JP2019035952A - Phase difference plate with optical compensation function for flexible display - Google Patents

Abstract

To provide a method for manufacturing a phase difference plate with an optical compensation function for flexible that prevents the occurrence of troubles, such as wrinkles and cracks even when bent, and does not reflect external light in a colored state even when folded.SOLUTION: A manufacturing method of the present invention includes: forming a horizontal alignment film through application, drying, and orientation processing steps, subsequently forming a horizontal alignment liquid crystal cured film through application, drying, and ultraviolet irradiation steps, forming a vertical alignment film through application and drying steps, and forming a vertical alignment liquid crystal cured film through application, drying, and ultraviolet irradiation steps. A phase difference plate with an optical compensation function for a flexible display is manufactured by the method of forming the horizontal alignment film, horizontal alignment liquid crystal cured film, vertical alignment film, and vertical alignment liquid crystal cured film in this order.SELECTED DRAWING: None

Description

The present invention relates to a retardation plate with an optical compensation function for a flexible display.

A flat panel display such as an organic EL image display device usually has a flat image display surface. The image display surface of the flat panel display is in a flat state as it is, whether or not an image is displayed.

A retardation plate is often used for such a flat panel display. For example, in an organic EL image display device, a circularly polarizing plate in which a retardation plate is combined with a polarizing plate is used in order to prevent light reflection at an electrode constituting the image display device.

For such a phase difference plate, a phase difference plate exhibiting reverse wavelength dispersion is preferable in that it exhibits an equivalent phase difference performance in a wide wavelength range of visible light. As a retardation plate exhibiting reverse wavelength dispersion, a retardation plate made of a horizontally aligned liquid crystal cured film obtained by polymerizing and curing a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion in a horizontal direction is known.

There is also a need for a retardation plate with an optical compensation function that has a function of compensating for the same optical performance as seen from the front direction even when viewed from an oblique direction. As a retardation film with a function, a liquid crystal cured film obtained by polymerizing and curing a polymerizable liquid crystal compound in a vertically aligned state together with a horizontally aligned liquid crystal cured film is further disclosed in JP-A-2015-163935. No.] is proposed. This document also discloses that the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film are laminated only through the alignment film or through a protective layer or the like. Further, this document only discloses that the retardation plate with an optical compensation function described in the document can be used for a flat panel display.

JP2015-163935A

On the other hand, so-called flexible displays that can be folded as displays have also been developed. In the flexible display, the retardation plate with an optical compensation function is also folded together with the display.

However, if a problem such as a wrinkle or a crack occurs when folded, when the flexible display is expanded again and an image is displayed, the defective part such as a wrinkle or a crack becomes a defect and the display image is damaged. In addition, when the image is folded with the image displayed, the folded angle is substantially reduced because the elevation angle (the angle formed by the film plane and the direction in which the viewer looks at the screen) becomes very small. It also becomes a problem that external light is reflected in this state.

Accordingly, an object of the present invention is to provide a flexible phase difference plate with an optical compensation function that does not cause defects such as wrinkles and cracks even when folded, and does not reflect outside light in a colored state when folded. Is to develop.

As a result of intensive studies in order to solve the above problems, the present inventors have completed the present invention.
That is, the present invention includes the following.

[1] A horizontal alignment film is formed through coating, drying, and alignment treatment steps.
Form a horizontal alignment liquid crystal cured film through coating, drying and ultraviolet irradiation processes,
Furthermore, a vertical alignment film is formed through a coating and drying process,
By forming a vertically aligned liquid crystal cured film through coating, drying, and ultraviolet irradiation processes,
A method of manufacturing a retardation film with an optical compensation function, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film are formed in this order.

[2] The retardation film with an optical compensation function according to [1], wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film having a film thickness of 1.0 μm or less are formed in this order. Production method.

[3] With an optical compensation function according to any one of the above [1] to [2], wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film made of a photo alignment film are formed in this order. A method of manufacturing a retardation film.

[4] The horizontal alignment film comprising a photo-alignment film containing a cinnamoyl group, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film are formed in this order. A method of manufacturing a retardation film with an optical compensation function.

[5] The optical compensation according to any one of [1] to [4], wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film having a thickness of 1.0 μm or less, and a vertical alignment liquid crystal cured film are formed in this order. A method for producing a functional retardation plate.

[6] A position with an optical compensation function according to any one of [1] to [5], wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film containing Si element, and a vertical alignment liquid crystal cured film are formed in this order. A method for producing a phase difference plate.

[7] The above [1] to [6] in which a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film having a Si / C element of 0.03 to 1.00, and a vertical alignment liquid crystal cured film are formed in this order. A method for producing a retardation plate with an optical compensation function according to any one of the above.

[8] A method for producing a phase difference plate with an optical compensation function by forming a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film in this order. The method for producing a retardation plate with an optical compensation function according to any one of [1] to [7], wherein the relationship (1) is satisfied.
ReA (450) / ReA (550) <1.00 (1)
In the formula, ReA (λ) represents an in-plane retardation value at a wavelength λ nm of the horizontally aligned liquid crystal cured film. The definition of the in-plane retardation value ReA (λ) is as follows.
ReA (λ) = (nxA (λ) −nyA (λ)) × dA
However, nxA (λ) is the main refractive index in the film plane of the horizontally aligned liquid crystal cured film, and nyA (λ) is in the same plane as nxA (λ). The refractive index in the orthogonal direction and the refractive index at the wavelength λ (nm), dA indicates the film thickness of horizontal alignment liquid crystal curing.

[9] A method for producing a phase difference plate with an optical compensation function by forming a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film in this order. The method for producing a retardation plate with an optical compensation function according to any one of [1] to [8], wherein the relationship (2) is satisfied.
RthC (450) / RthC (550) <1.00 (2)
In the formula, RthC (λ) represents a thickness direction retardation value of the vertically aligned liquid crystal cured film at a wavelength of λ nm. The definition of the phase difference value RthC (λ) is as follows.
RthC (λ) = ((nxC (λ) + nyC (λ)) / 2−nzC (λ)) × dC
However, nxC (λ) is the main refractive index in the film plane of the vertically aligned liquid crystal cured film, and the main refractive index at the wavelength λ (nm),
nyC (λ) is the refractive index in the direction orthogonal to nxC (λ) in the same plane, and the refractive index at the wavelength λ (nm),
nzC (λ) is the refractive index in the thickness direction of the vertically aligned liquid crystal cured film, and the refractive index at the wavelength λ (nm),
dC represents the film thickness of vertical alignment liquid crystal curing.
When nxC (λ) = nyC (λ), nxC (λ) can be a refractive index in an arbitrary direction within the film plane.

The present invention also includes the following.
[10] A vertical alignment film is formed through a coating / drying process,
Forming a vertically aligned liquid crystal cured film through coating, drying, and UV irradiation processes,
Furthermore, a horizontal alignment film is formed through coating, drying and alignment treatment steps,
By forming a horizontal alignment liquid crystal cured film through the application, drying, ultraviolet irradiation process,
Method of manufacturing retardation film with optical compensation function, forming vertical alignment film, vertical alignment liquid crystal cured film, horizontal alignment film, horizontal alignment liquid crystal cured film in this order

[11] The retardation film with an optical compensation function according to [10], wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film having a film thickness of 1.0 μm or less, and a horizontal alignment liquid crystal cured film are formed in this order. Production method.

[12] A phase difference with an optical compensation function according to [10] or [11], wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film composed of a photo alignment film, and a horizontal alignment liquid crystal cured film are formed in this order. A manufacturing method of a board.

[13] The vertical alignment film, the vertical alignment liquid crystal cured film, the horizontal alignment film composed of a photo alignment film containing a cinnamoyl group, and the horizontal alignment liquid crystal cured film are formed in this order, according to any one of the above [10] to [12] A method of manufacturing a retardation film with an optical compensation function.

[14] The optical compensation according to any one of [10] to [13], wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film having a thickness of 1.0 μm or less are formed in this order. A method for producing a functional retardation plate.

[15] A position with an optical compensation function according to any one of the above [10] to [14], wherein a vertical alignment film containing Si element, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film are formed in this order. A method for producing a phase difference plate.

[16] The above [10] to [15], in which a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film having a Si / C element of 0.03 to 1.00, and a vertical alignment liquid crystal cured film are formed in this order. A method for producing a retardation plate with an optical compensation function according to any one of the above.

[17] A method of manufacturing a retardation film with an optical compensation function by forming a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film in this order. The method for producing a retardation plate with an optical compensation function according to any one of [10] to [16], wherein the relationship (3) is satisfied.
ReA (450) / ReA (550) <1.00 (3)
In the formula, ReA (λ) represents an in-plane retardation value at a wavelength λ nm of the horizontally aligned liquid crystal cured film. The definition of the in-plane retardation value ReA (λ) is as follows.
ReA (λ) = (nxA (λ) −nyA (λ)) × dA
However, nxA (λ) is the main refractive index in the film plane of the horizontally aligned liquid crystal cured film and is the main refractive index at the wavelength λ (nm), and nyA (λ) is orthogonal to nxA (λ) in the same plane. The refractive index at the wavelength λ (nm), and dA represents the film thickness of horizontal alignment liquid crystal curing.

[18] A method of manufacturing a retardation film with an optical compensation function by forming a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film in this order. The method for producing a retardation plate with an optical compensation function according to the above [1] to [17], which satisfies the relationship (4).
RthC (450) / RthC (550) <1.00 (4)
In the formula, RthC (λ) represents a thickness direction retardation value of the vertically aligned liquid crystal cured film at a wavelength of λ nm. The definition of the phase difference value RthC (λ) is as follows.
RthC (λ) = ((nxC (λ) + nyC (λ)) / 2−nzC (λ)) × dC
However, nxC (λ) is the main refractive index in the film plane of the vertically aligned liquid crystal cured film, and the main refractive index at the wavelength λ (nm),
nyC (λ) is the refractive index in the direction orthogonal to nxC (λ) in the same plane, and the refractive index at the wavelength λ (nm),
nzC (λ) is the refractive index in the thickness direction of the vertically aligned liquid crystal cured film, and the refractive index at the wavelength λ (nm),
dC represents the film thickness of vertical alignment liquid crystal curing.
When nxC (λ) = nyC (λ), nxC (λ) can be a refractive index in an arbitrary direction within the film plane.

An elliptical polarizing plate with an optical compensation function can be manufactured by obtaining a retardation film with an optical compensation function by the manufacturing method of the present invention and laminating a polarizing plate on the retardation plate.
The elliptically polarizing plate with an optical compensation function is preferably used by being incorporated in, for example, an organic EL display device.

The retardation film with an optical compensation function of the present invention can suppress problems such as wrinkles and cracks that occur when bent.

[Horizontal alignment liquid crystal cured film]
The horizontally aligned liquid crystal cured film is a film having refractive index anisotropy in the plane of the film, and is made of a polymer containing a polymerizable liquid crystal compound. The horizontal alignment liquid crystal cured film is formed by a method in which a polymerizable liquid crystal composition is applied onto the horizontal alignment film and a composition containing the polymerizable liquid crystal compound in an alignment state is polymerized by heating and / or light irradiation. It is preferable in that the thickness of the horizontally aligned liquid crystal cured film and wavelength dispersion characteristics can be arbitrarily designed.

  The three-dimensional refractive index ellipsoid formed by the horizontally aligned liquid crystal cured film may have biaxiality, but preferably has uniaxiality. The horizontally aligned liquid crystal cured film may be a horizontally aligned liquid crystal cured film made of a polymer of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound in a state of being horizontally aligned with respect to the plane of the horizontally aligned liquid crystal cured film. Further, it may be a hybrid alignment liquid crystal cured film or a tilt alignment liquid crystal cured film. Refractive indices nx, ny and nz in three directions in the refractive index ellipsoid formed by the orientation of the polymerizable liquid crystal are nx> ny≈nz (referred to as positive A plate) or nx <ny≈nz (referred to as negative A plate). It may have the relationship. nx represents a main refractive index in a direction parallel to the plane of the horizontally aligned liquid crystal cured film in the refractive index ellipsoid formed by the horizontally aligned liquid crystal cured film. ny is a refractive index ellipsoid formed by the horizontally aligned liquid crystal cured film, and represents a refractive index in a direction parallel to the plane of the horizontally aligned liquid crystal cured film and orthogonal to the nx direction. nz represents the refractive index in the direction perpendicular to the plane of the horizontally aligned liquid crystal cured film in the refractive index ellipsoid formed by the horizontally aligned liquid crystal cured film.

  The horizontally aligned liquid crystal cured film can be either a rod-like polymerizable liquid crystal or a disk-like polymerizable liquid crystal, but is preferably a rod-like polymerizable liquid crystal. When the rod-like polymerizable liquid crystal forms a horizontal alignment liquid crystal cured film, the horizontal alignment liquid crystal cured film becomes a positive A plate.

When the horizontally aligned liquid crystal cured film has optical anisotropy in the plane of the film, Re1 (550), which is an in-plane retardation value for light having a wavelength of 550 nm, satisfies the optical characteristics represented by the following formula (21). Is preferred. The horizontally aligned liquid crystal cured film has an in-plane retardation value for light having a wavelength of 450 nm, Re1 (450) for light having a wavelength of 550 nm, an in-plane retardation value for light having a wavelength of 550 nm, and an in-plane for light having a wavelength of 650 nm. It is also preferable that Re1 (650) which is a phase difference value satisfies the optical characteristics represented by the equations (22) and (23). It is more preferable that the horizontally aligned liquid crystal cured film satisfies the optical characteristics represented by the following formula (21), the following formula (22), and the following formula (23).
120 nm ≦ ReA (550) ≦ 170 nm (21)
[In the formula, ReA (550) represents an in-plane retardation value (in-plane retardation) of the horizontally aligned liquid crystal cured film with respect to light having a wavelength of 550 nm. ]
ReA (450) / ReA (550) ≦ 1.0 (22)
1.00 ≦ ReA (650) / ReA (550) (23)
[In the formula, ReA (450) is the in-plane retardation value for light with a wavelength of 450 nm of the horizontally aligned liquid crystal cured film, ReA (550) is the in-plane retardation value for light with a wavelength of 550 nm of the horizontally aligned liquid crystal cured film, ReA (650) represents the in-plane retardation value of the horizontally aligned liquid crystal cured film with respect to light having a wavelength of 650 nm. ]

  When the in-plane retardation value ReA (550) of the horizontally aligned liquid crystal cured film exceeds the range of the equation (21), the hue of the front surface of the display to which the elliptically polarizing plate with an optical compensation function including the retardation plate with an optical compensation function is applied is obtained. It can cause problems that turn red and blue. A more preferable range of the in-plane retardation value is 130 nm ≦ ReA (550) ≦ 160 nm. When “ReA (450) / ReA (550)” of the horizontally aligned liquid crystal cured film exceeds 1.0, the ellipticity on the short wavelength side of the elliptically polarizing plate provided with the horizontally aligned liquid crystal cured film deteriorates. If the ellipticity of the elliptically polarizing plate deteriorates on the short wavelength side and deviates from 1.0, the function as an elliptically polarizing plate when viewed from the front on the short wavelength side tends to be impaired. The “ReA (450) / ReA (550)” is preferably 0.75 to 0.92, more preferably 0.77 to 0.87, and still more preferably 0.79 to 0.85.

The in-plane retardation value of the horizontally aligned liquid crystal cured film can be adjusted by the thickness of the horizontally aligned liquid crystal cured film. Since the in-plane retardation value is determined by the following formula (24), a desired in-plane retardation value (ReA (λ): in-plane retardation value of the horizontally aligned liquid crystal cured film at the wavelength λ (nm)) is obtained. In order to obtain this, the three-dimensional refractive index and the film thickness dA may be adjusted. The three-dimensional refractive index depends on the molecular structure and orientation state of the polymerizable liquid crystal compound described later.
ReA (λ) = (nxA (λ) −nyA (λ)) × dA (24)
[In the formula, the refractive index ellipsoid formed by the horizontally aligned liquid crystal cured film has a relationship of nxA (λ)> nyA (λ) ≈nzA (λ), where nxA (λ) is for light of wavelength λ (nm). It represents the main refractive index in the direction parallel to the horizontal alignment liquid crystal cured film plane. nyA (λ) is a refractive index ellipsoid formed by the horizontally aligned liquid crystal cured film with respect to light of wavelength λ (nm), is parallel to the horizontal aligned liquid crystal cured film plane, and is in the direction of nxA (λ). Represents the refractive index in the direction orthogonal to the direction. dA represents the thickness of the horizontally aligned liquid crystal cured film. ]

  The horizontally aligned liquid crystal cured film is preferably a polymer of a composition containing the polymerizable liquid crystal compound in an aligned state as described above. The polymerizable liquid crystal compound forming the horizontally aligned liquid crystal cured film is a liquid crystal compound having a polymerizable functional group, particularly a photopolymerizable functional group. The photopolymerizable functional group refers to a group that can participate in a polymerization reaction by an active radical or an acid generated from a photopolymerization initiator. Examples of the photopolymerizable functional group include a vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, and oxetanyl group. Among them, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable. The liquid crystalline property may be a thermotropic liquid crystal or a lyotropic liquid crystal, and the phase order structure may be a nematic liquid crystal or a smectic liquid crystal.

  In the present invention, the polymerizable liquid crystal compound has the following formula (I) from the viewpoint of satisfying the relationship of the above formulas (21) and (22) or (31) and (32) described later, which develops reverse wavelength dispersion.

で表される化合物が好ましい。

The compound represented by these is preferable.

  In formula (I), Ar represents a divalent aromatic group which may have a substituent. The aromatic group referred to here is a group having a planar structure having a planarity, and the number of π electrons of the ring structure is [4n + 2] according to the Hückel rule. Here, n represents an integer. In the case where a ring structure is formed by including a heteroatom such as -N = or -S-, the case where the Huckel's rule is satisfied including the non-covalent electron pair on the heteroatom and the aromatic structure is included is also included. The divalent aromatic group preferably contains at least one of a nitrogen atom, an oxygen atom and a sulfur atom.

G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group.
Here, the hydrogen atom contained in the divalent aromatic group or divalent alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or carbon. The carbon atom constituting the divalent aromatic group or divalent alicyclic hydrocarbon group which may be substituted with an alkoxy group of 1 to 4 groups, a cyano group or a nitro group is an oxygen atom or a sulfur atom Alternatively, it may be substituted with a nitrogen atom.

L ¹ , L ² _, B ¹ and B ² are each independently a single bond or a divalent linking group.

k and l each independently represent an integer of 0 to 3 and satisfy the relationship of 1 ≦ k + 1. Here, when 2 ≦ k + 1, B ¹ and B ² , G ¹ and G ² may be the same or different from each other.

E ¹ and E ² each independently represents an alkanediyl group having 1 to 17 carbon atoms, wherein a hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, The —CH ₂ — contained may be substituted with —O—, —S—, or —Si—. P ¹ and P ² each independently represent a polymerizable group or a hydrogen atom, and at least one 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. 1,4-cyclohexanediyl group optionally 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 1 substituted with a methyl group , 4-phenylenediyl group, unsubstituted 1,4-phenylenediyl group, or unsubstituted 1,4-trans-cyclohexanediyl group, particularly preferably unsubstituted 1,4-phenylenediyl group or A substituted 1,4-trans-cyclohexanediyl group. In addition, at least one of a plurality of G ¹ and G ² is preferably a divalent alicyclic hydrocarbon group, and at least one of G ¹ and G ² bonded to L ¹ or L ^2. More preferably, it is a divalent alicyclic hydrocarbon group.

L ¹ and L ² are preferably 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—. Here, R ^{a1 to} R ^a8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ^c and R ^d each represent 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 preferably 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 each independently represent 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 are each independently more preferably a single bond, —O—, —CH ₂ CH ₂ —, —COO—, —COOCH ₂ CH ₂ —, —OCO—, or OCOCH ₂ CH ₂ —. is there.

  k and l are preferably in the range of 2 ≦ k + l ≦ 6 from the viewpoint of expression of inverse wavelength dispersion, preferably k + l = 4, and more preferably k = 2 and l = 2. It is more preferable that k = 2 and l = 2 because a symmetrical structure is obtained.

E ¹ and E ² are each independently preferably an alkanediyl group having 1 to 17 carbon atoms, and more preferably an alkanediyl group having 4 to 12 carbon atoms.

Examples of the polymerizable group represented by P ¹ or P ² include an epoxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, and oxiranyl. Group, oxetanyl group, and the like. Among these, 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.

  Ar preferably 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 furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazole ring, triazine ring, pyrroline ring, imidazole ring, pyrazole ring. , Thiazole ring, benzothiazole ring, thienothiazole ring, oxazole ring, benzoxazole ring, phenanthrolin ring, and the like. Among these, it is preferable to have a thiazole ring, a benzothiazole ring, or a benzofuran ring, and it is more preferable to have a benzothiazole group. In addition, when Ar includes a nitrogen atom, the nitrogen atom preferably has π electrons.

In formula (I), the total number N _π of π electrons contained in the divalent aromatic group represented by Ar is preferably 8 or more, more preferably 10 or more, still more preferably 14 or more, particularly Preferably it is 16 or more. Moreover, Preferably it is 30 or less, More preferably, it is 26 or less, More preferably, it is 24 or less.

  Examples of the aromatic group represented by Ar include the following groups.

In formula (Ar-1) to formula (Ar-22), * represents a linking part, and Z ⁰ , Z ¹ and Z ² are each independently a hydrogen atom, a halogen atom, or an alkyl having 1 to 12 carbon atoms. Group, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, alkylsulfonyl group having 1 to 12 carbon atoms, carboxyl group, fluoroalkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 6 carbon atoms, C1-C12 alkylthio group, C1-C12 N-alkylamino group, C2-C12 N, N-dialkylamino group, C1-C12 N-alkylsulfamoyl group or carbon The N, N-dialkylsulfamoyl group represented by Formula 2 to 12 is represented.

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 represents 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 represents an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group.

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

Examples of the aromatic hydrocarbon group for Y ¹ , Y ² and Y ³ include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group. A naphthyl group is preferred, and a phenyl group is more preferred. The aromatic heterocyclic group has 4 to 20 carbon atoms and contains at least one hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group, or a benzothiazolyl group. An aromatic heterocyclic group is mentioned, and a furyl group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group are preferable.

Y ¹ and Y ² 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 group derived from a condensed polycyclic aromatic heterocyclic group or an aggregate of aromatic rings.

Z ⁰ , Z ¹ and Z ² are each independently preferably 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. 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.

Q ¹ and Q ² are preferably —NH—, —S—, —NR ^{2 ′} —, and —O—, and R ^{2 ′} is preferably a hydrogen atom. Among them, -S-, -O-, and -NH- are particularly preferable.

  Among formulas (Ar-1) to (Ar-22), formula (Ar-6) and formula (Ar-7) are preferred from the viewpoint of molecular stability.

In formulas (Ar-16) to (Ar-22), 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 the aromatic heterocyclic ring that Ar may have, for example, pyrrole ring, imidazole ring, pyrroline ring, pyridine ring, pyrazine ring, pyrimidine ring, indole Ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring and the like. This aromatic heterocyclic group may have a substituent. Y ¹ may be the above-described polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group which may be substituted together with the nitrogen atom to which it is bonded and Z ⁰ . For example, a benzofuran ring, a benzothiazole ring, a benzoxazole ring, etc. are mentioned. In addition, the compound represented by the said formula (I) can be manufactured according to the method as described in Unexamined-Japanese-Patent No. 2010-31223, for example.

  The polymerizable liquid crystal compounds can be used alone or in combination of two or more. When two or more kinds are used in combination, the content of the compound represented by the formula (I) is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, further preferably 100 parts by mass of the polymerizable liquid crystal compound. Is 80 parts by mass or more.

  A composition for forming a horizontally aligned liquid crystal cured film used for forming a horizontally aligned liquid crystal cured film (hereinafter also referred to as a polymerizable liquid crystal composition) is a solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, and a leveling agent. Further, an adhesion improver can be further included. These additives can be used alone or in combination of two or more.

  Content of a polymeric liquid crystal compound is 70-99.5 mass parts with respect to 100 mass parts of solid content of a polymeric liquid crystal composition, for example, Preferably it is 80-99 mass parts, More preferably, 90- 98 parts by mass. If content is in the said range, there exists a tendency for the orientation of a horizontal alignment liquid crystal cured film to become high. Here, solid content means the total amount of the component remove | excluding the solvent from the composition.

  As the solvent, a solvent capable of dissolving the polymerizable liquid crystal compound is preferable, and a solvent inert to the polymerization reaction of the polymerizable liquid crystal compound is preferable. Examples of the solvent include alcohols such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether. Solvent; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone, etc. Ketone solvent; aliphatic hydrocarbon solvent such as pentane, hexane and heptane; fat such as ethylcyclohexane Aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, anisole and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; dimethylacetamide, dimethylformamide, Examples thereof include amide solvents such as N-methyl-2-pyrrolidone (NMP) and 1,3-dimethyl-2-imidazolidinone. These solvents can be used alone or in combination of two or more. However, since the compound represented by the formula (I) generally has a relatively large conjugated system, its solubility in a solvent is low. Among the solvents exemplified above, an alcohol solvent, an ester solvent, a ketone solvent, a chlorine-containing solvent, an ether It is preferable to use a system solvent, an amide solvent, and an aromatic hydrocarbon solvent, and it is more preferable to use an ester solvent, a ketone solvent, a chlorine-containing solvent, an ether solvent, or an amide solvent.

  The content of the solvent is preferably 50 to 98 parts by weight, more preferably 70 to 95 parts by weight with respect to 100 parts by weight of the polymerizable liquid crystal composition. Therefore, the solid content in 100 parts by mass of the composition is preferably 2 to 50 parts by mass. When the solid content of the composition is 50 parts by mass or less, since the viscosity of the composition becomes low, the thickness of the horizontally aligned liquid crystal cured film becomes substantially uniform, and the unevenness in the horizontally aligned liquid crystal cured film tends to hardly occur. is there. The solid content can be appropriately determined in consideration of the thickness of the horizontally aligned liquid crystal cured film to be manufactured.

  The polymerization initiator is a compound capable of generating a reactive species by the contribution of heat or light and initiating a polymerization reaction such as a polymerizable liquid crystal. Examples of the reactive species include active species such as radicals, cations, and anions. Among these, from the viewpoint of easy reaction control, a photopolymerization initiator in which the reaction proceeds by light irradiation is preferable.

Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. Examples of the photoradical polymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, triazine compounds, and the like. Examples of photocationic polymerization initiators include aromatic diazonium salts and aromatic compounds. Onium salts such as group iodonium salts and aromatic sulfonium salts, and iron-arene complexes.
Specifically, Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (Inc. ), Sequol BZ, Sequol Z, Sequol BEE (manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 (Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (Dow), Adekaoptomer SP- 152, Adekaoptomer SP-170, Adekaoptomer N-1717, Adekaoptomer N-1919, Adeka Arcles NCI-831, Adeka Arcles NC -930 (above, manufactured by ADEKA Corporation), TAZ-A, TAZ-PP (above, manufactured by Nippon Shibel Hegner) and TAZ-104 (produced by Sanwa Chemical Co., Ltd.), Kayrad (registered trademark) series (Nippon Kayaku Co., Ltd.) ), Cyracure UVI series (manufactured by Dow Chemical Co., Ltd.), CPI series (manufactured by San Apro Co., Ltd.), TAZ, BBI and DTS (manufactured by Midori Chemical Co., Ltd.), RHODORSIL (registered trademark) (manufactured by Rhodia Co., Ltd.), etc. Can be mentioned. A photoinitiator can be used individually or in combination of 2 or more types. Among these, from the viewpoint of easy reaction control, a photo radical polymerization initiator that generates radicals by light irradiation is preferable.

  The photopolymerization initiator preferably has a maximum absorption wavelength in the range of 300 nm to 400 nm, preferably in the range of 300 nm to 380 nm, from the viewpoint that it can fully utilize the energy emitted from the light source and is excellent in productivity. Is more preferable. From the same viewpoint, α-acetophenone polymerization initiators and oxime photopolymerization initiators are preferred.

  Examples of the α-acetophenone polymerization initiator include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2. -Benzylbutan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, and the like, more preferably 2-methyl-2- And morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one. Examples of commercially available products of α-acetophenone compounds include Irgacure 369, 379EG, 907 (above, manufactured by BASF Japan Ltd.), Sequol BEE (manufactured by Seiko Chemical Co., Ltd.), and the like.

  The oxime photopolymerization initiator generates radicals when irradiated with light. Polymerization of the polymerizable liquid crystal compound in the deep part of the horizontally aligned liquid crystal cured film suitably proceeds by this radical. Moreover, it is preferable to use the photoinitiator which can utilize the ultraviolet-ray with a wavelength of 350 nm or more efficiently from a viewpoint of making a polymerization reaction in the deep part of a horizontal alignment liquid crystal cured film progress more efficiently. As a photopolymerization initiator capable of efficiently using ultraviolet rays having a wavelength of 350 nm or more, a triazine compound or an oxime ester type carbazole compound is preferable, and an oxime ester type carbazole compound is more preferable from the viewpoint of sensitivity. Examples of the oxime ester type carbazole compound include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like. Commercially available oxime ester type carbazole compounds include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, manufactured by BASF Japan Ltd.), Adekaoptomer N-1919, Adeka Arcles NCI-831 (or more ADEKA Co., Ltd.).

  The addition amount of the photopolymerization initiator is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. It is. If it is in the said range, reaction of a polymeric group will fully advance and it will be hard to disturb the orientation of a polymeric liquid crystal compound.

  By blending a polymerization inhibitor, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. Polymerization inhibitors include hydroquinones having substituents such as hydroquinone and alkyl ethers; catechols having substituents such as alkyl ethers such as butylcatechol; pyrogallols, 2,2,6,6-tetramethyl-1- And radical scavengers such as piperidinyloxy radical; thiophenols; β-naphthylamines and β-naphthols. In order to polymerize the polymerizable liquid crystal compound without disturbing the alignment of the polymerizable liquid crystal compound, the content of the polymerization inhibitor is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. Yes, preferably 0.1-5 parts by mass, more preferably 0.1-3 parts by mass. A polymerization inhibitor can be used individually or in combination of 2 or more types.

  Furthermore, the sensitivity of the photopolymerization initiator can be increased by using a photosensitizer. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone; anthracene having a substituent such as anthracene and alkyl ether; phenothiazine; and rubrene. A photosensitizer can be used individually or in combination of 2 or more types. Content of a photosensitizer is 0.01-10 mass parts normally with respect to 100 mass parts of polymeric liquid crystal compounds, Preferably it is 0.05-5 mass parts, More preferably, it is 0.1-10 mass parts. 3 parts by mass.

  The leveling agent is an additive having a function of adjusting the fluidity of the polymerizable liquid crystal composition and making the layer obtained by applying the composition more flat, for example, a silicone system such as a silane coupling agent and the like. Examples include polyacrylate-based and perfluoroalkyl-based leveling agents. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all are manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE- 502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBE-585, KBM-80 , KBM-802, KBM-803, KBE-846, KBE-9007 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (and above) , All by Momentive Performance Materials Japan LLC), Fluorinert (registered trademark) FC-72, FC-40, FC-43, FC-3283 (all above, all made by Sumitomo 3M), Megafuck (registered trademark) R-08, R-30, R-90, F-410, F-411, F-443, F-445, F-470, F-477, F-479, F-482, F-483 (all of which are DIC ( )), Ftop (trade name) EF301, EF303, EF351, EF351, EF352 (all manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Surflon (registered trademark) S-381, S-382, S -383, S-393, SC-101, SC-105, KH-40, SA-100 (all are manufactured by AGC Seimi Chemical Co., Ltd.), trade names E1830, E5844 (Daikin Fine Chemical Co., Ltd.) Laboratories), BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (all trade names: manufactured by BM Chemie). Leveling agents can be used alone or in combination of two or more.

  0.01-5 mass parts is preferable with respect to 100 mass parts of polymerizable liquid crystal compounds, and, as for content of a leveling agent, 0.05-3 mass parts is more preferable. It is preferable that the content of the leveling agent is within the above range because the obtained horizontal alignment liquid crystal cured film tends to be smoother.

  The polymerizable liquid crystal composition can be obtained by stirring the polymerizable liquid crystal compound and components other than the polymerizable liquid crystal compound such as an additive at a predetermined temperature.

  The horizontally aligned liquid crystal cured film is formed by applying the polymerizable liquid crystal composition onto a horizontal alignment film described later, then removing the solvent, and heating and / or activating the polymerizable liquid crystal composition containing the aligned polymerizable liquid crystal compound. It can be obtained by curing with energy rays.

  Examples of the method for applying the polymerizable liquid crystal composition on the horizontal alignment film (hereinafter sometimes referred to as application method A) include, for example, extrusion coating method, direct gravure coating method, reverse gravure coating method, CAP coating method, and slit coating method. , Micro gravure method, die coating method, ink jet method and the like. Moreover, the method of apply | coating using coaters, such as a dip coater, a bar coater, a spin coater, etc. are mentioned. Among these, in the case of continuous application in the Roll to Roll format, an application method by a micro gravure method, an inkjet method, a slit coating method, or a die coating method is preferable.

  Examples of the method for removing the solvent (hereinafter sometimes referred to as “solvent removal method A”) include natural drying, ventilation drying, heat drying, reduced pressure drying, and a combination thereof. Of these, natural drying or heat drying is preferable. The drying temperature is preferably in the range of 0 to 200 ° C, more preferably in the range of 20 to 150 ° C, and still more preferably in the range of 50 to 130 ° C. The drying time is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes.

  The active energy rays to be irradiated include the type of polymerizable liquid crystal compound (particularly the type of photopolymerizable functional group possessed by the polymerizable liquid crystal compound), the type of photopolymerization initiator when it contains a photopolymerization initiator, and those It is appropriately selected according to the amount of Specifically, one or more kinds of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays can be used. Among them, ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction and that a photopolymerization apparatus widely used in this field can be used. It is preferable to select the kind of the liquid crystalline compound.

  Examples of the light source of the active energy ray include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, and a wavelength range. Examples include LED light sources that emit light of 380 to 440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like.

The ultraviolet irradiation intensity is usually 10 to 3,000 mW / cm ² . The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activating the photocationic polymerization initiator or the photoradical polymerization initiator. The time for irradiating light is usually 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, and further preferably 0.1 second to 1 minute. is there.
When irradiating once or a plurality of times with such ultraviolet irradiation intensity, the integrated light quantity is 10 to 3,000 mJ / cm ² , preferably 50 to 2,000 mJ / cm ² , more preferably 100 to 1,000 mJ / cm ² . ² . When the integrated light quantity is less than or equal to the above lower limit, curing of the polymerizable liquid crystal compound becomes insufficient, and good transferability may not be obtained. On the contrary, when the integrated light quantity is equal to or more than the above upper limit, the retardation film with an optical compensation function including the horizontally aligned liquid crystal cured film may be colored.

  The thickness of the horizontally aligned liquid crystal cured film is preferably 5 μm or less, more preferably 3 μm or less, and further preferably 2.5 μm or less, from the viewpoint of thinning the functional film. Further, the lower limit of the thickness of the horizontally aligned liquid crystal cured film is preferably 0.1 μm or more, more preferably 0.5 μm or more, and further preferably 1.0 μm or more. The thickness of the horizontally aligned liquid crystal cured film can be measured using an ellipsometer or a contact-type film thickness meter.

[Horizontal alignment film]
The alignment film is a film having an alignment regulating force for aligning the polymerizable liquid crystal compound of the liquid crystal cured film in a predetermined direction. Examples of the alignment treatment necessary for developing the alignment regulating force include rubbing treatment, photo-alignment treatment, and light irradiation treatment. Various orientations such as vertical orientation, horizontal orientation, hybrid orientation, and tilt orientation can be controlled depending on the type of alignment film, rubbing conditions, and light irradiation conditions. Among these, the horizontal alignment film is an alignment film having an alignment regulating force for aligning the polymerizable liquid crystal compound of the liquid crystal cured film in the horizontal direction. For this reason, a horizontal alignment liquid crystal film can be formed by using a horizontal alignment film.

  The alignment film preferably has a solvent resistance that does not dissolve when the polymerizable liquid crystal composition is applied or the like, and has heat resistance in heat treatment for removing the solvent or aligning the polymerizable liquid crystal compound.

  Examples of the horizontal alignment film showing the alignment regulating force for aligning the horizontally aligned liquid crystal cured film in the horizontal direction include a rubbing alignment film, a photo alignment film, and a groove alignment film having a concavo-convex pattern and a plurality of grooves on the surface. For example, when applying to a long roll-shaped film, a photo-alignment film is preferable in that the alignment direction can be easily controlled.

  A rubbing alignment film is usually formed by applying a composition containing an orientation polymer and a solvent (hereinafter also referred to as a rubbing alignment film forming composition) onto a substrate, etc., and removing the solvent to form a coating film. The orientation regulating force can be applied by rubbing the coating film.

  Examples of the orientation polymer include polyamides and gelatins having an amide bond, polyimides having an imide bond, and polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene having imide bonds. , Polyvinyl pyrrolidone, polyacrylic acid and polyacrylic acid esters. These orientation polymers can be used alone or in combination of two or more.

  The concentration of the alignment polymer in the composition for forming a rubbing alignment film may be in a range in which the alignment polymer is completely dissolved in the solvent. The content of the orientation polymer is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the composition.

  The composition for forming a rubbing alignment film can be obtained from the market. Examples of commercially available products include San Ever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.), Optmer (registered trademark, manufactured by JSR).

  As the solvent, for example, the solvent exemplified in the section of the horizontally aligned liquid crystal cured film can be used. Examples of the method for applying the rubbing alignment film forming composition to a substrate or the like include the application method A, and examples of the method for removing the solvent include the solvent removal method A.

  Examples of the rubbing treatment include a method in which a rubbing cloth is wound and the coating film is brought into contact with a rotating rubbing roll. If masking is performed when the rubbing treatment is performed, a plurality of regions (patterns) having different orientation directions can be formed in the alignment film.

  For the photo-alignment film, a composition containing a polymer or monomer having a photoreactive group and a solvent (also referred to as a composition for forming a photo-alignment film) is usually applied on a base material, etc. Preferably, it is obtained by irradiation with polarized UV). The photo-alignment film can arbitrarily control the direction of the alignment regulating force by selecting the polarization direction of the polarized light to be irradiated.

  The photoreactive group refers to a group that generates alignment ability when irradiated with light. Specific examples include groups that are involved in photoreactions that are the origin of alignment ability, such as alignment-induced reactions, isomerization reactions, photodimerization reactions, photocrosslinking reactions, or photodecomposition reactions of molecules generated by light irradiation. As the photoreactive group, an unsaturated bond, particularly a group having a double bond is preferable, and a carbon-carbon double bond (C = C bond), a carbon-nitrogen double bond (C = N bond), and nitrogen-nitrogen. A group having at least one selected from the group consisting of a 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 stilbazole group, a stilbazolium group, a chalcone group, and a cinnamoyl group. Examples of the photoreactive group having a C═N bond include groups having a structure such as an aromatic Schiff base and an aromatic hydrazone. Examples of the photoreactive group 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 the photoreactive group 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, and a halogenated alkyl group.

  A group involved in the photodimerization reaction or the photocrosslinking reaction is preferable in terms of excellent orientation. Among them, a photoreactive group involved in the photodimerization reaction is preferable, and a cinnamoyl group is preferable in that a photoalignment film having a relatively small amount of polarized light irradiation necessary for alignment and having excellent thermal stability and stability over time can be easily obtained. And chalcone groups are preferred. As the polymer having a photoreactive group, a polymer having a cinnamoyl group in which the terminal portion of the polymer side chain has a cinnamic acid structure or a cinnamic acid ester structure is particularly preferable.

  Content of the polymer or monomer which has a photoreactive group can be adjusted with the kind of polymer or monomer, and the thickness of the target photo-alignment film | membrane, and is at least 0.00 with respect to 100 mass parts of compositions for photo-alignment film formation. It is preferable to set it as 2 mass parts or more, and the range of 0.3-10 mass parts is more preferable.

  As the solvent, for example, the solvent exemplified in the section of the horizontally aligned liquid crystal cured film can be used. Examples of the method for applying the composition for forming a photo-alignment film on a substrate and the like include the application method A, and examples of the method for removing the solvent include the solvent removal method A.

  In order to irradiate polarized light, for example, it may be in the form of irradiating polarized light directly to a composition obtained by removing a solvent from a composition for forming a photo-alignment film applied on a substrate or the like. The polarized light is preferably substantially parallel light. The wavelength of the polarized light to be irradiated should be in a wavelength range where the photoreactive group of the polymer or monomer having the photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) having a wavelength in the range of 250 to 400 nm is particularly preferable. Examples of the light source for irradiating the polarized light include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF and ArF, and the like. Among these, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, and a metal halide lamp are preferable because of high emission intensity of ultraviolet rays having a wavelength of 313 nm. By irradiating light from the light source through an appropriate polarizing element, polarized UV light can be irradiated. Examples of the polarizing element include a polarizing prism such as a polarizing filter, Glan Thompson, and Grand Taylor, and a wire grid. Among these, a wire grid type polarizing element is preferable from the viewpoint of an increase in area and resistance to heat.

  Note that a plurality of regions (patterns) having different liquid crystal alignment directions can be formed by performing masking when performing rubbing or polarized light irradiation.

  The groove alignment film is a film having a concavo-convex pattern or a plurality of grooves (grooves) on the film surface. When a polymerizable liquid crystal compound is applied to a film having a plurality of linear grooves arranged at equal intervals, liquid crystal molecules are aligned in a direction along the groove.

  As a method for obtaining a groove alignment film, a method of forming a concavo-convex pattern by performing development and rinsing after exposure through an exposure mask having a pattern-shaped slit on the photosensitive polyimide film surface, a plate having grooves on the surface A method of forming a layer of a UV curable resin before curing on a sheet-shaped master, transferring the formed resin layer to a base material, etc., and curing, and a UV curable resin before curing formed on the base material, etc. For example, a method in which a roll-shaped master having a plurality of grooves is pressed against the film to form irregularities and then cured is used.

  The composition for forming a horizontal alignment film such as the composition for forming a rubbing alignment film and the composition for forming a photo-alignment film can contain additives exemplified in the section of the horizontal alignment liquid crystal cured film in addition to the solvent. .

  The thickness of the horizontal alignment film is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.3 μm or less, from the viewpoint of thinning the retardation film with an optical compensation function. The film thickness of the horizontal alignment film is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, and particularly preferably 30 nm or more. The film thickness of the horizontal alignment film can be measured using an ellipsometer or a contact-type film thickness meter.

[Vertical alignment liquid crystal cured film]
The horizontally aligned liquid crystal cured film is a film having refractive index anisotropy in a direction perpendicular to the film plane, and is made of a polymer containing a polymerizable liquid crystal compound. The vertical alignment liquid crystal cured film is formed by a method in which a polymerizable liquid crystal composition is applied on the vertical alignment film, and the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound in an alignment state is polymerized by heating and / or light irradiation. It is preferable to perform this because the thickness of the vertically aligned liquid crystal cured film and the wavelength dispersion characteristics can be arbitrarily designed.

  The three-dimensional refractive index ellipsoid formed by the vertically aligned liquid crystal cured film may have biaxiality, but preferably has uniaxiality. The vertically aligned liquid crystal cured film may be a vertically aligned liquid crystal cured film made of a polymer of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound in a state of being aligned in a direction perpendicular to the plane of the liquid crystal cured film, It may be a hybrid alignment liquid crystal cured film or a tilt alignment liquid crystal cured film. Refractive indices nx, ny and nz in three directions in the refractive index ellipsoid formed by the alignment of the polymerizable liquid crystal are nz> nx≈ny (referred to as positive C plate) or nz <nx≈ny (referred to as negative C plate). It may have the relationship. nx represents a main refractive index in a direction parallel to the plane of the vertically aligned liquid crystal cured film in the refractive index ellipsoid formed by the vertically aligned liquid crystal cured film. ny represents a refractive index in a direction parallel to the plane of the vertically aligned liquid crystal cured film and perpendicular to the direction of nx in the refractive index ellipsoid formed by the vertically aligned liquid crystal cured film. When nx = ny, nx can take an arbitrary direction within the plane of the vertically aligned liquid crystal cured film. nz represents the refractive index in the direction perpendicular to the plane of the vertically aligned liquid crystal cured film in the refractive index ellipsoid formed by the vertically aligned liquid crystal cured film.

  The vertically aligned liquid crystal cured film may be either a rod-like polymerizable liquid crystal or a disk-like polymerizable liquid crystal, but is preferably a rod-like polymerizable liquid crystal. When the rod-like polymerizable liquid crystal forms a vertically aligned liquid crystal cured film, the vertically aligned liquid crystal cured film becomes a positive C plate.

When the vertically aligned liquid crystal cured film is a positive C plate, RthC (λ), which is a retardation value in the thickness direction with respect to light having a wavelength of λ nm, exhibits an optical characteristic represented by the following formula (31). It is preferable to satisfy. Moreover, it is also preferable to satisfy | fill the optical characteristic shown by following formula (32) and Formula (33). It is more preferable that the vertically aligned liquid crystal cured film satisfies the optical characteristics represented by the following formula (31), the following formula (32), and the following formula (33).
−100 nm ≦ RthC (550) ≦ −50 nm (31)
(In the formula, RthC (550) represents a retardation value in the thickness direction with respect to light having a wavelength of 550 nm.
)
RthC (450) / RthC (550) ≦ 1.0 (32)
1.00 ≦ RthC (650) / RthC (550) (33)
(Where RthC (450) is the thickness direction retardation value for light of wavelength 450 nm, RthC (550) is the thickness direction retardation value for light of wavelength 550 nm, and RthC (650) is for light of wavelength 650 nm. Represents the retardation value in the thickness direction.)

  When the retardation value RthC (550) in the thickness direction of the vertically aligned liquid crystal cured film exceeds the range of the formula (31), the display is obliquely applied with an elliptically polarizing plate with an optical compensation function including a retardation plate with an optical compensation function. This may cause a problem that the hue of the color becomes red or blue. A more preferable range of the retardation value in the thickness direction is −95 nm ≦ RthC (550) ≦ −55 nm, and a more preferable range is −90 nm ≦ RthC (550) ≦ −60 nm. When “RthC (450) / RthC (550)” of the vertically aligned liquid crystal cured film exceeds 1.0, when viewed from the oblique side on the short wavelength side of the elliptical polarizing plate provided with the vertically aligned liquid crystal cured film The ellipticity is worse. When the ellipticity of the elliptically polarizing plate deteriorates on the short wavelength side and becomes smaller than 1.0, the function as the elliptically polarizing plate tends to be impaired on the short wavelength side. “RthC (450) / RthC (550)” is preferably 0.75 to 0.92, more preferably 0.77 to 0.87, and still more preferably 0.79 to 0.85.

The retardation value in the thickness direction of the vertically aligned liquid crystal cured film can be adjusted by the thickness of the vertically aligned liquid crystal cured film. Since the retardation value in the thickness direction is determined by the following equation (34), the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a desired thickness direction retardation value (RthC (λ): wavelength λ (nm)) Value) can be obtained by adjusting the three-dimensional refractive index and the film thickness dC. The three-dimensional refractive index depends on the molecular structure and orientation of the polymerizable liquid crystal compound described later.
RthC (λ) = [(nxC (λ) + nyC (λ)) / 2−nzC (λ)] × dC (34)
(In the formula, the refractive index ellipsoid formed by the vertically aligned liquid crystal cured film has a relationship of nzC (λ)> nxC (λ) ≈nyC (λ), where nzC (λ) is the vertically aligned liquid crystal cured film. Represents the refractive index in the direction perpendicular to the plane of the vertically aligned liquid crystal cured film with respect to light of wavelength λ (nm), and nxC (λ) is the refractive index formed by the vertically aligned liquid crystal cured film. In the ellipsoid, nyC (λ) represents the maximum refractive index in the direction parallel to the plane of the vertical alignment liquid crystal cured film with respect to light having a wavelength λ (nm), and nyC (λ) represents the refractive index ellipsoid formed by the vertical alignment liquid crystal cured film. The refractive index for light having a wavelength λ (nm) parallel to the plane of the vertically aligned liquid crystal cured film and perpendicular to the nxC direction is expressed as nxC (λ) = nyC (λ) NxC (λ) is vertical alignment It represents any direction of the refractive index parallel to the crystal cured film plane. Here, dC represents the thickness of the vertical alignment liquid crystal cured layer.)

  The vertically aligned liquid crystal cured film is preferably a polymer of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound in a vertically aligned state as described above. The polymerizable liquid crystal compound forming the vertically aligned liquid crystal cured film is a liquid crystal compound having a polymerizable functional group, particularly a photopolymerizable functional group. The photopolymerizable functional group refers to a group that can participate in a polymerization reaction by an active radical or an acid generated from a photopolymerization initiator. Examples of the photopolymerizable functional group include a vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, and oxetanyl group. Among them, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable. The liquid crystalline property may be a thermotropic liquid crystal or a lyotropic liquid crystal, and the phase order structure may be a nematic liquid crystal or a smectic liquid crystal.

  As the polymerizable liquid crystal compound used for forming the vertically aligned liquid crystal cured film, the compound represented by the above formula (I) is preferably used. By using the compound represented by the formula (I), reverse wavelength dispersibility is exhibited, and the relationship of the above (31) and (32) can be satisfied.

  The polymerizable liquid crystal compounds used in the vertically aligned liquid crystal cured film can be used alone or in combination of two or more. When two or more kinds are used in combination, the content of the compound represented by the formula (I) is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, further preferably 100 parts by mass of the polymerizable liquid crystal compound. Is 80 parts by mass or more.

  The composition for forming a vertically aligned liquid crystal cured film used for the vertically aligned liquid crystal cured film (hereinafter also referred to as a polymerizable liquid crystal composition) is a solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, and an adhesion. A property improver may be further included. These additives can be used alone or in combination of two or more.

  Content of a polymeric liquid crystal compound is 70-99.5 mass parts with respect to 100 mass parts of solid content of a polymeric liquid crystal composition, for example, Preferably it is 80-99 mass parts, More preferably, 90- 98 parts by mass. If content is in the said range, there exists a tendency for the orientation of a vertical alignment liquid crystal cured film to become high. Here, solid content means the total amount of the component remove | excluding the solvent from the composition.

  As the solvent, a solvent capable of dissolving the polymerizable liquid crystal compound is preferable, and a solvent inert to the polymerization reaction of the polymerizable liquid crystal compound is preferable. As the solvent, the same solvents as those used for the composition for forming a horizontally aligned liquid crystal cured film can be used.

  The content of the solvent is preferably 50 to 98 parts by weight, more preferably 70 to 95 parts by weight with respect to 100 parts by weight of the polymerizable liquid crystal composition. Therefore, the solid content in 100 parts by mass of the composition is preferably 2 to 50 parts by mass. When the solid content of the composition is 50 parts by mass or less, since the viscosity of the composition becomes low, the thickness of the vertically aligned liquid crystal cured film becomes substantially uniform, and unevenness tends not to occur in the vertically aligned liquid crystal cured film. is there. The solid content can be appropriately determined in consideration of the thickness of the vertically aligned liquid crystal cured film to be produced.

  The polymerization initiator is a compound capable of generating a reactive species by the contribution of heat or light and initiating a polymerization reaction such as a polymerizable liquid crystal. Examples of the reactive species include active species such as radicals, cations, and anions. Among these, from the viewpoint of easy reaction control, a photopolymerization initiator in which the reaction proceeds by light irradiation is preferable. As the photopolymerization initiator, the same initiator as that used in the composition for forming a horizontally aligned liquid crystal cured film can be used.

  The addition amount of the photopolymerization initiator is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. It is. If it is in the said range, reaction of a polymeric group will fully advance and it will be hard to disturb the orientation of a polymeric liquid crystal compound.

  By blending a polymerization inhibitor, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. As the polymerization inhibitor, those similar to those used in the composition for forming a horizontally aligned liquid crystal cured film can be used. In order to polymerize the polymerizable liquid crystal compound without disturbing the alignment of the polymerizable liquid crystal compound, the content of the polymerization inhibitor is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. Yes, preferably 0.1-5 parts by mass, more preferably 0.1-3 parts by mass. A polymerization inhibitor can be used individually or in combination of 2 or more types.

  Furthermore, the sensitivity of the photopolymerization initiator can be increased by using a photosensitizer. As the photosensitizer, those similar to those used for the composition for forming a horizontally aligned liquid crystal cured film can be used. Content of a photosensitizer is 0.01-10 mass parts normally with respect to 100 mass parts of polymeric liquid crystal compounds, Preferably it is 0.05-5 mass parts, More preferably, it is 0.1-10 mass parts. 3 parts by mass.

  The leveling agent is an additive having a function of adjusting the fluidity of the polymerizable liquid crystal composition and flattening the layer obtained by applying the composition, and is used for a composition for forming a horizontally aligned liquid crystal cured film. Similar to those that can be used.

  0.01-5 mass parts is preferable with respect to 100 mass parts of polymerizable liquid crystal compounds, and, as for content of a leveling agent, 0.05-3 mass parts is more preferable. It is preferable that the content of the leveling agent is within the above range because the obtained vertical alignment liquid crystal cured film tends to be smoother.

  The polymerizable liquid crystal composition used for forming the vertically aligned liquid crystal cured film can be obtained by stirring the polymerizable liquid crystal compound and components other than the polymerizable liquid crystal compound such as an additive at a predetermined temperature.

  In the vertically aligned liquid crystal cured film, the polymerizable liquid crystal composition is applied onto the vertical alignment film described later, then the solvent is removed, and the polymerizable liquid crystal composition containing the aligned polymerizable liquid crystal compound is heated and / or activated. It can be obtained by curing with energy rays.

  The method for applying the polymerizable liquid crystal composition onto the vertical alignment film can be the same as that used for forming the horizontal alignment liquid crystal cured film.

  The method for removing the solvent can be the same as that used for forming the horizontally aligned liquid crystal cured film.

  The active energy rays to be irradiated include the type of polymerizable liquid crystal compound (particularly the type of photopolymerizable functional group possessed by the polymerizable liquid crystal compound), the type of photopolymerization initiator when it contains a photopolymerization initiator, and those It is appropriately selected according to the amount of Specifically, one or more kinds of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays can be used. Among them, ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction and that a photopolymerization apparatus widely used in this field can be used. It is preferable to select the kind of the liquid crystalline compound.

  As the light source of the active energy ray, the same light source as that used when forming a horizontally aligned liquid crystal cured film can be used.

The ultraviolet irradiation intensity is usually 10 to 3,000 mW / cm ² . The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activating the photocationic polymerization initiator or the photoradical polymerization initiator. The time for irradiating light is usually 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, and further preferably 0.1 second to 1 minute. is there.
When irradiating once or a plurality of times with such ultraviolet irradiation intensity, the integrated light quantity is 10 to 3,000 mJ / cm ² , preferably 50 to 2,000 mJ / cm ² , more preferably 100 to 1,000 mJ / cm ² . ² . When the integrated light quantity is less than or equal to the above lower limit, curing of the polymerizable liquid crystal compound becomes insufficient, and good transferability may not be obtained. On the contrary, when the integrated light quantity is not less than the above upper limit, the retardation plate with an optical compensation function including the vertically aligned liquid crystal cured film may be colored.

The thickness of the vertically aligned liquid crystal cured film is preferably 3 μm or less, more preferably 2 μm or less, and further preferably 1.5 μm or less, from the viewpoint of thinning the functional film. Further, the lower limit of the thickness of the vertically aligned liquid crystal cured film is preferably 0.1 μm or more, more preferably 0.3 μm or more, and further preferably 0.5 μm or more. The thickness of the vertically aligned liquid crystal cured film can be measured using an ellipsometer or a contact-type film thickness meter.
[Vertical alignment film]

  The alignment film is a film having an alignment regulating force for aligning the polymerizable liquid crystal compound of the liquid crystal cured film in a predetermined direction. Various orientations such as vertical orientation, horizontal orientation, hybrid orientation, and tilt orientation can be controlled depending on the type of alignment film, rubbing conditions, and light irradiation conditions. Among these, the vertical alignment film is an alignment film having an alignment regulating force for aligning the polymerizable liquid crystal compound of the liquid crystal cured film in the vertical direction. For this reason, a vertical alignment liquid crystal film can be formed by using a vertical alignment film.

  As the vertical alignment film, it is preferable to apply a material that lowers the surface tension of the surface of a substrate or the like. Examples of such materials include the above-mentioned orientation polymers such as polyimides, polyamides, polyamic acids that are hydrolyzed products thereof, fluorine-based polymers such as perfluoroalkyl, silane compounds, and polysiloxane compounds obtained by a condensation reaction thereof. Is mentioned. For the vertical alignment film, a composition containing such a material and a solvent, for example, the solvent exemplified in the section of the vertical alignment liquid crystal film (hereinafter also referred to as a composition for forming a vertical alignment film) is applied on a substrate or the like. After removal of the solvent, the coating film can be obtained by heating or the like.

  In the case of using a silane compound for the vertical alignment film, the vertical alignment film is composed of Si element and C element as constituent elements from the viewpoint of easily reducing the surface tension and improving the adhesion with the layer adjacent to the vertical alignment film. The film | membrane which consists of a compound containing is preferable, and a silane compound can be used conveniently. In the present invention, when a vertical alignment film is disposed between a horizontal alignment liquid crystal cured film and a vertical alignment liquid crystal cured film, high adhesion between the vertical alignment film, the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film is expressed. In the phase difference plate with an optical compensation function, peeling at the interface between the layers can be effectively suppressed or prevented.

  As the silane compound, silicones such as the above-mentioned silane coupling agents can be suitably applied. For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2- Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3- Dimethyl-butylidene) propylamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-Chloropropyltrimeth Sisilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3 -Glycidoxypropyl ethoxydimethylsilane etc. are mentioned.

  The silane compound may be of a silicone monomer type or a type silicone oligomer (polymer) type. When the silicone oligomer is shown in the form of (monomer)-(monomer) copolymer, 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercapto Mercaptopropyl group-containing copolymers such as propyltriethoxysilane-tetramethoxysilane copolymer and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane- Tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer, and mercaptomethyltriethoxysilane-tetrae A copolymer containing a mercaptomethyl group, such as a xysilane copolymer; 3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane- Tetramethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyl Oxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, And copolymers containing methacryloyloxypropyl groups, such as 3-methacryloxyyl propylmethyldiethoxysilane-tetraethoxysilane copolymer; 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane -Tetraethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3- Acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxy Copolymers containing acryloyloxypropyl groups, such as propylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer; vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxy Silane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldi Ethoxysilane-tetramethoxysilane copolymer and vinylmethyldiethoxysilane-tetrae Vinyl group-containing copolymers such as xyloxysilane copolymers; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymers, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymers, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymers 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetra Amino group-containing copolymers such as methoxysilane copolymer and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer And the like. A silane compound can be used individually or in combination of 2 or more types. Moreover, the silane coupling agent etc. which may be used also as a leveling agent can also be used.

  Among these, a silane compound having an alkyl group at the molecular end is preferable, and a silane compound having an alkyl group having 3 to 30 carbon atoms is more preferable.

  From the viewpoint of easily improving adhesion, from the viewpoint of applicability of the composition for forming a vertically aligned liquid crystal cured film, and from the viewpoint of difficulty in dissolving a layer disposed in the lower layer in the method of producing a retardation plate with an optical compensation function described later Therefore, the vertical alignment film is preferably a film made of a compound containing Si element, C element and O element as constituent elements. Moreover, the number of carbon atoms of the substituent containing a C atom bonded to the Si atom of the silane compound forming the vertical alignment film, preferably an alkyl group or an alkoxy group, is preferably 1-30, more preferably 2-25, Preferably it is 3-20. That is, the ratio of Si element to C element (Si / C, molar ratio) is preferably 0.03 to 1.00, more preferably 0.04 to 0.50, and still more preferably 0.05 to 0.00. 33. When the Si / C ratio is not less than the above lower limit, the applicability of the composition for forming a vertically aligned liquid crystal cured film is improved, and when the Si / C ratio is not more than the above upper limit, the adhesion with an adjacent layer is improved. it can.

  As the solvent, for example, the solvent exemplified in the section of the horizontally aligned liquid crystal cured film can be used. Examples of the method for applying the composition for forming a vertical alignment film include the application method A, and examples of the method for removing the solvent include the solvent removal method A.

  In addition to the solvent, the composition for forming a vertical alignment film can contain additives exemplified in the section of the horizontally aligned liquid crystal cured film.

  The thickness of the vertical alignment film is preferably 1 μm or less, more preferably 0.3 μm or less, and even more preferably 0.1 μm or less, from the viewpoints of thinning the retardation plate with an optical compensation function and expressing the alignment regulating force. is there. The thickness of the vertical alignment film is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, and particularly preferably 30 nm or more. The film thickness of the vertical alignment film can be measured using an ellipsometer or a contact-type film thickness meter.

〔Base material〕
The base material is used when applying the alignment film forming composition or the liquid crystal cured film forming composition, and even if the base material is designed to peel off the base material and transfer the film applied onto the base material. Either of the designs can be applied because the adhesion to the substrate is imparted and transfer is not possible, but from the viewpoint of thinning, a design that can be transferred to the transfer target and peeled off the substrate is preferable. Examples of the substrate as described above include a glass substrate and a film substrate. From the viewpoint of workability, a film substrate is preferable, and a long roll film is more preferable in that it can be produced continuously. Examples of the resin constituting the film substrate include polyolefins such as polyethylene, polypropylene, norbornene polymers, cyclic olefin resins, polyvinyl alcohol, polyethylene terephthalate, polymethacrylates, polyacrylates, triacetylcellulose, and diacetylcellulose. And cellulose esters such as cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; and plastics such as polyphenylene sulfide and polyphenylene oxide. The surface of the base material may be subjected to a release treatment such as silicone treatment. Examples of the commercially available cellulose ester base material include “Fujitac Film” (manufactured by Fuji Photo Film Co., Ltd.); “KC8UX2M”, “KC8UY” and “KC4UY” (manufactured by Konica Minolta Opto Co., Ltd.). Such a resin can be formed into a substrate by known methods such as a solvent casting method and a melt extrusion method.

  Commercially available cyclic olefin-based resins include “Topas” (registered trademark) (manufactured by Ticona (Germany)), “Arton” (registered trademark) (manufactured by JSR Corporation), “ZEONOR” (registered trademark), “ZEONEX” (registered trademark) (manufactured by Nippon Zeon Co., Ltd.) and “Apel” (registered trademark) (manufactured by Mitsui Chemicals, Inc.) can be mentioned. Commercially available cyclic olefin resin base materials can also be used. Commercially available cyclic olefin-based resin base materials include “Essina” (registered trademark), “SCA40” (registered trademark) (manufactured by Sekisui Chemical Co., Ltd.), “Zeonor Film” (registered trademark) (manufactured by Optes Corporation). ) And “Arton Film” (registered trademark) (manufactured by JSR Corporation).

  The substrate preferably has a thickness that facilitates laminating a horizontal alignment liquid crystal cured film, a horizontal alignment film, a vertical alignment liquid crystal cured film, or a vertical alignment film and is easy to peel off. The thickness of such a substrate is usually 5 to 300 μm, preferably 20 to 200 μm.

[Phase difference plate with optical compensation function]
The retardation plate with an optical compensation function of the present invention includes a horizontal alignment liquid crystal cured film, a horizontal alignment film or a vertical alignment film, and a vertical alignment liquid crystal cured film in this order, and satisfies the requirements (1) to (4) described below. It is preferable to satisfy.
The interlayer distance between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film is 5 μm or less. ... (1)
A horizontal alignment film or a vertical alignment film is included between the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film. ... (2)
The following relational expression ReA (450) / ReA (550) <1.00 (3)
To meet.
Here, ReA (λ) represents the in-plane retardation value at the wavelength λ nm of the horizontally aligned liquid crystal cured film. The definition of the phase difference value is as follows.
ReA (λ) = (nxA−nyA) × dA
However, nxA is the main refractive index in the film plane of the horizontally aligned liquid crystal cured film, nyA is the refractive index in the direction orthogonal to the same plane as nxA, and dA is the thickness of the horizontally aligned liquid crystal cured film.
The following relational expression RthC (450) / RthC (550) <1.00
To meet. ... (4)
Here, RthC (λ) represents the thickness direction retardation value of the vertically aligned liquid crystal cured film at the wavelength λ nm. The definition of the phase difference value is as follows.
RthC (λ) = ((nxC + nyC) / 2−nzC) × dC
However, nxC is the main refractive index in the film plane of the vertically aligned liquid crystal cured film, nyC is the refractive index in the direction orthogonal to the same plane as nxC, nzC is the refractive index in the thickness direction of the vertically aligned liquid crystal cured film, and dC is The film thickness of vertical alignment liquid crystal curing is shown.

When nxC = nyC, nxC can be a refractive index in an arbitrary direction within the film plane.
Further, the interlayer distance between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film is preferably 5 μm or less, more preferably 1 μm or less, still more preferably 0.5 μm or less, particularly preferably 0.3 μm or less, as represented by the formula (1). It is. The film thickness of the horizontal alignment film is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, and particularly preferably 30 nm or more.

The retardation film with an optical compensation function preferably satisfies the following relational expression (5). The value of | R0 (550) −R40 (550) | is the amount of light leakage near an oblique wavelength of 550 nm when an elliptically polarizing plate with an optical compensation function using a retardation plate with an optical compensation function is applied to a display. Smaller is better because it decreases. The value of | R0 (550) -R40 (550) | is preferably less than 10 nm, more preferably 5 nm or less, still more preferably 4 nm or less, and particularly preferably 3 nm or less.
| R0 (550) -R40 (550) | <10 nm (5)
Here, R0 (λ) represents an in-plane retardation value of a retardation plate with an optical compensation function including a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film. R40 is a direction plate (phase fast axis direction) orthogonal to the main refractive index direction in the film plane in the retardation film with an optical compensation function including a horizontal alignment liquid crystal cured film and a vertical alignment liquid crystal cured film. The apparent phase difference value is shown only when rotated around 40 °.

The retardation film with an optical compensation function preferably satisfies the following relational expression (6). The value of | R0 (450) −R40 (450) | is the amount of light leakage around an oblique wavelength of 450 nm when an elliptically polarizing plate with an optical compensation function using a retardation plate with an optical compensation function is applied to a display. Smaller is better because it decreases. The value of | R0 (450) −R40 (450) | is preferably less than 10 nm, more preferably 5 nm or less, still more preferably 4 nm or less, and particularly preferably 3 nm or less.
| R0 (450) -R40 (450) | <10 nm (6)
However, R0 (λ) represents an in-plane retardation value of a retardation plate with an optical compensation function including a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film. R40 is a direction plate (phase fast axis direction) orthogonal to the main refractive index direction in the film plane in the retardation film with an optical compensation function including a horizontal alignment liquid crystal cured film and a vertical alignment liquid crystal cured film. The apparent phase difference value is shown only when rotated around 40 °.

Furthermore, it is preferable that the difference between the values represented by the relational expressions (5) and (6) satisfies the following relational expression (7).
| {R0 (450) -R40 (450)}-{R0 (550) -R40 (550)} | <3 nm (7)
When satisfying the relational expression (7), the front and oblique reflection hues when the elliptically polarizing plate with the optical compensation function using the retardation plate with the optical compensation function is applied to the display are preferably black. The value of (7) is 3 nm or less, more preferably 2 nm or less, still more preferably 1 nm or less.

  Also, when the difference in average refractive index of each layer, that is, the difference between the average refractive index of each layer constituting the retardation plate with an optical compensation function of the present invention and the average refractive index of other layers adjacent to the layer is large. In some cases, light leakage may occur due to the influence of interface reflection between layers. The difference in average refractive index of each layer at a wavelength of 550 nm is preferably 0.20 or less, more preferably 0.15 or less, still more preferably 0.10 or less, and particularly preferably 0.05 or less. Within this range, occurrence of light leakage due to interface reflection can be suppressed.

Specifically, as the difference in average refractive index of each layer,
(1) The difference between the average refractive index of the horizontal alignment liquid crystal cured film and the average refractive index of the vertical alignment liquid crystal cured film,
(2) When a horizontal alignment film is included between the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film,
(2-a) difference between the average refractive index of the horizontal alignment liquid crystal cured film and the average refractive index of the horizontal alignment film,
(2-b) difference between the average refractive index of the horizontal alignment film and the average refractive index of the vertically aligned liquid crystal cured film,
(3) When a vertical alignment film is included between the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film,
(3-a) difference between the average refractive index of the horizontal alignment liquid crystal cured film and the average refractive index of the vertical alignment film,
(3-b) difference between the average refractive index of the vertical alignment film and the average refractive index of the vertical alignment liquid crystal cured film,
Etc.

  The retardation film with an optical compensation function of the present invention can include a layer other than a horizontal alignment liquid crystal cured film, a horizontal alignment film, a vertical alignment liquid crystal cured film, and a vertical alignment film. A liquid crystal cured film, another alignment film, a protective layer, etc. are mentioned. Examples of the other alignment liquid crystal cured film include the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film exemplified above, and examples of the other alignment film include the alignment film exemplified above.

  The protective layer is usually an acrylic oligomer or polymer composed of polyfunctional acrylate (methacrylate), urethane acrylate, polyester acrylate, epoxy acrylate, etc., polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl pyrrolidone, starches, methylcellulose, carboxy It is preferably formed from a composition for forming a protective layer containing a water-soluble polymer such as methylcellulose and sodium alginate and a solvent.

  Examples of the solvent contained in the composition for forming a protective layer include the same solvents as those exemplified above. Among them, at least one solvent selected from the group consisting of water, an alcohol solvent, and an ether solvent serves as the protective layer. It is preferable at the point which does not dissolve the layer to form. Examples of the alcohol solvent include methanol, ethanol, butanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether. Examples of the ether solvent include ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. Of these, ethanol, isopropyl alcohol, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferable.

The thickness of the protective layer is 0.1 μm to 10 μm, more preferably 0.1 μm to 3 μm.
[Method of manufacturing retardation plate with optical compensation function]

  The method for producing a retardation film with an optical compensation function of the present invention is not particularly limited as long as it is a method capable of laminating a horizontal alignment liquid crystal cured film, a horizontal alignment film or a vertical alignment film, and a vertical alignment liquid crystal cured film in this order, A method of laminating a horizontal alignment film on a substrate, then laminating a horizontal alignment liquid crystal cured film, further laminating a vertical alignment film, and then laminating a vertical alignment liquid crystal cured film (hereinafter referred to as production method A) or A method of laminating a vertical alignment film on a material, then laminating a vertical alignment liquid crystal cured film, further laminating a horizontal alignment film, and then laminating a horizontal alignment liquid crystal cured film (hereinafter referred to as production method B) is preferred. As a method of laminating the horizontal alignment liquid crystal cured film, horizontal alignment film, vertical alignment liquid crystal cured film, and vertical alignment film, the above-described method for forming each layer can be used.

  When a retardation plate with an optical compensation function is manufactured by the manufacturing method A or the manufacturing method B, alignment defects or alignment defects may occur due to the alignment of the liquid crystal cured film disposed in the lower layer. That is, in the case of the manufacturing method A, since the horizontal alignment liquid crystal cured film is laminated on the lower layer and then the vertical alignment liquid crystal cured film is laminated, the influence of the lower horizontal alignment liquid crystal cured film is formed when forming the vertical alignment liquid crystal cured film. In the case of manufacturing method B, a vertically aligned liquid crystal cured film is laminated on the lower layer and then a horizontally aligned liquid crystal cured film is laminated. When forming a cured film, alignment defects and alignment defects may occur due to the influence of the underlying vertically aligned liquid crystal cured film. Therefore, a composition used for forming each layer to be laminated (a composition for forming a horizontal alignment film, a composition for forming a horizontal alignment liquid crystal film, a composition for forming a vertical alignment film, a composition for forming a vertical alignment liquid crystal film) Depending on the type of solvent, the lower layer may be dissolved, resulting in changes in optical characteristics, alignment defects, alignment defects, and the like. Therefore, the material, solvent, solid content concentration, coating method, film thickness, and the like contained in the composition used to form each layer to be laminated must be selected as appropriate.

[Ellipse polarizing plate with optical compensation function]
The retardation plate with an optical compensation function of the present invention is optically bonded by being laminated with a substrate to be transferred and peeled off the substrate, or laminated with an adhesive or the like in a state with the substrate. The function of the retardation film with a compensation function, that is, the optical characteristics thereof can be imparted to the transferred material, and an optical laminate having the optical characteristics of the retardation film with an optical compensation function can be produced. Among these, when laminated with a polarizing plate, an elliptically polarizing plate with an optical compensation function can be produced. In the embodiment of the present invention, it is preferable to laminate so that the slow axis (optical axis) of the horizontally aligned liquid crystal cured film and the absorption axis of the polarizing plate are substantially 45 °. By laminating the slow axis (optical axis) of the optical film of the present invention and the absorption axis of the polarizing plate so as to be substantially 45 °, a function as a circularly polarizing plate can be obtained. Note that substantially 45 ° is usually in the range of 45 ± 5 °.

[Transfer]
As an object to be transferred, an optical film having a single layer structure, for example, a polarizing plate, a retardation plate, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, a condensing film, etc., an optical film having a multilayer structure, for example, a retardation A plate, an elliptically polarizing plate are mentioned, Among these, a phase difference plate, a phase difference plate, a polarizing plate, and an elliptical polarizing plate can be used conveniently. The optical laminate in the present invention is an image display device, for example, 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 (an electric field emission display device ( FED etc.), surface field emission display (SED)), electronic paper (display using electronic ink or electrophoretic element), plasma display, projection display (grating light valve (GLV) display, digital micro It can be used for a display device having a mirror device (DMD), a piezoelectric ceramic display, and the like, and can be suitably used particularly for an organic EL display device, a touch panel display device, and the like.

[Polarizer]
The polarizing plate is made of a polarizer having a polarizing function. Examples of the polarizer include a stretched film in which a dye having absorption anisotropy is adsorbed, or a film in which a dye having absorption anisotropy is applied and oriented. Examples of the dye having absorption anisotropy include a dichroic dye.

  A stretched film on which a dye having absorption anisotropy is adsorbed is usually a step of uniaxially stretching a polyvinyl alcohol resin film, and the dichroic dye is dyed by dying the polyvinyl alcohol resin film. It is manufactured through a step of adsorbing, a step of treating a polyvinyl alcohol-based resin film adsorbed with a dichroic dye with an aqueous boric acid solution, and a step of washing with water after the treatment with an aqueous boric acid solution. A polarizing plate is obtained by laminating the thus obtained polarizer and a transparent protective film. Examples of the dichroic dye include iodine and dichroic organic dyes. Examples of the dichroic organic dye include dichroic direct dyes composed of disazo compounds such as C.I. DIRECT RED 39, and dichroic direct dyes composed of compounds such as trisazo and tetrakisazo. As described above, the thickness of a polarizer obtained by subjecting a polyvinyl alcohol resin film to uniaxial stretching, dyeing with a dichroic dye, boric acid treatment, water washing and drying is preferably 5 μm to 40 μm.

[Adhesive]
Examples of the adhesive include pressure-sensitive adhesives, dry-solidifying adhesives, and chemically reactive adhesives. Examples of the chemically reactive adhesive include an active energy ray curable adhesive.

  The pressure-sensitive adhesive usually contains a polymer and may contain a solvent. Examples of the polymer include acrylic polymers, silicone polymers, polyesters, polyurethanes, and polyethers. Among them, acrylic pressure-sensitive adhesives containing acrylic polymers have excellent optical transparency, moderate wettability and cohesive strength, excellent adhesion, and high weather resistance and heat resistance. It is preferable because it does not easily float or peel off under humidifying conditions.

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

  The pressure-sensitive adhesive containing such a copolymer has excellent adhesiveness, and even when removed after being bonded to the transfer object, it is relatively easy to cause no adhesive residue on the transfer object. This is preferable because it can be removed. The glass transition temperature of the acrylic polymer is preferably 25 ° C. or less, and more preferably 0 ° C. or less. The mass average molecular weight of such an acrylic polymer is preferably 100,000 or more.

  As a solvent, the solvent etc. which were mentioned as the said solvent are mentioned. The pressure-sensitive adhesive may contain a light diffusing agent. The light diffusing agent is an additive that imparts light diffusibility to the pressure-sensitive adhesive and may be fine particles having a refractive index different from the refractive index of the polymer contained in the pressure-sensitive adhesive. Examples of the light diffusing agent include fine particles made of an inorganic compound and fine particles made of an organic compound (polymer). Since many of the polymers that the pressure-sensitive adhesive contains as an active ingredient, including acrylic polymers, have a refractive index of about 1.4 to 1.6, the light diffusing agent has a refractive index of 1.2 to 1.8. It is preferable to select appropriately. The refractive index difference between the polymer contained in the pressure-sensitive adhesive as an active ingredient and the light diffusing agent is usually 0.01 or more, and is preferably 0.01 to 0.2 from the viewpoint of the brightness and display properties of the display device. The fine particles used as the light diffusing agent are preferably spherical fine particles, or fine particles close to monodisperse, and more preferably fine particles having an average particle diameter of 2 to 6 μm. The refractive index is measured by a general minimum deviation method or Abbe refractometer.

  Examples of the fine particles made of an inorganic compound include aluminum oxide (refractive index 1.76) and silicon oxide (refractive index 1.45). Fine particles comprising an organic compound (polymer) include melamine beads (refractive index 1.57), polymethyl methacrylate beads (refractive index 1.49), methyl methacrylate / styrene copolymer resin beads (refractive index 1.50). To 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. Examples thereof include resin beads (refractive index: 1.46). The content of the light diffusing agent is usually 3 to 30 parts by mass with respect to 100 parts by mass of the polymer.

  The thickness of the pressure-sensitive adhesive is determined according to its adhesion and the like, and is not particularly limited, but is usually 1 μm to 40 μm. From the viewpoints of workability and durability, the thickness is preferably 3 μm to 25 μm, and more preferably 5 μm to 20 μm. By setting the thickness of the adhesive layer formed from the pressure-sensitive adhesive to 5 μm to 20 μm, the brightness of the display device when viewed from the front or obliquely is maintained, and blurring or blurring of the display image is prevented. It can be made difficult to occur.

  The dry-solidifying adhesive may contain a solvent. The dry-solidifying adhesive contains, as a main component, 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 urethane polymer. Examples include aldehydes, epoxy compounds, epoxy resins, melamine compounds, zirconia compounds, and compositions containing a curable compound such as 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, and an acrylamide. Examples include copolymers, saponified products of polyvinyl acetate, and polyvinyl alcohol resins.

  Examples of the polyvinyl alcohol resin 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. Can be mentioned. The content of the polyvinyl alcohol-based resin in the aqueous adhesive is usually 1 to 10 parts by mass, preferably 1 to 5 parts by mass with respect to 100 parts by mass of water.

Examples of the urethane resin include polyester ionomer type urethane resins.
The polyester ionomer type urethane resin here is a urethane resin having a polyester skeleton, and a resin in which a small amount of an ionic component (hydrophilic component) is introduced. Since such an ionomer type urethane resin is emulsified in water without using an emulsifier and becomes an emulsion, it can be an aqueous adhesive. When a polyester ionomer type urethane resin is used, it is effective to blend a water-soluble epoxy compound as a crosslinking agent.

  Examples of the epoxy resin include a polyamide epoxy resin obtained by reacting a polyalkylenepolyamine such as diethylenetriamine or triethylenetetramine with a dicarboxylic acid such as adipic acid and epichlorohydrin. Commercially available products of such polyamide epoxy resins include “Smiles Resin (registered trademark) 650” and “Smiles Resin 675” (manufactured by Sumika Chemtex Co., Ltd.), “WS-525” (manufactured by Nippon PMC Co., Ltd.). Etc. When mix | blending an epoxy resin, the addition amount is 1-100 mass parts normally with respect to 100 mass parts of polyvinyl alcohol-type resin, Preferably it is 1-50 mass parts.

  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, more preferably 0.01 to 0.5 μm. is there. When the adhesive layer formed from the dry-solidifying adhesive is too thick, the appearance is liable to be poor.

  The active energy ray-curable adhesive may contain a solvent. An active energy ray-curable adhesive is an adhesive that cures upon irradiation with active energy rays. Examples of the active energy ray-curable adhesive include a cationic polymerizable adhesive containing an epoxy compound and a cationic polymerization initiator, a radical polymerizable adhesive containing an acrylic curing component and a radical polymerization initiator, and an epoxy compound. Contains both a cationic polymerizable curing component such as an acrylic compound and a radical polymerizable curing component such as an acrylic compound, and further contains an adhesive containing a cationic polymerization initiator and a radical polymerization initiator, and these polymerization initiators. For example, an adhesive that is cured by irradiating an electron beam.

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

  Examples of the radical photopolymerization initiator and the cationic photopolymerization initiator include the aforementioned radical photopolymerization initiator and cationic photopolymerization initiator. Content of a radical polymerization initiator and a cationic polymerization initiator is 0.5-20 mass parts normally with respect to 100 mass parts of active energy ray hardening-type adhesives, Preferably it is 1-15 mass parts.

  The active energy ray-curable adhesive further contains an ion trap agent, an antioxidant, a chain transfer agent, a tackifier, a thermoplastic resin, a filler, a flow regulator, a plasticizer, an antifoaming agent, and the like. May be.

  In this specification, an active energy ray is defined as an energy ray capable of generating an active species by decomposing a compound that generates an active species. Examples of such active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays, and electron beams, and ultraviolet rays and electron beams are preferable. Preferable ultraviolet irradiation conditions are the same as the polymerization of the polymerizable liquid crystal compound described above.

  Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, “%” and “part” mean mass% and part by mass unless otherwise specified. In the following examples, the film thickness was measured using an ellipsometer M-220 manufactured by JASCO Corporation or a contact-type film thickness meter (MH-15M manufactured by Nikon, counter TC101, MS-5C). Further, the retardation value Rth (λ) in the thickness direction, the in-plane retardation value Re (λ), and the apparent retardation value R40 (λ) when measured from the 40 ° direction are Oji Scientific Instruments KOBRA-WPR, Or it measured and calculated using the ellipsometer M-220 by JASCO Corporation. The Si / C ratio can be calculated from elemental analysis of the vertical alignment film, measurement of surface constituent elements using X-ray photoelectric spectroscopy, or the structural formula of the compound used to form the vertical alignment film can be understood. Can be calculated from the structural formula. Moreover, AGF-B10 made from Kasuga Electric Co., Ltd. was used for the corona treatment apparatus. The corona treatment can be appropriately performed when the composition is applied to the substrate. Using the above corona treatment apparatus, the treatment was performed once under the conditions of an output of 0.3 kW and a treatment speed of 3 m / min.

[Example 1]
(Preparation of composition for forming horizontal alignment film)
A horizontal alignment film was prepared by mixing 5 parts (weight average molecular weight: 30000) and 95 parts of cyclopentanone (solvent) having the following structure as components and stirring the resulting mixture at 80 ° C. for 1 hour. A forming composition was obtained.

[Preparation of composition for forming vertical alignment film]
Silane coupling agent “KBE-9103” manufactured by Shin-Etsu Chemical Co., Ltd. is dissolved in a mixed solvent in which ethanol and water are mixed at a ratio of 9: 1 (mass ratio), and a vertical alignment film having a solid content of 0.5%. A forming composition was obtained.

[Preparation of horizontal alignment liquid crystal cured film forming composition and vertical alignment liquid crystal cured film forming composition]
1.0 parts of a leveling agent (F-556; manufactured by DIC) and polymerization start with respect to a mixture in which polymerizable liquid crystal compound A and polymerizable liquid crystal compound B shown below were mixed at a mass ratio of 90:10 6 parts of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (“Irgacure 369 (Irg369)”, manufactured by BASF Japan Ltd.) as an agent was added.

  Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%, and the mixture was stirred at 80 ° C. for 1 hour, whereby a composition for forming a horizontal alignment liquid crystal cured film, and a vertical alignment liquid crystal were obtained. A composition for forming a cured film was obtained.

  The polymerizable liquid crystal compound A was produced by the method described in JP 2010-31223 A. The polymerizable liquid crystal compound B was produced according to the method described in JP2009-173893A. Each molecular structure is shown below.

[Polymerizable liquid crystal compound A]

[Polymerizable liquid crystal compound B]

[Production of polarizing plate]
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 is immersed in pure water at 30 ° C., and then the mass ratio of iodine / potassium iodide / water is 0. Iodine dyeing was performed by immersing in an aqueous solution of 02/2/100 at 30 ° C. (iodine dyeing step). The polyvinyl alcohol film which passed through the iodine dyeing process was immersed in an aqueous solution having a mass ratio of potassium iodide / boric acid / water of 12/5/100 at 56.5 ° C. to perform boric acid treatment (boric acid treatment process). ). The polyvinyl alcohol film that had undergone the boric acid treatment step was washed with pure water at 8 ° C. and then dried at 65 ° C. to obtain a polarizer (thickness 27 μm after stretching) in which iodine was adsorbed and oriented on polyvinyl alcohol. . Under the present circumstances, it extended | stretched in the iodine dyeing process and the boric-acid treatment process. The total draw ratio in such drawing was 5.3 times. The obtained polarizer and a saponified triacetyl cellulose film (Konica Minolta KC4UYTAC 40 μm) were bonded together with a nip roll via an aqueous adhesive. While maintaining the tension of the obtained bonded product at 430 N / m, it was dried at 60 ° C. for 2 minutes to obtain a polarizing plate having a triacetyl cellulose film as a protective film on one side. The water-based adhesive is 100 parts of water, 3 parts of carboxyl group-modified polyvinyl alcohol (Kuraray, “Kuraray Poval KL318”), water-soluble polyamide epoxy resin (Sumika Chemtex, “Smiles Resin 650”, solid An aqueous solution having a partial concentration of 30%] was added to 1.5 parts.

  The optical characteristics of the obtained polarizing plate were measured. The measurement was carried out with a spectrophotometer (“V7100”, manufactured by JASCO Corporation) using the polarizer surface of the polarizing plate obtained above as an incident surface. The absorption axis of the polarizing plate coincides with the stretching direction of the polyvinyl alcohol, and the obtained polarizing plate has a visibility corrected single transmittance of 42.1%, a visibility corrected polarization degree of 99.996%, and a single hue a. -1.1, simple substance hue b was 3.7.

[Manufacture of a laminate comprising a substrate, a horizontal alignment film, and a horizontally aligned liquid crystal cured film]
After performing corona treatment on a COP film (ZF-14-50) manufactured by Nippon Zeon Co., Ltd., a composition for forming a horizontal alignment film was applied with a bar coater, dried at 80 ° C. for 1 minute, and a polarized UV irradiation device ( Using “SPOT CURE SP-9” (manufactured by Ushio Inc.), polarized UV exposure was carried out at an integrated light quantity of 100 mJ / cm ² at a wavelength of 313 nm and an axial angle of 45 °. When the film thickness of the obtained horizontal alignment film was measured with an ellipsometer, it was 100 nm.

Subsequently, the horizontal alignment liquid crystal cured film forming composition was applied to the horizontal alignment film using a bar coater, dried at 120 ° C. for 1 minute, and then subjected to a high-pressure mercury lamp (“Unicure VB-15201BY-A”, Ushio). By using UV light (accumulated light amount at a wavelength of 365 nm: 500 mJ / cm ² ) using an electric device, a horizontal alignment liquid crystal cured film is formed, and a base material, a horizontal alignment film, and a horizontal alignment are formed. A laminate composed of a liquid crystal cured film was obtained. The thickness of the horizontally aligned liquid crystal cured film was measured with an ellipsometer and found to be 2.3 μm.

[Re measurement of horizontally aligned liquid crystal cured film]
The in-plane retardation value ReA (λ) of the horizontally aligned liquid crystal cured film produced by the above method was bonded to glass via an adhesive, and then the COP as a substrate was peeled off, followed by a measuring machine (“KOBRA -WPR ", manufactured by Oji Scientific Instruments). The measurement results of the phase difference value ReA (λ) at each wavelength are ReA (450) = 121 nm, ReA (550) = 142 nm, ReA (650) = 146 nm, ReA (450) / ReA (550) = 0.85. there were.

[Manufacture of a laminate comprising a substrate, a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film]
After performing corona treatment on the laminate comprising the base material, the horizontal alignment film and the horizontal alignment liquid crystal cured film produced by the above-described method, the composition for forming the vertical alignment film was applied with a bar coater and 1 at 80 ° C. Dried for a minute to obtain a vertical alignment film. It was 50 nm when the film thickness of the obtained vertical alignment film was measured with the ellipsometer.

Further, a composition for forming a vertically aligned liquid crystal cured film was applied to the vertically aligned film using a bar coater and dried at 120 ° C. for 1 minute, and then a high pressure mercury lamp (“UNICURE VB-15201BY-A”, USHIO INC. By using UV light (cumulative light quantity at a wavelength of 365 nm: 500 mJ / cm ² ) using a company), a vertically aligned liquid crystal cured film is formed, and a substrate, a horizontal aligned film, and a horizontally aligned liquid crystal cured A laminate comprising a film, a vertical alignment film, and a vertically aligned liquid crystal cured film was obtained. The thickness of the vertically aligned liquid crystal cured film was measured by an ellipsometer and found to be 1.2 μm. The interlayer distance between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film was 50 nm. The constituent element ratio of the vertical alignment film was Si / C = 0.33.

[Rth measurement of vertically aligned liquid crystal cured film]
In order to measure Rth of the vertically aligned liquid crystal cured film, a vertical aligned film and a vertically aligned liquid crystal cured film are manufactured on a COP film (ZF-14-50) manufactured by Nippon Zeon Co., Ltd. in the same procedure as described above. A vertical alignment liquid crystal cured film is bonded to glass via an adhesive (pressure sensitive pressure sensitive adhesive 15 μm manufactured by Lintec Corporation), and after confirming that there is no phase difference in the COP, the angle of light incident on the sample is measured by an ellipsometer. The phase difference value was measured while changing. In addition, the average refractive index at wavelengths λ of 450 nm and 550 nm was measured using a refractometer (manufactured by Atago Co., Ltd., “Multiwave Abbe Refractometer DR-M4”). ReC calculated from the obtained film thickness, average refractive index, and ellipsometer measurement results are RthC (450) = − 63 nm and RthC (550) = − 73 nm, respectively, and RthC (450) / RthC (550). = 0.85.
[Measurement of R0 and R40 of laminated body (retard plate with optical compensation function) made of horizontal alignment liquid crystal cured film, vertical alignment film, vertical alignment liquid crystal cured film]

  A laminate comprising the substrate, the horizontal alignment film, the horizontal alignment liquid crystal cured film, the vertical alignment film, and the vertical alignment liquid crystal cured film produced by the above method is bonded to glass through an adhesive (pressure sensitive adhesive 15 μm manufactured by Lintec). After laminating and peeling the COP to prepare a measurement sample, after confirming that there is no phase difference between the horizontal alignment film and the vertical alignment film, the phase difference in the front direction of the phase difference plate with an optical compensation function The value R0 (λ) and the retardation value R40 (λ) when tilted by 40 ° around the fast axis of the horizontally aligned liquid crystal cured film were measured using KOBRA-WPR. From the values of R0 (λ) and R40 (λ) obtained, | R0 (550) -R40 (550) |, | R0 (450) -R40 (450) |, and | {R0 (450) -R40 (450 )}-{R0 (550) -R40 (550)} |

[Difference in in-plane average refractive index of each layer]
According to the above method, each layer was coated on glass, and the average refractive index of each layer was calculated using a refractometer (manufactured by Atago Co., Ltd., “Multiwave Abbe Refractometer DR-M4”) or an ellipsometer. It was confirmed that the in-plane average refractive index difference was 0.2 or less.

[Flexibility test]
A glass plate having a thickness of 0.7 mm is placed on the coating film side of the laminate comprising the substrate, the horizontal alignment film, the horizontal alignment liquid crystal cured film, the vertical alignment film, and the vertical alignment liquid crystal cured film prepared by the above method. The laminated body was bent 180 degrees so as to be bent, and then the bent portion was observed using a 10-fold magnifying glass through a fluorescent lamp to check for wrinkles and cracks. The results are shown in Table 1.

[Confirmation of reflection hue of bent part]
After performing corona treatment on the coating surface side of the laminate comprising the substrate, horizontal alignment film, horizontal alignment liquid crystal cured film, vertical alignment film, and vertical alignment liquid crystal cured film prepared by the above method, the absorption axis of the polarizing plate Is bonded to the polarizing plate produced by the above-described method through an adhesive so that the angle formed between the horizontal axis and the slow axis of the horizontal alignment film is 45 °, and the base material is peeled off and the elliptically polarized light with optical compensation function A plate was made. Then, it bonded to the aluminum foil through the adhesive, and it bent 180 degree | times so that it might become a radius of 1 cm at the polarizing plate side, and the reflective hue of the bending part was observed visually. The results are shown in Table 1.

(Examples 2 and 3)
A retardation plate with an optical compensation function was prepared in the same manner as in Example 1 except that the thickness of the vertical alignment film was changed as shown in Table 1, and the retardation value measurement, the flexibility test, and the reflection of the bent portion were performed. Hue confirmation was performed. The results are shown in Table 1.

Example 4
0.5% by weight of polyimide (“San Ever SE-610”, manufactured by Nissan Chemical Industries, Ltd.), 72.3% by weight of N-methyl-2-pyrrolidone, 18.1% by weight of 2-butoxyethanol, 9. 1% by weight of ethylcyclohexane and 0.01% by weight of DPHA (manufactured by Shin-Nakamura Chemical Co., Ltd.) were mixed to prepare a vertical alignment film forming composition B, and this vertical alignment film forming composition B was used. Except for the above, a retardation plate with an optical compensation function was prepared in the same manner as in Example 1, and the retardation value measurement, the flexibility test, and the reflection hue confirmation of the bent portion were performed. The results are shown in Table 1. In addition, it was 0.2 micrometer when the film thickness of the vertical alignment film was measured with the ellipsometer. From this, the interlayer distance between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film was 0.2 μm. Further, it was confirmed that the vertical alignment film was attacked by the solvent during the application of the composition for forming a vertical alignment liquid crystal cured film, and alignment defects and alignment defects were partially generated.

(Example 5)
The base material was changed to a polyethylene terephthalate film that had been subjected to a release treatment (SP-PLR382020, manufactured by Lintec Corporation, hereinafter abbreviated as “separator”), the stacking order was vertical alignment film, vertical alignment liquid crystal curing A phase difference plate with an optical compensation function is prepared in the same manner as in Example 1 except that the film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film are changed in this order, and the retardation value measurement, the flexibility test, and the reflection hue of the bent portion are performed. Confirmation was carried out. The results are shown in Table 1. In addition, it was 0.2 micrometer when the film thickness of the horizontal alignment film was measured with the ellipsometer. From this, the interlayer distance between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film was 0.2 μm.

(Examples 6 and 7)
Similar to Example 1, except that the values of RthC (450) and RthC (550) were changed as shown in Table 1 by changing the thickness of the vertically aligned liquid crystal cured film. A phase difference plate was prepared, and a phase difference value measurement, a flexibility test, and a reflection hue confirmation of a bent portion were performed. The results are shown in Table 1.

(Example 8)
Changing the composition for forming a vertically aligned liquid crystal cured film to the composition for forming a vertically aligned liquid crystal cured film (B) described below, drying after applying the composition for forming a vertically aligned liquid crystal cured film (B) A phase difference plate with an optical compensation function was prepared in the same manner as in Example 1 except that the temperature was changed from 120 ° C. to 80 ° C., and the retardation value measurement, the flexibility test, and the reflection hue confirmation of the bent portion were performed. Carried out. The results are shown in Table 1.

(Adjustment of composition for forming vertical alignment liquid crystal cured film (B))
To the liquid crystal compound LC242 described below: Paliocolor LC242 (registered trademark of BASF), 0.1 part of leveling agent F-556 and 3 parts of polymerization initiator Irg369 are added so that the solid content concentration becomes 13%. Cyclopentanone was added to to obtain a vertically aligned liquid crystal cured film forming composition (B). The name of the obtained liquid crystal composition is “Composition V”.
Liquid crystal compound LC242: Paliocolor LC242 (registered trademark of BASF)

(Comparative Example 1)
After a laminate of a horizontal alignment film and a horizontal alignment liquid crystal cured film was produced by the method described in Example 1, a vertical alignment film and a vertical alignment liquid crystal cured film laminate (Lintec Corporation) were separately prepared on the COP by the same method as in the example. Prepared). The obtained laminates were bonded using a pressure-sensitive adhesive (pressure-sensitive pressure-sensitive adhesive 15 μm manufactured by Lintec Corporation), and retardation measurement, flexibility test, and reflection hue confirmation of the bent portion were performed. The results are shown in Table 1.

Bending part reflection hue: ◯ for black, and x for obvious coloration.
Flexibility test: ◯ when no defect occurs, and x when defect such as wrinkles or cracks occurs.

By applying the manufacturing method of the present invention, a retardation plate with an optical compensation function capable of suppressing defects such as wrinkles and cracks generated when bent is obtained.

Claims (18)

A horizontal alignment film is formed through coating, drying, and alignment treatment steps.
Form a horizontal alignment liquid crystal cured film through coating, drying and ultraviolet irradiation processes,
Furthermore, a vertical alignment film is formed through a coating and drying process,
By forming a vertically aligned liquid crystal cured film through coating, drying, and ultraviolet irradiation processes,
A method of manufacturing a retardation film with an optical compensation function, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film are formed in this order. The method for producing a retardation plate with an optical compensation function according to claim 1, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film having a film thickness of 1.0 μm or less are formed in this order. The method for producing a retardation film with an optical compensation function according to claim 1, wherein a horizontal alignment film comprising a photo-alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film are formed in this order. . The phase difference with an optical compensation function according to claim 1, wherein a horizontal alignment film composed of a photo-alignment film containing a cinnamoyl group, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film are formed in this order. A manufacturing method of a board. The phase difference plate with an optical compensation function according to claim 1, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film having a thickness of 1.0 μm or less, and a vertical alignment liquid crystal cured film are formed in this order. Production method. The method for producing a retardation film with an optical compensation function according to claim 1, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film containing Si element, and a vertical alignment liquid crystal cured film are formed in this order. The horizontal alignment film, the horizontal alignment liquid crystal cured film, the vertical alignment film whose element of Si / C is 0.03 to 1.00, and the vertical alignment liquid crystal cured film are formed in this order. A method of manufacturing a retardation film with an optical compensation function. A method for producing a retardation film with an optical compensation function by forming a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film in this order, and the horizontal alignment liquid crystal cured film has the following relationship ( The manufacturing method of the phase difference plate with an optical compensation function in any one of Claims 1-7 which satisfy | fills 1).
ReA (450) / ReA (550) <1.00 (1)
In the formula, ReA (λ) represents an in-plane retardation value at a wavelength λ nm of the horizontally aligned liquid crystal cured film. The definition of the in-plane retardation value ReA (λ) is as follows.
ReA (λ) = (nxA (λ) −nyA (λ)) × dA
However, nxA (λ) is the main refractive index in the film plane of the horizontally aligned liquid crystal cured film, and nyA (λ) is in the same plane as nxA (λ). The refractive index in the orthogonal direction and the refractive index at the wavelength λ (nm), dA indicates the film thickness of horizontal alignment liquid crystal curing. A method of manufacturing a retardation film with an optical compensation function by forming a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film in this order, and the vertical alignment liquid crystal cured film has the following relationship ( The method for producing a retardation plate with an optical compensation function according to any one of claims 1 to 8, which satisfies 2).
RthC (450) / RthC (550) <1.00 (2)
In the formula, RthC (λ) represents a thickness direction retardation value of the vertically aligned liquid crystal cured film at a wavelength of λ nm. The definition of the phase difference value RthC (λ) is as follows.
RthC (λ) = ((nxC (λ) + nyC (λ)) / 2−nzC (λ)) × dC
However, nxC (λ) is the main refractive index in the film plane of the vertically aligned liquid crystal cured film, and the main refractive index at the wavelength λ (nm),
nyC (λ) is the refractive index in the direction orthogonal to nxC (λ) in the same plane, and the refractive index at the wavelength λ (nm),
nzC (λ) is the refractive index in the thickness direction of the vertically aligned liquid crystal cured film, and the refractive index at the wavelength λ (nm),
dC represents the film thickness of vertical alignment liquid crystal curing. Form a vertical alignment film through the coating and drying process,
Form a vertically aligned liquid crystal cured film through coating, drying, and UV irradiation processes,
Furthermore, a horizontal alignment film is formed through coating, drying and alignment treatment steps,
By forming a horizontal alignment liquid crystal cured film through the application, drying, ultraviolet irradiation process,
Method of manufacturing retardation film with optical compensation function, forming vertical alignment film, vertical alignment liquid crystal cured film, horizontal alignment film, horizontal alignment liquid crystal cured film in this order The method for producing a retardation plate with an optical compensation function according to claim 10, wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film having a film thickness of 1.0 μm or less, and a horizontal alignment liquid crystal cured film are formed in this order. The method for producing a retardation film with an optical compensation function according to claim 10 or 11, wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film composed of a photo alignment film, and a horizontal alignment liquid crystal cured film are formed in this order. The phase difference with an optical compensation function according to claim 10, wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film composed of a photo alignment film containing a cinnamoyl group, and a horizontal alignment liquid crystal cured film are formed in this order. A manufacturing method of a board. The retardation film with an optical compensation function according to claim 10, wherein a vertical alignment film having a film thickness of 1.0 μm or less, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film are formed in this order. Production method. The method for producing a retardation plate with an optical compensation function according to claim 10, wherein a vertical alignment film containing Si element, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film are formed in this order. The horizontal alignment film, the horizontal alignment liquid crystal cured film, the vertical alignment film whose element of Si / C is 0.03 to 1.00, and the vertical alignment liquid crystal cured film are formed in this order. A method of manufacturing a retardation film with an optical compensation function. A method of producing a retardation film with an optical compensation function by forming a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film in this order, and the horizontal alignment liquid crystal cured film has the following relationship ( The method for producing a retardation plate with an optical compensation function according to any one of claims 10 to 16, which satisfies 3).
ReA (450) / ReA (550) <1.00 (3)
In the formula, ReA (λ) represents an in-plane retardation value at a wavelength λ nm of the horizontally aligned liquid crystal cured film. The definition of the in-plane retardation value ReA (λ) is as follows.
ReA (λ) = (nxA (λ) −nyA (λ)) × dA
However, nxA (λ) is the main refractive index in the film plane of the horizontally aligned liquid crystal cured film and is the main refractive index at the wavelength λ (nm), and nyA (λ) is orthogonal to nxA (λ) in the same plane. The refractive index at the wavelength λ (nm), and dA represents the film thickness of horizontal alignment liquid crystal curing. A method of manufacturing a retardation film with an optical compensation function by forming a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film in this order, and the vertical alignment liquid crystal cured film has the following relationship ( The method for producing a retardation plate with an optical compensation function according to any one of claims 10 to 17, which satisfies 4).
RthC (450) / RthC (550) <1.00 (4)
In the formula, RthC (λ) represents a thickness direction retardation value of the vertically aligned liquid crystal cured film at a wavelength of λ nm. The definition of the phase difference value RthC (λ) is as follows.
RthC (λ) = ((nxC (λ) + nyC (λ)) / 2−nzC (λ)) × dC
However, nxC (λ) is the main refractive index in the film plane of the vertically aligned liquid crystal cured film, and the main refractive index at the wavelength λ (nm),
nyC (λ) is the refractive index in the direction orthogonal to nxC (λ) in the same plane, and the refractive index at the wavelength λ (nm),
nzC (λ) is the refractive index in the thickness direction of the vertically aligned liquid crystal cured film, and the refractive index at the wavelength λ (nm),
dC represents the film thickness of vertical alignment liquid crystal curing.