JP7692873B2 - LAMINATE AND DISPLAY DEVICE - Google Patents

Description

The present invention relates to a laminate and a display device including the laminate.

For applications such as mobile phones, laptops, and bank ATMs, there is a demand for display devices that can prevent others from peeking at the display. For example, Patent Document 1 proposes a light-absorbing anisotropic film that provides an anti-peeping effect.

JP 2016-27387 A

However, the optically absorbing anisotropic film described in Patent Document 1 absorbs light differently from oblique directions, which creates anisotropy depending on the direction from which the light is looked at, and the effect of preventing peeking is not necessarily sufficient, so there is a demand for further improvements in the effect of preventing peeking.

The object of the present invention is therefore to provide a laminate that has excellent transparency in the front direction, reduces the directional anisotropy of light absorption characteristics in oblique directions, and is excellent in preventing peeking from oblique directions, and a display device that includes the laminate.

As a result of intensive research into solving the above problems, the inventors discovered that the above problems could be solved by specifying the structure of the laminate, and thus completed the present invention. In other words, the present invention includes the following preferred aspects.

[1] A light absorption anisotropic film made of a cured product of a liquid crystal composition containing a dichroic dye and a liquid crystal compound, wherein an arbitrary position direction in the film plane is defined as the x-axis, a direction perpendicular to the x-axis in the film plane is defined as the y-axis, and a film thickness direction perpendicular to the x-axis and y-axis is defined as the z-axis, and the light absorption anisotropic film satisfies the following formulas (1) to (3):
Az>(Ax+Ay)/2 (1)
Ax (z=60°)/Ax>5 (2)
Ay (z=60°)/Ay>5 (3)
[In formulas (1) to (3),
Ax, Ay, Az, Ax(z=60°) and Ay(z=60°) are all absorbances at the absorption maximum wavelength of the dichroic dye in the optically absorptive anisotropic film,
Ax represents the absorbance of linearly polarized light vibrating in the x-axis direction,
Ay represents the absorbance of linearly polarized light vibrating in the y-axis direction,
Az represents the absorbance of linearly polarized light vibrating in the z-axis direction,
Ax (z=60°) represents the absorbance of linearly polarized light oscillating in the x-axis direction when the film is rotated 60° around the y-axis as the rotation axis,
Ay (z=60°) represents the absorbance of linearly polarized light oscillating in the y-axis direction when the film is rotated 60° around the x-axis as the rotation axis.
and a light absorbing anisotropic film satisfying the above.
The following formula (4):
70nm≦Re _i (550)≦170nm (4)
[In formula (4), Re _i (λ) represents an in-plane retardation value of the horizontally aligned retardation film i at a wavelength of λ nm]
A horizontally aligned retardation film i that satisfies the above formula:
A polarizer;
The following formula (5):
120nm≦Re _ii (550)≦160nm (5)
[In formula (5), Re _ii (λ) represents an in-plane retardation value of the horizontally aligned retardation film ii at a wavelength of λ nm]
and a horizontally aligned retardation film ii satisfying the above items in this order.
[2] The horizontally aligned retardation film ii has the following formula (6):
Re _ii (450)/Re _ii (550)<1.00 (6)
[In formula (6), Re _ii (λ) has the same meaning as in formula (5) above]
The range of the angle θ _ii between the slow axis of the horizontally aligned retardation film ii and the absorption axis of the polarizer satisfies the following formula (7):
15°≦｜θ _ii |≦75° (7)
The laminate according to [1],
[3] The horizontally aligned retardation film i has the following formula (8):
Re _i (450)/Re _i (550)≧1.00 (8)
[In formula (8), Re _i (λ) has the same meaning as in formula (4) above]
The range of the angle θ _i between the slow axis of the horizontally aligned retardation film i and the absorption axis of the polarizer satisfies the following formula (9):
15°≦｜ _θi ｜≦75° (9)
The laminate according to [1] or [2],
[4] The laminate according to any one of [1] to [3], in which the horizontally aligned retardation film i and a polarizer are laminated via a pressure-sensitive adhesive.
[5] The laminate according to any one of [1] to [4], wherein the horizontally aligned retardation film i is a film stretched in at least one direction.
[6] The laminate according to any one of [1] to [5], wherein the horizontal alignment retardation film ii is made of a cured product of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound.
[7] The laminate according to any one of [1] to [6], wherein the liquid crystal compound contained in the optically absorptive anisotropic film exhibits a smectic liquid crystal phase.
[8] The laminate according to any one of [1] to [7], further comprising a transparent protective film on the surface of the optically absorptive anisotropic film opposite to the horizontally aligned retardation film i.
[9] The following formula (10):
-100nm≦Rth _iii (550)≦-20nm (10)
[In formula (10), Rth _iii (λ) represents a thickness retardation value of the vertically aligned retardation film iii at a wavelength of λ nm]
The vertically aligned retardation film iii satisfies the following:
The vertically aligned retardation film iii is laminated between the polarizer and the horizontally aligned retardation film ii, or on the opposite side of the horizontally aligned retardation film ii from the polarizer. [1] to [8], the laminate according to any one of the above.
[10] The vertically aligned retardation film iii has the following formula (11):
Rth _iii (450)/Rth _iii (550)>1.00 (11)
[In formula (11), Rth _iii (λ) represents a thickness retardation value of the vertically aligned retardation film iii at a wavelength of λ nm]
The laminate according to any one of [1] to [9],
[11] The laminate according to [10], wherein the vertically aligned retardation film iii is made of a cured product of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound.
[12] An organic electroluminescence display device comprising the laminate according to any one of [1] to [11].

The present invention can provide a laminate that has excellent transparency in the front direction, reduces the directional anisotropy of light absorption characteristics in oblique directions, and is excellent in preventing peeking from oblique directions, and a display device that includes the laminate.

FIG. 2 is a diagram showing the X-axis, Y-axis, and Z-axis in an optically absorptive anisotropic film contained in a laminate of the present invention.

The following describes in detail the embodiments of the present invention. Note that the scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention.

The laminate of the present invention includes, in this order, a light absorbing anisotropic film, a horizontally aligned retardation film i, a polarizer, and a horizontally aligned retardation film ii. Hereinafter, the horizontally aligned retardation film i and the horizontally aligned retardation film ii may be collectively referred to as the "horizontally aligned retardation film."

In the present invention, the optically absorptive anisotropic film has the following formulas (1) to (3), where an arbitrary position direction in the film plane is defined as the x-axis, a direction in the film plane perpendicular to the x-axis is defined as the y-axis, and a film thickness direction perpendicular to the x-axis and y-axis is defined as the z-axis:
Az>(Ax+Ay)/2 (1)
Ax (z=60°)/Ax>5 (2)
Ay (z=60°)/Ay>5 (3)
[In formulas (1) to (3),
Ax, Ay, Az, Ax(z=60°) and Ay(z=60°) are all absorbances at the absorption maximum wavelength of the dichroic dye in the optically absorptive anisotropic film,
Ax represents the absorbance of linearly polarized light vibrating in the x-axis direction,
Ay represents the absorbance of linearly polarized light vibrating in the y-axis direction,
Az represents the absorbance of linearly polarized light vibrating in the z-axis direction,
Ax (z=60°) represents the absorbance of linearly polarized light oscillating in the x-axis direction when the film is rotated 60° around the y-axis as the rotation axis,
Ay (z=60°) represents the absorbance of linearly polarized light oscillating in the y-axis direction when the film is rotated 60° around the x-axis as the rotation axis.
Fulfilling
The horizontally aligned retardation film i has the following formula (4):
70nm≦Re _i (550)≦170nm (4)
[In formula (4), Re _i (λ) represents an in-plane retardation value of the horizontally aligned retardation film i at a wavelength of λ nm]
Fulfilling
The horizontally aligned retardation film ii has the following formula (5):
120nm≦Re _ii (550)≦160nm (5)
[In formula (5), Re _ii (λ) represents an in-plane retardation value of the horizontally aligned retardation film ii at a wavelength of λ nm]
Meet the following.

In the present invention, the horizontally aligned retardation film means a retardation film aligned in the horizontal direction relative to the film plane. The in-plane retardation in the horizontally aligned retardation film p can be calculated by Re _p (λ) = (nxp (λ) - nyp (λ)) x dp (where nxp (λ) represents the principal refractive index at a wavelength of λ nm in the plane of the horizontally aligned retardation film p, nyp (λ) represents the refractive index at a wavelength of λ nm in the same plane as nxp in a direction perpendicular to the direction of nxp, and dp represents the film thickness of the horizontally aligned retardation film p).

In the present invention, the in-plane retardation Re _i (550) of the horizontally aligned retardation film i satisfies formula (4) and the in-plane retardation Re _ii (550) of the horizontally aligned retardation film ii satisfies formula (5), so that the directional anisotropy of the light absorption characteristics in the oblique direction can be easily reduced, and sufficient anti-reflection properties can be obtained, particularly when used on an organic EL panel. Furthermore, by including a light-absorption anisotropic film, a horizontally aligned retardation film i, a polarizer, and a horizontally aligned retardation film ii in this order, the directional anisotropy of the light absorption characteristics in the oblique direction can be reduced while improving visibility from the front, thereby reducing visibility from the oblique direction. The laminate in the present invention may have the same in-plane retardation as described above or different. In particular, by including two different horizontally aligned retardation films, the directional anisotropy of the light absorption characteristics in the oblique direction can be further reduced when displayed on an organic EL panel, and anti-reflection properties from external light can be obtained.

<Light-absorbing anisotropic film>
In the present invention, the optically absorptive anisotropic film is made of a cured liquid crystal composition containing a dichroic dye and a liquid crystal compound.

The optically absorptive anisotropic film has a structure represented by the following formulas (1) to (3), where an arbitrary direction in the film plane is defined as the x-axis, a direction in the film plane perpendicular to the x-axis is defined as the y-axis, and a film thickness direction perpendicular to the x-axis and y-axis is defined as the z-axis (see FIG. 1 ):
Az>(Ax+Ay)/2 (1)
Ax (z=60°)/Ax>5 (2)
Ay (z=60°)/Ay>5 (3)
satisfy.
Here, in formulas (1) to (3), Ax, Ay, Az, Ax (z=60°), and Ay (z=60°) are all absorbances at the maximum absorption wavelengths of the dichroic dyes in the optically absorptive anisotropic film.
Ax represents the absorbance of linearly polarized light oscillating in the x-axis direction, and can be measured by directing linearly polarized light oscillating in the x-axis direction toward the film surface from the z-axis direction.
Ay represents the absorbance of linearly polarized light oscillating in the y-axis direction, and can be measured by directing linearly polarized light oscillating in the y-axis direction toward the film surface from the z-axis direction.
Az represents the absorbance of linearly polarized light vibrating in the z-axis direction. Az can be measured, for example, by irradiating linearly polarized light vibrating in the z-axis direction from the xy plane toward the side surface of the film, that is, perpendicular to the side surface (thickness direction) of the film when the film is in the xy plane.
Ax (z = 60°) represents the absorbance of linearly polarized light vibrating in the x-axis direction when the film is rotated 60° around the y-axis as the axis of rotation. Ax (z = 60°) can be measured by rotating the film 60° around the y-axis as the axis of rotation and then incidenting the same linearly polarized light as that used to measure Ax. Here, the film is rotated by rotating the film in the state where Ax is measured 60° around the y-axis as the axis of rotation in the direction of incidence of the linearly polarized light.
Ay (z = 60°) represents the absorbance of linearly polarized light vibrating in the y-axis direction when the film is rotated 60° around the x-axis as the axis of rotation. Ay (z = 60°) can be measured by rotating the film 60° around the x-axis as the axis of rotation and then incidenting the same linearly polarized light as that used to measure Ay. Here, the film is rotated by rotating the film in the state where Ay was measured 60° around the x-axis as the axis of rotation in the direction of incidence of the linearly polarized light.

The absorbance in the z direction in formula (1) is difficult to measure because the light is incident from the side of the film. Therefore, when the angle between the vibration plane of the linearly polarized light (measurement light) and the x-y plane of the film is set to 90°, the absorbance in the Az direction can be estimated by measuring the x-y plane of the film at an angle of 30° and 60° to the incidence direction of the linearly polarized light with respect to the vibration plane.
Specifically, it can be estimated by the following methods.
With the film rotated 30° and 60° around the y-axis as the axis of rotation, Ax(z=30°) and Ax(z=60°) are measured by incidenting the same linearly polarized light as that used to measure Ax. Similarly, with the film rotated 30° and 60° around the x-axis as the axis of rotation, Ay(z=30) and Ay(z=60) are measured by incidenting the same linearly polarized light as that used to measure Ay.
In this case, if Ax(z=30°)<Ax(z=60°) and Ay(z=30°)=Ay(z=60°), then Ax(z=30°)<Ax(z=60°)<Ax(z=90°)=Az, and if Ay(z=30°)<Ay(z=60°) and Ax(z=30°)=Ax(z=60°), then Ay(z=30°)<Ay(z=60°)<Ay(z=90°)=Az, which necessarily satisfies formula (1).

In particular, when there is no absorption anisotropy in the x-y plane, i.e., when Ax and Ay are equal, Ax(z=30°)=Ay(z=30°) and Ax(z=60°)=Ay(z=60°), so Ax(z=30°) and Ay(z=30°) can be A(z=30°), and Ax(z=60°) and Ay(z=60°) can be A(z=60°). In other words, if A(z=30°)<A(z=60°), then the relationship A(z=30°)<A(z=60°)<A(z=90°)=Az is satisfied. Furthermore, if A(z=30°)>(Ax+Ay)/2, then Az necessarily satisfies formula (1).

In the present invention, the optically absorptive anisotropic film satisfies the above formulas (2) and (3).
The larger the values of Ax(z=60°)/Ax and Ay(z=60°)/Ay, the better the optical absorption anisotropy. These values may be, for example, 50 or less, 30 or less, 6 or more, or 8 or more.
The optically absorptive anisotropic film of the present invention preferably has the formulas (2') and (3'):
Ax (z=60°)/Ax>10 (2')
Ay (z=60°)/Ay>10 (3')
Meet the following.

When the optically absorptive anisotropic film satisfies the formulas (1) to (3), the dichroic dye can be said to have excellent absorption anisotropy, i.e., excellent polarization performance. This excellent characteristic allows the film to effectively transmit light from the front direction and effectively absorb light from oblique directions.
In addition, when two or more dichroic dyes having different maximum absorption wavelengths are contained in the light absorption anisotropic film, Az>(Ax+Ay)/2, Ax(z=60°)/Ax, and Ay(z=60°)/Ay calculated based on the absorbances Ax, Ay, and Az at the maximum absorption wavelength of at least one of the dichroic dyes contained therein should satisfy the respective relationships of the above formulas (1) to (3). Since it is easy to effectively transmit light from the front direction and effectively absorb light from oblique directions, and to obtain a higher anti-peep effect, Az>(Ax+Ay)/2, Ax(z=60°)/Ax, and Ay(z=60°)/Ay calculated based on the absorbances Ax, Ay, and Az at the maximum absorption wavelength of the dichroic dye having a maximum absorption wavelength in the wavelength range of 500 to 600 nm should satisfy the respective relationships of the above formulas (1) to (3). It is also preferable that Az>(Ax+Ay)/2, Ax(z=60°)/Ax, and Ay(z=60°)/Ay, which are calculated based on the absorbances Ax, Ay, and Az at the maximum absorption wavelengths of each dichroic dye contained in the optically absorptive anisotropic film, satisfy the relationships of the above formulas (1) to (3), respectively. In particular, it is preferable to select a dichroic dye so as to satisfy the above formulas (1) to (3) over a wide range of 350 to 700 nm.

The film thickness of the optically absorptive anisotropic film is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, even more preferably 0.2 to 3 μm or 0.5 to 5 μm, and particularly preferably 0.5 to 3 μm. When the film thickness of the optically absorptive anisotropic film is within the above range, reduction in light absorption in oblique directions is unlikely to occur, making it easier to obtain good anti-spying properties. In addition, the orientation of the dichroic dye is unlikely to be disturbed, making it easier to increase transparency in the front direction.

<Dichroic dye>
A dichroic dye is a dye that has different absorbance in the long axis direction of the molecule and absorbance in the short axis direction.

As the dichroic dye, one that has a maximum absorption wavelength (λMAX) in the optically absorptive anisotropic film in the wavelength range of 300 to 700 nm is preferred, and one that has a maximum absorption wavelength in the wavelength range of 500 to 600 nm is even more preferred. By having a maximum absorption wavelength in the wavelength range of 500 to 600 nm, where human visual sensitivity is high, it is possible to more adequately prevent peeping. In other words, by using a dichroic dye that has a maximum absorption at a wavelength where visual sensitivity is high, it is possible to reduce the amount of dichroic dye used and make the optically absorptive anisotropic film thinner.

Examples of such dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes, and anthraquinone dyes, among which azo dyes are preferred. Azo dyes include monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes, and stilbene azo dyes, among which bisazo dyes and trisazo dyes are preferred. The dichroic dyes may be used alone or in combination, but when polarization characteristics are required over the entire visible light range, it is preferable to combine three or more types of dichroic dyes, and it is even more preferable to combine three or more types of azo dyes.

When multiple types of dichroic dyes are combined, it is preferable to include at least one type that has a maximum absorption wavelength in the wavelength range of 500 to 600 nm in the light absorption anisotropic film. When two types of dichroic dyes are combined, it is preferable to further include one that has a maximum absorption wavelength in the range of 350 to 499 nm or 601 to 750 nm, and when three types of dichroic dyes are combined, it is preferable to include dichroic dyes that have maximum absorption wavelengths in the ranges of 350 to 499 nm, 500 to 600 nm, and 601 to 750 nm, respectively. By combining dichroic dyes with such maximum absorption wavelengths, it is possible to more adequately prevent peeping.

Examples of the azo dye include those represented by the formula (I):
A ¹ (-N=NA ² ) _p -N=NA ³ (I)
[In formula (I),
A ¹ and A ³ each independently represent a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. ^{A 2} represents a p-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent heterocyclic group which may have a substituent. p represents an integer of 1 to 4. When p is an integer of 2 or more, multiple A ² 's may be the same or different from each other. The -N=N- bond may be replaced with a -C=C-, -COO-, -NHCO-, or -N=CH- bond within the range in which absorption is exhibited in the visible range.
(hereinafter, may be referred to as "compound (I)").

Examples of monovalent heterocyclic groups include groups in which one hydrogen atom has been removed from a heterocyclic compound such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole, and benzoxazole. Examples of divalent heterocyclic groups include groups in which two hydrogen atoms have been removed from the above heterocyclic compounds.

A ¹ and A ³ are each a phenyl group, a naphthyl group, or a monovalent heterocyclic group, and A Examples of the substituents that the p-phenylene group, naphthalene-1,4-diyl group, and divalent heterocyclic group in ² may optionally have include an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms having a polymerizable group, an alkenyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, or a butoxy group; an alkoxy group having 1 to 20 carbon atoms having a polymerizable group; a fluorinated alkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; a cyano group; a nitro group; a halogen atom; an amino group, a diethylamino group, or a substituted or unsubstituted amino group such as a pyrrolidino group (a substituted amino group means an amino group having one or two alkyl groups having 1 to 6 carbon atoms, an amino group having one or two alkyl groups having 1 to 6 carbon atoms having a polymerizable group, or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms. An unsubstituted amino group is _-NH2 .) and the like. Examples of the polymerizable group include an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group.

［式（Ｉ－１）～（Ｉ－８）中、
Ｂ^１～Ｂ^３０は、互いに独立して、水素原子、炭素数１～６のアルキル基、炭素数１～６のアルケニル基、炭素数１～４のアルコキシ基、シアノ基、ニトロ基、置換または無置換のアミノ基（置換アミノ基および無置換アミノ基の定義は前記のとおり）、塩素原子またはトリフルオロメチル基を表わす。
ｎ１～ｎ４は、互いに独立に０～３の整数を表わす。
ｎ１が２以上である場合、複数のＢ^２は互いに同一でも異なっていてもよく、
ｎ２が２以上である場合、複数のＢ^６は互いに同一でも異なっていてもよく、
ｎ３が２以上である場合、複数のＢ^９は互いに同一でも異なっていてもよく、
ｎ４が２以上である場合、複数のＢ^１４は互いに同一でも異なっていてもよい。］ Among the compounds (I), compounds represented by any one of the following formulas (I-1) to (I-8) are preferred.

[In formulas (I-1) to (I-8),
B ¹ to B ³⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, a substituted or unsubstituted amino group (the definitions of a substituted amino group and an unsubstituted amino group are as defined above), a chlorine atom, or a trifluoromethyl group.
n1 to n4 each independently represent an integer of 0 to 3.
When n1 is 2 or more, each ^B2 may be the same or different,
When n2 is 2 or more, multiple ^B6 may be the same or different from each other,
When n3 is 2 or more, multiple ^B9s may be the same or different from each other,
When n4 is 2 or more, multiple B ¹⁴ may be the same or different.

［式（Ｉ－９）中、
Ｒ^１～Ｒ^８は、互いに独立に、水素原子、－Ｒ^ｘ、－ＮＨ_２、－ＮＨＲ^ｘ、－ＮＲ^ｘ _２、－ＳＲ^ｘまたはハロゲン原子を表す。
Ｒ^ｘは、炭素数１～４のアルキル基または炭素数６～１２のアリール基を表す。］ The anthraquinone dye is preferably a compound represented by formula (I-9).

[In formula (I-9),
R ¹ to R ⁸ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.

［式（Ｉ－１０）中、
Ｒ^９～Ｒ^１５は、互いに独立に、水素原子、－Ｒ^ｘ、－ＮＨ_２、－ＮＨＲ^ｘ、－ＮＲ^ｘ _２、－ＳＲ^ｘまたはハロゲン原子を表す。
Ｒ^ｘは、炭素数１～４のアルキル基または炭素数６～１２のアリール基を表す。］ The oxazine dye is preferably a compound represented by formula (I-10).

[In formula (I-10),
R ⁹ to R ¹⁵ each independently represent a hydrogen atom, —R ^x , —NH ₂ , —NHR ^x , —NR ^x ₂ , —SR ^x or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.

［式（Ｉ－１１）中、
Ｒ^１６～Ｒ^２３は、互いに独立に、水素原子、－Ｒ^ｘ、－ＮＨ_２、－ＮＨＲ^ｘ、－ＮＲ^ｘ _２、－ＳＲ^ｘまたはハロゲン原子を表す。
Ｒ^ｘは、炭素数１～４のアルキル基または炭素数６～１２のアリール基を表す。］ The acridine dye is preferably a compound represented by formula (I-11).

[In formula (I-11),
R ¹⁶ to R ²³ each independently represent a hydrogen atom, —R ^x , —NH ₂ , —NHR ^x , —NR ^x ₂ , —SR ^x or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.

In formulae (I-9), (I-10), and (I-11), examples of the alkyl group having 1 to 6 carbon atoms represented by R ^x include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xylyl group, and a naphthyl group.

［式（Ｉ－１２）中、
Ｄ^１およびＤ^２は、互いに独立に、式（Ｉ－１２ａ）～式（Ｉ－１２ｄ）のいずれかで表される基を表す。

ｎ５は１～３の整数を表す。］ As the cyanine dye, a compound represented by formula (I-12) and a compound represented by formula (I-13) are preferable.

[In formula (I-12),
^D1 and ^D2 each independently represent a group represented by any one of formulae (I-12a) to (I-12d).

n5 represents an integer of 1 to 3.

［式（Ｉ－１３）中、
Ｄ^３およびＤ^４は、互いに独立に、式（Ｉ－１３ａ）～式（Ｉ－１３ｈ）のいずれかで表される基を表す。

ｎ６は１～３の整数を表す。］

[In formula (I-13),
^D3 and ^D4 each independently represent a group represented by any one of formulae (I-13a) to (I-13h).

n6 represents an integer of 1 to 3.

From the viewpoint of improving the alignment of the dichroic dye, the content of the dichroic dye in the liquid crystal composition forming the light absorption anisotropic film is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, even more preferably 0.1 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass, per 100 parts by mass of the solid content of the liquid crystal composition. If the content of the dichroic dye is within this range, it is preferable because it is less likely to disturb the liquid crystal alignment of the liquid crystal compound.

<Liquid crystal compound>
In the present invention, the liquid crystal composition forming the optically absorptive anisotropic film contains a liquid crystal compound, which is preferably a polymerizable liquid crystal compound in terms of film strength.

The polymerizable liquid crystal compound is a liquid crystal compound having a polymerizable group. The polymerizable group means a group that can participate in a polymerization reaction. In terms of ease of production, a photopolymerizable group is preferable. Here, the photopolymerizable group means a group that can participate in a polymerization reaction by a reactive species generated from a photopolymerization initiator described later, such as an active radical or an acid. Examples of the photopolymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, and an oxetanyl group. Among them, in terms of reactivity, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferable, and an acryloyloxy group is more preferable.

The liquid crystallinity exhibited by the liquid crystal compound may be thermotropic or lyotropic liquid crystal, but thermotropic liquid crystal is preferred because it allows precise control of the film thickness. The phase order structure in the thermotropic liquid crystal may be nematic or smectic liquid crystal. The polymerizable liquid crystal compound exhibiting liquid crystallinity may be a monomer, but may also be an oligomer or polymer in which a polymerizable group is polymerized. The higher the degree of orientation order of the liquid crystal cured film, the larger the values of Ax(z=60°)/Ax and Ay(z=60°)/Ay tend to be, so it is preferable for the compound to form a smectic liquid crystal phase.

Among the liquid crystallinity exhibited by the polymerizable liquid crystal compound, higher-order smectic liquid crystal compounds that form a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase, or a smectic L phase are more preferred, and higher-order smectic liquid crystal compounds that form a smectic B phase, a smectic F phase, or a smectic I phase are more preferred. When the liquid crystal phase formed by the polymerizable liquid crystal compound is one of these higher-order smectic phases, a liquid crystal cured film with a higher degree of orientation order can be produced, and high polarization performance is likely to be obtained. In addition, such a liquid crystal cured film with a high degree of orientation order is one that exhibits Bragg peaks derived from higher-order structures such as hexatic and crystalline phases in X-ray diffraction measurement. The Bragg peaks are peaks derived from the periodic structure of molecular orientation, and a film with a periodic interval of 3.0 to 6.0 Å can be obtained. The polymerizable liquid crystal compound may be used alone or in combination of two or more. The light absorption anisotropic film of the present invention contains a polymer of a polymerizable liquid crystal compound polymerized in a smectic phase state, which further improves the light absorption characteristics in oblique directions, resulting in a more excellent anti-peek effect, and since the orientation of the dichroic dye is less likely to be disturbed, the film has better transmittance in the front direction.

The polymerizable liquid crystal compound generally includes polymers (cured products) obtained by polymerizing the polymerizable liquid crystal compound alone while oriented in a specific direction, which exhibit positive wavelength dispersion and which exhibit reverse wavelength dispersion. In the light absorption anisotropic film of the present invention, only one type of polymerizable liquid crystal compound may be used, or both types of polymerizable liquid crystal compounds may be mixed and used.

Specific examples of the polymerizable compound exhibiting reverse wavelength dispersion include compounds represented by the following formula (X).

In formula (X), Ar represents a divalent group having an aromatic group which may have a substituent. The aromatic group referred to here refers to a ring structure having a π electron number of [4n+2] according to the Huckel rule, and may have two or more Ar groups, such as those exemplified in (Ar-1) to (Ar-23) described later, via a divalent linking group. Here, n represents an integer. When a ring structure is formed by including heteroatoms such as -N= and -S-, the Huckel rule is satisfied including the non-covalent bond electron pairs on these heteroatoms, and aromaticity is also included. The aromatic group preferably contains at least one of a nitrogen atom, an oxygen atom, and a sulfur atom. The aromatic group contained in the divalent group Ar may be one or more. When there is one aromatic group, the divalent group Ar may be a divalent aromatic group which may have a substituent. When the divalent group Ar contains two or more aromatic groups, the two or more aromatic groups may be bonded to each other via a divalent bonding group such as a single bond, -CO-O-, or -O-.
G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein a hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, and a carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom.
L ¹ , L ² , B ¹ and B ² each independently represent a single bond or a divalent linking group.
k and l each independently represent an integer of 0 to 3, and satisfy the relationship 1≦k+l, where, when 2≦k+l, B ¹ and B ² , G ¹ and G ² may be the same as or different from each other.
^E1 and ^E2 each independently represent an alkanediyl group having 1 to 17 carbon atoms, and more preferably an alkanediyl group having 4 to 12 carbon atoms. In addition, a hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and -CH ₂ - contained in the alkanediyl group may be substituted with -O-, -S-, -SiH ₂ - or -C(═O)-.
^P1 and ^P2 each independently represent a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group.

G ¹ and G ² are each independently preferably a 1,4-phenylenediyl group which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, or a 1,4-cyclohexanediyl group which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably a 1,4-phenylenediyl group substituted with a methyl group, an unsubstituted 1,4-phenylenediyl group, or an unsubstituted 1,4-trans-cyclohexanediyl group, and particularly preferably an unsubstituted 1,4-phenylenediyl group, or an unsubstituted 1,4-trans-cyclohexanediyl group.
At least one of a plurality of ^G1s and ^G2s is preferably a divalent alicyclic hydrocarbon group, and it is more preferable that at least one of ^G1s and ^G2s bonded to ^L1 or ^L2 is a divalent alicyclic hydrocarbon group.

L ¹ and L ² are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a1 OR ^a2 -, -R ^a3 COOR ^a4 -, -R ^a5 OCOR ^a6 -, -R ^a7 OC═OOR ^a8 -, -N═N-, -CR ^c ═CR ^d -, or -C≡C-, where R ^a1 to R ^a8 are each independently a single bond or an alkylene group having 1 to 4 carbon atoms, and R ^c and R ^d are an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. L ¹ and L ² are each independently more preferably a single bond, -OR ^a2-1 -, -CH ₂ -, -CH ₂ CH ₂ -, -COOR ^a4-1 -, or -OCOR ^a6-1 -. Here, R ^a2-1 , R ^a4-1 , and R ^a6-1 each independently represent a single bond, -CH ₂ -, or -CH ₂ CH ₂ -. L ¹ and L ² are each independently more preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, or -OCO-.

B ¹ and B ² are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a9 OR ^a10 -, -R ^a11 COOR ^a12 -, -R ^a13 OCOR ^a14 -, or -R ^a15 OC═OOR ^a16 -. Here, R ^a9 to R ^a16 are each independently a single bond, or an alkylene group having 1 to 4 carbon atoms. ^{B 1} and B ² are each independently more preferably a single bond, -OR ^a10-1 -, -CH ₂ -, -CH ₂ CH ₂ -, -COOR ^a12-1 -, or -OCOR ^a14-1 -. Here, R ^a10-1 , R ^a12-1 and R ^a14-1 each independently represent a single bond, -CH ₂ - or -CH ₂ CH ₂ -. ^{B 1} and B ² each independently represent more preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, -OCO- or -OCOCH ₂ CH ₂ -.

From the viewpoint of expressing reverse wavelength dispersion, k and l are preferably in the range of 2≦k+l≦6, preferably k+l=4, and more preferably k=2 and l=2. k=2 and l=2 are preferable because they result in a symmetrical structure.

Examples of the polymerizable group represented by ^P1 or ^P2 include an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, and an oxetanyl group.
Of these, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group and an oxetanyl group are preferred, and an acryloyloxy group is more preferred.

It is preferable that Ar has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle which may have a substituent, and an electron-withdrawing group. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring, and a benzene ring and a naphthalene ring are preferable. Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrroline ring, an imidazole ring, a pyrazole ring, a thiazole ring, a benzothiazole ring, a thienothiazole ring, an oxazole ring, a benzoxazole ring, and a phenanthroline ring. Among them, it is preferable that Ar has a thiazole ring, a benzothiazole ring, or a benzofuran ring, and it is more preferable that Ar has a benzothiazole group. In addition, when Ar contains a nitrogen atom, it is preferable that the nitrogen atom has π electrons.

In formula (X), the total number Nπ of π electrons contained in the divalent aromatic group represented by _Ar is preferably 8 or more, more preferably 10 or more, even more preferably 14 or more, and particularly preferably 16 or more. Also, it is preferably 30 or less, more preferably 26 or less, and even more preferably 24 or less.

Examples of aromatic groups represented by Ar include the following:

In formula (Ar-1) to formula (Ar-23), the symbol * represents a linking portion, and Z ⁰ , Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 12 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, an N-alkylamino group having 1 to 12 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 12 carbon atoms, or an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms. Z ⁰ , Z ¹ and Z ² may contain a polymerizable group.

Q ¹ and Q ² each independently represent -CR ^2' R ^3' -, -S-, -NH-, -NR ^2' -, -CO- or O-, and R ^2' and R ^3' each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

J ¹ and J ² each independently represent a carbon atom or a nitrogen atom.

Y ¹ , Y ² and Y ³ each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.

W ¹ and W ² each independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom; m represents an integer of 0 to 6.

Examples of the aromatic hydrocarbon group in Y ¹ , Y ² and Y ³ include aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and a biphenyl group, with a phenyl group and a naphthyl group being preferred, and a phenyl group being more preferred. Examples of the aromatic heterocyclic group include aromatic heterocyclic groups having 4 to 20 carbon atoms and containing at least one heteroatom, such as a nitrogen atom, an oxygen atom or a sulfur atom, such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group and a benzothiazolyl group, with a furyl group, a thienyl group, a pyridinyl group, a thiazolyl group and a benzothiazolyl group being preferred.

^Y1 , ^Y2 and ^Y3 may each independently be an optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly. The polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.

Z ⁰ , Z ¹ and Z ² are each preferably independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group or an alkoxy group having 1 to 12 carbon atoms, Z ⁰ is more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a cyano group, and Z ¹ and Z ² are more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group or a cyano group. Furthermore, Z ⁰ , Z ¹ and Z ² may contain a polymerizable group.

^Q1 and ^Q2 are preferably -NH-, -S-, ^-NR2'- or -O-, and R2 ^' is preferably a hydrogen atom. Among these, -S-, -O- or -NH- is particularly preferred.

Among formulas (Ar-1) to (Ar-23), formulas (Ar-6) and (Ar-7) are preferred from the viewpoint of molecular stability.

In formulae (Ar-16) to (Ar-23), Y ¹ may form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ^0. Examples of the aromatic heterocyclic group include those described above as aromatic heterocyclic rings that Ar may have, such as a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, an indole ring, a quinoline ring, an isoquinoline ring, a purine ring, and a pyrrolidine ring. This aromatic heterocyclic group may have a substituent. Furthermore, Y ¹ may be, together with the nitrogen atom to which it is bonded and Z ⁰ , the aforementioned polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group which may be substituted. Examples include a benzofuran ring, a benzothiazole ring, and a benzoxazole ring.

In addition, in the present invention, as the polymerizable liquid crystal compound that forms the light absorption anisotropic film, for example, a compound containing a group represented by the following formula (Y) (hereinafter also referred to as "polymerizable liquid crystal compound (Y)") may be used. The polymerizable liquid crystal compound (Y) generally tends to exhibit positive wavelength dispersion. The polymerizable liquid crystal compound may be used alone or in combination of two or more kinds.

P11-B11-E11-B12-A11-B13- (Y)
In formula (Y), P11 represents a polymerizable group.
A11 represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. A hydrogen atom contained in the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, or a nitro group, and a hydrogen atom contained in the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be substituted with a fluorine atom.
B11 represents -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ¹⁶ -, -NR ¹⁶ -CO-, -CO-, -CS- or a single bond, and R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
B12 and B13 each independently represent -C≡C-, -CH=CH-, -CH ₂ -CH ₂ -, -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -O-C(=O)-O-, -CH=N-, -N=CH-, -N=N-, -C(=O)-NR ¹⁶ -, -NR ¹⁶ -C(=O)-, -OCH ₂ -, -OCF ₂ -, -CH ₂ O-, -CF ₂ O-, -CH=CH-C(=O)-O-, -O-C(=O)-CH=CH- or a single bond.
E11 represents an alkanediyl group having 1 to 12 carbon atoms, a hydrogen atom contained in the alkanediyl group may be substituted with an alkoxy group having 1 to 5 carbon atoms, and a hydrogen atom contained in the alkoxy group may be substituted with a halogen atom. In addition, -CH ₂ - constituting the alkanediyl group may be replaced with -O- or -CO-.]

The number of carbon atoms in the aromatic hydrocarbon group and alicyclic hydrocarbon group of A11 is preferably in the range of 3 to 18, more preferably in the range of 5 to 12, and particularly preferably 5 or 6. A11 is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group.

E11 is preferably a linear alkanediyl group having 1 to 12 carbon atoms. --CH ₂ -- constituting the alkanediyl group may be replaced with --O--.
Specific examples of such alkyl groups include linear alkanediyl groups having 1 to 12 carbon atoms, such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11 _- diyl group, and a dodecane-1,12-diyl group; -CH ₂ -CH _{2 -O} -CH ₂ -CH ₂ -, -CH ₂ -CH 2 -O-CH ₂ -CH ₂ -O-CH _{2 -CH 2 - and -CH 2 -CH 2} -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ Examples include —CH ₂ —.
As B11, --O--, --S--, --CO--O-- and --O--CO-- are preferable, and among them, --CO--O-- is more preferable.
As B12 and B13, each independently is preferably -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)- or -O-C(=O)-O-, and among these, -O- or -O-C(=O)-O- is more preferable.

As the polymerizable group represented by P11, a radically polymerizable group or a cationic polymerizable group is preferred because of its high polymerization reactivity, particularly photopolymerization reactivity. In addition, the polymerizable group is preferably a group represented by the following formulae (P-11) to (P-15), because it is easy to handle and the liquid crystal compound itself is easy to manufacture.

［式（Ｐ－１１）～（Ｐ－１５）中、
Ｒ^１７～Ｒ^２１はそれぞれ独立に、炭素数１～６のアルキル基または水素原子を表す。
］

[In formulas (P-11) to (P-15),
R ¹⁷ to R ²¹ each independently represent an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.
］

Specific examples of the groups represented by formulae (P-11) to (P-15) include groups represented by the following formulae (P-16) to (P-20).

P11 is preferably a group represented by formula (P-14) to formula (P-20), and more preferably a vinyl group, a p-stilbene group, an epoxy group or an oxetanyl group.
The group represented by P11-B11- is more preferably an acryloyloxy group or a methacryloyloxy group.

Examples of the polymerizable liquid crystal compound (Y) include compounds represented by formula (Y-I), formula (Y-II), formula (Y-III), formula (Y-IV), formula (Y-V) or formula (Y-VI).
P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-B16-E12-B17-P12 (Y-I)
P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-F11 (Y-II)
P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-E12-B17-P12 (Y-III)
P11-B11-E11-B12-A11-B13-A12-B14-A13-F11 (Y-IV)
P11-B11-E11-B12-A11-B13-A12-B14-E12-B17-P12 (Y-V)
P11-B11-E11-B12-A11-B13-A12-F11 (Y-VI)
(In the formula,
A11, B11 to B13 and P11 are the same as those in formula (Y) above.
A12 to A14 each independently have the same meaning as A11, B14 to B16 each independently have the same meaning as B12, B17 has the same meaning as B11, E12 has the same meaning as E11, and P12 has the same meaning as P11.
F11 represents a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxy group, a methylol group, a formyl group, a sulfo group (—SO ₃ H), a carboxy group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or a halogen atom, and —CH ₂ — constituting the alkyl group and the alkoxy group may be replaced with —O—.)

Specific examples of the polymerizable liquid crystal compound (Y) include compounds having a polymerizable group among those described in "3.8.6 Network (fully cross-linked type)" and "6.5.1 Liquid crystal material b. Polymerizable nematic liquid crystal material" in Liquid Crystal Handbook (edited by Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000), and the polymerizable liquid crystals described in JP-A Nos. 2010-31223, 2010-270108, 2011-6360, and 2011-207765.

Specific examples of the polymerizable liquid crystal compound (Y) include compounds represented by the following formulae (Y-I-1) to (Y-I-4), (Y-II-1) to (Y-II-4), (Y-III-1) to (Y-III-26), (Y-IV-1) to (Y-IV-26), (Y-V-1) to (Y-V-2), and (Y-VI-1) to (Y-VI-6).
In the following formula, k1 and k2 each independently represent an integer of 2 to 12. These polymerizable liquid crystal compounds (Y) are preferable in terms of ease of synthesis or availability.

A polymerizable liquid crystal compound exhibiting smectic liquid crystallinity is a liquid crystal compound having at least one polymerizable group, and from the viewpoint of improving the heat resistance of the light absorption anisotropic film, it is preferable that the liquid crystal compound has two or more polymerizable groups. Examples of polymerizable groups include (meth)acryloyloxy groups, vinyl groups, vinyloxy groups, 1-chlorovinyl groups, isopropenyl groups, 4-vinylphenyl groups, oxiranyl groups, and oxetanyl groups. Among them, it is preferable that the compound contains a (meth)acryloyloxy group, because it is easy to manufacture, the heat resistance of the light absorption anisotropic film is easily improved, and the adhesion between the light absorption anisotropic film and the substrate is easily adjusted.

［式（Ｚ）中、Ｘ^１ｚおよびＸ^２ｚは、互いに独立して、２価の芳香族基または２価の脂環式炭化水素基を表し、ここで、該２価の芳香族基または２価の脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のフルオロアルキル基、炭素数１～４のアルコキシ基、シアノ基またはニトロ基に置換されていてもよく、該２価の芳香族基または２価の脂環式炭化水素基を構成する炭素原子が、酸素原子または硫黄原子または窒素原子に置換されていてもよい。ただし、Ｘ^１ｚおよびＸ^２ｚのうち少なくとも１つは、置換基を有していてもよい１，４－フェニレン基または置換基を有していてもよいシクロヘキサン－１，４－ジイル基である。
Ｙ^１ｚは、単結合または二価の連結基である。
ｎｚは１～３であり、ｎｚが２以上の場合、複数のＸ^１ｚは互いに同じであってもよいし、異なっていてもよい。Ｘ^２ｚは、複数のＸ^１ｚのうちのいずれかまたは全てと同じであってもよいし、異なっていてもよい。また、ｎｚが２以上の場合、複数のＹ^１ｚは互いに同じであってもよいし、異なっていてもよい。液晶性の観点からｎｚは２以上が好ましい。
Ｕ^１ｚは、水素原子または（メタ）アクリロイルオキシ基を表す。
Ｕ^２ｚは、重合性基を表す。
Ｗ^１ｚおよびＷ^２ｚは、互いに独立して、単結合または二価の連結基である。
Ｖ^１ｚおよびＶ^２ｚは、互いに独立して、置換基を有していてもよい炭素数１～２０のアルカンジイル基を表し、該アルカンジイル基を構成する－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－Ｓ－または－ＮＨ－に置き換わっていてもよい。］ An example of the polymerizable liquid crystal compound exhibiting smectic liquid crystallinity is a compound represented by the following formula (Z) (hereinafter, sometimes referred to as "polymerizable liquid crystal compound (Z)").

[In formula (Z), X ^1z and X ^2z each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein a hydrogen atom contained in the divalent aromatic group or divalent alicyclic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, and a carbon atom constituting the divalent aromatic group or divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. However, at least one of X ^1z and X ^2z is a 1,4-phenylene group which may have a substituent, or a cyclohexane-1,4-diyl group which may have a substituent.
Y ^1z is a single bond or a divalent linking group.
nz is 1 to 3, and when nz is 2 or more, the multiple X ^1z may be the same as or different from each other. X ^2z may be the same as or different from any or all of the multiple X ^1z . When nz is 2 or more, the multiple Y ^1z may be the same as or different from each other. From the viewpoint of liquid crystallinity, nz is preferably 2 or more.
U ^1z represents a hydrogen atom or a (meth)acryloyloxy group.
^U2z represents a polymerizable group.
W ^1z and W ^2z are each independently a single bond or a divalent linking group.
V ^1z and V ^2z each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - constituting the alkanediyl group may be replaced by -O-, -CO-, -S- or -NH-.]

In the polymerizable liquid crystal compound (Z), X ^1z and X ^2z are each independently preferably a 1,4-phenylene group which may have a substituent, or a cyclohexane-1,4-diyl group which may have a substituent, and at least one of X ^1z and X ^2z is a 1,4-phenylene group which may have a substituent, or a cyclohexane-1,4-diyl group which may have a substituent, and is preferably a trans-cyclohexane-1,4-diyl group. Examples of the substituent that the 1,4-phenylene group which may have a substituent or the cyclohexane-1,4-diyl group which may have a substituent optionally include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a butyl group, a cyano group, and a halogen atom such as a chlorine atom or a fluorine atom. It is preferably unsubstituted.

The polymerizable liquid crystal compound (Z) is represented by the formula (Z1):
-(X ¹ -Y ¹ -) _n -X ² - (Z1)
[In the formula, X ^1z , Y ^1z , X ^2z and nz are as defined above.]
[hereinafter, referred to as partial structure (Z1)] preferably has an asymmetric structure, since this facilitates the development of smectic liquid crystal properties.
Examples of the polymerizable liquid crystal compound (Z) having an asymmetric structure of the partial structure (Z1) include a polymerizable liquid crystal compound (Z) in which nz is 1 and one X ^1z and one X ^2z are different from each other. In addition, a polymerizable liquid crystal compound (Z) in which nz is 2 and two Y ^1z are the same structure, two X ^1z are the same structure, and one X ^2z is different from ^{these two X 1z ,} and a polymerizable liquid crystal compound (Z) in which the X ^1z bonded to W ^1z of two X 1z is different from the other X ^1z and X ^2z , and the other X ^1z and X ^2z are the same structure. In addition, a polymerizable liquid crystal compound (Z) in which nz is 3 and three Y ^1z are the same structure, and one of the three X ^1z and one X ^2z is different from all the other three.

Y ^1z is preferably -CH ₂ CH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ O-, -COO-, -OCOO-, a single bond, -N=N-, -CR ^az ≡CR ^bz -, -C≡C-, -CR ^az ≡N- or -CO-NR ^az -. R ^az and R ^bz each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y ^1z is more preferably -CH ₂ CH ₂ -, -COO- or a single bond, and when a plurality of Y ^1z are present, the Y ^1z bonded to X ^2z is more preferably -CH ₂ CH ₂ - or -CH ₂ O-. When X ^1z and X ^2z are all the same structure, it is preferable that there are two or more Y ^1z having different bonding modes. When a plurality of Y ^{1z groups} having mutually different bonding modes are present, an asymmetric structure is formed, and therefore smectic liquid crystallinity tends to be easily exhibited.

U ^2z is the above-mentioned polymerizable group. U ^1z is a hydrogen atom or a polymerizable group. The polymerizable group is preferably a (meth)acryloyloxy group because it is easy to manufacture, the heat resistance of the optically absorptive anisotropic film is easily improved, and the adhesion between the optically absorptive anisotropic film and the substrate is easily adjusted. The polymerizable group may be in a polymerized state or an unpolymerized state, but is preferably in an unpolymerized state.

Examples of the alkanediyl group represented by V ^1z and V ^2z include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a decane-1,10-diyl group, a tetradecane-1,14-diyl group, and an icosane-1,20-diyl group, etc. V ^1z and V ^2z are preferably alkanediyl groups having 2 to 12 carbon atoms, and more preferably alkanediyl groups having 6 to 12 carbon atoms.

Substituents that the alkanediyl group may optionally have include a cyano group and a halogen atom, but the alkanediyl group is preferably unsubstituted, and more preferably an unsubstituted linear alkanediyl group.

W ^1z and W ^2z each independently preferably represent a single bond, —O—, —S—, —COO— or —OCOO—, more preferably a single bond or —O—.

The polymerizable liquid crystal compound (Z) preferably has an asymmetric molecular structure, and more specifically, is more preferably a polymerizable liquid crystal compound having the partial structures (A-a) to (A-i) below. From the viewpoint of being more likely to exhibit high-order smectic liquid crystal properties, it is more preferable that it has the partial structure (A-a), (A-b) or (A-c). In the following (A-a) to (A-i), * represents a bond (single bond).

Specific examples of the polymerizable liquid crystal compound (Z) include compounds represented by formulas (A-1) to (A-25). When the polymerizable liquid crystal compound (Z) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans isomer.

Among these, at least one selected from the group consisting of compounds represented by formula (A-2), formula (A-3), formula (A-4), formula (A-5), formula (A-6), formula (A-7), formula (A-8), formula (A-13), formula (A-14), formula (A-15), formula (A-16) and formula (A-17) is preferred. As the polymerizable liquid crystal compound (Z), one type may be used alone, or two or more types may be used in combination. In addition, when two or more types of polymerizable liquid crystal compounds are combined, it is preferable that at least one type is compound (Z), and it is more preferable that two or more types are compound (Z). By combining, it may be possible to temporarily maintain liquid crystallinity even at a temperature below the liquid crystal-crystal phase transition temperature. The mixing ratio when combining two types of polymerizable liquid crystal compounds is usually 1:99 to 50:50, preferably 5:95 to 50:50, and more preferably 10:90 to 50:50. When two types of polymerizable liquid crystal compounds are combined and only one of them is compound (Z), it is preferable that compound (Z) be mixed in such a way that it occupies a higher proportion in the above mixture ratio.

The polymerizable liquid crystal compound (Z) can be produced by a known method, for example, as described in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996), or Japanese Patent No. 4719156.

The polymerizable liquid crystal compound forming the light-absorption anisotropic film is preferably a polymerizable liquid crystal compound having a maximum absorption wavelength between 300 and 400 nm. When the polymerizable liquid crystal composition contains a photopolymerization initiator, the polymerization reaction and gelation of the polymerizable liquid crystal compound may progress during long-term storage. However, if the maximum absorption wavelength of the polymerizable liquid crystal compound is 300 to 400 nm, even if the composition is exposed to ultraviolet light during storage, the generation of reactive species from the photopolymerization initiator and the polymerization reaction and gelation of the polymerizable liquid crystal compound caused by the reactive species can be effectively suppressed. This is therefore advantageous in terms of the long-term stability of the composition containing the polymerizable liquid crystal compound, and the alignment and uniformity of the film thickness of the resulting liquid crystal cured film can be improved. The maximum absorption wavelength of the polymerizable liquid crystal compound can be measured using a UV-visible spectrophotometer in a solvent. The solvent is a solvent that can dissolve the polymerizable liquid crystal compound, and examples of the solvent include chloroform.

From the viewpoint of increasing the alignment of the liquid crystal compound, the content of the liquid crystal compound in the liquid crystal composition forming the optically absorptive anisotropic film is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and preferably 99.5 parts by mass or less, more preferably 99 parts by mass or less, even more preferably 94 parts by mass or less, and even more preferably 90 parts by mass or less, relative to 100 parts by mass of the optically absorptive anisotropic film. The content of the liquid crystal compound can be calculated as the ratio of the liquid crystal compound to 100 parts by mass of the solid content of the liquid crystal composition forming the optically absorptive anisotropic film.

In the optically absorptive anisotropic film containing a dichroic dye and a liquid crystal compound, it is preferable that the dichroic dye is present by being encapsulated in a polymerizable liquid crystal compound, and that the dichroic dye and the polymerizable liquid crystal compound are oriented with a high degree of order in the vertical direction of the optically absorptive anisotropic film. Since the polymerizable liquid crystal compound and the dichroic dye are oriented with a high degree of order, when a laminate containing the optically absorptive anisotropic film is incorporated into an organic EL display device, the laminate tends to have excellent transparency in the front direction and reduced directional anisotropy of the optical absorption characteristics in oblique directions, resulting in excellent prevention of peeping from oblique directions.

In the present invention, the liquid crystal composition used to form the light absorbing anisotropic film may contain components other than the dichroic dye and the liquid crystal compound. Examples of such components include a polymerization initiator, a leveling agent, a solvent, an antioxidant, and a photosensitizer. These components may be used alone or in combination of two or more.

<Polymerization initiator>
The polymerization initiator is a compound capable of initiating a polymerization reaction of a polymerizable liquid crystal compound, etc. As the polymerization initiator, a photopolymerization initiator that generates active radicals by the action of light is preferable.

Examples of polymerization initiators include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and sulfonium salts.

Examples of benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone.

Examples of alkylphenone compounds include diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one.

Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl] ]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

Commercially available polymerization initiators can be used. Commercially available polymerization initiators include Irgacure (registered trademark) 907, 184, 651, 819, 250 and 369 (BASF); Seikuol (registered trademark) BZ, Z and BEE (Seiko Chemical Co., Ltd.); Kayacure (registered trademark) BP100 and UVI-6992 (Nippon Kayaku Co., Ltd.); Adeka Optomer SP-152 and SP-170 (ADEKA Co., Ltd.); TAZ-A and TAZ-PP (DKSH Japan Co., Ltd.); and TAZ-104 (Sanwa Chemical Co., Ltd.).

The content of the polymerization initiator is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 30 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound, from the viewpoint of not disturbing the orientation of the polymerizable liquid crystal compound.

<Leveling Agent>
The leveling agent has a function of adjusting the fluidity of the liquid crystal composition and making the light absorption anisotropic film flatter, and can be exemplified by a surfactant. Preferred leveling agents include a leveling agent mainly composed of a polyacrylate compound and a leveling agent mainly composed of a fluorine atom-containing compound.

Leveling agents that contain a polyacrylate compound as the main component include BYK-350, BYK-352, BYK-353, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380, BYK-381, and BYK-392 (BYK Chemie).

Leveling agents mainly containing fluorine atom-containing compounds include Megafac (registered trademark) R-08, R-30, R-90, F-410, F-411, F-443, F-445, F-470, F-471, F-477, F-479, F-482, F-483 (DIC Corporation); Surflon (registered trademark) S-381, S-382, S-383, S-393, SC-101, SC-105, KH-40, and SA-100 (AGC Seimi Chemical Co., Ltd.); E1830 and E5844 (Daikin Industries, Ltd.); EFTOP EF301, EF303, EF351, and EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd.), etc.

The content of the leveling agent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, relative to 100 parts by mass of the liquid crystal compound. If the content of the leveling agent is within the above range, the resulting liquid crystal cured film tends to be smoother, which is preferable. If the content of the leveling agent relative to the liquid crystal compound exceeds the above range, the resulting liquid crystal cured film tends to be uneven or to be aligned in the horizontal direction, which is not preferable. The light absorbing anisotropic film may contain two or more types of leveling agents.

<Solvent>
The solvent is preferably one that can completely dissolve the liquid crystal compound, and when the liquid crystal compound is a polymerizable liquid crystal compound, the solvent is preferably one that is inactive to the polymerization reaction.

Examples of the solvent include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone or propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene, and nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; and chlorine-containing solvents such as chloroform and chlorobenzene. These solvents may be used alone or in combination of two or more.

The content of the solvent is preferably 50 to 98% by mass based on the total amount of the liquid crystal composition, in other words, the ratio of the optically absorptive anisotropic film component is preferably 2 to 50% by mass based on the total amount of the liquid crystal composition.
When the solid content is 50% by mass or less with respect to the total amount of the liquid crystal composition, the viscosity of the liquid crystal composition is low, and therefore the thickness of the liquid crystal cured film becomes approximately uniform, and the optically absorptive anisotropic film tends to be less prone to unevenness. In addition, such a solid content can be determined in consideration of the thickness of the optically absorptive anisotropic film to be produced.

<Antioxidants>
The polymerization reaction of the polymerizable liquid crystal compound can be controlled by adding an antioxidant. The antioxidant may be a primary antioxidant selected from a phenol-based antioxidant, an amine-based antioxidant, a quinone-based antioxidant, and a nitroso-based antioxidant, or a secondary antioxidant selected from a phosphorus-based antioxidant and a sulfur-based antioxidant.
In order to polymerize the polymerizable liquid crystal compound without disturbing the alignment of the polymerizable liquid crystal compound, the content of the antioxidant is usually 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound.
The antioxidants may be used alone or in combination of two or more kinds.

<Photosensitizer>
The photosensitizer can be used to increase the sensitivity of the photopolymerization initiator. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone; anthracenes having a substituent such as anthracene and alkyl ether; phenothiazine; and rubrene. The photosensitizer can be used alone or in combination of two or more kinds. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal compound.

The optically absorptive anisotropic film of the present invention may be, for example,
A step of obtaining a liquid crystal composition by stirring a liquid crystal compound, a dichroic dye, and optionally an additive such as a solvent at a predetermined temperature;
The liquid crystal composition can be produced by a method including the steps of forming a coating film of the liquid crystal composition, and drying the coating film to form a dry coating film.

The temperature at which the liquid crystal compound and dichroic dye, and optionally additives such as a solvent, are stirred is usually 0 to 50°C, and preferably 10 to 40°C. There are no particular limitations on the stirring method, and stirring can be carried out by any conventionally known method.

The coating film of the liquid crystal composition can be formed, for example, by applying the liquid crystal composition onto a substrate, an alignment film, or a horizontal alignment retardation film i described later.
Examples of the substrate include glass substrates and film substrates, but resin film substrates are preferred from the viewpoint of processability. Examples of the resin constituting the film substrate include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid esters; polyacrylic acid esters; cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; plastics such as polyphenylene sulfide and polyphenylene oxide. Such resins can be formed into a film by known means such as solvent casting and melt extrusion to form a substrate. The substrate surface may have a protective layer formed from an acrylic resin, a methacrylic resin, an epoxy resin, an oxetane resin, a urethane resin, a melamine resin, or the like, and may be subjected to a surface treatment such as a release treatment such as silicone treatment, a corona treatment, or a plasma treatment.

Commercially available products may be used as the substrate. Examples of commercially available cellulose ester substrates include cellulose ester substrates manufactured by Fuji Photo Film Co., Ltd., such as Fujitac Film; cellulose ester substrates manufactured by Konica Minolta Opto Co., Ltd., such as "KC8UX2M", "KC8UY", and "KC4UY". Examples of commercially available cyclic olefin resins include cyclic olefin resins manufactured by Ticona (Germany), such as "Topas (registered trademark)", cyclic olefin resins manufactured by JSR Corporation, such as "Arton (registered trademark)", cyclic olefin resins manufactured by Zeon Corporation, such as "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)", and cyclic olefin resins manufactured by Mitsui Chemicals, Inc., such as "Apel (registered trademark)". Commercially available cyclic olefin resin substrates may also be used. Commercially available cyclic olefin resin substrates include cyclic olefin resin substrates manufactured by Sekisui Chemical Co., Ltd., such as "S-Cina (registered trademark)" and "SCA40 (registered trademark)"; cyclic olefin resin substrates manufactured by Optes Co., Ltd., such as "ZEONORFILM (registered trademark)"; and cyclic olefin resin substrates manufactured by JSR Corporation, such as "ARTONFILM (registered trademark)".

From the viewpoints of ease of peeling the substrate and ease of handling the substrate, the thickness of the substrate is usually 5 to 300 μm, and preferably 10 to 150 μm.

Methods for applying the liquid crystal composition to a substrate or the like include known methods such as coating methods such as spin coating, extrusion, gravure coating, die coating, bar coating, and applicator methods, and printing methods such as flexography.

Next, the solvent is removed by drying or the like to form a dried coating film. Examples of drying methods include natural drying, ventilation drying, heat drying, and reduced pressure drying. In this case, the coating film obtained from the liquid crystal composition can be heated to dry and remove the solvent from the coating film, and the liquid crystal compound can be aligned in a direction perpendicular to the coating film plane. The heating temperature of the coating film can be appropriately determined in consideration of the liquid crystal compound used and the material of the substrate on which the coating film is formed, but it is necessary that the temperature is equal to or higher than the liquid crystal phase transition temperature in order to phase-transition the liquid crystal compound to a liquid crystal layer state. In order to vertically align the liquid crystal compound while removing the solvent contained in the liquid crystal composition, the liquid crystal composition can be heated to a temperature equal to or higher than the liquid crystal phase transition temperature (smectic phase transition temperature or nematic phase transition temperature) of the liquid crystal compound contained in the liquid crystal composition.
The liquid crystal phase transition temperature can be measured, for example, using a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), or the like. When two or more liquid crystal compounds are used in combination, the phase transition temperature means a temperature measured in the same manner as when one liquid crystal compound is used, using a mixture of liquid crystal compounds in which all liquid crystal compounds constituting the liquid crystal composition are mixed in the same ratio as in the composition of the liquid crystal composition. It is generally known that the liquid crystal phase transition temperature of a liquid crystal compound in the liquid crystal composition may be lower than the liquid crystal phase transition temperature of the liquid crystal compound alone.

The heating time can be appropriately determined depending on the heating temperature, the type of polymerizable liquid crystal compound used, the type of solvent, its boiling point and its amount, etc., but is usually 15 seconds to 10 minutes, and preferably 0.5 to 5 minutes.

When a polymerizable liquid crystal compound is used as the liquid crystal compound, the polymerizable liquid crystal compound is polymerized in the obtained dry coating film while maintaining the vertical alignment state of the polymerizable liquid crystal compound, thereby forming a light absorption anisotropic film. The polymerization method may be a thermal polymerization method or a photopolymerization method, but photopolymerization is preferred from the viewpoint of easy control of the polymerization reaction. In photopolymerization, the light irradiated to the dry coating film is appropriately selected according to the type of photopolymerization initiator contained in the dry coating film, the type of polymerizable liquid crystal compound (particularly the type of polymerizable group possessed by the polymerizable liquid crystal compound) and the amount thereof. Specific examples thereof include one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays and γ-rays, and active electron beams. Among them, ultraviolet light is preferred because it is easy to control the progress of the polymerization reaction and photopolymerization devices widely used in this field can be used. It is preferable to select the type of polymerizable liquid crystal compound and photopolymerization initiator contained in the polymerizable liquid crystal composition (a composition containing a polymerizable liquid crystal compound may be referred to as a "polymerizable liquid crystal composition" hereinafter) so that photopolymerization can be performed by ultraviolet light. In addition, the polymerization temperature can be controlled by irradiating light while cooling the dried coating film with an appropriate cooling means during polymerization. By adopting such a cooling means, if the polymerization of the polymerizable liquid crystal compound is performed at a lower temperature, a light absorbing anisotropic film can be appropriately formed even if a substrate with relatively low heat resistance is used. In addition, it is also possible to promote the polymerization reaction by increasing the polymerization temperature within a range where defects due to heat during light irradiation (such as deformation of the substrate due to heat) do not occur. During photopolymerization, a patterned light absorbing anisotropic film can also be obtained by performing masking, development, etc.

Examples of light sources for the active energy rays include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, LED light sources emitting light in the wavelength range of 380 to 440 nm, chemical lamps, black light lamps, microwave excited mercury lamps, metal halide lamps, etc.

The ultraviolet irradiation intensity is usually 10 to 3,000 mW/ ^cm2 . The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activating a photopolymerization initiator. The time for irradiating light is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and even more preferably 0.1 seconds to 1 minute. When irradiating once or multiple times with such ultraviolet irradiation intensity, the integrated light amount is 10 to 3,000 mJ/ ^cm2 , preferably 50 to 2,000 mJ/ ^cm2 , and more preferably 100 to 1,000 mJ/ ^cm2 .

The thickness of the optically absorptive anisotropic film can be appropriately selected depending on the display device to which it is applied, and is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, even more preferably 0.2 to 3 μm or 0.5 to 5 μm, and particularly preferably 0.5 to 3 μm. When the thickness of the optically absorptive anisotropic film is within the above range, the effect of canceling the hue of the display when viewed from an oblique direction is easily enhanced, and the laminate can be made thinner. The thickness of the optically absorptive anisotropic film can be measured using, for example, a laser microscope, a stylus-type film thickness meter, etc.

In one embodiment of the present invention, a coating of the liquid crystal composition is formed on an alignment film. The alignment film has an alignment regulating force that aligns the liquid crystal compound in a desired direction. An alignment film that has an alignment regulating force that aligns the liquid crystal compound in the horizontal direction is sometimes called a horizontal alignment film, and an alignment film that has an alignment regulating force that aligns the liquid crystal compound in the vertical direction is sometimes called a vertical alignment film. The alignment regulating force can be adjusted arbitrarily by the type of alignment film, surface state, rubbing conditions, etc., and when the alignment film is formed from a photoalignable polymer, it can be adjusted arbitrarily by the polarized light irradiation conditions, etc.

As the alignment film, it is preferable that it has solvent resistance so that the liquid crystal composition does not dissolve when applied, and also has heat resistance during the heat treatment for removing the solvent and for orienting the liquid crystal compound described below. Examples of the alignment film include an alignment film containing an orienting polymer, a photo-alignment film, a groove alignment film having a concave-convex pattern or multiple grooves on the surface, and a stretched film stretched in the alignment direction, and from the viewpoint of the precision of the alignment angle and quality, a photo-alignment film is preferable.

Examples of oriented polymers include polyamides and gelatins having amide bonds in the molecule, polyimides having imide bonds in the molecule, and their hydrolyzates such as polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid esters. Of these, polyvinyl alcohol is preferred. Oriented polymers can be used alone or in combination of two or more.

An alignment film containing an alignment polymer is usually obtained by applying a composition in which an alignment polymer is dissolved in a solvent (hereinafter sometimes referred to as an "alignment polymer composition") to a substrate and then removing the solvent, or by applying an alignment polymer composition to a substrate, removing the solvent, and then rubbing (rubbing method). Examples of the solvent include the same solvents as those exemplified above as solvents that can be used in liquid crystal compositions.

The concentration of the oriented polymer in the oriented polymer composition may be within a range in which the oriented polymer material can be completely dissolved in the solvent, but is preferably 0.1 to 20% in terms of solids content relative to the solution, and more preferably approximately 0.1 to 10%.

As the oriented polymer composition, commercially available alignment film materials may be used as they are. Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optomer (registered trademark, manufactured by JSR Corporation).

Methods for applying the alignment polymer composition to a substrate include the same methods as those exemplified as the methods for applying the liquid crystal composition to a substrate.

Methods for removing the solvent contained in the oriented polymer composition include natural drying, ventilation drying, heat drying, and reduced pressure drying.

In order to impart an orientation control force to the orientation film, a rubbing treatment can be performed as necessary (rubbing method). One method for imparting an orientation control force by the rubbing method is to bring an orientation polymer film formed on the surface of a substrate by applying an orientation polymer composition to the substrate and annealing the composition into contact with a rotating rubbing roll wrapped with a rubbing cloth. If masking is performed during the rubbing treatment, multiple regions (patterns) with different orientation directions can also be formed in the orientation film.

Photo-alignment films are usually obtained by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter also referred to as a "photo-alignment film forming composition") to a substrate, removing the solvent, and then irradiating the substrate with polarized light (preferably polarized UV). Photo-alignment films are also advantageous in that the direction of the alignment control force can be freely controlled by selecting the polarization direction of the polarized light to be irradiated.

The photoreactive group refers to a group that generates liquid crystal alignment ability when irradiated with light. Specific examples include groups involved in photoreactions that are the origin of liquid crystal alignment ability, such as molecular alignment induction caused by light irradiation, or isomerization reactions, dimerization reactions, photocrosslinking reactions, or photodecomposition reactions. Among these, groups involved in dimerization reactions or photocrosslinking reactions are preferred in terms of excellent alignment ability. As the photoreactive group, a group having an unsaturated bond, particularly a double bond, is preferred, and a group having at least one bond selected from the group consisting of a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond (N=N bond), and a carbon-oxygen double bond (C=O bond) is particularly preferred.

Examples of the photoreactive group having a C═C bond include a vinyl group, a polyene group, a stilbene group, a stilbazolium group, a chalcone group, and a cinnamoyl group.
Examples of photoreactive groups having a C=N bond include groups having a structure such as an aromatic Schiff base or aromatic hydrazone. Examples of photoreactive groups having an N=N bond include an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group, a formazan group, and a group having an azoxybenzene structure. Examples of photoreactive groups having a C=O bond include a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group. These groups may have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, or a halogenated alkyl group.

Among these, photoreactive groups involved in photodimerization reactions are preferred, and cinnamoyl and chalcone groups are preferred because they require a relatively small amount of polarized light irradiation for photoalignment and are easy to obtain photoalignment films that are excellent in thermal stability and stability over time. As polymers having photoreactive groups, those having cinnamoyl groups such that the terminals of the polymer side chains form cinnamic acid structures are particularly preferred.

A photo-alignment-inducing layer can be formed on a substrate by applying the photo-alignment film-forming composition onto the substrate. Examples of the solvent contained in the composition include the same solvents as those exemplified above as solvents that can be used in liquid crystal compositions, and can be appropriately selected depending on the solubility of the polymer or monomer having a photoreactive group.

The content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be adjusted as appropriate depending on the type of polymer or monomer and the desired thickness of the photo-alignment film, but is preferably at least 0.2% by mass, more preferably in the range of 0.3 to 10% by mass, relative to the mass of the composition for forming a photo-alignment film. The composition for forming a photo-alignment film may contain a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer, as long as the properties of the photo-alignment film are not significantly impaired.

Methods for applying the photo-alignment film-forming composition to a substrate include the same methods as those for applying the alignment polymer composition to a substrate. Methods for removing the solvent from the applied photo-alignment film-forming composition include, for example, natural drying, ventilation drying, heat drying, and reduced pressure drying.

To irradiate polarized light, polarized UV may be irradiated directly onto the composition for forming a photo-aligned film coated on the substrate after removing the solvent, or polarized light may be irradiated from the substrate side and then transmitted through the substrate. In addition, it is particularly preferable that the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in a wavelength range in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) in the wavelength range of 250 to 400 nm is particularly preferable. Examples of light sources used for the polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF and ArF, and high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are more preferable. Among these, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferable because they have a high emission intensity of ultraviolet light with a wavelength of 313 nm. Polarized UV can be irradiated by passing the light from the light source through an appropriate polarizer. Such polarizers can be polarizing filters, polarizing prisms such as Glan-Thompson and Glan-Taylor, or wire grid type polarizers.

If masking is performed when rubbing or irradiating with polarized light, multiple regions (patterns) with different liquid crystal alignment directions can be formed.

A groove alignment film is a film that has a concave-convex pattern or multiple grooves on its surface. When a liquid crystal compound is applied to a film that has multiple equally spaced linear grooves, the liquid crystal molecules are oriented in the direction along the grooves.

Methods for obtaining a groove alignment film include a method in which the surface of a photosensitive polyimide film is exposed through an exposure mask having slits in the shape of a pattern, followed by development and rinsing to form a concave-convex pattern; a method in which a layer of uncured UV-cured resin is formed on a plate-shaped master having grooves on its surface, and the formed resin layer is transferred to a substrate and then cured; and a method in which a roll-shaped master having multiple grooves is pressed against an uncured UV-cured resin film formed on a substrate to form concave-convex patterns, followed by curing.

In addition to the above-mentioned orienting polymers, materials that exhibit an orientation control force that orients liquid crystal compounds in a direction perpendicular to the coating plane may also include fluorine-based polymers such as perfluoroalkyls, silane compounds, and polysiloxane compounds obtained by condensation reactions of these compounds.

When using a silane compound as a material for forming the alignment film, a compound containing Si and C elements as constituent elements is preferred from the viewpoint of easily reducing surface tension and easily increasing adhesion with layers adjacent to the alignment film, and a silane compound can be suitably used. The alignment control force can be increased by using a silane compound. These silane compounds may be used alone or in combination with two or more types, or may be used in combination with other materials.

The thickness of the alignment film (alignment film containing an alignment polymer or photoalignment film) is usually in the range of 10 to 10,000 nm, preferably in the range of 10 to 1000 nm, more preferably 10 to 500 nm or less, even more preferably 10 to 300 nm, and particularly preferably 50 to 250 nm.

In another embodiment of the present invention, the coating film of the liquid crystal composition does not require an alignment film and can be formed directly on the substrate. In such an embodiment, the liquid crystal composition for forming the light absorption anisotropic film usually contains an alignment promoter. In the present invention, the alignment promoter means a material that promotes the liquid crystal alignment of the liquid crystal compound in the desired direction. Examples of the alignment promoter that promotes the alignment of the liquid crystal compound include ionic compounds consisting of nonmetallic atoms and nonionic silane compounds. It is preferable that the liquid crystal composition that forms the light absorption anisotropic film contains at least one of the ionic compounds consisting of nonmetallic atoms and the nonionic silane compounds, and it is more preferable that it contains both the ionic compounds consisting of nonmetallic atoms and the nonionic silane compounds.

When the liquid crystal composition that forms the optically absorptive anisotropic film contains an ionic compound consisting of nonmetallic atoms, in the dried coating film formed on the substrate from the optically absorptive anisotropic film-forming composition, a vertical alignment control force is exerted on the liquid crystal compound due to electrostatic interaction, and the liquid crystal compound tends to be aligned vertically to the substrate surface in the dried coating film. This allows the liquid crystal compound to maintain a vertically aligned state and form a liquid crystal cured film.

Examples of ionic compounds consisting of nonmetallic atoms include onium salts (more specifically, quaternary ammonium salts in which the nitrogen atom has a positive charge, tertiary sulfonium salts, and quaternary phosphonium salts in which the phosphorus atom has a positive charge). Among these onium salts, quaternary onium salts are preferred from the viewpoint of further improving the vertical alignment of the liquid crystal compound, and quaternary phosphonium salts or quaternary ammonium salts are more preferred from the viewpoint of improving availability and mass production. The onium salt may have two or more quaternary onium salt sites in the molecule, and may be an oligomer or polymer.

The molecular weight of the ionic compound is preferably 100 or more and 10,000 or less. When the molecular weight is within the above range, it is easy to improve the vertical alignment of the liquid crystal compound while ensuring the coatability of the liquid crystal composition. The molecular weight of the ionic compound is more preferably 5000 or less, and even more preferably 3000 or less.

Examples of the cationic component of the ionic compound include inorganic cations and organic cations. Among them, organic cations are preferred because they are less likely to cause alignment defects in the polymerizable liquid crystal compound. Examples of organic cations include imidazolium cations, pyridinium cations, ammonium cations, sulfonium cations, and phosphonium cations.

Ionic compounds generally have a counter anion. Examples of an anion component that serves as a counter ion to the cationic component include inorganic anions and organic anions. Among these, organic anions are preferred because they are less likely to cause alignment defects in the liquid crystal compound. Note that cations and anions do not necessarily have to correspond one-to-one.

When the liquid crystal composition forming the light absorption anisotropic film contains an ionic compound, the content is usually preferably 0.01 to 5 mass %, more preferably 0.05 to 4 mass %, and even more preferably 0.1 to 3 mass %, relative to the solid content of the liquid crystal composition. When the content of the ionic compound is within the above range, the vertical alignment of the liquid crystal compound can be effectively promoted while maintaining good coatability of the liquid crystal composition.

When the liquid crystal composition that forms the optically absorptive anisotropic film contains a nonionic silane compound, the nonionic silane compound reduces the surface tension of the liquid crystal composition, and in a dried coating film formed on a substrate from the composition for forming an optically absorptive anisotropic film, the nonionic silane compound is present on the surface of the dried coating film opposite the substrate, increasing the vertical alignment control force for the liquid crystal compound, and the liquid crystal compound tends to be aligned vertically to the substrate surface in the dried coating film. This allows the liquid crystal compound to maintain a vertical alignment state and form a liquid crystal cured film.

A nonionic silane compound is a nonionic compound that contains the element Si. Examples of nonionic silane compounds include silicon polymers such as polysilanes, silicone resins such as silicone oils and silicone resins, silicone oligomers, organic and inorganic silane compounds such as silsesquioxanes and alkoxysilanes (more specifically, silane coupling agents, etc.), and silane-containing compounds described in the leveling agent section.

When the liquid crystal composition forming the light absorption anisotropic film contains a nonionic silane compound, the content is usually preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 4% by mass, and even more preferably 0.1% by mass to 3% by mass, based on the solid content of the liquid crystal composition. When the content of the nonionic silane compound is within the above range, the vertical alignment of the liquid crystal compound can be effectively promoted while maintaining good coatability of the liquid crystal composition.

When the liquid crystal composition that forms the optically absorptive anisotropic film contains both an ionic compound and a nonionic silane compound, the vertical alignment of the liquid crystal compound is more easily promoted in the dried coating film formed on the substrate from the optically absorptive anisotropic film-forming composition due to the electrostatic interaction derived from the ionic compound and the surface tension reducing effect derived from the nonionic silane compound. This makes it possible to form a liquid crystal cured film in which the liquid crystal compound maintains a more precisely vertically aligned state.

<Horizontal Alignment Retardation Film>
In the present invention, the horizontally aligned retardation film may be, for example, a stretched film, a cured product of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound, and the cured product is obtained by curing the polymerizable liquid crystal compound in a state where the polymerizable liquid crystal compound is aligned in the horizontal direction relative to the plane of the retardation film (hereinafter, also referred to as a "horizontally aligned liquid crystal cured film").

<Horizontal Alignment Retardation Film i>
The horizontally aligned retardation film i in the present invention (hereinafter, may be simply referred to as “film i”) has the following formula (4):
70nm≦Re _i (550)≦170nm (4)
[In formula (4), Re _i (λ) represents an in-plane retardation value of the horizontally aligned retardation film i at a wavelength of λ nm]
Meet the following.

The laminate of the present invention, since the in-plane retardation Re _i (550) of the horizontally aligned retardation film i is within the range of formula (4), when applied to an organic EL display device, has excellent transmittance in the front direction, reduces the directional anisotropy of the light absorption characteristics in oblique directions, has an excellent effect of preventing peeping from oblique directions, and has excellent visibility in the front direction when the organic EL display device is viewed through polarized sunglasses.
The in-plane retardation Re _i (550) is more preferably in the range of 80 nm≦Re _i (550)≦160 nm, and even more preferably in the range of 90 nm≦Re _i (550)≦150 nm, and may be, for example, 90 nm≦Rei (550)≦130 nm. The in-plane retardation Re _i (550) of the film i can be adjusted within the above range, for example, by appropriately adjusting the thickness (film thickness) of the film i; the type and/or blending amount of the additive contained in the film i; the manufacturing conditions of the film i, etc. The in-plane retardation Re _i (550) of the film i can be measured using a retardation measuring device, and can be measured, for example, by the method described in the examples below.

Furthermore, in the laminate of the present invention, the in-plane retardation Rei(λ) of the horizontally aligned retardation film i at the same wavelength as the maximum absorption wavelength λ _MAX of the optically absorptive anisotropic film is in the range of 0.6 to 2.0 as expressed by the following relational expression (A), and therefore when applied to an organic EL display device, the directional anisotropy of the optical absorption characteristics in oblique directions can be particularly reduced. This range is preferably 0.7 to 1.8, and more preferably 0.8 to 1.5.
(λMAX/4)/(Rei(λ)) (A)
The maximum absorption wavelength λ _MAX of the optically absorptive anisotropic film can be measured, for example, by a spectrophotometer.

The horizontally aligned retardation film i has the following formula (8):
Re _i (450)/Re _i (550)≧1.00 (8)
[In formula (8), Re _i (λ) has the same meaning as in formula (4) above]
It is preferable that the range of the angle θ _i between the slow axis of the horizontally aligned retardation film i and the absorption axis of the polarizer satisfies the following formula (9):
15°≦｜ _θi ｜≦75° (9)
It is preferable that:

When the film i satisfies the above formula (8), the film i exhibits so-called positive wavelength dispersion, in which the in-plane retardation value at a short wavelength is larger than the in-plane retardation value at a long wavelength. When the film i satisfies the above formula (8), the laminate of the present invention, when applied to an organic EL display device, is excellent in transmittance in the front direction, and reduces the directional anisotropy of the light absorption characteristics in the oblique direction, and is easy to improve the effect of preventing peeping from an oblique direction. In addition, the visibility when viewed from the front through polarized sunglasses is also excellent. Re _i (450)/Re _i (550) of the film i is more preferably 1.01 or more, and even more preferably 1.03 or more. The upper limit value of Re _i (450)/Re _i (550) of the film i is not particularly limited, and is, for example, 5.0 or less, preferably 2.0 or less, and more preferably 1.3 or less. Note that Re _i (450) can be adjusted in the same manner as the above-mentioned Re _i (550), and can be measured in the same manner.

When the film i satisfies the above formula (9), it can be a so-called quarter-wave plate (λ/4 plate) that can convert linearly polarized light into circularly polarized light. When the film i satisfies the above formula (9), the laminate of the present invention has excellent transmittance in the front direction, and reduces the directional anisotropy of the light absorption characteristics in the oblique direction, and is more likely to have an effect of preventing peeping from the oblique direction. |θ _i | is more preferably in the range of 25°≦|θ _i |≦65°, and even more preferably in the range of 35°≦|θ _i |≦55°. The angle θ _i between the slow axis of the film i and the absorption axis of the polarizer can be adjusted within the above range, for example, by adjusting the lamination angle, manufacturing the film i so that the slow axis or the absorption axis of the polarizer is adjusted to a predetermined angle in advance, and laminating them by roll to roll.

In the present invention, the horizontally aligned retardation film i may be a stretched film or a film formed from a composition containing a liquid crystal compound, but is preferably a film stretched in at least one direction. When the film i is a film stretched in at least one direction, the laminate of the present invention, when applied to an organic EL display device, has excellent transparency in the front direction and reduces the directional anisotropy of the light absorption characteristics in oblique directions, making it easier to prevent peeking from oblique directions. In addition, the thermal stability, dimensional stability, and mechanical strength of the laminate of the present invention tend to be improved.

The film stretched in at least one direction is not particularly limited, but from the viewpoint of dimensional stability and heat resistance stability, a film having a glass transition temperature (Tg) of 80 to 200° C. is preferable. Examples of the film stretched in at least one direction include films composed of polyolefin resins such as polyethylene, polypropylene, polymethylpentene, etc.; fluorinated polyolefin resins such as polyvinyl fluoride, polyvinylidene fluoride, and polyfluorinated ethylene; polyester resins such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, and polyethylene terephthalate/isophthalate copolymer; polyamides such as nylon 6 and nylon 6,6; vinyl polymers such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, and vinylon; cellulose resins such as triacetyl cellulose, diacetyl cellulose, and cellophane; (meth)acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate; and other films composed of polystyrene, polycarbonate, polyarylate, polyimide, etc. From the viewpoint of dimensional stability, a film containing a vinyl polymer, a (meth)acrylic resin or a polyolefin resin is preferable, and a film containing a cycloolefin resin is more preferable. The glass transition temperature can be measured, for example, by DSC (differential scanning calorimetry).
The film formed from a composition containing a liquid crystal compound can be obtained from the same material as the film ii described below, such as a cured product of a polymerizable liquid crystal composition containing at least one type of polymerizable liquid crystal compound.
In the present invention, the film i may be a single layer or a multilayer. An example of the multilayer film i is a film in which a film formed from a composition containing a liquid crystal compound is laminated on a substrate.

The horizontally aligned retardation film i can be produced by a method including, for example, a step of forming the above-mentioned resin, which optionally contains additives such as an antioxidant and an ultraviolet absorbing agent, into a film, and a step of stretching the film.

Methods for forming resin into a film include known methods such as melt extrusion, heat press molding, injection molding, and solvent casting.

The method for stretching the film includes, for example, uniaxial stretching, biaxial stretching, and the like.
The stretching direction may be the machine direction (MD) of the unstretched film, a direction perpendicular thereto (TD), or a direction oblique to the machine direction (MD). The uniaxial stretching may be uniaxial stretching between rolls with different peripheral speeds, or may be uniaxial stretching using a heated roll. The biaxial stretching may be simultaneous biaxial stretching in which the film is stretched in two stretching directions at the same time, or sequential biaxial stretching in which the film is stretched in a predetermined direction and then stretched in the other direction. The stretching process may be performed, for example, by using two or more pairs of nip rolls with a higher peripheral speed at the outlet side to stretch the film in the longitudinal direction (machine direction: MD), or by gripping both side ends of the unstretched film with chucks to spread it in the direction perpendicular to the machine direction (TD). In addition, as a method of stretching in an oblique direction, for example, a method of preparing a film roll in which a long film is wound in a roll shape, continuously unwinding the film from the film roll, transporting the unwound film, and stretching it in an oblique direction inclined at a desired angle to the long direction of the film while heating it is. The stretching ratio is usually 3 to 8. Note that the stretching ratio in biaxial stretching refers to the stretching ratio in the direction in which the stretching ratio is larger.

The horizontally aligned retardation film i may be subjected to a surface treatment known in the art, such as a plasma treatment, a corona treatment, an ozone treatment, or an ultraviolet irradiation treatment, before or after the stretching treatment.

The thickness of the horizontally aligned retardation film i is usually 200 μm or less, preferably 100 μm or less, and more preferably 50 μm or less, from the viewpoint of making the laminate thinner and improving its flexibility. There is no particular lower limit to the thickness of the horizontally aligned retardation film i, but if it is too thin, the strength may decrease, so it is usually 5 μm or more.

The horizontally oriented retardation film stretched in at least one direction as described above can be commercially available. Examples of commercially available cyclic olefin resins include cyclic olefin resins manufactured by Ticona (Germany) such as "Topas (registered trademark)"; cyclic olefin resins manufactured by JSR Corporation such as "Arton (registered trademark)"; cyclic olefin resins manufactured by Nippon Zeon Corporation such as "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)"; and cyclic olefin resins manufactured by Mitsui Chemicals, Inc. such as "Apel (registered trademark). Commercially available cyclic olefin resin substrates can also be used. Examples of commercially available cyclic olefin resin substrates include cyclic olefin resin substrates manufactured by Sekisui Chemical Co., Ltd. such as "S-Cina (registered trademark)" and "SCA40 (registered trademark)"; cyclic olefin resin substrates manufactured by Optes Co., Ltd. such as "ZEONOR Film (registered trademark)"; and cyclic olefin resin substrates manufactured by JSR Corporation such as "Arton Film (registered trademark)". Examples of commercially available cellulose ester substrates include cellulose ester substrates manufactured by Fuji Photo Film Co., Ltd., such as Fujitac Film; and cellulose ester substrates manufactured by Konica Minolta Opto, Inc., such as "KC8UX2M," "KC8UY," and "KC4UY."

In one embodiment of the present invention, the horizontally aligned retardation film i is preferably adjacent to the above-mentioned light absorbing anisotropic film. The horizontally aligned retardation film i can be laminated, for example, via a pressure-sensitive adhesive layer or an adhesive layer. In addition, the liquid crystal composition for forming the light absorbing anisotropic film may be directly applied onto the horizontally aligned retardation film i via the above-mentioned alignment film.

<Horizontal Alignment Retardation Film ii>
The horizontally aligned retardation film ii in the present invention (hereinafter, sometimes simply referred to as “film ii”) has the following formula (5):
120nm≦Re _ii (550)≦160nm (5)
[In formula (5), Re _ii (λ) represents an in-plane retardation value of the horizontally aligned retardation film ii at a wavelength of λ nm]
Meet the following.

When the laminate of the present invention is applied to an organic EL display device, if the in-plane retardation Re _ii (550) of the horizontally aligned retardation film ii is within the range of formula (5), reflection from the front direction during black display and coloring during reflection tend to be reduced, transparency in the front direction is excellent, and the directional anisotropy of the light absorption characteristics in the oblique direction is reduced, and the effect of preventing peeping from the oblique direction tends to be excellent. The in-plane retardation Re _ii (550) is more preferably in the range of 130 nm ≦ Re _i (550) ≦ 150 nm, and even more preferably 135 nm ≦ Re _i (550) ≦ 145 nm. The adjustment method and measurement method of the in-plane retardation Re _ii (550) of the film ii are the same as those described for the in-plane retardation of the film i.

The horizontally aligned retardation film ii has the following formula (6):
Re _ii (450)/Re _ii (550)<1.00 (6)
[In formula (6), Re _ii (λ) has the same meaning as in formula (5) above]
It is preferable that the angle θ _ii between the slow axis of the horizontally aligned retardation film ii and the absorption axis of the polarizer satisfies the following formula (7):
15°≦｜θ _ii |≦75° (7)
It is preferable that:

When the film ii satisfies the above formula (6), the film ii exhibits so-called reverse wavelength dispersion, in which the in-plane retardation value at a short wavelength is smaller than the in-plane retardation value at a long wavelength. When the laminate of the present invention including the film ii is applied to an organic EL display device, it is excellent in transparency in the front direction, and reduces the directional anisotropy of the light absorption characteristics in the oblique direction, and is easy to improve the effect of preventing peeping from the oblique direction. In addition, when incorporated into an organic EL display device, reflection from the front during black display and coloring during reflection tend to be reduced. Re _ii (450)/Re _ii (550) of the film ii is more preferably 0.90 or less, and even more preferably 0.85 or less. The lower limit of Re _ii (450)/Re _ii (550) of the film ii is not particularly limited, and is, for example, 0.1 or more. Incidentally, Re _ii (450) and Re _ii (550) of film ii can be adjusted in the same manner as Re _i (450) and Re _i (550) of film i, and can be measured in the same manner.

When the film ii satisfies the above formula (7), it can be a so-called quarter-wave plate (λ/4 plate) that can convert linearly polarized light into circularly polarized light. When the film ii satisfies the above formula (7), when a laminate including the film ii is applied to an organic EL display device, reflection from the front direction and coloring during reflection tend to be reduced, the transparency in the front direction is excellent, and the directional anisotropy of the light absorption characteristics in the oblique direction is reduced, and the effect of preventing peeping from the oblique direction is more likely to be enhanced. |θ _ii | is more preferably in the range of 25°≦|θ _ii |≦65°, and more preferably 35°≦|θ _ii |≦55°. The angle θ _ii between the slow axis of the film ii and the absorption axis of the polarizer can be adjusted in the same manner as the angle θ _i between the slow axis of the film i and the absorption axis of the polarizer, and can be measured in the same manner.

The horizontally aligned retardation film ii may be a stretched film or a film formed from a composition containing a liquid crystal compound, but is preferably made of a cured product of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound. When the film ii of the laminate of the present invention is a film made of a cured product of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound, reflection from the front direction and coloring during reflection tend to be reduced when applied to an organic EL display device, the transparency in the front direction is excellent, and the directional anisotropy of the light absorption characteristics in the oblique direction is reduced, making it easier to prevent peeping from the oblique direction. In addition, the front reflection hue of the laminate including the film ii tends to be improved.
In the present invention, it is preferable that the horizontally aligned retardation film i is a film stretched in at least one direction, and the horizontally aligned retardation film ii is made of a cured product of a polymerizable liquid crystal composition containing at least one kind of polymerizable liquid crystal compound. However, for example, the films i and ii may both be films stretched in at least one direction, or the films i and ii may both be made of a cured product of a polymerizable liquid crystal composition.
In the present invention, the film ii may be a single layer or a multilayer. An example of the multilayer film ii is a film in which a film formed from a composition containing a liquid crystal compound is laminated on a substrate.

As the polymerizable liquid crystal compound, a compound similar to the polymerizable liquid crystal compound that can be contained in the light absorption anisotropic film can be used, and among them, a compound that exhibits reverse wavelength dispersion is preferable, for example, a compound represented by the above formula (X).

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition used to form the horizontal alignment retardation film ii is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and even more preferably 90 to 95 parts by mass, relative to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. If the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the alignment of the obtained liquid crystal cured film.

The polymerizable liquid crystal composition used to form the horizontally aligned retardation film ii may further contain additives such as a solvent, a photopolymerization initiator, a leveling agent, an antioxidant, a photosensitizer, etc., in addition to the polymerizable liquid crystal compound. Examples of these components include the same ones as those exemplified above as components that can be contained in the light absorption anisotropic film, and each of them may be used alone or in combination of two or more.
When the horizontally aligned retardation film ii is a stretched film, it can be prepared in the same manner as the above-mentioned film i.

The horizontally aligned retardation film ii is, for example,
A step of obtaining a polymerizable liquid crystal composition by stirring a polymerizable liquid crystal compound and, if necessary, an additive such as a solvent at a predetermined temperature;
A step of applying the polymerizable liquid crystal composition onto a substrate or an alignment film to obtain a coating film;
drying the coating to form a dry coating; and
The film can be produced by a method including a step of irradiating a dried coating film with active energy rays to form a horizontally aligned liquid crystal cured film.

The formation of a coating film of the polymerizable liquid crystal composition can be carried out, for example, by applying the polymerizable liquid crystal composition onto a substrate or an alignment film. Substrates that can be used here include those similar to those exemplified above as substrates that can be used in the manufacture of light-absorption anisotropic films.

The alignment film can be appropriately selected from materials having a horizontal alignment regulating force that aligns the polymerizable liquid crystal compound in a horizontal direction relative to the coating film plane. The alignment regulating force can be adjusted arbitrarily depending on the type of alignment layer, the surface state, the rubbing conditions, etc., and when it is formed from a photo-alignable polymer, it can be adjusted arbitrarily depending on the polarized light irradiation conditions, etc. Examples of such materials include the alignment polymers mentioned above as alignment films that can be used in the manufacture of optically absorptive anisotropic films. The horizontal alignment film can be obtained by applying a composition containing such a material and a solvent, for example, the solvent exemplified in the optically absorptive anisotropic film, to a substrate, removing the solvent, and then heating the applied film. It is preferable to use a photo-alignment film as the horizontal alignment film from the viewpoint of quality.

Then, the solvent is removed by drying or the like to form a dry coating film. Examples of drying methods include natural drying, ventilation drying, heat drying, and reduced pressure drying. Heat drying is preferred from the viewpoint of productivity, and the heating temperature in this case is preferably high enough to remove the solvent and is equal to or higher than the phase transition temperature of the polymerizable liquid crystal compound. The procedures and conditions in this process may be similar to those that can be adopted in the manufacturing method of the light absorption anisotropic film.

The resulting dried coating film is irradiated with active energy rays (more specifically, ultraviolet rays, etc.) to polymerize the polymerizable liquid crystal compound while maintaining the state in which the polymerizable liquid crystal compound is aligned horizontally relative to the coating film plane, thereby forming a horizontally aligned liquid crystal cured film. Polymerization methods include the same methods that can be used in the manufacturing method of light absorption anisotropic films.

The thickness of the horizontally aligned retardation film ii is preferably 0.1 to 3 μm, more preferably 0.2 to 2 μm. When the thickness of the film ii is within the above range, the film has excellent transmittance in the front direction and excellent anti-reflection performance. In addition, the laminate can be made thinner.

The surface of the horizontally aligned retardation film ii may be subjected to a surface treatment known in the art, such as plasma treatment, corona treatment, ozone treatment, and ultraviolet irradiation treatment.

In one embodiment of the present invention, the horizontally aligned retardation film ii is adjacent to the polarizer on the side opposite to the horizontally aligned retardation film i described later. The horizontally aligned retardation film ii can be laminated, for example, by directly applying a polymerizable liquid crystal composition to the polarizer on the side opposite to the horizontally aligned retardation film i. Alternatively, the film may be laminated via a pressure-sensitive adhesive layer or an adhesive layer. Alternatively, the substrate and/or the alignment film may be peeled off after lamination, and only the horizontally aligned retardation film i may be laminated.
In another embodiment of the present invention, the horizontally aligned retardation film ii may be adjacent to a vertically aligned retardation film iii, which may be further included in the laminate, as described below. In this case, the horizontally aligned retardation film ii may be laminated, for example, by directly applying a polymerizable liquid crystal composition to the vertically aligned retardation film iii. Alternatively, the horizontally aligned retardation film ii may be laminated via a pressure-sensitive adhesive layer or an adhesive layer.

<Polarizer>
Examples of the polarizer include a stretched film having a dye having absorption anisotropy adsorbed thereon, a film including a film coated with a dye having absorption anisotropy, etc. Examples of the dye having absorption anisotropy include a dichroic dye.

A stretched film with an absorbent anisotropic dye adsorbed thereon is usually produced by sandwiching a transparent protective film, via an adhesive, on at least one side of a polarizer produced through the steps of uniaxially stretching a polyvinyl alcohol resin film, dyeing the polyvinyl alcohol resin film with a dichroic dye to adsorb the dichroic dye, treating the polyvinyl alcohol resin film with the adsorbed dichroic dye with an aqueous boric acid solution, and washing with water after the treatment with the aqueous boric acid solution.

Polyvinyl alcohol resins are obtained by saponifying polyvinyl acetate resins. Polyvinyl acetate resins include polyvinyl acetate, which is a homopolymer of vinyl acetate, as well as copolymers of vinyl acetate and other monomers that can be copolymerized with it. Examples of other monomers that can be copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides with ammonium groups.

The degree of saponification of polyvinyl alcohol resins is usually about 85 to 100 mol%, and preferably 98 mol% or more. Polyvinyl alcohol resins may be modified; for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used. The degree of polymerization of polyvinyl alcohol resins is usually about 1,000 to 10,000, and preferably in the range of 1,500 to 5,000.

A film made from such polyvinyl alcohol-based resin is used as the base film for a polarizer (polarizing film). The method for making a film from polyvinyl alcohol-based resin is not particularly limited, and a film can be made by a known method. The thickness of the polyvinyl alcohol-based base film can be, for example, about 10 to 150 μm.

The uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before, simultaneously with, or after dyeing with a dichroic dye. When the uniaxial stretching is performed after dyeing, it may be performed before or during the boric acid treatment. It is also possible to perform the uniaxial stretching at these multiple stages. The uniaxial stretching may be performed uniaxially between rolls with different peripheral speeds, or may be performed uniaxially using a heated roll. The uniaxial stretching may be dry stretching in which the stretching is performed in the atmosphere, or wet stretching in which the polyvinyl alcohol-based resin film is stretched in a swollen state using a solvent. The stretching ratio is usually about 3 to 8 times.

Dyeing of a polyvinyl alcohol-based resin film with a dichroic dye is carried out, for example, by immersing the polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye.

Specific examples of the dichroic pigment include iodine and dichroic organic dyes. Examples of the dichroic organic dye include dichroic direct dyes made of disazo compounds such as C.I. DIRECT RED 39, and dichroic direct dyes made of compounds such as trisazo and tetrakisazo. It is preferable to immerse the polyvinyl alcohol resin film in water before the dyeing process.

When iodine is used as the dichroic dye, a method is usually employed in which a polyvinyl alcohol resin film is immersed in an aqueous solution containing iodine and potassium iodide to dye it.
The content of iodine in this aqueous solution is usually about 0.01 to 1 part by mass per 100 parts by mass of water. The content of potassium iodide is usually about 0.5 to 20 parts by mass per 100 parts by mass of water. The temperature of the aqueous solution used for dyeing is usually about 20 to 40° C. The immersion time in this aqueous solution (dyeing time) is usually about 20 to 1,800 seconds.

On the other hand, when a dichroic organic dye is used as the dichroic coloring matter, a method of dyeing a polyvinyl alcohol resin film by immersing it in an aqueous solution containing a water-soluble dichroic dye is usually employed.
The content of the dichroic organic dye in this aqueous solution is usually about 1×10 ^{-4 to 10 parts by mass, preferably 1×10 -3 to} 1 part by mass, and more preferably 1×10 ^-3 to 1×10 ^-2 parts by mass, per 100 parts by mass of water. This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing assistant. The temperature of the aqueous dichroic dye solution used for dyeing is usually about 20 to 80° C. The immersion time in this aqueous solution (dyeing time) is usually about 10 to 1,800 seconds.

The boric acid treatment after dyeing with a dichroic dye can usually be carried out by immersing the dyed polyvinyl alcohol resin film in an aqueous boric acid solution. The content of boric acid in this aqueous boric acid solution is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water. When iodine is used as the dichroic dye, this aqueous boric acid solution preferably contains potassium iodide, and in this case the content of potassium iodide is usually about 0.1 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water. The immersion time in the aqueous boric acid solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature for the boric acid treatment is usually 50°C or higher, preferably 50 to 85°C, and more preferably 60 to 80°C.

The polyvinyl alcohol-based resin film after the boric acid treatment is usually washed with water. The washing can be performed, for example, by immersing the polyvinyl alcohol-based resin film treated with boric acid in water. The temperature of the water used in the washing is usually about 5 to 40°C.
The immersion time is usually about 1 to 120 seconds.

After washing with water, a drying process is performed to obtain a polarizer. The drying process can be performed using, for example, a hot air dryer or a far-infrared heater. The temperature of the drying process is usually about 30 to 100°C, and preferably 50 to 80°C. The time of the drying process is usually about 60 to 600 seconds, and preferably 120 to 600 seconds. The moisture content of the polarizer is reduced to a practical level by the drying process. The moisture content is usually about 5 to 20% by weight, and preferably 8 to 15% by weight. If the moisture content is within the above range, a polarizer having appropriate flexibility and excellent thermal stability can be obtained.

The thickness of the polarizer obtained by the above method is preferably 5 to 40 μm. It is usually 20 μm or less, preferably 5 μm or less, and more preferably 0.5 to 3 μm.

Examples of films coated with a dye having absorption anisotropy include films obtained by coating a composition containing a dichroic dye having liquid crystal properties, or a composition containing a dichroic dye and a polymerizable liquid crystal.

The film coated with the dye having absorption anisotropy is preferably thin, but if it is too thin, the strength decreases and the processability tends to be poor. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, and more preferably 0.5 to 3 μm.

Specific examples of films coated with a dye having the above-mentioned absorption anisotropy include the films described in JP 2012-33249 A and the like.

In the laminate of the present invention, the polarizer and the horizontally aligned retardation film i are preferably laminated via a pressure-sensitive adhesive or adhesive (hereinafter, pressure-sensitive adhesive and adhesive may be collectively referred to as "adhesive").

Examples of adhesives include pressure-sensitive adhesives, dry-hardening adhesives, and chemically reactive adhesives. Examples of chemically reactive adhesives include active energy ray-curing adhesives.

Pressure-sensitive adhesives usually contain a polymer and may contain a solvent. Examples of polymers include acrylic polymers, silicone polymers, polyesters, polyurethanes, and polyethers. Among them, acrylic adhesives containing acrylic polymers are preferred because they have excellent optical transparency, moderate wettability and cohesive strength, excellent adhesion, and high weather resistance and heat resistance, and are less likely to lift or peel under conditions of heating or humidity.

As the acrylic polymer, a copolymer of a (meth)acrylate in which the alkyl group in the ester portion is an alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, or a butyl group, and a (meth)acrylic monomer having a functional group, such as (meth)acrylic acid or hydroxyethyl (meth)acrylate, is preferred.

Pressure-sensitive adhesives containing such copolymers are preferred because they have excellent adhesive properties and can be removed relatively easily after application to a substrate without leaving any adhesive residue on the substrate. The glass transition temperature of the acrylic polymer is preferably 25°C or lower, more preferably 0°C or lower. The mass average molecular weight of such an acrylic polymer is preferably 100,000 or higher.

As the solvent, the solvents described above in the section on <Light-absorption anisotropic film> can be used in the same manner. The pressure-sensitive adhesive may contain a light diffusing agent. The light diffusing agent is an additive that imparts light diffusibility to the adhesive, and may be fine particles having a refractive index different from that of the polymer contained in the adhesive. Examples of light diffusing agents include fine particles made of inorganic compounds and fine particles made of organic compounds (polymers). Many of the polymers contained as active ingredients in adhesives, including acrylic polymers, have a refractive index of about 1.4 to 1.6, so it is preferable to appropriately select a light diffusing agent from those having a refractive index of 1.2 to 1.8. The difference in refractive index between the polymer contained as an active ingredient in the adhesive and the light diffusing agent is usually 0.01 or more, and from the viewpoint of the brightness and displayability of the display device, it is preferable that it is 0.01 to 0.2. The fine particles used as the light diffusing agent are preferably spherical fine particles, and more preferably fine particles close to monodispersion, and more preferably fine particles with an average particle size of 2 to 6 μm. The refractive index is measured by a general minimum deviation method or an Abbe refractometer.

Examples of inorganic compound particles include aluminum oxide (refractive index 1.76) and silicon oxide (refractive index 1.45). Examples of organic compound (polymer) particles include melamine beads (refractive index 1.57), polymethyl methacrylate beads (refractive index 1.49), methyl methacrylate/styrene copolymer resin beads (refractive index 1.50-1.59), polycarbonate beads (refractive index 1.55), polyethylene beads (refractive index 1.53), polystyrene beads (refractive index 1.6), polyvinyl chloride beads (refractive index 1.46), and silicone resin beads (refractive index 1.46). The content of the light diffusing agent is usually 3-30 parts by mass per 100 parts by mass of polymer.

The thickness of the pressure-sensitive adhesive is not particularly limited as it is determined according to its adhesion, but is usually 1 μm to 40 μm. From the standpoint of processability, durability, etc., the thickness is preferably 3 μm to 25 μm, and more preferably 5 μm to 20 μm. By making the thickness of the adhesive layer formed from the adhesive 5 μm to 20 μm, it is possible to maintain the brightness when the display device is viewed from the front, and to prevent bleeding or blurring of the displayed image.

The dry-setting adhesive may contain a solvent. Examples of the dry-setting adhesive include a polymer of a monomer having a protonic functional group such as a hydroxyl group, a carboxyl group, or an amino group and an ethylenically unsaturated group, or a composition containing a urethane resin as the main component and further containing a crosslinking agent or a curing compound such as a polyaldehyde, an epoxy compound, an epoxy resin, a melamine compound, a zirconia compound, or a zinc compound. Examples of the polymer of a monomer having a protonic functional group such as a hydroxyl group, a carboxyl group, or an amino group and an ethylenically unsaturated group include an ethylene-maleic acid copolymer, an itaconic acid copolymer, an acrylic acid copolymer, an acrylamide copolymer, a saponified product of polyvinyl acetate, and a polyvinyl alcohol resin.

Examples of polyvinyl alcohol resins include polyvinyl alcohol, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, methylol group-modified polyvinyl alcohol, and amino group-modified polyvinyl alcohol. The content of polyvinyl alcohol resin in the water-based pressure-sensitive adhesive is usually 1 to 10 parts by mass, and preferably 1 to 5 parts by mass, per 100 parts by mass of water.

The urethane resin may be a polyester ionomer type urethane resin.
The polyester ionomer urethane resin referred to here is a urethane resin having a polyester skeleton, into which a small amount of ionic component (hydrophilic component) is introduced. The ionomer urethane resin can be emulsified in water without using an emulsifier to form an emulsion, and can be used as a water-based adhesive. When using a polyester ionomer urethane resin, it is effective to add a water-soluble epoxy compound as a crosslinking agent.

Epoxy resins include polyamide epoxy resins obtained by reacting epichlorohydrin with polyamide polyamines obtained by reacting polyalkylene polyamines such as diethylenetriamine or triethylenetetramine with dicarboxylic acids such as adipic acid. Commercially available products of such polyamide epoxy resins include "Sumirez Resin (registered trademark) 650" and "Sumirez Resin 675" (both manufactured by Sumika Chemtex Corporation) and "WS-525" (manufactured by Nippon PMC Corporation). When epoxy resins are blended, the amount added is usually 1 to 100 parts by mass, and preferably 1 to 50 parts by mass, per 100 parts by mass of polyvinyl alcohol resin.

The thickness of the adhesive layer formed from the dry-solidifying adhesive is usually 0.001 to 5 μm, preferably 0.01 to 2 μm, and more preferably 0.01 to 0.5 μm. If the adhesive layer formed from the dry-solidifying adhesive is too thick, it is likely to result in poor appearance.

The active energy ray curable adhesive may contain a solvent. An active energy ray curable adhesive is an adhesive that cures when irradiated with active energy rays. Examples of active energy ray curable adhesives include cationic polymerizable adhesives that contain an epoxy compound and a cationic polymerization initiator, radical polymerizable adhesives that contain an acrylic curing component and a radical polymerization initiator, adhesives that contain both a cationic polymerizable curing component such as an epoxy compound and a radical polymerizable curing component such as an acrylic compound, and further contain a cationic polymerization initiator and a radical polymerization initiator, and adhesives that do not contain these polymerization initiators and are cured by irradiation with an electron beam.

Among them, a radically polymerizable active energy ray curable adhesive containing an acrylic curing component and a photoradical polymerization initiator, and a cationic polymerizable active energy ray curable adhesive containing an epoxy compound and a photocationic polymerization initiator are preferred. Examples of the acrylic curing component include (meth)acrylates such as methyl (meth)acrylate and hydroxyethyl (meth)acrylate, and (meth)acrylic acid. An active energy ray curable adhesive containing an epoxy compound may further contain a compound other than the epoxy compound. Examples of the compound other than the epoxy compound include an oxetane compound and an acrylic compound.

The photoradical polymerization initiator and photocationic polymerization initiator include the above-mentioned photoradical polymerization initiator and photocationic polymerization initiator. The content of the radical polymerization initiator and the cationic polymerization initiator is usually 0.5 to 20 parts by mass, and preferably 1 to 15 parts by mass, per 100 parts by mass of the active energy ray-curable adhesive.

The active energy ray curable adhesive may further contain an ion trapping agent, an antioxidant, a chain transfer agent, a tackifier, a thermoplastic resin, a filler, a flow control agent, a plasticizer, and an antifoaming agent.

In this specification, active energy rays are defined as energy rays that can decompose a compound that generates active species to generate active species. Examples of such active energy rays include visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, γ-rays, and electron beams, with ultraviolet light and electron beams being preferred. The preferred ultraviolet light irradiation conditions are the same as those for the polymerization of the polymerizable liquid crystal compound described above.

The laminate of the present invention preferably further comprises a transparent protective film on the surface of the optically absorptive anisotropic film opposite the horizontally aligned retardation film i. By further comprising a transparent protective film in the laminate of the present invention, dimensional changes, breakage, cracks, etc. caused by heat and/or humidity in the optically absorptive anisotropic film or other layers can be prevented. In addition, deterioration when exposed to ultraviolet rays, etc. can be prevented, and scratches and deterioration of the surface of the optically absorptive anisotropic film during storage and transportation can be prevented.

The transparent protective film is preferably a transparent film that has transparency that allows light, particularly visible light, to pass through, and preferably has a transmittance of 80% or more for light rays with wavelengths of 380 to 780 nm. As the transparent protective film, for example, the same materials as those exemplified above as resin substrates that can be used in the manufacture of light-absorption anisotropic films can be preferably used.

The thickness of the transparent protective film is preferably 3 to 20 μm, and more preferably 5 to 15 μm. If the thickness of the transparent protective film is within the above range, the surface of the light absorbing anisotropic film can be adequately protected. In addition, it may be possible to make the laminate thinner.

The transparent protective film may be laminated to the light absorbing anisotropic film via an adhesive. The adhesives that can be used include the adhesives exemplified above.

<Vertical Alignment Retardation Film iii>
The laminate of the present invention preferably further includes a vertically aligned retardation film iii (hereinafter, sometimes simply referred to as "film iii").

In the present invention, a vertically aligned retardation film means a retardation film oriented in a direction perpendicular to the film plane. The vertically aligned retardation film may be, for example, a stretched film, a cured product of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound, and the polymerizable liquid crystal compound is cured in a state where it is oriented in a direction perpendicular to the retardation film plane (hereinafter, also referred to as a "vertically aligned liquid crystal cured film").

The vertically aligned retardation film iii has the following formula (10):
-100nm≦Rth _iii (550)≦-20nm (10)
and further satisfying formula (11):
Rth _iii (450)/Rth _iii (550)>1.00 (11)
[In the formulas (10) and (11), Rth _iii (λ) represents a thickness retardation value of the vertically aligned retardation film iii at a wavelength of λ nm]
It is preferable to satisfy the following. Here, the thickness retardation Rth _iii (lambda) is Rth _iii (lambda) = ((nx _iii (lambda) + ny _iii (lambda)) / 2 - nz _iii (lambda)) × d _iii (wherein nx _iii (lambda) is the in-plane principal refractive index of the vertically aligned retardation film iii at a wavelength of λ nm, ny _iii (lambda) is the refractive index in the direction perpendicular to nx _iii (lambda) at a wavelength of λ nm, nz _iii (lambda) is the refractive index in the thickness direction of the vertically aligned retardation film iii at a wavelength of λ nm, and when nx _iii (lambda) = ny _iii (lambda), nx _iii (lambda) can be the refractive index in any direction in the film plane, and d _iii is the film thickness of the vertically aligned retardation film iii).

When the laminate of the present invention includes the above-mentioned film iii, the transparency in the front direction is excellent, and the directional anisotropy of the light absorption characteristics in the oblique direction is reduced, and in addition to being excellent in the effect of preventing peeping from an oblique direction, when the laminate including the film iii is incorporated into an organic EL display device, the oblique reflection hue during black display is also easily improved. As a result, when the laminate of the present invention is applied to an organic EL display device, the anti-reflection effect is also excellent. The thickness retardation Rth _iii (550) is more preferably in the range of -90 nm ≦ Rth _iii (550) ≦ -30 nm, and even more preferably -80 nm ≦ Rth _iii (550) ≦ -40 nm. The thickness retardation Rth _iii (550) of the film iii can be adjusted within the above range, for example, by appropriately adjusting the type and/or composition ratio of the polymerizable liquid crystal compound contained in the film iii; the thickness of the film iii; the type and/or blending amount of the additive contained in the film iii; the manufacturing conditions of the film iii, and the like. The thickness retardation Rth _iii (550) of the film iii can be measured using a retardation measuring device, for example, by the method described in the examples below.

The vertically aligned retardation film iii preferably contains a cured product of a polymerizable liquid crystal composition containing at least one type of polymerizable liquid crystal compound. When the film iii is a film made of a cured product of a polymerizable liquid crystal composition containing at least one type of polymerizable liquid crystal compound, it has an excellent effect of improving the oblique reflection hue, and also has an excellent anti-reflection effect when a laminate containing the film iii is applied to an organic EL display device.

As the polymerizable liquid crystal compound, a compound similar to the polymerizable liquid crystal compound that can be contained in the light absorption anisotropic film can be used.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition used to form the vertically aligned retardation film iii is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and even more preferably 90 to 95 parts by mass, relative to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. If the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the alignment of the obtained liquid crystal cured film.

The polymerizable liquid crystal composition used to form the vertically aligned retardation film iii may further contain additives such as a solvent, a photopolymerization initiator, a leveling agent, an antioxidant, and a photosensitizer in addition to the polymerizable liquid crystal compound. These components include the same ones as those exemplified above as components that can be contained in the light absorption anisotropic film, and each of them may be used alone or in combination of two or more.

The vertically aligned retardation film iii can be produced, for example, by a process of obtaining a polymerizable liquid crystal composition to be used for forming the vertically aligned retardation film iii by stirring a polymerizable liquid crystal compound and, if necessary, an additive such as a solvent at a predetermined temperature;
A step of applying the polymerizable liquid crystal composition onto a substrate or an alignment film to obtain a coating film;
drying the coating to form a dry coating; and
The film can be produced by a method including a step of irradiating a dried coating film with active energy rays to form a vertically aligned liquid crystal cured film.

The coating film of the polymerizable liquid crystal composition used to form the vertically aligned retardation film iii can be formed, for example, by applying the polymerizable liquid crystal composition onto a substrate or an alignment film. The substrate that can be used here can be the same as those exemplified above as substrates that can be used to manufacture the light absorbing anisotropic film.

The alignment film can be appropriately selected from materials having a vertical alignment regulating force that aligns the polymerizable liquid crystal compound in a direction perpendicular to the coating film plane. The alignment regulating force can be adjusted as desired by the type of alignment layer, surface state, rubbing conditions, etc., and when it is formed from a photoalignment polymer, it can be adjusted as desired by the polarized light irradiation conditions, etc. Examples of such materials include the alignment polymers mentioned above as alignment films that can be used in the manufacture of optically absorptive anisotropic films. The vertical alignment film can be obtained by applying a composition containing such a material and a solvent, for example, the solvent exemplified in the optically absorptive anisotropic film, to a substrate, removing the solvent, and then heating the applied film. It is preferable to use a photoalignment film as the vertical alignment film from the viewpoint of quality.

Then, the solvent is removed by drying or the like to form a dry coating film. The drying method and conditions can be the same as those that can be used in the manufacturing method of the optically absorptive anisotropic film.

The obtained dried coating film is irradiated with active energy rays (more specifically, ultraviolet rays, etc.) to polymerize the polymerizable liquid crystal compound while maintaining the state in which the polymerizable liquid crystal compound is oriented in the direction perpendicular to the coating film plane, thereby forming a vertically aligned liquid crystal cured film. Polymerization methods include the same methods that can be used in the manufacturing method of light absorption anisotropic films.

The thickness of the vertically aligned retardation film iii is preferably 0.2 to 3 μm, more preferably 0.2 to 2 μm. When the thickness of the film iii is within the above range, the laminate of the present invention is excellent in improving the oblique reflection hue, and also has excellent anti-reflection effect when applied to an organic EL display device. In addition, the laminate can be made thinner.

The surface of the vertically aligned retardation film iii may be subjected to a surface treatment known in the art, such as a plasma treatment, a corona treatment, an ozone treatment, or an ultraviolet irradiation treatment.

The vertically aligned retardation film iii is preferably laminated between the polarizer and the horizontally aligned retardation film ii, or on the side of the horizontally aligned retardation film ii opposite the polarizer. When the film iii is laminated on the side of the horizontally aligned retardation film ii opposite the polarizer, the anti-reflection effect tends to be more excellent. In one aspect of the present invention, the film iii is preferably laminated on the side of the horizontally aligned retardation film ii opposite the polarizer.

<Organic EL display device>
The laminate of the present invention can be used in various display devices.
A display device is a device having a display element, and includes a light-emitting element or a light-emitting device as a light source. Examples of the display device include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (e.g., a field emission display device (FED) and a surface field emission display device (SED)), electronic paper (electronic ink, a display device using an electrophoretic element, a plasma display device, a projection type display device (e.g., a display device having a grating light valve (GLV) display device and a digital micromirror device (DMD)), and a piezoelectric ceramic display. The liquid crystal display device includes any of a transmissive liquid crystal display device, a semi-transmissive liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, and a projection type liquid crystal display device. These display devices may be display devices that display two-dimensional images, or stereoscopic display devices that display three-dimensional images. In particular, the laminate of the present invention can be suitably used for an organic electroluminescence (EL) display device because its effect is easily exhibited remarkably, and the laminate of the present invention can be suitably used for a liquid crystal display device and a touch panel display device. These display devices have excellent transparency in the front direction and reduced directional anisotropy of the light absorption characteristics in the oblique direction, so that they can be excellent in preventing peeping from oblique directions.

The present invention will be explained in more detail below with reference to the following examples. In the examples, "%" and "parts" refer to mass % and mass parts, respectively, unless otherwise specified.

Example 1
1. Preparation of Optically Absorbent Anisotropic Film (1) Preparation of Optically Absorbent Anisotropic Composition The following components were mixed and stirred at 80°C for 1 hour to obtain an optically absorbent anisotropic composition. The dichroic dye used was an azo dye described in the examples of JP-A-2013-101328. The following polymerizable liquid crystal compound was synthesized according to the method described in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

７５部 Polymerizable liquid crystal compound 1:

75 copies

２５部 Polymerizable liquid crystal compound 2:

25 copies

２．８部 Dichroic Dye 1:

2.8 parts

２．８部 Dichroic Dye 2:

2.8 parts

２．８部 Dichroic Dye 3:

2.8 parts

Polymerization initiator:
2-Dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by Chiba Specialty Chemicals) 6 parts Leveling agent:
Polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) 0.3 parts Solvent: o-xylene 250 parts

(2) Measurement of phase transition temperature of polymerizable liquid crystal compound While heating the compound on a glass substrate on which an alignment film was formed, the phase transition temperature was confirmed by observing the texture with a polarizing microscope (BX-51, manufactured by Olympus Corporation). Polymerizable liquid crystal compound 1 exhibited a smectic A phase from a crystalline phase at 95°C during heating, a phase transition to a nematic phase at 111°C, and a phase transition to an isotropic liquid phase at 113°C. It was confirmed that the polymerizable liquid crystal compound 2 exhibited a smectic A phase from a crystalline phase at 81°C during heating, a phase transition to a nematic phase at 121°C, and a phase transition to an isotropic liquid phase at 137°C during heating. During cooling, it was confirmed that the liquid crystal transitioned to a nematic phase at 133° C., to a smectic A phase at 118° C., and to a smectic B phase at 78° C. In the same manner, the texture of thermotropic nematic liquid crystal LC242 manufactured by BASF was observed. The LC242 exhibited a nematic phase, but did not exhibit a smectic phase.

(3) Preparation of composition for forming alignment film Propylene glycol monomethyl ether was added to the alignment polymer to obtain a composition for forming an alignment film. The solid content of the alignment polymer was calculated by converting the solid content from the concentration described in the delivery specification.
Oriented polymer: SunEver (registered trademark) SE-610 (manufactured by Nissan Chemical Industries, Ltd.)
0.3 parts (1.0%)
Propylene glycol monomethyl ether: 27.7 parts

(4) Preparation of Optically Absorbent Anisotropic Film The surface of a polyethylene terephthalate film (Diafoil T140E25, manufactured by Mitsubishi Plastics, Inc.) was subjected to a corona treatment. The composition for forming an alignment film was applied to the corona-treated film surface using a bar coater, and then dried for 1 minute in a drying oven set at 120°C to obtain an alignment film. The optically absorbent anisotropic composition was applied to the obtained alignment film using a bar coater, and the film was heated at 100°C for 60 seconds. The dried coating film was then naturally cooled to room temperature, and ultraviolet light was irradiated from the surface coated with the optically absorbent anisotropic composition using a high-pressure mercury lamp (Uniquer VB-15201BY-A, manufactured by Ushio Inc.) (under a nitrogen atmosphere, cumulative light amount at a wavelength of 365 nm: 1000 mJ/cm ² ) to obtain an optically absorbent anisotropic film 1.

(5) Evaluation of optically absorptive anisotropic film [three-dimensional absorbance measurement]
The absorbance of the optically absorptive anisotropic film 1 was measured as follows.
Using a spectrophotometer (Shimadzu Corporation UV-3150) with a prism polarizer folder set, the three-dimensional absorbance was measured at the wavelength showing maximum absorption in the wavelength range of 380 to 680 nm in 2 nm steps by the double beam method. The three-dimensional absorbance here refers to the absorbance (Ax, Ay, Az) in each direction relative to linearly polarized light, where any direction in the film plane is the x-axis, the direction perpendicular to the x-axis in the film plane is the y-axis, and the thickness direction of the film is the z-axis. Specifically, the measurement was performed by rotating the sample with respect to the linearly polarized light that is the measurement light. In addition, the absorbance in the z direction is difficult to measure because, by definition, light is incident from the side of the sample. Therefore, the absorbance in the Az direction was estimated by measuring the x-y plane of the sample at an angle of 60° with respect to the vibration plane of the linearly polarized light that is the measurement light.
Specifically, Ax(z=60°) was measured by rotating the sample 60° so as to include the y-axis and then incidenting the same linearly polarized light as used to measure Ax. Similarly, Ay(z=60°) was measured by rotating the sample 60° so as to include the x-axis and then incidenting the same linearly polarized light as used to measure Ay.
In addition, when there is no absorption anisotropy in the xy plane, i.e., when Ax and Ay are equal, Ax(z=60°)=Ay(z=60°), and therefore Ax(z=60°) and Ay(z=60°) were defined as A(z=60°).
The optically absorptive anisotropic film of the present invention satisfies the relationship A(z=60°)<A(z=90°)=Az. Furthermore, if A(z=60)>(Ax+Ay)/2, then the following formula (1) is necessarily satisfied.
Meet the following.
Az>(Ax+Ay)/2 (1)
As a result of measuring the three-dimensional absorbance of the optically absorptive anisotropic film 1, maximum absorptions due to the three types of dyes were obtained.
First absorption:
The three-dimensional absorbance at a wavelength of 400 nm was Ax = 0.115, Ay = 0.115, and A(z = 60°) = 0.692.
That is, the optically absorptive anisotropic film satisfies the following formulas (1), (2), and (3).
Az>A(z=60°)>(Ax+Ay)/2 (1)
Ax (z=60°)/Ax = 6.0 > 5 (2)
Ay (z = 60°) / Ay = 6.0 > 5 (3)
Second absorption:
The three-dimensional absorbance at a wavelength of 526 nm was Ax = 0.062, Ay = 0.062, and A(z = 60) = 0.639.
That is, the optically absorptive anisotropic film satisfies the following formulas (1), (2), and (3).
Az>A(z=60°)>(Ax+Ay)/2 (1)
Ax (z=60°)/Ax = 10.2 > 5 (2)
Ay (z=60°)/Ay = 10.2 > 5 (3)
Third absorption:
The three-dimensional absorbance at a wavelength of 622 nm was Ax = 0.049, Ay = 0.049, and A(z = 60) = 0.468.
That is, the optically absorptive anisotropic film satisfies the following formulas (1), (2), and (3).
Az>A(z=60°)>(Ax+Ay)/2 (1)
Ax (z=60°)/Ax = 11.3 > 5 (2)
Ay (z=60°)/Ay = 11.3 > 5 (3)

[Film thickness measurement]
The thickness of the liquid crystal cured film in the optically absorptive anisotropic film 1 was measured using a laser microscope (LEXT, manufactured by Olympus Corporation) and found to be 2.3 μm.

2. Preparation of polarizer A polyvinyl alcohol film having an average degree of polymerization of about 2,400, a degree of saponification of 99.9 mol% or more, and a thickness of 75 μm was immersed in pure water at 30° C., and then immersed in an aqueous solution having a weight ratio of iodine/potassium iodide/water of 0.02/2/100 at 30° C. to perform iodine dyeing (iodine dyeing step). The polyvinyl alcohol film that has undergone the iodine dyeing step was immersed in an aqueous solution having a weight ratio of potassium iodide/boric acid/water of 12/5/100 at 56.5° C. to perform boric acid treatment (boric acid treatment step). The polyvinyl alcohol film that has undergone the boric acid treatment step was washed with pure water at 8° C., and then dried at 65° C. to obtain a horizontal polarizing film (thickness 27 μm after stretching) in which iodine is adsorbed and aligned in the polyvinyl alcohol. At this time, stretching was performed in the iodine dyeing step and the boric acid treatment step. The total stretching ratio in this stretching was 5.3 times.

3. Preparation of horizontally aligned retardation film i (1) Preparation of horizontally aligned retardation film i An unstretched film made of norbornene resin having a glass transition temperature (Tg) of 125°C and a thickness of 40 μm was uniaxially stretched horizontally by about 1.5 times in an atmosphere of 128°C to obtain a roll-shaped retardation film having a thickness of 30 μm. The uniaxial stretching was performed using a tenter-type stretching machine. This film is referred to as stretched film A.
The in-plane retardation value Re(λ) of the horizontally aligned retardation film produced by the above method was measured by a measuring device ("KOBRA-WPR", manufactured by Oji Scientific Instruments Co., Ltd.). As a result of measuring the retardation value Re(λ) at each wavelength, the in-plane retardation Re(550) of this retardation film i was 100 nm, and the in-plane retardation Re(450) was 103 nm. The direction of the slow axis was 90° to the longitudinal direction of the film.

（２）重合性液晶化合物の調製
下記分子構造を有する重合性液晶化合物（Ｘ１）および重合性液晶化合物（Ｘ２）を、それぞれ調製した。重合性液晶化合物（Ｘ１）は、特開２０１０－３１２２３号公報に記載の方法に準じて製造した。また、重合性液晶化合物（Ｘ２）は、特開２００９－１７３８９３号公報に記載の方法に準じて製造した。これらの重合性液晶化合物をあわせて重合性液晶化合物３とする。 4. Preparation of horizontal alignment retardation film II (1) Preparation of composition for forming horizontal alignment film 5 parts of photoalignment material (weight average molecular weight: 30000) having the following structure and 95 parts of cyclopentanone (solvent) were mixed as components, and the mixture obtained was stirred at 80°C for 1 hour to obtain a composition for forming a horizontal alignment film.

(2) Preparation of polymerizable liquid crystal compounds Polymerizable liquid crystal compound (X1) and polymerizable liquid crystal compound (X2) having the following molecular structures were prepared. Polymerizable liquid crystal compound (X1) was produced according to the method described in JP-A-2010-31223. Polymerizable liquid crystal compound (X2) was produced according to the method described in JP-A-2009-173893. These polymerizable liquid crystal compounds are collectively referred to as polymerizable liquid crystal compound 3.

重合性液晶化合物（Ｘ２）

Polymerizable liquid crystal compound (X1)

Polymerizable liquid crystal compound (X2)

A solution was obtained by dissolving 1 mg of polymerizable liquid crystal compound (X1) in 50 mL of tetrahydrofuran. The obtained solution was placed as a measurement sample in a measurement cell with an optical path length of 1 cm, and the measurement cell was then set in an ultraviolet-visible spectrophotometer (Shimadzu Corporation, "UV-2450") to measure the absorption spectrum. The wavelength at which the maximum absorbance was obtained was read from the obtained absorption spectrum, and the maximum absorption wavelength λmax in the wavelength range of 300 to 400 nm was 350 nm.

(3) Preparation of polymerizable liquid crystal composition for forming horizontally aligned retardation film II The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed in a mass ratio of 90:10 to obtain a mixture. 0.1 mass parts of a leveling agent "BYK-361N" (manufactured by BM Chemie) and 6 mass parts of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan Ltd.) as a photopolymerization initiator were added to 100 mass parts of the obtained mixture. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. The mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition for forming a horizontally aligned retardation film II.

(4) Preparation of horizontal alignment retardation film ii After performing corona treatment on a COP film (ZF-14-50) manufactured by Zeon Corporation, the composition for forming a horizontal alignment film was applied with a bar coater, dried at 80 ° C. for 1 minute, and exposed to polarized UV light with an integrated light amount of 100 mJ / cm ² at a wavelength of 313 nm using a polarized UV irradiation device (SPOT CURE SP-9; manufactured by Ushio Inc.) to obtain a horizontal alignment film. The thickness of the obtained horizontal alignment film was measured with an ellipsometer and found to be 200 nm.
Next, the polymerizable liquid crystal composition for forming the horizontally aligned retardation film ii was applied onto the horizontally aligned film using a bar coater, and heated at 120° C. for 60 seconds. Then, the polymerizable liquid crystal composition for forming the horizontally aligned retardation film ii was applied to the surface coated with the composition using a high-pressure mercury lamp (Unicur VB-15201BY-A, manufactured by Ushio Inc.) with ultraviolet light (under a nitrogen atmosphere, cumulative light amount at a wavelength of 365 nm: 500 mJ/cm ² ) to form the horizontally aligned retardation film ii. After confirming that the COP film had no retardation, the liquid crystal surface side was subjected to corona treatment, and the film was attached to glass via a 25 μm pressure-sensitive adhesive manufactured by Lintec Corporation, and the COP film was peeled off and removed. Using KOBRA-WPR manufactured by Oji Scientific Instruments Co., Ltd., Re(450) and Re(550) were measured in the same manner as the horizontally aligned retardation film i, and αA=Re(450)/Re(550) was calculated.

5. Preparation of Laminate The horizontally aligned retardation film i was cut out so that the relative angle with respect to the polarizer was 45 degrees, one side of the film was subjected to corona treatment, and the obtained polarizer was laminated with a nip roll via a water-based adhesive. When laminating, the relative angle between the slow axis of the horizontally aligned retardation film i and the absorption axis of the polarizer was set to 45 degrees. The laminate obtained was dried at 80°C for 3 minutes while applying tension to obtain a laminate having the horizontally aligned retardation film i on one side. The water-based adhesive was prepared by adding 3 parts of carboxyl group-modified polyvinyl alcohol (Kuraray Poval KL318, manufactured by Kuraray) and 1.5 parts of water-soluble polyamide epoxy resin (Sumirez Resin 650, manufactured by Sumika Chemtex, aqueous solution with solid content concentration of 30%) to 100 parts of water.
The liquid crystal cured film side of the light absorbing anisotropic film obtained was laminated to the surface opposite to the polarizer of the horizontally aligned retardation film i of this laminate via a pressure-sensitive adhesive, and the coated surface side (liquid crystal layer side) of the horizontally aligned retardation film ii was laminated to the polarizer side surface of the laminate via a pressure-sensitive adhesive to prepare a laminate. When laminating, the relative angle between the slow axis of the horizontally aligned retardation film ii and the absorption axis of the polarizer was set to 135 degrees. A laminate including the light absorbing anisotropic film 1, the horizontally aligned retardation film i (stretched film A), the polarizer, and the horizontally aligned retardation film ii (cured product of the polymerizable liquid crystal composition) in this order was obtained.

重合性液晶化合物４（ＬＣ２４２）１００質量部に対して、レベリング剤「Ｆ－５５６」（ＤＩＣ社製）０．２５質量部、特願２０１６－５１４８０２号公報を参考にして調製したイオン性化合物Ａ（分子量：６４５）２．０質量部、シランカップリング剤「ＫＢＥ－９１０３」（信越化学工業株式会社製）０．５質量部、光重合開始剤として２－ジメチルアミノ－２－ベンジル－１－（４－モルホリノフェニル）ブタン－１－オン（ＢＡＳＦジャパン株式会社製「イルガキュア（登録商標）３６９（Ｉｒｇ３６９）」）６質量部を添加した。さらに、固形分濃度が１３％となるようにＮ－メチル－２－ピロリドン（ＮＭＰ）を添加した。この混合物を８０℃で１時間攪拌することにより、垂直配向位相差フィルムｉｉｉ用重合性液晶組成物を得た。 Example 2
1. Preparation of vertically aligned retardation film iii (1) Preparation of polymerizable liquid crystal composition for vertically aligned retardation film iii

To 100 parts by mass of the polymerizable liquid crystal compound 4 (LC242), 0.25 parts by mass of a leveling agent "F-556" (manufactured by DIC Corporation), 2.0 parts by mass of an ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802, 0.5 parts by mass of a silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.), and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (BASF Japan Ltd. "Irgacure (registered trademark) 369 (Irg369)") as a photopolymerization initiator were added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. The mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition for vertically aligned retardation film iii.

Ionic compound A:

(2) Preparation of Substrate A solution was prepared by dissolving 50 parts by mass of dipentaerythritol hexaacrylate (Aronix M-403, a multifunctional acrylate manufactured by Toagosei Co., Ltd.), 50 parts by mass of an acrylate resin (Ebecryl 4858, manufactured by Daicel UCB Corporation), and 3 parts by mass of 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one (Irgacure 907, manufactured by Ciba Specialty Chemicals) in 250 parts by mass of isopropanol, to obtain a composition for forming a cured resin layer containing an acrylate compound.
Next, the composition for forming the cured resin layer was applied onto a TAC film (KC4UY) manufactured by Konica Minolta, Inc. using a bar coater and dried at 50°C for 1 minute. Thereafter, a cured resin layer was formed by irradiating ultraviolet light (under a nitrogen atmosphere, cumulative light amount at a wavelength of 365 nm: 400 mJ/cm ² ) using a high-pressure mercury lamp ("Uniqure VB-15201BY-A", manufactured by Ushio Inc.). The thickness of the obtained cured resin layer was measured with a contact thickness meter, and was found to be 2.0 μm. At this time, the retardation value Re (550) of the laminate of the TAC film and the cured resin layer was measured using "KOBRA-WPR" manufactured by Oji Scientific Instruments Co., Ltd., and the retardation value Re (550) derived from the TAC film was subtracted, and it was confirmed that the retardation value was 3 nm or less and was optically isotropic.

(3) Preparation of vertically aligned liquid crystal cured film On the cured resin layer on the substrate prepared as described above, the polymerizable liquid crystal composition for vertically aligned retardation film iii was applied using a bar coater, and heated at 120°C for 60 seconds. Next, while still heated to 120°C, a high-pressure mercury lamp (Uniqure VB-15201BY-A, manufactured by Ushio Inc.) was used to irradiate ultraviolet light (under a nitrogen atmosphere, accumulated light amount at a wavelength of 365 nm: 500 mJ/cm ² ) from the surface on which the polymerizable liquid crystal composition for vertically aligned retardation film iii was applied, thereby forming a vertically aligned retardation film. The thickness of the obtained liquid crystal layer was measured with an ellipsometer (M-220, manufactured by JASCO Corporation) and found to be 0.6 μm.

(4) Evaluation of Cured Film of Vertically Aligned Liquid Crystal [Measurement of Thickness Retardation Value]
The liquid crystal surface side of the vertically aligned retardation film iii prepared by the above procedure was subjected to corona treatment, and the film was attached to glass via a 25 μm pressure-sensitive adhesive manufactured by Lintec Corporation, and the TAC and cured resin layer were peeled off and removed. The front retardation value and the retardation value when tilted 40° from the center of the fast axis were measured by changing the incident angle of light to the sample for measuring optical properties using KOBRA-WPR manufactured by Oji Scientific Instruments Co., Ltd.
The average refractive index at each wavelength was measured using an Ellipsometer M-220 manufactured by JASCO Corporation. The film thickness of the polymerizable liquid crystal cured product layer was measured using an Optical NanoGauge film thickness meter C12562-01 manufactured by Hamamatsu Photonics K.K. From the above-mentioned front retardation value, retardation value when tilted 40° to the fast axis center, average refractive index, and film thickness values, the three-dimensional refractive index was calculated with reference to Oji Scientific Instruments Technical Documents (http://www.oji-keisoku.co.jp/products/kobra/reference.html). From the obtained three-dimensional refractive index, the optical properties of the vertically aligned retardation film were calculated according to the following formula, and the values of Rth (450), Rth (550), and Rth (450) / Rth (550) were calculated.
RthC(λ)=((nxC(λ)+nyC(λ))/2-nzC(λ))×dC
Here, RthC(λ) represents the retardation value in the thickness direction of the vertically aligned retardation film at a wavelength of λ nm. Also, nxC(λ) represents the in-plane main refractive index of the vertically aligned retardation film at a wavelength of λ nm, nyC(λ) represents the refractive index in the direction perpendicular to nxC(λ) at a wavelength of λ nm, nzC(λ) represents the refractive index in the thickness direction of the vertically aligned retardation film at a wavelength of λ nm, and when nxC(λ)=nyC(λ), nxC(λ) can be the refractive index in any direction in the film plane, and dC represents the thickness of the vertically aligned retardation film.

2. Preparation of Laminate The liquid crystal cured film side of the vertically aligned retardation film iii obtained above was subjected to corona treatment, and then the laminate was attached to the surface of the horizontally aligned retardation film ii of the laminate prepared in the same manner as in Example 1 opposite to the polarizer via the pressure-sensitive adhesive, to prepare a laminate including the light absorption anisotropic film 1, the horizontally aligned retardation film i (stretched film A), the polarizer, the horizontally aligned retardation film ii (cured product of the polymerizable liquid crystal composition), and the vertically aligned retardation film iii in this order, and was evaluated.

Example 3
Instead of the stretched film A used as the horizontally aligned retardation film i in Example 1, the retardation film (cured product of the polymerizable liquid crystal composition) used as the horizontally aligned retardation film ii in Example 1 was used as the horizontally aligned retardation film i in Example 3. The liquid crystal surface of this film was subjected to a corona treatment, and the film was laminated to the obtained polarizer via a water-based adhesive in the same manner as in Example 1. After lamination, the COP was peeled off and removed. Next, the liquid crystal cured film side of the obtained light absorption anisotropic film was laminated to the surface of the horizontally aligned retardation film i (cured product of the polymerizable liquid crystal composition) of this laminate opposite to the polarizer via a pressure-sensitive adhesive. In addition, the cured product of the polymerizable liquid crystal composition was laminated to the polarizer side surface of the laminate as the horizontally aligned retardation film ii via a pressure-sensitive adhesive in the same manner as in Example 1. A laminate including the light absorption anisotropic film 1, the horizontally aligned retardation film i (cured product of the polymerizable liquid crystal composition), the polarizer, and the horizontally aligned retardation film ii (cured product of the polymerizable liquid crystal composition) in this order was prepared and evaluated.

Example 4
In Example 1, the following stretched film B was used as the horizontally aligned retardation film ii instead of the cured product of the polymerizable liquid crystal composition used as the horizontally aligned retardation film ii. A rolled unstretched film made of a norbornene-based resin and having an original thickness of 50 μm was uniaxially stretched horizontally by about 1.5 times in an atmosphere at 128° C. to obtain a rolled retardation film having a thickness of 40 μm. The in-plane retardation Re(550) of the obtained film was 140 nm, and Re(450) was 145 nm. In addition, the relative angle between the slow axis and the absorption axis of the polarizer when bonding was set to 45 degrees.
The liquid crystal cured film side of the obtained light absorbing anisotropic film was attached to the surface of the horizontally aligned retardation film i opposite to the polarizer of the laminate of the horizontally aligned retardation film i and the polarizer in Example 1 via a pressure-sensitive adhesive, and the above-mentioned stretched film B, one side of which was subjected to a corona treatment, was attached to the polarizer side of the laminate via a pressure-sensitive adhesive to prepare a laminate. A laminate including the light absorbing anisotropic film 1, the horizontally aligned retardation film i (stretched film A), the polarizer, and the horizontally aligned retardation film ii (stretched film B) in this order was obtained.

Example 5
In the preparation of the light absorption anisotropic film, 0.25 parts by mass of a leveling agent "F-556" (manufactured by DIC Corporation), 6 parts by mass of dichroic dye 2, 1.5 parts by mass of ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802, 0.5 parts by mass of a silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.), and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (manufactured by BASF Japan Ltd. "Irgacure (registered trademark) 369 (Irg369)") as a photopolymerization initiator were added to 100 parts by mass of polymerizable liquid crystal compound 4 (LC242). Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. The mixture was stirred at 80 ° C. for 1 hour to obtain a light absorption anisotropic film preparation composition 2.
This was subjected to corona treatment on a COP film (ZF-14-50) manufactured by Zeon Corporation, the composition was applied using a bar coater, and heated at 120°C for 60 seconds. After that, a high-pressure mercury lamp (Unicur VB-15201BY-A, manufactured by Ushio Inc.) was used to irradiate ultraviolet light from the applied surface (under a nitrogen atmosphere, cumulative light amount at a wavelength of 365 nm: 500 mJ/cm ² ) to form an optically absorbing anisotropic film 2. The film thickness of the obtained film was 1.5 μm. The three-dimensional absorbance of the optically absorbing anisotropic film 2 was measured, and the maximum absorption wavelength was 600 nm. Using this optically absorbing anisotropic film 2, a laminate was produced in the same manner as in Example 1. A laminate including the optically absorbing anisotropic film 2, a horizontally aligned retardation film i (stretched film A), a polarizer, and a horizontally aligned retardation film ii (cured product of a polymerizable liquid crystal composition) in this order was obtained.

Comparative Example 1
A laminate was prepared in the same manner as in Example 4, except that a saponified TAC film (KC4UY) manufactured by Konica Minolta, Inc. was used as the horizontally aligned retardation film i, and evaluation was performed.

Evaluation Method and Results Visibility The front glass and polarizing plate were removed from SAMSUNG's "Galaxy S8" (screen area: approximately 5.8 inches, screen width: approximately 64.4 mm) to take out the organic EL display device.
Then, the substrate side of the horizontally aligned retardation film ii of the laminate prepared by the above-mentioned method was attached to the organic EL display device taken out via an adhesive (25 μm pressure-sensitive adhesive manufactured by Lintec Corporation), characters were displayed on the attached screen, and visually observed from the front of the screen and from a 45° diagonal direction to the front of the screen. Note that the observation at a 45° diagonal direction was performed in all directions while rotating the display device.
If the display content could be clearly confirmed or the appearance of the display content changed depending on the rotation, it was rated as A; if the display content was somewhat unclear, it was rated as B; and if the display content was unclear or not visible, it was rated as C.

Panel Reflection Hue As in the visibility evaluation, the laminate was attached to a "Galaxy S8" from which the organic EL display device had been removed, and the hue of the reflection was confirmed when the display device was turned off (when displaying black), and was evaluated according to the following criteria: A glossy black drawing paper was placed next to the display device at 1.5 m directly below a 40W 3-wavelength lamp, and the hue was confirmed visually from a distance of approximately 50 cm from the front (within an elevation angle of 20° from directly above). If almost no color was detected, it was rated as A; if the color was detected compared to the black drawing paper and looked black with a slight blue, green, or reddish color, it was rated as B; and if a strong color was observed, it was rated as C.

Heat Shock Test The laminates of Example 1 and Example 2 were attached to Corning Eagle XG glass (size: 50 mm x 50 mm) having a thickness of 0.7 mm via a pressure-sensitive adhesive, and a cycle test was carried out in a thermal shock test tank. One cycle consisted of exposure to -30°C for 30 minutes, followed by rapid heating to 70°C and exposure for 30 minutes, and the test was carried out for 100 cycles.
After the test, it was checked whether any significant cracks had occurred. If no cracks had occurred, it was rated as A, and if cracks had occurred, it was rated as B.

The configurations and optical properties of the light absorption anisotropic films, polarizers, and retardation films used in each of Examples 1 to 5 and Comparative Example 1 are shown in Table 1, and the evaluation results regarding the visibility of the laminate, the panel reflection hue, and the heat shock test are shown in Table 2.

In Examples 1 to 5, it was confirmed that the visibility from an oblique direction was reduced, the anti-peek function was obtained, and the difference in visibility was reduced even when the display device was rotated. In Examples 1 to 4, clear visibility was maintained from the front direction. On the other hand, in Example 5, the transparency was slightly reduced when viewed from the front direction, but clear visibility was maintained, while the anti-peek function was obtained when viewed from an oblique direction, and the difference in visibility was reduced even when the display device was rotated. Furthermore, in Examples 1 to 3 and 5, the reflected color was suppressed and a good black color was obtained. In addition to the above results, in Example 2, in addition to the results in Example 1, when the power supply of the display device was turned off (when displaying black), the display device was placed 1.5 m directly below a 40W 3-wavelength lamp, and the display device was rotated 360° from an elevation angle of approximately 60° and approximately 50 cm away, and the hue was visually confirmed. The color of the reflection from an oblique direction was suppressed and visibility was further improved.

Example 6
In the preparation of the optically absorptive anisotropic film, 0.25 parts by mass of a leveling agent "F-556" (manufactured by DIC Corporation), 2.8 parts by mass of dichroic dye 2, and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan Ltd.) as a photopolymerization initiator were added to 100 parts by mass of the polymerizable liquid crystal compounds 1 and 2 in total. Furthermore, o-xylene was added so that the solid content concentration became 30%. The mixture was stirred at 80°C for 1 hour to obtain a composition 3 for preparing an optically absorptive anisotropic film.
This was subjected to corona treatment on a TAC film (KC4UY) manufactured by Konica Minolta, Inc., the composition was applied using a bar coater, and heated at 100°C for 60 seconds. After that, ultraviolet light was irradiated from the applied surface using a high-pressure mercury lamp (Unicur VB-15201BY-A, manufactured by Ushio Inc.) (under a nitrogen atmosphere, cumulative light amount at a wavelength of 365 nm: 500 mJ/cm ² ), to form an optically absorptive anisotropic film 3. The film thickness of the obtained film was 1.8 μm. The three-dimensional absorbance of this optically absorptive anisotropic film 3 was measured, and the maximum absorption wavelength was 622 nm. The in-plane retardation Rei(λ) of the horizontally aligned retardation film i was 99 nm, and (λMAX/4)/(Rei(λ)) was 1.58.
Using this optically absorptive anisotropic film 3, a laminate was prepared in the same manner as in Example 1. A laminate was prepared containing the optically absorptive anisotropic film 3, a horizontally aligned retardation film i (stretched film A), a polarizer, and a horizontally aligned retardation film ii (cured product of a polymerizable liquid crystal composition) in this order. The visibility and panel reflection hue of the obtained laminate were evaluated in the same manner as in Example 1. Furthermore, the visibility through polarized sunglasses was evaluated according to the following method. The configuration of the laminate and the properties of each configuration are shown in Table 3, and the evaluation results of the laminate are shown in Table 4.

Visibility through polarized sunglasses was evaluated by an observer visually checking the color change of a panel containing the obtained laminate through polarized sunglasses while rotating the panel. Those for which the color change was not noticeable were rated A, those for which the color change was slightly noticeable were rated B, and those for which the color change was large or the panel became darker were rated C.

Example 7
Composition 4 for forming an optically absorptive anisotropic film was obtained in the same manner as in composition 3 for forming an optically absorptive anisotropic film, except that 2.8 parts by mass of dichroic dye 4 was added in addition to dichroic dye 2.
This was used to form an optically absorptive anisotropic film 4 on a TAC film (KC4UY) in the same manner as in Example 6. The film thickness of the obtained film was 2.0 μm. The three-dimensional absorbance of this optically absorptive anisotropic film 4 was measured, and the maximum absorption wavelength was 573 nm. The in-plane retardation Rei(λ) was 100 nm, and (λMAX/4)/(Rei(λ)) was 1.44.
Using this optically absorptive anisotropic film 4, a laminate was prepared in the same manner as in Example 2. A laminate including the optically absorptive anisotropic film 4, a horizontally aligned retardation film i (stretched film A), a polarizer, a horizontally aligned retardation film ii (cured product of a polymerizable liquid crystal composition), and a vertically aligned retardation film iii in this order was prepared, and evaluated in the same manner as in Example 6. The configuration of the laminate and the properties of each configuration are shown in Table 3, and the evaluation results of the laminate are shown in Table 4.

Dichroic Dye 4:

Example 8
Composition 5 for forming an optically absorptive anisotropic film was obtained in the same manner as in composition 3 for forming an optically absorptive anisotropic film, except that dichroic dye 2 was replaced with 2.8 parts of dichroic dye 5.
This was used to form an optically absorptive anisotropic film 5 on a TAC film (KC4UY) in the same manner as in Example 6. The film thickness of the obtained film was 2.0 μm. The three-dimensional absorbance of this optically absorptive anisotropic film 5 was measured, and the maximum absorption wavelength was 476 nm. The in-plane retardation Rei(λ) was 102 nm, and (λMAX/4)/(Rei(λ)) was 1.16.
Using this optically absorptive anisotropic film 5, a laminate was prepared in the same manner as in Example 2. A laminate including the optically absorptive anisotropic film 5, a horizontally aligned retardation film i (stretched film A), a polarizer, a horizontally aligned retardation film ii (cured product of a polymerizable liquid crystal composition), and a vertically aligned retardation film iii in this order was prepared, and evaluated in the same manner as in Example 6. The configuration of the laminate and the properties of each configuration are shown in Table 3, and the evaluation results of the laminate are shown in Table 4.

Dichroic Dye 5:

Example 9
In the preparation of the horizontally aligned retardation film i, a rolled unstretched film made of a norbornene resin having a glass transition temperature (Tg) of 125° C. and a thickness of 50 μm was uniaxially stretched horizontally by about 1.8 times in an atmosphere of 128° C. to obtain a rolled retardation film (stretched film C) having a thickness of about 35 μm. The in-plane retardation Re(550) of the obtained film was 120 nm, and Re(450) was 123 nm. The direction of the slow axis was 90° to the longitudinal direction of the film. The in-plane retardation Rei(λ) was 122 nm, and (λMAX/4)/(Rei(λ)) was 0.97.
A laminate was prepared in the same manner as in Example 8, except that the horizontally aligned retardation film i was changed from the stretched film A to the stretched film C. A laminate was prepared containing the light absorbing anisotropic film 5, the horizontally aligned retardation film i (stretched film C), a polarizer, the horizontally aligned retardation film ii (cured product of the polymerizable liquid crystal composition), and the vertically aligned retardation film iii in this order, and was evaluated in the same manner as in Example 6. The configuration of the laminate and the characteristics of each configuration are shown in Table 3, and the evaluation results of the laminate are shown in Table 4.

Example 10
A laminate was prepared in the same manner as in Example 8, except that the retardation film (cured product of polymerizable liquid crystal composition) used as the horizontally aligned retardation film ii in Example 1 was used instead of the stretched film A used as the horizontally aligned retardation film i in Example 8. The in-plane retardation Rei(λ) was 126 nm, and (λMAX/4)/(Rei(λ)) was 0.94. A laminate including the light absorption anisotropic film 5, the horizontally aligned retardation film i (cured product of polymerizable liquid crystal composition), the polarizer, the horizontally aligned retardation film ii (cured product of polymerizable liquid crystal composition), and the vertically aligned retardation film iii in this order was prepared, and the same evaluation as in Example 6 was performed. The configuration of the laminate and the characteristics in each configuration are shown in Table 3, and the evaluation results of the laminate are shown in Table 4.

For Comparative Example 1, visibility through polarized sunglasses was evaluated in the same manner as in Example 6. The results are shown in Table 4.

In Examples 6 to 10, the visibility of the color portion corresponding to the complementary color of each maximum absorption wavelength from an oblique direction was reduced, and a function to prevent peeping was obtained. It was also confirmed that the difference in visibility was reduced even when the display device was rotated. Also, in Examples 6 to 10, clear visibility was maintained from the front direction. Furthermore, in Examples 6 to 10, the reflected color was suppressed and a good black color was obtained. In addition to the above results, in Examples 7 to 10, compared to Examples 1 and 6, when the power supply of the display device was turned off (when displaying black), the display device was placed 1.5 m directly below a 40W 3-wavelength lamp, and the display device was rotated 360° from an elevation angle of approximately 60° and approximately 50 cm away, and the hue was visually confirmed. The color of the reflection from an oblique direction was also suppressed, and visibility was further improved.

Comparing Examples 6 and 7, it was confirmed that Example 7 had a greater reduction in the difference in visibility when the display device was rotated, and comparing Examples 8, 9, and 10, it was confirmed that Examples 8 and 9 had a greater reduction in the difference in visibility when the display device was rotated than Example 10, with an even greater reduction being confirmed in Example 9.

When the display device was turned on and the display content was viewed through polarized sunglasses, in Comparative Example 1, the display became dark at the position where the absorption axis of the polarized sunglasses and the absorption axis of the polarizer in the laminate were at 90°, and visibility in all directions was poor. On the other hand, in the laminates of Examples 6 to 10, the display content was visible when the display device was rotated, and in particular, in Examples 6 to 9, there was less change in color when the display device was rotated compared to Example 10.

Claims (12)

A light absorption anisotropic film made of a cured product of a liquid crystal composition containing a dichroic dye and a liquid crystal compound, wherein an arbitrary position direction in the film plane is defined as the x-axis, a direction perpendicular to the x-axis in the film plane is defined as the y-axis, and a thickness direction perpendicular to the x-axis and y-axis is defined as the z-axis, and the light absorption anisotropic film satisfies the following formulas (1) to (3):
Az>(Ax+Ay)/2 (1)
Ax (z=60°)/Ax>5 (2)
Ay (z=60°)/Ay>5 (3)
[In formulas (1) to (3),
Ax, Ay, Az, Ax(z=60°) and Ay(z=60°) are all absorbances at the absorption maximum wavelength of the dichroic dye in the optically absorptive anisotropic film,
Ax represents the absorbance of linearly polarized light vibrating in the x-axis direction,
Ay represents the absorbance of linearly polarized light vibrating in the y-axis direction,
Az represents the absorbance of linearly polarized light vibrating in the z-axis direction,
Ax (z=60°) represents the absorbance of linearly polarized light oscillating in the x-axis direction when the film is rotated 60° around the y-axis as the rotation axis,
Ay (z=60°) represents the absorbance of linearly polarized light oscillating in the y-axis direction when the film is rotated 60° around the x-axis as the rotation axis.
and a light absorbing anisotropic film satisfying the above.
The following formula (4):
70nm≦Re _i (550)≦170nm (4)
[In formula (4), Re _i (λ) represents an in-plane retardation value of the horizontally aligned retardation film i at a wavelength of λ nm]
A horizontally aligned retardation film i that satisfies the above formula:
A polarizer;
The following formula (5):
120nm≦Re _ii (550)≦160nm (5)
[In formula (5), Re _ii (λ) represents an in-plane retardation value of the horizontally aligned retardation film ii at a wavelength of λ nm]
and a horizontally aligned retardation film ii satisfying the above in this order. The horizontally aligned retardation film ii has the following formula (6):
Re _ii (450)/Re _ii (550)<1.00 (6)
[In formula (6), Re _ii (λ) has the same meaning as in formula (5) above]
The range of the angle θ _ii between the slow axis of the horizontally aligned retardation film ii and the absorption axis of the polarizer satisfies the following formula (7):
15°≦｜θ _ii |≦75° (7)
The laminate according to claim 1 , The horizontally aligned retardation film i has the following formula (8):
Re _i (450)/Re _i (550)≧1.00 (8)
[In formula (8), Re _i (λ) has the same meaning as in formula (4) above]
The range of the angle θ _i between the slow axis of the horizontally aligned retardation film i and the absorption axis of the polarizer satisfies the following formula (9):
15°≦｜ _θi ｜≦75° (9)
The laminate according to claim 1 or 2, The laminate according to claim 1 or 2, in which the horizontally aligned retardation film i and the polarizer are laminated via a pressure-sensitive adhesive. The laminate according to claim 1 or 2, wherein the horizontally aligned retardation film i is made of a film stretched in at least one direction. The laminate according to claim 1 or 2, wherein the horizontal alignment retardation film ii is made of a cured product of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound. The laminate according to claim 1 or 2, wherein the liquid crystal compound contained in the optically absorbing anisotropic film exhibits a smectic liquid crystal phase. The laminate according to claim 1 or 2, further comprising a transparent protective film on the surface of the optically absorbing anisotropic film opposite to the horizontally aligned retardation film i. The following formula (10):
-100nm≦Rth _iii (550)≦-20nm (10)
[In formula (10), Rth _iii (λ) represents a thickness retardation value of the vertically aligned retardation film iii at a wavelength of λ nm]
The vertically aligned retardation film iii satisfies the following:
The laminate according to claim 1 or 2, wherein the vertically aligned retardation film iii is laminated between the polarizer and the horizontally aligned retardation film ii, or on the opposite side of the horizontally aligned retardation film ii from the polarizer. The vertically aligned retardation film iii has the following formula (11):
Rth _iii (450)/Rth _iii (550)>1.00 (11)
[In formula (11), Rth _iii (λ) represents a thickness retardation value of the vertically aligned retardation film iii at a wavelength of λ nm]
The laminate according to claim 9 , The laminate according to claim 9, wherein the vertically aligned retardation film iii is made of a cured product of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound. An organic EL display device comprising the laminate according to claim 1 or 2.

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