JP2021143329A - Polymerizable liquid crystal composition, phase difference film, elliptical polarizing plate and optical display - Google Patents

Abstract

To provide a polymerizable liquid crystal composition excellent in solubility in a solvent.SOLUTION: A polymerizable liquid crystal composition having at least two kinds of polymerizable liquid crystalline compounds having the same molecular weight but different molecular structures from each other, and represented by a formula (1): P1-F1-B1-A1-E1-G1-D1-Ar-D2-G2-E2-A2-B2-F2-P2 (1), as the polymerizable liquid crystal compound, G1 and G2 in the formula (1) each contains a polymerizable liquid crystal compound (1-1) which is a 1,4-trans-cyclohexane diyl group and a polymerizable liquid crystal compound (1-2) that is different in a molecular structure only in that at least one of G1 and G2 in the polymerizable liquid crystal compound (1-1) and the formula (1) is 1,4-cis-cyclohexane diyl, and a ratio of a peak area of the polymerizable liquid crystal compound (1-2) relative to a total peak area of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), measured by liquid chromatography, is 0.01% or larger and 10% or smaller.SELECTED DRAWING: None

Description

The present invention relates to a polymerizable liquid crystal composition, a retardation film composed of a cured product of the polymerizable liquid crystal composition, and an elliptical polarizing plate and an optical display including the retardation film.

As an optical film such as a retardation film used in a flat panel display device (FPD), for example, a coating liquid obtained by dissolving a polymerizable liquid crystal compound in a solvent is applied to a supporting base material and then polymerized. There is an optical film. As a polymerizable liquid crystal compound for forming such an optical film, for example, a nematic liquid crystal compound having a rod-like structure in which 2 to 4 6-membered rings are connected is known.

On the other hand, the retardation film is required to be capable of uniform polarization conversion in the entire wavelength region as one of its characteristics. For example, the retardation value Re (λ) at a certain wavelength λ is set to 550 nm. Indicates a wavelength range in which the value [Re (λ) / Re (550)] divided by the phase difference value Re (550) is close to 1, or the inverse wavelength dispersibility of [Re (450) / Re (550)] <1. It is known that uniform polarization conversion is theoretically possible in the wavelength range. Polymerizable liquid crystal compounds that can form such a retardation film are disclosed in, for example, Patent Documents 1 and 2.

Japanese Unexamined Patent Publication No. 2011-207765 Japanese Unexamined Patent Publication No. 2015-143788

The solution (coating liquid) obtained by dissolving a polymerizable liquid crystal compound in a solvent used in the production of an optical film has poor solubility in various solvents due to the molecular structure of the polymerizable liquid crystal compound. In some cases. Such a polymerizable liquid crystal compound having low solubility may precipitate in the coating solution or may crystallize and precipitate, and the precipitation or precipitation of such a polymerizable liquid crystal compound is film-forming. Not only is it lowered, but it can also cause orientation defects in the resulting optical film. Therefore, the development of a polymerizable liquid crystal composition containing a polymerizable liquid crystal showing improved solubility in a solvent is expected.

An object of the present invention is to provide a polymerizable liquid crystal composition having excellent solubility in a solvent.

［式（１）中、
Ａｒは、置換基を有していてもよい２価の芳香族炭化水素基または２価の芳香族複素環基を表し、
Ｄ^１、Ｄ^２、Ｅ^１、Ｅ^２、Ｂ^１およびＢ^２は、それぞれ独立に、−ＣＲ^１１Ｒ^１２−、−ＣＨ_２−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−Ｃ（＝Ｓ）−Ｏ−、−Ｏ−Ｃ（＝Ｓ）−、−Ｏ−Ｃ（＝Ｓ）−Ｏ−、−ＣＯ−ＮＲ^１１−、−ＮＲ^１１−ＣＯ−、−Ｏ−ＣＨ_２−、−ＣＨ_２−Ｏ−、−Ｓ−ＣＨ_２−、−ＣＨ_２−Ｓ−または単結合を表し、Ｒ^１１およびＲ^１２は、それぞれ独立に、水素原子、フッ素原子又は炭素数１〜４のアルキル基を表し、
Ｇ^１およびＧ^２は、それぞれ、１，４−シクロヘキサンジイル基を表し、
Ａ^１およびＡ^２は、それぞれ独立に、炭素数３〜１６の２価の脂環式炭化水素基または炭素数６〜２０の２価の芳香族炭化水素基を表し、該脂環式炭化水素基および該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、−Ｒ^１３、−ＯＲ^１３、シアノ基またはニトロ基で置換されていてもよく、Ｒ^１３は炭素数１〜４のアルキル基を表し、該アルキル基に含まれる水素原子は、フッ素原子で置換されていてもよく、
Ｆ^１およびＦ^２は、それぞれ独立に、炭素数１〜１２のアルカンジイル基を表し、該アルカンジイル基に含まれる水素原子は、−ＯＲ^１４またはハロゲン原子で置換されていてもよく、Ｒ^１４は炭素数１〜４のアルキル基を表し、該アルキル基に含まれる水素原子は、フッ素原子で置換されていてもよく、該アルカンジイル基に含まれる−ＣＨ_２−は、−Ｏ−または−ＣＯ−で置き換わっていてもよく、
Ｐ^１およびＰ^２は、それぞれ独立に、水素原子または重合性基を表す（但し、Ｐ^１およびＰ^２のうちの少なくとも１つは重合性基である）］
で表される重合性液晶化合物を少なくとも２種含む重合性液晶組成物であって、
前記重合性液晶化合物として、式（１）中のＧ^１およびＧ^２が、それぞれ、１，４−ｔｒａｎｓ−シクロヘキサンジイル基である重合性液晶化合物（１−１）と、前記重合性液晶化合物（１−１）と式（１）中のＧ^１およびＧ^２の少なくとも一方が１，４−ｃｉｓ−シクロヘキサンジイル基であることのみにおいて分子構造の異なる重合性液晶化合物（１−２）とを含み、
液体クロマトグラフィーによって測定される、重合性液晶化合物（１−１）と重合性液晶化合物（１−２）との全ピーク面積に対する重合性液晶化合物（１−２）のピーク面積の割合が０．０１％以上１０％以下である、重合性液晶組成物。
［２］重合性液晶化合物（１−２）が、式（１）におけるＧ^１およびＧ^２のいずれか一方が１，４−ｃｉｓ−シクロヘキサンジイル基である重合性液晶化合物（１−２ａ）と、式（１）におけるＧ^１およびＧ^２のいずれもが１，４−ｃｉｓ−シクロヘキサンジイル基である重合性液晶化合物（１−２ｂ）とを含む、前記［１］に記載の重合性液晶組成物。
［３］式（１）中のＡｒが式（２−１）〜（２−５）のいずれかで表される基である、前記［１］または［２］に記載の重合性液晶組成物。

［式中、
＊は、Ｄ^１またはＤ^２との結合部を表す；
Ｑ^１は−Ｓ−、−Ｏ−または−ＮＲ^１５−を表し、Ｒ^１５は水素原子または置換基を有してもよい炭素数１〜６のアルキル基を表し、
Ｑ^２は水素原子または置換基を有してもよい炭素数１〜６のアルキル基を表す；
Ｗ^１およびＷ^２は、それぞれ独立に、−Ｏ−、−Ｓ−、−ＣＯ−、−ＮＲ^１５−を表し、Ｒ^１５は水素原子または置換基を有してもよい炭素数１〜６のアルキル基を表す；
Ｙ^１は炭素数１〜６のアルキル基、置換基を有していてもよい芳香族炭化水素基または芳香族複素環基を表し、該アルキル基、該芳香族炭化水素基又は該芳香族複素環基に含まれる水素原子は、ハロゲン原子で置換されていてもよく、該アルキル基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−で置換されていてもよく、
Ｙ^２はＣＮ基または置換基を有してもよい炭素数１〜１２のアルキル基を表し、該アルキル基に含まれる水素原子は、ハロゲン原子で置換されていてもよく、該アルキル基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−で置換されていてもよい；
Ｚ^１、Ｚ^２およびＺ^３は、それぞれ独立に、水素原子または炭素数１〜２０の脂肪族炭化水素基またはアルコキシ基、炭素数３〜２０の脂環式炭化水素基、１価の炭素数６〜２０の芳香族炭化水素基、ハロゲン原子、シアノ基、ニトロ基、−ＮＲ^１５Ｒ^１６または−ＳＲ^１５を表し、Ｚ^１およびＺ^２は、互いに結合して芳香環または芳香族複素環を形成してもよく、Ｒ^１５およびＲ^１６は、それぞれ独立に、水素原子または炭素数１〜６のアルキル基を表す；
Ａｘは芳香族炭化水素環および芳香族複素環からなる群から選ばれる少なくとも１つの芳香族環を有する、炭素数２〜３０の有機基を表し、Ａｙは水素原子、置換基を有してもよい炭素数１〜６のアルキル基、または芳香族炭化水素環および芳香族複素環からなる群から選ばれる少なくとも１つの芳香族環を有する、炭素数２〜３０の有機基を表し、ＡｘとＡｙは結合して環を形成してもよい；
Ｙ^３およびＹ^４は、それぞれ独立して、下記式（Ｙ−１）：

〔式（Ｙ−１）中、
Ｍ^１は水素原子または炭素数１〜６のアルキル基を表し、該アルキル基は、１つ以上の置換基Ｘ^３によって置換されていてもよく、置換基Ｘ^３は、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、ニトロ基、シアノ基、イソシアノ基、アミノ基、ヒドロキシル基、メルカプト基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、トリメチルシリル基、ジメチルシリル基、チオイソシアノ基、または、１個の−ＣＨ_２−または隣接していない２個以上の−ＣＨ_２−が各々独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−に置き換えられてもよい炭素数１〜２０の直鎖状または分岐状アルキル基を表し、該アルキル基中の任意の水素原子はフッ素原子に置換されてもよく、或いは、−Ｂ^１１−Ｆ^１１−Ｐ^１１で表される基であってもよく、Ｂ^１１、Ｆ^１１およびＰ^１１は、それぞれ、前記式（１）中のＢ^１、Ｆ^１およびＰ^１と同様に定義され、それぞれ前記Ｂ^１、Ｆ^１およびＰ^１と同一であっても異なっていてもよい；
Ｕ^１は、芳香族炭化水素基を有する炭素数２〜３０の有機基を表し、該芳香族炭化水素基の任意の炭素原子はヘテロ原子に置換されていてもよく、芳香族炭化水素基は、１つ以上の前記置換基Ｘ^３によって置換されていてもよい；
Ｔ^１は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯ−Ｏ−、−ＮＵ^２−、−Ｎ＝ＣＵ^２−、−ＣＯ−ＮＵ^２−、−ＯＣＯ−ＮＵ^２−または−Ｏ−ＮＵ^２−を表し、Ｕ^２は水素原子、炭素数１〜２０のアルキル基、炭素数３〜１２のシクロアルキル基、炭素数３〜１２のシクロアルケニル基、芳香族炭化水素基（該芳香族炭化水素基の任意の炭素原子はヘテロ原子に置換されていてもよい）を有する炭素数２〜３０の有機基、または（Ｅ^１１−Ａ^１１）_ｑ−Ｂ^１２−Ｆ^１２−Ｐ^１２を表し、該アルキル基、シクロアルキル基、シクロアルケニル基および芳香族炭化水素基はそれぞれ、無置換であるかまたは１つ以上の置換基Ｘ^３によって置換されていてもよく、該アルキル基は該シクロアルキル基またはシクロアルケニル基によって置換されていてもよく、該アルキル基中の１個の−ＣＨ_２−または隣接していない２個以上の−ＣＨ_２−は、それぞれ独立に、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−ＳＯ_２−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−に置き換えられてもよく、該シクロアルキル基またはシクロアルケニル基中の１個の−ＣＨ_２−または隣接していない２個以上の−ＣＨ_２−は、それぞれ独立に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−または−Ｏ−ＣＯ−Ｏ−に置き換えられてもよく、Ｅ^１１、Ａ^１１、Ｂ^１２、Ｆ^１２およびＰ^１２は、それぞれ、式（１）中のＥ^１、Ａ^１、Ｂ^１、Ｆ^１およびＰ^１と同様に定義され、それぞれ前記Ｅ^１、Ａ^１、Ｂ^１、Ｆ^１およびＰ^１と同一であっても異なっていてもよく、ｑは０〜４の整数を表し、Ｅ^１１および／またはＡ^１１が複数存在する場合は、それぞれ同一であっても異なっていてもよく、Ｕ^１とＵ^２とが結合して環を構成していてもよい〕
から選ばれる基を表す。］
［４］式（１）中のＡ^１およびＡ^２が、それぞれ独立に、１，４−シクロヘキサンジイル基または１，４−フェニレンジイル基である、前記［１］〜［３］のいずれかに記載の重合性液晶組成物。
［５］式（１）中のＰ^１およびＰ^２がそれぞれアクリロイル基である、前記［１］〜［４］のいずれかに記載の重合性液晶組成物。
［６］光重合開始剤を更に含む、前記［１］〜［５］のいずれかに記載の重合性液晶組成物。
［７］有機溶剤を更に含む、前記［１］〜［６］のいずれかに記載の重合性液晶組成物。
［８］前記［１］〜［７］のいずれかに記載の重合性液晶組成物の硬化物である液晶硬化膜を含む、位相差フィルム。
［９］液晶硬化膜が、式（ｉ）：
０．７５≦Ｒｅ（４５０）／Ｒｅ（５５０）＜１．００ （ｉ）
［式（ｉ）中、Ｒｅ（λ）は液晶硬化膜の波長λｎｍにおける面内位相差値を表す]
を満たす、前記［８］に記載の位相差フィルム。
［１０］前記［８］または［９］に記載の位相差フィルムを含む楕円偏光板。
［１１］前記［１０］に記載の楕円偏光板を含む光学ディスプレイ。
［１２］前記［１０］に記載の楕円偏光板を含むフレキシブル画像表示装置。 The present invention provides the following preferred embodiments.
[1] The molecular weights are the same, but the molecular structures are different from each other, and the formula (1):

[In equation (1),
Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent.
^{D 1, D 2, E 1} , E 2, B 1 and ^{B 2} are each _{^{independently, -CR 11 R 12 -, -}} CH 2 -CH 2 -, - O -, - S -, - CO-O -, -O-CO-, -O-CO-O-, -C (= S) -O-, -O-C (= S)-, -OC (= S) -O-, -CO _{^{-NR 11 -, - NR 11 -CO}} -, - O-CH 2 -, - CH 2 -O -, - S-CH 2 -, - CH 2 -S- or a single ^{bond, R 11} and ^{R 12} Independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
G ¹ and G ² represent 1,4-cyclohexanediyl groups, respectively.
A ¹ and A ² independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. The group and the hydrogen atom contained in the aromatic hydrocarbon group may be ^{substituted with a halogen atom, -R 13} , -OR ¹³ , a cyano group or a nitro group, where R ¹³ is an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.
F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be ^{substituted with −OR 14} or a halogen atom, and R ¹⁴ Represents an alkyl group having 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and −CH ₂ − contained in the alkanediyl group is −O− or −. It may be replaced by CO-,
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group (provided that ^{at least one of P 1} and P ² is a polymerizable group)].
A polymerizable liquid crystal composition containing at least two kinds of polymerizable liquid crystal compounds represented by.
As the polymerizable liquid crystal compound ^{, the polymerizable liquid crystal compound (1-1) in which G 1} and G ² in the formula (1) are 1,4-trans-cyclohexanediyl groups, respectively, and the polymerizable liquid crystal compound (1-1). 1-1) and a polymerizable liquid crystal compound (1-2) having a different molecular structure only that at least one ^{of G 1} and G ^{2 in the formula (1) is a 1,4-cis-cyclohexanediyl group is included.} ,
The ratio of the peak area of the polymerizable liquid crystal compound (1-2) to the total peak area of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) measured by liquid chromatography is 0. A polymerizable liquid crystal composition having a content of 01% or more and 10% or less.
[2] The polymerizable liquid crystal compound (1-2) is the polymerizable liquid crystal compound (1-2a) in which either ^{G 1} or G ^{2 in the formula (1) is a 1,4-cis-cyclohexanediyl group.} , The polymerizable liquid crystal composition according to the above [1], wherein both ^{G 1} and G ² in the formula (1) contain a polymerizable liquid crystal compound (1-2b) in which both G 1 and G 2 are 1,4-cis-cyclohexanediyl groups. thing.
[3] The polymerizable liquid crystal composition according to the above [1] or [2], wherein Ar in the formula (1) is a group represented by any of the formulas (2-1) to (2-5). ..

[During the ceremony,
* Represents the joint with ^{D 1} or D ^2;
Q ¹ is -S -, - O-or ^{-NR 15} - ^{represents, R 15} represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom or a substituent,
Q ² is an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom or a substituent;
W ¹ and ^{W 2} are each independently, -O -, - S -, - CO -, - NR 15 - ^{represents, R 15} is a hydrogen atom or a substituent and which may number 1 to 6 carbons have Represents an alkyl group;
Y ¹ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and the alkyl group, the aromatic hydrocarbon group or the aromatic complex. The hydrogen atom contained in the ring group may be substituted with a halogen atom, and -CH _2- contained in the alkyl group is -O-, -CO-, -O-CO- or -CO-O-. May be replaced with
Y ² represents an alkyl group having 1 to 12 carbon atoms which may have a CN group or a substituent, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom and is contained in the alkyl group. -CH _2- may be replaced with -O-, -CO-, -O-CO- or -CO-O-;
Z ¹ , Z ² and Z ³ are independently hydrogen atoms or aliphatic hydrocarbon groups or alkoxy groups having 1 to 20 carbon atoms, alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and monovalent carbon atoms. Represents 6 to 20 aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -NR ¹⁵ R ¹⁶ or -SR ¹⁵ , where Z ¹ and Z ² combine with each other to form an aromatic ring or aromatic heterocycle. May be formed, R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Ax represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and Ay may have a hydrogen atom or a substituent. Represents an organic group having 2 to 30 carbon atoms, having a good alkyl group having 1 to 6 carbon atoms or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and Ax and Ay. May combine to form a ring;
Y ³ and Y ⁴ are independently expressed by the following equation (Y-1):

[In formula (Y-1),
M ¹ represents an alkyl group having 1 to 6 carbon hydrogen atom or a C, the alkyl group may be substituted by one or more substituents X ^3, substituents X ³ is a fluorine atom, a chlorine atom, Bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethyl A silyl group, a thioisocyano group, or one -CH _2- or two or more non-adjacent -CH ₂ --independently -O-, -S-, -CO-, -COO-,- OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO- , -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- may be replaced with a linear or linear group having 1 to 20 carbon atoms. It represents a branched alkyl group, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or may be a group represented by ^{−B 11} −F ¹¹ −P ^{11. B 11} , F ¹¹ and P ¹¹ are defined in the same manner as ^{B 1} , F ¹ and P ^{1 in} the above formula (1), respectively, and are different even if they are the same ^{as the above B 1} , F ¹ and P ^{1, respectively.} May;
U ¹ represents an organic group having 2 to 30 carbon atoms having an aromatic hydrocarbon group, and any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom, and the aromatic hydrocarbon group is , it may be substituted by one or more of the substituents X ^3;
T ¹ is, -O -, - S -, - COO -, - OCO -, - OCO-O -, - NU 2 -, - N = CU 2 -, - CO-NU 2 -, - OCO-NU 2 -Or -O-NU ^2- , where U ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, and an aromatic hydrocarbon. An organic group having 2 to 30 carbon atoms having a group (any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom), or (E ^11- A ¹¹ ) _q- B ^12- F ¹² represents -P ^12, the alkyl group, cycloalkyl group, each cycloalkenyl group and aromatic hydrocarbon group may be substituted by or is one or more substituents X ³ is unsubstituted, the alkyl group may be substituted by the cycloalkyl group or cycloalkenyl group, one -CH 2 in the alkyl group _- or non-adjacent two or more -CH 2 _- are each independently - O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO _2- , -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or may be replaced by -C≡C-, the cycloalkyl group or cycloalkenyl one -CH in group ₂ - or non-adjacent two or more -CH ₂ - are each independently -O- , -CO-, -COO-, -OCO- or -O-CO-O-, and E ¹¹ , A ¹¹ , B ¹² , F ¹² and P ¹² , respectively, in equation (1). E ¹ , A ¹ , B ¹ , F ¹ and P ¹ , respectively, which may be the same as or different from the ^{above E 1} , A ¹ , B ¹ , F ¹ and P ^{1, respectively, q} Represents an integer from 0 to 4, ^{and when a plurality of E 11} and / or A ¹¹ exist, they may be the same or different from each other, and U ¹ and U ² are combined to form a ring. May]
Represents a group selected from. ]
[4] In any of the above [1] to [3], ^{A 1} and A ² in the formula (1) are independently 1,4-cyclohexanediyl groups or 1,4-phenylenediyl groups. The polymerizable liquid crystal composition according to the above.
[5] The polymerizable liquid crystal composition according to any one of [1] to [4] above, wherein ^{P 1} and P ² in the formula (1) are acryloyl groups, respectively.
[6] The polymerizable liquid crystal composition according to any one of [1] to [5] above, further comprising a photopolymerization initiator.
[7] The polymerizable liquid crystal composition according to any one of [1] to [6] above, further comprising an organic solvent.
[8] A retardation film containing a liquid crystal cured film which is a cured product of the polymerizable liquid crystal composition according to any one of the above [1] to [7].
[9] The liquid crystal cured film has the formula (i):
0.75 ≤ Re (450) / Re (550) <1.00 (i)
[In formula (i), Re (λ) represents the in-plane retardation value of the liquid crystal cured film at a wavelength of λ nm]
The retardation film according to the above [8].
[10] An elliptical polarizing plate containing the retardation film according to the above [8] or [9].
[11] An optical display including the elliptical polarizing plate according to the above [10].
[12] A flexible image display device including the elliptical polarizing plate according to the above [10].

According to the present invention, it is possible to provide a polymerizable liquid crystal composition having excellent solubility in a solvent.

Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described here, and various modifications can be made without impairing the gist of the present invention.

［式（１）中、
Ａｒは、置換基を有していてもよい２価の芳香族炭化水素基または２価の芳香族複素環基を表し、
Ｄ^１、Ｄ^２、Ｅ^１、Ｅ^２、Ｂ^１およびＢ^２は、それぞれ独立に、−ＣＲ^１１Ｒ^１２−、−ＣＨ_２−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−Ｃ（＝Ｓ）−Ｏ−、−Ｏ−Ｃ（＝Ｓ）−、−Ｏ−Ｃ（＝Ｓ）−Ｏ−、−ＣＯ−ＮＲ^１１−、−ＮＲ^１１−ＣＯ−、−Ｏ−ＣＨ_２−、−ＣＨ_２−Ｏ−、−Ｓ−ＣＨ_２−、−ＣＨ_２−Ｓ−または単結合を表し、Ｒ^１１およびＲ^１２は、それぞれ独立に、水素原子、フッ素原子又は炭素数１〜４のアルキル基を表し、
Ｇ^１およびＧ^２は、それぞれ、１，４−シクロヘキサンジイル基を表し、
Ａ^１およびＡ^２は、それぞれ独立に、炭素数３〜１６の２価の脂環式炭化水素基または炭素数６〜２０の２価の芳香族炭化水素基を表し、該脂環式炭化水素基および該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、−Ｒ^１３、−ＯＲ^１３、シアノ基またはニトロ基で置換されていてもよく、Ｒ^１３は炭素数１〜４のアルキル基を表し、該アルキル基に含まれる水素原子は、フッ素原子で置換されていてもよく、
Ｆ^１およびＦ^２は、それぞれ独立に、炭素数１〜１２のアルカンジイル基を表し、該アルカンジイル基に含まれる水素原子は、−ＯＲ^１４またはハロゲン原子で置換されていてもよく、Ｒ^１４は炭素数１〜４のアルキル基を表し、該アルキル基に含まれる水素原子は、フッ素原子で置換されていてもよく、該アルカンジイル基に含まれる−ＣＨ_２−は、−Ｏ−または−ＣＯ−で置き換わっていてもよく、
Ｐ^１およびＰ^２は、それぞれ独立に、水素原子または重合性基を表す（但し、Ｐ^１およびＰ^２のうちの少なくとも１つは重合性基である）］。 <Polymerizable liquid crystal composition>
The polymerizable liquid crystal composition of the present invention contains at least two polymerizable liquid crystal compounds having the same molecular weight but different molecular structures and represented by the formula (1). High solubility in a solution can be ensured by containing at least two kinds of polymerizable liquid crystal compounds having different molecular structures but having the same molecular weight and similar to each other as the molecular structure represented by the formula (1). ..

[In equation (1),
Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent.
^{D 1, D 2, E 1} , E 2, B 1 and ^{B 2} are each _{^{independently, -CR 11 R 12 -, -}} CH 2 -CH 2 -, - O -, - S -, - CO-O -, -O-CO-, -O-CO-O-, -C (= S) -O-, -O-C (= S)-, -OC (= S) -O-, -CO _{^{-NR 11 -, - NR 11 -CO}} -, - O-CH 2 -, - CH 2 -O -, - S-CH 2 -, - CH 2 -S- or a single ^{bond, R 11} and ^{R 12} Independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
G ¹ and G ² represent 1,4-cyclohexanediyl groups, respectively.
A ¹ and A ² independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. The group and the hydrogen atom contained in the aromatic hydrocarbon group may be ^{substituted with a halogen atom, -R 13} , -OR ¹³ , a cyano group or a nitro group, where R ¹³ is an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.
F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be ^{substituted with −OR 14} or a halogen atom, and R ¹⁴ Represents an alkyl group having 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and −CH ₂ − contained in the alkanediyl group is −O− or −. It may be replaced by CO-,
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group (provided that ^{at least one of P 1} and P ² is a polymerizable group)].

In the polymerizable liquid crystal composition of the present invention, G ¹ and G ² in the formula (1) are 1,4-trans-cyclohexanediyl groups, respectively, as the at least two polymerizable liquid crystal compounds. Compound (1-1) (hereinafter, also referred to as “polymerizable liquid crystal compound (1-1)”), the polymerizable liquid crystal compound (1-1), and at least one ^{of G 1} and G ^{2 in the formula (1).} Includes a polymerizable liquid crystal compound (1-2) (hereinafter, also referred to as “polymerizable liquid crystal compound (1-2)”) having a different molecular structure only when is a 1,4-cis-cyclohexanediyl group. In the present invention, the polymerizable liquid crystal composition may contain only one type of the polymerizable liquid crystal compound (1-1), or may contain two or more types. When a plurality of polymerizable liquid crystal compounds (1-1) are contained, the polymerizable liquid crystal composition of the present invention corresponds to at least one polymerizable liquid crystal compound (1-1) in the polymerizable liquid crystal compound (1-2). ) May be included, and the polymerizable liquid crystal compound (1-2) corresponding to each of the plurality of polymerizable liquid crystal compounds (1-1) constituting the polymerizable liquid crystal composition may be contained.

The polymerizable liquid crystal compound (1-1) and G ¹ and G ^{2 in} the formula (1) differ in molecular structure only in that at least one of them is a 1,4-cis-cyclohexanediyl group, that is, they are isomers. By including the polymerizable liquid crystal compound (1-2) in combination, the solubility of the polymerizable liquid crystal compound (1-1) in a solvent can be improved. That is, when the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) are contained in combination, compared with the case where the polymerizable liquid crystal compound (1-1) is dissolved alone in a solvent, It is possible to easily dissolve more polymerizable liquid crystal compounds (1-1) in the same amount or less amount of solvent. As a result, undissolved polymerizable liquid crystal compounds are unlikely to remain in the coating liquid, and precipitation, precipitation, and stacking of the polymerizable liquid crystal compounds in the coating liquid can be suppressed. Improving the solubility of the polymerizable liquid crystal compound (1-1) in a solvent leads to suppression of orientation defects caused by undissolved polymerizable liquid crystal compound, precipitates, etc., and improvement of storage stability.

で表される重合性液晶化合物である。式（１）で表される構造を有する化合物は、通常、一方向に配向した状態で重合させたときに逆波長分散性の複屈折を示す重合性液晶化合物であり、広い波長域において一様の偏光変換が可能である。したがって、式（１）で表される重合性液晶化合物を用いることにより、該重合性液晶化合物から形成された位相差フィルムや楕円偏光板を表示装置等の光学ディスプレイに用いた場合に良好な表示特性を付与し得る重合性液晶組成物を得ることができる。 The polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) are each represented by the formula (1):

It is a polymerizable liquid crystal compound represented by. The compound having the structure represented by the formula (1) is usually a polymerizable liquid crystal compound that exhibits birefringence with anti-wavelength dispersibility when polymerized in a unidirectionally oriented state, and is uniform over a wide wavelength range. Polarization conversion is possible. Therefore, by using the polymerizable liquid crystal compound represented by the formula (1), a good display is obtained when a retardation film or an elliptical polarizing plate formed from the polymerizable liquid crystal compound is used for an optical display such as a display device. A polymerizable liquid crystal composition that can impart properties can be obtained.

In formula (1), G ¹ and G ² each independently represent a 1,4-cyclohexanediyl group. The two polymerizable liquid crystal compounds (1-1) and the polymerizable liquid crystal compound (1-2) constituting the polymerizable liquid crystal composition of the present invention are represented by ^{G 1} and G ^{2 in the formula (1).} The structures differ from each other in whether they are all 1,4-trans-cyclohexanediyl groups ^{or one or all of G 1} and G ² are 1,4-cis-cyclohexanediyl groups.

Wherein ^{(1), D 1, D} 2, E 1, E 2, B 1 and ^{B 2} are each _{^{independently, -CR 11 R 12 -, -}} CH 2 -CH 2 -, - O -, - S -, -CO-O-, -O-CO-, -O-CO-O-, -C (= S) -O-, -OC (= S)-, -O-C (= S) ^{-O -, - CO-NR 11} -, - NR 11 -CO -, - O-CH 2 -, - CH 2 -O -, - S-CH 2 -, - represents a CH 2 -S- or a single bond .. Here, R ¹¹ and R ¹² each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and are preferably a hydrogen atom, a methyl group, or an ethyl group.

In formula (1), D ¹ and D ² are independently, preferably −CO—O−, −O—CO−, −C (= S) −O−, −OC (= S) −. _{, -O-CH 2 -, -} CH 2 -O -, - CO-NR 11 - or a ^-NR 11 -CO-, and more preferably -CO-O -, - O- CO -, - CO-NR ^{It is 11} − or −NR ¹¹ −CO−, and particularly preferably −CO—O− or −O—CO−. R ¹¹ is preferably a hydrogen atom, a methyl group or an ethyl group. In formula (1), D ¹ and D ² may be the same or different from each other. Note that D ¹ and D ² are the same as each other means that the structures ^{of D 1} and D ² are the same when viewed with Ar as the center. The same applies hereinafter to the ^{relationships between E 1} and E ² , A ¹ and A ² , B ¹ and B ² , and F ¹ and F ^2.

In formula (1), E ¹ , E ² , B ¹ and B ² are independently, preferably -O-, -S-, -CO-O-, -O-CO-, -O-CO-, respectively. ^{O -, - CO-NR 11} -, - NR 11 -CO- or a single bond, more preferably -O -, - O-CO- or -CO-O-. R ¹¹ is preferably a hydrogen atom, a methyl group or an ethyl group. In formula (1), E ¹ and E ² and B ¹ and B ² may be the same or different from each other.

In the formula (1), A ¹ and A ² independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Here, the alicyclic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may be ^{substituted with a halogen atom, −R 13} , −OR ¹³ , cyano group or nitro group, and R ^{13 may be substituted.} Represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.

In formula (1), A ¹ and A ² may be independently substituted with at least one substituent preferably selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms1. , 4-Penylenedyl group, a 1,4-cyclohexanediyl group which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably methyl. A group-substituted 1,4-phenylenediyl group, an unsubstituted 1,4-phenylenediyl group, or an unsubstituted 1,4-cyclohexanediyl group, particularly preferably an unsubstituted 1,4-phenylenediyl group. It is a group or unsubstituted 1,4-cyclohexandiyl group, and particularly preferably an unsubstituted 1,4-phenylenediyl group. In formula (1), A ¹ and A ² may be the same or different from each other.

In formula (1), F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms. Here, the hydrogen atom contained in the alkanediyl group may be ^{substituted with −OR 14} or a halogen atom, and R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group. May be substituted with a fluorine atom. _{Further, -CH 2-} contained in the alkanediyl group may be replaced by -O- or -CO- (however, when a plurality of -O- are present, they are not adjacent to each other).

In formula (1), F ¹ and F ² are each independently, preferably an alkanediyl group having 4 to 12 carbon atoms which may be substituted. In formula (1), F ¹ and F ² may be the same or different from each other.

The ^{polymerizable group represented by P 1} or P ² includes an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyl group, a methacryloyl group, an oxylanyl group and an oxetanyl group. The group etc. can be mentioned. Among them, an acryloyl group, a methacryloyl group, a vinyl group and a vinyloxy group are preferable, an acryloyl group and a methacryloyl group are more preferable, and an acryloyl group is further preferable. In formula (1), P ¹ and P ² may be the same or different from each other as long as either one is a polymerizable group, but both P ¹ and P ² are polymerizable groups. It is preferable that ^{both P 1} and P ² are acryloyl groups.

In the formula (1), Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent. In the present invention, the divalent aromatic hydrocarbon group which may have a substituent means a divalent linking group containing at least one aromatic hydrocarbon ring, and even if it has a substituent. A good divalent aromatic heterocyclic group means a divalent linking group containing at least one aromatic heterocycle. The aromatic hydrocarbon ring and the aromatic heterocycle referred to here are those in which the number of π electrons of the ring structure is [4n + 2] (n represents an integer) according to Hückel's law (in the case of an aromatic heterocycle, the aromatic heterocycle). Hückel's law is satisfied including non-covalently bonded electron pairs on heteroatoms such as −N = and −S−). Ar may contain one aromatic hydrocarbon ring or aromatic heterocycle, or may contain two or more aromatic rings. When one aromatic hydrocarbon ring or aromatic heterocycle is contained, Ar may be a divalent aromatic hydrocarbon group which may have a substituent or may have a substituent. It may be a divalent aromatic heterocyclic group. When two or more aromatic hydrocarbon rings or aromatic heterocycles are contained, only the aromatic hydrocarbon ring or only a plurality of aromatic heterocycles may be contained, and the aromatic hydrocarbon ring and the aromatic heterocycle may be contained. May contain one or more of each. Two or more aromatic hydrocarbon rings and / or aromatic heterocycles may be bonded to each other by a single bond or a divalent bonding group such as −CO—O−, −O−.

Examples of the aromatic hydrocarbon ring that can be contained in Ar include a benzene ring, a naphthalene ring, an anthracene ring and the like, and a benzene ring and a naphthalene ring are preferable. Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrrolin ring, an imidazole ring, and a pyrazole ring. Examples thereof include a thiazole ring, a benzothiazole ring, a thienothiazole ring, an oxazole ring, a benzoxazole ring, and a phenanthroline ring. When Ar contains a nitrogen atom, the nitrogen atom preferably has π electrons.

Among them, Ar preferably has an aromatic heterocycle containing at least two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and may have a thiazole ring, a benzothiazole ring or a benzofuran ring. More preferably, it has a benzothiazole ring. When Ar has an aromatic heterocycle containing at least two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, the aromatic heterocycle is D ¹ and D 1 in the formula (1). may constitute a direct bond to a divalent linking group and D ^2, may it be contained as the substituent of the divalent linking group bonded directly D ¹ and D ^2, said aromatic heterocyclic It is preferable that the entire Ar group including the ring is three-dimensionally arranged in a direction substantially orthogonal to the molecular orientation direction.

In the formula (1), the total number of π electrons contained in the divalent aromatic hydrocarbon group or the divalent aromatic heterocyclic group which may have a substituent represented by Ar is preferably _{N π.} It is 8 or more, more preferably 12 or more, particularly preferably 16 or more, and particularly preferably 20 or more. Further, it is preferably 36 or less, more preferably 32 or less, further preferably 30 or less, particularly preferably 26 or less, and particularly preferably 24 or less.

Examples of the divalent aromatic hydrocarbon group or the divalent aromatic heterocyclic group which may have a substituent represented by Ar in the formula (1) include the following formulas (2-1) to (1). Examples thereof include groups represented by 2-5).

In formulas (2-1) to (2-5), * represents a joint with ^{D 1} or D ^2.

Wherein (2-1), ^{Q 1} is -S -, - O-or ^{-NR 15} - ^{represents, R 15} represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom or a substituent .. In the formula (2-3) and (2-4), ^{Q 2} represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom or a substituent.

Wherein (2-2), ^{W 1} and ^{W 2} are each independently, -O -, - S -, - CO -, - NR 15 - ^{represents, R 15} is a hydrogen atom or a substituent It represents an alkyl group having 1 to 6 carbon atoms.

In the formula (2-1), Y ¹ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group, and has a substituent. A good aromatic hydrocarbon group having 6 to 12 carbon atoms and an aromatic heterocyclic group having 3 to 12 carbon atoms are preferable, and an aromatic hydrocarbon group having 6 to 12 carbon atoms and an aromatic heterocyclic group having 3 to 12 carbon atoms are preferable. Groups are more preferred. In formula (2-2), Y ² represents an alkyl group having 1 to 12 carbon atoms which may have a CN group or a substituent. Here, the hydrogen atom contained in the alkyl group, the aromatic heterocyclic group or the aromatic heterocyclic group may be substituted with a halogen atom, and −CH ₂ − contained in the alkyl group is −O−. , -CO-, -O-CO- or -CO-O- may be substituted.

In formulas (2-1) to (2-5), Z ¹ , Z ² and Z ³ are independently hydrogen atoms or aliphatic hydrocarbon groups or alkoxy groups having 1 to 20 carbon atoms, and carbon atoms 3 to 3 to 20 respectively. Represents 20 alicyclic hydrocarbon groups, monovalent 6-20 carbon aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -NR ¹⁵ R ¹⁶ or -SR ¹⁵ , Z ¹ and Z ² May combine with each other to form an aromatic ring or an aromatic heterocycle. R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In formulas (2-3) and (2-4), Ax comprises an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. Represented, Ay has a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. It represents an organic group having 2 to 30 carbon atoms, and Ax and Ay may be bonded to form a ring.

The groups represented by the formulas (2-1) to (2-4) are not particularly limited, but specifically, JP-A-2011-207765, JP-A-2008-107767, and WO2014 / 01325. Etc., and the groups described in the above can be mentioned.

で表される基から選択される。 In the formula (2-5), Y ³ and Y ⁴ are independently described in the following formula (Y-1):

Selected from the groups represented by.

In formula (Y-1), M ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group may be substituted by one or more substituents X ^3.

Substituents X ³ is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, an amino group, a hydroxyl group, a mercapto group, methylamino group, dimethylamino group , Diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one -CH _2- or two or more non-adjacent -CH ₂ --independently -O-,-, respectively. S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = Replaced by CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- It represents a linear or branched alkyl group having 1 to 20 carbon atoms, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or at −B ¹¹ −F ¹¹ −P ¹¹ . may be a group ^represented, B ^{11, F 11} and ^{P 11} are respectively defined as in ^B 1, ^{F 1} and ^{P 1} in the formula (1), each of said ^B 1, ^{F 1} and P ¹ and may be the same or different.

The substituent X ³ is preferably a fluorine atom, a chlorine atom, -CF ₃ , -OCF ₃ or a cyano group. M ¹ is preferably an alkyl group having 1 to 6 carbon atoms which is unsubstituted or substituted with a hydrogen atom or one or more fluorine atoms, and more preferably a hydrogen atom.

U ¹ represents an organic group having 2 to 30 carbon atoms having an aromatic hydrocarbon group. Any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom, and U ¹ has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. , An organic group having 2 to 30 carbon atoms. The aromatic hydrocarbon group may be substituted by one or more of the substituents X ^3.

U ¹ is preferably an organic group having an aromatic heterocycle in which one or more carbon atoms are substituted with heteroatoms from the viewpoint of improving wavelength dispersibility. U ¹ is more preferably an organic group having an aromatic heterocycle which is a fused ring of a 5-membered ring and a 6-membered ring from the viewpoint of having good wavelength dispersibility and exhibiting high birefringence.

Specifically, U ¹ preferably has a group represented by the following formula. In the following formula, these groups have a bond ^{with T 1 at an arbitrary position.}

T ¹ is, -O -, - S -, - COO -, - OCO -, - OCO-O -, - NU 2 -, - N = CU 2 -, - CO-NU 2 -, - OCO-NU 2 -Or -O-NU ^2- , where U ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon. An organic group having 2 to 30 carbon atoms having a group (any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom), or (E ^11- A ¹¹ ) _q- B ^12- F ¹² Represents −P ^12. The alkyl group, cycloalkyl group, cycloalkenyl group and the aromatic hydrocarbon group may each be substituted by or is one or more substituents X ³ is unsubstituted, the alkyl group, the cycloalkyl It may be substituted with an alkyl group or the cycloalkenyl group. Wherein alkyl one -CH ₂ in the group - or non-adjacent two or more -CH ₂ - are each independently, -O -, - S -, - CO -, - COO -, - OCO- , -CO-S-, -S-CO-, -SO _2- , -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH It may be replaced by −OCO−, −COO−CH = CH−, −OCO−CH = CH−, −CH = CH−, −CF = CF− or −C≡C−, said cycloalkyl group or cyclo. one -CH ₂ in the alkenyl - or nonadjacent two or more -CH ₂ - are each independently -O -, - CO -, - COO -, - OCO- or O-COO May be replaced with-. ^{E 11, A 11, B 12} , F 12 and ^{P 12,} respectively, as well as ^{E 1,} A ^1, B 1, ^{F 1} and ^{P 1} in the formula (1) are defined, wherein each ^E 1, It may be the same as or different from A ¹ , B ¹ , F ¹ and P ¹ , where q represents an integer from 0 to 4, ^{and if there are multiple E 11} and / or A ¹¹ , they are the same. It may or may not be different.

T ^1, from the viewpoint of easy good birefringence synthesis, -O -, - S -, - N = CU 2 - or -NU ² - is preferably, improve the wavelength dispersion and birefringence from Yasu that is, -O -, - S- or -NU ² - it is more preferable.

U ² may be optionally substituted by one or more of the substituents ^{X 3,} 1 single -CH ₂ - or non-adjacent two or more -CH ₂ - are each independently -O-, An alkyl or alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a cycloalkyl group having 1 to 20 carbon atoms, which may be replaced by −CO−, −COO−, −OCO− or −O—CO—O−. It is preferably a cycloalkenyl group having 3 to 12 carbon atoms, or the alkyl group or alkenyl group which may be substituted with the cycloalkyl group, cycloalkenyl group, or aryl group.

Among them, in U ² , the hydrogen atom may be replaced with a fluorine atom from the viewpoint of birefringence and solvent solubility, and one −CH ₂ − or two or more non-adjacent −CH ₂ − are independent of each other. More preferably, it is a linear alkyl group having 1 to 20 carbon atoms which may be replaced with −O−, −CO−, −COO− or −OCO−.

U ¹ and U ² may be combined to form a ring. In that case, for example, ^{a cyclic group represented by -NU 1} U ² or a cyclic group represented by -N = CU ¹ U ² can be mentioned.

^{Y 3} and Y ⁴ are groups selected from the following formulas (Y-1') to (Y-47'), respectively, because the raw materials are easily available, the solubility is good, and the birefringence is high. It is particularly preferable to represent.

The molecular structure of the polymerizable liquid crystal compound (1) is preferably symmetrical from the viewpoint that the orientation of the polymerizable liquid crystal compound (1) is improved, industrial production is easy, and productivity can be improved. Specific examples of the group represented by the formula (2-5) include the following groups. * In the following (2-5a) to (2-5t) represents a joint with ^{D 1} or D ^2.

Among the formulas (2-1) to (2-5), the formulas (2-1), the formulas (2-3), the formulas (2-4) and the formulas (2-5) are preferable, and the formulas (2-1) are preferable. ) And formula (2-5) are more preferable, and formula (2-1) is particularly preferable.

In the present invention, examples of the polymerizable liquid crystal compound represented by the formula (1) include compounds described in JP-A-2019-0031777, JP-A-2019-073496, and the like.

The polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) constituting the polymerizable liquid crystal composition of the present invention are represented by G ¹ and G ² in the structure represented by the above formula (1). Only the structures of the 1,4-cyclohexanediyl groups represented differ from each other. In the polymerizable liquid crystal compound (1-1), G ¹ and G ² in the formula (1) are both 1,4-trans-cyclohexanediyl groups, and the polymerizable liquid crystal compound (1-2) is the polymerizable liquid crystal compound (1-2). It differs only in that at least one of ^{the polymerizable liquid crystal compound (1-1) and G 1} and G ² is a 1,4-cis-cyclohexanediyl group based on the structure of the liquid crystal compound (1-1).

In the present invention, in the polymerizable liquid crystal compound (1-2), one of G ¹ and G ^{2 in} the formula (1) is a 1,4-trans-cyclohexanediyl group, and the other is 1,4-cis. -Even if the polymerizable liquid crystal compound (1-2a) which is a cyclohexanediyl group (hereinafter, also referred to as "polymerizable liquid crystal compound (1-2a))), both ^{G 1} and G ^{2 in the formula (1)} May be a polymerizable liquid crystal compound (1-2b) (hereinafter, also referred to as “polymerizable liquid crystal compound (1-2b)), which is a 1,4-cis-cyclohexanediyl group. The polymerizable liquid crystal composition of the present invention. The product may contain only one of the polymerizable liquid crystal compound (1-2a) and the polymerizable liquid crystal compound (1-2b), or may contain both.

The polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal compound (1-) with respect to the total peak area of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), which is measured by liquid chromatography. The polymerizable liquid crystal composition (1-1) and the polymerizable liquid crystal compound (1-) are in an amount such that the ratio of the peak area of 2) (hereinafter, also referred to as “area percentage value”) is 0.01% or more and 10% or less. 2) and are included. A polymerizable liquid crystal compound represented by the formula (1) having a so-called T-shaped structure in which constituent molecules are arranged in a major axis direction that is the main chain of the compound and a direction that intersects the major axis direction is a polymerizable liquid crystal compound. ^{When both G 1} and G ² in the formula (1) are 1,4-trans-cyclohexanediyl groups (that is, the polymerizable liquid crystal compound (1-1)), it is usually in the formula (1). Orientation because at least one of G ¹ and G ² is more stable in molecular structure than the polymerizable liquid crystal compound (1-2) having a 1,4-cis-cyclohexanediyl group and is easily oriented in a desired direction. An optical film having few defects can be produced. Therefore, from the viewpoint of orientation and optical properties, the polymerizable liquid crystal compound (1-1) is considered to be advantageous as the polymerizable liquid crystal compound represented by the formula (1). In the present invention, the orientation of the polymerizable liquid crystal compound (1-1) is affected by setting the amount of the polymerizable liquid crystal compound (1-2) with respect to the polymerizable liquid crystal compound (1-1) within a specific range. The solubility of the polymerizable liquid crystal compound (1-1) in a solvent can be sufficiently improved without exerting the above.

When the area percentage value of the polymerizable liquid crystal compound (1-2) is less than the above lower limit value, it is difficult to improve the solubility of the polymerizable liquid crystal compound (1-1) in the solution, but the polymerizable liquid crystal compound (1) When the area percentage value of -2) is at least the above lower limit value, the solubility of the polymerizable liquid crystal compound (1-1) in the solution tends to be sufficiently improved. When the area percentage value of the polymerizable liquid crystal compound (1-2) is not more than the above upper limit value, a liquid crystal for producing an optical film such as a retardation film from the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound. Since the alignment state of the above can be kept good, it is possible to obtain an optical film having excellent optical characteristics while suppressing alignment defects. In the present invention, the area percentage value of the polymerizable liquid crystal compound (1-2) is more preferably 9% or less, further preferably 8% or less, particularly preferably 7% or less, and particularly preferably 6% or less. In the present invention, the area percentage value of the polymerizable liquid crystal compound (1-2) is preferably 0.1% or more, more preferably 0.5%, still more preferably 2.5% or more. .. On the other hand, in the present invention, even when the polymerizable liquid crystal compound (1-2) is contained in a small amount, it is excellent in the effect of greatly improving the solubility of the polymerizable liquid crystal compound (1-1) in the solution. In one aspect of the present invention, the area percentage value of the polymerizable liquid crystal compound (1-2) may be less than 1.0%, for example, 0.5% or less or 0.1% or less. However, the above-mentioned advantageous effects in the present invention can be sufficiently obtained.
When a plurality of polymerizable liquid crystal compounds corresponding to the polymerizable liquid crystal compound (1-1) and / or the polymerizable liquid crystal compound (1-2) are contained, the area percentage value of the polymerizable liquid crystal compound (1-2) is , Calculated for the total peak area of the fully polymerizable liquid crystal compound (1-2) and the fully polymerizable liquid crystal compound (1-1). The area percentage value can be calculated based on the peak area measured by liquid chromatography, and in detail, it can be measured and calculated by the method described in Examples described later.

The method for producing a polymerizable liquid crystal compound represented by the formula (1) such as the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) constituting the polymerizable liquid crystal composition of the present invention is particularly limited. Known organic synthetic reactions (eg, condensation reaction, esterification reaction, Wielson reaction, esterification reaction, erythrium reaction, esterification reaction, esterification reaction, esterification reaction, esterification reaction, erythrium reaction, esterification reaction Reaction, Schiff base formation reaction, benzylation reaction, Sonoh reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Heartwig reaction, Friedelcraft reaction, Heck reaction, Aldor reaction, etc.) It can be manufactured by appropriately combining them according to the structure.

で表される重合性液晶化合物（１−１）は、
式（Ｂ）：
ＨＯ−Ａｒ−ＯＨ （Ｂ）
で表されるアルコール化合物（Ｂ）と、
式（Ｃ）：

で表されるカルボン酸化合物（Ｃ）のエステル化反応を行うことにより製造することができる。なお、前記式（Ａ−１）、式（Ｂ）および式（Ｃ）におけるＡｒ、Ｅ^１、Ｅ^２、Ａ^１、Ａ^２、Ｂ^１、Ｂ^２、Ｆ^１、Ｆ^２、Ｐ^１およびＰ^２は、上記式（１）で規定されたものと同一であり、式（Ａ−１）で表される重合性液晶化合物（１−１）の構造に対応して決定される。 ^{For example, D 1} and D ² in the formula (1) are * -O-CO- (* represents a bond with Ar), and G ¹ and G ² are 1,4-trans-cyclohexanediyl groups. Yes, and has a symmetrical structure centered on Ar (that is, E ¹ and E ² , A ¹ and A ² , B ¹ and B ² , F ¹ and F ² , P ¹ and P ² are the same, respectively) Equation (A-1):

The polymerizable liquid crystal compound (1-1) represented by
Equation (B):
HO-Ar-OH (B)
The alcohol compound (B) represented by
Equation (C):

It can be produced by carrying out an esterification reaction of the carboxylic acid compound (C) represented by. ^{In addition, Ar, E 1} , E ² , A ¹ , A ² , B ¹ , B ² , F ¹ , F ² , P ¹ and P in the above formula (A-1), formula (B) and formula (C). ^{Reference numeral 2} denotes the same as that defined by the above formula (1), and is determined corresponding to the structure of the polymerizable liquid crystal compound (1-1) represented by the formula (A-1).

The alcohol compound (B) may be a compound in which two hydroxyl groups are bonded to the aromatic group Ar corresponding to the aromatic group Ar in the formula (1) in the desired polymerizable liquid crystal compound (1-1). Just do it. The aromatic group Ar is the same as that defined above, and examples thereof include compounds in which the two * parts are hydroxyl groups in the formulas (2-1) to (2-5).

The carboxylic acid compound (C) has a structure corresponding to ^{P 1} -F ¹ -B ¹ -A ¹ -E ¹ -G ^1- in the formula (1) in the desired polymerizable liquid crystal compound (1-1). may be any compound which carboxyl groups are bonded to l, 4-trans- cyclohexane-diyl group bonded as G ^1.

で表される化合物を得て、該化合物と、下記式（Ｃ’）：

で表されるカルボン酸化合物（Ｃ’）とを反応させることにより製造できる。なお、前記式（Ｃ’）および（Ｄ）におけるＡｒ、Ｅ^１、Ｅ^２、Ａ^１、Ａ^２、Ｂ^１、Ｂ^２、Ｆ^１、Ｆ^２、Ｐ^１およびＰ^２は、上記式（１）で規定されたものと同一であり、式（Ａ−１）で表される重合性液晶化合物（１−１）の構造に対応して決定される。 ^{The polymerizable liquid crystal compound (1-2a) in which either G 1} or G ² in the formula (1) is a 1,4-cis-cyclohexanediyl group is, for example, the alcohol compound (B) and the carboxylic acid. By reacting with compound (C), the following formula (D):

Obtaining the compound represented by, the compound and the following formula (C'):

It can be produced by reacting with a carboxylic acid compound (C') represented by. In the formulas (C') and (D), Ar, E ¹ , E ² , A ¹ , A ² , B ¹ , B ² , F ¹ , F ² , P ¹ and P ² are the above formulas (1). ), And is determined corresponding to the structure of the polymerizable liquid crystal compound (1-1) represented by the formula (A-1).

^{Further, the polymerizable liquid crystal compound (1-2b) in which both G 1} and G ^{2 in} the formula (1) are 1,4-cis-cyclohexanediyl groups is, for example, the polymerizable liquid crystal compound (1-1). In the method exemplified as the production method of, it can be produced by using a carboxylic acid compound (C') instead of the carboxylic acid compound (C).

The esterification reaction of the alcohol compound (B) with the carboxylic acid compound (C) and / or the carboxylic acid compound (C') is preferably carried out in the presence of a condensing agent. By carrying out the esterification reaction in the presence of a condensing agent, the esterification reaction can be carried out efficiently and rapidly.

Examples of the condensing agent include 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimidemeth-para-toluenesulfonate, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1-. Carbodiimide compounds such as ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (water-soluble carbodiimide: commercially available as WSC), bis (2,6-diisopropylphenyl) carbodiimide, and bis (trimethylsilyl) carbodiimide, 2-methyl- 6-Nitrobenzoic acid anhydride, 2,2'-carbonylbis-1H-imidazole, 1,1'-oxalyldiimidazole, diphenylphosphoryl azide, 1 (4-nitrobenzenesulfonyl) -1H-1, 2, 4 -Triazole, 1H-benzotriazole-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzotriazole-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, N, N, N', N'-tetra Methyl-O- (N-succinimidyl) uronium tetrafluoroborate, N- (1,2,2,2-tetrachloroethoxycarbonyloxy) succinimide, N-carbodibenzoxis succinimide, O- (6-chlorobenzotriazole-) 1-yl) -N, N, N', N'-tetramethyluronium tetrafluoroborate, O- (6-chlorobenzotriazole-1-yl) -N, N, N', N'-tetramethyluro Nium hexafluorophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate, 2-chloro Examples thereof include -1-methylpyridinium iodide, 2-chloro-1-methylpyridinium para-toluenesulfonate, 2-fluoro-1-methylpyridinium para-toluenesulfonate and trichloroacetic acid pentachlorophenyl ester.

〔式中、Ｒ^１およびＲ^２は互いに独立して、反応性基を表し、
Ａｒ、Ｅ^１、Ｅ^２、Ａ^１、Ａ^２、Ｂ^１、Ｂ^２、Ｆ^１、Ｆ^２、Ｐ^１およびＰ^２は、式（１）中のＡｒ、Ｅ^１、Ｅ^２、Ａ^１、Ａ^２、Ｂ^１、Ｂ^２、Ｆ^１、Ｆ^２、Ｐ^１およびＰ^２と同じ意味を表す。〕
前者の方法であると、重合性液晶組成物中の重合性液晶化合物（１−１）と重合性液晶化合物（１−２）との含有量を制御しやすく、後者の方法であると、合成が簡便であり、重合性液晶組成物をより効率的に製造し得るという利点がある。 The polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) constituting the polymerizable liquid crystal composition of the present invention are used as a liquid crystal mixture by preparing each separately and then mixing them. be able to. Further, with the reactive group R ² of the compound represented by the following formula (I), with the reactive group R ² of the compound represented by Formula (II), and R ¹ of the compound represented by formula (III) Can also be prepared as a liquid crystal mixture containing a polymerizable liquid crystal compound (1-1) and a polymerizable liquid crystal compound (1-2a) and / or a polymerizable liquid crystal compound (1-2b) by a method including reacting. ..

[In the formula, R ¹ and R ² represent reactive groups independently of each other.
Ar, E ¹ , E ² , A ¹ , A ² , B ¹ , B ² , F ¹ , F ² , P ¹ and P ² are Ar, E ¹ , E ² , A ¹ , in equation (1). It has the same meaning as A ² , B ¹ , B ² , F ¹ , F ² , P ¹ and P ^2. ]
The former method makes it easy to control the content of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) in the polymerizable liquid crystal composition, and the latter method synthesizes. However, there is an advantage that the polymerizable liquid crystal composition can be produced more efficiently.

^{Ar, E 1} , E ² , A ¹ , A ² , B ¹ , B ² , F ¹ , F ² , P ¹ and P ² in formulas (I), formula (II) and formula (III) are desired. It is determined according to the corresponding molecular structures of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2).

And ^{R 1} in formula (III), ^{R 2} in formula (I) and formula (II) represents a polymerizable liquid crystal compound react together (1-1) and the polymerizable liquid crystal compound (1-2) Any material may be used as long as it can form a structure represented by ^{D 1} and D ² in the formula (1). For example, examples of the ^{reactive group represented by R 1} and / or R ² include a hydroxyl group, a carboxyl group, an amino group and the like, and R ¹ and R ^{2 depending on the reaction used in the production of the polymerizable liquid crystal compound.} The reactive groups represented by may be selected respectively.

From the viewpoint of ease of reaction, handleability of materials, availability, etc., typically, for example, an alcohol compound in which ^{R 1 in the formula (III) is a hydroxyl group as a compound represented by the formula (III).} , The esterification reaction using the compound represented by the formula (I) and the carboxylic acid compound in which ^{R 2} in the formulas (I) and (II) is a carboxyl group as the compound represented by the formula (II). A polymerizable liquid crystal compound (liquid crystal mixture) constituting the polymerizable liquid crystal composition of the present invention can be produced. The esterification reaction can be carried out according to the same method as the esterification reaction that can be used for producing a polymerizable liquid crystal compound represented by the formula (I). For example, the above-mentioned method or JP-A-2019- The methods and conditions described in No. 003177 and the like can be adopted.

The polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1) in the liquid crystal mixture obtained by adjusting the amounts of the compound represented by the formula (I) and the compound represented by the formula (II) used for the preparation. The content ratios of -2a) and the polymerizable liquid crystal compound (1-2b) can be controlled. By ^{using a plurality of carboxylic acid compounds in the above method of reacting R 1} and R ² , a large number of compounds can be synthesized at the same time.

The polymerizable liquid crystal composition of the present invention contains a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) as long as it does not affect the effect of the present invention. You may. Examples of the polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) include a polymerizable liquid crystal compound having no molecular structure represented by the formula (1), for example. A polymerizable liquid crystal compound that generally exhibits positive wavelength dispersibility when oriented and polymerized, for example, "3.8. Among the compounds described in "6 Network (completely crosslinked type)" and "6.5.1 Liquid crystal material b. Polymerizable nematic liquid crystal material", compounds having a polymerizable group and the like can be mentioned.

When the polymerizable liquid crystal composition of the present invention contains a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), a viewpoint of obtaining a liquid crystal cured film having a high degree of orientation order. Therefore, the ratio of the polymerizable liquid crystal compound (1) to the total mass of the total polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition is preferably 51% by mass or more, more preferably 70% by mass or more, and further. It is preferably 90% by mass or more, and may be 100% by mass.

When two or more kinds of polymerizable liquid crystal compounds (1-1) are contained, it is sufficient to include the polymerizable liquid crystal compound (1-2) corresponding to at least one polymerizable liquid crystal compound (1-1) among them. The content of the polymerizable liquid crystal compound (1-1) in which the polymerizable liquid crystal compound (1-2) is present and the corresponding polymerizable liquid crystal compound (1-2) is the total of the total polymerizable liquid crystal compounds. It is preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more with respect to the mass.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition (total amount of all the polymerizable liquid crystal compounds) is, for example, 70 to 99.5 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. It is preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and further preferably 90 to 95 parts by mass. When the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured film. In the present specification, the solid content of the polymerizable liquid crystal composition means all components excluding volatile components such as organic solvents from the polymerizable liquid crystal mixture.

In addition to the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), the polymerizable liquid crystal composition of the present invention includes a photopolymerization initiator, an organic solvent, a polymerization inhibitor, a photosensitizer, and the like. It may further contain an additive such as a leveling agent. As each of these components, only one kind may be used, or two or more kinds may be used in combination.

The polymerizable liquid crystal composition of the present invention preferably contains a polymerization initiator. The polymerization initiator is a compound capable of producing a reactive species by the contribution of heat or light and initiating a polymerization reaction of a polymerizable liquid crystal display or the like. Examples of the reactive active species include active species such as radicals, cations and anions. Of these, a photopolymerization initiator that generates radicals by light irradiation is preferable from the viewpoint of easy reaction control.

Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, triazine compounds, iodonium salts and sulfonium salts. Specifically, Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (above, BASF Japan Co., Ltd.) (Made), Sakeol BZ, Sakeol Z, Sakeol BEE (manufactured by Seiko Kagaku Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), ADEKA PUTMER SP- 152, ADEKA OPTMER SP-170, ADEKA OPTMER N-1717, ADEKA PTMER N-1919, ADEKA ARCLUDS NCI-831, ADEKA ARCULDS NCI-930 (all manufactured by ADEKA Corporation), TAZ-A, TAZ -PP (above, manufactured by Nippon Sibel Hegner) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.) can be mentioned.
In the present invention, the polymerizable liquid crystal composition preferably contains at least one kind of photopolymerization initiator, and may contain two or more kinds of photopolymerization initiators.

Since the photopolymerization initiator can fully utilize the energy emitted from the light source and is excellent in productivity, the maximum absorption wavelength is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm, and above all, the α-acetophenone type. A polymerization initiator and an oxime-based photopolymerization initiator are preferable.

Examples of the α-acetophenone-based polymerization initiator include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzyl. Examples thereof include butane-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butane-1-one, and more preferably 2-methyl-2-morpholino-. Included are 1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1-one. Examples of commercially available α-acetophenone compounds include Irgacure 369, 379EG, 907 (above, manufactured by BASF Japan Ltd.) and Sequol BEE (manufactured by Seiko Kagaku Co., Ltd.).

Oxime-based photopolymerization initiators generate methyl radicals when irradiated with light. The methyl radicals preferably allow the polymerization of the polymerizable liquid crystal compound in the deep part of the liquid crystal cured film to be formed. Further, from the viewpoint of more efficiently advancing the polymerization reaction in the deep part of the formed liquid crystal cured film, it is preferable to use a photopolymerization initiator capable of efficiently utilizing ultraviolet rays having a wavelength of 350 nm or more. As the photopolymerization initiator capable of efficiently utilizing ultraviolet rays having a wavelength of 350 nm or more, a triazine compound and an oxime ester type carbazole compound are preferable, and an oxime ester type carbazole compound is more preferable from the viewpoint of sensitivity. Examples of the oxime ester-type carbazole compound include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl)]. ) -9H-carbazole-3-yl] -1- (O-acetyloxime) and the like. Commercially available products of the oxime ester-type carbazole compound include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, manufactured by BASF Japan Ltd.), ADEKA OPTMER N-1919, and ADEKA ARCLUS NCI-831 (above). , Made by ADEKA CORPORATION) and the like.

The amount of the photopolymerization initiator added is usually 0.1 part by mass or more and 30 parts by mass or less, preferably 0.5 parts by mass or more, and more preferably 1 part by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. The above is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less. Within the above range, the reaction of the polymerizable group proceeds sufficiently, and the orientation of the polymerizable liquid crystal compound is not easily disturbed.

In the present invention, the polymerizable liquid crystal composition is usually applied to a substrate or the like in a state of being dissolved in a solvent, and therefore preferably contains a solvent. As the solvent, a solvent capable of dissolving the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition such as the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) is preferable, and the polymerizable liquid crystal is also preferable. It is preferable that the solvent is inert to the polymerization reaction of the compound. Examples of the solvent include water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol and alcohols such as propylene glycol monomethyl ether. Solvents: Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone. Ketone solvent; aliphatic hydrocarbon solvent such as pentane, hexane and heptane; alicyclic hydrocarbon solvent such as ethylcyclohexane; aromatic hydrocarbon solvent such as toluene and xylene; nitrile solvent such as acetonitrile; tetrahydrofuran and dimethoxyethane and the like Ether solvent; chlorine-containing solvent such as chloroform and chlorobenzene; amide-based solvent such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone, etc. Be done. These solvents can be used alone or in combination of two or more. Among these, organic solvents are preferable, and alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents and aromatic hydrocarbon solvents are more preferable.

The content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by mass, and more preferably 70 to 95 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal composition. Therefore, the solid content in 100 parts by mass of the polymerizable liquid crystal composition is preferably 2 to 50 parts by mass, more preferably 5 to 30 parts by mass. When the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition tends to be low, the thickness of the film tends to be substantially uniform, and unevenness tends to be less likely to occur. The solid content can be appropriately determined in consideration of the thickness of the liquid crystal cured film to be produced.

By blending a polymerization inhibitor, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. Polymerization inhibitors include hydroquinones having substituents such as hydroquinone and alkyl ethers; catechols having substituents such as alkyl ethers such as butyl catechols; pyrogallols, 2,2,6,6-tetramethyl-1- Radical trapping agents such as piperidinyloxy radicals; thiophenols; β-naphthylamines and β-naphthols. In order to polymerize the polymerizable liquid crystal compound without disturbing the orientation, the content of the polymerization inhibitor is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound, and is preferably 0. It is 1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.

Furthermore, by using a sensitizer, the photopolymerization initiator can be made highly sensitive. Examples of the photosensitizer include xanthones such as xanthones and thioxanthones; anthracenes having substituents such as anthracene and alkyl ethers; phenothiazines; rubrenes. Examples of the photosensitizer include xanthones such as xanthones and thioxanthones; anthracenes having substituents such as anthracene and alkyl ethers; phenothiazines; rubrenes. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. 3 parts by mass.

Furthermore, the polymerizable liquid crystal composition of the present invention may contain a leveling agent. The leveling agent is an additive having a function of adjusting the fluidity of the polymerizable liquid crystal composition and flattening the film obtained by applying the leveling agent, for example, silicone-based, polyacrylate-based and perfluoroalkyl-based. Leveling agent can be mentioned. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all of which are Momentive Performance Materials Japan LLC) , Florinert (registered trademark) FC-72, FC-40, FC-43, FC-3283 (all manufactured by Sumitomo 3M Co., Ltd.), Megafuck (registered trademark) R-08 , R-30, R-90, F-410, F-411, F-443, F-445, F-470, F-477, F-479, F-482. , F-483 (all manufactured by DIC Co., Ltd.), Ftop (trade name) EF301, EF303, EF351, EF352 (all manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Surflon (registered) Trademarks) S-381, S-382, S-383, S-393, SC-101, SC-105, KH-40, SA-100 (all manufactured by AGC Seimi Chemical Co., Ltd.) , Product name E1830, E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (all trade names: manufactured by BM Chemie), etc. Can be mentioned. Of these, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferable.

The content of the leveling agent in the polymerizable liquid crystal composition is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. When the content of the leveling agent is within the above range, it becomes easy to orient the polymerizable liquid crystal compound, and the obtained liquid crystal cured film tends to be smoother, which is preferable. The polymerizable liquid crystal composition may contain two or more kinds of leveling agents.

The polymerizable liquid crystal composition of the present invention is prepared by adding a solvent, a photopolymerization initiator, a polymerization inhibitor, and a photosensitizer to the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), if necessary. It can be prepared by adding an agent or an additive such as a leveling agent and stirring and mixing at a predetermined temperature.

<Phase difference film>
Since the polymerizable liquid crystal composition of the present invention has high solubility in a solvent of the polymerizable liquid crystal compound, the occurrence of orientation defects due to precipitation, precipitation, etc. of the undissolved polymerizable liquid crystal compound or the polymerizable liquid crystal compound during storage. Excellent effect of suppressing. Therefore, by using the polymerizable liquid crystal composition of the present invention, it is possible to form a film without deteriorating the optical characteristics that the polymerizable liquid crystal compound can originally develop, and the liquid crystal curing having excellent optical characteristics can be achieved. A film can be obtained. Therefore, the present invention is a cured product (liquid crystal cured film) of the polymerizable liquid crystal composition of the present invention, and is a liquid crystal cured film formed by curing the polymerizable liquid crystal compound in the polymerizable liquid crystal composition in an oriented state. It also relates to retardation films containing. The retardation film composed of the liquid crystal cured film can sufficiently exhibit the optical characteristics that the polymerizable liquid crystal compound used can originally exhibit, and can be a retardation film having high optical performance.

The liquid crystal cured film constituting the retardation film of the present invention may be composed of a homopolymer of a polymerizable liquid crystal compound (1-1) in an oriented state and a homopolymer of a polymerizable liquid crystal compound (1-2). Further, it may be composed of a copolymer in an oriented state of a mixture of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2). Since the polymerization reaction is easy and a uniform liquid crystal cured film can be easily obtained, the liquid crystal cured film constituting the retardation film of the present invention is a polymerizable liquid crystal compound (1-1) and a polymerizable liquid crystal compound (1-2). It is preferably composed of a copolymer in the oriented state of the mixture with.

In one aspect of the present invention, the retardation film of the present invention is configured to include a liquid crystal cured film which is a cured product of the polymerizable liquid crystal composition of the present invention, and the liquid crystal cured film is composed of the following formula (i):
0.75 ≤ Re (450) / Re (550) <1.0 (i)
[In formula (i), Re (λ) represents the in-plane retardation value of the liquid crystal cured film at a wavelength of λ nm]
It is preferable to have the optical characteristics represented by.
When the liquid crystal cured film satisfies the formula (i), the liquid crystal cured film exhibits so-called inverse wavelength dispersibility in which the in-plane retardation value at a short wavelength is smaller than the in-plane retardation value at a long wavelength. Re (450) / Re (550) is more preferably 0.76 or more, still more preferably 0.78 or more, and more preferably 0.78 or more, because the inverse wavelength dispersibility is improved and the optical characteristics of the retardation film are further improved. , More preferably 0.92 or less, still more preferably 0.90 or less, particularly preferably 0.87 or less, still more preferably 0.86 or less, and particularly preferably 0.85 or less.

In one aspect of the present invention, the retardation film of the present invention has the following formula (ii):
1.00 ≤ Re (650) / Re (550) (ii)
[In equation (ii), Re (λ) represents the in-plane retardation value of the retardation film at the wavelength λ nm]
It is preferable to include a liquid crystal cured film having optical characteristics represented by. From the viewpoint of the optical characteristics of the retardation film, Re (650) / Re (550) is more preferably 1.01 or more, still more preferably 1.02 or more.

Further, in one aspect of the present invention, the retardation film of the present invention has the following formula (iii):
100 nm ≤ Re (550) ≤ 180 nm (iii)
[In equation (iii), Re (λ) represents the in-plane retardation value of the retardation film at the wavelength λ nm]
It is preferable to include a liquid crystal cured film having optical characteristics represented by. The liquid crystal cured film satisfying the above formula (iii) functions as a λ / 4 plate, and the effect of improving the front reflection hue (coloring) when an elliptical polarizing plate including a retardation film containing the liquid crystal cured film is applied to an optical display or the like. Excellent effect). A more preferable range of the in-plane retardation value is 120 nm ≦ Re (550) ≦ 170 nm, and a more preferable range is 130 nm ≦ Re (550) ≦ 150 nm.

The in-plane retardation value can be adjusted by adjusting the thickness d of the liquid crystal cured film. Since the in-plane retardation value is determined by the above equation Re (λ) = (nx (λ) −ny (λ)) × d, a desired in-plane retardation value (Re (λ): wavelength λ ( In order to obtain the in-plane retardation value of the cured liquid crystal film at nm), the three-dimensional refractive index and the film thickness d may be adjusted. In the above formula, d represents the thickness of the target liquid crystal cured film, and nx is the main refraction at the wavelength λ nm in the direction parallel to the plane of the liquid crystal cured film in the refractive index ellipse formed by the liquid crystal cured film. Represents the rate, and ny is the refractive index at the wavelength λ nm in the direction parallel to the plane of the liquid crystal cured film and orthogonal to the direction of nx in the refractive index ellipse formed by the liquid crystal cured film. show.

The retardation film of the present invention is, for example,
A step of forming a coating film of the polymerizable liquid crystal composition of the present invention, drying the coating film, and orienting the polymerizable liquid crystal compound in the polymerizable liquid crystal composition, and
It can be produced by a method including a step of polymerizing a polymerizable liquid crystal compound by light irradiation while maintaining an oriented state to form a liquid crystal cured film.

The coating film of the polymerizable liquid crystal composition can be formed by applying the polymerizable liquid crystal composition on a substrate or an alignment film described later.
Examples of the base material include a glass base material and a film base material, and a resin film base material is preferable from the viewpoint of processability. Resins constituting the film substrate include, for example, polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohols; polyethylene terephthalates; polymethacrylic acid esters; polyacrylic acid esters; triacetylcellulose, Examples include diacetyl cellulose and cellulose esters such as cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyether ketones; polyphenylene sulfide and plastics such as polyphenylene oxide. Such a resin can be formed into a film by a known means such as a solvent casting method and a melt extrusion method to form a base material. The surface of the base material may have a protective layer formed of an acrylic resin, a methacrylic resin, an epoxy resin, an oxetane resin, a urethane resin, a melamine resin, or the like. Surface treatment such as plasma treatment may be applied.

A commercially available product may be used as the base material. As commercially available cellulose ester base materials, for example, cellulose ester base materials manufactured by Fuji Photo Film Co., Ltd. such as Fujitac Film; manufactured by Konica Minolta Opto Co., Ltd. such as "KC8UX2M", "KC8UY", and "KC4UY". Cellulose ester base material and the like. Commercially available cyclic olefin resins include, for example, cyclic olefin resins manufactured by Ticona (Germany) such as "Topas (registered trademark)"; cyclic olefins manufactured by JSR Corporation such as "Arton (registered trademark)". Resins; Cyclic olefin resins manufactured by Zeon Corporation such as "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)"; Mitsui such as "Apel" (registered trademark) Cyclic olefin resin manufactured by Kagaku Co., Ltd. can be mentioned. A commercially available cyclic olefin resin base material can also be used. As commercially available cyclic olefin resin base materials, cyclic olefin resin base materials manufactured by Sekisui Chemical Co., Ltd. such as "Scina (registered trademark)" and "SCA40 (registered trademark)"; "Zeonoa film (registered trademark)" A cyclic olefin resin base material manufactured by Optes Corporation; a cyclic olefin resin base material manufactured by JSR Corporation such as "Arton Film (registered trademark)" can be mentioned.

From the viewpoints of thinning the retardation film, easy peeling of the base material, handleability of the base material, and the like, the thickness of the base material is usually 5 to 300 μm, preferably 10 to 150 μm.

Examples of the method for applying the polymerizable liquid crystal composition to a substrate or the like include a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, an applicator method and other coating methods, and a flexography method and other printing methods. And the like, a known method can be mentioned.

Then, the solvent is removed by drying or the like to form a dry coating film. Examples of the drying method include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method. At this time, by heating the coating film obtained from the polymerizable liquid crystal composition, the solvent is dried and removed from the coating film, and the polymerizable liquid crystal compound is placed in a desired direction (for example, horizontal or vertical) with respect to the coating film plane. Can be oriented in the direction). The heating temperature of the coating film can be appropriately determined in consideration of the polymerizable liquid crystal compound to be used and the material of the base material or the like forming the coating film. , It is necessary that the temperature is equal to or higher than the liquid crystal phase transition temperature. In order to bring the polymerizable liquid crystal compound into a desired orientation state while removing the solvent contained in the polymerizable liquid crystal composition, for example, the liquid crystal phase transition temperature (smetic phase) of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. It can be heated to a temperature of about (transition temperature or nematic phase transition temperature) or higher. The liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermal weight differential thermal analyzer (TG-DTA), or the like. The phase transition temperature in the polymerizable liquid crystal composition of the present invention containing at least two kinds of polymerizable liquid crystal compounds is the same ratio as the composition of the fully polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition in the polymerizable liquid crystal composition. It means the temperature measured using a mixture of mixed polymerizable liquid crystal compounds.

The polymerizable liquid crystal composition of the present invention contains at least two types of polymerizable liquid crystal compounds (1-1) and polymerizable liquid crystal compounds (1-2), and usually each of them is a single polymerizable liquid crystal compound (1-). The liquid crystal phase can be transferred at a temperature lower than the temperature at which 1) or the polymerizable liquid crystal compound (1-2) is transferred to the liquid crystal phase. Therefore, in the production of the retardation film using the polymerizable liquid crystal composition of the present invention, excessive consumption of thermal energy can be suppressed and production efficiency can be improved. Further, since the liquid crystal phase transition can be performed by heating at a relatively low temperature, there is an advantage that the options of the supporting base material to which the polymerizable liquid crystal composition is applied are expanded.

The heating time can be appropriately determined depending on the heating temperature, the type of the polymerizable liquid crystal compound used, the type of the solvent, its boiling point and its amount, etc., but is usually 15 seconds to 10 minutes, preferably 0.5 to 0.5 minutes. 5 minutes.

The solvent may be removed from the coating film at the same time as heating the polymerizable liquid crystal compound to the liquid crystal phase transition temperature or higher, or separately, but it is preferable to remove the solvent at the same time from the viewpoint of improving productivity. Before heating the polymerizable liquid crystal compound to a temperature equal to or higher than the liquid crystal phase transition temperature, the solvent in the coating film should be appropriately added under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition does not polymerize. A pre-drying step may be provided for removal. Examples of the drying method in the pre-drying step include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method, and the drying temperature (heating temperature) in the drying step is the type of polymerizable liquid crystal compound used and the solvent. It can be appropriately determined according to the type of the above, its boiling point, its amount and the like.

Next, in the obtained dry coating film, the polymerizable liquid crystal compound is polymerized by light irradiation while maintaining the orientation state of the polymerizable liquid crystal compound, whereby the polymer of the polymerizable liquid crystal compound existing in the desired orientation state is used. A certain liquid crystal cured film is formed. Since the polymerizable liquid crystal composition of the present invention can be highly polymerized by irradiation with light such as high-intensity ultraviolet rays while suppressing damage to the polymerizable liquid crystal compound, the polymerization method is usually a photopolymerization method. Is used. In photopolymerization, the light to be applied to the dry coating film is appropriately selected according to the type of the polymerization initiator contained in the dry coating film, the type of the polymerizable liquid crystal compound, and the amount thereof. Specific examples thereof include one or more types of light and active electron beams selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays and γ-rays. Among them, ultraviolet light is preferable because it is easy to control the progress of the polymerization reaction and it is possible to use a photopolymerization apparatus widely used in the art. It is preferable to select the type of the polymerizable liquid crystal compound and the polymerization initiator contained in the polymerizable liquid crystal composition. Further, at the time of polymerization, the polymerization temperature can be controlled by irradiating light while cooling the dry coating film by an appropriate cooling means. By adopting such a cooling means, if the polymerizable liquid crystal compound is polymerized at a lower temperature, a liquid crystal cured film can be appropriately formed even if a base material having a relatively low heat resistance is used. It is also possible to promote the polymerization reaction by raising the polymerization temperature within a range in which defects due to heat during light irradiation (deformation due to heat of the base material, etc.) do not occur. A patterned cured film can also be obtained by masking or developing during photopolymerization.

Examples of the light source of the active energy ray include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excima laser, and a wavelength range. Examples thereof include an LED light source that emits 380 to 440 nm, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp.

The ultraviolet irradiation intensity is usually 10 to 3,000 mW / cm ² . The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activating the photopolymerization initiator. The time for irradiating light is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, still more preferably 0.1 seconds to 1 minute. be. When irradiated once or multiple times with such an ultraviolet irradiation intensity, the integrated light intensity is 10 to 3,000 mJ / cm ² , preferably 50 to 2,000 mJ / cm ² , and more preferably 100 to 1,000 mJ / cm. It is ^2.

The thickness of the liquid crystal cured film can be appropriately selected depending on the optical display to be applied and the like. It is preferably 0.2 to 3 μm, more preferably 0.2 to 2 μm.

The coating film of the polymerizable liquid crystal composition may be formed on the alignment film. The alignment film has an orientation-regulating force that aligns the polymerizable liquid crystal compound in a desired direction. For example, an alignment film having an orientation regulating force for horizontally aligning a polymerizable liquid crystal compound is a horizontal alignment film, and an alignment film having an orientation regulating force for vertically orienting a polymerizable liquid crystal compound is a vertical alignment film. The orientation regulating force can be arbitrarily adjusted according to the type of alignment film, surface condition, rubbing conditions, etc., and when the alignment film is formed of a photo-alignable polymer, it can be arbitrarily adjusted according to polarization irradiation conditions, etc. It is possible to do.

The alignment film preferably has solvent resistance that does not dissolve when the polymerizable liquid crystal composition is applied, and also has heat resistance in heat treatment for removing the solvent and aligning the polymerizable liquid crystal compound described later. Examples of the alignment film include an alignment film containing an orientation polymer, a photoalignment film, a grub alignment film having an uneven pattern or a plurality of grooves on the surface, a stretched film stretched in the orientation direction, and the like, and the accuracy of the orientation angle and From the viewpoint of quality, a photoalignment film is preferable.

Examples of the oriented polymer include polyamides and gelatins having an amide bond in the molecule, polyimide having an imide bond in the molecule and polyamic acid, which is a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, and poly. Examples thereof include oxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid esters. Of these, polyvinyl alcohol is preferable. The oriented polymer can be used alone or in combination of two or more.

The alignment film containing the orientation polymer is usually obtained by applying a composition in which the orientation polymer is dissolved in a solvent (hereinafter, may be referred to as "orientation polymer composition") to a base material to remove the solvent or. It is obtained by applying an oriented polymer composition to a substrate, removing a solvent, and rubbing (rubbing method). Examples of the solvent include the same solvents as those exemplified above as the solvents that can be used in the polymerizable liquid crystal composition.

The concentration of the oriented polymer in the oriented polymer composition may be within the range in which the oriented polymer material can be completely dissolved in the solvent, but is preferably 0.1 to 20% in terms of solid content with respect to the solution, and is 0. .1 to 10% is more preferable.

As the orientation polymer composition, a commercially available alignment film material may be used as it is. Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optomer (registered trademark, manufactured by JSR Corporation).

Examples of the method of applying the oriented polymer composition to the base material include the same methods as those exemplified as the method of applying the polymerizable liquid crystal composition to the base material.

Examples of the method for removing the solvent contained in the oriented polymer composition include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.

In order to impart an orientation regulating force to the alignment film, a rubbing treatment can be performed as needed (rubbing method). As a method of imparting orientation-regulating force by the rubbing method, a rubbing cloth is wrapped around a rotating rubbing roll, and an orientation polymer composition is applied to the substrate and annealed to form the surface of the substrate. A method of contacting a film of an oriented polymer can be mentioned. If masking is performed during the rubbing treatment, a plurality of regions (patterns) having different orientation directions can be formed on the alignment film.

The photoalignment film is usually formed by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter, also referred to as “composition for forming a photoalignment film”) to a base material, removing the solvent, and then polarized light. It is obtained by irradiating (preferably polarized UV). The photoalignment film is also advantageous in that the direction of the orientation regulating force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.

A photoreactive group is a group that produces a liquid crystal alignment ability when irradiated with light. Specific examples thereof include groups involved in photoreactions that are the origin of liquid crystal orientation ability such as molecular orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction generated by light irradiation. Of these, groups involved in the dimerization reaction or photocrosslinking reaction are preferable because they are excellent in orientation. As the photoreactive group, an unsaturated bond, particularly a group having a double bond is preferable, and a carbon-carbon double bond (C = C bond), a carbon-nitrogen double bond (C = N bond), and a nitrogen-nitrogen double bond are preferable. A group having at least one selected from the group consisting of a double bond (N = N bond) and a carbon-oxygen double bond (C = O bond) is particularly preferable.

Examples of the photoreactive group having a C = C bond include a vinyl group, a polyene group, a stilbene group, a stillbazole group, a stillvazolium group, a chalcone group, a cinnamoyl group and the like. Examples of the photoreactive group having a C = N bond include a group having a structure such as an aromatic Schiff base and an aromatic hydrazone. Examples of the photoreactive group having an N = N bond include an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group, a formazan group, and a group having an azoxybenzene structure. Examples of the photoreactive group having a C = O bond include a benzophenone group, a coumarin group, an anthraquinone group, a maleimide group and the like. These groups may have substituents such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group and an alkyl halide group.

Among them, a photoreactive group involved in a photodimerization reaction is preferable, and a photoalignment film having a relatively small amount of polarized light required for photoalignment and excellent thermal stability and stability over time can be easily obtained. A cinnamoyl group and a chalcone group are preferable. As the polymer having a photoreactive group, a polymer having a cinnamoyl group such that the terminal portion of the side chain of the polymer has a cinnamic acid structure is particularly preferable.

By applying the composition for forming a photoalignment film onto a base material, a photoalignment-inducing layer can be formed on the base material. Examples of the solvent contained in the composition include the same solvents as those exemplified above as the solvents that can be used in the polymerizable liquid crystal composition, and are appropriately selected depending on the solubility of the polymer having a photoreactive group or the monomer. can do.

The content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be appropriately adjusted depending on the type of the polymer or monomer and the thickness of the target photo-alignment film, but the composition for forming a photo-alignment film. It is preferably at least 0.2% by mass, and more preferably in the range of 0.3 to 10% by mass. The composition for forming a photoalignment film may contain a polymer material such as polyvinyl alcohol or polyimide or a photosensitizer as long as the characteristics of the photoalignment film are not significantly impaired.

Examples of the method of applying the composition for forming a photoalignment film to the base material include the same method as the method of applying the orientation polymer composition to the base material. Examples of the method for removing the solvent from the applied composition for forming a photoalignment film include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.

In order to irradiate polarized light, even in the form of directly irradiating polarized UV from the composition for forming a photoalignment film coated on the base material, the polarized light is irradiated from the base material side to obtain polarized light. It may be in the form of transmitting and irradiating. Further, it is particularly preferable that the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in the wavelength range in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength in the range of 250 to 400 nm is particularly preferable. Examples of the light source used for the polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet light lasers such as KrF and ArF, and high-pressure mercury lamps, ultra-high pressure mercury lamps and metal halide lamps. preferable. Among these, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp are preferable because they have a high emission intensity of ultraviolet rays having a wavelength of 313 nm. Polarized UV can be irradiated by irradiating the light from the light source through an appropriate polarizer. As such a polarizing element, a polarizing filter, a polarizing prism such as Gran Thomson or Gran Tailor, or a wire grid type polarizing element can be used.

If masking is performed during rubbing or polarized light irradiation, it is possible to form a plurality of regions (patterns) in which the directions of liquid crystal orientation are different.

A groove alignment film is a film having an uneven pattern or a plurality of grooves on the surface of the film. When the polymerizable liquid crystal compound is applied to a film having a plurality of linear grubs arranged at equal intervals, the liquid crystal molecules are oriented in the direction along the groove.

As a method of obtaining a grub alignment film, a method of forming an uneven pattern by developing and rinsing after exposure through an exposure mask having a pattern-shaped slit on the surface of a photosensitive polyimide film, or a plate having a groove on the surface. A method of forming a layer of UV-curable resin before curing on a shaped master, transferring the formed resin layer to a substrate and then curing, and a film of UV-curable resin before curing formed on the substrate. Examples thereof include a method in which a roll-shaped master having a plurality of grooves is pressed to form irregularities and then cured.

The thickness of the alignment film (alignment film containing an alignment polymer or photoalignment film) is usually in the range of 10 to 10000 nm, preferably in the range of 10 to 1000 nm, more preferably 10 to 500 nm or less, and further preferably. Is in the range of 10 to 300 nm, particularly preferably 50 to 250 nm.

<Elliptical polarizing plate>
The present invention includes an elliptical polarizing plate including the retardation film of the present invention. The elliptical polarizing plate of the present invention includes the retardation film and the polarizing film of the present invention.
The polarizing film is a film having a polarizing function, and examples thereof include a stretched film having a dye having an absorption anisotropy adsorbed and a film containing a film coated with a dye having an absorption anisotropy as a polarizer. Examples of the dye having absorption anisotropy include a dichroic dye.

A film containing a stretched film having a dye having absorption anisotropy adsorbed as a polarizer is usually obtained by uniaxially stretching a polyvinyl alcohol-based resin film and dyeing the polyvinyl alcohol-based resin film with a bicolor dye. At least of the polarizer produced through a step of adsorbing a bicolor dye, a step of treating a polyvinyl alcohol-based resin film on which the bicolor dye is adsorbed with an aqueous boric acid solution, and a step of washing with water after the treatment with the aqueous boric acid solution. It is produced by sandwiching one surface with a transparent protective film via an adhesive.

The polyvinyl alcohol-based resin is obtained by saponifying the polyvinyl acetate-based resin. As the polyvinyl acetate-based resin, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and another monomer copolymerizable therewith is used. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

The saponification degree of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually about 1,000 to 10,000, preferably in the range of 1,500 to 5,000.

A film formed of such a polyvinyl alcohol-based resin is used as a raw film for a polarizing film. The method for forming the film of the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method. The film thickness of the polyvinyl alcohol-based raw film can be, for example, about 10 to 150 μm.

The uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before dyeing with a dichroic dye, at the same time as dyeing, or after dyeing. When the uniaxial stretching is performed after dyeing, the uniaxial stretching may be performed before the boric acid treatment or during the boric acid treatment. It is also possible to perform uniaxial stretching at these multiple stages. In uniaxial stretching, rolls having different peripheral speeds may be uniaxially stretched, or thermal rolls may be used to uniaxially stretch the rolls. Further, the uniaxial stretching may be a dry stretching in which the stretching is performed in the atmosphere, or a wet stretching in which the polyvinyl alcohol-based resin film is swollen using a solvent. The draw ratio is usually about 3 to 8 times.

Dyeing of the polyvinyl alcohol-based resin film with a dichroic dye is performed, for example, by immersing the polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye.

Specifically, as the dichroic dye, iodine or a dichroic organic dye is used. Examples of the dichroic organic dye include C.I. I. Examples thereof include a dichroic direct dye composed of a disazo compound such as DIRECT RED 39, and a dichroic direct dye composed of a compound such as trisazo and tetrakisazo. The polyvinyl alcohol-based resin film is preferably immersed in water before the dyeing treatment.

When iodine is used as the dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide for dyeing is usually adopted. The iodine content in this aqueous solution is usually about 0.01 to 1 part by mass per 100 parts by mass of water. The content of potassium iodide is usually about 0.5 to 20 parts by mass per 100 parts by mass of water. The temperature of the aqueous solution used for dyeing is usually about 20 to 40 ° C. The immersion time (staining time) in this aqueous solution is usually about 20 to 1,800 seconds.

On the other hand, when a dichroic organic dye is used as the dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye and dyeing is usually adopted. The content of the dichroic organic dye in this aqueous solution is usually ^{about 1 × 10 -4} to 10 parts by mass, preferably 1 × 10 ^-3 to 1 part by mass, more preferably 1 × 10 -4 to 1 part by mass, per 100 parts by mass of water. Is 1 × 10 ^-3 to 1 × ^10-2 parts by mass. This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing aid. The temperature of the dichroic dye aqueous solution used for dyeing is usually about 20 to 80 ° C. The immersion time (staining time) in this aqueous solution is usually about 10 to 1,800 seconds.

The boric acid treatment after dyeing with a dichroic dye can usually be carried out by immersing the dyed polyvinyl alcohol-based resin film in an aqueous boric acid solution. The content of boric acid in this aqueous boric acid solution is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water. When iodine is used as the dichroic dye, this aqueous boric acid solution preferably contains potassium iodide, and the content of potassium iodide in that case is usually 0.1 to 1 parts by mass per 100 parts by mass of water. It is about 15 parts by mass, preferably 5 to 12 parts by mass. The immersion time in the boric acid aqueous solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature of the boric acid treatment is usually 50 ° C. or higher, preferably 50 to 85 ° C., and more preferably 60 to 80 ° C.

The polyvinyl alcohol-based resin film after the boric acid treatment is usually washed with water. The water washing treatment can be performed, for example, by immersing the boric acid-treated polyvinyl alcohol-based resin film in water. The temperature of water in the water washing treatment is usually about 5 to 40 ° C. The immersion time is usually about 1 to 120 seconds.

After washing with water, a drying treatment is performed to obtain a polarizer. The drying process can be performed using, for example, a hot air dryer or a far-infrared heater. The temperature of the drying treatment is usually about 30 to 100 ° C, preferably 50 to 80 ° C. The drying treatment time is usually about 60 to 600 seconds, preferably 120 to 600 seconds. By the drying treatment, the moisture content of the polarizer is reduced to a practical level. The water content is usually about 5 to 20% by mass, preferably 8 to 15% by mass. When the water content is in the above range, it is easy to obtain a polarizer having appropriate flexibility and excellent thermal stability.

The thickness of the polarizer obtained by uniaxially stretching, dyeing with a dichroic dye, boric acid treatment, washing with water, and drying the polyvinyl alcohol-based resin film is preferably 5 to 40 μm.

Examples of the film coated with the dye having absorption anisotropy include a composition containing a dichroic dye having liquid crystallinity, a film obtained by applying a composition containing a dichroic dye and a polymerizable liquid crystal compound, and the like. Can be mentioned. The film preferably has a protective film on one or both sides thereof. Examples of the protective film include the same as the resin film exemplified above as a base material that can be used for producing a liquid crystal cured film.

The film coated with the dye having absorption anisotropy is preferably thin, but from the viewpoint of strength and processability, the thickness of the film is usually 20 μm or less, preferably 5 μm or less, and more preferably 0. It is 5 to 3 μm.

Specific examples of the film coated with the dye having absorption anisotropy include the films described in JP-A-2013-33249.

A polarizing film can be obtained by laminating a transparent protective film on at least one surface of the polarizing element thus obtained via an adhesive. As the transparent protective film, a transparent film similar to the resin film exemplified above can be preferably used as a base material that can be used for producing a liquid crystal cured film constituting a retardation film.

The elliptical polarizing plate of the present invention is configured to include the retardation film and the polarizing film of the present invention. For example, the retardation film and the polarizing film of the present invention are combined with an adhesive layer or an adhesive layer. The elliptical polarizing plate of the present invention can be obtained by laminating through the polarizing plate.

In one aspect of the present invention, when the retardation film of the present invention including the liquid crystal cured film and the polarizing film are laminated, the slow axis (optical axis) of the liquid crystal cured film constituting the retardation film and the polarizing film It is preferable to stack the films so that the angle formed by the absorption shaft is 45 ± 5 °.

The elliptical polarizing plate of the present invention may have a configuration provided by a conventional general elliptical polarizing plate, or a polarizing film and a retardation film. Such a configuration includes, for example, an adhesive layer (sheet) for bonding an elliptical polarizing plate to a display element or the like constituting an optical display, and an object for protecting the surface of a polarizing film or a retardation film from scratches and stains. Protective film and the like used in.

The elliptical polarizing plate of the present invention can be used in various display devices, particularly optical displays.
The display device is a device having a display element, and includes a light emitting element or a light emitting device as a light emitting source. The display devices include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a flexible image display device, a touch panel display device, an electron emission display device (for example, an electric field emission display device (FED)). Surface electric field emission display device (SED)), electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection type display device (for example, grating light valve (GLV) display device, digital micromirror device (DMD)) ), A piezoelectric ceramic display, and the like. The liquid crystal display device includes a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct-view type liquid crystal display device, and a projection type liquid crystal display device. These display devices may be display devices that display two-dimensional images, or three-dimensional display devices that display three-dimensional images. In particular, the elliptical polarizing plate of the present invention. Can be suitably used for an organic electroluminescence (EL) display device and an inorganic electroluminescence (EL) display device. These display devices (optical displays) are provided with the elliptical polarizing plate of the present invention having excellent optical characteristics. , Good image display characteristics can be exhibited.

The flexible image display device having the elliptical polarizing plate of the present invention preferably further includes a window and a touch panel touch sensor.
The flexible image display device is composed of, for example, a laminated body for a flexible image display device and an organic EL display panel, and the laminated body for the flexible image display device is arranged on the visual side with respect to the organic EL display panel and is configured to be bendable. Has been done. The laminated body for a flexible image display device may include a window, a touch panel touch sensor, and the like in addition to the elliptical polarizing plate of the present invention described above. The stacking order thereof is arbitrary, but it is preferable that they are stacked in the order of the window, the elliptical polarizing plate, and the touch panel touch sensor, or in the order of the window, the touch panel touch sensor, and the elliptical polarizing plate from the visual side.

The presence of an elliptical polarizing plate on the visual side of the touch panel touch sensor is preferable because the pattern of the touch panel touch sensor is less likely to be visually recognized and the visibility of the displayed image is improved. Each member can be laminated using an adhesive, an adhesive, or the like. Further, the laminated body for a flexible image display device can be provided with a light-shielding pattern formed on at least one surface of any one of the windows, the elliptical polarizing plate, and the touch panel touch sensor.

The window is arranged on the visual side of the flexible image display device, and plays a role of protecting other components from external impacts or environmental changes such as temperature and humidity. Conventionally, glass has been used as such a protective layer, but a window in a flexible image display device is not rigid and hard like glass, but has flexible characteristics. The window is made of a flexible transparent substrate and may include a hard coat layer on at least one surface.

The transparent substrate preferably has a visible light transmittance of 70% or more, and more preferably 80% or more. Any transparent polymer film can be used as the transparent substrate. Of these, polyamide films, polyamideimide films or polyimide films, polyester films, olefin films, acrylic films, and cellulose films, which are excellent in transparency and heat resistance, are preferable. It is also preferable to disperse inorganic particles such as silica, organic fine particles, rubber particles and the like in the polymer film.

The thickness of the transparent substrate is preferably 5 to 200 μm, more preferably 20 to 100 μm.

A hard coat layer may be provided on at least one surface of the transparent base material constituting the window. The thickness of the hard coat layer is not particularly limited and may be, for example, 2 to 100 μm. When the thickness of the hard coat layer is within the above range, it is easy to secure sufficient impact resistance, scratch resistance and bending resistance.

The hard coat layer can be formed by curing a composition for forming a hard coat containing a reactive material that forms a crosslinked structure by irradiating with active energy rays or heat energy, but those by curing with active energy rays are preferable. .. An active energy ray is defined as an energy ray capable of decomposing a compound that generates an active species to generate an active species. Examples of the active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays and electron rays, and ultraviolet rays are particularly preferable. The composition for forming a hard coat usually contains at least one compound of a radically polymerizable compound and a cationically polymerizable compound, and a polymerization initiator. The radically polymerizable compound, the cationically polymerizable compound and the polymerization initiator are not particularly limited, and conventionally known ones can be mentioned. The hard coat composition can further comprise one or more selected from the group consisting of solvents and additives. The solvent is not limited to one known as a solvent for a composition for forming a hard coat in the field of optical films, as long as it can dissolve or disperse the polymerizable compound or the polymerization initiator. Can be used. Examples of the additive include inorganic particles, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents and the like.

The touch panel touch sensor is used as an input means. As the touch panel touch sensor, various types such as a resistive film method, a surface acoustic wave method, an infrared method, an electromagnetic induction method, and a capacitance method have been proposed, and any method may be used. Of these, the capacitance method is preferable. The capacitive touch panel touch sensor is divided into an active region and an inactive region located outside the active region. The active area is an area corresponding to the area where the screen is displayed on the display panel (display unit), the area where the user's touch is sensed, and the inactive area is the area where the screen is not displayed on the display device (non-active area). This is the area corresponding to the display unit). The touch panel touch sensor has a substrate having flexible characteristics; a sensing pattern formed in an active region of the substrate; and an external drive circuit formed in an inactive region of the substrate via the sensing pattern and a pad portion. Each sensing line for connecting can be included.

The substrate having flexible properties, the sensing pattern, and each sensing line are not particularly limited, and materials applicable to each technical field can be selected.

As the substrate having flexible characteristics, for example, a substrate made of the same material as the transparent substrate of the window can be used. The substrate of the touch panel touch sensor preferably has a toughness of 2,000 MPa% or more from the viewpoint of suppressing cracks in the touch panel touch sensor, and more preferably a toughness of 2,000 MPa% to 30,000 MPa%. Here, toughness is defined as the lower area of the curve to the fracture point by the stress-strain curve obtained through the tensile experiment of the polymer material.

Each layer (window, elliptical polarizing plate, touch panel touch sensor) forming the laminate for the flexible image display device and the film member (polarizing film, retardation film, etc.) constituting each layer can be formed by an adhesive. .. Adhesives include water-based adhesives, organic solvent-based adhesives, solvent-free adhesives, solid adhesives, solvent volatilization adhesives, moisture-curable adhesives, heat-curable adhesives, anaerobic curable adhesives, and active energy rays. General-purpose adhesives such as curable adhesives, hardener-mixed adhesives, heat-melt adhesives, pressure-sensitive adhesives (adhesives), and re-wet adhesives can be used. Of these, water-based solvent volatilization type adhesives, active energy ray-curable adhesives, and pressure-sensitive adhesives are preferably used. The thickness of the adhesive layer can be appropriately adjusted according to the required adhesive strength and the like, but is usually 0.01 μm to 500 μm, preferably 0.1 μm to 300 μm. When a plurality of adhesive layers are present in the laminate for a flexible image display device, the type and thickness of the adhesives constituting each adhesive layer may be the same or different.

Hereinafter, the present invention will be described in more detail with reference to Examples. Unless otherwise specified, "%" and "part" in the example mean mass% and parts by mass, respectively.

1. 1. Preparation of polymerizable liquid crystal compound and liquid crystal mixture Production Example 1: Production of polymerizable liquid crystal compound represented by the formula (A-1) The polymerizable liquid crystal compound represented by the following formula (A-1) (hereinafter, "polymerizable") A liquid crystal compound (A-1) ”) was synthesized according to the following scheme.

11.02 g of compound (E-1) synthesized with reference to Patent Document (Japanese Patent Laid-Open No. 2010-31223) with a nitrogen atmosphere in a 100 mL-four-necked flask equipped with a Dimroth condenser and a thermometer, Patent Document (Japanese Patent Laid-Open No. 2010-31223). Compound (D-1) synthesized with reference to 2011-207765) 4.00 g, DMAP (manufactured by Wako Pure Chemical Industries, Ltd.) 0.02 g, BHT (manufactured by Wako Pure Chemical Industries, Ltd.) 0.20 g, and After adding 58 g of chloroform (manufactured by Kanto Chemical Industries, Ltd.) and mixing, further add 4.05 g of IPC (manufactured by Wako Pure Chemical Industries, Ltd.) using a dropping funnel, and react these at 0 ° C. overnight. I let you. After completion of the reaction, insoluble components were removed by filtration. The obtained chloroform solution was added dropwise to acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) having a weight three times the weight of chloroform contained in the solution to precipitate a solid. Subsequently, the precipitated solid was taken out by filtration, washed with 20 g of acetonitrile three times, and then dried under reduced pressure at 30 ° C. to obtain 11.43 g of the polymerizable liquid crystal compound (A-1). The yield of the polymerizable liquid crystal compound (A-1) was 80% based on the compound (D-1).

特許文献（特開２０１０−３１２２３）を参考に、ｔｒａｎｓ−１，４―シクロヘキサンジカルボン酸をｃｉｓ−１，４―シクロヘキサンジカルボン酸に変更して化合物（Ｅ−２）で表される混合物を２７．０２ｇ合成した。得られた化合物（Ｅ−２）と化合物（Ｅ−１）を１０／９０で混合したものを用いて、製造例１の化合物（Ｅ−１）を、化合物（Ｅ−２）と化合物（Ｅ−１）との前記混合物に変更して合成を行うことにより、液晶混合物（Ａ’）を１０．５７ｇ得た。得られた液晶混合物（Ａ’）をＨＰＬＣ測定にて分析した結果、該液晶混合物は、上記化合物（Ａ−１）、化合物（Ａ−２）および化合物（Ａ−３）を含んでおり、上記化合物（Ａ−２）および化合物（Ａ−３）のピーク面積の合計は化合物（Ａ−１）、化合物（Ａ−２）および化合物（Ａ−３）の全ピーク面積１００％に対して３．００％であった。 Production Example 2: Production of Liquid Crystal Mixture (A') A liquid crystal mixture containing a polymerizable liquid crystal compound represented by the following formulas (A-1) to (A-3) (hereinafter, also referred to as "liquid crystal mixture (A')". ) Was synthesized according to the following scheme.

With reference to Patent Document (Japanese Patent Laid-Open No. 2010-31223), trans-1,4-cyclohexanedicarboxylic acid was changed to cis-1,4-cyclohexanedicarboxylic acid, and the mixture represented by compound (E-2) was prepared in 27. 02 g was synthesized. Using a mixture of the obtained compound (E-2) and compound (E-1) at 10/90, the compound (E-1) of Production Example 1 was mixed with the compound (E-2) and the compound (E-1). By changing to the above-mentioned mixture with -1) and synthesizing, 10.57 g of a liquid crystal mixture (A') was obtained. As a result of analyzing the obtained liquid crystal mixture (A') by HPLC measurement, the liquid crystal mixture contains the above compound (A-1), compound (A-2) and compound (A-3). The total peak area of compound (A-2) and compound (A-3) is 3. It was 00%.

[HLPC measurement]
The HPLC measurement may be carried out under any conditions as long as the peak derived from the polymerizable liquid crystal compound can be separated. The HPLC measurement conditions used for the analysis in the examples and comparative examples of the present invention are shown below.
(Measurement condition)
Measuring device: HPLC LC-10AT (manufactured by Shimadzu Corporation)
Column: L-Column ODS (inner diameter 3.0 mm, length 150 mm, particle size 3 μm)
Temperature: 40 ° C
Mobile phase A: 0.1% (v / v) -TFA / water Mobile phase B: 0.1% (v / v) -TFA / acetonitrile gradient: 0min 70% -B
30min 100% -B
60min 100% -B
60.01min 70% -B
75min 70% -B
Flow velocity: 0.5 mL / min
Injection volume: 5 μL
Detection wavelength: 254 nm

Production Example 3: Production of a polymerizable liquid crystal compound represented by the formula (B-1) A polymerizable liquid crystal compound represented by the following formula (B-1) (hereinafter referred to as “polymerizable liquid crystal compound (B-1)”). ) Was synthesized according to the following scheme.

The reaction was carried out in the same manner as in Production Example 1 except that the compound (D-2) was changed to 4.22 g to obtain 11.75 g of the polymerizable liquid crystal compound (B-1). The yield of the polymerizable liquid crystal compound (B-1) was 81% based on the compound (D-2).

Production Example 4: Production of Liquid Crystal Mixture (B') A liquid crystal mixture containing a polymerizable liquid crystal compound represented by the following formulas (B-1) to (B-3) (hereinafter, also referred to as "liquid crystal mixture (B')". ) Was synthesized according to the following scheme.

The reaction was carried out in the same manner as in Production Example 2 except that the compound (D-2) was changed to 4.22 g to obtain 10.88 g of the liquid crystal mixture (B'). As a result of analyzing the obtained liquid crystal mixture (B') under the above HPLC measurement conditions, the liquid crystal mixture contains the above compound (B-1), compound (B-2) and compound (B-3). The total peak area of the compound (B-2) and the compound (B-3) is 100% of the total peak area of the compound (B-1), the compound (B-2) and the compound (B-3). It was 5.23%.

Production Example 5: Production of Liquid Crystal Mixture (C') All described in Production Example 4 except that the mixing ratio of the compound (E-2) and the compound (E-1) used in Production Example 4 was changed to 20/80. The reaction was carried out in the same manner as in the method to obtain 10.44 g of a liquid crystal mixture (C'). As a result of analyzing the obtained liquid crystal mixture (C') under the above HPLC measurement conditions, the liquid crystal mixture contains the above compound (B-1), compound (B-2) and compound (B-3). The total peak area of the compound (B-2) and the compound (B-3) is 100% of the total peak area of the compound (B-1), the compound (B-2) and the compound (B-3). It was 12.3%.
In Production Examples 1 to 5, the compound (A-1) and the compound (B-1) correspond to the polymerizable liquid crystal compound (1-1) in the present invention, respectively, and the compound (A-2) and the compound (A-2) Compound (B-2) corresponds to the polymerizable liquid crystal compound (1-2a) in the present invention, respectively, and compound (A-3) and compound (B-3) correspond to the polymerizable liquid crystal compound in the present invention, respectively. Corresponds to (1-2b).

2. Polymerizable liquid crystal compounds / mixtures of Examples and Comparative Examples (1) Example 1: Preparation of liquid crystal mixture (1) The liquid crystal mixture (A') obtained in Production Example 2 and the polymerizable property obtained in Production Example 1 The liquid crystal compound (A-1) is mixed with the compound (A-1), the compound (A-2), and the compound (A-2) with respect to 100% of the total peak area of the compound (A-3) under the above HPLC measurement conditions. The compound (A-3) was mixed so as to have a peak area of 0.1% to obtain a liquid crystal mixture (1).

(2) Example 2: The liquid crystal mixture (A') obtained in Production Example 2 was used as the liquid crystal mixture (2).

(3) Example 3: Preparation of Liquid Crystal Mixture (4) The liquid crystal mixture (B') obtained in Production Example 4 and the polymerizable liquid crystal compound (B-1) obtained in Production Example 3 were measured by HPLC as described above. Under the conditions, the peak area of compound (B-2) and compound (B-3) is 0.4 with respect to 100% of the total peak area of compound (B-1), compound (B-2) and compound (B-3). The mixture was mixed so as to be%, and a liquid crystal mixture (3) was obtained.

(4) Example 4: The liquid crystal mixture (B') obtained in Production Example 4 was used as the liquid crystal mixture (4).

(5) Comparative Example 1: The polymerizable liquid crystal compound (A-1) obtained in Production Example 1 was designated as the liquid crystal compound (1).

(6) Comparative Example 2: The polymerizable liquid crystal compound (B-1) obtained in Production Example 3 was designated as the liquid crystal compound (2).

(7) Comparative Example 3: The liquid crystal mixture (C') obtained in Production Example 5 was designated as the liquid crystal mixture (5).

3. 3. Evaluation of Solubility N-methylpyrrolidone (NMP) and a stirrer were placed in a vial tube, and the mixture was prepared in Examples 1 to 4 and Comparative Examples 1 to 3 above while stirring with a magnetic stirrer (HS-30DN, AS ONE). The liquid crystal mixtures (1) to (5) and the liquid crystal compounds (1) and (2) were added until undissolved residue was visually confirmed. When the undissolved residue was confirmed, the solubility of each liquid crystal mixture and the polymerizable liquid crystal compound in NMP was determined (weight of each liquid crystal mixture and polymerizable liquid crystal compound) / (weight of each liquid crystal mixture and polymerizable liquid crystal compound + weight of NMP). ) As a weight percent concentration. The results are shown in Table 2.

溶剤（９５部）：シクロペンタノン 4. Evaluation of Orientation Defects (1) Preparation of Optical Film (Differential Film) An optical film (phase difference film) was manufactured according to the following procedure.
(I) Preparation of composition for forming a photo-alignment film The following components were mixed, and the obtained mixture was stirred at 80 ° C. for 1 hour to obtain a composition for forming a photo-alignment film.
Photo-oriented material represented by the following formula (5 parts) (number average molecular weight about 28,000):

Solvent (95 parts): Cyclopentanone

(Ii) Preparation of Polymerizable Liquid Crystal Composition A cycloolefin polymer film (COP) (ZF-14, manufactured by Nippon Zeon Corporation) is output using a corona treatment device (AGF-B10, manufactured by Kasuga Electric Co., Ltd.). The treatment was performed once under the conditions of 3 kW and a processing speed of 3 m / min. The composition for forming a photoalignment film was applied to a corona-treated surface with a bar coater, dried at 80 ° C. for 1 minute, and used with a polarized UV irradiation device (SPOT CURE SP-7; manufactured by Ushio, Inc.). Polarized UV exposure was performed with an integrated light intensity of 100 mJ / cm ^2. The film thickness of the obtained photoalignment film was measured with a laser microscope (LEXT, manufactured by Olympus Corporation) and found to be 100 nm.
Subsequently, the liquid crystal mixture (1) prepared in Example 1 was charged into a vial tube, a photopolymerization initiator, a leveling agent, a polymerization inhibitor and a solvent were charged according to the composition shown in Table 1, and a carousel was used. The mixture was stirred at 80 ° C. for 30 minutes to obtain a polymerizable liquid crystal composition.
The amount of the solvent blended was set so that the mass% of the liquid crystal mixture was 13% with respect to the total amount of the polymerizable liquid crystal composition (solution).

Polymerization Initiator: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one (Irgacure 369; manufactured by BASF Japan Ltd.)
Leveling agent: Polyacrylate compound (BYK-361N; manufactured by Big Chemie Japan)
Polymerization inhibitor: BHT (manufactured by Wako Pure Chemical Industries, Ltd.)
Solvent: N-methylpyrrolidone (NMP; manufactured by Kanto Chemical Co., Inc.)

(Iii) Preparation of Optical Film The obtained polymerizable liquid crystal composition was applied onto an alignment film using a bar coater, dried at 120 ° C. for 1 minute, and then a high-pressure mercury lamp (Unicure VB-15201BY-A, Ushio). An optical film was prepared by irradiating ultraviolet rays (in a nitrogen atmosphere, wavelength: 365 nm, integrated light intensity at wavelength 365 nm: 1000 mJ / cm ^{2) using (manufactured by Denki Co., Ltd.).}
Further, instead of the liquid crystal mixture (1), the liquid crystal mixtures (2) to (5), the liquid crystal compounds (1) and (2) prepared in Examples 2 to 5 and Comparative Examples 1 to 3 were used, respectively, and Table 1 A polymerizable liquid crystal composition and an optical film were prepared in the same manner as described above except that a photopolymerization initiator, a leveling agent, a polymerization inhibitor and a solvent were added according to the composition described in 1.

(2) Evaluation of orientation defects The obtained optical film was cut out in 10 cm squares, and the number of orientation defects on the screen was visually confirmed using a polarizing microscope (LEXT, manufactured by Olympus Corporation) and evaluated according to the following evaluation criteria. bottom. The results are shown in Table 1.
(Evaluation criteria for orientation defects)
1: Orientation defects occur on the entire surface (> 100)
2: 11-100 pieces 3: 1-10 pieces 4: No defects

As shown in Table 1, the polymerizable liquid crystal composition according to the present invention (Examples 1 to 4) contains a specific amount of the polymerizable liquid crystal compound (1-2) with respect to the polymerizable liquid crystal compound (1-1). As a result, it was confirmed that the solubility of the polymerizable liquid crystal compound (1-1) in the solvent can be improved while suppressing the orientation defect.

Claims (12)

It has the same molecular weight but different molecular structures, and the formula (1):

[In equation (1),
Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent.
^{D 1, D 2, E 1} , E 2, B 1 and ^{B 2} are each _{^{independently, -CR 11 R 12 -, -}} CH 2 -CH 2 -, - O -, - S -, - CO-O -, -O-CO-, -O-CO-O-, -C (= S) -O-, -O-C (= S)-, -OC (= S) -O-, -CO _{^{-NR 11 -, - NR 11 -CO}} -, - O-CH 2 -, - CH 2 -O -, - S-CH 2 -, - CH 2 -S- or a single ^{bond, R 11} and ^{R 12} Independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
G ¹ and G ² represent 1,4-cyclohexanediyl groups, respectively.
A ¹ and A ² independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. The group and the hydrogen atom contained in the aromatic hydrocarbon group may be ^{substituted with a halogen atom, -R 13} , -OR ¹³ , a cyano group or a nitro group, where R ¹³ is an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.
F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be ^{substituted with −OR 14} or a halogen atom, and R ¹⁴ Represents an alkyl group having 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and −CH ₂ − contained in the alkanediyl group is −O− or −. It may be replaced by CO-,
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group (provided that ^{at least one of P 1} and P ² is a polymerizable group)].
A polymerizable liquid crystal composition containing at least two kinds of polymerizable liquid crystal compounds represented by.
As the polymerizable liquid crystal compound ^{, the polymerizable liquid crystal compound (1-1) in which G 1} and G ² in the formula (1) are 1,4-trans-cyclohexanediyl groups, respectively, and the polymerizable liquid crystal compound (1-1). 1-1) and a polymerizable liquid crystal compound (1-2) having a different molecular structure only that at least one ^{of G 1} and G ^{2 in the formula (1) is a 1,4-cis-cyclohexanediyl group is included.} ,
The ratio of the peak area of the polymerizable liquid crystal compound (1-2) to the total peak area of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) measured by liquid chromatography is 0. A polymerizable liquid crystal composition having a content of 01% or more and 10% or less. The polymerizable liquid crystal compound (1-2) ^{is the polymerizable liquid crystal compound (1-2a) in which either G 1} or G ² in the formula (1) is a 1,4-cis-cyclohexanediyl group, and the formula (1-2a). The polymerizable liquid crystal composition according to claim 1, wherein both ^{G 1} and G ² in 1) contain a polymerizable liquid crystal compound (1-2b) in which both G 1 and G 2 are 1,4-cis-cyclohexanediyl groups. The polymerizable liquid crystal composition according to claim 1 or 2, wherein Ar in the formula (1) is a group represented by any of the formulas (2-1) to (2-5).

[During the ceremony,
* Represents the joint with ^{D 1} or D ^2;
Q ¹ is -S -, - O-or ^{-NR 15} - ^{represents, R 15} represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom or a substituent,
Q ² is an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom or a substituent;
W ¹ and ^{W 2} are each independently, -O -, - S -, - CO -, - NR 15 - ^{represents, R 15} is a hydrogen atom or a substituent and which may number 1 to 6 carbons have Represents an alkyl group;
Y ¹ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and the alkyl group, the aromatic hydrocarbon group or the aromatic complex. The hydrogen atom contained in the ring group may be substituted with a halogen atom, and -CH _2- contained in the alkyl group is -O-, -CO-, -O-CO- or -CO-O-. May be replaced with
Y ² represents an alkyl group having 1 to 12 carbon atoms which may have a CN group or a substituent, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom and is contained in the alkyl group. -CH _2- may be replaced with -O-, -CO-, -O-CO- or -CO-O-;
Z ¹ , Z ² and Z ³ are independently hydrogen atoms or aliphatic hydrocarbon groups or alkoxy groups having 1 to 20 carbon atoms, alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and monovalent carbon atoms. Represents 6 to 20 aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -NR ¹⁵ R ¹⁶ or -SR ¹⁵ , where Z ¹ and Z ² combine with each other to form an aromatic ring or aromatic heterocycle. May be formed, R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Ax represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and Ay may have a hydrogen atom or a substituent. Represents an organic group having 2 to 30 carbon atoms, having a good alkyl group having 1 to 6 carbon atoms or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and Ax and Ay. May combine to form a ring;
Y ³ and Y ⁴ are independently expressed by the following equation (Y-1):

[In formula (Y-1),
M ¹ represents an alkyl group having 1 to 6 carbon hydrogen atom or a C, the alkyl group may be substituted by one or more substituents X ^3, substituents X ³ is a fluorine atom, a chlorine atom, Bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethyl A silyl group, a thioisocyano group, or one -CH _2- or two or more non-adjacent -CH ₂ --independently -O-, -S-, -CO-, -COO-,- OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO- , -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- may be replaced with a linear or linear group having 1 to 20 carbon atoms. It represents a branched alkyl group, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or may be a group represented by ^{−B 11} −F ¹¹ −P ^{11. B 11} , F ¹¹ and P ¹¹ are defined in the same manner as ^{B 1} , F ¹ and P ^{1 in} the above formula (1), respectively, and are different even if they are the same ^{as the above B 1} , F ¹ and P ^{1, respectively.} May;
U ¹ represents an organic group having 2 to 30 carbon atoms having an aromatic hydrocarbon group, and any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom, and the aromatic hydrocarbon group is , it may be substituted by one or more of the substituents X ^3;
T ¹ is, -O -, - S -, - COO -, - OCO -, - OCO-O -, - NU 2 -, - N = CU 2 -, - CO-NU 2 -, - OCO-NU 2 -Or -O-NU ^2- , where U ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, and an aromatic hydrocarbon. An organic group having 2 to 30 carbon atoms having a group (any carbon atom of the aromatic hydrocarbon group may be substituted with a hetero atom), or (E ^11- A ¹¹ ) _q- B ^12- F ¹² represents -P ^12, the alkyl group, cycloalkyl group, each cycloalkenyl group and aromatic hydrocarbon group may be substituted by or is one or more substituents X ³ is unsubstituted, the alkyl group may be substituted by the cycloalkyl group or cycloalkenyl group, one -CH 2 in the alkyl group _- or non-adjacent two or more -CH 2 _- are each independently - O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO _2- , -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or may be replaced by -C≡C-, the cycloalkyl group or cycloalkenyl one -CH in group ₂ - or non-adjacent two or more -CH ₂ - are each independently -O- , -CO-, -COO-, -OCO- or -O-CO-O-, and E ¹¹ , A ¹¹ , B ¹² , F ¹² and P ¹² , respectively, in equation (1). E ¹ , A ¹ , B ¹ , F ¹ and P ¹ , respectively, which may be the same as or different from the ^{above E 1} , A ¹ , B ¹ , F ¹ and P ^{1, respectively, q} Represents an integer from 0 to 4, ^{and when a plurality of E 11} and / or A ¹¹ exist, they may be the same or different from each other, and U ¹ and U ² are combined to form a ring. May]
Represents a group selected from. ] The polymerizable liquid crystal composition according to any one of claims 1 to 3, wherein ^{A 1} and A ² in the formula (1) are independently 1,4-cyclohexanediyl groups or 1,4-phenylenediyl groups, respectively. thing. The polymerizable liquid crystal composition according to any one of claims 1 to 4, wherein ^{P 1} and P ² in the formula (1) are acryloyl groups, respectively. The polymerizable liquid crystal composition according to any one of claims 1 to 5, further comprising a photopolymerization initiator. The polymerizable liquid crystal composition according to any one of claims 1 to 6, further comprising an organic solvent. A retardation film comprising a liquid crystal cured film which is a cured product of the polymerizable liquid crystal composition according to any one of claims 1 to 7. The liquid crystal cured film has the formula (i):
0.75 ≤ Re (450) / Re (550) <1.00 (i)
[In formula (i), Re (λ) represents the in-plane retardation value of the liquid crystal cured film at the wavelength λ nm]
The retardation film according to claim 8. An elliptical polarizing plate including the retardation film according to claim 8 or 9. An optical display including the elliptical polarizing plate according to claim 10. A flexible image display device including the elliptical polarizing plate according to claim 10.