JP5221592B2 - Composition, optical compensation film, and liquid crystal display device - Google Patents

Description

  The present invention relates to a liquid crystal display device, and more particularly to an in-plane switching (IPS) mode liquid crystal display device that performs display by applying a horizontal electric field to a liquid crystal compound oriented in the horizontal direction. The present invention also relates to an optical compensation film and a composition useful for the production thereof.

  As a liquid crystal display device, a so-called TN mode, in which a liquid crystal layer in which nematic liquid crystal is twisted and arranged between two orthogonal polarizing plates, and an electric field is applied in a direction perpendicular to the substrate is widely used. In this method, since the liquid crystal rises with respect to the substrate during black display, birefringence due to the liquid crystalline compound occurs when viewed from an oblique direction, and light leakage occurs. To solve this problem, a system for optically compensating the liquid crystal cell and preventing this light leakage by using a film in which liquid crystal molecules are hybrid-aligned has been put into practical use. However, even if liquid crystal molecules are used, it is very difficult to completely optically compensate the liquid crystal cell without any problem, resulting in a problem that gradation reversal in the lower direction of the screen cannot be suppressed.

  In order to solve such a problem, a liquid crystal display device using a so-called in-plane switching (IPS) mode in which a lateral electric field is applied to the liquid crystal, or a liquid crystal having a negative dielectric anisotropy is vertically aligned in the panel. A vertical alignment (VA) mode in which alignment is divided by protrusions and slit electrodes has been proposed and put into practical use. In recent years, these panels have been developed not only for monitor applications but also for TV applications, and screen brightness has been greatly improved accordingly. For this reason, slight light leakage in the diagonally oblique incidence direction during black display, which has not been considered as a problem in these operation modes, has become apparent as a cause of deterioration in display quality.

  As one means for improving the color tone and the viewing angle of black display, the arrangement of an optical compensation material having birefringence characteristics between the liquid crystal layer and the polarizing plate is also studied in the IPS mode. For example, a white display or halftone display is viewed directly from an oblique direction by placing a birefringent medium having optical axes orthogonal to each other between the substrate and the polarizing plate to compensate for the increase / decrease in retardation of the liquid crystal layer during tilting. It is disclosed that the coloring in the case can be improved (see Patent Document 1). In addition, as a method using an optical compensation film made of a styrene polymer having a negative intrinsic birefringence or a discotic liquid crystalline compound (see Patent Documents 2, 3, and 4), the optical compensation film has a positive birefringence and an optical axis. A method of combining a film in the plane of a film with a film having positive birefringence and an optical axis in the normal direction of the film (see Patent Document 5), biaxial optical compensation sheet having a retardation of half wavelength Using a film having a negative retardation as a protective film of a polarizing plate and providing an optical compensation layer having a positive retardation on this surface (see Patent Document 7) Has been.

Japanese Patent Laid-Open No. 9-80424 Japanese Patent Laid-Open No. 10-54982 JP-A-11-202323 Japanese Patent Laid-Open No. 9-292522 JP 11-133408 A JP-A-11-305217 JP-A-10-307291

  However, many of the proposed methods are methods that improve the viewing angle by canceling the birefringence anisotropy of the liquid crystal in the liquid crystal cell, so the polarization axis crossing angle when the orthogonal polarizing plate is viewed from an oblique direction. There is a problem that the light leakage based on the deviation from orthogonality cannot be solved sufficiently. Even in a system that can compensate for this light leakage, it is very difficult to completely optically compensate the liquid crystal cell without any problem. Furthermore, in the optical compensation sheet for IPS mode liquid crystal cell that performs optical compensation with the stretched birefringent polymer film, it is necessary to use a plurality of films. As a result, the thickness of the optical compensation sheet increases, and the display device becomes thinner. It is disadvantageous. Moreover, since an adhesive layer is used for lamination | stacking of a stretched film, the adhesive layer contracted by the temperature / humidity change, and defects, such as peeling and a curvature between films, may generate | occur | produce.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an IPS liquid crystal display device with a simple configuration and not only display quality but also a viewing angle that is remarkably improved. Another object of the present invention is to provide an optical compensation film that contributes to an improvement in the viewing angle of a liquid crystal display device, particularly an IPS liquid crystal display device, and a composition useful for the production of the optical compensation film.

The object of the present invention has been achieved by the following compositions (1) to (6), optical compensation films (7) to (8), and liquid crystal display devices (9) to (15).
(1) Fluoroaliphatic group, carboxyl group (—COOH), sulfo group (—SO ₃ H), sulfato group (—OSO ₃ H), phosphonoxy group {—OP (═O) (OH) ₂ } and those A composition containing at least one kind of a compound containing at least one hydrophilic group selected from the group consisting of these salts, at least one kind of onium salt, and at least one kind of liquid crystal compound.
(2) The compound containing a fluoroaliphatic group is a copolymer containing a repeating unit derived from a fluoroaliphatic group-containing monomer and a repeating unit represented by the following general formula (1): Composition.

（式中、Ｒ¹、Ｒ²及びＲ³はそれぞれ独立に、水素原子又は置換基を表し；Ｌは下記の連結基群から選ばれる２価の連結基又は下記の連結基群から選ばれる２つ以上を組み合わせて形成される２価の連結基を表し、
（連結基群）
単結合、−Ｏ−、−ＣＯ−、−ＮＲ⁴−（Ｒ⁴は水素原子、アルキル基、アリール基、又はアラルキル基を表す）、−Ｓ−、−ＳＯ₂−、−Ｐ（＝Ｏ）（ＯＲ⁵）−（Ｒ⁵はアルキル基、アリール基、又はアラルキル基を表す）、アルキレン基及びアリーレン基；
Ｑはカルボキシル基（−ＣＯＯＨ）もしくはその塩、スルホ基（−ＳＯ₃Ｈ）もしくはその塩、又はホスホノキシ基｛−ＯＰ（＝Ｏ）（ＯＨ）₂｝もしくはその塩を表す。）

(Wherein R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent; L is a divalent linking group selected from the following linking group group or 2 selected from the following linking group group: Represents a divalent linking group formed by combining two or more,
(Linked group group)
Single bond, —O—, —CO—, —NR ⁴ — (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group), —S—, —SO ₂ —, —P (═O) (OR ⁵ ) — (R ⁵ represents an alkyl group, an aryl group, or an aralkyl group), an alkylene group, and an arylene group;
Q represents a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, or a phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof. )

(3) The composition according to (1), wherein the compound containing the fluoroaliphatic group is a compound represented by the following general formula (2).
General formula (2)
(R ⁰ ) _m −L ⁰ − (W) _n
(Wherein, R ⁰ is an alkyl group having an alkyl group, terminus CF ₃ group, or terminal to represent an alkyl group having a CF ₂ H group, m. A plurality of R ⁰ representing an integer of 1 or more the same However, at least one represents an alkyl group having a CF ₃ group or a CF ₂ H group at the terminal, L ⁰ represents an (m + n) -valent linking group, and W represents a carboxyl group (—COOH). Or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, a sulfato group (—OSO ₃ H) or a salt thereof, or a phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof, Represents an integer of 1 or more.)

(4) The composition according to any one of (1) to (3), wherein the onium salt is a quaternary ammonium salt.
(5) The composition according to any one of (1) to (4), wherein the liquid crystal compound is a discotic liquid crystal compound.
(6) The composition according to (5), wherein the discotic liquid crystalline compound is a triphenylene liquid crystal.

(7) An optical compensation film having an optically anisotropic layer formed from the composition according to any one of (1) to (6).
(8) An optical compensation film having an optically anisotropic layer formed from the composition of (5) or (6), wherein the discotic liquid crystalline compound is substantially vertically aligned.

(9) a first polarizing film, an optical compensation film comprising a first retardation region in contact with the first polarizing film and a second retardation region in contact with the first retardation region, a first substrate, and a nematic liquid crystal material A liquid crystal layer and a second substrate are arranged in this order, and a liquid crystal compound of the nematic liquid crystal material is aligned parallel to the surfaces of the pair of substrates at the time of black display,
Using the in-plane refractive indexes nx and ny (nx ≧ ny), the refractive index nz in the thickness direction, and the thickness d of the film, Re = (nx−ny) × d
The in-plane retardation Re of the first retardation region defined by is 20 nm or less, and Rth = ((nx + ny) / 2−nz) × d
The retardation Rth in the thickness direction of the first retardation region defined in (2) is 20 nm to 120 nm, the second retardation region is formed from the composition of (5) or (6), and the discotic liquid crystalline compound is The optically anisotropic layer is substantially vertically aligned, and the slow axis of the second retardation region is parallel to the transmission axis of the first polarizing film and the slow axis direction of the liquid crystal compound during black display. A liquid crystal display device.
(10) The liquid crystal display device according to (9), wherein a second polarizing film is provided outside the second substrate.
The “outside of the second substrate” refers to a side where the liquid crystal layer is not located when the second substrate is taken as the center.
(11) The liquid crystal display device according to (9) or (10), wherein Re of the second retardation region is 50 nm to 200 nm.
(12) The liquid crystal according to any one of (9) to (11), wherein the first retardation region is composed of a plurality of layers, and a layer in contact with the second retardation region among the plurality of layers is an alignment film. Display device.
(13) It has a pair of protective films arranged with the second polarizing film in between, and the retardation Rth in the thickness direction of the protective film on the liquid crystal layer side of the pair of protective films is 20 nm or less (9) Liquid crystal display device in any one of-(12).
(14) The liquid crystal display device according to (13), wherein the protective film on the liquid crystal layer side is a cellulose acylate film or a norbornene-based film among the pair of protective films arranged with the second polarizing film interposed therebetween.
(15) Of the pair of protective films arranged with the second polarizing film interposed therebetween, the protective film on the liquid crystal layer side has a layer containing a rod-like liquid crystalline compound vertically aligned with the cellulose acylate film. Liquid crystal display device.
(16) The first retardation region is composed of a plurality of layers, and a layer in contact with the first polarizing film among the plurality of layers functions as a protective film for the first polarizing film (9) to (15). Any one of the liquid crystal display devices.
(17) An optical compensation film having an alignment film and an optically anisotropic layer on a transparent support, wherein the optically anisotropic layer increases or decreases the tilt angle at the air interface between the liquid crystalline compound and the liquid crystalline compound. An optical compensation film comprising at least one compound to be increased and at least one compound to increase or decrease the tilt angle of the liquid crystal compound at the alignment film interface.

When the composition of the present invention is applied onto an alignment film to align molecules of a liquid crystalline compound, particularly a discotic liquid crystalline compound, in the presence of a fluoroaliphatic group-containing compound and an onium salt, substantially vertical alignment is achieved. Can be made.
Further, the in-plane letter defined by Re = (nx−ny) × d using the refractive index nx and ny (nx ≧ ny) in the layer plane, the refractive index nz in the thickness direction, and the thickness d of the film. The retardation Re is 20 nm or less, and the thickness direction retardation Rth defined by Rth = ((nx + ny) / 2−nz) × d is 20 nm to 120 nm. Of the second retardation region composed of a discotic liquid crystalline compound having a thickness of 50 nm to 200 nm, the slow axis of the second retardation region being the transmission axis of the first polarizing film, and the liquid crystalline compound of the liquid crystal layer during black display By arranging the second phase difference region so as to be closer to the liquid crystal layer side than the first phase difference region, the front direction characteristic is not changed at all. View from the azimuth direction In addition, it is possible to improve the decrease in contrast caused by the shift of the absorption axes of the two polarizing plates from 90 degrees, particularly the decrease in contrast from an oblique direction of 45 degrees. Furthermore, the contrast can be further improved by setting the Rth of the protective film of the second polarizing film to 20 nm or less.

It is the schematic which shows the pixel area example of the liquid crystal display device of this invention. It is the schematic which shows the example of the liquid crystal display device of this invention.

  Hereinafter, embodiments of the composition, the optical compensation film, and the liquid crystal display device of the present invention will be sequentially described. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value. FIG. 1 is a schematic diagram showing an example of a pixel region of the liquid crystal display device of the present invention. FIG. 2 is a schematic view of an embodiment of the liquid crystal display device of the present invention.

  In the present specification, “parallel” and “orthogonal” mean that the angle is within a range of strictly less than ± 10 °. In this range, an error from a strict angle is preferably less than ± 5 °, and more preferably less than ± 2 °. Further, “substantially vertical” means within a range of less than ± 20 ° from a strict vertical angle. In this range, an error from a strict angle is preferably less than ± 15 °, and more preferably less than ± 10 °. Further, the “slow axis” means a direction in which the refractive index is maximized. Further, the measurement wavelength of the refractive index is a value at λ = 550 nm in the visible light region unless otherwise specified.

  In this specification, “polarizing plate” is cut into a size to be incorporated into a long polarizing plate and a liquid crystal device unless otherwise specified (in this specification, “cutting” includes “punching” and “cutting out”. It is used in the meaning including both of the polarizing plates. In this specification, “polarizing film” and “polarizing plate” are distinguished from each other. “Polarizing plate” means a laminate having a transparent protective film for protecting the polarizing film on at least one side of the “polarizing film”. It shall be.

[Composition]
The composition of the present invention comprises a fluoroaliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a sulfato group (—OSO ₃ H), a phosphonoxy group {—OP (═O) (OH). ₂ } and at least one compound containing at least one hydrophilic group selected from the group consisting of salts thereof, at least one onium salt, and at least one liquid crystalline compound. The compound having the fluoroaliphatic group and one or more hydrophilic groups contributes to vertically aligning the molecules of the liquid crystal compound, particularly the discotic liquid crystal compound, on the air interface side. On the other hand, the onium salt contributes to the vertical alignment of the molecules of the liquid crystal compound, particularly the discotic liquid crystal compound, on the alignment film interface side. Each component is unevenly distributed on the air interface side and the alignment film interface side, and exerts an action of vertically aligning the molecules of the liquid crystal compound by its excluded volume effect, electrostatic effect, or surface energy effect. The action of vertically aligning the liquid crystal molecules corresponds to the action of reducing the tilt angle of the director, that is, the angle formed between the director and the coated liquid crystal air side surface for the molecules of the discotic liquid crystal compound. The compound having the fluoroaliphatic group and one or more hydrophilic groups is preferably a polymer containing a rigid structural unit having an excluded volume effect. The compound reduces the tilt angle of the director on the air interface side of the liquid crystal compound, particularly the discotic liquid crystal compound, improves the coating property of the composition, and contributes to the reduction of unevenness and repellency.
The compound having a fluoroaliphatic group and at least one of a hydrophilic group (including a polymer and a low molecular compound) may have a polymerizable group. It also contributes to fixing the molecular orientation.

(Compound having fluoroaliphatic group and hydrophilic group: air interface side vertical alignment agent)
The compound having a fluoroaliphatic group and one or more hydrophilic groups used in the present invention contains a fluoropolymer having a fluoroaliphatic group and one or more hydrophilic groups, or a compound represented by the following general formula (2). A fluorine compound is preferred.
First, the fluoropolymer that can be used in the composition of the present invention will be described.
<< Fluoropolymer >>
In the present invention, a fluoroaliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—OP (═O) (OH) ₂ }, and salts thereof are selected. A fluorine-based polymer having one or more hydrophilic groups can be used. The types of polymers are described in “Revised Chemistry of Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., 1968), pages 1-4, for example, polyolefins, polyesters, polyamides, polyimides. , Polyurethanes, polycarbonates, polysulfones, polycarbonates, polyethers, polyacetals, polyketones, polyphenylene oxides, polyphenylene sulfides, polyarylates, PTFEs, polyvinylidene fluorides, cellulose derivatives, etc. It is done. The fluoropolymer is preferably a polyolefin.

  The fluorine-based polymer is a polymer having a fluoroaliphatic group in the side chain. The fluoroaliphatic group preferably has 1 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms. The aliphatic group may be linear or cyclic, and when it is linear, it may be linear or branched. Of these, a linear fluoroaliphatic group having 6 to 10 carbon atoms is preferable. The degree of substitution with fluorine atoms is not particularly limited, but 50% or more of hydrogen atoms in the aliphatic group are preferably substituted with fluorine atoms, and more preferably 60% or more are substituted. The fluoroaliphatic group is contained in a side chain bonded to the polymer main chain via an ester bond, an amide bond, an imide bond, a urethane bond, a urea bond, an ether bond, a thioether bond, an aromatic ring, or the like. One of the fluoroaliphatic groups is derived from a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). Regarding the production method of these fluoroaliphatic compounds, for example, “Synthesis and Function of Fluorine Compounds” (Supervision: Nobuo Ishikawa, Issue: CMC Co., 1987), “Chemistry of Organic Fluorines Compounds”. II "(Monograph 187, Ed by Milos Hudricky and Attila E. Pavlath, American Chemical Society 1995). The telomerization method is a method of synthesizing a telomer by radical polymerization of a fluorine-containing vinyl compound such as tetrafluoroethylene using an alkyl halide having a large chain transfer constant such as iodide as a telogen (example in Scheme-1). showed that).

  The obtained terminal iodinated telomer is usually subjected to appropriate terminal chemical modification such as [Scheme 2], and led to a fluoroaliphatic compound. These compounds are further converted into a desired monomer structure as necessary, and used for the production of a fluoroaliphatic group-containing polymer.

  Specific examples of the fluoroaliphatic group-containing monomer that can be used in the production of the fluorine-based polymer that can be used in the present invention are listed below, but the present invention is not limited to the following specific examples.

  One aspect of the fluoropolymer usable in the present invention is a copolymer having a repeating unit derived from a fluoroaliphatic group-containing monomer and a repeating unit containing a hydrophilic group represented by the following general formula (1). It is a polymer.

In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent. Q represents a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, a phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof. L represents an arbitrary group selected from the following linking group group, or a divalent linking group formed by combining two or more thereof.
(Linked group group)
Single bond, —O—, —CO—, —NR ⁴ — (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group), —S—, —SO ₂ —, —P (═O) (OR ⁵ ) — (R ⁵ represents an alkyl group, an aryl group, or an aralkyl group), an alkylene group, and an arylene group.

In general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent selected from the following substituent group Y.
(Substituent group Y)
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like, alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, Particularly preferred is an alkenyl group having 2 to 8 carbon atoms, such as vinyl group, allyl group, 2-butenyl group, 3-pentenyl group and the like, and alkynyl group (preferably having 2 to 20 carbon atoms, more preferably Is an alkynyl group having 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include a propargyl group and a 3-pentynyl group. An aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as a phenyl group, a p-methylphenyl group, and a naphthyl group. Aralkyl groups (preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as benzyl group, phenethyl group, 3- Phenylpropyl group and the like), a substituted or unsubstituted amino group (preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, Unsubstituted amino group, methylamino group, dimethylamino group, diethylamino group, anilino group, etc.),

An alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group). An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group), acyloxy A group (preferably an acyloxy group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms such as an acetoxy group and a benzoyloxy group), an acylamino group (preferably 2-20 carbon atoms, more preferably 2-16 carbon atoms, particularly preferably 2-10 carbon atoms. A silamino group, for example, an acetylamino group, a benzoylamino group, and the like, an alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 12 carbon atoms). An alkoxycarbonylamino group, for example, a methoxycarbonylamino group), an aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 12 carbon atoms). Aryloxycarbonylamino group, for example, phenyloxycarbonylamino group and the like, sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms). 12 sulfonylamino groups such as methanesulfonyl And sulfamoyl groups (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms, such as sulfamoyl group). Group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group and the like), carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably carbon number). 1 to 12 carbamoyl groups, for example, unsubstituted carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group and the like),

An alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, more preferably an alkylthio group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a methylthio group and an ethylthio group), an arylthio group ( Preferably it is C6-C20, More preferably, it is C6-C16, Most preferably, it is C6-C12 arylthio group, for example, a phenylthio group etc. are mentioned, A sulfonyl group (preferably C1-C1). 20, more preferably a sulfonyl group having 1 to 16 carbon atoms, particularly preferably a sulfonyl group having 1 to 12 carbon atoms, such as a mesyl group and a tosyl group, and a sulfinyl group (preferably having a carbon number of 1 to 20, more A sulfinyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms is preferable. Zensulfinyl group and the like), ureido group (preferably a ureido group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, an unsubstituted ureido group , Methylureido group, phenylureido group, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms). Yes, for example, diethyl phosphoric acid amide group, phenyl phosphoric acid amide group, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, Carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having a carbon number of 1 to 0, more preferably a heterocyclic group of 1 to 12, for example, a heterocyclic group having a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, such as an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group , Piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group and the like), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably A silyl group having 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group). These substituents may be further substituted with these substituents. Moreover, when it has two or more substituents, they may be the same or different. If possible, they may be bonded to each other to form a ring.

R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), or a group represented by -LQ described later. It is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a chlorine atom, or a group represented by -LQ, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Particularly preferred are a hydrogen atom and an alkyl group having 1 to 2 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group and the like. The alkyl group may have a suitable substituent. Examples of the substituent include a halogen atom, aryl group, heterocyclic group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxyl group, acyloxy group, amino group, alkoxycarbonyl group, acylamino group, oxycarbonyl Group, carbamoyl group, sulfonyl group, sulfamoyl group, sulfonamido group, sulfolyl group, carboxyl group and the like. The carbon number of the alkyl group does not include the carbon atom of the substituent. The same applies to the carbon number of other groups.

L represents a divalent linking group selected from the above linking group group, or a divalent linking group formed by combining two or more thereof. In the linking group group, R ^{4 in} —NR ⁴ — represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom or an alkyl group. R ⁵ in —PO (OR ⁵ ) — represents an alkyl group, an aryl group or an aralkyl group, and preferably an alkyl group. When R ⁴ and R ⁵ represent an alkyl group, an aryl group or an aralkyl group, the preferred range of the carbon number is the same as that described in “Substituent group Y”. L preferably contains a single bond, —O—, —CO—, —NR ⁴ —, —S—, —SO ₂ —, an alkylene group or an arylene group, and —CO—, —O—, —NR ⁴ -, and more preferably contains an alkylene group or an arylene group. When L contains an alkylene group, the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Specific examples of particularly preferred alkylene groups include methylene, ethylene, trimethylene, tetrabutylene, hexamethylene groups and the like. When L contains an arylene group, the carbon number of the arylene group is preferably 6 to 24, more preferably 6 to 18, and particularly preferably 6 to 12. Specific examples of particularly preferred arylene groups include phenylene and naphthalene groups. When L contains a divalent linking group (that is, an aralkylene group) obtained by combining an alkylene group and an arylene group, the carbon number of the aralkylene group is preferably 7 to 34, more preferably 7 to 26, and particularly preferably. 7-16. Specific examples of particularly preferred aralkylene groups include a phenylenemethylene group, a phenyleneethylene group, and a methylenephenylene group. The group listed as L may have a suitable substituent. Examples of such a substituent include those similar to the substituents exemplified above as the substituents for R ^{1 to} R ³ .

  Although the specific structure of L is illustrated below, this invention is not limited to these specific examples.

  In the formula (1), Q is a carboxyl group, a salt of a carboxyl group (for example, lithium salt, sodium salt, potassium salt, ammonium salt (for example, ammonium, tetramethylammonium, trimethyl-2-hydroxyethylammonium, tetrabutylammonium, trimethyl). Benzylammonium, dimethylphenylammonium, etc.), pyridinium salts, etc.), sulfo groups, salts of sulfo groups (examples of cations forming salts are the same as those described above for carboxyl groups), phosphonoxy groups, salts of phosphonoxy groups (salts) Examples of the cation that forms are the same as those described above for the carboxyl group). A carboxyl group, a sulfo group, and a phospho group are more preferable, and a carboxyl group or a sulfo group is particularly preferable.

  The fluoropolymer may contain one type of repeating unit represented by the general formula (1) or two or more types. Moreover, the said fluorine-type polymer may have 1 type (s) or 2 or more types of repeating units other than said each repeating unit. The other repeating units are not particularly limited, and preferred examples thereof include repeating units derived from ordinary radical polymerizable monomers. Hereinafter, specific examples of monomers for deriving other repeating units will be given. The fluoropolymer may contain a repeating unit derived from one or more monomers selected from the following monomer group.

Monomer group (1) Alkenes Ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-dodecene, 1-octadecene, 1-eicocene, hexafluoropropene, vinylidene fluoride, chlorotrifluoroethylene, 3, 3, 3-trifluoropropylene, tetrafluoroethylene, vinyl chloride, vinylidene chloride, etc .;
(2) Dienes 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2-n-propyl-1,3-butadiene, 2,3-dimethyl-1,3 -Butadiene, 2-methyl-1,3-pentadiene, 1-phenyl-1,3-butadiene, 1-α-naphthyl-1,3-butadiene, 1-β-naphthyl-1,3-butadiene, 2-chloro -1,3-butadiene, 1-bromo-1,3-butadiene, 1-chlorobutadiene, 2-fluoro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1,1,2- Trichloro-1,3-butadiene and 2-cyano-1,3-butadiene, 1,4-divinylcyclohexane and the like;

(3) Derivatives of α, β-unsaturated carboxylic acid (3a) Alkyl acrylates Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate , Amyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, tert-octyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, 2-cyanoethyl acrylate, 2-acetoxyethyl acrylate, methoxybenzyl Chryrate, 2-chlorocyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, 2-methoxyethyl acrylate, ω-methoxypolyethylene glycol acrylate (number of added polyoxyethylene: n = 2 to 100), 3-methoxy Butyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, glycidyl acrylate Such);

(3b) Alkyl methacrylates Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2 -Ethylhexyl methacrylate, n-octyl methacrylate, stearyl methacrylate, benzyl methacrylate, phenyl methacrylate, allyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, ω Methoxypolyethylene glycol methacrylate (number of added polyoxyethylene: n = 2 to 100), 2-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate Glycidyl methacrylate, 3-trimethoxysilylpropyl methacrylate, allyl methacrylate, 2-isocyanatoethyl methacrylate, etc .;

(3c) Diesters of unsaturated polycarboxylic acids Dimethyl maleate, dibutyl maleate, dimethyl itaconate, dibutyl taconate, dibutyl crotonate, dihexyl crotonate, diethyl fumarate, dimethyl fumarate, etc .;

(3d) Amides of α, β-unsaturated carboxylic acids N, N-dimethylacrylamide, N, N-diethylacrylamide, Nn-propylacrylamide, N-tertbutylacrylamide, N-tertoctylmethacrylamide, N- Cyclohexylacrylamide, N-phenylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, N-benzylacrylamide, N-acryloylmorpholine, diacetone acrylamide, N-methylmaleimide and the like;

(4) Unsaturated nitriles Acrylonitrile, methacrylonitrile, etc .;
(5) Styrene and its derivatives Styrene, vinyl toluene, ethyl styrene, p-tert butyl styrene, methyl p-vinyl benzoate, α-methyl styrene, p-chloromethyl styrene, vinyl naphthalene, p-methoxy styrene, p-hydroxy Methyl styrene, p-acetoxy styrene, etc .;
(6) Vinyl esters Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl benzoate, vinyl salicylate, vinyl chloroacetate, vinyl methoxyacetate, vinyl vinyl acetate, etc .;

(7) Vinyl ethers Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl Vinyl ether, n-eicosyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, fluorobutyl vinyl ether, fluorobutoxyethyl vinyl ether, etc .; and (8) other polymerizable monomers N-vinyl pyrrolidone, methyl vinyl ketone, phenyl vinyl ketone, Methoxyethyl vinyl ketone, 2-vinyl oxazoline, 2-isopropenyl oxazoline, etc.

  In the fluoropolymer, the amount of the fluoroaliphatic group-containing monomer is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 30% by mass or more of the total amount of constituent monomers of the polymer. Is more preferable. In the fluoropolymer, the amount of the repeating unit represented by the general formula (1) is preferably 0.5% by mass or more, and 1 to 20% by mass of the total amount of the constituent monomers of the fluoropolymer. Is more preferable, and it is further more preferable that it is 1-10 mass%. Since the above-mentioned mass percentage easily varies in a preferable range depending on the molecular weight of the monomer used, the content of the repeating unit represented by the general formula (1) is expressed by the number of moles of the functional group per unit mass of the polymer. Can be accurately defined. When this notation is used, the preferable amount of the hydrophilic group (Q in the formula (1)) contained in the fluoropolymer is 0.1 mmol / g to 10 mmol / g, and the more preferable amount is 0. .2 mmol / g to 8 mmol / g.

  The fluorine-based polymer used in the present invention preferably has a mass average molecular weight of 1,000,000 or less, more preferably 500,000 or less, and even more preferably 100,000 or less. The mass average molecular weight can be measured as a value in terms of polystyrene (PS) using gel permeation chromatography (GPC).

  The manufacturing method of the said fluorine-type polymer is not specifically limited, It can manufacture by a well-known and usual method. For example, it can be produced by adding a general-purpose radical polymerization initiator to an organic solvent containing the above-described monomer having a fluoroaliphatic group, a monomer having a hydrogen bonding group, and the like, and polymerizing the mixture. Further, in some cases, other addition-polymerizable unsaturated compounds can be further added and produced by the same method as described above. Depending on the polymerizability of each monomer, a dropping polymerization method in which a monomer and an initiator are added dropwise to a reaction vessel is also effective for obtaining a polymer having a uniform composition. For example, a polymerization method such as cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group can be employed, and among these, radical polymerization is particularly preferable because it can be used for general purposes. As the polymerization initiator for radical polymerization, known compounds such as radical thermal polymerization initiators and radical photopolymerization initiators can be used, and it is particularly preferable to use radical thermal polymerization initiators. Here, the radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include diacyl peroxide (acetyl peroxide, benzoyl peroxide, etc.), ketone peroxide (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), hydroperoxide (hydrogen peroxide, tert. -Butyl hydroxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyesters (tert-butyl peroxyacetate, tert) -Butyl peroxypivalate, etc.), azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.), persulfates (ammonium persulfate, sodium persulfate) And potassium persulfate) and the like. Such radical thermal polymerization initiators can be used singly or in combination of two or more.

  The radical polymerization method is not particularly limited, and an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method, and the like can be adopted. The solution polymerization, which is a typical radical polymerization method, will be described more specifically. The outlines of other polymerization methods are the same, and details thereof are described, for example, in “Polymer Science Experimental Method” edited by Polymer Society (Tokyo Kagaku Dojin, 1981).

  An organic solvent is used for solution polymerization. These organic solvents can be arbitrarily selected as long as the objects and effects of the present invention are not impaired. These organic solvents are usually organic compounds having boiling points under atmospheric pressure in the range of 50 to 200 ° C., and organic compounds that uniformly dissolve each component are preferred. Examples of preferred organic solvents include alcohols such as isopropanol and butanol; ethers such as dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate and acetic acid And esters such as butyl, amyl acetate, and γ-butyrolactone; and aromatic hydrocarbons such as benzene, toluene, and xylene. In addition, these organic solvents can be used individually by 1 type or in combination of 2 or more types. Furthermore, a water-mixed organic solvent in which water is used in combination with the above organic solvent is also applicable from the viewpoint of the solubility of the monomer and the polymer to be produced.

  Also, the solution polymerization conditions are not particularly limited, but for example, it is preferable to heat within a temperature range of 50 to 200 ° C. for 10 minutes to 30 hours. Furthermore, in order not to deactivate the generated radicals, it is preferable to perform an inert gas purge not only during solution polymerization but also before the start of solution polymerization. Usually, nitrogen gas is suitably used as the inert gas.

  In order to obtain the fluoropolymer in a preferable molecular weight range, a radical polymerization method using a chain transfer agent is particularly effective. As chain transfer agents, mercaptans (for example, octyl mercaptan, decyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, octadecyl mercaptan, thiophenol, p-nonylthiophenol, etc.), polyhalogenated alkyls (for example, carbon tetrachloride, chloroform, etc.) , 1,1,1-trichloroethane, 1,1,1-tribromooctane, etc.) and low-activity monomers (α-methylstyrene, α-methylstyrene dimer, etc.) can be used, preferably carbon These are mercaptans of 4-16. The amount of these chain transfer agents used is remarkably influenced by the activity of the chain transfer agent, the combination of the monomers, the polymerization conditions and the like, and must be precisely controlled. It is about 01 mol% to 50 mol%, preferably 0.05 mol% to 30 mol%, particularly preferably 0.08 mol% to 25 mol%. These chain transfer agents may be present in the system simultaneously with the target monomer whose degree of polymerization is to be controlled in the polymerization process, and the addition method is not particularly limited. It may be added after being dissolved in the monomer, or may be added separately from the monomer.

  As described above, the fluorine-based polymer preferably has a polymerizable group as a substituent in order to fix the alignment state of molecules of a liquid crystal compound, particularly a discotic liquid crystal compound.

  Specific examples of the fluoroaliphatic group-containing copolymer preferably used in the present invention as the fluorine-based polymer are shown below, but the present invention is not limited to these specific examples. Here, the numerical values (numerical values such as a, b, c, and d) in the formula are mass percentages indicating the composition ratio of each monomer, and Mw is a mass average molecular weight in terms of PS measured by GPC.

  The preferred range of the content of the fluoropolymer in the composition varies depending on the application, but when used for forming the optically anisotropic layer, the composition (a composition excluding the solvent in the case of a coating solution) Among these, 0.005 to 8% by mass is preferable, 0.01 to 5% by mass is more preferable, and 0.05 to 1% by mass is even more preferable. If the addition amount of the fluorine-based polymer is less than 0.005% by mass, the effect is insufficient, and if it exceeds 8% by mass, the coating film cannot be sufficiently dried, or the performance as an optical film (for example, letter The uniformity of the foundation).

式中、Ｒ⁰はアルキル基、末端にＣＦ₃基を有するアルキル基、又は末端にＣＦ₂Ｈ基を有するアルキル基を表し、ｍは１以上の整数を表す。複数個のＲ⁰は同一でも異なっていてもよいが、少なくとも一つは末端にＣＦ₃基又はＣＦ₂Ｈ基を有するアルキル基を表す。Ｌ⁰は（ｍ＋ｎ）価の連結基を表し、Ｗはカルボキシル基（−ＣＯＯＨ）もしくはその塩、スルホ基（−ＳＯ₃Ｈ）もしくはその塩、スルファト基（−ＯＳＯ₃Ｈ）もしくはその塩、又はホスホノキシ基｛−ＯＰ（＝Ｏ）（ＯＨ）₂｝もしくはその塩を表し、ｎは１以上の整数を表す。 Next, the fluorine-containing compound represented by the general formula (2) will be described.
<< Fluorine-containing compound represented by formula (2) >>

In the formula, R ⁰ represents an alkyl group, an alkyl group having a CF ₃ group at the terminal, or an alkyl group having a CF ₂ H group at the terminal, and m represents an integer of 1 or more. A plurality of R ⁰ may be the same or different, but at least one represents an alkyl group having a CF ₃ group or a CF ₂ H group at the terminal. L ⁰ represents an (m + n) -valent linking group, W represents a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, a sulfato group (—OSO ₃ H) or a salt thereof, or A phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof is represented, and n represents an integer of 1 or more.

In Formula (2), R ⁰ functions as a hydrophobic group of the fluorine-containing compound. The alkyl group represented by R ⁰ is a substituted or unsubstituted alkyl group, which may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, more preferably Is an alkyl group of 4 to 16, particularly preferably an alkyl group of 6 to 16. As the substituent, any of the substituents exemplified as the substituent group D described later can be applied.

The alkyl group having a CF ₃ group at the terminal represented by R ⁰ preferably has 1 to 20 carbon atoms, more preferably 4 to 16 and particularly preferably 4 to 8. The alkyl group having a CF ₃ group at the terminal is an alkyl group in which part or all of the hydrogen atoms contained in the alkyl group are substituted with fluorine atoms. 50% or more of the hydrogen atoms in the alkyl group are preferably substituted with fluorine atoms, more preferably 60% or more are substituted, and particularly preferably 70% or more are substituted. The remaining hydrogen atoms may be further substituted with the substituents exemplified as the substituent group D described later. The alkyl group having a CF ₂ H group at the terminal represented by R ⁰ preferably has 1 to 20 carbon atoms, more preferably 4 to 16 and particularly preferably 4 to 8. The alkyl group having a CF ₂ H group at the terminal is an alkyl group in which some or all of the hydrogen atoms contained in the alkyl group are substituted with fluorine atoms. 50% or more of hydrogen atoms in the alkyl group are preferably substituted with fluorine atoms, more preferably 60% or more are substituted, and particularly preferably 70% or more are substituted. The remaining hydrogen atoms may be further substituted with the substituents exemplified as the substituent group D described later. Examples of an alkyl group having a CF ₃ group at the terminal represented by R ⁰ or an alkyl group having a CF ₂ H group at the terminal are shown below.

R1: n-C ₈ F _{17-
R2: n-C 6 F 13} -
_{R3: n-C 4 F 9} -
_{R4: n-C 8 F 17} - (CH 2) 2 -
_{R5: n-C 6 F 13} - (CH 2) 2 -
_{R6: n-C 4 F 9} - (CH 2) 2 -
_{R7: H- (CF 2) 8} -
_{R8: H- (CF 2) 6} -
_{R9: H- (CF 2) 4} -
_{R10: H- (CF 2) 8} - (CH 2) -
R11: H— (CF ₂ ) ₆ — (CH ₂ ) —
_{R12: H- (CF 2) 4} - (CH 2) -

In the formula (2), the (m + n) -valent linking group represented by L ⁰ is an alkylene group, an alkenylene group, an aromatic group, a heterocyclic group, —CO—, or —NR— (R has 1 carbon atom. A linking group in which at least two groups selected from the group consisting of —O—, —S—, —SO—, and —SO ₂ — are combined.

In the formula (2), W represents a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, a sulfato group (—OSO ₃ H) or a salt thereof, or a phosphonoxy group {—OP (= O) (OH) ₂ } or a salt thereof. The preferable range of W is the same as Q in the general formula (1).

  Among the fluorine-containing compounds represented by the general formula (2), a compound represented by the following general formula (2a) or a general formula (2b) described later is preferable.

式（２ａ）中、Ｒ⁵及びＲ⁶は各々アルキル基、末端にＣＦ₃基を有するアルキル基、又は末端にＣＦ₂Ｈ基を有するアルキル基を表すが、Ｒ⁵及びＲ⁶が同時にアルキル基であることはない。Ｗ¹及びＷ²は各々水素原子、カルボキシル基（−ＣＯＯＨ）もしくはその塩、スルホ基（−ＳＯ₃Ｈ）もしくはその塩、スルファト基（−ＯＳＯ₃Ｈ）もしくはその塩、ホスホノキシ基｛−ＯＰ（＝Ｏ）（ＯＨ）₂｝もしくはその塩、又は置換基としてカルボキシル基、スルホ基、スルファト基もしくはホスホノキシ基を有するアルキル基、アルコキシ基、又はアルキルアミノ基を表すが、Ｗ¹及びＷ²が同時に水素原子であることはない。

In formula (2a), R ⁵ and R ⁶ each represents an alkyl group, an alkyl group having a CF ₃ group at the terminal, or an alkyl group having a CF ₂ H group at the terminal, wherein R ⁵ and R ⁶ are simultaneously an alkyl group. Never. W ¹ and W ² are each a hydrogen atom, a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, a sulfato group (—OSO ₃ H) or a salt thereof, a phosphonoxy group {—OP ( ═O) (OH) ₂ } or a salt thereof, or an alkyl group, an alkoxy group or an alkylamino group having a carboxyl group, a sulfo group, a sulfato group or a phosphonoxy group as a substituent, wherein W ¹ and W ² are simultaneously It is not a hydrogen atom.

R ⁵ and R ⁶ have the same meaning as R ⁰ in the general formula (2), and their preferred ranges are also the same. Carboxyl group (—COOH) or a salt thereof represented by W ¹ and W ² , sulfo group (—SO ₃ H) or a salt thereof, sulfato group (—OSO ₃ H) or a salt thereof, phosphonoxy group {—OP (= O) (OH) ₂ } or a salt thereof is synonymous with W in the general formula (2), and its preferred range is also the same. The alkyl group having a carboxyl group, a sulfo group, a sulfato group or a phosphonoxy group as a substituent represented by W ¹ and W ² may be linear or branched, and preferably has 1 carbon atom. -20 alkyl groups, more preferably 1-8 alkyl groups, and particularly preferably 1-3 alkyl groups. The alkyl group having a carboxyl group, a sulfo group, a sulfato group, or a phosphonoxy group as the substituent may have at least one carboxyl group, sulfo group, sulfato group, or phosphonoxy group. The group and the phosphonoxy group are synonymous with the carboxyl group, the sulfo group, the sulfato group, and the phosphonoxy group represented by W in the general formula (2), and the preferred range is also the same. The alkyl group having a carboxyl group, a sulfo group, a sulfato group or a phosphonoxy group as the substituent may be substituted with a substituent other than this, and the substituent is exemplified as the substituent group D described later. Either of these can be applied. The alkoxy group having a carboxyl group, a sulfo group, a sulfato group or a phosphonoxy group as a substituent represented by W ¹ and W ² may be linear or branched, and preferably has 1 carbon atom. -20 alkoxy groups, more preferably 1-8 alkoxy groups, and particularly preferably 1-4 alkoxy groups. The alkoxy group having a carboxyl group, a sulfo group, a sulfato group or a phosphonoxy group as the substituent may have at least one carboxyl group, sulfo group, sulfato group or phosphonoxy group. The group and the phosphonoxy group are synonymous with the carboxyl group, the sulfo group, the sulfato group, and the phosphonoxy group represented by W in the general formula (2), and the preferred range is also the same. The alkoxy group having a carboxyl group, a sulfo group, a sulfato group, or a phosphonoxy group may be substituted with a substituent other than this, and the substituent is any of the substituents exemplified as Substituent Group D described later. Can be applied. The alkylamino group having a carboxyl group, a sulfo group, a sulfato group or a phosphonoxy group as a substituent represented by W ¹ and W ² may be linear or branched, and preferably has a carbon number. 1 to 20 alkylamino groups, more preferably 1 to 8 alkylamino groups, and particularly preferably 1 to 4 alkylamino groups. The alkylamino group having a carboxyl group, a sulfo group, a sulfato group, or a phosphonoxy group may have at least one carboxyl group, sulfo group, sulfato group, or phosphonoxy group, such as a carboxyl group, a sulfo group, a sulfato group, and The phosphonoxy group is synonymous with the carboxyl group, sulfo group, sulfato group and phosphonoxy group represented by W in the general formula (2), and the preferred range is also the same. The alkylamino group having a carboxyl group, a sulfo group, a sulfato group, or a phosphonoxy group may be substituted with other substituents, and any of the substituents exemplified as Substituent Group D described later can be used as the substituent. Can apply.

W ¹ and W ² are particularly preferably each a hydrogen atom or (CH ₂ ) _n SO ₃ M (n represents 0 or 1). M represents a cation, but M may not be present when the charge is 0 in the molecule. As cations represented by M, for example, protonium ions, alkali metal ions (lithium ions, sodium ions, potassium ions, etc.), alkaline earth metal ions (barium ions, calcium ions, etc.), ammonium ions and the like are preferably applied. . Of these, proton ions, lithium ions, sodium ions, potassium ions, and ammonium ions are particularly preferable.

Next, the following general formula (2b) will be described.
General formula (2b)
(R ⁷ -L ^1- ) _m2 (Ar ¹ ) -W ³
In the formula (2b), R ⁷ represents an alkyl group, an alkyl group having a CF ₃ group at the terminal, or an alkyl group having a CF ₂ H group at the terminal, m2 represents an integer of 1 or more, and a plurality of R ⁷ May be the same or different, but at least one represents an alkyl group having a CF ₃ group or a CF ₂ H group at the terminal. L ¹ is an alkylene group, an aromatic group, —CO—, —NR— (R is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), —O—, —S—, —SO—, —SO. _2- represents a divalent linking group selected from the group consisting of a combination thereof, and a plurality of L ¹ may be the same or different. Ar ¹ represents an aromatic hydrocarbon ring or an aromatic heterocycle, W ³ represents a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, a sulfato group (—OSO ₃ H) or A salt thereof, a phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof, or an alkyl group, an alkoxy group, or an alkylamino group having a carboxyl group, a sulfo group, a sulfato group, or a phosphonoxy group as a substituent. .

R ⁷ has the same meaning as R ⁰ in formula (2), and its preferred range is also the same. L ¹ is preferably an alkylene group having 1 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, —CO—, —NR—, —O—, —S—, —SO—, —SO ₂ — and Represents a linking group having a total carbon number of 0 to 40 consisting of a combination thereof, particularly preferably an alkylene group having 1 to 8 carbon atoms, a phenyl group, —CO—, —NR—, —O—, —S—, —SO. ₂ represents a linking group having 0 to 20 carbon atoms and a combination thereof. Ar ¹ preferably represents an aromatic hydrocarbon ring having 6 to 12 carbon atoms, particularly preferably a benzene ring or a naphthalene ring. Carboxyl group represented by W ³ (—COOH) or a salt thereof, sulfo group (—SO ₃ H) or a salt thereof, sulfato group (—OSO ₃ H) or a salt thereof, phosphonoxy group {—OP (═O) ( OH) ₂ } or a salt thereof, or an alkyl group, an alkoxy group, or an alkylamino group having a carboxyl group, a sulfo group, a sulfato group, or a phosphonoxy group as a substituent, as W ¹ and W ² in the general formula (2a). Carboxyl group (—COOH) or a salt thereof, sulfo group (—SO ₃ H) or a salt thereof, sulfato group (—OSO ₃ H) or a salt thereof, phosphonoxy group {—OP (═O) (OH) ₂ } Or a salt thereof, an alkyl group having a carboxyl group, a sulfo group, a sulfato group or a phosphonoxy group as a substituent, an alkoxy group Group, or has the same meaning as the alkylamino group and the preferable ranges thereof are the same.

W ³ is preferably a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, or a carboxyl group (—COOH) or a salt thereof or a sulfo group (—SO ₃ H) as a substituent. Alternatively, it is an alkylamino group having a salt thereof, and particularly preferably SO ₃ M or CO ₂ M. M represents a cation, but M may not be present when the charge is 0 in the molecule. As cations represented by M, for example, protonium ions, alkali metal ions (lithium ions, sodium ions, potassium ions, etc.), alkaline earth metal ions (barium ions, calcium ions, etc.), ammonium ions and the like are preferably applied. . Of these, proton ions, lithium ions, sodium ions, potassium ions, and ammonium ions are particularly preferable.

  In the present specification, the substituent group D includes an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms, such as a methyl group. , Ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (preferably having 2 carbon atoms) -20, more preferably an alkenyl group having 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group), alkynyl A group (preferably an alkynyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, And aryl groups (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms). Group, p-methylphenyl group, naphthyl group and the like), substituted or unsubstituted amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms). An amino group, for example, an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group and the like),

An alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group). An aryloxy group (preferably an aryloxy group having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenyloxy group and a 2-naphthyloxy group. An acyl group (preferably having a carbon number of 1-20, more preferably a carbon number of 1-16, particularly preferably a carbon number of 1-12, such as an acetyl group, a benzoyl group, a formyl group, a pivaloyl group, etc. An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 2 carbon atoms). 2 alkoxycarbonyl groups, for example, methoxycarbonyl group, ethoxycarbonyl group and the like, and aryloxycarbonyl groups (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably carbon numbers). An aryloxycarbonyl group having 7 to 10 carbon atoms, such as a phenyloxycarbonyl group, an acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 2 carbon atoms). 10 acyloxy groups such as an acetoxy group and a benzoyloxy group)

An acylamino group (preferably an acylamino group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as an acetylamino group and a benzoylamino group), alkoxycarbonyl An amino group (preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group), aryloxy Carbonylamino group (preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as a phenyloxycarbonylamino group) Sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferred Or a sulfonylamino group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfonylamino group and a benzenesulfonylamino group, and a sulfamoyl group (preferably having a carbon number of 0 to 20). More preferably, it is a sulfamoyl group having 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, and examples thereof include a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, and a phenylsulfamoyl group. ), A carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, an unsubstituted carbamoyl group, a methylcarbamoyl group, diethylcarbamoyl group Group, phenylcarbamoyl group, etc.),

An alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, more preferably an alkylthio group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a methylthio group and an ethylthio group), an arylthio group ( Preferably it is C6-C20, More preferably, it is C6-C16, Most preferably, it is C6-C12 arylthio group, for example, a phenylthio group etc. are mentioned, A sulfonyl group (preferably C1-C1). 20, more preferably a sulfonyl group having 1 to 16 carbon atoms, particularly preferably a sulfonyl group having 1 to 12 carbon atoms, such as a mesyl group and a tosyl group, and a sulfinyl group (preferably having a carbon number of 1 to 20, more A sulfinyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms is preferable. Zensulfinyl group and the like), ureido group (preferably a ureido group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, an unsubstituted ureido group , Methylureido group, phenylureido group, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms). Yes, for example, diethyl phosphoric acid amide group, phenyl phosphoric acid amide group, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, Carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having a carbon number of 1 to 0, more preferably a heterocyclic group of 1 to 12, for example, a heterocyclic group having a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, such as an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group , Piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group and the like), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably A silyl group having 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group). These substituents may be further substituted with these substituents. Further, when two or more substituents are present, they may be the same or different. If possible, they may be bonded to each other to form a ring.

  As described above, the fluorine-containing compound preferably has a liquid crystal compound, particularly a polymer having a polymerizable group as a substituent in order to fix the alignment state of molecules of the discotic liquid crystal compound.

  Specific examples of the fluorine-containing compound represented by the general formula (2) that can be used in the present invention are shown below, but the fluorine-containing compound used in the present invention is not limited thereto. In the following specific examples, no. I-1 to 42 are general formula (2a), No. I-43 to 66 are examples of the compound represented by the general formula (2b).

  The preferred range of the content of the fluorine-containing compound in the composition varies depending on the use, but when used for forming the optically anisotropic layer, the composition (a composition excluding the solvent in the case of a coating solution) Among these, 0.005 to 8% by mass is preferable, 0.01 to 5% by mass is more preferable, and 0.05 to 1% by mass is even more preferable.

Next, the onium salt used in the present invention will be described.
(Onium salt: vertical alignment agent on the alignment film interface side)
The composition of the present invention contains an onium salt. The onium salt functions as a vertical alignment agent on the alignment film interface side in the composition of the present invention. Examples of the onium salts include onium salts such as ammonium salts, sulfonium salts, and phosphonium salts. A quaternary onium salt is preferable, and a quaternary ammonium salt is particularly preferable.

  Quaternary ammonium is generally a tertiary amine (eg, trimethylamine, triethylamine, tributylamine, triethanolamine, N-methylpyrrolidine, N-methylpiperidine, N, N-dimethylpiperazine, triethylenediamine, N, N, N ', N'-tetramethylethylenediamine, etc.) or nitrogen-containing heterocycle (pyridine ring, picoline ring, 2,2'-bipyridyl ring, 4,4'-bipyridyl ring, 1,10-phenanthroline ring, quinoline ring, oxazole ring , Thiazole ring, N-methylimidazole ring, pyrazine ring, tetrazole ring, etc.) can be obtained by alkylation (Menstokin reaction), alkenylation, alkynylation or arylation.

  As the quaternary ammonium salt, a quaternary ammonium salt composed of a nitrogen-containing heterocyclic ring is preferable, and a quaternary pyridinium salt is particularly preferable.

  The quaternary ammonium salt is preferably selected from quaternary pyridinium salts represented by the following general formula (3a) or a general formula (3b) described later.

式（３ａ）中、Ｒ⁸は置換もしくは無置換の、アルキル基、アルケニル基、アルキニル基、アラルキル基、アリール基又は複素環基を表し、Ｄは水素結合性基を表し、ｍは１〜３の整数を表し、Ｘ―はアニオンを表す。

In the formula (3a), R ⁸ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group or heterocyclic group, D represents a hydrogen bonding group, and m represents 1 to 3 X— represents an anion.

First, the general formula (3a) will be described.
The alkyl group represented by R ⁸ is preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, and more preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. These may be linear, branched or cyclic. Examples of these include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, n-octyl, neopentyl, cyclohexyl, adamantyl and cyclopropyl.

  Examples of the substituent of the alkyl group include the following. A substituted or unsubstituted alkenyl group having 2 to 18 carbon atoms (preferably 2 to 8 carbon atoms) (eg, vinyl); a substituted or unsubstituted alkynyl group having 2 to 18 carbon atoms (preferably having 2 to 8 carbon atoms) (Eg, ethynyl); substituted or unsubstituted aryl group having 6 to 10 carbon atoms (eg, phenyl, naphthyl); halogen atom (eg, F, Cl, Br, etc.); 1-8) substituted or unsubstituted alkoxy group (eg, methoxy, ethoxy); C6-C10 substituted or unsubstituted aryloxy group (eg, phenoxy, biphenyloxy, p-methoxyphenoxy); carbon number A substituted or unsubstituted alkylthio group having 1 to 18 (preferably 1 to 8 carbon atoms) (eg, methylthio, ethylthio); a substituted or unsubstituted arylthio having 6 to 10 carbon atoms (E.g., phenylthio); a substituted or unsubstituted acyl group having 2 to 18 carbon atoms (preferably 2 to 8 carbon atoms) (e.g., acetyl, propionyl);

  C1-C18 (preferably C1-C8) substituted or unsubstituted alkylsulfonyl group or arylsulfonyl group (e.g., methanesulfonyl, p-toluenesulfonyl); C2-C18 (preferably C2-C2) To 8) substituted or unsubstituted acyloxy groups (eg, acetoxy, propionyloxy); substituted or unsubstituted alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxy) having 2 to 18 carbon atoms (preferably 2 to 8 carbon atoms). A substituted or unsubstituted aryloxycarbonyl group having 7 to 11 carbon atoms (eg, naphthoxycarbonyl); an unsubstituted amino group or a substituted amino group having 1 to 18 carbon atoms (preferably having 1 to 8 carbon atoms) Groups (eg methylamino, dimethylamino, diethylamino, anilino, methoxyphenylamino, chloro Phenylamino, pyridylamino, methoxycarbonylamino, n-butoxycarbonylamino, phenoxycarbonylamino, methylcarbamoylamino, ethylthiocarbamoylamino, phenylcarbamoylamino, acetylamino, ethylcarbonylamino, ethylthiocarbamoylamino, cyclohexylcarbonylamino, benzoylamino , Chloroacetylamino, methylsulfonylamino);

  A substituted or unsubstituted carbamoyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) (eg, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, dimethylcarbamoyl, morpholino) Carbamoyl, pyrrolidinocarbamoyl); unsubstituted sulfamoyl group, or substituted sulfamoyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) (eg, methylsulfamoyl, phenylsulfamoyl); cyano group; nitro group Group; carboxy group; hydroxyl group; heterocyclic group (eg, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, imidazole ring, benzimidazole ring, indolenine ring, pyridine ring, piperidine ring, pyrrolidine ring, morpholine ring, A sulfolane ring, Orchid ring, thiophene ring, pyrazole ring, pyrrole ring, chroman ring, a coumarin ring). The substituent for the alkyl group is particularly preferably an aryloxy group, an arylthio group, an arylsulfonyl group, or an aryloxycarbonyl group.

The alkenyl group represented by R ⁸ is preferably a substituted or unsubstituted alkenyl group having 2 to 18 carbon atoms, more preferably a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, such as vinyl, Examples include allyl, 1-propenyl, 1,3-butadienyl and the like. As the substituent for the alkenyl group, those exemplified as the substituent for the alkyl group are preferable.

The alkynyl group represented by R ⁸ is preferably a substituted or unsubstituted alkynyl group having 2 to 18 carbon atoms, more preferably a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms, such as ethynyl, 2-propynyl etc. are mentioned. As the substituent for the alkynyl group, those exemplified as the substituent for the alkyl group are preferable.

The aralkyl group represented by R ⁸ is preferably a substituted or unsubstituted aralkyl group having 7 to 18 carbon atoms, such as benzyl, methylbenzyl, biphenylmethyl, naphthylmethyl, and the like. Examples of the substituent for the aralkyl group include those exemplified as the substituent for the alkyl group.

The aryl group represented by R ⁸ is preferably a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, and examples thereof include phenyl, naphthyl, and fluorenyl. As the substituent for the aryl group, those exemplified as the substituent for the alkyl group are preferable. Besides these, an alkyl group (for example, methyl, ethyl, etc.), an alkynyl group, and a benzoyl group are also preferable.

The heterocyclic group represented by R ⁸ is a 5- or 6-membered saturated or unsaturated heterocyclic ring composed of a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and examples thereof include oxazole Ring, benzoxazole ring, thiazole ring, benzothiazole ring, imidazole ring, benzimidazole ring, indolenine ring, pyridine ring, piperidine ring, pyrrolidine ring, morpholine ring, sulfolane ring, furan ring, thiophene ring, pyrazole ring, pyrrole ring , Chroman ring, and coumarin ring. The heterocyclic group may be substituted, and as the substituent in that case, those exemplified as the substituent of the alkyl group are preferable. As the heterocyclic group represented by R ⁸ , a benzoxazole ring and a benzothiazole ring are particularly preferable.

R ⁸ is preferably a substituted or unsubstituted alkyl group, aralkyl group, aryl group or heterocyclic group.

  D represents a hydrogen bonding group. Hydrogen bonds exist between electronegative atoms (eg, O, N, F, Cl) and hydrogen atoms covalently bonded to electronegative atoms as well. As a theoretical interpretation of hydrogen bonding, for example, H.H. Unneyama and K.M. There are reports in Morokuma, Journal of American Chemical Society, Vol. 99, pp. 1316-1332, 1977. Specific examples of hydrogen bonding include J.I. N. Examples include Israes Ativiri, Yasuo Kondo, Hiroyuki Oshima, Intermolecular Force and Surface Force, McGraw Hill, 1991, page 98, FIG. Specific examples of hydrogen bonding include, for example, G.I. R. Examples include those described in Desiraju, Angewent Chemistry International Edition England, Vol. 34, p. 2311, 1995.

  Preferred hydrogen bonding groups include mercapto groups, hydroxy groups, amino groups, carbonamido groups, sulfonamido groups, acid amide groups, ureido groups, carbamoyl groups, carboxyl groups, sulfo groups, nitrogen-containing heterocyclic groups (for example, imidazolyl). Group, benzimidazolyl group, pyrazolyl group, pyridyl group, 1,3,5-triazyl group, pyrimidyl group, pyridazyl group, quinolyl group, benzimidazolyl group, benzthiazolyl group, succinimide group, phthalimide group, maleimide group, uracil group, thiouracil Group, barbituric acid group, hydantoin group, maleic hydrazide group, isatin group, uramil group and the like. More preferred hydrogen bonding groups include amino group, carbonamido group, sulfonamido group, ureido group, carbamoyl group, carboxyl group, sulfo group, and pyridyl group, and particularly preferred are amino group, carbamoyl group, A pyridyl group can be mentioned.

The anion represented by X ⁻ may be either an inorganic anion or an organic anion, such as a halogen anion (eg, fluorine ion, chlorine ion, bromine ion, iodine ion), sulfonate ion (eg, methanesulfone). Acid ion, trifluoromethanesulfonic acid ion, methylsulfuric acid ion, p-toluenesulfonic acid ion, p-chlorobenzenesulfonic acid ion, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalene Disulfonate ions, etc.), sulfate ions, thiocyanate ions, perchlorate ions, tetrafluoroborate ions, picrate ions, acetate ions, phosphate ions (for example, hexafluorophosphate ions), hydroxide ions, etc. . X ⁻ is preferably a halogen anion, a sulfonate ion, or a hydroxide ion. X ⁻ need not be a monovalent anion and may be a divalent or higher anion. In such a case, the ratio of the cation to the anion in the compound need not be 1: 1, It is determined.

  In the general formula (3a), m is preferably 1.

式（３ｂ）中、Ｒ⁹及びＲ¹⁰は各々置換もしくは無置換の、アルキル基、アルケニル基、アルキニル基、アラルキル基、アリール基又は複素環基を表し、Ｘ―はアニオンを表す。
Ｒ⁹及びＲ¹⁰で各々表される置換もしくは無置換の、アルキル基、アルケニル基、アルキニル基、アラルキル基、アリール基又は複素環基は、前記一般式（３ａ）中、Ｒ⁸で表される基と同義であり、その好ましい範囲も同一である。Ｘ^-で表されるアニオンは、前記一般式（３ａ）中、Ｘ^-で表されるアニオンと同義であり、その好ましい範囲も同一である。前記した様に、Ｘ^-は１価のアニオンである必要はなく、２価以上のアニオンであってもよく、かかる場合は、前記化合物中のカチオンとアニオンとの比率も１：２である必要はなく、適宜決定される。 Next, the general formula (3b) will be described.

In the formula (3b), R ⁹ and R ¹⁰ each represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group or heterocyclic group, and X— represents an anion.
The substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group or heterocyclic group represented by R ⁹ and R ¹⁰ respectively is represented by R ⁸ in the general formula (3a). It is synonymous with a group, and its preferable range is also the same. X ^- anion represented by the In the general formula (3a), X ^- has the same meaning as anion represented by, and the preferable ranges thereof are also the same. As described above, X ⁻ need not be a monovalent anion but may be a divalent or higher anion. In such a case, the ratio of the cation to the anion in the compound should be 1: 2. It is not determined.

  Specific examples of onium salts that can be used in the present invention are shown below, but the onium salts used in the present invention are not limited thereto. In the following specific examples, no. II-1 to 12 are general formulas (3b), No. II-13 to 32 are examples of the compound represented by the general formula (3a).

  The preferred range of the content of the onium salt in the composition varies depending on the application, but in the composition (a composition excluding the solvent in the case of a coating solution) when used for forming the optically anisotropic layer. 0.005 to 8% by mass is preferable, 0.01 to 5% by mass is more preferable, and 0.05 to 1% by mass is even more preferable.

(Liquid crystal compound)
The liquid crystal compound contained in the composition of the present invention is preferably a discotic liquid crystal compound, and among them, a triphenylene liquid crystal is more preferable. Discotic liquid crystalline compounds are disclosed in various documents (C. Destrade et al., Mol. Crysr. Liq. Cryst., Vol. 71, page 111 (1981); edited by The Chemical Society of Japan, Quarterly Chemical Review, No. 22, Liquid Crystal Chemistry, Chapter 5, Chapter 10 Section 2 (1994); B. Kohne et al., Angew. Chem. Soc. Chem. Comm., Page 1794 (1985); J. Zhang et al., J Am.Chem.Soc., Vol.116, page 2655 (1994)). The polymerization of discotic liquid crystalline compounds is described in JP-A-8-27284.

The discotic liquid crystalline compound preferably has a polymerizable group so that it can be fixed by polymerization. For example, a structure in which a polymerizable group is bonded as a substituent to a discotic core of a discotic liquid crystalline compound is conceivable. However, when a polymerizable group is directly connected to the discotic core, the alignment state is maintained in the polymerization reaction. It becomes difficult. Therefore, a structure having a linking group between the discotic core and the polymerizable group is preferable. That is, the discotic liquid crystalline compound having a polymerizable group is preferably a compound represented by the following formula.
D (-LP) _n
In the formula, D is a discotic core, L is a divalent linking group, P is a polymerizable group, and n is an integer of 4 to 12. Preferred specific examples of the discotic core (D), the divalent linking group (L) and the polymerizable group (P) in the above formula are (D1) to (D15) described in JP-A No. 2001-4837, respectively. ), (L1) to (L25), and (P1) to (P18), and the contents described in the publication can be preferably used.
In addition, the discotic nematic liquid crystal phase-solid phase transition temperature of the liquid crystal compound is preferably 70 to 300 ° C, and more preferably 70 to 170 ° C.

(Polymerization initiator)
The vertically aligned discotic liquid crystal compound is fixed while maintaining the alignment state. The immobilization is preferably performed by a polymerization reaction of the polymerizable group (P) introduced into the liquid crystal compound. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. A photopolymerization reaction is preferred. Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), 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. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Acridine and phenazine compounds (JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (described in U.S. Pat. No. 4,212,970).

The amount of the photopolymerization initiator used is preferably 0.01 to 20% by weight, more preferably 0.5 to 5% by weight, based on the solid content of the coating solution. Light irradiation for polymerization of discotic liquid crystalline molecules is preferably performed using ultraviolet rays. The irradiation energy is preferably ^{20mJ / cm 2 ~50J / cm 2} , further preferably 100 to 800 mJ / cm ^2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions.

(Other additives for optically anisotropic layers)
Along with the liquid crystal compound, a plasticizer, a surfactant, a polymerizable monomer, and the like can be used in combination to improve the uniformity of the coating film, the strength of the film, the orientation of the liquid crystal compound, and the like. These materials are preferably compatible with the liquid crystal compound and do not inhibit the alignment.

  Examples of the polymerizable monomer include radically polymerizable or cationically polymerizable compounds. Preferably, it is a polyfunctional radically polymerizable monomer and is preferably copolymerizable with the above-described polymerizable group-containing liquid crystal compound. Examples thereof include those described in paragraph numbers [0018] to [0020] in JP-A No. 2002-296423. The amount of the compound added is generally in the range of 1 to 50% by mass and preferably in the range of 5 to 30% by mass with respect to the discotic liquid crystalline molecules.

  Examples of the surfactant include conventionally known compounds, and fluorine compounds are particularly preferable. Specifically, for example, compounds described in JP-A-2001-330725, paragraphs [0028] to [0056], and paragraphs [0069] to [0126] in Japanese Patent Application No. 2003-295212. And the compounds described.

  The polymer used together with the liquid crystal compound is preferably capable of thickening the coating solution. A cellulose ester can be mentioned as an example of a polymer. Preferable examples of the cellulose ester include those described in paragraph [0178] of JP-A No. 2000-155216. The addition amount of the polymer is preferably in the range of 0.1 to 10% by mass, and in the range of 0.1 to 8% by mass with respect to the liquid crystal molecules so as not to inhibit the alignment of the liquid crystal compound. It is more preferable.

[Formation of Optically Anisotropic Layer] The composition of the present invention can be used as a material for forming a layer having optical anisotropy expressed by vertical alignment of a liquid crystalline compound, particularly a discotic liquid crystalline compound. The optically anisotropic layer formed using the composition of the present invention can be used for various applications, and when used as a member of a liquid crystal display device, particularly an IPS liquid crystal display device, improves the viewing angle. Contribute. The optically anisotropic layer can be formed by applying the composition of the present invention on an alignment film. For the convenience of application, it is preferably in the form of a coating solution. As a solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination. The coating liquid can be applied by a known method (eg, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method).

  The thickness of the optically anisotropic layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm, and most preferably 1 to 5 μm.

(Alignment film)
Since the alignment film has a function of defining the alignment direction of the liquid crystal compound, particularly the discotic liquid crystal compound, it is essential for realizing a preferred embodiment of the present invention. However, if the alignment state is fixed after aligning the liquid crystalline compound, the alignment film plays the role, and thus is not necessarily an essential component of the present invention. That is, it is not necessary for the alignment film to be present at the time of use, such as transferring only the optically anisotropic layer on the alignment film having a fixed alignment state onto the polarizer.
The alignment film is an organic compound (eg, ω-tricosanoic acid) formed by rubbing treatment of an organic compound (preferably polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir-Blodgett method (LB film). , Dioctadecylmethylammonium chloride, methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known.

  The alignment film is preferably formed by polymer rubbing treatment. In principle, the polymer used in the alignment film has a molecular structure having a function of aligning the discotic liquid crystalline compound. In the present invention, in addition to the function of aligning liquid crystal molecules, the cross-linkability has a function of aligning a polymer in which a side chain having a crosslinkable functional group (eg, a double bond) is bonded to the main chain or a liquid crystal molecule. A polymer having a functional group in the side chain is preferred. As the polymer used for the alignment film, either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent can be used, and a plurality of combinations thereof can be used.

  Examples of the polymer used for forming the alignment film include, for example, a methacrylate copolymer, a styrene copolymer, a polyolefin, polyvinyl alcohol, and modified polyvinyl as described in paragraph [0022] of JP-A-8-338913. Examples include alcohol, poly (N-methylolacrylamide), polyester, polyimide, vinyl acetate copolymer, carboxymethylcellulose, and polycarbonate. Silane coupling agents can be used as the polymer. Water-soluble polymers (eg, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, modified polyvinyl alcohol) are preferred, gelatin, polyvinyl alcohol and modified polyvinyl alcohol are more preferred, and polyvinyl alcohol and modified polyvinyl alcohol are most preferred. . It is particularly preferable to use two types of polyvinyl alcohol or modified polyvinyl alcohol having different degrees of polymerization.

  The saponification degree of polyvinyl alcohol is preferably 70 to 100%, more preferably 80 to 100%. The polymerization degree of polyvinyl alcohol is preferably 100 to 5000.

  A side chain having a function of aligning a discotic liquid crystalline compound generally has a hydrophobic group as a functional group. The specific type of functional group is determined according to the type of liquid crystal molecule and the required alignment state. For example, the modifying group of the modified polyvinyl alcohol can be introduced by copolymerization modification, chain transfer modification or block polymerization modification. Examples of modifying groups include hydrophilic groups (carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, amino groups, ammonium groups, amide groups, thiol groups, etc.), hydrocarbon groups having 10 to 100 carbon atoms, fluorine atoms Substituted hydrocarbon groups, thioether groups, polymerizable groups (unsaturated polymerizable groups, epoxy groups, azirinidyl groups, etc.), alkoxysilyl groups (trialkoxy, dialkoxy, monoalkoxy) and the like can be mentioned. As specific examples of these modified polyvinyl alcohol compounds, for example, paragraph numbers [0022] to [0145] in JP-A No. 2000-155216 and paragraph numbers [0018] to [0018] in JP-A No. 2002-62426 are described. [0022] and the like.

When a side chain having a crosslinkable functional group is bonded to the main chain of the alignment film polymer, or a crosslinkable functional group is introduced into a side chain having a function of aligning liquid crystalline molecules, the alignment film polymer and the optically anisotropic film The polyfunctional monomer contained in the conductive layer can be copolymerized. As a result, not only between the polyfunctional monomer and the polyfunctional monomer, but also between the alignment film polymer and the alignment film polymer and between the polyfunctional monomer and the alignment film polymer is firmly bonded by a covalent bond. Therefore, the strength of the optical compensation film can be remarkably improved by introducing the crosslinkable functional group into the alignment film polymer.
The crosslinkable functional group of the alignment film polymer preferably contains a polymerizable group in the same manner as the polyfunctional monomer. Specifically, for example, those described in paragraphs [0080] to [0100] of JP-A No. 2000-155216 can be mentioned.

  Apart from the crosslinkable functional group, the alignment film polymer can also be crosslinked using a crosslinking agent. Examples of the crosslinking agent include aldehydes, N-methylol compounds, dioxane derivatives, compounds that act by activating carboxyl groups, active vinyl compounds, active halogen compounds, isoxazole and dialdehyde starch. Two or more kinds of crosslinking agents may be used in combination. Specific examples include compounds described in paragraphs [0023] to [024] in JP-A-2002-62426. Aldehydes having high reaction activity, particularly glutaraldehyde are preferred.

  0.1-20 mass% is preferable with respect to a polymer, and, as for the addition amount of a crosslinking agent, 0.5-15 mass% is more preferable. The amount of the unreacted crosslinking agent remaining in the alignment film is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less. By adjusting in this way, even if the alignment film is used for a long time in a liquid crystal display device or left in a high temperature and high humidity atmosphere for a long time, sufficient durability without reticulation can be obtained.

  The alignment film can be basically formed by applying the polymer on the transparent support containing the alignment film forming material and the crosslinking agent, followed by drying by heating (crosslinking) and rubbing treatment. As described above, the crosslinking reaction may be performed at an arbitrary time after coating on the transparent support. When a water-soluble polymer such as polyvinyl alcohol is used as the alignment film forming material, the coating solution is preferably a mixed solvent of an organic solvent (eg, methanol) having a defoaming action and water. The ratio of water: methanol is preferably 0: 100 to 99: 1, and more preferably 0: 100 to 91: 9. Thereby, generation | occurrence | production of a bubble is suppressed and the defect of the layer surface of an orientation film and also an optically anisotropic layer reduces remarkably.

  The coating method is preferably a spin coating method, dip coating method, curtain coating method, extrusion coating method, rod coating method or roll coating method. A rod coating method is particularly preferable. The film thickness after drying is preferably 0.1 to 10 μm. Heating and drying can be performed at 20 ° C to 110 ° C. In order to form sufficient cross-linking, 60 ° C to 100 ° C is preferable, and 80 ° C to 100 ° C is more preferable. The drying time can be 1 minute to 36 hours, preferably 1 minute to 30 minutes. The pH is preferably set to an optimum value for the crosslinking agent to be used. When glutaraldehyde is used, the pH is 4.5 to 5.5, and 5 is particularly preferable.

  The alignment film is preferably provided on the transparent support. The alignment film can be obtained by rubbing the surface after crosslinking the polymer layer as described above.

  For the rubbing treatment, a treatment method widely adopted as a liquid crystal alignment treatment process of LCD can be applied. That is, a method of obtaining the orientation by rubbing the surface of the orientation film in a certain direction using paper, gauze, felt, rubber, nylon, polyester fiber or the like can be used. In general, it is carried out by rubbing several times using a cloth in which fibers having a uniform length and thickness are flocked on average.

  Next, the alignment film is caused to function to align the discotic liquid crystalline compound of the optically anisotropic layer provided on the alignment film. Thereafter, as necessary, the alignment film polymer and the polyfunctional monomer contained in the optically anisotropic layer are reacted, or the alignment film polymer is crosslinked using a crosslinking agent. The thickness of the alignment film is preferably in the range of 0.1 to 10 μm.

(Support)
In the present invention, a transparent support may be used. As the transparent support, it is preferable to use a polymer film having a small wavelength dispersion. The transparent support preferably has a small optical anisotropy. That the support is transparent means that the light transmittance is 80% or more. Specifically, the small chromatic dispersion means that the ratio of Re400 / Re700 is preferably less than 1.2. Specifically, the small optical anisotropy means that in-plane retardation (Re) is preferably 20 nm or less, and more preferably 10 nm or less. Examples of the polymer include cellulose ester, polycarbonate, polysulfone, polyethersulfone, polyacrylate and polymethacrylate. Cellulose esters are preferred, acetyl cellulose is more preferred, and triacetyl cellulose is most preferred. The polymer film is preferably formed by a solvent cast method. The thickness of the transparent support is preferably 20 to 500 μm, and more preferably 50 to 200 μm. In order to improve adhesion between the transparent support and the layer (adhesive layer, vertical alignment film or retardation layer) provided thereon, surface treatment (eg, glow discharge treatment, corona discharge treatment, ultraviolet light (UV) ) Treatment, flame treatment). An adhesive layer (undercoat layer) may be provided on the transparent support. Moreover, the average particle diameter is 10 to 100 nm in order to provide the transparent support or the long transparent support with slipperiness in the conveying process or to prevent the back surface and the surface from sticking after winding. It is preferable to use what formed the polymer layer which mixed the inorganic particle of about 5%-40% by solid content weight ratio by the application | coating or co-casting with the support body on the one side of the support body.

[Optical compensation film]
The optical compensation film of the present invention contains at least one compound that increases or decreases the tilt angle at the air interface of the liquid crystal compound and at least one compound that increases or decreases the tilt angle at the alignment film interface of the liquid crystal compound. Has an anisotropic layer. In the present invention, the compound that increases or decreases the tilt angle at the air interface of the liquid crystal compound is used in combination with the vicinity of the air interface of the discotic liquid crystal compound (for example, the compound used in Example 1 of the present application). It is a compound that can change the tilt angle by 10 to 40 degrees. Further, when used in combination with a compound that increases or decreases the tilt angle at the alignment film interface of the liquid crystal compound, the tilt in the vicinity of the alignment film of the discotic liquid crystal compound (for example, the compound used in Example 1 of the present application) is used. It is a compound that can change the angle by 10 to 90 degrees. The tilt angle is determined by applying a solution containing a discotic liquid crystalline compound (for example, the compound used in Example 1 of the present application) onto the alignment film formed on the transparent support in the same manner as in Example 1 of the present application. Coating, drying, heating to the liquid crystal phase formation temperature, and then maintaining the alignment state and cooling, and then polymerizing to produce an optical compensation film (APE-100, manufactured by Shimadzu Corporation) The retardation is measured by changing the observation angle using, and is assumed to be a refractive index ellipsoid model, and is calculated by the method described in Designing Concepts of the Discotic Negative Birefringence Compensation Films SID98 DIGEST. The change in the tilt angle is evaluated by the difference between the tilt angle with and without the compound that increases or decreases the tilt angle. The measurement wavelength is 632.8 nm. The concentration of the compound that increases or decreases the tilt angle is preferably 0.005 to 8% by mass in the composition (a composition excluding the solvent in the case of a coating solution), and 0.01 to 5% by mass. It is more preferable that it is 0.05 to 1% by mass.

The optical compensation film of the present invention particularly preferably has an optically anisotropic layer formed from the composition of the present invention. The optical compensation film of the present invention may consist of only one optically anisotropic layer or may be a laminate of two or more layers. It may be a laminate with an optically anisotropic layer and / or a polymer film made of another liquid crystal composition.
As described above, the alignment film and the support used when forming the optically anisotropic layer are not essential components in the optical compensation film of the present invention.

  When the optical compensation film of the present invention is applied to an IPS liquid crystal display device, it contains at least a discotic liquid crystal compound (preferably triphenylene liquid crystal), a compound having the fluoroaliphatic group and a hydrophilic group, and an onium salt. And a retardation region formed of an optically anisotropic layer formed by a composition in which the discotic liquid crystal molecules are substantially vertically aligned, Re (defined later) is 20 nm or less, and Rth (defined) Is described later) is preferably composed of a retardation region of 20 nm to 150 nm.

Next, an embodiment of an IPS liquid crystal display device having an optically anisotropic layer formed from the composition of the present invention will be described. FIG. 1 is a schematic diagram showing an example of a pixel region of the liquid crystal display device of the present invention. FIG. 2 is a schematic view of an embodiment of the liquid crystal display device of the present invention.
[Liquid Crystal Display]
The liquid crystal display device shown in FIG. 2 includes a first polarizing film 8, an optical compensation film 10, a first substrate 14, a liquid crystal layer 16, a second substrate 18, and a second polarizing film 21. The first polarizing film 8 and the second polarizing film 21 are sandwiched between protective films 7a and 7b and 20a and 20b, respectively. The optical compensation film 10 includes a first retardation region 11 including a protective film 7 b in contact with the first polarizing film 8 and a second retardation region 12 in contact with the first phase region 11.

  In the liquid crystal display device of FIG. 2, the liquid crystal cell includes a first substrate 14 and a second substrate 17, and a liquid crystal layer 16 sandwiched between them. The product Δn · d of the thickness d (μm) of the liquid crystal layer and the refractive index anisotropy Δn is optimal in the range of 0.2 to 0.4 μm for the IPS type having no twisted structure in the transmission mode. In this range, the white display luminance is high and the black display luminance is small, so that a bright and high-contrast display device can be obtained. An alignment film (not shown) is formed on the surfaces of the substrates 14 and 18 that are in contact with the liquid crystal layer 16 so that the liquid crystal molecules are aligned substantially parallel to the surface of the substrate and are rubbed on the alignment film. By the processing directions 15 and 19 and the like, the alignment direction of liquid crystal molecules in a state in which no voltage is applied or in a low application state is controlled. An electrode (not shown in FIG. 2) capable of applying a voltage to the liquid crystal molecules is formed on the inner surface of the substrate 14 or 17.

  FIG. 1 schematically shows the alignment of liquid crystal molecules in one pixel region of the liquid crystal layer 16. FIG. 1 shows the alignment of liquid crystal molecules in a very small area corresponding to one pixel of the liquid crystal layer 16 in the rubbing direction 4 of the alignment film formed on the inner surfaces of the substrates 14 and 18 and the substrates 14 and 18. It is the schematic diagram shown with the electrodes 2 and 3 which can apply a voltage to the liquid crystal molecule formed in the inner surface. When active driving is performed using a nematic liquid crystal having positive dielectric anisotropy as a field effect liquid crystal, the liquid crystal molecule alignment directions in a no voltage application state or a low application state are 5a and 5b. A display is obtained. When applied between the electrodes 2 and 3, the liquid crystal molecules change their alignment direction in the directions of 6 a and 6 b in accordance with the voltage. Usually, bright display is performed in this state.

  In FIG. 2 again, the transmission axis 9 of the first polarizing film 8 and the transmission axis 22 of the second polarizing film 21 are arranged orthogonally. The optical compensation film 10 is composed of two regions, a first retardation region 11 and a second retardation region 12. The slow axis 13 of the second retardation region 12 is parallel to the transmission axis 9 of the first polarizing film 8 and the slow axis direction 17 of the liquid crystal molecules in the liquid crystal layer 16 during black display, and the second The retardation region 12 is disposed closer to the liquid crystal layer 16 than the first retardation region 11. The second retardation region is an optically anisotropic layer formed from the composition of the present invention containing at least a discotic liquid crystalline compound, a compound having the fluoroaliphatic group and the hydrophilic group, and an onium salt. Consists of. In the optically anisotropic layer, the molecules of the discotic liquid crystalline compound are fixed in a substantially vertically aligned state, and a predetermined optical anisotropy is expressed. The optical characteristics of the two regions constituting the optical compensation film will be described later.

  In the liquid crystal display device shown in FIG. 2, the configuration in which the first polarizing film 8 is sandwiched between the two protective films 7a and 7b is shown, but the protective film 7b may be omitted. In the case where the protective film 7b is disposed, the protective film 7b is one of the layers constituting the first retardation region 11 in the present invention. In the liquid crystal display device shown in FIG. 2, the second polarizing film 21 is also sandwiched between two protective films 20a and 20b. The thickness direction retardation Rth of the protective film 20a on the side close to the liquid crystal layer 16 is preferably 20 nm or less.

  In addition, in FIG. 2, although the aspect of the display device of the transmission mode provided with the upper side polarizing plate and the lower side polarizing plate was shown, this invention may be the aspect of the reflection mode provided with only one polarizing plate, In such a case, since the optical path in the liquid crystal cell is doubled, the optimum value of Δn · d is about the above half value.

  The liquid crystal display device of the present invention is not limited to the configuration shown in FIGS. 1 and 2, and may include other members. For example, a color filter may be disposed between the liquid crystal layer and the polarizing film. Further, an antireflection treatment or a hard coat may be applied to the surface of the protective film of the polarizing film. Moreover, you may use what gave electroconductivity to the structural member. In the case of use as a transmission type, a cold cathode or a hot cathode fluorescent tube, or a backlight having a light emitting diode, a field emission element, or an electroluminescent element as a light source can be disposed on the back surface. In addition, a reflective polarizing plate, a diffusion plate, a prism sheet, or a light guide plate can be disposed between the liquid crystal layer and the backlight. In addition, the liquid crystal display device of the present invention may be of a reflective type. In such a case, only one polarizing plate may be disposed on the observation side, and reflected on the back surface of the liquid crystal cell or the inner surface of the lower substrate of the liquid crystal cell. Place the membrane. Of course, it is also possible to provide a front light using the light source on the liquid crystal cell observation side.

  The liquid crystal display device of the present invention includes an image direct view type, an image projection type, and a light modulation type. The present invention is particularly effective when applied to an active matrix liquid crystal display device using a three-terminal or two-terminal semiconductor element such as TFT or MIM. Of course, a mode applied to a passive matrix liquid crystal display device called time-division driving is also effective.

(First retardation region of optical compensation film)
The optical characteristics of the first retardation region are represented by Re = (nx−ny) × d using the in-plane refractive indexes nx and ny (nx ≧ ny), the refractive index nz in the thickness direction, and the thickness d of the film. The in-plane retardation Re defined by is 20 nm or less, more preferably 10 nm or less, and even more preferably 5 nm or less. The thickness direction retardation Rth defined by Rth = ((nx + ny) / 2−nz) × d is 20 nm to 120 nm, and more preferably 40 nm to 100 nm. When the protective film 7b that protects the first polarizing film 8 has optical anisotropy, the protective film 7b is a layer constituting the first retardation region 11, so that Rth of the protective film and others It is required that the total Rth of the layers is 40 nm to 100 nm.

  The retardation film having this optical characteristic includes a retardation film made of a birefringent polymer film, and an optically anisotropic layer formed by applying or transferring a low-molecular or high-molecular liquid crystalline compound on a transparent support. Although there is a phase difference film or the like, any of them can be used in the present invention.

  A retardation film made of a birefringent polymer film having the above optical characteristics can be easily formed by biaxially stretching a polymer film. In addition, cellulose acylates that exhibit this optical property by simply casting without stretching can be suitably used. As such cellulose acylate, those described in JP-A-2002-90541 can be used. As a material for the polymer film, a synthetic polymer (eg, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethacrylate, norbornene resin, cellulose acylate) is generally used.

  As a retardation film formed on a transparent support by coating or transfer, a rod-like cholesteric liquid crystal composition containing a chiral structural unit is aligned after its helical axis is oriented substantially perpendicular to the substrate, Examples thereof include those obtained by horizontally aligning a discotic liquid crystalline compound having a negative intrinsic birefringence (the director is perpendicular to the substrate), and those obtained by casting and fixing a polyimide polymer on the substrate.

(Second retardation region of optical compensation film)
The second retardation region is an optically anisotropic layer formed from the composition of the present invention containing at least a discotic liquid crystalline compound, a fluorine compound having a fluoroaliphatic group and a hydrophilic group, and an onium salt. Consists of. In the optically anisotropic layer, the molecules of the discotic liquid crystalline compound are fixed in a substantially vertically aligned state and exhibit predetermined optical characteristics. The optical compensation film is arranged so that the slow axis of the second retardation region is parallel to the transmission axis of the first polarizing film and the slow axis direction of the liquid crystal compound in the liquid crystal layer during black display. The Re of the second retardation region is preferably 50 nm to 200 nm, and more preferably 80 nm to 160 nm. This adjustment of Re is performed by controlling the thickness of the discotic liquid crystal layer to be formed by coating. Furthermore, the discotic liquid crystalline molecules need to be oriented substantially perpendicular to the film surface (average inclination angle in the range of 70 to 90 degrees). When the average inclination angle is smaller than this, the light leakage distribution becomes asymmetric. Substantially perpendicular means that the average angle (average inclination angle) between the disk surface and the surface of the optically anisotropic layer is in the range of 70 ° to 90 °. These discotic liquid crystalline molecules may be aligned obliquely or may be changed so that the inclination angle gradually changes (hybrid alignment). Even in the case of oblique orientation or hybrid orientation, the average inclination angle is preferably 70 ° to 90 °, more preferably 75 ° to 90 °, and most preferably 80 ° to 90 °. As described above, the compound having a fluoroaliphatic group and the onium salt contribute to bringing the molecules of the discotic liquid crystal compound (preferably triphenylene liquid crystal) into such a vertically aligned state.

  The second retardation region may be composed only of the optically anisotropic layer formed from the composition of the present invention, or may be composed of the optically anisotropic layer and other layers. Good. In the latter case, a laminate with a stretched polystyrene film or a laminate with an optically isotropic film such as a cycloolefin can be suitably used.

(Protective film for second polarizing plate)
The protective film for the second polarizing plate is preferably a protective film having no absorption in the visible light region, a light transmittance of 80% or more, and a small retardation based on birefringence. Specifically, the in-plane Re is preferably 20 nm or less, more preferably 10 nm or less, and most preferably 5 nm or less. Further, the retardation Rth in the thickness direction is preferably 20 nm or less, more preferably 10 nm or less, and most preferably 5 nm or less. Any film having this property can be preferably used, but from the viewpoint of durability of the polarizing film, a cellulose acylate or norbornene film is more preferable. As a method for reducing the Rth of the cellulose acylate film, it is effective to mix a liquid crystalline compound into the film.

(Bar-shaped liquid crystalline compound)
The liquid crystal display device of the present invention may have a retardation layer formed from a composition containing a rod-like liquid crystalline compound. As will be described later, the protective film of the second polarizing film is preferably composed of a retardation film formed from a polymer film, preferably a polymer film of cellulose acylate and a composition containing a rod-like liquid crystalline compound. Examples of the rod-like liquid crystal compound used for forming the optically anisotropic layer include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, Cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. In addition to the above low-molecular liquid crystalline molecules, high-molecular liquid crystalline molecules can also be used.

  In the liquid crystal display device of the present invention, it is preferable to use an optically anisotropic layer in which rod-like liquid crystalline compounds are substantially vertically aligned. In the case of a rod-like liquid crystalline compound, “substantially perpendicular” means that the angle formed by the film surface and the director of the rod-like liquid crystalline compound is in the range of 70 ° to 90 °. The rod-like liquid crystalline compound may be oriented obliquely or may be changed so that the inclination angle gradually changes (hybrid orientation). Even in the case of oblique orientation or hybrid orientation, the average inclination angle is preferably 70 ° to 90 °, more preferably 75 ° to 90 °, and most preferably 80 ° to 90 °.

(Vertical alignment film)
In order to align the rod-like liquid crystalline compound vertically on the alignment film side, it is important to reduce the surface energy of the alignment film. Specifically, the surface energy of the alignment film is lowered by the functional group of the polymer, thereby bringing the rod-like liquid crystal compound into a standing state. As the functional group for reducing the surface energy of the alignment film, a hydrocarbon group having 10 or more fluorine atoms and carbon atoms is effective. In order to make a fluorine atom or a hydrocarbon group exist on the surface of the alignment film, it is preferable to introduce a fluorine atom or a hydrocarbon group into the side chain rather than the main chain of the polymer. The fluoropolymer preferably contains fluorine atoms in a proportion of 0.05 to 80% by weight, more preferably in a proportion of 0.1 to 70% by weight, and in a proportion of 0.5 to 65% by weight. More preferably, it is most preferably contained in a proportion of 1 to 60% by weight. 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 exhibit strong hydrophilicity, such as a halogen atom. The number of carbon atoms of the hydrocarbon group is preferably 10 to 100, more preferably 10 to 60, and most preferably 10 to 40. The main chain of the polymer preferably has a polyimide structure or a polyvinyl alcohol structure.

  Polyimide is generally synthesized by a condensation reaction of tetracarboxylic acid and diamine. A polyimide corresponding to a copolymer may be synthesized using two or more kinds of tetracarboxylic acids or two or more kinds of diamines. The fluorine atom or hydrocarbon group may be present in the repeating unit derived from tetracarboxylic acid, may be present in the repeating unit derived from diamine, or may be present in both repeating units. When introducing a hydrocarbon group into polyimide, it is particularly preferable to form a steroid structure in the main chain or side chain of the polyimide. The steroid structure present in the side chain corresponds to a hydrocarbon group having 10 or more carbon atoms, and has a function of vertically aligning the liquid crystalline compound. In this specification, the steroid structure is a cyclopentanohydrophenanthrene ring structure or a ring structure in which a part of the ring bond is a double bond in the range of an aliphatic ring (a range that does not form an aromatic ring). means.

  Further, as a means for vertically aligning the rod-like liquid crystalline compound, a method of mixing an organic acid with a polymer of polyvinyl alcohol or polyimide can be suitably used. As the acid to be mixed, carboxylic acid, sulfonic acid and amino acid are preferably used. You may use what shows the acidity among the below-mentioned air interface aligning agent. The mixing amount is preferably 0.1% by weight to 20% by weight and more preferably 0.5% by weight to 10% by weight with respect to the polymer.

[Air interface side vertical alignment agent]
Ordinary rod-like liquid crystalline compounds have the property of being tilted and oriented on the air interface side, so it is necessary to control the orientation of the rod-like liquid crystal compound vertically on the air interface side in order to obtain a uniformly vertically aligned state. It is. As the air interface side vertical alignment agent of the rod-like liquid crystal compound, the same compound as the air interface side vertical alignment agent of the discotic liquid crystal compound can be used, and the preferred range of the amount used is also the same. In addition, the compounds described in JP 2002-20363 A and JP 2002-129162 A can be used as the air interface side vertical alignment agent. Also, paragraph numbers 0072 to 0075 of Japanese Patent Application No. 2002-212100, paragraph numbers 0038 to 0040 and 0048 to 0049 of Japanese Patent Application No. 2002-243600, and paragraph numbers 0037 to 0039 of Japanese Patent Application No. 2002-262239. The matters described in Paragraph Nos. 0071 to 0078 of Japanese Patent Application No. 2003-91752 can also be appropriately applied to the present invention.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1]
<Preparation of IPS mode liquid crystal cell 1>
The electrodes shown in FIG. 1 were provided on a single glass substrate so that the distance between adjacent electrodes was 20 μm, and a polyimide film was provided as an alignment film thereon, and a rubbing treatment was performed. The rubbing process was performed in the direction shown in FIG. A polyimide film was provided on one surface of a separately prepared glass substrate, and a rubbing treatment was performed to obtain an alignment film. Two glass substrates are laminated and bonded so that the alignment films face each other, the distance between the substrates (gap; d) is 3.9 μm, and the rubbing directions of the two glass substrates are parallel. A nematic liquid crystal composition having a refractive index anisotropy (Δn) of 0.0769 and a dielectric anisotropy (Δε) of 4.5 was enclosed. The value of d · Δn of the liquid crystal layer was 300 nm.

<Preparation of optical compensation film 1>
(Production of first retardation region)
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution having the following composition.
Composition of cellulose acetate solution Cellulose acetate with an acetylation degree of 60.9% 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 300 Mass part Methanol (second solvent) 54 parts by mass 1-butanol (third solvent) 11 parts by mass In another mixing tank, 16 parts by mass of the following retardation increasing agent, 80 parts by mass of methylene chloride, and 20 parts by mass of methanol were added. Then, the mixture was stirred while heating to prepare a retardation increasing agent solution. A dope was prepared by mixing 7 parts by mass of the retardation increasing agent solution with 487 parts by mass of the cellulose acetate solution and stirring sufficiently.

  The obtained dope was cast using a band casting machine. After the film surface temperature on the band reached 40 ° C., the film was dried with warm air of 60 ° C. for 1 minute, and the film was peeled off from the band. Next, the film was dried with a drying air at 140 ° C. for 10 minutes to produce a cellulose acetate film 1 having a thickness of 80 μm.

  The optical properties of this film were determined by measuring the dependency of Re on the light incident angle using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments). Re = 8 nm, Rth = 82 nm there were.

(Production of second retardation region)
After the surface of the cellulose acetate film 1 was saponified, an alignment film coating solution having the following composition was applied onto the film with a wire bar coater at 20 ml / m ² . The film was formed by drying with warm air of 60 ° C. for 60 seconds and further with warm air of 100 ° C. for 120 seconds. Next, the formed film was rubbed in a direction parallel to the slow axis direction of the film to obtain an alignment film.
Composition of alignment film coating solution Modified polyvinyl alcohol 10 parts by weight Water 371 parts by weight Methanol 119 parts by weight Glutaraldehyde 0.5 parts by weight

  Next, 1.8 g of the following discotic liquid crystalline compound, 0.2 g of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.), a photopolymerization initiator (IRGA) Cure 907, Ciba Geigy Co., Ltd.) 0.06 g, Sensitizer (Kaya Cure DETX, Nippon Kayaku Co., Ltd.) 0.02 g, Air interface side vertical alignment agent (Fluoropolymer, Exemplified Compound P-15) 0.0072 g The solution which melt | dissolved 0.009g of alignment film interface side vertical alignment agents (onium salt, exemplary compound II-23) in 3.9g of methyl ethyl ketone was apply | coated with the wire bar of # 3.4. This was affixed to a metal frame and heated in a thermostatic bath at 125 ° C. for 3 minutes to align the discotic liquid crystal compound. Next, using a 120 W / cm high-pressure mercury lamp at 100 ° C., UV irradiation was performed for 30 seconds to crosslink the discotic liquid crystal compound, thereby forming an optically anisotropic layer. Then, it stood to cool to room temperature. Thus, the optical compensation film 1 was produced.

  Using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments Co., Ltd.), the light incident angle dependence of Re of the optical compensation film 1 is measured, and the pre-measured contribution of the cellulose acetate film is subtracted. As a result, the optical characteristics of only the discotic optically anisotropic layer were calculated. As a result, Re was 130 nm, Rth was −65 nm, the average tilt angle of the liquid crystal was 89.9 °, and the discotic liquid crystal was It was confirmed that the alignment was vertical. The slow axis direction was parallel to the rubbing direction of the alignment film.

<Measurement of tilt angle near air interface and alignment film>
Using an ellipsometer (APE-100, manufactured by Shimadzu Corporation), the retardation is measured by changing the observation angle, hypothesized as a refractive index ellipsoid model, and described in Designing Concepts of the Discotic Negative Birefringence Compensation Films SID98 DIGEST It was calculated by the method. The measurement wavelength is 632.8 nm. The inclination angle near the air interface was 89.9 °, and the inclination angle near the alignment film was 89.9 °.
A polarizing film was produced by adsorbing iodine to a stretched polyvinyl alcohol film. Using the polyvinyl alcohol-based adhesive, the produced optical compensation film 1 was attached to one side of the polarizing film so that the cellulose acetate film was on the polarizing film side. The transmission axis of the polarizing film and the slow axis of the optical compensation film (the slow axis of the second retardation region also coincides with this) were arranged in parallel. A commercially available cellulose acetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) was subjected to saponification treatment and attached to the opposite side of the polarizing film using a polyvinyl alcohol adhesive. This is arranged so that the slow axis of the optical compensation film 1 is parallel to the rubbing direction of the liquid crystal cell on one of the IPS mode liquid crystal cells 1 produced above (that is, the slow axis of the second retardation region is It was attached so that the slow axis direction of the liquid crystal molecules during black display was parallel) and the discotic liquid crystal application surface side was the liquid crystal cell side. Subsequently, a commercially available polarizing plate (HLC2-5618, manufactured by Sanritz Co., Ltd.) was attached to the other side of the IPS mode liquid crystal cell 1 in a crossed Nicol arrangement to produce a liquid crystal display device.

<Measurement of leakage light of the manufactured liquid crystal display device>
The leakage light of the liquid crystal display device thus manufactured was measured. Leakage light when observed from the left diagonal direction of 70 ° was 0.12%.

[Example 2]
<Preparation of optical compensation film 2>
Using a commercially available cellulose acetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd., Re = 3 nm, Rth = 45 nm) as the first retardation region, the surface was saponified and carried out on this film The same alignment film coating solution as in Example 1 was applied at 20 ml / m ² with a wire bar coater. The film was formed by drying with warm air of 60 ° C. for 60 seconds and further with warm air of 100 ° C. for 120 seconds. Next, the formed film was rubbed in a direction parallel to the slow axis direction of the film to form an alignment film.

  Subsequently, on the alignment film, 1.8 g of the discotic liquid crystalline compound used in Example 1, 0.2 g of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.), photopolymerization Initiator (Irgacure 907, manufactured by Ciba Geigy) 0.06 g, Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.02 g, Air interface side vertical alignment agent (fluorinated compound, I-48) 0 A solution prepared by dissolving 0.009 g of alignment film interface side vertical alignment agent (onium salt, II-23) in 3.9 g of methyl ethyl ketone was applied with a # 3 wire bar. This was affixed to a metal frame and heated in a thermostatic bath at 125 ° C. for 3 minutes to align the discotic liquid crystal compound. Next, UV irradiation was performed for 30 seconds using a 120 W / cm high-pressure mercury lamp at 100 ° C. to crosslink the discotic liquid crystal compound, thereby forming an optically anisotropic layer. Then, it stood to cool to room temperature. Thus, the optical compensation film 2 was produced.

  Using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments Co., Ltd.), the light incident angle dependency of Re of the optical compensation film 2 is measured, and the pre-measured contribution of the cellulose acetate film is subtracted. As a result, only the optical characteristics of the discotic liquid crystal retardation layer were calculated. Re was 115 nm, Rth was −57 nm, the average tilt angle of the liquid crystal was 89.9 °, and the discotic liquid crystal was perpendicular to the film surface. It was confirmed that they were oriented. The slow axis direction was parallel to the rubbing direction of the alignment film.

<Measurement of tilt angle near air interface and alignment film>
Using an ellipsometer (APE-100, manufactured by Shimadzu Corporation), the retardation is measured by changing the observation angle, hypothesized as a refractive index ellipsoid model, and described in Designing Concepts of the Discotic Negative Birefringence Compensation Films SID98 DIGEST It was calculated by the method. The measurement wavelength is 632.8 nm. The inclination angle near the air interface was 89.9 °, and the inclination angle near the alignment film was 89.9 °.

  One of the IPS mode liquid crystal cells 1 produced as described above is arranged so that the optical compensation film 2 produced as described above has a slow axis parallel to the rubbing direction of the liquid crystal cell (that is, the slow axis of the second retardation region). Was attached so that the discotic liquid crystal application surface side was on the liquid crystal cell side. Subsequently, a commercially available polarizing plate (HLC2-5618, manufactured by Sanritz Co., Ltd.) is pasted on the optical compensation film 2 so that the transmission axis is parallel to the rubbing direction of the liquid crystal cell. The same polarizing plate was attached to the other side in a crossed Nicol arrangement to produce a liquid crystal display device.

(Measurement of leakage light of the manufactured liquid crystal display device)
The leakage light of the liquid crystal display device thus manufactured was measured. The leakage light when observed from the left diagonal direction of 70 ° was 0.13%.

[Example 3]
<Production of Second Polarizing Plate 1>
Using a commercially available cellulose acetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd., Re = 3 nm, Rth = 45 nm), the surface was saponified, and a commercially available vertical alignment film (JALS- 204R, manufactured by Nippon Synthetic Rubber Co., Ltd. was diluted 1: 1 with methyl ethyl ketone, and then 2.4 ml / m ^{2 was} applied with a wire bar coater. Immediately, it was dried with warm air of 120 ° C. for 120 seconds.

(Formation of vertically aligned rod-like liquid crystal compound layer)
On the alignment film, 1.8 g of the following rod-shaped liquid crystal compound, 0.06 g of photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy), 0.02 g of sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), A solution obtained by dissolving 0.002 g of the following air interface side vertical alignment agent in 9.2 g of methyl ethyl ketone was applied with a # 2 wire bar. This was affixed to a metal frame and heated in a constant temperature bath at 100 ° C. for 2 minutes to align the rod-like liquid crystal compound. Next, using a 120 W / cm high-pressure mercury lamp at 100 ° C., UV irradiation was performed for 30 seconds to crosslink the rod-like liquid crystal compound. Then, it stood to cool to room temperature. Thus, the protective film 1 for the second polarizing plate was produced.

  Using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments Co., Ltd.), the light incident angle dependency of Re of the protective film 1 was measured. As a result, Re was 3 nm and Rth was 5 nm.

  Next, iodine is adsorbed to the stretched polyvinyl alcohol film to produce a polarizing film, and using the polyvinyl alcohol-based adhesive, the protective film 1 thus prepared is arranged on one side of the polarizing film so that the cellulose acetate film is on the polarizing film side. Pasted on. Subsequently, a commercially available cellulose acetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) is subjected to saponification treatment, and a second polarizing plate is attached to the opposite side of the polarizing film using a polyvinyl alcohol adhesive. Formed. Further, in the same manner as in Example 1, the optical compensation film 1 was attached to one side of the polarizing film so that the cellulose acetate film was on the polarizing film side, and a commercially available cellulose acetate film was attached to the opposite side of the polarizing film. One polarizing plate is placed on one of the IPS mode liquid crystal cells 1 produced in Example 1 so that the slow axis of the optical compensation film 1 is parallel to the rubbing direction of the liquid crystal cell (that is, the retardation of the second retardation region). The phase axis was parallel to the slow axis direction of the liquid crystal molecules during black display), and the discotic liquid crystal application surface side was attached to the liquid crystal cell side. The transmission axis of this polarizing plate and the rubbing direction of the liquid crystal cell are parallel. Further, a second polarizing plate is attached to the other side of the liquid crystal cell so that the transmission axis is perpendicular to the rubbing direction of the liquid crystal cell and the surface of the protective film 1 is on the liquid crystal cell side. Produced.

(Measurement of leakage light of the manufactured liquid crystal display device)
The leakage light of the liquid crystal display device thus manufactured was measured. Light leakage when observed from the left oblique direction of 70 ° was 0.03%.

[Comparative Example 1]
A commercially available polarizing plate (HLC2-5618, manufactured by Sanritz Co., Ltd.) was attached to both sides of the produced IPS mode liquid crystal cell 1 in a crossed Nicol arrangement to produce a liquid crystal display device. An optical compensation film was not used. In the liquid crystal display device, as in Example 1, the polarizing plate was attached so that the transmission axis of the upper polarizing plate was parallel to the rubbing direction of the liquid crystal cell. The leakage light of the liquid crystal display device thus manufactured was measured. The leakage light when observed from the left diagonal direction of 70 ° was 0.55%.

[Comparative Example 2]
Compared to the IPS mode liquid crystal cell 1 produced in Example 1, the optical compensation film 2 produced in Example 2 is such that its slow axis is perpendicular to the rubbing direction of the liquid crystal cell and the discotic liquid crystal application surface side is liquid crystal. Affixed to the cell side. Subsequently, a commercially available polarizing plate (HLC2-5618, manufactured by Sanritz Co., Ltd.) is pasted on the optical compensation film 2 so that the transmission axis is parallel to the rubbing direction of the liquid crystal cell. The same polarizing plate was attached to the other side in a crossed Nicol arrangement to produce a liquid crystal display device. The leakage light of the liquid crystal display device thus manufactured was measured. The leakage light when observed from the left oblique direction of 70 ° was 1.52% and was extremely large.

[Comparative Example 3]
A liquid crystal display device was produced in the same manner as in Example 1 except that the air interface side vertical alignment agent (P-15) was removed from the discotic liquid crystal coating liquid composition in Example 1, and leakage light was measured. The light leakage when observed from the left diagonal direction of 70 ° was 1.2% and was extremely large.

[Comparative Example 4]
A liquid crystal display device was produced in the same manner as in Example 1 except that the alignment film interface-side vertical alignment agent (II-23) was removed from the discotic liquid crystal coating liquid composition in Example 1, and leakage light was measured. The leakage light when observed from the left oblique direction of 70 ° was as large as 0.50%.
<Measurement of tilt angle near air interface and alignment film>
Using an ellipsometer (APE-100, manufactured by Shimadzu Corporation), the retardation is measured by changing the observation angle. It was calculated by the method. The measurement wavelength is 632.8 nm. The tilt angle near the alignment film was 6.4 °, and the tilt angle near the air interface was 85.4 °.

[Comparative Example 5]
The liquid crystal was the same as in Example 1 except that the air interface side vertical alignment agent (I-48) and the alignment film interface side vertical alignment agent (II-23) were removed from the discotic liquid crystal coating liquid composition in Example 2. A display device was produced and leakage light was measured. The leakage light when observed from the left oblique direction of 70 ° was as large as 0.51%.
<Measurement of tilt angle near air interface and alignment film>
Using an ellipsometer (APE-100, manufactured by Shimadzu Corporation), the retardation is measured by changing the observation angle. It was calculated by the method. The measurement wavelength is 632.8 nm. The tilt angle near the alignment film was 6.4 °, and the tilt angle near the air interface was 46.0 °.

DESCRIPTION OF SYMBOLS 1 Liquid crystal element pixel area 2 Pixel electrode 3 Display electrode 4 Rubbing direction 5a, 5b Director of liquid crystal compound at the time of black display 6a, 6b Director of liquid crystal compound at the time of white display 7a, 7b First protective film for polarizing film 8 DESCRIPTION OF SYMBOLS 1 Polarizing film 9 Polarization transmission axis 10 of 1st polarizing film Optical compensation film 11 1st phase difference region 12 2nd phase difference region 13 Slow axis 14 of 2nd phase difference region 1st board | substrate 15 1st board | substrate rubbing direction 16 Liquid crystal Layer 17 Slow axis direction 18 of liquid crystalline compound Second substrate 19 Second substrate rubbing directions 20a, 20b Protective film for second polarizing film 21 Second polarizing film 22 Second polarizing film Polarized transmission axis

Claims (19)

An optical compensation film having an alignment film and an optically anisotropic layer on a transparent support, wherein the optically anisotropic layer increases a tilt angle at the air interface between the liquid crystalline compound and the liquid crystalline compound (hereinafter, At least one of “air interface side vertical alignment agent” and at least one compound that increases the tilt angle of the liquid crystal compound at the alignment film interface (hereinafter referred to as “alignment film interface side vertical alignment agent”), An optical compensation film in which the alignment film contains a modified polyvinyl alcohol having a crosslinkable functional group, and the alignment film interface vertical alignment agent is an onium salt . The air interface side vertical alignment agent includes a fluoro aliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a sulfato group (—OSO ₃ H), a phosphonoxy group {—OP (═O) ( The optical compensation film according to claim 1, which is a compound containing at least one hydrophilic group selected from the group consisting of OH) ₂ } and salts thereof. The air interface side vertical alignment agent is a copolymer containing a repeating unit derived from a fluoroaliphatic group-containing monomer and a repeating unit represented by the following general formula (1). Optical compensation film.

(Wherein R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent; L is a divalent linking group selected from the following linking group group or 2 selected from the following linking group group: Represents a divalent linking group formed by combining two or more,
(Linked group group)
Single bond, —O—, —CO—, —NR ⁴ — (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group), —S—, —SO ₂ —, —P (═O) (OR ⁵ ) — (R ⁵ represents an alkyl group, an aryl group, or an aralkyl group), an alkylene group, and an arylene group;
Q represents a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, or a phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof. ) The optical compensation film according to claim 1, wherein the air interface side vertical alignment agent is a compound represented by the following general formula (2).
General formula (2)
(R ⁰ ) _m −L ⁰ − (W) _n
(Wherein, R ⁰ is an alkyl group having an alkyl group, terminus CF ₃ group, or terminal to represent an alkyl group having a CF ₂ H group, m. A plurality of R ⁰ representing an integer of 1 or more the same However, at least one represents an alkyl group having a CF ₃ group or a CF ₂ H group at the terminal, L ⁰ represents an (m + n) -valent linking group, and W represents a carboxyl group (—COOH). Or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, a sulfato group (—OSO ₃ H) or a salt thereof, or a phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof, Represents an integer of 1 or more.) The optical compensation film according to claim 1, wherein the onium salt is a quaternary ammonium salt. It said onium salt is an optical compensation film according to claim 1, a quaternary pyridinium salt. The anion of the onium salt, optical compensation film of any one of claims 1 to 6 halogen anion or sulfonate ion. The optical compensation film according to any one of claims 1 to 4 , wherein the onium salt is a compound selected from quaternary pyridinium salts represented by the following general formula (3a) or (3b).

(In formula (3a), R ⁸ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group or heterocyclic group, D represents a hydrogen bonding group, and m represents 1 to Represents an integer of 3, and X ⁻ represents a halogen anion or a sulfonate ion.)

(In the formula (3b), R ⁹ and R ¹⁰ each represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group or heterocyclic group, and X ⁻ represents a halogen anion or a sulfonate ion. Represents.) The liquid crystalline compound, the optical compensation film of any one of claim 1 to 8 which is a discotic liquid crystal compound. The optical compensation film according to claim 9 , wherein the discotic liquid crystalline compound is triphenylene liquid crystal. A liquid crystal composed of a first polarizing film, an optical compensation film comprising a first retardation region in contact with the first polarizing film and a second retardation region in contact with the first retardation region, a first substrate, and a nematic liquid crystal material A liquid crystal display device in which a layer and a second substrate are arranged in this order, and a liquid crystalline compound of the nematic liquid crystal material is aligned in parallel to the surfaces of the pair of substrates during black display,
The optical compensation film is the optical compensation film according to any one of claims 1 to 10 , the first phase region is a transparent support of the optical compensation film, and the second retardation region is the optical compensation film. A liquid crystal display device which is an optically anisotropic layer of a compensation film. Using the in-plane refractive indices nx and ny (nx ≧ ny), the refractive index nz in the thickness direction, and the thickness d of the film, Re = (nx−ny) × d
The in-plane retardation Re of the first retardation region defined by is 20 nm or less, and Rth = ((nx + ny) / 2−nz) × d
The retardation Rth in the thickness direction of the first retardation region defined by the formula (1) is 20 nm to 120 nm, the slow axis of the second retardation region is the transmission axis of the first polarizing film, and the liquid crystalline compound at the time of black display the liquid crystal display device according to claim 1 1 which is parallel to the slow axis direction. More outside of the second substrate, a liquid crystal display device according to claim 1 1 or 1 2 has a second polarizing film. The liquid crystal display device according to any one of claims 1 1 to 1 3 Re of the second retardation region is 50 nm to 200 nm. Wherein and the first retardation region is composed of a plurality of layers, the layer in contact with the second retardation region of the plurality of layers according to any one of claims 1 1 to 1 4 are alignment film Liquid crystal display device. A pair of protective films sandwiching the second polarizing film, according to claim 1 1 to 1 thickness direction retardation Rth of the protective film of the liquid crystal layer side of the pair of protective film is 20nm or less The liquid crystal display device according to any one of 5 . The liquid crystal display device according to claim 16 , wherein the protective film on the liquid crystal layer side is a cellulose acylate film or a norbornene-based film among the pair of protective films arranged with the second polarizing film interposed therebetween. A pair of protective films disposed across the second polarizer, the protective film of the liquid crystal layer side, according to claim 1 6 and a layer comprising rod-like liquid crystal compound oriented cellulose acylate film and the vertical Liquid crystal display device. Wherein and the first retardation region is composed of a plurality of layers, one layer in contact with the first polarizing film of the plurality of layers of claim 1 1 to 1 8 which serves as a first polarizing protective film 2. A liquid crystal display device according to item 1.

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