JP2019144461A - In-cell phase-difference film - Google Patents

Abstract

To provide a high in-cell phase-difference with film front contrast and low wavelength dispersion characteristics.SOLUTION: The in-cell phase difference film is installed inside a liquid crystal cell with a liquid crystal layer between two substrates and has a polymer film made of a liquid crystal polymer formed on a photoalignment film, and the liquid crystal polymer is a polymer of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound expressed by the formula (1). (A1 is independently 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, and a divalent ring represented by tetrahydropyran-2,5-diyl, Z1 is independently -OCH2-, -CH2O-, -COO-, -OCO-, -CF2O2-, -O2-, -CH2CH2-, -CF2CF2-, -OCH2CH2O-, -CH=CHCOO- and the like, and P1 is a monovalent group having a polymerizable functional group.)SELECTED DRAWING: None

Description

  The present invention relates to an in-cell retardation film and a liquid crystal display element having the in-cell retardation film.

In the liquid crystal display device, a retardation film is disposed on the liquid crystal display device in order to enlarge the viewing angle, adjust the image color tone, and improve the contrast.
From the viewpoint of improving the contrast of a transflective liquid crystal display device, an in-cell retardation film has been proposed in which a retardation film in which a portion having a phase difference and a portion having no phase difference are arranged inside a liquid crystal cell is arranged. (Patent Document 1).

Also, in-cell retardation films will be developed in which a non-patterned retardation film is placed inside the liquid crystal cell from the viewpoint of improving productivity by reducing the thickness and weight of the liquid crystal display device and reducing the pasting process. (Patent Documents 2 and 3).
Furthermore, in order to improve visibility under sunlight, it has been studied to arrange an in-cell retardation film (Patent Document 4).

JP 2010-78971 A WO2015 / 129672 JP2015-105986A WO2017 / 017960 Publication

Due to the high definition of liquid crystal display devices, further improvements in display quality are required. Even in the in-cell retardation film, the control of optical characteristics is an indispensable problem.
In-cell retardation films are required to improve front contrast from the viewpoint of high-contrast image display. Further, from the viewpoint of optimizing color unevenness and color tone, it is required to control wavelength dispersion characteristics. The challenge is to achieve both high contrast and control of wavelength dispersion characteristics.

  In addition, even in heat treatment at around 230 ° C., which is required in the manufacturing process of the liquid crystal cell, it is required to have high heat resistance that does not greatly change the optical characteristics.

  Aspect 1 of the present invention is an in-cell retardation film installed inside a liquid crystal cell having a liquid crystal layer sandwiched between two substrates, the retardation film comprising a photo-alignment film and the photo-alignment film A polymer liquid crystal composition comprising a liquid crystal polymer formed on an alignment film, wherein the liquid crystal polymer contains at least one polymerizable liquid crystal compound represented by formula (1). It is a coalescence.

（式（１）中、
ｍは４であり、
Ａ¹は独立して１，４−フェニレン、１，４−シクロへキシレン、１，４−シクロヘキセニレン、テトラヒドロピラン−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、フルオレン−２，７−ジイル、またはインダノン−４，７−ジイルで表される二価の環であり、該二価の環において、少なくとも一つの水素はフッ素、塩素、トリフルオロメチル、炭素数１〜１０のアルキル、炭素数２〜１０のアルケニル、炭素数１〜１０のアルコキシ、炭素数１〜１０のアルコキシカルボニル、炭素数１〜１０のアルカノイル、炭素数１〜１０のアルカノイルオキシ、または重合性官能基を有する一価基で置き換えられてもよく、
Ｚ¹は独立して−ＯＣＨ₂−、−ＣＨ₂Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ₂Ｏ−、−ＯＣＦ₂−、−ＣＨ₂ＣＨ₂−、−ＣＦ₂ＣＦ₂−、−ＯＣＨ₂ＣＨ₂Ｏ−、−ＣＨ＝ＣＨＣＯＯ−、−ＯＣＯＣＨ＝ＣＨ−、−ＣＨ₂ＣＨ₂ＣＯＯ−、−ＯＣＯＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ₂ＯＣＯ−、−ＣＯＯＣＨ₂ＣＨ₂−、−ＣＨ＝ＣＨ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−、−Ｎ＝Ｃ（ＣＨ₃）−、−Ｃ（ＣＨ₃）＝Ｎ−、−Ｎ＝Ｎ−、−Ｃ≡Ｃ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−Ｃ（ＣＨ₃）＝Ｎ−Ｎ＝Ｃ（ＣＨ₃）−、または炭素数４〜２０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−で置き換えられてもよく、
Ｐ¹は独立して重合性官能基を有する一価基である。）

(In the formula (1),
m is 4,
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene. A divalent ring represented by -2,6-diyl, fluorene-2,7-diyl, or indanone-4,7-diyl, in which at least one hydrogen is fluorine, chlorine, Trifluoromethyl, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 10 carbons, alkoxycarbonyl having 1 to 10 carbons, alkanoyl having 1 to 10 carbons, 1 to 10 carbons Of alkanoyloxy, or a monovalent group having a polymerizable functional group,
Z ¹ is independently —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 -, -CH = CH -, - N = CH -, - CH = N -, - N = C (CH 3) -, - C (CH 3) = N -, - N = N -, - C≡C-, -CH = N-N = CH - , - C (CH 3) = N-N = C (CH 3) -, or alkylene of 4 to 20 carbon atoms, at least one -CH ₂ - in the alkylene - is May be replaced by -O-
P ¹ is independently a monovalent group having a polymerizable functional group. )

  Aspect 2 of the present invention is the in-cell retardation film of Aspect 1, further comprising a polymerizable liquid crystal compound represented by the formula (2) in the polymerizable liquid crystal composition.

（式（２）中、
ｎは独立して１または２であり、
Ａ²は独立して１，４−フェニレン、または１，４−シクロへキシレンであり、これらおいて、少なくとも一つの水素はフッ素、塩素、トリフルオロメチル、炭素数１〜１０のアルキル、炭素数２〜１０のアルケニル、炭素数１〜１０のアルコキシ、炭素数１〜１０のアルコキシカルボニル、炭素数１〜１０のアルカノイル、炭素数１〜１０のアルカノイルオキシ、または重合性官能基を有する一価基で置き換えられてもよく、
Ｚ²は独立して単結合、−ＯＣＨ₂−、−ＣＨ₂Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ₂ＣＨ₂−、−ＯＣＨ₂ＣＨ₂Ｏ−、−ＣＨ₂ＣＨ₂ＣＯＯ−、−ＯＣＯＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ₂ＯＣＯ−、または−ＣＯＯＣＨ₂ＣＨ₂−であり、
Ｐ²は独立して重合性官能基を有する一価基であり、
Ｇは、式（Ｇ−１）〜式（Ｇ−４）で表される基であり、

(In the formula (2),
n is independently 1 or 2,
A ² is independently 1,4-phenylene or 1,4-cyclohexylene, in which at least one hydrogen is fluorine, chlorine, trifluoromethyl, alkyl having 1 to 10 carbons, carbon number 2-10 alkenyl, C1-C10 alkoxy, C1-C10 alkoxycarbonyl, C1-C10 alkanoyl, C1-C10 alkanoyloxy, or a monovalent group having a polymerizable functional group May be replaced with
Z ² 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-, or -COOCH ₂ CH ₂ - and is,
P ² is independently a monovalent group having a polymerizable functional group,
G is a group represented by formula (G-1) to formula (G-4);

（式（Ｇ−１）〜式（Ｇ−４）中、
Ｘ¹は独立して−ＣＨ₂−、−ＮＨ−、−Ｏ−、−Ｓ−、または−ＣＯ−であり、−ＣＨ₂−または−ＮＨ−において、少なくとも一つの水素は炭素数１〜５のアルキルで置き換えられてもよく、
Ｘ²は独立して−ＣＨ＝または−Ｎ＝であり、
Ｚ³は独立して単結合、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−ＮＲ¹−、−Ｃ（ＣＨ₃）＝Ｎ−ＮＲ¹−または−ＣＨ＝Ｎ−Ｎ＝ＣＨ−であり、ここで、Ｒ¹は独立して水素、炭素数１〜１０のアルキルまたは重合性官能基を有する一価基であり、
Ｔ¹、Ｔ⁴およびＴ⁵はそれぞれπ電子の数が６〜１４である１価基であり、
Ｔ²、Ｔ³およびＴ⁶はそれぞれ独立して、水素、トリフルオロメチル、シアノ、炭素数１〜５のアルキル、炭素数２〜５のアルケニル、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、炭素数１〜５のアルカノイル、炭素数１〜５のアルカノイルオキシ、炭素数１〜５のアルキルスルフィド、または重合性官能基を有する一価基であり、
Ｔ²とＴ³は酸素原子、窒素原子、硫黄原子を含む５〜７員環の複素環または環状ケトンを形成してもよい。）

(In the formulas (G-1) to (G-4),
X ¹ is independently —CH ₂ —, —NH—, —O—, —S—, or —CO—, and in —CH ₂ — or —NH—, at least one hydrogen has 1 to 5 carbon atoms. May be substituted with
X ² is independently —CH═ or —N═,
Z ³ is independently a single bond, —CH═CH—, —C≡C—, —CH═N—, —N═CH—, —CH═N—NR ¹ —, —C (CH ₃ ) = N —NR ¹ — or —CH═N—N═CH—, wherein R ¹ is independently hydrogen, a C 1-10 alkyl or a monovalent group having a polymerizable functional group;
T ¹ , T ⁴ and T ⁵ are each a monovalent group having 6 to 14 π electrons,
T ² , T ³ and T ⁶ are each independently hydrogen, trifluoromethyl, cyano, C 1-5 alkyl, C 2-5 alkenyl, C 1-5 alkoxy, C 1 5 alkoxycarbonyl, C 1-5 alkanoyl, C 1-5 alkanoyloxy, C 1-5 alkyl sulfide, or a monovalent group having a polymerizable functional group,
T ² and T ³ may form a 5- to 7-membered heterocyclic ring or cyclic ketone containing an oxygen atom, a nitrogen atom, or a sulfur atom. )

  In aspect 3 of the present invention, the polymerizable liquid crystal composition has a polymerizable liquid crystal compound represented by formula (1), a polymerizable liquid crystal compound represented by formula (2), a photopolymerization initiator, a surfactant, and a polymerization agent. In-cell retardation film according to embodiment 1 or 2 containing an inhibitor.

Aspect 4 of the present invention
4. The in-cell retardation film according to any one of aspects 1 to 3, wherein the photo-alignment film is made of a photo-alignment agent containing polyamic acid or polyimide.

Aspect 5 of the present invention
The in-cell retardation film according to any one of aspects 1 to 4, wherein the liquid crystal polymer has liquid crystal molecules fixed in a homogeneous orientation.

Aspect 6 of the present invention
6. The in-cell retardation film according to any one of aspects 1 to 5, wherein an in-plane retardation Re (550) at a wavelength of 550 nm is 120 nm ≦ Re (550) ≦ 250 nm.

Aspect 7 of the present invention
7. The in-cell retardation film according to any one of aspects 1 to 6, which is laminated directly on a color filter layer of a liquid crystal cell or via a planarizing layer.

Aspect 8 of the present invention
A liquid crystal display element comprising the in-cell retardation film according to any one of aspects 1 to 7.

In-cell retardation films according to aspects 1 to 7 of the present invention have low wavelength dispersion characteristics and high front contrast.
The liquid crystal display element according to the aspect 8 of the present invention has improved color unevenness, viewing angle characteristics, and contrast.

In the present invention, “front contrast” is a value of (luminance in parallel Nicol state) / (luminance in crossed Nicol state) when an object is placed between two polarizing plates.
In the present invention, the “crossed Nicol state” is a state in which the polarization axes of the polarizing plates arranged opposite to each other are orthogonal.

In the present invention, the “parallel Nicol state” is a state in which the polarization axes of the polarizing plates arranged opposite to each other coincide.
In the present invention, the “wavelength dispersion characteristic” means the degree of retardation reduction accompanying an increase in wavelength in the visible light region. Therefore, when the degree of retardation decrease as the wavelength increases is expressed as “wavelength dispersion characteristics”. When the degree of retardation decrease with increasing wavelength, or when retardation increases with increasing wavelength, it is expressed that “wavelength dispersion characteristic” is low.

In the present invention, “Re” is retardation and is a phase delay of abnormal light with respect to ordinary light. The thickness of the liquid crystal polymer film is d, and Δn is expressed as Re = Δn · d as a birefringence.
In the present invention, “Re (λ)” is retardation when light having a wavelength of λ nm is incident on the film surface perpendicularly.

  In the present invention, the “number of π electrons” refers to the number of double bonds in the structural formula based on the valence mark in the structural formula based on the valence mark of the organic compound, which is shown by assuming that the valence electrons are localized. } × 2 is the number calculated.

In the present invention, “compound (X)” means a compound represented by the formula (X). Here, X in “compound (X)” is a character string, a number, a symbol or the like.
In the present invention, the “liquid crystal composition” is a mixture having a liquid crystal phase.

In the present invention, the “liquid crystal compound” is a generic term for (A) a compound having a liquid crystal phase as a pure substance and (B) a compound which is a component of a liquid crystal composition.
In the present invention, the “polymerizable group” is a functional group that, when contained in a compound, polymerizes by means of light, heat, catalyst, or the like and changes into a polymer having a larger molecular weight.

In the present invention, the “monofunctional compound” is a compound having one polymerizable group.
In the present invention, the “polyfunctional compound” is a compound having a plurality of polymerizable groups.
In the present invention, the “X functional compound” is a compound having X polymerizable groups. Here, X in the “X functional compound” is an integer.

In the present invention, the “polymerizable compound” is a compound having at least one polymerizable group.
In the present invention, the “polymerizable liquid crystal compound” is a polymerizable compound that is a liquid crystal compound.

In the present invention, the “non-liquid crystalline polymerizable compound” is a polymerizable compound that is a pure substance and does not have a liquid crystal phase.
In the present invention, the “polymerizable liquid crystal composition” means a composition containing a polymerizable liquid crystal compound and having a liquid crystal phase.

In the present invention, the “polymerizable liquid crystal composition solution” means a mixture containing a polymerizable liquid crystal composition and a solvent.
In the present invention, the “liquid crystal polymer” means a portion obtained by polymerizing and curing a polymerizable component such as a polymerizable liquid crystal compound in the polymerizable liquid crystal composition.

In the present invention, the “liquid crystal polymer film” means a film-like or plate-like liquid crystal polymer.
In the present invention, the “retardation film” is an element having optical anisotropy, and is a film-like or plate-like object.

In the present invention, “in-cell” refers to a cell in which a liquid crystal layer is sealed between two substrates and refers to the liquid crystal layer side that is inside the substrate.
In the present invention, “in-cell retardation film” means a retardation film installed inside a liquid crystal cell.

In the present invention, “homogeneous alignment” refers to an alignment state in which the tilt angle is 0 to 5 degrees.
In the present invention, “room temperature” refers to 15 ° C. to 35 ° C.

  When the following chemical structure is described in the chemical formula, the wavy line is the bonding position of the atom or the functional group. Here, the following C is any atom or functional group.

化学式中に、同一の符号があり、複数存在する場合は、符号が示す構造は同一であっても異なるものであってもよい。

In the chemical formula, when there are the same symbols and there are a plurality, the structures indicated by the symbols may be the same or different.

The alignment of the liquid crystal includes homogeneous alignment, homeotropic alignment, twist alignment, splay alignment, hybrid alignment, and the like.
The in-cell retardation film of the present invention is a laminate of a photo-alignment film and a liquid crystal polymer film.

≪Liquid crystal polymer film≫
The liquid crystal polymer film is produced by the following steps.
(I) A polymerizable liquid crystal composition solution is applied on the photo-alignment film,
(II) The solvent is removed from the polymerizable liquid crystal composition solution on the photo-alignment film by heating or other methods, and a coating film of the polymerizable liquid crystal composition is formed on the photo-alignment film.
(III) A film composed of a liquid crystal polymer on the photo-alignment film by polymerizing the polymerizable compound in the composition by irradiating with ultraviolet light in a state where the polymerizable liquid crystal composition on the photo-alignment film is aligned. Is made.

  The liquid crystal polymer film includes a liquid crystal polymer of a polymerizable liquid crystal compound represented by the formula (1), and is further represented by the formula (2) together with the liquid crystal polymer of the polymerizable liquid crystal compound represented by the formula (1). A liquid phase polymer with a polymerizable liquid crystal compound. The liquid crystal polymer may be a copolymer of a polymerizable liquid crystal compound represented by the formula (1) and a polymerizable liquid crystal compound represented by the formula (2), and further, a non-liquid crystalline polymerizable compound and It may be a copolymer with a polymerizable liquid crystal compound. The copolymer may be either a block copolymer or a random copolymer. The polymer is a homopolymer of a polymerizable liquid crystal compound represented by the formula (1), a homopolymer of a polymerizable liquid crystal compound represented by the formula (2), and if necessary, non-liquid crystalline polymerizability. A mixture of compounds composed of a homopolymer of compounds may be used.

≪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). When the polymerizable liquid crystal compound represented by the formula (1) is included, a liquid crystal polymer film having a high front contrast can be obtained.
The polymerizable liquid crystal compound represented by the formula (1) is shown below.

この式（１）中、ｍは４である。

In this formula (1), m is 4.

A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene. A divalent ring represented by -2,6-diyl, fluorene-2,7-diyl, or indanone-4,7-diyl, in which at least one hydrogen is fluorine, chlorine, Trifluoromethyl, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 10 carbons, alkoxycarbonyl having 1 to 10 carbons, alkanoyl having 1 to 10 carbons, 1 to 10 carbons Of alkanoyloxy, or a monovalent group having a polymerizable functional group.

When A ¹ is independently 1,4-phenylene or 1,4-cyclohexylene, it is more preferable because the compound is easy to produce and the temperature range of the liquid crystal phase is likely to be widened. From the viewpoint of high solubility in an organic solvent, at least one of A ¹ is more preferably 1,4-phenylene having a substituent.

Z ¹ is independently —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 -, -CH = CH -, - N = CH -, - CH = N -, - N = C (CH 3) -, - C (CH 3) = N -, - N = N -, - C≡C-, -CH = N-N = CH - , - C (CH 3) = N-N = C (CH 3) -, or alkylene of 4 to 20 carbon atoms, at least one -CH ₂ - in the alkylene - is It may be replaced by -O-.

From the viewpoint of high solubility in an organic solvent, at least one of Z ¹ is —CH ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, —CH ₂ CH ₂ OCO—, or —COOCH ₂ CH _2. -Is preferred.

P ¹ is independently a monovalent group having a polymerizable functional group.
From the viewpoints of high curability, solubility in a solvent, and ease of handling, P ¹ is preferably a structure represented by the following formula (P ¹ -1).

式（Ｐ¹−１）において、Ｙ¹は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−であり、
Ｑ¹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−ＣＨ₂−は−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、ＰＧ¹はアクリロイルオキシ基またはメタクリロイルオキシ基である。

In the formula (P ¹ -1), 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, in which at least one —CH ₂ — may be replaced by —O—, —COO—, or —OCO—, and PG ¹ is acryloyl An oxy group or a methacryloyloxy group;

  Specific examples of the polymerizable liquid crystal compound represented by formula (1) are shown in formula (1-1) to formula (1-7).

式（１−１）〜式（１−７）におけるＹ¹、Ｑ¹、およびＰＧ¹の定義は式（Ｐ¹−１）と同一である。

The definitions of Y ¹ , Q ¹ , and PG ¹ in Formula (1-1) to Formula (1-7) are the same as those in Formula (P ¹ -1).

  The amount of the polymerizable liquid crystal compound represented by the formula (1) in the polymerizable liquid crystal composition is not particularly limited as long as a predetermined polymer film can be formed, and is 5 to 100% by weight, preferably 10% based on the total amount of the composition. It is contained in a range of ˜100% by weight.

The polymerizable liquid crystal composition of the present invention preferably contains at least one polymerizable liquid crystal compound represented by formula (2) in addition to the polymerizable liquid crystal compound represented by formula (1). Since the polymerizable liquid crystal compound represented by the formula (2) can form a liquid crystal polymer film having a low wavelength dispersion characteristic, a high front contrast when used in combination with the polymerizable liquid crystal compound represented by the formula (1). And low chromatic dispersion characteristics can be achieved.
The polymerizable liquid crystal compound represented by the formula (2) is shown below.

この式（２）中、ｎは独立して１または２である。

In this formula (2), n is independently 1 or 2.

A ² is independently 1,4-phenylene or 1,4-cyclohexylene, in which at least one hydrogen is fluorine, chlorine, trifluoromethyl, alkyl having 1 to 10 carbons, carbon number 2-10 alkenyl, C1-C10 alkoxy, C1-C10 alkoxycarbonyl, C1-C10 alkanoyl, C1-C10 alkanoyloxy, or a monovalent group having a polymerizable functional group May be replaced. From the viewpoint of low wavelength dispersion characteristics, at least one of A ² is preferably 1,4-cyclohexylene.

Z ² 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—, or —COOCH ₂ CH ₂ —. From the viewpoint of high solubility in an organic solvent, at least one of Z ² is —CH ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, —CH ₂ CH ₂ OCO—, or —COOCH ₂ CH _2. -Is preferred.
G is a group represented by formula (G-1) to formula (G-4).

（式（Ｇ−１）〜式（Ｇ−４）中、
Ｘ¹は独立して−ＣＨ₂−、−ＮＨ−、−Ｏ−、−Ｓ−、または−ＣＯ−であり、−ＣＨ₂−または−ＮＨ−において、少なくとも一つの水素は炭素数１〜５のアルキルで置き換えられてもよく、
Ｘ²は独立して−ＣＨ＝または−Ｎ＝であり、
Ｚ³は独立して単結合、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−ＮＲ¹−、−Ｃ（ＣＨ₃）＝Ｎ−ＮＲ¹−または−ＣＨ＝Ｎ−Ｎ＝ＣＨ−であり、ここで、Ｒ¹は独立して水素、炭素数１〜１０のアルキルまたは重合性官能基を有する一価基であり、
Ｔ¹、Ｔ⁴およびＴ⁵はそれぞれπ電子の数が６〜１４である１価基であり、
Ｔ²、Ｔ³およびＴ⁶はそれぞれ独立して、水素、トリフルオロメチル、シアノ、炭素数１〜５のアルキル、炭素数２〜５のアルケニル、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、炭素数１〜５のアルカノイル、炭素数１〜５のアルカノイルオキシ、炭素数１〜５のアルキルスルフィド、または重合性官能基を有する一価基であり、
Ｔ²とＴ³は酸素原子、窒素原子、硫黄原子を含む５〜７員環の複素環または環状ケトンを形成しても良い。）
Ｐ²は独立して重合性官能基を有する一価基である。

(In the formulas (G-1) to (G-4),
X ¹ is independently —CH ₂ —, —NH—, —O—, —S—, or —CO—, and in —CH ₂ — or —NH—, at least one hydrogen has 1 to 5 carbon atoms. May be substituted with
X ² is independently —CH═ or —N═,
Z ³ is independently a single bond, —CH═CH—, —C≡C—, —CH═N—, —N═CH—, —CH═N—NR ¹ —, —C (CH ₃ ) = N —NR ¹ — or —CH═N—N═CH—, wherein R ¹ is independently hydrogen, a C 1-10 alkyl or a monovalent group having a polymerizable functional group;
T ¹ , T ⁴ and T ⁵ are each a monovalent group having 6 to 14 π electrons,
T ² , T ³ and T ⁶ are each independently hydrogen, trifluoromethyl, cyano, C 1-5 alkyl, C 2-5 alkenyl, C 1-5 alkoxy, C 1 5 alkoxycarbonyl, C 1-5 alkanoyl, C 1-5 alkanoyloxy, C 1-5 alkyl sulfide, or a monovalent group having a polymerizable functional group,
T ² and T ³ may form a 5- to 7-membered heterocyclic ring or cyclic ketone containing an oxygen atom, a nitrogen atom, or a sulfur atom. )
P ² is independently a monovalent group having a polymerizable functional group.

From the viewpoints of high curability, solubility in a solvent, and ease of handling, P ² is preferably a structure represented by the following formula (P ² -1).

式（Ｐ²−１）において、Ｙ²は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−であり、
Ｑ²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−ＣＨ₂−は−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、ＰＧ²はアクリロイルオキシ基またはメタクリロイルオキシ基である。

In the formula (P ² -1), Y ² is a single bond, —O—, —COO—, —OCO—, or —OCOO—,
Q ² is a single bond or alkylene having 1 to 20 carbon atoms, in which at least one —CH ₂ — may be replaced by —O—, —COO—, or —OCO—, and PG ² is acryloyl An oxy group or a methacryloyloxy group;

  Specific examples of the polymerizable liquid crystal compound represented by formula (2) include formulas (2-1-1) to (2-1-5) and formulas (2-2-1) to (2-2-2). 6), Formula (2-3-1) to Formula (2-3-6), and Formula (2-4-1) to Formula (2-4-5).

式（２−１−１）〜式（２−１−５）、式（２−２−１）〜式（２−２−６）、式（２−３−１）〜式（２−３−６）、および式（２−４−１）〜式（２−４−５）におけるＹ²、Ｑ²、およびＰＧ²の定義は式（Ｐ²−１）と同一である。

Formula (2-1-1) to Formula (2-1-5), Formula (2-2-1) to Formula (2-2-6), Formula (2-3-1) to Formula (2-3) −6), and the definitions of Y ² , Q ² , and PG ² in Formula (2-4-1) to Formula (2-4-5) are the same as those in Formula (P ² -1).

  The amount of the polymerizable liquid crystal compound represented by the formula (2) in the polymerizable liquid crystal composition is not particularly limited as long as a predetermined polymer film can be formed, and is 0 to 95% by weight, preferably 10 with respect to the total amount of the composition. It is contained in a range of ˜90% by weight.

  The weight ratio of the polymerizable liquid crystal compound represented by the formula (1) and the amount of the polymerizable liquid crystal compound represented by the formula (2) and the weight ratio of the formula (1): the formula (2) It is preferably in the range of 1/20. Within this range, it is possible to achieve both high front contrast and low chromatic dispersion characteristics, which are the objects of the present invention.

≪Additive to polymerizable liquid crystal composition≫
The polymerizable liquid crystal composition of the present invention may contain additives other than the polymerizable liquid crystal compound as long as the liquid crystal phase is not impaired.

Addition of a surfactant to the polymerizable liquid crystal composition improves the smoothness of the liquid crystal polymer film. Addition of a nonionic surfactant to the polymerizable liquid crystal composition further improves the smoothness of the liquid crystal polymer film.
Surfactants are classified into ionic surfactants and nonionic surfactants.

  A nonionic surfactant is preferable because it has an effect of suppressing tilt alignment on the air interface side of the liquid crystal polymer film. Silicone-based nonionic surfactants, fluorine-based nonionic surfactants, vinyl-based nonionic surfactants, hydrocarbon-based nonionic surfactants, and the like are nonionic surfactants.

  In order to improve the mechanical strength and chemical resistance of the liquid crystal polymer film surface, a surfactant which is a polymerizable compound may be added to the polymerizable liquid crystal composition. As the surfactant that is a polymerizable compound, a surfactant that initiates a polymerization reaction with ultraviolet rays is preferable.

  Since the liquid crystal polymer film tends to have a uniform orientation and the coating property of the polymerizable liquid crystal composition is improved, the surfactant in the polymerizable liquid crystal composition is in an amount of 0.00% relative to the total amount of the polymerizable liquid crystal composition. 01 to 5 weight% is preferable and 0.05 to 1 weight% is more preferable.

  A silicone-based nonionic surfactant is a linear polymer composed of a siloxane bond and having a side chain and / or a terminal introduced with an organic group such as polyether or long chain alkyl.

A compound having a C 2-7 perfluoroalkyl group or a perfluoroalkenyl group is a fluorine-based nonionic surfactant.
Examples of vinyl-based nonionic surfactants include (meth) acrylic polymers having a weight average molecular weight of 1,000 to 1,000,000.

  The polymerizable liquid crystal composition of the present invention may contain a non-liquid crystalline polymerizable compound. In order to maintain the liquid crystal phase, the total weight of the non-liquid crystalline polymerizable compound in the polymerizable liquid crystal composition is preferably 30% by weight or less based on the total amount of the polymerizable liquid crystal composition.

By adding a polyfunctional non-liquid crystalline polymerizable compound to the polymerizable liquid crystal composition, enhancement of the mechanical strength of liquid crystal polymer films and / or improvement of chemical resistance can be expected.
The non-liquid crystalline polymerizable compound is typically a compound having one or two or more vinyl polymerizable groups.

By adding a non-liquid crystalline polymerizable compound having a polar group at the side chain and / or terminal to the polymerizable liquid crystal composition, an improvement in the adhesion between the liquid crystal polymer film and the photo-alignment film can be expected.
Styrene, nucleus-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinyl pyrrolidone, vinyl sulfonic acid, fatty acid vinyl, α, β-ethylenically unsaturated carboxylic acid, alkyl has 1 to 18 carbon atoms Alkyl ester of (meth) acrylic acid, hydroxyalkyl ester of (meth) acrylic acid having 1 to 18 carbon atoms of hydroxyalkyl, aminoalkyl ester of (meth) acrylic acid having 1 to 18 carbon atoms of aminoalkyl Ether oxygen-containing alkyl ester of (meth) acrylic acid having 3 to 18 carbon atoms of ether oxygen-containing alkyl, N-vinylacetamide, vinyl tert-butylbenzoate, vinyl N, N-dimethylaminobenzoate, Vinyl benzoate, vinyl pivalate, 2,2-dimethylbuta Vinyl acetate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate, vinyl 2-ethyl-2-methylbutanoate, dicyclopentanyloxylethyl (meth) Acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2- Acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, 2-acryloyloxyethyl acid phosphate Mono- (meth) acrylic acid esters of polyalkylene glycols such as acrylate, 2-methacryloyloxyethyl acid phosphate, polyethylene glycol having a polymerization degree of 2 to 100, polypropylene glycol, a copolymer of ethylene oxide and propylene oxide, or Di (meth) acrylic acid ester or polyethylene glycol having a degree of polymerization of 2 to 100 capped with an alkyl having 1 to 6 carbon atoms, polypropylene glycol, and monoalkylene glycol (a copolymer of ethylene oxide and propylene oxide) A (meth) acrylic acid ester is a non-liquid crystalline polymerizable compound which is a monofunctional compound. Vinyl acetate and the like are “vinyl fatty acid”. Acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and the like are “α, β-ethylenically unsaturated carboxylic acids”. Methoxy ethyl ester, ethoxy ethyl ester, methoxy propyl ester, methyl carbyl ester, ethyl carbyl ester, butyl carbyl ester, etc. are "ether oxygen-containing alkyl of (meth) acrylic acid having 3 to 18 carbon atoms of ether oxygen-containing alkyl" Esters ".

  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, polyethylene glycol diacrylate, methacrylate compounds of these compounds, etc. are bifunctional non-liquid crystalline polymerizable compounds It is.

  Pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylol EO addition triacrylate, trisacryloyloxyethyl phosphate, tris (acryloyloxyethyl) isocyanurate, alkyl-modified dipentaerythritol triacrylate, EO-modified trimethylolpropane triacrylate Rate, PO-modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, alkyl-modified dipentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate , Pentaelistoo Trimethacrylate, trimethylolpropane trimethacrylate, trimethylol EO addition trimethacrylate, trismethacryloyloxyethyl phosphate, trismethacryloyloxyethyl isocyanurate, alkyl modified dipentaerythritol trimethacrylate, EO modified trimethylolpropane tri Methacrylate, PO-modified trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, alkyl-modified dipentaerythritol tetramethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxypentamethacrylate, Alkyl modified dipentaerythritol Such data methacrylate is a multifunctional non-liquid crystal polymerizable compound having three or more functional.

The addition of the polymerization initiator optimizes the polymerization rate of the polymerizable liquid crystal composition. In view of the ease of the curing process, the polymerization initiator is preferably a photoradical initiator.
1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one 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, Adekaoptomer N-1919, Adeka Cruz NCI-831, Adeka Cruz NCI -930, Omnirad 127, Omnirad 184, Omnirad 369, Omnirad 379, Omnirad 500, Omnirad 651, Omnirad 754, Omnirad 819, Omnirad 907, Omnirad 1173, Omnirad 2022, Omnirad 2021, Omnirad 202 Cure OXE02, Omnirad MBF, Omnirad TPO, etc. are photoradical initiators. Here, ADEKA, Omnilad and Irgacure are registered trademarks.

  From the viewpoint of improving the front contrast of the liquid crystal polymer film, preventing stickiness, and preventing changes in retardation over time, the total content weight of the radical photopolymerization initiator in the polymerizable liquid crystal composition is the polymerizable liquid crystal composition. 1 to 30% by weight is preferable, 1 to 15% by weight is more preferable, and 3 to 10% by weight is more preferable with respect to the total amount of the product.

  A sensitizer may be added to the polymerizable liquid crystal composition together with the radical photopolymerization initiator. Isopropylthioxanthone, diethylthioxanthone, ethyl-4dimethylaminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate and the like are sensitizers.

  By adding a chain transfer agent to the polymerizable liquid crystal composition, the reaction rate of the polymerizable liquid crystal compound and the length of the polymer chain in the liquid crystal polymer film can be adjusted. As the amount of the chain transfer agent increases, the reaction rate of the polymerizable liquid crystal compound decreases. Increasing the amount of chain transfer agent decreases the polymer chain length.

Thiol derivatives and styrene dimer derivatives are chain transfer agents.
Dodecanethiol, 2-ethylhexyl- (3-mercapto) propionate, etc. are monofunctional thiol derivatives.

  Trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate) 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like are polyfunctional thiol derivatives.

2,4-diphenyl-4-methyl-1-pentene, 2,4-diphenyl-1-butene, and the like are styrene dimer chain transfer agents.
Addition of a polymerization inhibitor to the polymerizable liquid crystal composition prevents polymerization from starting when the polymerizable liquid crystal composition and the polymerizable liquid crystal composition solution are stored. The addition of the polymerization inhibitor improves the storage stability of the polymerizable liquid crystal composition.

  (A) Phenol antioxidant, (b) Sulfur antioxidant, (c) Phosphate antioxidant, (d) Hindered amine antioxidant, etc. are polymerization inhibitors. From the viewpoint of compatibility with the polymerizable liquid crystal composition and the transparency of the liquid crystal polymer film, a phenolic antioxidant is preferred. From the viewpoint of compatibility, a phenolic antioxidant having a t-butyl group at the ortho position of the hydroxyl group is preferred.

  From the viewpoint of improving storage stability, preventing stickiness, and preventing changes in retardation over time, the total content of the polymerization inhibitor in the polymerizable liquid crystal composition is based on the total amount of the polymerizable liquid crystal composition. 0.01 to 5% by weight is preferable, and 0.01 to 0.5% by weight is more preferable.

Addition of an ultraviolet absorber to the polymerizable liquid crystal composition improves the weather resistance of the polymerizable liquid crystal composition.
Addition of a light stabilizer to the polymerizable liquid crystal composition improves the weather resistance of the polymerizable liquid crystal composition.
Addition of an antioxidant to the polymerizable liquid crystal composition improves the weather resistance of the polymerizable liquid crystal composition.
Addition of a silane coupling agent to the polymerizable liquid crystal composition improves the adhesion between the substrate and the liquid crystal polymer film.

≪Polymerizable liquid crystal composition solution≫
In order to facilitate application to the photo-alignment film, it is preferable to add a solvent to the polymerizable liquid crystal composition.
From the viewpoint of compatibility between the polymerizable liquid crystal compound and the solvent, the content of the polymerizable liquid crystal composition in the polymerizable liquid crystal composition solution is preferably 5 to 50% by weight, and more preferably 15 to 40% by weight.

  Ester solvent, amide solvent, alcohol solvent, ether solvent, cyclic ether solvent, aromatic hydrocarbon solvent, halogenated aromatic hydrocarbon solvent, aliphatic hydrocarbon solvent, halogenated aliphatic hydrocarbon System solvents, alicyclic hydrocarbon solvents, ketone solvents, acetate solvents, and the like are components of the solvent.

The ester solvent refers to a compound having an ester bond and serving as a solvent component.
Alkyl acetate, ethyl trifluoroacetate, alkyl propionate, alkyl butyrate, dialkyl malonate, alkyl glycolate, alkyl lactate, monoacetin, γ-butyrolactone, γ-valerolactone, and the like are ester solvents.

  Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, and the like are alkyl acetates.

Methyl propionate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate, butyl propionate and the like are alkyl propionates.
Methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, propyl butyrate and the like are alkyl butyrate.

Diethyl malonate and the like are dialkyl malonates.
Methyl glycolate, ethyl glycolate and the like are alkyl glycolates.
Methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, butyl lactate, ethyl hexyl lactate and the like are alkyl lactates.

The amide solvent refers to a compound having an amide bond, which is a component of the solvent.
N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N-methylpropionamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylacetamide dimethyl acetal N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone and the like are amide solvents.

The alcohol solvent refers to a compound having a hydroxyl group and serving as a solvent component.
Methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, t-butyl alcohol, sec-butyl alcohol, butanol, 3-methoxybutanol, 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-penta Diol, 2,4-pentanediol, 2,5-hexanediol, 3-methyl-3-methoxybutanol, cyclohexanol, methylcyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol Monoisobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, di Propylene glycol monopro Ether, dipropylene glycol monobutyl ether, terpineol, etc. dihydro terpineol is an alcohol.

The ether solvent refers to a compound having an ether bond, which is a component of the solvent.
Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, bis (2-propyl) ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, anisole, cyclopentyl methyl ether, methyl t-Butyl ether and the like are ether solvents.

The cyclic ether solvent refers to a cyclic compound having an ether bond, which is a component of the solvent.
1,4-dioxane, 1,3-dioxolane, tetrahydrofuran and the like are cyclic ether solvents.

The aromatic hydrocarbon solvent refers to a compound having an aromatic hydrocarbon, which is a component of the solvent.
Benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, i-propylbenzene, n-propylbenzene, t-butylbenzene, s-butylbenzene, n-butylbenzene, tetralin and the like are aromatic hydrocarbon solvents.

Examples of the halogenated aromatic hydrocarbon solvent include chlorobenzene and 1,2-dichlorobenzene.
Aliphatic hydrocarbon solvents include hexane, heptane, myrcene, and the like.

Examples of the halogenated aliphatic hydrocarbon solvent include chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethylene, and tetrachloroethylene.
As the alicyclic hydrocarbon solvent, cyclohexane, cycloheptane, decalin, α-pinene, β-pinene, D-limonene and the like are alicyclic hydrocarbons.

The ketone solvent refers to a compound having a ketone structure and serving as a solvent component.
Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, methyl propyl ketone and the like are ketone solvents.

An acetate solvent refers to a compound having an acetoxy group, which is a component of the solvent.
Ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, methyl acetoacetate, 1-methoxy-2-propyl acetate, etc. Is an acetate-based solvent.

  Various coating methods are used for applying the polymerizable liquid crystal composition solution. From the viewpoint of the uniformity of the film thickness of the coating film composed of the polymerizable liquid crystal composition, as a coating method, a spin coating method, a micro gravure coating method, a gravure coating method, a wire bar coating method, a dip coating method, a spray coating method. A slit coating method, a die coating method and an ink jet coating method are preferred.

  In order to remove the solvent, it is preferable to perform a heat treatment during drying when forming a coating film composed of the polymerizable liquid crystal composition. The heat treatment can be performed by a hot plate, a drying furnace, and hot air or hot air.

  In order to obtain the liquid crystal polymer film of the present invention, treatment means such as electron beam, ultraviolet light, visible light, and infrared light can be used for the coating film composed of the polymerizable liquid crystal composition. The range of the wavelength of light used for obtaining the liquid crystal polymer film is 150 to 500 nm. A preferable wavelength range of light is 250 to 450 nm, and a more preferable range is 300 to 400 nm.

  As the light source, a low-pressure mercury lamp, a high-pressure discharge lamp, or a short arc discharge lamp can be used. Disinfection lamps, fluorescent chemical lamps, black lights, etc. are low-pressure mercury lamps. High pressure mercury lamps, metal halide lamps, and the like are the high pressure discharge lamps. Ultra high pressure mercury lamps, xenon lamps, mercury xenon lamps and the like are short arc discharge lamps.

  The liquid crystal polymer film of the present invention can be disposed inside and outside the liquid crystal cell of the liquid crystal display element. Since the retardation of the liquid crystal polymer due to the thermal history is small and impurities are not eluted from the liquid crystal polymer, the liquid crystal polymer film can be disposed inside the liquid crystal cell.

The thickness of the liquid crystal polymer film is appropriately selected according to the purpose, but is preferably in the range of 0.1 to 10 μm, preferably 0.5 to 5 μm.
The in-cell retardation film of the present invention is a laminate of a photo-alignment film and a liquid crystal polymer film. The photo-alignment film hardly causes alignment defects and can reduce the tilt angle. By using the photo-alignment film, viewing angle characteristics and contrast are improved.

≪Photo alignment film≫
The photo-alignment film is provided on the surface of the substrate. A polyimide alignment film or the like is used as the photo-alignment film, which will be described later in detail.

The photo-alignment film is formed on the substrate by the following steps.
(1) A photo-alignment agent is applied on the substrate,
(2) By heating or other methods, the solvent is removed from the photoalignment agent on the substrate, and a coating film of the photoalignment film is provided on the substrate.
(3) The photo-alignment film on the substrate is irradiated with linearly polarized light having a wavelength of 250 to 400 nm,
(4) If necessary, heat treatment is performed to create a photo-alignment film.

  There is no restriction | limiting in particular in the material of the base material which forms a photo-alignment film, For example, glass, a plastic, a metal etc. are mentioned. The base material may be provided with a color filter layer or an overcoat layer on the color filter layer.

≪Photo alignment agent≫
The photo-alignment film of the present invention can be obtained by forming a photo-alignment agent on a substrate.
The photo-alignment agent of the present invention contains at least one polymer containing a photosensitive group. The polymer containing the photosensitive group is polyimide, polyamic acid, cycloolefin polymer or polyacrylate.

Examples of the photosensitive group include chalcone, cinnamoyl, cinnamylidene, stilbene, cyclobutane, and azobenzene.
From the viewpoint of improving contrast, the polymer containing a photosensitive group is preferably a polyimide or polyamic acid having an azobenzene structure or a cyclobutane structure as the photosensitive group. Polyimide or polyamic acid is a polymer obtained by a condensation reaction of diamine or diamine derivative and tetracarboxylic dianhydride or tetracarboxylic dianhydride derivative.
Specific examples of the diamine are represented by formulas (DA-1) to (DA-5).

式（ＤＡ−１）〜式（ＤＡ−５）において、Ｅ¹は１，４−フェニレン、１，３−フェニレンまたは炭素数１〜２０のアルキレンであり、該１，４−フェニレンおよび１，３−フェニレンにおいて、少なくとも一つの水素は１価の有機基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−ＣＨ₂−は−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、Ｅ²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−ＣＨ₂−は−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられても良く、少なくとも一つの−ＣＨ₂ＣＨ₂−は−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−で置き換えられてもよく、式（ＤＡ−１）、式（ＤＡ−２）、式（ＤＡ−４）、および式（ＤＡ−５）において、ベンゼン環上の水素は、１価の有機基で置き換えられてもよい。
テトラカルボン酸二無水物の具体例を、式（ＡＡ−１）〜（ＡＡ−４）で示す。

In the formula (DA-1) to the formula (DA-5), E ¹ is 1,4-phenylene, 1,3-phenylene or alkylene having 1 to 20 carbon atoms, and the 1,4-phenylene and 1,3 - in the phenylene, at least one hydrogen may be replaced by a monovalent organic group, at least one -CH ₂ - in the alkylene - is -O -, - COO-, or -OCO- may be replaced by , E ² is a single bond or alkylene having 1 to 20 carbon atoms, in which at least one —CH ₂ — may be replaced by —O—, —COO—, or —OCO—. —CH ₂ CH ₂ — may be replaced by —CH═CH—, or —C≡C—, and is represented by formula (DA-1), formula (DA-2), formula (DA-4), and formula (DA-4). DA-5) Odor Thus, the hydrogen on the benzene ring may be replaced with a monovalent organic group.
Specific examples of tetracarboxylic dianhydride are represented by formulas (AA-1) to (AA-4).

式（ＡＡ−１）〜式（ＡＡ−４）において、Ｆ¹は水素または炭素数１〜５のアルキルであり、Ｆ²は単結合、１，４−フェニレン、または炭素数１〜２０のアルキレンであり、該アルキレンにおいて少なくとも一つの−ＣＨ₂−は−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、Ｆ³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−ＣＨ₂−は−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられても良く、少なくとも一つの−ＣＨ₂ＣＨ₂−は−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−で置き換えられてもよい。

In Formula (AA-1) to Formula (AA-4), F ¹ is hydrogen or alkyl having 1 to 5 carbons, and F ² is a single bond, 1,4-phenylene, or alkylene having 1 to 20 carbons. And in the alkylene, at least one —CH ₂ — may be replaced by —O—, —COO—, or —OCO—, and F ³ is a single bond or alkylene having 1 to 20 carbons, In alkylene, at least one —CH ₂ — may be replaced by —O—, —COO—, or —OCO—, and at least one —CH ₂ CH ₂ — represents —CH═CH— or —C≡C It may be replaced with-.

In order to facilitate application to the substrate, the photo-alignment agent desirably contains a solvent.
The content of the solvent in the photoalignment agent is preferably 90 to 99% by weight, and more preferably 92 to 98% by weight.

An ester solvent, an amide solvent, an alcohol solvent, an ether solvent, a cyclic ether solvent, a ketone solvent, an acetate solvent, and the like are components of the solvent.
Various coating methods are used for application of the photo-alignment agent. From the viewpoint of the uniformity of the film thickness of the photo-alignment film, the coating method is preferably a spin coating method, an offset coating method, a slit coating method, a die coating method, or an ink jet coating method.

  In order to remove the solvent, it is preferable to perform a heat treatment during drying when the photo-alignment film is formed on the substrate. The heat treatment can be performed by a hot plate, a drying furnace, and hot air or hot air.

  In order to obtain the photo-alignment film of the present invention, linearly polarized light having a wavelength of 250 to 400 nm is irradiated. Light emitted from the light source is guided to linear deflection using a polarizing plate. The polarizing plate is an absorptive polarizing plate or a reflective polarizing plate such as a wire grid polarizing plate.

As a light source, a low-pressure mercury lamp, a high-pressure discharge lamp, or a short arc discharge lamp can be used.
The film thickness of the photo-alignment film is not particularly limited as long as it can exhibit its function, but is usually in the range of 0.01 to 0.5 μm, preferably 0.05 to 0.2 μm. Is desirable.

≪In-cell retardation film≫
The in-cell retardation film needs to be set to an appropriate phase difference in order to increase the viewing angle and improve the contrast of the liquid crystal display device. Therefore, the retardation of the retardation film is preferably 120 nm ≦ Re (550) ≦ 250 nm.

  The in-cell retardation film is required to have an appropriate phase difference for each wavelength. From the viewpoint of improving the visibility such as color unevenness and viewing angle characteristics, the retardation film preferably gives an appropriate retardation for all wavelengths. Therefore, a retardation film having low wavelength dispersion characteristics is required. The relative ratio of retardation at a wavelength of 450 nm and retardation at a wavelength of 550 nm of the retardation film is preferably 0.8 ≦ Re (450) / Re (550) ≦ 1.05.

  The liquid crystal cell of the present invention includes, for example, a pair of opposed substrates, electrodes formed on one or both of the opposed surfaces of the pair of substrates, and the pair of substrates. And a liquid crystal layer formed thereon.

Other configurations of the liquid crystal cell are not particularly limited, and known ones can be adopted.
The electrode used for the liquid crystal cell is an ITO or metal vapor deposition film. An electrode may be formed in a part of one surface of a base material, and may be patterned and formed in a desired shape. The patterned shape includes a comb shape and a zigzag structure.

  A color filter layer and a flattening layer (overcoat layer) for each color are provided on the substrate. A columnar spacer may be provided as a spacer for maintaining a constant distance between the substrates.

The in-cell retardation film of the present invention is laminated on the color filter layer of the substrate directly or via a planarization layer.
In the formation of the liquid crystal layer of the liquid crystal cell, a resin spacer can be used as necessary in order to form an appropriate interval between a pair of opposed substrates.

As the liquid crystal composition used for the liquid crystal layer, various liquid crystal compositions having positive or negative dielectric anisotropy can be used.
The liquid crystal composition containing any of the compound represented by the following formula (LC-1) and the compound represented by the formula (LC-2) can be a liquid crystal composition having positive dielectric anisotropy. .

（式（ＬＣ−１）中、Ｒ²¹は炭素数１〜１０のアルキル、炭素数１〜１０のアルコキシ、炭素数２〜１０のアルケニルまたは炭素数２〜１０のアルケニルオキシであり、Ｍ²¹〜Ｍ²³はそれぞれ独立してトランス−１，４−シクロへキシレンまたは１，４−フェニレンであり、該トランス−１，４−シクロへキシレン中の１つまたは２つの−ＣＨ₂−は酸素原子が直接隣接しないように、−Ｏ−で置換されていてもよく、該フェニレン基中の１つまたは２つの水素はフッ素で置換されていてもよく、Ｘ²¹およびＸ²²はそれぞれ独立して水素またはフッ素であり、R²²はフッ素、トリフルオロメトキシまたはトリフルオロメチルであり、Ｋ²¹は−ＣＨ₂Ｏ−、−ＯＣＨ₂−、−ＣＦ₂Ｏ−または−ＯＣＦ₂−であり、ｎ²¹は及びｎ²²はそれぞれ独立して０、１または２であり、ｎ²¹＋ｎ²²は０、１または２である。）
誘電率異方性が正の液晶組成物は下記式（ＬＣ−２）で表される化合物をさらに含有してもよい。

(In the formula (LC-1), R ²¹ is alkyl having 1 to 10 carbon atoms, having 1 to 10 carbon atoms an alkoxy, alkenyloxy, alkenyl or 2 to 10 carbon atoms having 2 to 10 carbon atoms, M ²¹ ~ M ²³ is each independently trans-1,4-cyclohexylene or 1,4-phenylene, and one or two —CH ₂ — in the trans-1,4-cyclohexylene is an oxygen atom. It may be substituted with —O— so that it is not directly adjacent, one or two hydrogens in the phenylene group may be substituted with fluorine, and X ²¹ and X ²² are each independently hydrogen or Fluorine, R ²² is fluorine, trifluoromethoxy or trifluoromethyl, K ²¹ is —CH ₂ O—, —OCH ₂ —, —CF ₂ O— or —OCF ₂ —, and n ²¹ is n ²² DE, respectively A 0, 1 or 2, n ²¹ + n ²² is 0, 1 or 2.)
The liquid crystal composition having a positive dielectric anisotropy may further contain a compound represented by the following formula (LC-2).

（式（ＬＣ−２）中、Ｒ³¹およびＲ³²はそれぞれ炭素数１〜１０のアルキル、炭素数１〜１０のアルコキシまたは炭素数２〜１０のアルケニルであり、Ｍ³¹およびＭ³²はおそれぞれ独立してトランス−１，４−シクロへキシレンまたは１，４−フェニレンであり、該フェニレン基中の１つの水素はフッ素で置換されていてもよく、ｎ³¹は１または２である。）
下記式（ＬＣ−３）で表される化合物および式（ＬＣ−４）で表される化合物をそれぞれ少なくとも一つ有する液晶組成物は、誘電率異方性が負の液晶組成物になり得る。当該組成物は、下記式（ＬＣ−３）で表される化合物の含有量が多いほど、誘電率異方性が負になる傾向がある。

(In the formula (LC-2), R ³¹ and R ³² are each alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and M ³¹ and M ³² are each independently selected. Trans-1,4-cyclohexylene or 1,4-phenylene, and one hydrogen in the phenylene group may be substituted with fluorine, and n ³¹ is 1 or 2.)
A liquid crystal composition having at least one of the compound represented by the following formula (LC-3) and the compound represented by the formula (LC-4) can be a liquid crystal composition having a negative dielectric anisotropy. The composition tends to have negative dielectric anisotropy as the content of the compound represented by the following formula (LC-3) increases.

（式（ＬＣ−３）中、Ｒ⁴¹およびＲ⁴²はそれぞれ独立して炭素数１〜８のアルキル、炭素数２〜８のアルケニル、炭素数１〜８のアルコキシまたは炭素数２〜８のアルケニルオキシであり、Ｚ⁴¹およびＺ⁴²はそれぞれ独立して単結合、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ₂ＣＨ₂−、−（ＣＨ₂）₄−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＨ₂−、−ＣＨ₂Ｏ−、−ＯＣＦ₂−又は−ＣＦ₂Ｏ−であり、Ｍ⁴¹およびＭ⁴²はそれぞれ独立してフッ素で置換されていてもよい、１，４−フェニレンまたはトランス−１，４−シクロヘキシレンであり、ｎ⁴¹およびｎ⁴²はそれぞれ独立して０〜４の整数であり、ｎ⁴¹＋ｎ⁴²＝１〜４である。）

(In the formula (LC-3), R ⁴¹ and R ⁴² are each independently alkyl having 1 to 8 carbons, alkenyl having 2 to 8 carbons, alkoxy having 1 to 8 carbons or alkenyl having 2 to 8 carbons. Z ⁴¹ and Z ⁴² are each independently a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCO _{-, - OCH 2 -, -} CH 2 O -, - OCF 2 - or -CF ₂ is a O-, M ⁴¹ and M ⁴² may be substituted with independently fluorine, 1,4-phenylene Or trans-1,4-cyclohexylene, n ⁴¹ and n ⁴² are each independently an integer of 0 to 4, and n ⁴¹ + n ⁴² = 1 to 4)

（式（ＬＣ−４）中、Ｒ⁵¹およびＲ⁵²はそれぞれ炭素数１〜８のアルキル、炭素数１〜８のアルコキシ、炭素数２〜８のアルケニルまたは炭素数２〜１０のアルケニルオキシであり、Ｍ⁵¹はトランス−１，４−シクロへキシレンまたは１，４−フェニレンである。）

(In the formula (LC-4), R ⁵¹ and R ⁵² are each alkyl having 1 to 8 carbons, alkoxy having 1 to 8 carbons, alkenyl having 2 to 8 carbons or alkenyloxy having 2 to 10 carbons. M ⁵¹ is trans-1,4-cyclohexylene or 1,4-phenylene.)

  The liquid crystal composition used in the liquid crystal cell of the present invention may have an additive. Additives include photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerization initiators, polymerization inhibitors, and the like.

  The in-cell retardation film according to the present invention is provided between substrates including a liquid crystal medium (using “in-cell”). Compared to conventional displays where an optical retardation plate is usually placed between the LC cell and the polarizer, the in-cell retardation plate of the present invention usually reduces or avoids parallax problems that can impair viewing angle characteristics. It is possible. For this reason, it is possible to provide a high-contrast LC cell in which color unevenness and color tone are optimized.

  Furthermore, the liquid crystal polymer film is suitable as an in-cell retardation plate because it has high heat resistance that does not greatly change its optical characteristics even in heat treatment at around 230 ° C., which is required in the manufacturing process of liquid crystal cells. It is.

The present invention is not limited to the published embodiments.
In the examples of the present invention, “Omn-907” is Omnirad (trademark) 907 manufactured by IGM Japan GK.

In an example of the present invention, “IRGANOX 1076” is IRGANOX ™ 1076 manufactured by BASF Japan.
In the examples of the present invention, “NCI-930” is Adeka Cruz ™ NCI-930 manufactured by ADEKA Corporation.

In the examples of the present invention, “FTX-218” is Footage ™ FTX-218 manufactured by Neos Co., Ltd.
In the example of the present invention, “TF370” is TEGOFlow (trademark) 370 of Evonik Japan.

In an embodiment of the present invention, “PGMEA” is propylene glycol monomethyl ether acetate.
In an embodiment of the present invention, “NMP” is N-methyl-2-pyrrolidone.

In an embodiment of the present invention, “BC” is ethylene glycol monobutyl ether.
In an embodiment of the present invention, “IPA” is 2-propanol.
In an embodiment of the present invention, the “wire grid polarizing plate” is UVT300A manufactured by Polatechno.

In an embodiment of the present invention, the “ultra-high pressure mercury lamp” is a multi-light USH-250BY manufactured by USHIO INC.
In Examples of the present invention, “polystyrene having a known molecular weight” is TSKgel standard polystyrene manufactured by Tosoh Corporation.

  In an embodiment of the present invention, the “gel permeation chromatograph” is a system consisting of a Waters 2695 separation module and a Waters 2414 differential refractometer.

In an example of the present invention, the “gel permeation chromatograph column” is Shodex ™ GF-7MHQ.
In the embodiment of the present invention, the “polarization analyzer” is an OPIPRO ellipsometer manufactured by Shintech Co., Ltd.

In the embodiment of the present invention, the “365 light receiver” is obtained by connecting UIT-150-A manufactured by USHIO INC. To UVD-S365 manufactured by USHIO INC.
In an embodiment of the present invention, the polarizing microscope is ECLIPSE E600 POL manufactured by Nikon Corporation.
In an embodiment of the present invention, the “luminance meter” is YOKOGAWA 3298F.

<Measurement of weight average molecular weight>
The weight average molecular weight was determined by using a gel permeation chromatograph and using polystyrene having a known molecular weight as a standard substance. The column temperature during the development was set to 50 ° C. As a developing solvent for gel permeation chromatography, a phosphoric acid-NMP mixed solution was used. The weight ratio of the phosphoric acid-NMP mixed solution was 0.6 / 100.

<Measurement of optical characteristics>
<Measurement with ellipsometer>
The retardation of the retardation film was measured with an ellipsometer at an incident angle of light of 0 °.

<Determination of homogeneous orientation>
Retardation was measured using an ellipsometer while changing the incident angle of light with respect to the surface of the liquid crystal polymer film 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 film. When both of the following conditions were satisfied, the liquid crystal polymer film was considered to have homogeneous alignment.
(A) When the retardation with respect to the incident angle of the liquid crystal polymer film is convex upward, and (b) the difference in the measured value of Re when the absolute value of each incident angle is the same is 5% If is within.

<Measurement of luminance in crossed Nicols>
The luminance in the crossed Nicols state was measured by the following procedure.
(1) The retardation film is sandwiched between two polarizing plates, and placed on a luminance meter so that both polarizing plates are crossed Nicols,
(2) The luminance that is minimized when the retardation film is rotated horizontally is defined as “luminance in the crossed Nicols state”.

<Measurement of luminance in parallel Nicol state>
The luminance in the parallel Nicol state was measured by the following procedure.
(1) The retardation film is sandwiched between two polarizing plates, and arranged on a luminance meter so that both polarizing plates are parallel Nicols,
(2) The luminance that was maximized when the retardation film was rotated horizontally was defined as “luminance in the parallel Nicol state”.

<Measurement of front contrast of liquid crystal polymer film>
The front contrast of the liquid crystal polymer film was calculated by “luminance in the parallel Nicol state” / “luminance in the crossed Nicol state”.

<Method for producing liquid crystal polymer film>
The liquid crystal polymer film was prepared by the following procedure.
Procedure (1) A polymerizable liquid crystal composition solution is spin-coated on a photo-alignment film to form a coating film.
Procedure (2) Heat with a hot plate at 60 to 80 ° C. for 1 to 5 minutes to remove the solvent from the coating film.
Procedure (3) The coating film on the alignment film is irradiated with ultraviolet rays having a constant output at a room temperature from a direction of 90 ° to form a liquid crystal polymer film. Here, the ultraviolet irradiation of the procedure (3) is performed using a 365 light receiver so that the irradiation amount of the linearly polarized ultraviolet light on the surface of the coating film on the substrate is 500 mJ / cm ^2. Adjustment was made between 5 seconds and 40 seconds.

<Preparation of polyamic acid solution>
[Example 1]
The polyamic acid solution was synthesized in the same manner as described in JP 2012-193167 A.
The structures of the diamine and tetracarboxylic dianhydride used are shown below.

化合物（ＤＡ−１−１）、化合物（ＤＡ−３−１）、化合物（ＤＡ−４−１）および化合物（ＤＡ−５−１）は市販品を使用した。化合物（ＤＡ−３−２）は特開２０１５−０２０９９９号公報に従い合成した。

Compound (DA-1-1), compound (DA-3-1), compound (DA-4-1) and compound (DA-5-1) used were commercially available products. The compound (DA-3-2) was synthesized according to JP-A-2015-020999.

化合物（ＡＡ−２−１）および化合物（ＡＡ−３−１）は市販品を使用した。化合物（ＡＡ−１−１）はＷＯ２０１５／１０８１７０に従い合成した。化合物（ＡＡ−４−１）は、ＷＯ２０１０／１５０６９３に従い合成した。

The compound (AA-2-1) and the compound (AA-3-1) used the commercial item. Compound (AA-1-1) was synthesized according to WO2015 / 108170. Compound (AA-4-1) was synthesized according to WO2010 / 150693.

  0.90 g of the compound (DA-1-1), 0.06 g of the compound (DA-3-2) and 17 ml of NMP were added, and the mixture was stirred and dissolved under a nitrogen stream. Next, 1.8 g of the compound (AA-4-1) and 10 ml of NMP were added and stirred at room temperature for 24 hours. To the obtained solution, 20.8 ml of BC was added and stirred at 75 ° C. for 4 hours to obtain a polyamic acid solution (PA-1). The concentration of polymer solids in the polyamic acid solution (PA-1) was 6% by weight. The weight average molecular weight of the polyamic acid solution (PA-1) was 23,000.

[Example 2]
In the synthesis of the polyamic acid solution (PA-1) described in Example 1, compound (DA-1-1), compound (DA-3-2) and compound (AA-4-1) are shown in Table 1. The diamine and tetracarboxylic dianhydride were replaced with polyamic acid solutions (PA-2) to (PA-4) having a polymer solid content concentration of 6% by weight.

<Creation of photo-alignment film>
[Example 3]
A substrate with a photo-alignment film was prepared by the following procedure.
(1) The polyamic acid described in Table 2 is mixed, NMP is added to the mixed solution, and a photo-alignment agent having a polymer solid concentration of 4% by weight is prepared,
(2) The photo-alignment agent is spin-coated on a glass substrate at 2000 rpm,
(3) The obtained glass substrate was placed on a hot plate at 60 ° C. for 1 minute, and the solvent in the photoalignment agent was removed to create a coating film. (4) Then, linearly polarized light having a wavelength of 365 nm was irradiated at an energy of ² J / cm ² from a direction of 90 degrees with respect to the coated surface.
(5) Thereafter, it was baked in an oven set at 220 ° C. for 30 minutes to obtain a photo-alignment film.

A base material AF-3 with a photo-alignment film using PA-3 was prepared by the following procedure.
(1) NMP is added to PA-3, and a photo-alignment agent having a polymer solid concentration of 4% by weight is prepared.
(2) The photo-alignment agent is spin-coated on a glass substrate at 2000 rpm,
(3) The glass substrate is placed on a hot plate at 80 ° C. for 1 minute to remove the solvent of the blend solution, thereby creating a coating film,
(4) The coating film is further baked in an oven at 220 ° C. for 10 minutes,
(5) The coating film was irradiated with linearly polarized light having a wavelength of 254 nm at an energy of 5 J / cm ² from a direction of 90 degrees with respect to the coated surface at room temperature.
(6) Then, after being immersed in an ethyl lactate solution at room temperature for 3 minutes, it was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a photo-alignment film.

<Creation of rubbing alignment film>
[Comparative Example 1]
A substrate with a rubbing alignment film (AFC-1) was prepared by the following procedure.
(1) A rubbing alignment agent PIA-5370 is spin-coated on glass to obtain glass with a coating film,
(2) On a hot plate at 80 ° C., the glass with the coating film facing up is left for 1 minute to remove the solvent from the coating film,
(3) The glass is baked in an oven at 220 ° C. for 30 minutes,
(4) The coating film portion of the glass was rubbed with a rayon cloth in one direction to obtain a substrate with a rubbing alignment film (AFC-1).
Here, “PIA-5370” is an alignment film Rixon aligner (registered trademark) PIA-5370 manufactured by JNC.

<Preparation of polymerizable liquid crystal composition>
[Example 4]
The amounts described in Table 3 were mixed to prepare polymerizable liquid crystal compositions (S-1) to (S-3).
The structure of the polymerizable liquid crystal compound used is shown below.

  The compound (1-3-1) was synthesized according to Japanese Patent Application No. 2006-156553. The compound (1-6-1) was synthesized according to Japanese Patent Application No. 2016-1771066. The compound (2-1-1-1) and the compound (2-3-3-1) were synthesized according to Japanese Patent Application Laid-Open No. 2006-128403. The compound (2-4-3-1) was synthesized according to Japanese Patent Application No. 2016-248317.

[Comparative Example 2]
A polymerizable liquid crystal composition (SC-1) was prepared by mixing at a ratio described in Table 4.
The structure of the polymerizable liquid crystal compound used is shown below.

ＬＣ−２４２は、ＢＡＳＦジャパン（株）製の重合性液晶化合物である。

LC-242 is a polymerizable liquid crystal compound manufactured by BASF Japan.

<Preparation of polymerizable liquid crystal composition solution>
[Example 9]
The polymerizable liquid crystal composition described in Table 5 and a solvent were mixed to prepare a polymerizable liquid crystal composition solution, and the names described in Table 5 were named.

[Comparative Example 3]
The polymerizable liquid crystal composition described in Table 6 and a solvent were mixed to prepare a polymerizable liquid crystal composition solution, and the names described in Table 6 were named.

<Production of retardation film>
[Example 10]
A retardation film was prepared by the following procedure.
Procedure (1) The polymerizable liquid crystal composition solution was applied by spin coating onto the glass substrate with an alignment film prepared in Example 3 and Comparative Example 1.
Procedure (2) The substrate is heated with a hot plate at 60 ° C. for 3 minutes,
Step (3) Continuing, the substrate is cooled for 3 minutes at room temperature,
Procedure (4) Irradiate the polymerizable liquid crystal composition on the substrate with light of an ultra-high pressure mercury lamp at a constant output from a direction perpendicular to the coating film on the substrate at room temperature in a nitrogen atmosphere. The polymerizable liquid crystal composition on the substrate was cured.

However, using a 365 light receiver, the irradiation time of the procedure (4) is set to 5 so that the exposure amount of the ultrahigh pressure mercury lamp to the surface of the polymerizable liquid crystal composition of the procedure (4) becomes 500 mJ / cm ^2. Adjusted between seconds and 40 seconds.
Table 7 shows the physical properties of a retardation film using a polymerizable liquid crystal composition solution as a raw material.

  When a retardation film was prepared from the photo-alignment films (AF-1) to (AF-3) and the polymerizable liquid crystal composition solutions (T-1) to (T-3), Re (450) / Re (550) ) <1.05 and a liquid crystal polymer with high front contrast is obtained.

When a retardation film was prepared from the rubbing alignment film (AFC-1) and the polymerizable liquid crystal composition solution (TC-1), a liquid crystal polymer having a high front contrast could not be obtained.
From this, it has been clarified that the retardation film of the present invention provides a liquid crystal polymer with a substrate having low wavelength dispersion characteristics and high front contrast.

Claims (8)

A liquid crystal cell having a liquid crystal layer sandwiched between two substrates, an in-cell retardation film disposed inside the liquid crystal cell, wherein the in-cell retardation film is formed on the photo-alignment film and the photo-alignment film An in-cell position which is a polymer of a polymerizable liquid crystal composition having a polymer film made of the prepared liquid crystal polymer, wherein the liquid crystal polymer contains at least one polymerizable liquid crystal compound represented by formula (1) Phase difference film.

(In the formula (1),
m is 4,
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene. A divalent ring represented by -2,6-diyl, fluorene-2,7-diyl, or indanone-4,7-diyl, in which at least one hydrogen is fluorine, chlorine, Trifluoromethyl, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 10 carbons, alkoxycarbonyl having 1 to 10 carbons, alkanoyl having 1 to 10 carbons, 1 to 10 carbons Of alkanoyloxy, or a monovalent group having a polymerizable functional group,
Z ¹ is independently —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 -, -CH = CH -, - N = CH -, - CH = N -, - N = C (CH 3) -, - C (CH 3) = N -, - N = N -, - C≡C-, -CH = N-N = CH - , - C (CH 3) = N-N = C (CH 3) -, or alkylene of 4 to 20 carbon atoms, at least one -CH ₂ - in the alkylene - is May be replaced by -O-
P ¹ is independently a monovalent group having a polymerizable functional group. ) The in-cell retardation film according to claim 1, wherein the polymerizable liquid crystal composition further contains a polymerizable liquid crystal compound represented by the formula (2).

(In the formula (2),
n is independently 1 or 2,
A ² is independently 1,4-phenylene or 1,4-cyclohexylene, in which at least one hydrogen is fluorine, chlorine, trifluoromethyl, alkyl having 1 to 10 carbons, carbon number 2-10 alkenyl, C1-C10 alkoxy, C1-C10 alkoxycarbonyl, C1-C10 alkanoyl, C1-C10 alkanoyloxy, or a monovalent group having a polymerizable functional group May be replaced with
Z ² 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-, or -COOCH ₂ CH ₂ - and is,
P ² is independently a monovalent group having a polymerizable functional group,
G is a group represented by formula (G-1) to formula (G-4);

(In the formulas (G-1) to (G-4),
X ¹ is independently —CH ₂ —, —NH—, —O—, —S—, or —CO—, and in —CH ₂ — or —NH—, at least one hydrogen has 1 to 5 carbon atoms. May be substituted with
X ² is independently —CH═ or —N═,
Z ³ is independently a single bond, —CH═CH—, —C≡C—, —CH═N—, —N═CH—, —CH═N—NR ¹ —, —C (CH ₃ ) = N —NR ¹ — or —CH═N—N═CH—, wherein R ¹ is independently hydrogen, a C 1-10 alkyl or a monovalent group having a polymerizable functional group;
T ¹ , T ⁴ and T ⁵ are each a monovalent group having 6 to 14 π electrons,
T ² , T ³ and T ⁶ are each independently hydrogen, trifluoromethyl, cyano, C 1-5 alkyl, C 2-5 alkenyl, C 1-5 alkoxy, C 1 5 alkoxycarbonyl, C 1-5 alkanoyl, C 1-5 alkanoyloxy, C 1-5 alkyl sulfide, or a monovalent group having a polymerizable functional group,
T ² and T ³ may form a 5- to 7-membered heterocyclic ring or cyclic ketone containing an oxygen atom, a nitrogen atom, or a sulfur atom. )   The polymerizable liquid crystal composition contains a polymerizable liquid crystal compound represented by formula (1), a polymerizable liquid crystal compound represented by formula (2), a photopolymerization initiator, a surfactant, and a polymerization inhibitor. 3. The in-cell retardation film according to 1 or 2.   The in-cell retardation film according to claim 1, wherein the photo-alignment film is made of a photo-alignment agent containing polyamic acid or polyimide.   The in-cell retardation film according to any one of claims 1 to 4, wherein the liquid crystal polymer has liquid crystal molecules fixed in a homogeneous orientation.   The in-cell retardation film according to claim 1, wherein an in-plane retardation Re (550) at a wavelength of 550 nm is 120 nm ≦ Re (550) ≦ 250 nm.   The in-cell retardation film according to claim 1, wherein the in-cell retardation film is laminated directly on the color filter layer of the liquid crystal cell or via a planarization layer.   The liquid crystal display element containing the in-cell retardation film of any one of Claims 1-7.