JP5604774B2 - Polymerizable liquid crystal composition - Google Patents
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- JP5604774B2 JP5604774B2 JP2008090452A JP2008090452A JP5604774B2 JP 5604774 B2 JP5604774 B2 JP 5604774B2 JP 2008090452 A JP2008090452 A JP 2008090452A JP 2008090452 A JP2008090452 A JP 2008090452A JP 5604774 B2 JP5604774 B2 JP 5604774B2
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- 239000000203 mixture Substances 0.000 title claims description 100
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
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- 125000005843 halogen group Chemical group 0.000 claims description 22
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- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 14
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
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- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 claims description 2
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- 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
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 claims description 2
- 150000001934 cyclohexanes Chemical class 0.000 claims description 2
- 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 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000005580 triphenylene group Chemical group 0.000 claims description 2
- 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 claims description 2
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- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
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- 239000000758 substrate Substances 0.000 description 30
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- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 7
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- 239000011734 sodium Substances 0.000 description 4
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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- 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
- 238000001514 detection method Methods 0.000 description 1
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- 125000001033 ether group Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
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- Polarising Elements (AREA)
- Liquid Crystal Substances (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。しかし、重合性液晶組成物を基板に塗布した場合、塗膜に膜厚むらが生じるといった問題があった。又、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該チルト角を減じることが求められていた。ここで空気界面におけるチルト角とは、棒状重合性液晶の場合、空気界面に存在する重合性液晶分子の長軸が基板面となす角を表し、基板面と平行になる場合を０°として定義し、円盤状重合性液晶の場合、円盤面が基板面となす角を表し、基板面と平行になる場合を０°として定義する。 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. However, when the polymerizable liquid crystal composition is applied to the substrate, there is a problem that the coating film has uneven thickness. Moreover, in order to have a certain tilt angle at the air interface and satisfy the optical characteristics required for a specific retardation film, it has been required to reduce the tilt angle. Here, the tilt angle at the air interface means, in the case of rod-like polymerizable liquid crystal, the angle formed by the major axis of the polymerizable liquid crystal molecules present at the air interface with the substrate surface, and is defined as 0 ° when parallel to the substrate surface. In the case of a discotic polymerizable liquid crystal, the angle formed by the disc surface and the substrate surface is defined, and the case where the disc surface is parallel to the substrate surface is defined as 0 °.
膜厚むらの低減及び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）。界面活性剤は膜厚むらを低減する効果を有するが、該チルト角を十分に減じる効果のある界面活性剤は少なく、膜厚むらの低減と該チルト角を減じる効果を併せ持つ界面活性剤を見つけることは容易ではなかった。更に、界面活性剤の有する非粘着性や撥水・撥油性から積層膜の形成が困難である。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。又、パーフルオロアルケニルオリゴマーから誘導した化合物からなる界面活性剤は知られていたが（特許文献４参照）、重合性液晶組成物に添加した場合の効果についての開示はされていない。 As a method of reducing film thickness unevenness and reducing the tilt angle, a method of adding a surfactant or a polymerizable surfactant to a polymerizable liquid crystal composition has been proposed (see Patent Documents 1, 2, and 3). . Surfactants have the effect of reducing film thickness unevenness, but few surfactants have the effect of sufficiently reducing the tilt angle, and find a surfactant that has both effects of reducing film thickness unevenness and reducing the tilt angle. That was not easy. Furthermore, it is difficult to form a laminated film because of the non-adhesiveness and water / oil repellency of the surfactant. Furthermore, when a long-chain perfluoroalkylsulfonic 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. there were. Further, a surfactant made of a compound derived from a perfluoroalkenyl oligomer has been known (see Patent Document 4), but there is no disclosure of the effect when added to a polymerizable liquid crystal composition.
一方、チルト角を減ずる方法として、重合性液晶組成物に長鎖の炭化水素化合物を添加する方法が開示されている（特許文献５参照）。しかし、炭化水素を添加した組成物はチルト角を低減する効果は高いものの、膜厚むらの低減については要求特性を十分満たしてはいなかった。
以上のように、光学異方体を作製した場合に膜厚むらがなく、空気界面のチルト角を十分に減じることができ、かつ、積層膜の形成が容易である重合性液晶組成物の開発が求められていた。
On the other hand, as a method for reducing the tilt angle, a method of adding a long-chain hydrocarbon compound to a polymerizable liquid crystal composition is disclosed (see Patent Document 5). However, although the composition to which the hydrocarbon is added has a high effect of reducing the tilt angle, it does not sufficiently satisfy the required characteristics for reducing the film thickness unevenness.
As described above, when an optical anisotropic body is produced, a polymerizable liquid crystal composition that has no film thickness unevenness, can sufficiently reduce the tilt angle of the air interface, and can easily form a laminated film is developed. Was demanded.
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、膜厚むらがなく、空気界面のチルト角を十分に減じることができ、かつ、積層膜の形成が容易である重合性液晶組成物を提供することにある。 An object of the present invention is to provide a polymerizable liquid crystal in which, when a polymerizable liquid crystal composition is applied to a substrate, there is no film thickness unevenness, the tilt angle of the air interface can be sufficiently reduced, and a laminated film can be easily formed. It is to provide a composition.
上記目的を達成するために約100種の界面活性剤を鋭意検討した結果、膜厚むらを低減させ、空気界面のチルト角を効果的に減じ、かつ、積層膜の形成を阻害しない界面活性剤の化学構造を特定し、該界面活性剤を重合性液晶組成物に添加することにより本願発明の完成に至った。本願発明は、パーフルオロアルケニルオリゴマーから誘導した化合物からなる界面活性剤を含有することを特徴とする重合性液晶組成物及び当該組成物の重合体より構成される光学異方体を提供する。 As a result of diligent investigation of about 100 types of surfactants to achieve the above object, surfactants that reduce film thickness unevenness, effectively reduce the tilt angle of the air interface, and do not hinder the formation of laminated films The present invention was completed by adding the surfactant to the polymerizable liquid crystal composition. The present invention provides a polymerizable liquid crystal composition containing a surfactant composed of a compound derived from a perfluoroalkenyl oligomer and an optical anisotropic body composed of a polymer of the composition.
本願発明の重合性液晶組成物を基板に塗布した場合、膜厚むらがなく、空気界面におけるチルト角を減じ、かつ、積層膜の形成が容易であ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る。 When the polymerizable liquid crystal composition of the present invention is applied to a substrate, there is no unevenness in film thickness, the tilt angle at the air interface is reduced, and the formation of a laminated film is easy. It is useful as an optical anisotropic 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、パーフルオロアルケニルオリゴマーから誘導した化合物からなる界面活性剤を含有するが、該界面活性剤がヘキサフルオロプロペンオリゴマーから誘導した化合物であることが好ましく、２〜６つのヘキサフルオロプロペンオリゴマー末端基を有する化合物でありことがより好ましい。
該ヘキサフルオロプロペンオリゴマーは具体的には式（I）
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 contains a surfactant composed of a compound derived from a perfluoroalkenyl oligomer, and the surfactant is preferably a compound derived from a hexafluoropropene oligomer. More preferably, it is a compound having two hexafluoropropene oligomer end groups.
The hexafluoropropene oligomer is specifically represented by the formula (I)
で表される化合物であることが特に好ましい。又、該界面活性剤はアルキレンオキシド鎖が付加した構造が好ましく、該アルキレンオキシド鎖は、エチレンオキシド鎖又はプロピレンオキシド鎖であることが好ましい。さらに具体的にはポリオキシエチレンエーテル構造を有する界面活性剤であることが好ましく、一般式（I） The compound represented by the formula is particularly preferred. Further, the surfactant preferably has a structure in which an alkylene oxide chain is added, and the alkylene oxide chain is preferably an ethylene oxide chain or a propylene oxide chain. More specifically, the surfactant preferably has a polyoxyethylene ether structure, and is represented by the general formula (I)
（式中、Rは炭素原子数１〜６のアルキル基を示し、nは３〜５０の整数を示す。）で表される含フッ素界面活性剤であることがさらに好ましい。一般式（I）において、Rは炭素原子数１〜２のアルキル基が特に好ましく、nは８〜２２の整数が特に好ましい。 (Wherein R represents an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 3 to 50), and is more preferably a fluorine-containing surfactant. In the general formula (I), R is particularly preferably an alkyl group having 1 to 2 carbon atoms, and n is particularly preferably an integer of 8 to 22.
本発明の重合性液晶組成物に含有することができる界面活性剤として具体的には「フタージェント１００」、「フタージェント１００Ｃ」、「フタージェント１１０」、「フタージェント１５０」、「フタージェント１５０ＣＨ」、「フタージェントＡ」、「フタージェント１００Ａ-Ｋ」、「フタージェント５０１」、「フタージェント３００」、「フタージェント３１０」、「フタージェント３２０」、「フタージェント４００ＳＷ」、「ＦＴＸ-４００Ｐ」、「フタージェント２５１」、「フタージェント２１５Ｍ」、「フタージェント２１２ＭＨ」、「フタージェント２５０」、「フタージェント２２２Ｆ」、「フタージェント２１２Ｄ」、「ＦＴＸ-２１８」、「ＦＴＸ-２０９Ｆ」、「ＦＴＸ-２１３Ｆ」、「ＦＴＸ-２３３Ｆ」、「フタージェント２４５Ｆ」、「ＦＴＸ-２０８Ｇ」、「ＦＴＸ-２４０Ｇ」、「ＦＴＸ-２０６Ｄ」、「ＦＴＸ-２２０Ｄ」、「ＦＴＸ-２３０Ｄ」、「ＦＴＸ-２４０Ｄ」、「ＦＴＸ-２０７Ｓ」、「ＦＴＸ-２１１Ｓ」、「ＦＴＸ-２２０Ｓ」、「ＦＴＸ-２３０Ｓ」、「ＦＴＸ-７５０ＦＭ」、「ＦＴＸ-７３０ＦＭ」、「ＦＴＸ-７３０ＦＬ」、「ＦＴＸ-７１０ＦＳ」、「ＦＴＸ-７１０ＦＭ」、「ＦＴＸ-７１０ＦＬ」、「ＦＴＸ-７５０ＬＬ」、「ＦＴＸ-７３０ＬＳ」、「ＦＴＸ-７３０ＬＭ」、「ＦＴＸ-７３０ＬＬ」、「ＦＴＸ-７１０ＬＬ」（以上、ネオス社製）等の例をあげることができる。 Specific examples of the surfactant that can be contained in the polymerizable liquid crystal composition of the present invention include “Furgent 100”, “Furgent 100C”, “Furgent 110”, “Furgent 150”, and “Furgent 150CH”. "," Factent A "," Factent 100A-K "," Factent 501 "," Factent 300 "," Factent 310 "," Factent 320 "," Factent 400SW "," FTX-400P " ”,“ Factent 251 ”,“ Factent 215M ”,“ Factent 212MH ”,“ Factent 250 ”,“ Factent 222F ”,“ Factent 212D ”,“ FTX-218 ”,“ FTX-209F ”, “FTX-213F”, “FTX-233F”, “F Agent 245F "," FTX-208G "," FTX-240G "," FTX-206D "," FTX-220D "," FTX-230D "," FTX-240D "," FTX-207S "," FTX-211S " ”,“ FTX-220S ”,“ FTX-230S ”,“ FTX-750FM ”,“ FTX-730FM ”,“ FTX-730FL ”,“ FTX-710FS ”,“ FTX-710FM ”,“ FTX-710FL ”, Examples include “FTX-750LL”, “FTX-730LS”, “FTX-730LM”, “FTX-730LL”, “FTX-710LL” (hereinafter, Neos).
本発明の重合性液晶組成物中における界面活性剤の好ましい添加量は、重合性液晶組成物中に含有される界面活性剤以外の成分や、使用温度等によって異なるが、重合性液晶組成物中に０．０１〜０．５質量％含有することが好ましく、０．０２〜０．３質量％含有することが特に好ましい。含有量が０．０１質量％より低いときは目的とする効果が得にくく、０．５質量％より高いときは、重合性液晶組成物の配向性や液晶性が著しく損なわれてしまうため好ましくない。 The preferred addition amount of the surfactant in the polymerizable liquid crystal composition of the present invention varies depending on components other than the surfactant contained in the polymerizable liquid crystal composition, the use temperature, etc., but in the polymerizable liquid crystal composition It is preferable to contain 0.01-0.5 mass%, and it is especially preferable to contain 0.02-0.3 mass%. When the content is lower than 0.01% by mass, it is difficult to obtain the intended effect. When the content is higher than 0.5% by mass, the orientation and liquid crystallinity of the polymerizable liquid crystal composition are remarkably impaired. .
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る。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（II）
The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition is not particularly limited and can be used. 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 (II)
（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、R1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R1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 1 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 1 may have the general formula (II-a)
（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が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。）、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 general formula (II), Sp represents an alkylene group (the alkylene group may be substituted by one or more halogen atoms or CN, and in this group 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-). General formula (II-b)
（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-ジイル基又はフルオレン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、アルケノイル基又は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）及び一般式（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 or 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 is 1 or more F as substituents, Cl, CF 3, OCF 3 , cyano Group, 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. , Z0, Z1, Z2 and Z3 are each independently -COO-, -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) and general formula (II- e)
（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（III）
(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 (III)
（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。
又、一般式（IV）
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 (IV)
（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。
又、一般式（V）
(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.
General formula (V)
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.
（式中、j、k、l及びmはそれぞれ独立的に２〜１８の整数を表す。）
又、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, k, l and m each independently represent an integer of 2 to 18)
Specific examples of the compound represented by the general formula (III) 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。）
又、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 represents 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.
（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。）
又、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.
（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。）
又、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 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 mother nucleus at the center 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)
（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))
（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（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。
さらに、一般式(VI-a)は具体的には一般式(VI-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 (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).
Furthermore, the general formula (VI-a) specifically represents the general formula (VI-e)
以上述べた重合性液晶組成物は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、シクロペンンタ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。 The polymerizable liquid crystal composition described above may be used in the form of a solution dissolved in an organic solvent or the like. Suitable organic solvents include, for example, alkyl-substituted benzenes such as toluene, xylene, cumene, propylene glycol monomethyl ether acetate, butyl acetate, cyclohexanone, cyclopentanone and the like. Further, dimethylformamide, γ-butyrolactone, N-methylpyrrolidinone, methyl ethyl ketone, ethyl acetate and the like may be added to these solvents.
又、以上の重合性液晶組成物中にパーフルオロアルケニルオリゴマーから誘導した化合物からなる界面活性剤の他に重合禁止剤、重合開始剤、酸化防止剤、又は紫外線吸収剤などの添加剤を含有しても良い。 Further, the polymerizable liquid crystal composition contains an additive such as a polymerization inhibitor, a polymerization initiator, an antioxidant, or an ultraviolet absorber in addition to a surfactant composed of a compound derived from a perfluoroalkenyl oligomer. May be.
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。 EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples.
空気界面におけるチルト角の測定は以下の方法によって行った。He-Neレーザーを使用して位相差の入射角依存を測定し、得られた測定結果をコンピュータシミュレーションソフト（シンテック社製LCD-Master）を用いて解析を行い、空気界面におけるチルト角を求めた。又、以下の実施例で述べる重量平均分子量は、TSKgel GMHXLを２本と、TSKgel G2000HXL、TSKgel G1000HXL（何れも東ソー製）のカラムを使用したGPC分析装置（東ソー社製HLC-8220GPC）により、溶媒テトラヒドロフラン、示差屈折計検出により検出し、ポリスチレン換算で求めた。
（実施例１）
式(a)の化合物50質量%
The tilt angle at the air interface was measured by the following method. The He-Ne laser was used to measure the incident angle dependency of the phase difference, and the obtained measurement results were analyzed using computer simulation software (LCD-Master, manufactured by Shintec) to determine the tilt angle at the air interface. . In addition, the weight average molecular weight described in the following examples was determined using a GPC analyzer (HLC-8220GPC manufactured by Tosoh Corporation) using two TSKgel GMHXL and TSKgel G2000HXL and TSKgel G1000HXL (both manufactured by Tosoh Corporation) columns. Tetrahydrofuran was detected by differential refractometer detection, and determined in terms of polystyrene.
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）96.8質量％に光重合開始剤Irgacure-907（チバスペシャリティケミカルズ社製）3.0質量%、FTX-730LS（ネオス社製）0.2質量%添加した本願発明の重合性液晶組成物（A1）を調製した後、重合性液晶組成物（A1）を25%質量含有するプロピレングリコールモノメチルエーテルアセテート溶液を調製した。次に、ガラス基板上にポリイミド配向剤AL1254（JSR社製）をスピンコート（2000回転/分、30秒）した後、150℃で1時間乾燥させることにより製膜した。このように製膜したポリイミド薄膜表面を基板の長手方向にラビング処理して、配向膜を形成した。この配向膜の上に、重合性液晶組成物（A1）を25質量%含有するプロピレングリコールモノメチルエーテルアセテート溶液をスピンコート（700回転/分、15秒）した。スピンコートした基板に30mW/cm2の紫外線を30秒照射して、重合性液晶組成物（A1）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°であった。又、得られた光学異方体をナトリウムランプで観察したところ、干渉縞は見られず、膜厚むらはなかった。又、このようにして得られた光学異方体の上に、重合性液晶組成物（A1）を25%質量含有するプロピレングリコールモノメチルエーテルアセテート溶液をスピンコート（700回転/分、15秒）し、30mW/cm2の紫外線を30秒照射して、重合性液晶組成物（A1）を硬化させたところ、はじきのない良好な積層光学異方体が得られた。 A polymerizable liquid crystal composition (A) comprising: Polymerizable liquid crystal composition of the present invention in which photopolymerization initiator Irgacure-907 (manufactured by Ciba Specialty Chemicals) 3.0 mass% and FTX-730LS (manufactured by Neos) 0.2 mass% are added to 96.8 mass% of polymerizable liquid crystal composition (A). After the product (A1) was prepared, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal composition (A1) was prepared. Next, a polyimide alignment agent AL1254 (manufactured by JSR) was spin-coated on a glass substrate (2000 rotations / minute, 30 seconds), and then dried at 150 ° C. for 1 hour to form a film. The polyimide thin film surface thus formed was rubbed in the longitudinal direction of the substrate to form an alignment film. On this alignment film, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal composition (A1) was spin-coated (700 rotations / minute, 15 seconds). The polymerizable liquid crystal composition (A1) was cured by irradiating the spin-coated substrate with 30 mW / cm 2 of ultraviolet rays for 30 seconds. 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 0 °. Further, when the obtained optical anisotropic body was observed with a sodium lamp, no interference fringes were observed and the film thickness was not uneven. Further, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal composition (A1) is spin-coated (700 rpm) for 15 seconds on the optical anisotropic body thus obtained. When the polymerizable liquid crystal composition (A1) was cured by irradiating with 30 mW / cm 2 of ultraviolet rays for 30 seconds, a good laminated optical anisotropic body without repelling was obtained.
（実施例２〜８）
添加する界面活性剤を変えて重合性液晶組成物（B）〜（H）を調製した。添加した界面活性剤を表１に示す。重合性液晶組成物（A）96.8質量％に光重合開始剤Irgacure-907（チバスペシャリティケミカルズ社製）を3.0質量%、界面活性剤を0.2質量%添加した本願発明の重合性液晶組成物（B1）〜（H1）を調製した後、重合性液晶組成物（B1）〜（H1）を25%質量含有するプロピレングリコールモノメチルエーテルアセテート溶液を調製した。次に、ガラス基板上にポリイミド配向剤AL1254（JSR社製）をスピンコート（2000回転/分、30秒）した後、150℃で1時間乾燥させることにより製膜した。このように製膜したポリイミド薄膜表面を基板の長手方向にラビング処理して、配向膜を形成した。この配向膜の上に、重合性液晶組成物（B1）〜（H1）を25質量%含有するプロピレングリコールモノメチルエーテルアセテート溶液をスピンコート（700回転/分、15秒）した。スピンコートした基板に30mW/cm2の紫外線を30秒照射して、重合性液晶組成物（B1）〜（H1）を硬化させた。このようにして得られた光学異方体の空気界面におけるチルト角、膜厚むらの有無を表１にまとめる。又、このようにして得られた光学異方体の上に、重合性液晶組成物（B1）〜（H1）を25%質量含有するプロピレングリコールモノメチルエーテルアセテート溶液をスピンコート（700回転/分、15秒）し、30mW/cm2の紫外線を30秒照射して、重合性液晶組成物（B1）〜（H1）を硬化させて積層光学異方体を作製した。このようにして得られた積層光学異方体のはじきの有無を表１にまとめる。
(Examples 2 to 8)
Polymerizable liquid crystal compositions (B) to (H) were prepared by changing the surfactant to be added. The added surfactant is shown in Table 1. Polymerizable liquid crystal composition (A) Polymerizable liquid crystal composition of the present invention (B1) in which 3.0% by mass of photopolymerization initiator Irgacure-907 (manufactured by Ciba Specialty Chemicals) and 0.2% by mass of a surfactant are added to 96.8% by mass. ) To (H1) were prepared, and then a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal compositions (B1) to (H1) was prepared. Next, a polyimide alignment agent AL1254 (manufactured by JSR) was spin-coated on a glass substrate (2000 rotations / minute, 30 seconds), and then dried at 150 ° C. for 1 hour to form a film. The polyimide thin film surface thus formed was rubbed in the longitudinal direction of the substrate to form an alignment film. On this alignment film, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal compositions (B1) to (H1) was spin-coated (700 rotations / minute, 15 seconds). The polymerizable liquid crystal compositions (B1) to (H1) were cured by irradiating the spin-coated substrate with 30 mW / cm 2 of ultraviolet rays for 30 seconds. Table 1 summarizes the tilt angle and the presence or absence of film thickness irregularities at the air interface of the optically anisotropic body thus obtained. Further, on the optical anisotropic body thus obtained, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal compositions (B1) to (H1) is spin-coated (700 rpm). 15 seconds), 30 mW / cm 2 of ultraviolet rays were irradiated for 30 seconds, and the polymerizable liquid crystal compositions (B1) to (H1) were cured to produce a laminated optical anisotropic body. Table 1 summarizes the presence or absence of repelling of the laminated optical anisotropic body thus obtained.
表１よりパーフルオロアルケニルオリゴマーから誘導した化合物からなる界面活性剤を含有する重合性液晶組成物を硬化して得られた光学異方体は膜厚むらがなく、かつ、空気界面におけるチルト角が約0°であり、かつ、はじきのない良好な積層光学異方体が得られたことがわかる。 From Table 1, the optically anisotropic body obtained by curing a polymerizable liquid crystal composition containing a surfactant composed of a compound derived from a perfluoroalkenyl oligomer has no film thickness unevenness and a tilt angle at the air interface. It can be seen that a good laminated optical anisotropic body having about 0 ° and no repelling was obtained.
（比較例１）
重合性液晶組成物（A）97質量％に光重合開始剤Irgacure-907（チバスペシャリティケミカルズ社製）3.0質量%を添加した重合性液晶組成物（A2）を調製した後、重合性液晶組成物（A2）を25質量%含有するプロピレングリコールモノメチルエーテルアセテート溶液を調製した。次に、ガラス基板上にポリイミド配向剤AL1254（JSR社製）をスピンコート（2000回転/分、30秒）した後、150℃で1時間乾燥させることにより製膜した。このように製膜したポリイミド薄膜表面を基板の長手方向にラビング処理して、配向膜を形成した。この配向膜の上に、重合性液晶組成物（A2）を25質量%含有するプロピレングリコールモノメチルエーテルアセテート溶液をスピンコート（700回転/分、15秒）した。スピンコートした基板に30mW/cm2の紫外線を30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°55であった。又、得られた光学異方体をナトリウムランプで観察したところ、干渉縞は見られ、膜厚むらがあった。又、このようにして得られた光学異方体の上に、重合性液晶組成物（A2）を25%質量含有するプロピレングリコールモノメチルエーテルアセテート溶液をスピンコート（700回転/分、15秒）し、30mW/cm2の紫外線を30秒照射して、重合性液晶組成物（A2）を硬化させたところ、はじきのない良好な積層光学異方体が得られた。
(Comparative Example 1)
Polymerizable liquid crystal composition (A) After preparing a polymerizable liquid crystal composition (A2) in which 3.0% by mass of a photopolymerization initiator Irgacure-907 (manufactured by Ciba Specialty Chemicals) was added to 97% by mass, a polymerizable liquid crystal composition A propylene glycol monomethyl ether acetate solution containing 25% by mass of (A2) was prepared. Next, a polyimide alignment agent AL1254 (manufactured by JSR) was spin-coated on a glass substrate (2000 rotations / minute, 30 seconds), and then dried at 150 ° C. for 1 hour to form a film. The polyimide thin film surface thus formed was rubbed in the longitudinal direction of the substrate to form an alignment film. On this alignment film, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal composition (A2) was spin-coated (700 rotations / minute, 15 seconds). The polymerizable liquid crystal composition (A2) was cured by irradiating the spin-coated substrate with 30 mW / cm 2 of ultraviolet rays for 30 seconds. 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 ° 55. Further, when the obtained optical anisotropic body was observed with a sodium lamp, interference fringes were observed and the film thickness was uneven. In addition, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal composition (A2) is spin-coated (700 rpm) for 15 seconds on the optical anisotropic body thus obtained. When the polymerizable liquid crystal composition (A2) was cured by irradiating with 30 mW / cm 2 of ultraviolet rays for 30 seconds, a good laminated optical anisotropic body without repelling was obtained.
（比較例２）
重合性液晶組成物（A）96.8質量％に光重合開始剤Irgacure-907（チバスペシャリティケミカルズ社製）3.0質量%、界面活性剤MEGAFAC R-08を0.2質量%添加した重合性液晶組成物（B2）を調製した後、重合性液晶組成物（B2）を25質量%含有するプロピレングリコールモノメチルエーテルアセテート溶液を調製した。次に、ガラス基板上にポリイミド配向剤AL1254（JSR社製）をスピンコート（2000回転/分、30秒）した後、150℃で1時間乾燥させることにより製膜した。このように製膜したポリイミド薄膜表面を基板の長手方向にラビング処理して、配向膜を形成した。この配向膜の上に、重合性液晶組成物（B2）を25質量%含有するプロピレングリコールモノメチルエーテルアセテート溶液をスピンコート（700回転/分、15秒）した。スピンコートした基板に30mW/cm2の紫外線を30秒照射して、重合性液晶組成物（B2）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°55であった。又、得られた光学異方体をナトリウムランプで観察したところ、干渉縞は見られず、膜厚むらはなかった。又、このようにして得られた光学異方体の上に、重合性液晶組成物（A2）を25%質量含有するプロピレングリコールモノメチルエーテルアセテート溶液をスピンコート（700回転/分、15秒）したところ、はじきが発生し、良好な積層光学異方体は得られなかった。
(Comparative Example 2)
Polymerizable liquid crystal composition (A) Polymeric liquid crystal composition (B2) comprising 96.8% by mass of photopolymerization initiator Irgacure-907 (manufactured by Ciba Specialty Chemicals) 3.0% by mass and surfactant MEGAFAC R-08 0.2% by mass Then, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal composition (B2) was prepared. Next, a polyimide alignment agent AL1254 (manufactured by JSR) was spin-coated on a glass substrate (2000 rotations / minute, 30 seconds), and then dried at 150 ° C. for 1 hour to form a film. The polyimide thin film surface thus formed was rubbed in the longitudinal direction of the substrate to form an alignment film. On this alignment film, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal composition (B2) was spin-coated (700 revolutions / minute, 15 seconds). The polymerizable liquid crystal composition (B2) was cured by irradiating the spin-coated substrate with 30 mW / cm 2 of ultraviolet rays for 30 seconds. 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 ° 55. Further, when the obtained optical anisotropic body was observed with a sodium lamp, no interference fringes were observed and the film thickness was not uneven. In addition, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal composition (A2) was spin-coated (700 rpm) for 15 seconds on the optical anisotropic body thus obtained. However, repelling occurred and a good laminated optical anisotropic body could not be obtained.
（比較例３）
重合性液晶組成物（A）96.9質量％に光重合開始剤Irgacure-907（チバスペシャリティケミカルズ社製）3.0質量%、重量平均分子量600の流動パラフィン（関東化学社製）を0.1質量%添加した重合性液晶組成物（C2）を調製した後、重合性液晶組成物（C2）を25質量%含有するプロピレングリコールモノメチルエーテルアセテート溶液を調製した。次に、ガラス基板上にポリイミド配向剤AL1254（JSR社製）をスピンコート（2000回転/分、30秒）した後、150℃で1時間乾燥させることにより製膜した。このように製膜したポリイミド薄膜表面を基板の長手方向にラビング処理して、配向膜を形成した。この配向膜の上に、重合性液晶組成物（C2）を25質量%含有するプロピレングリコールモノメチルエーテルアセテート溶液をスピンコート（700回転/分、15秒）した。スピンコートした基板を80℃で1分間乾燥した。乾燥した基板に30mW/cm2の紫外線を30秒照射して、重合性液晶組成物（C2）を硬化した。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であった。又、得られた光学異方体をナトリウムランプで観察したところ、干渉縞は見られ、膜厚むらがあった。又、このようにして得られた光学異方体の上に、重合性液晶組成物（C2）を25%質量含有するプロピレングリコールモノメチルエーテルアセテート溶液をスピンコート（700回転/分、15秒）し、30mW/cm2の紫外線を30秒照射して、重合性液晶組成物（C2）を硬化させたところ、はじきのない良好な積層光学異方体が得られた。
(Comparative Example 3)
Polymerization by adding 0.1% by mass of liquid paraffin (manufactured by Kanto Chemical Co., Inc.) with 3.0% by mass of photopolymerization initiator Irgacure-907 (manufactured by Ciba Specialty Chemicals) to 96.9% by mass of polymerizable liquid crystal composition (A) The liquid crystalline composition (C2) was prepared, and then a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal composition (C2) was prepared. Next, a polyimide alignment agent AL1254 (manufactured by JSR) was spin-coated on a glass substrate (2000 rotations / minute, 30 seconds), and then dried at 150 ° C. for 1 hour to form a film. The polyimide thin film surface thus formed was rubbed in the longitudinal direction of the substrate to form an alignment film. On this alignment film, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal composition (C2) was spin-coated (700 rotations / minute, 15 seconds). The spin-coated substrate was dried at 80 ° C. for 1 minute. The dried substrate was irradiated with 30 mW / cm 2 ultraviolet rays for 30 seconds to cure the polymerizable liquid crystal composition (C2). 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 0 °. Further, when the obtained optical anisotropic body was observed with a sodium lamp, interference fringes were observed and the film thickness was uneven. Further, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal composition (C2) is spin-coated (700 rpm) for 15 seconds on the optically anisotropic body thus obtained. When the polymerizable liquid crystal composition (C2) was cured by irradiating with 30 mW / cm 2 of ultraviolet rays for 30 seconds, a good laminated optical anisotropic body without repelling was obtained.
（比較例４〜１８）
添加する界面活性剤を変えて重合性液晶組成物（D2）〜（R2）を調製した。添加した界面活性剤を表２に示す。重合性液晶組成物（A）96.8質量％に光重合開始剤Irgacure-907（チバスペシャリティケミカルズ社製）を3.0質量%、界面活性剤を0.2質量%添加した重合性液晶組成物（D2）〜（R2）を調製した。次に重合性液晶組成物（D2）〜（G2）を25質量%含有するプロピレングリコールモノメチルエーテルアセテート溶液を調製した。次に、ガラス基板上にポリイミド配向剤AL1254（JSR社製）をスピンコート（2000回転/分、30秒）した後、150℃で1時間乾燥させることにより製膜した。このように製膜したポリイミド薄膜表面を基板の長手方向にラビング処理して、配向膜を形成した。この配向膜の上に、重合性液晶組成物（D2）〜（G2）を25質量%含有するプロピレングリコールモノメチルエーテルアセテート溶液をスピンコート（700回転/分、15秒）した。スピンコートした基板に30mW/cm2の紫外線を30秒照射して、重合性液晶組成物（D2）〜（G2）を硬化させた。このようにして得られた光学異方体の空気界面におけるチルト角、膜厚むらの有無を表２にまとめる。又、このようにして得られた光学異方体の上に、重合性液晶組成物（D2）〜（G2）を25%質量含有するプロピレングリコールモノメチルエーテルアセテート溶液をスピンコート（700回転/分、15秒）し、30mW/cm2の紫外線を30秒照射して、重合性液晶組成物（D2）〜（G2）を硬化させて積層光学異方体を作製した。このようにして得られた積層光学異方体のはじきの有無を表２にまとめる。
(Comparative Examples 4 to 18)
Polymerizable liquid crystal compositions (D2) to (R2) were prepared by changing the surfactant to be added. The added surfactant is shown in Table 2. Polymeric liquid crystal composition (D2)-(9) Photopolymerization initiator Irgacure-907 (manufactured by Ciba Specialty Chemicals) and 0.2% by mass of surfactant are added to 96.8% by mass of polymerizable liquid crystal composition (A). R2) was prepared. Next, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal compositions (D2) to (G2) was prepared. Next, a polyimide alignment agent AL1254 (manufactured by JSR) was spin-coated on a glass substrate (2000 rotations / minute, 30 seconds), and then dried at 150 ° C. for 1 hour to form a film. The polyimide thin film surface thus formed was rubbed in the longitudinal direction of the substrate to form an alignment film. On this alignment film, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal compositions (D2) to (G2) was spin-coated (700 rotations / minute, 15 seconds). The spin-coated substrate was irradiated with 30 mW / cm 2 ultraviolet rays for 30 seconds to cure the polymerizable liquid crystal compositions (D2) to (G2). Table 2 summarizes the tilt angle and the presence or absence of film thickness irregularities at the air interface of the optically anisotropic body thus obtained. Moreover, on the optically anisotropic body thus obtained, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal compositions (D2) to (G2) is spin-coated (700 rpm). 15 seconds) and then irradiated with 30 mW / cm 2 of ultraviolet rays for 30 seconds to cure the polymerizable liquid crystal compositions (D2) to (G2) to produce a laminated optical anisotropic body. Table 2 summarizes the presence or absence of repelling of the thus obtained laminated optical anisotropic body.
表２より表２記載の界面活性剤を含有する重合性液晶組成物を硬化して得られた光学異方体は膜厚むらがないが、空気界面におけるチルト角を減じる効果がなく、又、積層光学異方体にはじきが発生したことがわかる。 The optical anisotropic body obtained by curing the polymerizable liquid crystal composition containing the surfactant described in Table 2 from Table 2 has no film thickness unevenness, but has no effect of reducing the tilt angle at the air interface, It can be seen that repelling occurred in the laminated optical anisotropic body.
（比較例１９〜３３）
添加する界面活性剤を変えて重合性液晶組成物（S2）〜（AG2）を調製した。添加した界面活性剤を表３に示す。重合性液晶組成物（A）96.8質量％に光重合開始剤Irgacure-907（チバスペシャリティケミカルズ社製）を3.0質量%、界面活性剤を0.2質量%添加した重合性液晶組成物（S2）〜（AG2）を調製した。次に重合性液晶組成物（S2）〜（AG2）を25質量%含有するプロピレングリコールモノメチルエーテルアセテート溶液を調製した。次に、ガラス基板上にポリイミド配向剤AL1254（JSR社製）をスピンコート（2000回転/分、30秒）した後、150℃で1時間乾燥させることにより製膜した。このように製膜したポリイミド薄膜表面を基板の長手方向にラビング処理して、配向膜を形成した。この配向膜の上に、重合性液晶組成物（S2）〜（AG2）を25質量%含有するプロピレングリコールモノメチルエーテルアセテート溶液をスピンコート（700回転/分、15秒）した。スピンコートした基板に30mW/cm2の紫外線を30秒照射して、重合性液晶組成物（S2）〜（AG2）を硬化させた。このようにして得られた光学異方体の空気界面におけるチルト角、膜厚むらの有無を表３にまとめる。
(Comparative Examples 19 to 33)
Polymerizable liquid crystal compositions (S2) to (AG2) were prepared by changing the surfactant to be added. The added surfactant is shown in Table 3. Polymeric liquid crystal composition (S2) to (S2) to (S) having a photopolymerization initiator Irgacure-907 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 3.0 mass% and a surfactant 0.2 mass% added to 96.8 mass% polymerizable liquid crystal composition (A). AG2) was prepared. Next, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal compositions (S2) to (AG2) was prepared. Next, a polyimide alignment agent AL1254 (manufactured by JSR) was spin-coated on a glass substrate (2000 rotations / minute, 30 seconds), and then dried at 150 ° C. for 1 hour to form a film. The polyimide thin film surface thus formed was rubbed in the longitudinal direction of the substrate to form an alignment film. On this alignment film, a propylene glycol monomethyl ether acetate solution containing 25% by mass of the polymerizable liquid crystal compositions (S2) to (AG2) was spin-coated (700 rotations / minute, 15 seconds). The spin-coated substrate was irradiated with 30 mW / cm 2 ultraviolet rays for 30 seconds to cure the polymerizable liquid crystal compositions (S2) to (AG2). Table 3 summarizes the tilt angle and the presence or absence of film thickness irregularities at the air interface of the optically anisotropic body thus obtained.
表３より表３記載の界面活性剤を含有する重合性液晶組成物を硬化して得られた光学異方体は膜厚むらがないが、空気界面におけるチルト角を減じる効果がないことがわかる。 Table 3 shows that the optical anisotropic body obtained by curing the polymerizable liquid crystal composition containing the surfactant described in Table 3 has no film thickness unevenness but has no effect of reducing the tilt angle at the air interface. .
以上の実施例と比較例から、パーフルオロアルケニルオリゴマーから誘導した化合物からなる界面活性剤を含有する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ことができ、かつ、該重合性液晶組成物を硬化させた光学異方体は膜厚むらがなく、かつ、積層膜の形成が可能なので光学異方体の材料として好適である。 From the above examples and comparative examples, the polymerizable liquid crystal composition containing a surfactant made of a compound derived from a perfluoroalkenyl oligomer can reduce the tilt angle at the air interface, and the polymerizable liquid crystal composition An optically anisotropic body obtained by curing an object has no film thickness unevenness and can form a laminated film, and thus is suitable as a material for an optically anisotropic body.
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