JP2005062673A - Optically anisotropic layer, method for manufacturing the same, retardation plate using the same, elliptically polarizing plate and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optically anisotropic layer which contributes to the increasing of a viewing angle of a liquid crystal display, and to provide a retardation plate and an elliptically polarizing plate. <P>SOLUTION: The optically anisotropic layer comprises a composition containing a discotheque liquid-crystalline compound and a fluorine-containing compound, molecules of the discotheque liquid-crystalline compound take hybrid alignment in the layer at an average tilt angle of 35-85° to a flat surface of the layer, and a phase difference at 550 nm wavelength is 80-200 nm. The retardation plate comprises the optically anisotropic layer and a second optically anisotropic layer having a phase difference at 550 nm wavelength of 200-350 nm and an Nz factor (=(nx-nz)/(nx-ny)) of 0.5-2.0. The elliptically polarizing plate comprises the retardation plate and a polarizer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to various displays (for example, OA equipment, reflective and transflective liquid crystal display devices used for portable terminals), optically anisotropic layers used for optical disk pickups, retardation plates, elliptically polarizing plates, and the like. The present invention relates to a liquid crystal display device such as a reflective type or a transflective type. The present invention also relates to a method for producing an optically anisotropic layer in which discotic liquid crystalline molecules are highly chilled-oriented.

The λ / 4 plate has a great many applications, and is already used for a reflective LCD, a pickup for an optical disk, and a PS conversion element. However, even if it is referred to as a λ / 4 plate, most of them achieve λ / 4 at a specific wavelength. In order to achieve λ / 4 in a wider wavelength range, a technique of laminating two polymer films having optical anisotropy has been proposed (see, for example, Patent Documents 1 and 2). There has also been proposed a phase difference plate in which a polymer film having a phase difference of λ / 4 and a polymer film having a phase difference of λ / 2 are bonded together with a slow axis crossed (for example, Patent Documents). 3). Furthermore, a retardation plate is proposed in which at least two retardation plates having a retardation value of 160 to 320 nm are laminated so that their slow axes are not parallel or orthogonal to each other (for example, (See Patent Document 4). These retardation plates achieve λ / 4 in a wide wavelength region by using two polymer films. On the other hand, a broadband λ / 4 plate that has been thinned by laminating a plurality of optically anisotropic layers formed of liquid crystal molecules is also disclosed. (For example, see Patent Documents 5 and 6)
JP-A-10-68816 JP-A-10-90521 JP-A-10-68816 JP-A-10-90521 JP 2001-4837 A JP 2000-321576 A JP-A-11-148080

  However, in these retardation plate examples, the retardation in the front direction is set to an appropriate size to function as a λ / 4 plate, but from the oblique direction, the liquid crystal cell, the optically anisotropic layer In both cases, the retardation is dependent on the viewing angle, resulting in a shift, resulting in a decrease in contrast. That is, the optically anisotropic layer forming the conventional λ / 4 plate does not include a function for compensating the viewing angle of the liquid crystal cell, and a λ / 4 plate technology having a wider viewing angle range is desired. . In the present invention, it has been found that it is effective to use an optically anisotropic layer in which liquid crystal molecules are aligned and fixed at a high tilt angle in order to provide the viewing angle compensation function to the λ / 4 plate.

  By the way, in the reflection type liquid crystal display device, outside light such as room light or outdoor light is used, but these lights are incident not only vertically but also obliquely. When a λ / 4 plate formed of a plurality of optically anisotropic layers is incorporated in a reflective liquid crystal display device, it usually has about a quarter wavelength at normal incidence in order to obtain sufficient dark display. Because of the design, it is often the case that the obliquely incident light deviates from a quarter wavelength. Accordingly, there remains a problem that the contrast is lowered depending on the viewing angle. In order to improve the viewing angle dependency, a liquid crystal display element including two compensation elements including a liquid crystalline film in which nematic hybrid alignment is fixed is disclosed (for example, Patent Document 6), but is still insufficient. . In addition, a conventional λ / 4 plate made of a polymerizable liquid crystal composition may cause lattice-like unevenness. As a method for improving this unevenness, a method of incorporating a leveling agent together with a polymerizable liquid crystal into a composition constituting a λ / 4 plate is disclosed (for example, Patent Document 7). However, it has been found that this method is effective only when the polymerizable liquid crystal is homogeneously aligned, and cannot be applied to complicated alignment such as hybrid alignment as in the present invention.

  Accordingly, an object of the present invention is to provide an optically anisotropic layer, a phase difference plate and an elliptically polarizing plate that contribute to improvement of display quality and viewing angle characteristics, and display quality and viewing angle characteristics when used in a liquid crystal display device. It is an object of the present invention to provide an excellent liquid crystal display device, in particular, a reflective or transflective liquid crystal display device. Another object of the present invention is to provide a method for stably aligning discotic liquid crystalline molecules at a high tilt angle.

The object of the present invention has been achieved by the following means.
(1) An optically anisotropic layer comprising a composition comprising a discotic liquid crystalline compound and a fluorine-containing compound, wherein the molecules of the discotic liquid crystalline compound have an average tilt angle of 35 to 85 degrees with respect to the layer plane. And an optically anisotropic layer having a phase difference of 80 to 200 nm at a wavelength of 550 nm.
(2) The optically anisotropic layer according to (1), wherein the fluorine-containing compound is represented by the following general formula (I).
Formula (I)
(R ⁰ ) _m −L ⁰ − (W) _n
[Wherein, 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. When m is an integer of 2 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 a (m + n) -valent linking group, W represents a hydrophilic group, and n represents an integer of 1 or more. ]
(3) The optically anisotropic layer according to (1) or (2), wherein the fluorine-containing compound is a polymer containing a repeating unit derived from a monomer represented by the following general formula (II).

［式中、Ｈｆは水素原子又はフッ素原子を表し、Ｒ¹は水素原子又はメチル基を表し、Ｘは酸素原子、イオウ原子又はＮ（Ｒ²）−を表し、ｍ１は１〜６の整数、ｎ１は２〜４の整数を表す。Ｒ²は水素原子又は炭素数１〜４のアルキル基を表す。］
（４） 前記重合体が、さらに下記一般式（III）のモノマーから導かれる繰り返し単位を含む共重合体である（３）に記載の光学異方性層。

[In the formula, Hf represents a hydrogen atom or a fluorine atom, R ¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or N (R ² )-, m1 represents an integer of 1 to 6, n1 represents an integer of 2 to 4. R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
(4) The optically anisotropic layer according to (3), wherein the polymer is a copolymer further containing a repeating unit derived from a monomer represented by the following general formula (III).

［式中、Ｒ³は水素原子又はメチル基を表し、Ｙは２価の連結基を表し、Ｒ⁴は置換基を有していてもよいポリ（アルキレンオキシ）基又は置換基を有していてもよい炭素数１以上２０以下のアルキル基を表す。］
（５） 二層以上の光学異方性層を有し、少なくとも一層が（１）〜（４）のいずれかに記載の光学異方性層である光学異方性層。

[Wherein R ³ represents a hydrogen atom or a methyl group, Y represents a divalent linking group, and R ⁴ has a poly (alkyleneoxy) group or a substituent which may have a substituent. Represents an alkyl group having 1 to 20 carbon atoms. ]
(5) An optically anisotropic layer having two or more optically anisotropic layers, wherein at least one layer is the optically anisotropic layer according to any one of (1) to (4).

(6) The first optical anisotropic layer, which is the optical anisotropic layer according to any one of (1) to (4), and a phase difference of 200 to 350 nm at a wavelength of 550 nm, an Nz factor (the following formula) And a second optically anisotropic layer having a thickness of 0.5 to 2.0.
Nz factor = (nx−nz) / (nx−ny)
[Where nx and ny are in-plane main refractive indexes, and nz is the main refractive index in the thickness direction. ]
(7) The retardation plate according to (6), wherein the second optically anisotropic layer is obtained by horizontally aligning liquid crystals having positive optical anisotropy.
(8) The retardation plate according to (6), wherein the second optically anisotropic layer is made of a stretched polymer film.
(9) The retardation according to any one of (6) to (8), further including a third optically anisotropic layer having a thickness direction retardation Rth (the following formula) of 0 to 300 nm at a wavelength of 589.3 nm. Board.
Rth = {(nx + ny) / 2−nz} × d
[Where nx and ny are in-plane main refractive indexes, nz is the main refractive index in the thickness direction, and d is the thickness (nm). ]
(10) The retardation plate according to (9), wherein the third optically anisotropic layer is a layer formed from a material selected from liquid crystal, triacetylcellulose, and cyclic polyolefin.
(11) An elliptically polarizing plate having a polarizer and the retardation plate according to any one of (6) to (10).
(12) A TN type or ECB type liquid crystal display device having the elliptically polarizing plate according to (11) and a driving liquid crystal cell.
(13) The average direction of the axis in which the director of the liquid crystal molecules in the drive liquid crystal cell in black display is projected onto the plane parallel to the layer, and the director of the hybrid-oriented molecules in the first optically anisotropic layer are layered. The liquid crystal display device according to (12), wherein the direction projected onto the parallel plane is substantially parallel.

(14) A method for producing an optically anisotropic layer by orienting molecules of a discotic liquid crystalline compound in the presence of a fluorine-containing compound and hybridly orienting at an average tilt angle of 35 to 85 degrees with respect to the layer plane. .
(15) The method according to (14), wherein the fluorine compound is a compound represented by the general formula (I).
(16) The method according to (14), wherein the fluorine compound is a polymer containing a repeating unit derived from the monomer of the general formula (II).
(17) The method according to (14), wherein the polymer is a copolymer further comprising a repeating unit derived from the monomer of the general formula (III).
(18) The method according to any one of (14) to (17), wherein the optically anisotropic layer has a phase difference of 80 to 200 nm at a wavelength of 550 nm.

  According to the present invention, it is possible to provide an optically anisotropic layer, a phase difference plate, an elliptically polarizing plate, and a liquid crystal display device that have high display quality free from lattice unevenness and contribute to the improvement of viewing angle characteristics. In addition, according to the present invention, it is possible to provide a method capable of stably aligning molecules of a discotic liquid crystalline compound at a high tilt angle.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.
The optically anisotropic layer of the present invention comprises a composition containing a discotic liquid crystalline compound and a fluorine-containing compound, in which the molecules of the discotic liquid crystalline compound have an average tilt angle of 35 to 85 degrees with respect to the layer plane. Hybrid alignment is performed, and a phase difference at a wavelength of 550 nm is 80 to 200 nm. The optically anisotropic layer of the present invention is produced by nematic hybrid alignment of discotic liquid crystalline compound molecules, but the liquid crystalline molecules are fixed by polymerization or the like in the layer and no longer have liquid crystallinity. May be. Hereinafter, the optically anisotropic layer of the present invention may be referred to as “first optically anisotropic layer”.

  In the present invention, the “tilt angle” means an angle formed by tilted nematic-aligned liquid crystalline molecules with the layer plane, and the angle of the maximum refractive index in the refractive index ellipsoid of the liquid crystalline molecules with the layer plane. Of these, it means the maximum angle. Therefore, for rod-like liquid crystalline molecules having positive optical anisotropy, the tilt angle means the angle between the major axis direction of the rod-like liquid crystalline molecules, that is, the director direction and the layer plane, and negative optical anisotropy. In a discotic liquid crystal molecule having a disk-like molecular shape, the tilt angle means the inclination of the disk surface of the molecule from the layer plane. In the present invention, the “average tilt angle” means the average value of the tilt angle at the upper interface and the tilt angle at the lower interface of the optically anisotropic layer. Therefore, in the nematic hybrid orientation (simply referred to as “hybrid orientation” in the present invention), the value is an intermediate value between the tilt angle of the upper interface and the tilt angle of the lower interface. In the present invention, the average tilt angle of the discotic liquid crystal molecules in the optically anisotropic layer is 35 ° to 85 ° as an absolute value, preferably 37 ° to 70 °, more preferably 40 ° to 60 °. is there. When the average tilt angle is out of the range of 5 ° to 85 °, when used in a liquid crystal display device, the display contrast is lowered. The average tilt angle can be obtained by applying a crystal rotation method.

  In the first optically anisotropic layer, the discotic liquid crystalline molecules are preferably in a hybrid aligned state and are fixed in that state. In the present invention, “hybrid alignment” refers to an alignment form in which the discotic liquid crystalline molecules are nematic aligned and the discotic liquid crystalline molecules have different tilt angles between the upper surface and the lower surface of the layer. Accordingly, in the first optically anisotropic layer, the tilt angle of the discotic liquid crystalline molecules differs between the vicinity of the upper interface and the vicinity of the lower interface, and specifically, the difference in tilt angle between the upper interface and the lower interface. Is 5 ° or more. The tilt angle preferably changes continuously from the upper surface interface toward the lower surface interface.

  The first optically anisotropic layer preferably retains the hybrid alignment and does not lose its optical characteristics under the conditions in which the liquid crystal display element is used. In such a first optically anisotropic layer, the director of the discotic liquid crystal is oriented at different angles at all locations in the thickness direction of the layer. Therefore, the first optically anisotropic layer has no optical axis when viewed as a structure.

  The first optically anisotropic layer can be produced by hybrid-aligning discotic liquid crystalline molecules so as to be in the range of the average tilt angle and fixing the alignment state. As long as the said conditions are satisfy | filled, it may consist of what kind of material, and it does not limit about the aspect of fixation. For example, a low molecular discotic liquid crystal can be produced by hybrid alignment in a liquid crystal state and then fixed by photocrosslinking or thermal crosslinking. Alternatively, the polymer discotic liquid crystal can be prepared by hybrid alignment in a liquid crystal state and then cooling and fixing. Note that the liquid crystal compound is used for the production of the first optically anisotropic layer, but the optically anisotropic layer is a layer formed by fixing the compound by polymerization or the like. There is no need to show.

  The first optically anisotropic layer alone exhibits various optical properties by laminating two or more first optically anisotropic layers, or in combination with other optically anisotropic layers, When used in a liquid crystal display device, it can contribute to improvement of viewing angle characteristics, improvement of contrast, and the like.

[Optical properties of retardation plate]
One aspect of the retardation plate of the present invention has the first optical anisotropic layer of the present invention and a second optical anisotropic layer having a phase difference of substantially π / 2 at a wavelength of 550 nm. The first optically anisotropic layer has a phase difference of substantially π at a wavelength of 550 nm. Specifically, the phase difference is 80 to 200 nm, preferably 100 to 180 nm, more preferably 120 to 160 nm. The retardation value of the second optically anisotropic layer at a wavelength of 550 nm is ½ wavelength, specifically, the retardation value at a wavelength of 550 nm is 200 to 350 nm, preferably 220 to 330 nm, More preferably, it is 240-300 nm. The Nz factor derived from the following formula of the second optically anisotropic layer is preferably in the range of 0.5 to 2.0, more preferably in the range of 0.5 to 1.5. preferable.
Nz factor = (nx−nz) / (nx−ny)
In the formula, nx and ny are in-plane main refractive indexes, and nz is a main refractive index in the thickness direction. The retardation plate made of this laminate preferably has a retardation value / wavelength value measured at wavelengths of 450 nm, 550 nm, and 650 nm, all in the range of 0.2 to 0.3.

In another aspect of the retardation plate of the present invention, the first and second optically anisotropic layers and a third optical retardation having a thickness direction retardation (Rth) of 0 to 300 nm at a wavelength of 589.3 nm are provided. Has an anisotropic layer. Rth is defined by the following mathematical formula (2). Rth of the third optically anisotropic layer is preferably 10 to 300 nm, and more preferably 50 to 200 nm. The third optically anisotropic layer preferably has negative optical anisotropy, that is, it preferably satisfies the following formula (1). Furthermore, it is preferable that nx and ny of the third optical anisotropic layer are substantially equal.
Formula (1) nx ≧ ny> nz
Formula (2) Rth = {(nx + ny) / 2−nz} × d
In the formula, nx and ny are in-plane main refractive indexes of the optically anisotropic layer, nz is the main refractive index in the thickness direction, and d is the thickness (nm) of the optically anisotropic layer.

  Hereinafter, the optically anisotropic layer (first optically anisotropic layer) of the present invention and the second and third optically anisotropic layers preferably combined with the first optically anisotropic layer will be described in detail. explain.

[First optically anisotropic layer]
In the present invention, the first optically anisotropic layer is composed of a composition containing a discotic liquid crystal and a fluorine-containing compound.
(Discotic LCD)
Examples of discotic liquid crystals that can be used in the present invention include C.I. Benzene derivatives described in a research report of Destrade et al. (Mol. Cryst. 71, 111 (1981)), C.I. Destrode et al. (Mol. Cryst. 122, 141 (1985), Physics lett, A, 78, 82 (1990)) described in The cyclohexane derivatives described in the research report of Kohne et al. (Angew. Chem. 96, 70 (1984)) and M.M. Lehn et al. (J. Chem. Commun., 1794 (1985)), J. Chem. Azacrown-type and phenylacetylene-type macrocycles described in the research report of Zhang et al. (J. Am. Chem. Soc. 116, 2655 (1994)) are included.

  The discotic liquid crystal includes a compound having liquid crystallinity in which a linear alkyl group, an alkoxy group, and a substituted benzoyloxy group are radially substituted as a side chain of the mother nucleus with respect to the mother nucleus at the center of the molecule. It is. The molecule or the assembly of molecules is preferably a compound having rotational symmetry and imparting a certain orientation. In the optically anisotropic layer formed from the discotic liquid crystalline molecules, the compound finally contained in the optically anisotropic layer does not need to be a discotic liquid crystalline molecule. Also included are compounds having a group that reacts with heat or light and, as a result, polymerized or crosslinked by reaction with heat or light, resulting in a high molecular weight and loss of liquid crystallinity. A preferred example of the discotic liquid crystal is described in JP-A-8-50206. The polymerization of discotic liquid crystal is described in JP-A-8-27284.

In order to fix the discotic liquid crystal by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic core of the discotic liquid crystal. However, when the polymerizable group is directly connected to the disc-shaped core, it becomes difficult to maintain the orientation state in the polymerization reaction. Therefore, a linking group is introduced between the discotic core and the polymerizable group. Accordingly, the discotic liquid crystal having a polymerizable group is preferably a compound represented by the following formula (III).
Formula (III) D (-LQ) _n
In the formula (III), D is a discotic core, L is a divalent linking group, Q is a polymerizable group, and n is an integer of 4 to 12.

  An example of the disk-shaped core (D) is shown below. In each of the following examples, LQ (or QL) means a combination of a divalent linking group (L) and a polymerizable group (Q).

  In the formula (III), the divalent linking group (L) is selected from the group consisting of an alkylene group, an alkenylene group, an arylene group, —CO—, —NH—, —O—, —S—, and combinations thereof. A divalent linking group is preferred. The divalent linking group (L) is a divalent linking in which at least two divalent groups selected from the group consisting of an alkylene group, an arylene group, -CO-, -NH-, -O-, and S- are combined. More preferably, it is a group. The divalent linking group (L) is most preferably a divalent linking group in which at least two divalent groups selected from the group consisting of an alkylene group, an arylene group, -CO- and O- are combined. The alkylene group preferably has 1 to 12 carbon atoms. The alkenylene group preferably has 2 to 12 carbon atoms. The number of carbon atoms in the arylene group is preferably 6-10.

Examples of the divalent linking group (L) are shown below. The left side is bonded to the discotic core (D), and the right side is bonded to the polymerizable group (Q). AL represents an alkylene group or an alkenylene group, and AR represents an arylene group. The alkylene group, alkenylene group and arylene group may have a substituent (eg, an alkyl group).
L1: -AL-CO-O-AL-
L2: -AL-CO-O-AL-O-
L3: -AL-CO-O-AL-O-AL-
L4: -AL-CO-O-AL-O-CO-
L5: -CO-AR-O-AL-
L6: -CO-AR-O-AL-O-
L7: -CO-AR-O-AL-O-CO-
L8: -CO-NH-AL-
L9: -NH-AL-O-
L10: -NH-AL-O-CO-
L11: -O-AL-
L12: -O-AL-O-
L13: -O-AL-O-CO-
L14: -O-AL-O-CO-NH-AL-
L15: -O-AL-S-AL-
L16: -O-CO-AR-O-AL-CO-
L17: -O-CO-AR-O-AL-O-CO-
L18: -O-CO-AR-O-AL-O-AL-O-CO-
L19: -O-CO-AR-O-AL-O-AL-O-AL-O-CO-
L20: -S-AL-
L21: -S-AL-O-
L22: -S-AL-O-CO-
L23: -S-AL-S-AL-
L24: -S-AR-AL-

  In the formula (III), the polymerizable group (Q) is determined according to the kind of the polymerization reaction. The polymerizable group (Q) is preferably an unsaturated polymerizable group or an epoxy group, more preferably an unsaturated polymerizable group, and most preferably an ethylenically unsaturated polymerizable group.

  In formula (III), n is an integer of 4-12. A specific number is determined according to the type of the disk-shaped core (D). In addition, although the combination of several L and Q may differ, it is preferable that it is the same.

(Tilt angle of discotic liquid crystal)
The first optically anisotropic layer is asymmetric with respect to the layer plane because the tilt angle of the discotic liquid crystal molecules is different between the upper interface and the lower interface in the thickness direction. The viewing angle improvement effect when used in a liquid crystal display device differs depending on how much the vertical tilt angle differs and whether the average tilt angle is a high tilt angle or a low tilt angle. In the present invention, by setting the average tilt angle within the above range, the optically anisotropic layer contributes to the improvement of the viewing angle when used in a liquid crystal display device. In consideration of the optical parameters of the liquid crystal cell and the required optical performance, the average tilt angle, the tilt angle of the upper and lower interfaces, the in-plane orientation direction, the in-plane retardation of each layer, Rth, etc. should be optimized. Can do.

  The lower interface of the discotic liquid crystal in the first optically anisotropic layer, that is, the tilt angle on the support side, and the tilt angle on the upper interface, that is, the air interface side, are air interface alignment agents (for example, added to the alignment film or the liquid crystal layer) The fluorine-containing compound or the horizontal alignment agent of the present invention can be selected.

(Fluorine-containing compounds)
In the present invention, a fluorine-containing compound is used to control the average tilt angle of the discotic liquid crystal in the optically anisotropic layer. By using the fluorine-containing compound, the average tilt angle of the orientation of the discotic liquid crystal molecules can be set within a desired range, and the occurrence of uneven optical characteristics in the optically anisotropic layer can be reduced. As a result, when used in a liquid crystal display device, it contributes to the improvement of viewing angle characteristics. Further, even if the optically anisotropic layer is incorporated in a liquid crystal display device, it does not cause unevenness on the display surface. The fluorine-containing compound is preferably a compound having a fluorine-substituted alkyl group, more preferably an alkyl group having a terminal CF ₃ or a compound having an alkyl group having a terminal CF ₂ H. As the fluorine-containing compound, a compound represented by the following general formula (I) or (II) is particularly preferable.

  First, the fluorine-containing compound represented by the general formula (I) will be described in detail.

Formula (I)
(R ⁰ ) _m −L ⁰ − (W) _n
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. When m is an integer of 2 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 a (m + n) -valent linking group, W represents a hydrophilic group, and n represents an integer of 1 or more.

In the formula (I), 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 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.

R ¹ : nC ₈ F _{17-
^{R 2: n-C 6 F}} 13 -
_{^{R 3: n-C 4 F}} 9 -
_{^{R 4: n-C 8 F}} 17 - (CH 2) 2 -
_{^{R 5: n-C 6 F}} 13 - (CH 2) 2 -
_{^{R 6: n-C 4 F}} 9 - (CH 2) 2 -
_{^{R 7: H- (CF 2)}} 8 -
_{^{R 8: H- (CF 2)}} 6 -
R ⁹ : H— (CF ₂ ) ₄ —
R ¹⁰ : H— (CF ₂ ) ₈ — (CH ₂ ) —
R ¹¹ : H— (CF ₂ ) ₆ — (CH ₂ ) —
_{^{R 12: H- (CF 2)}} 4 - (CH 2) -

In the formula (I), the (m + n) -valent linking group represented by L ⁰ is an alkylene group, an alkenylene group, an aromatic group, a heterocyclic group, —CO—, —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 (I), W represents an anionic, cationic or nonionic hydrophilic group. The anionic group represented by W may be any as long as it has a negative charge, but is preferably a phosphoric acid group, phosphonic acid group, phosphinic acid group, sulfuric acid group, sulfonic acid group, sulfinic acid group or A carboxylic acid group, more preferably a phosphoric acid group, a phosphonic acid group, a sulfuric acid group, a sulfonic acid group, and a carboxylic acid group, and still more preferably a sulfuric acid group, a sulfonic acid group, and a carboxylic acid group. These anionic groups may be dissociated or non-dissociated.

  The cationic group represented by W may be any as long as it has a positive charge, but is preferably an organic cationic substituent, and more preferably a nitrogen or phosphorus cationic group. More preferably, it is a pyridinium cation or an ammonium cation, and more preferably a trialkylammonium cation.

Examples of the nonionic group represented by W include a mercapto group, a hydroxyl group, a substituted or unsubstituted amino group, a polyhydric alcohol (eg, glycerin, glucose, sorbitol, sucrose, etc.), an amino alcohol (eg, —N ( C ₂ H ₄ OH) ₂ ), polyethylene glycol (eg, — (C ₂ H ₄ O) _n H, etc.), and the like.

  W is preferably an anionic hydrophilic group.

  Among the compounds represented by the general formula (I), compounds represented by the following general formula (Ia) or (Ib) are preferable.

In the formula, R ⁵ and R ⁶ each represent 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 R ⁵ and R ⁶ are simultaneously an alkyl group. There is no. W ¹ and W ² each represent a hydrogen atom, a hydrophilic group, an alkyl group having a hydrophilic group, an alkoxy group having a hydrophilic group, or an alkylamino group having a hydrophilic group, and W ¹ and W ² are simultaneously It is not a hydrogen atom.

Formula (Ib)
(R ⁷ -L ^1- ) _m2 (Ar ¹ ) -W ³
Wherein, R ⁷ represents an alkyl group having an alkyl group, or terminal to CF ₂ H group having a CF ³ group alkyl group, the terminus, m ₂ represents an integer of 1 or more, m ₂ is an integer of 2 or more In this case, 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 when m ₂ is an integer of 2 or more, the plurality of L ¹ may be the same or different. Ar ¹ represents an aromatic hydrocarbon ring or an aromatic heterocycle, and W ³ represents a hydrophilic group, an alkyl group having a hydrophilic group, an alkoxy group having a hydrophilic group, or an alkylamino group having a hydrophilic group. .

The general formula (Ia) will be described in more detail.
R ⁵ and R ⁶ have the same meaning as R ⁰ in formula (I), and their preferred ranges are also the same. The hydrophilic groups represented by W ¹ and W ² are synonymous with W in the general formula (I), and their preferred ranges are also the same. The alkyl group having a hydrophilic group represented by W ¹ and W ² may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 8 alkyl groups, particularly preferably 1 to 3 alkyl groups. The alkyl group having the hydrophilic group only needs to have at least one hydrophilic group, and the hydrophilic group has the same meaning as the hydrophilic group represented by W in the general formula (I), The preferred range is also the same. The alkyl group having a hydrophilic group may be substituted with a substituent other than the hydrophilic group, and any of the substituents exemplified as the substituent group D described later can be applied as the substituent. The alkoxy group having a hydrophilic group represented by W ¹ and W ² may be linear or branched, preferably an alkoxy group having 1 to 20 carbon atoms, more preferably 1 to 8 alkoxy groups, particularly preferably 1 to 4 alkoxy groups. The alkoxy group having the hydrophilic group only needs to have at least one hydrophilic group, and the hydrophilic group is preferably the same as the hydrophilic group represented by W in the general formula (I). The range is also the same. The alkoxy group having a hydrophilic group may be substituted with a substituent other than the hydrophilic group, and any of the substituents exemplified as the substituent group D described later can be applied as the substituent. The alkylamino group having a hydrophilic group represented by W ¹ and W ² may be linear or branched, preferably an alkylamino group having 1 to 20 carbon atoms, Preferably they are 1-8 alkylamino groups, Most preferably, they are 1-4 alkylamino groups. The alkylamino group having the hydrophilic group only needs to have at least one hydrophilic group, and the hydrophilic group has the same meaning as the hydrophilic group represented by W in the general formula (I). The preferred range is also the same. The alkylamino group having a hydrophilic group may be substituted with a substituent other than the hydrophilic group, and any of the substituents exemplified as the substituent group D described later can be applied as the substituent.

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 general formula (Ib) will be described in more detail.
R ⁷ has the same meaning as R ⁰ in formula (I), 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. The hydrophilic group represented by W ₃ , the alkyl group having a hydrophilic group, the alkoxy group having a hydrophilic group, or the alkylamino group having a hydrophilic group is represented by W ¹ and W ² in the general formula (Ia). And the preferred range is the same as the hydrophilic group, the alkyl group having a hydrophilic group, the alkoxy group having a hydrophilic group, or the alkylamino group having a hydrophilic group.

W ³ is preferably a hydrophilic group or an alkylamino group having a hydrophilic group, 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). For example, phenyl 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.

  The fluorine-containing compound may have a polymerizable group as a substituent in order to fix the alignment state of the discotic liquid crystal.

  Specific examples of the fluorine-containing compound represented by formula (I) 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 (Ia), No. I-43 to 66 are examples of the compound represented by the general formula (Ib).

  Next, a polymer containing a repeating unit having a fluoroaliphatic group derived from a monomer represented by the following general formula (II) that can be used in the present invention (hereinafter sometimes referred to as “fluorine polymer”) explain.

In the formula, Hf represents a hydrogen atom or a fluorine atom, R ¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or N (R ² ) —, m ₁ represents an integer of ₁ to 6, n ₁ represents an integer of 2-4. R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

  The fluoropolymer is preferably a copolymer containing a repeating unit derived from a monomer represented by the following general formula (III).

In the formula, R ³ represents a hydrogen atom or a methyl group, Y represents a divalent linking group, and R ⁴ may have a poly (alkyleneoxy) group or a substituent which may have a substituent. An alkyl group having 1 to 20 carbon atoms is represented.

Hereinafter, the fluorine-based polymer that can be used in the present invention will be described in detail.
The fluoropolymer usable in the present invention includes a repeating unit having a fluoroaliphatic group derived from the monomer of the general formula (II), preferably further containing a repeating unit derived from the monomer of the general formula (III). It is preferably an acrylic resin, a methacrylic resin, or a copolymer with a vinyl monomer copolymerizable therewith.

  The fluoroaliphatic group in the general formula (II) can be 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 (exemplified in Scheme 1). .

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

In the general formula (II), R ¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom, or N (R ² ) —, and Hf represents a hydrogen atom or a fluorine atom. Here, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. X is more preferably an oxygen atom. M ₁ in the general formula (II) is preferably an integer of 1 or more and 6 or less, particularly preferably 1 or 2. In the general formula (II), n ₁ is 2 to 4, particularly 2 or 3, and a mixture thereof may be used.

  Although the example of the more specific monomer of the fluoro aliphatic group containing monomer represented by general formula (II) is given to the following, it is not this limitation.

In the general formula (III), R ³ represents a hydrogen atom or a methyl group, and Y represents a divalent linking group. As the divalent linking group, an oxygen atom, a sulfur atom or N (R ⁵ ) — is preferable. R ⁵ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group. More preferred forms of R ⁵ are a hydrogen atom and a methyl group.
Y is more preferably an oxygen atom, —N (H) — or N (CH ₃ ) —.
R ⁴ represents a poly (alkyleneoxy) group which may have a substituent or an alkyl group having 1 to 20 carbon atoms which may have a substituent. In the present specification, “alkyl group” is used to mean any of linear, branched and cyclic alkyl groups.

The poly (alkyleneoxy) group represented by R ^{4 can} be represented by (RO) _x , where R is an alkylene group having 2 to 4 carbon atoms, such as —CH ₂ CH ₂ —, —CH ₂ CH _2. It is preferably CH ₂ —, —CH (CH ₃ ) CH ₂ —, or CH (CH ₃ ) CH (CH ₃ ) —. The alkyleneoxy units in the poly (alkyleneoxy) group may be the same as in poly (propyleneoxy), or two or more different types of alkyleneoxy may be randomly distributed. It may be a linear or branched propyleneoxy or ethyleneoxy unit, or a linear or branched propyleneoxy unit block and an ethyleneoxy unit block. In this poly (alkyleneoxy) chain, a plurality of poly (alkyleneoxy) units are one or more chain bonds (for example, —CONH—Ph—NHCO—, —S—, etc., where Ph represents a phenylene group. ) Can be included. If the chain bond has a valence of 3 or more, this provides a means for obtaining branched alkyleneoxy units. When this copolymer is used in the present invention, the molecular weight of the poly (alkyleneoxy) group is suitably from 250 to 3,000.

Preferred examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group that may be linear or branched. A chain alkyl group such as a group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group; a monocyclic cycloalkyl group such as a cyclohexyl group or a cycloheptyl group; and A polycyclic cycloalkyl group such as a bicycloheptyl group, a bicyclodecyl group, a tricycloundecyl group, a tetracyclododecyl group, an adamantyl group, a norbornyl group, or a tetracyclodecyl group.

Examples of the substituent of the poly (alkyleneoxy) group or alkyl group represented by R ⁴ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, a carboxyl group, an alkyl ether group, an aryl ether group, a fluorine atom, Examples include, but are not limited to, halogen atoms such as chlorine atom and bromine atom, nitro group, cyano group and amino group.

  The monomer represented by the general formula (III) is particularly preferably alkyl (meth) acrylate or poly (alkyleneoxy) (meth) acrylate.

  Specific examples of the monomer represented by the general formula (III) are listed below, but not limited thereto.

Poly (alkyleneoxy) acrylate and methacrylate are commercially available hydroxypoly (alkyleneoxy) materials such as “Pluronic” (Pluronic (Asahi Denka Kogyo Co., Ltd.)), “Adeka Polyether” (Asahi Denka Kogyo ( “Carbowax” [Carbowax (Glico Products)], “Triton” [Toriton (Rohm and Haas) and “PEG” (Daiichi Kogyo Seiyaku Co., Ltd.) Can be produced by reacting what is sold as)) with acrylic acid, methacrylic acid, acrylic chloride, methacrylic chloride or acrylic acid anhydride in a known manner.
Separately, poly (oxyalkylene) diacrylate produced by a known method can also be used.

  The fluorine-based polymer is preferably a homopolymer of a monomer represented by the general formula (II) or a copolymer of a monomer represented by the general formula (II) and a polyalkyleneoxy (meth) acrylate, A copolymer of the monomer represented by formula (II) and polyethyleneoxy (meth) acrylate or polypropyleneoxy (meth) acrylate is more preferable.

  The copolymer of the monomer represented by the general formula (II) and the monomer represented by the general formula (III) was reacted by adding a monomer copolymerizable therewith in addition to the above monomers. A copolymer may also be used. A preferable copolymerization ratio of the copolymerizable monomer is 20 mol% or less, more preferably 10 mol% or less in all monomers. Such monomers include Polymer Handbook 2nd ed. , J .; Brandrup, Wiley interscience (1975) Chapter 2 Pages 1-483 can be used. For example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. I can give you.

Specifically, the following monomers can be mentioned.
Acrylic esters:
Furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.
Methacrylic acid esters:
Furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.
Allyl compounds:
Allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol, etc.
Vinyl ethers:
Alkyl vinyl ethers (eg hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, Diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.

Vinyl esters:
Vinyl bitylate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate, vinyl-β-phenyl Butyrate, vinyl cyclohexyl carboxylate, etc.
Dialkyl itaconates:
Dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.
Dialkyl or monoalkyl esters of fumaric acid:
Dibutyl fumarate etc. Others such as crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleilonitrile, styrene.

  The amount of the monomer represented by the general formula (II) in the fluoropolymer is preferably 5 mol% or more, more preferably 20 mol% or more, and more preferably 30 mol% of the total amount of constituent monomers of the polymer. The above is more preferable. The amount of the monomer represented by the general formula (III) in the fluorine-based polymer is preferably 10 mol% or more, more preferably 15 to 70 mol% of the total amount of the constituent monomers of the fluorine-based polymer, and 20 More preferably, it is -60 mol%.

  The preferred weight average molecular weight of the fluoropolymer is preferably from 3,000 to 100,000, more preferably from 6,000 to 80,000.

  Moreover, it is preferable that content of the said fluorine-type polymer in the composition (coating component except a solvent) used when producing a 1st optically anisotropic layer is 0.005-8 mass%, The content is more preferably 0.01 to 1% by mass, and further preferably 0.05 to 0.5% by mass. 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 May adversely affect the uniformity of the foundation.

  The fluoropolymer can be produced by a known and conventional method. For example, a general-purpose radical polymerization initiator is added and polymerized in an organic solvent containing monomers such as (meth) acrylate having a fluoroaliphatic group and (meth) acrylate having a polyalkyleneoxy group. It is manufactured by. 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.

  Examples of specific structures of the fluorine-based polymer are shown below, but are not limited thereto. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a weight average molecular weight.

In the present invention, when the first optically anisotropic layer and the second or third optically anisotropic layer are made of discotic liquid crystal, the optically anisotropic layer has a horizontal orientation of the discotic liquid crystal. It is also preferable to contain an inducing compound (hereinafter abbreviated as “horizontal alignment agent”). The horizontal alignment agent is not particularly limited as long as it is a compound that induces the horizontal alignment of the discotic liquid crystal, but the horizontal alignment agent suitably used in the first optically anisotropic layer includes the fluorine-containing compound of the present invention. A compound that induces horizontal alignment of the discotic liquid crystal when used in combination is preferred. Particularly preferred is a horizontal aligning agent that can cause a discotic liquid crystal to be horizontally aligned at a temperature T ₁ ° C. and then transferred to a hybrid alignment at a temperature T ₂ ° C. (where T ₁ <T ₂ ). By horizontally aligning the discotic liquid crystal once and then transferring to the hybrid alignment, a hybrid alignment optically anisotropic layer with few defects such as schlieren defects can be rapidly produced, and productivity can be improved.

  As the horizontal alignment agent in the present invention, a triazine-containing ring compound represented by the following general formula (IV) is preferably used.

In the formula, each of R ⁷ , R ⁸ and R ⁹ independently represents a hydrogen atom or a substituent, and the substituent is synonymous with the substituent exemplified as the substituent group D described above, and its preferred range is also the same. It is. R ⁷ , R ⁸ and R ⁹ are particularly preferably a substituted or unsubstituted alkyl group, an alkoxy group or a phenyl group, and most preferably an unsubstituted alkyl group having 6 to 20 carbon atoms and a 1 to 20 carbon atoms. It is an unsubstituted alkoxy group or a phenyl group substituted with an unsubstituted or substituted alkoxy group having 1 to 20 carbon atoms. R ⁷ , R ⁸ and R ⁹ may be linked to form a dimer or trimer, if possible. L ² , L ³ and L ⁴ are 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—, Represents a divalent linking group selected from the group consisting of —SO—, —SO ₂ — and combinations thereof, preferably an alkylene group, an aromatic group, —CO—, —NR—, —O—, —S; -And a divalent linking group selected from the group consisting of combinations thereof. L ² , L ³ and L ⁴ are particularly preferably a divalent linking group selected from the group consisting of an alkylene group, a phenyl group, —NH—, —O—, —S—, and combinations thereof, most preferably Is a divalent linking group selected from the group consisting of an ethylene group, a propylene group, -NH-, -O-, and combinations thereof.

  The horizontal alignment agent preferably has a polymerizable group as a substituent in order to fix the alignment state of the discotic liquid crystal.

  Although the specific example of the horizontal aligning agent which can be used for this invention is shown below, the horizontal aligning agent used for this invention is not limited to these.

  In the first optically anisotropic layer, the discotic liquid crystal is preferably hybrid-aligned, more preferably fixed in a hybrid-aligned state, and liquid crystalline molecules are fixed by a polymerization reaction. Most preferred.

  The first optically anisotropic layer can be formed by applying a coating liquid containing a discotic liquid crystal, a fluorine-containing compound, the following polymerizable initiator and other additives on the alignment film. 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 aligned discotic liquid crystal is preferably fixed while maintaining the alignment state. The immobilization is preferably carried out by a polymerization reaction of a polymerizable group introduced into the liquid crystalline molecule. 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) Description), acridine and phenazine compounds (JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (U.S. Pat. No. 4,212,970).

The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution. It is preferable to use ultraviolet rays for light irradiation for polymerization of liquid crystalline molecules. 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. The thickness of the optically anisotropic layer is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.

[Second optically anisotropic layer]
In the present invention, the second optically anisotropic layer may be made of any material as long as the optical properties are satisfied. Such an optically anisotropic layer may be a layer made of a composition containing a liquid crystalline compound or a stretched polymer film layer. The optical axis of the second optically anisotropic layer is preferably parallel to the layer plane. When the optically anisotropic layer is formed from a liquid crystalline compound, it is preferable that the liquid crystalline molecules are substantially horizontally (homogeneously) aligned in the layer. The substantially horizontal (homogeneous) orientation of the liquid crystal molecules means that the average angle between the director direction of the liquid crystal molecules and the film plane is in the range of 0 to 40 °, and the director is in the vicinity of the upper surface interface and the lower surface interface. Means that the angle formed by the film plane is smaller than 5 °.

  As described above, the second optically anisotropic layer may be formed from a composition containing a liquid crystal compound. The liquid crystal compound is preferably a rod-like liquid crystal compound. In the second optically anisotropic layer, the liquid crystalline molecules are preferably horizontally aligned, more preferably fixed in a horizontally aligned state, and the liquid crystalline molecules are fixed by a polymerization reaction. Most preferably. Examples of rod-like liquid crystalline molecules 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. It is more preferable to fix the orientation of the rod-like liquid crystalline molecules by polymerization, and examples of the polymerizable rod-like liquid crystalline molecules include those described in Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. Nos. 4,683,327, 5,622,648 and 5,770,107, World Patents (WO) 95/22586, 95/24455. No. 97/00600, No. 98/23580, No. 98/52905, JP-A-1-272551, JP-A-6-16616, JP-A-7-110469, JP-A-11-80081, and JP-A-2001-2001. The compounds described in No. 328973 can be used.

  The liquid crystal molecule coating method and the alignment state fixing method in the second optical anisotropic layer are the same as those in the first optical anisotropic layer.

  As described above, the second optically anisotropic layer may be formed from a polymer film. The polymer film is formed from a polymer that can exhibit optical anisotropy. Examples of such polymers include polyolefins (eg, polyethylene, polypropylene, norbornene-based polymers), polycarbonate, polyarylate, polysulfone, polyvinyl alcohol, polymethacrylic acid ester, polyacrylic acid ester and cellulose ester (eg, cellulose triacetate). Tate, cellulose diacetate). Moreover, a copolymer or a polymer mixture of these polymers may be used.

  The optical anisotropy of the polymer film is preferably obtained by stretching. The stretching is preferably uniaxial stretching or biaxial stretching. Specifically, longitudinal uniaxial stretching using a difference in peripheral speed between two or more rolls, tenter stretching for grasping both sides of the polymer film and stretching in the width direction, or biaxial stretching in combination of these is preferable. In addition, using two or more polymer films, the optical properties of the entire two or more films may satisfy the above conditions. The polymer film is preferably produced by a solvent cast method in order to reduce unevenness in birefringence. The thickness of the polymer film is preferably 20 to 500 μm, and most preferably 40 to 100 μm.

[Third optically anisotropic layer]
In the present invention, the third optically anisotropic layer may be made of any material as long as the above conditions are satisfied. For example, the third optically anisotropic layer may be a polymer film layer that exhibits optical anisotropy, or a layer that exhibits optical anisotropy by aligning liquid crystalline molecules. May be. Moreover, it may be formed from a single layer or may be formed from multiple layers.

  When the third optically anisotropic layer is a polymer film, examples of the material of the polymer film include triacetylcellulose, cyclic polyolefin, polyimide, and modified polycarbonate. These exhibit negative optical anisotropy. The material of the polymer film is not limited to the above material as long as the orientation state of the molecular chain is the same as the orientation state of the polymer molecular chain. Among them, a polymer film made of triacetyl cellulose or cyclic polyolefin is preferable. Moreover, you may express desired Rth by biaxially stretching a polymer film. In addition, an additive may be added to the polymer to adjust Rth. As methods for adjusting Rth of triacetyl cellulose, methods described in JP-A Nos. 2000-11914 and 2001-166144 are known. It has been.

  As described above, the third optically anisotropic layer may be formed from a composition containing a liquid crystalline compound. The liquid crystalline compound is preferably a discotic liquid crystalline compound or a cholesteric liquid crystalline compound, and more preferably a discotic liquid crystalline compound. A layer exhibiting negative optical anisotropy can be formed by aligning the discotic liquid crystalline molecules substantially horizontally with respect to the substrate. Such a technique is disclosed in Japanese Patent Laid-Open No. 11-352328. Substantially horizontal means that the tilt angle of the discotic liquid crystalline molecules is in the range of 0 ± 10 °. That is, the angle formed by the optical axis of the discotic liquid crystal molecules and the normal direction of the substrate is in a range of 0 ± 10 °. The tilt angle of the discotic liquid crystalline molecules may not be 0 ° (specifically, in a range of 0 ± 10 °), or may be a diagonal alignment, or a hybrid alignment in which the tilt angle gradually changes. In addition, a twisting deformation may be added to the orientation state by adding a chiral agent or applying a shear stress.

  An example of a preferable discotic liquid crystal that forms the third optically anisotropic layer is the same as the example of the discotic liquid crystal that can be used for the first optically anisotropic layer, and the preferable range thereof is also the same. The molecules of the cholesteric liquid crystalline compound exhibit negative optical anisotropy due to the helical twisted orientation. Desired optical properties can be obtained by arranging the cholesteric liquid crystalline molecules in a spiral and controlling the twist angle and retardation value of the alignment. The twisted orientation of cholesteric liquid crystalline molecules can be achieved by using a known method. The liquid crystalline molecules are preferably fixed in an aligned state, and more preferably fixed by polymerization.

[Alignment film]
When the first, second and third optically anisotropic layers are formed from liquid crystalline molecules, it is preferable to use an alignment film in order to align the liquid crystalline molecules. For example, when the first, second and third optical anisotropic layers are sequentially formed on the same support, the support / alignment film / second optical anisotropic layer / alignment film / first Optical anisotropic layer / alignment film / third optical anisotropic layer or support / alignment film / third optical anisotropic layer / alignment film / first optical anisotropic layer / alignment film / Like the second optically anisotropic layer, etc., each optically anisotropic layer can be formed on the alignment film to control the alignment and to exhibit desired optical characteristics.
The material of the alignment film can be selected according to the required optical properties and the type of liquid crystalline molecules used. In addition, even if an alignment film is not separately provided between each optically anisotropic layer, it can be laminated on the optically anisotropic layer by adding molecules having an alignment film function to the components constituting the optically anisotropic layer. The optically anisotropic layer thus formed can be brought into a desired orientation state.

  The alignment film is formed by rubbing treatment of an organic compound (preferably a polymer), oblique deposition of an inorganic compound, formation of a layer having a micro group, or an organic compound (for example, ω-tricosanoic acid, dioctadecyldimethyl by Langmuir-Blodgett method). It can be provided by means such as accumulation (LB film) of ammonium chloride and methyl stearate. Furthermore, an alignment film in which an alignment function is generated by application of an electric field or a magnetic field or light irradiation is also known. An alignment film formed by a polymer rubbing treatment is particularly preferable. The rubbing treatment is carried out by rubbing the surface of the polymer layer several times in a certain direction with paper or cloth.

  The type of polymer used for the alignment film is determined according to the alignment (particularly the average tilt angle) of the liquid crystal compound. It is preferable to adjust the surface energy according to the average tilt angle to be expressed. In the present invention, when the third optically anisotropic layer is formed of liquid crystalline molecules, it is preferable to use a polymer that does not reduce the surface energy of the alignment film. When the third optically anisotropic layer is formed using discotic liquid crystalline molecules, the rubbing treatment may not be performed and the alignment film may be omitted. However, for the purpose of improving the adhesion between the liquid crystalline molecules and the transparent support, an alignment film (described in JP-A-9-152509) forming a chemical bond with the liquid crystalline molecules at the interface may be used. When the alignment film is used for the purpose of improving adhesion, rubbing treatment need not be performed.

  In the second optically anisotropic layer, when the director of liquid crystalline molecules having positive optical anisotropy is oriented at an angle larger than 45 ° with respect to the major axis direction of the transparent support, the rubbing direction It is preferable to use an alignment film (hereinafter referred to as “orthogonal alignment film”) in which directors of rod-like liquid crystalline molecules are arranged in a direction orthogonal to the above. The orthogonal alignment film is described in JP-A No. 2002-62427 and JP-A No. 2002-268068.

  The thickness of the alignment film is preferably 0.01 to 5 μm, and more preferably 0.05 to 3 μm. In any of the alignment films, after the liquid crystalline molecules are fixed in the aligned state, they can be transferred onto another support. The liquid crystal compound fixed in the alignment state can maintain the alignment state even without the alignment film. Therefore, the retardation plate of the present invention requires each optically anisotropic layer formed on a temporary support, in addition to the method of sequentially forming each optically anisotropic layer on the same support. If it exists, it can also be produced by a method of bonding using an adhesive or the like.

  Any alignment film preferably has a polymerizable group. The polymerizable group can be introduced by introducing a repeating unit having a polymerizable group in the side chain or as a substituent of a cyclic group.

[Lamination of optically anisotropic layer]
When all the optically anisotropic layers to be laminated are made of a liquid crystal compound, the three layers may be sequentially laminated on the same support, or they may be bonded to each other after being formed on the temporary support. Then, one layer formed on the temporary support may be transferred to a laminate of two layers on the support.

  When one of the optically anisotropic layers to be laminated is a layer made of a liquid crystal compound and one is a layer made of a polymer film, the layer made of the polymer film is used as a support for forming a layer made of the liquid crystal compound. Can be used. For example, a polymer film having negative optical anisotropy, such as triacetyl cellulose, can be used as the third optical anisotropic layer and as a support for the first optical anisotropic layer made of a liquid crystalline compound. Can also be used. Furthermore, a liquid crystal compound may be applied thereon to form a second optical anisotropic layer, or a polymer film may be bonded to form a second optical anisotropic layer. Further, when the stretched polymer film is used as the second optically anisotropic layer, the optical anisotropy of the present invention comprising a liquid crystalline compound is formed on one surface of the film, and further on or on the film The third optical liquid crystal compound is laminated and applied to the other surface, the liquid crystal layer formed on the temporary support is transferred, or the polymer film is bonded to form the third optical anisotropic layer. It may be formed.

  The polymer film used as the support on which the liquid crystal compound is applied can be used as any one of the second and third optically anisotropic layers, and can be used as a protective film for the polarizer. It can also be used as a film that has both functions. In addition, the preferable form of the elliptically polarizing plate of this invention mentioned later is a thing which laminated | stacked the polarizer, the 2nd, 1st, and 3rd optically anisotropic layer in this order, but finally this order. If it becomes, the order which laminates | stacks is not ask | required.

[Support]
The retardation plate and the elliptically polarizing plate of the present invention may have a support, and the support is preferably a transparent support. As the transparent support, a glass plate or a polymer film, preferably a polymer film is used. That the support is transparent means that the light transmittance is 80% or more. The thickness of the support is preferably 10 to 500 μm, and more preferably 30 to 200 μm.

  In order to improve adhesion between the support and the layer (adhesive layer, alignment film or optically anisotropic layer) provided thereon, surface treatment (for example, glow discharge treatment, corona discharge treatment, ultraviolet treatment) is applied to the transparent support. , Flame treatment, etc.). An ultraviolet absorber may be added to the support. An adhesive layer (undercoat layer) may be provided on the transparent support. The adhesive layer is described in JP-A-7-333433. The thickness of the adhesive layer is preferably 0.1 to 2 μm, and preferably 0.2 to 1 μm.

  As the support, it is preferable to use a polymer film having a small wavelength dispersion. It is also preferable that the support has a small optical anisotropy. 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, polymethacrylate and cyclic polyolefin. Cellulose esters are preferred, acetyl cellulose is more preferred, and triacetyl cellulose is most preferred. Examples of the cyclic polyolefin include a polymer obtained by hydrogenating a ring-opening polymer of tetracyclododecenes or a ring-opening copolymer of tetracyclododecenes and norbornenes described in JP-B-2-9619. The polymer used as the constituent component and the product name can be used from Arton (manufactured by JSR), Zeonex, and Zeonore (manufactured by Nippon Zeon). The polymer film is preferably formed by a solvent cast method.

[Elliptically polarizing plate]
The retardation plate of the present invention is used as a λ / 4 plate used in a liquid crystal display device, a pickup for writing an optical disc, a λ / 4 plate used in a GH-LCD or a PS conversion element, or an antireflection film. It is particularly advantageously used as a λ / 4 plate. The λ / 4 plate is generally used in combination with a polarizing film. Therefore, if it is configured as an elliptically polarizing plate in which a retardation plate and a polarizing film are combined, it can be easily incorporated into a device for a purpose such as a reflection type or a transflective liquid crystal display device.

  The elliptically polarizing plate of the present invention has the retardation plate of the present invention and a linear polarizer. In the elliptically polarizing plate of the present invention, the first and second optically anisotropic layers and the linearly polarizing film are laminated so that the whole is almost completely circularly polarized. By setting the optical orientation in this way, it is possible to provide a broadband λ / 4 plate that achieves λ / 4 in a wide wavelength region. For example, the angle between the slow axis of the first optical anisotropic layer and the slow axis of the second optical anisotropic layer is 60 °, the slow axis of the first optical anisotropic layer and the polarizing film The angle between the polarization axis (the direction in which the transmittance is maximized in the plane) is set to 75 °, and the angle between the slow axis of the second optical anisotropic layer and the polarization axis of the polarizing film is set to 15 °. Thus, circularly polarized light, that is, broadband λ / 4 can be achieved in the entire visible region. The angle between the slow axis of the first optical anisotropic layer and the slow axis of the second optical anisotropic layer is 60 °, and the slow axis of the first optical anisotropic layer is The angle between the polarizing axis of the polarizing film and the polarizing axis of the polarizing film may be set to 15 ° and 15 ° and 75 °, respectively. The allowable range of the above angle is within ± 10 °, preferably within ± 8 °, more preferably within ± 6 °, further preferably within ± 5 °, and more preferably ± 4 °. Is most preferably within.

  A preferred embodiment of the elliptically polarizing plate of the present invention is an elliptically polarizing plate in which the linearly polarizing film and the second, first and third optically anisotropic layers are laminated in this order.

  In the present specification, the broad-band λ / 4 plate specifically means that the retardation value / wavelength value measured at wavelengths of 450 nm, 550 nm, and 650 nm are both in the range of 0.2 to 0.3. It means that there is. The retardation value / wavelength value is preferably in the range of 0.21 to 0.29, more preferably in the range of 0.22 to 0.28, and 0.23 to 0.27. Most preferably within the range.

  FIG. 1 is a schematic cross-sectional view showing a typical embodiment of an elliptically polarizing plate. The elliptically polarizing plate shown in FIG. 1 includes a linearly polarizing film (P), a second optically anisotropic layer (A), and a first optically anisotropic layer (both sides) sandwiched between protective films (T1, T2). B) and the third optically anisotropic layer (C) are stacked in this order. FIG. 2 is a plan view showing the direction of the slow axis of the optically anisotropic layer and the direction of the polarization transmission axis or polarization absorption axis of the linear polarizing film. In FIG. 2, the angle (a) of the slow axis (a) of the second optical anisotropic layer (A) and the slow axis (b) of the first optical anisotropic layer (B) in the same plane ( α) is preferably 50 to 70 °. In FIG. 2, the angle (β) between the slow axis (a) of the second optically anisotropic layer (A) and the polarization transmission axis or polarization absorption axis (p1) of the linear polarizing film is 10-20. It is preferable that it is (degree).

  The elliptically polarizing plate of the present invention is composed of the retardation plate of the present invention and a linear polarizing film. Examples of the linear polarizing film include an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film. The iodine polarizing film and the dye polarizing film are generally produced using a polyvinyl alcohol film. The polarizing axis (transmission axis) of the polarizing film corresponds to a direction perpendicular to the stretching direction of the film. The polarizing film generally has a protective film. The transparent support can function as an optically anisotropic layer made of a polymer film, or can function as a protective film on one side of the polarizing film. When a protective film is used separately from the transparent support, it is preferable to use a cellulose ester film having high optical isotropy, particularly a triacetyl cellulose film or a cyclic polyolefin film, as the protective film.

  In the elliptically polarizing plate according to the present invention, Rth of the protective film is 30 nm or less smaller than Rth of the third optical anisotropic layer. Rth of the protective film is preferably 0 to 50 nm, more preferably 0 to 30 nm, and most preferably 0 to 20 nm.

  In a different form of the elliptically polarizing plate according to the present invention, a linearly polarizing film having a protective film only on one side may be used. That is, there is no protective film between the linearly polarizing film and the first optical anisotropic layer, and only a substantially optically isotropic pressure-sensitive adhesive layer or adhesive layer is interposed.

[Liquid Crystal Display]
The liquid crystal display device of the present invention includes at least the elliptically polarizing plate, and includes a reflective, transflective, and transmissive liquid crystal display device. A liquid crystal display device generally includes a polarizing plate, a liquid crystal cell, and a retardation plate, a reflection layer, a light diffusion layer, a backlight, a front light, a light control film, a light guide plate, a prism sheet, a color filter, and the like as necessary. Although comprised from a member, in this invention, there is no restriction | limiting in particular except the point which makes it essential to use the said elliptically polarizing plate. Further, the use position of the elliptically polarizing plate is not particularly limited, and may be one place or a plurality of places. The liquid crystal cell is not particularly limited, and a general liquid crystal cell such as a liquid crystal layer sandwiched between a pair of transparent substrates provided with electrodes can be used. The transparent substrate constituting the liquid crystal cell is not particularly limited as long as the liquid crystal material constituting the liquid crystal layer is aligned in a specific alignment direction. Specifically, a transparent substrate in which the substrate itself has a property of orienting liquid crystals, a transparent substrate in which an alignment film having the property of orienting liquid crystals is provided, but the substrate itself lacks the alignment ability. Either can be used. Moreover, a well-known thing can be used for the electrode of a liquid crystal cell. Usually, it can be provided on the surface of the transparent substrate with which the liquid crystal layer is in contact, and when a substrate having an alignment film is used, it can be provided between the substrate and the alignment film. The material exhibiting liquid crystallinity for forming the liquid crystal layer is not particularly limited, and examples thereof include various ordinary low-molecular liquid crystal substances, polymer liquid crystal substances, and mixtures thereof that can constitute various liquid crystal cells. In addition, a dye, a chiral agent, a non-liquid crystal substance, or the like can be added to these as long as liquid crystallinity is not impaired.

  In addition to the electrode substrate and the liquid crystal layer, the liquid crystal cell may include various components necessary for forming various types of liquid crystal cells described later. As the liquid crystal cell system, a TN (Twisted Nematic) system, a STN (Super Twisted Nematic) system, an ECB (Electrically Controlled Birefringence) system, an IPS (In-Plane Switching) system, a VA (In-Plane Switching) system, a VA (In-Plane Switching) system, a VA (In-Plane Switching) system, a VA (In-Plane Switching) system, Alignment), PVA (Patterned Vertical Alignment), OCB (Optically Compensated Birefringence), HAN (Hybrid Aligned Nematic), ASM crocell) method, halftone gray scale method, domain division method, or display method using ferroelectric liquid crystal or antiferroelectric liquid crystal. The driving method of the liquid crystal cell is not particularly limited, and a passive matrix method used for STN-LCD and the like, and an active matrix method using an active electrode such as a TFT (Thin Film Transistor) electrode and a TFD (Thin Film Diode) electrode, Any driving method such as a plasma addressing method may be used. A field sequential method that does not use a color filter may be used.

  The elliptically polarizing plate in the present invention is preferably used for a reflection type and a transflective liquid crystal display device. The reflective liquid crystal display device has a configuration in which a reflector, a liquid crystal cell, and a polarizing plate are laminated in this order. The retardation plate is disposed between the reflecting plate and the linear polarizing film (between the reflecting plate and the liquid crystal cell or between the liquid crystal cell and the linear polarizing film). The reflector may share the liquid crystal cell and the substrate. The transflective liquid crystal display device includes an electro-liquid crystal cell, a polarizing plate disposed closer to the viewer than the liquid crystal cell, and at least one retardation plate disposed between the polarizing plate and the liquid crystal cell. And at least a transflective layer disposed behind the liquid crystal layer as viewed from the viewer, and at least one retardation plate and a polarizing plate behind the transflective layer as viewed from the viewer. Have In this type of liquid crystal display device, it is possible to use both a reflection mode and a transmission mode by installing a backlight.

  In the liquid crystal display device, at least one retardation plate and a polarizing plate function as an elliptical polarizing plate. The liquid crystal display device of the present invention uses the elliptically polarizing plate of the present invention in at least one place. In the present invention, it is not always necessary to integrate the polarizer and the retardation plate of the present invention into an elliptically polarizing plate, and then incorporate it into the liquid crystal display device. The first optical anisotropic layer and the polarizer are not included. Each of these is incorporated, and finally the elliptically polarizing plate of the present invention inside the liquid crystal display device is included in the scope of the liquid crystal display device of the present invention. In a preferred embodiment of the liquid crystal display device of the present invention, the average direction of the axis in which the director of the liquid crystal molecules in the liquid crystal cell at the time of black display is projected on the layer parallel plane and the hybrid orientation in the first optical anisotropic layer are aligned. This is an aspect in which the direction of the molecular director projected onto the layer parallel plane is substantially parallel. The director of the liquid crystal molecules in the liquid crystal cell can be adjusted to a desired direction by the rubbing direction of the alignment film provided on the opposing surface of the substrate.

  The phase difference plate and the elliptically polarizing plate of the present invention are not limited to the above applications, and can be used for various other applications. For example, it can be used for an antireflection film such as a host-guest type liquid crystal display device, a touch panel, an electroluminescence (EL) element, a reflection type polarizing plate, and the like.

The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following examples. In addition, the in-plane and thickness direction retardation values of the triacetyl cellulose film and the optically anisotropic layer can be measured with a birefringence meter (KOBRA-21ADH manufactured by Oji Scientific Instruments).
[Example 1]
(Production of retardation plate)
Both surfaces of a triacetylcellulose film having an Rth of 40 nm were saponified, and a diluted solution of polyvinyl alcohol (MP-203 manufactured by Kuraray Co., Ltd.) was applied to one surface to form a film. After rubbing this film to form an alignment film, a coating solution containing a discotic liquid crystal having the following composition is spin-coated on the rubbing surface of the alignment film, dried, and heated (alignment aging). Further, ultraviolet light irradiation was performed to form a liquid crystal fixing layer having a thickness of 0.7 μm. The laminate of triacetylcellulose and the discotic liquid crystal layer as a whole has negative optical anisotropy with a wavelength of 589.3 nm and Rth of 100 nm, and functions as the third optical anisotropic layer C1. I understood.
───────────────────────────────
Composition of coating liquid for discotic liquid crystal layer (C1) ───────────────────────────────
The following discotic liquid crystal (1) 32.6% by mass
Horizontal alignment agent (H-2) 0.7% by mass
The following modified trimethylolpropane triacrylate 3.2 mass%
0.4% by mass of the following sensitizer
1.1% by mass of the following photopolymerization initiator
Methyl ethyl ketone 62.0% by mass
───────────────────────────────

A diluted solution of polyvinyl alcohol (MP-203 manufactured by Kuraray Co., Ltd.) is again applied to the back surface to which the third optically anisotropic layer C1 thus prepared is applied, a film is formed, and the surface of the film is rubbed. Thus, an alignment film was formed. On the rubbing-treated surface of this alignment film, a coating solution containing a discotic liquid crystal having the following composition is spin-coated, dried and heated (alignment aging), and further irradiated with ultraviolet rays to form a 4.9 μm-thick 1 optically anisotropic layer B1 was formed. Using the same method, the first optical anisotropic layer B1 was previously formed on the glass and the optical performance was confirmed. As a result, the first optical anisotropic layer B1 had a slow axis in the direction perpendicular to the rubbing direction. Had. The retardation value (Re550) at 550 nm was 150 nm. When the average tilt angle was measured by applying the crystal rotation method, the tilt angle of the lower alignment film interface was 10 °, the tilt angle of the upper air interface side was 90 °, and the average tilt angle was 50 °. It was found to be hybrid oriented.
─────────────────────────────────
Coating liquid composition of discotic liquid crystal layer (B1) --------------------------
The following discotic liquid crystal (1) 32.6% by mass
Fluorine-containing compound (I-52) 0.12% by mass
Fluorine-containing compound (P-11) 0.03% by mass
The following modified trimethylolpropane triacrylate 3.2% by mass
Sensitizer below 0.4% by mass
The following photopolymerization initiator 1.1% by mass
Methyl ethyl ketone 62.6% by mass
─────────────────────────────────

  A uniaxially stretched arton film (manufactured by JSR) was used as the second optically anisotropic layer A1. The optical axis was parallel to the film plane, the retardation value measured at 550 nm was 260 nm, and the Nz factor was 1.0. The laminate of the optically anisotropic layer B1 and optically anisotropic layer C1 produced above and the Arton film were bonded together with an adhesive. At this time, the optically anisotropic layer A1, the optically anisotropic layer B1, and the optically anisotropic layer C1 are arranged in this order, and the slow axes of the optically anisotropic layer A1 and the optically anisotropic layer B1 intersect each other by 60 °. It was pasted together.

(Production of elliptically polarizing plate)
A roll-shaped polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an aqueous iodine solution and dried to obtain a linearly polarizing film. A 3% aqueous solution of polyvinyl alcohol (Kuraray PVA-117H) was bonded to a saponified triacetyl cellulose film as an adhesive to obtain a polarizing plate having both surfaces protected by triacetyl cellulose. The Rth value of the triacetyl cellulose film used here was 30 nm.

  Subsequently, the produced retardation plate (laminated body of optically anisotropic layer A1, optically anisotropic layer B1 and optically anisotropic layer C1) and a polarizing plate were bonded with an adhesive to prepare an elliptically polarizing plate. At this time, the optically anisotropic layer A1 and the polarizing plate are bonded so that they are in contact with each other, and the angle between the transmission axis of the polarizing plate and the slow axis of the optically anisotropic layer A1 and the optically anisotropic layer B1 is 75 °. 15 °. That is, the produced elliptically polarizing plate had the same layer configuration as shown in FIG. 1, and was an elliptically polarizing plate having β of 15 ° and α of 60 ° in FIG.

[Example 2]
(Production of retardation plate)
A triacetyl cellulose film having a thickness of 80 μm was used as a transparent support functioning as the third optically anisotropic layer C2. The Rth value of the triacetyl cellulose film at 589.3 nm measured with a birefringence meter (KOBRA-21ADH manufactured by Oji Scientific Instruments) was 100 nm. A diluted solution of polyvinyl alcohol (MP-203 manufactured by Kuraray Co., Ltd.) was applied to the third optically anisotropic layer C2 to form a film, and the film surface was rubbed to form an alignment film. On the rubbing-treated surface of this alignment film, a coating solution having the same composition as that used in the production of the first optically anisotropic layer (B1) in Example 1 was spin-coated, dried and heated (alignment). The film was aged) and further irradiated with ultraviolet rays to form a first optically anisotropic layer B1 having a thickness of 4.9 μm.

As in Example 1, a uniaxially stretched Arton film (manufactured by JSR) was used as the second optically anisotropic layer A1. The laminate of the optically anisotropic layer B1 and the optically anisotropic layer C2 produced above and the ARTON film were bonded with an adhesive. At this time, the optically anisotropic layer A1, the optically anisotropic layer B1, and the optically anisotropic layer C2 are arranged in this order, and the slow axes of the optically anisotropic layer A1 and the optically anisotropic layer B1 intersect each other by 60 °. It was pasted together.
(Production of elliptically polarizing plate)
An elliptically polarizing plate was produced in the same manner as in Example 1. That is, the produced elliptically polarizing plate had the same layer configuration as shown in FIG. 1, and was an elliptically polarizing plate having β of 15 ° and α of 60 ° in FIG.

[Example 3]
(Production of retardation plate)
In the same manner as in Example 1, a laminate of the optically anisotropic layer B1 and the optically anisotropic layer C1 was obtained. The surface of a triacetyl cellulose film having an Rth of 40 nm is saponified, and a diluted solution of polyvinyl alcohol (MP-203 manufactured by Kuraray Co., Ltd.) is applied thereon to form a film, and a rubbing process is performed on the film surface. Thus, an alignment film was obtained. On the rubbing-treated surface of this alignment film, a coating solution having the following composition is spin-coated, dried and heated (alignment aging), and further irradiated with ultraviolet rays to form a second optically anisotropic layer having a thickness of 1.73 μm. A2 was formed. The optically anisotropic layer A2 had a slow axis in the rubbing direction. The retardation value (Re550) at 550 nm was 260 nm, and the Nz factor was 1.0. When the average tilt angle was measured by applying the crystal rotation method, it was found that the average tilt angle in the film was horizontally oriented substantially at 0 °.
────────────────────────────
Composition of coating solution for optically anisotropic layer A2────────────────────────────
The following rod-like liquid crystalline compound (1) 14.5% by mass
0.15% by mass of the above sensitizer
0.29% by mass of the photopolymerization initiator
Methyl ethyl ketone 85.06 mass%
────────────────────────────

  The laminate of the optically anisotropic layer B1 and the optically anisotropic layer C1 prepared in Example 1 and the optically anisotropic layer A2 were bonded together with an adhesive. At this time, the optically anisotropic layer A2, the optically anisotropic layer B1, and the optically anisotropic layer C1 are arranged in this order, and the slow axes of the optically anisotropic layer A2 and the optically anisotropic layer B1 intersect each other by 60 °. It was pasted together.

(Production of elliptically polarizing plate)
The polarizing plate is a film whose only one surface is protected with triacetyl cellulose, and has an unprotected surface (a linearly polarizing film made of stretched polyvinyl alcohol) and an optically anisotropic layer A2 (triacetyl cellulose film). Surface) was bonded with an optically isotropic adhesive to produce an elliptically polarizing plate. At this time, the angles formed by the transmission axis of the polarizing plate and the slow axes of the optically anisotropic layer A2 and the optically anisotropic layer B1 were 75 ° and 15 °, respectively. That is, the produced elliptically polarizing plate had the same layer configuration as shown in FIG. 1, and was an elliptically polarizing plate having β of 15 ° and α of 60 ° in FIG.

[Example 4]
(Production of retardation plate)
As in Example 2, a triacetyl cellulose film having a thickness of 80 μm was used as a transparent support functioning as the optically anisotropic layer C2, and one side of this triacetyl cellulose film was saponified to produce polyvinyl alcohol (manufactured by Kuraray Co., Ltd.). A diluted solution of MP-203) was applied to form a film. The surface of this film was rubbed to form an alignment film. On the rubbing-treated surface of this alignment film, a coating solution having the same composition as that used in the production of the first optically anisotropic layer (B1) in Example 1 was spin-coated, dried and heated ( Orientation aging) and further irradiation with ultraviolet rays to form an optically anisotropic layer B1-1 having a thickness of 2.4 μm. When this optically anisotropic layer B1-1 was prepared in advance on glass by the same method and optical performance was confirmed, it had a slow axis in a direction perpendicular to the rubbing direction. The retardation value (Re550) at 550 nm was 75 nm. When the average tilt angle was measured by applying the crystal rotation method, the tilt angle at the lower alignment film interface was 10 °, the tilt angle at the upper air interface side was 90 °, and the average tilt angle was 50 °. It was found to be hybrid oriented.

  Another optical anisotropic layer B1-1 is prepared by the same method, and the discotic liquid crystal layer is peeled off from the triacetyl cellulose film by immersing it in hot water of about 60 degrees, which is optically anisotropic. An optically anisotropic layer B2 having a thickness of 4.8 μm was formed as an adhesive layer B1-2 by adhering the prepared optically anisotropic layer B1-1 with an adhesive. At this time, if the surfaces on which the optically anisotropic layer B1-1 and the optically anisotropic layer B1-2 are applied are tabled, the surfaces are both on top, and the respective slow axes are parallel. Were pasted together. The optically anisotropic layer B2 bonded with two layers had a retardation value (Re550) at 550 nm of 150 nm.

  Using an Arton film (manufactured by JSR) uniaxially stretched as in Example 2 as the optically anisotropic layer A1, the laminate of the optically anisotropic layer B2 and the optically anisotropic layer C2 prepared above and the Arton film were used as an adhesive. We pasted together. At this time, the optically anisotropic layer A1, the optically anisotropic layer B2, and the optically anisotropic layer C2 are arranged in this order, and the slow axes of the optically anisotropic layer A1 and the optically anisotropic layer B2 intersect each other by 60 °. It was pasted together.

(Production of elliptically polarizing plate)
An elliptically polarizing plate was produced in the same manner as in Example 1. That is, the produced elliptically polarizing plate has the same layer configuration as shown in FIG. 1 (however, the first optical anisotropic layer A is composed of two layers), and β in FIG. It was an elliptically polarizing plate having α of 60 °.

[Comparative Example 1] to [Comparative Example 3]
In Examples 1 to 3, elliptically polarizing plates were produced in the same manner except that the fluorine-containing compounds (I-52) and (P-11) were removed from the coating liquid composition of the optically anisotropic layer B1.

[Comparative Example 4]
In Example 1, an elliptical polarizing plate was produced using Arton film B2 having a retardation of 150 nm instead of optically anisotropic layer B1.

[Example 5]
(Viewing angle measurement)
ECB transflective display devices each incorporating the elliptically polarizing plates produced above were produced. First, a pair of 0.7 mm thick glass substrates were arranged to face each other with a gap of 4 μm. An ITO electrode was formed on the glass substrate on the observer side, and an aluminum reflective electrode with projections and depressions was formed on the other glass substrate as a counter electrode of the ITO electrode. An alignment film obtained by rubbing the surface of the polyimide film was formed on the opposing surfaces of the upper and lower substrates. The rubbing angles of the alignment films on the upper and lower substrates were made parallel (twist angle 0 degree). A nematic liquid crystal having Δn = 0.086 and a dielectric anisotropy of +10.0 was injected into the gap of the glass substrate to produce a liquid crystal cell (LC).

  Using this liquid crystal cell, a liquid crystal display device having a layer structure shown in FIG. 3 was produced. Below the liquid crystal cell LC, the elliptically polarizing plate prepared in Examples 1 to 4 (in the figure, the first optical anisotropy is B, the second optical anisotropy layer is A, the third optical anisotropy) Of the first optically anisotropic layer B (the optically anisotropic layer B1 in Examples 1 to 3 and the optically anisotropic layer B2 in Example 4). The director direction (direction perpendicular to the slow axis) was arranged to be parallel to the rubbing direction of the upper and lower substrates of the liquid crystal cell LC. That is, the average direction of the axis in which the director of the liquid crystal molecules in the liquid crystal cell LC at the time of black display is projected on the plane parallel to the layer and the director of the hybrid aligned molecules in the first optically anisotropic layer are layer parallel. Bonding was performed so that the direction projected onto the surface was substantially parallel.

  In addition, it is the same as the ARTON film used in the examples, and each of the optically anisotropic layer D having a retardation of 150 nm and the optically anisotropic layer E having a thickness of 260 nm has a slow axis of D and E of 60 °. Laminate so as to cross each other, and further laminate the polarizing plate P2 so that the transmission axis and the slow axis of the optically anisotropic layer E intersect at 15 °. The slow axis of the optically anisotropic layer D was arranged so as to be parallel to the rubbing direction of the upper and lower substrates of the liquid crystal cell LC. FIG. 4 shows the relationship between the slow axis d of the optically anisotropic layer D above the liquid crystal cell, the slow axis e of the optically anisotropic layer E, and the transmission axis p2 of the polarizing plate P2. In the manufactured liquid crystal display device, the crossing angle β between the slow axis e of the optically anisotropic layer E and the transmission axis p2 of the polarizing plate P2 is 15 °, and the slow axis e of the optically anisotropic layer E is The crossing angle α with the slow axis d of the optically anisotropic layer D was 60 °.

  Subsequently, transmission luminance from the lower side of the liquid crystal display device was measured using a spectral radiance meter under ordinary indoor fluorescent lamp illumination. At this time, with the liquid crystal display device placed horizontally, the polar angle is fixed every 10 ° in the direction of 0 to 80 ° from the normal line, and the azimuth angle of the liquid crystal display device is changed every 10 ° at each angle. The brightness was measured while the liquid crystal display device was on and off, and the contrast ratio, which is the ratio of the brightness when the liquid crystal display device was on and off, was calculated. The values obtained by adding the contrast ratios for all polar angles and azimuths in all directions were scored and listed in Table 1. Moreover, the nonuniformity of the produced 1st optically anisotropic layer was observed visually.

  In Examples 1, 2, and 4 having the optically anisotropic layer A1, the contrast ratio is superior to that of Comparative Examples 1, 2, and 4, and no lattice unevenness is observed. In Example 3 having the optically anisotropic layer A2, the contrast ratio is superior to that of Comparative Example 3, and no lattice unevenness is observed. Therefore. For the first time according to the embodiment of the present application, a display device having a high omnidirectional contrast ratio and no grid-like unevenness can be provided.

It is sectional drawing which shows the typical aspect of the elliptically polarizing plate of this invention. It is a top view which shows the direction of the slow axis of the optically anisotropic layer of the elliptically polarizing plate of FIG. 1, and the direction of the polarization transmission axis of a linearly-polarizing film. It is a schematic sectional drawing which shows the layer structure of the liquid crystal display device produced in the Example. FIG. 4 is a plan view showing the direction of the slow axis of the upper optically anisotropic layer (E, D) of FIG. 3 and the direction of the polarization transmission axis of the upper polarizing plate (P2).

Explanation of symbols

A Second optically anisotropic layer B First optically anisotropic layer C Third optically anisotropic layer P Linearly polarizing film P1 Lower linearly polarizing plate P2 Upper linearly polarizing plate T1 Protective film T2 for linearly polarizing film Protective film LC of linear polarizing film Liquid crystal cell D Upper optical anisotropic layer E composed of arton film (150 nm) Upper optical anisotropic layer a composed of arton film (260 nm) a slow axis of the second optical anisotropic layer b Slow axis of the first optical anisotropic layer d Slow axis of the upper optical anisotropic layer made of arton film (150 nm) e Slow axis p of the upper optical anisotropic layer made of arton film (260 nm) _1, p ₂ polarization transmission axis

Claims (18)

An optically anisotropic layer comprising a composition containing a discotic liquid crystalline compound and a fluorine-containing compound, wherein the molecules of the discotic liquid crystalline compound are in a hybrid orientation with an average tilt angle of 35 to 85 degrees with respect to the layer plane An optically anisotropic layer having a phase difference of 80 to 200 nm at a wavelength of 550 nm. An optically anisotropic layer having two or more optically anisotropic layers, wherein at least one layer is the optically anisotropic layer according to claim 1. The optically anisotropic layer according to claim 1, wherein the fluorine-containing compound is represented by the following general formula (I).
Formula (I)
(R ⁰ ) _m −L ⁰ − (W) _n
[Wherein, 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. When m is an integer of 2 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 a (m + n) -valent linking group, W represents a hydrophilic group, and n represents an integer of 1 or more. ] The optically anisotropic layer according to claim 1 or 2, wherein the fluorine-containing compound is a polymer containing a repeating unit derived from a monomer represented by the following general formula (II).

[In the formula, Hf represents a hydrogen atom or a fluorine atom, R ¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ² ) —, and m1 represents an integer of 1 to 6. , N1 represents an integer of 2-4. R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ] The optically anisotropic layer according to claim 4, wherein the polymer is a copolymer further comprising a repeating unit derived from a monomer represented by the following general formula (III).

[Wherein R ³ represents a hydrogen atom or a methyl group, Y represents a divalent linking group, and R ⁴ has an optionally substituted poly (alkyleneoxy) group or substituent. Represents an alkyl group having 1 to 20 carbon atoms. ] The first optical anisotropic layer which is the optical anisotropic layer according to any one of claims 1 to 5, a phase difference at a wavelength of 550 nm of 200 to 350 nm, and an Nz factor (the following formula) of 0. A retardation plate having a second optically anisotropic layer of 5 to 2.0.
Nz factor = (nx−nz) / (nx−ny)
[Wherein nx and ny are in-plane main refractive indexes, and nz is a main refractive index in the thickness direction. ] The retardation plate according to claim 6, wherein the second optically anisotropic layer is formed by horizontally aligning liquid crystalline molecules having positive optical anisotropy. The retardation plate according to claim 6, wherein the second optically anisotropic layer is made of a stretched polymer film. The retardation plate according to any one of claims 6 to 8, further comprising a third optical anisotropic layer having a thickness direction retardation Rth (the following formula) of 0 to 300 nm at a wavelength of 589.3 nm.
Rth = {(nx + ny) / 2−nz} × d
[Wherein nx and ny are in-plane main refractive indexes, nz is the main refractive index in the thickness direction, and d is the thickness (nm). ] The phase difference plate according to claim 9, wherein the third optically anisotropic layer is a layer formed of a material selected from liquid crystal, triacetylcellulose, and cyclic polyolefin. The elliptically polarizing plate which has a polarizer and the phase difference plate of any one of Claims 6-10. A TN type or ECB type liquid crystal display device comprising the elliptically polarizing plate according to claim 11 and a driving liquid crystal cell. The average direction of the axis in which the director of the liquid crystal molecules in the driving liquid crystal cell at the time of black display is projected on the layer parallel plane, and the director of the hybrid-oriented molecule in the first optically anisotropic layer on the layer parallel plane The liquid crystal display device according to claim 12, wherein the projected direction is substantially parallel to the projected direction. A method for producing an optically anisotropic layer by orienting molecules of a discotic liquid crystalline compound in the presence of a fluorine-containing compound so that the molecules are hybrid-aligned at an average tilt angle of 35 to 85 degrees with respect to the layer plane. The method according to claim 14, wherein the fluorine compound is a compound represented by formula (I) in claim 3. The method according to claim 14, wherein the fluorine compound is a polymer containing a repeating unit derived from the monomer of the general formula (II) in claim 4. The method according to claim 14, wherein the polymer is a copolymer further comprising a repeating unit derived from the monomer of the general formula (III) in claim 5. The method according to any one of claims 14 to 17, wherein the optically anisotropic layer has a phase difference of 80 to 200 nm at a wavelength of 550 nm.

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