JP2015072439A - Liquid crystal display - Google Patents

Abstract

A liquid crystal display device having excellent display performance even when thinned.
A first polarizer 1 and a second polarizer 5 which are arranged so that their absorption axes are orthogonal to each other, and a vertical alignment which is arranged between the first polarizer 1 and the second polarizer 5. A mode liquid crystal cell 3, a first optically anisotropic layer 2 provided on one side between the first polarizer 1 and the liquid crystal cell 3 and between the second polarizer 5 and the liquid crystal cell 3, A second optically anisotropic layer 4 provided on one side between the first polarizer 1 and the liquid crystal cell 3 and between the second polarizer 5 and the liquid crystal cell 3. At least one of the optically anisotropic layer 2 and the second optically anisotropic layer 4 contains a liquid crystal compound, has a thickness of 10 μm or less, and the first optically anisotropic layer relates to a predetermined retardation. A liquid crystal display device that satisfies the relational expression and the second optically anisotropic layer satisfies the relational expression related to a predetermined retardation.
[Selection] Figure 1

Description

  The present invention relates to a liquid crystal display device having a vertical alignment mode liquid crystal cell.

  In recent years, liquid crystal display devices have been made thinner, and accordingly, members (for example, polarizing plates) used are required to be made thinner. As a method of thinning the polarizing plate, for example, a method of thinning the polarizer itself or the protective film of the polarizer, a method of eliminating the protective film or retardation film disposed between the polarizer and the liquid crystal cell, etc. Can be mentioned.

  For such a situation, for example, Patent Document 1 discloses that “a polarizing plate having a polarizing film and an optically anisotropic layer formed of liquid crystalline molecules, and the optically anisotropic layer is formed on the surface of the polarizing film. The polarizing plate is provided directly or via an alignment film. ”[Claim 1].

JP 2004-053770 A

  When the optical film support is eliminated and the optically anisotropic layer is formed on the polarizing film as described in Patent Document 1, the present inventors can make the liquid crystal display device thin, but only by that, display performance (especially black It was found that the coloration at the time of display may be inferior to the requirement.

  Therefore, an object of the present invention is to provide a liquid crystal display device having excellent display performance even when it is thinned.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have compensated the liquid crystal cell when the support that is normally provided for forming the liquid crystal layer (optically anisotropic layer) for the purpose of thinning is eliminated. In the case where the liquid crystal display device is thinned by functionally separating the optical characteristics for compensating the optical characteristics for compensating the polarizer into the first optical anisotropic layer and the second optical anisotropic layer Even if it exists, it discovered that a display performance could be made favorable and completed this invention.
That is, it has been found that the above-described problem can be achieved by the following configuration.

[1] a first polarizer and a second polarizer arranged with their absorption axes orthogonal to each other;
A vertically aligned mode liquid crystal cell disposed between the first polarizer and the second polarizer;
A first optically anisotropic layer provided on one side between the first polarizer and the liquid crystal cell and between the second polarizer and the liquid crystal cell;
A second optically anisotropic layer provided on one side between the first polarizer and the liquid crystal cell and between the second polarizer and the liquid crystal cell,
At least one of the first optically anisotropic layer and the second optically anisotropic layer contains a liquid crystalline compound and has a thickness of 10 μm or less,
The first optical anisotropic layer satisfies the following formula (1-1-1),
The second optically anisotropic layer has the following formulas (1-2-1), (1-2-2), (1-2-3), (1-2-4) and (1-2-5) A liquid crystal display device that meets the requirements.
30 nm ≦ Rth (550) ≦ 300 nm Formula (1-1-1)
50 nm ≦ Re (550) ≦ 200 nm Formula (1-2-1)
40 nm ≦ Rth (550) ≦ 200 nm Formula (1-2-2)
Rth (550) ≧ (−12/5) × Re (550) +280 nm
Formula (1-2-3)
Rth (550) ≦ (−7/5) × Re (550) +340 nm
Formula (1-2-4)
Re (450) / Re (550) ≦ 1.05 Formula (1-2-5)
(Re (λ) represents in-plane retardation at wavelength λnm, and Rth (λ) represents retardation in the thickness direction at wavelength λnm.)
[2] Of the first optical anisotropic layer and the second optical anisotropic layer, an optical anisotropic layer containing a liquid crystalline compound and having a thickness of 10 μm or less, and the first polarizer or the first optical anisotropic layer The liquid crystal display device according to [1], wherein two polarizers are adjacent to each other.
[3] Of the first optical anisotropic layer and the second optical anisotropic layer, the optical anisotropic layer containing a liquid crystalline compound and having a thickness of 10 μm or less, and the first polarizer or the first optical anisotropic layer The liquid crystal display device according to [1], wherein the two polarizers are laminated via an alignment film.
[4] Of the first optical anisotropic layer and the second optical anisotropic layer, an optical anisotropic layer containing a liquid crystalline compound and having a thickness of 10 μm or less, and the first polarizer or the first optical anisotropic layer 2. The liquid crystal display device according to [1], wherein the two polarizers are laminated via an adhesive layer or an adhesive layer.
[5] Of the first optical anisotropic layer and the second optical anisotropic layer, at least the first optical anisotropic layer contains a liquid crystalline compound and has a thickness of 10 μm or less. Sex layer,
The liquid crystal display device according to any one of [1] to [4], wherein the first optical anisotropic layer satisfies the following formulas (2-1-1) and (2-1-2).
Re (550) ≦ 10 nm Formula (2-1-1)
30 nm ≦ Rth (550) ≦ 250 nm Formula (2-1-2)
[6] Of the first optical anisotropic layer and the second optical anisotropic layer, at least the second optical anisotropic layer contains a liquid crystalline compound and has a thickness of 10 μm or less. Sex layer,
The first optical anisotropic layer satisfies the following formula (3-1-1),
The liquid crystal display device according to any one of [1] to [4], wherein the second optical anisotropic layer satisfies the following formulas (3-2-1) and (3-2-2).
100 nm ≦ Rth (550) ≦ 300 nm Formula (3-1-1)
90 nm ≦ Re (550) ≦ 190 nm Formula (3-2-1)
40 nm ≦ Rth (550) ≦ 100 nm Formula (3-2-2)
[7] The liquid crystal display device according to [6], wherein the first optically anisotropic layer is an optically anisotropic layer containing a liquid crystalline compound.
[8] The liquid crystalline compound contained in the first optical anisotropic layer is a discotic liquid crystalline compound, and the first optical anisotropic layer satisfies the following formula (4-1-1): [5] Or the liquid crystal display device as described in [7].
0.9 <Re40 (450) / Re40 (550) ≦ 1.2 Formula (4-1-1)
(Re40 (λ) represents retardation measured from a polar angle of 40 ° at a wavelength of λnm.)
[9] The liquid crystal display device according to [6] or [7], wherein the liquid crystalline compound contained in the second optically anisotropic layer is a rod-like liquid crystalline compound.
[10] The liquid crystal display device according to [9], wherein the second optically anisotropic layer satisfies the following formula (5-2-1).
Re (450) / Re (550) <1.0 Formula (5-2-1)
[11] From the viewing side, the first polarizer, the first optical anisotropic layer, the liquid crystal cell, the second optical anisotropic layer, and the second polarizer are provided in this order. 10]. The liquid crystal display device according to any one of [10].
[12] From the viewer side, the first polarizer, the second optical anisotropic layer, the liquid crystal cell, the first optical anisotropic layer, and the second polarizer are included in this order. [10] The liquid crystal display device according to any one of [10].
[13] Any of the first optical anisotropic layer and the second optical anisotropic layer is between the first polarizer and the liquid crystal cell and between the second polarizer and the liquid crystal cell. The liquid crystal display device according to any one of [1] to [10], which is disposed only between the two.
[14] The polarizer on the side where the first optical anisotropic layer and the second optical anisotropic layer are not disposed is disposed in the liquid crystal cell via an adhesive or an adhesive, [13] A liquid crystal display device according to 1.
[15] A protective film is provided on at least one side of the first polarizer and the second polarizer opposite to the liquid crystal cell,
Moisture permeability of the protective film is not more than 100g / m ² / 24h, a liquid crystal display device according to any one of [1] to [14].
[16] At least one of the moisture permeability of the first optically anisotropic layer and the second optically anisotropic layer is not more than 100 g / m ² / 24h, according to any one of [1] to [6] Liquid crystal display device.
[17] A laminate film is provided on at least one side of the first polarizer and the second polarizer opposite to the liquid crystal cell,
Moisture permeability at 40 ° C. 90% RH of the laminated film is not more than 50g / m ² / 24h, a liquid crystal display device according to any one of [1] to [16].
[18] The liquid crystal display device according to any one of [1] to [17], wherein the thickness of at least one of the first polarizer and the second polarizer is 25 μm or less.

  According to the present invention, it is possible to provide a liquid crystal display device excellent in display performance even when it is thinned.

It is typical sectional drawing which shows the example of embodiment of the liquid crystal display device of this invention.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
Next, terms used in this specification will be described.

[Re (λ), Rth (λ)]
In this specification, Re (λ) and Rth (λ) represent in-plane retardation and retardation in the thickness direction at the wavelength λ, respectively.
Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or KOBRA WR (both manufactured by Oji Scientific Instruments). In selecting the measurement wavelength λnm, the wavelength selection filter can be exchanged manually, or the measurement value can be converted by a program or the like.

Here, 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 the film surface when Re (λ) is set to the in-plane slow axis (determined by KOBRA 21ADH or KOBRA WR) as the tilt axis (rotary axis). Measurement is performed at a total of 6 points by injecting light of wavelength λ nm from each inclined direction in steps of 10 degrees from the normal direction to 50 ° on one side with respect to the film normal direction (with any rotation direction as the rotation axis). Then, KOBRA 21ADH or KOBRA 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 KOBRA WR after changing its sign to negative. The retardation value is measured from two inclined directions with the slow axis as the tilt axis (rotation axis) (if there is no slow axis, the arbitrary direction in the film plane is the rotation axis). Rth can also be calculated from the following formula (A) and formula (B) based on the value, the assumed value of the average refractive index, and the input film thickness value.

Note that Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction. In the formula (A), nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction orthogonal to nx in the plane, and nz is the direction orthogonal to nx and ny. Represents the refractive index. d is the film thickness.
Rth = ((nx + ny) / 2−nz) × d (Equation (B)

In this specification, Re40 (λ) represents retardation measured from a polar angle of 40 ° at a wavelength λnm.
Further, the angle relationship (for example, “orthogonal”, “parallel”, “90 °”, etc.) includes a range of errors allowed in the technical field to which the present invention belongs. Specifically, it means that the angle is within a range of strict angle ± 10 °, and an error from the strict angle is preferably 5 ° or less, and more preferably 3 ° or less.

[Moisture permeability]
In this specification, moisture permeability refers to the area in an atmosphere at a temperature of 40 ° C. and a humidity of 90% RH in accordance with the method described in “Moisture permeability test method for moisture-proof packaging materials (cup method)” of JIS Z 0208: 1976. The amount of water vapor (g / m ² / day) passing through a 1 m ² sample in 24 hours.

[Liquid Crystal Display]
The liquid crystal display device of the present invention includes a first polarizer and a second polarizer that are arranged with their absorption axes orthogonal to each other, and a vertical alignment that is arranged between the first polarizer and the second polarizer. A mode liquid crystal cell, a first optically anisotropic layer provided between one of the first polarizer and the liquid crystal cell and one between the second polarizer and the liquid crystal cell, and the first polarizer And a second optically anisotropic layer provided between the liquid crystal cell and between the second polarizer and the liquid crystal cell, the first optically anisotropic layer and the second optical At least one of the anisotropic layers contains a liquid crystalline compound and has a thickness of 10 μm or less, and the first optical anisotropic layer and the second optical anisotropic layer have a specific optical property relationship. It is a liquid crystal display device.

  In the present invention, as described above, the liquid crystal having the first polarizer and the second polarizer, the first optical anisotropic layer and the second optical anisotropic layer, and the vertical alignment mode liquid crystal cell. Even when the display device is a thin liquid crystal display device, the display performance is good.

  Next, after describing the overall configuration of the liquid crystal display device of the present invention with reference to FIG. 1, each configuration will be described in detail.

FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a liquid crystal display device of the present invention.
A liquid crystal display device 10 shown in FIG. 1 includes a first polarizer 1, a second polarizer 5, a first optical anisotropic layer 2, a second optical anisotropic layer 4, and a vertical alignment mode liquid crystal. It has a cell 3. The absorption axis of the first polarizer 1 and the absorption axis of the second polarizer 5 are orthogonal.

  As shown in FIG. 1A, the liquid crystal display device 10 includes a first polarizer 1, a first optical anisotropic layer 2, a vertical alignment mode liquid crystal cell 3, and a second optical anisotropic layer. 4 and the second polarizer 5 are preferably laminated in this order. Here, the first optical anisotropic layer 2 and the second optical anisotropic layer 4 may be interchanged.

  In addition, as shown in FIG. 1B, the liquid crystal display device 10 includes a first polarizer 1, a first optical anisotropic layer 2, a second optical anisotropic layer 4, and a vertical alignment mode liquid crystal cell. 3 and the second polarizer 5 may be laminated in this order. Here, the first optical anisotropic layer 2 and the second optical anisotropic layer 4 may be interchanged. Further, the first optical anisotropic layer and the second optical anisotropic layer may be disposed between the second polarizer 5 and the vertical alignment mode liquid crystal cell 3.

Moreover, the liquid crystal display device 10 may have a protective film 6 on the opposite side of the first polarizer 1 from the vertical alignment mode liquid crystal cell 3 as shown in FIG. Further, a laminate film 7 may be provided on the opposite side of the first polarizer 1 from the vertical alignment mode liquid crystal cell 3.
Here, in the present invention, at least one or both of the protective film 6 and the laminate film 7 may be provided on the opposite side of the second polarizer 5 to the direct alignment mode liquid crystal cell 3, and the first polarization At least one or both of the protective film 6 and the laminate film 7 may be provided on both sides of the polarizer 1 and the second polarizer 5 opposite to the vertical alignment mode liquid crystal cell 3.

(Optically anisotropic layer)
The liquid crystal display device of the present invention has a first optical anisotropic layer and a second optical anisotropic layer.
Further, at least one of the first optical anisotropic layer and the second optical anisotropic layer contains a liquid crystalline compound and has a thickness of 10 μm or less.
Further, the first optical anisotropic layer satisfies the following formula (1-1-1), and the second optical anisotropic layer has the following formulas (1-2-1), (1-2-2), It satisfies (1-2-3), (1-2-4), and (1-2-5).
・ 30 nm ≦ Rth (550) ≦ 300 nm Formula (1-1-1)
・ 50 nm ≦ Re (550) ≦ 200 nm Formula (1-2-1)
・ 40 nm ≦ Rth (550) ≦ 200 nm Formula (1-2-2)
Rth (550) ≧ (−12/5) × Re (550) +280 nm
Formula (1-2-3)
Rth (550) ≦ (−7/5) × Re (550) +340 nm
Formula (1-2-4)
Re (450) / Re (550) ≦ 1.05 Formula (1-2-5)

<First aspect>
{First optical anisotropic layer}
When the first optical anisotropic layer used in the present invention is an optical anisotropic layer containing a liquid crystalline compound and having a thickness of 10 μm or less (first aspect), the first optical anisotropy The layer preferably satisfies the following formulas (2-1-1) and (2-1-2).
・ Re (550) ≦ 10 nm Formula (2-1-1)
・ 30 nm ≦ Rth (550) ≦ 250 nm Formula (2-1-2)
Here, Re (550) preferably satisfies 6 nm or less, and more preferably satisfies 3 nm or less.
Rth (550) preferably satisfies 50 nm ≦ Rth (550) ≦ 240 nm, and more preferably satisfies 70 nm ≦ Rth (550) ≦ 230 nm.

  The liquid crystalline compound contained in the first optically anisotropic layer is preferably a discotic liquid crystalline compound described later.

{Second optically anisotropic layer}
In the first aspect, Re (550) of the second optically anisotropic layer preferably satisfies 60 nm ≦ Re (550) ≦ 180 nm, and more preferably satisfies 65 nm ≦ Re (550) ≦ 170 nm.
Similarly, in the first aspect, Rth (550) of the second optical anisotropic layer preferably satisfies 45 nm ≦ Rth (550) ≦ 195 nm, and preferably satisfies 50 nm ≦ Rth (550) ≦ 190 nm. Further preferred.
The second optically anisotropic layer is preferably an optically anisotropic layer including a polymer film described later.

<Second aspect>
{First optical anisotropic layer}
When the second optical anisotropic layer used in the present invention is an optical anisotropic layer containing a liquid crystalline compound and having a thickness of 10 μm or less (second embodiment), the first optical anisotropy The layer preferably satisfies the following formula (3-1-1).
・ 100 nm ≦ Rth (550) ≦ 300 nm Formula (3-1-1)
Here, Rth (550) preferably satisfies 120 nm ≦ Rth (550) ≦ 280 nm, and more preferably satisfies 140 nm ≦ Rth (550) ≦ 270 nm.

  The first optically anisotropic layer may be an optically anisotropic layer containing a discotic liquid crystalline compound described later or an optically anisotropic layer containing a polymer film described later.

{Second optically anisotropic layer}
In the second aspect, the second optically anisotropic layer preferably satisfies the following formulas (3-2-1) and (3-2-2).
・ 90 nm ≦ Re (550) ≦ 190 nm Formula (3-2-1)
・ 40 nm ≦ Rth (550) ≦ 100 nm Formula (3-2-2)
Here, Re (550) preferably satisfies 100 nm ≦ Re (550) ≦ 180 nm, and more preferably satisfies 105 nm ≦ Re (550) ≦ 170 nm.
Rth (550) preferably satisfies 45 nm ≦ Rth (550) ≦ 90 nm, and more preferably satisfies 50 nm ≦ Rth (550) ≦ 85 nm.

  The liquid crystalline compound contained in the second optically anisotropic layer is preferably a rod-like liquid crystalline compound described later.

<Member used for optically anisotropic layer>
Next, the member used for the optical anisotropic layer used for this invention is demonstrated.

{Liquid crystal compound}
At least one of the first optical anisotropic layer and the second optical anisotropic layer used in the present invention is an optical anisotropic layer containing a liquid crystalline compound.
There may be no phase difference member between the polarizer on the side where the optically anisotropic layer containing the liquid crystalline compound is disposed and the liquid crystal cell, in addition to the optically anisotropic layer containing the liquid crystalline compound. preferable.
As the liquid crystal compound, various known discotic liquid crystal compounds and rod-like liquid crystal compounds can be used.

  When the optically anisotropic layer contains a liquid crystalline compound, the thickness of the optically anisotropic layer is 10 μm or less, preferably 7 μm or less, and more preferably 5 μm or less.

<Discotic liquid crystalline compound>
Various known compounds can be used for the discotic liquid crystalline compound used in the present invention. Examples of discotic liquid crystalline compounds include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives described in C.I. Destrade et al., Mol. Cryst. 122, 141 (1985), Physics lett, A, 78, 82 (1990); Kohne et al., Angew. Chem. 96, page 70 (1984) and the cyclohexane derivatives described in J. Am. M.M. Lehn et al. Chem. Commun. 1794 (1985), J. Am. Zhang et al., J. Am. Chem. Soc. 116, 2655 (1994), azacrown type and phenylacetylene type macrocycles are included. Specifically, those described in paragraphs [0151] to “0168” of JP-A No. 2000-155216 and those described in [0020] to [0036] of JP-A No. 2013-54201 can be used. .

When the discotic liquid crystalline compound is contained in the optically anisotropic layer, the optically anisotropic layer preferably satisfies the following formula (4-1-1).
0.9 <Re40 (450) / Re40 (550) ≦ 1.2 Formula (4-1-1)
Here, Re40 (450) / Re40 (550) more preferably satisfies 0.95 <Re40 (450) / Re40 (550) ≦ 1.19, and 0.99 <Re40 (450) / Re40 (550). More preferably, ≦ 1.18 is satisfied.

<Bar-shaped liquid crystalline compound>
Various known compounds can be used as the rod-like liquid crystal compound used in the present invention.
Examples of rod-like liquid crystalline compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used.
In addition, those described in [0025] to [0183] of International Publication No. 2013/018526 can be used.

When the rod-like liquid crystalline compound is contained in the optically anisotropic layer, the optically anisotropic layer preferably satisfies the following formula (5-2-1).
Re (450) / Re (550) <1.0 Formula (5-2-1)
Here, Re40 (450) / Re40 (550) preferably satisfies Re (450) / Re (550) <0.98, and satisfies Re (450) / Re (550) <0.96. Further preferred.

<Boronic acid compound>
In the present invention, when an optically anisotropic layer containing a liquid crystalline compound is directly formed on the polarizer, in order to improve the adhesion between the polarizer and the optically anisotropic layer, the optically anisotropic layer is combined with the liquid crystalline compound. Boronic acid compounds may be used.

  Examples of the boronic acid compound that can be used in the present invention represent a compound having at least one boronic acid group or a boronic ester group, and a metal complex or tetracoordinate having these as a ligand. The boronium ions having boron atoms are also represented at the same time, and those described in JP 2013-0542201 A, paragraph numbers [0040] to [0053] can be used.

  The preferred range of the boronic acid compound content in the optically anisotropic layer is in the optically anisotropic layer (in the total solid content excluding the solvent of the composition in the composition before layer formation), 0.005 to 0.005. The content is preferably 8% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.05 to 1% by mass.

{Polymer film}
Various known polymer films can be used as the polymer film used in the present invention, and specific examples include cellulose acylate films, (meth) acrylic resin films, polyester resin films, and cycloolefin resin films. It is done.

  The thickness of the polymer film is preferably 250 μm or less, more preferably 200 μm or less, and even more preferably 150 μm or less. Although a minimum is not specifically limited, Generally it is 10 micrometers or more.

Preferably the moisture permeability 40 ° C. 90% RH of the polymer film is less than 100g / m ² / 24h, more preferably 80 or less, more preferably 60 or less. Examples of the polymer film having moisture permeability satisfying this value include (meth) acrylic resin film, polyester resin film, cycloolefin resin film, and the like.

The (meth) acrylic resin is a concept including both a methacrylic resin and an acrylic resin, and includes an acrylate / methacrylate derivative, particularly an acrylate ester / methacrylate ester (co) polymer.
Further, the (meth) acrylic resin includes, in addition to the methacrylic resin and acrylic resin, a (meth) acrylic polymer having a ring structure in the main chain, a polymer having a lactone ring, and a succinic anhydride ring. A maleic anhydride-based polymer having, a polymer having a glutaric anhydride ring, and a glutarimide ring-containing polymer.

  As the polyester resin, polyethylene terephthalate and polyethylene naphthalate are preferable.

  Various known cycloolefin resin films that can be used in the present invention can be used, and specifically those described in paragraphs [0030] to [0144] of JP-A-2006-188671 are used. be able to.

  As the cellulose acylate film that can be used in the present invention, various known films can be used, and specifically, those described in JP2012-076051A can be used.

  The polymer film used for this invention can contain various additives as needed. Specific examples of the additive include an ultraviolet absorber, a plasticizer, and a matting agent fine particle, and various known ones can be used. When the polymer film of the present invention contains an additive, the total amount of the additive is preferably 5 to 50% by mass, more preferably 5 to 40% by mass with respect to the resin of the polymer film. More preferably, it is -30 mass%.

<Method for creating optically anisotropic layer>
The optically anisotropic layer used in the present invention can be prepared by various known methods.

{Method for producing optically anisotropic layer containing liquid crystalline compound}
The optically anisotropic layer containing the liquid crystalline compound used in the present invention is preferably formed directly on the polarizer by applying a composition containing the liquid crystalline compound to the polarizer. Here, after forming an alignment film on a polarizer, an optically anisotropic layer may be formed thereon. Also, another temporary support is prepared, an optically anisotropic layer containing a liquid crystalline compound is prepared on the temporary support, the optically anisotropic layer is peeled from the temporary support, and the polarizer and the optical anisotropy are separated. You may create by the transfer system which arrange | positions a layer through an adhesive or an adhesive agent.

A structure in which the polarizer and the optically anisotropic layer are adjacent to each other by forming an optically anisotropic layer containing a liquid crystal compound on the polarizer by coating or transfer method (see FIG. 1), or The optically anisotropic layer may be laminated with an alignment film or an adhesive or pressure-sensitive adhesive.
In these structures, the support which the normal optical film containing a liquid crystalline compound has can be eliminated, and it is effective for thinning the liquid crystal display device. Further, it is effective in reducing display unevenness of the liquid crystal display device caused by temperature and humidity changes.

  When the liquid crystal compound is aligned and cured on the polarizer because the deterioration of the polarizer performance and wrinkles due to the high temperature of the polarizer can be reduced, the temperature during the alignment and curing is determined by the glass transition of the polarizer. It is preferable to carry out below the temperature.

{Method for producing optically anisotropic layer including polymer film}
The optically anisotropic layer containing the polymer film used in the present invention can be prepared by various known methods.

[Polarizer]
Various known polarizers can be used in the present invention. Specifically, an iodine polarizer in which iodine is adsorbed on a polyvinyl alcohol (PVA) film, a polarizer using a dichroic organic dye, and the like. Can be mentioned.

<Thickness of polarizer>
The thickness of the polarizer is preferably 25 μm or less, more preferably 20 μm or less, and even more preferably 17 μm or less. The film thickness can be controlled by a known method. For example, the film thickness can be controlled by setting the die slit width in the casting process and the stretching conditions to appropriate values.
From the viewpoint of reducing the thickness of the polarizer, a coating type polarizer in which a PVA solution is applied on a temporary support and iodine is adsorbed and stretched together with the temporary support is also preferable. The coating type polarizer can be formed, for example, by a manufacturing method using a coating method described in Japanese Patent No. 4691205 and Japanese Patent No. 4751481.

〔Protective film〕
The liquid crystal display device of the present invention may have an arbitrary protective film as shown in FIG.
Various known protective films can be used for the present invention, and specific examples include the polymer films described above.

In order to suppress the amount of water entering the polarizing plate over time in a high temperature and high humidity environment and to suppress display unevenness due to warpage of the liquid crystal panel, the moisture permeability of the protective film at 40 ° C. and 90% relative humidity is 100 g. / M ² · day or less is preferable, 80 or less is more preferable, and 60 or less is still more preferable.
In order to lower the moisture permeability of the protective film, it is also preferable to provide a low moisture permeability layer with a member having a low moisture permeability on the polymer film. Examples of the member having low moisture permeability include a (meth) acrylic resin film, a polyester resin film, and a cycloolefin resin film.

  The protective film may be further provided with a functional layer according to various purposes. Examples of the functional layer include a hard coat layer, an antiglare layer, and a low reflection layer.

〔Laminate film〕
The liquid crystal display device of the present invention may have an arbitrary laminate film as shown in FIG.
Various known films can be used for the laminate film used in the present invention. The laminate film is disposed on the viewing side and / or the outermost surface of the backlight side of the liquid crystal display device, and is peeled off during use.
When transporting the liquid crystal display device, the moisture permeability of the laminate film at 40 ° C. and 90% RH is preferably 50 g / m ² · day or less because the adverse effect of moisture entering the liquid crystal display device can be reduced. , 40 or less, more preferably 30 or less.

[Brightness enhancement film]
The liquid crystal display device of the present invention can be used in combination with a brightness enhancement film. The brightness enhancement film has a function of separating circularly polarized light or linearly polarized light, and is disposed between the polarizing plate and the backlight, and reflects or backscatters one circularly polarized light or linearly polarized light to the backlight side. Re-reflected light from the backlight part partially changes the polarization state and partially transmits when re-entering the brightness enhancement film and the polarizing plate, so the light utilization rate is improved by repeating this process. The front luminance is improved to about 1.4 times. As the brightness enhancement film, an anisotropic reflection method and an anisotropic scattering method are known, and both can be combined with the polarizing plate used in the present invention.

  Further, in the present invention, the specifications of International Publication No. 97/32223, International Publication No. 97/32224, International Publication No. 97/32225, International Publication No. 97/32226, and Japanese Patent Laid-Open No. 9-274108. Used in combination with a brightness enhancement film of an anisotropic scattering method in which a positive intrinsic birefringent polymer and a negative intrinsic birefringent polymer are blended and uniaxially stretched as described in each publication of JP-A-11-174231 It is also preferable to do. As the anisotropic scattering system brightness enhancement film, DRPF-H (manufactured by 3M) is preferable.

[Liquid crystal cell]
The liquid crystal cell used in the present invention is a vertical alignment mode liquid crystal cell, and various known ones can be used.

  Δn · d of the liquid crystal cell in the vertical alignment mode is preferably 250 nm ≦ Δn · d ≦ 400 nm. Here, Δn represents the birefringence of the liquid crystal material used in the vertical alignment mode liquid crystal cell, and d represents the thickness of the cell liquid crystal layer.

  A structure called multi-domain in which one pixel is divided into a plurality of regions is preferable because the viewing angle characteristics in the vertical and horizontal directions are averaged and the display quality is improved.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[Configuration of liquid crystal display device]
In the preparation of the liquid crystal display device of each example and comparative example, the stacking order of the polarizer, the optically anisotropic layer, and the liquid crystal cell is as follows and is shown in Tables 2 to 6. In Tables 2 to 6, “Re / Rth” represents each value of Re and Rth, and “wavelength dispersion” represents a value of Re (450) / Re (550).
Configuration I: First protective film, first polarizer, first optical anisotropic layer, liquid crystal cell, second optical anisotropic layer, second polarizer, second protection from the viewing side Film Configuration II: From the viewer side, the first protective film, the first polarizer, the second optical anisotropic layer, the liquid crystal cell, the first optical anisotropic layer, the second polarizer, the second Protective film Configuration III: From the viewing side, the first protective film, the first polarizer, the liquid crystal cell, the first optical anisotropic layer, the second optical anisotropic layer, the second polarizer, and the second Protective film of composition IV: From the viewing side, the first protective film, the first polarizer, the second optical anisotropic layer, the first optical anisotropic layer, the liquid crystal cell, the second polarizer, the first Protective film 2: Configuration V: From the viewing side, the first protective film, the first polarizer, the liquid crystal cell, the second optically anisotropic layer, the first optically anisotropic layer, the second polarizer, Second protective film Configuration VI: First protective film from the viewing side First polarizer, a first optically anisotropic layer, the second optically anisotropic layer, the liquid crystal cell, a second polarizer, a second protective layer

[Example 1]
[Preparation of protective film]
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution (dope).
(Composition of cellulose acetate solution (dope))
―――――――――――――――――――――――――――――――――――
Cellulose acetate 100 parts by mass (acetyl substitution degree 2.86, viscosity average polymerization degree 310)
-Triphenyl phosphate 8.0 parts by mass-Biphenyl diphenyl phosphate 4.0 parts by mass-Tinuvin 328 Ciba Japan 1.0 part by mass-Tinuvin 326 Ciba Japan 0.2 part by mass-Methylene chloride 369 parts by mass-Methanol 80 parts by mass, 1-butanol 4 parts by mass -------------

  The obtained dope was heated to 30 ° C., and cast on a mirror surface stainless steel support, which was a drum having a diameter of 3 m, through a casting Giuser. The surface temperature of the support was set to -5 ° C. The space temperature of the entire casting part was set to 15 ° C. The cellulose ester film cast and rotated 50 cm before the end point of the casting part was peeled off from the drum, and then both ends were clipped with a pin tenter. The residual solvent amount of the cellulose ester web immediately after stripping was 70%, and the film surface temperature of the cellulose ester web was 5 ° C.

  The cellulose ester web held by the pin tenter was conveyed to the drying zone. In the initial drying, a drying air of 45 ° C. was blown. Next, it was dried at 110 ° C. for 5 minutes and further at 140 ° C. for 10 minutes. This was designated as a protective film 01.

The thickness of the resulting film is 60 [mu] m, the moisture permeability was 600g / m ² / 24h. Re (550) = 1.5 nm and Rth (550) = 40 nm. The refractive index was nx = 1.48.

[Production of hard coat layer]
As a coating solution for forming a hard coat layer, a hard coat curable composition hard coat 1 shown in Table 1 below was prepared.

  The hard coat 1 is applied onto the surface of the protective film 01 produced above, and then dried at 100 ° C. for 60 seconds, and irradiated with UV at 1.5 kW and 300 mJ under the condition of nitrogen 0.1% or less. Then, a hard coat layer-provided protective film 01 having a hard coat layer having a thickness of 5 μm was produced. The thickness of the hard coat layer was adjusted by using a slot die and adjusting the coating amount in a die coating method.

[Production of polarizing plate with single-sided protective film]
<Saponification of film>
The prepared protective film with hard coat layer 01 was immersed in a 4.5 mol / L sodium hydroxide aqueous solution (saponification solution) adjusted to 37 ° C. for 1 minute, and then the film was washed with water, and then 0.05 mol / L. After being immersed in an aqueous sulfuric acid solution for 30 seconds, the solution was further passed through a water washing bath. Then, draining with an air knife was repeated three times, and after dropping water, the film was retained in a drying zone at 70 ° C. for 15 seconds and dried to produce a saponified protective film 01 with a hard coat layer.
<Production of polarizer>
According to Example 1 of Japanese Patent Laid-Open No. 2001-141926, a peripheral speed difference was given between two pairs of nip rolls, and a polarizer having a width of 1330 mm and a thickness of 15 μm was prepared by stretching in the longitudinal direction. The polarizer thus produced was designated as a polarizer 1.
<Lamination>
The polarizer 1 thus obtained and the saponified protective coating film 01 with a hard coat layer were prepared by using a PVA (manufactured by Kuraray Co., Ltd., PVA-117H) 3% aqueous solution as an adhesive and a polarizing axis and a film. The polarizing plate 01 with a visible-side single-sided protective film was produced by laminating with a roll-to-roll so that the longitudinal direction of the film was orthogonal.
At this time, it bonded together so that the cellulose acylate film side of a protective film might become a polarizer side.

[Production of polarizing plate with single-sided protective film 2]
A polarizing plate 01 with a backlight side single-side protective film was prepared in the same manner as in the production of the polarizing plate 01 with a viewing-side single-side protective film, except that a hard coat layer was not provided on the surface of the protective film 01. In the following Examples and Comparative Examples, each polarizing plate was prepared using a polarizing plate 01 with a single-sided protective film on the viewing side and a polarizing plate 01 with a single-sided protective film on the backlight side, unless otherwise specified. did.

[First optically anisotropic layer]
The following compounds 3-1 to 3-6 were dissolved in methyl ethyl ketone to prepare a solid content concentration of 36.2%.
―――――――――――――――――――――――――――――――――――
-Discotic liquid crystalline compound 3-1 91.0 parts by mass-Compound 3-2 9.0 parts by mass-Polymerization initiator: Compound 3-3 3.0 parts by mass-Polymerization initiator: Compound 3-4 1.0 Part by mass / Fluorine-containing surfactant: Compound 3-5 0.8 part by mass / Adhesion improver: Compound 3-6 0.5 part by mass ―――――――――――――――――― ―――――――――――――――――

[Preparation of polarizing plate]
The coating solution was applied to the surface on the polarizer side of the prepared polarizing plate with a single-sided protective film 01 using a # 4.4 wire bar and dried. The discotic liquid crystalline compound was aligned by heating at 70 ° C. for 90 seconds. Thereafter, 290 mJ / cm ² of ultraviolet rays was immediately irradiated under a temperature condition of 70 ° C. to polymerize the discotic liquid crystalline compound, fix the alignment state, and form a first optical anisotropic layer. The thickness of the formed optically anisotropic layer was 2 μm. The thickness of the optically anisotropic layer was measured with a laser film thickness meter.

[Measurement of optical properties]
The first optically anisotropic layer was formed on the glass substrate under the same conditions as in the examples, and the retardation of only the optically anisotropic layer was measured. The refractive index was 1.583. The results are shown in Table 2.

[Production of Second Optically Anisotropic Layer]
Film sample No. described in Examples of JP-A-2009-063983. The second optical anisotropy in which the stretching temperature and the magnification were changed in the fabrication of 111, the film thickness was 53 μm, Re (550) = 110 nm, Rth (550) = 120 nm, Re (450) / Re (550) = 0.83 A layer was made. The refractive index was nx = 1.48.

[Preparation of polarizing plate]
The second optically anisotropic layer saponified under the same conditions as the protective film 01 is placed on the polarizer-side surface of the produced polarizing plate 01 with a single-side protective film (that is, the polarizer 1 is sandwiched). , PVA (manufactured by Kuraray Co., Ltd., PVA-117H) 3% aqueous solution as an adhesive, roll-to-roll bonding so that the polarizer absorption axis and the slow axis of the second optically anisotropic layer are orthogonal to each other A polarizing plate was produced.

[Production of liquid crystal display device]
The polarizing plates on the front and back of a commercially available vertical alignment mode liquid crystal display device (UN40EH6030F, manufactured by Samsung) are peeled off, and the polarizing plates having the first optical anisotropic layer and the second optical anisotropic layer thus created are mutually connected. The liquid crystal display device of Example 1 was produced by pasting together so that the absorption axes of the liquid crystal were orthogonal to each other.

[Evaluation of liquid crystal display devices]
The produced liquid crystal display device was evaluated by the following method, and the results are shown in Table 2.
<Evaluation of front contrast>
The black luminance and white luminance in the front direction were measured using a measuring device (EZ-Contrast XL88, manufactured by ELDIM) when the liquid crystal display device displayed black in a dark room. White brightness / black brightness was defined as front contrast.
(Evaluation criteria)
A: Front contrast is 3000 or more B: Front contrast is less than 3000

<Evaluation of oblique light leakage and color>
{Evaluation of light leakage}
The black luminance was measured using a measuring instrument (EZ-Contrast XL88, manufactured by ELDIM) when the liquid crystal display device displayed black in a dark room. The average value of luminance at an azimuth angle of 45 °, 135 °, 225 °, and 315 ° at a polar angle of 60 ° was evaluated as light leakage Y. The absorption axis of the polarizer is arranged with an azimuth angle of 0 ° on the viewing side and an azimuth angle of 90 ° on the backlight side unless otherwise specified.
(Evaluation criteria)
A: Y <0.6 (cd / m ² )
B: 0.6 (cd / m ² ) ≦ Y <0.8 (cd / m ² )
C: 0.8 (cd / m ² ) ≦ Y

{Evaluation of color change}
Chromaticity was measured using a measuring instrument (EZ-Contrast XL88, manufactured by ELDIM) when the liquid crystal display device displayed black in a dark room. Specifically, chromaticities u ′ and v ′ are calculated in increments of 15 ° from an azimuth angle of 0 ° to 345 ° at a polar angle of 60 °, and the minimum values of u ′ and v ′ (u′min and v′min), respectively. The maximum values (u′max, v′max) were extracted, and the color change Δu′v ′ was evaluated by the following formula.
Δu′v ′ = √ ((u′max−u′min) ² + (v′max−v′min) ² )
(Evaluation criteria)
A: Δu′v ′ <0.1
B: 0.1 ≦ Δu′v ′ <0.14
C: 0.14 ≦ Δu′v ′

<Evaluation of display unevenness>
About the produced liquid crystal display device, the backlight of a liquid crystal display device is lighted at 25 degreeC relative humidity 60% after thermostatting at 40 degreeC relative humidity 95% for 24 hours, About the panel 5-10 hours after lighting, the corner of the four corners A black display screen was shot from the front of the screen with the brightness measurement camera “ProMetric” (Radian Imaging), and the light leakage was determined based on the average brightness of the entire screen and the brightness difference between the four corners where light leakage is large. And evaluated.
{Evaluation criteria for display unevenness}
A: The light leakage at the four corners of the panel is not visually recognized (light leakage from the panel is about the same as before the thermo-injection).
B: Among the four corners of the panel, slight light leakage is visible at one or two corners, but is acceptable.
C: Among the four corners of the panel, slight light leakage is visible at 3 to 4 corners, but is acceptable.
D: The light leakage at the four corners of the panel is strong and unacceptable.
Also, instead of lighting the backlight of the liquid crystal display device at 25 ° C. and 60% relative humidity for 5 hours, the backlight of the liquid crystal display device is lighted for 24 hours at 25 ° C. and 60% relative humidity after thermostating for 2 hours in a 40 ° C. DRY environment. However, the evaluation results of the amount of light leakage and display unevenness were the same as in the case of leaving for 2 hours at 25 ° C. and 60% relative humidity.

[Example 2]
[Production of first optically anisotropic layer and polarizing plate]
A polarizing plate having a first optically anisotropic layer and a first optically anisotropic layer was prepared in the same manner as in Example 1 except that coating was performed using a wire bar of # 5.0.

[Production of Second Optically Anisotropic Layer]
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution B.
(Composition of cellulose acylate solution B)
――――――――――――――――――――――――――――――――
Cellulose acetate (substitution degree 2.46) 100.0 parts by mass Compound A01 19.0 parts by mass Methylene chloride 365.5 parts by mass Methanol 54.6 parts by mass ――――――――――――――――――――
01: Compound A represents a terephthalic acid / succinic acid / propylene glycol / ethylene glycol copolymer (copolymerization ratio [mol%] = 27.5 / 22.5 / 25/25).

The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution C.
(Composition of cellulose acylate solution C)
――――――――――――――――――――――――――――――――
Cellulose acetate (substitution degree 2.79) 100.0 parts by mass Compound A01 11.0 parts by mass Silica fine particles R972 (manufactured by Nippon Aerosil) 0.15 parts by mass Methylene chloride 395.0 parts by mass Methanol 59.0 Mass part ――――――――――――――――――――――――――――――――
01: Compound A represents a terephthalic acid / succinic acid / propylene glycol / ethylene glycol copolymer (copolymerization ratio [mol%] = 27.5 / 22.5 / 25/25).

The cellulose acylate solution B was cast so as to be a core layer having a thickness of 90 μm, and the cellulose acylate solution C was cast so as to be a skin A layer having a thickness of 2 μm and a skin B layer having a thickness of 2 μm.
The obtained web (film) was peeled from the band, dried and wound up. At this time, the residual solvent amount with respect to the mass of the entire film was 0 to 0.5%. Then, the said film was sent out and 75% of TD extending | stretching was performed at 190 degreeC with the tenter, and the 2nd optically anisotropic layer with a film thickness of 40 micrometers was produced. The optical characteristics were measured, and Re (550) = 100 nm, Rth (550) = 100 nm, and Re (450) / Re (550) = 1.02. The refractive index was nx = 1.48.

[Preparation of polarizing plate]
A polarizing plate was produced in the same manner as in Example 1 except that the second optically anisotropic layer was used.

[Production and evaluation of liquid crystal display devices]
A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the above polarizing plate was used. The evaluation results are shown in Table 2.

[Example 3]
[Synthesis Example 1]
<Synthesis of spiro [fluorene-9,8′-tricyclo [4.3.0.1 ^2,5 ] [3] decene] (endo form, see formula (A) below)

In a 1000 ml flask equipped with a dropping funnel, 15.52 g (0.0934 mol) of fluorene was weighed and the inside of the system was purged with nitrogen. To this was added 165 ml of dehydrated THF, and the mixture was stirred well with a stirrer and dissolved. Next, 117 ml of a 1.6 mol / l hexane solution of n-butyllithium was gradually added dropwise while maintaining the temperature of the reaction system at -78 ° C in a dry ice bath. After completion of dropping, stirring was continued for 1 hour while maintaining the reaction system at -78 ° C. In this reaction solution, 21.60 g of 2endo, 3endo-bis- (toluene-4-sulfonyloxy) -5-norbornene ((B), endo) was dissolved in 500 ml of dehydrated THF in advance. Was gradually added dropwise while maintaining at -78 ° C. After completion of the dropwise addition, stirring was continued for 1 hour in a dry ice bath, and then the cooling bath was removed, and stirring was continued until the reaction system completely returned to room temperature (about 3 hours). After quenching by adding saline, the reaction solution was washed three times with distilled water and dried using sodium sulfate. Thereafter, the solvent is removed by heating under reduced pressure, and the obtained crystal is recrystallized using methanol to give a spiro [fluorene-9,8′-tricyclo represented by the above formula (A) as a pale yellow crystal. 5.4.3 g of [4.3.0.1 ^2,5 ] [3] decene] (endo isomer) was obtained.

[Polymer Synthesis Example 1]
As the norbornene monomer (Im), spiro [fluorene-9,8′-tricyclo [4.3.0.1 ^2,5 ] [3] decene] represented by the structural formula (A) (endo isomer) ) 1.90 g, 8- methoxycarbonyl-8-methyl tetracyclododecene represented by the following formula ^{(C) [4.4.0.1 2,5 .1 7,10} ] -3- dodecene 5.5 g, molecular weight The regulator 1-hexene (0.391 g) and toluene (16.4 g) were charged into a nitrogen-substituted reaction vessel and heated to 80 ° C. To this, 0.169 ml of a toluene solution of triethylaluminum (0.6 mol / L) and 0.138 ml of a toluene solution of methanol-modified WCl6 (0.025 mol / L) were added and reacted at 80 ° C. for 3 hours to open the ring. A copolymer solution was obtained. The resulting ring-opening copolymer had a weight average molecular weight (Mw) of 10.0 × 10 4 and a molecular weight distribution (Mw / Mn) of 4.80.

Next, the obtained ring-opening copolymer solution was put in an autoclave, and 83.8 g of toluene was further added. The hydrogenation catalyst RuHCl (CO) [P (C ₆ H ₅ )] ₃ is added at 2500 ppm with respect to the monomer charge, the hydrogen gas pressure is adjusted to 9-10 MPa, and the reaction is carried out at 160-165 ° C. for 3 hours. went. After completion of the reaction, a hydrogenated product was obtained by precipitation in a large amount of methanol solution. The resulting hydrogenated ring-opening copolymer (resin (P1)) had a weight average molecular weight (Mw) = 9.15 × 10 ⁴ , a molecular weight distribution (Mw / Mn) = 3.76, an intrinsic viscosity [η ] = 0.63, and glass transition temperature (Tg) = 184.0 ° C.

Further, the proportion of the structural unit (I) derived from spiro [fluorene-9,8′-tricyclo [4.3.0.1 ^2,5 ] [3] decene] (endo isomer) in the resin (P1) is 20 .6 mole%, the proportion of the structural unit (II) derived from 8-methoxycarbonyloxy-8-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 79.4 Mol%. As a result of analyzing the resin (P1) by ¹ H-NMR, the hydrogenation rate with respect to the olefinic double bond was 99% or more, and the residual rate of the aromatic ring was substantially 100%.

[Production of Second Optically Anisotropic Layer]
A colorless and transparent cast film having a thickness of 150 μm and a solvent residual amount of 0.2% or less was obtained from the resin (P1) obtained in Synthesis Example 1 by a methylene chloride cast method. The film was heated in a tenter to 194 ° C., which is Tg + 10 ° C., stretched 50% in the TD direction and 5% in the MD direction at a stretching rate of 220% / min, then cooled and taken out. A layer was obtained. The optical characteristics were measured with a refractive index of nx = 1.52.

[Preparation of polarizing plate]
A UV curable adhesive having the following composition is formed on the second optically anisotropic layer so as to have a thickness of 5 μm using a micro gravure coater (gravure roll: # 300, rotational speed 140% / line speed). It was set as the coated film with an adhesive agent.
Subsequently, this film with an adhesive was bonded to the polarizer 1 immersed in the polyvinyl alcohol adhesive together with the protective film 01 and the optically anisotropic layer by a roll machine.

(Composition of UV curable adhesive)
―――――――――――――――――――――――――――――――――――
・ 100 parts by mass of 2-hydroxyethyl acrylate ・ Ditrimethylolpropane tetraacrylate (product name SR355, manufactured by Sartomer Japan) 11 parts by mass ―――――――――――――――――――― ――――――――――――――――

  Electron beams were applied from both sides of the bonded film to obtain a polarizing plate 2006 having films on both sides of the polarizer. The line speed was 20 m / min, the acceleration voltage was 250 kV, and the irradiation dose was 20 kGy.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the polarizing plate having the second optically anisotropic layer was used. The evaluation results are shown in Table 2.

[Example 4]
[Synthesis Example 2]
8-methoxycarbonyloxy-8-methyl tetracyclododecene represented by the above formula ^{(C) [4.4.0.1 2,5 .1 7,10} ] -3- dodecene 50 g, a molecular weight modifier 1-hexene 3 .6 g and 100 g of toluene were charged into a nitrogen-substituted reaction vessel and heated to 80.degree. To this, 0.09 ml of a toluene solution of triethylaluminum (0.6 mol / L) and 0.29 ml of a toluene solution of methanol-modified WCl6 (0.025 mol / L) were added and reacted at 80 ° C. for 3 hours to give a polymer. Got. Subsequently, hydrogenation reaction was performed like Example 1 and hydrogenation was obtained. The resulting hydrogenated ring-opened polymer (resin (P2)) has a glass transition temperature (Tg) = 167 ° C., a weight average molecular weight (Mw) = 5.6 × 10 ⁴ , and a molecular weight distribution (Mw / Mn). = 3.20.

[Production of Second Optically Anisotropic Layer]
A colorless and transparent cast film having a thickness of 80 μm and a solvent residual amount of 0.2% or less was obtained from the resin (P2) obtained in Synthesis Example 2 by a methylene chloride cast method. This film was heated in a tenter to 194 ° C., which is Tg + 10 ° C., stretched 90% in the TD direction and 10% in the MD direction at a stretching rate of 220% / min, then cooled and taken out. A layer was obtained. The optical characteristics were measured with a refractive index of nx = 1.52.

  A polarizing plate was produced in the same manner as in Example 3 except that the second optically anisotropic layer prepared above was used.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the polarizing plate having the second optically anisotropic layer was used. The evaluation results are shown in Table 2.

[Example 5]
[Production of first optically anisotropic layer and polarizing plate]
A polarizing plate having a first optically anisotropic layer and a first optically anisotropic layer was produced in the same manner as in Example 1 except that coating was performed using a # 6.0 wire bar.

[Production of second optically anisotropic layer and polarizing plate]
1 g of compound 1 described in International Publication No. 2013/018526, 30 mg of photopolymerization initiator (trade name: Irgacure 907, manufactured by BASF), surfactant (trade name: KH-40, manufactured by AGC Seimi Chemical Co., Ltd.) 100 mg of 1% cyclopentanone was dissolved in 2.3 g of cyclopentanone. This solution was filtered through a disposable filter having a pore diameter of 0.45 μm to obtain a liquid crystal composition.

The liquid crystal composition was applied onto the polarizer-side surface of the polarizing plate 01 with a single-side protective film that was rubbed in the TD direction using a # 4 wire bar. The coating film was dried at 110 ° C. for 30 seconds to form a liquid crystal layer having a thickness of 2 μm. Thereafter, an ultraviolet ray of 2000 mJ / cm ² was irradiated from the coated surface side of the liquid crystal layer to obtain a polarizing plate.

[Measurement of optical properties]
The first optically anisotropic layer was formed on the glass substrate under the same conditions as in the examples, and the retardation of only the optically anisotropic layer was measured. The refractive index was 1.53. The results are shown in Table 2.

[Production and evaluation of liquid crystal display devices]
A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the above polarizing plate was used. The evaluation results are shown in Table 2.

[Example 6]
[Production of first optically anisotropic layer]
The pellets of ZEONOR 1430R (norbornene-based ring-opening polymer hydride, manufactured by Nippon Zeon Co., Ltd., Tg 138 ° C.) were converted to a temperature of 240 ° C. with a single screw extruder (Mitsubishi Heavy Industries, Ltd .: cylinder inner diameter 90 mm, screw L / D 25). And a transparent resin having a thickness of 80 μm was obtained. Subsequently, it was sequentially sent to a zone-heated longitudinal uniaxial (MD) stretching apparatus and a tenter stretching (transverse uniaxial (TD) stretching) apparatus, and sequentially biaxially stretched to obtain a first optically anisotropic layer having a thickness of 40 μm. The stretching temperature was 140 ° C. for both longitudinal stretching and lateral stretching, and the stretching ratio was 30% in the MD direction and 30% in the TD direction. The optical characteristics were measured with a refractive index of nx = 1.52.

[Preparation of polarizing plate]
A polarizing plate was produced in the same manner as in Example 3 except that the first optically anisotropic layer prepared above was used.

[Production and evaluation of liquid crystal display devices]
A liquid crystal display device was prepared and evaluated in the same manner as in Example 5 except that the above polarizing plate was used. The evaluation results are shown in Table 2.

[Comparative Example 1]
[Production of Second Optically Anisotropic Layer]
The surface on the polarizer side of the polarizing plate 01 with a single-side protective film was subjected to a rubbing treatment in a direction orthogonal to the absorption axis of the polarizer. On the rubbing surface, the following coating liquid A for optically anisotropic layer was applied using a bar coater with a bar count of # 2.4. Next, the film was aged for 30 seconds at a film surface temperature of 60 ° C., and then immediately irradiated with ultraviolet rays of 290 mJ / cm ² using an air-cooled metal halide lamp (produced by Eye Graphics Co., Ltd.) at an air temperature of 60 ° C. Then, the second optical complementary anisotropic layer was formed by fixing the orientation state. In the formed second optically anisotropic layer, rod-like liquid crystals are horizontally aligned, and the slow axis direction is parallel to the rubbing direction, that is, the slow axis direction is perpendicular to the absorption axis direction of the polarizer. It was. At this time, the thickness of the optically anisotropic layer was 1 μm.

(Composition of coating liquid A for retardation layer)
───────────────────────────────────
-Rod-like liquid crystalline compound 1 80 parts by mass-Rod-like liquid crystalline compound 2 20 parts by mass-Photopolymerization initiator 3.0 parts by mass (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.)
・ Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by mass ・ Fluorine-containing compound A 0.8 part by mass ・ Methyl ethyl ketone 234 parts by mass ───────────── ──────────────────────

Rod-like liquid crystalline compound 1

Rod-like liquid crystalline compound 2

Fluorine-containing compound A

[Measurement of optical properties]
The first optically anisotropic layer was formed on the glass substrate under the same conditions as in the examples, and the retardation of only the optically anisotropic layer was measured. The refractive index was 1.53. The results are shown in Table 2.

[Production and evaluation of liquid crystal display devices]
A liquid crystal display device was prepared and evaluated in the same manner as in Example 5 except that the above polarizing plate was used. The evaluation results are shown in Table 2.

[Comparative Example 2]
[Production of first optically anisotropic layer and second optically anisotropic layer]
<Dope preparation>
The composition described below was put into a mixing tank and stirred while heating to dissolve each component to prepare a dope.

(Dope composition)
―――――――――――――――――――――――――――――――――――――
Cellulose acetate (substitution degree 2.81) 100 parts by mass Triphenyl phosphate 6.8 parts by mass Biphenyldiphenyl phosphate 4.9 parts by mass Retardation developer R-1 4.0 parts by mass Average particle size 16 nm Silica particles (aerosil R972, manufactured by Nippon Aerosil Co., Ltd.) 0.15 parts by mass, dichloromethane 429.7 parts by mass, methanol 64.2 parts by mass ---------- ――――――――――――――――――

(Retardation expression agent R-1)

<Preparation of cellulose acylate film>
Using the band casting apparatus, the prepared dope was uniformly cast from a casting die to a stainless steel endless band (casting support) having a width of 2000 mm. When the amount of residual solvent in the dope reaches 40% by mass, it is peeled off from the casting support as a polymer film, conveyed without being actively stretched by a tenter, and dried at 130 ° C. in a drying zone. After that, the film thickness of the obtained unstretched film was 70 μm, and the glass transition temperature Tg was 142 ° C.
Further, casting is performed in the same manner as described above, both ends of the polymer film peeled off from the casting support are fixed with a tenter having a clip, stretched in the width direction (TD direction), and transported into the drying zone. And dried at 130 ° C., slitting the ears to obtain a film having a width of 1500 mm. The amount of residual solvent in the polymer film when stretching with a tenter was 10% by mass. Here, the transport direction (MD direction) was slightly stretched by transport when calculated from the rotational speed of the stainless steel band and the casting support and the motion speed of the tenter. The temperature during stretching was 140 ° C., the stretching ratio in the MD direction was 1.02, and the stretching ratio in the TD direction was 1.30.
The produced optically anisotropic layer had Re (550) = 50 nm, Rth (550) = 115 nm, and Re (450) / Re (550) = 1.02. The refractive index was nx = 1.48.

[Preparation of polarizing plate]
A polarizing plate was produced in the same manner as the polarizing plate having the second optical anisotropic layer of Example 1 except that the optically anisotropic layer was used.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the above polarizing plate was used. The evaluation results are shown in Table 2.

[Comparative Example 3]
[Production of Second Optically Anisotropic Layer]
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a core layer cellulose acylate dope.
(Composition of core layer cellulose acylate dope)
―――――――――――――――――――――――――――――――――――
-Cellulose acetate with an acetyl substitution degree of 2.43 100 parts by mass-Retardation adjusting agent 6 parts by mass-Methylene chloride (first solvent) 625 parts by mass-Methanol (second solvent) 93 parts by mass ――――――――――――――――――――――――――――

(Retardation adjuster)

<Preparation of matting agent dispersion>
Next, the following components including the core layer cellulose acylate dope prepared by the above method were charged into a disperser to prepare a mat agent dispersion.
(Composition of matting agent dispersion)
―――――――――――――――――――――――――――――――――――――
Silica particles having an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 0.2 parts by mass. Methylene chloride (first solvent) 72.4 parts by mass. Methanol (second solvent) 10.8 parts by mass. Core layer cellulose acylate dope 10.3 parts by mass ―――――――――――――――――――――――――――――――――――――

  100 parts by mass of the core layer cellulose acylate dope and the above matting agent dispersion were mixed in an amount such that the silica fine particles were 0.02 parts by mass with respect to the cellulose acylate to prepare a dope for film formation.

<Preparation of cellulose acylate film>
Three layers of the core layer cellulose acylate dope and the outer layer cellulose acylate dope on both sides of the core layer cellulose acylate dope were simultaneously cast on a drum at 20 ° C. from the casting port. Stripped at a solvent content of about 20% by mass, stretched at a temperature of 200 ° C with a tenter at a stretch ratio of 50%, transported a pass roll, dried at 120 ° C for 20 minutes, wound up, and second optically anisotropic A conductive layer was prepared. The film thicknesses were 25 μm, Re (550) = 110 nm, Rth (550) = 120 nm, and Re (450) / Re (550) = 1.06. The refractive index was nx = 1.48.

[Preparation of polarizing plate]
A polarizing plate was produced in the same manner as the polarizing plate having the second optical anisotropic layer of Example 1 except that the optically anisotropic layer was used.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the above polarizing plate was used. The evaluation results are shown in Table 2.

[Comparative Example 4]
[First optically anisotropic layer]
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a core layer cellulose acylate dope.
(Composition of core layer cellulose acylate dope)
―――――――――――――――――――――――――――――――――――
-Cellulose acetate with an acetyl substitution degree of 2.88 100 parts by mass-Triphenyl phosphate (plasticizer) 7 parts by mass-Biphenyldiphenyl phosphate (plasticizer) 5 parts by mass-Retardation regulator 7 parts by mass-Methylene chloride (first Solvent) 555 parts by mass Methanol (second solvent) 83 parts by mass ―――――――――――――――――――――――――――――――――――

(Retardation adjuster)

<Preparation of matting agent dispersion>
Next, the following components including the core layer cellulose acylate dope prepared by the above method were charged into a disperser to prepare a mat agent dispersion.
(Composition of matting agent dispersion)
―――――――――――――――――――――――――――――――――――――
Silica particles having an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 0.2 parts by mass. Methylene chloride (first solvent) 72.4 parts by mass. Methanol (second solvent) 10.8 parts by mass. Core layer cellulose acylate dope 10.3 parts by mass ―――――――――――――――――――――――――――――――――――――

  100 parts by mass of the core layer cellulose acylate dope and the above matting agent dispersion were mixed in an amount such that the silica fine particles were 0.02 parts by mass with respect to the cellulose acylate to prepare a dope for film formation.

<Preparation of cellulose acylate film>
Three layers of the core layer cellulose acylate dope and the outer layer cellulose acylate dope on both sides of the core layer cellulose acylate dope were simultaneously cast on a drum at 20 ° C. from the casting port. It peeled off in the state of solvent content rate of about 20 mass%, conveyed the pass roll, dried at 120 degreeC for 20 minutes, and wound up, and produced the 1st optically anisotropic layer. The film thicknesses were 65 μm, Re (550) = 0 nm, Rth (550) = 135 nm, and Re (450) / Re (550) = 1.08. The refractive index was nx = 1.48.

[Preparation of polarizing plate]
A polarizing plate having the first optical anisotropic layer was produced in the same manner as the polarizing plate having the second optical anisotropic layer of Example 1 except that the first optical anisotropic layer was used.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the above polarizing plate was used. The evaluation results are shown in Table 2.

[Example 7]
[Production of first optically anisotropic layer and polarizing plate]
The following compound was dissolved in methyl ethyl ketone to prepare a solid content concentration of 30.6%.
――――――――――――――――――――――――――――――――――――
-Discotic liquid crystalline compound 4-1 72.0 parts by mass-Discotic liquid crystalline compound 4-2 18.0 parts by mass-Discotic liquid crystalline compound 3-1 10.0 parts by mass-Polymerization initiator: Compound 3- 3 3.0 parts by mass / polymerization initiator: compound 3-4 1.0 part by mass / fluorine-containing surfactant: compound 3-5 0.8 parts by mass / adhesion improver: compound 3-6 0.1 part by mass ――――――――――――――――――――――――――――――――――――

(Compound 4-1)

(Compound 4-2)

The coating solution was applied to the surface on the polarizer side of the polarizing plate 01 with a single-side protective film prepared above using a # 3.4 wire bar and dried. The discotic liquid crystalline compound was aligned by heating at 80 ° C. for 90 seconds. Thereafter, 290 mJ / cm ² of ultraviolet light was immediately irradiated at a temperature of 80 ° C. to polymerize the discotic liquid crystalline compound, fix the alignment state, and form the first optical anisotropic layer. The thickness of the formed optically anisotropic layer was 2 μm. The thickness of the optically anisotropic layer was measured with a laser film thickness meter.

[Measurement of optical properties]
The first optically anisotropic layer was formed on the glass substrate under the same conditions as in the examples, and the retardation of only the optically anisotropic layer was measured. The refractive index was 1.583. The results are shown in Table 2.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the above polarizing plate was used. The evaluation results are shown in Table 3.

[Example 8]
[Production of first optically anisotropic layer and polarizing plate]
It was produced in the same manner as in Example 7 except that coating was performed using a # 4.0 wire bar.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 2 except that the above polarizing plate was used. The evaluation results are shown in Table 3.

[Example 9]
A liquid crystal display device was produced and evaluated in the same manner as in Example 3 except that the first optically anisotropic layer produced in Example 7 and its polarizing plate were used. The evaluation results are shown in Table 3.

[Example 10]
A liquid crystal display device was produced and evaluated in the same manner as in Example 4 except that the first optically anisotropic layer produced in Example 7 and its polarizing plate were used. The evaluation results are shown in Table 3.

[Example 11]
[Production of first optically anisotropic layer and polarizing plate]
This was prepared in the same manner as in Example 7 except that coating was performed using a # 5.0 wire bar.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 5 except that the above polarizing plate was used. The evaluation results are shown in Table 3.

[Example 12]
[Production of Second Optically Anisotropic Layer]
<Synthesis Example 3>
Spiro [fluorene-9,8′-tricyclo [4.3.0.1 ^2,5 ] [3] decene] (endo isomer) represented by the above formula (A) obtained in the same manner as in Synthesis Example 1. 90 g, the above formula (C) represented by 8-methoxycarbonyloxy-8-methyl-tetracyclo in [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 6.20 g, a molecular weight regulator 0.419 g of 1-hexene and 18.6 g of toluene were charged into a nitrogen-substituted reaction vessel and heated to 80 ° C. To this was added 0.267 ml of a toluene solution of triethylaluminum (0.6 mol / L) and 0.066 ml of a toluene solution of methanol-modified WCl6 (0.025 mol / L), and the mixture was reacted at 80 ° C. for 3 hours to open the ring. A copolymer solution was obtained. The resulting ring-opening copolymer had a weight average molecular weight (Mw) of 11.4 × 10 4 and a molecular weight distribution (Mw / Mn) of 4.60.

  Next, a hydrogenation reaction was performed in the same manner as in Synthesis Example 1 to obtain a hydrogenated product. The resulting hydrogenated product of the ring-opening copolymer (resin (P3)) has a weight average molecular weight (Mw) = 10.6 × 10 4, a molecular weight distribution (Mw / Mn) = 3.52, and an intrinsic viscosity [η]. = 0.70 and glass transition temperature (Tg) = 184.0 ° C.

Further, the ratio of the structural unit (I) derived from spiro [fluorene-9,8′-tricyclo [4.3.0.1 ^2,5 ] [3] decene] (endo isomer) in the resin (P3) is 19 .6 mole%, the proportion of the structural unit (II) derived from 8-methoxycarbonyloxy-8-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 80.4 Mol%. As a result of analyzing the resin (P3) by 1H-NMR, the hydrogenation rate with respect to the olefinic double bond was 99% or more, and the residual rate of the aromatic ring was substantially 100%.

  A colorless and transparent cast film having a thickness of 120 μm and a solvent residual amount of 0.2% or less was obtained from the resin (P3) obtained in Synthesis Example 3 by a methylene chloride cast method. This film is heated in a tenter to 194 ° C. which is Tg + 10 ° C., stretched 50% in the TD direction and 5% in the MD direction at a stretching rate of 220% / min, and then cooled and taken out to obtain an optically anisotropic layer. It was. The optical characteristics were measured with a refractive index of nx = 1.52.

  A liquid crystal display device was produced and evaluated in the same manner as in Example 3 except that the second optically anisotropic layer was used. The evaluation results are shown in Table 3.

[Example 13]
[Production of Second Optically Anisotropic Layer]
<Synthesis Example 4>
1. Spiro [fluorene-9,8′-tricyclo [4.3.0.1 ^2,5 ] [3] decene] (endo form) represented by the above formula (A) obtained in the same manner as in Synthesis Example 1. 200 g, the above formula (C) represented by 8-methoxycarbonyloxy-8-methyl-tetracyclo in [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 4.90 g, a molecular weight regulator 0.358 g of 1-hexene and 13.8 g of toluene were charged into a nitrogen-substituted reaction vessel and heated to 80 ° C. To this, 0.050 ml of a toluene solution of triethylaluminum (0.6 mol / L) and 0.225 ml of a toluene solution of methanol-modified WCl6 (0.025 mol / L) were added and reacted at 80 ° C. for 3 hours to open the ring. A copolymer solution was obtained. The resulting ring-opening copolymer had a weight average molecular weight (Mw) of 8.32 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 5.06.

Next, a hydrogenation reaction was performed in the same manner as in Synthesis Example 1 to obtain a hydrogenated product. The resulting hydrogenated product of the ring-opening copolymer (resin (P4)) has a weight average molecular weight (Mw) = 7.39 × 10 ⁴ , a molecular weight distribution (Mw / Mn) = 4.06, an intrinsic viscosity [η ] = 0.54 and glass transition temperature (Tg) = 184.0 ° C. Further, the ratio of the structural unit (I) derived from spiro [fluorene-9,8′-tricyclo [4.3.0.1 ^2,5 ] [3] decene] (endo isomer) in the resin (P4) is 22 .7 mol%, the proportion of the structural unit (II) derived from 8-methoxycarbonyloxy-8-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 77.3 Mol%. As a result of analyzing the resin (P4) by ¹ H-NMR, the hydrogenation rate with respect to the olefinic double bond was 99% or more, and the residual rate of the aromatic ring was substantially 100%.

  A colorless and transparent cast film having a thickness of 250 μm and a residual solvent amount of 0.2% or less was obtained from the resin (P4) obtained in Synthesis Example 4 by a methylene chloride cast method. This film is heated in a tenter to 194 ° C. which is Tg + 10 ° C., stretched 50% in the TD direction and 5% in the MD direction at a stretching rate of 220% / min, and then cooled and taken out to obtain an optically anisotropic layer. It was. The optical characteristics were measured with a refractive index of nx = 1.52.

  A liquid crystal display device was produced and evaluated in the same manner as in Example 3 except that the second optically anisotropic layer was used. The evaluation results are shown in Table 3.

[Example 14]
[Production of Second Optically Anisotropic Layer]
<Synthesis Example 5>
2. Spiro [fluorene-9,8′-tricyclo [4.3.0.1 ^2,5 ] [3] decene] (endo form) represented by the above formula (A) obtained in the same manner as in Synthesis Example 1. 200 g, the above formula (C) represented by 8-methoxycarbonyloxy-8-methyl-tetracyclo in [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 5.70 g, a molecular weight regulator 0.443 g of 1-hexene and 17.4 g of toluene were charged into a nitrogen-substituted reaction vessel and heated to 80 ° C. To this, 0.069 ml of a toluene solution of triethylaluminum (0.6 mol / L) and 0.281 ml of a toluene solution of methanol-modified WCl6 (0.025 mol / L) were added and reacted at 80 ° C. for 3 hours to open the ring. A copolymer solution was obtained. The resulting ring-opening copolymer had a weight average molecular weight (Mw) of 7.63 × 10 4 and a molecular weight distribution (Mw / Mn) of 6.34.

Next, a hydrogenation reaction was performed in the same manner as in Synthesis Example 1 to obtain a hydrogenated product. The resulting hydrogenated product of the ring-opening copolymer (resin (P5)) has a weight average molecular weight (Mw) = 6.41 × 10 ⁴ , a molecular weight distribution (Mw / Mn) = 3.77, an intrinsic viscosity [η ] = 0.48, and glass transition temperature (Tg) = 173.0 ° C.

Moreover, the ratio of the structural unit (I) derived from spiro [fluorene-9,8′-tricyclo [4.3.0.1 ^2,5 ] [3] decene] (endo isomer) in the resin (P5) is 27. 2.0 mol%, the proportion of the structural unit (II) derived from 8-methoxycarbonyloxy-8-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 73.0 Mol%. As a result of analyzing the resin (P5) by 1H-NMR, the hydrogenation rate with respect to the olefinic double bond was 99% or more, and the residual rate of the aromatic ring was substantially 100%.

  A colorless and transparent cast film having a thickness of 300 μm and a solvent residual amount of 0.2% or less was obtained from the resin (P5) obtained in Synthesis Example 5 by a methylene chloride cast method. This film is heated in a tenter to 194 ° C. which is Tg + 10 ° C., stretched 50% in the TD direction and 5% in the MD direction at a stretching rate of 220% / min, and then cooled and taken out to obtain an optically anisotropic layer. It was. The optical characteristics were measured with a refractive index of nx = 1.52.

  A liquid crystal display device was produced and evaluated in the same manner as in Example 3 except that the second optically anisotropic layer was used. The evaluation results are shown in Table 3.

[Example 15]
A liquid crystal display device was produced and evaluated in the same manner as in Example 12 except that the first optical anisotropic layer produced in Example 7 and its polarizing plate were used. The evaluation results are shown in Table 3.

[Example 16]
A liquid crystal display device was produced and evaluated in the same manner as in Example 13 except that the first optically anisotropic layer produced in Example 7 and its polarizing plate were used. The evaluation results are shown in Table 3.

[Example 17]
[Preparation of protective film]
<Production of raw material polyester>
{Production of raw material polyester 1}
As shown below, terephthalic acid and ethylene glycol are directly reacted to distill off water, esterify, and then, using a direct esterification method in which polycondensation is performed under reduced pressure, raw polyester 1 ( Sb catalyst system PET) was obtained.

<Esterification reaction>
In the first esterification reactor, 4.7 tons of high-purity terephthalic acid and 1.8 tons of ethylene glycol are mixed for 90 minutes to form a slurry, and continuously at a flow rate of 3800 kg / h. Supplied to. Further, an ethylene glycol solution of antimony trioxide was continuously supplied, and the reaction was carried out at a reaction vessel temperature of 250 ° C. with stirring and an average residence time of about 4.3 hours. At this time, antimony trioxide was continuously added so that the amount of Sb added was 150 ppm in terms of element.

  This reaction product was transferred to a second esterification reaction vessel, and reacted with stirring at a temperature in the reaction vessel of 250 ° C. and an average residence time of 1.2 hours. To the second esterification reaction tank, an ethylene glycol solution of magnesium acetate and an ethylene glycol solution of trimethyl phosphate are continuously supplied so that the added amount of Mg and the added amount of P are 65 ppm and 35 ppm in terms of element, respectively. did.

<Polycondensation reaction>
The esterification reaction product obtained above was continuously supplied to the first polycondensation reaction tank, and with stirring, the reaction temperature was 270 ° C. and the reaction tank internal pressure was 20 torr (2.67 × 10 ⁻³ MPa). The polycondensation was carried out with a residence time of about 1.8 hours.

Further, the mixture was transferred to the second double condensation reaction tank, and while stirring in this reaction tank, the reaction tank temperature was 276 ° C., the reaction tank pressure was 5 torr (6.67 × 10 ⁻⁴ MPa), and the residence time was about 1.2 hours. The reaction (polycondensation) was performed under the conditions.

Subsequently, it was further transferred to the third triple condensation reaction tank. In this reaction tank, the reaction tank temperature was 278 ° C., the reaction tank pressure was 1.5 torr (2.0 × 10 ⁻⁴ MPa), and the residence time was 1.5 hours. The reaction product (polyethylene terephthalate (PET)) was obtained by reaction (polycondensation) under the following conditions.

  Next, the obtained reaction product was discharged into cold water in a strand shape and immediately cut to prepare polyester pellets (cross section: major axis: about 4 mm, minor axis: about 2 mm, length: about 3 mm).

  The obtained polymer had an intrinsic viscosity IV = 0.63. This polymer was designated as raw material polyester 1.

  IV is obtained by dissolving the raw material polyester film 1 in a 1,1,2,2-tetrachloroethane / phenol (= 2/3 [mass ratio]) mixed solvent, and from the solution viscosity at 25 ° C. in the mixed solvent. Asked.

{Production of raw material polyester 2}
10 parts by weight of dried ultraviolet absorber (2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazinon-4-one), raw material polyester 1 (IV = 0.63) 90 The raw material polyester 2 containing an ultraviolet absorber was obtained by mixing the mass parts and using a kneading extruder.

<Preparation of polyester film>
{Film forming process}
The raw material polyester 1 (90 parts by mass) and the raw material polyester 2 containing ultraviolet absorbers (10 parts by mass) are dried to a water content of 20 ppm or less and then put into the hopper 1 of a single-screw kneading extruder 1 having a diameter of 50 mm. Then, it was melted at 300 ° C. by the extruder 1 (intermediate layer II layer). Moreover, after drying the raw material polyester 1 to a water content of 20 ppm or less, it was put into a hopper 2 of a single screw kneading extruder 2 having a diameter of 30 mm and melted at 300 ° C. by the extruder 2 (outer layer I layer, outer layer III layer). .
These two kinds of polymer melts are respectively passed through a gear pump and a filter (pore diameter 20 μm), and then the polymer extruded from the extruder 1 is extruded into an intermediate layer (II layer) in a two-type three-layer confluence block. The polymer extruded from the machine 2 was laminated so as to be outer layers (I layer and III layer), and extruded from a die into a sheet.
The molten resin was extruded from the die under the conditions that the pressure fluctuation was 1% and the temperature distribution of the molten resin was 2%. Specifically, the back pressure was increased by 1% with respect to the average pressure in the barrel of the extruder, and the piping temperature of the extruder was heated at a temperature 2% higher than the average temperature in the barrel of the extruder.
The molten resin extruded from the die was extruded onto a cooling cast drum set at a temperature of 25 ° C., and was brought into close contact with the cooling cast drum using an electrostatic application method. It peeled off using the peeling roll arrange | positioned facing the cooling cast drum, and the unstretched polyester film 2 was obtained. At this time, the discharge amount of each extruder was adjusted so that the ratio of the thicknesses of the I layer, the II layer, and the III layer was 10:80:10.

  The obtained unstretched polyester film 2 was horizontally stretched under the following conditions to produce a polyester film having a thickness of 80 μm, an in-plane retardation Re of 8200 nm, and a thickness direction retardation Rth of 9400 nm.

<Horizontal stretching conditions>
-Transverse stretching temperature: 90 ° C
・ Horizontal stretch ratio: 4.3 times

Next, a heat setting treatment was performed while controlling the film surface temperature of the polyester film prepared in the following range.
<Heat setting conditions>
・ Heat setting temperature: 180 ℃
・ Heat setting time: 15 seconds

The polyester film after heat setting was heated to the following temperature to relax the film.
<Relaxation conditions>
-Thermal relaxation temperature: 170 ° C
-Thermal relaxation rate: TD direction (film width direction, lateral direction) 2%

  Next, the polyester film after heat relaxation was cooled at a cooling temperature of 50 ° C. (Hereinafter, the prepared polyester film after heat relaxation is abbreviated as “stretched PET 80 μm, three-layer co-casting”.)

<Preparation of stretched PET 80 μm with HC layer>
{Formation of easy adhesion layer}
<Formation of hard coat layer side easy adhesion layer>
The following compounds were mixed in the following ratio to prepare a coating liquid H1 for the hard coat layer-side easy-adhesion layer. On the stretched PET 80 μm three-layer co-casting obtained above, the coating liquid H1 for the hard coat layer side easy-adhesion layer was applied in a film thickness of 0.09 μm.

(Composition of coating liquid H1 for the hard coat layer side easy-adhesion layer)
――――――――――――――――――――――――――――――――――
-Polyester resin: (IC) 60 parts by mass-Acrylic resin: (II) 25 parts by mass-Melamine compound: (VIB) 10 parts by mass-Particles: (VII) 5 parts by mass-------- ―――――――――――――――――――――――
Details of the compounds used are shown below.
・ Polyester resin: (IC)
A sulfonic acid aqueous dispersion monomer composition of a polyester resin copolymerized with a monomer having the following composition: (acid component) terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // (diol component) ethylene glycol / 1,4- Butanediol / diethylene glycol = 56/40/4 // 70/20/10 (mol%)

・ Acrylic resin: (II)
Aqueous dispersion of acrylic resin polymerized with monomers of the following composition Ethyl acrylate / n-butyl acrylate / methyl methacrylate / N-methylol acrylamide / acrylic acid = 65/21/10/2/2 (mass%) emulsion polymer ( Emulsifier: Anionic surfactant)
-Urethane resin: (IIIB)
400 parts by weight of a polycarbonate polyol composed of 1,6-hexanediol and diethyl carbonate having a number average molecular weight of 2000, 10.4 parts by weight of neopentyl glycol, 58.4 parts by weight of isophorone diisocyanate, 74.3 parts by weight of dimethylol butanoic acid. An aqueous dispersion of urethane resin obtained by neutralizing a prepolymer consisting of parts by mass with triethylamine and extending the chain with isophoronediamine.
Melamine compound: (VIB) hexamethoxymethylmelamine Particles: (VII) Silica sol having an average particle size of 65 nm

{Formation by applying hard coat layer}
Thereafter, a mixed coating liquid (acryl-1) having the following composition was applied to the surface on which the coating liquid H1 for the hard coat layer side easy-adhesion layer of the stretched PET 80 μm three-layer co-cast obtained above was applied, and the dry film thickness was 5 μm. It was applied and dried to form a hard coat layer by irradiation with ultraviolet rays.
―――――――――――――――――――――――――――――――――――――
-85 parts by mass of dipentaerythritol hexaacrylate-15 parts by mass of 2-hydroxy-3-phenoxypropyl acrylate-Photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals)
5 parts by mass, 200 parts by mass of methyl ethyl ketone ―――――――――――――――――――――――――――――――――――――

  The PET film with a hard coat layer thus obtained was made into 80 μm of stretched PET with an HC layer, and a protective film was produced.

[Preparation of polarizing plate]
<Preparation of polarizer-side easy adhesion layer>
{Preparation of coating liquid P1 for polarizer side easy adhesion}
<Synthesis of Copolyester Resin (A-1)>
―――――――――――――――――――――――――――――――――――
-Dimethyl terephthalate 194.2 parts by mass-Dimethyl isophthalate 184.5 parts by mass-Dimethyl-5-sodium sulfoisophthalate 14.8 parts by mass-Diethylene glycol 233.5 parts by mass-Ethylene glycol 136.6 parts by mass-Tetra-n -Butyl titanate 0.2 parts by mass ---------
The above compound was charged, and a transesterification reaction was performed at a temperature of 160 to 220 ° C. over 4 hours. Next, the temperature was raised to 255 ° C., and the pressure of the reaction system was gradually reduced, followed by reaction for 1 hour 30 minutes under a reduced pressure of 30 Pa to obtain a copolymerized polyester resin (A-1).

<Preparation of polyester aqueous dispersion (Aw-1)>
―――――――――――――――――――――――――――――――――――
・ Copolymerized polyester resin (A-1) 30 parts by mass ・ Ethylene glycol n-butyl ether 15 parts by mass ―――――――――――――――――――――――――――― ―――――――
The above compound was added and heated and stirred at 110 ° C. to dissolve the resin. After the resin was completely dissolved, 55 parts by mass of water was gradually added to the polyester solution while stirring. After the addition, the solution was cooled to room temperature while stirring to prepare a milky white polyester aqueous dispersion (Aw-1) having a solid content of 30% by mass.

<Preparation of aqueous polyvinyl alcohol solution (Bw-1)>
90 parts by weight of water was added, and 10 parts by weight of polyvinyl alcohol resin (manufactured by Kuraray) (B-1) having a saponification degree of 88% and a polymerization degree of 500 was gradually added while stirring. After the addition, the solution was heated to 95 ° C. while stirring to dissolve the resin. After dissolution, the mixture was cooled to room temperature with stirring to prepare a polyvinyl alcohol aqueous solution (Bw-1) having a solid content of 10% by mass.

<Preparation of block polyisocyanate aqueous dispersion (C-1)>
―――――――――――――――――――――――――――――――――――――
・ Polyisocyanate compound with isocyanurate structure made from hexamethylene diisocyanate (Duranate TPA, manufactured by Asahi Kasei Chemicals)
100 parts by mass ・ Propylene glycol monomethyl ether acetate 55 parts by mass ・ Polyethylene glycol monomethyl ether (average molecular weight 750) 30 parts by mass ―――――――――――――――――――――――――― ――――――――――――
The above compound was charged and held at 70 ° C. for 4 hours under a nitrogen atmosphere. Thereafter, the reaction solution temperature was lowered to 50 ° C., and 47 parts by mass of methyl ethyl ketoxime was added dropwise. The infrared spectrum of the reaction solution was measured to confirm that the absorption of the isocyanate group had disappeared, and a block polyisocyanate aqueous dispersion (C-1) having a solid content of 75% by mass was obtained.

The following coating agent was mixed and the coating liquid P1 for polarizer side easy adhesion which the mass ratio of polyester-type resin (A) / polyvinyl alcohol-type resin (B) becomes 70/30 was produced.
―――――――――――――――――――――――――――――――――――――
・ Water 40.61 mass%
・ Isopropanol 30.00% by mass
-Polyester water dispersion (Aw-1) 11.67 mass%
-Polyvinyl alcohol aqueous solution (Bw-1) 15.00 mass%
-Block isocyanate type crosslinking agent (C-1) 0.67 mass%
・ Particles (silica sol with an average particle diameter of 100 nm, solid content concentration of 40% by mass)
1.25% by mass
・ Catalyst (organotin-based compound solid content concentration 14% by mass) 0.3% by mass
・ Surfactant (silicone, solid concentration 10% by mass) 0.5% by mass
―――――――――――――――――――――――――――――――――――――

<Preparation of easy-adhesion layer to protective film>
By applying the reverse roll method, the coating liquid P1 for polarizer side easy adhesion is adjusted to 0.12 g / m ² after drying on the PET 80 μm three-layer co-casting side of the protective film prepared above. Then, an easy-adhesion layer was produced on the protective film.

<Bonding of polarizer and protective film>
The surface of the protective film coated with the above easy-adhesion layer is laminated with a roll-to-roll with the surface on the easy-adhesion layer side as a polarizer side, and while transporting on the roll to cure the adhesive to the obtained laminate , 70 ° C., 60% relative humidity, and pasted. Thus, the polarizing plate 02 with a single-sided protective film was produced.
In the following examples and comparative examples, unless otherwise specified, a polarizing plate with a single-sided protective film having a hard coat layer on the viewing side and a polarizing plate with a single-sided protective film having no hard coat layer on the backlight side are provided. Each polarizing plate was prepared using the same.

  The stacking order of the first optically anisotropic layer, the second optically anisotropic layer and the vertical alignment mode liquid crystal cell is changed to the stacking order shown in Table 4, and the backlight side polarizing plate is changed to a polarizing plate with a single-side protective film 02. A liquid crystal display device was produced and evaluated in the same manner as in Example 1 except that the liquid crystal display device was produced using this. The evaluation results are shown in Table 4.

[Example 18]
A liquid crystal display device was produced in the same manner as in Example 3 except that the stacking order of the first optically anisotropic layer, the second optically anisotropic layer, and the vertical alignment mode liquid crystal cell was changed to the stacking order shown in Table 4. And evaluated. The evaluation results are shown in Table 4.

[Example 19]
A liquid crystal display device was produced in the same manner as in Example 5 except that the stacking order of the first optically anisotropic layer, the second optically anisotropic layer, and the vertical alignment mode liquid crystal cell was changed to the stacking order shown in Table 4. And evaluated. The evaluation results are shown in Table 4.

[Example 20]
A liquid crystal display device was produced and evaluated in the same manner as in Example 1 except that the polarizing plate 01 with a single-side protective film on the viewing side and the backlight side was changed to the polarizing plate 02 with a single-side protective film. The evaluation results are shown in Table 4.

[Example 21]
A liquid crystal display device was produced and evaluated in the same manner as in Example 3 except that the polarizing plate 01 with a single-side protective film on the viewing side and the backlight side was changed to the polarizing plate 02 with a single-side protective film. The evaluation results are shown in Table 4.

[Example 22]
A liquid crystal display device was produced and evaluated in the same manner as in Example 5 except that the polarizing plate 01 with a single-side protective film on the viewing side and the backlight side was changed to the polarizing plate 02 with a single-side protective film. The evaluation results are shown in Table 4.

[Example 23]
A liquid crystal display device was produced in the same manner as in Example 20 except that the stacking order of the first optically anisotropic layer, the second optically anisotropic layer, and the vertical alignment mode liquid crystal cell was changed to the stacking order shown in Table 4. And evaluated. The evaluation results are shown in Table 4.

[Example 24]
A liquid crystal display device was produced in the same manner as in Example 21 except that the stacking order of the first optically anisotropic layer, the second optically anisotropic layer and the vertical alignment mode liquid crystal cell was changed to the stacking order shown in Table 4. And evaluated. The evaluation results are shown in Table 4.

[Example 25]
A liquid crystal display device was produced in the same manner as in Example 22 except that the stacking order of the first optically anisotropic layer, the second optically anisotropic layer, and the vertical alignment mode liquid crystal cell was changed to the stacking order shown in Table 4. And evaluated. The evaluation results are shown in Table 4.

[Example 26]
Except for changing the stacking order of the first protective film, the second protective film, the first optically anisotropic layer, the second optically anisotropic layer and the vertical alignment mode liquid crystal cell to the stacking order shown in Table 5. A liquid crystal display device was produced and evaluated in the same manner as in Example 17. The evaluation results are shown in Table 5.

[Example 27]
A liquid crystal display device was produced in the same manner as in Example 3 except that the stacking order of the first optically anisotropic layer, the second optically anisotropic layer and the vertical alignment mode liquid crystal cell was changed to the stacking order shown in Table 5. And evaluated. The evaluation results are shown in Table 5.

[Example 28]
A liquid crystal display device was produced in the same manner as in Example 5 except that the stacking order of the first optically anisotropic layer, the second optically anisotropic layer, and the vertical alignment mode liquid crystal cell was changed to the stacking order shown in Table 5. And evaluated. The evaluation results are shown in Table 5.

[Example 29]
A liquid crystal display device was produced in the same manner as in Example 1 except that the stacking order of the first optically anisotropic layer, the second optically anisotropic layer, and the vertical alignment mode liquid crystal cell was changed to the stacking order shown in Table 5. And evaluated. The evaluation results are shown in Table 5.

[Example 30]
A liquid crystal display device was produced in the same manner as in Example 3 except that the stacking order of the first optically anisotropic layer, the second optically anisotropic layer and the vertical alignment mode liquid crystal cell was changed to the stacking order shown in Table 5. And evaluated. The evaluation results are shown in Table 5.

[Example 31]
A liquid crystal display device was produced in the same manner as in Example 5 except that the stacking order of the first optically anisotropic layer, the second optically anisotropic layer, and the vertical alignment mode liquid crystal cell was changed to the stacking order shown in Table 5. And evaluated. The evaluation results are shown in Table 5.

[Example 32]
A liquid crystal display device was produced and evaluated in the same manner as in Example 29 except that the polarizing plate 01 with a single-side protective film on the viewing side was changed to the polarizing plate 02 with a single-side protective film. The evaluation results are shown in Table 5.

[Example 33]
(Preparation of alignment film)
28 mL / m ² of an alignment film coating solution having the following composition was applied to the polarizer-side surface of the prepared polarizing plate 01 with a single-side protective film using a # 16 wire bar coater. The film was dried with warm air of 80 ° C. for 60 seconds to produce an alignment film. The thickness of the alignment film after drying was 0.5 μm.
(Composition of the coating liquid for forming the alignment film)
────────────────────────────────────
-10 parts by weight of the following modified polyvinyl alcohol-371 parts by weight of water-119 parts by weight of methanol-0.5 parts by weight of glutaraldehyde (crosslinking agent)-0.35 parts by weight of citric acid ester (AS-3 manufactured by Sankyo Chemical Co., Ltd.) ────────────────────────────────────

[Formation of first optically anisotropic layer]
The following compounds 3-1 to 3-5 were dissolved in methyl ethyl ketone to prepare a solid content concentration of 36.2%.
────────────────────────────────────
-Discotic liquid crystalline compound 3-1 91.0 parts by mass-Compound 3-2 9.0 parts by mass-Polymerization initiator: Compound 3-3 3.0 parts by mass-Polymerization initiator: Compound 3-4 1.0 Part by mass / Fluorine-containing surfactant: Compound 3-5 0.8 part by mass ───────────────────────────────── ────

The coating solution was applied to the alignment film surface of the polarizing plate 01 with a single-side protective film prepared above using a # 4.4 wire bar and dried. The discotic liquid crystalline compound was aligned by heating at 70 ° C. for 90 seconds. Thereafter, 290 mJ / cm ² of ultraviolet light was immediately irradiated under a temperature condition of 70 ° C. to polymerize the discotic liquid crystalline compound and fix the alignment state. The thickness of the formed optically anisotropic layer was 2 μm. The thickness of the optically anisotropic layer was measured with a laser film thickness meter.

[Measurement of optical properties]
The first optically anisotropic layer was formed on the glass substrate under the same conditions as in the examples, and the retardation of only the optically anisotropic layer was measured. The refractive index was 1.583. The results are shown in Table 5.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the polarizing plate prepared above was used. The evaluation results are shown in Table 5.

[Example 34]
[Production of transfer material]
<Preparation of temporary substrate>
As a temporary substrate, TD80 (manufactured by FUJIFILM Corporation) was used.

<Formation of alignment film>
The alignment film coating solution having the following composition was directly applied to the surface of the prepared temporary substrate directly with a # 14 wire bar without applying a saponification treatment. 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 the coating liquid for forming the alignment film)
────────────────────────────────────
-10 parts by weight of the following modified polyvinyl alcohol (PVA)-371 parts by weight of water-119 parts by weight of methanol-0.5 parts by weight of glutaraldehyde ──────────────────── ────────────────

<Preparation of optically anisotropic layer for transfer>
{Preparation of first optically anisotropic layer}
The following compound was mixed and dissolved to prepare a coating liquid B for optically anisotropic layer.
(Composition of coating liquid B for optically anisotropic layer)
──────────────────────────────
Discotic polymerizable liquid crystal compound 3-1 91.0 parts by mass Compound 3-2 9.0 parts by mass Polymerization initiator: Compound 3-3 3.0 parts by mass Polymerization initiator: Compound 3-4 1 0.0 part by mass, fluorine-containing surfactant: Compound 3-5 0.8 part by mass, adhesion improver: Compound 3-6 0.5 part by mass, methyl ethyl ketone 186.3 parts by mass ───────── ─────────────────────

The optically anisotropic layer coating solution B prepared above was applied onto the alignment film prepared above with a # 4.4 wire bar and dried. The discotic liquid crystalline compound was aligned by heating at 70 ° C. for 1 minute. Thereafter, 290 mJ / cm ² of ultraviolet light was immediately irradiated under a temperature condition of 70 ° C. to polymerize the discotic liquid crystalline compound, fix the alignment state, and produce an optically anisotropic layer for transfer. The thickness of the produced optically anisotropic layer was 2 μm. The thickness of the optically anisotropic layer was measured with a laser film thickness meter.

[Preparation of polarizing plate]
<Preparation of polarizing plate>
A UV curable resin was applied to the surface on the polarizer side of the polarizing plate 01 with a single-side protective film, and dried to form an adhesive layer.

<Transfer>
The transfer material prepared above is laminated by bringing the surface of the transfer optical anisotropic layer of the transfer material into contact with the surface of the adhesive layer of the polarizing plate 01 with a single-side protective film prepared above, and using a pressure roller After pressurization, UV light was irradiated to cure the UV curable composition, and the optically anisotropic layer was strongly adhered to the adhesive layer. Next, a strong adhesive roll is pressed against the back surface of the temporary substrate and rotated to separate the temporary substrate and the alignment film, and an optically anisotropic layer is laminated on the polarizing plate 01 with a single-side protective film via an adhesive. A polarizing plate was prepared.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the polarizing plate prepared above was used. The evaluation results are shown in Table 5.

[Example 35]
[Production of first optically anisotropic layer and polarizing plate]
A polarizing plate having a first optically anisotropic layer and a first optically anisotropic layer was prepared in the same manner as in Example 1 except that coating was performed using a wire bar of # 3.4.
[Production of Second Optically Anisotropic Layer]
A colorless and transparent cast film having a thickness of 190 μm and a solvent residual amount of 0.2% or less was obtained from the resin (P1) obtained in Synthesis Example 1 (Example 3) by a methylene chloride cast method. This film is heated in a tenter to 194 ° C. which is Tg + 10 ° C., stretched 30% in the TD direction and 7% in the MD direction at a stretching rate of 220% / min, and then cooled and taken out to obtain an optically anisotropic layer. It was.
A polarizing plate having a second optically anisotropic layer was prepared in the same manner as in Example 3 except that the optically anisotropic layer prepared above was used.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the polarizing plate prepared above was used. The evaluation results are shown in Table 6.

[Example 36]
[Production of first optically anisotropic layer and polarizing plate]
The first optically anisotropic layer and the first layer were the same as in Example 1 except that a # 6.0 wire bar was used and the amount of methyl ethyl ketone was adjusted and applied so that the solid content concentration was 34.3%. A polarizing plate having an optically anisotropic layer was prepared.
[Production of Second Optically Anisotropic Layer]
A colorless and transparent cast film having a thickness of 140 μm and a solvent residual amount of 0.2% or less was obtained from the resin (P1) obtained in Synthesis Example 1 (Example 3) by methylene chloride casting method. This film is heated in a tenter to 194 ° C. which is Tg + 10 ° C., stretched 95% in the TD direction and 4% in the MD direction at a stretching rate of 220% / min, and then cooled to obtain an optically anisotropic layer. It was.
A polarizing plate having a second optically anisotropic layer was prepared in the same manner as in Example 3 except that the optically anisotropic layer prepared above was used.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the polarizing plate prepared above was used. The evaluation results are shown in Table 6.

[Example 37]
[Production of Second Optically Anisotropic Layer]
A colorless and transparent cast film having a thickness of 230 μm and a residual solvent amount of 0.2% or less was obtained from the resin (P4) obtained in Synthesis Example 4 (Example 13) by a methylene chloride cast method. This film is heated in a tenter to 194 ° C. which is Tg + 10 ° C., stretched 95% in the TD direction and 4% in the MD direction at a stretching rate of 220% / min, and then cooled to obtain an optically anisotropic layer. It was.
A polarizing plate having a second optically anisotropic layer was prepared in the same manner as in Example 3 except that the optically anisotropic layer prepared above was used.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 36 except that the polarizing plate prepared above was used. The evaluation results are shown in Table 6.

[Comparative Example 5]
[Production of Second Optically Anisotropic Layer]
Cellulose acylate was synthesized by the method described in JP-A-10-45804 and 08-231761, and the degree of substitution was measured. Specifically, sulfuric acid (7.8 parts by mass with respect to 100 parts by mass of cellulose) was added as a catalyst, carboxylic acid serving as a raw material for the acyl substituent was added, and an acylation reaction was performed at 40 ° C. At this time, the kind and substitution degree of the acyl group were adjusted by adjusting the kind and amount of the carboxylic acid. In addition, aging was performed at 40 ° C. after acylation. Further, the low molecular weight component of the cellulose acylate was removed by washing with acetone.

<Preparation of cellulose acylate solution C01>
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution. The amount of the solvent (methylene chloride and methanol) was appropriately adjusted so that the solid content concentration of each cellulose acylate solution was 22% by mass.
――――――――――――――――――――――――――――――――
Cellulose acetate (substitution degree 2.45) 100.0 parts by mass The following additive Compound A 19.0 parts by mass Methylene chloride 365.5 parts by mass Methanol 54.6 parts by mass ―――――――――――――――――――――――

<Preparation of cellulose acylate solution C02>
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution. The amount of the solvent (methylene chloride and methanol) was appropriately adjusted so that the solid content concentration of each cellulose acylate solution was 22% by mass.
――――――――――――――――――――――――――――――――
Cellulose acetate (substitution degree 2.81) 100.0 parts by mass The following additive Compound A 12.0 parts by mass Methylene chloride 365.5 parts by mass Methanol 54.6 parts by mass ―――――――――――――――――――――――
Compound A represents a terephthalic acid / succinic acid / ethylene glycol / propylene glycol copolymer (copolymerization ratio [mol%] = 27.5 / 22.5 / 25/25).
Compound A is a non-phosphate ester compound and a retardation developer. The end of compound A is sealed with an acetyl group.

The cellulose acylate solution C01 was cast using a band stretching machine so that the cellulose acylate solution C02 became a skin layer A having a thickness of 2 μm so that the core layer had a thickness of 56 μm. Subsequently, the obtained web (film) was peeled from the band, sandwiched between clips, and transversely stretched using a tenter. The stretching temperature was set to 172 ° C. and the stretching ratio was set to 30%. Thereafter, the clip was removed from the film and dried at 130 ° C. for 20 minutes to obtain a film.
An optically anisotropic layer having a thickness of 60 μm was prepared. The optical properties were measured, and Re (550) = 50 nm, Rth (550) = 120 nm, and Re (450) / Re (550) = 0.98. The refractive index was nx = 1.48.

  A polarizing plate was produced in the same manner as the polarizing plate having the second optical anisotropic layer of Example 1 except that the second optical anisotropic layer was used.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 2 except that the polarizing plate prepared above was used. The evaluation results are shown in Table 6.

[Comparative Example 6]
[Formation of first optically anisotropic layer]
A polarizing plate having a first optically anisotropic layer and a first optically anisotropic layer was prepared in the same manner as in Example 1 except that coating was performed using a wire bar of # 7.0.
[Production of Second Optically Anisotropic Layer]
A colorless and transparent cast film having a thickness of 50 μm and a solvent residual amount of 0.2% or less was obtained from the resin (P2) obtained in Synthesis Example 2 (Example 4) by a methylene chloride cast method. This film was heated in a tenter to 194 ° C. which is Tg + 10 ° C., stretched 20% in the TD direction at a stretching speed of 220% / min, and contracted 3% in the MD direction, then cooled and taken out to remove the optically anisotropic layer. Obtained.

  A polarizing plate was produced in the same manner as the polarizing plate having the second optical anisotropic layer of Example 3 except that the second optical anisotropic layer was used.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the polarizing plate prepared above was used. The evaluation results are shown in Table 6.

[Comparative Example 7]
[Production of first optically anisotropic layer]
A first optically anisotropic layer was formed in the same manner as in Comparative Example 6.
[Production of Second Optically Anisotropic Layer]
A second optically anisotropic layer was formed in the same manner except that the # 6 wire bar was used in Example 5.

  A liquid crystal display device was prepared and evaluated in the same manner as Comparative Example 6 except that the polarizing plate prepared above was used. The evaluation results are shown in Table 6.

[Example 38]
[Thermoplastic resin film 1]

[In the above general formula (1), R ¹ is a hydrogen atom, R ² and R ³ are methyl groups, (meth) acrylic resin having a lactone ring structure {copolymerization monomer mass ratio = methyl methacrylate / 2- ( Hydroxymethyl) methyl acrylate = 8/2, lactone cyclization rate about 100%, lactone ring structure content 19.4%, mass average molecular weight 133000, melt flow rate 6.5 g / 10 min (240 ° C., 10 kgf) , Tg 131 ° C.} and 90 parts by mass of acrylonitrile-styrene (AS) resin {Toyo AS AS20, manufactured by Toyo Styrene Co., Ltd.} 10 parts by mass; Tg 127 ° C. And melt extruded into a sheet to obtain a (meth) acrylic resin sheet having a lactone ring structure. A thermoplastic resin film (thickness: 40 μm, in-plane retardation Re: 0.8 nm, thickness direction retardation Rth: 1.5 nm) is obtained by stretching the unstretched sheet vertically and horizontally under a temperature condition of 160 ° C. Got.

One side of the polarizer 1 was subjected to corona treatment on the produced thermoplastic resin film using an acrylic adhesive, and then bonded to produce a polarizing plate 03 with a single-side protective film.
In the following examples and comparative examples, unless otherwise specified, a polarizing plate 03 with a single-side protective film having a hard coat layer on the viewing side and a polarizing plate 03 with a single-side protective film having no hard coat layer on the backlight side are provided. Each polarizing plate was prepared using the same.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the polarizing plate 03 with a single-side protective film prepared above was used on the backlight side. The evaluation results are shown in Table 6.

[Example 39]
A liquid crystal display device was produced and evaluated in the same manner as in Example 1 except that the polarizing plate 03 with a single-side protective film produced above was used on the viewing side and the backlight side. The evaluation results are shown in Table 6.

[Example 40]
An imidized resin was obtained by the method described in JP-A-2011-138119, [0173] to [0176].
100 parts by weight of the imidized resin (III) obtained and 0.10 parts by mass of the following triazine compound A were pelletized using a single screw extruder.
A thermoplastic resin film was produced in the same manner as in Example 38 except that the unstretched film was stretched in the longitudinal and transverse directions using the pellets.

  The thickness of the obtained film was 40 μm. Re = 1.0 nm and Rth = 3.0 nm.

The prepared thermoplastic resin film was subjected to corona treatment on one surface of the polarizer 1 using an acrylic adhesive, and bonded to prepare a polarizing plate 04 with a single-side protective film.
In the following examples and comparative examples, unless otherwise specified, a polarizing plate 04 with a single-side protective film having a hard coat layer on the viewing side and a polarizing plate 04 with a single-side protective film having no hard coat layer on the backlight side are provided. Each polarizing plate was prepared using the same.

  A liquid crystal display device was produced and evaluated in the same manner as in Example 1 except that the polarizing plate 04 with a single-side protective film produced above was used on the backlight side. The evaluation results are shown in Table 6.

[Example 41]
A liquid crystal display device was produced and evaluated in the same manner as in Example 1 except that the polarizing plate 04 with a single-side protective film produced above was used on the viewing side and the backlight side. The evaluation results are shown in Table 6.

[Example 42]
[Production of low moisture-permeable layer laminated film]
<Preparation of composition for forming a low moisture permeable layer>
A composition for forming a low moisture-permeable layer was prepared as shown below.

(Composition of composition B-1 for forming a low moisture-permeable layer)
――――――――――――――――――――――――――――――――――――――
A-DCP (100%): Tricyclodecane dimethanol dimethacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.]
97.0 parts by mass-Irgacure 907 (100%): polymerization initiator [manufactured by Ciba Specialty Chemicals Co., Ltd.]
3.0 parts by mass · SP-13 (leveling agent): 0.04 parts by mass · MEK (methyl ethyl ketone): 81.8 parts by mass ――――――――――――――――――― ――――――――――――――――――

<Preparation of base film>
{Adjustment of cellulose ester dope}
The composition described below was put into a mixing tank and stirred while heating to dissolve each component to prepare a dope.
A cellulose ester having an acyl group total substitution degree of 2.75, an acetyl substitution degree of 0.19, a propionyl substitution degree of 2.56, and a weight average molecular weight of 200,000 was used.
This cellulose ester was synthesized as follows.
Sulfuric acid (7.8 parts by mass with respect to 100 parts by mass of cellulose) was added to cellulose as a catalyst, and carboxylic acid serving as a raw material for the acyl substituent was added to carry out an acylation reaction at 40 ° C. At this time, the substitution degree of the acetyl group and the propionyl group was adjusted by adjusting the amount of the carboxylic acid. In addition, aging was performed at 40 ° C. after acylation. Further, the low molecular weight component of this cellulose ester was removed by washing with acetone.

(Composition of dope)
――――――――――――――――――――――――――――――――――――
-30.0 parts by mass of cellulose ester-70.0 parts by mass of acrylic resin (Dianar BR85 manufactured by Mitsubishi Rayon Co., Ltd.)
-Tinuvin 328 manufactured by Ciba Japan 1.0 parts by mass-320 parts by weight of methylene chloride-45 parts by weight of ethanol-------------- ―――――――――

{Production of cellulose ester film}
Using the band casting apparatus, the prepared dope was uniformly cast from a casting die onto a stainless steel endless band (casting support). When the amount of residual solvent in the dope reaches 40% by mass, it is peeled off from the casting support as a polymer film, conveyed without being actively stretched by a tenter, and dried at 130 ° C. in a drying zone. It was.
The thickness of the obtained film was 40 μm. Moreover, when the value of Re and Rth of the obtained base film was measured by the method described later, Re = 1.0 nm and Rth = 5.0 nm. This film was used as a base film.

Using the low moisture-permeable layer forming composition B-1 for the base film, a die coating method using a slot die described in Example 1 of JP-A-2006-122889, under conditions of a conveyance speed of 30 m / min. It was applied and dried at 60 ° C. for 150 seconds. Thereafter, using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of about 0.1% under a nitrogen purge, ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 60 mJ / cm ² were irradiated. Then, the coating layer was cured and wound up. The coating amount was adjusted so that the thickness of the low moisture-permeable layer was 12 μm.
The obtained optical film was designated as a low moisture-permeable layer laminated film 1.

[Preparation of polarizing plate]
Corona treatment is applied to the base film side of the low moisture-permeable layer laminated film 1 produced as described above, and one side of the polarizer 1 and the corona treatment of the low moisture-permeable laminated film 1 are performed using the low moisture-permeable laminated film 1 as a protective film. The applied surface was bonded via an acrylic adhesive to produce a polarizing plate 05 with a single-sided protective film.
In the following examples and comparative examples, a polarizing plate 05 with a single-sided protective film having a hard coat layer on the viewing side and a polarizing plate 05 with a single-sided protective film having no hard coat layer on the backlight side unless otherwise specified. Each polarizing plate was prepared using the same.

  A liquid crystal display device was produced and evaluated in the same manner as in Example 1 except that the polarizing plate 05 with a single-side protective film produced above was used on the backlight side. The evaluation results are shown in Table 6.

[Example 43]
A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the polarizing plate 05 with a single-side protective film prepared above was used on the viewing side and the backlight side. The evaluation results are shown in Table 6.

[Example 44]
[Preparation of protective film]
<Preparation of core layer cellulose acylate dope>
The following composition was put into a mixing tank and stirred to dissolve each component, thereby preparing core layer cellulose acylate dope 1-A.
―――――――――――――――――――――――――――――――――――
Cellulose acetate with an acetyl substitution degree of 2.88 100 parts by mass Ester oligomer (Compound 1-1) 10 parts by weight Durability improver (Compound 1-2) 4 parts by weight Ultraviolet absorber (Compound 1-3) 3 Parts by mass, methylene chloride (first solvent) 438 parts by mass, methanol (second solvent) 65 parts by mass ――――――――――――――――――――――――――― ――――――――

<Preparation of outer layer cellulose acylate dope>
10 parts by mass of the following matting agent dispersion 1 was added to 190 parts by mass of the core layer cellulose acylate dope to prepare an outer layer cellulose acylate dope 1-A.
―――――――――――――――――――――――――――――――――――
-Silica particles having an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass-76 parts by mass of methylene chloride (first solvent)-11 parts by mass of methanol (second solvent)-Core layer cellulose acylate dope 1-A 1 part by mass ―――――――――――――――――――――――――――――――――――

<Preparation of cellulose acylate film>
Three layers of the core layer cellulose acylate dope 1-A and the outer layer cellulose acylate dope 1-A on both sides of the core layer cellulose acylate dope 1-A were simultaneously cast on a drum at 20 ° C. from the casting port. The film was peeled off at a solvent content of about 20% by mass, both ends in the width direction of the film were fixed with a tenter clip, and dried while being stretched 1.2 times in the lateral direction with a residual solvent of 3 to 15% by mass. . Thereafter, a cellulose acylate film having a thickness of 25 μm was produced by transporting between the rolls of the heat treatment apparatus to obtain a protective film.

A polarizing plate 06 with a single-side protective film was produced in the same manner as in Example 1 except that the protective film produced above was used.
In the following examples and comparative examples, unless otherwise specified, a polarizing plate 06 with a single-side protective film having a hard coat layer on the viewing side and a polarizing plate 06 with a single-side protective film having no hard coat layer on the backlight side are provided. Each polarizing plate was prepared using the same.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the polarizing plate 06 with a single-side protective film prepared above was used on the viewing side and the backlight side. The evaluation results are shown in Table 6.

[Example 45]
A liquid crystal display device was produced and evaluated in the same manner as in Example 3 except that the polarizing plate 06 with a single-side protective film produced above was used on the viewing side and the backlight side. The evaluation results are shown in Table 6.

[Example 46]
[Production of first optically anisotropic layer and polarizing plate]
The following compound was dissolved in methyl ethyl ketone to prepare a solid concentration of 36.2%.
―――――――――――――――――――――――――――――――――――
Discotic liquid crystal compound 3-1 91.0 parts by mass Compound 3-2 9.0 parts by mass Polymerization initiator: Compound 3-7 3.0 parts by mass Fluorine-containing surfactant: Compound 3-5 2 0 part by mass / adhesion improver: Compound 3-8 0.6 part by mass ―――――――――――――――――――――――――――――――― ―――

(Compound 3-7)

(Compound 3-8)

[Preparation of polarizing plate]
The coating solution was applied to the surface on the polarizer side of the prepared polarizing plate with a single-sided protective film 01 using a # 4.4 wire bar and dried. The discotic liquid crystalline compound was aligned by heating at 60 ° C. for 90 seconds. Thereafter, 290 mJ / cm ² of ultraviolet rays was immediately irradiated under a temperature condition of 60 ° C. to polymerize the discotic liquid crystalline compound, fix the alignment state, and form a first optical anisotropic layer. The thickness of the formed optically anisotropic layer was 2 μm. The thickness of the optically anisotropic layer was measured with a laser film thickness meter.

[Measurement of optical properties]
The first optically anisotropic layer was formed on the glass substrate under the same conditions as in the examples, and the retardation of only the optically anisotropic layer was measured. The refractive index was 1.583. The results are shown in Table 7.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the polarizing plate prepared above was used. Table 7 shows the evaluation results.

[Example 47]
[Production of first optically anisotropic layer and polarizing plate]
The following compound was dissolved in methyl ethyl ketone to prepare a solid concentration of 30.0%.
――――――――――――――――――――――――――――――――――――
-Discotic liquid crystalline compound 4-1 72.0 parts by mass-Discotic liquid crystalline compound 4-2 18.0 parts by mass-Discotic liquid crystalline compound 3-1 5.0 parts by mass-Compound 3-2 5.0 Mass parts / polymerization initiator: compound 3-7 3.0 parts by mass / fluorine-containing surfactant: compound 4-3 2.0 parts by mass / adhesion improver: compound 3-8 0.3 parts by mass ――――――――――――――――――――――――――――――――

(Compound 4-3)

[Preparation of polarizing plate]
The coating solution was applied to the surface on the polarizer side of the produced polarizing plate 01 with a single-side protective film using a # 3.4 wire bar and dried. The discotic liquid crystalline compound was aligned by heating at 80 ° C. for 90 seconds. Thereafter, 290 mJ / cm ² of ultraviolet rays was immediately irradiated under a temperature condition of 60 ° C. to polymerize the discotic liquid crystalline compound, fix the alignment state, and form a first optical anisotropic layer. The thickness of the formed optically anisotropic layer was 2 μm. The thickness of the optically anisotropic layer was measured with a laser film thickness meter.

[Measurement of optical properties]
The first optically anisotropic layer was formed on the glass substrate under the same conditions as in the examples, and the retardation of only the optically anisotropic layer was measured. The refractive index was 1.583. The results are shown in Table 7.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the polarizing plate prepared above was used. Table 7 shows the evaluation results.

[Example 48]
[Production of first optically anisotropic layer and polarizing plate]
The following compound was dissolved in methyl ethyl ketone to prepare a solid concentration of 30.0%.
――――――――――――――――――――――――――――――――――――
Discotic liquid crystalline compound 4-1 72.0 parts by mass Discotic liquid crystalline compound 4-2 18.0 parts by mass Compound 3-2 10.0 parts by mass Polymerization initiator: Compound 3-7 3.0 Part by mass / Fluorine-containing surfactant: Compound 4-3 2.0 parts by mass / Adhesion improver: Compound 3-8 0.3 parts by mass --------- ――――――――――――――――――

[Preparation of polarizing plate]
The coating solution was applied to the surface on the polarizer side of the produced polarizing plate 01 with a single-side protective film using a # 3.4 wire bar and dried. The discotic liquid crystalline compound was aligned by heating at 80 ° C. for 90 seconds. Thereafter, 290 mJ / cm ² of ultraviolet rays was immediately irradiated under a temperature condition of 60 ° C. to polymerize the discotic liquid crystalline compound, fix the alignment state, and form a first optical anisotropic layer. The thickness of the formed optically anisotropic layer was 2 μm. The thickness of the optically anisotropic layer was measured with a laser film thickness meter.

[Measurement of optical properties]
The first optically anisotropic layer was formed on the glass substrate under the same conditions as in the examples, and the retardation of only the optically anisotropic layer was measured. The refractive index was 1.583. The results are shown in Table 7.

  A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the polarizing plate prepared above was used. Table 7 shows the evaluation results.

[Example 49]
A liquid crystal display device was produced and evaluated in the same manner as in Example 46 except that the polarizing plate 06 with a single-side protective film produced above was used on the viewing side and the backlight side. Table 7 shows the evaluation results.

[Example 50]
A liquid crystal display device was produced and evaluated in the same manner as in Example 47 except that the polarizing plate 06 with a single-side protective film produced above was used on the viewing side and the backlight side. Table 7 shows the evaluation results.

[Example 51]
A liquid crystal display device was prepared and evaluated in the same manner as in Example 48 except that the polarizing plate 06 with a single-side protective film prepared above was used on the viewing side and the backlight side. Table 7 shows the evaluation results.

From the results shown in Tables 2 to 7, it is found that when the second optical anisotropic layer does not satisfy the wavelength dispersion, that is, the above formula (1-2-5), the display performance (particularly color change) is inferior. (Comparative Examples 1 and 3).
Further, it has been found that when neither the first optical anisotropic layer nor the second optical anisotropic layer has a liquid crystalline compound, the film cannot be thinned and display unevenness also occurs. (Comparative Examples 2 and 4).
Moreover, when the 2nd optically anisotropic layer did not satisfy | fill said Formula (1-2-3), it turned out that it is inferior to display performance (especially color change) (Comparative Examples 5 and 6).
Moreover, when the 2nd optically anisotropic layer did not satisfy | fill said Formula (1-2-4), it turned out that it is inferior to display performance (especially light leakage) (comparative example 7).

  On the other hand, at least one of the first optical anisotropic layer and the second optical anisotropic layer contains a liquid crystalline compound and has a thickness of 10 μm or less, and the first optical anisotropic layer Satisfies the above formula (1-1-1), and the second optically anisotropic layer has the above formulas (1-2-1), (1-2-2), (1-2-3), When satisfying (1-2-4) and (1-2-5), it was found that both were excellent in display performance and excellent in durability against temperature and humidity environment changes.

DESCRIPTION OF SYMBOLS 1 1st polarizer 2 1st optically anisotropic layer 3 Liquid crystal cell 4 2nd optically anisotropic layer 5 2nd polarizer 6 Protective film 7 Laminate film 10 Liquid crystal display device

Claims (18)

A first polarizer and a second polarizer arranged with their absorption axes orthogonal to each other;
A vertical alignment mode liquid crystal cell disposed between the first polarizer and the second polarizer;
A first optical anisotropic layer provided between one of the first polarizer and the liquid crystal cell and one of the second polarizer and the liquid crystal cell;
A second optically anisotropic layer provided on one side between the first polarizer and the liquid crystal cell and between the second polarizer and the liquid crystal cell,
At least one of the first optically anisotropic layer and the second optically anisotropic layer contains a liquid crystal compound and has a thickness of 10 μm or less,
The first optically anisotropic layer satisfies the following formula (1-1-1);
The second optical anisotropic layer has the following formulas (1-2-1), (1-2-2), (1-2-3), (1-2-4) and (1-2-5). A liquid crystal display device satisfying
30 nm ≦ Rth (550) ≦ 300 nm Formula (1-1-1)
50 nm ≦ Re (550) ≦ 200 nm Formula (1-2-1)
40 nm ≦ Rth (550) ≦ 200 nm Formula (1-2-2)
Rth (550) ≧ (−12/5) × Re (550) +280 nm
Formula (1-2-3)
Rth (550) ≦ (−7/5) × Re (550) +340 nm
Formula (1-2-4)
Re (450) / Re (550) ≦ 1.05 Formula (1-2-5)
(Re (λ) represents in-plane retardation at wavelength λnm, and Rth (λ) represents retardation in the thickness direction at wavelength λnm.)   Of the first optically anisotropic layer and the second optically anisotropic layer, the optically anisotropic layer containing the liquid crystalline compound and having a thickness of 10 μm or less, and the first polarizer or The liquid crystal display device according to claim 1, wherein the second polarizer is adjacent.   Of the first optically anisotropic layer and the second optically anisotropic layer, the optically anisotropic layer containing the liquid crystalline compound and having a thickness of 10 μm or less, and the first polarizer or The liquid crystal display device according to claim 1, wherein the second polarizer is laminated via an alignment film.   Of the first optically anisotropic layer and the second optically anisotropic layer, the optically anisotropic layer containing the liquid crystalline compound and having a thickness of 10 μm or less, and the first polarizer or The liquid crystal display device according to claim 1, wherein the second polarizer is laminated via an adhesive layer or a pressure-sensitive adhesive layer. Of the first optical anisotropic layer and the second optical anisotropic layer, at least the first optical anisotropic layer contains the liquid crystalline compound and has an optical thickness of 10 μm or less. Is an isotropic layer,
The liquid crystal display device according to claim 1, wherein the first optically anisotropic layer satisfies the following formulas (2-1-1) and (2-1-2).
Re (550) ≦ 10 nm Formula (2-1-1)
30 nm ≦ Rth (550) ≦ 250 nm Formula (2-1-2) Of the first optical anisotropic layer and the second optical anisotropic layer, at least the second optical anisotropic layer contains the liquid crystalline compound and has an optical thickness of 10 μm or less. Is an isotropic layer,
The first optically anisotropic layer satisfies the following formula (3-1-1),
The liquid crystal display device according to claim 1, wherein the second optically anisotropic layer satisfies the following formulas (3-2-1) and (3-2-2).
100 nm ≦ Rth (550) ≦ 300 nm Formula (3-1-1)
90 nm ≦ Re (550) ≦ 190 nm Formula (3-2-1)
40 nm ≦ Rth (550) ≦ 100 nm Formula (3-2-2)   The liquid crystal display device according to claim 6, wherein the first optically anisotropic layer is an optically anisotropic layer containing a liquid crystalline compound. The liquid crystalline compound contained in the first optically anisotropic layer is a discotic liquid crystalline compound, and the first optically anisotropic layer satisfies the following formula (4-1-1). Or a liquid crystal display device according to 7;
0.9 <Re40 (450) / Re40 (550) ≦ 1.2 Formula (4-1-1)
(Re40 (λ) represents retardation measured from a polar angle of 40 ° at a wavelength of λnm.)   The liquid crystal display device according to claim 6, wherein the liquid crystal compound contained in the second optical anisotropic layer is a rod-like liquid crystal compound. The liquid crystal display device according to claim 9, wherein the second optically anisotropic layer satisfies the following formula (5-2-1).
Re (450) / Re (550) <1.0 Formula (5-2-1)   The first polarizer, the first optical anisotropic layer, the liquid crystal cell, the second optical anisotropic layer, and the second polarizer are arranged in this order from the viewing side. 10. The liquid crystal display device according to any one of 10 to 10.   The first polarizer, the second optical anisotropic layer, the liquid crystal cell, the first optical anisotropic layer, and the second polarizer are arranged in this order from the viewing side. The liquid crystal display device according to any one of 1 to 10.   Both of the first optical anisotropic layer and the second optical anisotropic layer are disposed between the first polarizer and the liquid crystal cell and between the second polarizer and the liquid crystal cell. The liquid crystal display device according to claim 1, wherein the liquid crystal display device is disposed only between any one of them.   The polarizer on the side where the first optical anisotropic layer and the second optical anisotropic layer are not disposed is disposed in the liquid crystal cell via an adhesive or an adhesive. 14. A liquid crystal display device according to item 13. A protective film is provided on at least one of the first polarizer and the second polarizer opposite to the liquid crystal cell,
The moisture permeability of the protective film is not more than 100g / m ² / 24h, a liquid crystal display device according to any one of claims 1 to 14. At least one of the moisture permeability of the first optically anisotropic layer and the second optically anisotropic layer is not more than 100 g / m ² / 24h, according to any one of claims 1 to 6 Liquid crystal display device. At least one of the first polarizer and the second polarizer on the side opposite to the liquid crystal cell has a laminate film,
The laminate moisture permeability at 40 ° C. 90% RH of the film is not more than 50g / m ² / 24h, a liquid crystal display device according to any one of claims 1 to 16.   The liquid crystal display device according to claim 1, wherein a thickness of at least one of the first polarizer and the second polarizer is 25 μm or less.