JP2017226616A - Polymerizable compound and optical anisotropic material - Google Patents

Polymerizable compound and optical anisotropic material Download PDF

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JP2017226616A
JP2017226616A JP2016123541A JP2016123541A JP2017226616A JP 2017226616 A JP2017226616 A JP 2017226616A JP 2016123541 A JP2016123541 A JP 2016123541A JP 2016123541 A JP2016123541 A JP 2016123541A JP 2017226616 A JP2017226616 A JP 2017226616A
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JP6769131B2 (en
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雅弘 堀口
Masahiro Horiguchi
雅弘 堀口
青木　良夫
Yoshio Aoki
良夫 青木
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Dainippon Ink and Chemicals Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable compound having high storage stability when added to a polymerizable composition, less likely causing an alignment defect when a film type polymerized product is produced by using the polymerizable composition, and less likely causing discoloration of a film-like polymerized product obtained therefrom even when the product is irradiated with UV light for a long time, and to provide a polymer obtained by polymerizing the above polymerizable composition, and an optical anisotropic material using the polymer.SOLUTION: The present invention provides a compound represented by general formula (I), and also provides a polymerizable composition comprising the above compound, a polymer obtained by polymerizing the composition, and an optical anisotropic material or the like using the polymer.SELECTED DRAWING: None

Description

本発明は重合性基を有する化合物、当該化合物を含有する重合性組成物、重合性液晶組成物及び当該重合性液晶組成物を重合することにより得られる重合体を用いた光学異方体に関する。   The present invention relates to a compound having a polymerizable group, a polymerizable composition containing the compound, a polymerizable liquid crystal composition, and an optical anisotropic body using a polymer obtained by polymerizing the polymerizable liquid crystal composition.

重合性化合物は種々のフィルムに使用される。例えば、重合性化合物を液晶状態で配列させた後、重合させることにより、均一な配向を有するフィルムを作製することが可能である。このようにして作製したフィルムは、液晶ディスプレイに必要な偏光板、位相差板などに使用することができる。また、重合性化合物はコレステリック構造を有するフィルムの作製にも使用できる。特に、屈折率異方性（Δｎ）の低い重合性液晶化合物は、選択反射波長幅の狭いコレステリック相を有するフィルム用の材料として有用である。多くの場合、要求される光学特性、重合速度、溶解性、融点、ガラス転移温度、フィルムの透明性、機械的強度、表面硬度、耐熱性及び耐光性を満たすために、２種類以上の重合性化合物からなる組成物が使用される。その際、使用する重合性化合物には、他の特性に悪影響を及ぼすことなく、組成物に良好な物性をもたらすことが求められる。特に、コレステリック構造を有するフィルムの作製を目的とする場合、広い温度範囲でネマチック相又はコレステリック相として存在でき、かつ高いネマチック相又はコレステリック相液晶配向性を有する重合性化合物が必要である。   Polymerizable compounds are used in various films. For example, it is possible to produce a film having a uniform orientation by aligning a polymerizable compound in a liquid crystal state and then polymerizing it. Thus, the produced film can be used for a polarizing plate, a phase difference plate, etc. which are required for a liquid crystal display. The polymerizable compound can also be used to produce a film having a cholesteric structure. In particular, a polymerizable liquid crystal compound having a low refractive index anisotropy (Δn) is useful as a material for a film having a cholesteric phase having a narrow selective reflection wavelength width. In many cases, two or more types of polymerizability are required to satisfy the required optical properties, polymerization rate, solubility, melting point, glass transition temperature, film transparency, mechanical strength, surface hardness, heat resistance and light resistance. Compositions consisting of compounds are used. At that time, the polymerizable compound to be used is required to bring good physical properties to the composition without adversely affecting other properties. In particular, when the purpose is to produce a film having a cholesteric structure, a polymerizable compound that can exist as a nematic phase or a cholesteric phase in a wide temperature range and has a high nematic phase or cholesteric phase liquid crystal orientation is required.

重合性化合物を含有する重合性組成物をディスプレイ等の光学フィルム材料として使用する場合、重合性組成物を基材に塗布し重合させた際、配向欠陥が少ないことが好ましい。また、プロセス上の観点においては、重合性組成物を長期間保管しても成分中の重合性組成物が析出することが無く、高い保存安定性を有することが好ましい。また、光学フィルムをモバイル機器に使用する場合、紫外光を長時間照射した場合に変色が起こりにくいことが好ましい。しかしながら、従来知られていた化合物は、重合性組成物に添加し長期間保管した場合に析出が生じる問題や、フィルムを作製した場合に配向欠陥が多く生じる問題、得られたフィルムに長時間紫外光を照射した場合に変色が起こりやすいという問題があった（特許文献１から３）そのため、このような問題を解決することができる重合性化合物の開発が求められていた。   When a polymerizable composition containing a polymerizable compound is used as an optical film material for a display or the like, it is preferable that there are few orientation defects when the polymerizable composition is applied to a substrate and polymerized. Further, from the viewpoint of the process, it is preferable that the polymerizable composition in the component does not precipitate even when the polymerizable composition is stored for a long period of time and has high storage stability. Further, when the optical film is used in a mobile device, it is preferable that discoloration hardly occurs when ultraviolet light is irradiated for a long time. However, conventionally known compounds have a problem of precipitation when added to a polymerizable composition and stored for a long period of time, a problem of many alignment defects when a film is produced, and a long-time ultraviolet irradiation on the obtained film. There has been a problem that discoloration is likely to occur when irradiated with light (Patent Documents 1 to 3). Therefore, development of a polymerizable compound capable of solving such a problem has been demanded.

ＷＯ２００９／１４５３２１Ａ１号公報WO2009 / 145321A1 publication ＵＳ２００９／０２６８１４３Ａ１号公報US2009 / 0268143A1 ＷＯ２００８／０６１６０６Ａ１号公報WO2008 / 061606A1 publication

本発明が解決しようとする課題は、重合性組成物に添加した場合に高い保存安定性を有し、当該重合性組成物を用いてフィルム状の重合物を作製した場合に配向欠陥が生じにくく、得られるフィルム状の重合物に長時間紫外光を照射した場合でも変色が起こりにくい重合性化合物を提供することである。更に、当該重合性組成物を重合させることで得られる重合体及び当該重合体を用いた光学異方体を提供することである。   The problem to be solved by the present invention is that when added to a polymerizable composition, it has high storage stability, and when a film-like polymer is produced using the polymerizable composition, alignment defects are less likely to occur. An object of the present invention is to provide a polymerizable compound that hardly changes color even when the obtained film-like polymer is irradiated with ultraviolet light for a long time. Furthermore, it is providing the polymer obtained by polymerizing the said polymeric composition, and the optical anisotropic body using the said polymer.

本発明者らは、上記課題を解決すべく鋭意研究を行った結果、特定の部分構造を含むメソゲン基を有する重合性化合物の開発に至った。すなわち、本願発明は一般式（Ｉ）で表される化合物を提供し、併せて当該化合物を含有する重合性組成物、当該化合物を用いた樹脂、樹脂添加剤、オイル、フィルター、接着剤、粘着剤、油脂、インキ、医薬品、化粧品、洗剤、建築材料、包装材、液晶材料、有機ＥＬ材料、有機半導体材料、電子材料、表示素子、電子デバイス、通信機器、自動車部品、航空機部品、機械部品、農薬及び食品並びにそれらを使用した製品、重合性液晶組成物、当該重合性液晶組成物を重合させることにより得られる重合体及び当該重合体を用いた光学異方体を提供する。   As a result of intensive studies to solve the above problems, the present inventors have developed a polymerizable compound having a mesogenic group containing a specific partial structure. That is, the present invention provides a compound represented by the general formula (I), a polymerizable composition containing the compound, a resin using the compound, a resin additive, an oil, a filter, an adhesive, and an adhesive. Agents, oils and fats, inks, pharmaceuticals, cosmetics, detergents, building materials, packaging materials, liquid crystal materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, machine parts, Agrochemicals and foods, products using them, polymerizable liquid crystal compositions, polymers obtained by polymerizing the polymerizable liquid crystal compositions, and optical anisotropic bodies using the polymers are provided.

本願発明の化合物は、その他の重合性化合物を含有する重合性組成物に添加した場合に高い保存安定性を有し、フィルム状の重合物を作製した場合に配向欠陥が生じにくく、フィルム状の重合物に長時間紫外光を照射した場合に変色が起こりにくいことから、重合性組成物の構成部材として有用である。また、当該重合性組成物は位相差フィルム、選択反射フィルム等の光学材料の用途に有用である。   The compound of the present invention has high storage stability when added to a polymerizable composition containing another polymerizable compound, and when a film-like polymer is produced, alignment defects are less likely to occur. Since it is difficult for discoloration to occur when the polymer is irradiated with ultraviolet light for a long time, it is useful as a component of the polymerizable composition. Moreover, the said polymeric composition is useful for the use of optical materials, such as a phase difference film and a selective reflection film.

本願発明は特定の構造を有する化合物を提供し、併せて当該化合物を含有する重合性組成物、当該化合物を用いた樹脂、樹脂添加剤、オイル、フィルター、接着剤、粘着剤、油脂、インキ、医薬品、化粧品、洗剤、建築材料、包装材、液晶材料、有機ＥＬ材料、有機半導体材料、電子材料、表示素子、電子デバイス、通信機器、自動車部品、航空機部品、機械部品、農薬及び食品並びにそれらを使用した製品、重合性液晶組成物、当該重合性液晶組成物を重合させることにより得られる重合体及び当該重合体を用いた光学異方体を提供する。   The present invention provides a compound having a specific structure, a polymerizable composition containing the compound, a resin using the compound, a resin additive, an oil, a filter, an adhesive, a pressure-sensitive adhesive, an oil and fat, an ink, Pharmaceuticals, cosmetics, detergents, building materials, packaging materials, liquid crystal materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, machine parts, agricultural chemicals and foodstuffs and the like Provided are a product used, a polymerizable liquid crystal composition, a polymer obtained by polymerizing the polymerizable liquid crystal composition, and an optical anisotropic body using the polymer.

本願発明の化合物は、下記一般式（Ｉ）で表される。   The compound of the present invention is represented by the following general formula (I).

Figure 2017226616
Figure 2017226616

（式中、Ｐ１及びＰ２は各々独立してラジカル重合、カチオン重合又はアニオン重合により重合する基を表し、
Ｓｐ１及びＳｐ２は各々独立してスペーサー基を表すが、Ｓｐ１が複数存在する場合それらは同一であっても異なっていても良く、Ｓｐ２が複数存在する場合それらは同一であっても異なっていても良く、
Ｘ１及びＸ２は各々独立して−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｓ−、−ＳＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−、−ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−又は単結合を表すが、Ｘ１が複数存在する場合それらは同一であっても異なっていても良く、Ｘ２が複数存在する場合それらは同一であっても異なっていても良く、
ｋ１及びｋ２は０から１０の整数を表し、
Ａ１は下記の式（Ａ−１）から式（Ａ−７） (Wherein P 1 and P 2 each independently represent a group that is polymerized by radical polymerization, cationic polymerization or anionic polymerization;
Sp 1 and Sp 2 each independently represent a spacer group, but when there are a plurality of Sp 1, they may be the same or different, and when there are a plurality of Sp 2, they may be the same. May be different,
X 1 and X 2 are each independently —O—, —S—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —CO—S—, —S—. CO -, - O-CO- O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S- , -SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO- CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO —, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond. But they if X 1 there are a plurality may be the same or different and they if X 2 there are a plurality may be the same or different and
k1 and k2 represent an integer of 0 to 10,
A 1 is the following formula (A-1) to formula (A-7)

Figure 2017226616
Figure 2017226616

（式中、これらの基は無置換であるか又は１つ以上の置換基Ｌによって置換されても良い。）から選ばれる基を表し、
Ｌはフッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、ニトロ基、シアノ基、イソシアノ基、アミノ基、ヒドロキシル基、メルカプト基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、トリメチルシリル基、ジメチルシリル基、チオイソシアノ基、置換されていても良いフェニル基、置換されていても良いフェニルアルキル基、置換されていても良いシクロヘキシルアルキル基、又は、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＲ０−、−ＮＲ０−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＲ０＝Ｎ−、−Ｎ＝ＣＲ０−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−（式中、Ｒ０は水素原子又は炭素原子数１から８のアルキル基を表す。）によって置換されても良い炭素原子数１から２０の直鎖状又は分岐状アルキル基を表すが、当該アルキル基中の任意の水素原子はフッ素原子に置換されても良く、若しくは、ＬはＰＬ−（ＳｐＬ−ＸＬ）ｋＬ−で表される基を表しても良く、ここでＰＬはラジカル重合、カチオン重合又はアニオン重合により重合する基を表し、ＳｐＬはスペーサー基又は単結合を表すが、ＳｐＬが複数存在する場合それらは同一であっても異なっていても良く、ＸＬは−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｓ−、−ＳＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−、−ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−又は単結合を表すが、ＸＬが複数存在する場合それらは同一であっても異なっていても良く、ｋＬは０から１０の整数を表し、化合物内にＬが複数存在する場合それらは同一であっても異なっていても良く、
Ｂ１は下記の式（Ｂ−１）から式（Ｂ−１０） (Wherein these groups are unsubstituted or may be substituted by one or more substituents L),
L is fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, Diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, optionally substituted phenyl group, optionally substituted phenylalkyl group, optionally substituted cyclohexylalkyl group, or one —CH 2- or two or more non-adjacent —CH 2 — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO. -, - OCO-O -, - CO-NR 0 -, - NR 0 -CO -, - CH = CH-COO -, - CH = CH-OCO -, - C O-CH = CH -, - OCO-CH = CH -, - CH = CH -, - N = N -, - CR 0 = N -, - N = CR 0 -, - CH = N-N = CH- , —CF═CF— or —C≡C— (wherein R 0 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and is a straight chain having 1 to 20 carbon atoms. A hydrogen atom in the alkyl group may be substituted with a fluorine atom, or L is a group represented by P L- (Sp L -X L ) kL-. Where P L represents a group that is polymerized by radical polymerization, cationic polymerization, or anionic polymerization, and Sp L represents a spacer group or a single bond, but when there are a plurality of Sp L, they are the same. be different at best, X L is -O -, - S -, - OCH 2 , -CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO- , —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH═CH—COO—, —CH═CH—OCO—, -COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 - , - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, they if X L there are a plurality be the same or different KL represents an integer of 0 to 10, and when a plurality of L are present in the compound, they may be the same or different,
B 1 represents expression from the following formula (B-1) (B- 10)

Figure 2017226616
Figure 2017226616

（式中、これらの基は無置換であるか又は１つ以上の前記置換基Ｌによって置換されても良い。）から選ばれる基を表し、
Ｚ１は−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＯＣＯ−ＮＨ−、−ＮＨ−ＣＯＯ−、−ＮＨ−ＣＯ−ＮＨ−、−ＮＨ−Ｏ−、−Ｏ−ＮＨ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＦ２Ｓ−、−ＳＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−、−ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−を表すが、一般式中、−Ｏ−Ｏ−結合を含まない。）
一般式（Ｉ）において、Ｐ１及びＰ２は各々独立してラジカル重合、カチオン重合又はアニオン重合により重合する基を表すが、各々独立して下記の式（Ｐ−１）から式（Ｐ−２０） (Wherein these groups are unsubstituted or may be substituted by one or more said substituents L),
Z 1 represents —O—, —S—, —OCH 2 —, —CH 2 O—, —CH 2 CH 2 —, —CO—, —COO—, —OCO—, —CO—S—, —S—. CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-,- O—NH—, —SCH 2 —, —CH 2 S—, —CF 2 S—, —SCF 2 —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH— , —OCO—CH═CH—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —CH 2 CH 2 —OCO—, —COO—CH 2 -, - OCO-CH 2 - , - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = -, - N = CH -, - CH = N-N = CH -, - CF = CF- or represents a -C≡C-, in the general formula, contains no -O-O- bonds. )
In the general formula (I), P 1 and P 2 each independently represent a group that is polymerized by radical polymerization, cationic polymerization, or anionic polymerization, and each independently represents the following formula (P-1) to formula (P- 20)

Figure 2017226616
Figure 2017226616

から選ばれる基を表すことが好ましい。特に重合方法として紫外線重合を行う場合には、式（Ｐ−１）、式（Ｐ−２）、式（Ｐ−３）、式（Ｐ−４）、式（Ｐ−５）、式（Ｐ−７）、式（Ｐ−８）、式（Ｐ−１１）、式（Ｐ−１３）、式（Ｐ−１５）又は式（Ｐ−１８）が好ましく、式（Ｐ−１）、式（Ｐ−２）、式（Ｐ−３）、式（Ｐ−８）、式（Ｐ−１１）又は式（Ｐ−１３）がより好ましく、式（Ｐ−１）、式（Ｐ−２）又は式（Ｐ−３）がさらに好ましく、式（Ｐ−１）又は式（Ｐ−２）が特に好ましい。 It is preferable to represent a group selected from: In particular, when ultraviolet polymerization is performed as a polymerization method, the formula (P-1), formula (P-2), formula (P-3), formula (P-4), formula (P-5), formula (P -7), formula (P-8), formula (P-11), formula (P-13), formula (P-15) or formula (P-18) are preferred, and formula (P-1), formula (P-18) P-2), formula (P-3), formula (P-8), formula (P-11) or formula (P-13) are more preferred, and formula (P-1), formula (P-2) or Formula (P-3) is more preferable, and formula (P-1) or formula (P-2) is particularly preferable.

一般式（Ｉ）において、Ｓｐ１及びＳｐ２は各々独立してスペーサー基を表すが、Ｓｐ１が複数存在する場合それらは同一であっても異なっていても良く、Ｓｐ２が複数存在する場合それらは同一であっても異なっていても良く、液晶性、原料の入手容易さ及び合成の容易さの観点から、Ｓｐ１及びＳｐ２は複数存在する場合は各々同一であっても異なっていても良く、各々独立して１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｓ−、−ＳＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−、−ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−に置き換えられても良い炭素原子数１から２０のアルキレン基を表すことが好ましく、Ｓｐ１及びＳｐ２は複数存在する場合は各々同一であっても異なっていても良く、各々独立して１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−に置き換えられても良い炭素原子数１から２０のアルキレン基を表すことがより好ましく、Ｓｐ１及びＳｐ２は複数存在する場合は各々同一であっても異なっていても良く、各々独立して１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−ＣＯＯ−、−ＯＣＯ−又は−ＯＣＯ−Ｏ−に置き換えられても良い炭素原子数１から２０の直鎖状アルキレン基を表すことがさらに好ましく、Ｓｐ１及びＳｐ２は複数存在する場合は各々同一であっても異なっていても良く、各々独立して１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−に置き換えられても良い炭素原子数１から１２の直鎖状アルキレン基を表すことがさらにより好ましく、Ｓｐ１及びＳｐ２は複数存在する場合は各々同一であっても異なっていても良く、各々独立して炭素原子数１から１２の直鎖状アルキレン基を表すことが特に好ましい。 In the general formula (I), Sp 1 and Sp 2 each independently represent a spacer group. When a plurality of Sp 1 are present, they may be the same or different, and when there are a plurality of Sp 2 They may be the same or different, and from the viewpoint of liquid crystallinity, availability of raw materials and ease of synthesis, when there are a plurality of Sp 1 and Sp 2, they may be the same or different. Each independently of one —CH 2 — or two or more non-adjacent —CH 2 — may be independently —O—, —S—, —OCH 2 —, —CH 2 O—. , —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH 2 —, -CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 , -CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 - , -CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = It preferably represents an alkylene group having 1 to 20 carbon atoms which may be replaced by CH—, —N═N—, —CH═N—N═CH—, —CF═CF— or —C≡C—. , Sp 1 and Sp 2 may be the same or different when there are a plurality, and each independently represents one —CH 2 — or two or more non-adjacent —CH 2 —. Independently -O-, -COO-, -OCO-, -OCO-O-, -C More preferably, it represents an alkylene group having 1 to 20 carbon atoms which may be replaced by O—NH—, —NH—CO—, —CH═CH— or —C≡C—, wherein Sp 1 and Sp 2 are When there are a plurality, they may be the same or different, and each independently represents one —CH 2 — or two or more non-adjacent —CH 2 — each independently —O—, More preferably, it represents a linear alkylene group having 1 to 20 carbon atoms which may be replaced by —COO—, —OCO— or —OCO—O—, and when there are a plurality of Sp 1 and Sp 2, Carbons which may be the same or different and each independently represents one —CH 2 — or two or more non-adjacent —CH 2 — may be independently replaced with —O—. Represents a linear alkylene group having 1 to 12 atoms DOO even more preferably, Sp 1 and Sp 2 may be different even each identical in the presence of two or more, in particular can represent a straight-chain alkylene group having 1 to 12 carbon atoms each independently preferable.

一般式（Ｉ）において、Ｘ１及びＸ２は各々独立して−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｓ−、−ＳＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−、−ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−又は単結合を表すが、Ｘ１が複数存在する場合それらは同一であっても異なっていても良く、Ｘ２が複数存在する場合それらは同一であっても異なっていても良い。原料の入手容易さ及び合成の容易さの観点から、Ｘ１及びＸ２は複数存在する場合は各々同一であっても異なっていても良く、各々独立して−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−又は単結合を表すことが好ましく、各々独立して−Ｏ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−又は単結合を表すことがより好ましく、各々独立して−Ｏ−、−ＣＯＯ−、−ＯＣＯ−又は単結合を表すことがさらに好ましく、各々独立して−Ｏ−又は単結合を表すことがさらにより好ましく、それぞれ−Ｏ−を表すことが特に好ましい。 In the general formula (I), X 1 and X 2 are each independently —O—, —S—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —CO. -S -, - S-CO - , - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - ≡C- or represents a single bond, they if X 1 there are a plurality may be the same or different and they may be the same or different if X 2 there are a plurality. From the viewpoint of easy availability of raw materials and ease of synthesis, when there are a plurality of X 1 and X 2, they may be the same or different and each independently represents —O—, —S—, — OCH 2 -, - CH 2 O -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO-, -COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - it is preferable to represent a CH 2 CH 2 -OCO- or a single bond, each independently -O -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH more preferably represents an 2 CH 2 -OCO- or a single bond, each independently -O -, - OO -, - OCO- or more preferably a single bond, even more preferably represent each independently -O- or a single bond, and particularly preferably each represent -O-.

一般式（Ｉ）において、ｋ１及び存在するｋ２は各々独立して０から１０の整数を表すが、合成の容易さ及び液晶性の観点から、各々独立して０から５の整数を表すことが好ましく、各々独立して０から２の整数を表すことがより好ましく、各々独立して０又は１を表すことがさらに好ましく、フィルムにした場合の硬化収縮の少なさの観点から、各々１を表すことが特に好ましい。   In general formula (I), k1 and existing k2 each independently represent an integer of 0 to 10, but from the viewpoint of ease of synthesis and liquid crystallinity, each independently represents an integer of 0 to 5. Preferably, each independently represents an integer of 0 to 2, more preferably each independently represents 0 or 1, and each represents 1 from the viewpoint of low curing shrinkage when formed into a film. It is particularly preferred.

ただし、一般式（Ｉ）において、Ｐ１−（Ｓｐ１−Ｘ１）ｋ１−及び−（Ｘ２−Ｓｐ２）ｋ２−Ｐ２には−Ｏ−Ｏ−結合を含まない。 However, in the general formula (I), P 1 - ( Sp 1 -X 1) k1 - and - (X 2 -Sp 2) k2 in -P 2 do not contain -O-O- bond.

一般式（Ｉ）において、Ａ１は下記の式（Ａ−１）から式（Ａ−７） In the general formula (I), A 1 represents the following formula (A-1) to formula (A-7):

Figure 2017226616
Figure 2017226616

（式中、これらの基は無置換であるか又は１つ以上の置換基Ｌによって置換されても良い。）から選ばれる基を表す。原料の入手容易さ、合成の容易さ、液晶性、保存安定性、配向欠陥の少なさ及び変色の起こりにくさの観点から、無置換であるか又は１つ以上の置換基Ｌによって置換されても良い上記の式（Ａ−１）から式（Ａ−６）から選ばれる基を表すことが好ましく、無置換であるか又は１つ以上の置換基Ｌによって置換されても良い上記の式（Ａ−１）から式（Ａ−４）から選ばれる基を表すことがより好ましく、無置換であるか又は１つ以上の置換基Ｌによって置換されても良い上記の式（Ａ−１）又は式（Ａ−２）から選ばれる基を表すことがさらに好ましく、無置換であるか又は１つ以上の置換基Ｌによって置換されても良い上記の式（Ａ−１）で表される基を表すことがさらにより好ましく（ここで置換基Ｌの好ましい基は、下記置換基Ｌが採用する好ましい基と同様である。）、無置換の上記の式（Ａ−１）で表される基を表すことが特に好ましい。 (Wherein these groups are unsubstituted or may be substituted by one or more substituents L). From the viewpoints of availability of raw materials, ease of synthesis, liquid crystallinity, storage stability, few alignment defects, and difficulty of discoloration, they are unsubstituted or substituted by one or more substituents L. Preferably represents a group selected from the above formulas (A-1) to (A-6), and may be unsubstituted or substituted by one or more substituents L More preferably, it represents a group selected from A-1) to formula (A-4), which is unsubstituted or may be substituted by one or more substituents L. It is more preferable to represent a group selected from the formula (A-2), and a group represented by the above formula (A-1) that is unsubstituted or may be substituted by one or more substituents L. It is even more preferable to represent (wherein the preferred group of the substituent L is the following substituent L It is the same as the preferred group to employ.), And particularly preferably a group represented by unsubstituted above formula (A-1).

一般式（Ｉ）において、置換基Ｌはフッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、ニトロ基、シアノ基、イソシアノ基、アミノ基、ヒドロキシル基、メルカプト基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、トリメチルシリル基、ジメチルシリル基、チオイソシアノ基、置換されていても良いフェニル基、置換されていても良いフェニルアルキル基、置換されていても良いシクロヘキシルアルキル基、又は、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＲ０−、−ＮＲ０−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＲ０＝Ｎ−、−Ｎ＝ＣＲ０−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−（式中、Ｒ０は水素原子又は炭素原子数１から８のアルキル基を表す。）によって置換されても良い炭素原子数１から２０の直鎖状又は分岐状アルキル基を表すが、当該アルキル基中の任意の水素原子はフッ素原子に置換されても良く、若しくは、ＬはＰＬ−（ＳｐＬ−ＸＬ）ｋＬ−で表される基を表しても良いが、化合物内にＬが複数存在する場合それらは同一であっても異なっていても良い。液晶性、合成の容易さの観点から、置換基Ｌはフッ素原子、塩素原子、ペンタフルオロスルフラニル基、ニトロ基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、又は、任意の水素原子はフッ素原子に置換されても良く、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−は各々独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−から選択される基によって置換されても良い炭素原子数１から２０の直鎖状又は分岐状アルキル基を表すことが好ましく、置換基Ｌはフッ素原子、塩素原子、又は、任意の水素原子はフッ素原子に置換されても良く、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−は各々独立して−Ｏ−、−ＣＯＯ−又は−ＯＣＯ−から選択される基によって置換されても良い炭素原子数１から１２の直鎖状又は分岐状アルキル基を表すことがより好ましく、置換基Ｌはフッ素原子、塩素原子、又は、任意の水素原子はフッ素原子に置換されても良い炭素原子数１から１２の直鎖状又は分岐状アルキル基若しくはアルコキシ基を表すことがさらに好ましく、置換基Ｌはフッ素原子、塩素原子、又は、炭素原子数１から８の直鎖アルキル基若しくは直鎖アルコキシ基を表すことが特に好ましい。また、置換基ＬはＰＬ−（ＳｐＬ−ＸＬ）ｋＬ−で表される基を表しても良いが、ＰＬ、ＳｐＬ、ＸＬ及びｋＬの好ましい構造は、各々一般式（Ｉ）中のＰ１、Ｓｐ１、Ｘ１及びｋ１の好ましい構造と同一である。なお、ＰＬ−（ＳｐＬ−ＸＬ）ｋＬ−には−Ｏ−Ｏ−結合を含まない。 In the general formula (I), the substituent L is a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino. Group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, optionally substituted phenyl group, optionally substituted phenylalkyl group, optionally substituted cyclohexylalkyl A group, or one —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—, —S—, —CO—, —COO—, —OCO—, — CO-S -, - S- CO -, - O-CO-O -, - CO-NR 0 -, - NR 0 -CO -, - CH = CH-COO-, CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - CH = CH -, - N = N -, - CR 0 = N -, - N = CR 0 -, - Carbon which may be substituted by CH═N—N═CH—, —CF═CF— or —C≡C— (wherein R 0 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). Although the atoms 1 represents a linear or branched alkyl group of 20, any hydrogen atom in the alkyl group may be substituted by a fluorine atom, or, L represents P L - (Sp L -X L ) The group represented by kL- may be represented, but when a plurality of L are present in the compound, they may be the same or different. From the viewpoint of liquid crystallinity and ease of synthesis, the substituent L is a fluorine atom, chlorine atom, pentafluorosulfuranyl group, nitro group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, or any A hydrogen atom may be substituted with a fluorine atom, and one —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—, —S—, —CO—, — 1 to 20 carbon atoms which may be substituted by a group selected from COO—, —OCO—, —O—CO—O—, —CH═CH—, —CF═CF— or —C≡C—. It is preferable to represent a linear or branched alkyl group, and the substituent L may be a fluorine atom, a chlorine atom, or an arbitrary hydrogen atom may be substituted with a fluorine atom, and one —CH 2 — or adjacent group may be substituted. not two or more -CH 2 - More preferably, each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted with a group selected from —O—, —COO— or —OCO—. More preferably, L represents a fluorine atom, a chlorine atom, or an arbitrary hydrogen atom, a linear or branched alkyl group or alkoxy group having 1 to 12 carbon atoms, which may be substituted with a fluorine atom. L particularly preferably represents a fluorine atom, a chlorine atom, or a linear alkyl group or linear alkoxy group having 1 to 8 carbon atoms. The substitution group L P L - (Sp L -X L ) kL - group may represent represented by but, P L, Sp L, preferred structure of X L and kL are each formula (I ) In P 1 , Sp 1 , X 1 and k 1 . Note that P L- (Sp L -X L ) kL -does not include an -O-O- bond.

一般式（Ｉ）において、Ｂ１は下記の式（Ｂ−１）から式（Ｂ−１０） In the general formula (I), B 1 represents the following formulas (B-1) to (B-10):

Figure 2017226616
Figure 2017226616

（式中、これらの基は無置換であるか又は１つ以上の前記置換基Ｌによって置換されても良い。）から選ばれる基を表す。原料の入手容易さ、合成の容易さ、液晶性、低い屈折率異方性、保存安定性、配向欠陥の少なさ及び変色の起こりにくさの観点から、無置換であるか又は１つ以上の上記置換基Ｌによって置換されても良い上記の式（Ｂ−１）から式（Ｂ−８）から選ばれる基を表すことが好ましく、無置換であるか又は１つ以上の上記置換基Ｌによって置換されても良い上記の式（Ｂ−１）から式（Ｂ−３）から選ばれる基を表すことがより好ましく、無置換であるか又は１つ以上の上記置換基Ｌによって置換されても良い上記の式（Ｂ−１）又は式（Ｂ−２）から選ばれる基を表すことがさらに好ましく、無置換であるか又は１つ以上の上記置換基Ｌによって置換されても良い上記の式（Ｂ−１）で表される基を表すことがさらにより好ましく、無置換の上記の式（Ｂ−１）で表される基を表すことが特に好ましい。 (Wherein these groups are unsubstituted or may be substituted by one or more of the substituents L). From the viewpoint of availability of raw materials, ease of synthesis, liquid crystallinity, low refractive index anisotropy, storage stability, few alignment defects, and resistance to discoloration, it is unsubstituted or one or more It preferably represents a group selected from the above formulas (B-1) to (B-8) which may be substituted by the above substituent L, and is unsubstituted or substituted by one or more of the above substituents L. It is more preferable to represent a group selected from the above formulas (B-1) to (B-3) which may be substituted, and may be unsubstituted or substituted by one or more of the above substituents L. More preferably, it represents a group selected from the above-mentioned formula (B-1) or formula (B-2), which is unsubstituted or substituted by one or more of the above-mentioned substituents L Even more preferably, it represents a group represented by (B-1), and is unsubstituted. And particularly preferably a group represented by the serial formula (B-1).

一般式（Ｉ）において、Ｚ１は−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＯＣＯ−ＮＨ−、−ＮＨ−ＣＯＯ−、−ＮＨ−ＣＯ−ＮＨ−、−ＮＨ−Ｏ−、−Ｏ−ＮＨ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＦ２Ｓ−、−ＳＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−、−ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−を表す。 In the general formula (I), Z 1 represents —O—, —S—, —OCH 2 —, —CH 2 O—, —CH 2 CH 2 —, —CO—, —COO—, —OCO—, —CO. -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, —NH—O—, —O—NH—, —SCH 2 —, —CH 2 S—, —CF 2 S—, —SCF 2 —, —CH═CH—COO—, —CH═CH—OCO—, -COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 - , - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH- -N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, - representing the CF = CF- or -C≡C-.

特に保存安定性と液晶性のバランスを重視する場合は、Ｚ１は−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−Ｏ−、−Ｏ−ＮＨ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−を表すことが好ましく、Ｚ１は−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−を表すことがより好ましく、Ｚ１は−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＯ−ＣＨ２ＣＨ２−又は−ＣＨ２ＣＨ２−ＯＣＯ−を表すことが特に好ましい。 In particular, when importance is placed on the balance between storage stability and liquid crystallinity, Z 1 is —OCH 2 —, —CH 2 O—, —CH 2 CH 2 —, —COO—, —OCO—, —NH—O—, -O-NH -, - CH = CH-COO -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 —OCO—, —CH═CH—, —N═N—, —CH═N—, —N═CH—, —CH═N—N═CH—, —CF═CF— or —C Preferably represents ≡C—, Z 1 represents —OCH 2 —, —CH 2 O—, —CH 2 CH 2 —, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH = CH -, - COO-CH 2 CH 2 -, - CH 2 CH 2 -OCO -, - CH = CH -, - N = N- -CH = N-N = CH - , - it is more preferable that represent CF = CF- or -C≡C-, Z 1 is -OCH 2 -, - CH 2 O -, - CH 2 CH 2 -, - It is particularly preferable to represent COO—, —OCO—, —COO—CH 2 CH 2 — or —CH 2 CH 2 —OCO—.

特に配向欠陥の少なさを重視する場合は、Ｚ１は−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−を表すことが好ましく、Ｚ１は−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−を表すことがより好ましく、Ｚ１は−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−ＮＨ−又は−ＮＨ−ＣＯ−を表すことがさらに好ましく、Ｚ１は−ＣＯＯ−又は−ＯＣＯ−を表すことが特に好ましい。 In particular, when importance is attached to the small number of orientation defects, Z 1 is —OCH 2 —, —CH 2 O—, —CH 2 CH 2 —, —COO—, —OCO—, —CO—NH—, —NH—. CO -, - CH = CH- COO -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - CH 2 CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N—, —N═CH—, —CH═N—N═CH—, —CF═CF— or —C≡C— is preferably represented, and Z 1 represents —COO—, —OCO—, — CO-NH-, -NH-CO-, -CH = CH-COO-, -OCO-CH = CH-, -CH = CH-, -N = N-, -CH = N-N = CH-,- More preferably, it represents CF═CF— or —C≡C—, and Z 1 represents —COO—, —OCO—, —CO—NH— or —NH—CO—. Is more preferable, and Z 1 particularly preferably represents —COO— or —OCO—.

特に変色の起こりにくさを重視する場合は、Ｚ１は−Ｏ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＯＣＯ−ＮＨ−、−ＮＨ−ＣＯＯ−、−ＮＨ−ＣＯ−ＮＨ−、−ＮＨ−Ｏ−、−Ｏ−ＮＨ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−、−ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−を表すことが好ましく、Ｚ１は−Ｏ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＯＣＯ−ＮＨ−、−ＮＨ−ＣＯＯ−、−ＮＨ−ＣＯ−ＮＨ−、−ＮＨ−Ｏ−、−Ｏ−ＮＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−又は−ＣＨ２−ＯＣＯ−を表すことがより好ましく、Ｚ１は−Ｏ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−又は−ＣＨ２−ＯＣＯ−を表すことが特に好ましい。 In particular, when importance is attached to the difficulty of discoloration, Z 1 is —O—, —OCH 2 —, —CH 2 O—, —CH 2 CH 2 —, —CO—, —COO—, —OCO—, — O—CO—O—, —CO—NH—, —NH—CO—, —OCO—NH—, —NH—COO—, —NH—CO—NH—, —NH—O—, —O—NH— , —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 — , -CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = Preferably represents CH—, —CH═N—, —N═CH—, —CF═CF— or —C≡C—, 1 -O -, - OCH 2 -, - CH 2 O -, - CH 2 CH 2 -, - CO -, - COO -, - OCO -, - OCO-O -, - CO-NH-, —NH—CO—, —OCO—NH—, —NH—COO—, —NH—CO—NH—, —NH—O—, —O—NH—, —COO—CH 2 CH 2 —, —OCO— CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO- or -CH 2 --OCO It is more preferable that Z 1 represents —O—, —OCH 2 —, —CH 2 O—, —CH 2 CH 2 —, —COO—, —OCO—, —COO—CH 2 CH 2 —, -OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO-, COO-CH 2 -, - OCO -CH 2 -, - CH 2 -COO- or may represent a -CH 2 -OCO- particularly preferred.

特に原料の入手容易さ及び合成の容易さと、液晶性、保存安定性、配向欠陥の少なさ及び変色の起こりにくさのバランスを重視する場合は、Ｚ１は−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−を表すことが好ましく、Ｚ１は−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−を表すことがより好ましく、Ｚ１は−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＯ−ＣＨ２ＣＨ２−又は−ＣＨ２ＣＨ２−ＯＣＯ−を表すことがさらに好ましく、Ｚ１は−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯＯ−又は−ＯＣＯ−を表すことがさらにより好ましく、Ｚ１は−ＣＯＯ−又は−ＯＣＯ−を表すことが特に好ましい。 In particular, Z 1 is —OCH 2 —, —CH 2 O when importance is placed on the balance between the availability of raw materials and the ease of synthesis, liquid crystallinity, storage stability, few alignment defects, and the difficulty of discoloration. -, - CH 2 CH 2 - , - COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 - , -CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - CH = CH -, - it is preferable to represent a CF = CF- or -C≡C-, Z 1 is -OCH 2 -, -CH 2 O -, - CH 2 CH 2 -, - COO -, - OCO -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - display the CH = CH- or -C≡C- More preferably, Z 1 is -OCH 2 -, - CH 2 O -, - COO -, - OCO -, - COO-CH 2 CH 2 - or more preferably representing a -CH 2 CH 2 -OCO- Z 1 represents even more preferably —OCH 2 —, —CH 2 O—, —COO— or —OCO—, and Z 1 particularly preferably represents —COO— or —OCO—.

一般式（Ｉ）で表される化合物としては、下記の一般式（Ｉ−ｉ）   Examples of the compound represented by the general formula (I) include the following general formula (I-i)

Figure 2017226616
Figure 2017226616

（式中、Ｐ１、Ｐ２、Ｓｐ１、Ｓｐ２、Ｘ１、Ｘ２、ｋ１及びｋ２は各々一般式（Ｉ）におけるＰ１、Ｐ２、Ｓｐ１、Ｓｐ２、Ｘ１、Ｘ２、ｋ１及びｋ２と同じ意味を表し、Ａ１１は無置換であるか又は１つ以上の上記置換基Ｌによって置換されても良い上記の式（Ａ−１）から式（Ａ−７）から選ばれる基を表し、Ｂ１１は無置換であるか又は１つ以上の上記置換基Ｌによって置換されても良い上記の式（Ｂ−１）から式（Ｂ−１０）から選ばれる基を表し、置換基Ｌの好ましい構造は上記一般式（Ｉ）中の置換基Ｌの好ましい構造と同一であり、Ｚ１１は−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−を表す。）で表される化合物が好ましく、下記の一般式（Ｉ−ｉ−ｉ） (In the formula, P 1 , P 2 , Sp 1 , Sp 2 , X 1 , X 2 , k 1 and k 2 are respectively P 1 , P 2 , Sp 1 , Sp 2 , X 1 , X 2 in the general formula (I). , K1 and k2 have the same meaning, and A 11 is selected from the above formulas (A-1) to (A-7) which are unsubstituted or may be substituted by one or more of the above substituents L B 11 represents a group selected from the above formulas (B-1) to (B-10) which may be unsubstituted or substituted by one or more of the above substituents L; The preferred structure of the substituent L is the same as the preferred structure of the substituent L in the general formula (I), and Z 11 represents —OCH 2 —, —CH 2 O—, —CH 2 CH 2 —, —COO—. , -OCO -, - CH = CH -COO -, - OCO-CH = CH -, - COO-CH 2 CH -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - CH = CH -, - representing the CF = CF- or -C≡C-). A compound represented by the following general formula (I-i-i)

Figure 2017226616
Figure 2017226616

（式中、Ｐ１、Ｐ２、Ｓｐ１、Ｓｐ２、Ｘ１、Ｘ２、ｋ１及びｋ２は各々一般式（Ｉ）におけるＰ１、Ｐ２、Ｓｐ１、Ｓｐ２、Ｘ１、Ｘ２、ｋ１及びｋ２と同じ意味を表し、Ａ１１１は無置換であるか又は１つ以上の上記置換基Ｌによって置換されても良い上記の式（Ａ−１）又は式（Ａ−２）から選ばれる基を表し、Ｂ１１１は無置換であるか又は１つ以上の上記置換基Ｌによって置換されても良い上記の式（Ｂ−１）から式（Ｂ−３）から選ばれる基を表し、置換基Ｌの好ましい構造は上記一般式（Ｉ）中の置換基Ｌの好ましい構造と同一であり、Ｚ１１１は−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−を表す。）で表される化合物がより好ましく、下記の一般式（Ｉ−ｉ−ｉ−ｉ） (In the formula, P 1 , P 2 , Sp 1 , Sp 2 , X 1 , X 2 , k 1 and k 2 are respectively P 1 , P 2 , Sp 1 , Sp 2 , X 1 , X 2 in the general formula (I). , K1 and k2 have the same meaning, and A 111 is selected from the above formula (A-1) or formula (A-2) which is unsubstituted or may be substituted by one or more of the above substituents L B 111 represents a group selected from the above formulas (B-1) to (B-3) that may be unsubstituted or substituted by one or more of the above substituents L; The preferred structure of the substituent L is the same as the preferred structure of the substituent L in the general formula (I), and Z 111 is —OCH 2 —, —CH 2 O—, —CH 2 CH 2 —, —COO—. , -OCO -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 H 2 -COO -, - CH 2 CH 2 -OCO -, -. The CH = CH- or an -C≡C- is more preferably a compound represented by), the general formula (I-i-i- i)

Figure 2017226616
Figure 2017226616

（式中、Ｐ１、Ｐ２、Ｓｐ１、Ｓｐ２、Ｘ１、Ｘ２、ｋ１及びｋ２は各々一般式（Ｉ）におけるＰ１、Ｐ２、Ｓｐ１、Ｓｐ２、Ｘ１、Ｘ２、ｋ１及びｋ２と同じ意味を表し、Ａ１１１１は無置換であるか又は１つ以上の置換基Ｌによって置換されても良い上記の式（Ａ−１）で表される基を表し、Ｂ１１１１は無置換であるか又は１つ以上の上記置換基Ｌによって置換されても良い上記の式（Ｂ−１）又は式（Ｂ−２）から選ばれる基を表し、置換基Ｌの好ましい構造は上記一般式（Ｉ）中の置換基Ｌの好ましい構造と同一であり、Ｚ１１１１は−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＯ−ＣＨ２ＣＨ２−又は−ＣＨ２ＣＨ２−ＯＣＯ−を表す。）で表される化合物がさらに好ましく、下記の一般式（Ｉ−ｉ−ｉ−ｉ−ｉ） (In the formula, P 1 , P 2 , Sp 1 , Sp 2 , X 1 , X 2 , k 1 and k 2 are respectively P 1 , P 2 , Sp 1 , Sp 2 , X 1 , X 2 in the general formula (I). , K1 and k2, and A 1111 represents a group represented by the above formula (A-1) which may be unsubstituted or substituted by one or more substituents L, and B 1111 Represents a group selected from the above formula (B-1) or formula (B-2) which may be unsubstituted or substituted by one or more of the above substituents L, and a preferred structure of the substituent L is is identical to the preferred configuration of the substituents L in the general formula (I), Z 1111 is -OCH 2 -, - CH 2 O -, - COO -, - OCO -, - COO-CH 2 CH 2 - or compound more preferably represented by the representative.) the -CH 2 CH 2 -OCO-, under Of the general formula (I-i-i-i-i)

Figure 2017226616
Figure 2017226616

（式中、Ｐ１、Ｐ２、Ｓｐ１、Ｓｐ２、Ｘ１、Ｘ２、ｋ１及びｋ２は各々一般式（Ｉ）におけるＰ１、Ｐ２、Ｓｐ１、Ｓｐ２、Ｘ１、Ｘ２、ｋ１及びｋ２と同じ意味を表し、Ａ１１１１１は１，４−シクロヘキシレン基を表し、Ｂ１１１１１は無置換であるか又は１つ以上の上記置換基Ｌによって置換されても良い１，４−フェニレン基を表し、置換基Ｌの好ましい構造は上記一般式（Ｉ）中の置換基Ｌの好ましい構造と同一であり、Ｚ１１１１１は−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯＯ−又は−ＯＣＯ−を表す。）で表される化合物がさらにより好ましく、下記の一般式（Ｉ−ｉ−ｉ−ｉ−ｉ−１）又は一般式（Ｉ−ｉ−ｉ−ｉ−ｉ−２） (In the formula, P 1 , P 2 , Sp 1 , Sp 2 , X 1 , X 2 , k 1 and k 2 are respectively P 1 , P 2 , Sp 1 , Sp 2 , X 1 , X 2 in the general formula (I). , K1 and k2 have the same meaning, A 11111 represents a 1,4-cyclohexylene group, B 11111 is unsubstituted or optionally substituted by one or more of the above substituents L Represents a phenylene group, and the preferred structure of the substituent L is the same as the preferred structure of the substituent L in the general formula (I), and Z 11111 represents —OCH 2 —, —CH 2 O—, —COO— or — The compound represented by OCO- is even more preferable, and the following general formula (I-ii-ii-1) or general formula (I-ii-ii-2)

Figure 2017226616
Figure 2017226616

（式中、Ｐ１、Ｐ２、Ｓｐ１、Ｓｐ２、Ｘ１、Ｘ２、ｋ１及びｋ２は各々一般式（Ｉ）におけるＰ１、Ｐ２、Ｓｐ１、Ｓｐ２、Ｘ１、Ｘ２、ｋ１及びｋ２と同じ意味を表し、Ｂ１１１１１１は下記の式（Ｂ−１−１）から式（Ｂ−１−６） (In the formula, P 1 , P 2 , Sp 1 , Sp 2 , X 1 , X 2 , k 1 and k 2 are respectively P 1 , P 2 , Sp 1 , Sp 2 , X 1 , X 2 in the general formula (I). , K1 and k2 have the same meaning, and B 111111 is represented by the following formulas (B-1-1) to (B-1-6):

Figure 2017226616
Figure 2017226616

から選ばれる基を表し、置換基Ｌの好ましい構造は上記一般式（Ｉ）中の置換基Ｌの好ましい構造と同一である。）で表される化合物が特に好ましい。 The preferable structure of the substituent L is the same as the preferable structure of the substituent L in the general formula (I). ) Is particularly preferred.

また、液晶性の観点から、一般式（Ｉ）で表される化合物に含まれる１，４−シクロヘキシレン基、テトラヒドロピラン−２，５−ジイル基、１，３−ジオキサン−２，５−ジイル基及びデカヒドロナフタレン−２，６−ジイル基はシス体及びトランス体のいずれか一方のみであっても、両方の混合物であっても良いが、液晶性の観点からトランス体が主成分であることが好ましく、トランス体のみであることが特に好ましい。   Further, from the viewpoint of liquid crystallinity, 1,4-cyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl contained in the compound represented by the general formula (I) The group and decahydronaphthalene-2,6-diyl group may be either a cis isomer or a trans isomer or a mixture of both, but the trans isomer is the main component from the viewpoint of liquid crystallinity. It is particularly preferable that only the trans isomer is present.

一般式（Ｉ）で表される化合物として具体的には、下記の式（Ｉ−１）から式（Ｉ−１０５）で表される化合物が好ましい。   Specifically, as the compound represented by the general formula (I), compounds represented by the following formulas (I-1) to (I-105) are preferable.

Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
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Figure 2017226616
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Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
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Figure 2017226616
Figure 2017226616

Figure 2017226616
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Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
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本願発明の化合物は以下の製法で製造することができる。
（製法１）下記式（Ｓ−１０）で表される化合物の製造 The compound of this invention can be manufactured with the following manufacturing methods.
(Production method 1) Production of a compound represented by the following formula (S-10)

Figure 2017226616
Figure 2017226616

（式中、Ｐ１、Ｐ２、Ｓｐ１、Ｓｐ２及びＬは各々一般式（Ｉ）におけるＰ１、Ｐ２、Ｓｐ１、Ｓｐ２及びＬと同じ意味を表し、ＰＧは保護基を表し、ｈａｌｏｇｅｎはハロゲン原子又はハロゲン等価体を表す。）
式（Ｓ−１）で表される化合物のカルボキシル基を保護基（ＰＧ）によって保護する。保護基（ＰＧ）としては、脱保護工程に至るまで安定に保護しうるものであれば特に制限は無いが、例えば、ＧＲＥＥＮＥ’Ｓ ＰＲＯＴＥＣＴＩＶＥ ＧＲＯＵＰＳ ＩＮ ＯＲＧＡＮＩＣ ＳＹＮＴＨＥＳＩＳ（（Ｆｏｕｒｔｈ Ｅｄｉｔｉｏｎ）、ＰＥＴＥＲ Ｇ．Ｍ．ＷＵＴＳ、ＴＨＥＯＤＯＲＡ Ｗ．ＧＲＥＥＮＥ共著、Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ，Ｉｎｃ．，Ｐｕｂｌｉｃａｔｉｏｎ）等に挙げられている保護基（ＰＧ）が好ましい。保護基の具体例としてはテトラヒドロピラニル基、ｔｅｒｔ−ブチル基、メトキシメチル基、エトキシメチル基、メチル基、エチル基又はベンジル基等が挙げられる。 (Wherein, P 1, P 2, Sp 1, Sp 2 and L each represents the same meaning as P 1, P 2, Sp 1 , Sp 2 and L in the general formula (I), PG represents a protecting group Halogen represents a halogen atom or a halogen equivalent.)
The carboxyl group of the compound represented by the formula (S-1) is protected with a protecting group (PG). The protecting group (PG) is not particularly limited as long as it can be stably protected until the deprotection step. For example, GREEN'S PROTECTIVE GROUPS IN ORGANIC SYNTHESIS ((Fourth Edition), PETER GM. Protecting groups (PG) mentioned in WUTS, THEODORA W. GREENE, John Wiley & Sons, Inc., Publication) and the like are preferred. Specific examples of the protecting group include a tetrahydropyranyl group, a tert-butyl group, a methoxymethyl group, an ethoxymethyl group, a methyl group, an ethyl group, and a benzyl group.

式（Ｓ−２）で表される化合物の保護基（ＰＧ）を脱保護する。脱保護の反応条件としては、式（Ｓ−３）で表される化合物を与えるものであれば特に制限は無いが、前記文献に挙げられているものが好ましい。また、式（Ｓ−１）で表される化合物の一方のカルボキシル基のみを保護基（ＰＧ）によって保護することによって式（Ｓ−３）で表される化合物を得ることも可能である。   The protecting group (PG) of the compound represented by the formula (S-2) is deprotected. The reaction conditions for deprotection are not particularly limited as long as they give the compound represented by formula (S-3), but those listed in the above-mentioned literature are preferable. It is also possible to obtain a compound represented by the formula (S-3) by protecting only one carboxyl group of the compound represented by the formula (S-1) with a protecting group (PG).

式（Ｓ−３）で表される化合物を塩基存在下、式（Ｓ−４）で表される化合物と反応させることによって、式（Ｓ−５）で表される化合物を得ることができる。塩基としては例えば炭酸カリウム、炭酸セシウム、トリエチルアミン等が挙げられる。   The compound represented by the formula (S-5) can be obtained by reacting the compound represented by the formula (S-3) with the compound represented by the formula (S-4) in the presence of a base. Examples of the base include potassium carbonate, cesium carbonate, triethylamine and the like.

式（Ｓ−５）で表される化合物の保護基（ＰＧ）を脱保護する。脱保護の反応条件としては、式（Ｓ−６）で表される化合物を与えるものであれば特に制限は無いが、前記文献に挙げられているものが好ましい。   The protecting group (PG) of the compound represented by the formula (S-5) is deprotected. The reaction conditions for deprotection are not particularly limited as long as they give the compound represented by the formula (S-6), but those listed in the above-mentioned literature are preferable.

式（Ｓ−６）で表される化合物を式（Ｓ−７）で表される化合物と反応させることによって、式（Ｓ−８）で表される化合物を得ることができる。反応条件としては例えば縮合剤を用いる方法若しくは式（Ｓ−６）で表される化合物を酸クロリド、混合酸無水物又はカルボン酸無水物とした後、一般式（Ｓ−７）で表される化合物と塩基存在下反応させる方法が挙げられる。縮合剤を用いる場合、縮合剤として例えばＮ，Ｎ’−ジシクロヘキシルカルボジイミド、Ｎ，Ｎ’−ジイソプロピルカルボジイミド、１−エチル−３−（３−ジメチルアミノプロピル）カルボジイミド塩酸塩が挙げられる。塩基としては例えばトリエチルアミン、ジイソプロピルエチルアミン等が挙げられる。   The compound represented by the formula (S-8) can be obtained by reacting the compound represented by the formula (S-6) with the compound represented by the formula (S-7). As the reaction conditions, for example, a method using a condensing agent or a compound represented by the formula (S-6) is converted to an acid chloride, mixed acid anhydride or carboxylic acid anhydride, and then represented by the general formula (S-7). The method of making it react with a compound in base presence is mentioned. When a condensing agent is used, examples of the condensing agent include N, N′-dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride. Examples of the base include triethylamine and diisopropylethylamine.

式（Ｓ−８）で表される化合物を塩基存在下、式（Ｓ−９）で表される化合物と反応させることによって、式（Ｓ−１０）で表される化合物を得ることができる。塩基としては例えば炭酸カリウム、炭酸セシウム、トリエチルアミン等が挙げられる。
（製法２）下記式（Ｓ−１９）で表される化合物の製造 The compound represented by the formula (S-10) can be obtained by reacting the compound represented by the formula (S-8) with a compound represented by the formula (S-9) in the presence of a base. Examples of the base include potassium carbonate, cesium carbonate, triethylamine and the like.
(Production method 2) Production of a compound represented by the following formula (S-19)

Figure 2017226616
Figure 2017226616

式（Ｓ−１１）で表される化合物を塩基存在下、式（Ｓ−１２）で表される化合物と反応させることによって、式（Ｓ−１３）で表される化合物を得ることができる。塩基としては例えば炭酸カリウム、炭酸セシウム、トリエチルアミン等が挙げられる。   The compound represented by the formula (S-13) can be obtained by reacting the compound represented by the formula (S-11) with the compound represented by the formula (S-12) in the presence of a base. Examples of the base include potassium carbonate, cesium carbonate, triethylamine and the like.

式（Ｓ−１４）で表される化合物のカルボキシル基を還元する。還元反応の条件としては、式（Ｓ−１５）で表される化合物を与えるものであれば特に制限は無いが、例えば、ボラン−テトラヒドロフラン錯体等が挙げられる。   The carboxyl group of the compound represented by formula (S-14) is reduced. The conditions for the reduction reaction are not particularly limited as long as they give the compound represented by the formula (S-15), and examples thereof include borane-tetrahydrofuran complex.

式（Ｓ−１５）で表される化合物を式（Ｓ−１３）で表される化合物と反応させることによって、式（Ｓ−１６）で表される化合物を得ることができる。反応条件としては例えば光延反応が挙げられる。または、式（Ｓ−１５）で表される化合物のヒドロキシル基をメタンスルホキシ基又はｐ−トルエンスルホキシ基等とした後、塩基存在下、式（Ｓ−１３）で表される化合物と反応させることも可能である。塩基としては例えば炭酸カリウム、炭酸セシウム、リン酸カリウム等が挙げられる。   The compound represented by the formula (S-16) can be obtained by reacting the compound represented by the formula (S-15) with the compound represented by the formula (S-13). Examples of the reaction conditions include Mitsunobu reaction. Alternatively, the hydroxyl group of the compound represented by the formula (S-15) is changed to a methanesulfoxy group or p-toluenesulfoxy group, and then reacted with the compound represented by the formula (S-13) in the presence of a base. It is also possible to make it. Examples of the base include potassium carbonate, cesium carbonate, potassium phosphate and the like.

式（Ｓ−１６）で表される化合物の保護基（ＰＧ）を脱保護する。脱保護の反応条件としては、式（Ｓ−１７）で表される化合物を与えるものであれば特に制限は無いが、前記文献に挙げられているものが好ましい。   The protecting group (PG) of the compound represented by the formula (S-16) is deprotected. The reaction conditions for deprotection are not particularly limited as long as they give the compound represented by formula (S-17), but those listed in the above-mentioned literature are preferable.

式（Ｓ−１７）で表される化合物を塩基存在下、式（Ｓ−１８）で表される化合物と反応させることによって、式（Ｓ−１９）で表される化合物を得ることができる。塩基としては例えば炭酸カリウム、炭酸セシウム、トリエチルアミン等が挙げられる。   The compound represented by the formula (S-19) can be obtained by reacting the compound represented by the formula (S-17) with the compound represented by the formula (S-18) in the presence of a base. Examples of the base include potassium carbonate, cesium carbonate, triethylamine and the like.

製法１及び製法２の各工程において記載した以外の反応条件として、例えば実験化学講座（日本化学会編、丸善株式会社発行）、Ｏｒｇａｎｉｃ Ｓｙｎｔｈｅｓｅｓ（Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ，Ｉｎｃ．，Ｐｕｂｌｉｃａｔｉｏｎ）、Ｂｅｉｌｓｔｅｉｎ Ｈａｎｄｂｏｏｋ ｏｆ Ｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ（Ｂｅｉｌｓｔｅｉｎ−Ｉｎｓｔｉｔｕｔ ｆｕｅｒ Ｌｉｔｅｒａｔｕｒ ｄｅｒ Ｏｒｇａｎｉｓｃｈｅｎ Ｃｈｅｍｉｅ、Ｓｐｒｉｎｇｅｒ−Ｖｅｒｌａｇ Ｂｅｒｌｉｎ ａｎｄ Ｈｅｉｄｅｌｂｅｒｇ ＧｍｂＨ ＆ Ｃｏ．Ｋ）、Ｆｉｅｓｅｒｓ’ Ｒｅａｇｅｎｔｓ ｆｏｒ Ｏｒｇａｎｉｃ Ｓｙｎｔｈｅｓｉｓ（Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ，Ｉｎｃ．）等の文献に記載の条件又はＳｃｉＦｉｎｄｅｒ（Ｃｈｅｍｉｃａｌ Ａｂｓｔｒａｃｔｓ Ｓｅｒｖｉｃｅ，Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ）又はＲｅａｘｙｓ（Ｅｌｓｅｖｉｅｒ Ｌｔｄ．）等のオンライン検索サービスから提供される条件が挙げられる。   Examples of reaction conditions other than those described in each step of production method 1 and production method 2 include, for example, an experimental chemistry course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Synthesis (John Wiley & Sons, Inc., Publication), and Bilstein Handbook of. Organic Chemistry (Beilstein-Institut fuer Literatur der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co.K), Fiesers' Reagents for Organic Synthesis (John Wiley & Sons, Inc.) conditions or SciFind described in the literature such as r (Chemical Abstracts Service, American Chemical Society) or Reaxys conditions provided from the online search services (Elsevier Ltd.) and the like.

また、各工程において適宜反応溶媒を用いることができる。溶媒としては目的の化合物を与えるものであれば制限は無いが、例えばイソプロピルアルコール、エチレングリコール、メタノール、エタノール、クロロホルム、ジクロロメタン、１，２−ジクロロエタン、アセトン、アセトニトリル、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、ジエチルエーテル、エチレングリコールモノエチルエーテル、キシレン、酢酸エチル、１，４−ジオキサン、テトラヒドロフラン、ピリジン、１−メチル−２−ピロリジノン、トルエン、ヘキサン、シクロヘキサン、ヘプタン、メチルイソブチルケトン、ｔｅｒｔ−ブチルメチルエーテル、メチルエチルケトン等が挙げられる。有機溶媒及び水の二相系で反応を行う場合、相間移動触媒を添加することも可能である。相間移動触媒としては、例えば、ベンジルトリメチルアンモニウムクロリド、ポリオキシエチレン（２０）ソルビタンモノラウラート［Ｔｗｅｅｎ ２０］、ソルビタンモノオレアート［Ｓｐａｎ ８０］等が挙げられる。   In each step, a reaction solvent can be appropriately used. The solvent is not particularly limited as long as it gives the target compound. For example, isopropyl alcohol, ethylene glycol, methanol, ethanol, chloroform, dichloromethane, 1,2-dichloroethane, acetone, acetonitrile, N, N-dimethylformamide, N , N-dimethylacetamide, dimethyl sulfoxide, diethyl ether, ethylene glycol monoethyl ether, xylene, ethyl acetate, 1,4-dioxane, tetrahydrofuran, pyridine, 1-methyl-2-pyrrolidinone, toluene, hexane, cyclohexane, heptane, methyl Examples include isobutyl ketone, tert-butyl methyl ether, and methyl ethyl ketone. When the reaction is carried out in an organic solvent and water two-phase system, a phase transfer catalyst can be added. Examples of the phase transfer catalyst include benzyltrimethylammonium chloride, polyoxyethylene (20) sorbitan monolaurate [Tween 20], sorbitan monooleate [Span 80], and the like.

また、各工程において必要に応じて精製を行うことができる。精製方法としてはクロマトグラフィー、再結晶、蒸留、昇華、再沈殿、吸着、分液処理等が挙げられる。精製剤を用いる場合、精製剤としてシリカゲル、アルミナ、活性炭、活性白土、セライト、ゼオライト、メソポーラスシリカ、カーボンナノチューブ、カーボンナノホーン、備長炭、木炭、グラフェン、イオン交換樹脂、酸性白土、二酸化ケイ素、珪藻土、パーライト、セルロース、有機ポリマー、多孔質ゲル等が挙げられる。   In each step, purification can be performed as necessary. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. When using a purification agent, silica gel, alumina, activated carbon, activated clay, celite, zeolite, mesoporous silica, carbon nanotube, carbon nanohorn, Bincho charcoal, charcoal, graphene, ion exchange resin, acid clay, silicon dioxide, diatomaceous earth, Examples include perlite, cellulose, organic polymer, and porous gel.

本願発明の化合物は、ネマチック液晶組成物、スメクチック液晶組成物、キラルスメクチック液晶組成物及びコレステリック液晶組成物に使用することが好ましく、キラルスメクチック液晶組成物及びコレステリック液晶組成物に使用することが特に好ましい。
い。本願発明の反応性化合物を用いる液晶組成物において本願発明以外の化合物を添加しても構わない。 The compound of the present invention is preferably used for nematic liquid crystal compositions, smectic liquid crystal compositions, chiral smectic liquid crystal compositions and cholesteric liquid crystal compositions, and particularly preferably used for chiral smectic liquid crystal compositions and cholesteric liquid crystal compositions. .
Yes. In the liquid crystal composition using the reactive compound of the present invention, a compound other than the present invention may be added.

本願発明の重合性化合物と混合して使用される他の重合性化合物としては、具体的には一般式（Ｘ−１１）   Specifically, the other polymerizable compound used by mixing with the polymerizable compound of the present invention is represented by the general formula (X-11).

Figure 2017226616
Figure 2017226616

及び／又は一般式（Ｘ−１２） And / or general formula (X-12)

Figure 2017226616
Figure 2017226616

（式中、Ｐ１１、Ｐ１２及びＰ１３は各々独立して重合性基を表し、Ｓｐ１１、Ｓｐ１２及びＳｐ１３は各々独立して単結合又は炭素原子数１〜２０個のアルキレン基を表すが、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−に置き換えられても良く、Ｘ１１、Ｘ１２及びＸ１３は各々独立して−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｓ−、−ＳＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−、−ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−又は単結合を表し、Ｚ１１及びＺ１２は各々独立して−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｓ−、−ＳＣＦ２−、−ＣＨ２ＣＨ２−、−ＣＨ２ＣＦ２−、−ＣＦ２ＣＨ２−、−ＣＦ２ＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−、−ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−又は単結合を表し、Ａ１１、Ａ１２、Ａ１３及びＡ１４は各々独立して、１，４−フェニレン基、１，４−シクロヘキシレン基、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、ナフタレン−１，４−ジイル基、テトラヒドロナフタレン−２，６−ジイル基又は１，３−ジオキサン−２，５−ジイル基を表すが、Ａ１１、Ａ１２、Ａ１３及びＡ１４は各々独立して無置換であるか又はアルキル基、ハロゲン化アルキル基、アルコキシ基、ハロゲン化アルコキシ基、ハロゲン原子、シアノ基又はニトロ基に置換されていても良く、Ｒ１１は水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、シアノ基、ニトロ基、イソシアノ基、チオイソシアノ基、若しくは、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−によって置換されても良い炭素原子数１から２０の直鎖又は分岐アルキル基を表し、ｍ１１及びｍ１２は０、１、２又は３を表すが、ｍ１１及び／又はｍ１２が２又は３を表す場合、２個あるいは３個存在するＡ１１、Ａ１３、Ｚ１１及び／又はＺ１２は同一であっても異なっていても良い。）で表される化合物が好ましく、Ｐ１１、Ｐ１２及びＰ１３がアクリル基又はメタクリル基である場合が特に好ましい。一般式（Ｘ−１１）で表される化合物として具体的には、一般式（Ｘ−１１ａ） (In the formula, P 11 , P 12 and P 13 each independently represent a polymerizable group, and Sp 11 , Sp 12 and Sp 13 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms. represents but one -CH 2 - or nonadjacent two or more -CH 2 - is -O -, - COO -, - OCO -, - OCOO- may be replaced by, X 11, X 12 and X 13 are each independently —O—, —S—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO. -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S-, -SCF 2 -, - CH = CH -COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO- H = CH -, - COO- CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO -CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - CF = CF -, - C≡C- or a single bond, Z 11 and Z 12 are each independently , - - S -, - -O and OCH 2 -, - CH 2 O -, - COO -, - OCO -, - CO -, - CO-S -, - S-CO -, - O-CO- O -, - CO-NH - , - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 -, - CH = CH-COO -, - C = CH-OCO -, - COO -CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 —OCO—, —COO—CH 2 —, —OCO—CH 2 —, —CH 2 —COO—, —CH 2 —OCO—, —CH═CH—, —CF═CF—, —C Represents ≡C— or a single bond, and A 11 , A 12 , A 13 and A 14 each independently represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, Pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group It represents but, A 11, A 12, A 13 and 14 are each independently unsubstituted or substituted by an alkyl group, a halogenated alkyl group, alkoxy group, halogenated alkoxy group, a halogen atom, may be substituted with a cyano group or a nitro group, R 11 is a hydrogen atom, A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or one —CH 2 — or two or more non-adjacent — CH 2 — is independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO. —NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF = CF- or -C≡C- Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted, and m11 and m12 represent 0, 1, 2 or 3, but when m11 and / or m12 represents 2 or 3, Two or three A 11 , A 13 , Z 11 and / or Z 12 may be the same or different. ) Is preferred, and the case where P 11 , P 12 and P 13 are acrylic groups or methacrylic groups is particularly preferred. Specifically, the compound represented by the general formula (X-11) is represented by the general formula (X-11a).

Figure 2017226616
Figure 2017226616

（式中、Ｗ１１及びＷ１２は各々独立して水素原子又はメチル基を表し、Ｓｐ１４及びＳｐ１５は各々独立して炭素原子数２から１８のアルキレン基、Ｘ１４及びＸ１５は各々独立して−Ｏ−、−ＣＯＯ−、−ＯＣＯ−又は単結合を表し、Ｚ１３及びＺ１４は各々独立して−ＣＯＯ−又は−ＯＣＯ−を表し、Ａ１５、Ａ１６及びＡ１７は各々独立して無置換若しくはフッ素原子、塩素原子、炭素原子数１から４の直鎖状又は分岐状アルキル基、炭素原子数１から４の直鎖状又は分岐状アルコキシ基によって置換されていても良い１，４−フェニレン基を表す。）で表される化合物が好ましく、下記式（Ｘ−１１ａ−１）から式（Ｘ−１１ａ−４） Wherein W 11 and W 12 each independently represent a hydrogen atom or a methyl group, Sp 14 and Sp 15 each independently represent an alkylene group having 2 to 18 carbon atoms, and X 14 and X 15 each independently to -O -, - COO -, - OCO- or a single bond, Z 13 and Z 14 are each independently represents a -COO- or -OCO-, a 15, a 16 and a 17 are each independently And may be unsubstituted or substituted by a fluorine atom, a chlorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms. , A 4-phenylene group) is preferable, and the following formulas (X-11a-1) to (X-11a-4)

Figure 2017226616
Figure 2017226616

（式中、Ｗ１１、Ｗ１２、Ｓｐ１４及びＳｐ１５は一般式（Ｘ−１１ａ）と同様の意味を表す。）で表される化合物が特に好ましい。上記式（Ｘ−１１ａ−１）から式（Ｘ−１１ａ−４）において、Ｓｐ１４及びＳｐ１５が各々独立して炭素原子数２から８のアルキレン基である化合物が特に好ましい。 (Wherein, W 11 , W 12 , Sp 14 and Sp 15 represent the same meaning as in the general formula (X-11a)) are particularly preferable. In the above formulas (X-11a-1) to (X-11a-4), compounds in which Sp 14 and Sp 15 are each independently an alkylene group having 2 to 8 carbon atoms are particularly preferable.

この他、好ましい２官能重合性化合物としては下記一般式（Ｘ−１１ｂ−１）から式（Ｘ−１１ｂ−３）   In addition, preferable bifunctional polymerizable compounds include those represented by the following general formulas (X-11b-1) to (X-11b-3):

Figure 2017226616
Figure 2017226616

（式中、Ｗ１３及びＷ１４は各々独立して水素原子又はメチル基を表し、Ｓｐ１６及びＳｐ１７は各々独立して炭素原子数２から１８のアルキレン基を表す。）で表される化合物が挙げられる。上記式（Ｘ−１１ｂ−１）から式（Ｘ−１１ｂ−３）において、Ｓｐ１６及びＳｐ１７が各々独立して炭素原子数２から８のアルキレン基である化合物が特に好ましい。 (Wherein W 13 and W 14 each independently represent a hydrogen atom or a methyl group, and Sp 16 and Sp 17 each independently represent an alkylene group having 2 to 18 carbon atoms). Is mentioned. In the above formulas (X-11b-1) to (X-11b-3), compounds in which Sp 16 and Sp 17 are each independently an alkylene group having 2 to 8 carbon atoms are particularly preferable.

また、一般式（Ｘ−１２）で表される化合物として具体的には、下記一般式（Ｘ−１２−１）から式（Ｘ−１２−７）   Specific examples of the compound represented by the general formula (X-12) include the following general formula (X-12-1) to formula (X-12-7).

Figure 2017226616
Figure 2017226616

（式中、Ｐ１４は重合性基を表し、Ｓｐ１８は単結合又は炭素原子数１から２０個のアルキレン基を表すが、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−Ｏ−ＣＯ−Ｏ−に置き換えられても良く、Ｘ１６は単結合、−Ｏ−、−ＣＯＯ−、又は−ＯＣＯ−を表し、Ｚ１５は単結合、−ＣＯＯ−又は−ＯＣＯ−を表し、Ｌ１１はフッ素原子、塩素原子、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−ＣＯＯ−、−ＯＣＯ−に置き換えられても良い炭素原子数１から１０の直鎖状又は分岐状アルキル基を表し、ｓ１１は０から４の整数を表し、Ｒ１２は水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−に置き換えられても良い炭素原子数１から２０の直鎖状又は分岐状アルキル基を表す。）で表される化合物が挙げられる。 (Wherein P 14 represents a polymerizable group, and Sp 18 represents a single bond or an alkylene group having 1 to 20 carbon atoms, but one —CH 2 — or two or more non-adjacent — CH 2 — may be replaced by —O—, —COO—, —OCO—, —O—CO—O—, and X 16 represents a single bond, —O—, —COO—, or —OCO—. , Z 15 represents a single bond, —COO— or —OCO—, and L 11 is independently a fluorine atom, a chlorine atom, one —CH 2 — or two or more non-adjacent —CH 2 —. Te -O -, - COO -, - OCO- the replaced represents a linear or branched alkyl group from a good 1 -C even of 10, s11 represents an integer from 0 4, R 12 represents hydrogen Atom, fluorine atom, chlorine atom, cyano group, nitro group, one —CH 2 — or adjacent Two or more —CH 2 — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO. -O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH ═CH—, —CF═CF— or —C≡C— represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted.

本願発明の化合物を含有する重合性液晶組成物には、当該組成物の液晶性を大きく損なわない程度に、液晶性を示さない重合性化合物を添加することも可能である。具体的には、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化合物であれば特に制限なく使用可能である。具体例として例えば「光硬化技術データブック、材料編（モノマー，オリゴマー，光重合開始剤）」（市村國宏、加藤清視監修、テクノネット社）記載のものが挙げられる。   A polymerizable compound that does not exhibit liquid crystallinity can be added to the polymerizable liquid crystal composition containing the compound of the present invention to such an extent that the liquid crystallinity of the composition is not significantly impaired. Specifically, any compound that is recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field can be used without particular limitation. Specific examples include those described in “Photocuring Technology Data Book, Materials (Monomer, Oligomer, Photopolymerization Initiator)” (supervised by Kunihiro Ichimura, Kiyosuke Kato, Technonet).

また、本願発明の化合物は光重合開始剤を使用しなくても重合させることが可能であるが、目的により光重合開始剤を添加しても構わない。その場合は光重合開始剤の濃度は、本願発明の化合物に対し０．１質量％から１５質量％が好ましく、０．２質量％から１０質量％がより好ましく、０．４質量％から８質量％がさらに好ましい。光重合開始剤としては、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類等が挙げられる。光重合開始剤の具体例としては２−メチル−１−（４−メチルチオフェニル）−２−モルホリノプロパン−１−オン（ＩＲＧＡＣＵＲＥ ９０７）、安息香酸［１−［４−（フェニルチオ）ベンゾイル］ヘプチリデン］アミノ（ＩＲＧＡＣＵＲＥ ＯＸＥ ０１）等が挙げられる。熱重合開始剤としては、アゾ化合物、過酸化物等が挙げられる。熱重合開始剤の具体例としては２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２’−アゾビス（イソブチロニトリル）等が挙げられる。また、１種類の重合開始剤を用いても良く、２種類以上の重合開始剤を併用して用いても良い。   The compound of the present invention can be polymerized without using a photopolymerization initiator, but a photopolymerization initiator may be added depending on the purpose. In this case, the concentration of the photopolymerization initiator is preferably 0.1% by mass to 15% by mass, more preferably 0.2% by mass to 10% by mass, and 0.4% by mass to 8% by mass with respect to the compound of the present invention. % Is more preferable. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides. Specific examples of the photopolymerization initiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (IRGACURE 907), benzoic acid [1- [4- (phenylthio) benzoyl] heptylidene]. Amino (IRGACURE OXE 01) etc. are mentioned. Examples of the thermal polymerization initiator include azo compounds and peroxides. Specific examples of the thermal polymerization initiator include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile) and the like. One type of polymerization initiator may be used, or two or more types of polymerization initiators may be used in combination.

また、本発明の液晶組成物には、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、ヒドロキノン類、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、組成物に対して０．００５質量％から１質量％の範囲が好ましく、０．０２質量％から０．８質量％がより好ましく、０．０３質量％から０．５質量％がさらに好ましい。また、１種類の安定剤を用いても良く、２種類以上の安定剤を併用して用いても良い。安定剤としては、具体的には式（Ｘ−１３−１）から式（Ｘ−１３−３５）   In addition, a stabilizer can be added to the liquid crystal composition of the present invention in order to improve its storage stability. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. It is done. When the stabilizer is used, the addition amount is preferably in the range of 0.005% by mass to 1% by mass, more preferably 0.02% by mass to 0.8% by mass, and 0.03% by mass with respect to the composition. To 0.5% by mass is more preferable. One kind of stabilizer may be used, or two or more kinds of stabilizers may be used in combination. Specifically, as the stabilizer, the formula (X-13-1) to the formula (X-13-35)

Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

Figure 2017226616
Figure 2017226616

（式（Ｘ−１３−１）から式（Ｘ−１３−３５）中、ｎは０から２０の整数を表す。）で表される化合物が好ましい。 (In formula (X-13-1) to formula (X-13-35), n represents an integer of 0 to 20).

また、本願発明の化合物を含有する重合性液晶組成物をフィルム類、光学素子類、機能性顔料類、医薬品類、化粧品類、コーティング剤類、合成樹脂類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。   Further, when the polymerizable liquid crystal composition containing the compound of the present invention is used for applications such as films, optical elements, functional pigments, pharmaceuticals, cosmetics, coating agents, synthetic resins, Depending on the purpose, metals, metal complexes, dyes, pigments, dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants Further, metal oxides such as ion exchange resin and titanium oxide can be added.

本願発明の化合物を含有する重合性液晶組成物を重合することにより得られるポリマーは種々の用途に利用できる。例えば、本願発明の化合物を含有する重合性液晶組成物を、配向させずに重合することにより得られるポリマーは、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、配向させた後に重合することにより得られるポリマーは、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、本願発明の化合物を含有する重合性液晶組成物を、布等でラビング処理した基板、有機薄膜を形成した基板又はＳｉＯ２を斜方蒸着した配向膜を有する基板に担持させるか、基板間に挟持させた後、当該重合性液晶組成物を重合することによって製造することができる。 The polymer obtained by polymerizing the polymerizable liquid crystal composition containing the compound of the present invention can be used for various applications. For example, a polymer obtained by polymerizing a polymerizable liquid crystal composition containing the compound of the present invention without orientation can be used as a light scattering plate, a depolarizing plate, and a moire fringe prevention plate. Moreover, the polymer obtained by superposing | polymerizing after orientating has optical anisotropy, and is useful. Such an optical anisotropic body includes, for example, a substrate obtained by rubbing a polymerizable liquid crystal composition containing the compound of the present invention with a cloth, a substrate on which an organic thin film is formed, or an alignment film on which SiO 2 is obliquely deposited. It can be produced by polymerizing the polymerizable liquid crystal composition after it is supported on a substrate having it or sandwiched between substrates.

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、炭化水素系溶媒、ハロゲン化炭化水素系溶媒、エーテル系溶媒、アルコール系溶媒、ケトン系溶媒、エステル系溶媒、非プロトン性溶媒等を使用することができるが、例えば炭化水素系溶媒としてはトルエン又はヘキサンを、ハロゲン化炭化水素系溶媒としては塩化メチレンを、エーテル系溶媒としてはテトラヒドロフラン、アセトキシ−２−エトキシエタン又はプロピレングリコールモノメチルエーテルアセテートを、アルコール系溶媒としてはメタノール、エタノール又はイソプロパノールを、ケトン系溶媒としてはアセトン、メチルエチルケトン、シクロヘキサノン、γ−ブチルラクトン又はＮ−メチルピロリジノン類を、エステル系溶媒としては酢酸エチル又はセロソルブを、非プロトン性溶媒としてはジメチルホルムアミド又はアセトニトリル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。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事も有効である。基板上にポリイミド薄膜等の中間層を設ける方法は、重合性液晶材料を重合することにより得られるポリマーと基板との密着性を向上させるために有効である。   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. As the organic solvent, hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, alcohol solvents, ketone solvents, ester solvents, aprotic solvents and the like can be used. The solvent is toluene or hexane, the halogenated hydrocarbon solvent is methylene chloride, the ether solvent is tetrahydrofuran, acetoxy-2-ethoxyethane or propylene glycol monomethyl ether acetate, and the alcohol solvent is methanol, ethanol or Isopropanol, acetone, methyl ethyl ketone, cyclohexanone, γ-butyl lactone or N-methylpyrrolidinone as the ketone solvent, ethyl acetate or cellosolve as the ester solvent, dimethyl as the aprotic solvent It can be mentioned formamide or acetonitrile. 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. 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. The method of providing an intermediate layer such as a polyimide thin film on a substrate is effective for improving the adhesion between a polymer obtained by polymerizing a polymerizable liquid crystal material and the substrate.

上記以外の配向処理としては、液晶材料の流動配向の利用、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。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。   Examples of the alignment treatment other than the above include use of fluid alignment of a liquid crystal material, 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. 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.

本願発明の化合物を含有する重合性液晶組成物を重合させる際、迅速に重合が進行することが望ましいため、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り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く、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、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を有し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／ｃｍ２〜２Ｗ／ｃｍ２が好ましい。強度が０．１ｍＷ／ｃｍ２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／ｃｍ２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。 When the polymerizable liquid crystal composition containing the compound of the present invention is polymerized, it is desirable that the polymerization proceeds rapidly. Therefore, 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 have 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 exists in the temperature range by which the liquid crystal state of the polymeric liquid crystal composition of this invention is hold | 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当該光学異方体は、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℃の範囲であることが好ましく、熱処理時間は３０秒〜１２時間の範囲であることが好ましい。   The optical anisotropic body obtained by polymerization can be subjected to a 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当該光学異方体は、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 manufactured by such a method may be peeled off from the substrate and used alone or without being peeled off. 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記述するが、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。各工程において酸素及び／又は水分に不安定な物質を取り扱う際は、窒素ガス、アルゴンガス等の不活性ガス中で作業を行うことが好ましい。以下具体的に記載されている作業に加えて必要に応じて、当業者間において通常行われている反応のクエンチ、分液・抽出、中和、洗浄、分離、精製、乾燥、濃縮等の作業を行っても良い。
（実施例１）式（Ｉ−１）で表される化合物の製造 EXAMPLES Hereinafter, although an Example is given and this invention is further described, this invention is not limited to these Examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”. When handling a substance unstable to oxygen and / or moisture in each step, it is preferable to work in an inert gas such as nitrogen gas or argon gas. In addition to the operations specifically described below, as necessary, operations such as quenching, separation / extraction, neutralization, washing, separation, purification, drying, concentration, etc. that are commonly performed among those skilled in the art May be performed.
Example 1 Production of Compound Represented by Formula (I-1)

Figure 2017226616
Figure 2017226616

窒素雰囲気下、反応容器に式（Ｉ−１−１）で表される化合物２０．０ｇ、ｔｅｒｔ−ブチルアルコール８．８ｇ、Ｎ，Ｎ−ジメチルアミノピリジン１．３ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながらジイソプロピルカルボジイミド１６．３ｇを滴下し室温で８時間撹拌した。析出物を濾過により除去し、濾液を５％塩酸及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）により精製を行い、式（Ｉ−１−２）で表される化合物２０．８ｇを得た。   Under a nitrogen atmosphere, 20.0 g of the compound represented by the formula (I-1-1), 8.8 g of tert-butyl alcohol, 1.3 g of N, N-dimethylaminopyridine, and 100 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 16.3 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 8 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 20.8 g of a compound represented by the formula (I-1-2).

反応容器に式（Ｉ−１−２）で表される化合物２０．８ｇ、メタノール２００ｍＬ、２５％水酸化ナトリウム水溶液３０ｍＬを加え６０℃で加熱撹拌した。冷却しクロロホルムを加えた。１０％塩酸を加え水層のｐＨを４〜５とし、分液処理した。有機層を食塩水で洗浄し、硫酸ナトリウムで乾燥させた。不溶物をセライト濾過した後、溶媒を留去し乾燥させることにより、式（Ｉ−１−３）で表される化合物１７．７ｇを得た。   To the reaction vessel, 20.8 g of the compound represented by the formula (I-1-2), 200 mL of methanol, and 30 mL of 25% aqueous sodium hydroxide solution were added and heated and stirred at 60 ° C. Cool and add chloroform. 10% hydrochloric acid was added to adjust the pH of the aqueous layer to 4 to 5, followed by liquid separation treatment. The organic layer was washed with brine and dried over sodium sulfate. The insoluble material was filtered through celite, and the solvent was evaporated and dried to obtain 17.7 g of a compound represented by the formula (I-1-3).

反応容器に式（Ｉ−１−３）で表される化合物５．０ｇ、式（Ｉ−１−４）で表される化合物４．２ｇ、炭酸カリウム４．５ｇ、Ｎ，Ｎ−ジメチルホルムアミド２０ｍＬを加え９０℃で８時間加熱撹拌した。ジクロロメタンで希釈し水で洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）により精製を行い、式（Ｉ−１−５）で表される化合物６．７ｇを得た。   In a reaction vessel, 5.0 g of the compound represented by formula (I-1-3), 4.2 g of the compound represented by formula (I-1-4), 4.5 g of potassium carbonate, 20 mL of N, N-dimethylformamide. And heated and stirred at 90 ° C. for 8 hours. Dilute with dichloromethane and wash with water. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 6.7 g of a compound represented by the formula (I-1-5).

反応容器に式（Ｉ−１−５）で表される化合物６．７ｇ、ジクロロメタン２５ｍＬ、ギ酸１５ｍＬを加え４０℃で８時間加熱した。溶媒を留去した後、酢酸エチルで希釈し、水及び食塩水で洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）により精製を行い、式（Ｉ−１−６）で表される化合物４．６ｇを得た。   To the reaction vessel, 6.7 g of the compound represented by the formula (I-1-5), 25 mL of dichloromethane, and 15 mL of formic acid were added and heated at 40 ° C. for 8 hours. After the solvent was distilled off, it was diluted with ethyl acetate and washed with water and brine. Purification was performed by column chromatography (alumina, ethyl acetate) to obtain 4.6 g of a compound represented by the formula (I-1-6).

窒素雰囲気下、反応容器に式（Ｉ−１−６）で表される化合物３．０ｇ、式（Ｉ−１−７）で表される化合物２．４３ｇ、Ｎ，Ｎ−ジメチルアミノピリジン０．１ｇ、ジクロロメタン４０ｍＬを加えた。氷冷しながらジイソプロピルカルボジイミド１．４ｇを滴下し室温で１０時間撹拌した。析出物を濾過により除去した後、濾液を１％塩酸、水及び食塩水で順次洗浄した。再結晶（ジクロロメタン／メタノール）を行った後、カラムクロマトグラフィー（シリカゲル、ジクロロメタン）及び再結晶（ジクロロメタン／メタノール）により精製を行い、式（Ｉ−１）で表される化合物３．７ｇを得た。
相転移温度（昇温速度：５℃／分）Ｃ ３０ Ｉ
１Ｈ ＮＭＲ（ＣＤＣｌ３）δ １．４３−１．８４（ｍ，１８Ｈ）、２．１３（ｍ，２Ｈ），２．２３（ｍ，２Ｈ），２．３５（ｍ，１Ｈ），２．５３（ｍ，１Ｈ），３．９６（ｔ，２Ｈ），４．１０（ｔ，２Ｈ），４．１９（ｍ，４Ｈ），５．８４（ｄｄ，２Ｈ），６．１４（ｄｄ，２Ｈ），６．４３（ｄｄ，２Ｈ），６．８８（ｄ，２Ｈ），６．９８（ｄ，２Ｈ）ｐｐｍ．
ＬＣＭＳ：５７３［Ｍ＋１］
（実施例２）式（Ｉ−２）で表される化合物の製造 Under a nitrogen atmosphere, 3.0 g of the compound represented by the formula (I-1-6), 2.43 g of the compound represented by the formula (I-1-7), N, N-dimethylaminopyridine, and. 1 g and 40 mL of dichloromethane were added. While cooling with ice, 1.4 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. After recrystallization (dichloromethane / methanol), purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 3.7 g of a compound represented by the formula (I-1). .
Phase transition temperature (heating rate: 5 ° C./min) C 30 I
1 H NMR (CDCl 3 ) δ 1.43-1.84 (m, 18H), 2.13 (m, 2H), 2.23 (m, 2H), 2.35 (m, 1H), 2. 53 (m, 1H), 3.96 (t, 2H), 4.10 (t, 2H), 4.19 (m, 4H), 5.84 (dd, 2H), 6.14 (dd, 2H) ), 6.43 (dd, 2H), 6.88 (d, 2H), 6.98 (d, 2H) ppm.
LCMS: 573 [M + 1]
Example 2 Production of Compound Represented by Formula (I-2)

Figure 2017226616
Figure 2017226616

窒素雰囲気下、反応容器に式（Ｉ−２−１）で表される化合物１７．７ｇ、テトラヒドロフラン１００ｍＬを加えた。氷冷しながら０．９ｍｏｌ／Ｌボラン−テトラヒドロフラン錯体１０３ｍＬを滴下し１時間撹拌した。５％塩酸を滴下した後、酢酸エチルで抽出し、食塩水で洗浄した。硫酸ナトリウムで乾燥させ、溶媒を留去することにより、式（Ｉ−２−２）で表される化合物１４．９ｇを得た。   Under a nitrogen atmosphere, 17.7 g of the compound represented by the formula (I-2-1) and 100 mL of tetrahydrofuran were added to the reaction vessel. While cooling with ice, 103 mL of 0.9 mol / L borane-tetrahydrofuran complex was added dropwise and stirred for 1 hour. After 5% hydrochloric acid was added dropwise, the mixture was extracted with ethyl acetate and washed with brine. By drying with sodium sulfate and distilling off the solvent, 14.9 g of a compound represented by the formula (I-2-2) was obtained.

窒素雰囲気下、反応容器に式（Ｉ−２−２）で表される化合物１４．９ｇ、ピリジン７．２ｇ、ジクロロメタン１５０ｍＬを加えた。氷冷しながらメタンスルホニルクロリド８．８ｇを滴下し室温で３時間撹拌した。水に注ぎ、５％塩酸及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ヘキサン／酢酸エチル）及び再結晶（アセトン／ヘキサン）により精製を行い、式（Ｉ−２−３）で表される化合物１６．３ｇを得た。   Under a nitrogen atmosphere, 14.9 g of the compound represented by the formula (I-2-2), 7.2 g of pyridine, and 150 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 8.8 g of methanesulfonyl chloride was added dropwise and stirred at room temperature for 3 hours. Poured into water and washed sequentially with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) and recrystallization (acetone / hexane) to obtain 16.3 g of a compound represented by the formula (I-2-3).

反応容器に式（Ｉ−２−３）で表される化合物５．０ｇ、式（Ｉ−２−４）で表される化合物４．５ｇ、炭酸カリウム３．５ｇ、Ｎ，Ｎ−ジメチルホルムアミド７０ｍＬを加え９０℃で１５時間加熱撹拌した。反応液を冷却し、５％塩酸に注いだ。酢酸エチルで抽出し、水及び食塩水で洗浄した。カラムクロマトグラフィー（シリカゲル、ヘキサン／酢酸エチル）により精製を行い、式（Ｉ−２−５）で表される化合物６．３ｇを得た。   In a reaction vessel, 5.0 g of the compound represented by formula (I-2-3), 4.5 g of the compound represented by formula (I-2-4), 3.5 g of potassium carbonate, 70 mL of N, N-dimethylformamide. And heated and stirred at 90 ° C. for 15 hours. The reaction was cooled and poured into 5% hydrochloric acid. Extracted with ethyl acetate and washed with water and brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 6.3 g of a compound represented by the formula (I-2-5).

反応容器に式（Ｉ−２−５）で表される化合物６．３ｇ、ジクロロメタン３０ｍＬ、ギ酸３０ｍＬを加え４０℃で８時間加熱した。酢酸エチルで希釈した後、水及び食塩水で洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／酢酸エチル）及び再結晶（酢酸エチル／ヘキサン）により精製を行い、式（Ｉ−２−６）で表される化合物５．０ｇを得た。   To the reaction vessel, 6.3 g of a compound represented by the formula (I-2-5), 30 mL of dichloromethane, and 30 mL of formic acid were added and heated at 40 ° C. for 8 hours. After diluting with ethyl acetate, it was washed with water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) and recrystallization (ethyl acetate / hexane) gave 5.0 g of the compound represented by the formula (I-2-6).

反応容器に式（Ｉ−２−６）で表される化合物５．０ｇ、式（Ｉ−２−７）で表される化合物２．３ｇ、炭酸カリウム２．５ｇ、Ｎ，Ｎ−ジメチルホルムアミド７０ｍＬを加え９０℃で１５時間加熱撹拌した。反応液を冷却し、５％塩酸に注いだ。ジクロロメタンで抽出し、水及び食塩水で洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）及び再結晶（ジクロロメタン／メタノール）により精製を行い、式（Ｉ−２）で表される化合物４．８ｇを得た。
相転移温度（昇温速度：５℃／分）Ｃ ４７ Ｉ
１Ｈ ＮＭＲ（ＣＤＣｌ３）δ １．０１（ｍ，２Ｈ），１．４０−１．８０（ｍ，１９Ｈ），１．９６−２．０５（ｍ，４Ｈ），２．２７（ｍ，１Ｈ），３．７１（ｄ，２Ｈ），３．９０（ｔ，２Ｈ），４．０７（ｔ，２Ｈ），４．１６（ｔｄ，４Ｈ），５．８２（ｄｄ，２Ｈ），６．１２（ｄｄ，２Ｈ），６．４０（ｄｄ，２Ｈ），６．８１（ｓ，４Ｈ）ｐｐｍ．
ＬＣＭＳ：５５９［Ｍ＋１］
（実施例３）式（Ｉ−３）で表される化合物の製造 In a reaction vessel, 5.0 g of the compound represented by the formula (I-2-6), 2.3 g of the compound represented by the formula (I-2-7), 2.5 g of potassium carbonate, 70 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 15 hours. The reaction was cooled and poured into 5% hydrochloric acid. Extracted with dichloromethane and washed with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) and recrystallization (dichloromethane / methanol) to obtain 4.8 g of a compound represented by the formula (I-2).
Phase transition temperature (heating rate: 5 ° C./min) C 47 I
1 H NMR (CDCl 3 ) δ 1.01 (m, 2H), 1.40-1.80 (m, 19H), 1.96-2.05 (m, 4H), 2.27 (m, 1H) ), 3.71 (d, 2H), 3.90 (t, 2H), 4.07 (t, 2H), 4.16 (td, 4H), 5.82 (dd, 2H), 6.12 (Dd, 2H), 6.40 (dd, 2H), 6.81 (s, 4H) ppm.
LCMS: 559 [M + 1]
Example 3 Production of Compound Represented by Formula (I-3)

Figure 2017226616
Figure 2017226616

窒素雰囲気下、反応容器に式（Ｉ−３−１）で表される化合物３．０ｇ、式（Ｉ−３−２）で表される化合物４．４ｇ、Ｎ，Ｎ−ジメチルアミノピリジン０．１ｇ、ジクロロメタン４０ｍＬを加えた。氷冷しながらジイソプロピルカルボジイミド２．３ｇを滴下し室温で１０時間撹拌した。析出物を濾過により除去した後、濾液を１％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）により精製を行い、式（Ｉ−３−３）で表される化合物３．６ｇを得た。   Under a nitrogen atmosphere, 3.0 g of the compound represented by formula (I-3-1), 4.4 g of the compound represented by formula (I-3-2), N, N-dimethylaminopyridine, and. 1 g and 40 mL of dichloromethane were added. While cooling with ice, 2.3 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 3.6 g of a compound represented by the formula (I-3-3).

反応容器に式（Ｉ−３−３）で表される化合物３．６ｇ、ジクロロメタン１５ｍＬ、ギ酸１５ｍＬを加え４０℃で８時間加熱した。溶媒を留去した後、酢酸エチルで希釈し、水及び食塩水で洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）により精製を行い、式（Ｉ−３−４）で表される化合物２．８ｇを得た。   To the reaction vessel, 3.6 g of the compound represented by the formula (I-3-3), 15 mL of dichloromethane, and 15 mL of formic acid were added and heated at 40 ° C. for 8 hours. After the solvent was distilled off, it was diluted with ethyl acetate and washed with water and brine. Purification was performed by column chromatography (alumina, ethyl acetate) to obtain 2.8 g of a compound represented by the formula (I-3-4).

反応容器に式（Ｉ−３−４）で表される化合物２．８ｇ、式（Ｉ−３−５）で表される化合物１．４ｇ、炭酸カリウム１．４ｇ、Ｎ，Ｎ−ジメチルホルムアミド２０ｍＬを加え９０℃で８時間加熱撹拌した。ジクロロメタンで希釈し水で洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）及び再結晶（ジクロロメタン／メタノール）により精製を行い、式（Ｉ−３）で表される化合物３．１ｇを得た。
ＬＣＭＳ：５７３［Ｍ＋１］
（実施例４）式（Ｉ−４）で表される化合物の製造 In a reaction vessel, 2.8 g of the compound represented by the formula (I-3-4), 1.4 g of the compound represented by the formula (I-3-5), 1.4 g of potassium carbonate, 20 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 8 hours. Dilute with dichloromethane and wash with water. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) and recrystallization (dichloromethane / methanol) to obtain 3.1 g of a compound represented by the formula (I-3).
LCMS: 573 [M + 1]
Example 4 Production of Compound Represented by Formula (I-4)

Figure 2017226616
Figure 2017226616

ディーンスターク装置を備えた反応容器に式（Ｉ−４−１）で表される化合物８．０ｇ、メタクリル酸エチル５．３ｇ、ジブチルスズオキシド０．５ｇ、トルエン８０ｍＬを加え、反応溶媒を除去しながら、新たにトルエンを追加しながら、１０時間加熱還流させた。反応液を水及び食塩水で洗浄した後、カラムクロマトグラフィー（ヘキサン／酢酸エチル）により精製を行い、式（Ｉ−４−２）で表される化合物８．７ｇを得た。   While adding 8.0 g of the compound represented by the formula (I-4-1), 5.3 g of ethyl methacrylate, 0.5 g of dibutyltin oxide, and 80 mL of toluene to a reaction vessel equipped with a Dean-Stark apparatus, the reaction solvent was removed. The mixture was heated to reflux for 10 hours while adding new toluene. The reaction solution was washed with water and brine, and then purified by column chromatography (hexane / ethyl acetate) to obtain 8.7 g of a compound represented by the formula (I-4-2).

ＷＯ２０１５／１４７２４３Ａ１号公報に記載の方法によって式（Ｉ−４−３）で表される化合物を製造した。窒素雰囲気下、反応容器に式（Ｉ−４−２）で表される化合物３．０ｇ、式（Ｉ−４−３）で表される化合物３．５ｇ、Ｎ，Ｎ−ジメチルアミノピリジン０．１ｇ、ジクロロメタン４０ｍＬを加えた。氷冷しながらジイソプロピルカルボジイミド１．８ｇを滴下し室温で１０時間撹拌した。析出物を濾過により除去した後、濾液を１％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）により精製を行い、式（Ｉ−４）で表される化合物４．４ｇを得た。
ＬＣＭＳ：５３７［Ｍ＋１］
（実施例５）式（Ｉ−５）で表される化合物の製造 A compound represented by the formula (I-4-3) was produced by the method described in WO2015 / 147243A1. Under a nitrogen atmosphere, 3.0 g of the compound represented by formula (I-4-2), 3.5 g of the compound represented by formula (I-4-3), N, N-dimethylaminopyridine,. 1 g and 40 mL of dichloromethane were added. While cooling with ice, 1.8 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 4.4 g of a compound represented by the formula (I-4).
LCMS: 537 [M + 1]
Example 5 Production of Compound Represented by Formula (I-5)

Figure 2017226616
Figure 2017226616

特開平１１−０８００８１号公報に記載の方法によって式（Ｉ−５−１）で表される化合物を製造した。窒素雰囲気下、反応容器に式（Ｉ−５−１）で表される化合物３．０ｇ、式（Ｉ−５−２）で表される化合物２．９ｇ、Ｎ，Ｎ−ジメチルアミノピリジン０．１ｇ、ジクロロメタン４０ｍＬを加えた。氷冷しながらジイソプロピルカルボジイミド１．３ｇを滴下し室温で１０時間撹拌した。析出物を濾過により除去した後、濾液を１％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）により精製を行い、式（Ｉ−５）で表される化合物４．０ｇを得た。
ＬＣＭＳ：６４５［Ｍ＋１］
（実施例６）式（Ｉ−６）で表される化合物の製造 A compound represented by the formula (I-5-1) was produced by the method described in JP-A-11-080081. Under a nitrogen atmosphere, 3.0 g of the compound represented by the formula (I-5-1), 2.9 g of the compound represented by the formula (I-5-2), N, N-dimethylaminopyridine 1 g and 40 mL of dichloromethane were added. While cooling with ice, 1.3 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 4.0 g of a compound represented by the formula (I-5).
LCMS: 645 [M + 1]
Example 6 Production of Compound Represented by Formula (I-6)

Figure 2017226616
Figure 2017226616

反応容器に式（Ｉ−６−１）で表される化合物５．０ｇ、式（Ｉ−６−２）で表される化合物７．７ｇ、炭酸カリウム１６．７ｇ、Ｎ，Ｎ−ジメチルホルムアミド１００ｍＬを加え９０℃で１０時間加熱撹拌した。反応液を１％塩酸に注ぎ、酢酸エチルで抽出した。水及び食塩水で洗浄した後、カラムクロマトグラフィー（アルミナ、酢酸エチル）により精製を行い、式（Ｉ−６−３）で表される化合物５．６ｇを得た。   In a reaction vessel, 5.0 g of the compound represented by the formula (I-6-1), 7.7 g of the compound represented by the formula (I-6-2), 16.7 g of potassium carbonate, 100 mL of N, N-dimethylformamide. And heated and stirred at 90 ° C. for 10 hours. The reaction mixture was poured into 1% hydrochloric acid and extracted with ethyl acetate. After washing with water and brine, purification was performed by column chromatography (alumina, ethyl acetate) to obtain 5.6 g of a compound represented by the formula (I-6-3).

窒素雰囲気下、反応容器に式（Ｉ−６−３）で表される化合物５．６ｇ、式（Ｉ−６−４）で表される化合物６．６ｇ、Ｎ，Ｎ−ジメチルアミノピリジン０．２ｇ、ジクロロメタン８０ｍＬを加えた。氷冷しながらジイソプロピルカルボジイミド３．０ｇを滴下し室温で１０時間撹拌した。析出物を濾過により除去した後、濾液を１％塩酸、水及び食塩水で順次洗浄した。活性炭処理した後、カラムクロマトグラフィー（シリカゲル、ジクロロメタン）により精製を行い、式（Ｉ−６）で表される化合物７．１ｇを得た。
ＬＣＭＳ：５８７［Ｍ＋１］
（実施例７）式（Ｉ−７）で表される化合物の製造 Under a nitrogen atmosphere, 5.6 g of a compound represented by the formula (I-6-3), 6.6 g of a compound represented by the formula (I-6-4), N, N-dimethylaminopyridine 2 g, 80 mL dichloromethane was added. While cooling with ice, 3.0 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. After the activated carbon treatment, purification was performed by column chromatography (silica gel, dichloromethane) to obtain 7.1 g of a compound represented by the formula (I-6).
LCMS: 587 [M + 1]
Example 7 Production of Compound Represented by Formula (I-7)

Figure 2017226616
Figure 2017226616

窒素雰囲気下、反応容器に水素化ナトリウム２．５ｇ、テトラヒドロフラン２０ｍＬを加えた。式（Ｉ−７−２）で表される化合物５．０ｇをテトラヒドロフラン２０ｍＬに溶解させた溶液を滴下し、５０℃で３時間加熱撹拌した。式（Ｉ−７−１）で表される化合物７．７ｇをテトラヒドロフラン１５ｍＬに溶解させた溶液を滴下し５０℃で３時間加熱撹拌した。反応液を１％塩酸に注ぎ、ジクロロメタンで抽出した。水及び食塩水で洗浄した後、カラムクロマトグラフィー（ジクロロメタン／ヘキサン）により精製を行い、式（Ｉ−７−３）で表される化合物３．２ｇを得た。   Under a nitrogen atmosphere, 2.5 g of sodium hydride and 20 mL of tetrahydrofuran were added to the reaction vessel. A solution prepared by dissolving 5.0 g of the compound represented by the formula (I-7-2) in 20 mL of tetrahydrofuran was dropped, and the mixture was heated and stirred at 50 ° C. for 3 hours. A solution prepared by dissolving 7.7 g of the compound represented by the formula (I-7-1) in 15 mL of tetrahydrofuran was dropped, and the mixture was heated and stirred at 50 ° C. for 3 hours. The reaction mixture was poured into 1% hydrochloric acid and extracted with dichloromethane. After washing with water and brine, purification was performed by column chromatography (dichloromethane / hexane) to obtain 3.2 g of a compound represented by the formula (I-7-3).

窒素雰囲気下、反応容器に式（Ｉ−７−３）で表される化合物３．２ｇ、ピリジン０．９ｇ、ジクロロメタン２０ｍＬを加えた。氷冷しながらメタンスルホニルクロリド１．２ｇを滴下し室温で３時間撹拌した。反応液を１％塩酸に注ぎ分液処理した後、食塩水で洗浄した。カラムクロマトグラフィー（シリカゲル、ヘキサン／酢酸エチル）により精製を行い、式（Ｉ−７−４）で表される化合物３．２ｇを得た。   Under a nitrogen atmosphere, 3.2 g of the compound represented by the formula (I-7-3), 0.9 g of pyridine, and 20 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 1.2 g of methanesulfonyl chloride was added dropwise and stirred at room temperature for 3 hours. The reaction solution was poured into 1% hydrochloric acid and subjected to a liquid separation treatment, followed by washing with brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 3.2 g of a compound represented by the formula (I-7-4).

反応容器に式（Ｉ−７−５）で表される化合物５．０ｇ、式（Ｉ−７−６）で表される化合物６．５ｇ、炭酸カリウム１４．２ｇ、Ｎ，Ｎ−ジメチルホルムアミド７０ｍＬを加え９０℃で１０時間加熱撹拌した。酢酸エチルで希釈し１％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ヘキサン／酢酸エチル）により精製を行い、式（Ｉ−７−７）で表される化合物４．１ｇを得た。   In a reaction vessel, 5.0 g of the compound represented by the formula (I-7-5), 6.5 g of the compound represented by the formula (I-7-6), 14.2 g of potassium carbonate, 70 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 10 hours. The mixture was diluted with ethyl acetate and washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 4.1 g of a compound represented by the formula (I-7-7).

反応容器に式（Ｉ−７−７）で表される化合物３．０ｇ、式（Ｉ−７−４）で表される化合物４．１ｇ、炭酸カリウム２．１ｇ、Ｎ，Ｎ−ジメチルホルムアミド２０ｍＬを加え９０℃で１０時間加熱撹拌した。ジクロロメタンで希釈し水及び食塩水で洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）により精製を行い、式（Ｉ−７）で表される化合物４．３ｇを得た。
ＬＣＭＳ：６１３［Ｍ＋１］
（実施例８）式（Ｉ−８）で表される化合物の製造 In a reaction vessel, 3.0 g of the compound represented by the formula (I-7-7), 4.1 g of the compound represented by the formula (I-7-4), 2.1 g of potassium carbonate, 20 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 10 hours. Diluted with dichloromethane and washed with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 4.3 g of a compound represented by the formula (I-7).
LCMS: 613 [M + 1]
Example 8 Production of Compound Represented by Formula (I-8)

Figure 2017226616
Figure 2017226616

窒素雰囲気下、反応容器に式（Ｉ−８−１）で表される化合物５．０ｇ、式（Ｉ−８−２）で表される化合物３．３ｇ、Ｎ，Ｎ−ジメチルアミノピリジン０．３ｇ、ジクロロメタン７０ｍＬを加えた。氷冷しながらジイソプロピルカルボジイミド３．５ｇを滴下し室温で８時間撹拌した。析出物を濾過により除去し、濾液を５％塩酸及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）により精製を行い、式（Ｉ−８−３）で表される化合物５．５ｇを得た。   Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-8-1), 3.3 g of the compound represented by the formula (I-8-2), N, N-dimethylaminopyridine 3 g and 70 mL dichloromethane were added. While cooling with ice, 3.5 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 8 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 5.5 g of a compound represented by the formula (I-8-3).

反応容器に式（Ｉ−８−３）で表される化合物５．５ｇ、ジクロロメタン２５ｍＬ、ギ酸１５ｍＬを加え４０℃で８時間加熱した。溶媒を留去した後、酢酸エチルで希釈し、水及び食塩水で洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）により精製を行い、式（Ｉ−８−４）で表される化合物４．１ｇを得た。   5.5 g of the compound represented by the formula (I-8-3), 25 mL of dichloromethane, and 15 mL of formic acid were added to the reaction vessel and heated at 40 ° C. for 8 hours. After the solvent was distilled off, it was diluted with ethyl acetate and washed with water and brine. Purification was performed by column chromatography (alumina, ethyl acetate) to obtain 4.1 g of a compound represented by the formula (I-8-4).

窒素雰囲気下、反応容器に式（Ｉ−８−４）で表される化合物４．１ｇ、式（Ｉ−８−５）で表される化合物１．８ｇ、Ｎ，Ｎ−ジメチルアミノピリジン０．２ｇ、ジクロロメタン７０ｍＬを加えた。氷冷しながらジイソプロピルカルボジイミド２．２ｇを滴下し室温で８時間撹拌した。析出物を濾過により除去し、濾液を５％塩酸及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）により精製を行い、式（Ｉ−８−６）で表される化合物４．０ｇを得た。   Under a nitrogen atmosphere, 4.1 g of a compound represented by the formula (I-8-4), 1.8 g of a compound represented by the formula (I-8-5), N, N-dimethylaminopyridine 2 g, 70 mL dichloromethane was added. While cooling with ice, 2.2 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 8 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 4.0 g of a compound represented by the formula (I-8-6).

反応容器に式（Ｉ−８−６）で表される化合物４．０ｇ、メタノール８０ｍＬ、リン酸二水素ナトリウム二水和物２．５ｇを水３０ｍＬに溶解させた水溶液、３０％過酸化水素水５．０ｇを加えた。亜塩素酸ナトリウム５．０ｇを水５０ｍＬに溶解させた水溶液を滴下し、４５℃で５時間加熱撹拌した。水で希釈し、酢酸エチルで抽出した。水及び食塩水で順次洗浄した後、カラムクロマトグラフィー（アルミナ、酢酸エチル）により精製を行い、式（Ｉ−８−７）で表される化合物２．９ｇを得た。   An aqueous solution in which 4.0 g of a compound represented by the formula (I-8-6), 80 mL of methanol, and 2.5 g of sodium dihydrogen phosphate dihydrate are dissolved in 30 mL of water in a reaction vessel, 30% aqueous hydrogen peroxide 5.0 g was added. An aqueous solution in which 5.0 g of sodium chlorite was dissolved in 50 mL of water was dropped, and the mixture was heated and stirred at 45 ° C. for 5 hours. Dilute with water and extract with ethyl acetate. After sequentially washing with water and brine, purification was performed by column chromatography (alumina, ethyl acetate) to obtain 2.9 g of a compound represented by the formula (I-8-7).

窒素雰囲気下、反応容器に式（Ｉ−８−８）で表される化合物５．０ｇ、式（Ｉ−８−９）で表される化合物４．８ｇ、Ｎ，Ｎ−ジメチルアミノピリジン０．２ｇ、ジクロロメタン８０ｍＬを加えた。氷冷しながらジイソプロピルカルボジイミド８．０ｇを滴下し室温で８時間撹拌した。析出物を濾過により除去し、濾液を５％塩酸及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）により精製を行い、式（Ｉ−８−１０）で表される化合物６．２ｇを得た。   Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-8-8), 4.8 g of the compound represented by the formula (I-8-9), N, N-dimethylaminopyridine 2 g, 80 mL dichloromethane was added. While cooling with ice, 8.0 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 8 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 6.2 g of a compound represented by the formula (I-8-10).

反応容器に式（Ｉ−８−１０）で表される化合物１．３ｇ、式（Ｉ−８−７）で表される化合物２．９ｇ、炭酸カリウム１．５ｇ、Ｎ，Ｎ−ジメチルホルムアミド２０ｍＬを加え９０℃で８時間加熱撹拌した。ジクロロメタンで希釈し水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）により精製を行い、式（Ｉ−８）で表される化合物３．１ｇを得た。
ＬＣＭＳ：５３１［Ｍ＋１］
（実施例９）式（Ｉ−９）で表される化合物の製造 In a reaction vessel, 1.3 g of the compound represented by the formula (I-8-10), 2.9 g of the compound represented by the formula (I-8-7), 1.5 g of potassium carbonate, 20 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 8 hours. Diluted with dichloromethane and washed sequentially with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 3.1 g of a compound represented by the formula (I-8).
LCMS: 531 [M + 1]
Example 9 Production of Compound Represented by Formula (I-9)

Figure 2017226616
Figure 2017226616

Ｍａｃｒｏｍｏｌｅｃｕｌａｒ Ｃｈｅｍｉｓｔｒｙ ａｎｄ Ｐｈｙｓｉｃｓ誌、２００９年、２１０巻、７号、５３１−５４１頁に記載の方法によって式（Ｉ−９−１）で表される化合物を製造した。窒素雰囲気下、反応容器に式（Ｉ−９−１）で表される化合物５．０ｇ、式（Ｉ−９−２）で表される化合物５．３ｇ、Ｎ，Ｎ−ジメチルアミノピリジン０．３ｇ、ジクロロメタン７０ｍＬを加えた。氷冷しながらジイソプロピルカルボジイミド３．５ｇを滴下し室温で８時間撹拌した。析出物を濾過により除去し、濾液を５％塩酸及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）により精製を行い、式（Ｉ−９−３）で表される化合物６．３ｇを得た。   A compound represented by the formula (I-9-1) was produced by the method described in Macromolecular Chemistry and Physics, 2009, Vol. 210, No. 7, pp. 531-541. Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-9-1), 5.3 g of the compound represented by the formula (I-9-2), N, N-dimethylaminopyridine 3 g and 70 mL dichloromethane were added. While cooling with ice, 3.5 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 8 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 6.3 g of a compound represented by the formula (I-9-3).

反応容器に式（Ｉ−９−３）で表される化合物６．３ｇ、ジクロロメタン２５ｍＬ、ギ酸２５ｍＬを加え４０℃で８時間加熱した。溶媒を留去した後、酢酸エチルで希釈し、水及び食塩水で洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）により精製を行い、式（Ｉ−９−４）で表される化合物２．５ｇを得た。   To the reaction vessel, 6.3 g of the compound represented by the formula (I-9-3), 25 mL of dichloromethane, and 25 mL of formic acid were added and heated at 40 ° C. for 8 hours. After the solvent was distilled off, it was diluted with ethyl acetate and washed with water and brine. Purification was performed by column chromatography (alumina, ethyl acetate) to obtain 2.5 g of a compound represented by the formula (I-9-4).

窒素雰囲気下、反応容器に式（Ｉ−９−４）で表される化合物２．５ｇ、式（Ｉ−９−５）で表される化合物１．１ｇ、Ｎ，Ｎ−ジメチルアミノピリジン０．１ｇ、ジクロロメタン４０ｍＬを加えた。氷冷しながらジイソプロピルカルボジイミド１．８ｇを滴下し室温で１０時間撹拌した。析出物を濾過により除去した後、濾液を１％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ヘキサン／酢酸エチル）により精製を行い、式（Ｉ−９−６）で表される化合物１．４ｇを得た。   Under a nitrogen atmosphere, 2.5 g of the compound represented by the formula (I-9-4), 1.1 g of the compound represented by the formula (I-9-5), N, N-dimethylaminopyridine,. 1 g and 40 mL of dichloromethane were added. While cooling with ice, 1.8 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 1.4 g of a compound represented by the formula (I-9-6).

窒素雰囲気下、反応容器に式（Ｉ−９−６）で表される化合物１．４ｇ、式（Ｉ−９−７）で表される化合物０．４ｇ、トリフェニルホスフィン０．８ｇ、テトラヒドロフラン２０ｍＬを加えた。氷冷しながらアゾジカルボン酸ジイソプロピル０．６ｇを滴下し室温で５時間撹拌した。ジクロロメタンで希釈した後、水及び食塩水で洗浄した。カラムクロマトグラフィー（ジクロロメタン／ヘキサン）により精製を行い、式（Ｉ−９）で表される化合物１．２ｇを得た。
ＬＣＭＳ：６４９［Ｍ＋１］
（実施例１０）式（Ｉ−１０）で表される化合物の製造 Under a nitrogen atmosphere, 1.4 g of the compound represented by the formula (I-9-6), 0.4 g of the compound represented by the formula (I-9-7), 0.8 g of triphenylphosphine, 20 mL of tetrahydrofuran in a reaction vessel. Was added. While cooling with ice, 0.6 g of diisopropyl azodicarboxylate was added dropwise and stirred at room temperature for 5 hours. After dilution with dichloromethane, it was washed with water and brine. Purification was performed by column chromatography (dichloromethane / hexane) to obtain 1.2 g of a compound represented by the formula (I-9).
LCMS: 649 [M + 1]
Example 10 Production of Compound Represented by Formula (I-10)

Figure 2017226616
Figure 2017226616

窒素雰囲気下、反応容器に式（Ｉ−１０−１）で表される化合物５．０ｇ、ｐ−トルエンスルホン酸ピリジニウム０．２ｇ、ジクロロメタン３０ｍＬを加えた。氷冷しながら３，４−ジヒドロ−２Ｈ−ピラン３．８ｇを加え撹拌した。飽和炭酸水素ナトリウム水溶液及び食塩水で洗浄した後、カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行い、式（Ｉ−１０−２）で表される化合物７．６ｇを得た。   Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-10-1), 0.2 g of pyridinium p-toluenesulfonate, and 30 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 3.8 g of 3,4-dihydro-2H-pyran was added and stirred. After washing with a saturated aqueous sodium hydrogen carbonate solution and brine, purification was performed by column chromatography (alumina, dichloromethane) to obtain 7.6 g of a compound represented by the formula (I-10-2).

反応容器に式（Ｉ−１０−３）で表される化合物４．１ｇ、テトラヒドロフラン２０ｍＬ、水素化ナトリウム１．１ｇを加え室温で１時間撹拌した。式（Ｉ−１０−２）で表される化合物７．６ｇをテトラヒドロフラン２０ｍＬに溶解させた溶液を滴下し５０℃で８時間加熱撹拌した。反応液を氷水に注ぎ、ジクロロメタンで抽出した。カラムクロマトグラフィー（アルミナ、ヘキサン）により精製を行い、式（Ｉ−１０−４）で表される化合物７．３ｇを得た。   To the reaction vessel was added 4.1 g of the compound represented by the formula (I-10-3), 20 mL of tetrahydrofuran and 1.1 g of sodium hydride, and the mixture was stirred at room temperature for 1 hour. A solution prepared by dissolving 7.6 g of the compound represented by the formula (I-10-2) in 20 mL of tetrahydrofuran was dropped, and the mixture was heated and stirred at 50 ° C. for 8 hours. The reaction mixture was poured into ice water and extracted with dichloromethane. Purification was performed by column chromatography (alumina, hexane) to obtain 7.3 g of a compound represented by the formula (I-10-4).

反応容器にギ酸３０ｍＬ、ジクロロメタン３０ｍＬを加え、３５％過酸化水素水１５ｍＬを滴下し撹拌した。式（Ｉ−１０−４）で表される化合物７．３ｇをジクロロメタン２０ｍＬに溶解させた溶液を滴下し４０℃で６時間加熱撹拌した。水及び食塩水で洗浄した後、カラムクロマトグラフィー（アルミナ、ヘキサン）により精製を行い、式（Ｉ−１０−５）で表される化合物６．１ｇを得た。   30 mL of formic acid and 30 mL of dichloromethane were added to the reaction vessel, and 15 mL of 35% aqueous hydrogen peroxide was added dropwise and stirred. A solution prepared by dissolving 7.3 g of the compound represented by the formula (I-10-4) in 20 mL of dichloromethane was added dropwise, and the mixture was heated and stirred at 40 ° C. for 6 hours. After washing with water and brine, purification was performed by column chromatography (alumina, hexane) to obtain 6.1 g of a compound represented by the formula (I-10-5).

反応容器に式（Ｉ−１０−５）で表される化合物６．１ｇ、メタノール３０ｍＬ、テトラヒドロフラン３０ｍＬ、濃塩酸１ｍＬを加え室温で５時間撹拌した。ジクロロメタンで希釈した後、水及び食塩水で洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）により精製を行い、式（Ｉ−１０−６）で表される化合物４．０ｇを得た。   To the reaction vessel, 6.1 g of a compound represented by the formula (I-10-5), 30 mL of methanol, 30 mL of tetrahydrofuran, and 1 mL of concentrated hydrochloric acid were added and stirred at room temperature for 5 hours. After dilution with dichloromethane, it was washed with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 4.0 g of a compound represented by the formula (I-10-6).

Ｓｙｎｔｈｅｓｉｓ誌、２０１１年、５号、７６９−７７７頁に記載の方法によって式（Ｉ−１０−７）で表される化合物を製造した。窒素雰囲気下、反応容器に式（Ｉ−１０−７）で表される化合物５．０ｇ、式（Ｉ−１０−８）で表される化合物１．９ｇ、Ｎ，Ｎ−ジメチルアミノピリジン０．２ｇ、ジクロロメタン５０ｍＬを加えた。氷冷しながらジイソプロピルカルボジイミド３．４ｇを滴下し室温で１０時間撹拌した。析出物を濾過により除去した後、濾液を１％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）により精製を行い、式（Ｉ−１０−９）で表される化合物４．６ｇを得た。   A compound represented by the formula (I-10-7) was produced by the method described in Synthesis, 2011, No. 5, pages 769-777. Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-10-7), 1.9 g of the compound represented by the formula (I-10-8), N, N-dimethylaminopyridine 2 g, 50 mL dichloromethane was added. While cooling with ice, 3.4 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 4.6 g of a compound represented by the formula (I-10-9).

反応容器に式（Ｉ−１０−９）で表される化合物４．６ｇ、メタノール３０ｍＬ、テトラヒドロフラン３０ｍＬ、濃塩酸１ｍＬを加え室温で５時間撹拌した。ジクロロメタンで希釈した後、水及び食塩水で洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）により精製を行い、式（Ｉ−１０−１０）で表される化合物２．９ｇを得た。   To the reaction vessel, 4.6 g of the compound represented by the formula (I-10-9), 30 mL of methanol, 30 mL of tetrahydrofuran, and 1 mL of concentrated hydrochloric acid were added and stirred at room temperature for 5 hours. After dilution with dichloromethane, it was washed with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 2.9 g of a compound represented by the formula (I-10-10).

窒素雰囲気下、反応容器に式（Ｉ−１０−１０）で表される化合物２．９ｇ、式（Ｉ−１０−１１）で表される化合物３．２ｇ、Ｎ，Ｎ−ジメチルアミノピリジン０．２ｇ、ジクロロメタン５０ｍＬを加えた。氷冷しながらジイソプロピルカルボジイミド４．０ｇを滴下し室温で１０時間撹拌した。析出物を濾過により除去した後、濾液を１％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／酢酸エチル）により精製を行い、式（Ｉ−１０−１２）で表される化合物３．０ｇを得た。   Under a nitrogen atmosphere, 2.9 g of the compound represented by the formula (I-10-10), 3.2 g of the compound represented by the formula (I-10-11), N, N-dimethylaminopyridine 2 g, 50 mL dichloromethane was added. While cooling with ice, 4.0 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / ethyl acetate) to obtain 3.0 g of a compound represented by the formula (I-10-12).

窒素雰囲気下、反応容器に式（Ｉ−１０−１２）で表される化合物３．０ｇ、式（Ｉ−１０−６）で表される化合物１．５ｇ、Ｎ，Ｎ−ジメチルアミノピリジン０．２ｇ、ジクロロメタン５０ｍＬを加えた。氷冷しながらジイソプロピルカルボジイミド１．１ｇを滴下し室温で１０時間撹拌した。析出物を濾過により除去した後、濾液を１％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）により精製を行い、式（Ｉ−１０）で表される化合物３．０ｇを得た。
ＬＣＭＳ：６１１［Ｍ＋１］
（実施例１１）式（Ｉ−１１）で表される化合物の製造 Under a nitrogen atmosphere, 3.0 g of the compound represented by the formula (I-10-12), 1.5 g of the compound represented by the formula (I-10-6), N, N-dimethylaminopyridine,. 2 g, 50 mL dichloromethane was added. While cooling with ice, 1.1 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 3.0 g of a compound represented by the formula (I-10).
LCMS: 611 [M + 1]
Example 11 Production of Compound Represented by Formula (I-11)

Figure 2017226616
Figure 2017226616

反応容器に式（Ｉ−１１−１）で表される化合物１０．０ｇ、式（Ｉ−１１−２）で表される化合物９．６ｇ、炭酸カリウム２０．９ｇ、Ｎ，Ｎ−ジメチルホルムアミド１００ｍＬを加え９０℃で８時間加熱撹拌した。ジクロロメタンで希釈し水で洗浄した。カラムクロマトグラフィー（シリカゲル、ヘキサン／酢酸エチル）により精製を行い、式（Ｉ−１１−３）で表される化合物５．３ｇを得た。   In a reaction vessel, 10.0 g of the compound represented by the formula (I-11-1), 9.6 g of the compound represented by the formula (I-11-2), 20.9 g of potassium carbonate, 100 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 8 hours. Dilute with dichloromethane and wash with water. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 5.3 g of a compound represented by the formula (I-11-3).

実施例１において式（Ｉ−１−６）で表される化合物を式（Ｉ−１１−３）で表される化合物に置き換えた以外は同様の方法によって式（Ｉ−１１）で表される化合物を製造した。
ＬＣＭＳ：５９９［Ｍ＋１］
（実施例１２）式（Ｉ−１２）で表される化合物の製造 It is represented by the formula (I-11) by the same method except that the compound represented by the formula (I-1-6) in Example 1 is replaced with the compound represented by the formula (I-11-3). The compound was prepared.
LCMS: 599 [M + 1]
Example 12 Production of Compound Represented by Formula (I-12)

Figure 2017226616
Figure 2017226616

実施例１１において式（Ｉ−１１−１）で表される化合物を式（Ｉ−１２−１）で表される化合物に置き換えた以外は同様の方法によって式（Ｉ−１２）で表される化合物を製造した。
ＬＣＭＳ：５７５［Ｍ＋１］
（実施例１３）式（Ｉ−１３）で表される化合物の製造 In Example 11, the compound represented by the formula (I-11-1) is represented by the formula (I-12) by the same method except that the compound represented by the formula (I-12-1) is replaced. The compound was prepared.
LCMS: 575 [M + 1]
Example 13 Production of Compound Represented by Formula (I-13)

Figure 2017226616
Figure 2017226616

ディーンスターク装置を備えた反応容器に式（Ｉ−１３−１）で表される化合物５．０ｇ、ｐ−トルエンスルホン酸一水和物０．１ｇ、酢酸エチル５０ｍＬを加え、溶媒を除去しながら新たに酢酸エチルを追加しながら８時間加熱還流させた。飽和炭酸水素ナトリウム水溶液及び食塩水で洗浄した後、カラムクロマトグラフィー（シリカゲル、ヘキサン／酢酸エチル）により精製を行い、式（Ｉ−１３−２）で表される化合物５．６ｇを得た。   While adding 5.0 g of the compound represented by the formula (I-13-1), 0.1 g of p-toluenesulfonic acid monohydrate, and 50 mL of ethyl acetate to a reaction vessel equipped with a Dean-Stark apparatus, the solvent was removed. The mixture was refluxed with heating for 8 hours while adding new ethyl acetate. After washing with a saturated aqueous sodium hydrogen carbonate solution and brine, purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 5.6 g of a compound represented by the formula (I-13-2).

窒素雰囲気下、反応容器に式（Ｉ−１３−２）で表される化合物２．０ｇ、式（Ｉ−１３−３）で表される化合物３．０ｇ、Ｎ，Ｎ−ジメチルアミノピリジン０．１ｇ、ジクロロメタン３０ｍＬを加えた。氷冷しながらジイソプロピルカルボジイミド１．４ｇを滴下し室温で８時間撹拌した。析出物を濾過により除去し、濾液を５％塩酸及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）により精製を行い、式（Ｉ−１３−４）で表される化合物３．８ｇを得た。   Under a nitrogen atmosphere, 2.0 g of the compound represented by the formula (I-13-2), 3.0 g of the compound represented by the formula (I-13-3), N, N-dimethylaminopyridine,. 1 g and 30 mL of dichloromethane were added. While cooling with ice, 1.4 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 8 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 3.8 g of a compound represented by the formula (I-13-4).

反応容器に式（Ｉ−１３−４）で表される化合物３．８ｇ、メタノール５０ｍＬ、２５％水酸化ナトリウム水溶液３０ｍＬを加え、５０℃で３時間加熱撹拌した。１０％塩酸で中和した後、酢酸エチルで希釈し、食塩水で洗浄した。カラムクロマトグラフィー（シリカゲル、ヘキサン／酢酸エチル）により精製を行い、式（Ｉ−１３−５）で表される化合物２．５ｇを得た。   To the reaction vessel, 3.8 g of the compound represented by the formula (I-13-4), 50 mL of methanol, and 30 mL of 25% aqueous sodium hydroxide solution were added, and the mixture was heated and stirred at 50 ° C. for 3 hours. The mixture was neutralized with 10% hydrochloric acid, diluted with ethyl acetate, and washed with brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 2.5 g of a compound represented by the formula (I-13-5).

窒素雰囲気下、反応容器に式（Ｉ−１３−５）で表される化合物２．５ｇ、式（Ｉ−１３−６）で表される化合物０．４ｇ、Ｎ，Ｎ−ジメチルアミノピリジン０．１ｇ、ジクロロメタン３０ｍＬを加えた。氷冷しながらジイソプロピルカルボジイミド０．８ｇを滴下し室温で８時間撹拌した。析出物を濾過により除去し、濾液を５％塩酸及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）及び再結晶（ジクロロメタン／メタノール）により精製を行い、式（Ｉ−１３）で表される化合物２．０ｇを得た。
ＬＣＭＳ：５５５［Ｍ＋１］
（実施例１４）式（Ｉ−１４）で表される化合物の製造 Under a nitrogen atmosphere, 2.5 g of the compound represented by the formula (I-13-5), 0.4 g of the compound represented by the formula (I-13-6), N, N-dimethylaminopyridine,. 1 g and 30 mL of dichloromethane were added. While cooling with ice, 0.8 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 8 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 2.0 g of a compound represented by the formula (I-13).
LCMS: 555 [M + 1]
Example 14 Production of Compound Represented by Formula (I-14)

Figure 2017226616
Figure 2017226616

実施例４において式（Ｉ−４−１）で表される化合物を式（Ｉ−１４−１）で表される化合物に置き換えた以外は同様の方法によって式（Ｉ−１４）で表される化合物を製造した。
ＬＣＭＳ：５９１［Ｍ＋１］
（実施例１５）式（Ｉ−１５）で表される化合物の製造 The compound represented by formula (I-14) is prepared in the same manner as in Example 4 except that the compound represented by formula (I-4-1) is replaced with the compound represented by formula (I-14-1). The compound was prepared.
LCMS: 591 [M + 1]
Example 15 Production of Compound Represented by Formula (I-15)

Figure 2017226616
Figure 2017226616

ディーンスターク装置を備えた反応容器に式（Ｉ−１５−１）で表される化合物５．０ｇ、式（Ｉ−１５−２）で表される化合物７．６ｇ、ｐ−トルエンスルホン酸一水和物０．１ｇ、トルエン５０ｍＬを加え、水分を除去しながら８時間加熱還流させた。飽和炭酸水素ナトリウム水溶液及び食塩水で洗浄した後、カラムクロマトグラフィー（シリカゲル、ヘキサン／酢酸エチル）により精製を行い、式（Ｉ−１５−３）で表される化合物９．３ｇを得た。   In a reaction vessel equipped with a Dean-Stark apparatus, 5.0 g of the compound represented by the formula (I-15-1), 7.6 g of the compound represented by the formula (I-15-2), p-toluenesulfonic acid monohydrate 0.1 g of a Japanese product and 50 mL of toluene were added, and the mixture was heated to reflux for 8 hours while removing water. After washing with a saturated aqueous sodium hydrogen carbonate solution and brine, purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 9.3 g of a compound represented by the formula (I-15-3).

窒素雰囲気下、反応容器に式（Ｉ−１５−３）で表される化合物９．３ｇ、ジイソプロピルエチルアミン７．０ｇ、ジクロロメタン５０ｍＬを加えた。氷冷しながら式（Ｉ−１５−４）で表される化合物４．５ｇを滴下し、室温で６時間撹拌した。１％塩酸、水及び食塩水で洗浄した後、カラムクロマトグラフィー（シリカゲル、ヘキサン／酢酸エチル）により精製を行い、式（Ｉ−１５−５）で表される化合物９．４ｇを得た。   Under a nitrogen atmosphere, 9.3 g of the compound represented by the formula (I-15-3), 7.0 g of diisopropylethylamine, and 50 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 4.5 g of the compound represented by the formula (I-15-4) was added dropwise and stirred at room temperature for 6 hours. After washing with 1% hydrochloric acid, water and brine, purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 9.4 g of a compound represented by the formula (I-15-5).

反応容器に式（Ｉ−１５−５）で表される化合物９．４ｇ、メタノール８０ｍＬ、２５％水酸化ナトリウム水溶液５０ｍＬを加え、５０℃で３時間加熱撹拌した。１０％塩酸で中和した後、酢酸エチルで希釈し、食塩水で洗浄した。カラムクロマトグラフィー（シリカゲル、ヘキサン／酢酸エチル）により精製を行い、式（Ｉ−１５−６）で表される化合物７．１ｇを得た。   To the reaction vessel were added 9.4 g of the compound represented by the formula (I-15-5), 80 mL of methanol, and 50 mL of 25% aqueous sodium hydroxide, and the mixture was heated and stirred at 50 ° C. for 3 hours. The mixture was neutralized with 10% hydrochloric acid, diluted with ethyl acetate, and washed with brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 7.1 g of a compound represented by the formula (I-15-6).

実施例４において式（Ｉ−４−１）で表される化合物を式（Ｉ−１５−７）で表される化合物に、式（Ｉ−４−３）で表される化合物を式（Ｉ−１５−６）で表される化合物に置き換えた以外は同様の方法によって式（Ｉ−１５）で表される化合物を製造した。
ＬＣＭＳ：４９９［Ｍ＋１］
前記と同様の方法及び公知の方法を組み合わせることによって、式（Ｉ−１６）から式（Ｉ−１０５）で表される化合物を製造した。
（実施例１６〜６０、比較例１〜９）
実施例１から実施例１５に記載の式（Ｉ−１）から式（Ｉ−１５）で表される化合物及び特許文献１記載の化合物（Ｒ−１）、特許文献２記載の化合物（Ｒ−２）、特許文献３記載の化合物（Ｒ−３）を評価対象の化合物とした。 In Example 4, the compound represented by the formula (I-4-1) is changed to the compound represented by the formula (I-15-7), and the compound represented by the formula (I-4-3) is changed to the formula (I The compound represented by the formula (I-15) was produced by the same method except that the compound represented by -15-6) was used.
LCMS: 499 [M + 1]
A compound represented by formula (I-16) to formula (I-105) was produced by combining the same method as described above and a known method.
(Examples 16 to 60, Comparative Examples 1 to 9)
Compounds represented by formula (I-1) to formula (I-15) described in Example 1 to Example 15, compound (R-1) described in Patent Document 1, compound (R-) described in Patent Document 2 2) The compound (R-3) described in Patent Document 3 was used as an evaluation target compound.

Figure 2017226616
Figure 2017226616

また、特開２００５−０１５４７３号公報記載の化合物（Ｘ−１）：３５％、特開平１０−８７５６５号公報記載の化合物（Ｘ−２）：２５％、特表２００２−５３７２８０号公報記載の化合物（Ｘ−３）：３５％及びキラル化合物として、特開２００２−１７９６６９号公報記載の化合物（Ｘ−４）：５％からなる液晶組成物を母体液晶（Ｘ）とした。   Further, compound (X-1) described in JP-A-2005-015473: 35%, compound (X-2) described in JP-A-10-87565: 25%, compound described in JP-T-2002-537280 A liquid crystal composition comprising (X-3): 35% and a compound (X-4): 5% described in JP-A No. 2002-179669 as a chiral compound was used as a base liquid crystal (X).

Figure 2017226616
Figure 2017226616

保存安定性を評価するために、母体液晶（Ｘ）に対して評価対象の化合物を３０％から７０％まで５％刻みで添加し７０℃で加熱溶解させた重合性液晶組成物を各々調製した。調製した重合性液晶組成物を１５℃で５週間保管した後、結晶の析出が起こらない評価対象の化合物の最大添加濃度を下表に記載する。   In order to evaluate the storage stability, a polymerizable liquid crystal composition was prepared by adding the compound to be evaluated to the base liquid crystal (X) from 30% to 70% in increments of 5% and heating and dissolving at 70 ° C. . After the prepared polymerizable liquid crystal composition is stored at 15 ° C. for 5 weeks, the maximum concentration of the compound to be evaluated at which no precipitation of crystals occurs is described in the table below.

Figure 2017226616
Figure 2017226616

上記の結果から、本願発明の式（Ｉ−１）から式（Ｉ−１５）で表される化合物はいずれも良好な保存安定性を有することがわかる。   From the above results, it can be seen that the compounds represented by the formulas (I-1) to (I-15) of the present invention all have good storage stability.

配向膜用ポリイミド溶液を厚さ０．７ｍｍのガラス基材にスピンコート法を用いて塗布し、１００℃で１０分乾燥した後、２００℃で６０分焼成することにより塗膜を得た。得られた塗膜をラビング処理した。ラビング処理は、市販のラビング装置を用いて行った。   The polyimide solution for alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film. The obtained coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing apparatus.

母体液晶（Ｘ）を１１．８７％、評価対象となる化合物を７．９１％（母体液晶（Ｘ）と当該化合物の合計含有量に対し４０％）、光重合開始剤Ｉｒｇａｃｕｒｅ９０７（ＢＡＳＦ社製）を０．２０％、４−メトキシフェノールを０．０２％及びシクロヘキサノンを８０．００％混合することにより塗布液を調製した。この塗布液をラビングしたガラス基材にバーコーター（Ｎｏ．９）を使用して塗布した後、１００℃のホットプレートに載せ溶媒を蒸発させた。その後、高圧水銀ランプを用いて、紫外線を４０ｍＷ／ｃｍ２の強度で２５秒間照射することにより、評価対象のフィルムを作製した。得られたフィルムについて偏光顕微鏡観察によって配向欠陥を評価した。フィルムを縦１０マス×横１０マス、計１００マスの領域に区分し、配向欠陥の生じたマス目の数をカウントした。値が小さいほど、配向欠陥が少ないことを意味する。結果を下表に示す。 11.87% of the base liquid crystal (X), 7.91% of the compound to be evaluated (40% based on the total content of the base liquid crystal (X) and the compound), photopolymerization initiator Irgacure 907 (manufactured by BASF) Was mixed with 0.20%, 4-methoxyphenol 0.02% and cyclohexanone 80.00%. This coating solution was applied to a rubbed glass substrate using a bar coater (No. 9), and then placed on a hot plate at 100 ° C. to evaporate the solvent. Then, the film of evaluation object was produced by irradiating an ultraviolet-ray with the intensity | strength of 40 mW / cm < 2 > for 25 second using a high pressure mercury lamp. The obtained film was evaluated for alignment defects by observation with a polarizing microscope. The film was divided into 10 squares × 10 squares, for a total of 100 squares, and the number of squares having orientation defects was counted. It means that there are few orientation defects, so that a value is small. The results are shown in the table below.

Figure 2017226616
Figure 2017226616

上記の結果から、本願発明の式（Ｉ−１）から式（Ｉ−１５）で表される化合物は、得られたコレステリック液晶相に配向欠陥が少ないことがわかる。   From the above results, it can be seen that the compounds represented by the formulas (I-1) to (I-15) of the present invention have few alignment defects in the obtained cholesteric liquid crystal phase.

次に、評価対象のフィルムに対し、ＬＥＤランプ（３６５ｎｍ）で６０ｍＷの光を５００時間照射した。照射前と照射後のフィルムの黄色度（ＹＩ）を各々測定し、黄変度（ΔＹＩ）を求めた。黄色度はＪＡＳＣＯ ＵＶ／ＶＩＳ Ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ Ｖ−５６０で重合体の吸収スペクトルを測定し、付属のカラー診断プログラムで黄色度（ＹＩ）を計算した。計算式は、
ＹＩ＝１００（１．２８Ｘ−１．０６Ｚ）／Ｙ
（式中、ＹＩは黄色度、Ｘ、Ｙ、ＺはＸＹＺ表色系における三刺激値を表す（ＪＩＳ Ｋ７３７３）。）である。また、黄変度（ΔＹＩ）は初期の黄色度と暴露後の黄色度の差を意味する（ＪＩＳ Ｋ７３７３）。黄変度（ΔＹＩ）が小さいほど、変色が起こりにくいことを意味する。結果を下表に示す。 Next, 60 mW light was irradiated for 500 hours with the LED lamp (365 nm) with respect to the evaluation object film. The yellowness (YI) of the film before and after irradiation was measured to determine the yellowing degree (ΔYI). For yellowness, the absorption spectrum of the polymer was measured with JASCO UV / VIS Spectrophotometer V-560, and yellowness (YI) was calculated with the attached color diagnostic program. The formula is
YI = 100 (1.28X-1.06Z) / Y
(In the formula, YI represents yellowness, and X, Y, and Z represent tristimulus values in the XYZ color system (JIS K7373)). Yellowness (ΔYI) means the difference between the initial yellowness and the yellowness after exposure (JIS K7373). A smaller yellowing degree (ΔYI) means that discoloration hardly occurs. The results are shown in the table below.

Figure 2017226616
Figure 2017226616

上記の結果から、本願発明の式（Ｉ−１）から式（Ｉ−１５）で表される化合物は、得られたフィルムに紫外光を長時間照射した場合に変色が起こりにくいことがわかる。   From the above results, it can be seen that the compounds represented by the formulas (I-1) to (I-15) of the present invention are unlikely to discolor when the obtained film is irradiated with ultraviolet light for a long time.

以上の結果から、本願発明の式（Ｉ−１）から式（Ｉ−１５）で表される化合物はいずれも比較化合物（Ｒ−１）から比較化合物（Ｒ−３）と比較し、その他の重合性化合物を含有する重合性組成物に添加した場合に高い保存安定性を有し、フィルム状の重合物を作製した場合に配向欠陥が生じにくく、フィルム状の重合物に長時間紫外光を照射した場合に変色が起こりにくいことから、重合性組成物の構成部材として有用である。また、当該重合性組成物は位相差フィルム、選択反射フィルム等の光学材料の用途に有用である。   From the above results, all the compounds represented by the formulas (I-1) to (I-15) of the present invention were compared with the comparative compound (R-1) to the comparative compound (R-3). When it is added to a polymerizable composition containing a polymerizable compound, it has high storage stability. When a film-like polymer is produced, alignment defects are less likely to occur, and UV light is applied to the film-like polymer for a long time. Since it is difficult for discoloration to occur when irradiated, it is useful as a component of the polymerizable composition. Moreover, the said polymeric composition is useful for the use of optical materials, such as a phase difference film and a selective reflection film.

Claims (8)

下記の一般式（Ｉ）
Figure 2017226616
 （式中、Ｐ１及びＰ２は各々独立してラジカル重合、カチオン重合又はアニオン重合により重合する基を表し、
Ｓｐ１及びＳｐ２は各々独立してスペーサー基を表すが、Ｓｐ１が複数存在する場合それらは同一であっても異なっていても良く、Ｓｐ２が複数存在する場合それらは同一であっても異なっていても良く、
Ｘ１及びＸ２は各々独立して−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｓ−、−ＳＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−、−ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−又は単結合を表すが、Ｘ１が複数存在する場合それらは同一であっても異なっていても良く、Ｘ２が複数存在する場合それらは同一であっても異なっていても良く、
ｋ１及びｋ２は０から１０の整数を表し、
Ａ１は下記の式（Ａ−１）から式（Ａ−７）
Figure 2017226616
 （式中、これらの基は無置換であるか又は１つ以上の下記置換基Ｌによって置換されても良い。）から選ばれる基を表し、
Ｂ１は下記の式（Ｂ−１）から式（Ｂ−１０）
Figure 2017226616
 （式中、これらの基は無置換であるか又は１つ以上の下記置換基Ｌによって置換されても良い。）から選ばれる基を表し、
置換基Ｌはフッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、ニトロ基、シアノ基、イソシアノ基、アミノ基、ヒドロキシル基、メルカプト基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、トリメチルシリル基、ジメチルシリル基、チオイソシアノ基、置換されていても良いフェニル基、置換されていても良いフェニルアルキル基、置換されていても良いシクロヘキシルアルキル基、又は、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＲ０−、−ＮＲ０−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＲ０＝Ｎ−、−Ｎ＝ＣＲ０−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−（式中、Ｒ０は水素原子又は炭素原子数１から８のアルキル基を表す。）によって置換されても良い炭素原子数１から２０の直鎖状又は分岐状アルキル基を表すが、当該アルキル基中の任意の水素原子はフッ素原子に置換されても良く、若しくは、ＬはＰＬ−（ＳｐＬ−ＸＬ）ｋＬ−で表される基を表しても良く、ここでＰＬはラジカル重合、カチオン重合又はアニオン重合により重合する基を表し、ＳｐＬはスペーサー基又は単結合を表すが、ＳｐＬが複数存在する場合それらは同一であっても異なっていても良く、ＸＬは−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｓ−、−ＳＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−、−ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−又は単結合を表すが、ＸＬが複数存在する場合それらは同一であっても異なっていても良く、ｋＬは０から１０の整数を表し、化合物内にＬが複数存在する場合それらは同一であっても異なっていても良く、
Ｚ１は−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＯＣＯ−ＮＨ−、−ＮＨ−ＣＯＯ−、−ＮＨ−ＣＯ−ＮＨ−、−ＮＨ−Ｏ−、−Ｏ−ＮＨ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＦ２Ｓ−、−ＳＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−、−ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−を表すが、一般式中、−Ｏ−Ｏ−結合を含まない。）で表される化合物。 The following general formula (I)
Figure 2017226616
 (Wherein P 1 and P 2 each independently represent a group that is polymerized by radical polymerization, cationic polymerization or anionic polymerization;
Sp 1 and Sp 2 each independently represent a spacer group, but when there are a plurality of Sp 1, they may be the same or different, and when there are a plurality of Sp 2, they may be the same. May be different,
X 1 and X 2 are each independently —O—, —S—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —CO—S—, —S—. CO -, - O-CO- O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S- , -SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO- CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO —, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond. But they if X 1 there are a plurality may be the same or different and they if X 2 there are a plurality may be the same or different and
k1 and k2 represent an integer of 0 to 10,
A 1 is the following formula (A-1) to formula (A-7)
Figure 2017226616
 (Wherein these groups are unsubstituted or may be substituted by one or more of the following substituents L),
B 1 represents expression from the following formula (B-1) (B- 10)
Figure 2017226616
 (Wherein these groups are unsubstituted or may be substituted by one or more of the following substituents L),
Substituent L is fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino Group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, optionally substituted phenyl group, optionally substituted phenylalkyl group, optionally substituted cyclohexylalkyl group, or one —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S. -CO -, - O-COO - , - CO-NR 0 -, - NR 0 -CO -, - CH = CH-COO -, - CH = CH-OCO- -COO-CH = CH -, - OCO-CH = CH -, - CH = CH -, - N = N -, - CR 0 = N -, - N = CR 0 -, - CH = N-N = CH —, —CF═CF— or —C≡C— (wherein R 0 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) and is a straight chain having 1 to 20 carbon atoms which may be substituted. A chain or branched alkyl group is represented, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or L is represented by P L- (Sp L -X L ) kL-. In this case, P L represents a group that is polymerized by radical polymerization, cationic polymerization, or anionic polymerization, and Sp L represents a spacer group or a single bond, but when there are a plurality of Sp L, they are the same. may be different even, X L is -O -, - S -, - OC 2 -, - CH 2 O - , - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH- CO—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH═CH—COO—, —CH═CH—OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, even they are the same if X L there are multiple They may be different, kL represents an integer of 0 to 10, and when a plurality of L are present in the compound, they may be the same or different,
Z 1 represents —O—, —S—, —OCH 2 —, —CH 2 O—, —CH 2 CH 2 —, —CO—, —COO—, —OCO—, —CO—S—, —S—. CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-,- O—NH—, —SCH 2 —, —CH 2 S—, —CF 2 S—, —SCF 2 —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH— , —OCO—CH═CH—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —CH 2 CH 2 —OCO—, —COO—CH 2 -, - OCO-CH 2 - , - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = -, - N = CH -, - CH = N-N = CH -, - CF = CF- or represents a -C≡C-, in the general formula, contains no -O-O- bonds. ) A compound represented by 一般式（Ｉ）において、Ｐ１及びＰ２は、各々独立して下記の式（Ｐ−１）から式（Ｐ−２０）
Figure 2017226616
 から選ばれる基を表す請求項１に記載の化合物。 In general formula (I), P 1 and P 2 are each independently the following formulas (P-1) to (P-20):
Figure 2017226616
 The compound according to claim 1, which represents a group selected from: 一般式（Ｉ）において、Ｓｐ１及びＳｐ２は、各々独立して１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｓ−、−ＳＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−、−ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−に置き換えられても良い炭素原子数１から２０のアルキレン基を表す、請求項１又は請求項２に記載の化合物。 In the general formula (I), Sp 1 and Sp 2 are each independently one —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—, —S—. , —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, -NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —CH 2 CH 2 —OCO—, —COO—CH 2 —, —OCO—CH 2 —, —CH 2 —COO—, —CH 2 —OC Alkylene having 1 to 20 carbon atoms which may be replaced by O—, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF— or —C≡C— The compound according to claim 1 or 2, which represents a group. 請求項１から請求項３のいずれか一項に記載の化合物を含有する組成物。   The composition containing the compound as described in any one of Claims 1-3. 請求項１から請求項３のいずれか一項に記載の化合物を含有する液晶組成物。   The liquid crystal composition containing the compound as described in any one of Claims 1-3. 請求項４又は請求項５に記載の組成物を重合することにより得られる重合体。   A polymer obtained by polymerizing the composition according to claim 4. 請求項６に記載の重合体を用いた光学異方体。   An optical anisotropic body using the polymer according to claim 6. 請求項１から請求項３のいずれか一項に記載の化合物を用いた樹脂、樹脂添加剤、オイル、フィルター、接着剤、粘着剤、油脂、インキ、医薬品、化粧品、洗剤、建築材料、包装材、液晶材料、有機ＥＬ材料、有機半導体材料、電子材料、表示素子、電子デバイス、通信機器、自動車部品、航空機部品、機械部品、農薬及び食品並びにそれらを使用した製品。   A resin, a resin additive, an oil, a filter, an adhesive, an adhesive, a fat, an ink, a pharmaceutical, a cosmetic, a detergent, a building material, a packaging material using the compound according to any one of claims 1 to 3. , Liquid crystal materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, machine parts, agricultural chemicals and foods, and products using them.
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