JP2008241994A - Optical compensation film and manufacturing method thereof, polarizer using the same, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical compensation film to increase viewing angle of a liquid crystal display device and reduce coloring depending upon the viewing angle and easily manufactured at a low cost. <P>SOLUTION: The optical compensation film has a first optical anisotropic layer (10) satisfying nx>ny>nz, a second optical anisotropic layer (12) having liquid crystal aligning capability and satisfying nx≥ny>nz, and a third optical anisotropic layer (14) containing a liquid crystal compound fixed in an aligned state in this order, wherein, nx, ny, and nz represent a maximum refractive index of each optical anisotropic layer in a film surface, a refractive index in a direction crossing a direction wherein the maximum in-plane refractive index is obtained in a normal direction of the film surface, respectively. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an optical compensation film, a method for producing the same, a polarizing plate using the same, and a liquid crystal display device, particularly an OCB mode liquid crystal display device.

  Conventionally, liquid crystal display devices in various modes have been proposed. As one of them, attention is focused on the OCB mode (or bend mode), which is characterized by a high response speed. However, it is difficult to obtain a wide viewing angle characteristic in the OCB mode, and it is necessary to use an optical compensation film. For example, Patent Document 1 discloses a first optical anisotropy containing a discotic compound with a hybrid orientation as an optical compensation film that contributes to a reduction in coloring depending on the viewing angle direction during black display of an OCB mode liquid crystal display device. An optical compensation film having at least a second optically anisotropic layer and a third optically anisotropic layer satisfying predetermined optical characteristics has been proposed.

  The optical compensation film proposed in Patent Document 1 includes first, second, and third optically anisotropic layers, and an optically anisotropic layer that satisfies optical characteristics required for each is coated. It is difficult to produce continuously by a simple method such as, after forming each optically anisotropic layer on a temporary support, transfer or the like as a self-supporting polymer film After producing once, the process of bonding together through an adhesive layer is required. There are some aspects that do not meet the demands for thinning and the simplification of the manufacturing process, such as the need for a pressure-sensitive adhesive layer at the time of production and the inability to continuously produce by coating.

On the other hand, as a method capable of producing a retardation film including a plurality of retardation layers in a simple process, Patent Document 2 discloses a liquid crystalline compound and a polymer that reacts with polarized ultraviolet light on an optically anisotropic layer. Proposing a method for producing a retardation film comprising: a step of applying a solution comprising: a step of drying the solution to form a precursor layer of a retardation layer; and a step of irradiating the surface of the precursor layer with polarized ultraviolet light It is described that a retardation film in which a negative C-plate and an O-plate made of a nematic liquid crystal are laminated can be manufactured using the method (Example 1 of Patent Document 2). ).
However, in this method, it is necessary to use a special polymer called a polymer that reacts with polarized ultraviolet light, and there is a lack of versatility, and the use of the produced retardation film is limited.

In addition, in Patent Document 3, as a method for producing a birefringent film with a thinner process and fewer steps, a birefringent layer made of an alignment-treated non-liquid crystalline polymer is used as an alignment layer for a liquid crystal compound. A method has been proposed.
WO2006 / 095928A1 publication JP 2004-264345 A JP 2004-226945 A

The present invention contributes to the expansion of the viewing angle and the reduction of tint depending on the viewing angle of a liquid crystal display device, particularly an OCB mode liquid crystal display device, and an optical compensation film that can be produced easily and at low cost. The issue is to provide.
Moreover, this invention makes it a subject to provide the polarizing plate and liquid crystal display device of a favorable performance using this optical compensation film.

Means for solving the above-mentioned problems are as follows.
[1] A first optical anisotropic layer satisfying nx>ny> nz,
A second optically anisotropic layer having liquid crystal alignment ability and satisfying nx ≧ ny> nz, and a third optically anisotropic layer containing a liquid crystalline compound fixed in an alignment state,
In this order:
However, nx, ny, and nz are respectively the maximum refractive index in the film plane, the refractive index in the direction orthogonal to the direction giving the maximum refractive index, and the film plane method in each of the optically anisotropic layers. The refractive index in the line direction is shown.
[2] The optical compensation film according to [1], wherein the in-plane retardation Re of the first optically anisotropic layer exhibits reverse dispersion wavelength dependence in a visible light region.
[3] The optical compensation film according to [1] or [2], wherein the retardation Rth in the thickness direction of the second optically anisotropic layer exhibits forward dispersion wavelength dependency in the visible light region.
[4] The first optically anisotropic layer includes at least one polymer material selected from the group consisting of polyimide, polyetherketone, polyamideimide and polyesterimide. [1] to [3 ] The optical compensation film in any one of.
[5] The second optically anisotropic layer contains at least one polymer material selected from the group consisting of polyvinyl alcohol and modified polyvinyl alcohol having a polymerization degree of 1000 to 5000 and a saponification degree of 80% to 100%. The optical compensation film according to any one of [1] to [3].
[6] The optical compensation film according to any one of [1] to [5], wherein the second optically anisotropic layer is not stretched.

式中、Ｌ¹及びＬ²は各々独立に単結合又は二価の連結基を表し；Ａ¹及びＡ²は各々独立に、−Ｏ−、−ＮＲ−（Ｒは水素原子又は置換基を表す）、−Ｓ−及び−ＣＯ−からなる群から選ばれる基を表し；Ｒ¹、Ｒ²及びＲ³は各々独立に置換基を表し；Ｘは第１４〜１６族の非金属原子を表し（ただし、Ｘには水素原子又は置換基が結合してもよい）；ｎは０〜２までのいずれかの整数を表す。 [7] Any of [1] to [6], wherein the first optically anisotropic layer contains cellulose acylate and at least one compound represented by the following general formula (I). Optical compensation film:

In the formula, L ¹ and L ² each independently represent a single bond or a divalent linking group; A ¹ and A ² each independently represent —O— or —NR— (R represents a hydrogen atom or a substituent). ), -S- and -CO-; R ¹ , R ² and R ³ each independently represent a substituent; X represents a nonmetallic atom of Groups 14-16 ( However, a hydrogen atom or a substituent may be bonded to X); n represents any integer from 0 to 2.

[8] The optical system according to any one of [1] to [7], wherein the first optically anisotropic layer is formed by stretching a film containing cellulose acetate propionate. Compensation film.
[9] The optical compensation film according to any one of [1] to [8], wherein at least one liquid crystalline compound contained in the third optically anisotropic layer is a discotic compound.
[10] A step of applying a polymer composition on the first optically anisotropic layer to form a second optically anisotropic layer, and a liquid crystal composition on the surface of the second optically anisotropic layer Coating the liquid crystal composition on the surface of the second optical anisotropic layer, fixing the alignment state, and forming a third optical anisotropic layer, and The method for producing an optical compensation film according to any one of [1] to [9], which does not include a step of stretching the optically anisotropic layer of 2.
[11] A polarizing plate having at least the optical compensation film according to any one of [1] to [9] and a polarizing film.
[12] A liquid crystal display device having the polarizing plate of [11].
[13] The liquid crystal display device according to [12], wherein the liquid crystal mode of the liquid crystal display device is an electric field control birefringence mode.
[14] The liquid crystal display device according to [12], wherein a liquid crystal mode of the liquid crystal display device is an OCB mode.

INDUSTRIAL APPLICABILITY According to the present invention, optical compensation that contributes to widening the viewing angle and reducing tinting depending on the viewing angle of a liquid crystal display device, particularly an OCB mode liquid crystal display device, and that can be manufactured easily and at low cost. A film can be provided.
Further, according to the present invention, it is possible to provide a polarizing plate and a liquid crystal display device having good performance using such an optical compensation film.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, Re (λ) and Rth (λ) represent in-plane retardation and retardation in the thickness direction at the wavelength λ, respectively. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments).

When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth (λ) is calculated by the following method.
Rth (λ) is Re (λ), with the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotation axis) (if there is no slow axis, any in-plane film The light of wavelength λ nm is incident from each of the inclined directions in steps of 10 degrees from the normal direction to 50 degrees on one side with respect to the film normal direction (with the direction of the rotation axis as the rotation axis). KOBRA 21ADH or WR is calculated based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value.
In the above case, in the case of a film having a direction in which the retardation value is zero at a certain tilt angle with the in-plane slow axis from the normal direction as the rotation axis, retardation at a tilt angle larger than the tilt angle. The value is calculated by KOBRA 21ADH or WR after changing its sign to negative.
In addition, the retardation value is measured from the two inclined directions, with the slow axis as the tilt axis (rotation axis) (in the absence of the slow axis, the arbitrary direction in the film plane is the rotation axis), Based on the value, the assumed value of the average refractive index, and the input film thickness value, Rth can also be calculated from the following equations (10) and (11).

式中、上記のＲｅ（θ）は法線方向から角度θ傾斜した方向におけるレターデーション値をあらわす。
また式中、ｎｘは面内における遅相軸方向の屈折率を表し、ｎｙは面内においてｎｘに直交する方向の屈折率を表し、ｎｚはｎｘ及びｎｙに直交する方向の屈折率を表し、ｄは膜厚（μｍ）を表す。

In the formula, Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction.
In the formula, nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction orthogonal to nx in the plane, nz represents the refractive index in the direction orthogonal to nx and ny, d represents a film thickness (μm).

In the case where the film to be measured cannot be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film having no so-called optical axis, Rth (λ) is calculated by the following method.
Rth (λ) is the above-mentioned Re (λ), and the in-plane slow axis (determined by KOBRA 21ADH or WR) is the tilt axis (rotation axis) from −50 degrees to +50 degrees with respect to the film normal direction. The light of wavelength λ nm is incident from each inclined direction in 10 degree steps and measured at 11 points, and KOBRA 21ADH or WR is calculated.
In the above measurement, the assumed value of the average refractive index may be a value in a polymer handbook (John Wiley & Sons, Inc.) or a catalog of various optical films. Those whose average refractive index is not known can be measured with an Abbe refractometer. Examples of the average refractive index values of main optical films are given below:
Cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), and polystyrene (1.59).
The KOBRA 21ADH or WR calculates nx, ny, and nz by inputting the assumed value of the average refractive index and the film thickness. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.
Further, in this specification, unless a measurement wavelength is particularly added, it is assumed that Re and Rth are at a wavelength of 550 nm.

FIG. 1 shows a schematic cross-sectional view of an example of the optical compensation film of the present invention.
The optical compensation film shown in FIG. 1 has a first optical anisotropic layer 10, a second optical anisotropic layer 12, and a third optical anisotropic layer 14. The first optical anisotropic layer 10 is an optically biaxial layer that satisfies nx>ny> nz, and is made of a polymer film or the like. The second optically anisotropic layer 12 is a so-called negative C-plate that satisfies nx ≧ ny> nz, has the liquid crystal alignment ability, and forms the third optically anisotropic layer 14. It also functions as an alignment film. Therefore, the second optically anisotropic layer is preferably made of a polymer material for an alignment film such as polyimide or polyvinyl alcohol conventionally used for the alignment film. The third optically anisotropic layer contains a liquid crystalline compound fixed in the alignment state. For example, it is a layer formed by aligning a liquid crystalline compound on the surface of the second optically anisotropic layer 12 by its alignment ability and fixing it in that state.

The optical compensation film of the present embodiment is useful as an optical compensation film for a liquid crystal display device in an electric field control birefringence mode, particularly an OCB mode. From the viewpoint of further improving the tint depending on the viewing angle, the first optically anisotropic layer 10 has an in-plane retardation Re having a reverse dispersion wavelength dependency in the visible light region, that is, a long wavelength. It is preferable to show the property that Re becomes larger as it goes. However, in order to appropriately set Re to the inverse dispersion wavelength dependence within a range that does not impair the optical compensation capability of the OCB mode liquid crystal cell, specifically, the first optical anisotropic layer 10 has the following formula: It is preferable that (I) and (II) are satisfied.
(I): 1.0> Re (450 nm) / Re (550 nm)> 0.6
(II): 1.3> Re (630 nm) / Re (550 nm)> 1.0
From the same viewpoint, the retardation Rth in the thickness direction of the second optically anisotropic layer 12 exhibits forward dispersion wavelength dependency in the visible light region, that is, the property that Rth increases as the wavelength becomes shorter. preferable. However, in order to make Rth appropriately forward wavelength dispersible within a range that does not impair the optical compensation capability of the OCB mode liquid crystal cell, specifically, the second optical anisotropic layer 12 has the following formula ( It is preferable to satisfy III) and (IV).
(III): 1.5> Rth (450 nm) / Rth (550 nm) ≧ 1.0
(IV): 1.0 ≧ Rth (630 nm) / Rth (550 nm)> 0.8

Hereinafter, materials and methods used for producing each optically anisotropic layer constituting the optical compensation film of the present invention will be described in detail.
[First optically anisotropic layer]
The optical compensation film of the present invention has a first optical anisotropic layer that satisfies nx>ny> nz. The first optically anisotropic layer is preferably a polymer film. When the first optical anisotropic layer is a polymer film, the optical compensation film of the present invention can be bonded to a polarizer. Further, as a single member, for example, it can be incorporated into a liquid crystal display device as an optical compensation film. The polymer film material is preferably a polymer excellent in optical performance, transparency, mechanical strength, thermal stability, moisture shielding property, isotropy, etc., but any material that satisfies the above conditions May be used. For example, modified polycarbonates and modified cycloolefin polymers having a special structure in the side chain, cellulose polymers having an acetyl group in the side chain (hereinafter referred to as cellulose acylate), and the like, have the reverse wavelength dispersion of Re described above by stretching or the like. Is preferably used as one that expresses.

  A representative example of cellulose acylate is triacetyl cellulose. Examples of cellulose as a cellulose acylate raw material include cotton linter and wood pulp (hardwood pulp, softwood pulp). Cellulose acylate obtained from any raw material cellulose can be used, and in some cases, it may be mixed and used. Detailed descriptions of these raw material celluloses can be found in, for example, Marusawa and Uda, “Plastic Materials Course (17) Fibrous Resin”, published by Nikkan Kogyo Shimbun (published in 1970), and the Japan Society of Invention and Innovation Technical Bulletin No. 2001. The cellulose described in No. -1745 (pages 7 to 8) can be used, and the cellulose acylate film is not particularly limited.

The acyl substituent of the cellulose acylate of the cellulose acylate film for the first optically anisotropic layer includes, for example, a cellulose acylate having a plurality of acyl substituents even if it is a cellulose acylate composed of an acetyl group alone. A composition may be used. Preferable examples of such cellulose acylate have a total acylation degree of 2.3 to 3.0, more preferably 2.4 to 2.95, and further preferably 2.5 to 2.93.
As the acyl substituent of the cellulose acylate, a mixed fatty acid ester can also be preferably used. In the fatty acid ester residue, the aliphatic acyl group preferably has 2 to 20 carbon atoms. Specific examples include acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl, hexanoyl, octanoyl, lauroyl, stearoyl and the like, preferably acetyl, propionyl and butyryl. Among these, it is preferable to use either cellulose acetate propionate or cellulose acetate butyrate.

The cellulose acylate may be a mixed acid ester having a fatty acid acyl group and a substituted or unsubstituted aromatic acyl group.
In the case of a cellulose fatty acid monoester, the substitution degree of the aromatic acyl group is preferably 2.0 or less, more preferably 0.1 to 2.0 with respect to the remaining hydroxyl group. In the case of cellulose fatty acid diester (cellulose diacetate), it is preferably 1.0 or less, more preferably 0.1 to 1.0, based on the remaining hydroxyl group.

  The cellulose acylate preferably has a mass average degree of polymerization of 350 to 800, and more preferably has a mass average degree of polymerization of 370 to 600. The cellulose acylate used in the present invention preferably has a number average molecular weight of 70000 to 230,000, more preferably 75000 to 230,000, and more preferably 78000 to 120,000. Further preferred.

  The cellulose acylate can be synthesized using an acid anhydride or acid chloride as an acylating agent. In the industrially most general synthesis method, cellulose obtained from cotton linter, wood pulp, etc. is converted into organic acids (acetic acid, propionic acid, butyric acid) corresponding to acetyl groups and other acyl groups, or their acid anhydrides (anhydrous anhydride). A cellulose ester is synthesized by esterification with a mixed organic acid component containing acetic acid, propionic anhydride, and butyric anhydride).

  The cellulose acylate film is preferably produced by a solution casting method or a melt casting method. Examples of producing cellulose acylate films using the solution casting method are described in US Pat. Nos. 2,336,310, 2,367,603, 2,492,078, and 2,492,977. 2,492,978, 2,607,704, 2,739,069 and 2,739,070, British Patent Nos. 640731 and 736892 And JP-B Nos. 45-4554, 49-5614, JP-A-60-176834, JP-A-60-203430, JP-A-62-115035, and the like. The cellulose acylate film exhibits Re and Re reverse wavelength dispersibility by being subjected to stretching treatment. For the stretching method and conditions, see, for example, the examples described in JP-A-62-115035, JP-A-4-152125, JP-A-2842211, JP-A-298310, JP-A-11-48271, etc. Can be.

In the present invention, as described above, in the first optical anisotropic layer, Re preferably exhibits reverse dispersion wavelength dependence in the visible light region. In order to produce a polymer film having such properties, it is preferable to perform a stretching treatment after forming a composition containing cellulose acetate propionate and cellulose acetate by a melt film forming method.
In addition, a composition containing cellulose acylate (preferably cellulose acetate) and a Re enhancer represented by the following formula (I) is formed by a solution casting method, and stretched as desired. It is preferable to produce it.

(Re expression agent)
In order to produce a cellulose acylate film that satisfies the conditions as the first optically anisotropic layer, it is preferable to add a Re enhancer to the cellulose acylate film. Here, the “Re developing agent” is a compound having the property of developing birefringence within the film plane.

  The cellulose acylate film used as the first optically anisotropic layer preferably contains at least one compound represented by the following general formula (I) as a Re developing agent.

In the formula, L ¹ and L ² each independently represent a single bond or a divalent linking group; A ¹ and A ² each independently represent —O— or —NR— (R represents a hydrogen atom or a substituent). ), -S- and -CO-; R ¹ , R ² and R ³ each independently represent a substituent; X represents a nonmetallic atom of Groups 14-16 ( However, a hydrogen atom or a substituent may be bonded to X); n represents any integer from 0 to 2.

  Among the compounds represented by the general formula (I), the Re enhancer is preferably a compound represented by the following general formula (II).

In general formula (II), L ¹ and L ² each independently represents a single bond or a divalent linking group. A ¹ and A ² each independently represent a group selected from the group consisting of —O—, —NR— (R represents a hydrogen atom or a substituent), —S—, and CO—. R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represents a substituent. n represents an integer of 0 to 2.

In the general formula (I) or (II), the divalent linking group represented by L ¹ and L ² preferably includes the following examples.

  More preferred are -O-, -COO-, and -OCO-.

In general formula (I) or (II), R ¹ is a substituent, and when there are a plurality of R ^{1 s} , they may be the same or different and may form a ring. The following can be applied as examples of the substituent.

  A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert- Butyl group, n-octyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl) Group), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. Bicyclo [1,2,2] heptan-2-yl group, bicyclo [2,2,2] octan-3-yl group), a A kenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group or an allyl group), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, That is, it is a monovalent group in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms is removed, for example, a 2-cyclopenten-1-yl, 2-cyclohexen-1-yl group), a bicycloalkenyl group (substituted or substituted). An unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed. Bicyclo [2,2,1] hept-2-en-1-yl group, bicyclo [2,2,2] oct-2-en-4-yl group), alkynyl (Preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group or a propargyl group), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as a phenyl group, p-tolyl group, naphthyl group), a heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound. And more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group), a cyano group. Hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy group, ethoxy group, isopropoxy group, Si group, tert-butoxy group, n-octyloxy group, 2-methoxyethoxy group), aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy group, 2- Methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy group, tert -Butyldimethylsilyloxy group), heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group) An acyloxy group (preferably a formyloxy group, substituted or unsubstituted having 2 to 30 carbon atoms) Alkylcarbonyloxy group, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group ), A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N , N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy Base An ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, an n-octylcarbonyloxy group), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyl Oxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group), amino group (preferably amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, carbon number 6-30 substituted or unsubstituted anilino groups such as amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably formylamino group, C1-C30 substituted or unsubstituted a Alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group), aminocarbonylamino group (preferably A substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group), alkoxycarbonyl An amino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as a methoxycarbonylamino group, an ethoxycarbonylamino group, a tert-butoxycarbonylamino group, an n-octadecyloxycarboni group; Amino group, N-methyl-methoxycarbonylamino group), aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms such as phenoxycarbonylamino group, p-chlorophenoxy A carbonylamino group, an mn-octyloxyphenoxycarbonylamino group), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as a sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, 6 to 6 carbon atoms) 30 substituted or unsubstituted aryl sulfoni An amino group, such as a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, a p-methylphenylsulfonylamino group, a mercapto group, an alkylthio group (preferably, C1-C30 substituted or unsubstituted alkylthio group, for example, methylthio group, ethylthio group, n-hexadecylthio group), arylthio group (preferably C6-C30 substituted or unsubstituted arylthio group, for example, phenylthio group , P-chlorophenylthio group, m-methoxyphenylthio group), heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio group, 1- Phenyltetrazol-5-ylthio group), sulfamoyl group (preferably Preferably, the substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N -Acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N'-phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, p-methylphenylsulfinyl group), alkyl and arylsulfonyl groups (preferably , Substituted or unsubstituted alkyls having 1 to 30 carbon atoms Honyl group, substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p-methylphenylsulfonyl group), acyl group (preferably formyl group, carbon number) A substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms such as an acetyl group and a pivaloylbenzoyl group, and an aryloxycarbonyl group (preferably having a carbon number) 7-30 substituted or unsubstituted aryloxycarbonyl groups such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, p-tert-butylphenoxycarbonyl group), alkoxycarbonyl group (preferably , C2-C30 substitution or non-placement An alkoxycarbonyl group, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, an n-octadecyloxycarbonyl group), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, for example, Carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group), aryl and heterocyclic azo group (preferably carbon number) 6-30 substituted or unsubstituted arylazo groups, C3-C30 substituted or unsubstituted heterocyclic azo groups such as phenylazo group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazole -2-ylazo group), imide group (preferably N-succin) Imide group, N-phthalimido group), phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group), phosphinyl group (Preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl group, dioctyloxyphosphinyl group, diethoxyphosphinyl group), phosphinyloxy group (preferably having 2 carbon atoms) -30 substituted or unsubstituted phosphinyloxy group, for example, diphenoxyphosphinyloxy group, dioctyloxyphosphinyloxy group, phosphinylamino group (preferably substituted or substituted with 2 to 30 carbon atoms) Unsubstituted phosphinylamino group such as dimethoxyphosphinylamino group, dimethylaminophosphine Iniruamino group), a silyl group (preferably, represents a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, e.g., trimethylsilyl group, tert- butyldimethylsilyl group, a phenyldimethylsilyl group).

  Among the above substituents, those having a hydrogen atom may be substituted with the above groups after removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

R ¹ is preferably a halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, acyloxy group, cyano group, amino group, more preferably A halogen atom, an alkyl group, a cyano group, and an alkoxy group.

R ² and R ³ each independently represents a substituent. An example of R ¹ is given as an example. Preferred are a substituted or unsubstituted benzene ring and a substituted or unsubstituted cyclohexane ring. More preferred are a benzene ring having a substituent and a cyclohexane ring having a substituent, and further preferred are a benzene ring having a substituent at the 4-position and a cyclohexane ring having a substituent at the 4-position.

R ⁴ and R ⁵ each independently represents a substituent. An example of R ¹ is given as an example. Preferably, it is preferred that substituent constant sigma _p value of Hammett is greater than zero electron withdrawing group, sigma _p value has an electron withdrawing substituent of 0 to 1.5 Further preferred. Examples of such a substituent include a trifluoromethyl group, a cyano group, a carbonyl group, and a nitro group. R ⁴ and R ⁵ may combine to form a ring.
Regarding σ _p and σ _m of Hammett's substituent constants, for example, Naoki Inamoto's “Hammett's rule-structure and reactivity-” (Maruzen), edited by the Chemical Society of Japan “New Experimental Chemistry Course 14 Synthesis of Organic Compounds” Reaction V "2605 (Maruzen), Tadao Nakatani" Theoretical Organic Chemistry "217 (Tokyo Kagaku Dojin), Chemical Review, 91, 165-195 (1991) .

A ¹ and A ² each independently represent a group selected from the group consisting of —O—, —NR— (R is a hydrogen atom or a substituent), —S—, and CO—. Preferred is —O—, —NR— (R represents a substituent, and examples thereof include R ¹ ) and S—.

X represents a nonmetallic atom belonging to Groups 14-16. However, a hydrogen atom or a substituent may be bonded to X. X is preferably ═O, ═S, ═NR, ═C (R) R (wherein R represents a substituent, and examples of R ¹ are given as examples).
n represents an integer of 0 to 2, preferably 0 or 1.

  Specific examples of the compound represented by the general formula (I) or (II) are shown below, but examples of the Re enhancer are not limited to the following specific examples. Regarding the following compounds, unless otherwise specified, the number in parentheses () indicates the exemplified compound (X).

  The synthesis of the compound represented by the general formula (I) or (II) can be performed with reference to a known method. For example, exemplary compound (1) can be synthesized according to the following scheme.

In the above scheme, the synthesis from compound (1-A) to compound (1-D) is described in “Journal of Chemical Crystallography” (1997); 27 (9); p. 515-526. It can be performed with reference to the method described in 1.
Further, as shown in the above scheme, methanesulfonic acid chloride was added to a tetrahydrofuran solution of the compound (1-E), N, N-diisopropylethylamine was added dropwise and stirred, and then N, N-diisopropylethylamine was added, Exemplary solution (1) can be obtained by adding dropwise a tetrahydrofuran solution of compound (1-D) and then adding a tetrahydrofuran solution of N, N-dimethylaminopyridine (DMAP).

Moreover, you may use the rod-shaped aromatic compound of pages 11-14 of Unexamined-Japanese-Patent No. 2004-50516 as said Re expression agent.
Further, as the Re enhancer, one kind of compound can be used alone, or two or more kinds of compounds can be mixed and used. It is preferable to use two or more compounds different from each other as the Re enhancer because the retardation adjustment range is widened and can be easily adjusted to a desired range.
The addition amount of the Re enhancer is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass with respect to 100 parts by mass of cellulose acylate. When the cellulose acylate film is produced by a solvent cast method, the Re enhancer may be added to the dope. The addition may be performed at any timing. For example, the Re developing agent may be dissolved in an organic solvent such as alcohol, methylene chloride, dioxolane, etc., and then added to the cellulose acylate solution (dope) or directly. You may add during dope composition.

(Rth expression agent)
In order to produce a cellulose acylate film that satisfies the conditions for the first optically anisotropic layer, it is preferable to add an Rth enhancer to the cellulose acylate film. Here, the “Rth enhancer” is a compound having the property of developing birefringence in the thickness direction of the film.

  As the Rth enhancer, a compound having a large polarizability anisotropy having an absorption maximum in a wavelength range of 250 nm to 380 nm is preferable. As the Rth enhancer, a compound represented by the following general formula (I) can be particularly preferably used.

In the formula, X ¹ is a single bond, —NR ⁴ —, —O— or S—; X ² is a single bond, —NR ⁵ —, —O— or S—; X ³ is a single bond A bond, —NR ⁶ —, —O— or S—. R ¹ , R ² , and R ³ are each independently an alkyl group, an alkenyl group, an aromatic ring group, or a heterocyclic group; R ⁴ , R ^5, and R ⁶ are each independently a hydrogen atom , An alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

  Preferred examples (I- (1) to IV- (10)) of the compounds represented by the general formula (I) are shown below, but the present invention is not limited to these specific examples.

  As the Rth enhancer, a compound represented by the following general formula (III) is also preferable. Hereinafter, the compound of the general formula (III) will be described in detail.

In the general formula (III), R ² , R ⁴ and R ⁵ each independently represent a hydrogen atom or a substituent, R ¹¹ and R ¹³ each independently represent a hydrogen atom or an alkyl group, and L ¹ and L ² are Each independently represents a single bond or a divalent linking group. Ar ¹ represents an arylene group or an aromatic heterocyclic ring, Ar ² represents an aryl group or an aromatic heterocyclic ring, n represents an integer of 3 or more, and n ² types of L ² and Ar ¹ are the same. It may or may not be. However, R ¹¹ and R ¹³ are different from each other, and the alkyl group represented by R ¹³ does not contain a hetero atom.

In general formula (III), R ² , R ⁴ and R ⁵ each independently represents a hydrogen atom or a substituent. Substituent T described later can be applied as the substituent.

R ² in the general formula (III) is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group or an alkoxy group, still more preferably a hydrogen atom or an alkyl group. Group (preferably 1 to 4 carbon atoms, more preferably a methyl group), an alkoxy group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, particularly Preferably it is C1-C4. Particularly preferred are a hydrogen atom, a methyl group and a methoxy group, and most preferred is a hydrogen atom.

R ⁴ in the general formula (III) is preferably a hydrogen atom or an electron donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group, and still more preferably a hydrogen atom or a carbon number. An alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 12 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms And particularly preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and most preferably a hydrogen atom or a methoxy group.

R ⁵ in the general formula (III) is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amino group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group or an alkoxy group, still more preferably a hydrogen atom. An atom, an alkyl group (preferably having 1 to 4 carbon atoms, more preferably a methyl group), an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and further preferably 1 to 6 carbon atoms). Particularly preferably, it has 1 to 4 carbon atoms. Particularly preferred are a hydrogen atom, a methyl group, and a methoxy group. Most preferably, it is a hydrogen atom.

R ¹¹ and R ¹³ in the general formula (III) each independently represent a hydrogen atom or an alkyl group, R ¹¹ and R ¹³ are different from each other, and the alkyl group represented by R ¹³ does not contain a hetero atom. Here, the hetero atom means an atom other than a hydrogen atom or a carbon atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, phosphorus, silicon, a halogen atom (F, Cl, Br, I), and boron.
The alkyl group represented by R ¹¹ and R ¹³ is linear, branched or cyclic and represents a substituted or unsubstituted alkyl group, preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms (that is, a monovalent structure in which one hydrogen atom is removed from a bicycloalkane having 5 to 30 carbon atoms) And a tricyclo structure having more ring structures.

Preferable examples of the alkyl group represented by R ¹¹ and R ¹³ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl group, iso-pentyl group, n -Hexyl group, n-heptyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3-trimethylhexyl group, n-decyl group, 2-hexyldecyl group, Examples thereof include a cyclohexyl group, a cycloheptyl group, a 2-hexenyl group, an oleyl group, a linoleyl group, and a linolenyl group. Examples of the cycloalkyl group include cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl, and examples of the bicycloalkyl group include bicyclo [1,2,2] heptan-2-yl and bicyclo [2,2,2] octane-3. -Yl and the like.

R ¹¹ is more preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, or isopropyl group, particularly preferably a hydrogen atom or methyl group, and most preferably a methyl group.
R ¹³ is particularly preferably an alkyl group containing 2 or more carbon atoms, more preferably an alkyl group containing 3 or more carbon atoms. Those having a branched or cyclic structure are particularly preferably used.

Hereinafter, specific examples (O-1 to O-20) of the alkyl group represented by R ¹³ will be described. However, the present invention is not limited to the following specific examples. In the specific examples below, “#” means the oxygen atom side.

Ar ¹ in the general formula (III) represents an arylene group or an aromatic heterocyclic ring, and all Ar ¹ in the repeating unit may be the same or different. Ar ² represents an aryl group or an aromatic heterocyclic ring.
In the general formula (III), the arylene group represented by Ar ¹ is preferably an arylene group having 6 to 30 carbon atoms, which may be a single ring or may form a condensed ring with another ring. Good. Further, if possible, it may have a substituent, and the substituent T described later can be applied as the substituent. More preferably, the arylene group represented by Ar ¹ has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenylene group, a p-methylphenylene group, and a naphthylene group.
In general formula (III), the aryl group represented by Ar ² is preferably an aryl group having 6 to 30 carbon atoms, which may be monocyclic or may form a condensed ring with another ring. Good. Further, if possible, it may have a substituent, and the substituent T described later can be applied as the substituent. The aryl group represented by Ar ² has more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenyl group, a p-methylphenyl group, and a naphthyl group.

In the general formula (III), the aromatic heterocycle represented by Ar ¹ or Ar ² may be an aromatic heterocycle containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom, preferably 5 It is an aromatic heterocycle containing at least one of a 6-membered oxygen atom, nitrogen atom or sulfur atom. Moreover, you may have a substituent further if possible. Substituent T described later can be applied as the substituent.

In the general formula (III), specific examples of the aromatic heterocycle represented by Ar ¹ and Ar ² include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, Indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole , Benzotriazole, tetrazaindene, pyrrolotriazole, pyrazolotriazole and the like. Preferred as the aromatic heterocycle are benzimidazole, benzoxazole, benzthiazole, and benzotriazole.

In general formula (III), L ¹ and L ² each independently represents a single bond or a divalent linking group. L ¹ and L ² may be the same or different. Further, all L ² in the repeating unit may be the same or different.
Preferred as the divalent linking group are —O—, —NR— (R represents a hydrogen atom or an alkyl group or an aryl group which may have a substituent), —CO—, —SO ₂ —, -S-, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a group obtained by combining two or more of these divalent groups, more preferably -O-,- NR -, - CO -, - SO 2 NR -, - NRSO 2 -, - CONR -, - NRCO -, - COO-, and OCO-, an alkynylene group. R preferably represents a hydrogen atom.

In the compound represented by the general formula (III) in the present invention, Ar ¹ is bonded to L ¹ and L ^{2. When} Ar ¹ is a phenylene group, L ^1- Ar ¹ -L ² and L ^2- Ar ¹ -L ² is particularly preferably in a para-position (1,4-position) to each other.

  In general formula (III), n represents an integer greater than or equal to 3, Preferably it is 3-7, More preferably, it is 3-6, More preferably, it is 3-5.

  As the compound represented by the general formula (III), compounds represented by the following general formulas (IV) and (V) can be particularly preferably used.

In general formula (IV), R ² and R ⁵ each independently represent a hydrogen atom or a substituent, R ¹¹ and R ¹³ each independently represent a hydrogen atom or an alkyl group, and L ¹ and L ² Each independently represents a single bond or a divalent linking group. Ar ¹ represents an arylene group or an aromatic heterocyclic ring, Ar ² represents an aryl group or an aromatic heterocyclic ring, n represents an integer of 3 or more, and n ² types of L ² and Ar ¹ are the same. It may or may not be. However, R ¹¹ and R ¹³ are different from each other, and the alkyl group represented by R ¹³ does not contain a hetero atom.

In general formula (IV), R ² , R ⁵ , R ¹¹ , and R ¹³ have the same meanings as those in general formula (III), and preferred ranges are also the same. L ¹ , L ² , Ar ¹ and Ar ² are also synonymous with those in the general formula (III), and preferred ranges are also the same.

In general formula (V), R ² and R ⁵ each independently represent a hydrogen atom or a substituent, R ¹¹ , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an alkyl group, and L ¹ and L ² are Each independently represents a single bond or a divalent linking group. Ar ¹ represents an arylene group or an aromatic heterocyclic ring, Ar ² represents an aryl group or an aromatic heterocyclic ring, n represents an integer of 3 or more, and n ² types of L ² and Ar ¹ are the same. It may or may not be. However, R ¹¹ and R ¹³ are different from each other, and the alkyl group represented by R ¹³ does not contain a hetero atom.

In the general formula (V), R ² , R ⁵ , R ¹¹ and R ¹³ have the same meanings as those in the general formula (III), and preferred ranges are also the same. L ¹ , L ² , Ar ¹ and Ar ² have the same meanings as those in formula (III), and preferred ranges are also the same.
In the general formula (V), R ¹⁴ represents a hydrogen atom or an alkyl group, and as the alkyl group, alkyl groups shown as preferred examples of R ¹¹ and R ¹³ are preferably used. R ¹⁴ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group. R ¹¹ and R ¹⁴ may be the same or different, but both are particularly preferably methyl groups.

  Moreover, as a compound represented by the said general formula (V), the compound represented by general formula (VA) or general formula (VB) is also preferable.

In general formula (VA), R ² and R ⁵ each independently represent a hydrogen atom or a substituent, R ¹¹ and R ¹³ each independently represent a hydrogen atom or an alkyl group, L ¹ , L ² each independently represents a single bond or a divalent linking group. Ar ¹ represents an arylene group or an aromatic heterocyclic ring, n represents an integer of 3 or more, and n ² types of L ² and Ar ² may be the same or different. However, R ¹¹ and R ¹³ are different from each other, and the alkyl group represented by R ¹³ does not contain a hetero atom.

In general formula (VA), R ² , R ⁵ , R ¹¹ , R ¹³ , L ¹ , L ² , Ar ¹ , and n have the same meanings as those in general formula (III), and preferred ranges are also the same. is there.

In general formula (V-B), R ² and R ⁵ each independently represent a hydrogen atom or a substituent, and R ¹¹ , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an alkyl group, L ¹ and L ² each independently represents a single bond or a divalent linking group. Ar ¹ represents an arylene group or an aromatic heterocyclic ring, n represents an integer of 3 or more, and n types of L ¹ and Ar ² may be the same or different. However, R ¹¹ and R ¹³ are different from each other, and the alkyl group represented by R ¹³ does not contain a hetero atom.

In general formula (V-B), R ² , R ⁵ , R ¹¹ , R ¹³ , R ¹⁴ , L ¹ , L ² , Ar ¹ , n are as defined in general formulas (III) and (V). The preferred range is also the same.

The aforementioned substituent T will be described below.
The substituent T is preferably a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, Isopropyl group, t-butyl group, n-octyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4 -N-dodecylcyclohexyl group), a bicycloalkyl group (preferably a mono- or di-substituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom is removed from a bicycloalkane having 5 to 30 carbon atoms. For example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3 Yl), an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group or an allyl group), a cycloalkenyl group (preferably a substituted or unsubstituted cyclohexane having 3 to 30 carbon atoms). An alkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl), a bicycloalkenyl group ( A substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2-en-4-yl), al An aryl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl group, propargyl group), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl Group, p-tolyl group, naphthyl group), heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound And more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms (for example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group),

A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, n -Octyloxy group, 2-methoxyethoxy group), aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy group, 2-methylphenoxy group, 4-tert-butyl) Phenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group), hetero A ring oxy group (preferably a substituted or unsubstituted hete Ring oxy group, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, carbon number 6-30 substituted or unsubstituted arylcarbonyloxy groups such as formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably A substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octyl Aminocarbonyloxy group, Nn-oct Rucarbamoyloxy group), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n-octylcarbonyl group) Oxy group), aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexa Decyloxyphenoxycarbonyloxy group),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as an amino group, a methylamino group, a dimethylamino group; , Anilino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms, or Unsubstituted arylcarbonylamino group, for example, formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group), aminocarbonylamino group (preferably substituted or unsubstituted amino having 1 to 30 carbon atoms) Carbonylamino group, for example, carbamoylamino group, N, N-dimethylaminocarbonyl Mino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino Group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group), aryloxycarbonylamino group (preferably substituted or unsubstituted aryloxycarbonyl having 7 to 30 carbon atoms) An amino group such as a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, an mn-octyloxyphenoxycarbonylamino group, a sulfamoylamino group (preferably having 0 to 30 carbon atoms); Substituted or unsubstituted sulfamoylamino groups, such as sulfamoylamino groups, N, N-dimethylaminosulfonylamino groups, Nn-octylaminosulfonylamino groups, alkyl and arylsulfonylamino groups (preferably carbon A substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, 2, 3 , 5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio group, ethylthio group, n- Hexadecylthio group), arylthio group (Preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group), heterocyclic thio group (preferably substituted having 2 to 30 carbon atoms) Or an unsubstituted heterocyclic thio group, for example, 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group),

Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group , N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably substituted or non-substituted having 1 to 30 carbon atoms) Substituted alkylsulfinyl groups, 6-30 substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, p-methylphenylsulfinyl group), alkyl and arylsulfonyl groups (preferably C1-C30 substituted or unsubstituted An alkylsulfonyl group, a 6-30 substituted or unsubstituted arylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, a p-methylphenylsulfonyl group), an acyl group (preferably a formyl group, 2 carbon atoms) -30 substituted or unsubstituted alkylcarbonyl group, C7-30 substituted or unsubstituted arylcarbonyl group such as acetyl group and pivaloylbenzoyl group), aryloxycarbonyl group (preferably 7 carbon atoms) To 30 substituted or unsubstituted aryloxycarbonyl groups such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, p-tert-butylphenoxycarbonyl group), alkoxycarbonyl group (preferably, C2-C30 substitution or Unsubstituted alkoxycarbonyl group, for example, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, n-octadecyloxycarbonyl group), carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, For example, carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group), aryl and heterocyclic azo groups (preferably C6-C30 substituted or unsubstituted arylazo group, C3-C30 substituted or unsubstituted heterocyclic azo group, for example, phenylazo group, p-chlorophenylazo group, 5-ethylthio-1,3,4 -Thiadiazol-2-ylazo group), imide group (preferably N-sul Succinimide group, N-phthalimido group), phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group), phosphinyl group (Preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl group, dioctyloxyphosphinyl group, diethoxyphosphinyl group), phosphinyloxy group (preferably having 2 carbon atoms) -30 substituted or unsubstituted phosphinyloxy group, for example, diphenoxyphosphinyloxy group, dioctyloxyphosphinyloxy group, phosphinylamino group (preferably substituted or substituted with 2 to 30 carbon atoms) Unsubstituted phosphinylamino group such as dimethoxyphosphinylamino group, dimethylamino Phosphinyl amino group), a silyl group (preferably, represents a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, e.g., trimethylsilyl group, tert- butyldimethylsilyl group, a phenyldimethylsilyl group).

  Among the above substituents, those having a hydrogen atom may be substituted with the above groups after removing this. Examples of such a functional group include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Specific examples include a methylsulfonylaminocarbonyl group, p- Examples include methylphenylsulfonylaminocarbonyl group, acetylaminosulfonyl group, and benzoylaminosulfonyl group.

  Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.

Preferred compounds represented by formula (VA) are those in which R ¹¹ is a methyl group, R ² and R ⁵ are both hydrogen atoms, and R ¹³ has 3 or more carbon atoms. An alkyl group, and L ¹ is a single bond, —O—, —CO—, —NR—, —SO ₂ NR—, —NRSO ₂ —, —CONR—, —NRCO—, —COO—, and OCO—. , An alkynylene group (R represents a hydrogen atom, an optionally substituted alkyl group or an aryl group, preferably a hydrogen atom), and L ² represents —O— or NR— (R represents a hydrogen atom). Represents an alkyl group or an aryl group which may have a substituent, preferably a hydrogen atom.), Ar ¹ is an arylene group, and n is 3-6.

  Specific examples of the compounds represented by formulas (VA) and (VB) will be described below in detail, but the present invention is not limited to the following specific examples.

The compound represented by the general formula (III) can be synthesized by first synthesizing a substituted benzoic acid, followed by a general ester reaction or amidation reaction between the substituted benzoic acid and a phenol derivative or aniline derivative. Any reaction may be used as long as it is a formation reaction. Examples include a method in which a substituted benzoic acid is converted to an acid halide and then condensed with a phenol derivative or aniline derivative, and a method in which a substituted benzoic acid is condensed with a phenol derivative or aniline derivative using a condensing agent or catalyst. It is done.
As a method for producing the compound represented by the general formula (III), a method in which a substituted benzoic acid is functionally converted to an acid halide and then condensed with a phenol derivative or an aniline derivative is preferable in consideration of the production process and the like.

  In the method for producing the compound represented by the general formula (III), examples of the reaction solvent include hydrocarbon solvents (preferably toluene and xylene), ether solvents (preferably dimethyl ether, tetrahydrofuran, dioxane and the like). ), Ketone solvents, ester solvents, acetonitrile, dimethylformamide, dimethylacetamide, and the like. These solvents may be used alone or in admixture of several kinds, and the solvent is preferably toluene, acetonitrile, dimethylformamide, or dimethylacetamide.

The reaction temperature is preferably 0 to 150 ° C, more preferably 0 to 100 ° C, still more preferably 0 to 90 ° C, and particularly preferably 20 ° C to 90 ° C.
Moreover, it is preferable not to use a base for this reaction. When a base is used, it may be either an organic base or an inorganic base, preferably an organic base, such as pyridine or tertiary alkylamine (preferably triethylamine, ethyldiisopropylamine, etc.).

  The compounds represented by the general formulas (VA) and (VB) can be synthesized by a known method. For example, in the case of a compound where n = 4, a raw material compound having the following structure A and a hydroxyl group The following intermediate B 2 molecule obtained by reaction with a derivative having a reactive site such as an amino group can be obtained by linking with 1 molecule of the following compound C. However, the synthesis method of the compounds represented by the general formulas (VA) and (VB) is not limited to this example.

In the formula, A represents a reactive group such as a hydroxyl group or a halogen atom, R ¹¹ , R ² , R ¹³ , and R ⁵ are as described above, and R ⁴ is a hydrogen atom or OR ¹⁴ described above. Is a substituent.

In the formula, A ′ represents a reactive group such as a carboxyl group, and R ¹¹ , R ² , R ¹³ , R ⁴ , R ⁵ , Ar ¹ , and L ¹ are as described above.

In the formula, B and B ′ represent a reactive group such as a hydroxyl group and an amino group, and Ar ² and L ² have the same meanings as Ar ¹ and L ¹ described above.

The content of the Rth enhancer represented by the general formulas (I) and (III) to (V) in the present invention relative to 100 parts by mass of cellulose acylate is preferably 0.1 to 30% by mass, and 1 to 25% by mass. Is more preferable, and 3 to 15% by mass is even more preferable.
When the cellulose acylate film is produced by a solvent cast method, the Rth enhancer may be added to the dope. The timing of adding the Rth enhancer is not particularly limited, and the Rth enhancer is dissolved in an organic solvent such as alcohol, methylene chloride, dioxolane, etc., and then added to the cellulose acylate solution (dope) or directly in the dope composition. It may be added inside.

  As the Rth enhancer, one type of the compounds represented by the general formulas (I) and (III) to (V) may be used alone, or two or more types may be mixed and used. Moreover, in this invention, combined use of the Rth expression agent represented by general formula (I), (III)-(V) is also preferable.

  The cellulose acylate film used as the first optically anisotropic layer may contain an ultraviolet absorber. The ultraviolet absorber can also function as an Rth enhancer. Examples of the ultraviolet absorbers include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. System compounds are preferred. Further, ultraviolet absorbers described in JP-A-10-182621 and JP-A-8-337574 and polymer ultraviolet absorbers described in JP-A-6-148430 are also preferably used. The cellulose acylate film used as the second optically anisotropic layer has an excellent ability to absorb ultraviolet rays having a wavelength of 370 nm or less from the viewpoint of preventing deterioration of a polarizer and liquid crystal as an ultraviolet absorber, and From the viewpoint of liquid crystal display properties, those that absorb less visible light having a wavelength of 400 nm or more are preferred.

  Specific examples of the benzotriazole ultraviolet absorber useful in the present invention include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert). -Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl Phenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2,2 -Methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2 ' Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy Examples include, but are not limited to, a mixture of -5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate. As commercially available products, TINUVIN 109, TINUVIN 171 and TINUVIN 326 (all manufactured by Ciba Specialty Chemicals Co., Ltd.) can be preferably used.

The content of the Rth enhancer with respect to 100 parts by mass of cellulose acylate is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and still more preferably 3 to 15% by mass.
In addition, when manufacturing the said cellulose acylate film by the solvent cast method, you may add the said Rth expression agent in dope. The timing of adding the Rth enhancer is not particularly limited, and the Rth enhancer is dissolved in an organic solvent such as alcohol, methylene chloride, dioxolane, etc., and then added to the cellulose acylate solution (dope) or directly in the dope composition. It may be added inside.

(Plasticizer)
A plasticizer such as triphenyl phosphate or biphenyl phosphate may be added to the cellulose acylate film used as the first optically anisotropic layer.

  The thickness of the polymer film used as the first optically anisotropic layer is not particularly limited, but is generally preferably 40 to 120 μm, more preferably 60 to 100 μm.

[Second optically anisotropic layer]
The optical compensation film of the present invention has a second optical anisotropic layer having liquid crystal alignment ability and satisfying nx ≧ ny> nz. The second optically anisotropic layer is preferably a layer formed by a coating method using a polymer composition. In the polymer composition, one or two kinds of polymers that can exhibit optical anisotropy and liquid crystal alignment ability (including those that are expressed by post-treatment such as rubbing treatment) can be exhibited by coating. Contains above. Although there is no restriction | limiting in particular about the polymer used for formation of the said 2nd optically anisotropic layer, From a viewpoint that an optically anisotropic polymer layer can be formed by application | coating, polyvinyl alcohol, polyimide, polyolefin (example, Polyethylene, polypropylene, norbornene polymers), polycarbonate, polyarylate, polysulfone, polyvinyl alcohol, polymethacrylate, polyacrylate, cellulose ester (eg, cellulose triacetate, cellulose diacetate), polyamide, polyester, polyether Preference is given to at least one polymer material selected from the group consisting of ketones, polyamideimide polyesterimides, and polyaryletherketones. Among these, a polymer selected from the group consisting of polyimide, polyetherketone, polyamideimide, and polyesterimide is preferable. Further, polyvinyl alcohol having a predetermined polymerization degree and saponification degree, which will be described later, is also preferable. When a polymer layer is formed by coating using a predetermined polyvinyl alcohol and polyimide, Rth is expressed in the polymer layer, and the Rth exhibits forward dispersion wavelength dependency, which is preferable as the second optically anisotropic layer. Optical characteristics are shown.

(Polyimide)
There is no restriction | limiting in particular about the polyimide used for formation of the said 2nd optically anisotropic layer. It can be selected from various known polyimides. Examples of preferable polyimide include polyimides described in JP-A-2004-226945, [0011] to [0034]. More specifically, polyimide having high in-plane orientation and soluble in an organic solvent is preferable. Specifically, for example, it includes a condensation polymerization product of 9,9-bis (aminoaryl) fluorene and an aromatic tetracarboxylic dianhydride disclosed in JP 2000-511296 A, and has the following formula ( A polymer containing one or more repeating units shown in 1) can be used.

In the formula (1), R ³ to R ⁶ are hydrogen, halogen, a phenyl group, 1-4 halogen atoms, or C ₁ ~ ₁₀ alkyl-substituted phenyl, and C ₁ ~ ₁₀ alkyl group And at least one substituent selected independently from the group. Preferably, R ³ to R ⁶ is a halogen, a phenyl group, each independently from the group consisting of one to four halogen atoms or C ₁ ~ ₁₀ alkyl-substituted phenyl, and C ₁ ~ ₁₀ alkyl group It is at least one type of substituent selected.

In the formula (1), Z represents a tetravalent aromatic group C ₆ ~ _20, preferably a pyromellitic group, a polycyclic aromatic group, a derivative of a polycyclic aromatic group, or, It is group represented by following formula (2).

In the formula (2), Z ′ is, for example, a covalent bond, C (R ⁷ ) ₂ group, CO group, O atom, S atom, SO ₂ group, Si (C ₂ H ₅ ) ₂ group, or NR ^{There are 8} groups, and when there are multiple groups, they are the same or different. W represents an integer from 1 to 10. Each R ⁷ is independently hydrogen or C (R ⁹ ) ₃ . R ⁸ is hydrogen, an alkyl group or a C ₆ ~ ₂₀ aryl group, the carbon atom number from 1 to about 20, for a plurality, it may be the same or different. Each R ⁹ is independently hydrogen, fluorine, or chlorine.

Examples of the polycyclic aromatic group include a tetravalent group derived from naphthalene, fluorene, benzofluorene or anthracene. The substitution Examples of the substituted derivatives of polycyclic aromatic group, for example, an alkyl group of C ₁ ~ _10, at least one group selected from the group consisting of fluorinated derivatives, and F or a halogen such as Cl And the above-mentioned polycyclic aromatic group.

In addition, for example, a homopolymer described in JP-A-8-511812, wherein the repeating unit is represented by the following general formula (3) or (4), or the repeating unit is represented by the following general formula (5): And the polyimide shown. In addition, the polyimide of following formula (5) is a preferable form of the homopolymer of following formula (3).

In the general formulas (3) to (5), G and G ′ are, for example, a covalent bond, a CH ₂ group, a C (CH ₃ ) ₂ group, a C (CF ₃ ) ₂ group, or a C (CX ₃ ) ₂ group. (Wherein X is halogen), from the group consisting of CO group, O atom, S atom, SO ₂ group, Si (CH ₂ CH ₃ ) ₂ group, and N (CH ₃ ) group, respectively It represents independently selected groups, and may be the same or different.

In the above formulas (3) and (5), L is a substituent, and d and e represent the number of substitutions. L is, for example, a halogen, a C _1-3 alkyl group, a C _1-3 halogenated alkyl group, a phenyl group, or a substituted phenyl group, and in a plurality of cases, they are the same or different. Examples of the substituted phenyl group include substituted phenyl groups having at least one kind of substituent selected from the group consisting of halogen, C _1-3 alkyl group, and C _1-3 halogenated alkyl group. Examples of the halogen include fluorine, chlorine, bromine and iodine. d is an integer from 0 to 2, and e is an integer from 0 to 3.

In the formulas (3) to (5), Q is a substituent, and f represents the number of substitutions. Q is, for example, selected from the group consisting of hydrogen, halogen, alkyl group, substituted alkyl group, nitro group, cyano group, thioalkyl group, alkoxy group, aryl group, substituted aryl group, alkyl ester group, and substituted alkyl ester group And when Q is plural, they are the same or different. Examples of the halogen include fluorine, chlorine, bromine and iodine. Examples of the substituted alkyl group include a halogenated alkyl group. Examples of the substituted aryl group include a halogenated aryl group. f is an integer from 0 to 4, and g and h are integers from 0 to 3 and 1 to 3, respectively. Further, g and h are preferably larger than 1.

In the formula (4), R ¹⁰ and R ¹¹ are groups independently selected from the group consisting of hydrogen, halogen, phenyl group, substituted phenyl group, alkyl group, and substituted alkyl group. Among these, R ¹⁰ and R ¹¹ are preferably each independently a halogenated alkyl group.

In the formula (5), M ¹ and M ² are the same or different and are, for example, halogen, C _1-3 alkyl group, C _1-3 halogenated alkyl group, phenyl group, or substituted phenyl group. is there. Examples of the halogen include fluorine, chlorine, bromine and iodine. Examples of the substituted phenyl group include substituted phenyl groups having at least one type of substituent selected from the group consisting of halogen, C _1-3 alkyl groups, and C _1-3 halogenated alkyl groups. .

Specific examples of the polyimide represented by the formula (3) include those represented by the following formula (6).

Furthermore, examples of the polyimide include a copolymer obtained by appropriately copolymerizing an acid dianhydride other than the skeleton (repeating unit) as described above and a diamine.

Examples of the acid dianhydride include aromatic tetracarboxylic dianhydrides. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, heterocyclic aromatic tetracarboxylic dianhydride, 2, And 2'-substituted biphenyltetracarboxylic dianhydride.

Examples of the pyromellitic dianhydride include pyromellitic dianhydride, 3,6-diphenylpyromellitic dianhydride, 3,6-bis (trifluoromethyl) pyromellitic dianhydride, and 3,6-dibromo. Examples include pyromellitic dianhydride and 3,6-dichloropyromellitic dianhydride. Examples of the benzophenone tetracarboxylic dianhydride include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2 , 2 ′, 3,3′-benzophenonetetracarboxylic dianhydride and the like. Examples of the naphthalenetetracarboxylic dianhydride include 2,3,6,7-naphthalene-tetracarboxylic dianhydride, 1,2,5,6-naphthalene-tetracarboxylic dianhydride, 2,6 -Dichloro-naphthalene-1,4,5,8-tetracarboxylic dianhydride and the like. Examples of the heterocyclic aromatic tetracarboxylic dianhydride include thiophene-2,3,4,5-tetracarboxylic dianhydride and pyrazine-2,3,5,6-tetracarboxylic dianhydride. Pyridine-2,3,5,6-tetracarboxylic dianhydride and the like. Examples of the 2,2′-substituted biphenyltetracarboxylic dianhydride include 2,2′-dibromo-4,4 ′, 5,5′-biphenyltetracarboxylic dianhydride and 2,2′-dichloro. -4,4 ', 5,5'-biphenyltetracarboxylic dianhydride, 2,2'-bis (trifluoromethyl) -4,4', 5,5'-biphenyltetracarboxylic dianhydride, etc. can give.

Other examples of the aromatic tetracarboxylic dianhydride include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and bis (2,3-dicarboxyphenyl) methane dianhydride. Bis (2,5,6-trifluoro-3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3 3-hexafluoropropane dianhydride, 4,4′-bis (3,4-dicarboxyphenyl) -2,2-diphenylpropane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 4,4′-oxydiphthalic dianhydride, bis (3,4-dicarboxyphenyl) sulfonic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 4,4 ′ -[4,4′-isopropyl Den-di (p-phenyleneoxy)] bis (phthalic anhydride), N, N- (3,4-dicarboxyphenyl) -N-methylamine dianhydride, bis (3,4-dicarboxyphenyl) And diethylsilane dianhydride.

Among these, the aromatic tetracarboxylic dianhydride is preferably 2,2′-substituted biphenyltetracarboxylic dianhydride, more preferably 2,2′-bis (trihalomethyl) -4,4. ', 5,5'-biphenyltetracarboxylic dianhydride, more preferably 2,2'-bis (trifluoromethyl) -4,4', 5,5'-biphenyltetracarboxylic dianhydride It is.

Examples of the diamine include aromatic diamines, and specific examples include benzene diamine, diaminobenzophenone, naphthalene diamine, heterocyclic aromatic diamines, and other aromatic diamines.

Examples of the benzenediamine include o-, m- and p-phenylenediamine, 2,4-diaminotoluene, 1,4-diamino-2-methoxybenzene, 1,4-diamino-2-phenylbenzene, and 1, Examples include diamines selected from the group consisting of benzenediamines such as 3-diamino-4-chlorobenzene. Examples of the diaminobenzophenone include 2,2′-diaminobenzophenone and 3,3′-diaminobenzophenone. Examples of the naphthalene diamine include 1,8-diaminonaphthalene and 1,5-diaminonaphthalene. Examples of the heterocyclic aromatic diamine include 2,6-diaminopyridine, 2,4-diaminopyridine, and 2,4-diamino-S-triazine.

In addition to these, as the aromatic diamine, 4,4′-diaminobiphenyl, 4,4′-diaminodiphenylmethane, 4,4 ′-(9-fluorenylidene) -dianiline, 2,2′-bis ( Trifluoromethyl) -4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 2,2′-dichloro-4,4′-diaminobiphenyl, 2,2 ′, 5 5′-tetrachlorobenzidine, 2,2-bis (4-aminophenoxyphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) -1,1, 1,3,3,3-hexafluoropropane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-amino) Phenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3 -Hexafluoropropane, 4,4'-diaminodiphenyl thioether, 4,4'-diaminodiphenyl sulfone and the like.
Among these, as the polyimide, 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, Polyimide synthesized from is preferred.

  Although the molecular weight of the polymer is not particularly limited, for example, the weight average molecular weight (Mw) is preferably in the range of 1,000 to 1,000,000, more preferably in the range of 2,000 to 500,000. is there. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) using polyethylene oxide as a standard sample and using a dimethylformamide solvent.

(Polyvinyl alcohol)
It is also preferable that the polymer material for forming the second optically anisotropic layer is polyvinyl alcohol. The hydroxyl group in the polyvinyl alcohol may be partially modified (hereinafter referred to as “polyvinyl alcohol” in the sense of including “modified polyvinyl alcohol”). Moreover, it is preferable that the average degree of polymerization of polyvinyl alcohol used for formation of a 2nd optically anisotropic layer is 1000-5000. The average degree of polymerization is more preferably 1200 to 5000, and further preferably 1700 to 5000.
Further, the saponification degree of polyvinyl alcohol is preferably 80 to 100%, and more preferably 95 to 100%.

  Commercially available polyvinyl alcohol may be used. Examples of unmodified polyvinyl alcohol having a polymerization degree in the above range include PVA117, PVA124, PVA135, PVA217 manufactured by Kuraray Co., Ltd., JF17, JP25, JP18 manufactured by Nihon Vinegar Bipoval, etc. Can be used.

  In addition to the polyvinyl alcohol, other polymers may be used. Examples of polymers other than polyvinyl alcohol that can be added include, for example, methacrylate polymers, styrene polymers, polyolefins, and poly (N-methylolacrylamide) described in paragraph No. [0022] of JP-A-8-338913. Polyester, polyimide, vinyl acetate polymer, carboxymethyl cellulose, polycarbonate, gelatin, silane coupling agent and the like.

  Further, modified polyvinyl alcohol may be used. The modifying group of the modified polyvinyl alcohol can be introduced by modification by modification to the OH group of the side chain, copolymerization modification, chain transfer modification or block polymerization modification. Examples of the modifying group include those having an unsaturated bond (obtained by reacting (meth) acrylic acid chloride, 2-methacryloyloxyethyl isocyanate or the like with the side chain OH group), hydrophilic groups (carboxylic acid groups, Sulfonic acid group, phosphonic acid group, amino group, ammonium group, amide group, thiol group, etc.), hydrocarbon group having 10 to 100 carbon atoms, hydrocarbon group substituted with fluorine atom, thioether group, polymerizable group (unsaturated) Polymerizable groups, epoxy groups, azirinidyl groups, etc.), alkoxysilyl groups (trialkoxy, dialkoxy, monoalkoxy) and the like. Specific examples of these modified polyvinyl alcohol compounds include those described in paragraph numbers [0022] to [0145] of JP-A No. 2000-155216 and paragraph numbers [0018] to [0022] of JP-A No. 2002-62426, for example. Etc.

  If desired, a polymer having a crosslinkable functional group may be added. The crosslinkable functional group preferably contains a polymerizable group in the same manner as the polyfunctional monomer. Specific examples include those described in paragraphs [0080] to [0100] of JP-A No. 2000-155216.

Polyvinyl alcohol can be cross-linked using a cross-linking agent separately from the cross-linkable functional group.
Examples of the crosslinking agent include aldehydes, N-methylol compounds, dioxane derivatives, compounds that act by activating carboxyl groups, active vinyl compounds, active halogen compounds, isoxazole and dialdehyde starch. Two or more kinds of crosslinking agents may be used in combination. Specific examples include compounds described in paragraphs [0023] to [0024] in JP-A-2002-62426. Aldehydes having high reaction activity, particularly glutaraldehyde are preferred.

  0.1-20 mass% is preferable with respect to the said polyvinyl alcohol, and, as for the addition amount of the said crosslinking agent, 0.5-15 mass% is more preferable. The amount of the remaining unreacted crosslinking agent is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less.

(Formation of second optically anisotropic layer)
A polymer composition used for forming the second optically anisotropic layer may be prepared as a coating solution. The coating liquid can be prepared by dissolving and / or dispersing a liquid crystal material or a polymer material in a solvent. 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 method used for forming the second optically anisotropic layer is not particularly limited, and is a known method (eg, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating). Law). Especially, it is preferable to apply using a wire bar coating method. In addition, a die coating method is also preferably used for forming the second optically anisotropic layer, and in particular, a coating method using a slide coater or a slot die coater can also be preferably used.

  The second optically anisotropic layer is preferably formed by coating on the surface of the polymer film that is the first optically anisotropic layer and then drying. After the second optically anisotropic layer is formed, it is preferable to perform a rubbing process in which the coating film is rubbed with a rubbing cloth. Although orientation can be imparted by performing a stretching treatment, it is not preferable because the process becomes complicated and the productivity is deteriorated. The rubbing treatment is preferable because it can be performed online when the third optical anisotropic layer is formed in the next step and does not affect productivity.

  The surface of the second optically anisotropic layer may be subjected to an alignment treatment in order to add liquid crystal alignment ability or improve liquid crystal alignment ability. As the alignment treatment, rubbing treatment is preferable. As the rubbing treatment, a treatment method widely adopted as a liquid crystal alignment treatment process of the LCD can be applied. That is, a method of obtaining the orientation by rubbing the surface of the orientation film in a certain direction using paper, gauze, felt, rubber, nylon, polyester fiber or the like can be used. Generally, it is carried out by rubbing using a cloth in which fibers having a uniform length and thickness are flocked on average.

  The thickness of the second optical anisotropic layer is not particularly limited, and the thickness can be determined so as to satisfy the optical characteristics required for the second optical anisotropic layer. The preferred range varies depending on the material. For example, when the second optical anisotropic layer is formed using polyimide, the thickness is preferably 0.5 to 10 μm, and preferably 2 to 8 μm. More preferably, when the film is formed using polyvinyl alcohol, the thickness is preferably 1 to 30 μm, more preferably 5 to 20 μm.

[Third optically anisotropic layer]
The optical compensation film of the present invention has a third optically anisotropic layer containing a liquid crystal compound fixed in an aligned state. The third optically anisotropic layer preferably contains a discotic (hereinafter sometimes referred to as “discotic”) compound fixed in a hybrid alignment state. The compound finally contained in the optically anisotropic layer no longer needs to exhibit liquid crystallinity. For example, when a low-molecular liquid crystalline compound is used for the production of the optically anisotropic layer, the optically anisotropic layer In the process of forming, the compound may be cross-linked and no longer exhibits liquid crystallinity.

(Discotic liquid crystalline compounds)
Examples of the discotic liquid crystalline compound include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives described in C.I. Destrade et al., Mol. Cryst. 122, 141 (1985), Physics lett, A, 78, 82 (1990); Kohne et al., Angew. Chem. 96, page 70 (1984) and the cyclohexane derivatives described in J. Am. M.M. Lehn et al. Chem. Commun. , 1794 (1985), J. Am. Zhang et al., J. Am. Chem. Soc. 116, 2655 (1994), azacrown type and phenylacetylene type macrocycles are included.

  The discotic liquid crystalline compound exhibits liquid crystallinity in a structure in which a linear alkyl group, an alkoxy group or a substituted benzoyloxy group is radially substituted as a side chain of the mother nucleus with respect to the mother nucleus at the center of the molecule. Also included are compounds. The molecule or the assembly of molecules is preferably a compound having rotational symmetry and imparting a certain orientation.

  As described above, when an optically anisotropic layer is formed from a liquid crystalline compound, the compound finally contained in the optically anisotropic layer no longer needs to exhibit liquid crystallinity. For example, a low molecular weight discotic liquid crystalline compound has a group that reacts with heat or light, and the group reacts with heat or light to polymerize or crosslink to increase the molecular weight. When a layer is formed, the compound contained in the optically anisotropic layer may no longer have liquid crystallinity. Preferred examples of the discotic liquid crystalline compound are described in JP-A-8-50206. The polymerization of the discotic liquid crystalline compound is described in JP-A-8-27284.

  In order to fix the discotic liquid crystalline compound by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic core of the discotic liquid crystalline compound. 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. Therefore, the discotic liquid crystalline compound having a polymerizable group is preferably a compound represented by the following formula (IV).

Formula (IV)
D (-LQ) _n1
In formula (IV), D is a discotic core, L is a divalent linking group, Q is a polymerizable group, and n1 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 (IV), 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 selected is preferable. The divalent linking group (L) is a divalent combination of at least two divalent groups selected from the group consisting of an alkylene group, an arylene group, -CO-, -NH-, -O-, and S-. The linking group is more preferable. The divalent linking group (L) is 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. Further preferred. The alkylene group preferably has 1 to 12 carbon atoms. The alkenylene group preferably has 2 to 12 carbon atoms. The arylene group preferably has 6 to 10 carbon atoms.

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 alkenylene group, and AR represents an arylene group. The alkylene group, alkenylene group and arylene group may have a substituent (for example, 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-

The polymerizable group (Q) of the formula (IV) can be determined according to the type of polymerization reaction. The polymerizable group (Q) is preferably an unsaturated polymerizable group or an epoxy group, more preferably an unsaturated polymerizable group, and still more preferably an ethylenically unsaturated polymerizable group.
In formula (IV), 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.

  In addition, a discotic liquid crystal compound represented by the following general formula (DI) may be used for forming the third optically anisotropic layer. The following formula (DI) compound is preferable because it exhibits high birefringence.

In the general formula (DI), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a methine or nitrogen atom. L ¹ , L ² and L ³ each independently represents a single bond or a divalent linking group. H ^1, the H ^2, H ³ are each independently, represent the general formula (DI-A) or the following formula (DI-B). R ¹ , R ² and R ³ each independently represents the following general formula (DI-R).

In the general formula (DI), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a methine or nitrogen atom. When Y ¹¹ , Y ¹² and Y ¹³ are each methine, the hydrogen atom of methine may be substituted with a substituent. Examples of the substituent that methine may have include, for example, alkyl group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, alkylthio group, arylthio group, halogen Mention may be made of atoms and cyano groups. Among these, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom, and a cyano group are more preferable, and the number of carbon atoms (referred to as the number of carbon atoms that the substituent has, hereinafter referred to as a discotic liquid crystal compound). The same for the substituents which may be present) 1-12 alkyl groups, C1-12 alkoxy groups, C2-12 alkoxycarbonyl groups, C2-12 acyloxy groups, halogen atoms and cyano groups Is more preferable.

Y ¹¹ , Y ¹² and Y ¹³ are preferably all methine, and methine is preferably unsubstituted.

In the general formula (DI), L ¹ , L ² and L ³ are each independently a single bond or a divalent linking group. The divalent linking group includes —O—, —S—, —C (═O) —, —NR ⁷ —, —CH═CH—, —C≡C—, a divalent cyclic group, and combinations thereof. A divalent linking group selected from the group consisting of R ⁷ is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom, more preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and a methyl group, ethyl group or hydrogen atom. Is more preferable, and a hydrogen atom is particularly preferable.

The divalent cyclic group represented by L ¹ , L ² and L ³ is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, More preferably, it is a 6-membered ring. The ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. Further, the ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Examples of the aromatic ring include a benzene ring and a naphthalene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring. The cyclic group preferably contains an aromatic ring and a heterocyclic ring.

  Of the divalent cyclic group, the cyclic group having a benzene ring is preferably a 1,4-phenylene group. As the cyclic group having a naphthalene ring, a naphthalene-1,5-diyl group and a naphthalene-2,6-diyl group are preferable. The cyclic group having a cyclohexane ring is preferably a 1,4-cyclohexylene group. The cyclic group having a pyridine ring is preferably a pyridine-2,5-diyl group. The cyclic group having a pyrimidine ring is preferably a pyrimidine-2,5-diyl group.

The divalent cyclic group represented by L ¹ , L ² or L ³ may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, an alkynyl group having 2 to 16 carbon atoms, and 1 carbon atom. An alkyl group substituted with -16 halogen atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, and 2 carbon atoms -16 acyloxy groups, alkoxycarbonyl groups having 2 to 16 carbon atoms, carbamoyl groups, carbamoyl groups substituted with alkyl groups having 2 to 16 carbon atoms, and acylamino groups having 2 to 16 carbon atoms It is.

L ¹ , L ² and L ³ are a single bond, * —O—CO—, * —CO—O—, * —CH═CH—, * —C≡C—, * -2 valent cyclic group— * -O-CO-2 valent cyclic group-, * -CO-O-2 valent cyclic group-, * -CH = CH-2 valent cyclic group-, * -C≡C-2 valent cyclic. Group-, * -2 valent cyclic group-O-CO-, * -2 valent cyclic group-CO-O-, * -2 valent cyclic group-CH = CH-, or * -2 valent cyclic group- C≡C— is preferred. In particular, a single bond, * -CH = CH-, * -C≡C-, * -CH = CH-2 valent cyclic group- or * -C≡C-2 valent cyclic group- is more preferable, Is more preferable. Here, * represents a position bonded to a 6-membered ring including Y ¹¹ , Y ¹² and Y ¹³ in the general formula (I).

In the general formula (DI), H ¹ , H ² and H ³ each independently represent the following general formula (DI-A) or the following general formula (DI-B).

In formula (DI-A), YA ¹ and YA ² each independently represent a methine group or a nitrogen atom. At least one of YA ¹ and YA ² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. XA represents an oxygen atom, a sulfur atom, methylene or imino. XA is preferably an oxygen atom. * Represents a position where L ^{1 to} L ³ are bonded, and ** represents a position where R ^{1 to} R ³ are bonded.

In the general formula (DI-B), YB ¹ and YB ² each independently represent a methine or a nitrogen atom. At least one of YB ¹ and YB ² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. XB represents an oxygen atom, a sulfur atom, methylene or imino. XB is preferably an oxygen atom. * Represents a position where L ^{1 to} L ³ are bonded, and ** represents a position where R ^{1 to} R ³ are bonded.

R ¹ , R ² and R ³ each independently represents the following general formula (DI-R).
General formula (DI-R)
*-(-L ²¹ -F ¹ ) _n1 -L ²² -L ²³ -Q ¹

In the general formula (DI-R), * represents a position bonded to H ¹ , H ² or H ³ in the general formula (DI). F ¹ represents a divalent linking group having at least one cyclic structure. L ²¹ represents a single bond or a divalent linking group. When L ²¹ is a divalent linking group, it consists of —O—, —S—, —C (═O) —, —NR ⁷ —, —CH═CH—, —C≡C—, and combinations thereof. A divalent linking group selected from the group is preferable. R ⁷ is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom, more preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and a methyl group, ethyl group or hydrogen atom. Is more preferable, and a hydrogen atom is particularly preferable.

L ²¹ represents a single bond, ** — O—CO—, ** — CO—O—, ** — CH═CH— or ** — C≡C— (where ** represents a general formula (DI-R Represents the left side of L ^{21 in} the formula (A). A single bond is particularly preferable.

F ¹ in the general formula (DI-R) represents a divalent cyclic linking group having at least one cyclic structure. The cyclic structure is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring. The cyclic structure may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. Further, the ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.

Of F ¹ , those having a benzene ring are preferably a 1,4-phenylene group or a 1,3-phenylene group. Those having a naphthalene ring include naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-2,5-diyl group, naphthalene-2,6- A diylnaphthalene-2,7-diyl group is preferred. Those having a cyclohexane ring are preferably 1,4-cyclohexylene groups. Pyridine-2,5-diyl groups are preferred as those having a pyridine ring. As what has a pyrimidine ring, a pyrimidine-2,5-diyl group is preferable. F ¹ is particularly preferably a 1,4-phenylene group, a 1,3-phenylenenaphthalene-2,6-diyl group and a 1,4-cyclohexylene group.

F ¹ may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 1 to 16 carbon atoms, carbon An alkynyl group having 2 to 16 atoms, an alkyl group substituted with a halogen atom having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 1 to 1 carbon atoms 16 alkylthio groups, acyloxy groups having 2 to 16 carbon atoms, alkoxycarbonyl groups having 2 to 16 carbon atoms, carbamoyl groups, carbamoyl groups substituted with alkyl groups having 2 to 16 carbon atoms, and 2 to 2 carbon atoms 16 acylamino groups are included. The substituent is preferably a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms, and a halogen atom or an alkyl having 1 to 4 carbon atoms. Group, an alkyl group substituted with a halogen atom having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are particularly preferable.

n1 represents an integer of 0 to 4. As n1, the integer of 1-3 is preferable and 1 or 2 is preferable. When n1 is 0, L ²² in the formula (DI-R) is directly bonded to H ^{1 to} H ³ in the general formula (D1). When n1 is 2 or more, each -L ²¹ -F ¹ may be the same or different.

L ²² represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH. -Or -C≡C- is represented. Preferred is —O—, —O—CO—, —CO—O—, —O—CO—O—, —CH ₂ —, —CH═CH— or —C≡C—, and more preferred. —O—, —O—CO—, —CO—O—, —O—CO—O— or —CH ₂ —.
Here, when it is a group containing a hydrogen atom among the above, the hydrogen atom may be replaced by a substituent. Examples of other substituents include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. Alkoxy group having 2 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, acyloxy group having 2 to 6 carbon atoms, alkoxycarbonyl group having 2 to 6 carbon atoms, carbamoyl group, carbon atom The carbamoyl group substituted by the C2-C6 alkyl group and the C2-C6 acylamino group are contained. In particular, a halogen atom and an alkyl group having 1 to 6 carbon atoms are preferable.

L ²³ represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—, and two of these. A divalent linking group selected from the groups formed by linking the above. Here, the hydrogen atoms of —NH—, —CH ₂ —, and —CH═CH— may be replaced with other substituents. Examples of other substituents include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. Alkoxy group having 2 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, acyloxy group having 2 to 6 carbon atoms, alkoxycarbonyl group having 2 to 6 carbon atoms, carbamoyl group, carbon atom The carbamoyl group substituted by the C2-C6 alkyl group and the C2-C6 acylamino group are contained. In particular, a halogen atom and an alkyl group having 1 to 6 carbon atoms are preferable. By being substituted with these substituents, the solubility of the compound represented by the general formula (DI) in the solvent can be improved, and the composition of the present invention can be easily prepared as a coating solution. .

L ²³ is preferably a linking group selected from the group consisting of —O—, —C (═O) —, —CH ₂ —, —CH═CH—, —C≡C—, and combinations thereof. L ²³ preferably contains 1 to 20 carbon atoms, more preferably 2 to 14 carbon atoms. Furthermore, L ²³ is -CH ₂ - preferably contains 1 to 16 a, -CH ₂ - and more preferably a containing 2-12.

Q ¹ is a polymerizable group or a hydrogen atom. When the compound represented by the general formula (DI) is used for production of an optical film or the like that requires that the phase difference does not change due to heat like an optical compensation film, Q ¹ represents a polymerizable group. It is preferable that The polymerization reaction is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the polymerizable group is preferably a functional group capable of an addition polymerization reaction or a condensation polymerization reaction. Examples of polymerizable groups are shown below.

  Furthermore, the polymerizable group is particularly preferably a functional group capable of addition polymerization reaction. Such a polymerizable group is preferably a polymerizable ethylenically unsaturated group or a ring-opening polymerizable group.

  Examples of the polymerizable ethylenically unsaturated group include the following formulas (M-1) to (M-6).

  In formula (M-3) and formula (M-4), R represents a hydrogen atom or an alkyl group. R is preferably a hydrogen atom or a methyl group. Among the above (M-1) to (M-6), (M-1) or (M-2) is preferable, and (M-1) is more preferable.

  The ring-opening polymerizable group is preferably a cyclic ether group, and more preferably an epoxy group or an oxetanyl group, and most preferably an epoxy group.

  In the present invention, it is also preferable to use a compound represented by the following general formula (DII) or a compound represented by the following general formula (DIII) as the discotic liquid crystal compound.

（一般式（ＤＩＩ）中、Ｙ³¹、Ｙ³²、Ｙ³³はそれぞれ独立にメチン又は窒素原子を表す。Ｒ³¹、Ｒ³²、Ｒ³³はそれぞれ独立に下記一般式（ＤＩＩ−Ｒ）で表される。）

(In the general formula (DII), Y ³¹ , Y ³² and Y ³³ each independently represent a methine or nitrogen atom. R ³¹ , R ³² and R ³³ are each independently represented by the following general formula (DII-R). )

In the general formula (DII), Y ³¹ , Y ³² and Y ³³ each independently represent a methine or a nitrogen atom. Y ³¹ , Y ³² and Y ³³ are the same as the definitions of Y ¹¹ , Y ¹² and Y ^{13 in} the general formula (DI), respectively, and preferred ranges are also synonymous.

R ³¹ , R ³² and R ³³ are each independently represented by the general formula (DII-R).

In the general formula (DII-R), A ³¹ and A ³² each independently represents a methine or a nitrogen atom. As A ³¹ and A ³² , at least one is preferably a nitrogen atom, and more preferably both are nitrogen atoms.
X ³ represents an oxygen atom, a sulfur atom, methylene, or imino. X ³ is preferably an oxygen atom.

In General Formula (DII-R), F ² represents a divalent cyclic linking group having a 6-membered cyclic structure. The 6-membered ring contained in F ² may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. The 6-membered ring contained in F ² may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.

  Among the divalent cyclic groups, the cyclic group having a benzene ring is preferably a 1,4-phenylene group or a 1,3-phenylene group. As the cyclic group having a naphthalene ring, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-2,5-diyl group, naphthalene-2,6 -Diyl groups and naphthalene-2,7-diyl groups are preferred. The cyclic group having a cyclohexane ring is preferably a 1,4-cyclohexylene group. The cyclic group having a pyridine ring is preferably a pyridine-2,5-diyl group. The cyclic group having a pyrimidine ring is preferably a pyrimidine-2,5-diyl group. As the divalent cyclic group, 1,4-phenylene group, 1,3-phenylene group, naphthalene-2,6-diyl group and 1,4-cyclohexylene group are particularly preferable.

F ² may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, carbon An alkynyl group having 2 to 16 atoms, an alkyl group substituted with a halogen atom having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 1 to 1 carbon atoms 16 alkylthio groups, acyloxy groups having 2 to 16 carbon atoms, alkoxycarbonyl groups having 2 to 16 carbon atoms, carbamoyl groups, carbamoyl groups substituted with alkyl groups having 2 to 16 carbon atoms, and 2 to 2 carbon atoms 16 acylamino groups are included. As the substituent of the divalent cyclic group, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms are preferable. An alkyl group having 1 to 4 carbon atoms and an alkyl group substituted with a halogen atom having 1 to 4 carbon atoms are preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.

n3 represents an integer of 1 to 3. n3 is preferably 1 or 2. When n3 is 2 or more, each F ² may be the same or different.

L ³¹ is —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH—. , -C≡C-, and when the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced by a substituent. A preferred range for L ³¹ is the same as L ^{22 in} formula (DI-R).

L ³² represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—, or two or more thereof. Represents a divalent linking group selected from the group formed by linking and when the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced by a substituent. A preferred range for L ³² is the same as L ^{23 in} formula (DI-R).

Q ³ represents a polymerizable group or a hydrogen atom, and a preferred range is the same as Q ¹ in the general formula (DI-R).

  Next, the detail of the compound represented by general formula (DIII) is described.

In the general formula (DIII), Y ⁴¹ , Y ⁴² and Y ⁴³ each independently represent a methine or nitrogen atom. When Y ⁴¹ , Y ⁴² and Y ⁴³ are each methine, the hydrogen atom of methine is a substituent. May be substituted. Examples of the substituent that methine may have include an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, a halogen atom, and A cyano group can be mentioned as a preferred example. Among these substituents, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom and a cyano group are more preferable, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, Particularly preferred are an alkoxycarbonyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a halogen atom and a cyano group.
Y ⁴¹ , Y ⁴² and Y ⁴³ are more preferably methine, and methine is more preferably unsubstituted.

R ⁴¹ , R ⁴² and R ⁴³ each independently represent the following general formula (DIII-A), the following general formula (DIII-B), or the following general formula (DIII-C).
In the case of producing a retardation plate or the like having a small wavelength dispersion, R ⁴¹ , R ⁴² and R ⁴³ are each preferably represented by general formula (DIII-A) or general formula (DIII-C), What is represented by general formula (DIII-A) is more preferable.

In the general formula (DIII-A), A ⁴¹ , A ⁴² , A ⁴³ , A ⁴⁴ , A ⁴⁵ and A ⁴⁶ each independently represents a methine or nitrogen atom. At least one of A ⁴¹ and A ⁴² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. At least three of A ⁴³ , A ⁴⁴ , A ⁴⁵ and A ⁴⁶ are preferably methine, more preferably methine. When A ⁴³ , A ⁴⁴ , A ⁴⁵ and A ⁴⁶ are each methine, the hydrogen atom of methine may be substituted with a substituent. Examples of substituents that methine has include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, nitro groups, alkyl groups having 1 to 16 carbon atoms, and alkenyl groups having 2 to 16 carbon atoms. Group, an alkynyl group having 2 to 16 carbon atoms, an alkyl group substituted with a halogen atom having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, a carbon atom An alkylthio group having 1 to 16 carbon atoms, an acyloxy group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, a carbamoyl group and a carbon atom substituted with an alkyl group having 2 to 16 carbon atoms The acylamino group of several 2-16 is contained. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.
X ⁴¹ represents an oxygen atom, a sulfur atom, methylene or imino, and preferably an oxygen atom.

In the general formula (DIII-B), A ⁵¹ , A ⁵² , A ⁵³ , A ⁵⁴ , A ⁵⁵ and A ⁵⁶ each independently represents a methine or nitrogen atom. At least one of A ⁵¹ and A ⁵² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. At least three of A ⁵³ , A ⁵⁴ , A ⁵⁵ and A ⁵⁶ are preferably methine, more preferably methine. When A ⁵³ , A ⁵⁴ , A ⁵⁵ and A ⁵⁶ are each methine, the hydrogen atom of methine may be substituted with a substituent. Examples of the substituent that methine may have include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, and 2 to 2 carbon atoms. 16 alkenyl groups, an alkynyl group having 2 to 16 carbon atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, An alkylthio group having 1 to 16 carbon atoms, an acyloxy group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, a carbamoyl group substituted with an alkyl group having 2 to 16 carbon atoms, and An acylamino group having 2 to 16 carbon atoms is included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms are preferable, and a halogen atom and an alkyl group having 1 to 4 carbon atoms. An alkyl group substituted with a halogen atom having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a trifluoromethyl group is more preferable.
X ⁵² represents an oxygen atom, a sulfur atom, methylene or imino, and preferably an oxygen atom.

In the general formula (DIII-C), A ⁶¹ , A ⁶² , A ⁶³ , A ⁶⁴ , A ⁶⁵ and A ⁶⁶ each independently represent a methine or nitrogen atom. At least one of A ⁶¹ and A ⁶² is preferably a nitrogen atom, and more preferably both are nitrogen atoms. At least three of A ⁶³ , A ⁶⁴ , A ⁶⁵ and A ⁶⁶ are preferably methine, more preferably methine. When A ⁶³ , A ⁶⁴ , A ⁶⁵ and A ³⁶ are each methine, the hydrogen atom of the methine may be substituted with a substituent. Examples of the substituent that methine may have include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, carbon atom number An alkenyl group having 2 to 16 carbon atoms, an alkynyl group having 2 to 16 carbon atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, and an acyl having 2 to 16 carbon atoms Group, an alkylthio group having 1 to 16 carbon atoms, an acyloxy group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, and a carbamoyl substituted with an alkyl group having 2 to 16 carbon atoms Groups and acylamino groups of 2 to 16 carbon atoms are included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.
X ⁶³ represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom.

L ^{41 in} the general formula (DIII-A), L ^{51 in} the general formula (DIII-B), and L ⁶¹ in the general formula (DIII-C) are each independently —O— or —O—CO—. , —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH— or —C≡C—. Preferably, -O -, - O-CO -, - CO-O -, - O-CO-O -, - CH 2 -, - CH = CH -, - is C≡C-, more preferably, —O—, —O—CO—, —CO—O—, —O—CO—O— or —CH ₂ —. When the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent.
Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms, and an alkoxy having 1 to 6 carbon atoms. Group, an acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 carbon atoms Preferred examples include a carbamoyl group substituted with ~ 6 alkyl and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.

L ^{42 in} the general formula (DIII-A), L ^{52 in} the general formula (DIII-B), and L ⁶² in the general formula (DIII-C) are each independently —O—, —S—, — Selected from C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH— and —C≡C— and groups formed by linking two or more thereof. Represents a divalent linking group. Here, the hydrogen atoms of —NH—, —CH ₂ —, and —CH═CH— may be substituted with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms, and an alkoxy having 1 to 6 carbon atoms. Group, an acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 carbon atoms Preferred examples include a carbamoyl group substituted with ~ 6 alkyl and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.

L ⁴² , L ⁵² and L ⁶² each independently connect —O—, —C (═O) —, —CH ₂ —, —CH═CH— and —C≡C— and two or more thereof. It is preferable that it is a bivalent coupling group selected from the group formed in this way. L ⁴² , L ⁵² and L ⁶² each independently preferably contain 1 to 20 carbon atoms, more preferably 2 to 14 carbon atoms. Further, L ⁴² , L ⁵² and L ⁶² each independently preferably contain 1 to 16 —CH ₂ —, and more preferably ₂ to 12 —CH ₂ —.

Formula (DIII-A) in Q ^4, the general formula (DIII-B) Q ⁵ and formula in (DIII-C) Q ⁶ in each independently represents a polymerizable group or a hydrogen atom . These preferable ranges are the same as Q < ¹ > in general formula (DI-R).

  Although the specific example of a compound represented by general formula (DI), general formula (DII), and general formula (DIII) below is shown, this invention is not limited to these.

  The compounds represented by formula (DIII) are shown below.

  The compounds represented by the above general formula (DI), general formula (DII) and general formula (DIII) used in the present invention can be synthesized by applying known methods.

  In the present invention, as the liquid crystal compound, only one of the compounds represented by the above general formula (DI), general formula (DII) and general formula (DIII) may be used, or two or more kinds may be used. Good. The compounds represented by the general formulas (DI) to (DIII) are characterized by low birefringence wavelength dispersion when they exhibit birefringence due to their orientation. Therefore, for example, when an optically anisotropic film or the like is produced using the compound, if the optical characteristics of G light that is an intermediate wavelength in the visible light region are optimized, R light and B light can also be obtained. Since the optical characteristics are optimized in substantially the same manner, an optically anisotropic layer exhibiting desired optical characteristics over the entire visible light region can be easily manufactured by using such a liquid crystal compound.

  The discotic nematic liquid crystal phase-solid phase transition temperature of the discotic compound is preferably 70 to 300 ° C, more preferably 70 to 170 ° C.

  In the present invention, it is preferable that the molecules of the liquid crystal compound are fixed in a hybrid alignment state in the third optically anisotropic layer. In the hybrid alignment, the tilt angle, for example, the angle formed by the layer surface and the disk surface direction of the discotic liquid crystalline molecules changes in the thickness direction of the layer. Average tilt angle, minimum tilt angle (tilt angle at the interface with the second optical anisotropic layer or air interface), and maximum tilt angle (tilt angle at the interface with the air interface or second optical anisotropic layer) Can be determined according to the optical characteristics of the liquid crystal cell to be optically compensated and the optical characteristics of other optically anisotropic layers to be combined.

In addition, regarding the orientation average direction of the molecular symmetry axis of the liquid crystal molecules in the third optical anisotropic layer, the optical characteristics of the liquid crystal cell to be optically compensated and the optical properties of other optical anisotropic layers to be combined Depending on the characteristics, it can be determined. When used for optical compensation of an OCB mode liquid crystal cell, the orientation average direction of the molecular symmetry axis of the liquid crystal molecules in the third optical anisotropic layer is the slow axis in the plane of the first optical anisotropic layer. Is preferably approximately 45 degrees (crossing angle of axes projected on the same plane). In this specification, “approximately 45 °” refers to an angle in the range of 45 ° ± 5 °, preferably 42 to 48 °, and more preferably 43 to 47 °. When the first optically anisotropic layer is a polymer film stretched in the longitudinal direction, the average direction of the molecular symmetry axis of the liquid crystal compound in the third optically anisotropic layer is the first optical It is preferably 43 ° to 47 ° with respect to the longitudinal direction of the anisotropic layer (that is, the fast axis direction of the support).
The direction of the molecular symmetry axis of the liquid crystal molecules in the third optically anisotropic layer can be adjusted by the rubbing direction of the rubbing treatment applied to the surface of the second optically anisotropic layer.

(Other additives)
The third optically anisotropic layer can be formed from a liquid crystal composition containing a liquid crystal compound and optionally added additives. Examples of the additive that is optionally added include a polymerization system that contributes to curing of the liquid crystal composition, a polymerization system such as a polymerizable monomer, an alignment regulator that contributes to forming a desired alignment state, and a liquid crystal composition. A surfactant that contributes to the improvement of the applicability of the product may be mentioned. Among them, it is preferable to add a polymerization additive that contributes to curing (a radical polymerization system is preferable) and a fluorine-based polymer that contributes to the improvement of coating properties and also has orientation adjusting ability. Further, when a discotic compound is used, a polymer that has a certain degree of compatibility with the discotic compound and can change the tilt angle of the discotic compound, specifically, cellulose acetate, cellulose acetate propionate, It is preferable to add a cellulose acylate polymer such as hydroxypropyl cellulose and cellulose acetate butyrate. When the discotic liquid crystalline compound represented by the general formula (DI) is hybrid-aligned, it is preferable to add a 1,3,5-triazine compound-based alignment controller.
The addition amount of these additives is preferably in the range of 1 to 50% by mass, and more preferably in the range of 5 to 30% by mass with respect to the liquid crystal compound.

(Formation of third optically anisotropic layer)
The third optically anisotropic layer is formed by applying a liquid crystal composition coating liquid on the surface of the second optically anisotropic layer, aligning the liquid crystal on the second optically anisotropic layer, It can be formed in a fixed orientation state. When the coating solution contains a polymerization additive, it can be cured by polymerization by providing light irradiation and / or heat. Among these, it is preferable to cure by ultraviolet irradiation. The solvent used for preparing the coating solution is not particularly limited. This is the same as the example of the solvent used for preparing the polymer solution used to form the second optically anisotropic layer. The coating method is the same as the coating method used for forming the second optically anisotropic layer.

  The optical characteristics of the third optical anisotropic layer can be determined according to the mode and optical characteristics of the liquid crystal cell to be optically compensated and the optical characteristics of the other optical anisotropic layers to be combined. When used for optical compensation of an OCB mode liquid crystal cell, the in-plane retardation Re is preferably from 3 to 300 nm, more preferably from 5 to 200 nm, and even more preferably from 10 to 100 nm. The retardation Rth in the thickness direction of the third optically anisotropic layer is preferably 20 to 400 nm, and more preferably 50 to 200 nm. Moreover, the thickness of the optically anisotropic layer is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm, and further preferably 1 to 10 μm.

The optical compensation film of the present invention can be used in a liquid crystal display device as it is as a single member. Alternatively, it can be attached to a polarizing film and used in a liquid crystal display device as one member of a polarizing plate. Hereinafter, the polarizing plate having the optical compensation film of the present invention will be described.
[Polarizer]
The polarizing plate of the present invention has at least a polarizing film and the optical compensation film of the present invention. The optical compensation film may be directly bonded to the surface of the polarizing film and used as a protective film for the polarizing film. In such an embodiment, a polymer film is used for the first optically anisotropic layer, and the back surface of the polymer film (the surface on which the second optically anisotropic layer is not formed) is placed on the surface of the polarizing film. It is preferable to bond them together. Moreover, it is preferable that a protective film such as a cellulose acylate film is bonded to the other surface of the polarizing film.

(Polarizing film)
Examples of the polarizing film include an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, and a polyene-based polarizing film, and any of them may be used in the present invention. The iodine polarizing film and the dye polarizing film are generally produced using a polyvinyl alcohol film.
(Protective film)
It is preferable to use a transparent polymer film as the protective film to be bonded to the other surface. “Transparent” means that the light transmittance is 80% or more. As the protective film, a cellulose acylate film and a polyolefin film containing polyolefin are preferable. Among the cellulose acylate films, a cellulose triacetate film is preferable. Of the polyolefin films, a polynorbornene film containing a cyclic polyolefin is preferable.
The thickness of the protective film is preferably 20 to 500 μm, and more preferably 50 to 200 μm.

[Liquid Crystal Display]
The optical compensation film and polarizing plate of the present invention can be used for liquid crystal display devices of various modes. In addition, the liquid crystal display device can be any of a transmissive type, a reflective type, and a transflective type. Among them, it is suitable for use in an electric field control birefringence mode liquid crystal display device, and more suitable for use in an OCB mode liquid crystal display device.

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

Example 1
<Preparation of optical compensation film 1>
<< Preparation of Optical Anisotropic Layer A-1 >>
Cellulose acylate was prepared by mixing the components described in the table below. This was extruded from a die at a screw rotation speed of 300 rpm, a kneading time of 40 seconds, an extrusion rate of 200 kg / hr, and solidified in 60 ° C. water using a twin-screw kneading extruder with vacuum exhaust, and then cut into a diameter of 2 mm and a length of 3 mm A cylindrical pellet was obtained. Thereafter, the pellets were melted and formed into a film having a thickness of 140 μm by the same method as described in Example 1 in Reference Document JP 2007-2216. This film was stretched under the conditions shown in the table below to obtain an optically anisotropic layer A-1 having a thickness of 80 μm.

<< Preparation of Optical Anisotropic Layer B-1 >>
Weight average molecular weight synthesized from 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (Mw) 120,000 polyimide was dissolved in cyclohexanone to prepare a 15 wt% polyimide solution.
The prepared polyimide solution was applied onto the optically anisotropic layer A-1. This coating film was dried at 100 ° C. for 10 minutes to form an optically anisotropic layer B-1 having a thickness of 2.5 μm, thereby preparing an optically anisotropic layer A-1 / B-1 laminate.

  The optically anisotropic layer A-1 / B-1 laminate prepared above is transported to the surface of the optically anisotropic layer B-1 at a speed of 20 m / min and rubbed at 45 ° with respect to the longitudinal direction. Thus, a rubbing roll (300 mm diameter) was set and rotated at 750 rpm, and the alignment film installation surface was rubbed.

<< Preparation of Optical Anisotropic Layer C-1 >>
A coating solution for preparing optically anisotropic layer C-1 having the following composition was prepared.

This coating solution was applied to the rubbing treated surface of the optically anisotropic layer B-1 with a # 2.0 wire bar. Thereafter, the coating solvent was dried for 5 seconds in a windless state where the relative speed was approximately zero, and then heated in a constant temperature bath at 120 ° C. for 90 seconds to hybridize the discotic liquid crystal compound. Next, using a 120 W / cm metal halide ultraviolet lamp at a film surface temperature of 80 ° C., an irradiation amount of 200 mJ / cm ² was irradiated to polymerize the discotic liquid crystal compound. Then, it stood to cool to room temperature.
The Re retardation value of the obtained optically anisotropic layer measured at a wavelength of 550 nm was 51 nm. The film thickness was 1.3 μm. Thus, the optically anisotropic layer C-1 was formed, and the optical compensation film 1 made of the optically anisotropic layer A-1 / B-1 / C-1 laminate was produced.

<< Evaluation of optically anisotropic layer >>
For each of the optically anisotropic layers A-1, B-1, and C-1, Re (450), Re (550), and Re (630) using KOBRA 21ADH with light having wavelengths of 450 nm, 550 nm, and 630 nm. ), Rth (450), Rth (550), and Rth (630) were measured, and each characteristic value was calculated (the results are shown in Table 1). In addition, about B-1 and C-1, it transferred and measured through the adhesion layer on the glass plate.

<Preparation of Polarizing Plate 1>
First, iodine was adsorbed on a stretched polyvinyl alcohol film to prepare a polarizing film.
Thereafter, the back surface of the optically anisotropic layer A-1 of the optical compensation film 1 is attached to one surface of the polarizing film using a polyvinyl alcohol adhesive, and the other surface of the polarizing film is coated with polyvinyl. A commercially available cellulose triacetate film (Fujitac TD80UF, manufactured by Fuji Film Co., Ltd.) subjected to saponification treatment was attached using an alcohol-based adhesive. Thus, the polarizing plate 1 based on Example 1 was produced.

<Production of OCB Mode Liquid Crystal Display Device 1>
A pair of polarizing plates (an upper polarizing plate and a lower polarizing plate) provided in a 23-inch liquid crystal display device (manufactured by Nanao) using an OCB mode liquid crystal cell is peeled off, and the polarizing plate 1 produced instead is optically compensated. The films 1 were attached to the viewer side and the backlight side one by one through an adhesive so that the film 1 would be on the liquid crystal cell side. At this time, each polarizing plate was arranged so that the transmission axis of the polarizing plate on the observer side (upper polarizing plate) and the transmission axis of the polarizing plate on the backlight side (lower polarizing plate) were orthogonal to each other. The rubbing direction of the alignment film of the liquid crystal cell and the rubbing direction of the optical compensation film were arranged to be antiparallel.

<Evaluation of OCB Mode Liquid Crystal Display Device 1>
Next, the liquid crystal display device left in a room at room temperature and normal humidity (25 ° C., 60% RH) for one week is measured from black display (L1) to white display (L8) using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM). ) And the color tone and contrast ratio (transmittance during white display / transmittance during black display) were evaluated. The same measurement was performed after the liquid crystal display device was left in a room at room temperature and normal humidity (25 ° C., 10% RH) for one week. The evaluation results are shown in Table 1.
In Table 1, ΔCu′v ′ is the u′v ′ space with respect to the front when black is displayed at a polar angle of 60 ° with respect to the normal direction of the screen surface and an azimuth angle direction of 0 to 360 ° of the liquid crystal display screen. The absolute value of the value obtained by subtracting u′v ′ (front) from u′v ′ at the point farthest away in (color coordinates in CIELAB space) is shown.
The contrast is a value calculated from the contrast ratio (transmittance during white display / transmittance during black display).

The evaluation criteria are shown below.
[Evaluation criteria of ΔCu′v ′]
ΔCu′v ′ is less than 0.02 ΔCu′v ′ is 0.02 or more and less than 0.04 ΔΔCu′v ′ is 0.04 or more and less than 0.06 × ΔCu′v ′ is 0. 06 or more

[Evaluation Criteria for Contrast Viewing Angle (Polar Angle Range with Contrast Ratio of 10 or More and No Black-side Gradation Inversion)]
◎ Polar angle 80 ° or more in top / bottom / left / right ○ Polar angle 80 ° or more in three directions, top / bottom / left / right △ Polar angle 80 ° or more in two directions, top / bottom / left / right × Polar angle 80 ° in three directions, top / bottom / left / right Less than

<Evaluation of manufacturing aptitude>
Next, manufacturing aptitude was evaluated for this example, examples described later, and comparative examples based on the following criteria. The “process” is counted as one process every time a line from sending to winding is passed once. Therefore, for example, when the stretching process is incorporated in the line of the casting machine of the support, it is combined with one process. However, after the coating layer is applied, a separate stretching is required with an offline stretching machine. In that case, it is counted as one step only by stretching.
○ The process is 3 or less (Example: (i) casting of the support + stretching, (ii) coating layer coating, (iii) rubbing + coating layer coating)
△ The process is 4 (example: (i) casting of support, (ii) coating layer coating, (iii) stretching, (iv) rubbing + coating layer coating)
X The process is 5 or more (eg: (i) casting of the support + stretching, (ii) coating layer coating, (iii) transfer, (iv) coating layer coating, (v) rubbing + coating layer coating)

(Example 2)
<Preparation of optical compensation film 2>
In the same manner as in Example 1, an optically anisotropic layer A-1 was produced.

<< Preparation of Optical Anisotropic Layer B-2 >>
A 1.0 N potassium hydroxide solution (solvent: water / isopropyl alcohol / propylene glycol = 69.2 parts by mass / 15 parts by mass / 15.8 parts by mass) was applied to this surface at 10 mL / m 2, at a temperature of about 40 ° C. After holding for 30 seconds, the alkaline solution was scraped off, washed with pure water, water droplets were removed with an air knife, and then dried at 100 ° C. for 15 seconds to saponify one side.
On this saponified surface, a 7.5 wt% polyvinyl alcohol aqueous solution having a polymerization degree of 2400 (polyvinyl alcohol: Kuraray Poval PVA124 (manufactured by Kuraray Co., Ltd.), solvent: pure water) with a wet coating amount of 190 cc / m ^{2 on} a slide coater. It apply | coated with the application | coating speed | rate of 20 m / min, and it dried for 4 minutes with 120 degreeC drying air, and formed the optically anisotropic layer B-2 with a film thickness of 11 micrometers.

<< Preparation of Optical Anisotropic Layer C-2 >>
A coating composition for the optically anisotropic layer C-2 was prepared in the same manner as in Example 1, except that toluene in the coating composition used for the optically anisotropic layer C-1 was replaced with methyl ethyl ketone.
The optically anisotropic layer was obtained in the same manner as in Example 1 except that the surface of the optically anisotropic layer B-2 was rubbed and the coating composition for the optically anisotropic layer C-2 was applied to the rubbed surface. C-2 was formed. Thus, an optical compensation film 2 composed of the optically anisotropic layer A-1 / B-2 / C-2 laminate was produced.
The optical characteristics were evaluated in the same manner as in Example 1 (results are shown in Table 1).

<Production of Polarizing Plate 2 and Liquid Crystal Display>
A pair of polarizing plates 2 was produced in the same manner as in Example 1 except that the optical compensation film 2 was used instead of the optical compensation film 1. An OCB mode liquid crystal display device was produced in the same manner as in Example 1 except that this pair of polarizing plates 2 was used instead of the pair of polarizing plates 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)
<Preparation of optical compensation film 3>
<< Preparation of Optical Anisotropic Layer A-2 >>
Each component described in the following table was mixed to prepare a cellulose acylate solution. This cellulose acylate solution was cast on a metal support, the obtained web was peeled from the support, and then stretched under the conditions described in the following table. In the table below, the MD direction means the transport direction. After stretching, the film was dried to prepare an optically anisotropic layer A-2 having a film thickness of 85 μm.

On the optically anisotropic layer A-2 thus prepared, optically anisotropic layers B-1 and C-1 were prepared in the same manner as in Example 1. Thus, an optical compensation film 3 composed of the optically anisotropic layer A-2 / B-1 / C-1 laminate was produced. The optical characteristics were evaluated in the same manner as in Example 1 (results are shown in Table 1). Similar to Example 1,
<Production of Polarizing Plate 3 and Liquid Crystal Display>
A pair of polarizing plates 3 was produced in the same manner as in Example 1 except that the optical compensation film 3 was used in place of the optical compensation film 1. An OCB mode liquid crystal display device was produced in the same manner as in Example 1 except that this pair of polarizing plates 3 was used in place of the pair of polarizing plates 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4
<Preparation of optical compensation film 4>
In the same manner as in Example 3, an optically anisotropic layer A-2 was produced.
Further, in the same manner as in Example 2, the surface of the optically anisotropic layer A-2 was saponified, and optically anisotropic layers B-2 and C-2 were laminated. Thus, an optical compensation film 4 composed of the optically anisotropic layer A-2 / B-2 / C-2 laminate was produced. The optical characteristics were evaluated in the same manner as in Example 1 (results are shown in Table 1).

<Preparation of Polarizing Plate 4 and Liquid Crystal Display>
A pair of polarizing plates 4 was produced in the same manner as in Example 1 except that the optical compensation film 1 was replaced with the optical compensation film 4. An OCB mode liquid crystal display device was produced in the same manner as in Example 1 except that the pair of polarizing plates 1 was replaced with this pair of polarizing plates 4 and evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 5)
<Preparation of optical compensation film 5>

<< Preparation of Optical Anisotropic Layer C-2 >>
In the same manner as in Example 1, an optically anisotropic layer A-1 / B-1 laminate was produced, and the surface of the optically anisotropic layer B-1 was rubbed.

<< Preparation of Optical Anisotropic Layer C-2 >>
A coating solution for preparing the optically anisotropic layer C-2 having the following composition was prepared.

  An optically anisotropic layer C-2 was formed in the same manner as in Example 1 except that the coating solution was applied to the orientation-treated surface of the optically anisotropic layer B-1 with a # 2.0 wire bar. . The Re retardation value of the obtained optically anisotropic layer measured at a wavelength of 550 nm was 30 nm. The thickness was 0.8 μm.

  Thus, an optical compensation film 5 composed of the optically anisotropic layer A-1 / B-1 / C-2 laminate was produced. The optical characteristics were evaluated in the same manner as in Example 1 (results are shown in Table 1).

<Production of Polarizing Plate 5 and Liquid Crystal Display>
A pair of polarizing plates 5 was produced in the same manner as in Example 1 except that the optical compensation film 1 was replaced with the optical compensation film 5. An OCB mode liquid crystal display device was produced in the same manner as in Example 1 except that the pair of polarizing plates 1 was replaced with the pair of polarizing plates 5 and evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
<Preparation of optical compensation film 6>
<< Preparation of optically anisotropic layer A + B >>
A 15% by weight solution of polyimide was applied to a triacetylcellulose (TAC) substrate having a thickness of about 80 μm, dried by heating at 130 ° C. for 1 minute, and a thickness of about 9 μm showing negative uniaxial C-plate retardation characteristics. An optically anisotropic layer A + B was prepared by stretching 10% at 150 ° C. by free end uniaxial stretching. In addition, this optically anisotropic layer A + B showed the optical characteristic with the same optical compensation effect as the laminated body of optically anisotropic layer A-1 and B-1 with respect to the liquid crystal display device of OCB mode.

The surface of the polyimide layer of the optically anisotropic layer A + B was rubbed in the same manner as in Example 1, and an optically anisotropic layer C-1 was formed in the same manner as in Example 1. In this way, an optical compensation film 6 composed of the optically anisotropic layer A + B / C-1 laminate was produced. The optical characteristics were evaluated in the same manner as in Example 1 (results are shown in Table 1).
<Production of Polarizing Plate 6 and Liquid Crystal Display Device>
A pair of polarizing plates 6 was produced in the same manner as in Example 1 except that the optical compensation film 1 was replaced with the optical compensation film 6. An OCB mode liquid crystal display device was produced in the same manner as in Example 1 except that the pair of polarizing plates 1 was replaced with this pair of polarizing plates 6 and evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
<Preparation of optical compensation film 7>
<< Preparation of Optical Anisotropic Layer A-3 >>
Bisphenol A type polycarbonate (C1400 manufactured by Teijin Chemicals Ltd.) was dissolved in methylene chloride to prepare a dope solution having a solid content concentration of 18% by weight. From this dope solution, a film flow was produced on a support by a solution casting method. This was peeled from the support and dried by gradually raising the temperature to Tg-20 ° C. to obtain a film. Next, this film was uniaxially stretched 1.6 times at 230 ° C. The characteristic values of the obtained film were a film thickness of 35 μm, Re = 32 nm, and Rth = 16 nm. Re (450) / Re (550) = 0.82, Re (650) / Re (550) = 1.07.

<< Preparation of optically anisotropic layer B-3 >>
On Fujitac (Fuji Film Co., Ltd.), a coating solution having the following composition was applied at 24 ml / m ² with a # 14 wire bar coater. The alignment film was produced by drying with warm air of 60 ° C. for 60 seconds and further with warm air of 90 ° C. for 150 seconds.

  On the unrubbed alignment film formed on the long support pair, a coating composition for optically anisotropic layer B-3 having the following composition was continuously applied for 500 m with a # 3 wire bar.

(Coating composition for optically anisotropic layer B-3)
The following discotic liquid crystal compound (3) 32.6% by mass
Air interface alignment controller (1) 0.15% by mass
Ethylene oxide modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 3.2% by mass
Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.4% by mass
Photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) 1.1% by mass
Methyl ethyl ketone 62.0% by mass

  After the coating solution was applied, it was then dried by heating in a 130 ° C. drying zone for 2 minutes to align the discotic liquid crystalline compound. Next, UV irradiation was performed for 4 seconds using a 120 W / cm high pressure mercury lamp at 80 ° C. in the UV irradiation zone to polymerize the discotic liquid crystalline compound. Then, it stood to cool to room temperature and wound up. The produced optically anisotropic layer exhibited an optically negative refractive index anisotropy, and had a thickness of 2.38 μm, Re = 0 nm, and Rth = 150 nm at a wavelength of 550 nm. Rth (450) / Rth (550) = 1.21 and Re (650) / Re (550) = 0.92. The discotic liquid crystalline compound of the optically anisotropic layer was horizontally aligned within a range of ± 1 °. The optically anisotropic layer B-3 thus formed is transferred to the optically anisotropic layer A-3 via an adhesive layer to produce an optically anisotropic layer A-3 / B-3 laminate. did.

<< Preparation of Optical Anisotropic Layer C-3 >>
20 parts by weight of the modified polyvinyl alcohol and parts by weight of glutaraldehyde (crosslinking agent) were dissolved in 360 parts by weight of water and 120 parts by weight of methanol to prepare a coating solution. The coating liquid is applied with a # 16 wire bar coater on the optically anisotropic layer A-3 surface side of the optically anisotropic layer A-3 / B-3 laminate, and warm air at 60 ° C. for 60 seconds. Further, the alignment film was produced by drying with warm air of 90 ° C. for 150 seconds. Next, the produced alignment film was rubbed in a direction of 45 ° with respect to the direction parallel to the casting direction of the film.

  90 parts by weight of the discotic liquid crystal compound (1), 10 parts by weight of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.), melamine formaldehyde / acrylic acid copolymer (Aldrich Reagent) 6 parts by weight, 3.0 parts by weight of photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy Japan) and 1.0 part by weight of photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) are added to methyl ethyl ketone. By dissolving, a coating solution having a solid content concentration of 38% by weight was prepared.

  On the alignment film, the coating solution was applied with a # 3 wire bar. This was heated in a constant temperature bath at 120 ° C. for 3 minutes, the discotic liquid crystalline compound was aligned, irradiated with ultraviolet rays, the discotic liquid crystalline compound was polymerized, and the alignment state was fixed. The thickness of the produced optically anisotropic layer was 1.5 μm. Re (550) was 30 nm. Thus, the optically anisotropic layer C-3 was formed, and the optical compensation film 7 made of the optically anisotropic layer B-3 / A-3 / C-3 laminate was produced. The optical characteristics were evaluated in the same manner as in Example 1 (results are shown in Table 1).

<Production of Polarizing Plate 7 and Liquid Crystal Display Device>
A pair of polarizing plates 7 was produced in the same manner as in Example 1 except that the optical compensation film 1 was replaced with the optical compensation film 7. An OCB mode liquid crystal display device was produced in the same manner as in Example 1 except that the pair of polarizing plates 1 was replaced with this pair of polarizing plates 7 and evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 3)
<Preparation of optical compensation film 8>
<< Preparation of Optical Anisotropic Layer A-4 >>
At room temperature, 120 parts by weight of cellulose acetate having an average degree of acetylation of 59.7%, 9.36 parts by weight of triphenyl phosphate, 4.68 parts by weight of biphenyl diphenyl phosphate, the following retardation increasing agent. 20 parts by weight, 704 parts by weight of methylene chloride, and 61.2 parts by weight of methanol were mixed to prepare a solution (dope).

The obtained dope was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 45 ° C. for 5 minutes. The residual amount of solvent after drying was 30% by weight. The cellulose acetate film was peeled from the glass plate and dried at 100 ° C. for 20 minutes and 130 ° C. for 10 minutes. The film was cut to an appropriate size and then stretched 1.45 times at 130 ° C. in a direction parallel to the casting direction. The direction perpendicular to the stretching direction was allowed to shrink freely. After stretching, the film was cooled to room temperature, and then the stretched film was taken out. As described above, an optically anisotropic layer A-4 was produced.
The residual solvent amount after stretching was 0.2% by weight. The thickness of the obtained film was 60 μm. The characteristic values of the obtained cellulose acetate film were Re = 82 nm and Rth = 88 nm. In addition, Re (450) / Re (550) = 0.87 and Re (650) / Re (550) = 1.06.

<< Preparation of Optical Anisotropic Layer B-4 >>
On the optically anisotropic layer A-4, an optically anisotropic layer B-4 having a film thickness of 1.35 μm and optical properties of Re = 0 and Rth = 85 nm was prepared in the same manner as in Comparative Example 2. Further, an optically anisotropic layer C-3 was formed thereon as in Comparative Example 2. Thus, the optical compensation film 8 which consists of an optically anisotropic layer A-4 / B-4 / C-3 laminated body was produced. The optical characteristics were evaluated in the same manner as in Example 1 (results are shown in Table 1).

<Production of Polarizing Plate 8 and Liquid Crystal Display>
A pair of polarizing plates 8 was produced in the same manner as in Example 1 except that the optical compensation film 1 was replaced with the optical compensation film 8. An OCB mode liquid crystal display device was produced in the same manner as in Example 1 except that the pair of polarizing plates 1 was replaced with the pair of polarizing plates 8 and evaluated in the same manner as in Example 1. The results are shown in Table 1.

  From the results shown in Table 1, the OCB liquid crystal display device including the optical compensation films of Examples 1 to 5 can display a high contrast image with a wide viewing angle, and the color tone generated depending on the viewing angle. It was confirmed that stickiness was reduced. Moreover, all of the optical compensation films of Examples 1 to 5 had good production suitability.

It is a section schematic diagram of an example of the optical compensation film of the present invention.

Explanation of symbols

10 First optical anisotropic layer 12 Second optical anisotropic layer 14 Third optical anisotropic layer

Claims (14)

a first optical anisotropic layer satisfying nx>ny>nz;
A second optically anisotropic layer having liquid crystal alignment ability and satisfying nx ≧ ny> nz, and a third optically anisotropic layer containing a liquid crystalline compound fixed in an alignment state,
In this order:
However, nx, ny, and nz are respectively the maximum refractive index in the film plane, the refractive index in the direction orthogonal to the direction giving the maximum refractive index, and the film plane method in each of the optically anisotropic layers. The refractive index in the line direction is shown. The optical compensation film according to claim 1, wherein the in-plane retardation Re of the first optically anisotropic layer exhibits reverse dispersion wavelength dependence in a visible light region. 3. The optical compensation film according to claim 1, wherein retardation Rth in the thickness direction of the second optically anisotropic layer exhibits forward dispersion wavelength dependency in a visible light region. The said 2nd optically anisotropic layer contains the at least 1 sort (s) of polymer material selected from the group which consists of a polyimide, polyetherketone, polyamideimide, and polyesterimide, The any one of Claims 1-3 characterized by the above-mentioned. The optical compensation film according to item. The second optically anisotropic layer contains at least one polymer material selected from the group consisting of polyvinyl alcohol and modified polyvinyl alcohol having a polymerization degree of 1000 to 5000 and a saponification degree of 80% to 100%. The optical compensation film according to any one of claims 1 to 3. The optical compensation film according to any one of claims 1 to 5, wherein the second optically anisotropic layer is not stretched. The first optically anisotropic layer contains at least one of a compound represented by cellulose acylate and the following general formula (I), according to any one of claims 1 to 6. Optical compensation film:

In the formula, L ¹ and L ² each independently represent a single bond or a divalent linking group; A ¹ and A ² each independently represent —O— or —NR— (R represents a hydrogen atom or a substituent). ), -S- and -CO-; R ¹ , R ² and R ³ each independently represent a substituent; X represents a nonmetallic atom of Groups 14-16 ( However, a hydrogen atom or a substituent may be bonded to X); n represents any integer from 0 to 2. The optical compensation according to any one of claims 1 to 7, wherein the first optically anisotropic layer is formed by stretching a film containing cellulose acetate propionate. the film. The optical compensation film according to claim 1, wherein at least one liquid crystalline compound contained in the third optically anisotropic layer is a discotic compound. A step of applying a polymer composition on the first optically anisotropic layer to form a second optically anisotropic layer, and applying a liquid crystal composition on the surface of the second optically anisotropic layer And a step of aligning the liquid crystal composition on the surface of the second optically anisotropic layer, fixing the alignment state, and forming a third optically anisotropic layer, and The method for producing an optical compensation film according to claim 1, which does not include a step of stretching the anisotropic layer. A polarizing plate having at least the optical compensation film according to claim 1 and a polarizing film. A liquid crystal display device comprising the polarizing plate according to claim 11. The liquid crystal display device according to claim 12, wherein the liquid crystal mode of the liquid crystal display device is an electric field control birefringence mode. The liquid crystal display device according to claim 12, wherein a liquid crystal mode of the liquid crystal display device is an OCB mode.

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