JP2002098836A - Method for aligning cylindrical liquid-crystalline molecule, optical compensating sheet and polarizing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To orient cylindrical liquid-crystalline molecules perpendicularly to a rubbing direction. SOLUTION: An oriented film is formed using an acrylic acid copolymer having a side chain containing a 10-100C hydrocarbon group, a side chain containing a fluorine substituted hydrocarbon group or a cyclic structure bonding directly to the principal chain.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method of aligning rod-like liquid crystalline molecules using an alignment film. The present invention also relates to an optical compensatory sheet having a transparent support, an alignment film, and an optically anisotropic layer formed of rod-like liquid crystalline molecules in this order, and a polarizing plate using the same.

[0002]

2. Description of the Related Art A liquid crystal display device comprises a liquid crystal cell, a polarizing element, and an optical compensation sheet (retardation plate). In a transmission type liquid crystal display device, two polarizing elements are attached to both sides of a liquid crystal cell, and one or two optical compensation sheets are arranged between the liquid crystal cell and the polarizing element. In a reflection type liquid crystal display device, a reflection plate, a liquid crystal cell, one optical compensation sheet, and one polarization element are arranged in this order. The liquid crystal cell includes a rod-like liquid crystal molecule layer, two substrates for enclosing the same, an electrode layer for applying a voltage to the rod-like liquid crystal molecules, and an alignment film layer for controlling the alignment of the rod-like liquid crystal molecules. The liquid crystal cell has a different alignment state of rod-like liquid crystal molecules.
(Twisted Nematic), IPS (In-Plane Switchin)
g), FLC (Ferroelectric Liquid Crystal), OC
B (Optically Compensatory Bend), STN (Supper
Twisted Nematic), VA (Vertically Aligned), E
CB (Electrically Controlled Birefringence), TN and HAN (Hybrid Aligned Nemat)
ic) and various display modes such as GH (Guest-Host).

[0003] Optical compensatory sheets are used in various liquid crystal display devices in order to eliminate coloring of images and to increase the viewing angle. As the optical compensation sheet, a stretched birefringent polymer film has been conventionally used. It has been proposed to use an optical compensatory sheet having an optically anisotropic layer formed of liquid crystal molecules on a transparent support instead of an optical compensatory sheet made of a stretched birefringent film. Since liquid crystal molecules have various alignment forms, it has become possible to realize optical properties that cannot be obtained by a conventional stretched birefringent polymer film by using liquid crystal molecules.

[0004] The optical properties of the optical compensatory sheet are determined according to the optical properties of the liquid crystal cell, specifically, the above-mentioned difference in display mode. When liquid crystal molecules are used, an optical compensation sheet having various optical properties corresponding to various display modes of a liquid crystal cell can be manufactured. Generally, rod-like liquid crystal molecules or discotic liquid crystal molecules are used as the liquid crystal molecules. As the optical compensation sheet using liquid crystal molecules, ones corresponding to various display modes have already been proposed. For example, an optical compensation sheet for a TN mode liquid crystal cell is disclosed in JP-A-6-214116,
It is described in U.S. Pat. Nos. 5,583,679 and 5,646,703 and German Patent Publication No. 391620A1. An optical compensatory sheet for a liquid crystal cell in the IPS mode or the FLC mode is described in JP-A-10-54982. Further, an optical compensatory sheet for a liquid crystal cell of OCB mode or HAN mode is disclosed in US Pat.
No. 3 and International Patent Application WO 96/37804. Further, an optical compensatory sheet for a liquid crystal cell in the STN mode is described in JP-A-9-26572. An optical compensation sheet for a VA mode liquid crystal cell is described in Japanese Patent No. 2866372.

[0005]

SUMMARY OF THE INVENTION An optical compensatory sheet having an optically anisotropic layer formed from rod-like liquid crystalline molecules,
The average direction of the line obtained by projecting the major axis direction of the rod-like liquid crystal molecules onto the surface of the transparent support corresponds to the slow axis of the optical compensation sheet. The average direction of the line obtained by projecting the major axis direction of the rod-like liquid crystal molecules onto the surface of the transparent support generally corresponds to the rubbing direction of the alignment film. The optical compensatory sheet is in the form of a roll in actual production, and the rubbing treatment is most easily performed in the longitudinal direction of the roll-shaped optical compensatory sheet. Therefore, in an optical compensatory sheet having an optically anisotropic layer formed from rod-like liquid crystalline molecules, an embodiment having a slow axis in the longitudinal direction can be most easily produced. The transmission axis of the polarizing film corresponds to a direction perpendicular to the stretching direction of the polymer film forming the polarizing film. The polarizing element is also in a roll shape in actual production, and it is easiest to perform the stretching process in the longitudinal direction of the roll-shaped polarizing film. Accordingly, a polarizing element having a transmission axis in a direction (width direction) perpendicular to the longitudinal direction can be most easily produced.

From the above relationship, when laminating the roll-shaped optical compensation sheet and the roll-shaped polarizing element, the slow axis of the optical compensation sheet and the transmission axis of the polarizing film are arranged so as to be substantially perpendicular to each other. Is the easiest to produce. On the other hand, depending on the display mode of the liquid crystal cell, it may be preferable to arrange the slow axis of the optical compensation sheet and the transmission axis of the polarizing film so as to be substantially parallel. In order for the slow axis of the roll-shaped optical compensatory sheet to be in the width direction of the optical compensatory sheet, it is necessary to align the rod-like liquid crystalline molecules such that the major axis direction is perpendicular to the rubbing direction of the alignment film. is there. In the present specification, "the major axis direction of the rod-shaped liquid crystalline molecules is perpendicular to the rubbing direction of the alignment film" means that the average direction of a line obtained by projecting the major axis direction of the rod-shaped liquid crystalline molecules on the transparent support surface is referred to. ,
It means perpendicular to the rubbing direction. In order to align the rod-like liquid crystal molecules so as to be perpendicular to the rubbing direction, an alignment film having such an alignment function is required. The conventional alignment film has a function of aligning the rod-like liquid crystal molecules in parallel with the rubbing direction.

An object of the present invention is to align rod-like liquid crystal molecules perpendicular to the rubbing direction. Another object of the present invention is to provide a roll-shaped optical compensation sheet having a slow axis in the width direction. Still another object of the present invention is to provide a polarizing plate that can be easily arranged such that the slow axis of the optical compensation sheet and the transmission axis of the polarizing film are substantially parallel.

[0008]

An object of the present invention is to provide the following (1) to (7) methods for aligning rod-like liquid crystalline molecules, the following (8) optical compensation sheet, the following (9) polarizing plate and This was achieved by the following polymerizable copolymer (10). (1) A coating film is formed by applying a solution of a copolymer containing a repeating unit represented by the following formula (I) and a repeating unit represented by the following formula (II) or (III) on a support: A step of rubbing the surface of the coating film to form an alignment film; and a step of applying a coating liquid containing rod-like liquid crystal molecules on the alignment film and drying the liquid, whereby the long-axis direction of the rod-like liquid crystal molecules is obtained. Of rod-like liquid crystalline molecules such that the average direction of a line obtained by projecting the liquid crystal onto the support surface and the rubbing direction of the alignment film are substantially orthogonal to each other:

[0009]

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Wherein R ¹ and R ² are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; M is a proton, an alkali metal ion or an ammonium ion L ⁰ is -O
-, - CO -, - NH -, - SO 2 -, an alkylene group,
A divalent linking group selected from the group consisting of alkenylene, arylene and combinations thereof;
⁰ is a hydrocarbon group having 10 to 100 carbon atoms or a fluorine atom-substituted hydrocarbon group having 1 to 100 carbon atoms; Cy is an aliphatic ring group, an aromatic group or a heterocyclic group; m is 10-99 mol%; and n
Is 1 to 90 mol%].

(2) The copolymer comprises a repeating unit represented by the formula (I) and a repeating unit represented by the formula (II), wherein in the formula (II), R ⁰ is at least two aromatic compounds. The method according to (1), wherein the rod-shaped liquid crystalline molecule is a hydrocarbon group having 10 to 100 carbon atoms including a ring or an aromatic heterocyclic ring. (3) The rod-shaped liquid crystal molecules have a polymerizable group, and after the rod-shaped liquid crystal molecules are aligned, the rod-shaped liquid crystal molecules are polymerized to fix the alignment state. (1) The rod-shaped liquid crystal molecules are aligned. How to let. (4) The copolymer has a polymerizable group, and after the rod-shaped liquid crystal molecules are aligned, the rod-shaped liquid crystal molecules are polymerized with the copolymer to fix the alignment state. (3) The rod-shaped liquid crystal molecules are aligned. How to let.

(5) The support has a longitudinal direction, and the average direction of a line obtained by projecting the major axis direction of the rod-like liquid crystal molecules onto the support surface is substantially orthogonal to the longitudinal direction of the support. (1) The method for aligning rod-like liquid crystal molecules according to (1). (6) The method according to (1), wherein the support has a longitudinal direction, and the rubbing direction of the alignment film is substantially parallel to the longitudinal direction of the support. (7) The method for aligning rod-like liquid crystal molecules according to (8), wherein the average inclination angle between the major axis direction of the rod-like liquid crystal molecules and the support surface is less than 5 °.

(8) A roll-shaped optical compensation sheet having a transparent support, an alignment film and an optically anisotropic layer formed of rod-shaped liquid crystalline molecules in this order, wherein the alignment film is represented by the formula (I). An average of lines obtained by projecting the major axis direction of rod-like liquid crystalline molecules onto the transparent support surface, comprising a copolymer containing a repeating unit represented by the formula (II) or (III) and a repeating unit represented by the formula (II) or (III). An optical compensatory sheet characterized in that rod-like liquid crystalline molecules are oriented so that the direction is substantially orthogonal to the rubbing direction of the alignment film. (9) an optically anisotropic layer formed from rod-like liquid crystal molecules,
A roll-shaped polarizing plate having an alignment film, a transparent support, a polarizing film, and a transparent protective film in this order, wherein the alignment film is composed of a repeating unit represented by the formula (I) and the formula (II) or (III) ), Wherein the rod-like liquid crystal molecules are oriented in a state in which the average tilt angle between the major axis direction of the rod-like liquid crystal molecules and the transparent support surface is less than 5 °, The average direction of the line obtained by projecting the major axis direction of the rod-like liquid crystal molecules on the transparent support surface and the longitudinal direction of the polarizing plate are substantially orthogonal, and the transmission axis of the polarizing film and the rod-like liquid crystal molecules are A polarizing plate, wherein the average direction of a line obtained by projecting a major axis direction onto a surface of a transparent support is substantially parallel.

(10) A polymerizable copolymer containing a repeating unit represented by the following formula (I), a repeating unit represented by the following formula (III) and a repeating unit represented by the following formula (IX):

[0015]

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Wherein R ¹ , R ² and R ⁶ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; M is a proton, alkali metal ion or ammonium An ion; Cy
Is an aliphatic, aromatic or heterocyclic group; L ²⁶
Is a single bond or a divalent linking group; Q is a polymerizable group; m is 10 to 99 mol%; n is 1 to 90 mol%; ~ 20 mol%
Is].

In this specification, substantially parallel or substantially orthogonal means that the angle difference between the strict parallel and the strict orthogonal is less than 5 °. Preferably, the angle difference is less than 4 °, more preferably less than 3 °, even more preferably less than 2 °, and most preferably less than 1 °.

[0018]

As a result of the research, the present inventors have found that a side chain containing a hydrocarbon group having 10 to 100 carbon atoms, a side chain containing a fluorine-substituted hydrocarbon group, or a cyclic structure directly connected to the main chain. Using an acrylic acid-based copolymer having
We succeeded in uniformly aligning the rod-like liquid crystal molecules so as to be substantially perpendicular to the rubbing direction. Thereby, an optical compensation sheet in which the rod-like liquid crystalline molecules are oriented substantially perpendicular to the rubbing direction can be manufactured. Therefore, it has become possible to easily produce a roll-shaped optical compensation sheet having a slow axis in a direction (width direction) perpendicular to the longitudinal direction. On the other hand, as described above, a roll-shaped polarizing element having a transmission axis in a direction perpendicular to the longitudinal direction (width direction) can be most easily produced. Therefore, by laminating the roll-shaped optical compensation sheet and the roll-shaped polarizing element according to the present invention in a roll state, a polarizing plate having a slow axis of the optical compensation sheet and a transmission axis of the polarizing film substantially parallel to each other. Can be produced. As described above, by using the optical compensation sheet according to the present invention, the optical compensation sheet can be easily arranged such that the slow axis of the optical compensation sheet and the transmission axis of the polarizing film are substantially parallel.

[0019]

FIG. 1 is a schematic diagram showing the basic structure of a transmission type liquid crystal display device. The transmission type liquid crystal display device shown in FIG. 1A includes a transparent protective film (1a), a polarizing film (2a), a transparent support (3a), and an optically anisotropic layer in order from the backlight (BL) side. (4a), lower substrate (5a) of liquid crystal cell, rod-like liquid crystalline molecular layer (6), upper substrate of liquid crystal cell (5b), optically anisotropic layer (4b), transparent support (3
b), a polarizing film (2b), and a transparent protective film (1b). The transparent support and the optically anisotropic layers (3a to 4a and 4b to 3b) constitute an optical compensation sheet. Then, the transparent protective film, the polarizing film, the transparent support, and the optically anisotropic layers (1a to 4a and 4b to 1b) constitute a polarizing plate. The transparent support (3a, 3b) comprises an optically anisotropic layer (4
a) An alignment film is provided on the 4b) side. In addition, the lower substrate (5a) and the upper substrate (5b) of the liquid crystal cell also have an alignment film on the side of the rod-shaped liquid crystalline molecular layer (6).

The transmission type liquid crystal display device shown in FIG. 1B has a transparent protective film (1) in order from the backlight (BL) side.
a), a polarizing film (2a), a transparent support (3a), an optically anisotropic layer (4a), a lower substrate (5a) of a liquid crystal cell, a rod-shaped liquid crystalline molecular layer (6), and an upper substrate of a liquid crystal cell ( 5b), the transparent protective film (1b), the polarizing film (2b), and the transparent protective film (1
c). Transparent support and optically anisotropic layer (3a
4a) constitute an optical compensation sheet. Then, a transparent protective film, a polarizing film, a transparent support and an optically anisotropic layer (1a
To 4a) constitute a polarizing plate. The transparent support (3a)
An alignment film is provided on the optically anisotropic layer (4a) side. In addition, the lower substrate (5a) and the upper substrate (5b) of the liquid crystal cell also have an alignment film on the side of the rod-shaped liquid crystalline molecular layer (6).

The transmission type liquid crystal display device shown in FIG. 1C has a transparent protective film (1) in order from the backlight (BL) side.
a), a polarizing film (2a), a transparent protective film (1b), a lower substrate (5a) of a liquid crystal cell, a rod-like liquid crystalline molecular layer (6), an upper substrate (5b) of a liquid crystal cell, and an optically anisotropic layer ( 4b), a transparent support (3b), a polarizing film (2b), and a transparent protective film (1
c). Transparent support and optically anisotropic layer (4b
3b) constitute an optical compensation sheet. Then, a transparent protective film, a polarizing film, a transparent support, and an optically anisotropic layer (4b
To 1c) constitute a polarizing plate. The transparent support (3b)
An alignment film is provided on the optically anisotropic layer (4b) side. In addition, the lower substrate (5a) and the upper substrate (5b) of the liquid crystal cell also have an alignment film on the side of the rod-shaped liquid crystalline molecular layer (6).

FIG. 2 is a schematic diagram showing a basic configuration of a reflection type liquid crystal display device. The reflection type liquid crystal display device shown in FIG. 2 includes, in order from the bottom, a lower substrate (5a) of a liquid crystal cell, a reflector (RP), a rod-like liquid crystal molecular layer (6), an upper substrate (5b) of the liquid crystal cell, Anisotropic layer (4), transparent support (3),
It comprises a polarizing film (2) and a transparent protective film (1). The transparent support and the optically anisotropic layer (4 to 3) constitute an optical compensation sheet. Then, the transparent protective film, the polarizing film, the transparent support, and the optically anisotropic layer (4-1) constitute a polarizing plate. The transparent support (3) has an alignment film on the optically anisotropic layer (4) side. Further, the reflection plate (RP) and the upper substrate (5b) of the liquid crystal cell also have an alignment film on the rod-like liquid crystal molecular layer (6) side.

FIG. 3 is a schematic view showing a step of bonding a roll-shaped polarizing element and a roll-shaped optical compensation sheet. As shown in FIG. 3, the roll-shaped polarizing element includes a transparent protective film (1) and a polarizing film (2). The roll-shaped optical compensation sheet comprises a transparent support (3) and an optically anisotropic layer (4). The transparent support (3) has an alignment film on the optically anisotropic layer (4) side. The transmission axis of the polarizing film (2) (T
A) is substantially orthogonal to the longitudinal direction (LD) of the roll-shaped polarizing element. The average direction of the line obtained by projecting the major axis direction of the rod-like liquid crystalline molecules of the optically anisotropic layer (4) onto the transparent support surface, that is, the slow axis (SA) is the longitudinal direction of the roll-shaped optical compensation sheet. (LD) is substantially orthogonal. Therefore, as shown in FIG. 3, the transmission axis (TA) of the polarizing film (2) and the retardation of the optically anisotropic layer (4) can be obtained simply by bonding the roll-shaped polarizing element and the roll-shaped optical compensation sheet as they are. It can be arranged such that the phase axis (SA) is substantially parallel. 1 to 3, the order of the transparent support (3) and the optically anisotropic layer (4) may be reversed.

[Alignment Film] The alignment film is made of an acrylic acid copolymer containing a repeating unit represented by the following formula (I) and a repeating unit represented by the following formula (II) or (III).

[0025]

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In the formula (I), R ¹ is a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms. R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, methyl or ethyl, and most preferably a hydrogen atom or methyl. When R ¹ is a hydrogen atom, it is an acrylic acid copolymer, and when R ¹ is methyl, it is a methacrylic acid copolymer. In the formula (I), M is a proton, an alkali metal (eg, Na, K)
Ion or ammonium ion. Ammonium ion is substituted by an organic group (eg, methyl) (primary to quaternary)
Class). Examples of ammonium ions include:
NH ₄ , NH ₃ CH ₃ , NH ₂ (CH ₃ ) ₂ , NH (C
H _{3) 3} and N (CH _{3) 4} are included. By the fact that COOM of formula (I) is such a hydrophilic group,
Acrylic acid copolymers are water-soluble. Therefore, an alignment film can be formed using an aqueous solvent. Formula (I)
In the formula, m is from 10 to 99 mol%. m is 1
0 to 95 mol%, preferably 25 to 90 mol%.
More preferably, it is mol%.

In the formula (II), R ² is a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms. R ² is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, methyl or ethyl, and most preferably a hydrogen atom or methyl.

In the formula (II), L ⁰ represents —O—, —C
O -, - NH -, - SO 2 -, an alkylene group, an alkenylene group, a divalent linking group selected from the group consisting of arylene groups and combinations thereof. L ⁰ is -CO
-L ⁰⁰ -(-CO- is bonded to the main chain, and L ⁰⁰ is-
O -, - CO -, - NH -, - SO 2 -, an alkylene group, an alkenylene group, a divalent linking group selected from the group consisting of arylene groups and combinations thereof) is particularly preferred.

L ⁰ is -CO-O-, -CO-O-alkylene group-, -CO-O-alkylene group-alkenylene group-, -CO-O-alkylene group-arylene group-,-
CO-O-alkylene group -O-, -CO-O-alkylene group -O-CO-, -CO-O-alkylene group -NH-
SO ₂ -arylene group -O-, -CO-O-alkylene group -O-CO-alkylene group -O-, -CO-O-alkylene group -CO-NH-, -CO-O-alkylene group-
_{NH-SO 2 -, - CO} -O- alkylene group -O-CO
-Arylene group-, -CO-NH-, -CO-NH-arylene group-, -CO-NH-arylene group -CO-O
-, -CO-O-arylene group -O-CO-alkylene group -O-arylene group-, -CO-O-arylene group-, -CO-NH-arylene group -NH-CO-, -C
O-NH-arylene group -O-, -CO-O-alkylene group -CO-O-, -CO-O-alkylene group -CO
-, -CO-O-arylene group -CO-O- or -C
O-NH- is preferably an alkylene group -NH-CO-O- in which, -CO-O -, - CO -O- alkylene group -NH-SO ₂ - arylene group -O -, - CO-NH
-, -CO-NH-arylene group -O-, -CO-O-
An alkylene group-, -CO-O-alkylene group-arylene group- or -CO-O-alkylene group -O-CO-arylene group- is more preferable, and -CO-O
-Or -CO-NH- is most preferred. In these linking groups, the left side is bonded to the main chain, and the right side is R
^Bind to ⁰ .

The alkylene group may have a branched or cyclic structure. The number of carbon atoms in the alkylene group is 1
It is preferably from 30 to 30, more preferably from 1 to 15, and most preferably from 1 to 12. The alkenylene group may have a branched or cyclic structure. The alkylene group has 2 to 3 carbon atoms.
It is preferably 0, more preferably 2 to 16, and most preferably 2 to 4. The arylene group is preferably phenylene or naphthylene, more preferably phenylene, and most preferably p-phenylene. The arylene group may have a substituent. Examples of the substituent of the arylene group include a halogen atom, carboxyl, cyano, nitro, carbamoyl, sulfamoyl, an alkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group, an acyl group, an acyloxy group, an alkyl-substituted carbamoyl group, and an alkyl-substituted sulfamoyl. Groups, amide groups, sulfonamide groups and alkylsulfonyl groups.

In the formula (II), R ⁰ is a hydrocarbon group having 10 to 100 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 100 carbon atoms. The hydrocarbon group is an aliphatic group, an aromatic group, or a combination thereof. The aliphatic group may be cyclic, branched, or linear. The aliphatic group is preferably an alkyl group (may be a cycloalkyl group) or an alkenyl group (may be a cycloalkenyl group). The hydrocarbon group may have a substituent that does not show strong hydrophilicity, such as a halogen atom. The number of carbon atoms in the hydrocarbon group is 1
It is preferably 0 to 80, more preferably 10 to 60, and most preferably 10 to 40.

The hydrocarbon group preferably has a steroid structure. In the present specification, the steroid group means a cyclopentanohydrophenanthrene ring group or a ring group in which a part of the bond of the ring is a double bond. The hydrocarbon group having a steroid group preferably has 18 to 100 carbon atoms, more preferably 19 to 60, and most preferably 20 to 40. Further, the hydrocarbon group also preferably contains at least two aromatic rings or aromatic heterocycles. A hydrocarbon group containing at least two aromatic rings or aromatic heterocycles and a repeating unit having the same in a side chain will be described later.

The hydrocarbon group of the fluorine atom-substituted hydrocarbon group is an aliphatic group, an aromatic group or a combination thereof. The aliphatic group may be cyclic, branched or linear. The aliphatic group is preferably an alkyl group (may be a cycloalkyl group) or an alkenyl group (may be a cycloalkenyl group). The aliphatic group may have a substituent that does not show strong hydrophilicity, such as another halogen atom, in addition to the fluorine atom. The fluorine atom-substituted hydrocarbon group preferably has 5 to 80 carbon atoms, more preferably 10 to 60, and most preferably 10 to 40. The rate at which the hydrogen atoms of the hydrocarbon groups are replaced by fluorine atoms is
It is preferably 50 to 100 mol%, more preferably 70 to 100 mol%, and 80 to 10 mol%.
0 mol%, more preferably 90 to 100
Most preferably, it is mol%.

In the formula (II), n is 1 to 90 mol%. n is preferably from 5 to 80 mol%, more preferably from 10 to 70 mol%.
Hereinafter, a repeating unit represented by the formula (II) wherein R ⁰ is a hydrocarbon group having 10 to 100 carbon atoms (excluding a hydrocarbon group containing at least two aromatic rings or aromatic heterocycles). The example of a unit (HyC) is shown.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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In the following, R ⁰ has 10 to 10 carbon atoms.
Examples of an acrylic acid-based copolymer containing a repeating unit (HyC) represented by the formula (II) that is a hydrocarbon group of 0 (excluding a hydrocarbon group containing at least two aromatic rings or aromatic heterocycles) Is shown. AA is a repeating unit derived from acrylic acid, and MA is a repeating unit derived from methacrylic acid. The ratio of repeating units is mol%
It is.

PA1:-(AA) 60- (HyC1) 40- PA2:-(AA) 70- (HyC1) 30- PA3:-(AA) 60- (HyC2) 40- PA4:-(AA) 75- (HyC2) 25-PA5 :-( AA) 65- (HyC3) 35-PA6 :-( AA) 80- (HyC3) 30- PA7 :-( AA) 60- (HyC4) 40-PA8 :-( AA) 70- (HyC4) 30-PA9 :-( AA) 70- (HyC5) 30- PA10 :-( AA) 80- (HyC5) 20- PA11 :-( AA) 60- (HyC6) 40- PA12 :-( AA) 70- (HyC6) 30- PA13 :-( AA) 60- (HyC7) 40- PA14 :-( AA) 70- (HyC7) 30- PA15 :-( AA) 60- (HyC8) 40-P A16:-(AA) 85- (HyC8) 15- PA17:-(AA) 60- (HyC9) 40- PA18:-(AA) 70- (HyC9) 30- PA19:-(AA) 60- (HyC10) 40- PA20:-(AA) 70- (HyC10) 30-

PA21:-(AA) 60- (HyC11) 40- PA22:-(AA) 85- (HyC11) 15- PA23:-(AA) 60- (HyC12) 40- PA24:-(AA) 50- (HyC12) 50-PA25 :-( AA) 60- (HyC13) 40- PA26 :-( AA) 50- (HyC13) 50- PA27 :-( AA) 60- (HyC14) 40-PA28 :-( AA) 70- (HyC14) 30- PA29 :-( AA) 50- (HyC15) 50- PA30 :-( AA) 60- (HyC15) 40- PA31 :-( AA) 80- (HyC16) 20- PA32 :-( AA) 70- (HyC16) 30- PA33 :-( AA) 85- (HyC17) 15- PA34 :-( AA) 70- (HyC17) 30- A35 :-( AA) 60- (HyC18) 40- PA36 :-( AA) 70- (HyC18) 30- PA37 :-( AA) 80- (HyC19) 20- PA38 :-( AA) 70- (HyC19) 30- PA39:-(AA) 60- (HyC20) 40- PA40:-(AA) 70- (HyC20) 30-

PA41:-(AA) 60- (HyC21) 40- PA42:-(AA) 70- (HyC21) 30- PA43:-(AA) 60- (HyC22) 40- PA44:-(AA) 70- (HyC22) 30-PA45 :-( AA) 90- (HyC23) 10- PA46 :-( AA) 80- (HyC23) 20- PA47 :-( AA) 90- (HyC24) 10-PA48 :-( AA) 80- (HyC24) 20- PA49 :-( AA) 85- (HyC25) 15- PA50 :-( AA) 70- (HyC25) 30- PA51 :-( AA) 60- (HyC26) 40- PA52 :-( AA) 70- (HyC26) 30- PA53 :-( AA) 65- (HyC27) 35- PA54 :-( AA) 60- (HyC27) 40- A55:-(AA) 75- (HyC28) 25- PA56:-(AA) 60- (HyC28) 40- PA57:-(AA) 60- (HyC29) 40- PA58:-(AA) 70- (HyC29) 30- PA59:-(AA) 60- (HyC30) 40- PA60:-(AA) 70- (HyC30) 30-

PA61:-(AA) 60- (HyC31) 40- PA62:-(AA) 70- (HyC31) 30- PA63:-(AA) 80- (HyC32) 20- PA64:-(AA) 70- (HyC32) 30-PA65 :-( AA) 80- (HyC33) 20- PA66 :-( AA) 70- (HyC33) 30- PA67 :-( AA) 60- (HyC34) 40-PA68 :-( AA) 70- (HyC34) 30- PA69 :-( AA) 90- (HyC35) 10- PA70 :-( AA) 80- (HyC35) 20- PA71 :-( AA) 60- (HyC36) 40- PA72 :-( AA) 50- (HyC36) 50- PA73 :-( AA) 60- (HyC37) 40- PA74 :-( AA) 70- (HyC37) 30- A75 :-( AA) 90- (HyC38) 10- PA76 :-( AA) 80- (HyC38) 20- PA77 :-( AA) 60- (HyC39) 40- PA78 :-( AA) 70- (HyC39) 30- PA79:-(AA) 80- (HyC40) 20- PA80:-(AA) 70- (HyC40) 30-

PA81:-(AA) 60- (HyC41) 40- PA82:-(AA) 70- (HyC41) 30- PA83:-(AA) 60- (HyC42) 40- PA84:-(AA) 70- (HyC42) 30- PA85 :-( MA) 70- (HyC1) 30- PA86 :-( MA) 60- (HyC2) 40- PA87 :-( MA) 70- (HyC3) 30- PA88 :-( MA) 60- (HyC4) 40- PA89 :-( MA) 70- (HyC5) 30- PA90 :-( MA) 60- (HyC6) 40- PA91 :-( MA) 70- (HyC7) 30- PA92 :-( MA) 60- (HyC8) 40- PA93 :-( MA) 70- (HyC9) 30- PA94 :-( MA) 60- (HyC10) 40- PA95 :-( MA 70- (HyC11) 30- PA96 :-( MA) 60- (HyC12) 40- PA97 :-( MA) 70- (HyC13) 30- PA98 :-( MA) 60- (HyC14) 40- PA99 :-( MA) 70- (HyC15) 30- PA100 :-( MA) 60- (HyC16) 40-

PA101:-(MA) 70- (HyC17) 30- PA102:-(MA) 60- (HyC18) 40- PA103:-(MA) 70- (HyC19) 30- PA104:-(MA) 60- (HyC20) 40- PA105 :-( MA) 60- (HyC21) 40- PA106 :-( MA) 60- (HyC22) 40- PA107 :-( MA) 60- (HyC23) 40- PA108 :-( MA) 60- (HyC24) 40- PA109 :-( MA) 60- (HyC25) 40- PA110 :-( MA) 60- (HyC26) 40- PA111 :-( MA) 60- (HyC27) 40- PA112 :-( MA) 60- (HyC28) 40- PA113 :-( MA) 60- (HyC29) 40- PA114 :-( MA 60- (HyC30) 40- PA115 :-( MA) 60- (HyC31) 40- PA116 :-( MA) 60- (HyC32) 40- PA117 :-( MA) 60- (HyC33) 40- PA118 :-( MA) 60- (HyC34) 40- PA119 :-( MA) 60- (HyC35) 40- PA120 :-( MA) 60- (HyC36) 40- PA121 :-( MA) 60- (HyC37) 40-PA122: -(MA) 60- (HyC38) 40- PA123 :-( MA) 60- (HyC39) 40- PA124 :-( MA) 60- (HyC40) 40- PA125 :-( MA) 60- (HyC41) 40- PA126:-(MA) 60- (HyC42) 40-

In the following, R ⁰ has 1 to 100 carbon atoms.
Of the repeating unit (FRU) represented by the formula (II), which is a fluorine atom-substituted hydrocarbon group of

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The following is an example of an acrylic acid copolymer containing a repeating unit (FRU) represented by the formula (II) wherein R ⁰ is a fluorine atom-substituted hydrocarbon group of 1 to 100.
AA is a repeating unit derived from acrylic acid,
MA is a repeating unit derived from methacrylic acid. The ratio of the repeating unit is mol%.

PA201 :-( AA) 60- (FRU1) 40- PA202 :-( AA) 70- (FRU1) 30- PA203 :-( AA) 60- (FRU2) 40- PA204 :-( AA) 70- (FRU2) 30-PA205 :-( AA) 70- (FRU3) 30- PA206 :-( AA) 80- (FRU3) 20- PA207 :-( AA) 70- (FRU4) 30-PA208 :-( AA) 80- (FRU4) 20- PA209 :-( AA) 60- (FRU5) 40- PA210 :-( AA) 70- (FRU5) 30- PA211 :-( AA) 60- (FRU6) 40- PA212 :-( AA) 70- (FRU6) 30- PA213 :-( AA) 60- (FRU7) 40- PA214 :-( AA) 70- (FRU7) 30- A215:-(AA) 60- (FRU8) 40- PA216:-(AA) 50- (FRU8) 50- PA217:-(AA) 60- (FRU9) 40- PA218:-(AA) 70- (FRU9) 30- PA219:-(AA) 60- (FRU10) 40- PA220:-(AA) 70- (FRU10) 30-

PA221 :-( AA) 60- (FRU11) 40- PA222 :-( AA) 50- (FRU11) 50- PA223 :-( AA) 60- (FRU12) 40- PA224 :-( AA) 70- (FRU12) 30-PA225 :-( AA) 80- (FRU13) 20- PA226 :-( AA) 75- (FRU13) 25-PA227 :-( AA) 60- (FRU14) 40-PA228 :-( AA) 70- (FRU14) 30- PA229 :-( AA) 85- (FRU15) 15- PA230 :-( AA) 75- (FRU15) 25- PA231 :-( AA) 60- (FRU16) 40- PA232 :-( AA) 70-(FRU16) 30-PA233:-(AA) 60-(FRU17) 40-PA234:-(AA 70- (FRU17) 30- PA235 :-( AA) 60- (FRU18) 40- PA236 :-( AA) 50- (FRU18) 50- PA237 :-( AA) 60- (FRU19) 40- PA238 :-( AA) 70-(FRU19) 30-PA239:-(AA) 60-(FRU20) 40-PA240:-(AA) 70-(FRU20) 30-

PA241 :-( MA) 60- (FRU1) 40- PA242 :-( MA) 60- (FRU2) 40- PA243 :-( MA) 60- (FRU3) 40- PA244 :-( MA) 60- (FRU4) 40-PA245 :-( MA) 60- (FRU5) 40- PA246 :-( MA) 60- (FRU6) 40- PA247 :-( MA) 60- (FRU7) 40- PA248 :-( MA) 60- (FRU8) 40- PA249 :-( MA) 60- (FRU9) 40- PA250 :-( MA) 60- (FRU10) 40- PA251 :-( MA) 60- (FRU11) 40- PA252 :-( MA) 60- (FRU12) 40- PA253 :-( MA) 60- (FRU13) 40- PA254 :-( MA) 60- (FRU1 ) 40- PA255 :-( MA) 60- (FRU15) 40- PA256 :-( MA) 60- (FRU16) 40- PA257 :-( MA) 60- (FRU17) 40- PA258 :-( MA) 60- (FRU18) 40- PA259 :-( MA) 60- (FRU19) 40- PA260 :-( MA) 60- (FRU20) 40-

A polymerizable group may be introduced into the acrylic copolymer. When an acrylic acid-based copolymer having a polymerizable group and a rod-shaped liquid crystal molecule having a polymerizable group are used in combination, the acrylic acid-based copolymer and the rod-shaped liquid crystal molecule are chemically formed through the interface between the liquid crystal layer and the alignment film. Can be combined. Thereby, the durability of the liquid crystal element using the rod-like liquid crystal molecules can be improved. The polymerizable group undergoes a polymerization reaction with a polymerizable group (Q) of a rod-like liquid crystal molecule described later to chemically form the rod-like liquid crystal molecule and the acrylic acid-based copolymer via the interface between the liquid crystal layer and the alignment film. Join. Therefore, the type of the polymerizable group is determined according to the type of the polymerizable group (Q) of the rod-like liquid crystal molecule described below. The polymerizable group (Q) of the rod-like liquid crystal molecule is preferably an unsaturated polymerizable group (Q1 to Q7 described below), an epoxy group (Q8) or an aziridinyl group (Q9), as described later. It is more preferably an unsaturated polymerizable group, and most preferably an ethylenically unsaturated polymerizable group (Q1 to Q6). The polymerizable group of the acrylic acid-based copolymer is also preferably an unsaturated polymerizable group, an epoxy group or an aziridinyl group, more preferably an unsaturated polymerizable group, and more preferably an ethylenically unsaturated polymer, like the rod-shaped liquid crystalline molecules. Most preferably, it is a saturated polymerizable group.

It is preferable that the main chain and the polymerizable group are not directly linked but are linked via a linking group. Examples of linking groups include-
CO-, -CO-O-, -CO-NH-, -CO-NH
-Alkylene group-, -CO-NH-alkylene group-O
-, -CO-NH-alkylene group -CO-O-, -CO
-NH-alkylene group -O-CO-, -CO-NH-alkylene group -CO-NH-, -CO-alkylene group -O
-CO-, -CO-arylene group-O-alkylene group-
O-CO-, -CO-arylene group -O-alkylene group -O-, -CO-arylene group -O-alkylene group- and -CO-alkylene group -O-CO- (the left side is the main chain. And the right side is bonded to the polymerizable group). The alkylene group may have a branched or cyclic structure. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 20,
It is more preferably 1 to 15, and most preferably 1 to 12. The arylene group is preferably phenylene or naphthylene, more preferably phenylene, and most preferably p-phenylene. The arylene group may have a substituent. Examples of the substituent of the arylene group include a halogen atom (F, Cl, Br), carboxyl, cyano, nitro, carbamoyl, sulfamoyl, alkyl group, cycloalkyl group, alkoxy group, alkylthio group, acyl group, acyloxy group, alkyl Includes substituted carbamoyl, alkyl-substituted sulfamoyl, amide, sulfonamide and alkylsulfonyl groups.

The above alkyl group may have a branch. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and preferably 1 to 15 carbon atoms.
It is more preferably from 10 to 10, and most preferably from 1 to 6. The cycloalkyl group is preferably cyclohexyl. The alkoxy group is
It may have a branch. The alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 15, more preferably 1 to 10, and most preferably 1 to 6. The alkylthio group may have a branch. The number of carbon atoms of the alkylthio group is preferably 1 to 20, more preferably 1 to 15, and more preferably 1 to 10
Is more preferable, and most preferably 1 to 6. The acyl group has 2 to 20 carbon atoms.
Is preferably 2 to 15, more preferably 2 to 10, and most preferably 2 to 6. The acyloxy group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, further preferably 2 to 10 carbon atoms, and most preferably 2 to 6 carbon atoms.

The alkyl-substituted carbamoyl group preferably has 2 to 20 carbon atoms, and preferably has 2 to 15 carbon atoms.
Is more preferable, 2 to 10 is more preferable, and 2 to 6 is most preferable. The alkyl part of the alkyl-substituted carbamoyl group may further have a substituent (eg, an alkoxy group). The alkyl-substituted sulfamoyl group has 2 to 2 carbon atoms.
It is preferably 0, more preferably 2 to 15, further preferably 2 to 10, and 2
It is most preferably from 6 to 6. The alkyl part of the alkyl-substituted sulfamoyl group may further have a substituent (eg, an alkoxy group). The amide group preferably has 2 to 20 carbon atoms, and preferably has 2 to 15 carbon atoms.
Is more preferable, 2 to 10 is more preferable, and 2 to 6 is most preferable. The number of carbon atoms of the sulfonamide group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and more preferably 1 to 6.
Is most preferred. The alkylsulfonyl group preferably has 1 to 20 carbon atoms,
It is more preferably from 15 to 15, further preferably from 1 to 10, and most preferably from 1 to 6. The alkyl part of the alkylsulfonyl group may further have a substituent (eg, an alkoxy group).

The side chain may have two or more polymerizable groups. The polymerizable group is introduced into the acrylic acid copolymer as a repeating unit having a polymerizable group in the side chain, or a polymerizable group is introduced into the repeating unit having the hydrocarbon group or the fluorine atom-substituted hydrocarbon group. . The repeating unit having a polymerizable group in the side chain and the repeating unit having a hydrocarbon group or a fluorine atom-substituted hydrocarbon group and a polymerizable group are described in this order. The repeating unit having a polymerizable group in the side chain is preferably represented by the following formula (IV).

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In the formula (IV), R ³ is a hydrogen atom or methyl. In the formula (IV), L ¹¹ represents —NH—
Alkylene group -O-CO-, -alkylene group -O-CO
-, -O-alkylene group -O-CO-, -O-arylene group -O-alkylene group -O-CO-, -O-arylene group -O-alkylene group-, -O-arylene group -O
-, -NH-alkylene group -O-CO-, -NH-alkylene group -O- and -NH-alkylene group-. -NH-alkylene group-
O-CO-, -alkylene group -O-CO-, -O-alkylene group -O-CO-, -O-arylene group -O-alkylene group -O-CO-, -O-arylene group -O- and -NH-alkylene group -O-CO-,
An H-alkylene group -O-CO- is particularly preferred. The alkylene group may have a branched or cyclic structure. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 20,
It is more preferably 1 to 15, and most preferably 1 to 12. The arylene group is preferably phenylene or naphthylene, more preferably phenylene, and most preferably p-phenylene. The arylene group may have a substituent. Examples of the substituent of the arylene group are the same as the examples of the substituent of the arylene group described above. In the formula (IV), Q is a polymerizable group. As described above, the polymerizable group is preferably the same as the polymerizable group (Q) of the liquid crystal molecule. Examples of the repeating unit having a polymerizable group in the side chain are shown below.

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When a repeating unit having a polymerizable group in the side chain is introduced into the acrylic acid-based copolymer, the acrylic acid-based copolymer has a repeating unit having a polymerizable group in the side chain in an amount of 0.1.
Preferably, it contains 1 to 10 mol%, and 3 to 5 mol%
More preferably, it is included in the range.

The above-mentioned polymerizable group can be introduced into the repeating unit having a hydrocarbon group or a fluorine atom-substituted hydrocarbon group. The polymerizable group is preferably a substituent of a hydrocarbon group or a fluorine atom-substituted hydrocarbon group, and more preferably a substituent of the most terminal hydrocarbon group or a fluorine atom-substituted hydrocarbon group. It is preferable that the hydrocarbon group or the fluorine atom-substituted hydrocarbon group and the polymerizable group are not directly linked but are linked via a linking group. Examples of the linking group include -O-, -CO-, -O-CO-, -C
O-O-, -O-CO-O-, -CO-NH-, -SO
₂ -NH-, -NH-CO-, -NH-CO-O-,-
NH-SO _2- , -alkylene group-, -alkenylene group-, -alkynylene group-, -O-alkylene group- and -alkylene group -O- (the left side is bonded to a hydrocarbon group, and the right side is polymerized. Bond to a functional group). The alkylene group may have a branched or cyclic structure. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and more preferably 1 to 15 carbon atoms.
Is more preferable, and most preferably 1 to 12. The alkenylene group and the alkynylene group may have a branched or cyclic structure. The number of carbon atoms of the alkenylene group and the alkynylene group is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 15,
Most preferably, it is 2 to 12. The hydrocarbon group or the fluorine atom-substituted hydrocarbon group may have two or more polymerizable groups as substituents.

The repeating unit having a hydrocarbon group or a fluorine atom-substituted hydrocarbon group in the side chain and a polymerizable group is preferably represented by the following formula (V).

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In the formula (V), R^FourIs a hydrogen atom or
Is methyl. In equation (V), L^{twenty one}Is -CO
-, -SO_Two-, -NH-, alkylene group, alkenylene
Group, arylene group and their combination
Is a divalent linking group. L^{twenty one}For equation (II)
L⁰Is the same as In equation (V), L^{twenty two}Is
A divalent hydrocarbon group having 10 to 100 carbon atoms or
Divalent fluorine-substituted carbon atoms having 1 to 100 carbon atoms
It is a hydrogen group. L ^{twenty two}With respect to p substituents
L^{twenty three}Except that -Q is bonded,
R⁰Is the same as In equation (V), L^{twenty three}Is simple
When -O-, -CO-, -O-CO-, -CO-O-,
-O-CO-O-, -CO-NH-, -SO_Two-NH
-, -NH-CO-, -NH-CO-O-, -NH-S
O_Two-, -Alkylene group-, -alkenylene group-, -A
Lucinylene group-, -O-alkylene group- and -alkyl
A linking group selected from the group consisting of a len group -O-. Up
Alkylene group, alkenylene group and alkynylene group
Is as described above. In equation (V),
Q is a polymerizable group. The polymerizable group, as described above,
It is preferably a group similar to the polymerizable group (Q) of the liquid crystal molecule.
Good. In the formula (V), p is 1, 2 or 3.
You. p is preferably 1 or 2, and is preferably 1.
Is more preferable.

When a repeating unit having a hydrocarbon group having 10 to 100 carbon atoms or a fluorine-substituted hydrocarbon group having 10 to 100 carbon atoms in the side chain and a polymerizable group is used, the acrylic acid copolymer is A hydrocarbon group having 10 to 100 carbon atoms or 10 carbon atoms in the side chain;
The repeating unit having from 100 to 100 fluorine-substituted hydrocarbon groups and the polymerizable group is preferably contained in an amount of 1 to 90 mol%, more preferably 3 to 50 mol%.

An acrylic acid copolymer obtained by combining the above repeating units may be used. For example, an acrylic copolymer having a repeating unit having a hydrocarbon group or a fluorine atom-substituted hydrocarbon group in a side chain and a repeating unit having a hydrocarbon group or a fluorine atom-substituted hydrocarbon group and a polymerizable group in a side chain An acrylic acid-based copolymer having a repeating unit having a polymerizable group in a side chain and a repeating unit having a hydrocarbon group or a fluorine atom-substituted hydrocarbon group and a polymerizable group in a side chain, or a hydrocarbon in a side chain A repeating unit having a group or a fluorine atom-substituted hydrocarbon group,
Acrylic acid copolymers having a repeating unit having a polymerizable group in the side chain and a repeating unit having a hydrocarbon group or a fluorine atom-substituted hydrocarbon group and a polymerizable group in the side chain can also be used.

The acrylic copolymer having a hydrocarbon group having 10 to 100 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 100 carbon atoms in the side chain can be produced by a known method. For example, it can be obtained by an ester bond between a carboxyl group of poly (meth) acrylic acid and a terminal hydroxyl group of a group corresponding to a side chain. Further, it can also be obtained by an amide bond between a carboxyl group of poly (meth) acrylic acid and a terminal amino group of a group corresponding to a side chain.

As described above, the hydrocarbon group preferably contains at least two aromatic rings or aromatic heterocycles. More preferably, the hydrocarbon group contains two, three or four aromatic rings or aromatic heterocycles.
The repeating unit having a hydrocarbon group containing two, three or four aromatic rings or aromatic heterocycles in a side chain is preferably represented by the following formula (VI).

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In the formula (VI), R ² is a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms. R ² is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, methyl or ethyl, and most preferably a hydrogen atom or methyl. In the formula (VI), L ¹ is a divalent linking group selected from the group consisting of —O—, —CO—, —NH—, an —alkylene group— and a combination thereof. L ¹ is -CO-L ¹⁰ -(-CO- is bonded to the main chain, and L ¹⁰ is -O-, -CO
, -NH-, -alkylene group- and a combination thereof. L ¹ is -CO-O-, -CO-NH
-, -CO-O-alkylene group-, -CO-O-alkylene group -O- or -CO-O-alkylene group -CO-
O-, preferably -CO-O- or -CO
More preferably, it is -NH-. In the formula (VI), L ² , L ³ and L ⁴ are each independently a -ethynylene group-(-C≡C-), a single bond, -CO-, -O-
CO-, -CO-O-, -alkylene group -O-, -CO
-NH -, - O-CO- O -, - NHSO 2 - or -
NHCO-O-. At least one of L ² , L ³ and L ⁴ is a single bond or -ethynylene group-(-C≡).
C-) is preferred. The alkylene group may have a branched or cyclic structure. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 12 carbon atoms.

In the formula (VI), Ar ¹ , Ar ² , Ar
³ and Ar ⁴ are each independently an aromatic ring or an aromatic heterocyclic ring which may have a substituent. The aromatic ring or aromatic heterocyclic ring is preferably an aromatic ring, and more preferably an aromatic ring having 6 to 18 ring carbon atoms. Examples of the aromatic ring include a benzene ring,
It includes naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring and naphthacene ring. Examples of the aromatic heterocyclic ring include a pyridine ring and a pyrimidine ring.
A benzene ring or a naphthalene ring is preferred, and a benzene ring is most preferred. The substituent which the aromatic ring or aromatic heterocyclic ring may have includes a halogen atom, carboxyl, cyano, nitro, carbamoyl, sulfamoyl,
Examples include an alkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group, an acyl group, an acyloxy group, an alkyl-substituted carbamoyl group, an alkyl-substituted sulfamoyl group, an amide group, a sulfonamide group, and an alkylsulfonyl group.

In the formula (VI), q and r are each 0 or 1. It is preferable that q is 0 or 1, and r is 0 (the number of aromatic rings or aromatic heterocycles is 2 or 3), and both q and r are 0 (aromatic rings or aromatic heterocycles). It is particularly preferred that the number is 2).
In the formula (VI), n is 1 to 90 mol%. n
Is preferably 5 to 80 mol%, more preferably 10 to 70 mol%. Hereinafter, a repeating unit having a hydrocarbon group containing two, three or four aromatic rings or aromatic heterocycles in the side chain (L ² ,
Except where L ³ or L ⁴ is -C≡C-) shows an example.

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The repeating units having a hydrocarbon group containing two, three or four aromatic rings or aromatic heterocyclic rings in the side chain (L ² , L ³ or L ⁴ is —C≡C Examples of acrylic acid-based copolymers (excluding-) are shown below. AA is a repeating unit derived from acrylic acid, and MA is a repeating unit derived from methacrylic acid. The ratio of the repeating unit is mol%.

PA301:-(AA) 60- (VI-1) 40- PA302:-(AA) 70- (VI-2) 30- PA303:-(AA) 60- (VI-5) 40- PA304: -(AA) 65-(VI-9) 55-PA305:-(AA) 70-(VI-11) 30-PA306:-(AA) 80-(VI-15) 20-PA307:-(AA) 70 -(VI-15) 30- PA308 :-( AA) 60- (VI-15) 40- PA309 :-( AA) 70- (VI-16) 30- PA310 :-( AA) 60- (VI-16) ) 40-PA311:-(AA) 50- (VI-16) 50- PA312:-(AA) 70- (VI-18) 30- PA313:-(AA) 60- (VI-18) 40-PA314: -(AA) 50- (VI-18) 50- PA315 :-( A A) 60- (VI-23) 40- PA316 :-( AA) 60- (VI-25) 40- PA317 :-( AA) 60- (VI-32) 40- PA318 :-( AA) 60- ( VI-35) 40- PA319 :-( AA) 60- (VI-37) 40- PA320 :-( AA) 60- (VI-45) 40- PA321 :-( AA) 60- (VI-55) 40 −

PA322:-(MA) 60- (VI-1) 40- PA323:-(MA) 70- (VI-2) 30- PA324:-(MA) 60- (VI-5) 40- PA325: -(MA) 65- (VI-9) 35- PA326 :-( MA) 70- (VI-11) 30- PA327 :-( MA) 80- (VI-15) 20- PA328 :-( MA) 70 -(VI-15) 30- PA329 :-( MA) 60- (VI-15) 40- PA330 :-( MA) 70- (VI-16) 30- PA331 :-( MA) 60- (VI-16) ) 40-PA332:-(MA) 50- (VI-16) 50- PA333:-(MA) 70- (VI-18) 30- PA334:-(MA) 60- (VI-18) 40-PA335: -(MA) 50- (VI-18) 50- PA336 :-( M A) 60- (VI-23) 40- PA337 :-( MA) 60- (VI-25) 40- PA338 :-( MA) 60- (VI-32) 40- PA339 :-( MA) 60- ( VI-35) 40- PA340 :-( MA) 60- (VI-37) 40- PA341 :-( MA) 60- (VI-45) 40- PA342 :-( MA) 60- (VI-55) 40 −

The repeating unit having a hydrocarbon group containing two, three or four aromatic rings or aromatic heterocycles in the side chain has a tolan structure (L ² , L ³ or L ⁴ is —C≡). C
, And the ring on both sides of -C≡C- is an aromatic ring). Examples of the repeating unit having a hydrocarbon group containing two, three, or four aromatic rings or aromatic heterocycles having a tolan structure in the side chain are shown below.

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Hereinafter, examples of acrylic acid copolymers containing a repeating unit having a hydrocarbon group containing two, three or four aromatic rings or aromatic heterocycles having a tolan structure in the side chain will be described. . AA is a repeating unit derived from acrylic acid, and MA is a repeating unit derived from methacrylic acid. In addition, EA and ClA are repeating units represented by the following formula (M is the same definition as M in formula (I)). The ratio of the repeating unit is mol%.

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PA401:-(AA) 60- (VI-101) 40- PA402:-(AA) 70- (VI-101) 30- PA403:-(AA) 60- (VI-102) 40-PA404: -(AA) 65-(VI-107) 35-PA405:-(AA) 70-(VI-111) 30-PA406:-(AA) 80-(VI-114) 20-PA407:-(AA) 70 -(VI-120) 30- PA408 :-( AA) 60- (VI-123) 40- PA409 :-( AA) 70- (VI-125) 30- PA410 :-( AA) 60- (VI-125) ) 40-PA411 :-( AA) 50- (VI-125) 50- PA412 :-( AA) 70- (VI-126) 30- PA413 :-( AA) 60- (VI-128) 40-PA414: − (AA) 50− ( VI-132) 50- PA415 :-( AA) 70- (VI-133) 30- PA416 :-( AA) 60- (VI-133) 40- PA417 :-( AA) 70- (VI-138) 30 -PA418:-(AA) 60-(VI-138) 40-PA419:-(AA) 60-(VI-139) 40-PA420:-(AA) 60-(VI-141) 40-PA421:-( AA) 60- (VI-143) 40-

PA422:-(MA) 60- (VI-101) 40- PA423:-(MA) 70- (VI-101) 30- PA424:-(MA) 60- (VI-102) 40- PA425: -(MA) 65- (VI-107) 35- PA426 :-( MA) 70- (VI-111) 30- PA427 :-( MA) 80- (VI-114) 20- PA428 :-( MA) 70 -(VI-120) 30- PA429 :-( MA) 60- (VI-123) 40- PA430 :-( MA) 70- (VI-125) 30- PA431 :-( MA) 60- (VI-125) ) 40-PA432:-(MA) 50- (VI-125) 50- PA433:-(MA) 70- (VI-126) 30- PA434:-(MA) 60- (VI-128) 40-PA435: − (MA) 50− ( VI-132) 50- PA436 :-( MA) 70- (VI-133) 30- PA437 :-( MA) 60- (VI-133) 40- PA438 :-( MA) 70- (VI-138) 30 -PA439:-(MA) 60- (VI-138) 40- PA440:-(MA) 60- (VI-139) 40- PA441 :-( MA) 60- (VI-141) 40- PA442 :-( MA) 60- (VI-142) 40-PA451 :-( ClA) 60- (VI-145) 40- PA452 :-( EA) 60- (VI-146) 40- PA453 :-( ClA) 60- ( VI-147) 40- PA454:-(EA) 60- (VI-148) 40-

The polymerizable group described above can be introduced into a repeating unit having a hydrocarbon group containing two, three or four aromatic rings or aromatic heterocycles in the side chain. The polymerizable group is preferably a substituent of an aromatic ring or an aromatic heterocyclic ring, and particularly preferably a substituent of the most terminal aromatic ring or an aromatic heterocyclic ring. It is preferable that the aromatic ring or the aromatic heterocyclic ring and the polymerizable group are not directly linked but are linked via a linking group. Examples of linking groups include:
-O-, -CO-, -O-CO-, -CO-O-, -O
-CO-O -, - CO- NH -, - SO 2 -NH -, -
NH-CO-, -NH-CO-O-, -NH-SO
_2- , -alkylene group-, -alkenylene group-, -alkynylene group-, -O-alkylene group- and -alkylene group -O- are included (the left side is bonded to an aromatic ring or an aromatic heterocyclic ring, The right side binds to the polymerizable group). The alkylene group may have a branched or cyclic structure. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 20,
It is more preferably 1 to 15, and most preferably 1 to 12. The alkenylene group and the alkynylene group may have a branched or cyclic structure. The number of carbon atoms of the alkenylene group and the alkynylene group is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 15, and most preferably 2 to 12. The aromatic ring or aromatic heterocyclic ring may have two or more polymerizable groups as substituents. The repeating unit having 2 to 4 aromatic rings or aromatic heterocycles in the side chain and a polymerizable group is preferably represented by the following formula (VII).

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In the formula (VII), R ⁵ is a hydrogen atom or methyl. In the formula (VII), L ²¹ is a single bond,
-CO-, -CO-NH-, -alkylene group-, -CO
A linkage selected from the group consisting of -NH-alkylene-, -CO-NH-alkylene-O-, -CO-NH-alkylene-CO-O-, and -CO-NH-alkylene-CO-NH-. Group. -CO-, -CO-NH
-And -alkylene group-, preferably -C
Particularly preferred is O-NH-. The alkylene group may have a branched or cyclic structure. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and more preferably 1 to 15 carbon atoms.
Is more preferable, and 1 to 12 is particularly preferable.

In the formula (VII), L ²² , L ²³ , L ²⁴ and L ²⁵ each independently represent a single bond, —O—, —CO
-, -O-CO-, -CO-O-, -O-CO-O-,
_{-CO-NH -, - SO 2} -NH -, - NH-CO-,
-NH-CO-O -, - NH-SO 2 -, - alkylene group -, - alkenylene group -, - alkynylene group -, - O
A linking group selected from the group consisting of -alkylene group- and -alkylene group -O-. At least one of L ^22, L ²³ and L ²⁴ is a single bond or - preferably a - alkynylene group.

In the formula (VII), Ar ²¹ , Ar ²² , Ar
²³ and Ar ²⁴ are each independently an aromatic ring or an aromatic heterocyclic ring. It is preferably a benzene ring. Ar ²¹ , Ar ²² and Ar ²³ are particularly preferably p-phenylene. The aromatic ring or aromatic heterocyclic ring may have a substituent. Examples of substituents are those of the formula (V
It is the same as the example of the substituent of the aromatic ring or aromatic heterocyclic ring of I). In the formula (VII), q and r are
It is 0 or 1. It is preferable that q is 0 or 1, and r is 0 (the number of aromatic rings or aromatic heterocycles is 2 or 3), and both q and r are 0 (aromatic rings or aromatic heterocycles). It is particularly preferred that the number is 2). In the formula (VII), Q is a polymerizable group. The polymerizable group is
As described above, the group is preferably the same as the polymerizable group (Q) of the liquid crystal molecule. In the formula (VII), p is
1, 2, or 3. p is preferably 1 or 2, and more preferably 1. Examples of the repeating unit having 2 to 4 aromatic rings or aromatic heterocycles in the side chain and a polymerizable group are shown below.

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In the formula (III), R ² is a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms. R ² is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, methyl or ethyl, and most preferably a hydrogen atom or methyl.

In the formula (III), Cy represents an aliphatic cyclic group,
It is an aromatic group or a heterocyclic group. The aliphatic ring of the aliphatic ring group is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and most preferably a 6-membered ring. Examples of the aliphatic ring include a cyclohexane ring, a cyclohexene ring, and a bicyclo [2.2.1] hept-2-ene ring. Another aliphatic ring, aromatic ring or heterocyclic ring may be condensed to the aliphatic ring. Examples of the aromatic ring of the aromatic group include a benzene ring, a naphthalene ring,
Includes anthracene, phenanthrene, pyrene and naphthacene rings. An aliphatic ring or a heterocyclic ring may be fused to the aromatic ring. The heterocyclic ring of the heterocyclic group is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring. The heterocyclic ring preferably has aromaticity. The aromatic heterocycle is generally unsaturated and preferably has the most double bonds. Examples of the heterocycle include a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazane ring, a pyran ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring. Is included. Another heterocyclic ring, aliphatic ring or aromatic ring may be fused to the heterocyclic ring.

An aliphatic ring group, an aromatic group and a heterocyclic group are
It may have a substituent. Examples of the substituent include an alkyl group (eg, methyl, ethyl, t-butyl), a substituted alkyl group (eg, chloromethyl, hydroxymethyl, trimethylammonio chloride), an alkoxy group (eg, methoxy), a halogen atom (eg, F, Cl, Br), carboxyl, acyl group (eg, formyl), amino, sulfo, aryl group (eg, phenyl), aryloxy group (eg, phenoxy) and oxo. In the formula (III), n
Is 1 to 90 mol%. n is 5 to 80 mol%
And more preferably 10 to 70 mol%. Examples of the repeating unit represented by the formula (III) are shown below.

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The following is an example of an acrylic acid-based copolymer containing a repeating unit represented by the formula (III). AA is a repeating unit derived from acrylic acid, and MA is a repeating unit derived from methacrylic acid. The ratio of the repeating unit is mol%.

PA501:-(AA) 70- (III-1) 30- PA502:-(AA) 60- (III-1) 40- PA503:-(AA) 50- (III-1) 50-PA504: -(AA) 40- (III-1) 60- PA505 :-( AA) 60- (III-2) 40- PA506 :-( AA) 60- (III-3) 40- PA507 :-( AA) 60 -(III-4) 40- PA508 :-( AA) 60- (III-5) 40- PA509 :-( AA) 40- (III-6) 40- PA510 :-( AA) 50- (III-7) ) 50- PA511 :-( AA) 70- (III-8) 30-

PA512:-(AA) 60- (III-9) 40- PA513:-(AA) 60- (III-10) 40- PA514:-(AA) 60- (III-11) 40- PA515: -(AA) 50- (III-12) 50- PA516 :-( AA) 50- (III-13) 50- PA517 :-( AA) 70- (III-14) 30- PA518 :-( AA) 50 -(III-15) 50- PA519 :-( AA) 60- (III-16) 40- PA520 :-( AA) 60- (III-17) 40- PA521 :-( AA) 60- (III-18) ) 40- PA522:-(AA) 60- (III-19) 40-

PA523:-(AA) 75- (III-20) 25- PA524:-(AA) 60- (III-20) 40- PA525:-(AA) 70- (III-21) 30-PA526: -(AA) 80- (III-22) 20- PA527 :-( AA) 70- (III-22) 30- PA528 :-( AA) 60- (III-22) 40- PA529 :-( AA) 70 -(III-23) 30- PA530 :-( AA) 70- (III-24) 30- PA531 :-( AA) 80- (III-25) 20- PA532 :-( AA) 70- (III-25) ) 30- PA533:-(AA) 60- (III-25) 40-

PA534:-(AA) 60- (III-26) 40- PA535:-(AA) 70- (III-27) 30- PA536:-(AA) 80- (III-28) 20- PA537: -(AA) 70- (III-29) 30- PA538 :-( AA) 60- (III-30) 40- PA539 :-( AA) 70- (III-31) 30- PA540 :-( AA) 70 -(III-32) 30- PA541 :-( AA) 60- (III-33) 40- PA542 :-( AA) 70- (III-34) 30- PA543 :-( AA) 70- (III-35) ) 30-

PA601:-(MA) 70- (III-1) 30- PA602:-(MA) 60- (III-1) 40- PA603:-(MA) 50- (III-1) 50- PA604: -(MA) 40- (III-1) 60- PA605 :-( MA) 60- (III-2) 40- PA606 :-( MA) 60- (III-3) 40- PA607 :-( MA) 60 -(III-4) 40- PA608 :-( MA) 60- (III-5) 40- PA609 :-( MA) 40- (III-6) 40- PA610 :-( MA) 50- (III-7) ) 50- PA611 :-( MA) 70- (III-8) 30-

PA612:-(MA) 60- (III-9) 40- PA613:-(MA) 60- (III-10) 40- PA614:-(MA) 60- (III-11) 40- PA615: -(MA) 50- (III-12) 50- PA616 :-( MA) 50- (III-13) 50- PA617 :-( MA) 70- (III-14) 30- PA618 :-( MA) 50 -(III-15) 50- PA619 :-( MA) 60- (III-16) 40- PA620 :-( MA) 60- (III-17) 40- PA621 :-( MA) 60- (III-18) ) 40- PA622:-(MA) 60- (III-19) 40-

PA623:-(MA) 75- (III-20) 25- PA624:-(MA) 60- (III-20) 40- PA625:-(MA) 70- (III-21) 30- PA626: -(MA) 80- (III-22) 20- PA627 :-( MA) 70- (III-22) 30- PA628 :-( MA) 60- (III-22) 40- PA629 :-( MA) 70 -(III-23) 30- PA630 :-( MA) 70- (III-24) 30- PA631 :-( MA) 80- (III-25) 20- PA632 :-( MA) 70- (III-25) ) 30- PA633:-(MA) 60- (III-25) 40-

PA634:-(MA) 60- (III-26) 40- PA635:-(MA) 70- (III-27) 30- PA636:-(MA) 80- (III-28) 20- PA637: -(MA) 70- (III-29) 30- PA638 :-( MA) 60- (III-30) 40- PA639 :-( MA) 70- (III-31) 30- PA640 :-( MA) 70 -(III-32) 30- PA641 :-( MA) 60- (III-33) 40- PA642 :-( MA) 70- (III-34) 30- PA643 :-( MA) 70- (III-35) ) 30-

An acrylic acid copolymer containing a repeating unit represented by the formula (III) can also have a polymerizable group. The polymerizable group may be introduced into the acrylic acid copolymer as a repeating unit having a polymerizable group in the side chain, or may be an aliphatic ring group, an aromatic group, or a heterocyclic group of the repeating unit represented by the formula (III). Is introduced as a substituent. For the repeating unit having a polymerizable group in the side chain, the above-mentioned formula (I
As described in V). When a polymerizable group is introduced as a substituent into an aliphatic ring group, an aromatic group, or a heterocyclic group of the repeating unit represented by the formula (III), the polymerizable group is not directly linked to a cyclic structure, It is preferable to bond via a linking group. The definition and examples of the divalent linking group are the same as those of L ^{25 in the} formula (VII). Examples of the repeating unit (VIII) in which a polymerizable group is introduced as a substituent into the aliphatic ring group, aromatic group, and heterocyclic group of the repeating unit represented by the formula (III) are shown.

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A repeating unit represented by the following formula (I), a repeating unit represented by the following formula (III) and a repeating unit represented by the following formula (IX)
The polymerizable copolymer containing a repeating unit represented by the following formula is most preferred.

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In the formulas (I), (III) and (IX),
R ¹ , R ² and R ⁶ are each independently a hydrogen atom,
Halogen atom or carbon atoms an alkyl group of 1 to 6; M is a proton, an alkali metal ion or an ammonium ion; Cy is an aliphatic cyclic group, an aromatic group or a heterocyclic group; L ²⁶ Is a single bond or a divalent linking group; Q is a polymerizable group; m is 10 to 99 mol% (preferably 10 to 95 mol%);
n is 1 to 90 mol% (preferably 5 to 90 mol%); and l is 1 to 20 mol%.
Examples of the divalent linking group include -CO-L in the formula (IV).
^Same as ¹¹ . Hereinafter, examples of the acrylic acid-based copolymer having a polymerizable group and containing a repeating unit represented by the formula (III) will be described. AA is a repeating unit derived from acrylic acid, and MA is a repeating unit derived from methacrylic acid. The ratio of the repeating unit is mol%.

PA701:-(AA) 70- (III-1)
25- (IV-12) 5-PA702:-(AA) 70- (III-1) 25- (IV-
1) 5-PA703:-(AA) 50- (III-1) 40- (IV-
12) 10-PA704:-(AA) 40- (III-1) 55- (IV-
12) 5-PA705:-(AA) 60- (III-2) 35- (IV-
12) 5-PA706:-(AA) 60- (III-3) 35- (IV-
12) 5-PA707:-(AA) 60- (III-4) 35- (IV-
12) 5-PA708:-(AA) 60- (III-5) 35- (IV-
12) 5-PA709:-(AA) 60- (III-6) 35- (IV-
12) 5-PA710:-(AA) 50- (III-7) 45- (IV-
12) 5-PA711:-(AA) 70- (III-8) 25- (IV-
12) 5-

PA712:-(AA) 60- (III-9)
35- (IV-1) 5- PA713:-(AA) 60- (III-10) 35- (IV-
3) 5-PA714:-(AA) 60- (III-11) 35- (IV-
4) 5-PA715:-(AA) 50- (III-12) 47- (IV-
8) 3-PA716:-(AA) 50- (III-13) 40- (VIII-
6) 10-PA717:-(AA) 70- (III-14) 25- (VIII-
7) 5-PA718:-(AA) 50- (III-15) 45- (IV-
12) 5-PA719:-(AA) 60- (III-16) 35- (IV-
12) 5-PA720:-(AA) 60- (III-17) 35- (IV-
12) 5-PA721:-(AA) 60- (III-18) 35- (IV-
12) 5-PA722:-(AA) 60- (III-19) 35- (IV-
1) 5-

PA723:-(AA) 70- (III-20)
25- (IV-12) 5-PA724:-(AA) 50- (III-20) 40- (IV-
12) 10-PA725:-(AA) 70- (III-21) 25- (IV-
12) 5-PA726:-(AA) 75- (III-22) 20- (IV-
12) 5-PA727:-(AA) 70- (III-22) 25- (IV-
12) 5-PA728:-(AA) 60- (III-22) 35- (IV-
12) 5-PA729:-(AA) 70- (III-23) 25- (IV-
12) 5-PA730:-(AA) 70- (III-24) 25- (IV-
12) 5-PA731:-(AA) 70- (III-25) 25- (IV-
1) 5-PA732:-(AA) 70- (III-25) 25- (IV-
12) 5-PA733:-(AA) 60- (III-25) 40- (IV-
12) 10-

PA734:-(AA) 60- (III-26)
35- (IV-12) 5-PA735:-(AA) 70- (III-27) 25- (IV-
12) 5-PA736:-(AA) 75- (III-28) 20- (IV-
12) 5-PA737:-(AA) 70- (III-29) 25- (IV-
1) 5-PA738:-(AA) 60- (III-30) 35- (IV-
2) 5-PA739:-(AA) 70- (III-31) 25- (IV-
3) 5-PA740:-(AA) 70- (III-32) 25- (IV-
4) 5-PA741:-(AA) 60- (III-33) 35- (IV-
7) 5-PA742:-(AA) 70- (III-34) 25- (IV-
8) 5-PA743:-(AA) 70- (III-35) 25- (IV-
9) 5-

PA801:-(MA) 70- (III-1)
25- (IV-12) 5-PA802:-(MA) 60- (III-1) 35- (IV-
1) 5-PA803:-(MA) 50- (III-1) 40- (IV-
12) 10-PA804:-(MA) 40- (III-1) 55- (IV-
12) 5-PA805:-(MA) 60- (III-2) 35- (IV-
12) 5-PA806:-(MA) 60- (III-3) 35- (IV-
12) 5-PA807:-(MA) 60- (III-4) 35- (IV-
12) 5-PA808:-(MA) 60- (III-5) 35- (IV-
12) 5-PA809:-(MA) 60- (III-6) 35- (IV-
12) 5-PA810:-(MA) 50- (III-7) 45- (IV-
12) 5-PA811:-(MA) 70- (III-8) 25- (IV-
12) 5-

PA812:-(MA) 60- (III-9)
35- (IV-1) 5-PA813:-(MA) 60- (III-10) 35- (IV-
3) 5-PA814:-(MA) 60- (III-11) 35- (IV-
4) 5-PA815:-(MA) 50- (III-12) 47- (IV-
8) 3-PA816:-(MA) 50- (III-13) 40- (VIII-
6) 10-PA817:-(MA) 70- (III-14) 25- (VIII-
7) 5-PA818:-(MA) 50- (III-15) 45- (IV-
12) 5-PA819:-(MA) 60- (III-16) 35- (IV-
12) 5-PA820:-(MA) 60- (III-17) 35- (IV-
12) 5-PA821:-(MA) 60- (III-18) 35- (IV-
12) 5-PA822:-(MA) 60- (III-19) 35- (IV-
1) 5-

PA823:-(MA) 70- (III-20)
25- (IV-12) 5-PA824:-(MA) 50- (III-20) 40- (IV-
12) 10-PA825:-(MA) 70- (III-21) 25- (IV-
12) 5-PA826:-(MA) 75- (III-22) 20- (IV-
12) 5-PA827:-(MA) 70- (III-22) 25- (IV-
12) 5-PA828:-(MA) 60- (III-22) 35- (IV-
12) 5-PA829:-(MA) 70- (III-23) 25- (IV-
12) 5-PA830:-(MA) 70- (III-24) 25- (IV-
12) 5-PA831:-(MA) 70- (III-25) 25- (IV-
1) 5-PA832:-(MA) 70- (III-25) 25- (IV-
12) 5-PA833:-(MA) 60- (III-25) 30- (IV-
12) 10-

PA834:-(MA) 60- (III-26)
35- (IV-12) 5-PA835:-(MA) 70- (III-27) 25- (IV-
12) 5-PA836:-(MA) 75- (III-28) 20- (IV-
12) 5-PA837:-(MA) 70- (III-29) 25- (IV-
1) 5-PA838:-(MA) 60- (III-30) 35- (IV-
2) 5-PA839:-(MA) 70- (III-31) 25- (IV-
3) 5-PA840:-(MA) 70- (III-32) 25- (IV-
4) 5-PA841:-(MA) 60- (III-33) 35- (IV-
7) 5-PA842:-(MA) 70- (III-34) 25- (IV-
8) 5-PA843:-(MA) 70- (III-35) 25- (IV-
9) 5-

Two or more acrylic acid copolymers may be used in combination. Acrylic acid-based copolymers can be used after crosslinking. The cross-linking reaction is preferably performed simultaneously with or after the application of the coating liquid for the alignment film. For example, the acrylic acid copolymer can be crosslinked by a crosslinking reaction between a carboxyl group of the acrylic acid copolymer and the crosslinking agent using a crosslinking agent. The details of the crosslinking agent are described in “Handbook of Crosslinking Agent” (Taiseisha) edited by Shinzo Yamashita and Tosuke Kaneko. Examples of the crosslinking agent include a methylol phenol resin, an amino resin (eg, a resin obtained by addition polymerization of melamine, benzoquanamine or urea with formaldehyde or alcohol), an amine compound, a triazine compound, an isocyanate compound, an epoxy compound, a metal oxide. Compounds, metal halides, organic metal halides, metal salts of organic acids, metal alkoxides, and compounds containing oxazoline groups. The amount of the cross-linking agent used is 0.1 to 2 times the coating amount of the alignment film.
0% by weight, preferably 0.5 to 15% by weight
Is more preferable. The amount of the cross-linking agent remaining in the alignment film without being reacted is 1.0% of the coating amount of the alignment film.
It is preferably at most 0.5% by weight, more preferably at most 0.5% by weight.

The alignment film is obtained by applying an acrylic acid-based copolymer to form a coating layer, and subjecting the surface of the coating layer to a rubbing treatment. The rubbing treatment is performed by rubbing the surface of the polymer coating layer several times with paper or cloth in a certain direction (usually the longitudinal direction). In some cases, a heat treatment is performed before the rubbing treatment in order to apply a precursor of the acrylic acid-based copolymer and to perform a condensation reaction after the application. The thickness of the alignment film is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm, and most preferably 0.1 to 1 μm.
The optically anisotropic layer may be transferred onto a transparent support after the rod-shaped liquid crystalline molecules of the optically anisotropic layer are aligned using an alignment film. The rod-like liquid crystal molecules fixed in the alignment state can maintain the alignment state without the alignment film.

The orientation film is formed by applying a coating solution comprising an acrylic acid-based copolymer solution on a support to form a coating film; drying the coating film; and rubbing the surface of the dried coating film. And a step of heating the coating film after the rubbing treatment. In heating the coating film after the rubbing treatment, the heating temperature is preferably in the range of 50 to 300 ° C.,
More preferably in the range of 50 to 250 ° C.,
The temperature is more preferably in the range of 100 to 250 ° C.

As a heating method, a method in which the coating film on the transparent support is brought into contact with a heating carrier set at the above temperature, and a method in which the transparent support having the coating film is left in a box-shaped container set at the above temperature. A method in which a gas having the above temperature (preferably air) is sprayed directly onto the coating film on the transparent support along the rubbing direction can be used. It is preferable to use a hot plate as the heating carrier. The time of the heat treatment is determined by the treatment temperature. The heat treatment requires a longer time as the temperature is lower.
When the heat treatment is performed at 100 ° C., the range is 1 to 30 minutes. When the heat treatment is performed at 130 ° C., the range is 30 seconds to 10 minutes. When the heat treatment is performed at 160 ° C., the range is 10 seconds to 3 minutes. Takes time. The time required to start the heat treatment after the rubbing treatment is preferably within one week, more preferably within three days, and most preferably within three hours.

[Optically Anisotropic Layer] The optically anisotropic layer is formed from rod-like liquid crystalline molecules. The rod-like liquid crystalline molecules are preferably oriented in a state where the average tilt angle between the major axis direction of the rod-like liquid crystalline molecules and the transparent support surface is less than 5 °. It is preferable to adjust the retardation of the entire optical compensation sheet by providing an optically anisotropic layer. The in-plane retardation (Re) of the entire optical compensation sheet is preferably from 20 to 200 nm, and more preferably from 20 to 100 nm.
Is more preferable, and most preferably 20 to 70 nm. The retardation (Rth) in the thickness direction of the entire optical compensation sheet is preferably from 70 to 500 nm, more preferably from 70 to 400 m, and further preferably from 70 to 300 nm. The in-plane retardation (Re) and the retardation in the thickness direction (Rth) of the optical compensation sheet are respectively defined by the following equations. Re = (nx−ny) × d Rth = [{(nx + ny) / 2} −nz] × d where nx and ny are in-plane refractive indices of the optical compensation sheet, and nz is the thickness of the optical compensation sheet. And d is the thickness of the optical compensatory sheet. By combining an optically anisotropic layer and a transparent support having optical uniaxiality or optical biaxiality, the retardation of the entire optical compensatory sheet can be adjusted. The transparent support having optical uniaxiality or optical biaxiality will be described later.

The rod-like liquid crystalline molecules used for the optically anisotropic layer are preferably fixed in an aligned state. Although the alignment state can be fixed using a polymer binder, it is preferable to fix the alignment state by a polymerization reaction. Depending on the display mode of the liquid crystal cell, the rod-like liquid crystalline molecules may be cholesterically aligned. When the rod-like liquid crystalline molecules are cholesterically aligned, the selective reflection region is preferably outside the visible region. Examples of rod-like liquid crystal molecules include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, and alkoxy-substituted phenylpyrimidines. , Phenyldioxane, tolan and alkenylcyclohexylbenzonitrile are preferably used. The rod-like liquid crystal molecules also include metal complexes. Further, a liquid crystal polymer containing a rod-like liquid crystal molecule in a repeating unit can also be used as the rod-like liquid crystal molecule. In other words, the rod-like liquid crystalline molecules may be bonded to a (liquid crystal) polymer. For rod-like liquid crystal molecules, see Quarterly Chemistry Review Vol. 22, Chapters 4, 7, and 11 of the Chemical Society of Japan (1994), edited by The Chemical Society of Japan, and the Liquid Crystal Device Handbook, edited by the 142nd Committee of the Japan Society for the Promotion of Science There is a description in Chapter 3. The birefringence of the rod-like liquid crystalline molecules is preferably 0.001 to 0.7.

The rod-like liquid crystalline molecule preferably has a polymerizable group. Examples of the polymerizable group (Q) are shown below.

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The polymerizable group (Q) is an unsaturated polymerizable group (Q1
To Q7), an epoxy group (Q8) or an aziridinyl group (Q9), more preferably an unsaturated polymerizable group, and more preferably an ethylenically unsaturated polymerizable group (Q
1 to Q6) are most preferred. The rod-like liquid crystal molecules preferably have a molecular structure that is substantially symmetric with respect to the minor axis direction. For that purpose, it is preferable to have a polymerizable group at both ends of the rod-shaped molecular structure. Hereinafter, examples of rod-like liquid crystal molecules will be described.

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The optically anisotropic layer is composed of rod-like liquid crystalline molecules or the following polymerizable initiators and optional additives (eg, plasticizer, monomer, surfactant, cellulose ester, 1,3,5
-A liquid crystal composition (coating solution) containing a triazine compound and a chiral agent) is applied on the alignment film.
As the solvent used for preparing the liquid crystal composition, an organic solvent is preferably used. Examples of organic solvents include amides (eg,
N, N-dimethylformamide), sulfoxide (eg,
Dimethyl sulfoxide), heterocyclic compound (eg, pyridine), hydrocarbon (eg, benzene, hexane), alkyl halide (eg, chloroform, dichloromethane), ester (eg, methyl acetate, butyl acetate), ketone (eg, acetone, Methyl ethyl ketone) and ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination. The liquid crystal composition can be applied by a known method (eg, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a die coating method).

The polymerization reaction of the rod-like liquid crystal molecules includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. Photopolymerization reactions are preferred. Examples of photopolymerization initiators include α-carbonyl compounds (U.S. Pat.
No. 661, No. 2367670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Patents 3046127 and 2951758), triarylimidazole dimer and p
-Combination with aminophenyl ketone (US Patent 35
No. 49367), acridine and phenazine compounds (described in JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (described in U.S. Pat. No. 4,221,970). The amount of the photopolymerization initiator used is 0.1% of the solid content of the coating solution.
It is preferably from 0.01 to 20% by mass, and more preferably from 0.5 to 5% by mass. Light irradiation for the polymerization of the rod-like liquid crystalline molecules is preferably performed using ultraviolet light. The irradiation energy is 20 mJ / cm ^{2 to} 50 J /
cm ² , preferably 100 to 800 mJ /
cm ² is more preferable. Light irradiation may be performed under heating conditions to promote the photopolymerization reaction. The thickness of the optically anisotropic layer is preferably from 0.1 to 20 μm, more preferably from 0.2 to 15 μm, and most preferably from 0.3 to 10 μm.

[Support] The support is preferably transparent. As the transparent support of the optical compensation sheet, a glass plate or a polymer film, preferably a polymer film is used. The support is transparent when the light transmittance is 8
It means 0% or more. Generally, an optically isotropic polymer film is used as a transparent support. Specifically, the optical isotropy means that the in-plane retardation (Re) is preferably less than 10 nm, and 5n
More preferably, it is less than m. In the case of an optically isotropic transparent support, the retardation in the thickness direction (Rth)
Is also preferably less than 10 nm, more preferably less than 5 nm. The in-plane retardation (Re) of the transparent support and the retardation in the thickness direction (Rt)
h) is each defined by the following equation. Re = (nx−ny) × d Rth = [{(nx + ny) / 2} −nz] × d where nx and ny are in-plane refractive indices of the transparent support, and nz is the thickness of the transparent support. Is the refractive index in the direction, and d is the thickness of the transparent support.

Depending on the type of liquid crystal display mode, an optically anisotropic polymer film may be used as the transparent support. That is, in some cases, the optical anisotropy of the optically anisotropic layer is added to the optical anisotropy of the transparent support to correspond to the optical anisotropy of the liquid crystal cell (optical compensation). In such a case, the transparent support preferably has optical uniaxiality or optical biaxiality. In the case of an optically uniaxial support, even if it is optically positive (the refractive index in the optical axis direction is larger than the refractive index in the direction perpendicular to the optical axis), it is negative (the refractive index in the optical axis direction is (Smaller than the refractive index in the vertical direction).
In the case of an optically biaxial support, the refractive indices nx, ny of the above formula
And nz all have different values (nx ≠ ny ≠ nz). In-plane retardation of optically anisotropic transparent support (R
e) is preferably 0 to 300 nm, more preferably 0 to 200 nm, and 0 to 10 nm.
Most preferably, it is 0 nm. The retardation (Rth) in the thickness direction of the optically anisotropic transparent support is preferably from 10 to 1,000 nm, and from 50 to 400 n.
m, more preferably 100 to 300 nm.

The material for forming the transparent support is determined depending on whether it is an optically isotropic support or an optically anisotropic support. In the case of an optically isotropic support, glass or cellulose ester is generally used. In the case of an optically anisotropic support, a synthetic polymer (eg, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethacrylate, norbornene resin) is generally used. However, the use of (1) the use of a retardation increasing agent (a birefringence increasing agent), (2) a decrease in the degree of acetylation of cellulose acetate, or (3) a cooling dissolution method described in EP0911656A2. By producing a film, an optically anisotropic (high retardation) cellulose ester film can also be produced. The transparent support made of a polymer film is preferably formed by a solvent casting method.

In order to obtain an optically anisotropic transparent support, it is preferable to carry out a stretching treatment on the polymer film.
When an optically uniaxial support is produced, ordinary uniaxial stretching or biaxial stretching may be performed. When producing an optically biaxial support, it is preferable to carry out an unbalanced biaxial stretching treatment. In unbalanced biaxial stretching, a polymer film is stretched in a certain direction at a certain magnification (for example, 3
To 100%, preferably 5 to 30%), and a higher magnification (eg, 6 to 200%) in the direction perpendicular thereto.
%, Preferably 10 to 90%). The bidirectional stretching may be performed simultaneously. It is preferable that the stretching direction (the direction of higher stretching ratio in unbalanced biaxial stretching) and the in-plane slow axis of the stretched film be substantially the same. The angle between the stretching direction and the slow axis is preferably less than 10 °, more preferably less than 5 °, and most preferably less than 3 °. When a transparent support having optical uniaxiality or optical biaxiality is used, the average direction of a line obtained by projecting the major axis direction of the rod-like liquid crystalline molecules of the optically anisotropic layer onto the transparent support surface. Are preferably arranged so as to be substantially parallel or orthogonal to the in-plane slow axis of the transparent support.

The thickness of the transparent support is from 10 to 500 μm
Is more preferable, and more preferably 50 to 200 μm. In order to improve the adhesion between the transparent support and the layer provided thereon (adhesion layer, alignment film or optically anisotropic layer), the transparent support is subjected to a surface treatment (eg, glow discharge treatment, corona discharge treatment, ultraviolet light). (UV) treatment, flame treatment). An ultraviolet absorber may be added to the transparent support. Adhesion layer (undercoat layer) on transparent support
May be provided. For the adhesion layer, see JP-A-7-333.
No. 433. The thickness of the adhesion layer is preferably from 0.1 to 2 μm, more preferably from 0.2 to 1 μm.

[Polarizing Film] As the polarizing film, an iodine-based polarizing film,
There are a dye-based polarizing film using a dichroic dye and a polyene-based polarizing film. The iodine-based polarizing film and the dye-based polarizing film are generally manufactured using a polyvinyl alcohol-based film. The transmission axis of the polarizing film corresponds to a direction perpendicular to the stretching direction of the film. The transmission axis of the polarizing film is disposed so as to be substantially parallel to the average direction (slow axis) of a line obtained by projecting the major axis direction of the rod-shaped liquid crystal molecules onto the surface of the transparent support.

[Transparent protective film] As the transparent protective film, a transparent polymer film is used. That the protective film is transparent means that the light transmittance is 80% or more. As the transparent protective film, a cellulose ester film, preferably a triacetyl cellulose film, is generally used. The cellulose ester film is preferably formed by a solvent casting method. The thickness of the transparent protective film is preferably 20 to 500 μm,
More preferably, it is 0 to 200 μm.

[Liquid Crystal Display Device] The present invention can be applied to liquid crystal cells of various display modes. As described above, the optical compensation sheet using liquid crystal molecules is formed of a TN (Twisted Nemati).
c), IPS (In-Plane Switching), FLC (Ferroel
ectric Liquid Crystal), OCB (Optically Compensa)
tory Bend), STN (Supper Twisted Nematic), V
A (Vertically Aligned), ECB (Electrically Cont
rolled Birefringence) and HAN (Hybrid Aligne)
dNematic) mode liquid crystal cells have already been proposed. The optical compensatory sheet and the polarizing plate of the present invention are preferably arranged such that the slow axis of the optical compensatory sheet and the transmission axis of the polarizing film are substantially parallel to each other, for example, a TN mode or a VA mode. It is preferable to use it for a liquid crystal display device. The present invention is particularly effective in a VA mode liquid crystal display device. The VA mode liquid crystal cell includes (1) a VA mode liquid crystal cell in a narrow sense in which rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied and substantially horizontally when voltage is applied. 176
625), and (2) a liquid crystal cell (SID97, Digest of tech. Papers) in which the VA mode is multi-domain (in the MVA mode) in order to enlarge the viewing angle.
(Proceedings) 28 (1997) 845), (3) A mode in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied, and twisted multi-domain alignment is performed when a voltage is applied (n
-ASM mode) liquid crystal cell (described in Proceedings 58-59 (1998) of Japanese Liquid Crystal Symposium) and (4) SURVA
Includes IVAL mode liquid crystal cells (presented at LCD International 98).

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[Example 1] Acrylic acid copolymer (PA4
10) and triethylamine (neutralizing agent) were dissolved in a mixed solvent of methanol and water (weight ratio = 30/70),
A 4% by weight solution of the triethylamine salt of an acrylic acid copolymer (PA410) was prepared.

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The solution was applied to a thickness of 1 μm on a glass substrate using a bar coater. The coating layer was dried at 120 ° C. for 5 minutes, and the surface was rubbed to form an alignment film. A coating solution having the following composition was applied to a thickness of 0.7 μm on the alignment film using a bar coater.

<< Coating Liquid for Optically Anisotropic Layer >>棒 100 parts by weight of rod-shaped liquid crystalline compound (N26) Photopolymerization initiator (Irgacure 907) 3 parts by weight Sensitizer (Kayacure DEXT, manufactured by Nippon Kayaku Co., Ltd.) 1 part by weight Methyl ethyl ketone 400 parts by weight ───────────────── ───────────────────

The coating layer was heated at 100 ° C. for 1 minute to align rod-like liquid crystalline molecules. At that temperature, ultraviolet rays were irradiated for 4 seconds to polymerize the rod-like liquid crystalline molecules and fix the alignment state. When the orientation of the thin film thus obtained and the director of the rod-like liquid crystalline molecules were observed using a polarizing microscope,
The rod-like liquid crystal molecules were oriented such that the major axis direction was perpendicular to the rubbing axis. When the retardation (Rth) in the thickness direction was measured using an ellipsometer, the retardation was 110
nm.

[Example 2] Acrylic acid copolymer (PA
Except for using -421), a thin film was prepared and evaluated in the same manner as in Example 1. Observation of the orientation of the obtained thin film and the director of the rod-like liquid crystal molecules using a polarizing microscope revealed that the long axis direction of the rod-like liquid crystal molecules was perpendicular to the rubbing direction.

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[Example 3] Acrylic acid copolymer (PA
Except for using -442), a thin film was prepared and evaluated in the same manner as in Example 1. Observation of the orientation of the obtained thin film and the director of the rod-like liquid crystal molecules using a polarizing microscope revealed that the long axis direction of the rod-like liquid crystal molecules was perpendicular to the rubbing direction.

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Example 4 (1) Preparation of Transparent Support To cellulose triacetate was added 4.0 wt% of the following birefringence increasing agent to prepare a roll-shaped cellulose triacetate film having a thickness of 100 μm.

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(2) Preparation of Alignment Film Acrylic acid copolymer (PA-442) and triethylamine (neutralizing agent) were dissolved in a mixed solvent of methanol and water (weight ratio = 30/70), and acrylic acid copolymer (PA-442) was dissolved. A 4% by weight solution of the triethylamine salt of PA-442) was prepared. This solution was continuously applied onto the roll-shaped transparent support prepared in the above (1) while being transported using a bar coater. 5 coats at 120 ° C
After drying for 1 minute, an alignment film having a thickness of 1 μm was formed. While transporting the roll-shaped transparent support provided with the alignment film, a rubbing treatment was continuously performed in the longitudinal direction (transport direction).

(3) Formation of Optically Anisotropic Layer A coating solution having the following composition was continuously applied on the alignment film using a bar coater.

<< Coating Liquid for Optically Anisotropic Layer >>棒 100 parts by weight of rod-shaped liquid crystalline compound (N26) Photopolymerization initiator (Irgacure 907) 3 parts by weight Sensitizer (Kayacure DEXT, manufactured by Nippon Kayaku Co., Ltd.) 1 part by weight Methyl ethyl ketone 400 parts by weight ───────────────── ───────────────────

The coating layer was heated at 100 ° C. for 1 minute, and irradiated with ultraviolet rays of 600 mJ / cm ² at that temperature for 4 seconds to polymerize the rod-like liquid crystalline molecules and fix the alignment state. Thus, an optically anisotropic layer was formed to produce an optical compensation sheet. The rod-like liquid crystal molecules were oriented such that the major axis direction was orthogonal to the longitudinal direction of the optical compensation sheet. Wavelength 550
In-plane retardation (Re) and thickness direction retardation (Rth) of the entire optical compensation sheet in nm.
To an ellipsometer (M-150, manufactured by JASCO Corporation)
As a result, Re was 30 nm and Rth was 11
It was 0 nm.

(4) Preparation of Polarizing Plate A roll-shaped polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an aqueous iodine solution and dried to obtain a polarizing film. On one surface of the polarizing film, a saponified rolled cellulose triacetate film (Fujitack T
D80UF (manufactured by Fuji Photo Film Co., Ltd.) and the optically anisotropic layer of a roll-shaped optical compensation sheet having been saponified on its other surface were continuously bonded to produce a polarizing plate. The slow axis of the optical compensation sheet (the major axis direction of the rod-like liquid crystal molecules) was parallel to the transmission axis of the polarizing film.

(5) Production of Liquid Crystal Display Device The polarizing plate and the optical compensation sheet on the observer side and the backlight side were deleted from a commercially available MVA liquid crystal display device (VL-1530S, manufactured by Fujitsu Ltd.), and The above two polarizing plates were attached. For the manufactured MVA liquid crystal display device, the viewing angle was measured using a viewing angle measuring device (EZContrast 160).
D, manufactured by ELDIM). As a result, the viewing angle in the transmission axis direction of the polarizing film and the viewing angle in the direction at 45 ° from the transmission axis direction exceeded 80 °.

[Example 5] (Formation of alignment film) Acrylic acid copolymer (PA505)
And triethylamine (neutralizing agent) were dissolved in a mixed solvent of methanol / water (mass ratio = 30/70) to prepare a 4% by mass solution. This solution was applied to a thickness of 1 μm on a glass support using a bar coater. 1 coating layer
Heat at 20 ° C. for 5 minutes and dry. The surface of the coating layer was rubbed to form an alignment film.

[0265]

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(Formation of Optically Anisotropic Layer) On the alignment film,
Using a bar coater, a coating solution having the following composition was 0.7 μm
To a thickness of

{Composition of Optically Anisotropic Layer Coating Solution}棒 100 parts by mass of rod-like liquid crystalline molecule (N71) Photopolymerization initiator (Irgacure 907, manufactured by Nippon Ciba Geigy Co., Ltd.) 3 parts by mass Photopolymerization sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass Methyl ethyl ketone 400 parts by mass ──────────────────────

The coating layer was heated at 100 ° C. for 1 minute to align rod-like liquid crystalline molecules. At that temperature, ultraviolet rays were irradiated for 4 seconds to polymerize the rod-like liquid crystalline molecules, and the alignment state was fixed. Thus, an optically anisotropic layer was formed to produce an optical compensation sheet. Observation of the orientation of the optically anisotropic layer and the director (long axis direction) of the rod-like liquid crystal molecules using a polarizing microscope revealed that the rod-like liquid crystal molecules were oriented so that the long axis direction was perpendicular to the rubbing direction. I was Further, the retardation in the thickness direction (R
When th) was measured, it was 115 nm.

Example 6 Acrylic acid copolymer (PA
505) instead of acrylic acid copolymer (PA52
An optical compensatory sheet was prepared and evaluated in the same manner as in Example 5, except that 3) was used in the same amount. Observation of the orientation of the optically anisotropic layer and the director (long axis direction) of the rod-like liquid crystal molecules using a polarizing microscope revealed that the rod-like liquid crystal molecules were oriented so that the long axis direction was perpendicular to the rubbing direction. I was
Further, when the retardation (Rth) in the thickness direction was measured using an ellipsometer, it was 115 nm.

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Example 7 Acrylic acid copolymer (PA
505) instead of acrylic acid copolymer (PA53)
An optical compensatory sheet was prepared and evaluated in the same manner as in Example 5, except that the same amount of 2) was used. Observation of the orientation of the optically anisotropic layer and the director (long axis direction) of the rod-like liquid crystal molecules using a polarizing microscope revealed that the rod-like liquid crystal molecules were oriented so that the long axis direction was perpendicular to the rubbing direction. I was
Further, when the retardation (Rth) in the thickness direction was measured using an ellipsometer, it was 115 nm.

[0272]

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[Example 8] (Preparation of transparent support) 4.0% by mass of the birefringence increasing agent used in Example 4 was added to cellulose triacetate to prepare a roll-shaped cellulose triacetate film having a thickness of 100 µm. . The obtained cellulose triacetate film was used as a transparent support.

(Formation of Alignment Film) Acrylic acid copolymer (PA532) and triethylamine (neutralizing agent) were
It was dissolved in a mixed solvent of methanol / water (mass ratio = 30/70) to prepare a 4% by mass solution. This solution was continuously applied onto a roll-shaped transparent support while transporting it using a bar coater. The coating layer was heated at 120 ° C. for 5 minutes and dried to form a layer having a thickness of 1 μm. While transporting the roll-shaped transparent support provided with the coating layer, rubbing the surface of the coating layer continuously in the longitudinal direction (transport direction),
An alignment film was formed.

(Formation of Optically Anisotropic Layer) On the alignment film,
A coating solution having the following composition was continuously applied using a bar coater.

<< Composition of Optically Anisotropic Layer Coating Solution >>棒 100 parts by mass of rod-like liquid crystalline molecule (N71) Photopolymerization initiator (Irgacure 907, manufactured by Nippon Ciba Geigy Co., Ltd.) 3 parts by mass Photopolymerization sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass Methyl ethyl ketone 400 parts by mass ──────────────────────

The coating layer was heated at 100 ° C. for 1 minute to align rod-like liquid crystalline molecules. 400m for 4 seconds at that temperature
The rod-like liquid crystalline molecules were polymerized by irradiating ultraviolet rays of j / cm ² to fix the alignment state. Thus, an optically anisotropic layer was formed to produce an optical compensation sheet. The rod-like liquid crystal molecules were oriented such that the major axis direction was orthogonal to the longitudinal direction of the optical compensation sheet. The ellipsometer (M-1)
50, manufactured by JASCO Corporation, the retardation of the entire optical compensation sheet at a wavelength of 550 nm was measured. The in-plane retardation (Re) was 30 nm, and the retardation in the thickness direction (Rth) was 115 nm. .

(Preparation of Polarizing Plate) A roll-shaped polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an aqueous iodine solution and dried to obtain a polarizing film. On one surface of the polarizing film, a saponified rolled cellulose triacetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) was provided, and on the other surface, a transparent support of a saponified rolled optical compensation sheet was prepared. By continuously bonding, a polarizing plate was produced. The slow axis of the optical compensation sheet (the major axis direction of the rod-like liquid crystal molecules) was parallel to the transmission axis of the polarizing film.

(Preparation of Liquid Crystal Display Device) A commercially available MVA liquid crystal display device (VL-1530S, manufactured by Fujitsu Ltd.) was used.
The polarizing plate and the optical compensatory sheet on the observer side and the backlight side were deleted, and instead, two sheets of polarizing plates produced were stuck. The viewing angle of the manufactured MVA liquid crystal display device was measured with a viewing angle measuring device (EZContrast 160D, manufactured by ELDIM). As a result, the viewing angle in the transmission axis direction of the polarizing film and the viewing angle in the direction at 45 ° from the transmission axis direction exceeded 80 °.

[Example 9] (Formation of alignment film) Acrylic acid copolymer (PA701)
And triethylamine (neutralizing agent) were dissolved in a mixed solvent of methanol / water (mass ratio = 30/70) to prepare a 4% by mass solution. This solution was applied to a thickness of 1 μm on a glass support using a bar coater. 1 coating layer
Heat at 20 ° C. for 5 minutes and dry. The surface of the coating layer was rubbed to form an alignment film.

[0281]

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(Formation of Optically Anisotropic Layer) On the alignment film,
Using a bar coater, a coating solution having the following composition was 0.7 μm
To a thickness of

<< Composition of Optically Anisotropic Layer Coating Solution >>棒 100 parts by mass of rod-like liquid crystalline molecule (N71) Photopolymerization initiator (Irgacure 907, manufactured by Nippon Ciba Geigy Co., Ltd.) 3 parts by mass Photopolymerization sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass Methyl ethyl ketone 400 parts by mass ──────────────────────

The coating layer was heated at 100 ° C. for 1 minute to align the rod-like liquid crystal molecules. At that temperature, ultraviolet rays were irradiated for 4 seconds to polymerize the rod-like liquid crystalline molecules, and the alignment state was fixed. Thus, an optically anisotropic layer was formed to produce an optical compensation sheet. Observation of the orientation of the optically anisotropic layer and the director (long axis direction) of the rod-like liquid crystal molecules using a polarizing microscope revealed that the rod-like liquid crystal molecules were oriented so that the long axis direction was perpendicular to the rubbing direction. I was Further, the retardation in the thickness direction (R
When th) was measured, it was 115 nm. Oh,
A cellophane tape was attached to the surface of the optically anisotropic layer, and then the tape was pulled in parallel with the optically anisotropic layer and peeled off. As a result, nothing was adhered to the surface of the tape.

Example 10 Acrylic acid copolymer (P
A701) instead of acrylic acid copolymer (PA72)
An optical compensatory sheet was prepared and evaluated in the same manner as in Example 9 except that the same amount of 7) was used. Observation of the orientation of the optically anisotropic layer and the director (long axis direction) of the rod-like liquid crystal molecules using a polarizing microscope revealed that the rod-like liquid crystal molecules were oriented so that the long axis direction was perpendicular to the rubbing direction. I was
Further, when the retardation (Rth) in the thickness direction was measured using an ellipsometer, it was 115 nm.

[0286]

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Example 11 Acrylic acid copolymer (P
A701) instead of acrylic acid copolymer (PA73)
An optical compensatory sheet was prepared and evaluated in the same manner as in Example 1 except that 1) was used in the same amount. Observation of the orientation of the optically anisotropic layer and the director (long axis direction) of the rod-like liquid crystal molecules using a polarizing microscope revealed that the rod-like liquid crystal molecules were oriented so that the long axis direction was perpendicular to the rubbing direction. I was
Further, when the retardation (Rth) in the thickness direction was measured using an ellipsometer, it was 115 nm.

[0288]

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[Example 12] (Preparation of transparent support) 4.0% by mass of the birefringence increasing agent used in Example 4 was added to cellulose triacetate to prepare a roll-shaped cellulose triacetate film having a thickness of 100 µm. . The obtained cellulose triacetate film was used as a transparent support.

(Formation of Alignment Film) An acrylic acid copolymer (PA732) and triethylamine (neutralizing agent) were
It was dissolved in a mixed solvent of methanol / water (mass ratio = 30/70) to prepare a 4% by mass solution. This solution was continuously applied onto a roll-shaped transparent support while transporting it using a bar coater. The coating layer was heated at 120 ° C. for 5 minutes and dried to form a layer having a thickness of 1 μm. While transporting the roll-shaped transparent support provided with the coating layer, rubbing the surface of the coating layer continuously in the longitudinal direction (transport direction),
An alignment film was formed.

[0291]

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(Formation of Optically Anisotropic Layer) On the alignment film,
A coating solution having the following composition was continuously applied using a bar coater.

<< Coating Composition of Optically Anisotropic Layer Coating Solution >>棒 100 parts by mass of rod-like liquid crystalline molecule (N71) Photopolymerization initiator (Irgacure 907, manufactured by Nippon Ciba Geigy Co., Ltd.) 3 parts by mass Photopolymerization sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass Methyl ethyl ketone 400 parts by mass ──────────────────────

The coating layer was heated at 100 ° C. for 1 minute to align the rod-like liquid crystal molecules. 400m for 4 seconds at that temperature
The rod-like liquid crystalline molecules were polymerized by irradiating ultraviolet rays of j / cm ² to fix the alignment state. Thus, an optically anisotropic layer was formed to produce an optical compensation sheet. The rod-like liquid crystal molecules were oriented such that the major axis direction was orthogonal to the longitudinal direction of the optical compensation sheet. The ellipsometer (M-1)
50, manufactured by JASCO Corporation, the retardation of the entire optical compensation sheet at a wavelength of 550 nm was measured. The in-plane retardation (Re) was 30 nm, and the retardation in the thickness direction (Rth) was 115 nm. .

(Preparation of Polarizing Plate) A roll-shaped polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an aqueous iodine solution and dried to obtain a polarizing film. On one surface of the polarizing film, a saponified rolled cellulose triacetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) was provided, and on the other surface, a transparent support of a saponified rolled optical compensation sheet was prepared. By continuously bonding, a polarizing plate was produced. The slow axis of the optical compensation sheet (the major axis direction of the rod-like liquid crystal molecules) was parallel to the transmission axis of the polarizing film.

(Production of Liquid Crystal Display) A commercially available MVA liquid crystal display (VL-1530S, manufactured by Fujitsu Ltd.) was used.
The polarizing plate and the optical compensatory sheet on the observer side and the backlight side were deleted, and instead, two sheets of polarizing plates produced were stuck. The viewing angle of the manufactured MVA liquid crystal display device was measured with a viewing angle measuring device (EZContrast 160D, manufactured by ELDIM). As a result, the viewing angle in the transmission axis direction of the polarizing film and the viewing angle in the direction at 45 ° from the transmission axis direction exceeded 80 °.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a basic configuration of a transmission type liquid crystal display device.

FIG. 2 is a schematic diagram showing a basic configuration of a reflection type liquid crystal display device.

FIG. 3 is a schematic view showing a step of bonding a roll-shaped polarizing element and a roll-shaped optical compensation sheet.

[Explanation of symbols]

 BL Backlight LD Longitudinal direction RP Reflector SA Slow axis of optically anisotropic layer TA Transmission axis of polarizing film 1, 1a, 1b, 1c Transparent protective film 2, 2a, 2b Polarizing film 3, 3a, 3b Transparent support Body 4, 4a, 4b Optically anisotropic layer 5a Lower substrate of liquid crystal cell 5b Upper substrate of liquid crystal cell 6 Rod-like liquid crystalline molecular layer

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H049 BA02 BA06 BA46 BB03 BB33 BB43 BB51 BB62 BC04 BC09 BC14 BC22 2H090 HB13Y KA05 KA07 KA08 LA06 LA09 LA16 MA01 MA06 4J100 AA20Q AB00Q AB02Q AB04Q AB07Q AB08Q AL15Q AL08Q AL08Q AL75Q AM17Q AM21Q AM23Q AQ12Q AQ15Q AQ19Q AQ26Q AQ28Q AT08Q BA03Q BA04Q BA05Q BA08Q BA11Q BA12Q BA13Q BA16Q BA20Q BA22Q BA29Q BA34Q BA35Q BA40Q BA41Q BA53Q BA56Q BA59Q BB01Q BB03Q BB07Q BB17Q BB18Q BC04Q BC12Q BC26Q BC43Q BC44Q BC45Q BC48Q BC49Q BC54Q BC65Q BC73Q BC79Q BC83Q CA04 JA39

Claims (10)

[Claims] 1. A coating film obtained by applying a solution of a copolymer containing a repeating unit represented by the following formula (I) and a repeating unit represented by the following formula (II) or (III) on a support: Rubbing the surface of the coating film to form an alignment film; and applying a coating solution containing rod-like liquid crystal molecules on the alignment film and drying the coating film to obtain a long rod-like liquid crystal molecule. A method for aligning rod-like liquid crystalline molecules such that the average direction of a line obtained by projecting the axial direction onto the support surface and the rubbing direction of the alignment film are substantially orthogonal to each other: [In the formula, R ¹ and R ² are each independently a hydrogen atom, a halogen atom or a carbon atoms is an alkyl group of 1 to 6; M is a proton, an alkali metal ion or an ammonium ion; L ⁰ Is -O-, -CO
—, —NH—, —SO ₂ —, a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an arylene group and a combination thereof; R ⁰ is a carbon atom having 10 to 100 carbon atoms. 1 hydrogen group or 1 carbon atom
From 100 to 100 fluorine-substituted hydrocarbon groups; Cy
Is an aliphatic, aromatic or heterocyclic group; m
Is 10-99 mol%; and n is 1-90 mol%]. 2. A copolymer comprising a repeating unit represented by the formula (I) and a repeating unit represented by the formula (II), wherein in the formula (II), R ⁰ is at least two aromatic rings. Or 10 to 1 carbon atoms containing an aromatic heterocyclic ring
2. The method for aligning rod-like liquid crystalline molecules according to claim 1, which is a hydrocarbon group of 00. 3. The rod-shaped liquid crystal molecule according to claim 1, wherein the rod-shaped liquid crystal molecule has a polymerizable group, and after the rod-shaped liquid crystal molecule is aligned, the rod-shaped liquid crystal molecule is polymerized to fix the alignment state. A method of orienting. 4. The rod-shaped liquid crystal molecule according to claim 3, wherein the copolymer has a polymerizable group, and after the rod-shaped liquid crystal molecule is aligned, the alignment state is fixed by polymerizing the rod-shaped liquid crystal molecule and the copolymer. A method of orienting. 5. The support has a longitudinal direction, and the average direction of a line obtained by projecting the major axis direction of the rod-like liquid crystal molecules onto the support surface is substantially orthogonal to the longitudinal direction of the support. The method for aligning rod-like liquid crystalline molecules according to claim 1. 6. The method for aligning rod-like liquid crystalline molecules according to claim 1, wherein the support has a longitudinal direction, and the rubbing direction of the alignment film is substantially parallel to the longitudinal direction of the support. 7. The rod-shaped liquid crystal molecules according to claim 1, wherein the rod-shaped liquid crystal molecules are aligned in a state where the average inclination angle between the major axis direction of the rod-shaped liquid crystal molecules and the support surface is less than 5 °. Method. 8. A roll-shaped optical compensation sheet having a transparent support, an alignment film and an optically anisotropic layer formed of rod-like liquid crystalline molecules in this order, wherein the alignment film has the following formula (I)
And a repeating unit represented by the following formula (II) or (III)
Consisting of a copolymer containing a repeating unit represented by
The rod-like liquid crystal molecules are oriented such that the average direction of the lines obtained by projecting the major axis direction of the rod-like liquid crystal molecules onto the transparent support surface and the rubbing direction of the alignment film are substantially orthogonal. Optical compensation sheet: [In the formula, R ¹ and R ² are each independently a hydrogen atom, a halogen atom or a carbon atoms is an alkyl group of 1 to 6; M is a proton, an alkali metal ion or an ammonium ion; L ⁰ Is -O-, -CO
—, —NH—, —SO ₂ —, a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an arylene group and a combination thereof; R ⁰ is a carbon atom having 10 to 100 carbon atoms. 1 hydrogen group or 1 carbon atom
From 100 to 100 fluorine-substituted hydrocarbon groups; Cy
Is an aliphatic, aromatic or heterocyclic group; m
Is 10-99 mol%; and n is 1-90 mol%]. 9. A roll-shaped polarizing plate having an optically anisotropic layer formed from rod-shaped liquid crystalline molecules, an alignment film, a transparent support, a polarizing film and a transparent protective film in this order, wherein the alignment film is as follows: A repeating unit represented by the formula (I);
Or a copolymer comprising a repeating unit represented by (III), wherein the rod-like liquid crystal molecules are oriented in a state where the average tilt angle between the major axis direction of the rod-like liquid crystal molecules and the transparent support surface is less than 5 °. The average direction of the line obtained by projecting the major axis direction of the rod-like liquid crystal molecules on the transparent support surface and the longitudinal direction of the polarizing plate are substantially orthogonal, and the transmission axis of the polarizing film and the rod-like liquid crystal A polarizer characterized in that the average direction of a line obtained by projecting the major axis direction of the hydrophilic molecule onto the surface of the transparent support is substantially parallel to: [In the formula, R ¹ and R ² are each independently a hydrogen atom, a halogen atom or a carbon atoms is an alkyl group of 1 to 6; M is a proton, an alkali metal ion or an ammonium ion; L ⁰ Is -O-, -CO
—, —NH—, —SO ₂ —, a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an arylene group and a combination thereof; R ⁰ is a carbon atom having 10 to 100 carbon atoms. 1 hydrogen group or 1 carbon atom
From 100 to 100 fluorine-substituted hydrocarbon groups; Cy
Is an aliphatic, aromatic or heterocyclic group; m
Is 10-99 mol%; and n is 1-90 mol%]. 10. A polymerizable copolymer comprising a repeating unit represented by the following formula (I), a repeating unit represented by the following formula (III) and a repeating unit represented by the following formula (IX): Wherein R ¹ , R ² and R ⁶ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; M is a proton, an alkali metal ion or an ammonium ion Cy is an aliphatic ring group, an aromatic group, or a heterocyclic group; L ²⁶ is a single bond or a divalent linking group; Q is a polymerizable group;
Is 10 to 99 mol%; n is 1 to 90 mol%; and 1 is 1 to 20 mol%.