例４）重合性液晶組成物の調製
以下に示す組成の重合性液晶組成物（組成物１）を調製した。 (Example 4) Preparation of polymerizable liquid crystal composition A polymerizable liquid crystal composition (composition 1) having the following composition was prepared.

重合性液晶組成物は、良好な相溶安定性を有し、コレステリック液晶相を示した。この組成物に光重合開始剤イルガキュアー６５１（チバスペシャリティーケミカル社製）を1%分添加して重合性液晶組成物（組成物２）を調製した。この組成物２を、真空注入法により、縦5cm、横5cm、ギャップ5μｍのポリイミド付きセルに注入した。これに高圧水銀ランプを用いて4mW/cm2の紫外線を120秒間照射したところ、組成物２が均一な配向状態を保ったまま重合し、光学異方体が得られた。この光学異方体は良好な円偏光特性を有していた。 The polymerizable liquid crystal composition had good compatibility stability and exhibited a cholesteric liquid crystal phase. A photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) was added to this composition in an amount of 1% to prepare a polymerizable liquid crystal composition (Composition 2). This composition 2 was injected into a cell with polyimide having a length of 5 cm, a width of 5 cm, and a gap of 5 μm by a vacuum injection method. When this was irradiated with ultraviolet rays of 4 mW / cm 2 for 120 seconds using a high-pressure mercury lamp, the composition 2 polymerized while maintaining a uniform orientation, and an optically anisotropic substance was obtained. This optical anisotropic body had good circular polarization characteristics.

Claims

Formula (I)

(In the formula, ^{R 1} and ^{R 2} represent independently of one another, are a polymerizable group, ^{S 1} and ^{S 2} represents a spacer group or a single bond independently from each other, ^{Y 1} and ^{Y 2} are independently from each other -O _{_{-, - S -, - OCH}} 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - OCOO -, - CO-NR 11 -, - NR 11 -CO -, - SCH 2 _{-, - CH 2 S -,} - CH = CH-COO -, - OOC-CH = CH -, - COOC 2 H 4 -, - CH 2 H 4 COO- or a single bond, ^{X 1} and ^{X 2} Independently of each other, —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —OCOO—, —CO—NR ¹¹ —, —NR ¹¹ _{_{-CO -, - SCH 2 -,}} - CH 2 S -, - CH = CH-COO -, - OOC-CH ═CH—, —NR ¹¹ —CO—, —CO—CH═CH—, —CH ₂ —, —C ₂ H ₄ —, —CF ₂ —, —CF ₂ O—, —OCF ₂ —, —CF ₂ _{_{_{_{CH 2 -, - CH 2 CF}}}} 2 -, - CF 2 CF 2 -, - CH = N -, - N = CH -, - N = N -, - CH = CH -, - CF = CH -, - CH ═CF—, —C≡C—, —C ₂ H ₄ COO—, —COOC ₂ H ₄ — or a single bond, and B ¹ and B ² are independently of each other, —O—, —S—, — _{_{OCH 2 -, - CH 2 O}} -, - CO -, - COO -, - OCO -, - OCOO -, - CO-NR 11 -, - NR 11 -CO -, - SCH 2 -, - CH 2 S- ^{, -CH = CH-COO -,} - OOC-CH = CH -, - NR 11 -CO -, - CO-CH = CH -, - CH 2 -, - C 2 H _{_{_{_{4 -, - CF 2 -,}}}} - CF 2 O -, - OCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, - CH = N -, - N = CH -, - N = N -, - CH = CH -, - CF = CH -, - CH = CF -, - C≡C -, - C 2 H 4 COO -, - COOC 2 H 4 -, - OC 2 H ₄ O—, or —OC ₃ H ₆ —, —C ₃ H ₆ O— or a single bond, but at least one of B ¹ and B ² is —OC ₂ H ₄ O— or —OC ₃ H _6- , -C ₃ H ₆ O-, (in Y ¹ , Y ² , B ¹ , B ² , X ¹ and X ² , R ¹¹ independently represents an alkyl group having 1 to 4 carbon atoms. . ), A ¹ , A ² , A ³ and A ⁴ are each independently 1,4-cyclohexylene group, 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl Group, naphthalene-2,6-diyl group, tetrahydronaphthalene-2,6-diyl group, 1,3-dioxane-2,5-diyl group, A ¹ , A ² , A ³ and A ⁴ represent each other Independently substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen, a cyano group, or a nitro group, and Z ¹ is —CO—, —CH═CH—CO—, —CH ₂ —, —C ₂ H ₄ —, —CF ₂ —, —NR ¹¹ —CO— or a single bond is represented, and Z ² represents —OC—, —OC—CH═CH—, —CH ₂ —, —C ₂ H _4. _{-, - CF 2 -, -} CO-NR 11 - or a single bond M represents 1, 2 or 3, and n represents 0, 1, 2 or 3. The polymerizable chiral compound represented by this.

A ¹ , A ² , A ³ and A ⁴ are each independently 1,4-cyclohexylene group, 1,4-phenylene group, naphthalene-2,6-diyl group, tetrahydronaphthalene-2,6-diyl group Or a 1,3-dioxane-2,5-diyl group, wherein A ¹ , A ² , A ³ and A ⁴ are unsubstituted or a hydrogen atom in the group is an alkyl group, a halogenated alkyl group, an alkoxy group The polymerizable chiral compound according to claim 1, which may be substituted with a group, a halogen or a cyano group, and n represents 1, 2 or 3.

Y ¹ and Y ² are independently of each other —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—COO—, _{_{-OOC-CH = CH -, -}} COOC 2 H 4 -, - CH 2 H 4 COO- or a single bond, ^{X 1} and ^{X 2} are independently from each _{other, -O -, - OCH 2 -} , - CH ₂ O—, —COO—, —OCO—, —CH═CH—COO—, —OOC—CH═CH—, —CO—CH═CH—, —CH ₂ —, —C ₂ H ₄ —, —N ═N—, —CH═CH—, —C≡C—, —C ₂ H ₄ COO—, —COOC ₂ H ₄ — or a single bond, and B ¹ and B ² independently of each other, —OC ₂ H ₄ O-, or _{_{_{-OC 3 H 6 -, - C}}} 3 H 6 claim 1 or 2 polymerizable chiral compound according representing the O-

The spacer group in S ¹ and S ² represents an alkylene group having 2 to 10 carbon atoms in which a carbon atom may be replaced with an oxygen atom, assuming that oxygen atoms are not directly bonded to each other. The polymerizable chiral compound.

A liquid crystal composition containing the polymerizable chiral compound according to claim 1.

An optical anisotropic body using the liquid crystal composition according to claim 5.

An optical element using the liquid crystal composition according to claim 5.