JP2019206677A - Polymerizable liquid crystal compound, composition and polymer thereof - Google Patents

Abstract

To provide a polymerizable liquid crystal compound for the production of an optically anisotropic film that can control wavelength dispersion characteristics and shows low wavelength dispersion characteristics and reverse wavelength dispersion characteristics.SOLUTION: The present invention provides a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound represented by formula (1) of 30 wt.% or more. In formula (1), Aindependently represent 1,4-phenylene or the like; Zindependently represent a single bond, -OCH- or the like; m independently represent an integer of 0-3; at least one m is 1 or more; Aris an aromatic ring or the like; Arhas carbon atoms of 18 or less; Rindependently represent hydrogen or the like or a group represented by formula (2).SELECTED DRAWING: None

Description

  The present invention relates to a polymerizable liquid crystal compound, a polymerizable liquid crystal composition containing the compound, a polymer obtained from the composition, an optically anisotropic film, and uses thereof.

In recent years, liquid crystal compounds having a polymerizable group have been utilized for optically anisotropic films exhibiting birefringence (optical anisotropy) such as reflective polarizing plates and retardation plates. When this compound is oriented in a liquid crystal state and polymerized, the orientation of the liquid crystal can be fixed. Examples of the orientation include homogeneous (horizontal orientation), tilt (tilted orientation), homeotropic (vertical orientation), and twist (twist orientation).

  A retardation plate obtained using a polymerizable liquid crystal compound exhibits a large birefringence as compared with a conventionally used stretched film retardation plate, and thus can be thinned. A retardation plate obtained using a polymerizable liquid crystal compound can be directly applied to a substrate, and therefore does not require an adhesive layer. A retardation plate obtained by using a polymerizable liquid crystal compound has excellent characteristics such as a low rate of change in characteristics with respect to the external environment because a strong network can be constructed. Since the three-dimensional refractive index can be easily controlled by controlling the orientation of the liquid crystal, the retardation plate obtained using the polymerizable liquid crystal compound has excellent moldability.

  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. Can do.

An optically anisotropic film having homeotropic orientation has an optical axis direction in the _nz direction, and the refractive index in the optical axis direction is larger than the refractive index in the orthogonal direction. Classified into plates. 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. .

  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. Moreover, since it is often difficult to control the above-mentioned anisotropy and alignment characteristics alone, a polymerizable liquid crystal composition in which various compounds are mixed is used.

  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 a substrate, the solvent is dried, and the polymerizable liquid crystal composition is aligned on the substrate. At this time, if a substrate subjected to an alignment treatment is used, a uniform alignment state is easily obtained. Next, it is polymerized by irradiating with ultraviolet rays to fix the alignment state. Usually, the process from drying and removal of the solvent to polymerization is performed at room temperature, and during this time, a uniform liquid crystal state must be maintained without precipitation of crystals and the like. Good compatibility with compounds and high solubility in organic solvents are required. The polymerizable liquid crystal composition is required 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 is also required to have properties such as high transparency, mechanical strength, adhesion to a substrate, low shrinkage, heat resistance, and chemical resistance.

  In an optically anisotropic layer formed of rod-like molecules, normally, two refractive indexes ne of an anisotropic molecule (ne is an extraordinary refractive index in a direction parallel to the molecular long axis) and no (no is The normal refractive index in the direction perpendicular to the molecular long axis decreases as the wavelength increases. At this time, ne has a larger refractive index change with respect to the wavelength than ne, so that the birefringence (Δn = ne−no) decreases as the wavelength increases. Therefore, in such an optically anisotropic layer, a phase shift occurs as the distance from the center wavelength increases, and appropriate optical compensation cannot be performed. In order to prevent this problem, there is a demand for a material having reverse wavelength dispersion characteristics in which the birefringence increases as the wavelength increases. In addition, in order to perform optimum optical compensation in accordance with the characteristics of other optical members and the like, a material that can easily control the wavelength dispersion characteristics is required.

  In recent years, in an organic EL display (OLED), it is known to use a circularly polarizing plate including a quarter-wave plate and a polarizer on the viewing side for the purpose of preventing external light reflection. Even in such applications, materials having reverse wavelength dispersion characteristics are required in order to exhibit effective antireflection performance for all wavelengths in the viewing region (Patent Documents 1 to 6).

  Since the compound described in Patent Document 1 has a low birefringence, the optically anisotropic layer containing the compound needs to be thick in order to obtain a desired retardation. Further, since the optically anisotropic layer has a small aspect ratio, it is difficult to control the alignment uniformity of the optically anisotropic layer. Due to the long synthetic route, the compound is difficult to produce. These issues are a concern. Since the compounds described in Patent Documents 2 to 5 have a high temperature range and clearing point of the liquid crystal phase, a complicated process such as polymerization by irradiation with ultraviolet rays while applying temperature is required. In addition, the compounds described in Patent Documents 1 to 5 generally have low solubility in organic solvents, and the production margin is narrow due to the short liquid crystal phase retention time at room temperature. Improvements are also required for such problems. In addition, there is a demand for materials with high so-called weather resistance that are resistant to environments such as heat and light. Furthermore, with respect to Patent Document 6, although compounds are listed, there is no disclosure of compound information that gives good liquid crystallinity and reverse wavelength dispersion characteristics.

Special table 2010-522893 JP 2009-179563 A International Publication No. 2012/06001 JP 2005-289980 A JP 2010-31223 A International Publication No. 2016/104317

  The present invention has high solubility in an organic solvent and a long liquid crystal phase retention time at room temperature, so that it is easy to handle and can control wavelength dispersion characteristics without requiring complicated steps. It is an object of the present invention to provide a polymerizable liquid crystal compound capable of easily producing an optically anisotropic film exhibiting wavelength dispersion characteristics and reverse wavelength dispersion characteristics.

  As a result of intensive studies, the inventors have found that a specific polymerizable liquid crystal compound can solve the object and completed the invention.

    1st aspect of this invention is a composition which contains 30 weight% or more of compounds represented by Formula (1) with respect to the total amount of a polymerizable liquid crystal component as a polymerizable liquid crystal component.

式（１）中、
Ａ^１は独立して、１，４−フェニレン、１，４−シクロへキシレン、１−シクロへキセン−１，４−イレン、２−シクロへキセン−１，４−イレン、ピリジン−２，５−ジイルまたはナフタレン−２，６−ジイルであり、この１，４−フェニレンまたはナフタレン−２，６−ジイルにおいて、すくなくとも１つの水素は、フッ素、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；
Ｚ^１は独立して、単結合、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＯＣＨ_２ＣＨ_２Ｏ−、−ＣＨ＝ＣＨＣＯＯ−、−ＯＣＯＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２ＣＯＯ−、−ＯＣＯＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２ＯＣＯ−、−ＣＯＯＣＨ_２ＣＨ_２−、−ＯＣＨ_２ＣＯＯ−、−ＯＣＯＣＨ_２Ｏ−、−ＣＨ＝ＣＨ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＣＨ_３−、−ＣＣＨ_３＝Ｎ−、−Ｎ＝Ｎ−、または−Ｃ≡Ｃ−であり；
ｍは独立して、０〜３の整数であり；
すくなくとも１つのｍは、１以上であり；
Ａｒ^１は芳香環であり、この芳香環は、水素がアルキル、シアノまたはニトロで置換されていてもよく、アルキルの−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯ−または−ＮＨ−で置換されていてもよく、アルキル基の−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝ＮＨ−または−Ｎ＝ＣＨ−で置換されていてもよく、アルキル基の水素は、シアノまたはニトロで置換されていてもよく；
Ａｒ^１の炭素数は、１８以下であり；
Ｒ^１は独立して、水素、フッ素、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１〜１２のアルキル、炭素数１〜１２のアルコキシ、炭素数１〜１２のアルケニル、炭素数１〜１２のアルキルエステル、または式（２）で表される基であり、
すくなくとも１つのＲ^１は式（２）で表される基であり；

In formula (1),
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, 1-cyclohexene-1,4-ylene, 2-cyclohexene-1,4-ylene, pyridine-2,5. -Diyl or naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, trifluoromethyl, alkyl of 1 to 5 carbons, carbon May be replaced by alkoxy of 1 to 5, alkoxycarbonyl of 1 to 5 carbons, or alkanoyl of 1 to 5 carbons;
Z ¹ is 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 = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH 2 CH 2 OCO -, - COOCH 2 _{CH 2 -, - OCH 2 COO} -, - OCOCH 2 O -, - CH = CH -, - N = CH -, - CH = N -, - N = CCH 3 -, - CCH 3 = N -, - N = N-, or -C≡C-;
m is independently an integer from 0 to 3;
At least one m is 1 or more;
Ar ¹ is an aromatic ring, in which hydrogen may be substituted with alkyl, cyano or nitro, and —CH ₂ — of alkyl is —O—, —S—, —CO— or —NH The alkyl group —CH ₂ —CH ₂ — may be substituted with —CH═CH—, —C≡C—, —CH═NH—, or —N═CH—. Well, the hydrogen of the alkyl group may be substituted with cyano or nitro;
Ar ¹ has 18 or less carbon atoms;
R ¹ is independently hydrogen, fluorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons, or 1 to 12 carbons. Or a group represented by formula (2):
At least one R ¹ is a group represented by formula (2);

式（２）中、
Ｙ^１は、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−であり；
Ｑ^１は、単結合または炭素数１〜２０のアルキレンであり、このアルキレンにおいて、すくなくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−で置き換えられてもよく；
ＰＧは、式（ＰＧ−１）〜式（ＰＧ−９）のいずれか１つで表される基であり

In formula (2),
Y ¹ is 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 — is —O—, —COO—, —OCO—, —CH═CH—, or — May be replaced by C≡C-;
PG is a group represented by any one of formula (PG-1) to formula (PG-9)

（式（ＰＧ−１）〜式（ＰＧ−９）中、
Ｒ^ＰＧは独立して、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。）

(In the formula (PG-1) to the formula (PG-9),
^RPG is independently hydrogen, halogen, methyl, ethyl, or trifluoromethyl. )

In a second aspect of the present invention, N in Ar ¹ —NH— in formula (1) is
Constituting the ring of Ar ¹ = a N- or Ar ¹ of the cyano group on the ring or the polymerizable liquid crystal composition of the first aspect which is conjugated with a nitro group.

A third aspect of the present invention is the polymerizable liquid crystal composition according to the second aspect, wherein PG in the formula (2) is a group represented by the formula (PG-1) and ^RPG is hydrogen or methyl. is there.

In a fourth aspect of the present invention, in the formula (1),
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, 1-cyclohexene-1,4-ylene, 2-cyclohexene-1,4-ylene, , 4-phenylene, at least one hydrogen is fluorine, trifluoromethyl, 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 May be replaced by;
Z ¹ is independently a single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ CH ₂ O—, —CH ₂ CH ₂ COO. _{-, - OCOCH 2 CH 2 -} , - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCH 2 COO-, or -OCOCH ₂ O-a and;
The polymerizable liquid crystal composition according to the third aspect, wherein R ¹ is independently a group represented by the formula (2).

The fifth aspect of the present invention is the polymerization according to the fourth aspect, wherein the compound represented by the formula (1) is a compound represented by any one of the formulas (1-1) to (1-6). Liquid crystal composition.

In formula (1-1) to formula (1-6),
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, 1-cyclohexene-1,4-ylene, 2-cyclohexene-1,4-ylene, pyridine-2,5. -Diyl or naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, trifluoromethyl, alkyl of 1 to 5 carbons, May be substituted with alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons, or alkanoyl having 1 to 5 carbons;
Z ¹ is 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═CHCOO—, —OCOCH═CH—, —CH ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCH ₂ COO—, —OCOCH ₂ O—, —CH═CH—, —N═CH—, —CH═N—, —N═CCH ₃ —, —CCH ₃ = N—, — N = N-, or -C≡C-;
Ar ¹ is a group consisting of an aromatic ring, and at least one hydrogen may be replaced by an alkyl, and —CH ₂ — of the alkyl is —O—, —S—, —CO—, Or —NH— may be replaced by —CH ₂ —CH ₂ — in which the alkyl is replaced by —CH═CH—, —C≡C—, —CH═NH—, or —N═CH—. May be;
Ar ¹ has 18 or less carbon atoms;
m1 is independently an integer from 0 to 2;
m2 is 0 or 1;
R ¹ is independently hydrogen, fluorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons, or 1 to 12 carbons. Or a group represented by formula (2):
At least one R ¹ is a group represented by formula (2);

式（２）中、
Ｙ^１は、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−であり；
Ｑ^１は、単結合または炭素数１〜２０のアルキレンであり、このアルキレンにおいてすくなくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−で置き換えられてもよく；
ＰＧは、式（ＰＧ−１）〜式（ＰＧ−９）のいずれか１つで表される基であり：

式（ＰＧ−１）〜式（ＰＧ−９）中、
Ｒ^ＰＧは独立して、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。

In formula (2),
Y ¹ is a single bond, —O—, —COO—, —OCO—, or —OCOO—;
Q ¹ is a single bond or alkylene having 1 to 20 carbon atoms, and at least one —CH ₂ — in the alkylene is —O—, —COO—, —OCO—, —CH═CH—, or —C. May be replaced by ≡C-;
PG is a group represented by any one of formula (PG-1) to formula (PG-9):

In formula (PG-1) to formula (PG-9),
^RPG is independently hydrogen, halogen, methyl, ethyl, or trifluoromethyl.

A sixth aspect of the present invention is an optically anisotropic film obtained by curing the polymerizable liquid crystal composition according to the first to fifth aspects.

The seventh aspect of the present invention is that {birefringence for light with a wavelength of 450 nm} / {birefringence for light with a wavelength of 550 nm} ≦ 1.05 and {birefringence for light with a wavelength of 650 nm} / {wavelength The optically anisotropic film according to the sixth or seventh aspect, wherein the birefringence for light at 550 nm} ≧ 0.97.

An eighth aspect of the present invention is a polarizing plate comprising the optically anisotropic film according to any one of the sixth to eighth aspects.

A ninth aspect of the present invention is a display element comprising the optically anisotropic film according to any one of the sixth to eighth aspects.

A 10th aspect of this invention is a display element provided with the polarizing plate of an 8th aspect.

The eleventh aspect of the present invention is
(I) Application of the polymerizable liquid crystal composition of the first to fifth aspects to the substrate;
(Ii) heat treatment;
(Iii) A method for producing an optically anisotropic film, comprising curing a polymerizable liquid crystal composition by irradiation with light.

The twelfth aspect of the present invention provides
It is a compound represented by Formula (1-1-a).

式（１−１−ａ）中、
Ａ^１は独立して、１，４−フェニレン、１，４−シクロへキシレン、１−シクロへキセン−１，４−イレン、２−シクロへキセン−１，４−イレン、ピリジン−２，５−ジイル、またはナフタレン−２，６−ジイルであり、この１，４−フェニレンまたはナフタレン−２，６−ジイルにおいて、すくなくとも１つの水素は、フッ素、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：
Ｚ^１は独立して、単結合、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＯＣＨ_２ＣＨ_２Ｏ−、−ＣＨ＝ＣＨＣＯＯ−、−ＯＣＯＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２ＣＯＯ−、−ＯＣＯＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２ＯＣＯ−、−ＣＯＯＣＨ_２ＣＨ_２−、−ＯＣＨ_２ＣＯＯ−、−ＯＣＯＣＨ_２Ｏ−、−ＣＨ＝ＣＨ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＣＨ_３−、−ＣＣＨ_３＝Ｎ−、−Ｎ＝Ｎ−、または−Ｃ≡Ｃ−であり、
Ａｒ^１は、芳香環からなる基であり、この芳香環は、少なくとも１つの水素がアルキルで置き換えられてもよく、このアルキルの−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯ−または−ＮＨ−で置換されていてもよく、このアルキルの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝ＮＨ−、または−Ｎ＝ＣＨ−で置き換えられてもよく、
Ａｒ^１の炭素数は１８以下であり；
ｍ３は独立して、０または１であり：
Ｒ^１は独立して、水素、フッ素、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１〜１２のアルキル、炭素数１〜１２のアルコキシ、炭素数１〜１２のアルケニル、炭素数１〜１２のアルキルエステル、または式（２）で表される基であり、
すくなくとも１つのＲ^１は式（２）で表される基であり；

式（２）中、
Ｙ^１は、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−であり；
Ｑ^１は、単結合または炭素数１〜２０のアルキレンであり、このアルキレンにおいて、すくなくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−で置き換えられてもよく；
ＰＧは、式（ＰＧ−１）〜式（ＰＧ−９）のいずれか１つで表される基であり；

式（ＰＧ−１）〜式（ＰＧ−９）中、
Ｒ^ＰＧは独立して、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。

In formula (1-1-a),
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, 1-cyclohexene-1,4-ylene, 2-cyclohexene-1,4-ylene, pyridine-2,5. -Diyl or naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, trifluoromethyl, alkyl of 1 to 5 carbons, It may be replaced with alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons, or alkanoyl having 1 to 5 carbons:
Z ¹ is 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 = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH 2 CH 2 OCO -, - COOCH 2 _{CH 2 -, - OCH 2 COO} -, - OCOCH 2 O -, - CH = CH -, - N = CH -, - CH = N -, - N = CCH 3 -, - CCH 3 = N -, - N = N- or -C≡C-
Ar ¹ is a group consisting of an aromatic ring, in which at least one hydrogen may be replaced by an alkyl, and —CH ₂ — of the alkyl is —O—, —S—, —CO—. Or optionally substituted with —NH—, wherein —CH ₂ —CH ₂ — in this alkyl is replaced with —CH═CH—, —C≡C—, —CH═NH—, or —N═CH—. May be
Ar ¹ has 18 or less carbon atoms;
m3 is independently 0 or 1:
R ¹ is independently hydrogen, fluorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons, or 1 to 12 carbons. Or a group represented by formula (2):
At least one R ¹ is a group represented by formula (2);

In formula (2),
Y ¹ is 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 — is —O—, —COO—, —OCO—, —CH═CH—, or — May be replaced by C≡C-;
PG is a group represented by any one of formula (PG-1) to formula (PG-9);

In formula (PG-1) to formula (PG-9),
^RPG is independently hydrogen, halogen, methyl, ethyl, or trifluoromethyl.

In a thirteenth aspect of the present invention, in formula (1-1-a),
Ar ¹ is 1,3,5-triazinyl,
At least one hydrogen of the triazinyl may be replaced with alkyl, and —CH ₂ — of the alkyl may be replaced with —O—, —S—, —CO—, or —NH—, This alkyl —CH ₂ —CH ₂ — is a compound of the twelfth aspect which may be replaced by —CH═CH—, —C≡C—, —CH═NH—, or —N═CH—. .

The optically anisotropic film prepared from the raw material containing the composition according to the first to fifth aspects of the present invention can be controlled and easily manufactured.
The films according to the sixth to seventh aspects of the present invention can control wavelength dispersion characteristics, and can be easily manufactured while exhibiting low wavelength dispersion characteristics and reverse wavelength dispersion characteristics.
The polarizing plate of the eighth aspect of the present invention can control the wavelength dispersion characteristics and can be easily manufactured while exhibiting the low wavelength dispersion characteristics and the reverse wavelength dispersion characteristics.
The display elements according to the ninth to tenth aspects of the present invention easily solve the problem that the light becomes colored due to the phase difference.
The optically anisotropic film prepared from the raw material containing the compound according to the twelfth to thirteenth aspects of the present invention can be controlled and easily manufactured.

In the present invention, “liquid crystallinity” represents a compound or composition having a liquid crystal phase. The liquid crystal phase includes a nematic phase (cholesteric phase) and a smectic phase. In the present invention, it 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 the compound has one polymerizable group is called a monofunctional or monofunctional compound. Further, when the compound has a plurality of polymerizable groups, it is called by a name corresponding to the number of polyfunctional or polymerizable groups.

In the present invention, the “liquid crystal film” is a polymer obtained by polymerizing a polymerizable liquid crystal composition.
A compound represented by the formula (X) may be referred to as a compound (X). Here, “X” is a number, a character, a character string, or the like.

  In the present invention, the optically anisotropic film represents a film that can be used for an optical element. The optical classification includes “+ A plate”, “+ C plate”, “−C plate”, and the like. In the present invention, it refers to a film in which a polymerizable liquid crystal composition is aligned in a predetermined direction and fixed.

In the present invention, “Δn” is the birefringence of the optically anisotropic film.
In the present invention, “Δn (X)” is Δn at a wavelength Xnm. Here, “X” is a numerical value.
In the present invention, “Re” is retardation and is a phase delay of abnormal light with respect to ordinary light. When the thickness of the liquid crystal polymer film is d, Re = Δn · d is satisfied.
In the present invention, “Re _x ” is retardation when light having a wavelength of X nm is incident on the surface of the optically anisotropic film perpendicularly. Here, X is a numerical value.
In the present invention, “Re _450/550 ” is a calculated value of Re ₄₅₀ / Re ₅₅₀ .
In the present invention, “Re _650/550 ” is a calculated value of Re ₆₅₀ / Re ₅₅₀ .

In the present invention, the “wavelength dispersion characteristic” is the dependence of Δn (X) on the wavelength Xnm of light.
In the present invention, “low wavelength dispersion” means that Δn (X) has a small dependency on the wavelength Xnm of light.

  In the present invention, “reverse wavelength dispersion” means that Δn increases as the wavelength of light increases.

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 (2) 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 also applies to 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, in other words, has not been replaced.

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

≪Polymerizable liquid crystal compound≫
The polymerizable liquid crystal composition according to the first to fifth aspects of the present invention (hereinafter sometimes abbreviated as “polymerizable liquid crystal composition of the present invention”) is a polymerizable liquid crystal compound represented by the formula (1). It contains at least one. By using the polymerizable liquid crystal composition of the present invention, an optically anisotropic film satisfying the relationship of Δn (450) / Δn (550) ≦ 1.05 and Δn (650) / Δn (550) ≧ 0.97 That is, an optically anisotropic film exhibiting low wavelength dispersion characteristics and reverse wavelength dispersion characteristics can be produced.
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 core skeleton in which an aromatic ring extends through NH in the minor axis direction of a rod-like molecule.
By containing the polymerizable liquid crystal compound represented by the formula (1), the mechanism for obtaining an optically anisotropic film exhibiting low wavelength dispersion characteristics and reverse wavelength dispersion characteristics is considered as follows. The wavelength dispersion characteristic 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 a wavelength of no (ordinary 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.

  The polymerizable liquid crystal composition of the present invention has (I) a good liquid crystal phase around room temperature, (II) good solubility in an organic solvent, and (III) a long time at room temperature after removing the solvent. The composition can have a property such as maintaining a liquid crystal phase, and the obtained film has optical anisotropy, transparency, heat resistance, adhesion, dimensional stability, and mechanical properties. Since the strength and the like are excellent, the polymerizable liquid crystal composition of the present invention is a material that is very suitable 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 may contain two or more types of compounds corresponding to the formula (1).

この式（１）中、Ａ¹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−シクロへキセン−１，４−イレン、２−シクロへキセン−１，４−イレン、ピリジン−２，５−ジイルまたはナフタレン−２，６−ジイルである。Ｚ¹がそれぞれ独立して１，４−フェニレン、１，４−シクロへキシレン、１−シクロへキセン−１，４−イレン、または、２−シクロへキセン−１，４−イレンである場合は、高い液晶性を有し、他の液晶性化合物および有機溶剤に対する良好な混和性を有し、かつ化合物を安価に製造することができる。より良好な波長分散特性を有するために、Ａｒ^１ＮＨが置換している中央のベンゼン環に隣接するＡ¹は、１，４−シクロへキシレンであることがより好ましい。より大きな複屈折率を有すために、Ａ¹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、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。高い液晶性を化合物に付与するためには、この１，４−フェニレン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, 1,4-cyclohexylene, 1-cyclohexene-1,4-ylene, 2-cyclohexene-1,4- Irene, pyridine-2,5-diyl or naphthalene-2,6-diyl. When Z ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, 1-cyclohexene-1,4-ylene, or 2-cyclohexene-1,4-ylene It has high liquid crystallinity, good miscibility with other liquid crystal compounds and organic solvents, and the compound can be produced at low cost. In order to have better wavelength dispersion properties, A ¹ adjacent to the central benzene ring substituted by Ar ¹ NH is more preferably 1,4-cyclohexylene. In order to have a larger birefringence, A ¹ is more preferably 1,4-phenylene. In the 1,4-phenylene, at least one hydrogen is fluorine, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons, or 1 to 5 carbons. May be replaced by alkanoyl. In order to impart high liquid crystallinity to the compound, this 1,4-phenylene is preferably unsubstituted.

In formula (1), Z ¹ is 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 = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH 2 CH 2 OCO _{-, - COOCH 2 CH 2 -} , - OCH 2 COO -, - OCOCH 2 O -, - CH = CH -, - N = CH -, - CH = N -, - N = C (CH 3) -, - C (CH ₃ ) ═N—, —N═N— or —C≡C—. Z ¹ is independently a single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —OCH ₂ CH _{2 O -, - CH 2 CH} 2 COO -, - OCOCH 2 CH 2 -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, or -OCH ₂ COO -, - OCOCH ₂ If O- is the It has high liquid crystallinity and can produce a compound at low cost. Further, when at least one of Z ¹ is —CH ₂ CH ₂ COO— or —OCOCH ₂ CH ₂ —, it has good miscibility with other liquid crystal compounds and organic solvents, and lowers the clearing point. And recrystallization can be further reduced.

  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 0 to 3 independently. is there. However, at least one of m is not 0. Moreover, when m is 2, it is excellent in the balance of liquid crystallinity and miscibility with an organic solvent.

Ar ¹ is preferably an aromatic ring having up to 18 carbon atoms because the wavelength dispersion characteristic of the polymerizable liquid crystal compound represented by formula (1) is good. Here, the aromatic ring may have a substituent, or the ring structure may be condensed.

From the viewpoint of the liquid crystal and the wavelength dispersion characteristic, it is preferable to select a group of formula (Ar1-19) from the following equation as Ar ¹ (Ar1-1). From the viewpoint of easy production, it is more preferable to select a group of the formula (Ar1-19) from the following formula (Ar1-8).

  In the groups of formula (Ar1-1) to formula (Ar1-19), H on the aromatic ring may be substituted with an organic group in order to improve liquid crystallinity and reverse wavelength dispersion. Examples of the substituent include F, alkyl, cycloalkyl, alkenyl, alkoxy, carbonyl, alkylcarbonyl, alkoxycarbonyl, nitro, cyano, fluoroalkyl, alkylamino, alkanoyl, alkylsulfide, and aromatic ring.

  Among these substituents, alkenyl, alkoxy, carbonyl, alkylcarbonyl, alkoxycarbonyl, nitro, cyano, alkylamino, alkanoyl, alkyl sulfide, or aromatic ring should be selected in order to improve reverse wavelength dispersion. It is more preferable to select nitro, cyano, alkylamino, alkyl sulfide, or an aromatic ring.

  Further, from the viewpoint of facilitating compound production, it is preferable to select nitro or cyano and introduce them so as to be conjugated with N in the formula (1).

As an aromatic ring that can be selected as a substituent for Ar ¹ , any of the aromatic rings described in the formulas (T-1) to (T-9) has liquid crystallinity, solubility in organic solvents, and wavelength dispersion characteristics. It is preferable for improving the quality.

（式（Ｔ−１）〜式（Ｔ−９）中、Ｘ^２は−Ｏ−、−Ｓ−または−ＮＲ^４−であり、ここでＲ^４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フェニルであり、少なくとも一つの−ＣＨ＝は-Ｎ＝に置き換えられてもよく、少なくとも一つの水素はフッ素、塩素、シアノ、トリフルオロメチル、トリフルオロアセチル、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のアルキルエステルまたは炭素数１〜５のアルカノイルで置き換えられてもよい）

(In formula (T-1) to formula (T-9), X ² is —O—, —S— or —NR ⁴ —, wherein R ⁴ is hydrogen, alkyl having 1 to 5 carbons, carbon 1 to 5 alkanoyl or phenyl, and at least one —CH═ may be replaced by —N═, and at least one hydrogen is fluorine, chlorine, cyano, trifluoromethyl, trifluoroacetyl, carbon number 1 -5 alkyl, C1-5 alkoxy, C1-5 alkyl ester or C1-5 alkanoyl may be substituted)

The substituent of formula (T-1) to formula (T-9) and Ar ¹ may be substituted directly or via a bonding group. At this time, it is preferable to select a single bond, —C≡C—, —O—, —NR ¹⁰ —, and —S— in order to improve liquid crystallinity, solubility in an organic solvent, and wavelength dispersion characteristics. . ^{However, R 10} represents an organic group.

  The substituents described above may be used in combination.

In formula (1), R ¹ is independently hydrogen, fluorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons, The alkyl ester having 1 to 12 carbon atoms or a group represented by the formula (2), provided that at least one of R ¹ is a group represented by the formula (2).

式（２）中、Ｙ^１は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−であり、
Ｑ^１は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−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、または−ＣＨ≡ＣＨ−で置き換えられてもよく、
ＰＧは式（ＰＧ−１）〜式（ＰＧ−９）のいずれか１つで表される重合性基である。）

In Formula (2), Y ¹ is 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 — is —O—, —COO—, —OCO—, —CH═CH—, or —CH≡CH. -May be replaced by
PG is a polymerizable group represented by any one of formulas (PG-1) to (PG-9). )

（式（ＰＧ−１）〜式（ＰＧ−９）中、Ｒ^ＰＧはそれぞれ独立して水素、フッ素、メチル、エチル、またはトリフルオロメチルである。）

(In formula (PG-1) to formula (PG-9), R ^PG is independently hydrogen, fluorine, methyl, ethyl, or trifluoromethyl.)

  In formula (2), as the selection of the polymerizable group represented by formula (PG-1) to formula (PG-9), an appropriate one can be selected depending on the film production conditions. When producing a film by photocuring, it is preferable to select the formula (PG-1) containing an acrylic group or a methacrylic group from the viewpoints of high curability, solubility in a solvent, ease of handling, and the like. It is.

  In order to increase the reverse wavelength dispersion, the compound represented by the formula (1) is preferably the following formulas (1-1) to (1-6). From the viewpoint of ease of production, ), (1-2) and (1-4) are more preferred.

式（１−１）から式（１−６）中、Ａ^１、Ｚ^１、Ａｒ^１、およびＲ^１の定義は、上記式（１）と同じであり、ｍ１は独立して０〜２の整数であり、ｍ２は０または１である。

In formulas (1-1) to (1-6), the definitions of A ¹ , Z ¹ , Ar ¹ , and R ¹ are the same as in formula (1) above, and m1 is independently 0-2. It is an integer and m2 is 0 or 1.

  In order to improve the compatibility of the polymerizable liquid crystal composition, prevent crystallization during film formation, and facilitate the production, the polymerizable liquid crystal composition is represented by the following formula (1-1-a). It is preferable to include a compound.

式（１−１−ａ）中、Ａ^１、Ｚ^１、Ａｒ^１、およびＲ^１の定義は、上記式（１）と同じであり、ｍ３はそれぞれ独立して０または１である。

In formula (1-1-a), the definitions of A ¹ , Z ¹ , Ar ¹ , and R ¹ are the same as those in the above formula (1), and m3 is independently 0 or 1.

Specific preferred examples of the polymerizable liquid crystal compound represented by the formula (1) include formulas (1-1-1) to (1-1-29) and formulas (1-2-1) to (1). -6-4).
However, it is not limited to what is shown below.

  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) Has been described.

In the compound represented by the formula (1), a 1,4-phenylene skeleton (hereinafter referred to as “core skeleton”) in which the 2-position that gives characteristics such as reverse wavelength dispersion is substituted with Ar ¹ NH is, for example, Procedure (1) which may be synthesized as in the formula: 2,5-dimethoxyaniline and an aromatic halide are reacted in the presence of a base to obtain a compound of the formula (1-A),
Procedure (2): The compound of formula (1-A) is demethylated with a reagent such as BBr3 to obtain the compound of formula (1-B).

（ただし、Ａｒ^１の定義は、式（１）のＡｒ^１上記と同じであり、Ｘ^１はＣｌ、Ｂｒ、またはＩである。）

(However, the definition of Ar ¹ are the same as Ar ¹ above formula (1), ^{X 1} is Cl, Br or I,.)

  From the viewpoint of the yield of the compound, the synthesis of 2,5-dimethoxyaniline to the compound of the formula (1-A) may use a catalyst such as a copper catalyst or Pd. The synthesis method is described in Angew. Chem. Int. Ed. 56, 16136 (2017). And so on.

Without using an expensive catalyst, it is possible to better utilize the synthesis yield, -N of formula (1) <but a cyano group present on = N- or Ar ¹ constituting the ring of Ar ^1, a nitro group Is preferable. Since the synthesis method can be used with high yield without using an expensive catalyst, the compound Ar ¹ -X in which —N <in the formula (1) has a conjugated structure with a plurality of adjacent atoms is preferable.

  The 1,4-cyclohexylene group in the compound of formula (1) can be introduced using 4-hydroxycyclohexanecarboxylic acid.

  The following chemical reaction formula is a synthesis example using 4-hydroxycyclohexanecarboxylic acid.

ここで、当該式においてｒは２〜２０の整数である。

Here, r is an integer of 2 to 20 in the formula.

In the present invention, the “tilt angle” is an angle between the alignment direction of the liquid crystal molecules and the surface of the substrate.
In the present invention, “homogeneous alignment” refers to an alignment having a tilt angle of 0 to 5 degrees.
In the present invention, the “homeotropic orientation” is an orientation having a tilt angle of 85 to 90 degrees.
In the present invention, “tilt alignment” refers to a state in which the alignment direction of the major axis of liquid crystal molecules rises from parallel to perpendicular to the substrate as the liquid crystal molecules move away from the substrate.
In the present invention, “twist alignment” means that the alignment direction in the major axis direction of the liquid crystal molecules is parallel to the base material, and as it goes away from the base material, a step-like shape with the perpendicular of the base material surface as the axis A state that is twisted.

<< 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 exhibits a nematic or smectic liquid crystal phase in the range of 0 ° C to 120 ° C.
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 substrate whose surface is coated with a plastic thin film, The composition is in a homogeneous orientation or a tilt orientation. The polymerizable liquid crystal composition of the present invention exhibits twist alignment when an optically active compound described later is added. The polymerizable liquid crystal composition of the present invention can have homeotropic alignment by adding a compound having a cardo structure, which will be described later, or a compound having a polar group at the terminal. Here, examples of the polar group include, but are not limited to, 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.

Since the solubility of the composition is maintained and the wavelength dispersion of Δn is easily controlled, the ratio of the total amount of the compound of formula (1) in the composition is preferably 30% by weight to 100% by weight of the whole composition. .
Other liquid crystal compounds can be selected from compounds described in a liquid crystal compound database (LiqCryst, LCI Publisher GmbH, Hamburg, Germany). A compound represented by the formula (LC) is preferred.

式（ＬＣ）中、Ａ²は独立して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−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、または−Ｃ≡Ｃ−で置き換えられてもよく、該アルキレンにおいて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；Ｒ³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−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよい。

In formula (LC), A ² is independently 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, and naphthalene-2. , 6-diyl, wherein at least one hydrogen is fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, carbon number May be substituted with 1-5 alkyl, 1-5 alkoxy, 1-5 alkoxycarbonyl, or 1-5 alkanoyl; Z ² is independently a single bond or carbon number 1 to 20 alkylene, wherein at least one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, —CH═CH—, —CF═C. F— or —C≡C— may be substituted, and in the alkylene, at least one hydrogen may be substituted with halogen; b is an integer of 1 to 5; R ³ 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 -May be replaced by -O- or -CH = CH-.

  Formulas (LC-1) to (LC-38) are specific examples of the compound represented by Formula (LC).

  When the polymerizable liquid crystal composition contains the compounds represented by the formulas (LC-1) to (LC-38), the polymerizable liquid crystal composition may have a content of usually 50% by weight or less based on the total amount of the polymerizable liquid crystal composition. preferable.

  The polymerizable liquid crystal composition may contain a known polymerizable liquid crystal compound. In that case, the polymerizable liquid crystal compound is preferably a compound represented by the formulas (M1), (M2) and (M3).

式（Ｍ１）、（Ｍ２）および（Ｍ３）中、Ａ^Mは独立して１，４−フェニレン、１，４−シクロへキシレン、１−シクロへキセン−１，４−イレン、２−シクロへキセン−１，４−イレン、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は独立して単結合、−ＯＣＨ₂−、−ＣＨ₂Ｏ−、−ＣＯＯ−、−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−、−Ｃ≡Ｃ−または−Ｃ≡Ｃ−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を満たし；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。

In formulas (M1), (M2) and (M3), A ^M is independently 1,4-phenylene, 1,4-cyclohexylene, 1-cyclohexene-1,4-ylene, 2-cyclohexene. Any selected from xene-1,4-ylene, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or fluorene-2,7-diyl A divalent group, wherein at least one hydrogen is fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbon atoms, 1 to carbon atoms May be substituted with 5 alkoxy, 1-5 alkoxycarbonyl, or 1-5 alkanoyl; 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—, —C≡C— or —C≡C—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; An integer of 4; c and d are each an integer of 0 to 3 and 1 ≦ c meets d ≦ 4; a is an integer from 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.

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 the formula (M1) or (M2), A ^M is 1,4-phenylene or 1,4-cyclohexylene, but at least one is 1,4-cyclohexylene, and Z ^M Is a single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH ₂ CH ₂ —, —CH ₂ CH ₂ COO—, or —OCOCH ₂ CH ₂ —. Is more preferred.

  The compound represented by the formula (M1) is a monofunctional polymerizable liquid crystal compound. By adjusting the composition of the monofunctional polymerizable liquid crystal compound, the liquid crystal temperature range, optical characteristics and orientation of the liquid crystal composition can be controlled. 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. Since a polymer comprising a composition containing a large amount has a three-dimensional structure, the polymer is harder than the compound represented by the formula (M1) having only one polymerizable group. The compound represented by the formula (M3) is a trifunctional polymerizable liquid crystal compound. Since a polymer composed of a composition containing a large amount can form a stronger network, the polymer is harder than a polymer containing a large amount of compounds having one or two polymerizable groups. 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, the compounds represented by the formulas (M1-1) to (M1-24) are examples of the compound represented by the formula (M1).

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, and a is independently an integer of 1 to 12.

  The compounds represented by the formulas (M2-1) to (M2-31) are examples of the compound represented by the formula (M2).

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。

In formulas (M2-1) to (M2-31), R ^M is independently hydrogen or methyl, and a is independently an integer of 1 to 12.

  The compounds represented by formulas (M3-1) to (M3-10) are examples of the compound represented by formula (M3).

式（Ｍ３−１）〜（Ｍ３−１０）において、Ｒ^Mは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。

In formulas (M3-1) to (M3-10), R ^M is independently hydrogen or methyl, and a is each independently an integer of 1 to 12.

  When the polymerizable liquid crystal composition contains a compound represented by the formula (M), at least one polymerizable liquid crystal compound of the present invention represented by the formula (1) and a compound represented by the formula (M) It is preferable to contain 30 to 99% by weight of at least one of the polymerizable liquid crystal compounds of the present invention represented by the formula (1) with respect to a total amount of 100% by weight of at least one of 40 to 99% by weight. % Content is more preferable. When the content of each component in the polymerizable liquid crystal composition is in this range, the polymerizable liquid crystal has a wide liquid crystal phase near room temperature, easy birefringence wavelength dispersion control, and good coatability. A composition can be obtained.

  The polymerizable liquid crystal composition may further contain a surfactant. Surfactants include ionic surfactants and nonionic surfactants. It is more preferable to use a nonionic surfactant because the effect of improving the smoothness of the coating film formed from the polymerizable liquid crystal composition and the effect of suppressing the tilt alignment on the air interface side are high.

    Regardless of whether or not it contains other liquid crystal compounds and / or other polymerizable liquid crystal compounds, the surfactant in the polymerizable liquid crystal composition is based on the polymerizable liquid crystal compound represented by the formula (1). 0.01 to 10 wt% is preferable, and 0.01 to 0.5 wt% is more preferable.

  Ionic surfactants include titanate compounds, imidazolines, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and its esters, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl sulfate. Amines, alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, laurylamidopropylbetaine, laurylaminoacetic acid betaine, polyethylene glycol fatty acid esters, polyoxyethylene alkylamine, Although the compound of a fluoroalkyl sulfonate and a perfluoroalkyl carboxylate can be illustrated, it is not limited to these.

  Examples of the nonionic surfactant include, but are not limited to, silicone-based, fluorine-based, vinyl-based, and hydrocarbon-based compounds.

  Silicone-based nonionic surfactants include polyflow KL-400HF, polyflow KL-401, polyflow KL-402, polyflow KL-403, polyflow KL-404, BYK-300 based on unmodified silicone or modified silicone. BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, 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, BY -3500, BYK-3510, BYK-3530, BYK-3570, BYK-Silclean3720, and TEGOFlow425 Although exemplified, but not limited to.

  Fluorine-based nonionic surfactants include 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, Mega Fuck F-444, Mega Fuck F-477, Mega Fuck F-551, Mega Fuck F-553, Mega Fuck F-554, Mega Fuck F-556, Mega Fuck 557, Mega Fuck F-558, Mega Fuck F-559, Mega Fuck F-562, Mega Fuck F-563, Mega Fuck F-565, Mega Fuck F-570, Mega Fuck R-40, Mega Fuck R -41, Megafuck R-43, or Megafuck R-94 can be exemplified, but not limited thereto.

  Vinyl-based nonionic surfactants are polyflow Nos. Mainly composed of acrylic polymers. 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 can be exemplified, but not limited thereto.

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, but are not limited to, a UV-reactive functional group or a thermal polymerizable functional group. From the viewpoint of reactivity with the polymerizable liquid crystal compound, the polymerizable group is preferably a UV-reactive functional group.
Non-ionic surfactants of UV reaction type are as follows: Aftergent 601AD, Aftergent 602A, Aftergent 650A, Megafuck RS-55, Megafuck RS-56, Megafuck RS-72-K, Megafuck RS-75, Mega-Fuck RS-78 and Mega-Fuck RS-90 can be exemplified, but are not limited thereto.

  In order to optimize the wettability to the substrate, a surfactant classified as a 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. Such wetting agents are 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), but is not limited thereto. 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. Examples of this include the 3000 series (for example, 3277, 3700, 3770, etc.) manufactured by AFCONA, but are not limited thereto.

  The Polyflow series is sold by Kyoeisha Chemical Co., Ltd. The BYK series is sold by Big Chemie Japan. The footent series is sold by Neos. The Megafuck series is sold by DIC Corporation. The TEGOFlow series is sold by Evonik Japan.

  Surfactant may be used independently and may mix and use 2 or more.

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, 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.

  Compounds having one polymerizable group are styrene, nucleus-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinyl pyrrolidone, vinyl sulfonic acid, fatty acid vinyl (such as vinyl acetate), α, β-ethylenic. Unsaturated carboxylic acids (acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.), alkyl esters of (meth) acrylic acid, hydroxyalkyl esters of (meth) acrylic acid, aminoalkyl esters of (meth) acrylic acid , (Meth) acrylic acid alkoxyalkyl ester ((meth) acrylic acid methoxyethyl ester, (meth) acrylic acid ethoxyethyl ester, (meth) acrylic acid methoxypropyl ester, (meth) acrylic acid methylcarbyl ester, (meth) acrylic Acid ethyl Ester, butyl carbyl ester of (meth) acrylate), N-vinylacetamide, vinyl tert-butylbenzoate, vinyl N, N-dimethylaminobenzoate, vinyl benzoate, vinyl pivalate, 2,2-dimethyl Vinyl butanoate, 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- Acrylo Loxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, 2-acryloyloxyethyl acid phosphate, 2 -Mono (meth) acrylic acid of polyalkylene glycol such as methacryloyloxyethyl acid phosphate, polyethylene glycol having a polymerization degree of 1 to 100, polypropylene glycol, copolymer of ethylene oxide and propylene oxide Esters or di (meth) acrylic acid esters, or polyethylene glycols with a degree of polymerization of 1 to 100 capped with alkyl groups having 1 to 6 carbon atoms, polypropylene glycol, and copolymer weight of ethylene oxide and propylene oxide Coalesced etc. Real chelating down glycolate - but Le mono (meth) acrylic acid ester can be exemplified, without limitation.

  The compounds having two polymerizable groups are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, dimethylol tricyclodecane 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 diacrylate, and Although the compound which substituted the acrylate of these compounds with the methacrylate can be illustrated, it is not limited to these.

  Compounds having three or more polymerizable groups are pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol EO-added tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, 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 (meth) acrylate , Dipentaerythritol monohydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, biscoat V # 802 (functional group number = 8), biscoat V # 1000 (functional group number = average 14). However, it is not limited to these. “Biscoat” is a product 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 other polymerizable compounds include, but are not limited to, a polymerizable fluorene derivative having a cardo structure and a polymerizable compound having a bisphenol structure. The polymerizable fluorene derivative having a cardo structure further enhances the control of orientation and the degree of cure of the polymer. The polymerizable compound having a bisphenol structure is suitable for assisting the film forming ability and alignment uniformity of the liquid crystal composition. Examples of the polymerizable fluorene derivative having a cardo structure are shown by the formulas (α-1) to (α-3). Examples of the polymerizable bisphenol derivative are shown by formulas (N-1) to (N-8).

式（α−１）〜（α−３）において、Ｒ^α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), R ^α 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 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.

  In order to optimize the polymerization rate, a polymerization initiator may be added to the polymerizable liquid crystal composition. As the polymerization initiator, a photo radical initiator can be exemplified. Photoradical polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173), 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1- ON (Irgacure 651), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184), Irgacure 127, Irgacure 500 (Irgacure 184 and benzophenone mixture), Irgacure 2959, Irgacure 907, Irgacure 369 , Irgacure 379, Irgacure 754, Irgacure 1300, Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Irgacure 1870, Darocur 4 65, Darocur MBF, Darocur TPO, Irgacure 784, Irgacure 754, Irgacure OXE01, Irgacure OXE02, Adekaputomer N-1919, Adeka Cruz NCI-831 and Adeka Cruz NCI-930 are limited to these. Not. The Darocur series and Irgacure series are sold by BASF Japan. The Adeka optomer series and Adeka cruise series are sold by ADEKA Corporation.

  The radical photopolymerization initiator further includes 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 mixture Can be exemplified, but Not a constant.

  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. A radical photoinitiator may be used independently and may mix and use 2 or more.

  Further, a sensitizer may be added to these photo radical polymerization initiators. Examples of the sensitizer include, but are not limited to, isopropylthioxanthone, diethylthioxanthone, ethyl-4 dimethylaminobenzoate (Darocur EDB), and 2-ethylhexyl-4-dimethylaminobenzoate (Darocur EHA). These sensitizers may be used alone or in combination of two or more.

  A chain transfer agent may be added to the polymerizable 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 may be controlled. Increasing the amount of chain transfer agent decreases the polymerization reaction rate and decreases the length of the polymer chain. Examples of the chain transfer agent include, but are not limited to, thiol compounds or styrene dimers. These chain transfer agents may be used alone or in combination of two or more.

  Examples of the thiol chain transfer agent include, but are not limited to, monofunctional thiols and polyfunctional thiols. Examples of the monofunctional thiol include, but are not limited to, dodecanethiol and 3-mercaptopropion 2-ethylhexyl. The polyfunctional thiol includes trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane (Karenz MT BD1) ), Pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MT PE1), and 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H) , 3H, 5H) -trione (Karenz MT NR1), but is not limited thereto. The Karenz series is sold by Showa Denko.

  Examples of the styrene dimer chain transfer agent include, but are not limited to, 2,4-diphenyl-4-methyl-1-pentene and 2,4-diphenyl-1-butene.

  A polymerization inhibitor can be added to the polymerizable liquid crystal composition in order to prevent the initiation of polymerization during storage. A known polymerization inhibitor can be used. Polymerization inhibitors include 2,5-di (t-butyl) hydroxytoluene (BHT), hydroquinone, methylene blue, diphenylpicric hydrazide (DPPH), phenothiazine, nitroso compounds such as N, N-dimethyl-4-nitrosoaniline, Examples include, but are not limited to, o-hydroxybenzophenone and benzothiazine derivatives such as 2H-1,3-benzothiazine-2,4- (3H) dione.

  In order to improve the storage stability of the polymerizable liquid crystal composition, a polymerization inhibitor may be added. When radicals are generated in the polymerizable liquid crystal composition or the solution thereof, the polymerization reaction of the polymerizable compound is promoted. In order to prevent this, it is preferable to add a polymerization inhibitor. Examples of the polymerization inhibitor include, but are not limited to, phenolic antioxidants, sulfur antioxidants, and phosphoric acid antioxidants.

  In order to further improve the weather resistance of the polymerizable liquid crystal composition, an ultraviolet absorber, a light stabilizer (radical scavenger), an antioxidant and the like may be added. The UV absorbers are 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, and ADK STAB LA-51 It is not limited to. The Tinuvin series is sold by BASF Japan. The ADK STAB series is sold by ADEKA. These ultraviolet absorbers may be used alone or in combination of two or more.

  The light stabilizers are 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, Chimassorb 119FL 944FL, Kimabsorb 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-87, Examples include, but are not limited to, Siasorb UV-3346 manufactured by Cytec and Goodlite UV-3034 manufactured by Goodrich. The Kimasorb series is sold by BASF Japan. These light stabilizers may be used alone or in combination of two or more.

  Antioxidants are ADEKA's ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, Sumitizer BHT, Sumilizer BBM-S sold by Sumitomo Chemical Co., Ltd. And Irganox 1076, Irganox 1010, Irganox 3114, and Irganox 245 sold by BASF Japan, Inc. These antioxidants may be used alone or in combination of two or more.

  A silane coupling agent may be added to the polymerizable liquid crystal composition in order to control the adhesion with the substrate. Silane coupling agents include vinyltrialkoxysilane, 3-isocyanatopropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropyltrialkoxysilane, N- (1,3-dimethylbutylidene) -3- (Trialkoxysilyl) -1-propanamine, 3-glycidoxypropyltrialkoxysilane, 3-chlorotrialkoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrialkoxysilane and the like can be exemplified. However, it is not limited to these. Also, in the 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.

  The polymerizable liquid crystal composition of the present invention may contain a solvent in order to facilitate application. Solvents include ester solvents, amide solvents, alcohol solvents, ether solvents, glycol monoalkyl ether solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, halogens. Examples thereof include, but are not limited to, alicyclic hydrocarbon solvents, alicyclic hydrocarbon solvents, ketone solvents, and acetate solvents.

  Ester solvents include alkyl acetate (methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, etc.), ethyl trifluoroacetate, alkyl propionate (propionate) Methyl acetate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate, butyl propionate, etc., alkyl butyrate (methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, propyl butyrate, etc.), dialkyl malonate (malonic acid Diethyl), alkyl glycolate (methyl glycolate, ethyl glycolate, etc.), alkyl lactate (methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, butyl lactate, ethylhexyl lactate, etc.), monoacetin, γ -Butyrolactone and γ-valerolactone can be exemplified, but are not limited thereto.

  Amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N-methylpropionamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N, N Examples include, but are not limited to, dimethylacetamide dimethylacetal, N-methylcaprolactam and dimethylimidazolidinone.

  Alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, t-butyl alcohol, sec-butyl alcohol, butanol, 2-ethylbutanol, n-hexanol, 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-pentanedi Lumpur, 2,4-pentanediol, 2,5-hexanediol, 3-methyl-3-methoxybutanol, can be exemplified cyclohexanol and methylcyclohexanol, without limitation.

  Examples of the ether solvent include, but are not limited to, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, bis (2-propyl) ether, 1,4-dioxane, and tetrahydrofuran (THF).

  Examples of the glycol monoalkyl ether solvent include ethylene glycol monoalkyl ether (including but not limited to ethylene glycol monomethyl ether and ethylene glycol monobutyl ether), diethylene glycol monoalkyl ether (including diethylene glycol monoethyl ether, Not limited thereto), triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether (including but not limited to propylene glycol monobutyl ether), dipropylene glycol monoalkyl ether (including dipropylene glycol monomethyl ether). But not limited thereto), ethylene glycol monoalkyl ether acetate (ethylene Examples include, but are not limited to, recall monobutyl ether acetate), diethylene glycol monoalkyl ether acetate (including but not limited to diethylene glycol monoethyl ether acetate), triethylene glycol monoalkyl ether acetate, propylene glycol mono Alkyl ether acetate (including but not limited to propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate), dipropylene glycol monoalkyl ether acetate (exemplifying dipropylene glycol monomethyl ether acetate) But not limited to this), and It can be exemplified diethylene glycol methyl ethyl ether, but not limited thereto.

  Aromatic hydrocarbon solvents are benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, i-propylbenzene, n-propylbenzene, t-butylbenzene, s-butylbenzene, n-butylbenzene, and tetralin. The halogenated aromatic hydrocarbon solvent is preferably chlorobenzene or the like. The aliphatic hydrocarbon solvent is preferably hexane or heptane. The halogenated aliphatic hydrocarbon solvent is preferably chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethylene, tetrachloroethylene or the like. Examples of the alicyclic hydrocarbon solvent include, but are not limited to, cyclohexane and decalin.

Examples of ketone solvents include, but are not limited to, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, and methyl propyl ketone. Acetate solvents include ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene. Examples include, but are not limited to, glycol monoethyl ether acetate, methyl acetoacetate, and 1-methoxy-2-propyl acetate.

  From the viewpoint of the solubility of the polymerizable 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, the combined use of an ester solvent, an alcohol solvent, an ether solvent, or a glycol monoalkyl ether solvent is also preferable. There are no particular restrictions on the choice of solvent. When a plastic substrate is used as the substrate, it is necessary to lower the drying temperature and prevent the solvent from attacking the substrate in order to prevent deformation of the substrate. Preferred examples of such solvents include aromatic hydrocarbon solvents, ketone solvents, ester solvents, ether solvents, alcohol solvents, acetate solvents, and 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 another polymerizable liquid crystal compound in the formula (1). The content is 30 to 96% by weight based on the total weight of the polymerizable liquid crystal compound and the compound. 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.

The liquid crystal film may be obtained by the following process:
Procedure (1) A polymerizable liquid crystal composition or a solution of a polymerizable liquid crystal composition is applied onto a substrate to obtain a coating film,
Procedure (2) Drying the coating film to obtain a dry coating film,
Procedure (3) Irradiate light to the dried coating film to polymerize the polymerizable liquid crystal composition,
The nematic alignment polymerizable liquid crystal composition is fixed in the nematic alignment.
Here, although a base material can illustrate glass and a plastic, it is not limited to these.
Plastics are polyimide, polyamideimide, polyamide, polyetherimide, polyetheretherketone, polyetherketone, polyketonesulfide, polyethersulfone, polysulfone, polyphenylenesulfide, polyphenyleneoxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, Examples include, but are not limited to, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, triacetyl cellulose and partially saponified products thereof, epoxy resin, phenol resin, and cycloolefin resin. The substrate is usually in the form of a sheet or film.

Examples of the cycloolefin resin include a norbornene resin and a dicyclopentadiene resin, but are not limited thereto. The norbornene resin is a hydrogenated product of a ring-opening (co) polymer of one or more norbornene monomers, an addition (co) polymer of one or more norbornene monomers, a norbornene monomer, Addition copolymers with olefin monomers (ethylene, α-olefin, etc.), addition copolymers of norbornene monomers and cycloolefin monomers (cyclopentene, cyclooctene, 5,6-dihydrodicyclopentadiene, etc.), and These modified products can be exemplified, but are not limited thereto.
Commercial products corresponding to this are ZEONEX, ZEONOR (both trade names, manufactured by ZEON CORPORATION), ARTON (trade names, manufactured by JSR Corporation), TOPAS (trade names, manufactured by Ticona), APEL (trade names) , Mitsui Chemicals, Inc.), Essina (trade name, manufactured by Sekisui Chemical Co., Ltd.), and OPTORZ (trade name, manufactured by Hitachi Chemical Co., Ltd.), but are not limited thereto.

  The polymer film (plastic film) as the base material may be a uniaxially stretched film or a biaxially stretched film. These films may be subjected to surface treatment such as hydrophilization treatment such as corona treatment or plasma treatment, or hydrophobic treatment. There is no particular limitation on the method of hydrophilic treatment. The hydrophilic treatment is preferably corona treatment or plasma treatment. 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. Such an anchor coat layer is effective as long as it improves the adhesion between the liquid crystal film and the plastic film, whether it is an inorganic material or an organic material. The plastic film may be a laminated film. Instead of plastic films, metal substrates such as aluminum, iron, and copper with slit-like grooves on the surface, or glass substrates such as alkali glass, borosilicate glass, and flint glass whose surfaces are etched into slits, etc. Is also available.

  When forming a liquid crystal film of homogeneous alignment and tilt alignment, prior to the formation of the coating film of the polymerizable liquid crystal composition, these glass substrates and substrates such as plastic films are physically and mechanically rubbed. Surface treatment is performed. When forming a homeotropic alignment liquid crystal film, surface treatment such as rubbing is often not performed. The substrate may be rubbed in order to prevent alignment defects and the like. Any method can be adopted for the rubbing treatment. Usually, a rubbing cloth made of materials such as rayon, cotton, polyamide, etc. is applied to a metal roll and moved while rotating the roll while in contact with the base material or polymer film. A method of moving the is adopted. The rubbing treatment may be performed directly on the substrate, or a polymer coating such as polyimide generally called an alignment film may be provided on the substrate in advance, and the polymer coating may be subjected to the rubbing treatment. The rubbing process is as described above. Depending on the type of substrate, silicon oxide may be deposited on the surface by tilt deposition to impart orientation ability.

  In addition, when forming a liquid crystal film of homogeneous alignment and tilt alignment, a polymer film such as polyimide or polyacrylate generally called a photo-alignment film is previously provided on a base material, and the polymer film is subjected to polarized UV treatment. Also good.

  When coating a polymerizable liquid crystal composition or a solution thereof, it is necessary to obtain a uniform film thickness. Examples of the coating method at this time include, but are not limited to, spin coating, micro gravure coating, gravure coating, wire bar coating, dip coating, spray coating, meniscus coating, and die coating. A wire bar coating method or the like in which shearing stress is applied to the polymerizable liquid crystal composition at the time of coating without performing surface treatment of the substrate by rubbing or the like may be used for controlling the alignment of the polymerizable liquid crystal composition.

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

  Preferred ranges such as the temperature and time for heat-treating the coating, the wavelength of light used for light irradiation, and the amount of light irradiated from the light source are the types and composition ratios of the compounds used in the polymerizable liquid crystal composition, and the initiation of photopolymerization Depends on whether or not the agent is added 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 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 generally completed in a coating film by heating the coating film to a high temperature range of the temperature range, and then a more ordered orientation is formed by lowering the temperature. Regardless of which heat treatment method is employed, the heat treatment temperature is from room temperature to 120 ° C. A preferable range of this temperature is room temperature to 100 ° C. Further, for the purpose of further improving the alignment uniformity, after heat treatment in a temperature range of 80 ° C. to 120 ° C., heat treatment may be further performed in a temperature range of NI point −15 ° C. to NI point. 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. A preferred range of light intensity is 10~3000mJ / cm ^2, and more preferred range is 100 to 2000 mJ / cm ^2. The temperature condition at the time of light irradiation is preferably set similarly to the heat treatment temperature. The atmosphere of the polymerization environment may be a nitrogen atmosphere, an inert gas atmosphere, or an air atmosphere. 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 of the methods for controlling the tilt angle is a method for 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 type and amount of the surfactant added as one of the other components, the type and amount of the solvent in the polymerizable liquid crystal composition. The tilt angle of the liquid crystal film can also be controlled by the type of substrate or polymer film, rubbing conditions, drying conditions or heat treatment conditions of the coating film of the polymerizable liquid crystal composition. 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 distributed from 0 to 5 degrees, particularly from 0 to 5 degrees, from the substrate interface to the free interface. This alignment state can be obtained by applying the polymerizable liquid crystal composition of the present invention to the surface of a 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記載の化合物がある。

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

  A polymerizable liquid crystal composition containing a compound having optical activity or a polymerizable liquid crystal composition containing a polymerizable compound having optical activity is coated on an alignment-treated substrate and polymerized to form a helical structure. A retardation film showing (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 by 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 a liquid crystal film containing the composition, a helical structure acts on incident light to reflect 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 adjusted as appropriate. In order to improve the color purity, the wavelength width (Δλ) may be reduced. In order to improve broadband reflection, 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 of the polymer must not be too small. In order to maintain uniform orientation, the thickness of the polymer must not be too large. Accordingly, it is necessary to appropriately adjust the thickness of the polymer, 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. The shortening of the helical pitch 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. The 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.

  The optically active compound may be any optically active compound as long as it induces a helical structure and can be appropriately mixed with the polymerizable liquid crystal composition as a base. Moreover, 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 according to the target element and the birefringence (optical anisotropy value) of the liquid crystal film. Accordingly, the thickness range depends on the purpose. The thickness range is 0.05 to 100 μm. A more preferable range is 0.1 to 50 μm. A more 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 preferred haze value is 1.0% or less. A more preferable transmittance is 90% or more. It is preferable to have a transmittance that 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 (deformation effect of aligned phase), CSH type (color super homeotropic), VAN / VAC type (nematic / cholesteric vertically aligned), OMI type (optical mode interference), SBE type (super birefringence effect), etc. 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. Moreover, there is no restriction | limiting in particular in the kind of polarizing plate used for the optical element which can apply this liquid crystal film. It can be suitably used for optical compensation of a reflective polarizing plate such as a wire grid polarizing plate as well as an absorption polarizing plate doped with iodine widely used.

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, but are not limited to, acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes, and anthraquinone dyes. Examples of the azo dye include, but are not limited to, a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, and a stilbene azo dye. 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.

The optically anisotropic film according to the present invention satisfies Δn (450) / Δn (550) ≦ 1.05, Δn (650) / Δn (550) ≧ 0.97, and has wavelength dispersion characteristics. An optically anisotropic film satisfying such 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 compound.
In particular, it has chromatic dispersion characteristics satisfying the relationship of 0.75 ≦ Δn (450) / Δn (550) ≦ 1.05 and 0.97 ≦ Δn (650) / Δn (550) ≦ 1.24. preferable.
If the value of Δn (450) / Δn (550) is too small, when the optimum retardation is set for green, the blue retardation will be too small from the optimum value. Becomes worse. If the value is too large, when an optimum retardation is set for green, the blue retardation becomes too large from the optimum value, so that the viewing angle characteristics are deteriorated.
Further, if the value of Δn (650) / Δn (550) is too small, when the optimum retardation is set for green, the red retardation becomes too small from the optimum value. Angular characteristics deteriorate. When the optimum retardation is set for green, which is too large, the red retardation becomes too large from the optimum value, resulting in poor viewing angle characteristics.
Those satisfying the relational expression of Δn, unlike the conventional one, have a low refractive index wavelength dispersion characteristic or a birefringence that increases as the wavelength increases. Those satisfying the relational expression become a more optimized optically anisotropic film material.

  The present invention will be specifically described with reference to examples. The present invention is not limited to these examples.

<Acquisition of compound>
In this example, “DMAP” is 4-dimethylaminopyridine.
In this example, “FTX-218” is Neosurf's surfactant, FTERGENT (registered trademark) FTX-218.
In this example, “IRG-907” is a polymerization initiator, IRGACURE (registered trademark) 907, manufactured by BASF Japan.
In this example, “TG370” is TEGO (registered trademark) Flow 375, a surfactant manufactured by Evonik Japan.
In this example, “NCI-930” is ADEKA polymerization initiator, ADEKA® Cruise NCI-930.

  In this example, compound (D-1) and compound (D-2) are compounds having the following structures.

化合物（Ｄ−１）および化合物（Ｄ−２）は、特開２０１７−１２５００９公報に従って合成した。

The compound (D-1) and the compound (D-2) were synthesized according to Japanese Patent Application Laid-Open No. 2017-125209.

  In this example, compound (M2-7-1), compound (M2-1-1) and compound (M1-24-1) are compounds having the following structures.

化合物（Ｍ２−７−１）および化合物（Ｍ２−１−１）は、市販品を購入して使用した。

Compound (M2-7-1) and compound (M2-1-1) were commercially used.

Compound (M1-24-1) was synthesized according to the following. Namely, 30.0 g (93.6 mmol) of 2- (4- (6-acryloxy-n-hexyloxy) phenyl) propionic acid synthesized according to JP 2007-269640, commercially available 4- (4-n-pentyl). Cyclohexyl) phenol 23.1 g (93.6 mmol), 2.3 g (18 mmol) of DMAP was added to 200 mL of CH ₂ Cl ₂ and stirred while cooling on an ice bath under a nitrogen atmosphere. Thereto, 100 mL of a CH ₂ Cl ₂ solution in which 20.3 g (98.3 mmol) of 1,3-dicyclohexylcarbodiimide in g was dissolved was dropped. After dropwise addition, the mixture was stirred overnight at room temperature. The deposited precipitate was separated by filtration, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate and water, and dried over anhydrous magnesium sulfate. CH ₂ Cl ₂ was distilled off under reduced pressure, the residue was purified by column chromatography, and then recrystallized from acetone-methanol to obtain 38.5 g of the compound (M1-24-1). The column chromatography packing was silica gel. The eluent was a toluene-ethyl acetate mixture (v / v = 40/1).
Phase transition temperature C 39.5 S 75.9 N 85.7 I

<Obtaining a glass substrate with a rubbing-treated alignment film>
A glass substrate with a rubbed alignment film was prepared by the following procedure:
(1) A polyamic acid for horizontal alignment mode is spin-coated on a glass substrate having a thickness of 1.1 mm,
(2) Remove the solvent from the spin-coated film on a hot plate at 80 ° C.,
(3) The coating film is baked in an oven at 230 ° C. for 30 minutes,
(4) A glass substrate with a rubbing-treated alignment film was obtained by rubbing with a rayon cloth.
However, the polyamic acid for horizontal alignment mode is Rixon (registered trademark) aligner PIA-5370 manufactured by JNC Corporation, the roller pushing of the rubbing process is 0.32 mm, and the rotation speed of the rubbing process is 1000 rpm. .

<Exposure conditions>
In this example, “exposure” is irradiation for 30 seconds with light having an intensity of 30 mW / cm ² (365 nm) using an ultra-high pressure mercury lamp (manufactured by USHIO INC., Multilight-250) of 250 W at room temperature. .

<Confirmation of compound structure>
H ¹ -NMR was measured with a 500 MHz Bruker: DRX-500. The unit of the measured value of H ¹ -NMR is ppm. s is a singlet, d is a doublet, t is a triplet, and m is a multiplet.

<Confirmation of sample phase transition temperature and liquid crystal phase>
The sample was checked for the phase transition temperature and liquid crystal phase by the following procedure:
(1) Place a sample on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope or a differential scanning calorimeter,
(2) While observing with a polarizing microscope, the temperature was raised at a rate of 3 ° C./min, and the phase transition temperature and the presence or absence of a liquid crystal phase were confirmed.
The differential scanning calorimeter is a Diamond DSC from Perkin Elmer.
The transition temperature was expressed by describing the Celsius temperature between the notations indicating the phases.
In the notation indicating a phase, C is a crystalline layer, N is a nematic phase, S is a smectic phase, and I is an isotropic liquid. In the notation indicating a phase, the description of the phase in parentheses indicates a monotropic liquid crystal phase.
In the notation indicating the phase, for example, “C50N63I” indicates that the crystal transitioned to the nematic phase at 50 ° C. and the nematic phase to the isotropic liquid at 63 ° C.

<Confirmation of alignment defects>
The presence or absence of orientation defects was confirmed by both procedures (A) and (B) below:
(A) (1) A sample is sandwiched between two polarizing plates placed on a crossed Nicol placed on a backlight, the sample is rotated in a horizontal plane, and observed for light leakage,
(2) If there is no light leakage, “no alignment defect” is assumed, and if there are many light leaks, “alignment defect is severe”.
(B) (1) A sample is observed with a polarizing microscope,
(2) The degree of orientation defects was reconfirmed.
Here, an ECLIPSE E600 POL manufactured by Nikon Corporation was used as the polarizing microscope.

<Measurement with ellipsometer>
Re was measured using an OPIPRO ellipsometer manufactured by Shintech Co., Ltd. The incident angle of light with respect to the surface of the liquid crystal polymer was changed from -50 ° to 50 in increments of 5 °. Here, the inclination direction of the incident angle of light is the same as the slow axis of the liquid crystal polymer. When both of the following conditions were satisfied, the liquid crystal polymer was considered to be homogeneously aligned.
(A) The retardation with respect to the incident angle of the liquid crystal polymer is convex upward (b) The difference in retardation at the same incident angle with the same absolute value is within 5%

<Film thickness measurement>
The layer of the optically anisotropic film of the glass substrate with the optically anisotropic film was shaved, and the step was measured using a fine shape measuring device (Alphastep IQ manufactured by KLA TENCOR Co., Ltd.).

<Evaluation of Δn>
Δn was determined by Δn = Re / d. Where Re is the retardation of the optically anisotropic film having a wavelength of 550 nm when the incident angle of light is 90 ° with respect to the film surface, and d is the film thickness of the optically anisotropic film.

[Example 1]
Compound (1-1-12) was synthesized by the following procedure.

2,4-Diethylthio-6-chloro-1,3,5-triazine was synthesized according to Angew. Chem., Int. Ed., 52, 4945-4949 (2013). A mixture of 5.0 g 2,5-dimethoxyaniline, 7.7 g 2,4-diethoxythio-6-chloro-1,3,5-triazine, 5.4 g potassium carbonate and 50 ml 1,4-dioxane was added for 4 hours. Refluxed. The mixture after refluxing was cooled, mixed with 50 ml of pure water, and washed with 50 ml of toluene. The organic layer was dried over anhydrous MgSO ₄ , filtered, evaporated under reduced pressure, and the residue was purified by column chromatography to obtain 8.3 g of compound (1-1-12-A). The column chromatography packing was silica gel. The eluent was a mixture of toluene and ethyl acetate (v / v = 10/1).

8.0 g of compound (1-1-12-A) was dissolved in 80 ml of CH ₂ Cl ₂ and 12.5 g of BBr ₃ was added at −50 ° C. or lower. After stirring overnight at room temperature, the residue is slowly added to 50 ml ice water. The solvent was suction filtered, and the resulting solid was dried to obtain 5.0 g of the compound (1-1-12-B).

3.0 g of compound (1-1-12-B), 8.5 g of compound (1-1-A) and 0.25 g of DMAP are added to 50 mL of CH ₂ Cl ₂ and an ice bath is added under a nitrogen atmosphere. Stir with cooling above. Thereto, 60 mL of a CH ₂ Cl ₂ solution in which 4.32 g of 1,3-dicyclohexylcarbodiimide was dissolved was dropped. After dropwise addition, the mixture was stirred overnight at room temperature. The deposited precipitate was separated by filtration, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate and water, and dried over anhydrous magnesium sulfate. CH ₂ Cl ₂ was distilled off under reduced pressure, the residue was purified by column chromatography, and then recrystallized from toluene-methanol to obtain 6.1 g of the compound (1-1-12). The column chromatography packing was silica gel. The eluent was a toluene-ethyl acetate mixture (v / v = 10/1).

The phase transition temperature and NMR analysis value of the obtained compound (1-1-12) are as follows:
C 88.6 (N 82.4) I
H ¹ -NMR: (CDCl ₃ ; δ ppm): 8.08 (d, 1H), 7.10 (d, 5H), 6.98 (s, 1H), 6.83-6.80 (m, 5H) ), 6.41 (d, 2H), 6.15-6.09 (m, 2H), 5.83-5.79 (m, 2H), 4.85-4.70 (m, 2H), 4.17 (t, 4H), 3.93 (t, 4H), 3.11-3.06 (m, 4H), 2.90-2.87 (m, 4H), 2.68-2. 50 (m, 6H), 2.17-2.10 (m, 4H), 2.10-2.02 (m, 4H), 1.84-1.65 (m, 12H), 1.56- 1.32 (m, 18H).

窒素気流中で、２．５０ｇの化合物（１−１−１２−Ａ）を溶かした２０ｍｌのＴＨＦ溶液に、 ０．３４ｇのＮａＨを溶かした（６０重量％、８．５０ｍｍｏｌ）溶液を４回に分けて投入した。室温で３０分撹拌後、０．５７ｍｌ（９．２ｍｍｏｌ）のＭｅＩ を溶解させたのを加えた。室温で３日間撹拌後、反応液を３０ｍｌの純水に注ぎ、５０ｍｌの酢酸エチルで抽出した。有機層を無水ＭｇＳＯ_４で乾燥させ、ろ過した。溶媒を減圧留去した。残渣をカラムクロマトグラフィーで精製し、２．６ｇの化合物ｒ（１−１−１２−Ａ）を得た（収率１００％）。カラムクロマトグラフィーの充填物は、シリカゲルであった。溶離液はトルエン−酢酸エチル混合物（ｖ／ｖ＝２０／１）であった。 [Comparative Example 1]
Compound r (1-1-12) was synthesized by the following procedure.

In a nitrogen stream, 0.34 g of NaH (60 wt%, 8.50 mmol) was dissolved four times in 20 ml of THF solution in which 2.50 g of compound (1-1-12-A) was dissolved. I put them separately. After stirring for 30 minutes at room temperature, 0.57 ml (9.2 mmol) of MeI was dissolved. After stirring at room temperature for 3 days, the reaction solution was poured into 30 ml of pure water and extracted with 50 ml of ethyl acetate. The organic layer was dried over anhydrous MgSO ₄ and filtered. The solvent was removed under reduced pressure. The residue was purified by column chromatography to obtain 2.6 g of compound r (1-1-12-A) (yield 100%). The column chromatography packing was silica gel. The eluent was a toluene-ethyl acetate mixture (v / v = 20/1).

    The compound r (1-1-12-A) was replaced with the compound (1-1-12-A) of Example 1 to obtain 7.4 g of compound r (1-1-12) ( Yield 84%). However, the eluent of column chromatography was a toluene-ethyl acetate mixture (v / v = 6/1).

The NMR analysis value of the obtained compound r (1-1-12) is as follows:
¹ H-NMR (CDCl ₃ ; δ ppm): 7.30-7.00 (m, 7H), 6.81 (dd, 4H), 6.40 (d, 2H), 6.15-6.09 ( m, 2H), 5.82 (d, 2H), 4.80-4.63 (m, 2H), 4.17 (t, 4H), 3.93 (t, 4H), 3.75-3. .69 (m, 2H), 3.36 (S, 3H), 3.19-3.05 (m, 2H), 2.90-2.80 (m, 4H), 2.75-2.2 .60 (m, 2H), 2.61-2.50 (m, 4H), 2.20-1.20 (m, 38H).
Compound r (1-1-12) was a viscous liquid at −50 ° C. or lower.
As mentioned above, when -NMe- of compound r (1-1-12-A) was substituted with -NH-, the liquid crystal property was remarkably improved. Therefore, the compound (1) is preferably NH.

<Preparation of polymerizable liquid crystal composition>
[Example 2]
Table 1 shows the type and content of the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition, the type and content of the other polymerizable liquid crystal compound, and the content of the surfactant. Here, cyclopentanone was added to each polymerizable liquid crystal composition so that the concentration of the solid content was 20% by weight with respect to the total weight of the polymerizable liquid crystal solution.

[Comparative Example 2]
Table 2 shows the type and content of the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition, the type and content of the other polymerizable liquid crystal compound, and the content of the surfactant. Here, cyclopentanone was added to each polymerizable liquid crystal composition so that the solid content would be 20% by weight with respect to the total weight of the polymerizable liquid crystal solution.

<Preparation of optically anisotropic film>
[Example 3]
The polymerizable liquid crystal compositions (C1) to (C5) were applied onto a glass substrate with a rubbed alignment film by spin coating. Spin coating was performed for 15 seconds at 800 rpm.
These substrates were heated at the heating temperatures listed in Table 3 for 3 minutes and cooled at room temperature for 1 minute.
The layer of the polymerizable liquid crystal composition from which the solvent of the polymerizable liquid crystal composition was removed was exposed in air, and the alignment state of the liquid crystal was fixed to obtain an optically anisotropic film. The results of confirming the optically anisotropic film with a polarizing microscope and an ellipsometer are shown in Table 3.

[Comparative Example 3]
The polymerizable liquid crystal composition in the method for producing the optically anisotropic film of Example 3 was replaced with the polymerizable liquid crystal compositions (R1) to (R3), and optically anisotropic films were produced at the heating temperatures shown in Table 4. .

  Table 5 shows the optical characteristics of the optically anisotropic films prepared in Example 3 and Comparative Example 3.

Ｒｅ_{４５０／５５０}は、小さいほど波長分散特性が良好である。Ｒｅ_{４５０／５５０}は、１より小さい場合は、逆波長分散特性を有することを示す。
Ｒｅ_{６５０／５５０}は、大きいほど波長分散特性が良好である。Ｒｅ_{６５０／５５０}は、１より大きい場合は、逆波長分散特性を有することを示す。

The smaller the Re _450/550 , the better the wavelength dispersion characteristic. When Re _450/550 is smaller than 1, it indicates that it has reverse wavelength dispersion characteristics.
The larger the Re _650/550 , the better the wavelength dispersion characteristic. When Re _650/550 is greater than 1, it indicates that it has reverse wavelength dispersion characteristics.

  From Examples 3 to 8 and Comparative Examples 3 to 5, the optically anisotropic films (FR1) to (FR5) have substantially the same wavelength dispersion characteristics as the optically anisotropic films (FR1) and anisotropic films (FR3). Was found to be obtained.

<Heat resistance of optically anisotropic film>
[Examples 9 to 13, Comparative Examples 4 and 5]
A comparison of chromatic dispersion characteristics before and after heating was performed in the following procedure:
(1) Place the optically anisotropic film in an oven at room temperature of 120 ° C. for 200 hours together with the glass substrate,
(2) After returning to room temperature, Re ₅₅₀ was measured.
Table 6 shows a comparison of wavelength dispersion characteristics before and after heating.
The rate of change in Table 6 was calculated by [{Re ₅₅₀ before heating}-{Re ₅₅₀ after heating}] / {Re ₅₅₀ before heating} × 100.

From Table 6, it was found that the optically anisotropic film of the present invention had a low rate of change, and that Re did not easily decrease even after heating.

Claims (13)

A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound represented by formula (1) as a polymerizable liquid crystal component in an amount of 30% by weight or more based on the total amount of the polymerizable liquid crystal component.

In formula (1),
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, 1-cyclohexene-1,4-ylene, 2-cyclohexene-1,4-ylene, pyridine-2,5. -Diyl or naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, trifluoromethyl, alkyl of 1 to 5 carbons, carbon May be replaced by alkoxy of 1 to 5, alkoxycarbonyl of 1 to 5 carbons, or alkanoyl of 1 to 5 carbons;
Z ¹ is 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 = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH 2 CH 2 OCO -, - COOCH 2 _{CH 2 -, - OCH 2 COO} -, - OCOCH 2 O -, - CH = CH -, - N = CH -, - CH = N -, - N = CCH 3 -, - CCH 3 = N -, - N = N-, or -C≡C-;
m is independently an integer from 0 to 3;
At least one m is 1 or more;
Ar ¹ is an aromatic ring, in which the hydrogen may be substituted with alkyl, cyano or nitro, and —CH ₂ — of the alkyl group is —O—, —S—, —CO— or — The alkyl group —CH ₂ —CH ₂ — may be substituted with NH—, and is substituted with —CH═CH—, —C≡C—, —CH═NH— or —N═CH—. The alkyl hydrogen may be substituted with cyano or nitro;
Ar ¹ has 18 or less carbon atoms;
R ¹ is independently hydrogen, fluorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons, or 1 to 12 carbons. Or a group represented by formula (2):
At least one R ¹ is a group represented by formula (2);

In formula (2),
Y ¹ is 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 — is —O—, —COO—, —OCO—, —CH═CH—, or — May be replaced by C≡C-;
PG is a group represented by any one of formula (PG-1) to formula (PG-9);

In formula (PG-1) to formula (PG-9),
^RPG is independently hydrogen, halogen, methyl, ethyl, or trifluoromethyl. N in Ar ¹ —NH— in formula (1) is
Constituting the ring of Ar ¹ = N-or Ar ¹ of cyano on the ring or the polymerizable liquid crystal composition according to claim 1 which is nitro and conjugated. The polymerizable liquid crystal composition according to claim 1, wherein PG in the formula (2) is a group represented by the formula (PG-1), and ^RPG is hydrogen or methyl. In equation (1),
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, 1-cyclohexene-1,4-ylene, 2-cyclohexene-1,4-ylene, , 4-phenylene, at least one hydrogen is fluorine, trifluoromethyl, 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 May be replaced by;
Z ¹ is independently a single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ CH ₂ O—, —CH ₂ CH ₂ COO. _{-, - OCOCH 2 CH 2 -} , - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCH 2 COO-, or -OCOCH ₂ O-a and;
The polymerizable liquid crystal composition according to claim 1, wherein R ¹ is independently a group represented by the formula (2). The polymerizable liquid crystal composition according to claim 1, wherein the compound represented by formula (1) is a compound represented by any one of formulas (1-1) to (1-6).

In formula (1-1) to formula (1-6),
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, 1-cyclohexene-1,4-ylene, 2-cyclohexene-1,4-ylene, pyridine-2,5. -Diyl or naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, trifluoromethyl, alkyl of 1 to 5 carbons, May be substituted with alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons, or alkanoyl having 1 to 5 carbons;
Z ¹ is 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═CHCOO—, —OCOCH═CH—, —CH ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCH ₂ COO—, —OCOCH ₂ O—, —CH═CH—, —N═CH—, —CH═N—, —N═CCH ₃ —, —CCH ₃ = N—, — N = N-, or -C≡C-;
Ar ¹ is a group consisting of an aromatic ring, and at least one hydrogen may be replaced by an alkyl, and —CH ₂ — of the alkyl is —O—, —S—, —CO—, Or —NH— may be replaced by —CH ₂ —CH ₂ — in which the alkyl is replaced by —CH═CH—, —C≡C—, —CH═NH—, or —N═CH—. May be;
Ar ¹ has 18 or less carbon atoms;
m1 is independently an integer from 0 to 2;
m2 is 0 or 1;
R ¹ is independently hydrogen, fluorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons, or 1 to 12 carbons. Or a group represented by formula (2):
At least one R ¹ is a group represented by formula (2);

In formula (2),
Y ¹ is a single bond, —O—, —COO—, —OCO—, or —OCOO—;
Q ¹ is a single bond or alkylene having 1 to 20 carbon atoms, and at least one —CH ₂ — in the alkylene is —O—, —COO—, —OCO—, —CH═CH—, or —C. May be replaced by ≡C-;
PG is a group represented by any one of formula (PG-1) to formula (PG-9):

In formula (PG-1) to formula (PG-9),
^RPG is independently hydrogen, halogen, methyl, ethyl, or trifluoromethyl.   An optically anisotropic film obtained by curing the polymerizable liquid crystal composition according to claim 1.   {Birefringence for light with a wavelength of 450 nm} / {birefringence for light with a wavelength of 550 nm} ≦ 1.05 and {birefringence for light with a wavelength of 650 nm} / {birefringence for light with a wavelength of 550 nm} The optically anisotropic film according to claim 6, wherein ≧ 0.97.   A polarizing plate provided with the optically anisotropic film of any one of Claims 6-7.   A display element provided with the optically anisotropic film of any one of Claims 6-7.   A display element comprising the polarizing plate according to claim 8. (I) Application of the polymerizable liquid crystal composition according to claim 1 to a substrate;
(Ii) heat treatment;
(Iii) A method for producing an optically anisotropic film, comprising curing a polymerizable liquid crystal composition by irradiation with light. A compound represented by formula (1-1-a).

In formula (1-1-a),
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, 1-cyclohexene-1,4-ylene, 2-cyclohexene-1,4-ylene, pyridine-2,5. -Diyl or naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, trifluoromethyl, alkyl of 1 to 5 carbons, It may be replaced with alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons, or alkanoyl having 1 to 5 carbons:
Z ¹ is 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 = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH 2 CH 2 OCO -, - COOCH 2 _{CH 2 -, - OCH 2 COO} -, - OCOCH 2 O -, - CH = CH -, - N = CH -, - CH = N -, - N = CCH 3 -, - CCH 3 = N -, - N = N- or -C≡C-
Ar ¹ is a group consisting of an aromatic ring, in which at least one hydrogen may be replaced by an alkyl, and —CH ₂ — of the alkyl is —O—, —S—, —CO—. Or optionally substituted with —NH—, wherein —CH ₂ —CH ₂ — in this alkyl is replaced with —CH═CH—, —C≡C—, —CH═NH—, or —N═CH—. May be
Ar ¹ has 18 or less carbon atoms;
m3 is independently 0 or 1:
R ¹ is independently hydrogen, fluorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons, or 1 to 12 carbons. Or a group represented by formula (2):
At least one R ¹ is a group represented by formula (2);

In formula (2),
Y ¹ is 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 — is —O—, —COO—, —OCO—, —CH═CH—, or — May be replaced by C≡C-;
PG is a group represented by any one of formula (PG-1) to formula (PG-9);

In formula (PG-1) to formula (PG-9),
^RPG is independently hydrogen, halogen, methyl, ethyl, or trifluoromethyl.
In formula (1-1-a),
Ar ¹ is 1,3,5-triazinyl,
At least one hydrogen of the triazinyl may be replaced with alkyl, and —CH ₂ — of the alkyl may be replaced with —O—, —S—, —CO—, or —NH—, _{is, -CH = CH - - -CH 2} -CH 2 in the alkyl, - C≡C -, - CH = NH-, or a compound according to or claim 12, be replaced by -N = CH-.