JP2018095847A - Liquid crystal polymerized films using alignment film and polymerizable liquid crystal - Google Patents

Abstract

PROBLEM TO BE SOLVED: To significantly enhance a front contrast of liquid crystal polymerized films so as to further improve display quality of a liquid crystal display device.SOLUTION: Liquid crystal polymerized films are prepared by calcining a composition comprising a polymer represented by a repeating unit of formula (1) to form an alignment film, then applying a polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound represented by formula (2) on the alignment film, and subsequently polymerizing the polymerizable liquid crystal composition. In formula (1), Rindependently represents a tetravalent functional group; Rindependently represents a divalent functional group; and Rindependently represents a hydrogen atom or a monovalent functional group. In formula (2), Rrepresents a divalent group formed by combining 5 or more and 9 or less alicyclic and/or aromatic rings; SPand SPrepresent a spacer group; and PGand PGrepresent an alkyl group, an alkoxy group, a cyano group, fluorine or a polymerizable functional group, in which either group is a polymerizable functional group.SELECTED DRAWING: None

Description

The present invention relates to a liquid crystal polymer film using a liquid crystal polymerizable composition as a raw material. More specifically, the present invention relates to a liquid crystal polymer film having optical anisotropy and an alignment film of the liquid crystal polymer film.

  A liquid crystal polymer film obtained by polymerizing a polymerizable liquid crystal composition includes a retardation film, an optical compensation film, a reflection film, a selective reflection film, an antireflection film, a viewing angle compensation film, a liquid crystal alignment film, a polarizing element, a circular polarizing element, It can be used as a film or element made of an elliptically polarizing element or other optically anisotropic material.

  A stretched polymer film exhibiting birefringence has been used in a liquid crystal display device as an optical compensation film for the purpose of improving the quality of image display. In order to further improve the display quality of the liquid crystal display device and reduce the thickness of the liquid crystal display element of the liquid crystal display device, it has been studied to replace the polymer film with a liquid crystal polymer film. In this case, for example, when the liquid crystal polymer film is used as a + A plate, it is required to align the liquid crystal in higher order in order to perform ideal optical compensation.

The liquid crystal polymer film is prepared by polymerizing a polymerizable liquid crystal composition on a substrate with an alignment film. An alignment film in which the alignment of molecules in the alignment film is aligned in a certain direction induces the alignment of the liquid crystal compound on the alignment film. The alignment film induces the alignment of the liquid crystal compound, particularly in the azimuth angle and / or polar angle direction with respect to the substrate plane.
Examples of a method for aligning molecules in the alignment film in a certain direction include a rubbing method and a photo-alignment method. The rubbing method is a method of imparting liquid crystal alignment ability to the alignment film by rubbing the alignment film surface with a cloth. The photo-alignment method is a method in which alignment ability is imparted to the alignment film with light. Therefore, the photo-alignment film has a photosensitive group in its material. As the photosensitive group, an azobenzene structure, a cyclobutane structure, a cinnamic acid structure, a chalcone structure, or a coumarin structure is known.
With respect to known raw materials for the liquid crystal polymer film, the following prior literatures can be cited.

JP 2014-205819 A Japanese Patent Laying-Open No. 2015-040950 Japanese Patent Laying-Open No. 2015-212807

An object of the present invention is to provide a retardation film having high contrast.

  The present inventors have found that liquid crystal polymer films prepared by combining a specific alignment film and a specific polymerizable liquid crystal composition have a liquid crystal skeleton that is a constituent component thereof aligned in a highly unprecedented manner, Completed the invention.

The contents of the present invention are the following [1] to [12].
[1] A polymerizable liquid crystal composition containing a compound represented by formula (2) is applied onto an alignment film prepared by firing a composition containing a polymer represented by the repeating unit of formula (1). continue,
Liquid crystal polymer films prepared by polymerizing the polymerizable liquid crystal composition.

（式（１）中、Ｒ^１は独立して４価の基であり、Ｒ^２は独立して２価の官能基であり、Ｒ^３は独立して水素原子または１価の基である。）

(In Formula (1), R ¹ is independently a tetravalent group, R ² is independently a divalent functional group, and R ³ is independently a hydrogen atom or a monovalent group. )

（式（２）中、Ｒ^４は脂環および／または芳香環を５つ以上９つ以下組合わせた２価の基を表し、ＳＰ^１およびＳＰ^２はスペーサー基を表し、ＰＧ^１およびＰＧ^２はアルキル基、アルコキシル基、シアノ基、フッ素または重合可能な官能基であり、どちらか一方は重合可能な官能基である。）

(In Formula (2), R ⁴ represents a divalent group in which 5 to 9 alicyclic and / or aromatic rings are combined, SP ¹ and SP ² represent a spacer group, and PG ¹ and PG ² Is an alkyl group, an alkoxyl group, a cyano group, fluorine or a polymerizable functional group, one of which is a polymerizable functional group.)

  [2] The liquid crystal polymer film according to [1], wherein the content of hydroxyl group, amino group, or carboxyl group contained in the alignment film is 0.1 or more and less than 2 with respect to the repeating unit of the formula (1). Kind.

  [3] The liquid crystal polymer film according to [1], which is prepared by polymerizing the polymerizable liquid crystal composition and then baking it at 140 ° C. or higher.

  [4] The liquid crystal polymer film according to any one of [1] to [3], wherein the alignment film is a photo-alignment film.

  [5] The liquid crystal polymer film according to [4], wherein the photosensitive group in the photo-alignment film has an azobenzene structure, a cyclobutane structure, a cinnamic acid structure, a chalcone structure, or a coumarin derivative structure.

  [6] The liquid crystal polymer film according to any one of [1] to [5], which has a characteristic of a positive A plate.

[7] The liquid crystal polymer film according to [1] to [6], wherein R ¹ in the formula (1) is represented by any ^one of the formulas (1-A) to (1-D).

[8] Liquid crystal polymer films according to [7], wherein R ² in formula (1) is a group represented by any one of formulas (1-F) to (1-N)

  [9] The liquid crystal polymer film according to [8], comprising a compound represented by the formula (2-A)

（式（２−Ａ）中、
Ｒ^４Ａは独立して以下の式（２−Ａ−ａ）から式（２−Ａ−ｏ）で表される基であり、

(In the formula (2-A),
R ^4A is independently a group represented by the following formulas (2-Aa) to (2-Ao):

（式（２−Ａ−ａ）〜式（２−Ａ−ｏ）中、
＊はＳＰ^１ＡまたはＳＰ^２Ａへの結合位置を示し、
Ａｒは、炭素数１４までの芳香族基または芳香族が共役した基であり、
Ｘ^５０は、−ＮＨ−、−Ｏ−または−Ｓ−であり、
Ｘ^５１は、＝ＣＨ−または＝Ｎ−であり、
Ｒ^５０は、単結合または−ＣＨ＝ＣＨ−であり、
Ｒ^５１は、−ＣＯ_２Ｒ^５１１または−ＣＮであり、
Ｒ^５１１は、炭素数１０以下のアルキル基を表し、このアルキル基中の１つのメチレンまたはメチル基の水素は（メタ）アクリルオキシ基で置換されていてもよく、
Ｒ^５２は、水素原子、炭素数１０以下のアルキル基を表し、このアルキル基中の１つのメチレンまたはメチル基の水素は（メタ）アクリルオキシ基で置換されていてもよく、
Ｒ^５３は、独立して、水素原子、炭素数５以下のアルキル基、または炭素数１０までの芳香族基であり、
Ｒ^５４は、炭素数５以下のアルキル基を表し、２つのＲ^５４が結合して環構造となってもよく、
これら式（２−Ａ−ａ）〜式（２−Ａ−ｏ）において
一つの水素は、炭素数１から５のアルキル基（ただし、該アルキル基の任意の−ＣＨ_２−は、−Ｏ−、−ＣＯ−、または−ＣＯＯ−に置き換えてもよく、任意の−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−で置換してもよく、該アルキル基中の水素は、ハロゲン基に置き換えてもいい。）またはハロゲン基に置き換えてもよく、
ＳＰ^１ＡおよびＳＰ^２Ａは、独立して、単結合、炭素数２から４のアルキレンであって、アルキレンの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、または−ＣＯＯ−に置き換えてもよく、
ＳＰ^１ＡおよびＳＰ^２Ａは、独立して、単結合、炭素数２から４のアルキレンであって、アルキレンの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、または−ＣＯＯ−に置き換えてもよく、
ＰＧ^１Ａは、式（２−Ｂ）で表される官能基であり、

(In the formula (2-Aa) to the formula (2-Ao),
* Indicates the binding position to SP ^1A or SP ^2A ,
Ar is an aromatic group having up to 14 carbon atoms or an aromatic conjugated group,
X ⁵⁰ is —NH—, —O— or —S—,
X ⁵¹ is ═CH— or ═N—,
R ⁵⁰ is a single bond or —CH═CH—,
R ⁵¹ is —CO ₂ R ⁵¹¹ or —CN,
R ⁵¹¹ represents an alkyl group having 10 or less carbon atoms, and the hydrogen of one methylene or methyl group in the alkyl group may be substituted with a (meth) acryloxy group,
R ⁵² represents a hydrogen atom or an alkyl group having 10 or less carbon atoms, and the hydrogen of one methylene or methyl group in the alkyl group may be substituted with a (meth) acryloxy group,
R ⁵³ is independently a hydrogen atom, an alkyl group having 5 or less carbon atoms, or an aromatic group having up to 10 carbon atoms,
R ⁵⁴ represents an alkyl group having 5 or less carbon atoms, and two R ⁵⁴ may be bonded to form a ring structure;
In these formulas (2-Aa) to (2-Ao), one hydrogen is an alkyl group having 1 to 5 carbon atoms (provided that any —CH ₂ — of the alkyl group is —O— , —CO—, or —COO— may be substituted, any —CH ₂ —CH ₂ — may be substituted with —CH═CH—, and the hydrogen in the alkyl group is replaced with a halogen group. Or a halogen group,
SP ^1A and SP ^2A are each independently a single bond or alkylene having 2 to 4 carbon atoms, and —CH ₂ — in alkylene may be replaced by —O—, —CO—, or —COO—. ,
SP ^1A and SP ^2A are each independently a single bond or alkylene having 2 to 4 carbon atoms, and —CH ₂ — in alkylene may be replaced by —O—, —CO—, or —COO—. ,
PG ^1A is a functional group represented by the formula (2-B),

（式（２‐Ｂ）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−、または−ＯＣＯ−で置き換えられてもよく、ＰＧは（メタ）アクリル基である。
ＰＧ^２は、アルキル基、アルコキシル基、シアノ基、フッ素、または、式（２−Ｂ）で表される官能基であり、
ｎは、５から９の整数である。）

(In the formula (2-B),
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 is (meta ) Acrylic group.
PG ² is an alkyl group, an alkoxyl group, a cyano group, fluorine, or a functional group represented by the formula (2-B),
n is an integer of 5 to 9. )

[10] The liquid crystal polymer film according to [9], wherein the content of the compound represented by the formula (2-A) in the polymerizable liquid crystal composition is 70% by weight or more based on the other polymerizable compounds. Kind

[11] The liquid crystal polymer film according to [9], wherein the polymerizable liquid crystal composition contains only the compound represented by the formula (2-A).

[12] A retardation film using the liquid crystal polymer film according to [1] to [11]

 According to the present invention, the contrast of liquid crystal polymer films used for a retardation film is improved.

In the present invention, "contrast" means that between the two polarizing plates, the alignment direction of the liquid crystal polymer film with a substrate coincides with the axis of one polarizing plate, and the liquid crystal polymer film with a substrate is disposed. It means the value of (luminance in the parallel Nicol state) / (luminance in the crossed Nicol state).
In the present invention, the “cross Nicol state” refers to 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” refers to a state in which the polarization axes of the polarizing plates arranged opposite to each other coincide.

In the present invention, “Δn” represents the birefringence of the retardation film.

In the present invention, “compound (X)” means a compound represented by the formula (X). Here, X in “compound (X)” means a character string, a number, a symbol or the like.

  In the present invention, “liquid crystal compound” is a general 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 gives a compound the ability to be polymerized by light, heat, catalyst, or other means to change to a compound having a larger molecular weight. Acrylic groups, methacrylic groups, and the like are polymerizable groups.
In the present invention, the “hydrogen donating group” is a hydroxyl group, amino group, carboxyl group, or other functional group in which hydrogen is adjacent to an atom having a higher electronegativity than carbon.
In the present invention, the “photosensitive group” is a functional group unique to a compound that causes a chemical reaction by excitation of electrons in the molecule. Photolytic reaction, photoisomerization reaction, and the like are the chemical reactions.

In the present invention, the “polymerizable compound” is a compound having a polymerizable group.
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 liquid crystal compound” is a liquid crystal compound and a compound having a polymerizable group.
In the present invention, the “non-liquid crystalline polymerizable compound” is a polymerizable compound and is a compound having no liquid crystal phase alone.

In the present invention, “polymerizable liquid crystal composition” means a composition containing a polymerizable compound and a liquid crystal compound, and a composition containing “polymerizable liquid crystal compound”.

In the present invention, the “alignment film” is a film for aligning liquid crystals.
In the present invention, the “photo-alignment film” is an alignment film formed by light.
In the present invention, the “substrate with an alignment film” is a substrate having an alignment film.
In the present invention, the “substrate” is a general term for a substrate with an alignment film and a substrate without an alignment film.
In the present invention, the “liquid crystal polymer film” is a film obtained by polymerizing a polymerizable liquid crystal composition.
In the present invention, the “liquid crystal polymer film with a base material” is a material containing a base material obtained by polymerizing a polymerizable liquid crystal composition on the base material.
In the present invention, “liquid crystal polymer film” is a general term for “liquid crystal polymer film” and “liquid crystal polymer film with a substrate”.
In the present invention, the “retardation film” is a light conversion element having optical anisotropy. The retardation film includes liquid crystal polymer films.

In the present invention, “alignment” refers to a state where the major axes (easy orientation axes) of liquid crystal molecules are optically available and aligned in a certain direction.
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, the “homogeneous orientation” means a state in which the tilt angle is 0 to 5 degrees and the orientation is uniaxially oriented in the azimuth direction with respect to the substrate plane.
In the present invention, “homeotropic alignment” refers to a uniaxial alignment state with a tilt angle of 85 to 90 degrees.
In the present invention, “tilt orientation” represents a state in which the tilt angle is oriented so as to increase according to the distance from the substrate surface.
In the present invention, the term “twist alignment” means that the alignment direction in the major axis direction of the liquid crystal molecules is parallel to the substrate, and the perpendicular to the surface of the substrate is the axis as the liquid crystal molecules are separated from the substrate. An orientation that is twisted in a staircase pattern.

  When the following functional group is described in the chemical formula, it means that the wavy line is the bonding position of the functional group. Here, the following C is an arbitrary atom or functional part.

≪Alignment film≫
By aligning the orientation of the functional group in contact with the liquid crystal compound in the orientation film in a certain direction, the orientation of the polymerizable liquid crystal in the azimuth angle and / or polar angle direction relative to the plane of the substrate can be induced.
The polyamic acid represented by the formula (1) and its derivative serve as a raw material for the alignment film.
A rubbing method in which the surface of the alignment film is rubbed with a cloth, a photo-alignment method by irradiation with polarized light, and the like are methods for aligning the alignment in a certain direction.
In the present invention, the photo-alignment method is preferable because the contrast of the liquid crystal polymer film can be improved.

In the photo-alignment method, it is necessary to incorporate a photosensitive group in the alignment film. As the photosensitive group, an azobenzene structure, a cyclobutane structure, a cinnamic acid structure, a chalcone structure, or a coumarin derivative structure is preferable because it is oriented with a small exposure amount.
In order to improve the contrast, an azobenzene structure or a cyclobutane derivative structure, which has a high anchor energy for the liquid crystal compound and can easily align the liquid crystal compound, is more preferable.
A plurality of types of photosensitive groups can be used in combination.

A photosensitive group is added to a diamine that is a raw material of the alignment film or a diamine derivative that is a raw material of the alignment film, or a tetracarboxylic dianhydride that is a raw material of the alignment film By introducing, the photo-alignment film of the present invention can be obtained. Such a diamine having a photosensitive group and a tetracarboxylic dianhydride having a photosensitive group and derivatives thereof may be used in combination.
Structures represented by formula (P-1) to formula (P-7) are photosensitive groups.

式（Ｐ−１）中、Ｒ^１０は独立して、水素原子、炭素数１〜５のアルキル基、またはフェニル基である。

In formula (P-1), R ¹⁰ is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

Since it can be oriented with a small amount of exposure, compounds represented by formula (PA-1) to formula (PA-6) are preferred as the compound having a photosensitive group having formula (P-1).

In formula (PA-4) and formula (PA-5),
One of R ¹¹ and R ¹² is an alkyloxy group having 1 to 5 carbon atoms, and the other of R ¹¹ and R ¹² is —OH or —Cl.
One of R ¹³ and R ¹⁴ is an alkoxy group having 1 to 5 carbon atoms, and the other of R ¹³ and R ¹⁴ is —OH or —Cl.

Since it can be oriented with a small amount of exposure, as a compound having a photosensitive group having formula (P-2) to formula (P-5), formula (II-1), formula (II-2), formula ( Compounds represented by III-1), formula (III-2), formula (IV-1) and formula (VI-2) are preferred.

In the formula (V-2),
R ¹⁵ is independently —CH ₃ , —OCH ₃ , —CF ₃ , or —COOCH ₃ ;
a is an integer of 0-2 independently.
In the formula (V-3),
Ring A and Ring B are independently monocyclic hydrocarbons, fused polycyclic hydrocarbons and heterocycles;
R ²⁰ and R ²¹ are each a straight chain alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —NHCO— or —N (CH ₃ ) CO—, and —CH ₂ — of the straight chain alkylene. One or two may be replaced by -O-
R ^{16 to} R ¹⁹ are independently —F, —CH ₃ , —OCH ₃ , —CF ₃ or —OH;
b to e are independently integers of 0 to 4.

From the viewpoint of improving the contrast of the liquid crystal polymer films, compounds represented by the above formulas (V-2), (V-3), and (VI-2) are more preferable as components of the raw material of the liquid crystal polymer film.
In order to induce the alignment of the liquid crystal compound by the photosensitive group, a compound having an amino group at the para position of the —N═N— bond in the formula (V-2) is more preferable as a raw material component of the liquid crystal polymer film.

From the viewpoint of improving the contrast of the liquid crystal polymer films, as a raw material component of the liquid crystal polymer film, in the formula (VI-2), when ring A is a six-membered ring, a compound having an amino group at the para position of R ²⁰ More preferred.
From the viewpoint of improving the contrast of the liquid crystal polymer films, as a raw material component of the liquid crystal polymer film, in the formula (VI-2), when ring B is a six-membered ring, a compound having an amino group at the para position of R ²¹ More preferred.
From the viewpoint of improving the contrast of the liquid crystal polymer films, a compound of a = 0 in the formula (V-2) is preferable as a component of the raw material of the liquid crystal polymer film.

  The compounds of the following formulas are examples of compounds represented by formulas (II-1) to (VI-2).

Since the alignment is performed even if the exposure amount is small, the components of the raw material for the photo-alignment film are represented by formula (II-2-1), formula (III-1-1), formula (III-2-1), formula (IV- 1-1), Formula (IV-2-1), Formula (V-2-1), Formula (V-2-4), Formula (V-2-6), Formula (V-2-7), Formula (V-3-1), Formula (V-3-2), Formula (V-3-3), Formula (V-3-5), Formula (V-3-7), (VI-2- The compound represented by 1) is more preferable.
Since there is little coloring of an alignment film, as a raw material component of a photo-alignment film, Formula (II-2-1), Formula (III-1-1), Formula (III-2-1), Formula (IV-1-) The compounds represented by 1), formula (V-2-1), formula (V-3-1), formula (V-3-2), and (VI-2-1) are more preferable.

  Since the anisotropy of the liquid crystal polymer film formed on the alignment film is increased, a compound represented by the formula (V-2-1) is more preferable as a raw material component of the alignment film.

  The compounds of formulas (PDI-1) to (PDI-5) are examples of compounds having a cinnamic acid structure which is a photosensitive group.

式（ＰＤＩ−４）において、Ｒ^２２は炭素数１〜１０のアルキルまたはアルコキシであり、該アルキルまたは該アルコキシの少なくとも１つの水素はフッ素に置き換えられていてもよい。

In formula (PDI-4), R ²² represents alkyl having 1 to 10 carbons or alkoxy, and at least one hydrogen of the alkyl or alkoxy may be replaced by fluorine.

Since it aligns even if there is little exposure amount, the compound represented by Formula (PDI-1) and (PDI-3) is more preferable as a component of the raw material of the alignment film by a photo-alignment method.

In order to improve the contrast of the liquid crystal polymer films, a material that can amplify liquid crystal alignment ability by firing is preferable as the photo-alignment film. As a raw material for such a material, a diamine having a flexible skeleton or tetracarboxylic dianhydride and derivatives thereof are preferable, and compounds represented by the formulas (FL-1) to (FL-4) are more preferable.

式（ＦＬ−１）〜式(ＦＬ−４）において、
Ｒ^３０は炭素数２から１２のアルキレンであり、このアルキレンの−ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ−、−ＮＣＨ_３−、−ＣＯ_２−、−ＣＯＮＲ^３３−で置き換えられていてもよく、
Ｒ^３１およびＲ^３２は単結合、または炭素数２から１２のアルキレンであり、
Ｒ^３３はＨまたはＣＨ_３であり、
ｐおよびｑは０または１である。
式（ＦＬ−２）〜式(ＦＬ−３）のベンゼン環は、炭素数１から２の−ＣＨ_３、−ＣＨ_２ＣＨ_３、−ＯＣＨ_３、またはフッ素で置き換えられていてもよい。

In formula (FL-1) to formula (FL-4),
R ³⁰ is alkylene having 2 to 12 carbons, and —CH ₂ — of the alkylene is —CH═CH—, —C≡C—, —O—, —NCH ₃ —, —CO ₂ —, —CONR. ^33- may be replaced by
R ³¹ and R ³² are a single bond or alkylene having 2 to 12 carbons,
R ³³ is H or CH ₃
p and q are 0 or 1.
The benzene ring in the formula (FL-2) to the formula (FL-3) may be replaced with —CH ₃ , —CH ₂ CH ₃ , —OCH ₃ , or fluorine having 1 to 2 carbon atoms.

Compounds of formulas (FL-1-1) to (FL-4-6) are examples of compounds represented by formulas (FL-1) to (FL-4). From the viewpoint of improving contrast, in the compounds of the formulas (FL-1-1) to (FL-4-6), the compounds represented by the formulas (FL-3-2) to (FL-3-5) Most preferred.

  Since the contrast of the liquid crystal polymer film with the base material is improved and the difficulty of peeling between the liquid crystal polymer film and the base material is improved at the same time, the amount of hydrogen donating groups with respect to the repeating unit in the raw material of the alignment film is 0.001. 1 to 2 is preferable, and 0.1 to 1 is more preferable. Conventionally, if the bond between the alignment film and the liquid crystal polymer film is to be strengthened, the alignment of the liquid crystal polymer film by the alignment film is disturbed, and the contrast of the liquid crystal polymer film with the substrate is lowered. For this reason, it has been considered that the contrast of the liquid crystal polymer film and the difficulty of peeling between the liquid crystal polymer film and the substrate are not compatible due to the improvement of the alignment film.

By introducing such a hydrogen-donating group into diamine or tetracarboxylic dianhydride and its derivative, which are raw materials for the alignment film, the alignment film of the present invention can be obtained. Such a diamine having a hydrogen donor group and a tetracarboxylic dianhydride having a hydrogen donor group and derivatives thereof may be used in combination. As such diamine, tetracarboxylic dianhydride, and derivatives thereof, known ones can be used without any particular limitation. However, since they are easily available, it is possible to use a compound represented by the formula (PQ-1). preferable.

In the formula (PQ-1),
R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ are independently a group having —OH, —CO—C (CH ₃ ) ₃ , —COOH, —CONH 2 or —NH—CO—C (CH ₃ ) _3. Yes,
a, b, c and d are independently 1 to 4,
R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are a single bond or alkylene having 2 to 12 carbon atoms, and —CH ₂ — of the alkylene is —CH═CH—, —C≡C—, —O—, —N (CH 3) —, —COO—, —CONR ⁴³ — may be substituted, and R ⁴³ is —H or —CH ₃ ;
p, q and r are independently 0 or 1.

  The diamine represented by the formula (PQ-1) is preferably the formula (PQ-1-1) to the formula (PQ-1-17).

  Of the diamines having a hydrogen donor group, compounds represented by the following formulas (PQ-2) and (PQ-3) are also preferable.

  By adjusting the reaction conditions such as the preparation of the raw material and the temperature, the content of the hydrogen donating group in the alignment film prepared using the polyamic acid represented by the formula (1) can be adjusted.

  In order to improve the adhesion to the substrate, it is preferable to contain a silane coupling agent in the alignment film prepared using polyamic acid.

≪Polymerizable liquid crystal compound≫

  In order to obtain a liquid crystal polymer having a high contrast, it is preferable to use a polymerizable liquid crystal compound represented by the following general formulas (2-1) to (2-10) as a raw material.

In formula (2-1),
W ¹ is hydrogen, fluorine, chlorine, or an organic group having 1 to 5 carbon atoms. Viewpoints such as the expansion of the temperature range in which the liquid crystal phase is expressed as a composition, compatibility with other liquid crystalline compounds, solubility in solvents, etc. (hereinafter referred to as “easy to handle”) From)
W ¹ is more preferably an alkyl having 1 to 5 carbon atoms, an alkoxycarbonyl having 1 to 4 carbon atoms, an aldehyde, or an alkylcarbonyl having 1 to 4 carbon atoms.
In Formula (2-2), W ² is hydrogen, fluorine, or an organic group having 1 to 5 carbon atoms. From the viewpoint of easy handling, W ² is more preferably an alkyl having 1 to 5 carbon atoms.
In Formula (2-3), W ⁴ is hydrogen, fluorine, or an organic group having 1 to 5 carbon atoms. From the viewpoint of easy handling, W ⁴ is preferably alkyl having 1 to 5 carbons, alkoxycarbonyl having 1 to 4 carbons, aldehyde, or alkylcarbonyl having 1 to 4 carbons.
In the formula (2-4), Ar is an aromatic group having up to 14 carbon atoms or an aromatic conjugated group. From the viewpoint of easy handling, Ar is preferably a phenyl, pyridyl, naphthyl or thiophene group.
In the formula (2-5), R ⁵⁰ represents a single bond or —CH═CH—. From the viewpoint of light resistance, R ⁵⁰ is preferably a single bond.
In Formula (2-6), R ⁵¹ represents —CO ₂ R ⁵¹¹ or —CN, and R ⁵¹¹ represents an alkyl group having 10 or less carbon atoms, which may be substituted with a (meth) acryloxy group. Since the expansion of the temperature range in which the liquid crystal phase is expressed and the contrast is improved when the composition is used, R ⁵¹ is preferably —CO ₂ Me or —CN.
In the formula (2-7), Ar is an aromatic group having up to 14 carbon atoms or an aromatic conjugated group. From the viewpoint of easy handling and contrast, phenyl, pyridyl, naphthyl and thiophene groups are preferable as Ar.
In the formula (2-8), R ⁵² represents a hydrogen atom or an alkyl group having 10 or less carbon atoms, and one methylene or methyl group in the alkyl group may be substituted with a (meth) acryloxy group. . At this time, a hydrogen atom and an alkyl group having 5 or less carbon atoms are more preferable as Ak ⁵⁰ because the expansion of the liquid crystal temperature range when the composition is used and the contrast are improved.
In Formula (2-9), R ⁵³¹ and R ⁵³² represent a hydrogen atom, an alkyl group having 3 or less carbon atoms, or an aromatic group having up to 10 carbon atoms. In view of easy handling and contrast, R ⁵³¹ and R ⁵³² are independently preferably a hydrogen atom, a carbon number methyl group, a phenyl group, a pyridyl group, or a thiophene group.
In Formula (2-10), R ⁵⁴ represents an alkyl group having 3 or less carbon atoms, and two R ^54s may be bonded to form a ring structure, and R ⁵⁵ is a hydrogen atom or an alkyl group having 3 or less carbon atoms. Represents. To improve the aspect and contrast that handling is easy, preferably an alkyl group having 3 or less carbon atoms as R ^54, also the two R ⁵⁴ is crosslinked to 5 or 6-membered ring structure preferably as R ^55, A hydrogen atom or a methyl group is more preferable.

Further, in formulas (2-1) to (2-10), A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene, or naphthalene-2,6-diyl; In -phenylene and naphthalene-2,6-diyl, at least one hydrogen may be replaced by fluorine, chlorine, or an organic group having 1 to 5 carbon atoms. The contrast is improved, as ^{A 1,} independently 1,4-phenylene or 1,4-cyclohexylene is more preferable.

In formulas (2-1) to (2-10), Z ¹ is independently a single bond, —CH ₂ CH ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH _{2. -, - OCH 2 CH 2 O} -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH 2 CH 2 OCO- or -COOCH ₂ CH ₂ -. From the viewpoint of easy handling, it is preferable that at least one of Z ¹ is —CH ₂ CH ₂ COO— or —OCOCH ₂ CH ₂ —.

In Formula (2-1) to Formula (2-10), m and n are each an integer of 0 to 7, and 3 ≦ m + n ≦ 8. In order to improve the contrast, it is preferable that m + n ≧ 3 in the expressions (2-1) to (2-10). From the viewpoint of easy handling, it is preferable that m + n ≦ 8 in the formulas (2-1) to (2-10).

In formulas (2-1) to (2-10), Y ¹ is independently a single bond, —O—, —COO—, —OCO— or —OCOO—.

In formulas (2-1) to (2-10), Q ¹ is independently a single bond or alkylene having 1 to 20 carbons, and in the alkylene, at least one —CH ₂ — is —O—. , -COO- or -OCO-. From the viewpoint of handling easily, in the formula (2-10) from equation (2-1), as ^{Q 1,} an alkylene having 1 to 20 carbon atoms, more preferably.

  In formula (2-1) to formula (2-10), PG represents a polymerizable group. Groups represented by formula (PG-1) to formula (PG-3) are polymerizable groups. From the viewpoint of improving the reaction rate of the polymerization reaction of the compound having a polymerizable group and improving the solubility in a solvent, the formula (PG-1) and derivatives thereof are preferred.

In Formula (PG-1) and Formula (PG-2), R ¹ is independently hydrogen, fluorine, methyl, ethyl, or trifluoromethyl.

Of the compounds represented by the above formulas (2-1) to (2-10), from the viewpoints of induction of the composition into the liquid crystal phase, compatibility with other liquid crystal compounds, and solubility in solvents. ,
The compounds represented by formula (2-1-1) to formula (2-10-6) are particularly preferable.

In the above formula (2-1-1) to formula (2-9-6),
Y ¹ is independently a single bond, —O—, —COO—, —OCO— or —OCOO—.
Q ¹ is independently a single bond or alkylene having 1 to 20 carbon atoms, and in the alkylene, at least one —CH ₂ — may be replaced by —O—, —COO— or —OCO—,
PG is independently any one functional group represented by the above formula (PG-1) to formula (PG-3),
Ak ⁵⁰ represents an alkylene group having 2 to 10 carbon atoms,
Ak ⁵¹ represents a hydrogen atom or an alkyl group having 10 or less carbon atoms.

  These polymerizable liquid crystal compounds represented by the formula (2) include “Organic Synthesis” (John Wiley & Sons, Inc.) and “Organic Reactions” (Organic Reactions, John Wiley & Sons, Inc.). It can be synthesized by a combination of books such as “Comprehensive Organic Synthesis” (Pergamon Press), “New Experimental Chemistry Course” (Maruzen), and techniques known to those skilled in the art.

≪Polymerizable liquid crystal composition≫

From the viewpoints of preventing crystal precipitation during film formation, inducing a liquid crystal phase, and improving solubility in a solvent, the raw material for the liquid crystal polymer is preferably a composition.

  Applying and polymerizing a polymerizable liquid crystal composition containing a compound represented by the formula (2) on an alignment film prepared by firing a composition containing a polymer represented by the repeating unit of the formula (1). Thus, the contrast of the liquid crystal polymer is improved. From the viewpoint of contrast, the content of the compound represented by the formula (2) in the polymerizable liquid crystal composition is preferably 50% by weight or more, and more preferably 70% by weight or more.

Other polymerizable compounds may be added to the polymerizable liquid crystal composition from the viewpoint of prevention of crystal precipitation during film formation, induction of a liquid crystal phase, and improvement of solubility in a solvent. From the viewpoints of high liquid crystallinity, heat resistance, and ease of production, such polymerizable compounds include compounds (2M-1-1) to (2M-1-18) and compounds (2M-2-1). (2M-2-30) and compounds (2M-3-1) to (2M-3-8) are preferred.

Formulas (2M-1-1) to (2M-1-18), Formulas (2M-2-1) to (2M-2-30), and Formulas (2M-3-1) to (2M-3-8) in, ^{R M} is independently hydrogen or methyl, a is an integer from 1 to 12 independently.

Compounds (2M-1-1) to (2M-1-18) are monofunctional compounds and polymerizable liquid crystal compounds.
An increase in the amount of a monofunctional compound that is a polymerizable liquid crystal compound in the polymerizable liquid crystal composition increases the tilt angle of the polymerizable liquid crystal composition. An increase in the amount of a monofunctional compound that is a polymerizable liquid crystal compound in the polymerizable liquid crystal composition is induced in homeotropic alignment of the polymerizable liquid crystal composition.

Compounds (2M-2-1) to (2M-2-30) are bifunctional compounds and are polymerizable liquid crystal compounds.
By adding a bifunctional compound that is a polymerizable liquid crystal compound in the polymerizable liquid crystal composition, a polymer film prepared from the polymerizable liquid crystal composition has a three-dimensional structure. The mechanical strength and / or chemical resistance of the liquid crystal polymer film having a three-dimensional structure is improved.

  From the viewpoint of improving the contrast of a liquid crystal polymer film with a substrate, compatibility with other liquid crystal compounds in the composition, and solubility with the composition (2M-1- 1) to (2M-3-8) is preferably 50% by weight or less, and more preferably 30% by weight or less.

  The alignment film prepared by polymerizing a raw material containing a polyamic acid containing the repeating unit of the formula (1) is subjected to an alignment treatment such as polarization exposure or rubbing, and the polymerization represented by the general formula (2) on the alignment film When the liquid crystal is directly laminated, the liquid crystal polymer film is uniformly aligned. A liquid crystal polymer film having no side chain or a short side chain induces tilt alignment and homogeneous alignment. Introducing a long-chain alkyl group or a linked alicyclic structure into the side chain of the liquid crystal polymer film reduces the surface free energy of the alignment film prepared using the polyamic acid represented by the repeating unit of formula (1) By doing so, homeotropic alignment of the polymerizable liquid crystal is easily induced.

  Addition of a non-liquid crystalline polymerizable compound having a bisphenol structure or a cardo structure to a polymerizable liquid crystal composition induces improvement in the degree of cure of the polymer and homeotropic alignment of the liquid crystal polymer. Compounds (α-1) to (α-3) are non-liquid crystalline polymerizable compounds having a cardo structure.

In formulas (α-1) to (α-3), R ^α is independently hydrogen or methyl, and s is independently an integer of 0 to 4.

  In order to induce homeotropic alignment and suppress deterioration in liquid crystallinity, the content of the additive for inducing the vertical alignment is 0.005 or more and 0.1 or less by weight with respect to the solid content of the composition. Preferably there is.

≪Additive to polymerizable liquid crystal composition≫
One or more kinds of additives may be added to the polymerizable liquid crystal composition of the present invention.

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. The nonionic surfactant 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, it is preferable to add a surfactant that is a polymerizable compound to the polymerizable liquid crystal composition, and a surfactant that initiates a polymerization reaction with ultraviolet rays is more preferable. .
Since the liquid crystal polymer film tends to have uniform alignment and the coating property of the polymerizable liquid crystal composition is improved, the surfactant in the polymerizable liquid crystal composition is 0% relative to the total amount of the polymerizable liquid crystal composition. 0.0001 to 0.5% by weight is preferable, and 0.01 to 0.2% by weight is more preferable.

Surfactants are classified into ionic surfactants and nonionic surfactants.
Silicone-based nonionic surfactants, fluorine-based nonionic surfactants, vinyl-based nonionic surfactants and the like are nonionic surfactants.

  Titanate compounds, imidazolines, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl sulfate amines, alkyl-substituted fragrances Aromatic sulfonate, alkyl phosphate, aliphatic or aromatic sulfonic acid formalin condensate, laurylamidopropylbetaine, laurylaminoacetic acid betaine, polyethylene glycol fatty acid esters, polyoxyethylene alkylamine, perfluoroalkylsulfonate Perfluoroalkylcarboxylates are ionic surfactants.

  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.

A (meth) acrylic polymer having a weight average molecular weight of 1,000 to 1,000,000 is a vinyl-based nonionic surfactant.
Addition of a surfactant having a polymerizable functional group to a polymerizable liquid crystal composition that is a raw material of the liquid crystal polymer film improves the surface hardness of the liquid crystal polymer film.

  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 1/5 or less of the total weight of the polymerizable compound in the polymerizable liquid crystal composition. .

By adding a polyfunctional compound to the polymerizable liquid crystal composition, enhancement of mechanical strength of liquid crystal polymer films, improvement of chemical resistance, or both can be expected.
The non-liquid crystalline polymerizable compound is typically a compound having one or more vinyl polymerizable functional groups.
By adding a non-liquid crystalline polymerizable compound having a hydrogen donating group at the side chain and / or terminal to the polymerizable liquid crystal composition, adhesion between the polymerizable liquid crystal composition and the substrate is improved.

  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 Monoalkylene glycol (polymethacrylate) such as 2-methacryloyloxyethyl acid phosphate, polyethylene glycol having a polymerization degree of 2 to 100, polypropylene glycol, and a copolymer of ethylene oxide and propylene oxide. ) Acrylic acid esters, or di (meth) acrylic acid esters or polyethylene glycols having a degree of polymerization of 2 to 100 capped with alkyls having 1 to 6 carbon atoms, polypropylene glycol, and copolymers of ethylene oxide and propylene oxide. A poly (alkylene glycol) mono (meth) acrylate ester as a polymer is a non-liquid crystalline polymerizable compound as 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 and polyethylene glycol diacrylate, and the methacrylate compounds of these compounds are bifunctional compounds. It is a non-liquid crystalline polymerizable compound.

  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 non-liquid crystalline polymerizable compound of not bifunctional compound polyfunctional compound. Addition of a polymerizable compound having a bisphenol structure or a cardo structure to the polymerizable liquid crystal composition induces improvement in the degree of cure of the polymer and homeotropic alignment of the liquid crystal polymer film.

  The addition of the polymerization initiator optimizes the polymerization rate of the polymerizable liquid crystal composition. A photo radical initiator or the like is a polymerization 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-morpholino propan-1-one, 2,4-diethyl thioxanthone / p- dimethylaminobenzoic acid methyl mixtures, benzophenone / methyl triethanolamine mixture, etc., a photo radical initiator.

  From the viewpoint of contrast, stickiness prevention, and retardation change of liquid crystal polymer films, the total content of the photo radical polymerization initiator in the polymerizable liquid crystal composition is based on the total amount of the polymerizable liquid crystal composition. 0.01 to 10 weight% is preferable, 0.1 to 4 weight% is more preferable, and 0.5 to 4 weight% is still more preferable.

  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.

A thiol derivative that is a monofunctional compound and a thiol derivative that is a polyfunctional compound are thiol derivatives.
Dodecanethiol, 2-ethylhexyl- (3-mercapto) propionate, and the like are thiol derivatives that are monofunctional compounds. 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 is a polyfunctional compound thiol derivative. is there.
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 is stored. Phenol derivatives, phenothiazine derivatives, compounds having a nitroso group, benzothiazine derivatives, and the like are polymerization inhibitors. 2,5-di (t-butyl) hydroxytoluene, hydroquinone, o-hydroxybenzophenone, methylene blue, diphenylpicric acid hydrazide and the like are polymerization inhibitors that are phenol derivatives. Phenothiazine, methylene blue, and the like are polymerization inhibitors that are phenothiazine derivatives. N, N-dimethyl-4-nitrosoaniline is a polymerization inhibitor which is a compound having a typical low nitroso group.

Addition of a polymerization inhibitor to the polymerizable liquid crystal composition suppresses a polymerization reaction in the polymerizable liquid crystal composition due to generation of radicals in the polymerizable liquid crystal composition. Addition of a 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.

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.

In order to facilitate application, it is preferable to add a solvent to the polymerizable liquid crystal composition.
Esters, amide compounds, alcohols, ethers, glycol monoalkyl ethers, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, alicyclic hydrocarbons, ketones, acetate solvents Etc. are components of the solvent.

  The amide compound refers to a compound having an amide group and serving as a solvent component. An acetate solvent refers to a compound having an acetate structure 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 esters.

  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 malonate. Methyl glycolate, ethyl glycolate and the like are“ alkyl glycolate ”. Methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, butyl lactate, ethyl hexyl lactate and the like are “alkyl lactate”.

  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, dimethylimidazolidinone and the like are amide compounds.

  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, tri Propylene glycol, hexylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,4-pen Njioru, 2,5-hexanediol, 3-methyl-3-methoxybutanol, cyclohexanol, methyl cyclohexanol, is an alcohol.

  Ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, bis (2-propyl) ether, 1,4-dioxane, tetrahydrofuran and the like are ethers.

  Ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, triethylene glycol monoalkyl ether Acetate, propylene glycol monoalkyl ether acetate, dipropylene glycol monoalkyl ether acetate, diethylene glycol methyl ethyl ether and the like are glycol monoalkyl ethers.

  Ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and the like are ethylene glycol monoalkyl ethers. Diethylene glycol monoethyl ether and the like are diethylene glycol monoalkyl ethers. Propylene glycol monobutyl ether and the like are propylene glycol monoalkyl ethers. Dipropylene glycol monomethyl ether and the like are dipropylene glycol monoalkyl ethers. Ethylene glycol monobutyl ether acetate and the like are ethylene glycol monoalkyl ether acetates. Diethylene glycol monoethyl ether acetate and the like are diethylene glycol monoalkyl ether acetates. Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate and the like are propylene glycol monoalkyl ether acetates. Dipropylene glycol monomethyl ether acetate and the like are dipropylene glycol monoalkyl ether acetates.

  Benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, i-propylbenzene, n-propylbenzene, t-butylbenzene, s-butylbenzene, n-butylbenzene, tetralin and the like are the aromatic hydrocarbons.

  Chlorobenzene and the like are halogenated aromatic hydrocarbons. Hexane, heptane and the like are aliphatic hydrocarbons. Chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethylene, tetrachloroethylene and the like are halogenated aliphatic hydrocarbons. Cyclohexane, decalin and the like are alicyclic hydrocarbons.

  Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, methyl propyl ketone and the like are ketones.

  Ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetoacetate, 1-methoxy-2-propyl acetate and the like are acetate solvents.

  From the viewpoint of compatibility with the polymerizable liquid crystal compound, the solvent in the polymerizable liquid crystal composition is preferably 30 to 96% by weight, more preferably 50 to 90% by weight, based on the total amount of the polymerizable liquid crystal composition. More preferred is -80% by weight.

  The polymerizable liquid crystal composition of the present invention may contain a compound having optical activity. Addition of a compound having optical activity to the liquid crystal composition induces the liquid crystal polymer film in twist alignment. The liquid crystal polymer film can be used as a selective reflection film and a negative C plate in a wavelength region of 300 to 2000 nm.

  Examples of the optically active compound include a compound having an asymmetric carbon, an axially asymmetric compound having a binaphthyl structure and a helicene structure, a surface asymmetric compound having a cyclophane structure, and the like. From the viewpoint of fixing the twisted helical pitch, the compound having optical activity in this case is preferably a polymerizable compound.

  The liquid crystal polymer film of the present invention may contain a dichroic dye. Liquid crystal polymer films combined with a dichroic dye can be used as an absorption polarizing plate.

≪Base material≫
Examples of the material of the substrate include glass, plastic, and metal. The glass or metal may be slit-like processed on the surface. The plastic may be subjected to a surface treatment such as a stretching treatment and a hydrophilic treatment and a hydrophobic treatment.

≪Creation of liquid crystal polymer film≫

<Creation of alignment film>
The alignment film can be formed on the substrate by the following procedure (I) or procedure (II).
Procedure (I)
Procedure (I-1)
A solution containing a polyamic acid represented by the repeating unit of formula (1) is applied onto a substrate and dried to form a coating film.
Procedure (I-2)
The coating film made of the polyamic acid formed in the procedure (I-1) is baked at a temperature equal to or higher than the imidization temperature to form an imidized coating film,
Procedure (I-3)
An orientation treatment is applied to the imidized coating film formed in the procedure (I-2), anisotropy is imparted, and an orientation film is formed on the substrate;
Procedure (II)
Procedure (II-1)
A solution containing a polyamic acid represented by the repeating unit of formula (1) is applied onto a substrate and dried to form a coating film.
Procedure (II-2)
The coating film made of the polyamic acid formed in the procedure (II-1) is subjected to an alignment treatment to impart anisotropy,
Procedure (II-3)
The coating film made of the polyamic acid in step (II-2) is baked at a temperature equal to or higher than the imidization temperature to form an imidized coating film, and an alignment film is formed on the substrate.

At this time, from the viewpoint of film thickness and uniformity thereof, an offset printing method and an ink jet printing method are preferable in the formation of the liquid crystal polymer film. In order to remove the solvent of the solution on the substrate, a hot plate, a drying furnace, and blowing of warmed air and other heat treatments are simultaneously performed in any of steps (I-1) to (I-2). It is preferable.

Since the alignment treatment is easy, it is preferable to use the photo-alignment method and the rubbing method in the procedure (I-3) or the procedure (II-2).
In order to improve the contrast of the liquid crystal polymer films, it is more preferable to use the photo-alignment method in the procedure (I-3) or the procedure (II-2).

  A low-pressure mercury lamp, a high-pressure discharge lamp, a short arc discharge lamp, etc. can be used for the photo-alignment treatment. A sterilization lamp, a fluorescent chemical lamp, a black light, and the like are the low-pressure mercury lamp. High pressure mercury lamps, metal halide lamps, and the like are the high pressure discharge lamps. An ultra-high pressure mercury lamp, a xenon lamp, a mercury xenon lamp, etc. are the short arc discharge lamps. Since the alignment film can be formed with a small exposure amount, it is preferable to use linearly polarized light in the procedure (I-3) or the procedure (II-3). In order to prevent damage to the alignment film due to the backlight of the liquid crystal display device or visible light, the polyamic acid which is a raw material for the coating film is preferably one having a light absorption wavelength of 400 nm or more.

<Creation of liquid crystal polymer film with substrate>
A liquid crystal polymer film with a substrate can be formed by the following procedure.
Procedure (III-1)
A solution containing a polymerizable liquid crystal compound represented by the formula (2) is applied to an alignment film on a substrate and dried to form a coating film.
Procedure (III-2)
At a temperature at which the coating film exhibits a liquid crystal phase,
Procedure (III-3)
It exposes with respect to a coating film, and creates the liquid crystal polymer film with a base material.

  From the viewpoint of improving the adhesion between the liquid crystal polymer film and the substrate, the liquid crystal polymer film with the substrate is preferably heated after the step (III-3). The temperature of this heat treatment is lower than the endurance temperature required for the liquid crystal polymer film with a substrate.

In the procedure (III-1), from the viewpoint of film thickness and uniformity at this time, spin coating method, micro gravure coating method, gravure coating method, wire bar coating method, dip coating method, spray coating method, meniscus coating method and Application by a die coating method is preferred.

In an LCD, a liquid crystal polymer film can be used for in-cell use because it causes little decrease in retardation due to heating and little elution of impurities into nematic liquid crystals.

A polarizing plate having functions such as optical compensation can be produced by forming a liquid crystal polymer film with a base material using the polarizing plate as a base material. If a liquid crystal polymer film having a quarter wavelength is formed on the polarizing plate, a liquid crystal polymer film with a substrate that is a circularly polarizing plate can be produced. An absorbing polarizing plate doped with iodine or a dichroic dye, and a reflective polarizing plate such as a wire grid polarizing plate can be the polarizing plate.

The present invention is not limited to the published embodiments.

In the examples of the present invention, the room temperature is 25 ° C.

In the Example of this invention, a compound (DA-1) to a compound (DA-9) are compounds represented by the following formula | equation.

（ＤＡ−１）

(DA-1)

（ＤＡ−２）

(DA-2)

（ＤＡ−３）

(DA-3)

（ＤＡ−４）

(DA-4)

（ＤＡ−５）

(DA-5)

（ＤＡ−６）

(DA-6)

（ＤＡ−７）

(DA-7)

（ＤＡ−８）

(DA-8)

（ＤＡ−９）

(DA-9)

Compound (DA-1), compound (DA-5), compound (DA-7), compound (DA-8) and compound (DA-9) were commercially available products. Compound (DA-2), Compound (DA-3), Compound (DA-4), and Compound (DA-6) are disclosed in Japanese Patent Publication No. 5929298, Japanese Patent Application Laid-Open No. 2015-020999, Japanese Patent Publication No. 5634985, and WO2013 /. It was synthesized according to No. 039168.

In the Example of this invention, a compound (AA-1) to a compound (AA-4) and a compound (AE-1) are compounds represented by the following formula | equation.

（ＡＡ−１）

(AA-1)

（ＡＡ−２）

(AA-2)

（ＡＡ−３）

(AA-3)

（ＡＡ−４）

(AA-4)

（ＡＥ−１）

(AE-1)

The compound (AA-2) and the compound (AA-3) used the commercial item. Compound (AA-1) and compound (AA-4) were synthesized according to Japanese Patent Publication No. 5407394. Compound (AE-1) was synthesized according to WO2013 / 039168.
Compound (DA-1) to Compound (DA-9) and Compound (AA-1) to Compound (AA-4) and Compound (AE-1) are polyamic acids represented by the repeating unit of formula (1). It becomes a raw material.

In the examples of the present invention, “Irg-907” is Irgacure (trademark) 907 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, “TEGOFlow 370” is TEGOFlow (trademark) 370 manufactured by Evonik Japan.

In the examples of the present invention, “BOC” means —CO—C (CH ₃ ) ₃ which is a functional group.

In the examples of the present invention, “NMP” is 1-methyl-2-pyrrolidone.
In the examples of the present invention, “BC” is ethylene glycol = monobutyl = ether.
In the examples of the present invention, “GBL” is γ-butyrolactone.
In the examples of the present invention, “IPA” is 2-propanol.

In an embodiment of the present invention, the glass substrate is EagleXG manufactured by Corning.

In the examples of the present invention, “DMAP” is N, N-dimethyl-4-aminopyridine.
In the examples of the present invention, “DCC” is N, N′-dicyclohexylcarbodiimide.
In the examples of the present invention, “THF” is tetrahydrofuran.

<Polymerizable liquid crystal composition>
In the examples of the present invention, the structures of the compounds used in the polymerizable liquid crystal composition are shown below. Each of these compounds was synthesized according to the literature listed after the compound structure.

（２−１−３−１）
特願２０１６−２１１２１２号

(2-1-3-1)
Japanese Patent Application No. 2006-211212

（２−１−８−１）
ＷＯ２０１５−１４７２４３

(2-1-8-1)
WO2015-147243

（２−１−９−１）
特開２００８−２３９５６７号

(2-1-9-1)
JP 2008-239567 A

（２−１−１１−１）
特願２０１６−２１１２１２号

(2-1-11-1)
Japanese Patent Application No. 2006-211212

（２−１−１７−１）
特願２０１６−１５６５５３号

(2-1-17-1)
Japanese Patent Application No. 2006-156553

（２−１−１８−１）
特願２０１６−１５６５５３号

(2-1-18-1)
Japanese Patent Application No. 2006-156553

（２-１-１９-１）
特願２０１６−１５６５５３号

(2-1-19-1)
Japanese Patent Application No. 2006-156553

（２−１−３５−１）
特願２０１６−２１１２１２号

(2-1-35-1)
Japanese Patent Application No. 2006-211212

（２−２−１−１）
特願２０１６−１７１０６６号

(2-2-1-1)
Japanese Patent Application No. 2006-171066

（２−４−１−１）
特許５４５３７９８号公報

(2-4-1-1)
Japanese Patent No. 5453798

（２−５−４−１）
特願２０１５−０４０５０９号

(2-5-4-1)
Japanese Patent Application No. 2015-040509

（２−６−４−１）
特開２００９−２４２７１８号公報

(2-6-4-1)
JP 2009-242718 A

（２−−５−１）
ＷＯ２０１６−１１４２１１号公報

(2--5-1)
WO2016-114211 gazette

（２−８−２−１）
特願２０１５−２４８２２６号

(2-8-2-1)
Japanese Patent Application No. 2015-248226

（２−９−２−１）
特願２０１６−１３７２６２号

(2-9-2-1)
Japanese Patent Application No. 2006-137262

In the examples of the present invention, “standard polystyrene” is TSK standard polystyrene manufactured by Tosoh Corporation.
In an embodiment of the present invention, “GPC” is a system consisting of a Waters 2695 separation module and a Waters 2414 differential refractometer.
In the examples of the present invention, the “viscosity meter” is TV-22 manufactured by Toki Sangyo Co., Ltd.
In the embodiment of the present invention, the “optical film thickness measurement system” is DF-1030R manufactured by Techno Synergy.
In the embodiment of the present invention, the “step meter” is an alpha step IQ manufactured by KLA TENCOR.

In the Example of this invention, a "Fourier transform infrared spectrophotometer" is FT / IR-610 by JASCO Corporation.
In the embodiment of the present invention, the “light alignment light source device” is model number APL-L01212S1-ASN01 manufactured by USHIO INC.
In an embodiment of the present invention, the “ultra-high pressure mercury lamp” is a multilight-250 manufactured by USHIO INC. Having an output of 250 W.
In the embodiment of the present invention, the “polarization analyzer” is an OPIPRO ellipsometer manufactured by Shintech Co., Ltd.
In an embodiment of the present invention, the “luminance meter” is YOKOGAWA 3298F.

<Measurement of molecular weight of polyamic acid>
The weight average molecular weight was measured by GPC in comparison with standard polystyrene. The column was HSPgel RT MB-M manufactured by Waters.
A product obtained by dissolving the analyte in the phosphoric acid-DMF mixed solution so as to be 2% by weight was developed by GPC under conditions of a column temperature of 50 ° C. and a flow rate of 0.40 ml / min. The weight ratio of the phosphoric acid-DMF mixed solution was 0.6 / 100. The developing agent was the phosphoric acid-DMF mixed solution.

<Measurement of viscosity of polyamic acid>
The viscosity was measured with a viscometer in accordance with the manual of the apparatus with the object at 25 ° C.

<Film thickness measurement>
The film thickness of the alignment film was measured with an optical film thickness measurement system.
The film thickness of the liquid crystal polymer film having a glass substrate was measured by the following procedure.
(1) A liquid crystal polymer film is cut out from a glass substrate having a liquid crystal polymer film,
(2) Measure the step between the part having the liquid crystal polymer film and the part excluding the liquid crystal polymer film,
(3) The measured value was taken as the film thickness.
In the Example of this invention, the level | step difference of the part of a liquid crystal polymer film was measured with the level difference meter.

<Measurement of imidation ratio of alignment film>
The imidization rate was determined by the following procedure.
(1-1) Create a KBr tablet from the alignment film scraped from the substrate, and name it as a sample.
(1-2) A sample prepared by the same method as in the procedure (1-1) was baked at 280 ° C. for 30 minutes, and named control.
(2-1) The ratio of the area of the absorption peak derived from the imide group near 1780 cm ⁻¹ of the sample to the area of the absorption ring of the aromatic ring of the polyimide near 1500 cm ⁻¹ of the sample is measured with a Fourier transform infrared spectrophotometer. Measured and named as "Absorption peak area ratio of sample"
(2-2) In the same manner as in the procedure (2-1), the area ratio of the absorption peak of the control was measured instead of the sample, and named “the area ratio of the absorption peak of the control”.
(3) The value calculated by “area ratio of absorption peak of sample” / “area ratio of absorption peak of control” * 100 was defined as the imidation ratio of the alignment film. However, the unit of the imidization rate is “%”.

<Exposure conditions>
The exposure for forming the alignment film was performed with a light alignment light source device.
The exposure for preparing the liquid crystal polymer film was performed with an ultrahigh pressure mercury lamp.

<Confirmation of alignment defects>
The presence or absence of alignment defects was determined by sandwiching a liquid crystal polymer film with a substrate between two polarizing plates arranged in crossed Nicols. The substrate was rotated in a horizontal plane, and the bright and dark state was visually confirmed. “There was no alignment defect” when there was no spot where light could be seen in the dark state and both the bright state and the dark state could be confirmed.

<Confirmation of homogeneous orientation>
Retardation was measured by changing the incident angle of light with respect to the surface of the liquid crystal polymer film with a base material in increments of 5 ° from −50 ° to 50 ° using an ellipsometer. 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 retardation>
The retardation of the liquid crystal polymer film was measured with an ellipsometer while decreasing the incident angle of light on the surface from 90 °. The retardation in the table is a value at a measurement wavelength of 550 nm.

<Evaluation of birefringence Δn>
The birefringence Δn was calculated by the retardation of the liquid crystal polymer film / the film thickness of the liquid crystal polymer film.

<Chromatic dispersion>
The retardation ratio of the measurement wavelength of 450 nm to the measurement wavelength of 550 nm was shown.

<Measurement of luminance in crossed Nicol state and luminance in parallel Nicol state>
The luminance in the crossed Nicol state and the luminance in the parallel Nicol state were measured using a luminance meter with a liquid crystal polymer film with a substrate sandwiched between two polarizing plates of a polarizing microscope. The substrate was horizontally rotated in the crossed Nicol state, and the minimum luminance was regarded as “the luminance in the crossed Nicol state”. The substrate was rotated in a horizontal plane in the parallel Nicol state, and the maximum luminance was regarded as “luminance in the parallel Nicol state”.

<Adhesion test>
According to the former JIS K5400 “Paint General Test Method”, the adhesion test of the liquid crystal polymer film with the substrate was conducted. In the examples of the present specification, the number of wrinkles is the number of wrinkles in which peeling did not occur in the 100 wrinkles tried by the test method.

<Preparation of polyamic acid solution>
[Example 1]
In the same manner as described in JP 2012-193167 A, a 100 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet is charged with 0.6605 g of the compound (DA-1), 0 5328 g of the compound (DA-2) and 17.4 ml of NMP were added and dissolved by stirring under a nitrogen stream. Next, 1.8067 g of compound (AA-1) and 10 ml of NMP were added and stirred at room temperature for 24 hours. 20.8 ml of BC was added to the resulting solution and named the varnish solution. The varnish solution was stirred at 75 ° C. for 4 hours, and named polyamic acid solution (PA-1). The concentration of polymer solids in the polyamic acid solution (PA-1) was 6% by weight. The viscosity of the polyamic acid solution (PA-1) was 11.3 mPa · s. The weight average molecular weight of the polyamic acid solution (PA-1) was 23,000.

[Example 2]
In the preparation of the polyamic acid solution (PA-1), the compound (DA-1) and the compound (DA-2) and / or the acid dianhydride (AA-1) are converted into the diamine and acid dianhydride described in Table 1. A polyamic acid solution (PA-2) (PA-8) and a polyamic acid solution (PA-I) (PA-II) having a polymer solid content concentration of 6% by weight were prepared. The polyamic acid in the polyamic acid solution (PA-8) to the polyamic acid solution (PA-8) is a polyamic acid represented by the formula (1) of the present invention.

<Preparation of polyamic acid ester solution (PAE-1)>
[Example 3]
In the same manner as in Synthesis Example 7 and Synthesis Example 8 described in International Publication No. 2013/039168, 2.80 g of Compound (DA-8) and 1.45 g of Compound (DA- 6), 6.18 g of pyridine and 110 ml of NMP. The four-necked flask was transferred onto an ice bath, and 9.89 g of the compound (AE-1) was slowly added to the four-necked flask and stirred at room temperature overnight. Thereafter, 0.38 g of acryloyl chloride was added and reacted at room temperature for 5 hours. Thereafter, the obtained solution was added to 1.2 L of pure water, and the precipitated white precipitate was filtered, washed with 1.2 L of IPA three times, and finally vacuum dried. The obtained polyamic acid ester was 9.5 g (yield 77%). Moreover, the weight average molecular weight measured by GPC of this polymer was 32,000.
To 1.00 g of the polyamic acid ester, 19.0 g of GBL was added and stirred at room temperature for 30 minutes to dissolve. To this solution was added 0.35 g N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl L-histidine and 5.0 g BC to give an approximately 5.6 wt% solution. And named as polyamic acid ester solution (PAE-1).

<Preparation of polymerizable liquid crystal composition>
[Example 4]
A polymerizable liquid crystal composition (LC-1) was prepared by the following method.
0.2040 g of the compound (2-1-3-1) and 0.3060 g of the compound (2-1-19-1) were dissolved in 2.49 g of cyclohexanone, and 0.0306 g of Irg-907 and 0.0153 g Of TEGOFlow 370 was further added and dissolved.
In the preparation of the polymerizable liquid crystal composition (LC-1), the corresponding compound and the amount thereof are changed as shown in Table 2 to change the polymerizable liquid crystal composition (LC-2) to the polymerizable liquid crystal composition. (LC-17) was prepared. However, the amount of cyclohexane was adjusted so that the total amount of the polymerizable liquid crystal compounds in the polymerizable liquid crystal composition was 17% by weight.

<Creation of photo-alignment film>
[Example 5]
A substrate with a photo-alignment film was prepared by the following procedure.
(1) Prepare the solutions in Table 3,
(2) NMP is added to the mixed solution to obtain a polyamic acid blend solution having a polymer solid concentration of 4% by weight,
(3) The blend solution is spin-coated on a glass substrate at 2000 rpm,
(4) The glass substrate is placed on a hot plate at 80 ° C., the solvent of the blend solution is evaporated for 1 minute, and a coating film is formed.
(5) The coating film was irradiated with linearly polarized light having a wavelength of 365 nm at an energy of ² J / cm ² from a direction of 90 degrees with respect to the coated surface at room temperature.
(6) Thereafter, it was baked in an oven set at 220 ° C. for 30 minutes to obtain a photo-alignment film.

Moreover, the base material (AF-6) using a polyamic acid solution (PA-6) was created in the following procedures. NMP was added to the polyamic acid solution (PA-6) to obtain a polyamic acid having a polymer solid content concentration of 4% by weight. The solution was spin-coated on a glass substrate at a rotational speed of 2000 rpm, the solvent was evaporated on a hot plate at 80 ° C. for 1 minute, and then baked in an oven at 220 ° C. for 10 minutes to form a coating film. The coating film was irradiated with linearly polarized light having a wavelength of 254 nm from a direction of 90 degrees with respect to the coated surface. The irradiation energy at this time was 5.0 J / cm ² . ) Thereafter, it was immersed in an ethyl lactate solution at room temperature for 3 minutes, rinsed with IPA for 1 minute, and dried in an oven at 80 ° C. for 10 minutes to obtain a substrate (AF-6).

Furthermore, the base material (AF-7) using the polyamic acid ester solution (PAE-1) was prepared by the following procedure. A polyamic acid ester solution (PAE-1) was spin-coated on a glass substrate at a rotational speed of 2500 rpm, the solvent was evaporated on a hot plate at 80 ° C. for 1 minute, and then baked in an oven at 220 ° C. for 10 minutes. A coating was created. The coating film was irradiated with linearly polarized light having a wavelength of 254 nm from a direction of 90 degrees with respect to the coated surface. The irradiation energy at this time was 1.0 J / cm ² . After that, 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 substrate (AF-7).

<Production of liquid crystal polymer film with substrate>
[Example 6]
A liquid crystal polymer film with a substrate was prepared by the following procedure.
(1) The base material described in Table 4 was coated with the polymerizable liquid crystal composition described in Table 5 by spin coating at 1000 rpm to form a film.
(2) The film was heated on a hot plate at 80 ° C. for 3 minutes, cooled at room temperature for 3 minutes,
(3) The film was irradiated in a nitrogen stream at room temperature from a direction of 90 degrees with respect to the coated surface until the exposure amount to the film reached 1.0 J / cm ^2. A liquid crystal polymer film was obtained. According to measurement by UVD-S365 manufactured by USHIO INC., The illuminance of ultraviolet rays at this time was 30 mW / cm ² .
(4) After that, it was baked at 220 ° C. for 30 minutes, and the name of the liquid crystal polymer film with a substrate shown in Table 5 was named.

At the end of the procedure (3) in the production of the liquid crystal polymer film (RF-1) with the substrate (RF-28), these liquid crystal polymer films with the substrate have no alignment defect and are homogeneously oriented. Met.
At the end of the procedure (4) in the production of the liquid crystal polymer film (RF-1) with a substrate (RF-28), these liquid crystal polymer films with a substrate have no alignment defect and are homogeneously oriented. Met.
The liquid crystal polymer film with a base material at the end of the procedure (3) in the production of the liquid crystal polymer film with a base material (RF-1) was named a liquid crystal polymer film with a base material (RF-1b).

<Optical properties and adhesion of liquid crystal polymer film with substrate>
[Example 7]
Table 5 shows the retardation, Δn, contrast, wavelength dispersion, and power of the liquid crystal polymer film with a substrate.

  In Table 5, “-” indicates that a numerical value is not obtained due to lack of data or no measurement.

As shown in Table 5, the liquid crystal polymer film with a substrate made from the polymerizable composition of the present invention has a high contrast.

<Imidation ratio of photo-alignment film>
[Example 8]
In the preparation method of the base material with the photo-alignment film, the base material with the photo-alignment film was prepared under the conditions of the solution, light beam and exposure amount shown in Table 6, and the name of the base material shown in Table 6 was named. Named. The imidization ratio of the alignment film of each substrate was measured and listed in Table 6.

表５に記載の枡数から、配向膜中に含まれるプロトン供与基の含有量が、繰り返し単位に対して０．１以上の場合、密着性が高いことがわかった。
表５に記載の実験結果にかかるプロトン供与基は、ヒドロキシル基やアミノ基である。

From the numbers in Table 5, it was found that the adhesion was high when the content of the proton donating group contained in the alignment film was 0.1 or more with respect to the repeating unit.
The proton donating groups according to the experimental results described in Table 5 are hydroxyl groups and amino groups.

[Comparative Example 1]
A photo-alignment film (AF-1 / AF-1 /) was used in accordance with Example 3, except that a polyamic acid solution (PA-1) and a polyamic acid solution (PA-I) were used, and the firing temperature in the photo-alignment film preparation conditions was 100 ° C. I-2) was prepared. On this photo-alignment film, a polymerizable liquid crystal composition (LC-1) was formed according to Example 4 to obtain a liquid crystal polymer (RF-1-2).
Next, the imidation ratio of the component (AF-1-2) in contact with the liquid crystal polymer (polymer of LC-1) of the photo-alignment film (AF-1 / I-2) was measured in the same manner as in Example 7. As a result, it was 0%.
Table 7 shows the characteristics of the liquid crystal polymer films.

When the imidation ratio is low and the content of the carboxyl group contained in the alignment film is 2 or more with respect to the repeating unit, prepared using the polyamic acid represented by the repeating unit of the above formula (1), the contrast Is significantly reduced.

[Comparative Example 2]
<Synthesis of Comparative Compound (Ref. 1)>

（Ｒｅｆ．１）

(Ref. 1)

（２Ｍ−２１−１−１）

(2M-21-1-1)

Compound (IM-1) was synthesized by the method described in Japanese Patent No. 5453798. Compound (IM-2) was synthesized by the method described in Example 5 of JP-A-2006-047813. 5.0 g (21 mmol) of compound (IM-1), 14.5 g (45.2 mmol) of compound (IM-2) and 0.25 g (2.0 mmol) of DMAP were added to 80 ml of dichloromethane, and nitrogen atmosphere was added. Stirring with cooling under. Thereto was added dropwise 20 ml of a dichloromethane solution in which 10.2 g (49.4 mmol) of DCC was dissolved. After dropwise addition, the mixture was stirred overnight at room temperature. The deposited precipitate was filtered off, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography and recrystallized from methanol to obtain 12.5 g of a compound (Ref. 1). Here, the packing material for column chromatography is silica gel. Here, the eluent is a toluene-ethyl acetate mixture v / v = 10/1. Compound (Ref. 1) had a melting point of 81.7 ° C.

<Preparation of polymerizable liquid crystal composition>
0.2550 g of compound (Ref. 1) and 0.2550 g of compound (2M-21-1-1) were dissolved in 2.49 g of cyclohexanone, and 0.0306 g of Irg-907 and 0.0153 g of TEGOFlow 370 were further added. In addition, it was dissolved to obtain a polymerizable liquid crystal composition (RefLC-1).

<Preparation of liquid crystal polymer film with substrate and properties of polymer film>
In the same manner as in Example 5, a liquid crystal polymer film with a substrate was prepared using the polymerizable liquid crystal composition (RefLC-1) and the substrate (AF-4 / II). The characteristics of this polymerized film are shown in Table 8.

Claims (12)

A polymerizable liquid crystal composition containing a compound represented by the formula (2) is applied on an alignment film prepared by firing a composition containing a polymer represented by the repeating unit of the formula (1). Liquid crystal polymer films prepared by polymerizing the polymerizable liquid crystal composition.

(In Formula (1), R ¹ is independently a tetravalent group, R ² is independently a divalent functional group, and R ³ is independently a hydrogen atom or a monovalent group. )

(In Formula (2), R ⁴ represents a divalent group in which 5 to 9 alicyclic and / or aromatic rings are combined, SP ¹ and SP ² represent a spacer group, and PG ¹ and PG ² Is an alkyl group, an alkoxyl group, a cyano group, fluorine or a polymerizable functional group, one of which is a polymerizable functional group.) The liquid crystal polymer film according to claim 1, wherein the content of the hydroxyl group, amino group, or carboxyl group contained in the alignment film is 0.1 or more and less than 2 with respect to the repeating unit of the formula (1). The liquid crystal polymer film according to claim 1, which is prepared by polymerizing the polymerizable liquid crystal composition and then baking it at 140 ° C or higher. The liquid crystal polymer film according to any one of claims 1 to 3, wherein the alignment film is a photo-alignment film. The liquid crystal polymer film according to claim 4, wherein the photosensitive group in the photo-alignment film has an azobenzene structure, a cyclobutane structure, a cinnamic acid structure, a chalcone structure, or a coumarin derivative structure. The liquid crystal polymer film according to any one of claims 1 to 5, which has a characteristic of a positive A plate. The liquid crystal polymer film according to any one of claims 1 to 6, wherein R ¹ in the formula (1) is represented by any ^one of the formulas (1-A) to (1-D).

The liquid crystal polymer film according to claim 7, wherein R ² in the formula (1) is a group represented by any one of the formulas (1-F) to (1-N).

The liquid crystal polymer film according to claim 8, comprising a compound represented by the formula (2-A).

(In formula (2-A), R ^4A is independently a group represented by formula (2-Aa) to formula (2-Ao) below,

(In the formula (2-Aa) to the formula (2-Ao),
* Indicates the binding position to SP ^1A or SP ^2A ,
Ar is an aromatic group having up to 14 carbon atoms or an aromatic conjugated group,
X ⁵⁰ is —NH—, —O— or —S—,
X ⁵¹ is ═CH— or ═N—,
R ⁵⁰ is a single bond or —CH═CH—,
R ⁵¹ is —CO ₂ R ⁵¹¹ or —CN,
R ⁵¹¹ represents an alkyl group having 10 or less carbon atoms, and the hydrogen of one methylene or methyl group in the alkyl group may be substituted with a (meth) acryloxy group,
R ⁵² represents a hydrogen atom or an alkyl group having 10 or less carbon atoms, and the hydrogen of one methylene or methyl group in the alkyl group may be substituted with a (meth) acryloxy group,
R ⁵³ is independently a hydrogen atom, an alkyl group having 5 or less carbon atoms, or an aromatic group having up to 10 carbon atoms,
R ⁵⁴ represents an alkyl group having 5 or less carbon atoms, and two R ⁵⁴ may be bonded to form a ring structure;
In these formulas (2-Aa) to (2-Ao), one hydrogen is an alkyl group having 1 to 5 carbon atoms (provided that any —CH ₂ — of the alkyl group is —O— , —CO—, or —COO— may be substituted, any —CH ₂ —CH ₂ — may be substituted with —CH═CH—, and the hydrogen in the alkyl group is replaced with a halogen group. Or a halogen group,
SP ^1A and SP ^2A are each independently a single bond or alkylene having 2 to 4 carbon atoms, and —CH ₂ — in alkylene may be replaced by —O—, —CO—, or —COO—. ,
SP ^1A and SP ^2A are each independently a single bond or alkylene having 2 to 4 carbon atoms, and —CH ₂ — in alkylene may be replaced by —O—, —CO—, or —COO—. ,
SP ^1A and SP ^2A are each independently a single bond or alkylene having 2 to 4 carbon atoms, and —CH ₂ — in alkylene may be replaced by —O—, —CO—, or —COO—. ,
PG ^1A is a functional group represented by the formula (2-B),

(In the formula (2-B),
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 is (meta ) Acrylic group.
PG ² is an alkyl group, an alkoxyl group, a cyano group, fluorine, or a functional group represented by the formula (2-B),
n is an integer from 5 to 9)   The liquid crystal polymer film according to claim 9, wherein the content of the compound represented by the formula (2-A) in the polymerizable liquid crystal composition is 70% by weight or more based on the other polymerizable compounds.   The liquid crystal polymer film according to claim 9, wherein the polymerizable liquid crystal composition contains only the compound represented by the formula (2-A). A retardation film using the liquid crystal polymer film according to any one of claims 1 to 11.