WO2019039287A1

WO2019039287A1 - Phase difference plate having optical compensation function for flexible display

Info

Publication number: WO2019039287A1
Application number: PCT/JP2018/029756
Authority: WO
Inventors: 辰昌葛西; 伸行幡中
Original assignee: 住友化学株式会社
Priority date: 2017-08-21
Filing date: 2018-08-08
Publication date: 2019-02-28
Also published as: TW201921000A; CN111033331B; JP2019035952A; CN111033331A; KR20200036928A; TWI780207B

Abstract

Provided is a method for manufacturing a phase difference plate having an optical compensation function for flexibility, the method being such that no crumples, cracks, or other such imperfections are produced even when the phase difference plate is bent, and no external light is reflected in a colored state even when the phase difference plate has been folded. This manufacturing method pertains to manufacturing a phase difference plate having an optical compensation function for a flexible display through a method that comprises: forming a horizontally oriented film through steps for application, drying, and orientation processing; subsequently forming a horizontally oriented liquid crystal cured film through steps for application, drying, and ultraviolet irradiation; furthermore forming a vertically oriented film through steps for application and drying; and forming a vertically oriented liquid crystal cured film through steps for application, drying, and ultraviolet irradiation; the horizontally oriented film, the horizontally oriented liquid crystal cured film, the vertically oriented film, and the vertically oriented liquid crystal cured film being formed in the stated order.

Description

Retardation plate with optical compensation function for flexible display

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

Flat panel displays such as organic EL image display devices usually have a flat image display surface. The image display surface of the flat panel display was in a flat state as it was when displaying or not displaying an image.

Retardation plates are often used in such flat panel displays. 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 electrodes constituting the image display device.

A retardation plate exhibiting reverse wavelength dispersion is preferable for such a retardation plate in that it exhibits equivalent retardation performance in a wide wavelength range of visible light. As a retardation plate exhibiting reverse wavelength dispersion, there is known a retardation plate formed of a horizontally aligned liquid crystal cured film obtained by polymerizing and curing the polymerizable liquid crystal compound exhibiting reverse wavelength dispersion in a state of being aligned in the horizontal direction.

In addition, also when viewed from an oblique direction, a retardation plate with an optical compensation function is also required which has a function of performing compensation so as to exert the same optical performance as when viewed from the front direction. Patent Document 1 [Japanese Patent Laid-Open No. 2015-163935] further includes a vertically aligned 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 as a functional retardation plate. No. 11] has been proposed. The same 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, the document only discloses that the retardation plate with an optical compensation function described in the document can be used for a flat panel display.

Unexamined-Japanese-Patent No. 2015-163935

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

However, if defects such as wrinkles and cracks occur when folded, when the flexible display is again spread and an image is displayed, parts of defects such as wrinkles and cracks become defects and the displayed image is damaged. In addition, when the image is folded with the image displayed, the folded portion substantially reduces the elevation angle (the angle between the film plane and the direction in which the viewer looks at the screen), so the optical performance is not sufficiently compensated. It is also a problem to reflect external light in the state of

Therefore, an object of the present invention is to provide a retardation plate with an optical compensation function for flexible which does not cause problems such as wrinkles and cracks even when bent and does not reflect external light in a colored state even when folded. To develop.

As a result of intensive studies 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 UV irradiation processes,
Further, 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 steps,
A manufacturing method of a retardation plate with an optical compensation function which forms 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.

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

[3] The optical compensation function according to any one of the above [1] to [2], wherein a horizontal alignment film made of 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 Method of manufacturing a retardation plate.

[4] The horizontal alignment film comprising a photoalignment film containing a cinnamoyl group, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film according to any one of the above [1] to [3] Manufacturing method of retardation plate with optical compensation function.

[5] The optical compensation according to any one of the above [1] to [4], wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film with a film thickness of 1.0 μm or less, and a vertical alignment liquid crystal cured film are formed in this order. Method of manufacturing a retardation plate with a function.

[6] The optical compensation function according to any one of the above [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. Method of manufacturing a phase difference plate.

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

[8] A method of manufacturing a retardation 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 having an optical compensation function according to any one of the above [1] to [7], which satisfies the relationship (1).
ReA (450) / ReA (550) <1.00 (1)
In formula, ReA ((lambda)) shows the in-plane phase difference value in wavelength (lambda) nm of a horizontal alignment liquid crystal cured film. The definition of the in-plane retardation value ReA (λ) is as follows.
ReA (λ) = (nxA (λ) -nyA (λ)) × dA
Where nxA (λ) is the main refractive index in the film plane of the horizontal alignment liquid crystal cured film, and the main refractive index at wavelength λ (nm) is nyA (λ) in the same plane as nxA (λ) The refractive index at a wavelength λ (nm) is a refractive index in the orthogonal direction, and dA indicates the film thickness of the horizontal alignment liquid crystal curing.

[9] A method of manufacturing a retardation 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 having an optical compensation function according to any one of the above [1] to [8], which satisfies the relationship (2).
RthC (450) / RthC (550) <1.00 (2)
In the formula, RthC (λ) represents the retardation value in the thickness direction at the wavelength λ nm of the vertically aligned liquid crystal cured film. The definition of the phase difference value RthC (λ) is as follows.
RthC (λ) = ((nxC (λ) + nyC (λ)) / 2−nzC (λ)) × dC
Where nxC (λ) is the main refractive index in the film plane of the vertical alignment liquid crystal cured film, and the main refractive index at wavelength λ (nm) is
nyC (λ) is a refractive index in a direction orthogonal to nxC (λ) in the same plane, and has a refractive index at a wavelength λ (nm),
nzC (λ) is the refractive index in the thickness direction of the vertical alignment liquid crystal cured film, and the refractive index at the wavelength λ (nm) is
dC indicates the film thickness of the vertical alignment liquid crystal curing, respectively.
In the case of nxC (λ) = nyC (λ), nxC (λ) can be a refractive index in any direction in the film plane.

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

[11] A retardation plate with an optical compensation function according to the above [10], wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film with 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] The retardation with the optical compensation function according to the above [10] or [11], wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film comprising a photo alignment film, and a horizontal alignment liquid crystal cured film are formed in this order How to make a board.

[13] A vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film comprising a photo alignment film containing cinnamoyl groups, and a horizontal alignment liquid crystal cured film according to any one of the above [10] to [12] Manufacturing method of retardation plate with optical compensation function.

[14] The optical compensation according to any one of the above [10] to [13], 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 Method of manufacturing a retardation plate with a function.

[15] The optical compensation function according to any one of the above [10] to [14], wherein a vertical alignment film containing a 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. Method of manufacturing a phase difference plate.

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

[17] A method of manufacturing a retardation plate 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 having an optical compensation function according to any one of the above [10] to [16] which satisfies the relationship (3).
ReA (450) / ReA (550) <1.00 (3)
In formula, ReA ((lambda)) shows the in-plane phase difference value in wavelength (lambda) nm of a horizontal alignment 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 horizontal alignment liquid crystal cured film, and the main refractive index at wavelength λ (nm) is orthogonal to nyA (λ) in the same plane as nxA (λ) (D) indicates the film thickness of the horizontal alignment liquid crystal curing.

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

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

The retardation plate with an optical compensation function of the present invention can suppress defects such as wrinkles and cracks which occur when it is bent.

[Horizontal alignment liquid crystal cured film]
The horizontal alignment liquid crystal cured film is a film having refractive index anisotropy in the film plane, and is made of a polymer containing a polymerizable liquid crystal compound. A horizontally aligned liquid crystal cured film may be formed by applying a polymerizable liquid crystal composition on the horizontal alignment film and polymerizing a composition including a polymerizable liquid crystal compound in an aligned state by heating and / or light irradiation. It is preferable at the point which can make thin film formation and wavelength dispersion characteristic of a horizontal alignment liquid crystal cured film arbitrarily.

The three-dimensional index ellipsoid formed by the horizontal alignment 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 oriented with respect to the plane of the horizontally aligned liquid crystal cured film. And may be a hybrid alignment liquid crystal cured film or a tilt alignment liquid crystal cured film. The refractive indexes nx, ny and nz in three directions in the refractive index ellipsoid formed by the alignment of the polymerizable liquid crystal are nx> ny ≒ nz (referred to as positive A plate) or nx <ny nynz (referred to as negative A plate) It may have a relationship of In the refractive index ellipsoid formed by the horizontally aligned liquid crystal cured film, nx represents the main refractive index in the 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 represents the refractive index in the direction parallel to the plane of the horizontally aligned liquid crystal cured film and orthogonal to the direction of the nx. 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 horizontal alignment liquid crystal cured film can be used as either a rod-like polymerizable liquid crystal or a disc-like polymerizable liquid crystal, but a rod-like polymerizable liquid crystal is preferable. When the rod-like polymerizable liquid crystal forms a horizontally aligned liquid crystal cured film, the horizontally aligned 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 of wavelength 550 nm, satisfies the optical characteristics shown in the following formula (21) Is preferred. In addition, the horizontal alignment liquid crystal cured film has an in-plane retardation value Re1 (450) for light of wavelength 450 nm, an in-plane retardation value Re1 (550) for light of wavelength 550 nm, and an in-plane light of wavelength 650 nm. It is also preferable that the retardation value Re1 (650) satisfies the optical characteristics shown in Equation (22) and Equation (23). It is more preferable that the horizontal alignment liquid crystal cured film satisfies optical properties represented by the following formula (21), the following formula (22) and the following formula (23).
120 nm ≦ ReA (550) ≦ 170 nm (21)
[In Formula, ReA (550) represents the in-plane retardation value (in-plane retardation) with respect to the light of wavelength 550 nm of a horizontal alignment liquid crystal cured film. ]
ReA (450) / ReA (550) ≦ 1.0 (22)
1.00 ≦ ReA (650) / ReA (550) (23)
[Wherein, ReA (450) represents the in-plane retardation value of the horizontally aligned liquid crystal cured film to light of wavelength 450 nm, and ReA (550) represents the in-plane retardation value of the horizontally aligned liquid crystal cured film to light of wavelength 550 nm. ReA (650) represents the in-plane retardation value to the light of wavelength 650 nm of the horizontal alignment liquid crystal cured film. ]

When the in-plane retardation value ReA (550) of the horizontal alignment liquid crystal cured film exceeds the range of the equation (21), the hue of the front of the display to which the elliptically polarizing plate with optical compensation function is applied including the retardation plate with optical compensation function It can cause problems such as reddish or bluish. A further 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 in the elliptically polarizing plate provided with the horizontally aligned liquid crystal cured film is deteriorated. If 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 lost when viewed from the front on the short wavelength side. 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 equation (24), the desired in-plane retardation value (ReA (λ): in-plane retardation value of the horizontal alignment liquid crystal cured film at wavelength λ (nm)) In order to obtain, it is sufficient to adjust the three-dimensional refractive index and the film thickness dA. The three-dimensional refractive index depends on the molecular structure and alignment state of the polymerizable liquid crystal compound described later.
ReA (λ) = (nxA (λ) -nyA (λ)) × dA (24)
[Wherein, the refractive index ellipsoid formed by the horizontal alignment liquid crystal cured film has a relationship of nxA (λ)> nyA (λ) ≒ nzA (λ), and nxA (λ) is for light of wavelength λ (nm) The main refractive index in the direction parallel to the horizontal alignment liquid crystal cured film plane is represented. nyA (λ) is a refractive index ellipsoid formed by the horizontal alignment liquid crystal cured film with respect to light of wavelength λ (nm), which is parallel to the horizontal alignment liquid crystal cured film plane and the direction of the nxA (λ) Represents the refractive index in the direction orthogonal to. dA represents the thickness of the horizontal alignment liquid crystal cured film. ]

The horizontally aligned liquid crystal cured film is preferably a polymer of a composition containing a 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 means a group capable of participating in the polymerization reaction by active radicals or acids generated from the photopolymerization initiator. Examples of the photopolymerizable functional group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, oxetanyl group and the like. Among them, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable. The liquid crystallinity 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, from the viewpoint of satisfying the relationship of the above formulas (21) and (22) or (31) and (32) which will be described later, the polymerizable liquid crystal compound exhibits reverse wavelength dispersion.

The compound represented by is preferable.

In formula (I), Ar represents a divalent aromatic group which may have a substituent. The term "aromatic group" as used herein refers to a group having a planar ring structure, and the ring structure has [4n + 2] [pi] electrons in accordance with the Huckels rule. Here, n represents an integer. When a ring structure is formed by containing a hetero atom such as -N = or -S-, the case where Heckel's rule is satisfied including non-covalent electron pairs on these hetero atoms and also has aromaticity is included. The divalent aromatic group preferably contains at least one or more 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, a 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, carbon The carbon atom constituting the divalent aromatic group or divalent alicyclic hydrocarbon group may be an oxygen atom or a sulfur atom, which may be substituted with an alkoxy group, cyano group or nitro group of 1 to 4 Or may be substituted by 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 as or different from each other.

E ¹ and E ² each independently represent an alkanediyl group having 1 to 17 carbon atoms, wherein a hydrogen atom contained in the alkanediyl group may be substituted by a halogen atom, and the alkanediyl group may be substituted The —CH ₂ — contained may be substituted by —O—, —S— or —Si—. Each of P ¹ and P ² independently represents 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 by at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms And a 1,4-cyclohexanediyl group which may be substituted by at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, and more preferably 1 substituted by 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 unsubstituted It is a substituted 1,4-trans-cyclohexanediyl group. In addition, at least one of G ¹ and G ² which are present in a plurality 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, one is a divalent alicyclic hydrocarbon group.

L ¹ and L ² are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a1 OR ^a2- , -R ^a3 COOR ^a4- , -R ^a5 ^{^{^{OCOR a6 -, R a7 OC =}}} OOR a8 -, - N = N -, - CR c = CR d -, or C≡C-. 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} - a . Here, R ^a2-1 , R ^a4-1 and R ^a6-1 each independently represent a single bond, -CH _2- or -CH ₂ CH _2- . L ¹ and L ² are each independently more preferably a single bond, —O—, —CH ₂ CH ₂ —, —COO—, —COOCH ₂ CH ₂ — or OCO—.

B ¹ and B ² are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a9 OR ^a10- , -R ^a11 COOR ^a12- , -R ^a13 OCOR ^a14 -, or ^R a15 OC ^{= OOR a16} - a. 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 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 + 1 ≦ 6 from the viewpoint of reverse wavelength dispersive expression, preferably k + 1 = 4, and more preferably k = 2 and l = 2. It is further preferable that k = 2 and l = 2 because of a symmetrical structure.

Each of E ¹ and E ² is preferably independently an alkanediyl group having 1 to 17 carbon atoms, and more preferably an alkanediyl group having 4 to 12 carbon atoms.

The polymerizable group represented by P ¹ or P ² is, for example, an epoxy group, a vinyl group, a vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl And oxetanyl groups and the like. Among these, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable.

Ar preferably has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocyclic ring which may have a substituent, and an electron-withdrawing group. As the said aromatic hydrocarbon ring, a benzene ring, a naphthalene ring, an anthracene ring etc. are mentioned, for example, A benzene ring and a naphthalene ring are preferable. As the aromatic heterocyclic ring, 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 And thiazole ring, benzothiazole ring, thienothiazole ring, oxazole ring, benzoxazole ring, phenanthroline 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. When Ar contains a nitrogen atom, the nitrogen atom preferably has a π electron.

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

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

In formulas (Ar-1) to (Ar-22), * represents a linking moiety, and Z ⁰ , Z ¹ and Z ² each independently represent 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, Alkylthio group having 1 to 12 carbons, N-alkylamino group having 1 to 12 carbons, N, N-dialkylamino group having 2 to 12 carbons, N-alkylsulfamoyl group having 1 to 12 carbons or carbon 2 to 12 represent N, N-dialkylsulfamoyl groups.

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 represent an aromatic hydrocarbon group or aromatic heterocyclic group which may be substituted.

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

Examples of the aromatic hydrocarbon group in Y ¹ , Y ² and Y ³ include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl group, naphthyl group, anthryl group, phenanthryl group and biphenyl group, and a phenyl group And a naphthyl group is preferable, and a phenyl group is more preferable. The aromatic heterocyclic group is a nitrogen atom such as furyl group, pyrrolyl group, thienyl group, pyridinyl group, thiazolyl group, benzothiazolyl group and the like, nitrogen atom such as oxygen atom and sulfur atom, etc. and having at least one hetero atom having 4 to 20 carbon atoms 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 be each independently an optionally substituted polycyclic aromatic hydrocarbon group or a 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 means a group derived from a fused polycyclic aromatic heterocyclic group or an aromatic ring assembly.

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

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

In formulas (Ar-16) to (Ar-22), Y ¹ may form an aromatic heterocyclic group together with the nitrogen atom to which it is attached and Z ⁰ . Examples of the aromatic heterocyclic group include those described above as the aromatic heterocyclic ring which Ar may have, and examples thereof include pyrrole ring, imidazole ring, pyrroline ring, pyridine ring, pyrazine ring, pyrimidine ring, indole And rings, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring and the like. The aromatic heterocyclic group may have a substituent. Y ¹ may be, together with the nitrogen atom to which it is attached and Z ⁰ , an optionally substituted polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group as described above. For example, benzofuran ring, benzothiazole ring, benzoxazole ring and the like can be mentioned. The compound represented by the formula (I) can be produced, for example, according to the method described in JP-A-2010-31223.

The polymerizable liquid crystal compounds can be used alone or in combination of two or more. When two or more types 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, and further preferably 100 parts by mass of the polymerizable liquid crystal compound. Is 80 parts by mass or more.

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

The content of the polymerizable liquid crystal compound is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, and more preferably 90 to 90 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. It is 98 parts by mass. If the content is within the above range, the orientation of the horizontally oriented liquid crystal cured film tends to be high. Here, the solid content refers to the total amount of the components 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, for example, 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 Solvents: 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 and methyl isobutyl ketone etc. Ketone solvents; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; fats such as ethylcyclohexane Formula hydrocarbon solvents; 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, Amide solvents such as N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone and the like can be mentioned. These solvents can be used alone or in combination of two or more. However, since the compound represented by the above formula (I) generally has a relatively large conjugated system, the solubility in solvents is low, and among the solvents exemplified above, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, ethers 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 and an amide solvent.

The content of the solvent is preferably 50 to 98 parts by mass, more preferably 70 to 95 parts by mass, with respect to 100 parts by mass 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, the viscosity of the composition is low, so that the thickness of the horizontal alignment liquid crystal cured film becomes substantially uniform, and unevenness tends not to occur in the horizontal alignment liquid crystal cured film. is there. The said solid content can be suitably determined in consideration of the thickness of the horizontal alignment liquid crystal cured film which it is going to manufacture.

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 polymerizable liquid crystal. The reactive species include active species such as radicals, cations or anions. Among them, from the viewpoint of easy reaction control, a photopolymerization initiator in which the reaction proceeds by light irradiation is preferable.

As a photoinitiator, a radical photopolymerization initiator, a cationic photopolymerization initiator, etc. are mentioned. Examples of photo radical polymerization initiators include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, triazine compounds and the like, and as photo cationic polymerization initiators, aromatic diazonium salts, aromatic compounds And onium salts such as aromatic iodonium salts and aromatic sulfonium salts, and iron-arene complexes.
Specifically, Irgacure (Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (all, BASF Japan Ltd.) ), Seikor BZ, Seikall Z, Seikall BEE (all, SEIKO CHEMICAL Co., Ltd.), Kayacure (Kayacure) BP 100 (Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (Dow), Adeka Optomer SP- 152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer N-1919, Adeka Awruz NCI-831, Adeka Ark Rus NC -930 (above, made by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (above, made by Nihon Shiber-Hegner Co., Ltd.) and TAZ-104 (made by Sanwa Chemical Co., Ltd.), Kayarad (registered trademark) series (Nippon Kayaku Co., Ltd.) Made by), Cyracure UVI series (made by Dow Chemical Co., Ltd.), CPI series (made by Sun Apro Ltd.), TAZ, BBI and DTS (above, made by Midori Chemical Co., Ltd.), RHODORSIL (registered trademark) (made by Rhodia Co., Ltd.), etc. It can be mentioned. The photopolymerization initiators can be used alone or in combination of two or more. Among these, from the viewpoint of easy reaction control, a photo radical polymerization initiator that generates a radical by light irradiation is preferable.

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

Examples of the α-acetophenone type polymerization initiator include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2. -Benzylbutan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one and the like, and more preferably 2-methyl-2-one. There may be mentioned morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one. Examples of commercially available α-acetophenone compounds include IRGACURE 369, 379 EG, 907 (above, manufactured by BASF Japan Ltd.) and Seikall BEE (manufactured by SEIKO CHEMICAL CO., LTD.).

The oxime photopolymerization initiator generates radicals by being irradiated with light. The polymerization of the polymerizable liquid crystal compound in the deep portion of the horizontal alignment liquid crystal cured film proceeds suitably by this radical. Moreover, it is preferable to use the photoinitiator which can utilize efficiently the ultraviolet-ray more than wavelength 350nm from a viewpoint of advancing the polymerization reaction in the deep part of a horizontal alignment liquid crystal cured film more efficiently. As a photopolymerization initiator capable of efficiently utilizing ultraviolet light with a wavelength of 350 nm or more, a triazine compound or an oxime ester carbazole compound is preferable, and from the viewpoint of sensitivity, an oxime ester carbazole compound is more preferable. Examples of oxime ester carbazole compounds 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 products of oxime ester type carbazole compounds include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, made by BASF Japan Ltd.), Adeka Optomer N-1919, Adeka Arms NCI-831 (above , Manufactured by ADEKA Co., Ltd.) and the like.

The addition amount of the photopolymerization initiator is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and 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 is hard to disturb alignment of a polymeric liquid crystal compound.

The polymerization reaction of the polymerizable liquid crystal compound can be controlled by blending the polymerization inhibitor. As a polymerization inhibitor, hydroquinones having a substituent such as hydroquinone and alkyl ether; catechols having a substituent such as alkyl ether such as butyl catechol; pyrogallols, 2,2,6,6-tetramethyl-1- Radical scavengers such as piperidinyloxy radical; thiophenols; β-naphthylamines and β-naphthols. In order to polymerize the polymerizable liquid crystal compound without disturbing the orientation 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. The amount is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass. The polymerization inhibitors can be used alone or in combination of two or more.

Furthermore, by using a photosensitizer, it is possible to sensitize the photopolymerization initiator. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone; anthracenes having a substituent such as anthracene and alkyl ether; phenothiazine; rubrene. Photosensitizers can be used alone or in combination of two or more. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. 3 parts by mass.

The leveling agent is an additive having a function of adjusting the flowability of the polymerizable liquid crystal composition and making the layer obtained by applying the composition more flat, and, for example, a silicone type such as a silane coupling agent, There may be mentioned polyacrylate and perfluoroalkyl leveling agents. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Toray Dow Corning Co., Ltd.), KP 321, KP 323, KP 324, KP 326, KP 340, 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 available from Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4400, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (above , All Momentive Performance Materials Japan Ltd.), Fluorinert (registered trademark) FC-72, FC-40, FC-43, FC-3283 (all manufactured by Sumitomo 3M Co., Ltd.), Megafuck (registered trademark) R-08, R-30, R-90, F-410, F-443, F-445, F-470, F-477, F-479, F-482, F-483 (all are DIC ), F-top (trade names) EF301, EF303, EF351, EF352 (all of which are manufactured by Mitsubishi Materials Electronics Kasei Co., Ltd.), Surfron (registered trademark) S-381, S-382, and the like S-383, S-393, SC-101, SC-105, KH-40, SA-100 (all available from AGC Seimi Chemical Co., Ltd.), trade names E1830, E5844 (Daikin Corporation) And BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (all trade names: manufactured by BM Chemie). The leveling agents can be used alone or in combination of two or more.

The content of the leveling agent is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. It is preferable for the content of the leveling agent to be in the above range, since the resulting horizontally aligned 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 additives at a predetermined temperature.

The horizontally aligned liquid crystal cured film is coated with the above-mentioned polymerizable liquid crystal composition on the later described horizontal alignment film, 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 by energy rays.

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

Examples of the method of removing the solvent (hereinafter sometimes referred to as the solvent removal method A) include natural drying, air drying, heat drying, reduced pressure drying and a combination thereof. Among these, natural drying or heat drying is preferred. 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.

As the active energy ray to be irradiated, the type of the polymerizable liquid crystal compound (in particular, the type of the photopolymerizable functional group possessed by the polymerizable liquid crystal compound), the type of the photopolymerization initiator when the photopolymerization initiator is included, and those According to the amount of Specifically, one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays can be mentioned. Among them, ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction, and in that it can be used widely as an apparatus for photopolymerization, polymerization is preferably performed so that it can be photopolymerized by ultraviolet light. It is preferable to select the type of the liquid crystal compound.

As a light source of the active energy ray, for example, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, super high pressure mercury lamp, xenon lamp, halogen lamp, carbon arc lamp, tungsten lamp, gallium lamp, excimer laser, wavelength range Examples of the light source include an LED light source emitting 380 to 440 nm, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, a metal halide lamp 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 range effective for activating the photocationic polymerization initiator or the photoradical polymerization initiator. The light irradiation time is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, still more preferably 0.1 seconds to 1 minute. is there.
When it is irradiated with such ultraviolet irradiation intensity one or more times, its 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 When the accumulated light amount is equal to or less than the above lower limit, curing of the polymerizable liquid crystal compound may be insufficient and good transferability may not be obtained. On the contrary, when the accumulated light amount is equal to or more than the above upper limit, the retardation plate with the optical compensation function including the horizontal alignment liquid crystal cured film may be colored.

The film thickness of the horizontal alignment liquid crystal cured film is preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 2.5 μm or less, from the viewpoint of thinning of the functional film. The lower limit of the film thickness of the horizontal alignment liquid crystal cured film is preferably 0.1 μm or more, more preferably 0.5 μm or more, and still more preferably 1.0 μm or more. The film thickness of the horizontal alignment liquid crystal cured film can be measured using an ellipsometer or a contact 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 required to develop the alignment control force include rubbing treatment, photoalignment treatment, light irradiation treatment and the like. In addition, control of various alignments such as vertical alignment, horizontal alignment, hybrid alignment, and inclined alignment is possible 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 control 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.

It is preferable that the alignment film has solvent resistance which is not dissolved by application of the polymerizable liquid crystal composition and the like, and has heat resistance in heat treatment for removal of the solvent and alignment of the polymerizable liquid crystal compound.

As a horizontal alignment film which shows the alignment control force which aligns a horizontal alignment liquid crystal cured film in a horizontal direction, a rubbing alignment film, a photo alignment film, a glue alignment film which has a concavo-convex pattern and a plurality of grooves on the surface, etc. are mentioned. For example, in the case of applying to a long roll-shaped film, a photoalignment film is preferable in that the orientation direction can be easily controlled.

In the rubbing alignment film, a composition containing an alignment polymer and a solvent (hereinafter, also referred to as a composition for forming a rubbing alignment film) is usually coated on a substrate or the like, and the solvent is removed to form a coating film. By rubbing the coating film, an alignment regulating force can be imparted.

Examples of orientation polymers include polyamides and gelatins having an amide bond, polyimides having an imide bond and polyamic acid which is a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethylene imine, polystyrene And polyvinyl pyrrolidone, polyacrylic acid and polyacrylic acid esters. These orientable 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 the range in which the alignment polymer is completely dissolved in the solvent. The content of the orienting 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. Commercially available products include Sun Ever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.), Optomer (registered trademark, manufactured by JSR Corporation), and the like.

As the solvent, for example, the solvents exemplified in the section of the horizontal alignment liquid crystal cured film can be used. The method for applying the composition for forming a rubbing alignment film to a substrate or the like includes the application method A, and the method for removing the solvent includes the solvent removal method A.

As a method of rubbing treatment, for example, a method in which the coating film is brought into contact with a rotating rubbing roll on which a rubbing cloth is wound is mentioned. When the rubbing process is performed, masking may be performed to form a plurality of regions (patterns) having different orientation directions in the alignment film.

The photo alignment film is usually coated with a composition (also referred to as a photo alignment film forming composition) containing a polymer or monomer having a photo reactive group and a solvent on a substrate or the like, and after removing the solvent Preferably, it is obtained by irradiating polarized UV). The photo alignment film can arbitrarily control the direction of the alignment regulation force by selecting the polarization direction of the polarized light to be irradiated.

A photoreactive group refers to a group that produces alignment ability by light irradiation. Specific examples thereof include groups involved in the photoreaction that is the source of the alignment ability such as alignment induction reaction, isomerization reaction, photodimerization reaction, photocrosslinking reaction or photolysis reaction of molecules generated by light irradiation. The photoreactive group is preferably a group having an unsaturated bond, particularly a double bond, a carbon-carbon double bond (CCC bond), a carbon-nitrogen double bond (C = N bond), a nitrogen-nitrogen Particularly preferred is 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).

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. As a photoreactive group which has a C = N bond, the group which has structures, such as aromatic Schiff base and aromatic hydrazone, is mentioned, for example. 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 benzophenone group, coumarin group, anthraquinone group and maleimide group. These groups may have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group or a halogenated alkyl group.

The group which participates in the photodimerization reaction or the photocrosslinking reaction is preferable in that the orientation is excellent. Among them, a cinnamoyl group is preferable in that a photoreactive group involved in the photodimerization reaction is preferable, a light irradiation amount necessary for alignment is relatively small, and a photoalignment film excellent in thermal stability and temporal stability is easily obtained. And chalcone groups are preferred. As the polymer having a photoreactive group, those 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 are particularly preferable.

The content of the polymer or monomer having a photoreactive group can be adjusted by the type of the polymer or monomer and the thickness of the target photoalignment film, and is at least 0.5 parts by weight based on 100 parts by weight of the composition for forming a photoalignment film. The amount is preferably 2 parts by mass or more, and more preferably 0.3 to 10 parts by mass.

As the solvent, for example, the solvents exemplified in the section of the horizontal alignment liquid crystal cured film can be used. As a method of apply | coating the composition for photoalignment film formation on a base material etc., the said application method A is mentioned, As a method of removing a solvent, the said solvent removal method A is mentioned.

In order to irradiate polarized light, for example, a composition in which the solvent is removed from the composition for forming a light alignment film applied on a substrate or the like may be directly irradiated with polarized light. In addition, the polarized light is preferably substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in the wavelength range in which the photoreactive group of the polymer or monomer having the photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) having a wavelength of 250 to 400 nm is particularly preferable. As a light source for irradiating the polarized light, an ultraviolet light laser such as a xenon lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, KrF, ArF or the like can be mentioned. Among them, a high pressure mercury lamp, an ultrahigh pressure mercury lamp and a metal halide lamp are preferable because the emission intensity of the ultraviolet light having a wavelength of 313 nm is large. Polarized UV can be irradiated by irradiating the light from the light source through an appropriate polarizing element. Polarizing elements include polarizing filters, polarizing prisms such as Glan-Thomson, and Glan-Taylor, and wire grids. Among them, a wire grid type polarizing element is preferable from the viewpoint of increasing the area and resistance to heat.

Note that when rubbing or polarized irradiation is performed, masking can be performed to form a plurality of regions (patterns) having different liquid crystal alignment directions.

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 aligned at equal intervals, liquid crystal molecules are aligned in the direction along the groove.

As a method of obtaining a globular alignment film, a method of forming a concavo-convex pattern by performing development and rinsing after exposure through an exposure mask having slits of a pattern shape on the surface of a photosensitive polyimide film, a plate having grooves on the surface Method of forming a layer of a UV curable resin before curing on a sheet-like master, transferring the formed resin layer to a substrate and then curing, and a UV curable resin before curing formed on a substrate or the like A roll-like master having a plurality of grooves is pressed against the film of (4) to form asperities, followed by curing.

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

The film 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 reducing the thickness of the retardation plate 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 film thickness meter.

[Vertical alignment liquid crystal cured film]
The horizontally aligned liquid crystal cured film is a film having refractive index anisotropy in the direction perpendicular to the film plane, and is made of a polymer containing a polymerizable liquid crystal compound. A vertically aligned liquid crystal cured film is formed by applying a polymerizable liquid crystal composition on the vertical alignment film and polymerizing a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound in an aligned state by heating and / or light irradiation. It is preferable to carry out since the thin film formation and wavelength dispersion characteristic of a vertical alignment liquid crystal cured film can be designed arbitrarily.

The three-dimensional 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 oriented 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. The refractive indexes 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 <nxnxny (referred to as negative C plate) It may have a relationship of nx represents the main refractive index in the 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. 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 orthogonal to the direction of the nx. In the case of nx = ny, nx can take any direction in the plane of the vertical alignment 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 a 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 disc-like polymerizable liquid crystal, but 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, the vertically aligned liquid crystal cured film has an optical characteristic such that RthC (λ), which is a retardation value in the thickness direction for light of wavelength λ nm, is represented by the following equation (31). It is preferable to satisfy. Moreover, it is also preferable to satisfy the optical properties shown in the 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)
(Wherein, 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)
(Wherein, RthC (450) is the retardation value in the thickness direction for light of wavelength 450 nm, RthC (550) is the retardation value in the thickness direction for light of wavelength 550 nm, and RthC (650) is for light of wavelength 650 nm Represent 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 obliqueness of the display to which the elliptically polarizing plate with optical compensation function is applied including the retardation plate with optical compensation function. Can cause problems such as reddish or bluish hue. A more preferable range of the retardation value in the thickness direction is −95 nm ≦ RthC (550) ≦ −55 nm, and a further 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, as viewed from an oblique direction on the short wavelength side in the elliptically polarizing plate provided with the vertically aligned liquid crystal cured film The ellipticity of the If the ellipticity of the elliptically polarizing plate is deteriorated on the short wavelength side and becomes smaller than 1.0, the function as the elliptically polarizing plate tends to be lost 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 desired retardation value in the thickness direction (RthC (λ): retardation in the thickness direction of the vertically aligned liquid crystal cured film at wavelength λ (nm) In order to obtain the value), the three-dimensional refractive index and the film thickness dC may be adjusted. 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)
(Wherein the refractive index ellipsoid formed by the vertical alignment liquid crystal cured film has a relationship of nzC (λ)> nxC (λ) ≒ nyC (λ), where nzC (λ) is the vertical alignment liquid crystal cured film Represents the refractive index in the direction perpendicular to the plane of the vertical alignment liquid crystal cured film for light of wavelength λ (nm) in the refractive index ellipsoid formed by nxC (λ) is the refractive index that the vertical alignment liquid crystal cured film forms In an ellipsoid, it represents the maximum refractive index in the direction parallel to the plane of the liquid crystal cured vertical alignment to light of wavelength λ (nm) nyC (λ) is a refractive index ellipsoid formed by the cured liquid crystal of the vertical alignment Represents the refractive index for light of wavelength λ (nm) in the direction parallel to the vertical alignment liquid crystal cured film plane and orthogonal to the direction of nx C. However, nx C (λ) = ny C (λ) NxC (λ) is vertically oriented if 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 including the polymerizable liquid crystal compound in the 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, in particular, a photopolymerizable functional group. The photopolymerizable functional group means a group capable of participating in the polymerization reaction by active radicals or acids generated from the photopolymerization initiator. Examples of the photopolymerizable functional group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, oxetanyl group and the like. Among them, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable. The liquid crystallinity 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.

It is preferable to use the compound shown by above-mentioned Formula (I) as a polymeric liquid crystal compound used for formation of a vertical alignment liquid crystal cured film. By using the compound represented by the formula (I), reverse wavelength dispersion is exhibited, and the relationship of the above (31) and (32) can be satisfied.

The polymerizable liquid crystal compounds used for the vertically aligned liquid crystal cured film can be used alone or in combination of two or more. When two or more types 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, and 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 (hereinafter, also referred to as a polymerizable liquid crystal composition) used for the vertically aligned liquid crystal cured film comprises a solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, and adhesion. It can further contain a quality improver. These additives may be used alone or in combination of two or more.

The content of the polymerizable liquid crystal compound is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, and more preferably 90 to 90 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. It is 98 parts by mass. If the content is within the above range, the orientation of the vertically aligned liquid crystal cured film tends to be high. Here, the solid content refers to the total amount of the components 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 horizontal alignment liquid crystal cured film can be used.

The content of the solvent is preferably 50 to 98 parts by mass, more preferably 70 to 95 parts by mass, with respect to 100 parts by mass 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, the viscosity of the composition is lowered, so that 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 polymerizable liquid crystal. The reactive species include active species such as radicals, cations or anions. Among them, 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 horizontal alignment liquid crystal cured film can be used.

The polymerization reaction of the polymerizable liquid crystal compound can be controlled by blending the polymerization inhibitor. As the polymerization inhibitor, the same one as used in the composition for forming a horizontal alignment liquid crystal cured film can be used. In order to polymerize the polymerizable liquid crystal compound without disturbing the orientation 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. The amount is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass. The polymerization inhibitors can be used alone or in combination of two or more.

Furthermore, by using a photosensitizer, it is possible to sensitize the photopolymerization initiator. As a photosensitizer, the thing similar to what is used for the composition for horizontal alignment liquid crystal cured film formation can be used. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. 3 parts by mass.

The leveling agent is an additive having the function of adjusting the flowability of the polymerizable liquid crystal composition and making the layer obtained by applying the composition flatter, and is used for the composition for forming a horizontal alignment liquid crystal cured film The same ones can be used.

The content of the leveling agent is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. When the content of the leveling agent is in the above range, the resulting vertically aligned liquid crystal cured film tends to be smoother, which is preferable.

The polymerizable liquid crystal composition used to form 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 additives at a predetermined temperature.

The vertically aligned liquid crystal cured film is coated with the above-mentioned polymerizable liquid crystal composition on the later described vertical alignment film, 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 by energy rays.

The method of apply | coating a polymeric liquid crystal composition on a vertical alignment film can use the same method as the time of forming a horizontal alignment liquid crystal cured film.

The method for removing the solvent can be the same as that for forming the horizontal alignment liquid crystal cured film.

As a light source of the said active energy ray, the same thing as what is used when forming a horizontal alignment 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 range effective for activating the photocationic polymerization initiator or the photoradical polymerization initiator. The light irradiation time is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, still more preferably 0.1 seconds to 1 minute. is there.
When it is irradiated with such ultraviolet irradiation intensity one or more times, its 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 When the accumulated light amount is equal to or less than the above lower limit, curing of the polymerizable liquid crystal compound may be insufficient and good transferability may not be obtained. On the contrary, when the integrated light amount is equal to or more than the above upper limit, the retardation plate with the optical compensation function including the vertically aligned liquid crystal cured film may be colored.

The film thickness of the vertically aligned liquid crystal cured film is preferably 3 μm or less, more preferably 2 μm or less, and still more preferably 1.5 μm or less from the viewpoint of thinning of the functional film. The lower limit of the film thickness of the vertically aligned liquid crystal cured film is preferably 0.1 μm or more, more preferably 0.3 μm or more, and still more preferably 0.5 μm or more. The film thickness of the vertically aligned liquid crystal cured film can be measured using an ellipsometer or a contact 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. In addition, control of various alignments such as vertical alignment, horizontal alignment, hybrid alignment, and inclined alignment is possible depending on the type of alignment film, rubbing conditions, and light irradiation conditions. Among them, the vertical alignment film is an alignment film having an alignment control force to align the polymerizable liquid crystal compound of the liquid crystal cured film in the vertical direction. Therefore, by using the vertical alignment film, a vertical alignment liquid crystal film can be formed.

As the vertical alignment film, it is preferable to use a material that lowers the surface tension of the surface of the substrate or the like. Examples of such materials include the oriented polymers described above, such as polyimide, polyamide, polyamic acid which is a hydrolyzate thereof, fluorine-based polymer such as perfluoroalkyl, and silane compounds, and polysiloxane compounds obtained by condensation reaction thereof. Can be mentioned. The vertical alignment film is formed by applying a composition (hereinafter also referred to as a composition for forming a vertical alignment film) containing such a material and a solvent, for example, the solvent exemplified in the paragraph of the vertical alignment liquid crystal film, on a substrate or the like. After removing 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 contains Si element and C element as constituent elements from the viewpoint of easily reducing the surface tension and enhancing 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 suitably. In the present invention, when the vertical alignment film is disposed between the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film, high adhesion between the vertical alignment film and the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film is exhibited. In the retardation plate with an optical compensation function, peeling at the interface between each layer can be effectively suppressed or prevented.

As the silane compound, silicone systems such as the above-mentioned silane coupling agents are preferably applicable, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and N- (2- (2-methoxyethoxy) silane. Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3- (3) Dimethyl-butylidene) propylamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyl trime Xylan, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3 And glycidoxypropyl ethoxydimethylsilane and the like.

The silane compound may be of silicone monomer type or of type silicone oligomer (polymer) type. A silicone oligomer is shown in the form of (monomer)-(monomer) copolymer, 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercapto Mercaptopropyl-containing copolymers, such as propyltriethoxysilane-tetramethoxysilane copolymer and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane Tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer, and mercaptomethyltriethoxysilane-tetramethane Mercaptomethyl group-containing copolymers such as xysilane copolymers; 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 ester Oxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, And methacryloyloxypropyl-containing copolymers such as 3-methacryloxypropylpropyldiethoxysilane-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 Acryloyloxypropyl group-containing copolymers 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 xylan silanes; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetra Amino group-containing copolymers such as methoxysilane copolymers and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymers And the like. The silane compounds can be used alone or in combination of two or more. Moreover, a silane coupling agent etc. which may be used also as a leveling agent can be used.

Among these, silane compounds having an alkyl group at the molecular terminal are preferable, and silane compounds having an alkyl group having 3 to 30 carbon atoms are more preferable.

From the viewpoint of easier improvement of adhesion, from the viewpoint of coatability of the composition for forming a vertically aligned liquid crystal cured film, and from the viewpoint that the layer disposed in the lower layer is difficult to dissolve in the method for 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. The number of carbon atoms of a substituent, preferably an alkyl group or an alkoxy group, containing a C atom bonded to the Si atom of the silane compound forming the vertical alignment film is preferably 1 to 30, more preferably 2 to 25, and further preferably 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. 33. The coatability of the composition for forming a vertically aligned liquid crystal cured film is improved when the Si / C ratio is not less than the above lower limit, and the adhesion to the adjacent layer is improved when the Si / C ratio is not more than the above upper limit. it can.

As the solvent, for example, the solvents exemplified in the section of the horizontal alignment liquid crystal cured film can be used. As a method of applying the composition for forming a vertical alignment film, the application method A can be mentioned, and as a method of removing the solvent, the solvent removal method A can be mentioned.

The composition for forming a vertical alignment film may contain, in addition to the solvent, additives exemplified in the section of the horizontal alignment liquid crystal cured film, and the like.

The film thickness of the vertical alignment film is preferably 1 μm or less, more preferably 0.3 μm or less, and still more preferably 0.1 μm or less from the viewpoint of thinning of the retardation plate with an optical compensation function and expression of alignment control force. is there. The film 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 film thickness meter.

〔Base material〕
The substrate is used when applying the composition for forming an alignment film or the composition for forming a liquid crystal cured film, and is designed to peel off the substrate and transfer the film applied onto the substrate. The design may be such that adhesion with the substrate is imparted and transfer can not be performed, but from the viewpoint of thinning, a design capable of transferring to a transfer target and peeling the substrate is preferable. Examples of the substrate as described above include a glass substrate and a film substrate. From the viewpoint of processability, a film substrate is preferable, and a long roll-shaped film is more preferable in that it can be continuously produced. As a resin which comprises a film base material, For example, Polyolefins, such as polyethylene, a polypropylene, a norbornene-type polymer; Cyclic olefin resin; Polyvinyl alcohol; Polyethylene terephthalate; Polymethacrylates; Polyacrylates; Triacetylcellulose, diacetylcellulose And cellulose esters such as cellulose acetate propionate; polyethylene naphthalate; polycarbonates; polysulfones; polyethersulfones; polyether ketones; plastics such as polyphenylene sulfides and polyphenylene oxides. The substrate surface may be subjected to a release treatment such as silicone treatment. Examples of commercially available cellulose ester substrates include "Fujitack film" (manufactured by Fuji Photo Film Co., Ltd.); "KC8UX2M", "KC8UY" and "KC4UY" (all manufactured by Konica Minolta Opto Co., Ltd.). Such a resin can be formed into a film by a known means such as a solvent casting method, a melt extrusion method or the like to make a substrate.

Examples of commercially available cyclic olefin resins include “Topas” (registered trademark) (manufactured by Ticona, Germany), “Arton” (registered trademark) (manufactured by JSR Corporation), “ZEONOR” (registered trademark), Examples include "ZEONEX" (registered trademark) (manufactured by Nippon Zeon Co., Ltd.) and "APEL" (registered trademark) (manufactured by Mitsui Chemicals, Inc.). A commercially available cyclic olefin-based resin substrate can also be used. As a commercially available cyclic olefin resin base material, "essina" (registered trademark), "SCA 40" (registered trademark) (above, Sekisui Chemical Co., Ltd. made), "Zeonor film" (registered trademark) (made by Optes Co., Ltd.) And “Arton Film” (registered trademark) (manufactured by JSR Corporation).

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

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

When nxC = nyC, nxC can be a refractive index in any direction in the film plane.
Further, the interlayer distance between the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film is preferably 5 μm or less according to the formula (1), more preferably 1 μm or less, still more preferably 0.5 μm or less, particularly preferably 0.3 μm or less 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 plate with the optical compensation function preferably satisfies the following relational expression (5). The value of | R0 (550) -R40 (550) | is the amount of light loss near the oblique wavelength of 550 nm when an elliptically polarizing plate with optical compensation function using a retardation plate with optical compensation function is applied to a display The smaller the better, the better. The value of | R 0 (550) −R 40 (550) | is preferably less than 10 nm, more preferably 5 nm or less, still more preferably 4 nm or less, particularly preferably 3 nm or less.
| R0 (550)-R40 (550) | <10 nm (5)
Here, R 0 (λ) indicates the in-plane retardation value of the retardation plate with an optical compensation function including the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film. R40 is a direction orthogonal to the main refractive index direction in the film plane (a phase advancing axis direction) of the retardation plate with an optical compensation function including a horizontal alignment liquid crystal cured film and a vertical alignment liquid crystal cured film It shows the apparent phase difference value when rotated around 40 °.

The retardation plate with an optical compensation function preferably satisfies the following relational expression (6). The value of | R0 (450) -R40 (450) | is the amount of light loss near the oblique wavelength 450 nm when an elliptically polarizing plate with optical compensation function using a retardation plate with optical compensation function is applied to a display The smaller the better, the better. The value of | R 0 (450) −R 40 (450) | is preferably less than 10 nm, more preferably 5 nm or less, still more preferably 4 nm or less, particularly preferably 3 nm or less.
| R0 (450) -R40 (450) | <10 nm (6)
However, R0 ((lambda)) shows the in-plane phase difference value of the retardation plate with an optical compensation function containing a horizontal alignment liquid crystal cured film and a vertical alignment liquid crystal cured film. R40 is a direction orthogonal to the main refractive index direction in the film plane (a phase advancing axis direction) of the retardation plate with an optical compensation function including a horizontal alignment liquid crystal cured film and a vertical alignment liquid crystal cured film It shows the apparent phase difference value when rotated around 40 °.

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

In addition, when the average refractive index difference 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 generated between layers. The difference in average refractive index at a wavelength of 550 nm of each layer 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, the difference in the average refractive index of each layer is
(1) The difference between the average refractive index of the horizontally aligned liquid crystal cured film and the average refractive index of the vertically aligned 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 cured liquid crystal and the average refractive index of the horizontal alignment,
(2-b) The difference between the average refractive index of the horizontal alignment film and the average refractive index of the vertical alignment 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) the average refractive index of the horizontal alignment liquid crystal cured film and the average refractive index of the vertical alignment film Difference with,
(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 plate 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, and as a specific example thereof, other alignments Examples thereof include liquid crystal cured films, other alignment films, and protective layers. As another alignment liquid crystal cured film, the vertical alignment liquid crystal cured film illustrated above, a horizontal alignment liquid crystal cured film, etc. are mentioned, As an alignment film, the alignment film illustrated above, etc. are mentioned.

The protective layer is usually an acrylic oligomer or polymer comprising polyfunctional acrylate (methacrylate), urethane acrylate, polyester acrylate, epoxy acrylate etc., polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl pyrrolidone, starches, methyl cellulose, carboxy It is preferable to form from the composition for protective layer formation containing water-soluble polymers, such as methylcellulose and sodium alginate, and a solvent.

The solvent contained in the composition for forming a protective layer may be the same as the solvent exemplified above, and among them, at least one solvent selected from the group consisting of water, an alcohol solvent and an ether solvent is a protective layer. It is preferable in that the layer to be formed is not dissolved. Alcohol solvents include methanol, ethanol, butanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol monomethyl ether. Ether solvents include ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. Among them, ethanol, isopropyl alcohol, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferable.

The film 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 plate 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, and further laminating a vertical alignment film, and then laminating a vertical alignment liquid crystal cured film (hereinafter referred to as production method A), Preferably, a vertical alignment film is stacked on the material, then a vertically aligned liquid crystal cured film is stacked, and then a horizontal alignment film is stacked, and then a horizontally aligned liquid crystal cured film is stacked (hereinafter, manufacturing method B). The method for forming each of the layers described above can be used as the method for laminating the horizontal alignment liquid crystal cured film, the horizontal alignment film, the vertical alignment liquid crystal cured film, and the vertical alignment film.

When manufacturing a retardation plate with an optical compensation function by the manufacturing method A or the manufacturing method B, alignment failure or alignment defect may occur due to the alignment of the liquid crystal cured film disposed in the lower layer. That is, in the case of the production method A, after laminating the horizontally aligned liquid crystal cured film in the lower layer, and then laminating the vertically aligned liquid crystal cured film, the influence of the lower horizontally aligned liquid crystal cured film in forming the vertically aligned liquid crystal cured film In the case of manufacturing method B, after laminating the vertically aligned liquid crystal cured film on the lower layer for the same purpose, the horizontally aligned liquid crystal cured film is laminated. When forming a cured film, under the influence of the vertically aligned liquid crystal cured film in the lower layer, alignment defects or alignment defects may occur. Therefore, a composition used to form each layer to be laminated (a composition for forming a horizontal alignment film, a composition for forming a horizontal alignment liquid crystal cured film, a composition for forming a vertical alignment film, a composition for forming a vertical alignment liquid crystal cured film Depending on the solvent type of the product, the lower layer may be dissolved to cause a change in optical characteristics, an alignment failure, an alignment defect, or the like. Therefore, materials, solvents, 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 appropriately.

[Elliptically Polarizing Plate with Optical Compensation Function]
The retardation plate with an optical compensation function of the present invention is bonded to a transfer target, peeled off from a substrate to be transferred, or laminated in a state with a substrate via an adhesive or the like. The function of the retardation plate with compensation function, that is, the optical characteristics thereof can be imparted to the transfer target, and an optical laminate to which the optical characteristics of the retardation plate with optical compensation function are imparted can be manufactured. Among them, when laminated with a polarizing plate, it is possible to produce an elliptically polarizing plate with an optical compensation function. In the embodiment of the present invention, it is preferable to laminate so that the slow axis (optical axis) of the horizontal alignment 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 to be substantially 45 °, the function as a circularly polarizing plate can be obtained. Note that substantially 45 ° is usually in the range of 45 ± 5 °.

[Subject]
As the transfer target, an optical film having a single layer structure, for example, a polarizing plate, a retardation plate, a brightness enhancement film, an antiglare film, an antireflective film, a diffusion film, a light collecting film, an optical film having a multilayer structure, for example, a retardation Among these, a retardation plate, a retardation plate, a polarizing plate and an elliptically polarizing plate can be suitably used. 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 (field emission display device FED etc.), surface field emission display (SED), electronic paper (display using electronic ink or electrophoretic element), plasma display, projection type display (grating light valve (GLV) display, digital micro) The present invention can be applied to a display device having a mirror device (DMD) and the like, a piezoelectric ceramic display, and the like, and in particular, to an organic EL display device and a touch panel display device.

[Polarizer]
The polarizing plate is made of a polarizer having a polarizing function. As a polarizer, the stretched film to which the pigment | dye which has absorption anisotropy was made to adsorb | suck, or the film | membrane which apply | coated and orientated the pigment | dye which has absorption anisotropy is mentioned. Examples of the dye having absorption anisotropy include dichroic dyes.

In a stretched film on which a dye having absorption anisotropy is adsorbed, the dichroic dye is generally obtained by uniaxially stretching a polyvinyl alcohol-based resin film, or by staining the polyvinyl alcohol-based resin film with a dichroic dye. It is manufactured through a process of adsorption, a process of treating a polyvinyl alcohol-based resin film to which a dichroic dye is adsorbed with an aqueous solution of boric acid, and a process of washing with water after treatment with an aqueous solution of boric acid. A polarizing plate is obtained by bonding the thus obtained polarizer and the transparent protective film. The dichroic dye includes iodine and a dichroic organic dye. Examples of the dichroic organic dye include a dichroic direct dye consisting of a disazo compound such as C. I. DIRECT RED 39 and a dichroic direct dye consisting of a compound such as trisazo or tetrakisazo. As described above, the thickness of a polarizer obtained by uniaxially stretching, dyeing with a dichroic dye, boric acid treatment, washing with water and drying on a polyvinyl alcohol-based resin film is preferably 5 μm to 40 μm.

[Adhesive agent]
Examples of the pressure-sensitive adhesive include pressure-sensitive adhesives, dry-setting adhesives, and chemically-reactive adhesives. As a chemical reaction type adhesive agent, an active energy ray hardening-type adhesive agent is mentioned, for example.

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, an acrylic adhesive containing an acrylic polymer is excellent in optical transparency, has appropriate wettability and cohesion, is excellent in adhesiveness, and further has high weather resistance and heat resistance, etc., and is heated. It is preferable because floating and peeling do not easily occur under humidified conditions.

As acrylic polymers, (meth) acrylates in which the alkyl group in the ester part is an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl or butyl, (meth) acrylic acid and hydroxyethyl (meth) acrylate Copolymers with (meth) acrylic monomers having functional groups such as

A pressure-sensitive adhesive containing such a copolymer is excellent in tackiness, and it is relatively easy to form a transfer residue without causing adhesive residue or the like even when it is removed after being attached to the transfer member. It is preferable because it can be removed. 25 degrees C or less is preferable, and, as for the glass transition temperature of an acryl-type polymer, 0 degrees C or less is more preferable. 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 for imparting a light diffusing property 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. As a light diffusing agent, the microparticles | fine-particles which consist of inorganic compounds, and the microparticles | fine-particles which consist of organic compounds (polymer) are mentioned. Most of the polymers that the adhesive contains as an active ingredient, including acrylic polymers, have a refractive index of about 1.4 to 1.6, so a light diffusing agent having a refractive index of 1.2 to 1.8 It is preferable to select suitably. The refractive index difference between the polymer that the pressure-sensitive adhesive contains as an active ingredient and the light diffusing agent is usually 0.01 or more, and preferably 0.01 to 0.2 from the viewpoint of the brightness and display performance of the display device. The fine particles used as the light diffusing agent are preferably spherical fine particles or fine particles close to monodispersion, and more preferably fine particles having an average particle diameter of 2 to 6 μm. The refractive index is measured by a common minimum deflection method or an Abbe refractometer.

Examples of fine particles made of an inorganic compound include aluminum oxide (refractive index 1.76) and silicon oxide (refractive index 1.45). As fine particles made of an organic compound (polymer), melamine beads (refractive index 1.57), polymethyl methacrylate beads (refractive index 1.49), methyl methacrylate / styrene copolymer resin beads (refractive index 1.50) ~ 1.59), polycarbonate beads (refractive index 1.55), polyethylene beads (refractive index 1.53), polystyrene beads (refractive index 1.6), polyvinyl chloride beads (refractive index 1.46), and silicone Resin beads (refractive index 1.46) and the like can be mentioned. 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 not particularly limited because it is determined according to the adhesive strength and the like, but it is usually 1 μm to 40 μm. The thickness is preferably 3 μm to 25 μm, and more preferably 5 μm to 20 μm from the viewpoint of processability, durability, and the like. By setting the thickness of the pressure-sensitive adhesive layer formed of the adhesive to 5 μm to 20 μm, the brightness when the display device is viewed from the front or viewed obliquely is maintained, and blurring or blurring of the displayed image is caused. It can be made hard to occur.

The dry setting adhesive may contain a solvent. The dry-setting adhesive contains as a main component a polymer of a monomer having a protic functional group such as a hydroxyl group, a carboxyl group or an amino group and an ethylenic unsaturated group, or a urethane polymer as a main component. The composition etc. which contain crosslinking agents or curable compounds, such as an aldehyde, an epoxy compound, an epoxy resin, a melamine compound, a zirconia compound, and a zinc compound, are mentioned. Examples of polymers of monomers having a protic functional group such as a hydroxyl group, a carboxyl group or an amino group and an ethylenically unsaturated group include ethylene-maleic acid copolymer, itaconic acid copolymer, acrylic acid copolymer, and acrylamide Examples thereof include copolymers, saponified polyvinyl acetates, and polyvinyl alcohol resins.

As polyvinyl alcohol resin, polyvinyl alcohol, partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol, carboxyl group modified polyvinyl alcohol, acetoacetyl group modified polyvinyl alcohol, methylol group modified polyvinyl alcohol, amino group modified polyvinyl alcohol, etc. It can be mentioned. The content of the polyvinyl alcohol-based resin in the water-based pressure-sensitive 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 urethane resins.
The polyester-based ionomer-type urethane resin as referred to herein is a urethane resin having a polyester skeleton, in which a small amount of ionic component (hydrophilic component) is introduced. Such an ionomer-type urethane resin is emulsified in water to form an emulsion without using an emulsifying agent, and thus can be made a water-based adhesive. When using a polyester type ionomer type urethane resin, it is effective to mix a water soluble epoxy compound as a crosslinking agent.

The epoxy resin may, for example, be a polyamide epoxy resin obtained by reacting epichlorohydrin with a polyamide polyamine obtained by the reaction of a polyalkylene polyamine such as diethylene triamine or triethylene tetramine and a dicarboxylic acid such as adipic acid. As a commercial item of the related polyamide epoxy resin, "Sumiles resin (registered trademark) 650" and "Sumires resin 675" (above, Sumika Chemtex Co., Ltd. made), "WS-525" (made by Japan PMC Co., Ltd.) Etc. When the epoxy resin is blended, the amount thereof is usually 1 to 100 parts by mass, preferably 1 to 50 parts by mass, with respect to 100 parts by mass of the polyvinyl alcohol resin.

The thickness of the pressure-sensitive adhesive layer formed from the dry-setting adhesive is usually 0.001 to 5 μm, preferably 0.01 to 2 μm, and more preferably 0.01 to 0.5 μm. is there. If the pressure-sensitive adhesive layer formed of the dry-setting adhesive is too thick, the appearance tends 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. As an active energy ray-curable adhesive, a cationically polymerizable adhesive containing an epoxy compound and a cationic polymerization initiator, a radically polymerizable adhesive containing an acrylic curing component and a radical polymerization initiator, an epoxy compound And both a cationically polymerizable curing component such as acrylic resin and a radically polymerizable curing component such as an acrylic compound, and an adhesive containing a cationic polymerization initiator and a radical polymerization initiator, and these polymerization initiators. An adhesive etc. which are hardened by irradiating an electron beam without it are mentioned.

Among them, radically polymerizable active energy ray-curable adhesives containing an acrylic curing component and a photo radical polymerization initiator, cationically polymerizable active energy ray curable adhesives containing an epoxy compound and a photo cationic polymerization initiator 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.

The photo radical polymerization initiator and the photo cationic polymerization initiator include the above-described photo radical polymerization initiator and the photo cationic polymerization initiator. The content of the radical polymerization initiator and the cationic polymerization initiator is usually 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass, with respect to 100 parts by mass of the active energy ray-curable adhesive.

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 control agent, a plasticizer, an antifoamer, and the like. May be

In the present specification, an active energy ray is defined as an energy ray capable of decomposing a compound generating an active species to generate 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, with ultraviolet rays and electron beams being preferred. The preferred ultraviolet irradiation conditions are the same as in the polymerization of the polymerizable liquid crystal compound described above.

Hereinafter, the present invention will be more specifically described by way of examples. In the examples, “%” and “parts” mean mass% and parts 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 film thickness meter (MH-15M manufactured by Nikon Corp., counter TC101, MS-5C). In addition, 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, Alternatively, it was measured and calculated using an ellipsometer M-220 manufactured by JASCO Corporation. In addition, the ratio of Si / C can be calculated from elemental analysis of the vertical alignment film, measurement of surface constituent elements using X-ray photoelectric spectroscopy, or all structural formulas of compounds used for formation of the vertical alignment film are known. If it does, it can be calculated from the structural formula. In addition, AGF-B10 manufactured by Kasuga Denki Co., Ltd. was used for the corona treatment apparatus. Corona treatment can be suitably carried out when applying a composition to a substrate. Using the above-mentioned corona treatment device, it carried out once under 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 is obtained by mixing 5 parts (weight average molecular weight: 30000) of a photoalignment material having the following structure and 95 parts of cyclopentanone (solvent) as components and stirring the obtained mixture at 80 ° C. for 1 hour The composition for formation was obtained.

[Preparation of composition for forming vertical alignment film]
Shin-Etsu Chemical Co., Ltd.'s silane coupling agent "KBE-9103" is dissolved in a mixed solvent of ethanol and water mixed at a ratio of 9: 1 (mass ratio), and a vertical alignment film with a solid content of 0.5% The composition for formation was obtained.

[Preparation of Composition for Forming Horizontally Aligned Liquid Crystal Cured Film, and Composition for Forming Vertically Aligned Liquid Crystal Cured Film]
1.0 part of a leveling agent (F-556; manufactured by DIC) and a polymerization start with respect to a mixture in which the polymerizable liquid crystal compound A and the polymerizable liquid crystal compound B shown below are 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.), which is an agent, was added.

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

The polymerizable liquid crystal compound A was produced by the method described in JP-A-2010-31223. The polymerizable liquid crystal compound B was produced according to the method described in JP-A-2009-173893. The respective molecular structures are shown below.

[Polymerizable Liquid Crystal Compound A]

[Polymerizable Liquid Crystal Compound B]

[Manufacture of polarizing plate]
After immersing a polyvinyl alcohol film having an average degree of polymerization of about 2,400, a degree of saponification of at least 99.9 mol%, and a thickness of 75 μm in pure water at 30 ° C., the mass ratio of iodine / potassium iodide / water is 0. It was immersed in an aqueous solution of 02/2/100 at 30 ° C. to perform iodine staining (iodine staining step). The polyvinyl alcohol film subjected to 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 subjected to the boric acid treatment step was washed with pure water at 8 ° C. and then dried at 65 ° C. to obtain a polarizer (27 μm thickness after stretching) in which iodine is adsorbed and oriented to polyvinyl alcohol . At this time, stretching was performed in the iodine dyeing step and the boric acid treatment step. The total draw ratio in this drawing was 5.3. The obtained polarizer and a saponified triacetyl cellulose film (KC4 MinTAR KC4UYTAC 40 μm) were pasted together with a water-based adhesive using a nip roll. It dried at 60 degreeC for 2 minutes, maintaining the tension | tensile_strength of the obtained bonded article to 430 N / m, and obtained the polarizing plate which has a triacetyl-cellulose film as a protective film on single side | surface. The water-based adhesive is 100 parts of water, 3 parts of carboxyl group-modified polyvinyl alcohol (Kuraray Co., Ltd., "Klare Poval KL318"), and a water-soluble polyamide epoxy resin (Suzumi Chemtex Co., Ltd., "Sumirez Resin 650", solid) Aqueous solution with a concentration of 30%) and 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) with the polarizer surface of the polarizing plate obtained above as the incident surface. The absorption axis of the polarizing plate is the same as the stretching direction of polyvinyl alcohol, and the transmittance of the obtained polarizing plate is 42.1%, the transmittance of the visual sensitivity is 99.996%, the single hue a is The single color b was 3.7.

[Production of a laminate comprising a substrate, a horizontal alignment film, and a horizontal alignment liquid crystal cured film]
After performing corona treatment on a COP film (ZF-14-50) manufactured by ZEON CORPORATION, a composition for forming a horizontal alignment film is applied by 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 performed at an axis angle of 45 ° with an integrated light quantity at a wavelength of 313 nm: 100 mJ / cm ² . It was 100 nm when the film thickness of the obtained horizontal alignment film was measured with the ellipsometer.

Subsequently, a composition for forming a horizontal alignment liquid crystal cured film is applied to the horizontal alignment 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 A horizontal alignment liquid crystal cured film is formed by irradiating ultraviolet rays (in a nitrogen atmosphere, integrated light quantity at a wavelength of 365 nm: 500 mJ / cm ² ) using an electric appliance Co., Ltd., and a substrate, horizontal alignment film and horizontal alignment The laminated body which consists of a liquid-crystal cured film was obtained. It was 2.3 micrometers when the film thickness of the horizontal alignment liquid crystal cured film was measured with the ellipsometer.

[Re measurement of horizontal alignment liquid crystal cured film]
The in-plane retardation value ReA (λ) of the horizontal alignment liquid crystal cured film manufactured by the above method is a measuring machine (“KOBRA,” after it is bonded to glass via an adhesive and after peeling off the substrate COP. -WPR ", manufactured by Oji Scientific Instruments Co., Ltd.). The measurement results of the retardation 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.

[Production 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 corona treatment is performed on the laminate formed of the base material, the horizontal alignment film and the horizontal alignment liquid crystal cured film manufactured by the method described above, a composition for forming a vertical alignment film is applied by a bar coater, and 1 at 80 ° C. It was 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.

Furthermore, a composition for forming a vertical alignment liquid crystal cured film is applied to the vertical alignment film using a bar coater, dried at 120 ° C. for 1 minute, and then a high pressure mercury lamp (“Unique VB-15201BY-A”, Ushio Inc. A vertically aligned liquid crystal cured film is formed by irradiating ultraviolet light (integrated light quantity at a wavelength of 365 nm: 500 mJ / cm ² ) using a company-made product, and a substrate, horizontal alignment film, horizontal alignment liquid crystal curing A laminate comprising a film, a vertical alignment film, and a vertical alignment liquid crystal cured film was obtained. It was 1.2 micrometers when the film thickness of the vertical alignment liquid crystal cured film was measured with the ellipsometer. In addition, the interlayer distance between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film was 50 nm. Further, the constituent element ratio of the vertical alignment film was Si / C = 0.33.

[Rth measurement of vertical alignment liquid crystal cured film]
In order to measure the Rth of the vertically aligned liquid crystal cured film, a vertically 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, The vertically aligned liquid crystal cured film is bonded to glass via a pressure sensitive adhesive (Lintec's pressure sensitive adhesive 15 μm), and after confirming that there is no phase difference in COP, the incident angle of light to the sample is measured by an ellipsometer. It changed and measured the phase difference value. In addition, the average refractive index at a wavelength λ of 450 nm and 550 nm was measured using a refractometer (manufactured by Atago Co., Ltd., “multi-wavelength Abbe refractometer DR-M4”). The obtained film thickness, average refractive index, and ReC calculated from the measurement results of the ellipsometer are RthC (450) =-63 nm and RthC (550) =-73 nm, respectively. RthC (450) / RthC (550) It was 0.85.
[Measurement of R0 and R40 of a Laminate (Retardation Plate with Optical Compensation Function) Composed of a Horizontal Alignment Liquid Crystal Cured Film, a Vertical Alignment Film, and a Vertical Alignment Liquid Crystal Cured Film]

A laminate composed of the substrate, horizontal alignment film, horizontal alignment liquid crystal cured film, vertical alignment film, vertical alignment liquid crystal cured film manufactured by the above method is mixed with glass via an adhesive (Lintec pressure sensitive adhesive 15 μm) After bonding and peeling COP to prepare a measurement sample, it was confirmed that there is no phase difference between the horizontal alignment film and the vertical alignment film, and then the phase difference in the front direction of the retardation plate with the optical compensation function The value R 0 (λ) and the retardation value R 40 (λ) when tilted by 40 ° about the fast axis of the horizontal alignment 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) Table 1 shows the results of calculating)}-{R 0 (550) -R 40 (550)} |.

[Difference in in-plane average refractive index of each layer]
Each layer is coated on glass according to the above-mentioned method, and the average refractive index of each layer is calculated using a refractometer (manufactured by Atago Co., Ltd., "Multi-wavelength Abbe refractometer DR-M4") or an ellipsometer. It was confirmed that the difference in in-plane average refractive index was 0.2 or less.

[Flexibility test]
A glass plate with a thickness of 0.7 mm is placed on the coated film side of a laminate comprising the substrate produced by the above method, a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film, The laminate was bent 180 degrees as it was, and then the light of a fluorescent lamp was transmitted using a 10-fold loupe and the bent portion was observed to confirm the presence or absence of wrinkles and cracks. The results are shown in Table 1.

[Confirmation of reflection hue of bent part]
After applying a corona treatment to the coated film side of a laminate comprising the substrate produced by the above method, a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film, the absorption axis of the polarizing plate It bonds to the polarizing plate produced by the above-mentioned method via an adhesive so that the angle between the liquid crystal and the slow axis of the horizontal alignment film is 45 °, the base material is peeled off, and the elliptically polarized light with optical compensation function A board was made. Then, it was bonded to an aluminum foil through a pressure sensitive adhesive, was bent 180 ° so as to have a radius of 1 cm on the polarizing plate side, and the reflected hue of the bent portion was visually observed. The results are shown in Table 1.

(Examples 2 and 3)
A retardation plate with an optical compensation function is produced in the same manner as in Example 1 except that the film thickness of the vertical alignment film is changed as described in Table 1, retardation value measurement, bending test, and reflection of a bent portion The hue confirmation was carried out. The results are shown in Table 1.

(Example 4)
9. 0.5 wt% polyimide ("Sun Ever SE-610" manufactured by Nissan Chemical Industries, Ltd.), 72.3 wt% N-methyl-2-pyrrolidone, 18.1 wt% 2-butoxyethanol, A composition B for forming a vertical alignment film was prepared by mixing 1% by weight of ethylcyclohexane and 0.01% by weight of DPHA (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the composition B for forming a vertical alignment film was used. A retardation plate with an optical compensation function was produced in the same manner as in Example 1 except for the above, and retardation value measurement, a flexibility test, and reflection hue confirmation of a bent portion were carried out. The results are shown in Table 1. The film thickness of the vertical alignment film was 0.2 μm when measured by an 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. In addition, when the composition for forming a vertically aligned liquid crystal cured film was applied, it was confirmed that the vertical alignment film was corroded by a solvent, and that alignment defects and alignment defects were partially generated.

(Example 5)
The substrate was changed to a polyethylene terephthalate film (manufactured by Lintec Co., Ltd., SP-PLR 382050, hereinafter abbreviated as “separator”) subjected to release treatment, the lamination order was vertical alignment film, vertical alignment liquid crystal curing A retardation plate with an optical compensation function is manufactured 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 order, retardation value measurement, a flexibility test, and a reflected hue of the bent portion. Confirmation was carried out. The results are shown in Table 1. The film thickness of the horizontal alignment film was 0.2 μm when measured with an 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)
The position with the optical compensation function is the same as in Example 1 except that the values of RthC (450) and RthC (550) are changed as described in Table 1 by changing the film thickness of the vertical alignment liquid crystal cured film. The phase difference plate was manufactured, and retardation value measurement, a flexibility test, and reflection hue confirmation of a bending part were implemented. The results are shown in Table 1.

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

(Preparation of Composition (B) for Forming Vertically Aligned Liquid Crystal Cured Film)
0.1 part of the leveling agent F-556 and 3 parts of the polymerization initiator Irg 369 are added to the liquid crystal compound LC242 described below: Paliocolor LC242 (registered trademark of BASF AG) so that the solid content concentration becomes 13% Then, cyclopentanone was added thereto to obtain a composition (B) for forming a vertically aligned liquid crystal cured film. The name of the obtained liquid crystal composition is referred to as "composition V".
Liquid crystal compound LC242: Paliocolor LC242 (registered trademark of BASF)

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

Reflected hue at bent portion: 黒色 for black, and x for clearly confirmed coloring.
Flexibility test: A case where no defect occurs is represented by ○, and a case where a defect such as wrinkles or a crack occurs is represented by x.

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

Claims

Form a horizontal alignment film through coating, drying and alignment processing steps,
Form a horizontal alignment liquid crystal cured film through coating, drying and UV irradiation processes,
Further, 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 steps,
A manufacturing method of a retardation plate with an optical compensation function which forms 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 having an optical compensation function according to claim 1, wherein a horizontal alignment film having a film thickness of 1.0 μm or less, 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 according to any one of claims 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 comprising a photo alignment film are formed in this order. .
The retardation with the optical compensation function according to any one of claims 1 to 3, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film comprising a photo alignment film containing a cinnamoyl group are formed in this order. How to make a board.
The retardation plate with an optical compensation function according to any one of claims 1 to 4, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film with a film 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 plate having an optical compensation function according to any one of claims 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 horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film having an element of Si / C of 0.03 to 1.00, and a vertical alignment liquid crystal cured film are formed in this order. Manufacturing method of retardation plate with optical compensation function.
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 to produce a retardation plate with an optical compensation function, and the horizontal alignment liquid crystal cured film has the following relationship ( The method for producing an optical compensation function retardation plate according to any one of claims 1 to 7, wherein 1) is satisfied.
ReA (450) / ReA (550) <1.00 (1)
In formula, ReA ((lambda)) shows the in-plane phase difference value in wavelength (lambda) nm of a horizontal alignment liquid crystal cured film. The definition of the in-plane retardation value ReA (λ) is as follows.
ReA (λ) = (nxA (λ) -nyA (λ)) × dA
Where nxA (λ) is the main refractive index in the film plane of the horizontal alignment liquid crystal cured film, and the main refractive index at wavelength λ (nm) is nyA (λ) in the same plane as nxA (λ) The refractive index at a wavelength λ (nm) is a refractive index in the orthogonal direction, and dA indicates the film thickness of the horizontal alignment liquid crystal curing.
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 to produce a retardation plate with an optical compensation function, 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, wherein 2) is satisfied.
RthC (450) / RthC (550) <1.00 (2)
In the formula, RthC (λ) represents the retardation value in the thickness direction at the wavelength λ nm of the vertically aligned liquid crystal cured film. The definition of the phase difference value RthC (λ) is as follows.
RthC (λ) = ((nxC (λ) + nyC (λ)) / 2−nzC (λ)) × dC
Where nxC (λ) is the main refractive index in the film plane of the vertical alignment liquid crystal cured film, and the main refractive index at wavelength λ (nm) is
nyC (λ) is a refractive index in a direction orthogonal to nxC (λ) in the same plane, and has a refractive index at a wavelength λ (nm),
nzC (λ) is the refractive index in the thickness direction of the vertical alignment liquid crystal cured film, and the refractive index at the wavelength λ (nm) is
dC indicates the film thickness of the vertical alignment liquid crystal curing, respectively.
Vertical alignment film is formed through 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 application, drying and alignment treatment steps.
By forming a horizontal alignment liquid crystal cured film through coating, drying, and ultraviolet irradiation steps,
A method of manufacturing a retardation plate with an optical compensation function in which a vertical alignment film, 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 method for producing a retardation plate having 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 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 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 comprising a photo alignment film, and a horizontal alignment liquid crystal cured film are formed in this order.
The phase difference with the optical compensation function according to any one of claims 10 to 12, wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film comprising a photo alignment film containing cinnamoyl groups, and a horizontal alignment liquid crystal cured film are formed in this order. How to make a board.
The retardation plate with an optical compensation function according to any one of claims 10 to 13, 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 having an optical compensation function according to any one of claims 10 to 14, wherein a vertical alignment film containing a 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 horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film having an element of Si / C of 0.03 to 1.00, and a vertical alignment liquid crystal cured film are formed in this order. Manufacturing method of retardation plate with optical compensation function.
A vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film are formed in this order to produce a retardation plate with an optical compensation function, and the horizontal alignment liquid crystal cured film has the following relationship ( The method for producing an optical compensation function retardation plate according to any one of claims 10 to 16, wherein 3) is satisfied.
ReA (450) / ReA (550) <1.00 (3)
In formula, ReA ((lambda)) shows the in-plane phase difference value in wavelength (lambda) nm of a horizontal alignment 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 horizontal alignment liquid crystal cured film, and the main refractive index at wavelength λ (nm) is orthogonal to nyA (λ) in the same plane as nxA (λ) (D) indicates the film thickness of the horizontal alignment liquid crystal curing.
A vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film are formed in this order to produce a retardation plate with an optical compensation function, and the vertical alignment liquid crystal cured film has the following relationship ( The method for producing an optical compensation function retardation plate according to any one of claims 10 to 17, wherein 4) is satisfied.
RthC (450) / RthC (550) <1.00 (4)
In the formula, RthC (λ) represents the retardation value in the thickness direction at the wavelength λ nm of the vertically aligned liquid crystal cured film. The definition of the phase difference value RthC (λ) is as follows.
RthC (λ) = ((nxC (λ) + nyC (λ)) / 2−nzC (λ)) × dC
Where nxC (λ) is the main refractive index in the film plane of the vertical alignment liquid crystal cured film, and the main refractive index at the wavelength λ (nm),
nyC (λ) is a refractive index in a direction orthogonal to nxC (λ) in the same plane, and has a refractive index at a wavelength λ (nm),
nzC (λ) is the refractive index in the thickness direction of the vertical alignment liquid crystal cured film, and the refractive index at the wavelength λ (nm) is
dC indicates the film thickness of the vertical alignment liquid crystal curing, respectively.