JP2012162742A - Polymerizable liquid crystal composition - Google Patents

Polymerizable liquid crystal composition Download PDF

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JP2012162742A
JP2012162742A JP2012115583A JP2012115583A JP2012162742A JP 2012162742 A JP2012162742 A JP 2012162742A JP 2012115583 A JP2012115583 A JP 2012115583A JP 2012115583 A JP2012115583 A JP 2012115583A JP 2012162742 A JP2012162742 A JP 2012162742A
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polymerizable liquid
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Osamu Yamazaki
修 山崎
Hiroshi Hasebe
浩史 長谷部
Kiyofumi Takeuchi
清文 竹内
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable liquid crystal composition capable of producing an optically anisotropic material having a small change in phase difference under a high temperature.SOLUTION: This polymerizable liquid crystal composition contains an antioxidant having a phenol backbone of which at least one or more hydrogen atom is substituted by a tert-butyl group, and having less than 700 molecular weight. The optically anisotropic material is a cured material of the polymerizable liquid crystal composition. Since the optically anisotropic material constituted by the polymerizable liquid crystal composition can reduce the decrease of phase difference accompanying with the decrease of an order parameter even under a high temperature, it is possible to suitably use the same as the optically anisotropic material built-in at the inside of a liquid crystal cell.

Description

本願発明は、液晶ディスプレイ等の光学補償に用いられる光学異方体の構成部材として有用な重合性液晶組成物及び当該組成物の重合体により構成される光学異方体に関する。   The present invention relates to a polymerizable liquid crystal composition useful as a constituent member of an optical anisotropic body used for optical compensation of a liquid crystal display or the like, and an optical anisotropic body composed of a polymer of the composition.

重合性液晶組成物は光学異方体の構成部材として有用であり、光学異方体は例えば位相差フィルムとして種々の液晶ディスプレイに応用されている。位相差フィルムは、重合性液晶組成物を基板に塗布して、配向膜等により重合性液晶組成物を配向させた状態で活性エネルギー線を照射して重合性液晶組成物を硬化することにより得られる。   The polymerizable liquid crystal composition is useful as a constituent member of an optical anisotropic body, and the optical anisotropic body is applied to various liquid crystal displays as a retardation film, for example. The retardation film is obtained by applying a polymerizable liquid crystal composition to a substrate and curing the polymerizable liquid crystal composition by irradiating active energy rays in a state where the polymerizable liquid crystal composition is aligned by an alignment film or the like. It is done.

現在、薄型・軽量化やコスト低減を目的として、液晶ディスプレイの液晶セル内に位相差フィルムを組み込む方式が注目されている。液晶ディスプレイの製造プロセスにおいては、高温下で製造を行わなければならない工程が存在することから、位相差フィルム製造プロセスにおいて２００℃以上の高温に曝されることになる。光学異方体は耐熱性に劣るものではないが、微妙な光学特性を維持することは必ずしも容易では無く高温度においては、光学異方体のオーダーパラメーターの低下が発生し易い。これに伴い光学異方体の位相差が減少し、光学特性の変化により画質が低下してしまう問題があった。   At present, a method of incorporating a retardation film in a liquid crystal cell of a liquid crystal display attracts attention for the purpose of reducing the thickness and weight and reducing the cost. In the manufacturing process of the liquid crystal display, there are steps that must be performed at a high temperature. Optical anisotropic bodies are not inferior in heat resistance, but it is not always easy to maintain delicate optical characteristics, and the order parameters of optical anisotropic bodies are likely to decrease at high temperatures. Accordingly, there is a problem that the phase difference of the optical anisotropic body is reduced, and the image quality is deteriorated due to the change of the optical characteristics.

一方、重合性液晶組成物にフェノール骨格を有する酸化防止剤を添加した構成は既に知られている（特許文献１参照）。しかしながら、当該引用文献においては、フェノール骨格を有する化防止剤は、不要な重合を抑制するために用いられており、高温時における光学特性の劣化を抑制するために用いられているものではない。又、当該引用文献に記載の重合性液晶組成物においては、酸化防止剤として4-エトキシフェノール又はブチル化ヒドロキシトルエン(BHT)が用いられている。ところが、これらの酸化防止剤は分子量が何れも２５０以下と小さいことから、微妙な光学特性の変化を抑制することができないものであった。   On the other hand, the structure which added the antioxidant which has a phenol skeleton to the polymeric liquid crystal composition is already known (refer patent document 1). However, in the cited document, the antioxidant having a phenol skeleton is used for suppressing unnecessary polymerization, and is not used for suppressing deterioration of optical properties at high temperatures. In the polymerizable liquid crystal composition described in the cited document, 4-ethoxyphenol or butylated hydroxytoluene (BHT) is used as an antioxidant. However, since these antioxidants have a molecular weight as small as 250 or less, they cannot suppress subtle changes in optical properties.

以上より、２００℃以上の高温において位相差が変化しない光学異方体を作製することが可能な重合性組成物の開発が望まれていた。   From the above, it has been desired to develop a polymerizable composition capable of producing an optical anisotropic body whose phase difference does not change at a high temperature of 200 ° C. or higher.

特表２０００−５０７３６２号公報JP 2000-507362 A

本願発明の課題は、高温下において位相差の変化が少ない光学異方体を作製することが可能な重合性液晶組成物を提供することにある。   The subject of this invention is providing the polymeric liquid crystal composition which can produce the optically anisotropic body with little change of a phase difference under high temperature.

上記課題を解決するために種々の重合性液晶と酸化防止剤の組み合わせを鋭意検討した結果、本願発明の重合性液晶組成物に最適な酸化防止剤とその分子量の範囲を明らかにすることに成功し本願発明の完成に至った。   As a result of intensive studies on combinations of various polymerizable liquid crystals and antioxidants in order to solve the above-mentioned problems, the inventors have succeeded in clarifying the optimum antioxidant and the molecular weight range for the polymerizable liquid crystal composition of the present invention. The present invention has been completed.

本願発明は、少なくとも１つ以上の水素原子がtert-ブチル基で置換されているフェノール骨格を有する分子量３００以上の酸化防止剤を含有することを特徴とする重合性液晶組成物を提供し、併せて当該重合性液晶組成物の硬化物である光学異方体を提供する   The present invention provides a polymerizable liquid crystal composition comprising an antioxidant having a molecular weight of 300 or more having a phenol skeleton in which at least one hydrogen atom is substituted with a tert-butyl group. To provide an optical anisotropic body that is a cured product of the polymerizable liquid crystal composition.

本願発明の重合性液晶組成物は、光学異方体を構成した場合において高温に曝されても位相差は減少しにくいことから、光学異方体の材料、特に液晶セル内部に組み込む光学異方体の材料として好適である。   Since the polymerizable liquid crystal composition of the present invention is an optically anisotropic material, the retardation is difficult to decrease even when exposed to high temperatures. Suitable as body material.

以下に本願発明による重合性液晶組成物の最良の形態について説明する。本願発明の重合性液晶組成物は、少なくとも１つ以上の水素原子がtert-ブチル基で置換されているフェノール骨格を有する分子量３００以上の酸化防止剤を含有することが好ましく、該酸化防止剤の分子量が５００以上であることがさらに好ましく、分子量が７００以上であることことが特に好ましい。また、該酸化防止剤は、重合性液晶組成物中に０．１〜５質量％含有することが好ましく、さらには０．２〜２質量％含有することが好ましく、０．３〜１質量％含有することが特に好ましい。   The best mode of the polymerizable liquid crystal composition according to the present invention will be described below. The polymerizable liquid crystal composition of the present invention preferably contains an antioxidant having a molecular weight of 300 or more having a phenol skeleton in which at least one hydrogen atom is substituted with a tert-butyl group. The molecular weight is more preferably 500 or more, and the molecular weight is particularly preferably 700 or more. The antioxidant is preferably contained in the polymerizable liquid crystal composition in an amount of 0.1 to 5% by mass, more preferably 0.2 to 2% by mass, and 0.3 to 1% by mass. It is particularly preferable to contain it.

好適な酸化防止剤の具体例として以下の式（I-1）〜式（I-8）で表される化合物を挙げることができる。   Specific examples of suitable antioxidants include compounds represented by the following formulas (I-1) to (I-8).

Figure 2012162742
Figure 2012162742

Figure 2012162742
Figure 2012162742

以上に挙げた式（I-1）〜式（I-8）の化合物のうち、中でも式（I-1）〜式（I-5）がさらに好ましく、式（I-1）〜式（I-3）が特に好ましい。   Among the compounds of formula (I-1) to formula (I-8) listed above, among them, formula (I-1) to formula (I-5) are more preferable, and formula (I-1) to formula (I-5) -3) is particularly preferred.

以上に述べた重合性液晶組成物中に含有する重合性液晶化合物については、特に制限はなく使用することができ、該重合性液晶組成物を有機溶媒などに溶かした溶液の状態で使用してもよい。好適な有機溶媒として例えばトルエン、キシレン、クメンなどのアルキル置換ベンゼンやプロピレングリコールモノメチルエーテルアセテート、酢酸ブチル、シクロヘキサノン等を挙げることができる。さらにこれらの溶媒にジメチルホルムアミド、γ−ブチロラクトン、N-メチルピロリジノン、メチルエチルケトン、酢酸エチル等を添加しても良い。重合性液晶化合物として棒状重合性液晶化合物又は円盤状重合性液晶化合物を使用することが好ましく、棒状重合性液晶化合物が特に好ましい。   The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition described above can be used without any particular limitation, and the polymerizable liquid crystal composition can be used in a solution in an organic solvent. Also good. Suitable organic solvents include, for example, alkyl-substituted benzenes such as toluene, xylene and cumene, propylene glycol monomethyl ether acetate, butyl acetate and cyclohexanone. Further, dimethylformamide, γ-butyrolactone, N-methylpyrrolidinone, methyl ethyl ketone, ethyl acetate and the like may be added to these solvents. As the polymerizable liquid crystal compound, a rod-like polymerizable liquid crystal compound or a disk-like polymerizable liquid crystal compound is preferably used, and a rod-like polymerizable liquid crystal compound is particularly preferred.

棒状重合性液晶化合物は、一般式（II）   The rod-like polymerizable liquid crystal compound has the general formula (II)

Figure 2012162742
Figure 2012162742

（式中、Pは反応性官能基を表し、Spは炭素原子数１〜２０のスペーサー基を表し、mは０又は１を表し、MGはメソゲン基又はメソゲン性支持基を表し、R9は、ハロゲン原子、シアノ基又は炭素原子数１〜２５のアルキル基を表すが、該アルキル基は１つ以上のハロゲン原子又はCNにより置換されていても良く、この基中に存在する１つのCH2基又は隣接していない２つ以上のCH2基はそれぞれ相互に独立して、酸素原子が相互に直接結合しない形で、-O-、-S-、-NH-、-N(CH3)-、-CO-、-COO-、-OCO-、-OCOO-、-SCO-、-COS-又は-C≡C-により置き換えられていても良く、あるいはR9は一般式（II-a） (Wherein P represents a reactive functional group, Sp represents a spacer group having 1 to 20 carbon atoms, m represents 0 or 1, MG represents a mesogenic group or a mesogenic support group, and R 9 represents Represents a halogen atom, a cyano group or an alkyl group having 1 to 25 carbon atoms, and the alkyl group may be substituted by one or more halogen atoms or CN, and one CH 2 present in the group. Group or two or more non-adjacent CH 2 groups are each independently of each other such that —O—, —S—, —NH—, —N (CH 3 ) -, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- may be substituted, or R 9 is represented by the general formula (II-a)

Figure 2012162742
Figure 2012162742

（式中、Pは反応性官能基を表し、Spは炭素原子数１〜２０のスペーサー基を表し、mは０又は１を表す。）で表される構造を表す。）で表される化合物を含有することが好ましく、一般式（II）において、Spはアルキレン基を表し、該アルキレン基は１つ以上のハロゲン原子又はCNにより置換されていても良く、この基中に存在する１つのCH2基又は隣接していない２つ以上のCH2基はそれぞれ相互に独立して、酸素原子が相互に直接結合しない形で、-O-、-S-、-NH-、-N(CH3)-、-CO-、-COO-、-OCO-、-OCOO-、-SCO-、-COS-又は-C≡C-により置き換えられていても良い。）で表される構造を表し、MGが一般式（II-b） (Wherein P represents a reactive functional group, Sp represents a spacer group having 1 to 20 carbon atoms, and m represents 0 or 1). In the general formula (II), Sp represents an alkylene group, and the alkylene group may be substituted with one or more halogen atoms or CN. One CH 2 group or two or more non-adjacent CH 2 groups present in each other independently of each other in a form in which oxygen atoms are not directly bonded to each other, —O—, —S—, —NH— , —N (CH 3 ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS— or —C≡C— may be substituted. ), Where MG is the general formula (II-b)

Figure 2012162742
Figure 2012162742

（式中、A1、A2及びA3はそれぞれ独立的に、1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、テトラヒドロチオピラン-2,5-ジイル基、1,4-ビシクロ(2,2,2)オクチレン基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基、フルオレン2,7-ジイル基を表し、該1,4-フェニレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基及びフルオレン2,7-ジイル基は置換基として１個以上のF、Cl、CF3、OCF3、シアノ基、炭素原子数１〜８のアルキル基、アルコキシ基、アルカノイル基、アルカノイルオキシ基、炭素原子数２〜８のアルケニル基、アルケニルオキシ基、アルケノイル基、アルケノイルオキシ基を有していても良く、Z0、Z1、Z2及びZ3はそれぞれ独立して、-COO-、-OCO-、-CH2 CH2-、-OCH2-、-CH2O-、-CH=CH-、-C≡C-、-CH=CHCOO-、-OCOCH=CH-、-CH2CH2COO-、-CH2CH2OCO-、-COO CH2CH2-、-OCOCH2CH2-、-CONH-、-NHCO-又は単結合を表し、nは０、１又は２を表す。）で表される構造を表し、Pが一般式（II-c）、一般式（II-d）又は一般式（II-e） (In the formula, A1, A2 and A3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1, 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine- 2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, Phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group, fluorene 2, Represents a 7-diyl group, the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9 , 10-dihydrophenanthrene-2,7-diyl group, 1, 2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group and fluorene 2,7-diyl group are substituted with one or more F, Cl, CF 3 , OCF 3 , cyano group, It may have an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkanoyl group, an alkanoyloxy group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group, an alkenoyl group or an alkenoyloxy group. , - - independently, -COO, the Z1, Z2 and Z3 OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH 2 O -, - CH = CH -, - C≡C-, -CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COO CH 2 CH 2 -, - OCOCH 2 CH 2 -, - CONH -, - NHCO- Or a single bond, n represents 0, 1 or 2), and P represents a general formula (II-c), general formula (II-d) or general formula (II-e)

Figure 2012162742
Figure 2012162742

（式中、R61、R62、R63、R71、R72、R73、R81、R82及びR83はそれぞれ独立的に水素原子、ハロゲン原子又は炭素原子数１〜５のアルキル基を表し、nは０又は１を表す。）で表される置換基からなる群より選ばれる置換基で表される化合物を含有することがさらに好ましい。 (In the formula, R 61 , R 62 , R 63 , R 71 , R 72 , R 73 , R 81 , R 82 and R 83 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. And n represents 0 or 1. It is more preferable to contain a compound represented by a substituent selected from the group consisting of substituents represented by:

ここで、重合性液晶組成物に含有される化合物として、より具体的には一般式（III）   Here, the compound contained in the polymerizable liquid crystal composition is more specifically represented by the general formula (III)

Figure 2012162742
Figure 2012162742

（式中、mは０又は１を表し、W1及びW2はそれぞれ独立的に単結合、-O-、-COO-又は-OCO-を表し、Y1及びY2はそれぞれ独立的に-COO-又は-OCO-を表し、r及びsはそれぞれ独立的に２〜１８の整数を表すが、式中に存在する1,4−フェニレン基は炭素原子数１〜７のアルキル基、アルコキシ基、アルカノイル基、シアノ基、又はハロゲン原子で一つ以上置換されていても良い。）で表される化合物を用いると、機械的強度や耐熱性に優れた光学異方体が得られるので好ましい。 Wherein m represents 0 or 1, W 1 and W 2 each independently represent a single bond, —O—, —COO— or —OCO—, and Y 1 and Y 2 each independently represent — COO- or -OCO- is represented, and r and s each independently represent an integer of 2 to 18, the 1,4-phenylene group present in the formula is an alkyl group or alkoxy group having 1 to 7 carbon atoms , An alkanoyl group, a cyano group, or a halogen atom may be substituted, which is preferable because an optically anisotropic body excellent in mechanical strength and heat resistance can be obtained.

また、一般式（IV）   In addition, general formula (IV)

Figure 2012162742
Figure 2012162742

（式中、Z1は水素原子、ハロゲン原子、シアノ基又は炭素原子数１〜２０の炭化水素基を表し、Z2は水素原子又はメチル基を表し、tは０又は1を表し、A、B及びCはそれぞれ独立的に、1,4−フェニレン基、隣接しないCH基が窒素で置換された1,4−フェニレン基、1,4−シクロヘキシレン基、１つ又は隣接しない２つのCH2基が酸素又は硫黄原子で置換された1,4−シクロヘキシレン基、1,4−シクロヘキセニレン基を表すが、式中に存在する1,4−フェニレン基は炭素原子数１〜７のアルキル基、アルコキシ基、アルカノイル基、シアノ基又はハロゲン原子で一つ以上置換されていても良く、Y3及びY4はそれぞれ独立的に単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、-OCO-、-C≡C-、-CH=CH-、-CF=CF-、-（CH2）4-、-CH2CH2CH2O-、-OCH2CH2CH2-、-CH=CHCH2CH2-、-CH2CH2CH=CH-、-CH=CHCOO-、-OCOCH=CH-、-CH2CH2COO-、-CH2CH2OCO-、-COO CH2CH2-又は-OCOCH2CH2-を表し、Y5は単結合、-O-、-COO-、-OCO-又は-CH=CHCOO-を表す。）で表される化合物を用いると、重合性液晶組成物の粘度低減や液晶温度範囲を室温もしくは室温付近まで低減することができるので好ましい。 (In the formula, Z 1 represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms, Z 2 represents a hydrogen atom or a methyl group, t represents 0 or 1, A, B and C are each independently a 1,4-phenylene group, a 1,4-phenylene group in which a non-adjacent CH group is substituted with nitrogen, a 1,4-cyclohexylene group, one or two non-adjacent CH 2 Represents a 1,4-cyclohexylene group or 1,4-cyclohexenylene group in which the group is substituted with an oxygen or sulfur atom, and the 1,4-phenylene group present in the formula is an alkyl having 1 to 7 carbon atoms Group, an alkoxy group, an alkanoyl group, a cyano group or a halogen atom, and Y 3 and Y 4 are each independently a single bond, —CH 2 CH 2 —, —CH 2 O—, -OCH 2 -, - COO -, - OCO -, - C≡C -, - CH = CH -, - CF = CF -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2- , -CH = CHCH 2 CH 2- , -CH 2 CH 2 CH = CH -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COO CH 2 CH 2 - or -OCOCH 2 CH 2 - and Y 5 represents a single bond, —O—, —COO—, —OCO—, or —CH═CHCOO—)), the viscosity of the polymerizable liquid crystal composition can be reduced and the liquid crystal temperature range can be reduced. Is preferable because it can be reduced to room temperature or near room temperature.

また、一般式（V）   The general formula (V)

Figure 2012162742
Figure 2012162742

（式中、Z3は水素原子、ハロゲン原子、シアノ基、炭素原子１〜２０の炭化水素基を表し、Z4は水素原子又はメチル基を表し、W3はそれぞれ独立的に単結合、-O-、-COO-、-OCO-を表し、vは２〜１８の整数を表し、uは０又は１の整数を表し、D、E及びFはそれぞれ独立的に、1,4-フェニレン基、隣接しないCH基が窒素で置換された1,4-フェニレン基、1,4-シクロヘキシレン基、１つ又は隣接しない２つのCH２基が酸素又は硫黄原子で置換された1,4−シクロヘキシレン基、1,4−シクロヘキセニレン基を表し、これらのD、E及びFは、さらに炭素原子数１〜７のアルキル基、アルコキシ基、アルカノイル基、シアノ基、又はハロゲン原子で一つ以上置換されていても良く、Y6及びY7はそれぞれ独立的に単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、-OCO-、-C≡C-、-CH=CH-、-CF=CF-、-（CH2）4-、-CH2CH2CH2O-、-OCH2CH2CH2-、-CH=CHCH2CH2-、-CH2CH2CH=CH-、-CH=CHCOO-、-OCOCH=CH-、-CH2CH2COO-、-CH2CH2OCO-、-COOCH2CH2-又は-OCOCH2CH2-を表し、Y8は単結合、-O-、-COO-、-OCO-又は-CH=CHCOO-を表す。）で表される化合物を用いると、重合性液晶組成物の粘度を大幅に増加させることなく液晶物性を調節することができるので好ましい。 (In the formula, Z 3 represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, Z 4 represents a hydrogen atom or a methyl group, and W 3 each independently represents a single bond,- O—, —COO—, —OCO—, v represents an integer of 2 to 18, u represents an integer of 0 or 1, and D, E, and F are each independently a 1,4-phenylene group. 1,4-phenylene group in which non-adjacent CH groups are substituted with nitrogen, 1,4-cyclohexylene group, 1,4-cyclohexene group in which one or two non-adjacent CH 2 groups are substituted with oxygen or sulfur atoms Represents a silene group or a 1,4-cyclohexenylene group, and these D, E, and F are one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups, or halogen atoms having 1 to 7 carbon atoms. Y 6 and Y 7 may each independently be a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —C≡C -, -CH = C H -, - CF = CF - , - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CHCH 2 CH 2 -, - CH 2 CH 2 CH = CH -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 - or -OCOCH 2 CH 2 -, Y represents 8 represents a single bond, —O—, —COO—, —OCO—, or —CH═CHCOO—.) When the compound represented by It is preferable because the physical properties can be adjusted.

一般式（II）で表される化合物の具体例を以下に挙げることができる。   Specific examples of the compound represented by the general formula (II) can be given below.

Figure 2012162742
Figure 2012162742

（式中、j及びkはそれぞれ独立的に２〜１８の整数を表す。）
また、一般式（III）で表される化合物の具体例を以下に挙げることができる。 (Wherein j and k each independently represents an integer of 2 to 18)
Specific examples of the compound represented by the general formula (III) can be given below.

Figure 2012162742
Figure 2012162742

（式中、（式中、j及びkはそれぞれ独立的に２〜１８の整数を表す。）
また、一般式（IV）で表される化合物の具体的な例として、化合物の構造と相転移温度を以下に挙げることができる。 (Wherein j and k each independently represent an integer of 2 to 18)
Specific examples of the compound represented by the general formula (IV) include the structure of the compound and the phase transition temperature.

Figure 2012162742
Figure 2012162742

Figure 2012162742
Figure 2012162742

Figure 2012162742
Figure 2012162742

（式中、シクロヘキサン環はトランスシクロヘキサン環を表し、数字は相転移温度を表し、Cは結晶相、Nはネマチック相、Sはスメクチック相、Iは等方性液体相をそれぞれ表す。）
また、一般式（V）で表される化合物の具体例を以下に挙げることができる。 (In the formula, a cyclohexane ring represents a transcyclohexane ring, a number represents a phase transition temperature, C represents a crystalline phase, N represents a nematic phase, S represents a smectic phase, and I represents an isotropic liquid phase.)
Specific examples of the compound represented by the general formula (V) can be given below.

Figure 2012162742
Figure 2012162742

（式中、X1は水素原子又はメチル基を表し、R1は炭素原子数１から２０のアルキル基表す。）
また、円盤状液晶化合物は、ベンゼン誘導体、トリフェニレン誘導体、トルキセン誘導体、フタロシアニン誘導体又はシクロヘキサン誘導体を分子の中心の母核とし、直鎖のアルキル基、直鎖のアルコキシ基又は置換ベンゾイルオキシ基がその側鎖として放射状に置換した構造を有することが好ましく、一般式（VI） (In the formula, X 1 represents a hydrogen atom or a methyl group, and R 1 represents an alkyl group having 1 to 20 carbon atoms.)
The discotic liquid crystal compound has a benzene derivative, a triphenylene derivative, a truxene derivative, a phthalocyanine derivative or a cyclohexane derivative as a central nucleus of the molecule, and a linear alkyl group, a linear alkoxy group, or a substituted benzoyloxy group on its side. It preferably has a structure that is radially substituted as a chain, and has the general formula (VI)

Figure 2012162742
Figure 2012162742

（式中、R5はそれぞれ独立して一般式（VI-a）で表される置換基を表す。） (In the formula, each R 5 independently represents a substituent represented by the general formula (VI-a).)

Figure 2012162742
Figure 2012162742

（式中、R6及びR7はそれぞれ独立的に水素原子、ハロゲン原子又はメチル基を表し、R8は炭素原子数１〜２０アルコキシ基を表すが、該アルコキシ基中の水素原子は一般式（VI-b）、一般式（VI-c）又は一般式（VI-d）で表される置換基によって置換されていても良い。） (In the formula, R 6 and R 7 each independently represent a hydrogen atom, a halogen atom or a methyl group, and R 8 represents an alkoxy group having 1 to 20 carbon atoms, and the hydrogen atom in the alkoxy group represents a general formula. (It may be substituted with a substituent represented by (VI-b), general formula (VI-c) or general formula (VI-d))

Figure 2012162742
Figure 2012162742

（式中、R61、R62、R63、R71、R72、R73、R81、R82及びR83はそれぞれ独立的に水素原子、ハロゲン原子又は炭素原子数１〜５のアルキル基を表し、nは０又は１を表す。）で表される構造を有することがさらに好ましく、一般式（VI）においてR8の内少なくとも一つは一般式（VI-b）、一般式（VI-c）又は一般式（VI-d）で表される置換基によって置換されたアルコキシ基を表すことが好ましく、R8の全てが一般式（VI-b）、一般式（VI-c）又は一般式（VI-d）で表される置換基によって置換されたアルコキシ基を表すことが特に好ましい。 (In the formula, R 61 , R 62 , R 63 , R 71 , R 72 , R 73 , R 81 , R 82 and R 83 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. And n represents 0 or 1). In general formula (VI), at least one of R 8 is represented by general formula (VI-b) or general formula (VI -c) or an alkoxy group substituted by a substituent represented by the general formula (VI-d), preferably all of R 8 are represented by the general formula (VI-b), the general formula (VI-c) or It is particularly preferable to represent an alkoxy group substituted by a substituent represented by the general formula (VI-d).

更に、一般式(VI-a)は具体的には一般式(VI-e)   Furthermore, the general formula (VI-a) specifically represents the general formula (VI-e)

Figure 2012162742
Figure 2012162742

（式中nは２〜９の整数を表す。）で表される構造を有することが特に好ましい。
また、以上の重合性液晶組成物中に酸化防止剤の他に重合禁止剤、重合開始剤、界面活性剤、又は紫外線吸収剤などの添加剤を含有しても良い。 It is particularly preferable to have a structure represented by the formula (wherein n represents an integer of 2 to 9).
In addition to the antioxidant, the above polymerizable liquid crystal composition may contain an additive such as a polymerization inhibitor, a polymerization initiator, a surfactant, or an ultraviolet absorber.

以下、実施例を挙げて本願発明を更に詳述するが、本願発明はこれらの実施例に限定されるものではない。
（実施例１）
式(a)の化合物50質量% EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples.
Example 1
50% by mass of the compound of the formula (a)

Figure 2012162742
Figure 2012162742

式(b)の化合物50質量% 50% by mass of the compound of the formula (b)

Figure 2012162742
Figure 2012162742

からなる重合性液晶組成物（A）を調製した。重合性液晶組成物（A）97.5質量％に光重合開始剤Irgacure-651（チバスペシャリティケミカルズ社製）2.0質量%、酸化防止剤（I-1）を0.5質量%添加した本発明の重合性液晶組成物（A1）を調製した。次に重合性液晶組成物（A1）を33質量%含有するキシレン溶液を調製した。このキシレン溶液をポリイミド配向膜付きガラス基板にスピンコート（3000回転/分、30秒）した。スピンコートした基板に窒素雰囲気中で4mW/cm2の紫外線を120秒照射して、重合性液晶組成物（A1）を硬化させた。得られた光学異方体の加熱前の位相差及び230℃で30分加熱後の位相差を測定し、位相差の減少率を算出した。評価結果を表１に示す。 A polymerizable liquid crystal composition (A) comprising: Polymerizable liquid crystal composition (A) according to the present invention comprising 97.5% by mass of photopolymerization initiator Irgacure-651 (manufactured by Ciba Specialty Chemicals) 2.0% by mass and antioxidant (I-1) 0.5% by mass. Composition (A1) was prepared. Next, a xylene solution containing 33% by mass of the polymerizable liquid crystal composition (A1) was prepared. This xylene solution was spin-coated (3000 rpm / 30 seconds) on a glass substrate with a polyimide alignment film. The polymerizable liquid crystal composition (A1) was cured by irradiating the spin-coated substrate with 4 mW / cm 2 of ultraviolet light for 120 seconds in a nitrogen atmosphere. The phase difference before heating of the obtained optical anisotropic body and the phase difference after heating at 230 ° C. for 30 minutes were measured, and the reduction rate of the phase difference was calculated. The evaluation results are shown in Table 1.

（実施例２〜８）
酸化防止剤として式（I-1）に替えて、式（I-2）〜式（I-8）をそれぞれ用いる以外は実施例１と同様にして重合性液晶組成物（A2）〜（A8）を作製し、同様に光学異方体を作製した。得られた光学異方体の加熱前の位相差及び230℃で30分加熱後の位相差を測定し、位相差の減少率を算出した。評価結果を実施例１と共に表１に示す。 (Examples 2 to 8)
The polymerizable liquid crystal compositions (A2) to (A8) were treated in the same manner as in Example 1 except that the formula (I-2) to the formula (I-8) were used in place of the formula (I-1) as the antioxidant. ) And an optically anisotropic body was produced in the same manner. The phase difference before heating of the obtained optical anisotropic body and the phase difference after heating at 230 ° C. for 30 minutes were measured, and the reduction rate of the phase difference was calculated. The evaluation results are shown in Table 1 together with Example 1.

（実施例９）
酸化防止剤の添加量を0.1質量%とした以外は実施例１と同様にして重合性液晶組成物（A9）を作製し、同様に光学異方体を作製した。得られた光学異方体の加熱前の位相差及び230℃で30分加熱後の位相差を測定し、位相差の減少率を算出した。評価結果を実施例１と共に表１に示す。 Example 9
A polymerizable liquid crystal composition (A9) was produced in the same manner as in Example 1 except that the addition amount of the antioxidant was 0.1% by mass, and an optically anisotropic substance was produced in the same manner. The phase difference before heating of the obtained optical anisotropic body and the phase difference after heating at 230 ° C. for 30 minutes were measured, and the reduction rate of the phase difference was calculated. The evaluation results are shown in Table 1 together with Example 1.

（実施例１０）
酸化防止剤として式（I-1）に替えて、式（I-5）を用い、添加量を0.1質量%とした以外は実施例１と同様にして重合性液晶組成物（A10）を作製し、同様に光学異方体を作製した。得られた光学異方体の加熱前の位相差及び230℃で30分加熱後の位相差を測定し、位相差の減少率を算出した。評価結果を実施例１と共に表１に示す。 (Example 10)
A polymerizable liquid crystal composition (A10) was produced in the same manner as in Example 1, except that the formula (I-5) was used instead of the formula (I-1) as an antioxidant and the addition amount was 0.1% by mass. Similarly, an optical anisotropic body was produced. The phase difference before heating of the obtained optical anisotropic body and the phase difference after heating at 230 ° C. for 30 minutes were measured, and the reduction rate of the phase difference was calculated. The evaluation results are shown in Table 1 together with Example 1.

Figure 2012162742
Figure 2012162742

表１より特定の酸化防止剤を0.5質量%添加した重合性液晶組成物（A1）〜（A8）では何れも位相差の減少率が４％以内に抑えられていることがわかる。酸化防止剤の添加量を0.1質量%とした重合性液晶組成物（A9）及び（A10）は、同じ酸化防止剤を用い添加量の多い重合性液晶組成物（A1）及び（A5）には及ばないものの、位相差の減少率が４％以内に抑えられていることがわかる。   From Table 1, it can be seen that in any of the polymerizable liquid crystal compositions (A1) to (A8) to which 0.5% by mass of a specific antioxidant is added, the retardation reduction rate is suppressed to 4% or less. The polymerizable liquid crystal compositions (A9) and (A10) in which the addition amount of the antioxidant is 0.1% by mass are the same as the polymerizable liquid crystal compositions (A1) and (A5) that use the same antioxidant and have a large addition amount Although it does not reach, it can be seen that the reduction rate of the phase difference is suppressed within 4%.

（比較例１）
重合性液晶組成物（A）98質量％に光重合開始剤Irgacure-651（チバスペシャリティケミカルズ社製）2.0質量%を添加した本発明の重合性液晶組成物（B1）を調製した。次に重合性液晶組成物（B1）を33質量%含有するキシレン溶液を調製した。このキシレン溶液をポリイミド配向膜付きガラス基板にスピンコート（3000回転/分、30秒）した。スピンコートした基板に窒素雰囲気中で4mW/cm2の紫外線を120秒照射して、重合性液晶組成物（B1）を硬化させた。得られた光学異方体の加熱前の位相差及び230℃で30分加熱後の位相差を測定し、位相差の減少率を算出した。評価結果を表２に示す。表２よりB1の位相差の減少率は10%であり、酸化防止剤として式（I-1）〜式（I-8）を0.5%添加した場合と比較して減少率が大きいことがわかる。 (Comparative Example 1)
The polymerizable liquid crystal composition (B1) of the present invention was prepared by adding 2.0% by mass of a photopolymerization initiator Irgacure-651 (manufactured by Ciba Specialty Chemicals) to 98% by mass of the polymerizable liquid crystal composition (A). Next, a xylene solution containing 33% by mass of the polymerizable liquid crystal composition (B1) was prepared. This xylene solution was spin-coated (3000 rpm / 30 seconds) on a glass substrate with a polyimide alignment film. The polymerizable liquid crystal composition (B1) was cured by irradiating the spin-coated substrate with 4 mW / cm 2 of ultraviolet light for 120 seconds in a nitrogen atmosphere. The phase difference before heating of the obtained optical anisotropic body and the phase difference after heating at 230 ° C. for 30 minutes were measured, and the reduction rate of the phase difference was calculated. The evaluation results are shown in Table 2. From Table 2, it can be seen that the reduction rate of the phase difference of B1 is 10%, and the reduction rate is larger than when 0.5% of the formulas (I-1) to (I-8) are added as antioxidants. .

Figure 2012162742
Figure 2012162742

（比較例２）
重合性液晶組成物（A）97.5質量％に光重合開始剤Irgacure-651（チバスペシャリティケミカルズ社製）2.0質量%、式（c）及び式（d）に示す低分子量タイプの酸化防止剤をそれぞれ0.5質量%添加した本発明の重合性液晶組成物（C1）及び(C2)を調製した。 (Comparative Example 2)
Polymeric liquid crystal composition (A) 97.5% by mass Photopolymerization initiator Irgacure-651 (manufactured by Ciba Specialty Chemicals) 2.0% by mass, low molecular weight type antioxidants represented by formula (c) and formula (d), respectively Polymerizable liquid crystal compositions (C1) and (C2) of the present invention added with 0.5% by mass were prepared.

Figure 2012162742
Figure 2012162742

次に重合性液晶組成物（C1）及び(C2)を33質量%含有するキシレン溶液を調製した。このキシレン溶液をポリイミド配向膜付きガラス基板にスピンコート（3000回転/分、30秒）した。スピンコートした基板に窒素雰囲気中で4mW/cm2の紫外線を120秒照射して、重合性液晶組成物（C1）及び(C2)を硬化させた。得られた光学異方体の加熱前の位相差及び230℃で30分加熱後の位相差を測定し、位相差の減少率を算出した。評価結果を表３に示す。表３より低分子量タイプの酸化防止剤として式（c）及び式（d）を添加したC1及びC2の位相差の減少率は8%及び17%であり、高分子量タイプの酸化防止剤として式（I-1）〜式（I-8）を0.5質量%添加した場合と比較して減少率が大きいことがわかる。 Next, a xylene solution containing 33% by mass of the polymerizable liquid crystal compositions (C1) and (C2) was prepared. This xylene solution was spin-coated (3000 rpm / 30 seconds) on a glass substrate with a polyimide alignment film. The polymerizable liquid crystal compositions (C1) and (C2) were cured by irradiating the spin-coated substrate with 4 mW / cm 2 of ultraviolet rays for 120 seconds in a nitrogen atmosphere. The phase difference before heating of the obtained optical anisotropic body and the phase difference after heating at 230 ° C. for 30 minutes were measured, and the reduction rate of the phase difference was calculated. The evaluation results are shown in Table 3. From Table 3, the reduction rate of the retardation of C1 and C2 with the addition of formula (c) and formula (d) as low molecular weight type antioxidants is 8% and 17%, and the formula as high molecular weight type antioxidants. It can be seen that the reduction rate is larger than when 0.5 mass% of (I-1) to formula (I-8) is added.

Figure 2012162742
Figure 2012162742

Claims (12)

少なくとも１つ以上の水素原子がtert-ブチル基で置換されているフェノール骨格を有する分子量３００以上７００未満の酸化防止剤を含有することを特徴とする重合性液晶組成物。 A polymerizable liquid crystal composition comprising an antioxidant having a phenol skeleton in which at least one hydrogen atom is substituted with a tert-butyl group and having a molecular weight of 300 or more and less than 700. 少なくとも１つ以上の水素原子がtert-ブチル基で置換されているフェノール骨格を有する分子量３００以上５００以下の酸化防止剤を含有することを特徴とする重合性液晶組成物。 A polymerizable liquid crystal composition comprising an antioxidant having a phenol skeleton in which at least one hydrogen atom is substituted with a tert-butyl group and having a molecular weight of 300 to 500. 酸化防止剤の含有量が０．１〜５質量％である請求項１又は２記載の重合性液晶組成物。 The polymerizable liquid crystal composition according to claim 1 or 2, wherein the content of the antioxidant is 0.1 to 5% by mass. 請求項１から３のいずれかに記載の重合性液晶組成物及び有機溶媒を含有する重合性組成物。 A polymerizable composition comprising the polymerizable liquid crystal composition according to claim 1 and an organic solvent. 一般式（I）
Figure 2012162742
 （式中、Pは反応性官能基を表し、Spは炭素原子数１〜２０のスペーサー基を表し、mは０又は１を表し、MGはメソゲン基又はメソゲン性支持基を表し、R9は、ハロゲン原子、シアノ基又は炭素原子数１〜２５のアルキル基を表すが、該アルキル基は１つ以上のハロゲン原子又はCNにより置換されていても良く、この基中に存在する１つのCH2基又は隣接していない２つ以上のCH2基はそれぞれ相互に独立して、酸素原子が相互に直接結合しない形で、-O-、-S-、-NH-、-N(CH3)-、-CO-、-COO-、-OCO-、-OCOO-、-SCO-、-COS-又は-C≡C-により置き換えられていても良く、あるいはR9は一般式（I-a）
Figure 2012162742
 （式中、Pは反応性官能基を表し、Spは炭素原子数１〜２０のスペーサー基を表し、mは０又は１を表す。）で表される構造を表す。）で表される化合物を含有する請求項１から４の何れか一項に記載の重合性液晶組成物。 Formula (I)
Figure 2012162742
 (Wherein P represents a reactive functional group, Sp represents a spacer group having 1 to 20 carbon atoms, m represents 0 or 1, MG represents a mesogenic group or a mesogenic support group, and R 9 represents Represents a halogen atom, a cyano group or an alkyl group having 1 to 25 carbon atoms, and the alkyl group may be substituted by one or more halogen atoms or CN, and one CH 2 present in the group. Group or two or more non-adjacent CH 2 groups are each independently of each other such that —O—, —S—, —NH—, —N (CH 3 ) -, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- may be substituted, or R 9 is represented by the general formula (Ia)
Figure 2012162742
 (Wherein P represents a reactive functional group, Sp represents a spacer group having 1 to 20 carbon atoms, and m represents 0 or 1). The polymerizable liquid crystal composition according to any one of claims 1 to 4, comprising a compound represented by: 一般式（I）において、Spはアルキレン基を表し、該アルキレン基は１つ以上のハロゲン原子又はCNにより置換されていても良く、この基中に存在する１つのCH2基又は隣接していない２つ以上のCH2基はそれぞれ相互に独立して、酸素原子が相互に直接結合しない形で、-O-、-S-、-NH-、-N(CH3)-、-CO-、-COO-、-OCO-、-OCOO-、-SCO-、-COS-又は-C≡C-により置き換えられていても良い。）で表される構造を表し、MGが一般式（I-b）
Figure 2012162742
 （式中、A1、A2及びA3はそれぞれ独立的に、1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、テトラヒドロチオピラン-2,5-ジイル基、1,4-ビシクロ(2,2,2)オクチレン基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基、フルオレン2,7-ジイル基を表し、該1,4-フェニレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基及びフルオレン2,7-ジイル基は置換基として１個以上のF、Cl、CF3、OCF3、シアノ基、炭素原子数１〜８のアルキル基、アルコキシ基、アルカノイル基、アルカノイルオキシ基、炭素原子数２〜８のアルケニル基、アルケニルオキシ基、アルケノイル基、アルケノイルオキシ基を有していても良く、Z0、Z1、Z2及びZ3はそれぞれ独立して、-COO-、-OCO-、-CH2 CH2-、-OCH2-、-CH2O-、-CH=CH-、-C≡C-、-CH=CHCOO-、-OCOCH=CH-、-CH2CH2COO-、-CH2CH2OCO-、-COO CH2CH2-、-OCOCH2CH2-、-CONH-、-NHCO-又は単結合を表し、nは０、１又は２を表す。）で表される構造を表し、Pが一般式（I-c）、一般式（I-d）又は一般式（I-e）
Figure 2012162742
 （式中、R61、R62、R63、R71、R72、R73、R81、R82及びR83はそれぞれ独立的に水素原子、ハロゲン原子又は炭素原子数１〜５のアルキル基を表し、nは０又は１を表す。）で表される置換基からなる群より選ばれる置換基を表す、請求項６記載の重合性液晶組成物。 In general formula (I), Sp represents an alkylene group, which may be substituted by one or more halogen atoms or CN, and is not adjacent to one CH 2 group present in this group Two or more CH 2 groups are independently of each other, in a form in which oxygen atoms are not directly bonded to each other, —O—, —S—, —NH—, —N (CH 3 ) —, —CO—, It may be replaced by -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-. ), Where MG is the general formula (Ib)
Figure 2012162742
 (In the formula, A1, A2 and A3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1, 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine- 2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, Phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group, fluorene 2, Represents a 7-diyl group, the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9 , 10-dihydrophenanthrene-2,7-diyl group, 1, 2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group and fluorene 2,7-diyl group are substituted with one or more F, Cl, CF 3 , OCF 3 , cyano group, It may have an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkanoyl group, an alkanoyloxy group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group, an alkenoyl group or an alkenoyloxy group. , - - independently, -COO, the Z1, Z2 and Z3 OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH 2 O -, - CH = CH -, - C≡C-, -CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COO CH 2 CH 2 -, - OCOCH 2 CH 2 -, - CONH -, - NHCO- Or n represents 0, 1 or 2), and P represents a general formula (Ic), general formula (Id) or general formula (Ie)
Figure 2012162742
 (In the formula, R 61 , R 62 , R 63 , R 71 , R 72 , R 73 , R 81 , R 82 and R 83 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. And n represents 0 or 1. The polymerizable liquid crystal composition according to claim 6, which represents a substituent selected from the group consisting of substituents represented by: 一般式（II）
Figure 2012162742
 （式中、mは０又は１を表し、W1及びW2はそれぞれ独立的に単結合、-O-、-COO-又は-OCO-を表し、Y1及びY2はそれぞれ独立的に-COO-又は-OCO-を表し、r及びsはそれぞれ独立的に２〜１８の整数を表すが、式中に存在する1,4−フェニレン基は炭素原子数１〜７のアルキル基、アルコキシ基、アルカノイル基、シアノ基、又はハロゲン原子で一つ以上置換されていても良い。）で表される化合物を含有する請求項６記載の重合性液晶組成物。 Formula (II)
Figure 2012162742
 Wherein m represents 0 or 1, W 1 and W 2 each independently represent a single bond, —O—, —COO— or —OCO—, and Y 1 and Y 2 each independently represent — COO- or -OCO- is represented, and r and s each independently represent an integer of 2 to 18, the 1,4-phenylene group present in the formula is an alkyl group or alkoxy group having 1 to 7 carbon atoms , An alkanoyl group, a cyano group, or a halogen atom, which may be substituted with one or more compounds). 一般式（III）
Figure 2012162742
 （式中、Z1は水素原子、ハロゲン原子、シアノ基又は炭素原子数１〜２０の炭化水素基を表し、Z2は水素原子又はメチル基を表し、tは０又は1を表し、A、B及びCはそれぞれ独立的に、1,4−フェニレン基、隣接しないCH基が窒素で置換された1,4−フェニレン基、1,4−シクロヘキシレン基、１つ又は隣接しない２つのCH2基が酸素又は硫黄原子で置換された1,4−シクロヘキシレン基、1,4−シクロヘキセニレン基を表すが、式中に存在する1,4−フェニレン基は炭素原子数１〜７のアルキル基、アルコキシ基、アルカノイル基、シアノ基又はハロゲン原子で一つ以上置換されていても良く、Y3及びY4はそれぞれ独立的に単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、-OCO-、-C≡C-、-CH=CH-、-CF=CF-、-（CH2）4-、-CH2CH2CH2O-、-OCH2CH2CH2-、-CH=CHCH2CH2-、-CH2CH2CH=CH-、-CH=CHCOO-、-OCOCH=CH-、-CH2CH2COO-、-CH2CH2OCO-、-COO CH2CH2-又は-OCOCH2CH2-を表し、Y5は単結合、-O-、-COO-、-OCO-又は-CH=CHCOO-を表す。）で表される化合物を含有する請求項６記載の重合性液晶組成物。 General formula (III)
Figure 2012162742
 (In the formula, Z 1 represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms, Z 2 represents a hydrogen atom or a methyl group, t represents 0 or 1, A, B and C are each independently a 1,4-phenylene group, a 1,4-phenylene group in which a non-adjacent CH group is substituted with nitrogen, a 1,4-cyclohexylene group, one or two non-adjacent CH 2 Represents a 1,4-cyclohexylene group or 1,4-cyclohexenylene group in which the group is substituted with an oxygen or sulfur atom, and the 1,4-phenylene group present in the formula is an alkyl having 1 to 7 carbon atoms Group, an alkoxy group, an alkanoyl group, a cyano group or a halogen atom, and Y 3 and Y 4 are each independently a single bond, —CH 2 CH 2 —, —CH 2 O—, -OCH 2 -, - COO -, - OCO -, - C≡C -, - CH = CH -, - CF = CF -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2- , -CH = CHCH 2 CH 2- , -CH 2 CH 2 CH = CH -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COO CH 2 CH 2 - or -OCOCH 2 CH 2 - and The polymerizable liquid crystal composition according to claim 6, comprising a compound represented by the formula: Y 5 represents a single bond, —O—, —COO—, —OCO—, or —CH═CHCOO—. 一般式（IV）
Figure 2012162742
 （式中、Z3は水素原子、ハロゲン原子、シアノ基又は炭素原子数１〜２０の炭化水素基を表し、Z4は水素原子又はメチル基を表し、W3は単結合、-O-、-COO-又は-OCO-を表し、vは２〜１８の整数を表し、uは０又は１を表し、D、E及びFはそれぞれ独立的に、1,4−フェニレン基、隣接しないCH基が窒素で置換された1,4−フェニレン基、1,4−シクロヘキシレン基、１つ又は隣接しない２つのCH2基が酸素又は硫黄原子で置換された1,4−シクロヘキシレン基、1,4−シクロヘキセニレン基を表すが、式中に存在する1,4−フェニレン基は炭素原子数１〜７のアルキル基、アルコキシ基、アルカノイル基、シアノ基又はハロゲン原子で一つ以上置換されていても良く、Y6及びY7はそれぞれ独立的に単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、-OCO-、-C≡C-、-CH=CH-、-CF=CF-、-（CH2）4-、-CH2CH2CH2O-、-OCH2CH2CH2-、-CH=CHCH2CH2-、-CH2CH2CH=CH-、-CH=CHCOO-、-OCOCH=CH-、-CH2CH2COO-、-CH2CH2OCO-、-COO CH2CH2-又は-OCOCH2CH2-を表し、Y8は単結合、-O-、-COO-、-OCO-又は-CH=CHCOO-を表す。）で表される化合物を含有する請求項５記載の重合性液晶組成物。 Formula (IV)
Figure 2012162742
 (Wherein Z 3 represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms, Z 4 represents a hydrogen atom or a methyl group, W 3 represents a single bond, —O—, -COO- or -OCO-, v represents an integer of 2 to 18, u represents 0 or 1, D, E and F are each independently a 1,4-phenylene group or a non-adjacent CH group. 1,4-phenylene group substituted with nitrogen, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CH 2 groups are substituted with oxygen or sulfur atoms, 1, Represents a 4-cyclohexenylene group, but the 1,4-phenylene group present in the formula is substituted by one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms having 1 to 7 carbon atoms. Y 6 and Y 7 are each independently a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —C≡C—, — CH = CH-, -CF = CF -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CHCH 2 CH 2 -, - CH 2 CH 2 CH = CH -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COO CH 2 CH 2 - or -OCOCH 2 CH 2 - represents, Y 8 represents a single bond, - The polymerizable liquid crystal composition according to claim 5, comprising a compound represented by the formula: O—, —COO—, —OCO— or —CH═CHCOO—. ベンゼン誘導体、トリフェニレン誘導体、トルキセン誘導体、フタロシアニン誘導体又はシクロヘキサン誘導体を分子の中心の母核とし、直鎖のアルキル基、直鎖のアルコキシ基又は置換ベンゾイルオキシ基がその側鎖として放射状に置換した構造である円盤状液晶化合物を含有する請求項１記載の重合性液晶組成物。 A structure in which a benzene derivative, triphenylene derivative, truxene derivative, phthalocyanine derivative or cyclohexane derivative is used as the mother nucleus of the molecule, and a linear alkyl group, linear alkoxy group, or substituted benzoyloxy group is radially substituted as its side chain. The polymerizable liquid crystal composition according to claim 1, comprising a discotic liquid crystal compound. 円盤状液晶化合物が一般式（V）で表される請求項１０記載の重合性液晶組成物。
Figure 2012162742
 （式中、R5はそれぞれ独立して一般式（V-a）で表される置換基を表す。
Figure 2012162742
 （式中、R6及びR7はそれぞれ独立的に水素原子、ハロゲン原子又はメチル基を表し、R8は炭素原子数１〜２０アルコキシ基を表すが、該アルコキシ基中の水素原子は一般式（V-b）、一般式（V-c）又は一般式（V-d）で表される置換基によって置換されていても良い。）
Figure 2012162742
 （式中、R61、R62、R63、R71、R72、R73、R81、R82及びR83はそれぞれ独立的に水素原子、ハロゲン原子又は炭素原子数１〜５のアルキル基を表し、nは０又は１を表す。） The polymerizable liquid crystal composition according to claim 10, wherein the discotic liquid crystal compound is represented by the general formula (V).
Figure 2012162742
 (In the formula, each R 5 independently represents a substituent represented by the general formula (Va).
Figure 2012162742
 (In the formula, R 6 and R 7 each independently represent a hydrogen atom, a halogen atom or a methyl group, and R 8 represents an alkoxy group having 1 to 20 carbon atoms, and the hydrogen atom in the alkoxy group represents a general formula. (It may be substituted by a substituent represented by (Vb), general formula (Vc) or general formula (Vd).)
Figure 2012162742
 (In the formula, R 61 , R 62 , R 63 , R 71 , R 72 , R 73 , R 81 , R 82 and R 83 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. And n represents 0 or 1.) 請求項１から１１の何れかに記載の重合性液晶組成物の重合体を含有する光学異方体。 An optical anisotropic body containing the polymer of the polymerizable liquid crystal composition according to claim 1.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150039106A (en) * 2013-10-01 2015-04-09 주식회사 엘지화학 Liquid crystal composition

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06172265A (en) * 1992-09-18 1994-06-21 Yoshitomi Pharmaceut Ind Ltd Pentaerythritol ester compound and its use
JPH09291282A (en) * 1996-04-26 1997-11-11 Sumitomo Chem Co Ltd Stabilized liquid crystal material and liquid crystal element using the same
JP2002529562A (en) * 1998-11-09 2002-09-10 ユニロイヤル ケミカル カンパニー インコーポレイテッド Thermoplastics stabilized by mixtures of sterically hindered phenols, secondary amines and thioethers
JP2002256267A (en) * 2000-12-27 2002-09-11 Dainippon Ink & Chem Inc Antioxidative liquid crystal composition
JP2003193053A (en) * 2001-12-26 2003-07-09 Dainippon Ink & Chem Inc Polymerizable liquid crystal composition and optical anisotropic object using the same
JP2005105066A (en) * 2003-09-29 2005-04-21 Fuji Photo Film Co Ltd Cellulose acylate film, polarizing plate and liquid crystal display device
JP2005241710A (en) * 2004-02-24 2005-09-08 Fuji Photo Film Co Ltd Liquid crystal composition, retardation plate and liquid crystal display device
JP2005272561A (en) * 2004-03-24 2005-10-06 Dainippon Ink & Chem Inc Polymerizable liquid crystal composition and polymer of the same
WO2006001444A1 (en) * 2004-06-29 2006-01-05 Asahi Glass Company, Limited Liquid crystal light modulating element and optical head device
JP2006064805A (en) * 2004-08-25 2006-03-09 Konica Minolta Holdings Inc Display medium
JP2007504484A (en) * 2003-08-26 2007-03-01 メルク　パテント　ゲゼルシャフト　ミット　ベシュレンクテル　ハフトング Polymer film with twist pattern
JP2007506813A (en) * 2003-07-12 2007-03-22 メルク　パテント　ゲゼルシャフト　ミット　ベシュレンクテル　ハフトング Polymerized liquid crystal film with improved adhesion
JP2008512504A (en) * 2004-09-06 2008-04-24 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング Polymerizable liquid crystal material

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06172265A (en) * 1992-09-18 1994-06-21 Yoshitomi Pharmaceut Ind Ltd Pentaerythritol ester compound and its use
JPH09291282A (en) * 1996-04-26 1997-11-11 Sumitomo Chem Co Ltd Stabilized liquid crystal material and liquid crystal element using the same
JP2002529562A (en) * 1998-11-09 2002-09-10 ユニロイヤル ケミカル カンパニー インコーポレイテッド Thermoplastics stabilized by mixtures of sterically hindered phenols, secondary amines and thioethers
JP2002256267A (en) * 2000-12-27 2002-09-11 Dainippon Ink & Chem Inc Antioxidative liquid crystal composition
JP2003193053A (en) * 2001-12-26 2003-07-09 Dainippon Ink & Chem Inc Polymerizable liquid crystal composition and optical anisotropic object using the same
JP2007506813A (en) * 2003-07-12 2007-03-22 メルク　パテント　ゲゼルシャフト　ミット　ベシュレンクテル　ハフトング Polymerized liquid crystal film with improved adhesion
JP2007504484A (en) * 2003-08-26 2007-03-01 メルク　パテント　ゲゼルシャフト　ミット　ベシュレンクテル　ハフトング Polymer film with twist pattern
JP2005105066A (en) * 2003-09-29 2005-04-21 Fuji Photo Film Co Ltd Cellulose acylate film, polarizing plate and liquid crystal display device
JP2005241710A (en) * 2004-02-24 2005-09-08 Fuji Photo Film Co Ltd Liquid crystal composition, retardation plate and liquid crystal display device
JP2005272561A (en) * 2004-03-24 2005-10-06 Dainippon Ink & Chem Inc Polymerizable liquid crystal composition and polymer of the same
WO2006001444A1 (en) * 2004-06-29 2006-01-05 Asahi Glass Company, Limited Liquid crystal light modulating element and optical head device
JP2006064805A (en) * 2004-08-25 2006-03-09 Konica Minolta Holdings Inc Display medium
JP2008512504A (en) * 2004-09-06 2008-04-24 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング Polymerizable liquid crystal material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
K. FATEH-ALAVI, M. E. NUNEZ, S. KARLSSON, U. W. GEDDE: "The effect of stabilizer concentration on the air-plasma-induced surface oxidation of crosslinked po", POLYMER DEGRADATION AND STABILITY, vol. 78, no. 1, JPN6013063200, 2002, NL, pages 17 - 25, XP004374669, ISSN: 0002710437, DOI: 10.1016/S0141-3910(02)00114-3 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150039106A (en) * 2013-10-01 2015-04-09 주식회사 엘지화학 Liquid crystal composition
JP2016510820A (en) * 2013-10-01 2016-04-11 エルジー・ケム・リミテッド Liquid crystal composition
KR101640990B1 (en) 2013-10-01 2016-07-19 주식회사 엘지화학 Liquid crystal composition

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