JP6497241B2 - Polymerizable liquid crystal compound, composition and polymer thereof - Google Patents

Description

  The present invention relates to a polymerizable liquid crystal compound containing a skeleton having a substituent at the β-position of styrene, a polymerizable liquid crystal composition containing the compound, a polymer obtained from the composition, an optically anisotropic film, and their Regarding usage.

  Optical compensation technology using a retardation plate is known for the purpose of widening the viewing angle and contrast of liquid crystal displays (LCDs), and as such a retardation plate, a polymer film is generally stretched. By doing so, what is called a stretched film in which birefringence is controlled is used.

In recent years, liquid crystal compounds having a polymerizable group have been used for optically anisotropic films exhibiting birefringence (optical anisotropy) such as reflective polarizing plates and retardation plates. This compound exhibits birefringence in a liquid crystal state, and its orientation is fixed by polymerization. Examples of the fixed alignment state of the polymer include homogeneous (horizontal alignment), tilt (tilt alignment), homeotropic (vertical alignment), and twist (twist alignment).
The retardation plate obtained by using a polymerizable liquid crystal compound exhibits a large birefringence compared to a stretched film that has been used conventionally, so that it can be thinned and can be directly applied to a substrate. Therefore, an adhesive layer is unnecessary. Further, since a strong network can be constructed, it has excellent characteristics such as a small change rate of the characteristics with respect to the external environment. Furthermore, since the three-dimensional refractive index can be easily controlled by controlling the orientation of the liquid crystal, the moldability is also excellent.

  An optically anisotropic film having homogeneous orientation can be used as, for example, a composite retardation plate or a circularly polarizing plate by combining with a half-wave plate, a quarter-wave plate, or a film having other optical functions. (See Patent Document 1).

An optically anisotropic film having homeotropic orientation has an optical axis direction in the _nz direction,
Since the refractive index in the optical axis direction is larger than the refractive index in the orthogonal direction, the refractive index ellipsoid is classified as a positive C-plate. This positive C-plate can be applied to optical compensation such as a horizontally aligned liquid crystal mode, so-called IPS (In-Plane Switching) mode, for example, improvement of viewing angle characteristics of a polarizing plate by combining with a film having other optical functions. (Non-patent documents 1 to 3, Patent documents 2 and 3).

  Since the optical properties necessary for the optically anisotropic film vary depending on the application and purpose, various polymerizable liquid crystal compounds have been developed as compounds to be used. Moreover, since it is often difficult to control the above-mentioned anisotropy and orientation characteristics alone, it is used as a polymerizable liquid crystal composition in combination with various compounds.

Such a polymerizable liquid crystal composition is dissolved in an organic solvent for the purpose of adjusting coating properties and used as an ink. In order to produce a film having optical anisotropy using a polymerizable liquid crystal composition, a polymerizable liquid crystal compound, a photopolymerization initiator, a surfactant, etc. are dissolved in an organic solvent, and the solution viscosity, leveling property, etc. are adjusted. Prepare the adjusted ink. This ink is applied to the substrate, the solvent is dried, and the polymerizable liquid crystal composition is aligned on the substrate. At this time, it is easy to obtain a uniform alignment state by using a substrate subjected to alignment treatment. Next, the polymer is irradiated with ultraviolet rays to fix the alignment state. Usually, after the solvent is removed by drying, the polymerization is carried out at room temperature until polymerization, and during this time, a uniform liquid crystal state must be maintained without precipitation of crystals and the like. Therefore, the polymerizable liquid crystal compound needs to have good compatibility with other compounds and high solubility in an organic solvent. As the organic solvent, it is preferable to use a highly safe organic solvent in consideration of environmental impacts and influence on the human body. The polymerizable liquid crystal composition needs to maintain a liquid crystal phase for a long time at around room temperature after removing the solvent.

  In addition, the polymer obtained from the polymerizable liquid crystal composition has high transparency, mechanical strength, high adhesion to the substrate, low shrinkage, and high heat resistance in addition to the optical anisotropy characteristics. Also, characteristics such as high chemical resistance are required.

In an optically anisotropic layer formed of rod-like molecules, usually two refractive indexes ne (abnormal refractive index in a direction parallel to the molecular long axis) and no (normal in a direction perpendicular to the molecular long axis) of the anisotropic molecule (Refractive index) decreases as the wavelength increases. At this time, since ne has a larger refractive index change rate with respect to the wavelength than no, the birefringence (Δn = ne−no) becomes smaller as the applied wavelength becomes larger. On the other hand, in a display device such as a liquid crystal display (LCD), the light source is white light composed of light having a wavelength of about 380 to 800 nm. A normal optical anisotropic layer is used to form a 1 / 2λ or 1 / 4λ plate. When designing and applying, the above-mentioned wavelength dispersion causes a phase shift as the distance from the center wavelength increases, and the polarization state changes accordingly, which causes problems such as the color of light. In order to prevent this problem, it is necessary to control the chromatic dispersion so that the designed phase difference is achieved at each wavelength, a material having a low birefringence dependency (low wavelength dispersion characteristics), and even a wavelength. Therefore, there is a demand for a material having an increased birefringence (inverse wavelength dispersion characteristic) as the value increases.

  In recent years, in an organic EL display (OLED), it is known to use a circularly polarizing plate composed of a quarter-wave plate and a polarizer on the viewing side for the purpose of preventing external light reflection (Patent Document 4). Even in such an application, the phase difference due to the wavelength dispersion characteristic changes the polarization state. For this reason, there arises a problem that the antireflection function cannot be effectively obtained for all wavelengths in the visible region, so that a material having reverse wavelength dispersion characteristics is required.

In order to obtain an optically anisotropic layer having reverse wavelength dispersion characteristics, methods have been proposed in which two retardation layers are laminated with an angle in the direction of the alignment axis (Patent Documents 5 and 6). . However, in such a laminate, two retardation layers are required, and the angle of anisotropy between the two retardation layers needs to be adjusted. There are problems such as complexity and an increase in the thickness of the optically anisotropic layer.
In recent years, there has been a demand for an optically anisotropic layer having reverse wavelength dispersion without being laminated in order to solve such problems, and polymerizable liquid crystalline compounds having reverse wavelength dispersion characteristics have been proposed (Patent Documents). 7-11).

  However, since the compound described in Patent Document 7 has a low birefringence, it is necessary to increase the film thickness in order to obtain a desired phase difference, and since the aspect ratio is small, it is difficult to control the alignment uniformity. Since the synthetic route is long, there are concerns about problems such as difficulty in manufacturing. The compounds described in Patent Documents 8 to 11 have a high temperature range and clearing point of the liquid crystal phase, and require complicated steps such as polymerization by irradiation with ultraviolet rays while applying temperature. In addition, the compounds described in Patent Documents 7 to 11 generally have low solubility in organic solvents, and there is a problem that the manufacturing margin is narrow due to a short liquid crystal phase retention time at room temperature, so improvement is required. .

JP 2002-372623 A International Publication No. 2005/38517 US Patent Application Publication No. 2006/182900 Japanese Patent Laid-Open No. 8-322138 JP-A-10-68816 JP 2001-4837 A Special table 2010-522893 JP 2009-179563 A International Publication No. 2012/06001 JP 2005-289980 A JP 2010-31223 A

M.S.Park et al, IDW '04 FMC8-4 M.Nakata et al, SID '06 P-58 K.J.Kim et al, SID '06 Digest p.1158-1161

  The present invention is easy to handle, can control wavelength dispersion characteristics without requiring complicated steps, and can easily produce an optically anisotropic film exhibiting low wavelength dispersion characteristics and reverse wavelength dispersion characteristics. An object of the present invention is to provide a polymerizable liquid crystal compound.

  As a result of intensive studies, the inventors have found that a specific polymerizable liquid crystal compound having a substituent at the β-position of styrene solves the above problems, and has completed the invention. That is, the present invention is as follows.

（式（１）中、
Ａ¹はそれぞれ独立して１，４−フェニレンまたは１，４−シクロへキシレンであり、こ
の１，４−フェニレンにおいて、少なくとも一つの水素はフッ素、塩素、トリフルオロメチル、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルコキシカルボニル、または炭素数１〜５のアルカノイルで置き換えられてもよく；
Ｚ¹はそれぞれ独立して単結合、−ＯＣＨ₂−、−ＣＨ₂Ｏ−、−ＣＯＯ−、−ＯＣＯ−、
−ＣＦ₂Ｏ−、−ＯＣＦ₂−、−ＣＨ₂ＣＨ₂−、−ＣＦ₂ＣＦ₂−、−ＯＣＨ₂ＣＨ₂Ｏ−、−ＣＨ₂ＣＨ₂ＣＯＯ−、−ＯＣＯＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ₂ＯＣＯ−、または−ＣＯＯＣＨ₂ＣＨ₂−であり；
Ｔ¹は水素またはメチルであり；
Ｔ²およびＴ³はそれぞれ独立してシアノ、炭素数１〜１０のアルコキシカルボニルまたは炭素数１〜１０のアルカノイルであり、Ｔ²とＴ³は互いに結合して環を形成してもよく；ｍはそれぞれ独立して１〜３の整数であり；
Ｙ¹はそれぞれ独立して単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−
であり；
Ｑ¹はそれぞれ独立して単結合または炭素数１〜２０のアルキレンであり、該アルキレン
において少なくとも一つの−ＣＨ₂−は−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換
えられてもよく；
ＰＧはそれぞれ独立して式（ＰＧ−１）〜式（ＰＧ−９）のいずれか１つで表される重合性の基である。）

（式（ＰＧ−１）〜式（ＰＧ−９）中、Ｒ¹はそれぞれ独立して水素、ハロゲン、メチル
、エチル、またはトリフルオロメチルである。なお、式（ＰＧ−１）〜（ＰＧ−９）中の米印（※）は、隣接するＱ¹と単結合する位置を示すものである。）
［２］ 式（１）のＴ²とＴ³が互いに結合して環を形成しており、以下の式（１−１）で表される、［１］に記載の重合性液晶化合物。

式（１−１）において、Ａ¹、Ｚ¹、Ｔ¹、ｍ、Ｙ¹、Ｑ¹およびＰＧは［１］に記載の式（
１）に記載の通りであり、Ｇは式（Ｇ−１）〜（Ｇ−１２）のいずれか１つで表される基である。

（式（Ｇ−１）〜（Ｇ−１２）中、Ｘ¹はそれぞれ−ＣＨ₂−、−ＣＯ−、−Ｏ−または−Ｓ−であり；Ｘ²はそれぞれ独立してＯまたはＳであり；Ｒ²は水素、炭素数１〜５のアルキル、炭素数１〜５のアルカノイルまたは置換基を有してもよいフェニルであり；少なくとも一つの水素はフッ素、塩素、シアノ、トリフルオロアセチル、トリフルオロメチル、置換基を有してもよいフェニル、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルコキシカルボニル、または炭素数１〜５のアルカノイルで置き換えられてもよい。なお、式（Ｇ−１）〜（Ｇ−１２）中の米印（※）は、二重結合のある炭素の位置を示すものである。）
［３］ Ａ¹のうち少なくとも一つが１，４−シクロへキシレンである、［１］または［
２］に記載の重合性液晶化合物。
［４］ ＰＧが以下の式（ＰＧ−１）で表される重合性の基である、［１］〜［３］のいずれかに記載の重合性液晶化合物。

（式（ＰＧ−１）中、Ｒ¹は水素またはメチルである。なお、式（ＰＧ−１）中の米印（
※）は、隣接するＱ¹と単結合する位置を示すものである。）
［５］ Ｚ¹のうち少なくとも一つが、−ＣＨ₂ＣＨ₂ＣＯＯ−または−ＯＣＯＣＨ₂ＣＨ₂
−である、［１］〜［４］のいずれかに記載の重合性液晶化合物。
［６］ ［１］〜［５］のいずれかに記載の重合性液晶化合物を少なくとも１つ含有する重合性液晶組成物。
［７］ ［１］〜［５］のいずれかに記載の重合性液晶化合物の含有量が、重合性液晶組成物の全量に対し、４重量％以上、５０重量％以下である、［６］に記載の重合性液晶組成物。
［８］ ［７］に記載の重合性液晶組成物に光を照射して得られる光学異方性フィルム。［９］ 液晶分子が基材に対し水平配向した状態で固定化した[８]に記載の光学異方性フィルム。
［１０］ 液晶分子が基材に対し垂直配向した状態で固定化した[８]に記載の光学異方性フィルム。
［１１］ 液晶分子が基材に対しツイスト配向した状態で固定化した[８]に記載の光学異方性フィルム。
［１２］ 液晶分子が基材に対し傾斜配向した状態で固定化した[８]に記載の光学異方性フィルム。
［１３］ 波長４５０ｎｍの光に対する複屈折率Δｎ（４５０）と波長５５０ｎｍの光に対する複屈折率Δｎ（５５０）が、Δｎ（４５０）／Δｎ（５５０）≦１．０５の関係を満たす、［８］〜［１２］のいずれかに記載の光学異方性フィルム。
［１４］ ［８］〜［１３］のいずれかに記載の光学異方性フィルムを有する偏光板。
［１５］ ［８］〜［１３］のいずれかに記載の光学異方性フィルムを有する表示素子。［１６］ ［１４］に記載の偏光板を有する表示素子。 [1] A polymerizable liquid crystal compound represented by the formula (1).

(In the formula (1),
A ¹ is each independently 1,4-phenylene or 1,4-cyclohexylene, and in this 1,4-phenylene, at least one hydrogen is fluorine, chlorine, trifluoromethyl, C 1-5. May be substituted with alkyl, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons, or alkanoyl having 1 to 5 carbons;
Z ¹ is each independently a single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—,
_{-CF 2 O -, - OCF 2} -, - CH 2 CH 2 -, - CF 2 CF 2 -, - OCH 2 CH 2 O -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH ₂ CH ₂ OCO—, or —COOCH ₂ CH ₂ —;
T ¹ is hydrogen or methyl;
T ² and T ³ are each independently cyano, alkoxycarbonyl having 1 to 10 carbons or alkanoyl having 1 to 10 carbons, and T ² and T ³ may be bonded to each other to form a ring; m Are each independently an integer from 1 to 3;
Y ¹ is independently a single bond, —O—, —COO—, —OCO—, or —OCOO—.
Is;
Each Q ¹ is independently a single bond or alkylene having 1 to 20 carbon atoms, and in the alkylene, at least one —CH ₂ — may be replaced by —O—, —COO—, or —OCO—;
PG is each independently a polymerizable group represented by any one of formulas (PG-1) to (PG-9). )

(In Formula (PG-1) to Formula (PG-9), each R ¹ is independently hydrogen, halogen, methyl, ethyl, or trifluoromethyl. In addition, Formulas (PG-1) to (PG- 9) asterisk in (※) is a diagram showing the adjacent Q ¹ and the position of a single bond.)
[2] The polymerizable liquid crystal compound according to [1], wherein T ² and T ^{3 in} the formula (1) are bonded to each other to form a ring and represented by the following formula (1-1).

In the formula (1-1), A ¹ , Z ¹ , T ¹ , m, Y ¹ , Q ¹ and PG are represented by the formula (1)
1), G is a group represented by any one of formulas (G-1) to (G-12).

(In formulas (G-1) to (G-12), X ¹ is —CH ₂ —, —CO—, —O— or —S—, respectively; X ² is independently O or S; R ² is hydrogen, alkyl having 1 to 5 carbon atoms, alkanoyl having 1 to 5 carbon atoms or optionally substituted phenyl; at least one hydrogen is fluorine, chlorine, cyano, trifluoroacetyl, trimethyl; Substituted with fluoromethyl, optionally substituted phenyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons, or alkanoyl having 1 to 5 carbons In addition, the rice symbol (*) in the formulas (G-1) to (G-12) indicates the position of carbon having a double bond.)
[3] At least one of A ¹ is 1,4-cyclohexylene, [1] or [
2].
[4] The polymerizable liquid crystal compound according to any one of [1] to [3], wherein PG is a polymerizable group represented by the following formula (PG-1).

(In the formula (PG-1), R ¹ is hydrogen or methyl.
*) Indicates a single bond position with the adjacent Q ¹ . )
[5] At least one of Z ¹ is —CH ₂ CH ₂ COO— or —OCOCH ₂ CH _2.
The polymerizable liquid crystal compound according to any one of [1] to [4], which is-.
[6] A polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound according to any one of [1] to [5].
[7] The content of the polymerizable liquid crystal compound according to any one of [1] to [5] is 4% by weight or more and 50% by weight or less with respect to the total amount of the polymerizable liquid crystal composition, [6] The polymerizable liquid crystal composition described in 1.
[8] An optically anisotropic film obtained by irradiating the polymerizable liquid crystal composition according to [7] with light. [9] The optically anisotropic film according to [8], wherein the liquid crystal molecules are fixed in a state of being horizontally aligned with respect to the substrate.
[10] The optically anisotropic film according to [8], wherein the liquid crystal molecules are fixed in a state of being vertically aligned with respect to the substrate.
[11] The optically anisotropic film according to [8], wherein the liquid crystal molecules are fixed in a state where the liquid crystal molecules are twisted with respect to the substrate.
[12] The optically anisotropic film according to [8], wherein the liquid crystal molecules are fixed in a state in which the liquid crystal molecules are inclined with respect to the substrate.
[13] The birefringence index Δn (450) for light having a wavelength of 450 nm and the birefringence index Δn (550) for light having a wavelength of 550 nm satisfy the relationship Δn (450) / Δn (550) ≦ 1.05. ] The optically anisotropic film according to any one of [12] to [12].
[14] A polarizing plate having the optically anisotropic film according to any one of [8] to [13].
[15] A display device having the optically anisotropic film according to any one of [8] to [13]. [16] A display device having the polarizing plate according to [14].

  According to the present invention, it is possible to control the wavelength dispersion characteristics, and it is possible to produce an optically anisotropic film exhibiting low wavelength dispersion characteristics and reverse wavelength dispersion characteristics.

Terms used in this specification are as follows. First, the meaning of the term “liquid crystalline” is not limited to having a liquid crystal phase. That is, a liquid crystal compound is a generic term for a compound having a liquid crystal phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition. The liquid crystal phase is a nematic phase, a smectic phase, a cholesteric phase or the like, and often means a nematic phase. The liquid crystal lower limit temperature is a lower limit temperature indicating a liquid crystal phase, and is a temperature at which the liquid crystal phase transitions to a crystal. Polymerizability means the ability of a monomer to polymerize and give a polymer by means such as light, heat, or catalyst. In the liquid crystal compound, a liquid crystal compound having a polymerizable group is referred to as a polymerizable liquid crystal compound, and the polymerizable liquid crystal compound is included in the liquid crystal compound. The polymerizable compound means a compound having a polymerizable group that does not exhibit liquid crystallinity. A case where a compound has one polymerizable group may be referred to as a monofunctional or monofunctional compound. Moreover, when a compound has two or more polymeric groups, it may be called by the name corresponding to the number of polyfunctionality or polymeric groups. The compound represented by formula (1) may be referred to as compound (1). The compounds represented by other formulas may be referred to according to the same simplified method.

The term “at least one” used in describing the structure of a compound means that there is at least one of the number as well as the position. For example, the expression “at least one A may be replaced by B, C or D” means that at least one A is replaced by B, at least one A is replaced by C, and at least one A In addition to the case where A is replaced by D, the case where a plurality of A are replaced by at least two of B to D is also included. However, the definition that at least one —CH ₂ — may be replaced by —O— does not include such replacement that results in the bonding group —O—O—. Further, when at least one —CH ₂ — is replaced by —O—, the carbon number does not exceed the stated range.
For example, Q ¹ in the formula (1) is alkylene having 1 to 20 carbon atoms, and in this alkylene, at least one —CH ₂ — may be replaced by —O— or the like, but is replaced by —O— or the like. In this case, the number of carbon atoms of the alkylene containing does not exceed 20. This rule is the same for other definitions.

When the following description is given as a chemical formula, the straight line from A to B means a bond, hydrogen in ring A is replaced by group B, and the position is arbitrary Means. X represents the number of groups B to be replaced. When X is 0, it indicates that B does not exist and has not been replaced.

In addition, when a group as shown in C below is described as a chemical formula, it means that the mark * is a bonding position as a group.

≪Compound≫
The polymerizable liquid crystal composition which is one embodiment of the present invention (hereinafter sometimes abbreviated as “polymerizable liquid crystal composition of the present invention”) includes at least one polymerizable liquid crystal compound represented by the formula (1). It is characterized by containing. By using the polymerizable liquid crystal composition of the present invention, the birefringence Δn (450) for light with a wavelength of 450 nm and the birefringence Δn (550) for light with a wavelength of 550 nm are Δn (450) / Δn (550). An optically anisotropic film satisfying the relationship of ≦ 1.05, that is, an optically anisotropic film exhibiting low wavelength dispersion characteristics and reverse wavelength dispersion can be produced. Therefore, the optically anisotropic film obtained by using the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound of the present invention does not need to control the wavelength dispersion characteristics by laminating the retardation layer as in the prior art. Therefore, the film thickness can be reduced.
Usually, a liquid crystalline compound has a rod-like or disk-like molecular shape in which an aromatic ring or an alicyclic ring is used as a core skeleton, and a flexible group composed of alkyl or the like is bonded thereto. On the other hand, the polymerizable liquid crystal compound represented by the formula (1) in the present invention has a skeleton having a substituent at the β-position of styrene in the core.
By containing the polymerizable liquid crystal compound represented by the formula (1), the mechanism by which an optically anisotropic film exhibiting low wavelength dispersion characteristics and reverse wavelength dispersion is obtained is considered as follows. The wavelength dispersion of the refractive index is closely related to the absorption waveform of the substance, as represented by the Lorentz-Lorenz equation. In the region where the light absorption maximum of the substance occurs, there is an anomalous dispersion region where the refractive index increases rapidly as the absorption wavelength is approached from the long wavelength side to the short wavelength side (as the wavelength becomes shorter). In other words, by introducing a substituent that is rigid and extends the conjugated system to the side, absorption in the short axis direction can be expanded to a long wavelength region, and accordingly, refraction with respect to the wavelength of no (normal refractive index). The rate change rate can be increased. Further, by introducing a cyclohexane ring or the like in the major axis direction, absorption in the major axis direction can be shortened, and the refractive index change rate with respect to the wavelength of ne (abnormal refractive index) can be reduced. It is considered that the wavelength dispersion characteristic of the birefringence can be controlled by these two effects.
In addition, the polymerizable liquid crystal composition of the present invention has (1) a good liquid crystal phase near room temperature, (2) a good solubility in an organic solvent, and (3) even after removing the solvent at room temperature. It can be made into a composition having characteristics such as being able to maintain a liquid crystal phase for a long time, and the obtained film has optical anisotropy, transparency, heat resistance, adhesion, dimensional stability, and Since it is excellent in mechanical strength and the like, the polymerizable liquid crystal composition of the present invention can be said to be a very suitable material for the production of an optically anisotropic film.
Hereinafter, the polymerizable liquid crystal compound represented by the formula (1) will be described in detail. In the polymerizable liquid crystal composition of the present invention, the polymerizable liquid crystal compound represented by the formula (1) is not limited to one type, and two or more compounds corresponding to the formula (1) may be included.

この式（１）中、Ａ¹はそれぞれ独立して１，４−フェニレンまたは１，４−シクロへ
キシレンである。ここで、式（１）中の２つ以上のＡ¹は同じでもよく、異なっていても
よい。より低い波長分散特性を有するためには、１，４−シクロへキシレンであることがより好ましく、より大きな複屈折率を有すためには１，４−フェニレンであることがより好ましい。この１，４−フェニレンにおいて、少なくとも一つの水素はフッ素、塩素、トリフルオロメチル、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルコキシカルボニル、または炭素数１〜５のアルカノイルで置き換えられてもよい。しかしながら高い液晶性を化合物に付与するためには、無置換であることが好適である。

In this formula (1), A ¹ is each independently 1,4-phenylene or 1,4-cyclohexylene. Here, two or more A ¹ in the formula (1) may be the same or different. In order to have a lower wavelength dispersion characteristic, 1,4-cyclohexylene is more preferable, and in order to have a larger birefringence, 1,4-phenylene is more preferable. In the 1,4-phenylene, at least one hydrogen is fluorine, chlorine, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons, or 1 carbon. May be replaced by -5 alkanoyl. However, in order to impart high liquid crystallinity to the compound, it is preferable that it is unsubstituted.

In formula (1), Z ¹ is each independently a single bond, —OCH ₂ —, —CH ₂ O—, —COO—.
_{, -OCO -, - CF 2 O} -, - OCF 2 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - OCH 2 CH 2 O -, - CH 2 CH 2 COO -, - OCOCH 2 CH _2- , -CH ₂ CH ₂ OCO-, or -COOCH ₂ CH _2- . Here, two or more Z ¹ in the formula (1) may be the same or different. Z ¹ is -COO -, - OCO -, - CH 2 CH 2 COO-, or -OCOCH ₂ CH ₂ - if it has a high liquid crystallinity, and the compound can be produced at low cost. Further, at least one of Z ¹ is —CH ₂ CH ₂ COO— or —OCO.
In the case of CH ₂ CH ₂ —, it has good miscibility with other liquid crystal compounds and organic solvents, can reduce the clearing point, and can further reduce recrystallization.

In order for the polymerizable liquid crystal compound represented by the formula (1) to have high liquid crystallinity and good miscibility with other liquid crystal compounds and organic solvents, m is an integer of 1 to 3 each independently. And T ¹ is hydrogen or methyl.

式（１−１）において、Ａ¹、Ｚ¹、Ｔ¹、ｍ、Ｙ¹、Ｑ¹およびＰＧは上記式（１）に記載
の通りであり、Ｇは以下の式（Ｇ−１）〜（Ｇ−１２）で表される基である。

式（Ｇ−１）〜（Ｇ−１２）中、Ｘ¹はそれぞれ−ＣＨ₂−、−ＣＯ−、−Ｏ−または−Ｓ−であり；Ｘ²はそれぞれ独立してＯまたはＳであり；Ｒ²は水素、炭素数１〜５のアルキル、炭素数１〜５のアルカノイルまたは置換基を有してもよいフェニルであり；少なくとも一つの水素はフッ素、塩素、シアノ、トリフルオロアセチル、トリフルオロメチル、置換基を有してもよいフェニル、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルコキシカルボニル、または炭素数１〜５のアルカノイルで置き換えられてもよい。
また、「置換基を有してもよいフェニル」の「置換基」としては、フッ素、塩素、シアノ、トリフルオロアセチル、トリフルオロメチル、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルコキシカルボニル、または炭素数１〜５のアルカノイル等が挙げられる。
なお、式（Ｇ−１）〜（Ｇ−１２）中の米印（※）は、二重結合のある炭素の位置を示すものである。 In formula (1), T ² and T ³ are each independently cyano, C 1-10 alkoxycarbonyl or C 1-10 alkanoyl. Or, it is a ring structure in which T ² and T ³ are bonded to each other. In order to have a low wavelength dispersion characteristic, it is preferable that T ² and T ³ have a ring structure bonded to each other, and the ring structure forms a 5-membered ring or a 6-membered ring. When T ² and T ³ are bonded to each other to form a five-membered or six-membered ring structure, G represented by the following formula (1-1) represents the ease of synthesis and wavelength dispersion characteristics. In view of ease of control, the groups represented by formulas (G-1) to (G-12) are more preferable.

In the formula (1-1), A ¹ , Z ¹ , T ¹ , m, Y ¹ , Q ¹ and PG are as described in the above formula (1), and G is the following formula (G-1) to It is group represented by (G-12).

In formulas (G-1) to (G-12), X ¹ is —CH ₂ —, —CO—, —O— or —S—, respectively; X ² is independently O or S; R ² is hydrogen, alkyl having 1 to 5 carbons, alkanoyl having 1 to 5 carbons or phenyl optionally having substituents; at least one hydrogen is fluorine, chlorine, cyano, trifluoroacetyl, trifluoro It may be substituted with methyl, optionally substituted phenyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons, or alkanoyl having 1 to 5 carbons. Good.
The “substituent” of “optionally substituted phenyl” is fluorine, chlorine, cyano, trifluoroacetyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons. , Alkoxy having 1 to 5 carbon atoms, or alkanoyl having 1 to 5 carbon atoms.
In addition, the rice symbol (*) in the formulas (G-1) to (G-12) indicates the position of carbon having a double bond.

In formula (1), each Y ¹ is independently a single bond, —O—, —COO—, —OCO—, or —OCOO—, and each Q ¹ is independently a single bond or 1 to 20 carbon atoms. In which at least one —CH ₂ — may be replaced by —O—, —COO— or —OCO—. When Q ¹ is alkylene having 1 to 20 carbon atoms,
High liquid crystallinity and good miscibility with other liquid crystal compounds and organic solvents.

式（ＰＧ−１）〜式（ＰＧ−９）中、Ｒ¹はそれぞれ独立して水素、ハロゲン、メチル
、エチル、またはトリフルオロメチルである。
式（ＰＧ−１）〜式（ＰＧ−９）で表される重合性基の選択は、フィルムの製造条件により、適切なものを選ぶことが出来る。しかしながら通常用いられる光硬化でフィルムを作製する場合、アクリル基やメタクリル基等の式（ＰＧ−１）を選択する事が、高い硬化性、溶剤への溶解性、取扱いのしやすさなどの点から、好適である。なお、式（ＰＧ−１）〜（ＰＧ−９）中の米印（※）は、隣接するＱ¹と単結合する位置を示すものである。 PG is a polymerizable group represented by any one of formulas (PG-1) to (PG-9).

In Formula (PG-1) to Formula (PG-9), R ¹ is independently hydrogen, halogen, methyl, ethyl, or trifluoromethyl.
As the selection of the polymerizable group represented by the formula (PG-1) to the formula (PG-9), an appropriate one can be selected depending on the production conditions of the film. However, when producing a film by photocuring usually used, it is possible to select a formula (PG-1) such as an acryl group or a methacryl group, such as high curability, solubility in a solvent, and ease of handling. Therefore, it is preferable. In the formulas (PG-1) to (PG-9), an asterisk (*) indicates a position where a single bond is formed with the adjacent Q ¹ .

  Preferred examples of the polymerizable liquid crystal compound represented by the formula (1) are shown below. However, it is not limited to what is shown below.

In Formula (1-1-1) to Formula (1-1-18) or Formula (1-2-1) to Formula (1-2-5), Y ¹ represents a single bond, —O—, —COO—. , -OCO-, or -OCOO-,
Q ¹ is a single bond or alkylene having 1 to 20 carbon atoms, and in the alkylene, at least one —CH ₂ — may be replaced by —O—, —COO—, or —OCO—,
PG is a polymerizable group represented by the above formula (PG-1) to formula (PG-9).

式（１−１）で表される化合物のコア骨格であるスチレン−β−置換構造は、例えば２，５−ジメトキシベンズアルデヒドのような活性な官能基を有するベンゼンジオール誘導体を利用することによって形成することができる。ここで、上記式においてＸ¹は−ＣＨ₂−、−ＣＯ−、−Ｏ−または−Ｓ−である。具体的には２，５−ジメトキシベンズアルデヒドのアルデヒドとインデン−１，３−ジオンを反応させて、スチレンのβ−位にインデン−１，３−ジオン構造を導入することができる。これを脱保護しジエステル化することで、式（１−１）で表される化合物へと誘導できる。
また、下記式のように４−ヒドロキシシクロヘキサンカルボン酸等を用いることにより、１，４−シクロへキシレンを導入することができる。

ここで、上記式においてｒは２〜２０の整数である。
なお、合成された化合物の構造は、例えば、プロトンＮＭＲスペクトルにより確認することができる。 The polymerizable liquid crystal compound represented by the formula (1) can be synthesized by combining known organic synthetic chemistry techniques. Methods for introducing the desired end groups, rings and linking groups into the starting material are described by Houben-Wyle, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Organic Syntheses, John Wily & Sons. , Inc.), Organic Reactions (John Wily & Sons Inc.), Comprehensive Organic Synthesis (Pergamon Press), and New Experimental Chemistry Course (Maruzen) Have been described.
For example, the compound represented by the formula (1-1) can be synthesized through a reaction step represented by the following formula.

The styrene-β-substituted structure, which is the core skeleton of the compound represented by the formula (1-1), is formed by using a benzenediol derivative having an active functional group such as 2,5-dimethoxybenzaldehyde. be able to. Here, in the above formula, X ¹ is —CH ₂ —, —CO—, —O— or —S—. Specifically, an aldehyde of 2,5-dimethoxybenzaldehyde and indene-1,3-dione can be reacted to introduce an indene-1,3-dione structure at the β-position of styrene. By deprotecting and diesterifying this, it can be derived into the compound represented by the formula (1-1).
Moreover, 1,4-cyclohexylene can be introduce | transduced by using 4-hydroxycyclohexanecarboxylic acid etc. like a following formula.

Here, r is an integer of 2 to 20 in the above formula.
The structure of the synthesized compound can be confirmed by, for example, a proton NMR spectrum.

The alignment of the liquid crystal molecules is classified into homogeneous, parallel, homeotropic, tilted, twisted, and the like based on the size of the tilt angle. The tilt angle is an angle between the alignment state of the liquid crystal molecules and the support substrate. Homogeneous means a state in which the alignment state of liquid crystal molecules in the major axis direction is parallel to the substrate and aligned in one direction. An example of the tilt angle in the homogeneous alignment is 0 degree to 5 degrees. Homeotropic means a state in which the alignment state in the major axis direction of liquid crystal molecules is perpendicular to the substrate. An example of the tilt angle in homeotropic alignment is 85 degrees to 90 degrees. The tilt refers to a state in which the alignment state of the liquid crystal molecules in the major axis direction rises from parallel to vertical as the distance from the substrate increases. An example of a tilt angle (tilt angle) in the tilt alignment is 5 degrees to 85 degrees. The twist refers to a state in which the alignment state of the liquid crystal molecules in the major axis direction is parallel to the substrate, but is twisted stepwise around the helical axis. An example of the tilt angle in the twist orientation is 0 degree to 5 degrees.

≪Polymerizable liquid crystal composition≫
The polymerizable liquid crystal composition of the present invention contains at least one polymerizable liquid crystal compound represented by the formula (1). The polymerizable liquid crystal composition of the present invention has a nematic or smectic liquid crystal phase at a relatively low temperature. When the polymerizable liquid crystal composition of the present invention is coated on a plastic substrate that has been subjected to an alignment treatment such as a rubbing treatment or a support substrate whose surface is coated with a plastic thin film, a homogeneous alignment or tilt is formed. Orientation. In addition, when a non-polymerizable or polymerizable optically active compound described later is added to the polymerizable liquid crystal composition of the present invention, twist alignment is obtained. When a compound having a cardo structure to be described later or a compound having a polar group at the terminal is added to the polymerizable liquid crystal composition of the present invention, homeotropic alignment is easily obtained. Here, the polar group is a hydroxyl group, a carboxyl group, an amino group, a thiol group, a sulfonic acid group, an ester group, an amide group or an ammonium group.

In the polymerizable liquid crystal composition of the present invention, at least one of the polymerizable liquid crystal compounds of the present invention represented by the formula (1) is usually 10% by weight or more with respect to 100% by weight of the total amount of compounds having a polymerizable group. , Preferably 30% by weight or more. When the content of the polymerizable liquid crystal compound (1) is in the above range, it is easy to control the wavelength dispersion of the birefringence, and the effects of the polymer of the present invention can be remarkably exhibited.
Further, when the total weight of the polymerizable liquid crystal composition is 100% by weight, 4% by weight or more and 50% by weight or less of at least one polymerizable liquid crystal compound of the present invention represented by the formula (1) is contained. It is preferable.

  Constituent components other than compound (1) include other liquid crystal compounds (excluding polymerizable liquid crystal compounds), other polymerizable liquid crystal compounds, surfactants, and other polymerizable compounds (however, polymerizable liquid crystal compounds are excluded). ), Polymerization initiators, photosensitizers, chain transfer agents, antioxidants, UV absorbers, radical scavengers, light stabilizers, optically active compounds, silane coupling agents, solvents, and other additives. You may contain in the range which does not impair the effect of invention.

  Other liquid crystal compounds can be selected from compounds described in a liquid crystal compound database (LiqCryst, LCI Publisher GmbH, Hamburg, Germany). Among these, a compound represented by the following formula (LC) is preferable.

式（ＬＣ）中、Ａ²はそれぞれ独立して１，４−フェニレン、１，４−シクロへキシレ
ン、ピリジン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、およびナフタレン−２，６−ジイルから選ばれるいずれかの二価基であり、該二価基において、少なくとも一つの水素はフッ素、塩素、シアノ、ヒドロキシ、ホルミル、トリフルオロアセチル、ジフルオロメチル、トリフルオロメチル、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルコキシカルボニル、または炭素数１〜５のアルカノイルで置き換えられてもよく；Ｚ²はそれぞれ独立して単結合または炭素数１〜２０のアルキレン
であり、該アルキレンにおいて少なくとも一つの−ＣＨ₂−は−Ｏ−、−ＣＯ−、−ＣＯ
Ｏ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、または−Ｃ≡Ｃ−で置き換えられてもよく、少なくとも一つの水素はハロゲンで置き換えられてもよく；ｂは１〜５の整数であり；Ｒ²はそれぞれ独立して水素、フッ素、塩素、シアノ、ヒドロキシ、ホルミル、
トリフルオロアセチル、ジフルオロメチル、トリフルオロメチル、炭素数１〜１０のアルキル、または炭素数１〜１０のアルコキシであり、該アルキルにおいて少なくとも一つの
−ＣＨ₂−は−ＣＨ＝ＣＨ−で置き換えられてもよい。

In formula (LC), A ² is each independently 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, and naphthalene- Any one divalent group selected from 2,6-diyl, in which at least one hydrogen is fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, carbon May be substituted with an alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons, or alkanoyl having 1 to 5 carbons; each Z ² independently represents a single bond or carbon An alkylene having a number of 1 to 20, in which at least one —CH ₂ — is —O—, —CO—, —CO;
O—, —OCO—, —CH═CH—, —CF═CF—, or —C≡C— may be substituted, and at least one hydrogen may be substituted with halogen; Each R ² is independently hydrogen, fluorine, chlorine, cyano, hydroxy, formyl,
Trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons, in which at least one —CH ₂ — is replaced by —CH═CH—. Also good.

  Specific examples of the compound represented by the above formula (LC) are shown below.

  When the polymerizable liquid crystal composition of the present invention contains the compound represented by the above formula (LC), the content is usually preferably 50% by weight or less based on the total amount of the polymerizable liquid crystal composition.

  As other polymerizable liquid crystal compounds, compounds represented by the following formulas (M1), (M2) and (M3) are preferable.

式（Ｍ１）、（Ｍ２）および（Ｍ３）中、Ａ^Mはそれぞれ独立して１，４−フェニレン
、１，４−シクロへキシレン、１，４−シクロへキセニレン、ピリジン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、ナフタレン−２，６−ジイル、またはフルオレン−２，７−ジイルから選ばれるいずれかの二価基であり、該二価基において、少なくとも一つの水素はフッ素、塩素、シアノ、ヒドロキシ、ホルミル、トリフルオロアセチル、ジフルオロメチル、トリフルオロメチル、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、炭素数１〜５のアルコキシカルボニル、または炭素数１〜５のアルカノイルで置き換えられてもよく；Ｚ^Mはそれぞれ独立して単結合、−ＯＣＨ₂−、−ＣＨ₂Ｏ−、−Ｃ
ＯＯ−、−ＯＣＯ−、−ＣＯＳ−、−ＳＣＯ−、−ＯＣＯＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＦ₂Ｏ−、−ＯＣＦ₂−、−ＣＨ₂ＣＨ₂−、−ＣＦ₂ＣＦ₂−、−ＣＨ＝ＣＨＣＯＯ−、−ＯＣＯＣＨ＝ＣＨ−、−ＣＨ₂ＣＨ₂ＣＯＯ−、−ＯＣＯＣＨ₂ＣＨ₂−、−ＣＨ＝ＣＨ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−、−Ｎ＝Ｃ（ＣＨ₃）−、−Ｃ（ＣＨ₃）＝Ｎ−、−Ｎ＝Ｎ−、または−Ｃ≡Ｃ−であり；Ｘ^Mは水素、フッ素、塩素、トリフルオロメチル、
トリフルオロメトキシ、シアノ、炭素数１〜２０のアルキル、炭素数１〜２０のアルケニル、炭素数１〜２０のアルコキシ、または炭素数１〜２０のアルコキシカルボニルであり；ｑは１〜４の整数であり；ｃおよびｄはそれぞれ０〜３の整数であり、かつ１≦ｃ＋ｄ≦４の関係であり；ａは０〜２０の整数であり；Ｒ^Mは水素またはメチルであり；Ｙ^Mは単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−である。
ここで、ｑ、ｃ、またはｄが２以上である場合、このＡ^MおよびＺ^Mはその繰り返し毎に異なっていてもよい。

In formulas (M1), (M2) and (M3), A ^M is independently 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, pyridine-2,5-diyl. , 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or fluorene-2,7-diyl, in which at least one divalent group is selected. Hydrogen is fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons, or carbon May be replaced by alkanoyl having 1 to 5; each Z ^M is independently a single bond, —OCH ₂ —, —CH ₂ O—, —C
OO -, - OCO -, - COS -, - SCO -, - OCOO -, - CONH -, - NHCO -, - CF 2 O -, - OCF 2 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH = CH -, - N = CH -, - CH = N -, - N = C (CH ₃ ) —, —C (CH ₃ ) ═N—, —N═N—, or —C≡C—; X ^M is hydrogen, fluorine, chlorine, trifluoromethyl,
Trifluoromethoxy, cyano, alkyl having 1 to 20 carbons, alkenyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, or alkoxycarbonyl having 1 to 20 carbons; q is an integer of 1 to 4 Yes; c and d are each an integer of 0 to 3 and 1 ≦ c + d ≦ 4; a is an integer of 0 to 20; R ^M is hydrogen or methyl; Y ^M is a single bond , -O-, -COO-, -OCO-, or -OCOO-.
Here, when q, c, or d is 2 or more, A ^M and Z ^M may be different for each repetition.

  In the compounds represented by the above formulas (M1), (M2) and (M3), it is more preferable to use the compound represented by the formula (M1) or (M2).

Low wavelength dispersion characteristics, good liquid crystallinity, low clearing point, high solubility in organic solvents, high compatibility with other compounds, easy and inexpensive production of compounds, etc. in terms of the, in the formula (M1) or (M2), but a ^M is 1,4-phenylene or 1,4-cyclohexylene, at least one is a 1,4-cyclohexylene, Z ^M is represented by a single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH ₂ CH ₂ —, —CH ₂ CH ₂ COO—, or —OCOCH ₂ CH ₂ —. Compounds are more preferred.

The compound represented by the formula (M1) is a monofunctional polymerizable liquid crystal compound, and it is easy to control the liquid crystal temperature range, optical characteristics, and orientation of the liquid crystal composition. In addition, increasing the addition amount tends to increase the tilt angle, making it easier to obtain homeotropic alignment. The compound represented by the formula (M2) is a bifunctional polymerizable liquid crystal compound, and since this polymer has a three-dimensional structure, it is compared with the compound represented by the formula (M1) having only one polymerizable group. And hard polymer. The compound represented by the formula (M3) is a trifunctional polymerizable liquid crystal compound, and this polymer can form a stronger network and can be further compared with a compound having one and two polymerizable groups. It becomes a hard polymer. Hereinafter, the compound represented by the formulas (M1), (M2), and (M3) or a compound derived therefrom may be collectively referred to as the formula (M).

  Hereinafter, preferable examples of the compound represented by the formula (M1) are shown.

式（Ｍ１−１）〜（Ｍ１−２４）において、Ｒ^Mは独立して水素またはメチルであり、
ａは独立して１〜１２の整数である。

In formulas (M1-1) to (M1-24), R ^M is independently hydrogen or methyl,
a is an integer of 1-12 independently.

  Hereinafter, preferable examples of the compound represented by the formula (M2) are shown.

式（Ｍ２−１）〜（Ｍ２−３１）において、Ｒ^Mは独立して水素またはメチルであり、
ａは独立して１〜１２の整数である。式中に２つ以上のａがあるとき、任意の２つのａは同一でもよく、異なっていてもよい。

In formulas (M2-1) to (M2-31), R ^M is independently hydrogen or methyl,
a is an integer of 1-12 independently. When there are two or more a's in the formula, any two a's may be the same or different.

  Hereinafter, preferable examples of the compound represented by the formula (M3) are shown.

式（Ｍ３−１）〜（Ｍ３−１０）において、Ｒ^Mはそれぞれ独立して水素またはメチル
であり、ａはそれぞれ独立して１〜１２の整数である。式中に２つ以上のａがあるとき、任意の２つのａは同一でもよく、異なっていてもよい。

In formulas (M3-1) to (M3-10), R ^M is independently hydrogen or methyl, and a is independently an integer of 1 to 12. When there are two or more a's in the formula, any two a's may be the same or different.

  When the polymerizable liquid crystal composition of the present invention contains a compound represented by the formula (M), at least one compound of the present invention represented by the formula (1) and a compound represented by the formula (M) It is preferable to contain at least one compound of the present invention represented by the formula (1) in an amount of 30 to 95% by weight with respect to a total amount of 100% by weight of at least one of these. When the content of each component in the liquid crystal composition is within the above range, a liquid crystal composition having a wide liquid crystal phase near room temperature, easy birefringence wavelength dispersion control, and good coating properties is obtained. be able to.

  The polymerizable liquid crystal composition of the present invention may further contain a surfactant. Surfactants include ionic surfactants and nonionic surfactants, but the effect of improving the smoothness of the coating film formed from the polymerizable liquid crystal composition and the tilt alignment on the air interface side are suppressed. Since the effect is high, it is more preferable to use a nonionic surfactant.

  A preferable ratio in the case of adding a surfactant is the ratio of the formula (1) to the weight of the polymerizable liquid crystal compound represented by the formula (1) or the case where the other liquid crystal compound or the other polymerizable liquid crystal compound is contained. It is 0.0001-0.1 by weight ratio with respect to the total weight with the polymerizable liquid crystal compound represented by. A more preferable range of the weight ratio is 0.0001 to 0.005.

  Examples of ionic surfactants include titanate compounds, imidazolines, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl. Amine sulfates, alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, laurylamidopropylbetaine, laurylaminoacetic acid betaine, polyethylene glycol fatty acid esters, polyoxyethylene alkylamines, Examples of the compound include perfluoroalkyl sulfonate and perfluoroalkyl carboxylate.

  Examples of the nonionic surfactant include silicones, fluorines, vinyls, and hydrocarbons.

Examples of the silicone-based nonionic surfactant include polyflow KL-400HF, polyflow KL-401, polyflow KL-402, polyflow KL-403, polyflow KL-404, BYK mainly composed of unmodified silicone or modified silicone. -300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-31
5, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-342, BYK-344, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-371, BYK-375, BYK-377, BYK-378, BYK-3455, BYK-3500, BYK-3510, BYK- 3530, BYK-3570, BYK-Silklean 3720, TEGOFlow 425, and the like.

  As the fluorine-based nonionic surfactant, for example, BYK-340, and as the fluorine-based nonionic surfactant, for example, BYK-340, aftergent 251, aftergent 212M, aftergent 215M, aftergent 250, Aftergent 222F, Aftergent 245F, Aftergent 208G, Aftergent 240G, Aftergent 220P, Aftergent 228P, Aftergent FTX-218, Aftergent DFX-18, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 730LM, Megafuck F-251, Megafuck F-410, Megafuck F-430, Megafuck F-444, Megafuck F-477, Megafuck F-551, Gafuck F-553, Megafuck F-554, Megafuck F-556, Megafuck F-557, Megafuck F-558, Megafuck F-559, Megafuck F-562, Megafuck F-563, Megafuck F -565, Megafuck F-570, Megafuck R-40, Megafuck R-41, Megafuck R-43, or Megafuck R-94.

  Examples of the vinyl-based nonionic surfactant include Polyflow No. 1 mainly composed of an acrylic polymer. 7, Polyflow No. 50EHF, Polyflow No. 54N, Polyflow No. 75, Polyflow No. 77, Polyflow No. 85HF, Polyflow No. 90, polyflow no. 95, Polyflow No. 99C, BYK-350, BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380N, BYK-381, BYK-392, BYK-399, BYK-Silclean3700, TEGOFlow300, TEGOFlow370, And TEGOFlowZFS460.

Further, the surfactant may have a polymerizable group so as to be integrated with the polymerizable liquid crystal compound. Examples of the polymerizable group introduced into the surfactant include a UV reactive functional group and a thermal polymerizable functional group. From the viewpoint of reactivity with the polymerizable liquid crystal compound, a UV-reactive functional group is preferable.
Examples of the UV-reactive nonionic surfactant include, but are not limited to, Footent 601AD, Footer 602A, Footer 650A, Megafuck RS-55, Megafuck RS-56, Megafuck RS-72-K, Megafuck RS -75, Megafuck RS-78, Megafuck RS-90, and the like.

  In order to optimize the wettability to the substrate, a surfactant classified as a (substrate) wetting agent may be used in combination. The wetting agent has the effect of reducing the surface tension of the polymerizable liquid crystal composition and improving the wettability to the coated substrate. As such a wetting agent, polyflow series (KL-100, KL-700, LE-604, LE-605, LE-606), TEGO Twin series (4000), TEGO Wet series (KL245, 250, 260, 265, 270, 280, 500, 505, 510) and the like. A surfactant mainly composed of a fluorinated modified polymer or a fluorinated modified acrylic polymer may be applied as an auxiliary agent for the wetting agent. As such a thing, 3000 series (For example, 3277, 3700, 3770 etc.) by AFCONA company are mentioned.

  The above polyflow is the name of a product sold by Kyoeisha Chemical Co., Ltd. BYK is the name of a product sold by Big Chemie Japan. Footage is the name of a product sold by Neos. Mega Fuck is the name of a product sold by DIC Corporation. TEGOFlow is the name of a product sold by Evonik Japan.

  Said surfactant may be used independently and may mix and use 2 or more.

  Next, other polymerizable compounds, additives, and organic solvents are exemplified. These compounds may be commercially available products.

Other polymerizable compounds include compounds such as vinyl derivatives, styrene derivatives, (meth) acrylic acid derivatives, oxirane derivatives, oxetane derivatives, sorbic acid derivatives, fumaric acid derivatives, and itaconic acid derivatives, which do not have liquid crystallinity. Is mentioned. Other polymerizable compounds having no liquid crystallinity include a compound having one polymerizable group, a compound having two polymerizable groups, and a polyfunctional compound having three or more polymerizable groups.
Other polymerizable compounds may be added as long as the liquid crystal phase can be maintained. The weight of the polymerizable liquid crystal compound represented by formula (1) and the weight relative to the total weight of the polymerizable liquid crystal compound represented by formula (1) when other liquid crystal compounds and other polymerizable liquid crystal compounds are contained. The ratio is preferably 0.5 or less.

  Examples of the compound having one polymerizable group include styrene, nucleus-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinyl pyrrolidone, vinyl sulfonic acid, vinyl fatty acid (eg, vinyl acetate), α, β-ethylenically unsaturated carboxylic acid (eg, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.), alkyl ester of (meth) acrylic acid (alkyl having 1 to 18 carbon atoms), (meth) acrylic Hydroxyalkyl esters of acids (hydroxyalkyls having 1 to 18 carbon atoms), aminoalkyl esters of (meth) acrylic acid (aminoalkyls having 1 to 18 carbon atoms), alkyl ethers containing ether oxygen of (meth) acrylic acid (ether oxygen) Containing alkyl having 3 to 18 carbon atoms, such as methoxyethyl ester, Toxiethyl ester, methoxypropyl ester, methyl carbyl ester, ethyl carbyl ester, and butyl carbyl ester), N-vinylacetamide, vinyl pt-butylbenzoate, vinyl N, N-dimethylaminobenzoate, vinyl benzoate, Vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate, vinyl 2-ethyl-2-methylbutanoate, Dicyclopentanyloxylethyl (meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, dicyclopentanyl (meth) Acrylate, dicyclopentenyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl Phthalic acid, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, polyethylene glycol having a polymerization degree of 1 to 100, polypropylene glycol, copolymer of ethylene oxide and propylene oxide, etc. A poly (alkylene glycol) mono (meth) acrylate ester or di (meth) acrylate ester, or a polyethylene glycol having a degree of polymerization of 1 to 100 whose end is capped with an alkyl group having 1 to 6 carbon atoms, Polypropylene Co - le, and polyalkylene glycol having a copolymer of ethylene oxide and propylene oxide - such as Le mono (meth) acrylic acid esters.

Examples of the compound having two polymerizable groups include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, and dimethylol tricyclo. Decane diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A EO addition diacrylate, bisphenol A glycidyl diacrylate (Biscoat V # 700), polyethylene glycol di Examples thereof include acrylates and methacrylate compounds of these compounds.

  Examples of the compound having three or more polymerizable groups include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol EO-added tri (meth) acrylate, and tris (meth) acryloyloxyethylphosphine. Fate, tris ((meth) acryloyloxyethyl) isocyanurate, alkyl-modified dipentaerythritol tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa ( ) Acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, biscoat V # 802 (number of functional groups = 8), biscoat V # 1000 (number of functional groups = average 14), etc. Can be mentioned. “Biscoat” is a trade name of Osaka Organic Chemical Co., Ltd. Those having a functional group of 16 or more can be obtained by acrylating them using Boltorn H20 (16 functions), Boltorn H30 (32 functions), and Boltorn H40 (64 functions) sold by Perstorp Specialty Chemicals.

  Examples of the other polymerizable compound further include a polymerizable fluorene derivative having a cardo structure and a polymerizable compound having a bisphenol structure. The polymerizable fluorene derivative having a cardo structure is suitable for controlling the alignment and further increasing the degree of curing of the polymer, and the polymerizable compound having a bisphenol structure assists in the film forming ability and alignment uniformity of the liquid crystal composition. Suitable for Examples of polymerizable fluorene derivatives having a cardo structure are shown in formulas (α-1) to (α-3), and examples of polymerizable bisphenol derivatives are shown in formulas (N-1) to (N-8).

式（α−１）〜（α−３）において、Ｒαはそれぞれ独立して水素またはメチルであり、ｓはそれぞれ独立して０〜４の整数である。式中に２つ以上のｓがあるとき、任意の２
つのｓは同一でもよく、異なっていてもよい。

In formulas (α-1) to (α-3), Rα is independently hydrogen or methyl, and s is each independently an integer of 0 to 4. When there are two or more s in the formula, any 2
The two s may be the same or different.

式（Ｎ−１）〜（Ｎ−８）において、Ｒ^Nはそれぞれ独立して水素またはメチルであり
、ｔはそれぞれ独立して２〜１２の整数である。式中に２つ以上のｔがあるとき、任意の２つのｔは同一でもよく、異なっていてもよい。

In formulas (N-1) to (N-8), R ^N is each independently hydrogen or methyl, and t is each independently an integer of 2 to 12. When there are two or more t in the formula, any two t may be the same or different.

  Other polymerizable compounds may be used alone or in combination of two or more. These compounds may be commercially available products.

In order to optimize the polymerization rate, a polymerization initiator may be added to the liquid crystal composition. Examples of the polymerization initiator include a photo radical initiator. Examples of the photo radical polymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173), 1-hydroxycyclohexyl phenyl ketone, and 2,2-dimethoxy-1,2-diphenylethane. -1-one (Irgacure 651), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184), Irgacure 127, Irgacure 500 (mixture of Irgacure 184 and benzophenone), Irgacure 295
9, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 754, Irgacure 1300, Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Irgacure 1870, Darocur 4265, Darocur MBF, Darocur TPO IRGACURE 784, IRGACURE 754, IRGACURE OXE01, IRGACURE OXE02, Adekaputomer N-1919, Adeka Cruz NCI-831, Adeka Cruz NCI-930, and the like. Both Darocur and Irgacure are names of products sold by BASF Japan, and Adekaoptomer and Adeka Cruz are both names of products sold by ADEKA.

  Examples of the photo radical polymerization initiator include p-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole. 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, Benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, benzophenone / methyltriethanolamine Such as a mixture .

  The preferred addition amount of the radical photopolymerization initiator is based on the weight of the polymerizable liquid crystal compound represented by the formula (1), or when it contains other liquid crystal compounds or other polymerizable liquid crystal compounds, the formula (1) It is 0.0001-0.20 by weight ratio with respect to the total weight with the polymeric liquid crystal compound represented by these. A more preferable range of this weight ratio is 0.001 to 0.15. A more preferable range is 0.01 to 0.15. The said photo radical initiator may be used independently, and may mix and use 2 or more. These polymerization initiators may be commercially available products.

  Further, a sensitizer may be added to these photo radical polymerization initiators. Examples of the sensitizer include isopropylthioxanthone, diethylthioxanthone, ethyl-4dimethylaminobenzoate (Darocur EDB), 2-ethylhexyl-4-dimethylaminobenzoate (Darocur EHA), and the like. These sensitizers may be used alone or in combination of two or more. These sensitizers may be commercially available products.

  A chain transfer agent may be added to the liquid crystal composition in order to control the polymerization reaction rate and mechanical properties of the polymer. By using a chain transfer agent, the reaction rate and chain length of the resulting polymer can be controlled. Increasing the amount of chain transfer agent decreases the polymerization reaction rate and decreases the length of the polymer chain. Preferred chain transfer agents are thiol compounds and styrene dimers. These chain transfer agents may be used alone or in combination of two or more. These chain transfer agents may be commercially available products.

  Examples of the thiol chain transfer agent include monofunctional thiols such as dodecane thiol and 2-ethylhexyl- (3-mercaptopropionate), and polyfunctional thiols such as trimethylolpropane tris (3-mercapto Propionate), pentaerythritol tetrakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane (Karenz MT BD1), pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MT) PE1), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (Karenz MT NR1) and the like. “Karenzu” is a trade name of Showa Denko KK

  Examples of the styrene dimer chain transfer agent include 2,4-diphenyl-4-methyl-1-pentene and 2,4-diphenyl-1-butene.

  A polymerization inhibitor can be added to the liquid crystal composition in order to prevent initiation of polymerization during storage. Known polymerization inhibitors can be used, but preferred examples thereof include 2,5-di (t-butyl) hydroxytoluene (BHT), hydroquinone, methylene blue, diphenylpicric hydrazide (DPPH), phenothiazine, N, N-dimethyl. Nitroso compounds such as -4-nitrosoaniline, o-hydroxybenzophenone, and benzothiazine derivatives such as 2H-1,3-benzothiazine-2,4- (3H) dione.

  In order to improve the storage stability of the liquid crystal composition, a polymerization inhibitor may be added. When radicals are generated in the liquid crystal composition or the liquid crystal composition solution, the polymerization reaction of the polymerizable compound is promoted. In order to prevent this, it is preferable to add a polymerization inhibitor. As the polymerization inhibitor, a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphoric acid-based antioxidant can be used.

  In order to further improve the weather resistance of the liquid crystal composition, an ultraviolet absorber, a light stabilizer (radical scavenger), an antioxidant and the like may be added. Examples of the ultraviolet absorber include Tinuvin PS, Tinuvin P, Tinuvin 99-2, Tinuvin 109, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 328, Tinuvin 329, Tinuvin 384-2, Tinuvin 571, Tinuvin 900, Tinuvin 928 , Tinuvin 1130, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 479, Tinuvin 5236, ADK STAB LA-32, ADK STAB LA-34, ADK STAB LA-36, ADK STAB LA-31, ADK STAB 1413, ADK STAB LA-51 and the like It is done. “Tinubin” is a trade name of BASF Japan, and “Adeka Stub” is a trade name of ADEKA. These ultraviolet absorbers may be used alone or in combination of two or more. These ultraviolet absorbers may be commercially available products.

  Examples of the light stabilizer include Tinuvin 111FDL, Tinuvin 123, Tinuvin 144, Tinuvin 152, Tinuvin 292, Tinuvin 622, Tinuvin 770, Tinuvin 765, Tinuvin 780, Tinuvin 905, Tinuvin 5100, Tinuvin 5050, 5060, Tinuvin 5151, Chimassorb 119FL, Kimasorb 944FL, Kimasorb 944LD, ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63P, ADK STAB LA-68LD, ADK STAB LA-77, ADK STAB LA-82, ADK STAB LA-82 -87, Siasorb UV-3346 manufactured by Cytec, Goodlite UV-3034 manufactured by Goodrich, and the like. “Kimasorb” is a trade name of BASF Japan. These light stabilizers may be used alone or in combination of two or more. These light stabilizers may be commercially available products.

  Antioxidants include, for example, ADEKA ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, Sumitizer BHT and Sumitizer BBM sold by Sumitomo Chemical Co., Ltd. -S, and Sumilizer GA-80, and Irganox 1076, Irganox 1010, Irganox 3114, and Irganox 245 etc. which are sold from BASF Japan Ltd. are mentioned. These antioxidants may be used alone or in combination of two or more. These antioxidants may be commercially available products.

A silane coupling agent may be added to the liquid crystal composition in order to control the adhesion with the substrate. Examples of the silane coupling agent include vinyl trialkoxysilane, 3-
Isocyanatopropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropyltrialkoxysilane, N- (1,3-dimethylbutylidene) -3- (trialkoxysilyl) -1-propanamine, 3-glycol Sidoxypropyltrialkoxysilane, 3-chlorotrialkoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrialkoxysilane and the like can be mentioned. Also, in the above alkoxysilane, dialkoxymethylsilane in which one of the alkoxy groups (three) is replaced with methyl may be used as the silane coupling agent. These silane coupling agents may be used alone or in combination of two or more. These silane coupling agents may be commercially available products.

  The polymerizable liquid crystal composition of the present invention may contain a solvent in order to facilitate application. Examples of the solvent include ester solvents, amide solvents, alcohol solvents, ether solvents, glycol monoalkyl ether solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents. Examples include solvents, halogenated aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ketone solvents, and acetate solvents.

  Examples of ester solvents include alkyl acetate (eg, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, pentyl acetate and isopentyl acetate), ethyl trifluoroacetate, alkyl propionate (Eg, methyl propionate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate and butyl propionate), alkyl butyrate (eg: methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate and propyl butyrate), malonic acid Dialkyl (eg, diethyl malonate), alkyl glycolate (eg, methyl glycolate and ethyl glycolate), alkyl lactate (eg, methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, butyl lactate and ethyl lactate) Hexyl), monoacetin, such as γ- butyrolactone and γ- valerolactone is preferred.

  Examples of amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N-methylpropionamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylacetamidodimethylacetal, N-methylcaprolactam, dimethylimidazolidinone and the like are preferable.

  Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, t-butyl alcohol, sec-butyl alcohol, butanol, 2-ethylbutanol, n-hexanol, and n-heptanol. , N-octanol, 1-dodecanol, ethylhexanol, 3,5,5-trimethylhexanol, n-amyl alcohol, hexafluoro-2-propanol, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol , Dipropylene glycol, tripropylene glycol, hexylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pen Njioru, 2,4-pentanediol, 2,5-hexanediol, 3-methyl-3-methoxybutanol, cyclohexanol and methylcyclohexanol is preferred.

  As the ether solvent, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, bis (2-propyl) ether, 1,4-dioxane, tetrahydrofuran (THF) and the like are preferable.

Glycol monoalkyl ether solvents include ethylene glycol monoalkyl ether (eg, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether), diethylene glycol monoalkyl ether (eg, diethylene glycol monoethyl ether), triethylene glycol monoalkyl ether, propylene glycol Monoalkyl ether (eg, propylene glycol monobutyl ether), dipropylene glycol monoalkyl ether (eg, dipropylene glycol monomethyl ether), ethylene glycol monoalkyl ether acetate (eg, ethylene glycol monobutyl ether acetate), diethylene glycol monoalkyl ether acetate ( Example: Diethylene glycol Ethyl ether acetate), triethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate (eg, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate), dipropylene glycol monoalkyl ether acetate ( Examples: Dipropylene glycol monomethyl ether acetate) and diethylene glycol methyl ethyl ether are preferred.

  Aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, i-propylbenzene, n-propylbenzene, t-butylbenzene, s-butylbenzene, n-butylbenzene, and tetralin. . Preferred examples of the halogenated aromatic hydrocarbon solvent include chlorobenzene. As the aliphatic hydrocarbon solvent, hexane and heptane are preferable. As the halogenated aliphatic hydrocarbon solvent, chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethylene, tetrachloroethylene and the like are preferable. As the alicyclic hydrocarbon solvent, cyclohexane, decalin and the like are preferable.

As the ketone solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, methyl propyl ketone, and the like are preferable.
As the acetate solvent, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetoacetate, 1-methoxy-2-propyl acetate and the like are preferable.

  From the viewpoint of the solubility of the liquid crystal compound, it is preferable to use an amide solvent, an aromatic hydrocarbon solvent, or a ketone solvent. Considering the boiling point of the solvent, an ester solvent, an alcohol solvent, an ether solvent, a glycol monoalkyl A combined use of an ether solvent is also preferred. Although there is no particular limitation regarding the selection of the solvent, when a plastic substrate is used as the supporting base, it is necessary to lower the drying temperature in order to prevent deformation of the substrate and to prevent the solvent from attacking the substrate. Solvents preferably used in such cases are aromatic hydrocarbon solvents, ketone solvents, ester solvents, ether solvents, alcohol solvents, acetate solvents, glycol monoalkyl ether solvents.

  A preferable ratio in the case of using a solvent is based on the weight of the polymerizable liquid crystal compound represented by the formula (1) or in the case of containing another liquid crystal compound or other polymerizable liquid crystal compound in the formula (1). It is 30 to 96 weight% with respect to the total weight with the polymeric liquid crystal compound represented. A preferable range of this ratio is 50 to 90% by weight, and a more preferable range is 60 to 80% by weight. These solvents may be used alone or in combination of two or more. These solvents may be commercially available products.

In the following description, a polymer (optical anisotropic film) obtained by polymerizing a polymerizable liquid crystal composition may be referred to as a liquid crystal film. The liquid crystal film can be obtained as follows. First, a polymerizable liquid crystal composition is applied on a support substrate in a fluid state to form a coating film. When a solution of the polymerizable liquid crystal composition is prepared, it is applied onto a support substrate and dried to form a coating film. The coating film is irradiated with light to polymerize the polymerizable liquid crystal composition, and the nematic alignment formed in the liquid crystal state by the polymerizable liquid crystal composition in the coating film is fixed. Examples of the material of the support substrate that can be used include glass and plastic. Plastics include polyimide, polyamideimide, polyamide, polyetherimide, polyetheretherketone, polyetherketone, polyketonesulfide, polyethersulfone, polysulfone, polyphenylenesulfide, polyphenyleneoxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate. , Polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, triacetyl cellulose and partially saponified product thereof, epoxy resin, phenol resin, and cycloolefin resin. The support substrate is usually in the form of a sheet or film.

  Examples of cycloolefin resins include, but are not limited to, norbornene resins and dicyclopentadiene resins. Among these, those having no unsaturated bond or hydrogenated unsaturated bond are preferably used. For example, hydrogenated products of ring-opening (co) polymers of one or more norbornene monomers, addition (co) polymers of one or more norbornene monomers, norbornene monomers and olefin monomers Addition copolymers with (ethylene, α-olefin, etc.), norbornene monomers and cycloolefin monomers (cyclopentene, cyclooctene, 5,6-dihydrodicyclopentadiene, etc.), and these Examples include modified products such as ZEONEX, ZEONOR (both trade names, manufactured by ZEON Corporation), ARTON (trade names, manufactured by JSR Corporation), TOPAS (trade names, manufactured by Ticona), APEL (trade name, manufactured by Mitsui Chemicals), Essina (trade name, manufactured by Sekisui Chemical Co., Ltd.), OPTOREZ (trade name, Hitachi) Adult Co., Ltd.) and the like.

  A film made of these plastics (plastic film) that can be used as a support substrate may be a uniaxially stretched film or a biaxially stretched film. These films may be subjected to a surface treatment such as a hydrophilic treatment such as corona treatment or plasma treatment, or a hydrophobic treatment. There are no particular restrictions on the method of hydrophilization treatment, but corona treatment or plasma treatment is preferred, and a particularly preferred method is plasma treatment. For the plasma treatment, a method described in JP 2002-226616 A, JP 2002-121648 A, or the like may be used. Further, an anchor coat layer may be formed in order to improve the adhesion between the liquid crystal film and the plastic film. As long as such an anchor coat layer enhances the adhesion between the liquid crystal film and the plastic film, there is no problem whether it is an inorganic material or an organic material. The plastic film may be a laminated film. Instead of plastic film, use a metal substrate such as aluminum, iron or copper with slit-shaped grooves on the surface, or a glass substrate such as alkali glass, borosilicate glass or flint glass whose surface is etched into a slit shape. You can also.

In the case of forming a homogeneous alignment and a tilt alignment liquid crystal film on a supporting substrate such as a glass substrate or a plastic film before forming a coating film of the polymerizable liquid crystal composition, physical and mechanical properties such as rubbing are used. Surface treatment. When a homeotropic alignment liquid crystal film is formed, surface treatment such as rubbing is often not performed, but rubbing treatment may be performed in order to prevent alignment defects. Any method can be used for the rubbing treatment, but usually a rubbing cloth made of materials such as rayon, cotton, polyamide, etc. is applied to a metal roll etc., while rotating the roll while in contact with the support substrate or polymer film. A method of moving, a method of moving the support substrate side while fixing the roll, and the like are employed. The rubbing treatment may be performed directly on the support substrate, or a polymer film such as polyimide generally called an alignment film may be provided on the support substrate in advance, and the polymer film may be subjected to the rubbing treatment. The rubbing process is as described above. Depending on the type of the supporting substrate, silicon oxide can be inclinedly deposited on the surface to impart orientation ability.

  In addition, when forming a liquid crystal film of homogeneous alignment and tilt alignment, in addition to performing physical and mechanical surface treatment by rubbing or the like, polyimide or polyacrylate or the like generally called a photo-alignment film on the support substrate in advance. A polymer film may be provided, and the polymer film may be subjected to polarized UV treatment.

  Examples of coating methods for obtaining a uniform film thickness when applying a polymerizable liquid crystal composition or a solution thereof include spin coating, micro gravure coating, gravure coating, wire bar coating, dip coating, and spray. Coating method, meniscus coating method and die coating method. In particular, a wire bar coating method or the like in which a shear stress is applied to the liquid crystal composition at the time of application may be used when the orientation of the polymerizable liquid crystal composition is controlled without performing surface treatment of the substrate by rubbing or the like.

  When applying the solution of the polymerizable liquid crystal composition of the present invention, a heat treatment may be performed to form a polymerizable liquid crystal layer having a uniform film thickness on the support substrate after application, that is, a layer of the liquid crystal composition. . For the heat treatment, a hot plate, a drying furnace, blowing of hot air or hot air can be used.

  The temperature and time when heat-treating the coating, the wavelength of light used for light irradiation, the amount of light irradiated from the light source, etc. are the types and composition ratios of the compounds used in the polymerizable liquid crystal composition, and the addition of a photopolymerization initiator. The preferred range varies depending on the presence or absence and the amount added. Accordingly, the conditions regarding the temperature and time of the heat treatment of the coating film described below, the wavelength of the light used for light irradiation, and the amount of light irradiated from the light source are merely an approximate range.

  It is preferable to perform the heat treatment of the coating film under conditions that allow uniform alignment of the polymerizable liquid crystal composition. You may carry out above the liquid crystal phase transition point of a polymeric liquid crystal composition. An example of the heat treatment method is a method in which the coating film is heated to a temperature at which the polymerizable liquid crystal composition exhibits a nematic liquid crystal phase to form a nematic alignment in the polymerizable liquid crystal composition in the coating film. The nematic alignment may be formed by changing the temperature of the coating film within a temperature range in which the polymerizable liquid crystal composition exhibits a nematic liquid crystal phase. This method is a method in which a nematic orientation is substantially completed in a coating film by heating the coating film to a high temperature range of the above temperature range, and then the order is further ordered by lowering the temperature. Regardless of which of the above heat treatment methods is employed, the heat treatment temperature is from room temperature to 120 ° C. A preferable range of this temperature is room temperature to 80 ° C, and a more preferable range is room temperature to 60 ° C. The heat treatment time is 5 seconds to 2 hours. A preferable range of this time is 10 seconds to 40 minutes, and a more preferable range is 20 seconds to 20 minutes. In order to raise the temperature of the layer made of the polymerizable liquid crystal composition to a predetermined temperature, the heat treatment time is preferably 5 seconds or more. In order not to lower the productivity, it is preferable to set the heat treatment time within 2 hours. In this way, the polymerizable liquid crystal layer of the present invention is obtained.

The nematic alignment state of the liquid crystal compound formed in the polymerizable liquid crystal layer is fixed by polymerizing the liquid crystal compound by light irradiation. The wavelength of light used for light irradiation is not particularly limited. Electron beams, ultraviolet rays, visible rays, infrared rays (heat rays), etc. can be used. Usually, ultraviolet rays or visible rays may be used. The wavelength range is 150 to 500 nm. A preferable range is 250 to 450 nm, and a more preferable range is 300 to 400 nm. Examples of light sources are low-pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), short arc discharge lamps (ultra-high pressure mercury lamps, xenon lamps, mercury xenon lamps). is there. Preferred examples of the light source are a metal halide lamp, a xenon lamp, an ultrahigh pressure mercury lamp, and a high pressure mercury lamp. The wavelength region of the irradiation light source may be selected by installing a filter or the like between the light source and the polymerizable liquid crystal layer and passing only a specific wavelength region. The amount of light irradiated from the light source is ² to 5000 mJ / cm ² when reaching the coating surface. The preferred range of light intensity is 10 to 3000 mJ
/ Cm ² , and a more preferable range is 100 to 2000 mJ / cm ² . It is preferable that the temperature condition at the time of light irradiation is set similarly to the above heat treatment temperature. The atmosphere of the polymerization environment may be any of a nitrogen atmosphere, an inert gas atmosphere, and an air atmosphere, but a nitrogen atmosphere or an inert gas atmosphere is preferable from the viewpoint of improving curability.

  When the polymerizable liquid crystal layer of the present invention and a liquid crystal film obtained by polymerizing the polymerizable liquid crystal layer with light or heat are used for various optical elements, or when applied as an optical compensation element for a liquid crystal display device, the liquid crystal in the thickness direction is used. Control of the tilt angle distribution of the molecule is extremely important.

  One method of controlling the tilt angle is a method of adjusting the type and composition ratio of the liquid crystal compound used in the polymerizable liquid crystal composition. The tilt angle can also be controlled by adding other components to the polymerizable liquid crystal composition. The tilt angle of the liquid crystal film can also be controlled by the kind and amount of the solvent in the polymerizable liquid crystal composition, the kind and amount of the surfactant added as one of the other components, and the like. The tilt angle of the liquid crystal film can also be controlled by the type of support substrate or polymer film, rubbing conditions, drying conditions of the coating film of the polymerizable liquid crystal composition, heat treatment conditions, and the like. Furthermore, the irradiation atmosphere in the photopolymerization step after alignment, the temperature at the time of irradiation, etc. also affect the tilt angle of the liquid crystal film. That is, it can be considered that almost all conditions in the manufacturing process of the liquid crystal film affect the tilt angle to some extent. Therefore, by optimizing the polymerizable liquid crystal composition and appropriately selecting various conditions for the production process of the liquid crystal film, an arbitrary tilt angle can be obtained.

  In the homogeneous orientation, the tilt angle is uniformly close to 0 degrees from the substrate interface to the free interface, and is particularly distributed in the range of 0 to 5 degrees. This alignment state is obtained by applying the polymerizable liquid crystal composition of the present invention to the surface of a support substrate that has been subjected to a surface treatment such as rubbing to form a coating film.

A chiral compound, that is, a compound having optical activity, may be added to the polymerizable liquid crystal composition of the present invention. Preferred examples of the optically active compound are compounds represented by formulas (Op-1) to (Op-25). In these formulas, Ak represents alkyl having 1 to 15 carbons or alkoxy having 1 to 15 carbons, and Me, Et and Ph represent methyl, ethyl and phenyl, respectively. P ² is a polymerizable group, and is preferably a group containing (meth) acryloyloxy, vinyloxy, oxiranyl, or oxetanyl. The polymerizable liquid crystal composition of the present invention may be used as a raw material of a polymer described below, or as a liquid crystal that is a constituent element of a liquid crystal display element.

具体例として、特開２０１１−１４８７６２号公報のｐ．７０の段落０１５９〜ｐ．８１の段落０１７０記載のものがある。

As a specific example, p. 70, paragraphs 0159-p. 81, paragraph 0170.

  By polymerizing a polymerizable liquid crystal composition containing a suitable amount of a compound having optical activity or a polymerizable liquid crystal composition containing a suitable amount of a polymerizable compound having optical activity on an alignment-treated substrate. A retardation film showing a helical structure (twist structure) is obtained. The helical structure is fixed by polymerization of the polymerizable liquid crystal composition. The properties of the obtained liquid crystal film depend on the helical pitch of the obtained helical structure. The helical pitch length can be adjusted depending on the type and amount of the optically active compound. One optically active compound may be added, but a plurality of optically active compounds may be used for the purpose of offsetting the temperature dependence of the helical pitch. The polymerizable liquid crystal composition may contain other polymerizable compounds in addition to the optically active compound.

In the selective reflection of visible light, which is a characteristic of the liquid crystal film as described above, the helical structure acts on incident light and reflects circularly polarized light and elliptically polarized light. The selective reflection characteristic is expressed by λ = n · Pitch (λ is the central wavelength of selective reflection, n is the average refractive index, and Pitch is the helical pitch). By changing n or Pitch, the center wavelength (λ) and wavelength width are changed. (Δλ) can be appropriately prepared. In order to improve color purity, the wavelength width (Δλ) may be reduced, and when broadband reflection is desired, the wavelength width (Δλ) may be increased. Furthermore, this selective reflection is greatly influenced by the thickness of the polymer. In order to maintain color purity, the thickness must not be too small. In order to maintain uniform orientation, the thickness must not be too large. Accordingly, it is necessary to prepare an appropriate thickness, preferably 0.5 to 25 μm, and more preferably 1 to 10 μm.

  By making the helical pitch shorter than visible light, a negative C plate described in W. H. de Jeu, Physical Properties of Liquid Crystalline Materials, Gordon and Breach, New York (1980) can be prepared. In order to shorten the helical pitch, it can be achieved by using an optically active compound having a large twisting force (HTP: helical twisting power) and further increasing the amount of addition. Specifically, a negative C plate can be prepared by setting λ to 350 nm or less, preferably 250 nm or less. This negative type C plate is an optical compensation film suitable for VAN type, VAC type, OCB type and the like among liquid crystal display elements.

  The liquid crystal film may be used for a reflective film in which the reflection wavelength region as described in JP-A-2004-333671 is set to the near infrared (wavelength 800 to 2500 nm) by making the helical pitch longer than visible light. it can. Increasing the helical pitch can be achieved, for example, by using an optically active compound having a small twisting force or by reducing the amount of optically active compound added.

  Any optically active compound may be used as long as it induces a helical structure and can be appropriately mixed with the polymerizable liquid crystal composition as a base. In addition, either a polymerizable compound or a non-polymerizable compound may be used, and an optimum compound can be added according to the purpose. In view of heat resistance and solvent resistance, a polymerizable compound is more preferable.

  Further, among the optically active compounds, those having a large twisting force (HTP: helical twisting power) are suitable for shortening the helical pitch. Representative examples of compounds having a large torsional force are disclosed in GB2298202 and DE10221751.

  The thickness (film thickness) of the liquid crystal film varies depending on the retardation corresponding to the target element and the birefringence (optical anisotropy value) of the liquid crystal film. Accordingly, the thickness range is 0.05 to 100 μm as a guide, although it varies depending on the purpose. A more preferable range is 0.1 to 50 μm, and a further preferable range is 0.5 to 20 μm. The preferred haze value of the liquid crystal film is 2.0% or less, and the preferred transmittance is 80% or more. A more preferable haze value is 1.0% or less, and a more preferable transmittance is 90% or more. The transmittance preferably satisfies these conditions in the visible light region.

As the birefringence (optical anisotropy value) of the liquid crystal film is higher, the thickness can be reduced. The thinner the thickness, the better the optical properties such as haze value and transmittance.
The liquid crystal film is effective as an optical compensation element applied to liquid crystal display elements (particularly active matrix type and passive matrix type liquid crystal display elements). Examples of liquid crystal display element types suitable for using this liquid crystal film as an optical compensation film are IPS type (in-
Plane switching), OCB type (optically compensated birefringence), TN type (twisted nematic), STN type (super twisted nematic), ECB type (electrically controlled birefringence), DAP Type (alignment phase deformation effect), CSH type (color super homeotropic), VAN / VAC type (vertically oriented nematic / cholesteric), OMI type (optical mode interference), SBE type (super birefringence effect), etc. It is. Further, the liquid crystal film can be used as a phase letter for a display element such as a guest-host type, a ferroelectric type, or an antiferroelectric type. Note that the optimum values of parameters such as the thickness distribution and thickness of the tilt angle required for the liquid crystal film strongly depend on the type of liquid crystal display element to be compensated and its optical parameters, and therefore differ depending on the type of element.

The liquid crystal film can also be used as an optical element integrated with a polarizing plate or the like. In this case, the liquid crystal film is disposed outside the liquid crystal cell. On the other hand, since the liquid crystal film as the optical compensation element has little or no elution of impurities into the liquid crystal filled in the cell, it can be arranged inside the liquid crystal cell. For example, when the method disclosed in Japanese Patent Application Laid-Open No. 2008-01943 is applied, the function of the color filter can be further improved by forming the polymerizable liquid crystal layer of the present invention on the color filter. The type of polarizing plate used in the optical element to which the present liquid crystal film can be applied is not particularly limited, and includes not only a widely used absorption type polarizing plate doped with iodine, but also a reflective polarizing type such as a wire grid polarizing plate. It can also be suitably used for optical compensation of the plate.

The liquid crystal film may contain additives such as a dichroic dye. The dichroic dye preferably has a maximum absorption wavelength (λ _MAX ) in the range of 300 to 700 nm. Examples of such dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes and anthraquinone dyes, and among them, azo dyes are preferable. Examples of the azo dye include a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, and a stilbene azo dye, and a bisazo dye and a trisazo dye are preferable. The homogeneously oriented liquid crystal film combined with the dichroic dye can also be used as an absorptive polarizing plate. The homogeneously oriented liquid crystal film combined with the fluorescent dye can also be used as a polarized light emitting film.

In the optically anisotropic film according to the present invention, the birefringence Δn (450) at a wavelength of 450 nm and the birefringence Δn (550) at a wavelength of 550 nm satisfy the relationship of Δn (450) / Δn (550) ≦ 1.05. Has wavelength dispersion. An optically anisotropic film satisfying the above-mentioned wavelength dispersion characteristics can improve visibility such as color unevenness and viewing angle as compared with a conventional optically anisotropic film using a polymerizable liquid crystal.
In particular, it is more preferable to have wavelength dispersion satisfying the relationship of 0.75 ≦ Δn (450) / Δn (550) ≦ 1.05.
If the value of Δn (450) / Δn (550) is too small, the optimal retardation for green will cause the blue retardation to be too small from the optimum value, so the viewing angle characteristics will be poor. On the other hand, if the retardation is too large, the optimal retardation for green will cause the blue retardation to become too large from the optimum value, resulting in poor viewing angle characteristics.
Those satisfying the above relational expression are different from the conventional ones in that the wavelength dispersion of the refractive index is low and further reversed (the birefringence increases as the wavelength increases), and the optical system is more optimized. An anisotropic film material can be provided.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not restrict | limited by these Examples.
<Confirmation of compound structure>
The structure of the synthesized compound was confirmed by measurement of proton NMR (Bruker: DRX-500) at 500 MHz. The described numerical value represents ppm, s represents a singlet, d represents a doublet, t represents a triplet, and m represents a multiplet.

<Phase transition temperature>
A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope, and the temperature was raised at a rate of 3 ° C./min. The temperature at which the phase transitions to another phase was measured. C is a crystal, N is a nematic phase, S is a smectic phase, and I is an isotropic liquid. The NI point is the upper limit temperature of the nematic phase or the transition temperature from the nematic phase to the isotropic liquid. “C50N63I” indicates that the crystal transitioned to the nematic phase at 50 ° C., and the transition from the nematic phase to the isotropic liquid at 63 ° C. The parentheses indicate a monotropic liquid crystal phase.

<Polymerization conditions>
In a nitrogen atmosphere, light having an intensity of 30 mW / cm ² (365 nm) was irradiated for 30 seconds using a 250 W ultrahigh pressure mercury lamp (manufactured by USHIO INC., Multilight-250) at room temperature.

<Evaluation of orientation>
(1) Preparation of glass substrate with alignment film after rubbing treatment A 1.1 mm-thick glass substrate was spin-coated with polyamic acid for low pretilt angle (horizontal alignment mode) (Rixon aligner: manufactured by PIA-5370 JNC Corporation). After removing the solvent from the spin-coated film on an 80 ° C. hot plate, the film was baked in an oven at 230 ° C. for 30 minutes and rubbed using a rayon cloth.

(2) Observation method by visual observation A substrate on which a retardation film was formed was sandwiched and observed between two polarizing plates arranged in crossed Nicols, and the substrate was rotated in a horizontal plane to confirm the light and dark state. The substrate on which the retardation film was formed was observed with a polarizing microscope, and the presence or absence of alignment defects was confirmed.

(3) Measurement by ellipsometer Using an OPIPRO ellipsometer manufactured by Shintech Co., Ltd., the substrate on which the retardation film was formed was irradiated with light having wavelengths of 550 nm and 450 nm. Retardation was measured while decreasing the incident angle of these lights from 90 ° with respect to the film surface. Retardation (retardation; also called retardation, retardation) is represented by Δn × d. Symbol Δn is the birefringence (optical anisotropy value), and symbol d is the thickness of the polymer film.

<Film thickness measurement>
The layer of the liquid crystal film of the glass substrate with a liquid crystal film was cut out, and the step was measured using a fine shape measuring apparatus (Alphastep IQ, manufactured by KLA TENCOR Co., Ltd.).

<Evaluation of birefringence (Δn)>
Birefringence (Δn) = Retardation (Re) / Thickness (d) From the retardation and film thickness when the incident angle of light obtained for the liquid crystal film having homogeneous orientation is 90 ° with respect to the film surface. Calculated as

<Evaluation of wavelength dispersion characteristics>
As a chromatic dispersion characteristic, a value obtained from the following equation was used as an index.
Wavelength dispersion characteristic = Retardation measured with 450 nm light (Re _{450 nm} ) / 550
Retardation measured with light of nm (Re _{550 nm} ). That is, the smaller the chromatic dispersion characteristic value, the higher the low chromatic dispersion property, and the reverse chromatic dispersion characteristic when the value is 1 or less.

<Pencil hardness>
It measured according to the method of JIS standard "JIS-K-5400 8.4 pencil scratch test".
In other words, using a pencil hardness meter (C-221 manufactured by Yoshimitsu Seiki), the shape of the pencil lead when scratching is caused by scratching with a lead (Mitsubishi Pencil Co., Ltd. Uni) fixed at an angle of 45 °. It was measured.

[Example 1]
The following compound (1-1-1-1) was synthesized as follows.

  1,6.6 g of 2,5-dimethoxybenzaldehyde, 14.6 g of indene-1,3-dione, and 1.8 g of p-toluenesulfonic acid (PPTS) were added to 166 mL of toluene, and the mixture was stirred under reflux for 8 hours under a nitrogen atmosphere. After allowing to cool, the precipitate was filtered off. The obtained crystals were dissolved in dichloromethane, washed with saturated aqueous sodium hydrogen carbonate and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and dried under reduced pressure to obtain 19.4 g of compound (ex-1).

8.9 g of the compound (ex-1) was added to 178 mL of dichloromethane, and the mixture was stirred while cooling at −78 ° C. under a nitrogen atmosphere. There, 19.2 g of boron tribromide (BBr ₃ ) was added dropwise. After dropping, the mixture was stirred at -78 ° C for 1 hour, and then stirred at room temperature for 16 hours. The reaction mixture was quenched by pouring into ice water, and the precipitate was filtered off. The obtained crystals were washed well with water and dried under reduced pressure to obtain 7.8 g of compound (ex-2).

25.0 g of trans-4-hydroxycyclohexanecarboxylic acid and 26.3 g of triethylamine were added to 125 mL of N, N-dimethylformamide (DMF) and stirred while cooling at 10 ° C. or lower in a nitrogen atmosphere. Thereto, 14.7 g of chloromethyl methyl ether was slowly added dropwise. After dropping, the mixture was stirred at room temperature for 8 hours. Ethyl acetate and water were added to extract the organic layer, and the organic layer was washed with saturated multilayer water and water, and dried over anhydrous magnesium sulfate. The ethyl acetate was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 2/1)) and dried under reduced pressure. , 25.2 g of compound (ex-3) was obtained.

25.2 g of compound (ex-3), 42.9 g of compound (ex-4), and 3.3 g of 4-dimethylaminopyridine (DMAP) were added to 430 mL of dichloromethane, and the mixture was stirred while cooling under a nitrogen atmosphere. Thereto was added dropwise 60 mL of a dichloromethane solution of 29.0 g of 1,3-dicyclohexylcarbodiimide (DCC). After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with saturated multistory water and water, and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) and dried under reduced pressure. The obtained residue and 2.1 g of p-toluenesulfonic acid (pTSA) were added to a mixed solution of 110 mL of THF and 55 mL of IPA, and the mixture was heated and stirred at 40 ° C. for 8 hours. Ethyl acetate and water were added to extract the organic layer, and the organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized with a mixed solution of ethyl acetate and heptane to obtain 31.8 g of compound (ex-5).

  Compound (ex-2) (1.5 g), compound (ex-5) (5.0 g) and DMAP (0.3 g) were added to dichloromethane (50 mL), and the mixture was stirred under cooling in a nitrogen atmosphere. Thereto, 5 mL of a dichloromethane solution of 2.4 g of DCC was dropped. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane is distilled off under reduced pressure, and the residue is purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and recrystallized from methanol. As a result, 2.4 g of the compound (1-1-1-1) was obtained.

The phase transition temperature and NMR analysis value of the obtained compound (1-1-1-1) are as follows.
Phase transition temperature (° C.): C 121 I
¹ H-NMR (CDCl ₃ ; δ ppm): 8.89 (d, 1H), 8.06 to 8.00 (m
, 2H), 7.94 (s, 1H), 7.87-7.82 (m, 2H), 7.32-7.28 (m, 1H), 7.16 (d, 1H), 7. 11 (d, 4H), 6.82 (d, 4H), 6.40 (d, 2H), 6.15-6.08 (m, 2H), 4.83-4.75 (m, 2H) , 4.17 (t, 4H), 3.94 (t, 4H), 2.90 (t, 4H), 2.73-2.88 (m, 4H), 2.73-2.65 (m , 1H), 2.64-2.56 (m, 5H), 2.30-2.19 (m, 4H), 2.14-2.05 (m, 4H), 1.84-1.68. (M, 12H), 1.55-1.41 (m, 12H).

[Example 2]
The compound (1-1-2-1) shown below was synthesized as follows.

  2,5-Dimethoxybenzaldehyde (5.0 g) and inden-1-one (4.0 g) were added to EtOH (50 mL), followed by stirring while cooling at 10 ° C. or lower in a nitrogen atmosphere. Thereto, 3.1 g of 40 wt% NaOH aqueous solution was slowly dropped. After dropping, the mixture was stirred at room temperature for 16 hours. 100 mL of water was added, the precipitate was filtered off, the crystals were washed with water and MeOH, and the obtained crystals were dried under reduced pressure to obtain 7.7 g of compound (ex-6).

7.7 g of compound (ex-6) was added to 155 mL of dichloromethane, and the mixture was stirred while cooling at −78 ° C. under a nitrogen atmosphere. There, 15.2 g of boron tribromide (BBr ₃ ) was added dropwise. After dropping, the mixture was stirred at -78 ° C for 1 hour, and then stirred at room temperature for 16 hours. The reaction mixture was quenched by pouring into ice water, and the precipitate was filtered off. The crystals were washed thoroughly with water and dried under reduced pressure to obtain 6.9 g of compound (ex-7).

  Compound (ex-7) (1.4 g), compound (ex-5) (5.0 g), and DMAP (0.3 g) were added to dichloromethane (50 mL), and the mixture was stirred under cooling in a nitrogen atmosphere. Thereto, 5 mL of a dichloromethane solution of 2.4 g of DCC was dropped. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane is distilled off under reduced pressure, and the residue is purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and recrystallized from methanol. Gave 3.8 g of compound (1-1-2-1).

The phase transition temperature and NMR analysis value of the obtained compound (1-1-2-1) are as follows.
Phase transition temperature (° C): C 89 (N 70) I
¹ H-NMR (CDCl ₃ ; δ ppm): 7.90 (d, 1H), 7.65-7.61 (m
, 2H), 7.57 (d, 1H), 7.48-7.41 (m, 2H), 7.14-7.08 (m, 6H), 6.82 (d, 4H), 6. 40 (d, 2H), 6.16-6.09 (m, 2H), 5.82 (d, 2H), 4.83-4.74 (m, 2H), 4.17 (t, 4H) 3.98 (S, 2H), 3.94 (t, 4H), 2.92-2.86 (m, 4H), 2.68-2.55 (m, 6H), 2.26-2 .18 (m, 4H), 2.12-2.05 (m, 4H), 1.83-1.67 (m, 12H), 1.55-1.41 (m, 12H).

[Example 3]
The following compound (1-1-5-1) was synthesized as follows.

10.0 g of 2,5-dimethoxybenzaldehyde, 10.5 g of 3-methyl-1-phenylpyrazolone, and 1.5 g of MgO were added to 100 mL of acetonitrile, and the mixture was stirred at reflux for 8 h under a nitrogen atmosphere. After cooling, ethyl acetate and water were added for extraction. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was toluene / MeOH.
Was recrystallized to obtain 8.8 g of compound (ex-8).

Compound (ex-8) 6.0g was added to dichloromethane 120mL, and it stirred, cooling at -78 degreeC by nitrogen atmosphere. To this, 10.3 g of boron tribromide (BBr ₃ ) was added dropwise. After dropping, the mixture was stirred at -78 ° C for 1 hour, and then stirred at room temperature for 16 hours. The reaction mixture was quenched by pouring into ice water, and the precipitate was filtered off. The crystal was washed well with water and dried under reduced pressure to obtain 4.1 g of Compound (ex-9).

  1.6 g of compound (ex-9), 5.0 g of compound (ex-5), and 0.3 g of DMAP were added to 50 mL of dichloromethane, and the mixture was stirred while cooling under a nitrogen atmosphere. Thereto, 5 mL of a dichloromethane solution of 2.4 g of DCC was dropped. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was filtered off, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and recrystallized from methanol. As a result, 0.7 g of the compound (1-1-5-1) was obtained.

The phase transition temperature and NMR analysis value of the obtained compound (1-1-5-1) are as follows.
Phase transition temperature (° C.): C 95 (N 57) I
¹ H-NMR (CDCl ₃ ; δ ppm): 8.94 (d, 1H), 7.89 (d, 2H),
7.41 (t, 3H), 7.31-7.25 (m, 1H), 7.23-7.15 (m, 2H), 7.11 (d, 4H), 6.82 (d, 4H), 6.40 (d, 2H), 6.16-6.09 (m, 2H), 5.82 (d, 2H), 4.80-4.73 (m, 2H), 4.17 (T, 4H), 3.93 (t, 4H), 2.89 (t, 4H), 2.68-2.54 (m, 6H), 2.29 (s, 3H), 2.26 2.03 (m, 8H), 1.82-1.66 (m, 12H), 1.55-1.38 (m, 12H).

[Example 4]
The following compound (1-1-3-1) was synthesized as follows.

  Compound (ex-10) was obtained by using naphthalene as a starting material. Org. Chem. 76, 8599-8610 (2011).

2.5 g of 2,5-dimethoxybenzaldehyde and 2.7 g of the compound (ex-10) were added to 25 mL of EtOH and stirred while cooling at 10 ° C. or lower under a nitrogen atmosphere. Thereto, 1.6 g of 40 wt% NaOH aqueous solution was slowly dropped. After dropping, the mixture was stirred at room temperature for 16 hours. 50 mL of water was added, the precipitate was filtered off, and the crystals were washed with water and MeOH. The obtained crystals were recrystallized from toluene / MeOH to obtain 3.8 g of compound (ex-11).
Got.

3.8 g of the compound (ex-11) was added to 76 mL of dichloromethane, and the mixture was stirred while cooling at −78 ° C. under a nitrogen atmosphere. There, 6.4 g of boron tribromide (BBr ₃ ) was added dropwise.
After dropping, the mixture was stirred at -78 ° C for 1 hour, and then stirred at room temperature for 16 hours. The reaction mixture was quenched by pouring into ice water, and the precipitate was filtered off. The crystals were washed well with water and dried under reduced pressure to obtain 3.4 g of compound (ex-12).

  1.7 g of compound (ex-12), 5.0 g of compound (ex-5), and 0.3 g of DMAP were added to 50 mL of dichloromethane, and the mixture was stirred while cooling under a nitrogen atmosphere. Thereto, 5 mL of a dichloromethane solution of 2.4 g of DCC was dropped. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane is distilled off under reduced pressure, and the residue is purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and recrystallized from methanol. As a result, 4.6 g of the compound (1-1-3-1) was obtained.

The phase transition temperature and NMR analysis value of the obtained compound (1-1-3-1) are as follows.
Phase transition temperature (° C.): C 115 (N 81) I
¹ H-NMR (CDCl ₃ ; δ ppm): 9.29 (d, 1H), 8.10 (d, 1H),
7.93 (d, 1H), 7.72 (t, 1H), 7.66 (s, 1H), 7.63-7.58 (m, 2H), 7.51 (s, 1H), 7 .12 (d, 4H), 6.83 (d, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 4.83-4.75 (m, 2H) ), 4.19-4.14 (m, 4H), 4.07 (s, 2H), 3.94 (t, 4H), 2.90 (t, 4H), 2.71-2.56 ( m, 6H), 2.30-2.19 (m, 4H), 2.14 to 2.06 (m, 4H), 1.83 to 1.68 (m, 12H), 1.55-1. 41 (m, 12H).

[Example 5]
The compound (1-1-4-1) shown below was synthesized as follows.

  Compound (ex-13) was obtained by using 2-naphthyloxyacetic acid as a starting material. Lett. , Vol. 2, pp. 2817-2820 (2000).

1.8 g of 2,5-dimethoxybenzaldehyde, 2.0 g of the compound (ex-13) and 0.2 g of piperidine were added to 20 mL of toluene, and the mixture was stirred under reflux for 3 hours under a nitrogen atmosphere. After allowing to cool, water was added to wash the organic layer, and it was dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue was recrystallized with toluene / MeOH to give compound (ex-14) 3.1.
g was obtained.

Compound (ex-14) (3.1 g) was added to dichloromethane (16 mL), and the mixture was stirred while cooling at -78 ° C under a nitrogen atmosphere. There, 5.1 g of boron tribromide (BBr ₃ ) was added dropwise.
After dropping, the mixture was stirred at -78 ° C for 1 hour, and then stirred at room temperature for 16 hours. The reaction mixture was quenched by pouring into ice water, and the precipitate was filtered off. The crystals were thoroughly washed with water and dried under reduced pressure to obtain 2.7 g of compound (ex-15).

  2.7 g of compound (ex-15), 8.1 g of compound (ex-5), and 0.4 g of DMAP were added to 80 mL of dichloromethane, and the mixture was stirred while cooling under a nitrogen atmosphere. Thereto was added dropwise 8 mL of a DCC 3.9 g dichloromethane solution. After dropping, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 14/1)) and recrystallized from methanol. Gave 7.8 g of compound (1-1-4-1).

The phase transition temperature and NMR analysis value of the obtained compound (1-1-4-1) are as follows.
Phase transition temperature (° C.): C 122 (N 96) I
¹ H-NMR (CDCl ₃ ; δ ppm): 8.83 (d, 1H), 8.15 (d, 1H),
8.06 (s, 1H), 7.90 (d, 1H), 7.72 (t, 1H), 7.54 (t, 1H), 7.47 (d, 1H), 7.13 (d , 4H), 6.94 (s, 1H), 6.83 (d, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 5.81 (d, 2H), 4.83-4.76 (m, 2H), 4.17 (t, 4H), 3.96-3.92 (m, 4H), 2.89 (t, 4H), 2.75. -2.68 (m, 1H), 2.67-2.58 (m, 5H), 2.32-2.20 (m, 4H), 2.15-2.06 (m, 4H), 1 .85-1.67 (m, 12H), 1.55-1.41 (m, 12H).

重合性液晶組成物における本発明化合物の種類と含有量、その他の重合性液晶化合物の種類と含有量、重合開始剤の含有量、界面活性剤の含有量、および溶剤の含有量を表１および表２に示した。ここで表１および表２中、％は重合性液晶組成物の総重量を１００重量％としたときの各材料の含有重量％を示す。重合開始剤はイルガキュアー９０７（Ｉｒｇ−９０７、ＢＡＳＦジャパン（株）製）またはアデカクルーズＮＣＩ−９３０（（株）ＡＤＥＫＡ製）を用い、界面活性剤はフタージェントＦＴＸ−２１８（（株）ネオス製 ）またはＴＥＧＯＦｌｏｗ３７０（エボニック・ジャパン（株））を用い、溶剤はシクロヘキサノンを使用した。 <Preparation of polymerizable liquid crystal composition>
[Example 6]
The compound of the present invention synthesized above and the following compounds (M2-7-1), (M1-15-1), (M1-16-1), (M2-1-1) and (M1-24-1) The polymerizable liquid crystal compositions shown in Table 1 and Table 2 were prepared using

Table 1 shows the type and content of the compound of the present invention in the polymerizable liquid crystal composition, the type and content of other polymerizable liquid crystal compounds, the content of the polymerization initiator, the content of the surfactant, and the content of the solvent. It is shown in Table 2. Here, in Tables 1 and 2, “%” indicates the content weight% of each material when the total weight of the polymerizable liquid crystal composition is 100% by weight. Irgacure 907 (Irg-907, manufactured by BASF Japan) or Adeka Cruz NCI-930 (manufactured by ADEKA) was used as the polymerization initiator, and surfactant FTX-218 (manufactured by Neos) was used as the surfactant. ) Or TEGOFlow 370 (Evonik Japan Co., Ltd.), and cyclohexanone was used as the solvent.

[Comparative Example 1]
Similar to the method described in Example 6, the compounds (M2-7-1), (M1-15-1), (M1-16-1), (M2-1-1) and (M1-24-1) The liquid crystal composition shown in Table 3 was produced.

<Preparation of optically anisotropic film>

[Example 7]
The liquid crystal compositions (S-1) to (S-7) produced in Example 3 were applied onto a glass substrate with a rubbed alignment film by spin coating. The substrate was heated at 80 ° C. for 2 minutes, further heated at 60 ° C. for 1 minute, then cooled at room temperature for 1 minute, and the polymerizable liquid crystal layer from which the solvent had been removed was polymerized by irradiation with ultraviolet rays in the air, An optically anisotropic film having a fixed orientation state was obtained. When the obtained optically anisotropic films were confirmed with a polarizing microscope and an ellipsometer, they had no homogeneous defects and had uniform homogeneous orientation.

[Comparative Example 2]
In the same manner as in the method described in Example 7, optically anisotropic films were obtained from the liquid crystal compositions (SC-1) and (SC-2) prepared in Comparative Example 1. These obtained optically anisotropic films were confirmed with a polarizing microscope and an ellipsometer, and confirmed to have homogeneous orientation.

<Optical characteristics of optically anisotropic film>
[Examples 8 to 14, Comparative Examples 3 to 4]
The measured value of 450 nm wavelength (Re ₄₅₀ ) and the measured value of 550 nm wavelength (Re ₅₅₀ ), the film thickness of the retardation of 90 degrees with respect to the film surface of the optically anisotropic film produced in Example 4 and Comparative Example 2. Table 4 shows Δn at a wavelength of 550 nm and wavelength dispersion characteristics (Re ₄₅₀ / Re ₅₅₀ ).

  The optically anisotropic films of Examples 8 to 14 showed a low value of wavelength dispersion characteristics of 1.05 or less as compared with Comparative Examples 3 and 4. This indicates that the composition containing the polymerizable liquid crystal compound of the present invention can exhibit lower wavelength dispersion characteristics, and optical anisotropy is achieved by using the polymerizable liquid crystal composition of the present invention. It was revealed that the wavelength dispersion characteristics of the film can be controlled. In addition, in the optically anisotropic films of Examples 13 and 14, the wavelength dispersion characteristics showed a value of 1 or less, and it was confirmed that the optical anisotropic films had reverse wavelength dispersion characteristics.

  By using the polymerizable liquid crystal composition of the present invention, an optically anisotropic film having low wavelength dispersion characteristics or reverse wavelength dispersion characteristics can be easily obtained. Therefore, the obtained optical anisotropic film includes, for example, a retardation film, an optical compensation film, a reflection film, a selective reflection film, an antireflection film, a viewing angle compensation film, a liquid crystal alignment film, a polarizing element, a circular polarizing element, and It is suitable for a display element having a film or element made of an optically anisotropic film such as an elliptically polarizing element.

Claims (15)

A polymerizable liquid crystal compound represented by the formula ( 1-1 ).

(In the formula ( 1-1 ),
A ¹ is each independently 1,4-phenylene or 1,4-cyclohexylene, and in this 1,4-phenylene, at least one hydrogen is fluorine, chlorine, trifluoromethyl, C 1-5. May be substituted with alkyl, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons, or alkanoyl having 1 to 5 carbons;
Z ¹ is each independently a single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—,
_{-CF 2 O -, - OCF 2} -, - CH 2 CH 2 -, - CF 2 CF 2 -, - OCH 2 CH 2 O -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH ₂ CH ₂ OCO—, or —COOCH ₂ CH ₂ —;
T ¹ is hydrogen or methyl ;
Y ¹ is independently a single bond, —O—, —COO—, —OCO—, or —OCOO—.
Is;
Each Q ¹ is independently a single bond or alkylene having 1 to 20 carbon atoms, and in the alkylene, at least one —CH ₂ — may be replaced by —O—, —COO—, or —OCO—;
PG _{is, -O-CO-C (=} CH 2) polymerizable groups der represented by ^{R 1} is, in PG, hydrogen R ¹ is independently, halogen, methyl, ethyl or trifluoromethyl, der Ri; G is a group represented by any one of formulas (G-1) ~ (G -12). )

(In formulas (G-1) to (G-12), X ¹ is —CH ₂ —, —CO—, —O— or —S—, respectively ; X ² is independently O or S ; R ² is hydrogen, alkyl having 1 to 5 carbon atoms, alkanoyl having 1 to 5 carbon atoms or optionally substituted phenyl; at least one hydrogen is fluorine, chlorine, cyano, trifluoroacetyl, trimethyl; Substituted with fluoromethyl, optionally substituted phenyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons, or alkanoyl having 1 to 5 carbons In addition, the rice symbol (*) in the formulas (G-1) to (G-12) indicates the position of carbon having a double bond. The polymerizable liquid crystal compound according to claim 1, wherein at least one of A ¹ is 1,4-cyclohexylene. The polymerizable liquid crystal compound according to claim 1, wherein R ¹ is hydrogen or methyl . At least one of Z ¹ is -CH ₂ CH ₂ COO- or -OCOCH ₂ CH ₂ - is a polymerizable liquid crystal compound according to any one of claims 1-3. A polymerizable liquid crystal composition comprising at least one polymerizable liquid crystal compound according to any one of claims 1 to 4 . The content of the polymerizable liquid crystal compound according to any one of claims 1 to 4, relative to the total amount of the polymerizable liquid crystal composition, 4 wt% or more and 50 wt% or less, according to claim 5 Polymerizable liquid crystal composition. Optically anisotropic film obtained by irradiating light to the polymerizable liquid crystal composition according to claim 5 or 6. The optically anisotropic film according to claim 7 , wherein the liquid crystal molecules are fixed in a state of being horizontally aligned with respect to the substrate. The optically anisotropic film according to claim 7 , wherein the liquid crystal molecules are fixed in a state of being vertically aligned with respect to the substrate. The optically anisotropic film according to claim 7 , wherein the liquid crystal molecules are fixed in a twist aligned state. The optically anisotropic film according to claim 7 , wherein the liquid crystal molecules are fixed in a state in which the liquid crystal molecules are inclined and aligned with respect to the substrate. Birefringence wavelength 450nm to light [Delta] n (450) and the birefringence at a wavelength of 550nm to light [Delta] n (550) satisfies the relation of Δn (450) / Δn (550 ) ≦ 1.05, claims 7 to 11 The optically anisotropic film according to any one of the above. A polarizing plate having an optical anisotropic film according to any one of claims 7 to 12. Display device having an optical anisotropic film according to any one of claims 7 to 12. A display element comprising the polarizing plate according to claim 13 .