JPWO2014132978A1 - Phase difference plate, antireflection plate, image display device, and method of manufacturing phase difference plate - Google Patents

Abstract

Provided are a retardation plate that suppresses reflection of external light, improves viewing angle, color change, and adhesion to a polarizing film, an antireflection plate using the same, an image display device, and a method of manufacturing a retardation plate. A transparent support and an optically anisotropic layer containing a liquid crystal compound, wherein the transparent support is −10 nm ≦ Re (550) ≦ 10 nm, −100 nm ≦ Rth (550) ≦ −20 nm, and 1.3 < The cellulose acylate film satisfies DS <2.8 (DS is the total substitution degree of acyl groups), and the optically anisotropic layer satisfies the following formulas (1) to (4). Formula (1): 120 nm ≦ Re (550) ≦ 150 nm Formula (2): Re (450) / Re (550) <1 Formula (3): Re (650) / Re (550)> 1 Formula (4): 20 nm ≦ Rth (550) ≦ 100 nm

Description

  The present invention relates to a retardation plate, an antireflection plate using the same, an image display device, and a method of manufacturing a retardation plate.

  Retardation plates have a great many applications, and are already used for reflective LCDs, transflective LCDs, brightness enhancement films, organic EL display devices, touch panels, and the like. For example, since an organic EL display device has a structure in which layers having different refractive indexes are stacked or a structure using a metal electrode, external light may be reflected at the interface between the layers, resulting in problems such as a decrease in contrast and reflection. is there.

On the other hand, Patent Document 1 discloses a polarizing film in which a polarizing film, a first retardation film having a slow axis substantially perpendicular to the longitudinal direction, and a second retardation film having a predetermined retardation are stacked in this order. An integrated optical compensation film is disclosed.
Patent Document 2 discloses a retardation plate having an alignment film and an optically anisotropic layer containing a liquid crystal compound with reverse wavelength dispersion on a transparent support. Such a retardation plate is assumed to be used as a λ / 4 plate.

JP 2007-286578 A JP 2010-84032 A

Here, as in Patent Document 2, in a retardation plate for a λ / 4 plate using a polymer film, when an inverse wavelength dispersion layer is used as an optically anisotropic layer, the front surface is obtained when it is incorporated in an image display device. It was also found that the display performance of the liquid crystal display is improved, but such a phase difference plate may deteriorate the viewing angle characteristics.
Further, such a retardation plate is beneficial if it can be used as a polarizing plate protective film that is directly attached to a polarizing film, but in this case, there is also a problem of adhesion to the polarizing film.

  The present invention was made in order to solve the above-described problems, and when incorporated in an image display device, it is a phase difference plate that is excellent in display performance at the front, and also excellent in viewing angle characteristics, An object of the present invention is to provide a retardation plate having improved adhesion to a polarizing film. It is another object of the present invention to provide an antireflection plate, an image display device, and a method for manufacturing the retardation plate using the retardation plate.

  As a result of intensive studies, the inventors have adjusted the thickness direction retardation (Rth) of each layer constituting the retardation plate, and when incorporated in an image display device, the display performance at the front is excellent. It has been found that a retardation plate having excellent angular characteristics can be provided. Further, as a means for adjusting Rth, by disposing an optically anisotropic layer having reverse wavelength dispersibility having predetermined optical characteristics on a transparent support having a predetermined total acyl group substitution degree and predetermined retardation. In addition to the above, the inventors have found that the adhesion to the polarizing plate is improved, and have completed the present invention.

式中、Ａ¹及びＡ²は各々独立に、−Ｏ−、−ＮＲ、−Ｓ−及び−ＣＯ−からなる群から選ばれる基を表し、Ｒは水素原子または置換基を表す；Ｚは、第１４〜１６族の非金属原子からなる群から選択される１つ又は２つの原子を表し、式中の２つの炭素原子と共に５又は６員環を形成する。Ｂ、Ｒ¹は各々独立に置換基を表し、Ｒ²は二価の連結基を表す；複数のＢ及びＲ²は同一でも異なっていてもよい；ｍは０〜４の整数である；Ｌ¹及びＬ²は各々独立に二価の連結基を表す；Ｒ⁴及びＲ⁵は各々独立に置換基を表す；なお、重合性基を有する場合、Ｂ、Ｒ、Ｒ¹、Ｒ²、Ｒ⁴、及びＲ⁵の少なくとも１つが、重合性基を含む；ｎは１〜１０の整数である。
＜４＞一般式（１）で表される液晶化合物において、ｎが２〜１０の整数である、＜３＞に記載の位相差板。
＜５＞液晶化合物が、下記一般式（２）で表される、＜１＞または＜２＞に記載の位相差板；
一般式（２）：
Ｌ１−Ｇ１−Ｄ１−Ａｒ−Ｄ２−Ｇ２−Ｌ２
一般式（２）中、Ａｒは下記一般式（２−１）、（２−２）、または（２−３）で表される２価の芳香環基を表し、Ｄ１及びＤ２は、それぞれ独立に、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｃ（＝Ｓ）Ｏ−、−Ｏ−Ｃ（＝Ｓ）−、−ＣＲ¹Ｒ²−、−ＣＲ¹Ｒ²−ＣＲ³Ｒ⁴−、−Ｏ−ＣＲ¹Ｒ²−、−ＣＲ¹Ｒ²−Ｏ−、−ＣＲ¹Ｒ²−Ｏ−ＣＲ³Ｒ⁴−、−ＣＲ¹Ｒ²−Ｏ−ＣＯ−、−Ｏ−ＣＯ−ＣＲ¹Ｒ²−、−ＣＲ¹Ｒ²−Ｏ−ＣＯ−ＣＲ³Ｒ⁴−、−ＣＲ¹Ｒ²−ＣＯ−Ｏ−ＣＲ³Ｒ⁴−、−ＮＲ¹−ＣＲ²Ｒ³−、−ＣＲ¹Ｒ²−ＮＲ³−、−ＣＯ−ＮＲ¹−、または−ＮＲ¹−ＣＯ−を表し、Ｒ¹、Ｒ²、Ｒ³、及びＲ⁴は、それぞれ独立に、水素原子、ハロゲン原子、又は炭素数１〜４のアルキル基を表し、Ｇ１およびＧ２は、それぞれ独立に、炭素数６〜１２の２価の芳香族炭化水素基、または炭素数５〜８の２価の脂環式炭化水素基を表し、脂環式炭化水素基に含まれるメチレン基は、−Ｏ−、−Ｓ−、−ＮＨ−、−Ｎ（Ｒ）−で置換されていてもよく、Ｒは水素原子又は炭素数１〜６のアルキル基を表し、Ｌ１及びＬ２は、それぞれ独立に、１価の有機基を表し、Ｌ１及びＬ２からなる群から選ばれる少なくとも一種が、重合性基を有する１価の基を表す；

一般式（２−１）中、Ｑ¹は、−Ｓ−、−Ｏ−、又は−ＮＲ¹−を表す。Ｒ¹は、水素原子又は炭素数１〜６のアルキル基を表す；Ｙ¹は、炭素数６〜１２の芳香族炭化水素基、又は、炭素数３〜１２の芳香族複素環基を表す；Ｚ¹およびＺ²は、それぞれ独立に、水素原子又は炭素数１〜２０の脂肪族炭化水素基、炭素数３〜２０の脂環式炭化水素基、１価の炭素数６〜２０の芳香族炭化水素基、ハロゲン原子、シアノ基、ニトロ基、−ＮＲ²Ｒ³又は−ＳＲ²を表し、Ｚ¹及びＺ²は、互いに結合して芳香環又は芳香族複素環を形成してもよい；Ｒ²及びＲ³は、それぞれ独立に水素原子又は炭素数１〜６のアルキル基を表す；
一般式（２−２）及び（２−３）中、Ａｘは芳香族炭化水素環及び芳香族複素環からなる群から選ばれる少なくとも一つの芳香環を有する、炭素数２〜３０の有機基を表し、Ａｙは水素原子、置換基を有していてもよい炭素数１〜６のアルキル基、又は、芳香族炭化水素環及び芳香族複素環からなる群から選ばれる少なくとも一つの芳香環を有する、炭素数２〜３０の有機基を表し、Ａｘ及びＡｙが有する芳香環は置換基を有していてもよい；また、ＡｘとＡｙは互いに結合して環を形成していてもよい；Ｚ¹、Ｚ²、Ｚ³はそれぞれ独立に、水素原子又は置換基を表す；Ｑ²は、水素原子、又は、置換基を有していてもよい炭素数１〜６のアルキル基を表す。
＜６＞光学異方性層が、さらに、非液晶性の重合性モノマーを含有する、＜１＞〜＜５＞のいずれかに記載の位相差板。
＜７＞光学異方性層の膜厚が、３．０〜５．５μｍである、＜１＞〜＜６＞のいずれかに記載の位相差板。
＜８＞光学異方性層が１層のみからなる、＜１＞〜＜７＞のいずれかに記載の位相差板。
＜９＞透明支持体が未延伸フィルムである、＜１＞〜＜８＞のいずれかに記載の位相差板。
＜１０＞透明支持体の波長５５０ｎｍにおける厚み方向のレターデーションＲｔｈ（５５０）と、光学異方性層の波長５５０ｎｍにおける厚み方向のレターデーションＲｔｈ（５５０）との合計値の絶対値が、５０ｎｍ以下である、＜１＞〜＜９＞のいずれかに記載の位相差板。
＜１１＞光学異方性層の波長５５０ｎｍにおける面内レターデーションＲｅ（５５０）が１２５〜１４５ｎｍである、＜１＞〜＜１０＞のいずれかに記載の位相差板。
＜１２＞透明支持体の波長５５０ｎｍにおける厚み方向のレターデーションＲｔｈ（５５０）が、−９０〜−２３ｎｍである、＜１＞〜＜１１＞のいずれかに記載の位相差板。
＜１３＞アシル基の総置換度ＤＳが、１．５〜２．７である、＜１＞〜＜１２＞のいずれかに記載の位相差板。
＜１４＞＜１＞〜＜１３＞のいずれかに記載の位相差板と、偏光膜とを有する反射防止板。
＜１５＞＜１４＞に記載の反射防止板を有する画像表示装置。
＜１６＞有機ＥＬ表示装置である＜１５＞に記載の画像表示装置。
＜１７＞＜１＞〜＜１３＞のいずれかに記載の位相差板の製造方法であって、セルロースアセテートベンゾエートを含有する溶液を支持体に流延しフィルム状に形成した後、延伸処理を行わずに、光学異方性層を形成することを含む、位相差板の製造方法。The means for solving the above problems is the means <1> below, preferably <2> below.
It is means of <17>.
<1> having a transparent support and an optically anisotropic layer containing a liquid crystal compound,
The transparent support is a cellulose acylate film satisfying the formula (A), the formula (B), and the formula (I);
A phase difference plate in which the optically anisotropic layer satisfies the following formulas (1) to (4);
Formula (A): −10 nm ≦ Re (550) ≦ 10 nm
Formula (B): −100 nm ≦ Rth (550) ≦ −20 nm
Formula (1): 120 nm ≦ Re (550) ≦ 150 nm
Formula (2): Re (450) / Re (550) <1
Formula (3): Re (650) / Re (550)> 1
Formula (4): 20 nm ≦ Rth (550) ≦ 100 nm
In the above formula, Re (λ) represents in-plane retardation at wavelength λnm, and Rth (λ) represents retardation in the thickness direction at wavelength λnm;
Formula (I): 1.3 <DS <2.8
In formula (I), DS represents the total substitution degree of the acyl group.
<2> The retardation plate according to <1>, wherein the transparent support is a cellulose acylate film satisfying the following formula (II);
Formula (II): 0.8 ≦ DSA ≦ 1.3
In formula (II), DSA represents the substitution degree of an acyl group containing an aromatic group.
<3> The retardation plate according to <1> or <2>, wherein the liquid crystal compound is represented by the following general formula (1);

In the formula, A ¹ and A ² each independently represents a group selected from the group consisting of —O—, —NR, —S— and —CO—, R represents a hydrogen atom or a substituent; Represents one or two atoms selected from the group consisting of non-metal atoms of Groups 14-16 and forms a 5- or 6-membered ring with the two carbon atoms in the formula. B and R ¹ each independently represent a substituent, R ² represents a divalent linking group; a plurality of B and R ² may be the same or different; m is an integer of 0 to 4; ¹ and L ² each independently represent a divalent linking group; R ⁴ and R ⁵ each independently represent a substituent; when having a polymerizable group, B, R, R ¹ , R ² , R ⁴ and at least one of R ⁵ contains a polymerizable group; n is an integer of 1 to 10.
<4> The phase difference plate according to <3>, wherein n is an integer of 2 to 10 in the liquid crystal compound represented by the general formula (1).
<5> The retardation plate according to <1> or <2>, wherein the liquid crystal compound is represented by the following general formula (2);
General formula (2):
L1-G1-D1-Ar-D2-G2-L2
In General Formula (2), Ar represents a divalent aromatic ring group represented by the following General Formula (2-1), (2-2), or (2-3), and D1 and D2 are each independently a, -CO-O -, - O -CO -, - C (= S) O -, - O-C (= S) -, - CR 1 R 2 -, - CR 1 R 2 -CR 3 R 4 ^{-, - O-CR 1 R} 2 -, - CR 1 R 2 -O -, - CR 1 R 2 -O-CR 3 R 4 -, - CR 1 R 2 -O-CO -, - O-CO- CR ¹ R ² —, —CR ¹ R ² —O—CO—CR ³ R ⁴ —, —CR ¹ R ² —CO—O—CR ³ R ⁴ —, —NR ¹ —CR ² R ³ —, —CR ¹ R ² —NR ³ —, —CO—NR ¹ —, or —NR ¹ —CO—, wherein R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a halogen atom, or Represents an alkyl group having 1 to 4 carbon atoms, and G1 and G2 are Each independently represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and methylene contained in the alicyclic hydrocarbon group The group may be substituted with -O-, -S-, -NH-, -N (R)-, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and L1 and L2 are Each independently represents a monovalent organic group, and at least one selected from the group consisting of L1 and L2 represents a monovalent group having a polymerizable group;

In General Formula (2-1), Q ¹ represents —S—, —O—, or —NR ¹ —. R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Y ¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms; Z ¹ and Z ² are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic having 6 to 20 carbon atoms. Represents a hydrocarbon group, a halogen atom, a cyano group, a nitro group, —NR ² R ³ or —SR ² , and Z ¹ and Z ² may combine with each other to form an aromatic ring or an aromatic heterocyclic ring; R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
In general formulas (2-2) and (2-3), Ax represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Ay represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Represents an organic group having 2 to 30 carbon atoms, and the aromatic ring of Ax and Ay may have a substituent; Ax and Ay may be bonded to each other to form a ring; ¹ , Z ² and Z ³ each independently represent a hydrogen atom or a substituent; Q ² represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.
<6> The retardation plate according to any one of <1> to <5>, wherein the optically anisotropic layer further contains a non-liquid crystalline polymerizable monomer.
<7> The retardation plate according to any one of <1> to <6>, wherein the thickness of the optically anisotropic layer is 3.0 to 5.5 μm.
<8> The retardation plate according to any one of <1> to <7>, wherein the optically anisotropic layer is composed of only one layer.
<9> The retardation plate according to any one of <1> to <8>, wherein the transparent support is an unstretched film.
<10> The absolute value of the total value of the retardation Rth (550) in the thickness direction at a wavelength of 550 nm of the transparent support and the retardation Rth (550) in the thickness direction at a wavelength of 550 nm of the optically anisotropic layer is 50 nm or less. The retardation film according to any one of <1> to <9>.
<11> The retardation plate according to any one of <1> to <10>, wherein the in-plane retardation Re (550) at a wavelength of 550 nm of the optically anisotropic layer is 125 to 145 nm.
<12> The retardation plate according to any one of <1> to <11>, wherein a retardation Rth (550) in a thickness direction at a wavelength of 550 nm of the transparent support is −90 to −23 nm.
<13> The retardation plate according to any one of <1> to <12>, wherein the total substitution degree DS of the acyl group is 1.5 to 2.7.
<14> An antireflection plate comprising the retardation plate according to any one of <1> to <13> and a polarizing film.
<15> An image display device having the antireflection plate according to <14>.
<16> The image display device according to <15>, which is an organic EL display device.
<17> A method for producing a retardation plate according to any one of <1> to <13>, wherein a solution containing cellulose acetate benzoate is cast on a support to form a film, and then subjected to a stretching treatment. A method for producing a retardation plate, which includes forming an optically anisotropic layer without performing it.

  According to the present invention, a retardation plate having excellent front display performance and excellent viewing angle characteristics when incorporated in an image display device, an antireflection plate using the same, an image display device, and a retardation plate The manufacturing method of can be provided.

It is the schematic sectional drawing which showed an example of the phase difference plate of this invention. It is the schematic sectional drawing which showed an example of the reflection preventing plate of this invention. It is the schematic sectional drawing which showed an example of the organic electroluminescent display apparatus of this invention.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

  In the present specification, Re (λ) and Rth (λ) represent in-plane retardation (nm) and retardation in the thickness direction (nm) at 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 is incident at a wavelength of λ nm from the inclined direction in steps of 10 degrees from the normal direction to 50 degrees on one side with respect to the film normal direction of the rotation axis of 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 (11) and (12).

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

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 from −50 degrees to +50 degrees with respect to the normal direction of the film, with Re (λ) being the in-plane slow axis (determined by KOBRA 21ADH or WR) and the tilt axis (rotating axis). In each of the 10 degree steps, light of wavelength λ nm is incident from the inclined direction and measured at 11 points. Based on the measured retardation value, the assumed average refractive index, and the input film thickness value, KOBRA 21ADH or WR is calculated.

Here, as the assumed value of the average refractive index, values in the polymer handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can be used. 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 as follows: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Examples include polystyrene (1.59).
By inputting the assumed value of the average refractive index and the film thickness, nx, ny, and nz can be calculated by KOBRA 21ADH.

In this specification, the “slow axis” means a direction in which the refractive index becomes maximum in the plane, and the “polarizing plate” means a long polarizing plate and a display device unless otherwise specified. It is used to include both polarizing plates cut to the size to be incorporated. Here, “cutting” includes “punching” and “cutting out”. In the description of the present embodiment, “polarizing film” and “polarizing plate” are distinguished from each other. Among the “polarizing plates”, in particular, the retardation plate of the present invention or a general λ / 4 plate and a polarizing plate are used. A form including a laminate with a film is called an “antireflection plate” or a “circularly polarizing plate”.
The organic EL display device means an organic electroluminescence display device.

<Phase difference plate>
The retardation plate of the present invention has a transparent support and an optically anisotropic layer containing a liquid crystal compound, and the transparent support satisfies formula (A), formula (B), and formula (I). It is a cellulose acylate film, and the optically anisotropic layer satisfies the following formulas (1) to (4).
Formula (A): −10 nm ≦ Re (550) ≦ 10 nm
Formula (B): −100 nm ≦ Rth (550) ≦ −20 nm
Formula (1): 120 nm ≦ Re (550) ≦ 150 nm
Formula (2): Re (450) / Re (550) <1
Formula (3): Re (650) / Re (550)> 1
Formula (4): 20 nm ≦ Rth (550) ≦ 100 nm
In the above formula, Re (λ) represents in-plane retardation at wavelength λnm, and Rth (λ) represents retardation in the thickness direction at wavelength λnm.
Formula (I): 1.3 <DS <2.8
In formula (I), DS represents the total substitution degree of the acyl group.

The optically anisotropic layer containing a liquid crystal compound is usually used in a state where it is formed and laminated on a transparent support such as a polymer film that supports it. Here, when the optically anisotropic layer is used as a λ / 4 plate, if the optically anisotropic layer containing a liquid crystal compound having reverse wavelength dispersion is formed on the transparent support, the reflectance and color change of the front surface are changed. Can be reduced. However, when such an optically anisotropic layer having reverse wavelength dispersion is formed on a transparent support, the viewing angle characteristics relating to reflectance and color may be inferior. When this reason was examined, it was found that the Rth of the transparent support had an influence. That is, it was found that the cause is that Rth becomes large as a whole of the laminated transparent support and optically anisotropic layer.
In the present invention, this problem is solved by using a transparent support having a predetermined Rth. That is, by making the Rth of the transparent support negative, the Rth of the optically anisotropic layer can be canceled out, and the Rth of the retardation plate as a whole does not affect the reflectance and color viewing angle characteristics. Can be suppressed.
Further, in the support having such negative Rth, it was found that the adhesion with the polarizing film can be improved by using a specific total acyl substitution degree, and the present invention has been completed. .

  FIG. 1 is a schematic cross-sectional view of an example of the retardation plate of the present invention. The retardation plate 10 has a transparent support 11 and an optically anisotropic layer 12 that functions as a λ / 4 plate, and the optically anisotropic layer 12 is formed of a composition containing a liquid crystal compound. An alignment film (not shown) may be provided between the transparent support 11 and the optically anisotropic layer 12 as necessary. Details of these members will be described later.

The in-plane retardation Re (550) at a wavelength of 550 nm of the transparent support satisfies the following formula (A), preferably satisfies the following formula (A-1), and more preferably satisfies the following formula (A-2). preferable. When Re (550) of the transparent support satisfies the following formula (A), the effect of the present invention is more effectively exhibited.
Formula (A): −10 nm ≦ Re (550) ≦ 10 nm
Formula (A-1): −7 nm ≦ Re (550) ≦ 10 nm
Formula (A-2): −2 nm ≦ Re (550) ≦ 1 nm

In-plane retardation Re (450), Re (550), and Re (650) at wavelengths of 450 nm, 550 nm, and 650 nm of the optically anisotropic layer satisfy the following formulas (1) to (3), respectively. It is preferable to satisfy the following formulas (1-1) to (3-1), and it is more preferable to satisfy the following formulas (1-2) to (3-2), respectively. By adopting such a configuration, the effect of the present invention is more effectively exhibited.
Formula (1): 120 nm ≦ Re (550) ≦ 150 nm
Formula (2): Re (450) / Re (550) <1
Formula (3): Re (650) / Re (550)> 1
Formula (1-1): 125 nm ≦ Re (550) ≦ 145 nm
Formula (2-1): 0.55 ≦ Re (450) / Re (550) ≦ 0.70
Formula (3-1): 1 <Re (650) / Re (550) ≦ 1.30
Formula (1-2): 135 nm ≦ Re (550) ≦ 140 nm
Formula (2-2): 0.60 ≦ Re (450) / Re (550) ≦ 0.65
Formula (3-2): 1 <Re (650) / Re (550) ≦ 1.10.

  An example of the optically anisotropic layer is an embodiment formed by curing a liquid crystal compound exhibiting reverse wavelength dispersion as shown in formulas (2) to (3), and shown in formula (1). As described above, the optically anisotropic layer functions as a λ / 4 plate. By forming the optically anisotropic layer from a liquid crystal compound exhibiting reverse wavelength dispersion, the effect of reducing the reflectance in the front direction and the oblique direction can be obtained.

The retardation Rth (550) in the thickness direction at a wavelength of 550 nm of the transparent support satisfies the following formula (B), preferably satisfies the following formula (B-1), and satisfies the following formula (B-2). It is more preferable.
Formula (B): −100 nm ≦ Rth (550) ≦ −20 nm
Formula (B-1): −90 nm ≦ Rth (550) ≦ −23 nm
Formula (B-2): −82 nm ≦ Rth (550) ≦ −28 nm

The retardation Rth (550) in the thickness direction at a wavelength of 550 nm of the optically anisotropic layer satisfies the following formula (4), preferably satisfies the following formula (4-1), and satisfies the following formula (4-2). It is more preferable.
Formula (4): 20 nm ≦ Rth (550) ≦ 100 nm
Formula (4-1): 50 nm ≦ Rth (550) ≦ 90 nm
Formula (4-2): 60 nm ≦ Rth (550) ≦ 80 nm

As a result of intensive studies by the inventor, it has been found that when the retardation plate is disposed in an image display device described later, the total Rth of each member constituting the retardation plate affects the viewing angle characteristics. For this reason, it is preferable that the absolute value of the total value of each Rth of the members constituting the retardation plate of the present invention is small. Specifically, the Rth (550) of the transparent support and the Rth ( 550) is preferably 50 nm or less, more preferably 30 nm or less, and particularly preferably 10 nm or less.
When Rth (550) of the transparent support satisfies the above formula (B) and Rth (550) of the optically anisotropic layer satisfies the above formula (4), the viewing angle characteristics are improved and the color change is also achieved. The effect of being suppressed is obtained.

<< Transparent support >>
The retardation plate of the present invention has a transparent support that supports the optically anisotropic layer, and the transparent support is a cellulose acylate film.

Cellulose acylate is a compound having a cellulose skeleton obtained by introducing an acyl group (substituent A) containing at least an aromatic group biologically or chemically using cellulose as a raw material.
The raw material cotton of cellulose acylate has a low polymerization degree obtained by acid hydrolysis of wood pulp such as microcrystalline cellulose as well as natural cellulose such as cotton linter and wood pulp (hardwood pulp, conifer pulp). 300) Cellulose can also 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, “Plastic Materials Course (17) Fibrous Resin” (Marusawa, Uda, Nikkan Kogyo Shimbun, published in 1970) and Invention Association Publication Technical Report 2001-1745 ( 7 to 8) and “Encyclopedia of Cellulose (page 523)” (edited by Cellulose Society, Asakura Shoten, published in 2000) can be used, and is not particularly limited.

  The cellulose acylate used for the transparent support is, for example, cellulose acetate (acetyl substitution degree 2.45) manufactured by Aldrich, or cellulose acetate (acetyl substitution degree 2.41 (trade name: L-70), manufactured by Daicel Corporation. 19 (trade name: FL-70)) and 1.76 (trade name: LL-10) as starting materials, and can be obtained by reaction with the corresponding acid chloride.

The cellulose acylate film used for the transparent support preferably satisfies the formula (I) and satisfies the formula (I-1) from the viewpoint of securing the adhesion, brittleness, and stable film-forming property of the polarizer. More preferably, the formula (I-2) is satisfied. If DS is out of the range of formula (I), the adhesion is poor.
Formula (I): 1.3 <DS <2.8
Formula (I-1): 1.5 ≦ DS ≦ 2.7
Formula (I-2): 1.7 ≦ DS ≦ 2.0
(In each formula, DS represents the total substitution degree of the acyl group.)

The cellulose acylate film used for the transparent support preferably satisfies the formula (II) and satisfies the formula (II-1) from the viewpoint of adjusting the Rth of the transparent support to satisfy the formula (B). It is preferable to satisfy the formula (II-2). By setting DSA to be 0.8 or more and 1.3 or less, a suitable Rth can be obtained.
Formula (II): 0.8 ≦ DSA ≦ 1.3
Formula (II-1): 0.9 ≦ DSA ≦ 1.2
Formula (II-2): 0.9 ≦ DSA ≦ 1.0
(In each formula, DSA represents the substitution degree of an acyl group containing an aromatic group.)

  The cellulose acylate film used in the present invention preferably contains cellulose acylate as a main component, specifically, preferably contains 50% by mass or more, more preferably contains 80% or more, and contains 95% or more. Is more preferable. Of course, it may be 100%.

  The cellulose acylate preferably further has an aliphatic acyl group (hereinafter also referred to as substituent B) together with an acyl group containing an aromatic group (hereinafter also referred to as substituent A). That is, it is preferable that DSA <DS. By having an aliphatic alkyl group, particularly an aliphatic alkyl group having a small number of carbon atoms, an appropriate strength as a film can be obtained without reducing Tg, elastic modulus and the like. The substitution degree DSB of the substituent B is not particularly limited as long as DSA and DS satisfy the above formulas (I) and (II). It is preferably 0 or more and less than 1.1, and more preferably 0.1 to 1.0.

In the present invention, the degree of substitution of the substituent is determined by ¹ H-NMR or ¹³ C-NMR using the method described in Cellulose Communication 6, 73-79 (1999) and Chirality 12 (9), 670-674. Can be determined.

(Acyl group containing aromatic group (Substituent A))
In the present invention, the acyl group containing an aromatic group (substituent A) may be directly bonded to the ester bond or may be bonded via a linking group. Direct bonding is preferred. Here, the linking group represents an alkylene group, an alkenylene group, or an alkynylene group, and the linking group may have a substituent. The linking group is preferably an alkylene group having 1 to 10 atoms, an alkenylene group and an alkynylene group, more preferably an alkylene group having 1 to 6 atoms and an alkenylene group, and particularly preferably an alkylene and alkenylene group having 1 to 4 atoms. It is.

  The aromatic may have a substituent, and the substituent substituted by the aromatic and the substituent substituted by the above-described linking group may be, for example, an alkyl group (preferably having 1 to 20 carbon atoms, Preferably it is 1-12, particularly preferably 1-8, such as methyl, ethyl, propyl, isopropyl, tert-butyl, n-butyl, n-octyl, n-decyl, n-hexadecyl group, cyclopropyl group, cyclopentyl, cyclohexyl group and the like), alkenyl group (preferably 2-20 carbon atoms, more preferably 2-12, particularly preferably 2-8, for example, vinyl group , An allyl group, a 2-butenyl group, a 3-pentenyl group, etc.), an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8, for example, a propargyl group, a 3-pentynyl group, etc., an aryl group (preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, For example, a phenyl group, a biphenyl group, a naphthyl group, etc. are mentioned), an amino group (preferably 0-20 carbon atoms, more preferably 0-10, particularly preferably 0-6, for example, an amino group, a methylamino group. , A dimethylamino group, a diethylamino group, a dibenzylamino group, etc.), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12, particularly preferably 1 to 8, such as a methoxy group, Ethoxy group, butoxy group and the like), aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms) Preferably they are 6-12, for example, a phenyloxy group, 2-naphthyloxy group etc. are mentioned, An acyl group (preferably 1-20 carbon atoms, More preferably, it is 1-16, Most preferably, it is 1-12. For example, an acetyl group, a benzoyl group, a formyl group, a pivaloyl group, etc.), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, A methoxycarbonyl group, an ethoxycarbonyl group, etc.), an aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms such as a phenyloxycarbonyl group). An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 1). 6, particularly preferably 2 to 10, and examples thereof include an acetoxy group and a benzoyloxy group), an acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms). For example, an acetylamino group, a benzoylamino group, etc.), an alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, for example, methoxycarbonylamino Group), aryloxycarbonylamino group (preferably having 7 to 20, more preferably 7 to 16, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino group), Sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 1 In particular, the number is 1 to 12, and examples thereof include a methanesulfonylamino group and a benzenesulfonylamino group), a sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16, and particularly preferably 0 to 0). 12, for example, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group and the like), carbamoyl group (preferably 1-20 carbon atoms, more preferably 1-16, Particularly preferably 1 to 12, for example, carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group and the like, alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly Preferably it is 1-12, for example methylthio group, ethyl Thio group, etc.), arylthio group (preferably 6-20 carbon atoms, more preferably 6-16, particularly preferably 6-12, such as phenylthio group), sulfonyl group (preferably The number of carbon atoms is 1 to 20, more preferably 1 to 16, particularly preferably 1 to 12, and examples thereof include a mesyl group and a tosyl group. A sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, for example, methanesulfinyl group, benzenesulfinyl group, etc.), ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 and particularly preferably 1). -12, for example, ureido group, methylureido group, phenylureido group etc.), phosphoric acid amide group (preferably Preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as diethyl phosphoric acid amide and phenyl phosphoric acid amide), hydroxy group, mercapto group, halogen atom (For example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 carbon atom) -30, more preferably 1-12. Examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a piperidyl group, a morpholino group, Benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, etc.), silyl group (preferred Is from 3 to 40 carbon atoms, more preferably 3 to 30, particularly preferably 3 to 24, e.g., a trimethylsilyl group, etc. triphenylsilyl group), and the like. These substituents may be further substituted. 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.

Aromatic is defined as an aromatic compound in the physics and chemistry dictionary (Iwanami Shoten) 4th edition, page 1208, and the aromatic group in the present invention may be an aromatic hydrocarbon group or an aromatic heterocyclic group, more preferably It is an aromatic hydrocarbon group.
The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, and most preferably 6 to 10 carbon atoms. Specific examples of the aromatic hydrocarbon group include, for example, a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a terphenyl group, a benzoyl group, more preferably a benzoyl group and a phenyl group, and still more preferably It is a benzoyl group. As the aromatic heterocyclic group, those containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom are preferable. Specific examples of the heterocycle include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline. , Isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene and the like. As the aromatic heterocyclic group, a pyridyl group, a triazinyl group, and a quinolyl group are particularly preferable.

  Preferred examples of the acyl group containing an aromatic group (substituent A) include phenylacetyl group, hydrocinnamoyl group, diphenylacetyl group, phenoxyacetyl group, benzyloxyacetyl group, O-acetylmandelyl group, and 3-methoxyphenylacetyl group. Group, 4-methoxyphenylacetyl group, 2,5-dimethoxyphenylacetyl group, 3,4-dimethoxyphenylacetyl group, 9-fluorenylmethylacetyl group, cinnamoyl group, 4-methoxy-cinnamoyl group, benzoyl group, ortho -Toluoyl group, meta-toluoyl group, para-toluoyl group, m-anisoyl group, p-anisoyl group, phenylbenzoyl group, 4-ethylbenzoyl group, 4-propylbenzoyl group, 4-t-butylbenzoyl group, 4- Butylbenzoyl group, 4-pentylbenzoy Group, 4-hexylbenzoyl group, 4-heptylbenzoyl group, 4-octylbenzoyl group, 4-vinylbenzoyl group, 4-ethoxybenzoyl group, 4-butoxybenzoyl group, 4-hexyloxybenzoyl group, 4-heptyloxy Benzoyl, 4-pentyloxybenzoyl, 4-octyloxybenzoyl, 4-nonyloxybenzoyl, 4-decyloxybenzoyl, 4-undecyloxybenzoyl, 4-dodecyloxybenzoyl, 4-isopropoxy Benzoyl group, 2,3-dimethoxybenzoyl group, 2,5-dimethoxybenzoyl group, 3,4-dimethoxybenzoyl group, 2,6-dimethoxybenzoyl group, 2,4-dimethoxybenzoyl group, 3,5-dimethoxybenzoyl group 3,4,5-trimethoxybenzoyl group, 2, , 5-trimethoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, 2-biphenylcarbonyl group, 4-biphenylcarbonyl group, 4′-ethyl-4-biphenylcarbonyl group, 4′-octyloxy-4-biphenylcarbonyl Group, piperonylyl group, diphenylacetyl group, triphenylacetyl group, phenylpropionyl group, hydrocinnamoyl group, α-methylhydrocinnamoyl group, 2,2-diphenylpropionyl group, 3,3-diphenylpropionyl group, 3,3 , 3-triphenylpropionyl group, 2-phenylbutyryl group, 3-phenylbutyryl group, 4-phenylbutyryl group, 5-phenylvaleryl group, 3-methyl-2-phenylvaleryl group, 6-phenyl Hexanoyl group, α-methoxyphenylacetyl group, phenoxyacetate Til group, 3-phenoxypropionyl group, 2-phenoxypropionyl group, 11-phenoxydecanoyl group, 2-phenoxybutyryl group, 2-methoxyacetyl group, 3- (2-methoxyphenyl) propionyl group, 3- (p -Toluyl) propionyl group, (4-methylphenoxy) acetyl group, 4-isobutyl-α-methylphenylacetyl group, 4- (4-methoxyphenyl) butyryl group, (2,4-di-t-pentylphenoxy)- Acetyl group, 4- (2,4-di-t-pentylphenoxy) -butyryl group, (3,4-dimethoxyphenyl) acetyl group, 3,4- (methylenedioxy) phenylacetyl group, 3- (3 4-dimethoxyphenyl) propionyl group, 4- (3,4-dimethoxyphenyl) butyryl group, (2,5-dimethoxyphenyl) Nyl) acetyl group, (3,5-dimethoxyphenyl) acetyl group, 3,4,5-trimethoxyphenylacetyl group, 3- (3,4,5-trimethoxyphenyl) -propionyl group, acetyl group, 1- Naphthylacetyl group, 2-naphthylacetyl group, α-trityl-2-naphthalene-propionyl group, (1-naphthoxy) acetyl group, (2-naphthoxy) acetyl group, 6-methoxy-α-methyl-2-naphthaleneacetyl group 9-fluoreneacetyl group, 1-pyreneacetyl group, 1-pyrenebutyryl group, γ-oxo-pyrenebutyryl group, styreneacetyl group, α-methylcinnamoyl group, α-phenylcinnamoyl group, 2-methylcinnamoyl group, 2-methoxycinnamoyl group, 3-methoxycinnamoyl group, 2,3-dimethoxycinnamoyl group 2,4-dimethoxycinnamoyl group, 2,5-dimethoxycinnamoyl group, 3,4-dimethoxycinnamoyl group, 3,5-dimethoxycinnamoyl group, 3,4- (methylenedioxy) cinnamoyl group, 3, 4,5-trimethoxycinnamoyl group, 2,4,5-trimethoxycinnamoyl group, 3-methylidene-2-carbonyl group, 4- (2-cyclohexyloxy) benzoyl group, 2,3-dimethylbenzoyl group, 2,6-dimethylbenzoyl group, 2,4-dimethylbenzoyl group, 2,5-dimethylbenzoyl group, 3-methoxy-4-methylbenzoyl group, 3,4-diethoxybenzoyl group, α-phenyl-o-toluyl Group, 2-phenoxybenzoyl group, 2-benzoylbenzoyl group, 3-benzoylbenzoyl group, 4-benzoylbenzoyl , 2-ethoxy-1-naphthoyl group, 9-fluorene group, 1-fluorene group, 4-fluorene group, 9-anthracene group, such as 1-pyrene carbonyl group.

  More preferably, the substituent A is phenylacetyl, hydrocinnamoyl, diphenylacetyl, phenoxyacetyl, benzyloxyacetyl, O-acetylmandelyl, 3-methoxyphenylacetyl, 4-methoxyphenylacetyl. Group, 2,5-dimethoxyphenylacetyl group, 3,4-dimethoxyphenylacetyl group, 9-fluorenylmethylacetyl group, cinnamoyl group, 4-methoxy-cinnamoyl group, benzoyl group, ortho-toluoyl group, meta-toluoyl Group, para-toluoyl group, m-anisoyl group, p-anisoyl group, phenylbenzoyl group, 4-ethylbenzoyl group, 4-propylbenzoyl group, 4-t-butylbenzoyl group, 4-butylbenzoyl group, 4-pentyl Benzoyl group, 4-hexylbenzo Group, 4-heptylbenzoyl group, 4-octylbenzoyl group, 4-vinylbenzoyl group, 4-ethoxybenzoyl group, 4-butoxybenzoyl group, 4-hexyloxybenzoyl group, 4-heptyloxybenzoyl group, 4- Pentyloxybenzoyl group, 4-octyloxybenzoyl group, 4-nonyloxybenzoyl group, 4-decyloxybenzoyl group, 4-undecyloxybenzoyl group, 4-dodecyloxybenzoyl group, 4-isopropyloxybenzoyl group, 2, 3-dimethoxybenzoyl group, 2,5-dimethoxybenzoyl group, 3,4-dimethoxybenzoyl group, 2,6-dimethoxybenzoyl group, 2,4-dimethoxybenzoyl group, 3,5-dimethoxybenzoyl group, 2,4,4 5-trimethoxybenzoyl group, 3,4,5-trimethoxyben Yl group, a 1-naphthoyl group, 2-naphthoyl group, 2-biphenyl group, 4-biphenylcarbonyl group, or 4'-ethyl-4-biphenylcarbonyl group, 4'-octyloxy-4-biphenyl group.

  More preferably, the substituent A is a phenylacetyl group, a diphenylacetyl group, a phenoxyacetyl group, a cinnamoyl group, a 4-methoxy-cinnamoyl group, a benzoyl group, a phenylbenzoyl group, a 4-ethylbenzoyl group, a 4-propylbenzoyl group, 4-t-butylbenzoyl group, 4-butylbenzoyl group, 4-pentylbenzoyl group, 4-hexylbenzoyl group, 4-heptylbenzoyl group, 3,4-dimethoxybenzoyl group, 2,6-dimethoxybenzoyl group, 2, 4-dimethoxybenzoyl group, 3,5-dimethoxybenzoyl group, 3,4,5-trimethoxybenzoyl group, 2,4,5-trimethoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, 2-biphenylcarbonyl Group, or 4-biphenylcarbonyl group.

More preferably, the substituent A is a benzoyl group, a phenylbenzoyl group, a 4-heptylbenzoyl group, a 2,4,5-trimethoxybenzoyl group, or a 3,4,5-trimethoxybenzoyl group, particularly preferably. It is a benzoyl group.
The substituent A possessed by the cellulose acylate may be one type or two or more types.

(Aliphatic acyl group (substituent B))
The aliphatic acyl group (substituent B) may be a linear, branched or cyclic aliphatic acyl group, or may be an aliphatic acyl group containing an unsaturated bond. The aliphatic acyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and still more preferably 2 to 4 carbon atoms. Preferable examples of the substituent B are an acetyl group, a propionyl group, and a butyryl group, and among them, an acetyl group is preferable.
In the present invention, cellulose acylate containing no aliphatic acyl group can be used as in the case of DSA = DS.

  Although there is no restriction | limiting in particular about the viscosity average polymerization degree of a cellulose acylate, 80-700 are preferable, 90-500 are still more preferable, 100-500 are still more preferable. By setting the average degree of polymerization to 500 or less, the viscosity of the cellulose acylate dope solution does not become too high, and the film production by casting tends to be easy. Moreover, it is preferable for the degree of polymerization to be 140 or more because the strength of the produced film tends to be further improved. The average degree of polymerization can be measured by the intrinsic viscosity method of Uda et al. (Kazuo Uda, Hideo Saito, “Journal of the Textile Society”, Vol. 18, No. 1, pages 105-120, 1962). Specifically, it can be measured according to the method described in JP-A-9-95538.

The cellulose acylate composition can take various shapes such as particles, powders, fibers, lumps, solutions, and melts.
Since the raw material for film production is preferably in the form of particles or powder, the cellulose acylate composition after drying is pulverized and sieved in order to make the particle size uniform and improve handleability. Also good.

  In the present invention, only one type of cellulose acylate may be used, or two or more types may be mixed and used. In addition, polymer components other than cellulose acylate and various additives can be appropriately mixed. The component to be mixed is preferably one having excellent compatibility with cellulose acylate, and the transmittance when formed into a film is preferably 80% or more, more preferably 90% or more, and particularly preferably 92% or more. It is preferable.

  In the present invention, the cellulose acylate is added with various additives that can generally be added to the cellulose acylate (for example, UV inhibitors, plasticizers, deterioration inhibitors, fine particles, optical property modifiers, etc.) It can be. Moreover, the addition time of the additive to the cellulose acylate may be added in any of the dope preparation steps, and these additives may be added as a preparation step at the end of the dope preparation step.

  The cellulose acylate can achieve a low Rth without adding an Rth reducing agent, but an additive that contributes to a low Rth may be added. Examples of additives that can be added include high molecular weight additives. The high molecular weight additive is one having a repeating unit in the compound. In general, it may be a compound classified as an oligomer. The high molecular weight additive is used in the solution casting method to increase the volatilization rate of the solvent or reduce the residual solvent amount. Also in a film formed by the melt film forming method, the high molecular weight additive is a useful material for preventing coloring and film strength deterioration. Furthermore, the addition of the high molecular weight additive to cellulose acylate has a useful effect from the viewpoint of film modification such as improvement of mechanical properties, imparting flexibility, imparting water absorption resistance, and reducing moisture permeability.

The high molecular weight additive is selected from polyester polymers, styrene polymers and acrylic polymers and copolymers thereof, and is preferably aliphatic polyester, aromatic polyester, acrylic polymer and styrene polymer.
These can be referred to the descriptions of [0031] to [0048] of JP-A-2009-263619, and the high molecular weight additives described therein can be preferably used.

  Although the manufacturing method of the cellulose acylate film in the manufacturing method of the phase difference plate of this invention is not specifically limited, It is preferable to manufacture by the solvent cast method. About the manufacture example of the cellulose acylate film using a solvent cast method, U.S. Pat. Nos. 2,336,310, 2,367,603, 2,492,078, 2,492,977, 2,492,978, 2,607,704, 2,739,069 and 2,739,070, British Patent Nos. 640731 and 736892, JP-B Nos. 45-4554, 49-5614, JP-A-60-176834, JP-A-60-203430, and JP-A-62-115035 can be referred to.

Rth of the cellulose acylate film used as the transparent support can be adjusted by the film thickness and DSA. In addition, Rth can be made more negative by stretching, but since the absolute value of Re increases, the stretching ratio is preferably 0 to 15%, more preferably 0 to 10%, and an unstretched film that is not stretched. More preferably it is. Here, “does not perform stretching” means that intentional stretching is not performed, and does not include stretching that occurs unintentionally due to a transport process or the like.
With respect to the stretching method and conditions, for example, refer to JP-A-62-115035, JP-A-4-152125, 4-284221, 4-298310, and 11-48271. can do. The stretching direction of the cellulose acylate film may be either the film transport direction (longitudinal direction) or the direction (transverse direction) orthogonal to the transport direction.

  The film thickness may be adjusted by adjusting the solid content concentration contained in the dope, the slit gap of the die base, the extrusion pressure from the die, the metal support speed, and the like so as to obtain a desired thickness.

  The in-plane slow axis of the cellulose acylate film may be either the film transport direction or the direction orthogonal to the transport direction.

  Further, the variation in the Rth (550) value in the film transport direction is preferably ± 10 nm, and more preferably ± 5 nm. Also, the variation in the Rth value in the length direction is preferably within the range of the variation in the width direction.

[Haze of cellulose acylate film]
The cellulose acylate film used for the transparent support preferably has a value measured using, for example, a haze meter (1001DP type, manufactured by Nippon Denshoku Industries Co., Ltd.) of 0.01 or more and 0.8 or less. It is more preferably 0.02 or more and 0.7 or less, and particularly preferably 0.05 or more and 0.60 or less. By controlling the haze within the above range, a high-contrast image can be obtained when incorporated in an image display device as a retardation plate.

[Photoelastic coefficient of cellulose acylate film]
The cellulose acylate film used for the transparent support may change its birefringence (Re, Rth) due to the stress due to stretching and shrinkage due to moisture absorption. The change in birefringence due to such stress can be measured as a photoelastic coefficient, and the range is preferably 5 × 10 ⁻⁷ (cm ² / kgf) to 30 × 10 ⁻⁷ (cm ² / kgf), and 6 × 10 ⁻⁷ (cm ² / kgf) to 25 × 10 ⁻⁷ (cm ² / kgf) is more preferable, and 7 × 10 ⁻⁷ (cm ² / kgf) to 20 × 10 ⁻⁷ (cm ² / kgf) It is particularly preferred.

[Glass transition temperature of cellulose acylate film]
The glass transition temperature of the cellulose acylate film was measured by the DMA method. Specifically, the test piece is heated from room temperature at a rate of 5 ° C./min, the dynamic viscoelasticity and tan δ of the test piece are measured with a viscoelasticity measuring device, and the glass transition temperature is obtained from the peak temperature of tan δ. It was.
The glass transition temperature of the cellulose acylate film used for the support is preferably from 80 to 300 ° C, more preferably from 100 to 250 ° C. The glass transition temperature can be lowered by including a low molecular compound such as a plasticizer or a solvent.

The cellulose acylate contained as a main component in the cellulose acylate film used for the transparent support has high adhesion to a polarizing film mainly composed of hydrophilic polyvinyl alcohol (PVA), and does not cause problems such as peeling. Specifically, a laminate sample obtained by laminating the phase difference plate of the present invention having the cellulose acylate film of the present invention and a polyvinyl alcohol film is prepared, and the PVA residual ratio in the cross-cut test is 85% or more. Preferably, it is 90% or more, more preferably 95% or more, and most preferably the residual rate is 100%, that is, the state where PVA does not peel at all.
The cross-cut test can be performed according to JIS K5600-5-6, Section 6. For the preparation of the sample, a polyvinyl alcohol adhesive such as polyvinyl alcohol or polyvinyl butyral, a vinyl latex such as butyl acrylate, or the like can be used.

  The film thickness of the transparent support is preferably 20 to 60 μm, more preferably 20 to 50 μm, and further preferably 25 to 40 μm. When the film thickness exceeds 60 μm, the film thickness of the retardation plate of the present invention becomes too thick, and when it is less than 20 μm, wrinkles are likely to occur during handling.

式中、Ａ¹及びＡ²は各々独立に、−Ｏ−、−ＮＲ−（Ｒは水素原子または置換基を表す。）、−Ｓ−及び−ＣＯ−からなる群から選ばれる基を表す。Ｚは、第１４〜１６族の非金属原子からなる群から選択される１つ又は２つの原子を表し、式中の２つの炭素原子と共に５又は６員環を形成する。Ｂ、Ｒ¹は各々独立に置換基を表し、Ｒ²は二価の連結基を表す。複数のＢ及びＲ²は同一でも異なっていてもよい。ｍは０〜４の整数である。Ｌ¹及びＬ²は各々独立に二価の連結基を表す。Ｒ⁴及びＲ⁵は各々独立に置換基を表す。なお、
重合性基を有する場合、Ｂ、Ｒ、Ｒ¹、Ｒ²、Ｒ⁴、及びＲ⁵の少なくとも１つが、重合性基を含む。ｎは１〜１０の整数である。<< Optically anisotropic layer >>
The optically anisotropic layer used in the retardation plate of the present invention has a liquid crystal compound having optical characteristics satisfying the relationships of the above formulas (1) to (4) and preferably having reverse wavelength dispersion. The liquid crystal compound used for the optically anisotropic layer is not particularly limited as long as it is a reverse wavelength dispersible liquid crystal compound, but a preferred example is a compound represented by the following general formula (1).

In the formula, 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—. Z represents one or two atoms selected from the group consisting of non-metal atoms of Groups 14 to 16 and forms a 5- or 6-membered ring with the two carbon atoms in the formula. B and R ¹ each independently represent a substituent, and R ² represents a divalent linking group. A plurality of B and R ² may be the same or different. m is an integer of 0-4. L ¹ and L ² each independently represent a divalent linking group. R ⁴ and R ⁵ each independently represents a substituent. In addition,
When it has a polymerizable group, at least one of B, R, R ¹ , R ² , R ⁴ , and R ⁵ contains a polymerizable group. n is an integer of 1-10.

Examples of the divalent linking group L ¹ and L ² represent, but are not particularly limited, preferably include the following examples. In addition, regarding the bonding position, the bonding position of the 5- to 6-membered ring formed by Z and C—C═C—C or C═C—C═C is on the left side of the linking group exemplified below. Shall.

The divalent linking group represented by R ² include, but are not particularly limited, include those shown below. Several R < ² > may mutually be same or different. The dotted line represents a bond with L ¹ or L ^2.

Z represents one or two atoms selected from the group consisting of non-metal atoms of Groups 14 to 16, and is 5 or together with C—C═C—C or C═C—C═C described in the formula A 6-membered ring is formed. Although it does not specifically limit as a 5-6 membered ring formed by Z and C-C = C-C or C = C-C = C, The following example is mentioned suitably. In the following example, the dotted line represents binding to L ¹ or L ² .

The ring formed by Z and C—C═C—C or C═C—C═C is preferably a 6-membered ring. By using a 6-membered ring, it becomes possible to align with a higher degree of alignment order. For the same reason, it is preferably an aromatic ring, more preferably an aromatic ring and a 6-membered ring.
From these viewpoints and synthetic viewpoints, the ring formed by Z and C—C═C—C or C═C—C═C is preferably a thiophene ring, a benzene ring, or a pyridine ring, and the benzene ring is most preferred. preferable.

R ¹ represents a substituent, and when a plurality of R ¹ are present, they may be the same or different and may form a ring. Examples of the substituent include the substituents exemplified in the substituent group A.

Substituent group A:
A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably a linear, branched or unsubstituted alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl group) , Cyclopentyl group, 4-n-dodecylcyclohexyl group), bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. Monovalent groups removed, for example, bicyclo [1,2,2] heptan-2-yl group, bicyclo [2 2,2] octan-3-yl group),

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 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. A bicyclo [2,2,1] hept-2-en-1-yl group, a bicyclo [2,2,2] oct-2-en-4-yl group), Rukiniru 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 a phenyl group, a p-tolyl group, a naphthyl group), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic group A monovalent group obtained by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Alkoxy groups such as methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, n-octyloxy group, 2-methoxyethoxy group), aryloxy (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-tetradecanoylamino group. Phenoxy group),

A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy group or tert-butyldimethylsilyloxy group), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocycle having 2 to 30 carbon atoms) 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 Or substitution of 1 to 30 carbon atoms Is an unsubstituted carbamoyloxy group, 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, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n- Octylcarbonyloxy group), aryloxycarbonyloxy group (preferably substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group) , P-n-hexadecyloxycarbonyl phenoxycarbonyl 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 acid having 1 to 30 carbon atoms) Carbonylamino group, for example, carbamoylamino group, N, N-dimethylamino Sulfonylamino 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, ethoxycarbonyl) Amino group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group), aryloxycarbonylamino group (preferably substituted or unsubstituted aryloxy having 7 to 30 carbon atoms) Carbonylamino group, for example, phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group),

Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn-octylamino Sulfonylamino group), alkyl or arylsulfonylamino group (preferably substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, for example, methylsulfonyl An amino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, a p-methylphenylsulfonylamino group, a mercapto group, and an alkylthio group (preferably a substituent having 1 to 30 carbon atoms) Or an unsubstituted alkylthio group such as meth Thio group, ethylthio group, n-hexadecylthio group), arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group), A heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, 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 or arylsulfinyl group (preferably having 1 to 30 carbon atoms substituted or Unsubstituted 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 or arylsulfonyl group ( Preferably, the device having 1 to 30 carbon atoms A substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, a p-methylphenylsulfonyl group),

An acyl group (preferably a formyl group, 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 or a pivaloylbenzoyl group), Aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, p-tert-butylphenoxy Carbonyl group), alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, n-octadecyloxycarbonyl group), carbamoyl Base Preferably, the 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),

An aryl or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as a phenylazo group, a p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide group, N-phthalimide group), phosphino group (preferably substituted or non-substituted having 2 to 30 carbon atoms) Substituted phosphino groups such as dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group), phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms such as phosphinyl group, dioctyl Oxyphosphinyl group, diethoxyphosphinyl group), phosphinyloxy group (preferred Is a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group or a dioctyloxyphosphinyloxy group, or a phosphinylamino group (preferably having 2 carbon atoms). -30 substituted or unsubstituted phosphinylamino groups such as dimethoxyphosphinylamino group and dimethylaminophosphinylamino group, silyl groups (preferably substituted or unsubstituted silyl having 3 to 30 carbon atoms) Group, for example, trimethylsilyl group, tert-butyldimethylsilyl group, 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. Specific examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

m represents the number of substitutions of R ¹ , and the possible number varies depending on the ring structure formed by Z and C—C═C—C or C═C—C═C. When m is 0 at the minimum, Z represents two carbon atoms, and the ring formed by Z and C—C═C—C or C═C—C═C has no aromaticity The maximum is 4. m is preferably 0 or 1, more preferably 0.

  Each B independently represents a substituent. Examples of the substituent include the substituents exemplified in the above substituent group A, and preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group, and an alkynyl group.

A ¹ and A ² each independently represent a group selected from the group consisting of —O—, —NR— (wherein R is a hydrogen atom or a substituent), —S—, and —CO—. Preferably -O-, -NR- (R represents a hydrogen atom or a substituent, and examples include those of the above-mentioned substituent group A, preferably an alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. An alkoxy group, an alkenyl group, and an alkynyl group, which may be linked to a polymerizable group via L ¹ or L ² ) or —S—.

R ⁴ and R ⁵ each independently represents a substituent. Examples of the substituent group A are given as examples. Preferably, R ⁴ and at least one preferably substituent constant sigma _p value of Hammett is greater than zero electron withdrawing group, sigma _p value of the electron-withdrawing 0 to 1.5 of R ⁵ More preferably, it has the following substituent. 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 be bonded to form a ring.
As for Hammett's substituent constants σ _p and σ _m , 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) Yes.

  n is an integer of 1 to 10, preferably an integer of 2 to 10, and particularly preferably an integer of 2 to 5.

It is preferable that at least one of B, R, R ¹ , R ² , R ⁴ and R ⁵ is substituted with a polymerizable group. Preferably 1-6, more preferably 1-4, most preferably 1-3 are substituted. The substituent that the polymerizable group preferably substitutes is B.

  The polymerizable group is preferably a group capable of addition polymerization reaction or condensation polymerization reaction. Such a polymerizable group is preferably a polymerizable ethylenically unsaturated group or a ring-opening polymerizable group. 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.
The polymerizable group is preferably a group represented by any of the following general formulas P1, P2, P3 or P4.

（式中、Ｒ⁵¹¹、Ｒ⁵¹²、Ｒ⁵¹³、Ｒ⁵²¹、Ｒ⁵²²、Ｒ⁵²³、Ｒ⁵³¹、Ｒ⁵³²、Ｒ⁵³³、Ｒ⁵⁴¹、Ｒ⁵⁴²、Ｒ⁵⁴³、Ｒ⁵⁴⁴及びＲ⁵⁴⁵はそれぞれ各々独立に水素原子またはアルキル基を表す。ｎ⁵は０または１を表す。）

(In the formula, R ⁵¹¹ , R ⁵¹² , R ⁵¹³ , R ⁵²¹ , R ⁵²² , R ⁵²³ , R ⁵³¹ , R ⁵³² , R ⁵³³ , R ⁵⁴¹ , R ⁵⁴² , R ⁵⁴³ , R ⁵⁴⁴ and R ⁵⁴⁵ are each independently Represents a hydrogen atom or an alkyl group, and n ⁵ represents 0 or 1.)

R ⁵¹¹ , R ⁵¹² , R ⁵¹³ , R ⁵²¹ , R ⁵²² , R ⁵²³ , R ⁵³¹ , R ⁵³² , R ⁵³³ , R ⁵⁴¹ , R ⁵⁴² ,
R ⁵⁴³ , R ⁵⁴⁴ and R ⁵⁴⁵ each independently represent a hydrogen atom or an alkyl group. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, and nonyl. Lower alkyl groups such as methyl and ethyl are preferable, and methyl is more preferable.

In the general formula (1), A ¹ , A ² , B, L ¹ , L ² , R ¹ , R ² , R ⁴ , R ⁵ , n, m, and P1 to P4 are disclosed in JP 2010-84032 A. In the paragraphs 0021 to 0066, the preferable range is also the same. These contents are incorporated herein.

Specific examples of the compound represented by the general formula (1) include specific examples described in paragraphs 0067 to 0071 of JP2010-84032A, and specific examples described in paragraphs 0080 to 0100 of JP2011-6360A. In addition to the examples, the following compounds may be mentioned, but the present invention is not limited by the following specific examples.

式（２−１）中、Ｑ¹は、−Ｓ−、−Ｏ−、又は−ＮＲ１−を表す。Ｒ１は、水素原子又は炭素数１〜６のアルキル基を表す。
Ｙ¹は、炭素数６〜１２の芳香族炭化水素基、又は、炭素数３〜１２の芳香族複素環基を表す。
Ｚ¹およびＺ²は、それぞれ独立に、水素原子又は炭素数１〜２０の脂肪族炭化水素基、炭素数３〜２０の脂環式炭化水素基、１価の炭素数６〜２０の芳香族炭化水素基、ハロゲン原子、シアノ基、ニトロ基、−ＮＲ²Ｒ³又は−ＳＲ²を表し、Ｚ¹及びＺ²は、互いに結合して芳香環又は芳香族複素環を形成してもよい。Ｒ²及びＲ³は、それぞれ独立に水素原子又は炭素数１〜６のアルキル基を表す。
式（２−２）及び（２−３）中、Ａｘは芳香族炭化水素環及び芳香族複素環からなる群から選ばれる少なくとも一つの芳香環を有する、炭素数２〜３０の有機基を表し、Ａｙは水素原子、置換基を有していてもよい炭素数１〜６のアルキル基、又は、芳香族炭化水素環及び芳香族複素環からなる群から選ばれる少なくとも一つの芳香環を有する、炭素数２〜３０の有機基を表し、Ａｘ及びＡｙが有する芳香環は置換基を有していてもよい。また、ＡｘとＡｙは互いに結合して、環を形成していてもよい。
Ｚ¹、Ｚ²、Ｚ³はそれぞれ独立に、水素原子又は置換基を表す。
Ｑ²は、水素原子、又は、置換基を有していてもよい炭素数１〜６のアルキル基を表す。As the reverse wavelength dispersion liquid crystal compound, a compound represented by the following general formula (2) is also preferable.
General formula (2):
L1-G1-D1-Ar-D2-G2-L2
In the formula, Ar represents a divalent aromatic ring group represented by the following general formula (2-1), (2-2), or (2-3), and D1 and D2 are each independently -CO. -O -, - O-CO - , - C (= S) O -, - O-C (= S) -, - CR 1 R 2 -, - CR 1 R 2 -CR 3 R 4 -, - O ^{-CR 1 R 2 -, - CR} 1 R 2 -O -, - CR 1 R 2 -O-CR 3 R 4 -, - CR 1 R 2 -O-CO -, - O-CO-CR 1 R 2 ^{-, - CR 1 R 2 -O} -CO-CR 3 R 4 -, - CR 1 R 2 -CO-O-CR 3 R 4 -, - NR 1 -CR 2 R 3 -, - CR 1 R 2 - NR ³ —, —CO—NR ¹ —, or —NR ¹ —CO—, wherein R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 4 and G1 and G2 are each independently German Represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and the methylene group contained in the alicyclic hydrocarbon group is: -O-, -S-, -NH-, -N (R)-may be substituted, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and L1 and L2 each independently represents 1 Represents a monovalent organic group, and at least one selected from the group consisting of L1 and L2 represents a monovalent group having a polymerizable group.

In formula (2-1), Q ¹ represents —S—, —O—, or —NR ¹ —. R1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Y ¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms.
Z ¹ and Z ² are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic having 6 to 20 carbon atoms. It represents a hydrocarbon group, a halogen atom, a cyano group, a nitro group, —NR ² R ³ or —SR ² , and Z ¹ and Z ² may be bonded to each other to form an aromatic ring or an aromatic heterocyclic ring. R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
In formulas (2-2) and (2-3), Ax represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. , Ay has a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, An aromatic group represented by an organic group having 2 to 30 carbon atoms and having Ax and Ay may have a substituent. Ax and Ay may be bonded to each other to form a ring.
Z ¹ , Z ² and Z ³ each independently represent a hydrogen atom or a substituent.
Q ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

D1 and D2 are each independently —CO—O—, —O—CO—, —C (═S) O—, —O—C (═S) —, —CR ¹ R ² —, —CR ^1. R ² —CR ³ R ⁴ —, —O—CR ¹ R ² —, —CR ¹ R ² —O—, —CR ¹ R ² —O—CR ³ R ⁴ —, —CR ¹ R ² —O—CO -, - O-CO-CR 1 R 2 -, - CR 1 R 2 -O-CO-CR 3 R 4 -, - CR 1 R 2 -CO-O-CR 3 R 4 -, - NR 1 -CR ² R ³ —, —CR ¹ R ² —NR ³ —, —CO—NR ¹ —, or —NR ¹ —CO—, and —O—CO—, —O—C (═S) —, —O —CR ¹ R ² —, —NR ¹ —CR ² R ³ — or —NR ¹ —CO— is preferable, and —O—CO—, —O—C (═S) —, —O—CR ¹ is more preferable. ^{R 2 -, - NR 1 -CR} 2 R 3 - or -NR ¹ -CO-, further good It is properly -O-CO -, - O- C (= S) - or -NR ¹ -CO-.

R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Are preferable, and a hydrogen atom, a methyl group, or an ethyl group is more preferable.

G1 and G2 each independently represent a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms. The methylene group contained in the alicyclic hydrocarbon group may be substituted with —O—, —S—, —NH—, or —N (R) — (R is a hydrogen atom or a carbon number of 1 to 6). Represents an alkyl group. Examples of the divalent alicyclic hydrocarbon group include a monocyclic hydrocarbon group and a bridged cyclic hydrocarbon group, and a 5-membered ring or a 6-membered ring is preferable. The alicyclic hydrocarbon group may be saturated or unsaturated, but is preferably a saturated alicyclic hydrocarbon group. The alicyclic hydrocarbon group may divalent contain a hetero atom represented by G ¹ and G ^2, for example, those represented by the formula (g-1) ~ formula (g-10).

炭素数６〜１２の２価の芳香族炭化水素基としては、１，２−フェニレン基、１，３−フェニレン基、１，４−フェニレン基、１，４−ナフチレン基、１，５−ナフチレン基、２，６−ナフチレン基等が挙げられ、１，４−フェニレン基が好ましい。

Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene. Group, a 2,6-naphthylene group, and the like, and a 1,4-phenylene group is preferable.

L1 and L2 each independently represent a monovalent organic group, and at least one selected from the group consisting of L1 and L2 represents a monovalent group having a polymerizable group.
L1 is preferably a group represented by the formula (A1), and L2 is preferably a group represented by the formula (A2).
P ¹ -F ^1- (B ¹ -A ¹ ) _k -E ^1- (A1)
P ² -F ^2- (B ² -A ² ) _l -E ^2- (A2)
Wherein (A1) and formula ^{(A2), B 1, B} 2, E 1 and E ^2, each ^{independently, -CR 11 R 12 -, -} CH 2 -CH 2 -, - O -, - S- , —CO—O—, —O—CO—O—, —CS—O—, —O—CS—O—, —CO—NR ¹¹ —, —O—CH ₂ —, —S—CH ₂ — or Represents a single bond.
A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the alicyclic hydrocarbon —CH ₂ — contained in the group may be replaced by —O—, —S— or —NH—, and —CH (—) — contained in the alicyclic hydrocarbon group represents —N (-)-May be replaced.
k and l each independently represents an integer of 0 to 3. When k is an integer of 2 or more, the plurality of B ¹ and A ¹ may be the same as or different from each other. If l is an integer of 2 or more, a plurality of B ² and A ² may be the same or different from each other.
F ¹ and F ² represents a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms.
P ¹ and P ² represent a hydrogen atom or a polymerizable group, and at least one is a polymerizable group.
R ¹¹ and R ¹² represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

The divalent alicyclic hydrocarbon group represented by A ¹ and A ² can be selected from the same range as exemplified as G ¹ and G ² , and the preferred embodiment is the same as G ¹ and G ^2. It is. In addition, the divalent aromatic hydrocarbon group represented by A ¹ and A ² may be monocyclic or polycyclic (polycyclic or condensed polycyclic in which a plurality of aromatic rings are linked by a single bond). Formula). Examples of the divalent aromatic hydrocarbon group represented by A ¹ and A ² include those represented by formula (a-1) to formula (a-8). The aromatic hydrocarbon group represented by A ¹ and A ² preferably has an axis of symmetry and a plane of symmetry.

The hydrogen atom contained in the alicyclic hydrocarbon group and aromatic hydrocarbon group represented by A ¹ and A ² may be substituted with a substituent. The substituent can be selected from the same range as exemplified as the substituent Z ² .

A ¹ and A ² are each independently preferably a monocyclic 1,4-phenylene group or cyclohexane-1,4-diyl group, and in particular, the production of the compound represented by the general formula (2) Is easily 1,4-phenylene group. Furthermore, A ¹ and A ² are preferably the same type of group because the compound represented by the general formula (2) tends to be easily produced.

B ¹ and B ² are preferably the same type of group because the compound represented by the general formula (2) tends to be easily produced. Further, when k and l are integers of 2 or more, a plurality of B ¹ and B ² are bonded to only A ¹ because the production of the compound represented by the general formula (2) becomes easier. B ¹ and B ² bonded only to A ² are each independently —CH ₂ —CH ₂ —, —CO—O—, —CO—NH—, —O—CH ₂ — or a single bond. Preferably there is. In particular, -CO-O- is preferable because it exhibits high liquid crystallinity. Further, B ¹ bonded to F ¹ and B ² bonded to F ² are each independently —O—, —CO—O—, —O—CO—O—, —CO—NH. -Or more preferably a single bond.

  It is preferable that k and l each independently represent an integer of 0 to 3, and k and l are more preferably 0 to 2. The total of k and l is preferably 5 or less, and more preferably 4 or less. When k and l are in the above ranges, the compound represented by the general formula (2) tends to exhibit liquid crystallinity.

F ¹ and F ² are preferably an alkanediyl group having 1 to 12 carbon atoms, and more preferably a linear alkanediyl group. In particular, an unsubstituted alkanediyl group is preferred. A hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom. Moreover, —CH ₂ — contained in the alkanediyl group may be substituted with —O— or —CO—.

P ¹ and P ² are a hydrogen atom or a polymerizable group, and at least one is a polymerizable group. Since the hardness of the obtained optical film tends to be excellent, it is preferable that both P ¹ and P ² are polymerizable groups.

Here, the polymerizable group means a substituent capable of polymerizing the compound represented by the general formula (2), and specifically includes a vinyl group, a vinyloxy group, a styryl group, p- (2-phenyl). Ethenyl) Phenyl group, acryloyl group, methacryloyl group, acryloyloxy group, polymerizable group having an ethylenically unsaturated group such as methacryloyloxy group, carboxy group, acetyl group, hydroxy group, carbamoyl group, having 1 to 4 carbon atoms Examples include an alkylamino group, an amino group, an oxiranyl group, an oxetanyl group, a formyl group, an isocyanato group or an isothiocyanato group.
As the polymerizable group, a radical polymerizable group and a cationic polymerizable group suitable for photopolymerization are preferable, and since they are particularly easy to handle and easy to manufacture, acryloyl group, methacryloyl group, acryloyl group An oxy group and a methacryloyloxy group are preferred. Among them, the polymerizable group is preferably each independently an acryloyloxy group or a methacryloyloxy group, and particularly preferably an acryloyloxy group.

  In the compound represented by the general formula (2), D1 and D2, G1 and G2, and L1 and L2 are the same, that is, -D1-G1-L1 and -D2-G2-L2 have the same structure. It is preferable.

In General Formula (2-1), Q ¹ represents —S—, —O—, or —NR ¹ —. R1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group. Etc. Among these, a C1-C4 alkyl group is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is especially preferable.

Y ¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms.
Examples of the aromatic hydrocarbon group represented by Y ¹ include monocyclic aromatic hydrocarbon groups such as phenyl groups; polycyclic aromatic hydrocarbon groups such as naphthyl groups, anthryl groups, phenanthryl groups, and biphenyl groups (condensation). And a polycyclic aromatic hydrocarbon group). Among these, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable. Examples of the aromatic heterocyclic group represented by Y ¹ include monocyclic aromatic heterocyclic groups such as furyl group, pyrrolyl group, thienyl group, pyridinyl group, thiazolyl group; benzothiazolyl group, benzofuryl group, benzothienyl group, etc. And aromatic heterocyclic groups containing at least one hetero atom such as a nitrogen atom, oxygen atom, sulfur atom and the like such as a polycyclic aromatic heterocyclic group (including a condensed polycyclic aromatic heterocyclic group). . Among these, a furyl group, a thienyl group, a thiazolyl group, a benzothiazolyl group, a benzofuryl group, and a benzothienyl group are preferable.

The aromatic hydrocarbon group and aromatic heterocyclic group represented by Y ¹ may have a substituent (hereinafter referred to as substituent Z ¹ ). Examples of the substituent Z ¹ include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a nitroso group, a carboxy group, an alkylsulfinyl group having 1 to 6 carbon atoms, and an alkylsulfonyl group having 1 to 6 carbon atoms. , A C1-C6 fluoroalkyl group, a C1-C6 alkoxy group, a C1-C6 alkylsulfanyl group, a C1-C6 N-alkylamino group, a C2-C12 N, Examples thereof include N-dialkylamino groups, N-alkylsulfamoyl groups having 1 to 6 carbon atoms, and N, N-dialkylsulfamoyl groups having 2 to 12 carbon atoms.

Z ¹ and Z ² are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic having 6 to 20 carbon atoms. It represents a hydrocarbon group, a halogen atom, a cyano group, a nitro group, —NR ² R ³ or —SR ² , and Z ¹ and Z ² may be bonded to each other to form an aromatic ring or an aromatic heterocyclic ring. R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Examples of the aliphatic hydrocarbon group represented by Z ¹ and Z ² include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, 1- Methylbutyl group, 3-methylbutyl group, hexyl group, 1-methylpentyl group, 4-methylpentyl group, heptyl group, 1-methylhexyl group, 5-methylhexyl group, octyl group, 1-methylheptyl group, nonyl group, Examples include 1-methyloctyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group. Among these, a C1-C12 alkyl group is preferable and a methyl group and an ethyl group are especially preferable.

Examples of the alicyclic hydrocarbon group represented by Z ¹ and Z ² include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and the like. A cyclic alkyl group having a number of 3 to 12 is preferred.

Examples of the aromatic hydrocarbon group represented by Z ¹ and Z ² include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 3-fluorenyl group. And an aromatic hydrocarbon group having 6 to 14 carbon atoms is preferred.

The aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group represented by Z ¹ and Z ² may each have a substituent. Examples of the substituent include those exemplified as the aforementioned Y ¹ .
The alkyl group having 1 to 6 carbon atoms represented by R ² and R ³ can be selected from the same groups as the above R ^1. Among them, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable. A methyl group is particularly preferred.

Z ¹ and Z ² may be bonded to each other to form an aromatic ring or an aromatic heterocyclic ring.

In General Formula (2-2) and General Formula (2-3), Ax has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and has 2 to 30 carbon atoms. Represents a group. The organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring of Ax may have a plurality of aromatic rings, It may have an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring. Examples of the aromatic heterocycle include 5-membered aromatic heterocycles such as pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring and thiazole ring; pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, etc. 6-membered aromatic heterocycles; condensed aromatic heterocycles such as benzimidazole ring, benzothiophene ring, benzoxazole ring, benzothiazole ring, carbazole ring, benzothiazoline ring; and the like.

The aromatic ring which Ax has may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom and chlorine atom; cyano group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; vinyl group; An alkenyl group having 1 to 6 carbon atoms such as a trifluoromethyl group; a substituted amino group such as an amino group, a methylamino group, a dimethylamino group, and an acetylamino group; a methoxy group, an ethoxy group, and an isopropoxy group An alkoxy group having 1 to 6 carbon atoms such as: a nitro group; an aryl group such as a phenyl group or a naphthyl group; a —C (═O) —OR group; an —SO ₂ R group; Here, R represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms.

  Further, the aromatic ring of Ax may have a plurality of the same or different substituents, and two adjacent substituents may be bonded to each other to form a ring. The ring formed may be monocyclic or condensed polycyclic.

  As the organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring of Ax, an aromatic hydrocarbon ring group; an aromatic heterocyclic group An alkyl group having 3 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring group and an aromatic heterocyclic group; consisting of an aromatic hydrocarbon ring group and an aromatic heterocyclic group An alkenyl group having 4 to 30 carbon atoms having at least one aromatic ring selected from the group; and having 4 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring group and an aromatic heterocyclic group -30 alkynyl groups; and the like.

Ay is a carbon atom having at least one aromatic ring selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an aromatic hydrocarbon ring and an aromatic heterocyclic ring. The organic group of several 2-30 is represented.
Ay is preferably a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom.

  As the alkyl group having 1 to 6 carbon atoms of the alkyl group having 1 to 6 carbon atoms which may have a substituent, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group , Sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group and the like.

Examples of the substituent of the alkyl group having 1 to 6 carbon atoms which may have a substituent of Ay include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a substituted amino group such as a dimethylamino group; a methoxy group Alkoxy groups having 1 to 6 carbon atoms such as ethoxy group and isopropoxy group; nitro group; aryl groups such as phenyl group and naphthyl group; —C (═O) —OR group; —SO ₂ R group; It is done. Here, R represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms.

  Examples of the organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle of Ay include those similar to those exemplified for Ax above. It is done.

Q ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a substituent include the same groups as those exemplified for Ax.
Among these, Q ² is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom.

Z ¹ , Z ² and Z ³ each independently represent a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified in the substituent group A.

Specific examples of the compound represented by the general formula (2) are exemplified in paragraphs 0110 to 0185 of JP201221068A, examples of WO2013 / 018526, and examples of WO2014 / 010325. In addition to the above compounds, the following compounds may be mentioned, but the present invention is not limited to these specific examples.

  Other preferable examples of the liquid crystal compound used for the optically anisotropic layer are not limited to the liquid crystal compound represented by the general formula (1) as long as the reverse wavelength dispersibility is exhibited. For example, JP 2010-52892 A No. 0195, JP 2010-522893, paragraphs 0051 to 0119, JP 2010-537954, paragraphs 0013 to 0124, JP 2010-537955, paragraphs 0013 to 0143, and JP 2010-540472. The liquid crystal compounds described in Paragraphs 0056 to 0124 of Japanese Patent Publication No. Gazette and paragraphs 0019 to 0135 of Japanese Unexamined Patent Publication No. 2012-500234 can be used, and the contents thereof are incorporated in the present specification.

The content of the liquid crystal compound (particularly the liquid crystal compound represented by the general formula (1)) in the optically anisotropic layer is not particularly defined unless departing from the gist of the present invention. 80-99.9 mass% is preferable in solid content, and 90-99.9 mass% is more preferable.

  In addition to the liquid crystal compound, the optically anisotropic layer may contain additives such as an air interface alignment controller, a repellency inhibitor, a polymerization initiator, a chiral agent, and a coating solvent. These can be referred to the descriptions in paragraphs 0095 to 0102 of JP-A-2010-84032, and additives such as air interface orientation control agents, repellency inhibitors, polymerization initiators, chiral agents and coating solvents described therein are preferably used. Can be used.

  The optically anisotropic layer preferably contains a non-liquid crystalline polymerizable monomer. The polymerizable monomer is not particularly limited as long as it has compatibility with the liquid crystal compound and does not significantly change the tilt angle or disturb the alignment of the liquid crystal compound.

  Examples of the non-liquid crystalline polymerizable monomer include monomers having 2 to 5 reactive functional groups.

  Examples of the monomer having two reactive functional groups include propanediol, butanediol, hexanediol, ethylene glycol, diethylene glycol, triethylene glycol and tetrapropylene glycol acrylate, divinyl ether or dimethacrylate.

  Examples of the monomer having three reactive functional groups include, for example, trimethylolpropane, ethoxylated trimethylolpropane having 1 to 20 ethylene oxide structural units, and propoxylated trimethylolpropane having 1 to 20 propylene oxide structural units. And an ethoxylated / propoxylated trimethylolpropane triacrylate, trivinyl ether or trimethacrylate having a total of 1 to 20 ethylene oxide structural units and propylene oxide structural units; 1 to 20 ethylene oxide structural units such as glycerin epoxy triacrylate Ethoxylated glycerin, propoxylated glycerin triacrylate, trivinyl ether or triacrylate having 1-20 propylene oxide building blocks Etc., and the like.

  Examples of monomers having four reactive functional groups include, for example, pentaerythritol tetraacrylate, ethoxylated bis-tetramethylolpropane having 1 to 20 ethylene oxide structural units, and propoxylation having 1 to 20 propylene oxide structural units. Examples include bis-trimethylolpropane and ethoxylated / propoxylated bistrimethylolpropane triacrylate, trivinyl ether, or trimethacrylate having a total of 1 to 20 ethylene oxide structural units and propylene oxide structural units.

  Examples of the monomer having 5 reactive functional groups include dipentaerythritol pentaacrylate, ethoxylated dipentaerythritol pentaacrylate having 1 to 20 ethylene oxide structural units, and propoxy having 1 to 20 propylene oxide structural units. Examples include dipentaerythritol pentaacrylate and pentaacrylate, pentavinyl ether or pentatrimethacrylate of ethoxylated / propoxylated dipentaerythritol in which the total of ethylene oxide structural units and propylene oxide structural units is 1 to 20.

  Among these, alkylene oxide-modified monomers are preferable, and by adding these, the orientation temperature can be appropriately lowered, the strength of the film can be maintained, and the orientation of the liquid crystal can be maintained. For example, modified trimethylolpropane acrylate, ethylene oxide modified trimethylolpropane acrylate, and propylene oxide modified trimethylolpropane acrylate are preferably used, and ethylene oxide modified trimethylolpropane acrylate is more preferable.

The thickness of the optically anisotropic layer is preferably 3.0 μm or more, more preferably 4.5 μm or more, further preferably 4.7 μm or more, and particularly preferably 4.9 μm or more. Moreover, 5.5 micrometers or less are preferable, 5.3 micrometers or less are more preferable, and 5.1 micrometers or less are more preferable. When the film thickness is within the above range, it has a function of a λ / 4 plate, which is preferable.
The optically anisotropic layer may be a single layer or two or more optically anisotropic layers. However, the present invention is highly significant in that the effects of the present invention can be achieved even with a single optically anisotropic layer.

<< Alignment film >>
In the retardation plate of the present invention, an alignment film may be disposed between the transparent support and the optically anisotropic layer, and a liquid crystal composition may be applied to the surface of the alignment film to align liquid crystal compound molecules. . Since the alignment film has a function of defining the alignment direction of the liquid crystalline compound, it is preferably used for realizing a preferred embodiment of the present invention.
The alignment film is preferably formed by polymer rubbing treatment. The “rubbing alignment film” that can be used in the present invention means a film that has been processed by rubbing so as to have alignment ability of liquid crystal molecules. The rubbing alignment film has an alignment axis that regulates alignment of liquid crystal molecules, and the liquid crystal molecules are aligned according to the alignment axis. The liquid crystal molecules are aligned so that the slow axis of the liquid crystal is parallel to the rubbing direction in the ultraviolet irradiation part of the alignment film, and the slow axis of the liquid crystal molecules is orthogonally aligned with the rubbing direction in the unirradiated part. Thus, the material of the alignment film, the acid generator, the liquid crystal, and the alignment control agent are selected.

The rubbing alignment film generally contains a polymer as a main component. The polymer material for alignment film is described in many documents, and many commercially available products can be obtained. The polymer material used in the present invention is preferably polyvinyl alcohol or polyimide, and derivatives thereof. In particular, modified or unmodified polyvinyl alcohol is preferred. Polyvinyl alcohols having various saponification degrees exist. In the present invention, those having a saponification degree of about 85 to 99 are preferably used. Commercial products may be used. For example, “PVA103”, “PVA203” (manufactured by Kuraray Co., Ltd.) and the like are PVA having the above saponification degree. For the rubbing alignment film, reference can be made to the modified polyvinyl alcohol described in WO01 / 88574A1, page 43, line 24 to page 49, line 8, and paragraph Nos. [0071] to [0095] of Japanese Patent No. 3907735.
The film thickness of the rubbing alignment film is preferably 0.01 to 10 μm, and more preferably 0.01 to 1 μm.

  The rubbing treatment can be generally performed by rubbing the surface of a film containing a polymer as a main component several times in a certain direction with paper or cloth. A general method of rubbing is described in, for example, “Liquid Crystal Handbook” (issued by Maruzen, October 30, 2000).

  In addition to the rubbing treatment of an organic compound (preferably a polymer), the alignment film is formed by oblique deposition of an inorganic compound, formation of a layer having a microgroove, or an organic compound (eg, a Langmuir-Blodgett method (LB film)). , Ω-tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation (preferably polarized light) is also known.

<Method of forming retardation plate>
Although the manufacturing method of the phase difference plate of the present invention is not particularly limited, it is preferable to carry out the following steps (1) to (3).
Step (1): An alignment film is provided on the transparent support.
Step (2): On the alignment film, a composition containing a liquid crystal compound is applied, and if necessary, heat treatment is performed, and the liquid crystal compound is aligned. Step (3): The liquid crystal compound is cured. Step of forming optically anisotropic layer

  Step (1) is a step of forming an alignment film on the transparent support. The alignment film is preferably formed by forming a polymer layer and then rubbing the surface to obtain an alignment film.

Step (2) is a step of applying a composition containing a liquid crystal compound on the alignment film and performing a heat treatment as necessary to align the liquid crystal compound.
The composition can be applied by a known method (eg, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method).
As the conditions for the heat treatment, an optimal temperature is appropriately selected according to the type of the liquid crystal compound to be used, but it is usually 20 to 200 ° C. (preferably 40 to 160 ° C.) for 10 to 600 seconds ( Preferably, the heat treatment is performed for 30 to 300 seconds.

Step (3) is a step of forming an optically anisotropic layer by subjecting the liquid crystal compound in the aligned state to a curing treatment.
The method of the curing treatment is not particularly limited as long as the reaction proceeds between the polymerizable groups, and examples thereof include heat treatment or light irradiation treatment (preferably ultraviolet irradiation treatment).

  In addition, the state in which the alignment state is fixed is a state in which the alignment is maintained is the most typical and preferred embodiment, but is not limited thereto. Specifically, it is usually 0 to 50 ° C. Under severe conditions, in the temperature range of −30 to 70 ° C., the immobilized composition has no fluidity, and does not cause a change in the orientation form due to an external field or an external force. This indicates a state where it can be kept stable.

<Antireflection plate>
The antireflection plate of the present invention includes the retardation plate of the present invention and a polarizing film. More specifically, as shown in an example in FIG. 2, the antireflection plate 100 includes a retardation plate 10 and a polarizing film 20. In FIG. 2, the transparent support 11 is provided on the polarizing film 20 side, but is not limited to this mode, and the optically anisotropic layer 11 may be provided on the polarizing film 20 side.
The antireflection plate of the present invention having the above configuration is used for antireflection of an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). For improving the contrast ratio of display light.
For example, the aspect which used the reflection preventing board of this invention for the light extraction surface side of an organic electroluminescent display apparatus is mentioned. In this case, external light becomes linearly polarized light by the polarizing film and then becomes circularly polarized light by passing through the retardation plate. When this is reflected by the metal electrode, the circularly polarized state is reversed, and when it passes through the phase difference plate again, it becomes linearly polarized light inclined by 90 ° from the incident time and reaches the polarizing film and is absorbed. As a result, the influence of external light can be suppressed.

The angle formed by the slow axis of the optically anisotropic layer and the absorption axis of the polarizing film is not particularly limited, and an optimal angle is appropriately adjusted according to the properties of the optically anisotropic layer.
For example, the angle formed by the slow axis direction of the optically anisotropic layer and the absorption axis direction of the polarizer layer is preferably in the range of 75 ° ± 10 °, and more preferably in the range of 75 ° ± 8 °. Preferably, the range is 75 ° ± 5 °. The above range is preferable because light leakage of reflected light can be reduced to a level where it is not visually recognized.

<< Polarizing film >>
The polarizing film (polarizer layer) may be a member having a function of converting natural light into specific linearly polarized light, and an absorptive polarizer can be used.
The type of the polarizing film is not particularly limited, and a commonly used polarizing film can be used. For example, any of an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, and a polyene-based polarizing film Can also be used. The iodine-based polarizing film and the dye-based polarizing film are generally produced by adsorbing iodine or a dichroic dye to polyvinyl alcohol and stretching it.
In addition, it is common that a polarizing film is used as a polarizing plate by which the protective film was bonded on both surfaces.

  Although the manufacturing method in particular of an antireflection plate is not restrict | limited, For example, it is preferable that the said retardation plate and polarizing film include the process of laminating | stacking continuously in a respectively elongate state. The long polarizing plate is cut according to the size of the screen of the image display device used.

The antireflection plate is not limited to the embodiment of FIG. 2 and may further include another layer.
For example, in the antireflection plate, a protective film and / or a functional layer may be disposed on the surface opposite to the surface on which the retardation film of the polarizing film is disposed.
As the protective film, it is preferable to use a cellulose ester film having high optical isotropy.
Examples of the functional layer include at least one selected from the group consisting of an antireflection layer, an antiglare layer, and a hard coat layer. A known layer material is used for these. Note that a plurality of these layers may be stacked.
For example, the antireflection layer has a simplest configuration in which only the low refractive index layer is coated on the outermost surface of the film. In order to further reduce the reflectivity, it is preferable to configure the antireflection layer by combining a high refractive index layer having a high refractive index and a low refractive index layer having a low refractive index. As a configuration example, two layers of a high refractive index layer / low refractive index layer or three layers having different refractive indexes are arranged in order from the bottom, and a medium refractive index layer (having a higher refractive index than the lower layer and a high refractive index). In some cases, a layer having a lower refractive index than a layer) / a layer having a higher refractive index / a layer having a lower refractive index are stacked in this order. Among them, from the viewpoint of durability, optical characteristics, cost, productivity, etc., it is preferable to have a medium refractive index layer / high refractive index layer / low refractive index layer in this order on the hard coat layer, for example, JP-A-8-122504. Examples include the configurations described in JP-A-8-110401, JP-A-10-300902, JP-A 2002-243906, JP-A 2000-11706, and the like. Japanese Patent Application Laid-Open No. 2008-262187 discloses an antireflection film having a three-layer structure that is excellent in robustness to film thickness fluctuations. When the antireflection film having the above three-layer structure is installed on the surface of an image display device, the average value of reflectance can be reduced to 0.5% or less, reflection can be remarkably reduced, and a three-dimensional effect can be achieved. An excellent image can be obtained. Further, each layer may be provided with other functions, for example, an antifouling low refractive index layer, an antistatic high refractive index layer, an antistatic hard coat layer, an antiglare hard coat layer, and the like. (For example, JP-A-10-206603, JP-A-2002-243906, JP-A-2007-264113, etc.) and the like.

<Organic EL (electroluminescence) display device>
The retardation plate or antireflection plate of the present invention can be used for an image display device. Examples of the image display device include an organic EL display device and a liquid crystal display device, and an organic EL display device is preferable.
The organic EL display device of the present invention has the above-described retardation plate (or antireflection plate). Usually, the antireflection plate is provided on the organic EL panel of the organic EL display device. More specifically, as shown in FIG. 3, the organic EL display device 200 includes at least an organic EL panel 30, a retardation plate 10, and a polarizing film 20.
The organic EL display device is not limited to the embodiment shown in FIG. 3, and may have a protective film and / or a functional film on the surface opposite to the surface on which the retardation film of the polarizing film is disposed.

  An organic EL panel is a member in which a plurality of organic compound thin films including a light emitting layer or a light emitting layer are formed between a pair of electrodes of an anode and a cathode. In addition to the light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer , An electron transport layer, a protective layer, etc., and each of these layers may have other functions. Various materials can be used for forming each layer.

  The anode supplies holes to a hole injection layer, a hole transport layer, a light emitting layer, and the like, and a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Is a material having a work function of 4 eV or more. Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide and indium tin oxide (ITO), metals such as gold, silver, chromium and nickel, and these metals and conductive metal oxides. Inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO, preferably conductive metals It is an oxide, and ITO is particularly preferable from the viewpoint of productivity, high conductivity, transparency, and the like. Although the film thickness of the anode can be appropriately selected depending on the material, it is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, still more preferably 100 nm to 500 nm.

  The present invention will be described more specifically with reference to the following 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 is not limited to the specific examples shown below. The “part” indicating the added amount indicates “part by weight”.

<Example 1>
1. Synthesis of Cellulose Acylate Cellulose acylate having various substitution degrees DSA and DS shown in the following table was converted into cellulose saponification described in JP 2008-163193 A [0121], and [0124] It was synthesized according to the method of aromatic acylation of cellulose acetate described in the above. In addition, all the substituent A which each synthesized cellulose acylate has is a benzoyl group.

2. Production of Cellulose Acylate Film (2-1) Preparation of Cellulose Acylate Solution Each solution of cellulose acylate synthesized above was prepared as follows.
The following raw materials were put into a mixing tank, stirred while heating, dissolved, and a solution having a cellulose acylate solution was prepared.
Cellulose acylate (substitution degree shown in Table 1) 100 parts by mass Dichloromethane 462 parts by mass

(2-2) Production of Cellulose Acylate Film The cellulose acylate solution prepared above was cast using a band casting machine. A film with a residual solvent amount of 10% by mass is peeled off from the band, sandwiched between both ends with clips, transported with a tenter while holding the width, dried, then transported with a roll group of a drying device, dried and wound. The cellulose acylate film shown in the following table was produced by winding with a take-up machine. The retardation value of the cellulose acylate film (transparent support) was measured by the above-described method. As a result, Re (550) was 0 nm and Rth (550) was -66 nm.

3. Production of Retardation Plate (3-1) Alkali Saponification Treatment The produced cellulose acylate film was passed through a dielectric heating roll having a temperature of 60 ° C., and the film surface temperature was raised to 40 ° C. An alkaline solution having the composition shown below was applied at a coating amount of 14 ml / m ² using a bar coater, and was heated for 10 seconds under a steam far infrared heater manufactured by Noritake Company Limited that was heated to 110 ° C. did. Subsequently, 3 ml / m ^{2 of} pure water was applied using the same bar coater. Then
Washing with a fountain coater and draining with an air knife were repeated three times, followed by transporting to a drying zone at 70 ° C. for 10 seconds and drying to prepare an alkali saponified cellulose acylate film (transparent support).

──────────────────────────────────
Alkaline solution composition ──────────────────────────────────
Potassium hydroxide 4.7 parts by weight Water 15.8 parts by weight Isopropanol 63.7 parts by weight Surfactant SF-1: C ₁₄ H ₂₉ O (CH ₂ CH ₂ O) ₂₀ H
1.0 part by weight Propylene glycol 14.8 parts by weight -------------------

(3-2) Preparation of transparent support with rubbing alignment film On the surface of the transparent support prepared above, a coating liquid for forming an alignment film having the following composition was continuously applied with a # 8 wire bar. did. The alignment film was formed by drying with warm air of 60 ° C. for 60 seconds and further with warm air of 100 ° C. for 120 seconds.
──────────────────────────────────
Composition of coating solution for alignment film formation ───────────────────────────────────
Polymer material for alignment film 4.0 parts by mass (PVA103, Kuraray Co., Ltd. polyvinyl alcohol)
Methanol 36 parts by mass Water 60 parts by mass──────────────────────────────────

(3-3) Preparation of optically anisotropic layer The surface of the alignment film thus prepared was continuously rubbed in the direction of 45 ° to the left with respect to the longitudinal direction of the transparent support. The following coating solution for optically anisotropic layer was applied onto the rubbing surface using a bar coater. Next, after heating and aging at a film surface temperature of 140 ° C., cooling to 100 ° C., and using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 20 mW / cm ^{2 in} the air, an ultraviolet ray dose of 200 mJ / cm ² Then, the optically anisotropic layer was formed by fixing the alignment state. In the formed optically anisotropic layer, the following liquid crystal compound 1 was horizontally aligned with the slow axis direction parallel to the rubbing direction. The retardation values at wavelengths of 450 nm, 550 nm and 650 nm of the optically anisotropic layer were measured by the method described above and were as follows. The optical anisotropic layer had a thickness of 5.0 μm. In addition, what applied the thing which does not add modified | denatured trimethylol propane acrylate as a coating liquid for optical anisotropy requires 180 degreeC for the heat aging for stabilizing orientation, and the nonuniformity resulting from a deformation | transformation of a support film is required. Since it occurred, it was not used as a sample.
Re (450): 85 nm
Re (550): 137 nm
Re (650): 148 nm
──────────────────────────────────
Composition of coating solution for optically anisotropic layer ──────────────────────────────────
Liquid crystal compound 1 100 parts by weight modified trimethylolpropane triacrylate 10 parts by weight photopolymerization initiator 3.0 parts by weight (Irgacure 819, manufactured by Ciba Specialty Chemicals)
700 parts by mass of chloroform──────────────────────────────────

4). Production of Antireflection Plate (4-1) Production of Antireflection Plate The polarizing plate is a polarizing plate having a 20 μm-thick polarizer protected only on one side with triacetylcellulose (thickness 40 μm). An anti-reflection plate (circular polarizing plate) is prepared by laminating the unprotected surface (polarized film made of stretched polyvinyl alcohol) and the optically anisotropic layer prepared above with an optically isotropic adhesive. did. At this time, the angle formed by the transmission axis of the polarizing film and the slow axis of the optically anisotropic layer was 45 °.

<Examples 2 to 5>
In the production of the optically anisotropic layer of Example 1, the bar coater was changed to adjust the thickness of the optically anisotropic layer so that Re (550) at 550 nm was 120 nm to 150 nm. According to the same procedure as in No. 1, an antireflection plate was produced.

<Example 6>
An antireflection plate was produced according to the same procedure as in Example 1 except that the liquid crystal compound 1 was changed to the following liquid crystal compound 2 in Example 1.

<Examples 7 and 8>
In Example 1, an antireflection plate was produced according to the same procedure as in Example 1 except that the transparent support was stretched and adjusted so that Re (550) was −10 nm ≦ Re (550) ≦ 10 nm.

<Examples 9 to 12>
According to the same procedure as in Example 1, except that cellulose acetate benzoate contained in the transparent support was different in Bz substitution degree DSA and was adjusted so that the Rth (550) of the transparent support was −100 to −20 nm. Then, an antireflection plate was produced.

<Examples 13 to 16>
An antireflection plate was prepared according to the same procedure as in Example 1 except that the cellulose acetate benzoate contained in the transparent support was different in the total substitution degree DS within the range of 1.3 <DS <2.8. .

<Example 17>
An antireflection plate was produced in the same manner as in Example 1 except that the liquid crystal compound 1 was changed to the following liquid crystal compound 11 in Example 1. The thickness of the optically anisotropic layer was 3.0 μm.

<Example 18>
An antireflection plate was produced in the same manner as in Example 1 except that the liquid crystal compound 1 was changed to the following liquid crystal compound 12 in Example 1. The thickness of the optically anisotropic layer was 3.0 μm.

<Example 19>
An antireflection plate was produced in the same manner as in Example 1 except that the liquid crystal compound 1 was changed to the following liquid crystal compound 13 in Example 1. The thickness of the optically anisotropic layer was 3.0 μm.

<Example 20>
An antireflection plate was produced in the same manner as in Example 1 except that the liquid crystal compound 1 was changed to the following liquid crystal compound 14 in Example 1. The thickness of the optically anisotropic layer was 3.0 μm.

<Comparative Examples 1 and 2>
In the production of the optically anisotropic layer, the bar coater was changed to adjust the thickness of the liquid crystal compound layer, so that Re (550) <120 nm and Re (550)> 160 nm were obtained. An antireflection plate was produced according to the same procedure.

<Comparative Example 3>
An antireflection plate was produced according to the same procedure as in Example 1 except that the liquid crystal compound 1 was changed to the liquid crystal compound 3. The thickness of the optically anisotropic layer was 1.2 μm.

<Comparative Examples 4 and 5>
An antireflection plate was produced according to the same procedure as in Example 1 except that the transparent support was stretched and adjusted so that Re (550) <− 10 nm or Re (550)> 10 nm.

<Comparative Examples 6 and 7>
Examples except that the cellulose acetate benzoate contained in the transparent support has a different Bz substitution degree DSA, and the transparent support was adjusted so that Rth (550) <-100 nm or Rth (550)>-20 nm. According to the same procedure as in No. 1, an antireflection plate was produced.

<Comparative Examples 8 and 9>
An antireflection plate was prepared according to the same procedure as in Example 1 except that the cellulose acetate benzoate contained in the transparent support had a different total substitution DS in the range of DS <1.3 and DS> 2.8. did.

<Comparative Examples 10-12>
An antireflection plate was prepared according to the same procedure as in Example 1 except that cellulose acetate benzoate contained in the transparent support had different Bz substitution degree DSA and total substitution degree DS.

5). Mounting on organic EL elements and evaluation of display performance <Mounting on display devices>
The organic EL panel-mounted GALAXY SII manufactured by SAMSUNG was disassembled, the circularly polarizing plate was peeled off, and the antireflection plates of Examples 1 to 20 and Comparative Examples 1 to 12 were bonded to produce display devices.

6). Various evaluations (6-1) Evaluation of display performance Visibility and display quality were evaluated under bright light for the produced organic EL display devices.
The display device displayed white, black, and images, and the reflected light when a fluorescent lamp was reflected from the front and a polar angle of 60 degrees was observed. The display quality at the front and polar angle of 60 degrees was evaluated according to the following criteria.
4: Coloration is not visually recognized at all. (Acceptable)
3: Although slight color difference is visible, very slight (allowable)
2: Although the color difference is visually recognized, the reflected light is small and there is no problem in use. (Acceptable)
1: A color difference is visually recognized and a lot of reflected light is unacceptable.

(6-2) Evaluation of polarizer adhesion Each obtained film and a PVA film were bonded with a polyvinyl alcohol adhesive to prepare a laminate sample. Each sample was subjected to a cross-cut test according to JIS K5600-5-6, Section 6, and evaluated according to the following criteria.
4: No peeling at all. (Acceptable)
3: Peeling is 15% or less, that is, the residual rate is 85% or more. (Acceptable)
2: Peeling exceeds 15% and is 30% or less, that is, the residual rate is 70% or more and less than 85%. (Acceptable)
1: Peeling exceeds 30%, that is, the residual rate is less than 30%. (Unacceptable)

  From the above table, the retardation plate of the present invention has a low reflectance from the front and polar angles, a small color change from the front and polar angles, and further improved adhesion to the polarizing plate. Recognize.

DESCRIPTION OF SYMBOLS 10 Phase difference plate 11 Transparent support 12 Optically anisotropic layer 20 Polarizing film 30 Display EL panel 100 Antireflection plate 200 Organic EL display apparatus

Claims (17)

Having a transparent support and an optically anisotropic layer containing a liquid crystal compound,
The transparent support is a cellulose acylate film satisfying the formula (A), the formula (B), and the formula (I);
A phase difference plate in which the optically anisotropic layer satisfies the following formulas (1) to (4);
Formula (A): −10 nm ≦ Re (550) ≦ 10 nm
Formula (B): −100 nm ≦ Rth (550) ≦ −20 nm
Formula (1): 120 nm ≦ Re (550) ≦ 150 nm
Formula (2): Re (450) / Re (550) <1
Formula (3): Re (650) / Re (550)> 1
Formula (4): 20 nm ≦ Rth (550) ≦ 100 nm
In the above formula, Re (λ) represents in-plane retardation at wavelength λnm, and Rth (λ) represents retardation in the thickness direction at wavelength λnm;
Formula (I): 1.3 <DS <2.8
In formula (I), DS represents the total substitution degree of the acyl group. The retardation plate according to claim 1, wherein the transparent support is a cellulose acylate film satisfying the following formula (II);
Formula (II): 0.8 ≦ DSA ≦ 1.3
In formula (II), DSA represents the substitution degree of an acyl group containing an aromatic group. The retardation plate according to claim 1, wherein the liquid crystal compound is represented by the following general formula (1):

In the formula, A ¹ and A ² each independently represents a group selected from the group consisting of —O—, —NR, —S— and —CO—, R represents a hydrogen atom or a substituent; Represents one or two atoms selected from the group consisting of non-metal atoms of Groups 14-16 and forms a 5- or 6-membered ring with the two carbon atoms in the formula. B and R ¹ each independently represent a substituent, R ² represents a divalent linking group; a plurality of B and R ² may be the same or different; m is an integer of 0 to 4; ¹ and L ² each independently represent a divalent linking group; R ⁴ and R ⁵ each independently represent a substituent; when having a polymerizable group, B, R, R ¹ , R ² , R ⁴ and at least one of R ⁵ contains a polymerizable group; n is an integer of 1 to 10. The phase difference plate of Claim 3 whose n is an integer of 2-10 in the liquid crystal compound represented by the said General formula (1). The retardation plate according to claim 1, wherein the liquid crystal compound is represented by the following general formula (2);
General formula (2):
L1-G1-D1-Ar-D2-G2-L2
In General Formula (2), Ar represents a divalent aromatic ring group represented by the following General Formula (2-1), (2-2), or (2-3), and D1 and D2 are each independently a, -CO-O -, - O -CO -, - C (= S) O -, - O-C (= S) -, - CR 1 R 2 -, - CR 1 R 2 -CR 3 R 4 ^{-, - O-CR 1 R} 2 -, - CR 1 R 2 -O -, - CR 1 R 2 -O-CR 3 R 4 -, - CR 1 R 2 -O-CO -, - O-CO- CR ¹ R ² —, —CR ¹ R ² —O—CO—CR ³ R ⁴ —, —CR ¹ R ² —CO—O—CR ³ R ⁴ —, —NR ¹ —CR ² R ³ —, —CR ¹ R ² —NR ³ —, —CO—NR ¹ —, or —NR ¹ —CO—, wherein R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a halogen atom, or Represents an alkyl group having 1 to 4 carbon atoms, and G1 and G2 are Each independently represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and is included in the alicyclic hydrocarbon group. The methylene group may be substituted with -O-, -S-, -NH-, -N (R)-, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and L1 and L2 are Each independently represents a monovalent organic group, and at least one selected from the group consisting of L1 and L2 represents a monovalent group having a polymerizable group;

In General Formula (2-1), Q ¹ represents —S—, —O—, or —NR ¹ —. R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Y ¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms; Z ¹ and Z ² are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic having 6 to 20 carbon atoms. Represents a hydrocarbon group, a halogen atom, a cyano group, a nitro group, —NR ² R ³ or —SR ² , and Z ¹ and Z ² may combine with each other to form an aromatic ring or an aromatic heterocyclic ring; R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
In general formulas (2-2) and (2-3), Ax represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Ay represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Represents an organic group having 2 to 30 carbon atoms, and the aromatic ring of Ax and Ay may have a substituent; Ax and Ay may be bonded to each other to form a ring; ¹ , Z ² and Z ³ each independently represent a hydrogen atom or a substituent; Q ² represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. The phase difference plate according to claim 1, wherein the optically anisotropic layer further contains a non-liquid crystalline polymerizable monomer. The phase difference plate of any one of Claims 1-6 whose film thickness of the said optically anisotropic layer is 3.0-5.5 micrometers. The phase difference plate according to claim 1, wherein the optically anisotropic layer is composed of only one layer. The phase difference plate according to claim 1, wherein the transparent support is an unstretched film. The absolute value of the total value of the retardation Rth (550) in the thickness direction at a wavelength of 550 nm of the transparent support and the retardation Rth (550) in the thickness direction at a wavelength of 550 nm of the optically anisotropic layer is 50 nm or less. The phase difference plate according to any one of claims 1 to 9. 11. The retardation plate according to claim 1, wherein an in-plane retardation Re (550) at a wavelength of 550 nm of the optically anisotropic layer is 125 to 145 nm. The retardation plate according to claim 1, wherein a retardation Rth (550) in a thickness direction at a wavelength of 550 nm of the transparent support is −90 to −23 nm. The retardation plate according to claim 1, wherein the acyl group has a total substitution degree DS of 1.5 to 2.7. An antireflection plate comprising the retardation plate according to any one of claims 1 to 13 and a polarizing film. An image display device comprising the antireflection plate according to claim 14. The image display device according to claim 15, which is an organic EL display device. It is a manufacturing method of the phase difference plate given in any 1 paragraph of Claims 1-13, Comprising: After carrying out the solution containing cellulose acetate benzoate to a support and forming it in the shape of a film, without performing stretching processing A method for producing a retardation plate, comprising forming an optically anisotropic layer.

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