JP5354238B2 - Polymerizable liquid crystal composition - Google Patents
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- JP5354238B2 JP5354238B2 JP2006151595A JP2006151595A JP5354238B2 JP 5354238 B2 JP5354238 B2 JP 5354238B2 JP 2006151595 A JP2006151595 A JP 2006151595A JP 2006151595 A JP2006151595 A JP 2006151595A JP 5354238 B2 JP5354238 B2 JP 5354238B2
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 67
- 239000000203 mixture Substances 0.000 title claims description 54
- 230000003287 optical effect Effects 0.000 claims description 27
- -1 tetrahydropyran-2,5-diyl group Chemical group 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 22
- 125000005843 halogen group Chemical group 0.000 claims description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims description 9
- 125000002252 acyl group Chemical group 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 claims description 4
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 4
- 101150065749 Churc1 gene Proteins 0.000 claims description 4
- 102100038239 Protein Churchill Human genes 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- 125000005714 2,5- (1,3-dioxanylene) group Chemical group [H]C1([H])OC([H])([*:1])OC([H])([H])C1([H])[*:2] 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims 1
- 239000012071 phase Substances 0.000 description 24
- 239000000758 substrate Substances 0.000 description 11
- 239000008096 xylene Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 150000003738 xylenes Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 210000002858 crystal cell Anatomy 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- LKVFCSWBKOVHAH-UHFFFAOYSA-N 4-Ethoxyphenol Chemical compound CCOC1=CC=C(O)C=C1 LKVFCSWBKOVHAH-UHFFFAOYSA-N 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 231100000584 environmental toxicity Toxicity 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- VTFXHGBOGGGYDO-UHFFFAOYSA-N 2,4-bis(dodecylsulfanylmethyl)-6-methylphenol Chemical compound CCCCCCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCCCCCC)=C1 VTFXHGBOGGGYDO-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)(C)c1cc(*)cc(C(C)(C)C)c1O Chemical compound CC(C)(C)c1cc(*)cc(C(C)(C)C)c1O 0.000 description 1
- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 description 1
- 241000219289 Silene Species 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- YGPLLMPPZRUGTJ-UHFFFAOYSA-N truxene Chemical class C1C2=CC=CC=C2C(C2=C3C4=CC=CC=C4C2)=C1C1=C3CC2=CC=CC=C21 YGPLLMPPZRUGTJ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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- Polarising Elements (AREA)
- Liquid Crystal Substances (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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し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 polymerized 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。
しかし、重合性液晶組成物を基板に塗布した場合、空気界面においてある程度のチルト角を有し、ある特定の位相差フィルムに要求される光学特性を満たすためにはチルト角を減じることが求められていた。また、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が、位相差フィルムを液晶セル内に組み込んだ場合、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。
該チルト角を減じる方法として、界面活性剤や重合可能な界面活性剤を重合性液晶組成物中に添加する方法が提案されている（特許文献１、２及び３参照）。しかし、重合性液晶組成物に界面活性剤を含有させた場合、空気界面のチルト角を減じる目的は達成できるが、界面活性剤を含有した光学異方体が高温に曝されると、位相差が顕著に減少してしまう。更に、界面活性剤として長鎖パーフルオロアルキルスルホン酸アミド誘導体を用いた場合（特許文献３参照）には当該化合物は環境毒性の点で懸念があることから液晶ディスプレイとしての応用には問題があった。
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.
However, when a polymerizable liquid crystal composition is applied to a substrate, it has a certain tilt angle at the air interface, and it is required to reduce the tilt angle in order to satisfy the optical characteristics required for a specific retardation film. It was. In addition, for the purpose of reducing the thickness and weight and reducing the cost, a method of incorporating a retardation film in the liquid crystal cell of the liquid crystal display is attracting attention. However, when the retardation film is incorporated in the liquid crystal cell, the manufacturing process of the liquid crystal display In the method, since there is a process that must be performed at a high temperature, the film is exposed to a high temperature of 200 ° C. or higher in the retardation film manufacturing process. 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.
As a method of reducing the tilt angle, a method of adding a surfactant or a polymerizable surfactant to the polymerizable liquid crystal composition has been proposed (see Patent Documents 1, 2, and 3). However, when a surfactant is contained in the polymerizable liquid crystal composition, the purpose of reducing the tilt angle of the air interface can be achieved, but when the optically anisotropic body containing the surfactant is exposed to a high temperature, the retardation is increased. Will be significantly reduced. Furthermore, when a long-chain perfluoroalkyl sulfonic acid amide derivative is used as a surfactant (see Patent Document 3), there is a problem in application as a liquid crystal display because the compound has a concern in terms of environmental toxicity. It was.
一方、重合性液晶組成物にフェノール骨格を有する安定剤を添加した構成は既に知られている（特許文献４参照）。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安定剤は、不要な重合を抑制するために用いられており、空気界面のチルト角を減じる効果もなく、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もない。また、当該引用文献に記載の重合性液晶組成物においては、安定剤として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、これらの安定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 stabilizer which has a phenol skeleton to the polymeric liquid crystal composition is already known (refer patent document 4). However, in the cited document, a stabilizer having a phenol skeleton is used to suppress unnecessary polymerization, and has no effect of reducing the tilt angle of the air interface, and suppresses deterioration of optical characteristics at high temperatures. It is not used for the purpose. Further, in the polymerizable liquid crystal composition described in the cited document, 4-ethoxyphenol or butylated hydroxytoluene (BHT) is used as a stabilizer. However, since these stabilizers 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こと及び空気界面のチルト角を減じることを同時に達成可能な光学異方体を作製することができる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 capable of simultaneously achieving that the phase difference does not change at a high temperature of 200 ° C. or higher and the tilt angle of the air interface is reduced. .
本願発明の目的は、重合性液晶組成物を基板に塗布した場合、空気界面におけるチルト角を減じる効果を有し、かつ、重合性液晶組成物の硬化物である光学異方体が高温に曝されても位相差を減じにくい重合性液晶組成物を提供することにある。 The object of the present invention is to reduce the tilt angle at the air interface when the polymerizable liquid crystal composition is applied to a substrate, and the optically anisotropic body, which is a cured product of the polymerizable liquid crystal composition, is exposed to a high temperature. It is an object of the present invention to provide a polymerizable liquid crystal composition in which the retardation is difficult to reduce.
上記課題を解決するために種々の酸化防止剤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を明らかにすることに成功し本願発明の完成に至った。本願発明は、一般式（I） As a result of intensive studies on various antioxidants in order to solve the above-mentioned problems, the inventors have succeeded in clarifying the optimum antioxidant for the polymerizable liquid crystal composition of the present invention, and completed the present invention. The present invention relates to the general formula (I)
（式中、k及びlはそれぞれ独立的に０〜３０の整数を表し、Tは、-O-、-S-、-NH-、-N(CH3)-、-CO-、-COO-、-OCO-、-OCOO-、-SCO-、-COS-、-C≡C-又は単結合を表し、1,4−フェニレン基中に存在する１つ又は２つ以上の水素原子がメチル基、エチル基、tert-ブチル基又は一般式（II） (In the formula, k and l each independently represents an integer of 0 to 30, and T represents —O—, —S—, —NH—, —N (CH 3 ) —, —CO—, —COO— , -OCO-, -OCOO-, -SCO-, -COS-, -C≡C- or a single bond, and one or more hydrogen atoms present in the 1,4-phenylene group are methyl groups , Ethyl group, tert-butyl group or general formula (II)
（式中、m及びnはそれぞれ独立的に０〜３０の整数を表し、Uは、-O-、-S-、-NH-、-N(CH3)-、-CO-、-COO-、-OCO-、-OCOO-、-SCO-、-COS-、-C≡C-又は単結合を表す。）で表される置換基で置換されていても良い。）で表される分子量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。 (In the formula, m and n each independently represents an integer of 0 to 30, and U represents —O—, —S—, —NH—, —N (CH 3 ) —, —CO—, —COO— , -OCO-, -OCOO-, -SCO-, -COS-, -C≡C- or a single bond). And a polymerizable liquid crystal composition characterized by containing an antioxidant having a molecular weight of 300 or more, and 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、空気界面におけるチルト角を減じる効果を有することから空気界面において水平配向となる光学異方体の材料として有用であり、かつ、光学異方体の位相差が減少しにくいという優れた特徴を有する。よって本願発明の重合性液晶組成物は、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に使用でき、かつ、環境毒性の心配もない。 The polymerizable liquid crystal composition of the present invention has an effect of reducing the tilt angle at the air interface and thus is useful as a material for an optical anisotropic body that is horizontally aligned at the air interface, and has a phase difference of the optical anisotropic body. It has an excellent feature that it is difficult to decrease. Therefore, the polymerizable liquid crystal composition of the present invention can be suitably used particularly as an optical anisotropic material incorporated into the liquid crystal cell, and there is no concern about environmental toxicity.
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。本願発明の重性液晶組成物は一般式（I）で表される分子量３００以上の酸化防止剤を含有する。一般式（I）において、Ｔは-O-、-S-、-COO-、-OCO-又は単結合が好ましい。又、ｋ及びｌの和は５以上であることが好ましく、８以上がより好ましく、１０以上が特に好ましい。ｋは、８以下が好ましく、５以下がより好ましく、３以下が特に好ましい。 The best mode of the polymerizable liquid crystal composition according to the present invention will be described below. The heavy liquid crystal composition of the present invention contains an antioxidant having a molecular weight of 300 or more represented by the general formula (I). In general formula (I), T is preferably —O—, —S—, —COO—, —OCO— or a single bond. The sum of k and l is preferably 5 or more, more preferably 8 or more, and particularly preferably 10 or more. k is preferably 8 or less, more preferably 5 or less, and particularly preferably 3 or less.
芳香環上に存在する４つの水素原子はメチル基、エチル基、tert-ブチル基又は一般式（II）により置換されていても良いが、少なくとも一つは置換されていることが好ましく、一つ又は二つの水素原子が置換されていることが好ましい。又、置換位置は一般式（I）において、フェノール性水酸基を１位とした場合、２位又は６位に置換しているか、２位及び６位に置換していることが好ましい。 The four hydrogen atoms present on the aromatic ring may be substituted by a methyl group, an ethyl group, a tert-butyl group or general formula (II), but at least one is preferably substituted. Or it is preferable that two hydrogen atoms are substituted. In addition, in the general formula (I), the substitution position is preferably substituted at the 2-position or 6-position or substituted at the 2-position and 6-position when the phenolic hydroxyl group is at the 1-position.
置換基としては、tert-ブチル基又は一般式（II）で表される置換基が好ましいが、一般式（II）で表される置換基においてＵは-O-、-S-、-COO-、-OCO-又は単結合が好ましい。又、ｍ及びｎの和は５以上であることが好ましく、８以上がより好ましく、１０以上が特に好ましい。ｍは、８以下が好ましく、５以下がより好ましい。
一般式（I）で表される酸化防止剤として具体的には、以下の一般式一般式（III）
As the substituent, a tert-butyl group or a substituent represented by the general formula (II) is preferable. In the substituent represented by the general formula (II), U represents —O—, —S—, —COO—. , -OCO- or a single bond is preferred. The sum of m and n is preferably 5 or more, more preferably 8 or more, and particularly preferably 10 or more. m is preferably 8 or less, and more preferably 5 or less.
Specific examples of the antioxidant represented by the general formula (I) include the following general formula (III)
（式中、k、l、m及びnはそれぞれ独立的に０〜３０の整数を表し、T及びUはそれぞれ独立的に、-O-、-S-、-NH-、-N(CH3)-、-CO-、-COO-、-OCO-、-OCOO-、-SCO-、-COS-、-C≡C-又は単結合を表し、ベンゼン環中に存在する１つ又は２つ以上の水素原子がメチル基、エチル基又はtert-ブチル基で置換されていても良い。）で表される分子量３００以上の酸化防止剤を含有することが特に好ましい。該酸化防止剤の分子量は３００以上であるが、４００以上であることが好ましく、５００以上であることがより好ましい。 (Wherein k, l, m and n each independently represents an integer of 0 to 30; T and U each independently represent —O—, —S—, —NH—, —N (CH 3 )-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS-, -C≡C- or a single bond, one or more existing in the benzene ring It is particularly preferable to contain an antioxidant having a molecular weight of 300 or more represented by the formula (1), wherein the hydrogen atom may be substituted with a methyl group, an ethyl group or a tert-butyl group. The molecular weight of the antioxidant is 300 or more, preferably 400 or more, and more preferably 500 or more.
また、これらの酸化防止剤は、重合性液晶組成物中に０．０１〜５質量％含有することが好ましく、さらには０．０５〜２質量％が好ましく、０．１〜1質量％が特に好ましい。 These antioxidants are preferably contained in the polymerizable liquid crystal composition in an amount of 0.01 to 5% by mass, more preferably 0.05 to 2% by mass, particularly 0.1 to 1% by mass. preferable.
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。
棒状重合性液晶化合物は、一般式（V）
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.
The rod-like polymerizable liquid crystal compound has the general formula (V)
（式中、R21、R22、R23、R31、R32、R33、R41、R42及びR43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。
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（VI）
(In the formula, R 21 , R 22 , R 23 , R 31 , R 32 , R 33 , R 41 , R 42 and R 43 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:
Here, the compound contained in the polymerizable liquid crystal composition is more specifically represented by the general formula (VI)
（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。
また、一般式（VII）
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.
In addition, general formula (VII)
（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。
また、一般式（VIII）
(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.
In addition, the general formula (VIII)
（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。
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, 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.
Specific examples of the compound represented by the general formula (V) can be given below.
（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（VI）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 (VI) can be given below.
また、一般式（VII）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。
Further, specific examples of the compound represented by the general formula (VII) include the structure of the compound and the phase transition temperature.
（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（VIII）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 (VIII) can be given below.
（式中、X1は水素原子又はメチル基を表し、R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（IX）
(In the formula, X 1 represents a hydrogen atom or a methyl group, and R 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 radially substituted structure as a chain and is represented by the general formula (IX)
（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（IX-b）、一般式（IX-c）又は一般式（IX-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 by a substituent represented by (IX-b), general formula (IX-c) or general formula (IX-d).)
（式中、R81、R82、R83、R84、R85、R86、R87、R88及びR89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（IX）においてR8の内少なくとも一つは一般式（IX-b）、一般式（IX-c）又は一般式（IX-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（IX-b）、一般式（IX-c）又は一般式（IX-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。
更に、一般式(IX-a)は具体的には一般式(IX-e)
Wherein R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 , R 88 and R 89 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 (IX), at least one of R 8 is represented by general formula (IX-b) or general formula (IX -c) or an alkoxy group substituted by a substituent represented by the general formula (IX-d), preferably all of R 8 are represented by the general formula (IX-b), general formula (IX-c) or It is particularly preferable to represent an alkoxy group substituted by a substituent represented by the general formula (IX-d).
Furthermore, the general formula (IX-a) specifically represents the general formula (IX-e)
（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。
（参考例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.
( Reference Example 1 )
50% by mass of the compound of the formula (a)
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%、式(c)の酸化防止剤Irganox-1076（チバスペシャリティケミカルズ社製） A polymerizable liquid crystal composition (A) comprising: Polymerizable liquid crystal composition (A) 97.5% by mass, photopolymerization initiator Irgacure-651 (manufactured by Ciba Specialty Chemicals) 2.0% by mass, antioxidant Irganox-1076 of formula (c) (manufactured by Ciba Specialty Chemicals)
（実施例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(d)の酸化防止剤Irganox-1726（チバスペシャリティケミカルズ社製）
(Example 2)
Polymerizable liquid crystal composition (A) 97.5% by mass, photopolymerization initiator Irgacure-651 (manufactured by Ciba Specialty Chemicals) 2.0% by mass, antioxidant Irganox-1726 of formula (d) (manufactured by Ciba Specialty Chemicals)
を0.5質量%添加した本願発明の重合性液晶組成物（A2）を調製した。次に重合性液晶組成物（A2）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（A2）を硬化させた。このようにして得られた光学異方体の位相差の入射角依存測定をした結果、空気界面におけるチルト角は約°0であることが確認できた。また、光学異方体の加熱前の位相差は173.2nm、230℃で4時間加熱後の位相差は138.8nmであり、位相差の減少率は20%であった。 A polymerizable liquid crystal composition (A2) of the present invention to which 0.5% by mass was added was prepared. Next, a xylene solution containing 33% by mass of the polymerizable liquid crystal composition (A2) 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 (A2) was cured by irradiating the spin-coated substrate with 4 mW / cm 2 of ultraviolet light for 120 seconds in a nitrogen atmosphere. As a result of measuring the incident angle dependence of the phase difference of the optical anisotropic body thus obtained, it was confirmed that the tilt angle at the air interface was about 0 °. The phase difference before heating of the optical anisotropic body was 173.2 nm, the phase difference after heating at 230 ° C. for 4 hours was 138.8 nm, and the reduction rate of the phase difference was 20%.
（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%を添加した本願発明の重合性液晶組成物（A3）を調製した。次に重合性液晶組成物（A3）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（A3）を硬化させた。このようにして得られた光学異方体の位相差の入射角依存測定をした結果、空気界面におけるチルト角は約°30であった。また、光学異方体の加熱前の位相差は141.6nm、230℃で4時間加熱後の位相差は101.2nmであり、位相差の減少率は29%であった。以上のことより酸化防止剤として式（c）又は式（d）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)
A polymerizable liquid crystal composition (A3) 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 (A3) 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 (A3) was cured by irradiating the spin-coated substrate with 4 mW / cm 2 of ultraviolet light for 120 seconds in a nitrogen atmosphere. As a result of measuring the incident angle dependence of the phase difference of the optical anisotropic body thus obtained, the tilt angle at the air interface was about 30 °. The phase difference before heating of the optical anisotropic body was 141.6 nm, the phase difference after heating at 230 ° C. for 4 hours was 101.2 nm, and the reduction rate of the phase difference was 29%. From the above, it can be seen that the reduction rate is large compared to the case where 0.5% of the formula (c) or the formula (d) is added as an antioxidant.
（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%、界面活性剤FC171（3M社製）を0.5質量%添加した本願発明の重合性液晶組成物（A4）を調製した。次に重合性液晶組成物（A4）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（A4）を硬化させた。このようにして得られた光学異方体の位相差の入射角依存測定をした結果、空気界面におけるチルト角は約0°であることが確認できた。また、光学異方体の加熱前の位相差は167.5nm、230℃で4時間加熱後の位相差は114.1nmであり、位相差の減少率は32%であった。以上のことより酸化防止剤として式（c）又は式（d）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 2)
Polymerizability of the present invention in which a polymerizable liquid crystal composition (A) 97.5% by mass is added with 2.0% by mass of a photopolymerization initiator Irgacure-651 (Ciba Specialty Chemicals) and 0.5% by mass of a surfactant FC171 (3M). A liquid crystal composition (A4) was prepared. Next, a xylene solution containing 33% by mass of the polymerizable liquid crystal composition (A4) 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 (A4) was cured by irradiating the spin-coated substrate with 4 mW / cm 2 of ultraviolet rays for 120 seconds in a nitrogen atmosphere. As a result of measuring the incident angle dependence of the phase difference of the optical anisotropic body thus obtained, it was confirmed that the tilt angle at the air interface was about 0 °. The phase difference before heating of the optical anisotropic body was 167.5 nm, the phase difference after heating at 230 ° C. for 4 hours was 114.1 nm, and the reduction rate of the phase difference was 32%. From the above, it can be seen that the reduction rate is large compared to the case where 0.5% of the formula (c) or the formula (d) is added as an antioxidant.
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