KR20200036928A - Phase difference plate with optical compensation function for flexible display - Google Patents

Abstract

Provided is a method of manufacturing a retardation plate with an optical compensation function for flexible that does not cause problems such as wrinkles or cracks even when folded, and does not reflect external light in a colored state even when folded. In the manufacturing method of the present invention, after a horizontal alignment film is formed through a coating, drying, and alignment treatment process, a horizontal alignment liquid crystal cured film is formed through a coating, drying, and ultraviolet irradiation process, and a vertical alignment film is further subjected to a coating and drying process. By forming, forming a vertically aligned liquid crystal cured film through coating, drying, and ultraviolet irradiation processes, and forming a horizontally aligned film, a horizontally aligned liquid crystal cured film, a vertically aligned film, and a vertically aligned liquid crystal cured film in this order, the optical for flexible display A retardation plate with a compensation function is manufactured.

Description

Phase difference plate with optical compensation function for flexible display

The present invention relates to a phase difference 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 remained flat even when the image was displayed or not.

In such flat panel displays, retardation plates are frequently used. For example, in the organic EL image display device, in order to prevent light reflection from the electrodes constituting the image display device, a circular polarizing plate in which a retardation plate is combined with a polarizing plate is used.

For such a retardation plate, a retardation plate exhibiting reverse wavelength dispersion is preferable in that it exhibits equivalent retardation performance over a wide wavelength range of visible light. As a retardation plate exhibiting reverse wavelength dispersibility, a retardation plate made of a horizontally oriented liquid crystal cured film polymerized and cured in a state in which a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion is aligned in the horizontal direction is known.

Further, even when viewed from the oblique direction, a phase difference plate with an optical compensation function having a function to compensate for exerting the same optical performance as viewed from the front direction is also required. As such a phase difference plate with an optical compensation function, a horizontally oriented liquid crystal It is proposed in patent document 1 [Japanese Patent Publication No. 2015-163935] to further provide a vertically oriented liquid crystal cured film obtained by polymerization-curing a polymerizable liquid crystal compound in a vertically aligned state together with a cured film. The document also discloses that the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film are laminated through only the alignment film or through a protective layer or the like. In addition, this document only discloses that a retardation plate with an optical compensation function described in the document can be used for a flat panel display.

Japanese Patent Application Publication 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, the retardation plate with an optical compensation function is also folded together with the display.

However, when a problem such as wrinkles or cracks occurs when folded, when the flexible display is unfolded again to display an image, a portion of the problem such as wrinkles or cracks becomes a defect and the displayed image is inhibited. Further, when folded while displaying an image, the folded portion is substantially small in elevation angle (the angle formed by the film plane and the direction in which the viewer sees the screen) becomes very small, so that the optical performance is not sufficiently compensated for coloring. It is also a problem to reflect the external light in the state of being.

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

As a result of earnest examination to solve the above problems, the present inventors have accomplished the present invention.

That is, the following are included in the present invention.

[1] A horizontal alignment film is formed through a coating, drying, and alignment treatment process.

After applying, drying, and irradiating ultraviolet rays, a horizontally oriented liquid crystal cured film is formed,

In addition, a vertical alignment layer is formed through a coating and drying process.

By forming a vertically aligned liquid crystal cured film through coating, drying, and ultraviolet irradiation processes,

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

[3] Production of a phase difference plate with an optical compensation function according to any one of [1] to [2] above, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film made of a photo-alignment film are formed in this order. Way.

[4] The optical compensation according to any one of [1] to [3], in which a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film made of a photo-alignment film containing a cinnamoyl group are formed in this order. Manufacturing method of retardation plate with function.

[5] A phase difference plate with an optical compensation function according to any one of [1] to [4], in which a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film having a thickness of 1.0 µm or less, and a vertical alignment liquid crystal cured film are formed in this order. Method of manufacture.

[6] Of the retardation plate with an optical compensation function according to any one of [1] to [5], in which a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film containing Si elements, and a vertical alignment liquid crystal cured film are formed in this order. Manufacturing method.

[7] The optical compensation according to any one of [1] to [6], in which a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film having an Si / C element 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 function.

[8] As a method for producing 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 horizontal alignment liquid crystal cured film satisfies the following relationship (1) The manufacturing method of the phase difference plate with an optical compensation function in any one of said [1]-[7].

ReA (450) / ReA (550) <1.00 … (One)

In the formula, ReA (λ) represents the in-plane retardation value at a wavelength λ nm of the horizontally oriented liquid crystal cured film. The definition of the in-plane retardation value ReA (λ) is as follows.

ReA (λ) = (nxA (λ)-nyA (λ)) × dA

However, nxA (λ) is the main refractive index in the film plane of the horizontally oriented liquid crystal cured film, the main refractive index at wavelength λ (nm), and nyA (λ) is the direction orthogonal to nxA (λ) in the same plane. As the refractive index, the refractive index at the wavelength λ (nm), and dA represents the thickness of the horizontally oriented liquid crystal cured film, respectively.

[9] As a method for producing 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 vertical alignment liquid crystal cured film satisfies the following relationship (2) The manufacturing method of the phase difference plate with an optical compensation function in any one of said [1]-[8].

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 oriented 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

However, nxC (λ) is the main refractive index in the film plane of the vertically oriented liquid crystal cured film, and the main refractive index at wavelength λ (nm),

nyC (λ) is a refractive index in the direction orthogonal to nxC (λ) in the same plane, and the refractive index at wavelength λ (nm),

nzC (λ) is the refractive index in the thickness direction of the vertically aligned liquid crystal cured film, and the refractive index at wavelength λ (nm),

dC represents the thickness of the vertically oriented liquid crystal cured film, respectively.

In addition, when nxC (λ) = nyC (λ), nxC (λ) can be a refractive index in any direction within the film plane.

In addition, the present invention includes the following.

[10] A vertical alignment film is formed through a coating and drying process,

A vertical alignment liquid crystal cured film is formed through coating, drying, and ultraviolet irradiation processes,

In addition, a horizontal alignment film is formed through a process of coating, drying, and alignment,

By forming a horizontally oriented liquid crystal cured film through coating, drying, and ultraviolet irradiation processes,

The manufacturing method of the phase difference plate with an optical compensation function which forms a vertical alignment film, a vertically aligned liquid crystal cured film, a horizontally aligned film, and a horizontally aligned liquid crystal cured film in this order.

[11] A method for producing a phase difference plate with an optical compensation function according to [10] above, 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.

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

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

[14] A phase difference plate with an optical compensation function according to any one of [10] to [13], 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 having a film thickness of 1.0 µm or less are formed in this order. Method of manufacture.

[15] Of the retardation plate with an optical compensation function according to any one of [10] to [14], in which the vertical alignment film containing the Si element, the vertical alignment liquid crystal cured film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film are formed in this order. Manufacturing method.

[16] The optical compensation according to any one of [10] to [15], in which a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film having elements 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 function.

[17] As a method for producing 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 horizontal alignment liquid crystal cured film satisfies the following relationship (3) The manufacturing method of the phase difference plate with an optical compensation function in any one of said [10]-[16].

ReA (450) / ReA (550) <1.00 … (3)

In the formula, ReA (λ) represents the in-plane retardation value at a wavelength λ nm of the horizontally oriented liquid crystal cured film. The definition of the in-plane retardation value ReA (λ) is as follows.

ReA (λ) = (nxA (λ)-nyA (λ)) × dA

However, nxA (λ) is the main refractive index in the film plane of the horizontally oriented liquid crystal cured film, and nyA (λ) is the refractive index in the direction perpendicular to the same plane as nxA (λ). As, the refractive index at wavelength λ (nm), and dA represents the thickness of the horizontally aligned liquid crystal cured film, respectively.

[18] As a method for producing 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 vertical alignment liquid crystal cured film satisfies the following relationship (4) The manufacturing method of the phase difference plate with an optical compensation function as described in said [1]-[17] mentioned above.

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 oriented 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

However, nxC (λ) is the main refractive index in the film plane of the vertically oriented liquid crystal cured film, and the main refractive index at wavelength λ (nm),

nyC (λ) is a refractive index in the direction orthogonal to nxC (λ) in the same plane, and the refractive index at wavelength λ (nm),

nzC (λ) is the refractive index in the thickness direction of the vertically aligned liquid crystal cured film, and the refractive index at wavelength λ (nm),

dC represents the thickness of the vertically oriented liquid crystal cured film, respectively.

In addition, in the case of nxC (λ) = nyC (λ), nxC (λ) can be a refractive index in any direction within the film plane.

By obtaining the retardation plate with an optical compensation function by the manufacturing method of this invention, and laminating a polarizing plate on this, an elliptical polarizing plate with an optical compensation function can be manufactured.

This elliptical polarizing plate with an optical compensation function is preferably attached to, for example, an organic EL display device.

The retardation plate with an optical compensation function of the present invention can suppress problems such as wrinkles and cracks generated when bending.

[Horizontal alignment liquid crystal cured film]

The horizontally aligned 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. The horizontal alignment liquid crystal cured film is formed by applying a polymerizable liquid crystal composition onto the horizontal alignment film, and heating and / or light irradiation to polymerize the composition containing the polymerizable liquid crystal compound in an aligned state. It is preferable from the viewpoint of being able to arbitrarily design the thin film and wavelength dispersion characteristics of the alignment liquid crystal cured film.

The three-dimensional refractive ellipsoid formed by the horizontally aligned liquid crystal cured film may have biaxiality, but preferably has uniaxiality. The horizontally aligned liquid crystal cured film may be a horizontally aligned liquid crystal cured film made of a polymer of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound in a state aligned in a horizontal direction with respect to a plane of the horizontally aligned liquid crystal cured film, or a hybrid aligned liquid crystal cured film or It may be an inclined alignment liquid crystal cured film. The refractive indexes nx, ny, and nz in three directions in the refractive ellipsoid formed by the alignment of the polymerizable liquid crystal are nx> ny ≒ nz (referred to as a positive A plate) or nx <ny ≒ nz (referred to as a negative A plate) ). nx represents the main refractive index in the direction parallel to the plane of the horizontally oriented liquid crystal cured film in the refractive index ellipsoid formed by the horizontally oriented liquid crystal cured film. ny is a refractive index ellipsoid formed by the horizontally aligned liquid crystal cured film, and represents a refractive index in a direction parallel to the plane of the horizontally aligned liquid crystal cured film and perpendicular 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 horizontally aligned liquid crystal cured film can be either a rod-shaped polymerizable liquid crystal or a disc-shaped polymerizable liquid crystal, but is preferably a rod-shaped polymerizable liquid crystal. When the rod-shaped 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 oriented liquid crystal cured film has optical anisotropy in the plane of the film, it is preferable that the in-plane retardation value Re1 (550) for light having a wavelength of 550 nm satisfies the optical properties represented by the following formula (21). In addition, the horizontally aligned liquid crystal cured film has an in-plane retardation value for light having a wavelength of 450 nm, Re1 (450), an in-plane retardation value for light having a wavelength of 550 nm, Re1 (550), and an in-plane retardation value for light having a wavelength of 650 nm. It is also preferable that phosphorus Re1 (650) satisfies the optical properties represented by the formulas (22) and (23). It is more preferable that the horizontally aligned liquid crystal cured film satisfies the optical properties represented by the following formulas (21), (22), and (23).

120 nm ≤ ReA (550) ≤ 170 nm … (21)

[In the formula, ReA 550 represents an in-plane retardation value (in-plane retardation) for light of a wavelength of 550 nm in the horizontally oriented liquid crystal cured film.]

ReA (450) / ReA (550) ≤ 1.0 … (22)

1.00 ≤ ReA (650) / ReA (550) … (23)

[Wherein, ReA 450 is the in-plane retardation value for light of a wavelength of 450 nm of the horizontally oriented liquid crystal cured film, ReA 550 is the in-plane retardation value for light of a wavelength 550 nm of the horizontally oriented liquid crystal cured film, ReA ( 650) denotes in-plane retardation values for light having a wavelength of 650 nm in the horizontally aligned liquid crystal cured film.]

When the in-plane retardation value ReA (550) of the horizontally aligned liquid crystal cured film exceeds the range of Expression (21), the color of the front surface of the display using the elliptical polarizing plate with an optical compensation function, including the retardation plate with an optical compensation function, may become red or blue. Problems may arise. A more preferable range of the in-plane retardation value is 130 nm ≤ ReA (550) ≤ 160 nm. When the "ReA (450) / ReA (550)" of the horizontally aligned liquid crystal cured film exceeds 1.0, the ellipticity at the short wavelength side of the elliptical polarizing plate provided with the horizontally aligned liquid crystal cured film deteriorates. When the ellipticity of the elliptical polarizing plate deteriorates on the short wavelength side and becomes smaller than 1.0, the function as an elliptical polarizing plate when viewed from the front on the short wavelength side tends to be impaired. The "ReA (450) / ReA (550)" is preferably 0.75 to 0.92, more preferably 0.77 to 0.87, 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), in order to obtain the desired in-plane retardation value (ReA (λ): in-plane retardation value of the horizontally oriented liquid crystal cured film at wavelength λ (nm)), the 3D refractive index and the film Adjust the thickness dA. In addition, the three-dimensional refractive index depends on the molecular structure and orientation state of the polymerizable liquid crystal compound described later.

ReA (λ) = (nxA (λ)-nyA (λ)) × dA (24)

[Wherein, in the refractive index ellipsoid formed by the horizontally aligned liquid crystal cured film, nxA (λ)> nyA (λ) ≒ nzA (λ) has a relationship, and nxA (λ) has a horizontal orientation with respect to light having a wavelength λ (nm) The main refractive index in a direction parallel to the plane of the liquid crystal cured film is shown. nyA (λ) is a refractive index ellipsoid formed by the horizontally aligned liquid crystal cured film with respect to light having a wavelength of λ (nm), parallel to the horizontally aligned liquid crystal cured film plane, and orthogonal to the direction of the nxA (λ) It shows the refractive index in the direction. dA represents the thickness of the horizontally oriented liquid crystal cured film.]

It is preferable that the horizontally aligned liquid crystal cured film is 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 refers to a group capable of participating in the polymerization reaction with active radicals or acids generated from a 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, and oxetanyl group. You can. Especially, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferable, and an acryloyloxy group is more preferable. The liquid crystal property may be a thermotropic liquid crystal, a lyotropic liquid crystal, or a nematic liquid crystal or a smectic liquid crystal as an image order structure.

In the present invention, the polymerizable liquid crystal compound is expressed by the following formula (I) from the viewpoint of satisfying the relationship between the above formulas (21) and (22) or (31) and (32), which express reverse wavelength dispersion. )

The compound represented by is preferable.

In formula (I), Ar represents a divalent aromatic group which may have a substituent. The aromatic group referred to herein is a group having a planar cyclic structure, and the number of π electrons in the ring structure is [4n + 2] individual according to Hickel's law. Here, n represents an integer (整數). When a ring structure is formed including a hetero atom such as -N = or -S-, non-covalent bonding electron pairs on these hetero atoms are satisfied to satisfy Hickel's rule, and also include a case having aromaticity. It is preferable that at least one of a nitrogen atom, an oxygen atom, and a sulfur atom is contained in the divalent aromatic group.

G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group.

Here, the hydrogen atom contained in the divalent aromatic group or divalent alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or The nitro group may be substituted, and the carbon atom constituting the divalent aromatic group or divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom.

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 + l. Here, when 2 ≦ k + l, B ¹ and B ² , G ¹ and G ² may be the same or different from each other.

E ¹ and E ² each independently represent an alkanediyl group having 1 to 17 carbon atoms, wherein the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and -CH ₂ contained in the alkanediyl group -May be substituted with -O-, -S-, -Si-. P ¹ and P ² independently of each other represent a polymerizable group or a hydrogen atom, and at least one is a polymerizable group.

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

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 a8} OC = OOR - a, or C≡C- -, -N = N-, -CR c = CR d. 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 represent an alkyl group or a hydrogen atom having 1 to 4 carbon atoms. L ¹ and L ² each independently is, 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- , -CH ₂ CH _2- . L ¹ and L ² are each independently, more preferably a single bond, -O-, -CH ₂ CH _2- , -COO-, -COOCH ₂ CH _2- , or OCO-.

B ¹ and B ² are each independently, preferably, a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a9 OR ^a10- , -R ^a11 COOR ^a12- , -R ^a13 OCOR ^a14- , or R ^a15 OC = OOR ^a16- . Here, R ^a9 to R ^a16 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms. B ¹ and B ² are each independently, more preferably a single bond, -OR ^a10-1- , -CH _2- , -CH ₂ CH _2- , -COOR ^a12-1- , or OCOR ^a14-1- . Here, R ^a10-1 , R ^a12-1 , and R ^a14-1 each independently represent a single bond, -CH _2- , -CH ₂ CH _2- . B ¹ and B ² each independently is, more preferably a single _{bond, -O-, -CH 2 CH 2 -} , -COO-, -COOCH 2 CH 2 -, -OCO-, or OCOCH ₂ CH ₂ - is .

k and l are preferably 2 ≦ k + l ≦ 6 in terms of reverse wavelength dispersion expression, more preferably k + l = 4, and more preferably k = 2 and l = 2. k = 2 and l = 2 are more preferable because they are symmetrical.

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

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

It is preferable that Ar 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 said aromatic hydrocarbon ring, a benzene ring, a naphthalene ring, anthracene ring, etc. are mentioned, for example, A benzene ring and a naphthalene ring are preferable. Examples of the aromatic heterocyclic ring include furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazole ring, triazine ring, pyrroline ring , Imidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, thienothiazole ring, oxazole ring, benzoxazole ring, and phenanthroline ring. 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. Moreover, when a nitrogen atom is contained in Ar, it is preferable that the said nitrogen atom has π electrons.

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

The following groups are mentioned as an aromatic group represented by Ar, for example.

In formulas (Ar-1) to (Ar-22), the symbol * represents a connecting portion, and Z ⁰ , Z ¹ and Z ² are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms, cyan A furnace group, a nitro group, a C1-C12 alkylsulfinyl group, a C1-C12 alkylsulfonyl group, a carboxyl group, a C1-C12 fluoroalkyl group, a C1-C6 alkoxy group, a C1-C12 alkylthio group , N-alkylamino group having 1 to 12 carbon atoms, N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkyl sulfamoyl group having 1 to 12 carbon atoms, or N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms Indicates.

Q ¹ and Q ² are, each ^{independently, -CR 2 'R 3' -} , -S-, -NH-, -NR 2 '-, -CO- , or represents a O-, R ^2' and R ^{3 '} Each independently represents a hydrogen atom or a C1-C4 alkyl group.

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

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

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

Examples of the aromatic hydrocarbon groups for 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 phenyl group and naphthyl group It is preferable, and a phenyl group is more preferable. The aromatic heterocyclic group includes 4 to 4 carbon atoms containing at least one hetero atom such as nitrogen atom, oxygen atom, sulfur atom, such as furyl group, pyrrolyl group, thienyl group, pyridinyl group, thiazolyl group, and benzothiazolyl group. The aromatic heterocyclic group of 20 is mentioned, and a furyl group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group are preferable.

Y ¹ and Y ² may each independently be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly. The polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from a set of aromatic rings.

Z ⁰ , Z ¹ and Z ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, preferably an alkoxy group having 1 to 12 carbon atoms, and Z ⁰ is a hydrogen atom , An alkyl group having 1 to 12 carbon atoms and a cyano group are more preferable, 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 '} -, -O-, and R ^2' is preferably a hydrogen atom. Especially, -S-, -O-, and -NH- are especially preferable.

Among 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 and Z ^{0 to} which it is bonded. Examples of the aromatic heterocyclic group include the aromatic heterocyclic rings that Ar may have, but, for example, pyrrole ring, imidazole ring, pyrroline ring, pyridine ring, pyrazine ring, pyrimidine ring, indole ring, And a quinoline ring, an isoquinoline ring, a purine ring, and a pyrrolidine ring. This aromatic heterocyclic group may have a substituent. Further, Y ¹ may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted together with the nitrogen atom and Z ^{0 to} which it is bonded. For example, benzofuran ring, benzothiazole ring, benzoxazole ring, etc. are mentioned. Moreover, the compound represented by said Formula (I) can be manufactured according to the method of Unexamined-Japanese-Patent No. 2010-31223, for example.

The polymerizable liquid crystal compound may be used alone or in combination of two or more. When used in combination of two or more, 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 even more preferably 100 parts by mass of the polymerizable liquid crystal compound. 80 parts by mass or more.

The composition for forming a horizontally aligned liquid crystal cured film used for forming a horizontally aligned liquid crystal cured film (hereinafter also referred to as a polymerizable liquid crystal composition) includes a solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, and an adhesion improving agent. It can contain as. 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 98 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. . When content is in the said range, there exists a tendency for the orientation of the horizontally-oriented liquid crystal cured film to become high. Here, the solid content refers to the total amount of components excluding the solvent from the composition.

The solvent is preferably a solvent capable of dissolving the polymerizable liquid crystal compound, and is preferably a solvent inert to the polymerization reaction of the polymerizable liquid crystal compound. As the solvent, for example, 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 Alcohol solvents such as glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Alicyclic hydrocarbon solvents such as ethyl cyclohexane; 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; And amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone. These solvents can be used alone or in combination of two or more. However, since the compound represented by the formula (I) generally has a relatively large conjugated system, solubility in a solvent is low, and among the solvents exemplified above, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, ether-based solvents, It is preferable to use 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 weight, relative to 100 parts by mass of the polymerizable liquid crystal composition. Therefore, the solid content of 100 parts by mass of the composition is preferably 2 to 50 parts by mass. When the solid content of the composition is 50 parts by mass or less, since the viscosity of the composition is low, the thickness of the horizontally oriented liquid crystal cured film becomes approximately uniform, and there is a tendency that non-uniformity is less likely to occur in the horizontally oriented liquid crystal cured film. The solid content may be appropriately determined in consideration of the thickness of the horizontally oriented liquid crystal cured film to be produced.

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

Examples of the photopolymerization initiator include a photo-radical polymerization initiator and a photocationic polymerization initiator. Examples of the photo-radical polymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, triazine compounds, and the like, and aromatic photocationic polymerization initiators include And onium salts such as diazonium salts, aromatic iodonium salts and aromatic sulfonium salts, and iron-arylene complexes.

Specifically, Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (above, manufactured by BASF Japan Co., Ltd.), Sakeol BZ, Sakeol Z, Sakeol BEE (above, manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 ( Nippon Gunpowder Co., Ltd.), Kayacure UVI-6992 (manufactured by Dausa), Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer N-1919, Ah Deca Acruze NCI-831, Adeka Acruz NCI-930 (above, manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (above, manufactured by Siebel Hegna Japan) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.), Kayard (registered trademark) series (manufactured by Nippon Gunpowder Co., Ltd.), Syracure UVI series (manufactured by Dow Chemical Co., Ltd.), CPI series (sanya In the like Co., Ltd.), TAZ, BBI and DTS (or more, Midori Chemical Co., Ltd.), RHODORSIL (TM) (Rhodia Co., Ltd.). The photopolymerization initiator may 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 radicals by light irradiation is preferable.

From the viewpoint of being able to fully utilize the energy emitted from the light source and having excellent productivity, the photopolymerization initiator is preferably present in a range of 300 nm to 400 nm, and is present in a range of 300 nm to 380 nm. It is more preferable to do. Moreover, from the same viewpoint, an α-acetophenone-based polymerization initiator and an oxime-based photo polymerization initiator are preferable.

As an α-acetophenone polymerization initiator, for example, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4- Morpholinophenyl) -2-benzylbutan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one; More preferably 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane And -1-one. Commercially available products of the α-acetophenone compound include Irgacure 369, 379EG, 907 (above, manufactured by BASF Japan Co., Ltd.) and Sakeol BEE (manufactured by Seiko Chemical Co., Ltd.).

The oxime-based photopolymerization initiator generates radicals by being irradiated with light. Polymerization of the polymerizable liquid crystal compound in the core portion of the horizontally aligned liquid crystal cured film proceeds favorably by this radical. Moreover, it is preferable to use the photoinitiator which can utilize ultraviolet rays of wavelength 350nm or more efficiently from a viewpoint of progressing a polymerization reaction in the core part of a horizontally-oriented liquid crystal cured film more efficiently. As a photopolymerization initiator that can efficiently use ultraviolet rays having a wavelength of 350 nm or more, a triazine compound or an oxime ester type carbazole compound is preferable, and from the viewpoint of sensitivity, an oxime ester type carbazole compound is more preferable. Examples of the oxime ester type carbazole compound include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone, and 1- [9-ethyl-6 -(2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like. As commercial products of the oxime ester type carbazole compound, Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, manufactured by BASF Japan Co., Ltd.), Adeka Optomer N-1919, Adeka And ACROUZE NCI-831 (above, manufactured by ADEKA Corporation).

The amount of the photopolymerization initiator added 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. If it is within the above range, the reaction of the polymerizable group proceeds sufficiently, and the orientation of the polymerizable liquid crystal compound is not disturbed.

The polymerization reaction of the polymerizable liquid crystal compound can be controlled by adding a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinones having substituents such as hydroquinone and alkyl ethers; Catechols having substituents such as alkyl ethers such as butyl catechol; Radical scavengers such as pyrogallols and 2,2,6,6-tetramethyl-1-piperidinyloxy radicals; Thiophenols; and β-naphthylamines and β-naphthols. In order to polymerize a polymerizable liquid crystal compound without disturbing the alignment of the polymerizable liquid crystal compound, the content of the polymerization inhibitor is usually 0.01 to 10 parts by mass, preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. It is 5 mass parts, More preferably, it is 0.1-3 mass parts. The polymerization inhibitor may be used alone or in combination of two or more.

Moreover, a photosensitive initiator can be made highly sensitive by using a photosensitive agent. As a photosensitizer, For example, xanthones, such as xanthone and thioxanthone; Anthracenes having substituents such as anthracene and alkyl ethers; Phenothiazine; And rubrene. The photosensitizer can be used alone or in combination of two or more. Content of a photosensitizer is 0.01-10 mass parts normally with respect to 100 mass parts of polymerizable liquid crystal compounds, Preferably it is 0.05-5 mass parts, More preferably, it is 0.1-3 mass parts.

The leveling agent is an additive having a function of adjusting the fluidity of the polymerizable liquid crystal composition to make the layer obtained by applying the composition more flat, for example, silicone-based and polyacrylate-based and perfluoro such as silane coupling agent And an alkyl-based leveling agent. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341 , X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502 , KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBE-585, KBM-802, KBM-803, KBE -846, KBE-9007 (above, all manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (above, all Momentive Performance Materials Japan joint ventures) Manufactured), fluorinert (registered trademark) FC-72, copper FC-40, copper FC-43, copper FC-3283 (above, manufactured by Sumitomo 3M Co., Ltd.), Megapak (registered trademark) R -08, East R-30, East R-90, East F-410, East F-411, East F-443, East F-445, East F-470, East F-477, East F-479, East F -482, Copper F-483 (above, all manufactured by DIC Corporation), F-top ( Product name) EF301, copper EF303, copper EF351, copper EF352 (above, all manufactured by Mitsubishi Material Electronic Hwasung Co., Ltd.), SUPRON (registered trademark) S-381, copper S-382, copper S-383, copper S-393 , Dong SC-101, Dong SC-105, KH-40, SA-100 (above, all manufactured by AGC Seimi Chemical Co., Ltd.), trade names E1830, Dong E5844 (manufactured by Daikin Fine Chemical Research Institute), BM -1000, BM-1100, BYK-352, BYK-353 and BYK-361N (all are brand names: manufactured by BM Chemie) and the like. The leveling agent 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, more preferably 0.05 to 3 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. When the content of the leveling agent is within the above range, it is preferable because the resulting horizontally oriented liquid crystal cured film tends to be smoother.

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

The horizontally oriented liquid crystal cured film is coated with the polymerizable liquid crystal composition on a horizontally oriented film to be described later, and then the solvent is removed, so that the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound in an aligned state is heated and / or active energy rays. It can be obtained by curing.

As a method of applying the polymerizable liquid crystal composition on the horizontal alignment film (hereinafter, sometimes referred to as coating method A), for example, extrusion coating method, direct gravure coating method, reverse gravure coating method, CAP coating method, slit coating Method, micro gravure method, die coating method, inkjet method and the like. Moreover, the method of apply | coating using a coater, such as a dip coater, a bar coater, and a spin coater, etc. are mentioned. Among them, in the case of continuously applying in a roll-to-roll form, a coating method by a micro gravure method, an inkjet method, a slit coating method, or a die coating method is preferable.

As a method of removing a solvent (hereinafter, it may be referred to as a solvent removal method A), for example, natural drying, air drying, heat drying, drying under reduced pressure, and a combination of these may be mentioned. Among them, 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 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, depending on the type of the polymerizable liquid crystal compound (especially, the type of the photopolymerizable functional group of the polymerizable liquid crystal compound), and when the photopolymerization initiator is included, the type of the photopolymerization initiator and the amount It is properly selected. Specifically, at least one light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays can be cited. Among them, ultraviolet light is preferred because it is easy to control the progress of the polymerization reaction and that a photopolymerization device that is widely used in the art can be used, and the polymerizable liquid crystal is capable of photopolymerization with ultraviolet light. It is preferred to select the type of compound.

As the light source of the active energy ray, for example, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, halogen lamp, carbon arc lamp, tungsten lamp, gallium lamp, excimer laser, wavelength range 380 And an LED light source that emits 440 nm, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp.

The ultraviolet irradiation intensity is usually 10 to 3,000 Pa / cm 2. The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activation of a photocationic polymerization initiator or a photoradical polymerization initiator. The time for irradiating light is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, further preferably 0.1 seconds to 1 minute.

When irradiated once or plural times with such an ultraviolet irradiation intensity, the accumulated light amount 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 cumulative light amount is less than or equal to the above lower limit, curing of the polymerizable liquid crystal compound is insufficient, and good transferability may not be obtained. Conversely, when the accumulated light amount is equal to or greater than the above upper limit, the retardation plate with an optical compensation function including a horizontally aligned liquid crystal cured film may be colored.

The film thickness of the horizontally aligned liquid crystal cured film is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 2.5 μm or less from the viewpoint of thinning of the functional film. Moreover, the lower limit of the film thickness of the horizontally oriented liquid crystal cured film is preferably 0.1 µm or more, more preferably 0.5 µm or more, still more preferably 1.0 µm or more. The film thickness of the horizontally oriented 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 that orients the polymerizable liquid crystal compound of the liquid crystal cured film in a predetermined direction. Examples of the alignment treatment required to express the orientation regulating force include rubbing treatment, light alignment treatment, and light irradiation treatment. Moreover, various orientations, such as a vertical orientation, a horizontal orientation, a hybrid orientation, and an inclined orientation, can be controlled by the kind of alignment film, rubbing conditions, or light irradiation conditions. Among these, the horizontal alignment film is an alignment film having an alignment regulating force to align 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.

As the alignment film, it is preferable to have solvent resistance that does not dissolve by application of the polymerizable liquid crystal composition, and heat resistance in heat treatment for removal of the solvent and alignment of the polymerizable liquid crystal compound.

Horizontal alignment The horizontal alignment film which shows the alignment regulating force to orient the liquid crystal cured film in the horizontal direction includes a rubbing alignment film, a photo alignment film, and a groove alignment film having an uneven pattern or a plurality of grooves on the surface. For example, when applied to a long roll-shaped film, a photo-alignment film is preferable because the orientation direction can be easily controlled.

The rubbing alignment film is usually oriented by applying a composition (hereinafter also referred to as a composition for forming a rubbing alignment film) comprising an alignment polymer and a solvent onto a substrate or the like, removing a solvent to form a coating film, and rubbing the coating film. Regulatory powers can be given.

As the oriented polymer, for example, polyamide or gelatin having an amide bond, polyimide having an imide bond, and polyamic acid, a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxa And sol, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid esters. These oriented polymers can be used alone or in combination of two or more.

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

The composition for forming a rubbing alignment film can be obtained from the market. Examples of commercial products include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.), and optomer (registered trademark, manufactured by JSR Corporation).

As the solvent, for example, the solvent exemplified in the section of the horizontally oriented liquid crystal cured film can be used. The coating method A is mentioned as a method of apply | coating the composition for forming a rubbing alignment film to a base material, etc. As a method of removing a solvent, the said solvent removal method A is mentioned.

As a method of a rubbing process, the method of making the said coating film contact the rubbing roll which a rubbing cloth is wound and rotates is mentioned, for example. When performing the rubbing treatment, if masking is performed, a plurality of regions (patterns) having different orientation directions may be formed on the alignment film.

In the photo-alignment film, a composition comprising a polymer or monomer having a photo-reactive group and a solvent (also referred to as a composition for forming a photo-alignment film) is usually applied onto a substrate or the like, and after removal of the solvent, polarization (preferably, polarized UV light) ). The photo-alignment film can arbitrarily control the direction of the orientation regulating force by selecting the polarization direction of the polarized light to be irradiated.

The photoreactive group refers to a group that generates alignment ability by irradiation with light. Specifically, the group involved in the photoreaction which is the origin of the orientation ability, such as an orientation-inducing reaction of a molecule | numerator produced by light irradiation, an isomerization reaction, a photodimerization reaction, a photocrosslinking reaction, or a photolysis reaction, is mentioned. As the photoreactive group, a group having an unsaturated bond, particularly a double bond, is preferable, and a carbon-carbon double bond (C = C bond), a carbon-nitrogen double bond (C = N bond), and a nitrogen-nitrogen double bond (N = N Groups having at least one selected from the group consisting of a bond) and a carbon-oxygen double bond (C = O bond) are particularly preferred.

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

The group involved in the photo-dimerization reaction or the photo-crosslinking reaction is preferable from the viewpoint of excellent orientation. Among them, a cinnamoyl group and chalcone are preferred because a photoreactive group involved in the photo-dimerization reaction is preferable, a photo-alignment film having a relatively small amount of polarization required for orientation, and excellent thermal stability and time stability is easily obtained. Group is preferred. As a polymer having a photoreactive group, it is particularly preferable to have a cinnamoyl group in which the terminal end of the polymer side chain is a cinnamic acid structure or a cinnamic acid ester structure.

The content of the polymer or monomer having a photoreactive group can be adjusted according to the type of the polymer or monomer or the thickness of the target photo-alignment film, and it is preferable that the content of the photo-alignment film-forming composition is at least 0.2 parts by mass or more. And, the range of 0.3 to 10 parts by mass is more preferable.

As the solvent, for example, the solvent exemplified in the section of the horizontally oriented liquid crystal cured film can be used. The said coating method A is mentioned as a method of apply | coating the composition for photo-alignment film formation on a base material etc., The said solvent removal method A is mentioned as a method of removing a solvent.

In order to irradiate the polarized light, for example, a form in which the polarized light is directly irradiated with the solvent removed from the composition for forming a photo-alignment film applied on a substrate or the like. Moreover, it is preferable that the said polarization is substantially parallel light. It is preferable that the wavelength of the polarized light to be irradiated is a wavelength range in which a photoreactive group of a polymer or a monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) in the wavelength range of 250 to 400 nm is particularly preferable. Examples of the light source irradiating the polarized light include xenon lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, and ultraviolet light lasers such as KrF and ArF. Among them, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp are preferable because the emission intensity of ultraviolet rays having a wavelength of 313 nm is large. Polarization UV can be irradiated by irradiating light from the said light source through an appropriate polarizing element. Examples of the polarization element include polarization filters, polarization prisms such as Glen Thompson, and Glen Taylor, and a wire grid. Among them, a wire grid type polarizing element is preferable from the viewpoint of large area and resistance to heat.

In addition, when performing rubbing or polarization irradiation, masking can also form a plurality of regions (patterns) with different orientations of liquid crystal alignment.

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

As a method of obtaining a groove alignment film, after exposure through a photosensitive polyimide film surface through an exposure mask having a patterned slit, a method of developing and rinsing to form an uneven pattern, a plate-like disk having grooves on the surface A method of forming a layer of the UV cured resin before curing and then curing the formed resin layer after transferring it to a substrate, etc., and a roll-like film having a plurality of grooves in the film of the UV cured resin before curing formed on the substrate or the like And a method of pressing the disk to form irregularities and then curing.

The composition for forming a horizontal alignment film such as the composition for forming a rubbing alignment film and the composition for forming a photo-alignment film may include, in addition to a solvent, additives exemplified in the terms 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 even more preferably 0.3 µm or less from the viewpoint of thinning of the retardation plate with an optical compensation function. In addition, 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, 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 a direction perpendicular to the film plane, and is made of a polymer containing a polymerizable liquid crystal compound. The formation of the vertically aligned liquid crystal cured film is performed by applying a polymerizable liquid crystal composition onto the vertically aligned film and polymerizing the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound in an aligned state by heating and / or light irradiation. It is preferable from the viewpoint of being able to arbitrarily design thinning and wavelength dispersion characteristics of the vertically aligned liquid crystal cured film.

The three-dimensional refractive ellipsoid formed by the vertically aligned liquid crystal cured film may have biaxiality, but is preferably uniaxial. The vertically aligned liquid crystal cured film may be a vertically aligned liquid crystal cured film composed of a polymer of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound in a state perpendicular to the plane of the liquid crystal cured film, or a hybrid aligned liquid crystal cured film or inclined alignment. It may be a liquid crystal cured film. The refractive indexes nx, ny, and nz in three directions in the refractive ellipsoid formed by the alignment of the polymerizable liquid crystal are nz> nx ≒ ny (referred to as a positive C plate) or nz <nx ≒ ny (referred to as a negative C plate) ). 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. ny is a refractive index ellipsoid formed by the vertically aligned liquid crystal cured film, and represents a refractive index in a direction parallel to the plane of the vertically aligned liquid crystal cured film and perpendicular to the direction of the nx. In addition, when nx = ny, nx can take any direction in the plane of the vertically aligned liquid crystal cured film. nz represents the refractive index in the direction perpendicular to the plane of the vertically aligned liquid crystal cured film in the refractive index ellipsoid formed by the vertically aligned liquid crystal cured film.

The vertically oriented liquid crystal cured film can be either a rod-shaped polymerizable liquid crystal or a disc-shaped polymerizable liquid crystal, but is preferably a rod-shaped polymerizable liquid crystal. When the rod-shaped 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, it is preferable that the vertically aligned liquid crystal cured film satisfies the optical properties represented by the following formula (31) by RthC (λ), which is a retardation value in the thickness direction with respect to light having a wavelength of λ nm. Do. Moreover, it is also preferable to satisfy the optical properties represented by the following formulas (32) and (33). It is more preferable that the vertically aligned liquid crystal cured film satisfies the optical properties represented by the following formulas (31), (32) and (33).

-100 nm ≤ RthC (550) ≤ -50 nm… (31)

(In the formula, RthC 550 represents the 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 a thickness direction retardation value for light having a wavelength of 450 nm, RthC 550 is a phase difference value in a thickness direction for light having a wavelength of 550 nm, RthC 650 is wavelength 650 nm The phase difference values in the thickness direction for each of the light are shown.

When the retardation value RthC 550 in the thickness direction of the vertically aligned liquid crystal cured film exceeds the range of Equation (31), the color of the four sides of the display using the elliptical polarizing plate with an optical compensation function including the retardation plate with an optical compensation function becomes red or It may cause problems such as becoming green. A more preferable range of the retardation value in the thickness direction is -95 nm ≤ RthC (550) ≤ -55 nm, and a more preferred range is -90 nm ≤ RthC (550) ≤ -60 nm. When "RthC (450) / RthC (550)" of the vertically aligned liquid crystal cured film exceeds 1.0, the ellipticity when viewed from all directions on the short wavelength side of the elliptical polarizing plate provided with the vertically aligned liquid crystal cured film is deteriorated. If the ellipticity of the elliptical polarizing plate deteriorates on the short wavelength side and becomes smaller than 1.0, the function as an elliptical polarizing plate on the short wavelength side tends to be impaired. "RthC (450) / RthC (550)" is preferably 0.75 to 0.92, more preferably 0.77 to 0.87, 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), in order to obtain the desired retardation value in the thickness direction (RthC (λ): retardation value in the thickness direction of the vertically oriented liquid crystal cured film at wavelength λ (nm)) , Adjust the 3D refractive index and film thickness dC. In addition, 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, in the refractive index ellipsoid formed by the vertically aligned liquid crystal cured film, nzC (λ)> nxC (λ) ≒ nyC (λ), in the formula, nzC (λ) is the refractive index formed by the vertically aligned liquid crystal cured film In the ellipsoid, the refractive index in the direction perpendicular to the plane of the vertically oriented liquid crystal cured film with respect to the light having the wavelength λ (nm) nxC (λ) is the refractive index ellipsoid formed by the vertically oriented liquid crystal cured film, the wavelength λ (nm ) Represents the maximum refractive index in the direction parallel to the plane of the vertically aligned liquid crystal cured film with respect to light, nyC (λ) is the refractive index ellipsoid formed by the vertically aligned liquid crystal cured film, and is parallel to the vertically aligned liquid crystal cured film plane, In addition, the refractive index for light at a wavelength λ (nm) in a direction orthogonal to the direction of nxC is provided, provided that when nxC (λ) = nyC (λ), nxC (λ) is a vertically aligned liquid crystal cured film. plane To indicate the refractive index in the direction parallel to any where, dC is a vertical alignment liquid crystal cured film thickness.)

It is preferable that the vertically aligned liquid crystal cured film is a polymer of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound in a vertically aligned state as described above. The polymerizable liquid crystal compound forming the vertically aligned liquid crystal cured film is a liquid crystal compound having a polymerizable functional group, particularly a photopolymerizable functional group. The photopolymerizable functional group refers to a group capable of participating in the polymerization reaction with active radicals or acids generated from a 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, and oxetanyl group. You can. Especially, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferable, and an acryloyloxy group is more preferable. The liquid crystal property may be a thermotropic liquid crystal, a lyotropic liquid crystal, or a nematic liquid crystal or a smectic liquid crystal as an image order structure.

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

The polymerizable liquid crystal compound used in the vertically aligned liquid crystal cured film can be used alone or in combination of two or more. When used in combination of two or more, 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 even more preferably 100 parts by mass of the polymerizable liquid crystal compound. 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 in the vertically aligned liquid crystal cured film further includes a solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, and an adhesion promoter. It can contain. 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 98 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. . When content is in the said range, there exists a tendency for the orientation of the vertically-oriented liquid crystal cured film to become high. Here, the solid content refers to the total amount of components excluding the solvent from the composition.

The solvent is preferably a solvent capable of dissolving the polymerizable liquid crystal compound, and is preferably a solvent inert to the polymerization reaction of the polymerizable liquid crystal compound. As the solvent, the same solvent as that used in the composition for forming a horizontally oriented 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 weight, relative to 100 parts by mass of the polymerizable liquid crystal composition. Therefore, the solid content of 100 parts by mass of the composition is preferably 2 to 50 parts by mass. When the solid content of the composition is 50 parts by mass or less, since the viscosity of the composition is low, the thickness of the vertically aligned liquid crystal cured film is approximately uniform, and there is a tendency that nonuniformity is less likely to occur in the vertically aligned liquid crystal cured film. 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 active species by contribution of heat or light, and initiating a polymerization reaction such as a polymerizable liquid crystal. Examples of the reactive active species include active species such as radicals, cations, and anions. Among them, from the viewpoint of easy reaction control, a photopolymerization initiator in which the reaction proceeds by light irradiation is preferable. The photoinitiator can use the same initiator used for the composition for forming a horizontally oriented liquid crystal cured film.

The amount of the photopolymerization initiator added 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. If it is within the above range, the reaction of the polymerizable group proceeds sufficiently, and the orientation of the polymerizable liquid crystal compound is not disturbed.

The polymerization reaction of the polymerizable liquid crystal compound can be controlled by adding a polymerization inhibitor. As the polymerization inhibitor, the same one used in the composition for forming a horizontally oriented liquid crystal cured film can be used. In order to polymerize a polymerizable liquid crystal compound without disturbing the alignment of the polymerizable liquid crystal compound, the content of the polymerization inhibitor is usually 0.01 to 10 parts by mass, preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. It is 5 mass parts, More preferably, it is 0.1-3 mass parts. The polymerization inhibitor may be used alone or in combination of two or more.

Moreover, a photosensitive initiator can be made highly sensitive by using a photosensitizer. As the photosensitizer, the same ones used in the composition for forming a horizontally oriented liquid crystal cured film can be used. Content of a photosensitizer is 0.01-10 mass parts normally with respect to 100 mass parts of polymerizable liquid crystal compounds, Preferably it is 0.05-5 mass parts, More preferably, it is 0.1-3 mass parts.

The leveling agent is an additive having a function of adjusting the fluidity of the polymerizable liquid crystal composition to make the layer obtained by coating the composition more flat, and the same one used in the composition for forming a horizontally oriented liquid crystal cured film can be used.

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

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

In the vertically aligned liquid crystal cured film, the polymerizable liquid crystal composition is coated on a vertically aligned film described later, and then the solvent is removed, so that the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound in an aligned state is heated and / or active energy rays. It can be obtained by curing.

As the method of applying the polymerizable liquid crystal composition on the vertical alignment film, the same method as when forming the horizontal alignment liquid crystal cured film can be used.

The method of removing a solvent can use the same method as when forming a horizontally oriented liquid crystal cured film.

As the active energy ray to be irradiated, depending on the type of the polymerizable liquid crystal compound (especially, the type of the photopolymerizable functional group of the polymerizable liquid crystal compound), and when the photopolymerization initiator is included, the type of the photopolymerization initiator and the amount It is properly selected. Specifically, at least one light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays can be cited. Among them, ultraviolet light is preferred because it is easy to control the progress of the polymerization reaction and that a photopolymerization device that is widely used in the art can be used, and the polymerizable liquid crystal is capable of photopolymerization with ultraviolet light. It is preferred to select the type of compound.

As the light source of the active energy ray, the same one used for forming the horizontally oriented liquid crystal cured film can be used.

The ultraviolet irradiation intensity is usually 10 to 3,000 Pa / cm 2. The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activation of a photocationic polymerization initiator or a photoradical polymerization initiator. The time for irradiating light is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, further preferably 0.1 seconds to 1 minute.

When irradiated once or plural times with such an ultraviolet irradiation intensity, the accumulated light amount 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 cumulative light amount is less than or equal to the above lower limit, curing of the polymerizable liquid crystal compound is insufficient, and good transferability may not be obtained. Conversely, when the accumulated light amount is more than the above upper limit, the retardation plate with an optical compensation function including the vertically aligned liquid crystal cured film may be colored.

The film thickness of the vertically aligned liquid crystal cured film is preferably 3 μm or less, more preferably 2 μm or less, and even more preferably 1.5 μm or less from the viewpoint of thinning of the functional film. Moreover, the lower limit of the film thickness of the vertically oriented liquid crystal cured film is preferably 0.1 µm or more, more preferably 0.3 µm or more, and even 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 that orients the polymerizable liquid crystal compound of the liquid crystal cured film in a predetermined direction. Moreover, various orientations, such as a vertical orientation, a horizontal orientation, a hybrid orientation, and an inclined orientation, can be controlled by the kind of alignment film, rubbing conditions, or light irradiation conditions. Among these, the vertical alignment film is an alignment film having an alignment regulating force to align the polymerizable liquid crystal compound of the liquid crystal cured film in the vertical direction. For this reason, by using a vertical alignment film, a vertical alignment liquid crystal film can be formed.

As the vertical alignment film, it is preferable to apply a material that lowers the surface tension of the surface of the substrate or the like. Examples of such materials include oriented polymers such as polyimide, polyamide, fluorine-based polymers such as polyamic acid and perfluoroalkyl, which are hydrolysates thereof, and silane compounds and polysiloxane compounds obtained by condensation reaction thereof. Can be lifted. For the vertical alignment film, a composition comprising such a material and a solvent, for example, a solvent exemplified in the section of the vertical alignment liquid crystal film (hereinafter, also referred to as a composition for forming a vertical alignment film) is applied onto a substrate or the like, and after removal of the solvent, It can be obtained by subjecting the coating film to heating or the like.

When a silane compound is used for the vertical alignment film, the vertical alignment film is composed of a compound containing a Si element and a C element as constituent elements from the viewpoint of easily lowering the surface tension and increasing the adhesion with the layer adjacent to the vertical alignment film. A membrane is preferred, and a silane compound can be preferably used. In the present invention, when the vertical alignment film is disposed between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film, high adhesion between the vertically aligned film and the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film is exhibited, and a phase difference with an optical compensation function In the plate, peeling at the interface between the layers can be effectively suppressed or prevented.

As the silane compound, a silicone system such as the silane coupling agent described above can be preferably applied, but, for example, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N -(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl -N- (1,3-dimethyl-butylidene) propylamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycine Cydoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-gly When the sidok propyl, and the like ethoxy dimethylsilane.

The silane compound may be of a silicone monomer type or of a type silicone oligomer (polymer) type. When a silicone oligomer is represented in the form of a (monomer)-(monomer) copolymer, 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer A copolymer containing a mercaptopropyl group such as, 3-mercaptopropyl triethoxysilane-tetramethoxysilane copolymer, and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer; Mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer, and mercaptomethyltri A mercaptomethyl group-containing copolymer such as an ethoxysilane-tetraethoxysilane copolymer; 3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropyltrie Methoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-methacryloxyylopropylmethyldie A copolymer containing a methacryloyloxypropyl group such as a methoxysilane-tetraethoxysilane copolymer; 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane- Tetramethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-acryloyl Oxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane A copolymer containing an acryloyloxypropyl group such as a copolymer; Vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer Polymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane-tetramethoxysilane copolymer, and vinylmethyldiethoxysilane-tetrae Vinyl group-containing copolymers, such as a methoxysilane copolymer; 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-aminopropyl And amino group-containing copolymers such as methyldiethoxysilane-tetramethoxysilane copolymer and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer. The silane compounds may 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 also be used.

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

From the viewpoint of easy to improve the adhesion more, and from the viewpoint of the applicability of the composition for forming a vertically oriented liquid crystal cured film, and from the viewpoint that the layer disposed on the lower layer does not dissolve well in the method of manufacturing a retardation plate with an optical compensation function described later, vertical It is preferable that the alignment film is a film composed of a compound containing a Si element, a C element, and an O element in the constituent elements. Moreover, the number of carbon atoms of the substituent, preferably an alkyl group or an alkoxy group, which includes 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, More 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, still more preferably 0.05 to 0.33. When the Si / C ratio is equal to or more than the lower limit, the coatability of the composition for forming a vertically oriented liquid crystal cured film is improved, and if the Si / C ratio is equal to or less than the upper limit, adhesion to an adjacent layer can be improved.

As the solvent, for example, the solvent exemplified in the section of the horizontally oriented liquid crystal cured film can be used. The said coating method A is mentioned as a method of apply | coating the composition for vertical alignment film formation, The said solvent removal method A is mentioned as a method of removing a solvent.

The composition for forming a vertical alignment film may include, in addition to a solvent, additives exemplified in the terms of the horizontal alignment liquid crystal cured film.

The film thickness of the vertical alignment film is preferably 1 µm or less, more preferably 0.3 µm or less, and even more preferably 0.1 µm or less from the viewpoint of thinning of the retardation plate with an optical compensation function and development of the orientation regulating force. Moreover, 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, 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.

[materials]

The base material is used when applying a composition for forming an alignment film or a composition for forming a liquid crystal cured film, and may be a design capable of peeling off the substrate and transferring the film applied on the substrate, and can be transferred by providing adhesion to the substrate. The design may be either absent or any, but from the viewpoint of thinning, a design capable of transferring the object to be transferred and peeling the substrate is preferable. A glass base material and a film base material are mentioned as a base material as mentioned above, The film base material is preferable from a viewpoint of workability, and a long roll-shaped film is more preferable at the point which can be manufactured continuously. Examples of the resin constituting the film base material include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; Cyclic olefin resins; Polyvinyl alcohol; Polyethylene terephthalate; Polymethacrylic acid esters; Polyacrylic acid esters; Cellulose esters such as triacetyl cellulose, diacetyl cellulose and cellulose acetate propionate; Polyethylene naphthalate; Polycarbonate; Polysulfone; Polyether sulfone; Polyether ketone; And plastics such as polyphenylene sulfide and polyphenylene oxide. A release treatment such as silicon treatment may be performed on the surface of the substrate. As a commercially available cellulose-ester base material, "Fujitack film" (made by Fuji Photo Film Co., Ltd.); "KC8UX2M", "KC8UY" and "KC4UY" (above, manufactured by Konica Minolta Opto Corporation) and the like. Such resin can be formed into a base material by forming into a film by known means such as a solvent casting method and a melt extrusion method.

As commercially available cyclic olefin resins, "Topas" (registered trademark) (manufactured by Ticona (dock)), "Aton" (registered trademark) (manufactured by JSR Corporation), "ZEONOR" (registered trademark) , "ZEONEX" (registered trademark) (above, manufactured by Nippon Xeon Corporation) and "Apel" (registered trademark) (manufactured by Mitsui Chemicals Corporation). A commercially available cyclic olefin resin substrate can also be used. As commercially available cyclic olefin-based resin substrates, "Essina" (registered trademark), "SCA40" (registered trademark) (above, manufactured by Sekisui Chemical Industry Co., Ltd.), "Zeonoa film" (registered trademark) (Optes) And Atone Film (trademark) (manufactured by JSR Corporation).

It is preferable that the base material has a thickness in which a horizontally oriented liquid crystal cured film, a horizontally oriented film, a vertically oriented liquid crystal cured film, or a vertically oriented film is easily laminated and easily peelable. The thickness of such a substrate is usually 5 to 300 μm, and preferably 20 to 200 μm.

[Phase retarder with optical compensation function]

The retardation plate with an optical compensation function of the present invention includes a horizontally aligned liquid crystal cured film, a horizontally aligned film or a vertically aligned film, and a vertically aligned liquid crystal cured film in this order, and satisfies the requirements of (1) to (4) described below. desirable.

The distance between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film is 5 µm or less. … (One)

What comprises a horizontal alignment film or a vertical alignment film between the layers of a horizontally-oriented liquid crystal cured film and a vertically-oriented liquid crystal cured film. … (2)

The following relationship

ReA (450) / ReA (550) <1.00 … (3)

Satisfying.

Here, ReA (λ) represents the in-plane retardation value at a wavelength λ nm of the horizontally oriented liquid crystal cured film.

The definition of the phase difference value is as follows.

ReA (λ) = (nxA-nyA) × dA

However, nxA represents the main refractive index in the film plane of the horizontally aligned liquid crystal cured film, nyA represents the refractive index in the direction orthogonal to the same surface as nxA, and dA represents the thickness of the horizontally aligned liquid crystal cured film.

The following relationship

RthC (450) / RthC (550) <1.00

Satisfying. … (4)

Here, RthC (λ) represents the retardation value in the thickness direction at a wavelength λ nm of the vertically oriented liquid crystal cured film. The definition of the phase difference value is as follows.

RthC (λ) = ((nxC + nyC) / 2-nzC) × dC

However, nxC is the main refractive index in the film plane of the vertically aligned liquid crystal cured film, nyC is the refractive index in the direction orthogonal to the same plane as nxC, nzC is the refractive index in the thickness direction of the vertically aligned liquid crystal cured film, dC is the vertically aligned liquid crystal cured film It shows the thickness.

In addition, when nxC = nyC, nxC can be made into the refractive index of arbitrary directions in the film plane.

In addition, the distance between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film is preferably 5 µm or less as in the formula (1), more preferably 1 µm or less, more preferably 0.5 µm or less, and particularly preferably 0.3 µm. Is below. In addition, 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, particularly preferably 30 nm or more.

It is preferable that the phase difference plate with an optical compensation function satisfies the following relational expression (5). The value of | R0 (550)-R40 (550) | is small because the amount of light leakage around the wavelength 550 nm in all directions is reduced when an elliptical polarizing plate with an optical compensation function using a phase difference plate with an optical compensation function is applied to the display. The more preferable. The value of | R0 (550)-R40 (550) | is preferably less than 10 nm, more preferably 5 nm or less, still more preferably 4 nm or less, particularly preferably 3 nm or less.

｜ R0 (550)-R40 (550) ｜ <10 ㎚ … (5)

Here, R0 (λ) represents the in-plane retardation value of the phase difference plate with an optical compensation function including a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film. Moreover, among the retardation plates with an optical compensation function including a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film, R40 was rotated 40 ° around a direction orthogonal to the main refractive index direction in the film plane (orthogonal axis direction). The apparent phase difference value at the time.

It is preferable that the phase difference plate with an optical compensation function satisfies the following relational expression (6). The value of ｜ R0 (450)-R40 (450) ｜ is small because the amount of light leakage near the wavelength of 450 nm in all directions is reduced when an elliptical polarizing plate with an optical compensation function using a phase difference plate with an optical compensation function is applied to the display. The more preferable. The value of | R0 (450)-R40 (450) | is preferably less than 10 nm, more preferably 5 nm or less, still more preferably 4 nm or less, particularly preferably 3 nm or less.

｜ R0 (450)-R40 (450) ｜ <10 nm … (6)

However, R0 (λ) represents an in-plane retardation value of a retardation plate with an optical compensation function including a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film. Moreover, among the retardation plates with an optical compensation function including a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film, R40 was rotated 40 ° around a direction orthogonal to the main refractive index direction in the film plane (orthogonal axis direction). The apparent phase difference value at the time.

Moreover, it is preferable that the difference between the values represented by the relations (5) and (6) satisfies the relational expression (7) below.

｜ {R0 (450)-R40 (450)}-{R0 (550)-R40 (550)} ｜ <3 nm … (7)

When the relational expression (7) is satisfied, the reflection color of the front and all directions when the elliptical polarizing plate with an optical compensation function using a retardation plate with an optical compensation function is applied to the display becomes closer to black. The value is 3 nm or less, more preferably 2 nm or less, and even more preferably 1 nm or less.

In addition, when the difference between the average refractive index of each layer, that is, the average refractive index of each layer constituting the retardation plate with the optical compensation function of the present invention, and the average refractive index of other layers adjacent to the layer is large, it occurs between layers. Light leakage may occur due to the influence of interfacial reflection. The difference in the 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, particularly preferably 0.05 or less. Within this range, the occurrence of light leakage due to interfacial reflection can be suppressed.

Specifically as the difference in the average refractive index of each layer,

(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 horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film are included in a horizontally aligned film,

(2-a) the difference between the average refractive index of the horizontally aligned liquid crystal cured film and the average refractive index of the horizontally aligned film,

(2-b) the difference between the average refractive index of the horizontal alignment film and the average refractive index of the vertically aligned liquid crystal cured film,

(3) When a vertical alignment film is included between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film,

(3-a) the difference between the average refractive index of the horizontally aligned liquid crystal cured film and the average refractive index of the vertically aligned film,

(3-b) Difference between the average refractive index of the vertical alignment film and the average refractive index of the vertically aligned liquid crystal cured film

And the like.

The retardation plate with an optical compensation function of the present invention may include a horizontal alignment liquid crystal cured film, a horizontal alignment film, a vertical alignment liquid crystal cured film, and layers other than the vertical alignment film, and specific examples thereof include other aligned liquid crystal cured films, And other alignment films, protective layers, and the like. Examples of the other alignment liquid crystal cured film include the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film, and examples of the other alignment films include the alignment film and the like.

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

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 forms a protective layer. It is preferable from the point of not dissolving a layer. Examples of the alcohol solvent include methanol, ethanol, butanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether. Examples of the ether solvent include ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. Among them, ethanol, isopropyl alcohol, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred.

The film thickness of the protective layer is 0.1 µm to 10 µm, more preferably 0.1 µm to 3 µm.

[Manufacturing method of retardation plate with optical compensation function]

The manufacturing method of the 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 horizontally aligned liquid crystal cured film, a horizontally aligned film or a vertically aligned film, and a vertically aligned liquid crystal cured film in this order. After laminating, and then laminating the horizontally aligned liquid crystal cured film, and further laminating the vertically aligned film, a method of laminating the vertically aligned liquid crystal cured film (hereinafter referred to as manufacturing method A) or a vertically aligned film on the substrate, and then The method of laminating the vertically aligned liquid crystal cured film, and further laminating the horizontally aligned liquid crystal film and then laminating the horizontally aligned liquid crystal cured film (hereinafter, manufacturing method B) is preferred. For the method of laminating the horizontally aligned liquid crystal cured film, the horizontally aligned film, the vertically aligned liquid crystal cured film, and the vertically aligned film, a method for forming each layer described above can be used.

When manufacturing a retardation plate with an optical compensation function by manufacturing method A or manufacturing method B, there is a possibility that misalignment or alignment defects occur due to the orientation of the liquid crystal cured film disposed in the lower layer. That is, in the case of the manufacturing method A, since the vertically aligned liquid crystal cured film is laminated after laminating the horizontally aligned liquid crystal cured film on the lower layer, when forming the vertically aligned liquid crystal cured film, it is influenced by the horizontally aligned liquid crystal cured film of the lower layer and misalignment or orientation. Defects may occur, and in the case of manufacturing method B, since the vertically aligned liquid crystal cured film is laminated to the lower layer for the same purpose, the horizontally aligned liquid crystal cured film is laminated. Under the influence of the vertically aligned liquid crystal cured film, misalignment or alignment defects may occur. For this reason, depending on the solvent type of the composition (horizontal alignment film forming composition, horizontal alignment liquid crystal cured film forming composition, vertical alignment film forming composition, vertical alignment liquid crystal cured film forming composition) used to form each layer to be laminated. In some cases, the lower layer is dissolved to cause changes in optical properties, misalignment, and orientation defects. Therefore, in order to form each layer to be laminated, the material, solvent, solid content concentration, coating method, film thickness, and the like contained in the composition used must be appropriately selected.

[Oval polarizer with optical compensation function]

The retardation plate with an optical compensation function of the present invention is a function of a retardation plate with an optical compensation function by being peeled off by transferring the substrate by bonding to an object to be transferred or laminated with an adhesive or the like while the substrate is attached, That is, the optical properties can be imparted to the object to be transferred, and an optical laminate in which the optical properties of the retardation plate with an optical compensation function is provided can be produced. Among these, when laminated with a polarizing plate, it is possible to manufacture an elliptical polarizing plate with an optical compensation function. In the embodiment of the present invention, it is preferable to laminate the slow axis (optical axis) of the horizontally oriented liquid crystal cured film and the absorption axis of the polarizing plate to be substantially 45 °. A function as an original polarizing plate can be obtained 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 °. Further, substantially 45 ° is usually in the range of 45 ± 5 °.

[Subject]

As an object to be transferred, an optical film having a single-layer structure, for example, a polarizing plate, a retardation plate, a brightness enhancing film, an anti-glare film, an antireflection film, a diffusing film, a condensing film, etc. A polarizing plate is mentioned, among these, a retardation plate, a polarizing plate, and an elliptical polarizing plate can be used preferably. The optical laminate in the present invention includes 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, and an electronic device. Emission display device (electric field emission display device (FED, etc.), surface field emission display device (SED)), electronic paper (display device using electronic ink or electrophoretic elements), plasma display device, projection type display device (grating light valve ( GLV) display device, a display device having a digital micro-mirror device (DMD), and piezoelectric ceramic displays, and the like, and is particularly preferably used for organic EL display devices and touch panel display devices.

[Polarizing plate]

As a polarizing plate, it consists of a polarizer which has a polarization function. Examples of the polarizer include a stretched film in which a dye having absorption anisotropy is adsorbed, or a film coated with a dye having absorption anisotropy. A dichroic dye is mentioned as a dye which has absorption anisotropy.

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

[Adhesive]

Examples of the point adhesive include pressure-sensitive adhesives, dry solid adhesives, and chemically reactive adhesives. As a chemical reaction adhesive, active energy ray hardening adhesive is mentioned, for example.

The pressure-sensitive adhesive usually contains a polymer and may contain a solvent. Examples of the polymer include acrylic polymer, silicone polymer, polyester, polyurethane, and polyether. Among them, an acrylic adhesive containing an acrylic polymer is excellent in optical transparency, has moderate wettability and cohesiveness, is excellent in adhesion, and further has high weatherability, heat resistance, etc., and floats under conditions of heating or humidification. It is preferable because peeling and the like are less likely to occur.

As an acrylic polymer, the alkyl group of the ester part has (meth) acrylate, which is an alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, or a butyl group, and functional groups such as (meth) acrylic acid and hydroxyethyl (meth) acrylate. Copolymers of (meth) acrylic monomers are preferred.

The pressure-sensitive adhesive containing such a copolymer is preferable because it is excellent in adhesiveness and can be removed relatively easily without generating any residual of glue on the transferred object even when it is removed after bonding to the transferred object. The glass transition temperature of the acrylic polymer is preferably 25 ° C or lower, and more preferably 0 ° C or lower. It is preferable that the mass average molecular weight of such an acrylic polymer is 100,000 or more.

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

Aluminum oxide (refractive index 1.76), silicon oxide (refractive index 1.45), etc. are mentioned as a fine particle which consists of an inorganic compound. As the 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 to 1.59), polycarbonate beads ( Refractive index 1.55), polyethylene beads (refractive index 1.53), polystyrene beads (refractive index 1.6), polyvinyl chloride beads (refractive index 1.46), and silicone resin beads (refractive index 1.46). The content of the light diffusing agent is usually 3 to 30 parts by mass based on 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 force and the like, but is usually 1 μm to 40 μm. From the viewpoints of processability and durability, the thickness is preferably 3 µm to 25 µm, and more preferably 5 µm to 20 µm. By setting the thickness of the point adhesive layer formed of the adhesive to 5 µm to 20 µm, it is possible to maintain the brightness when the display device is viewed from the front or at an angle, and to prevent blurring or blurring of the display image from occurring. .

The dry solidifying adhesive may contain a solvent. The dry solidifying adhesive contains a polymer of a monomer having a protonic functional group such as a hydroxyl group, a carboxyl group, or an amino group and an ethylenically unsaturated group, or a urethane polymer as a main component, and further contains a polyhydric aldehyde, epoxy compound, epoxy resin, melamine compound, And a composition containing a crosslinking agent such as a zirconia compound and a zinc compound or a curable compound, and the like. As a polymer of a monomer having a protonic functional group such as a hydroxyl group, a carboxyl group or an amino group and an ethylenically unsaturated group, ethylene-maleic acid copolymer, itaconic acid copolymer, acrylic acid copolymer, acrylamide copolymer, saponified polyvinyl acetate, And polyvinyl alcohol-based resins.

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

As a urethane resin, polyester-type ionomer-type urethane resin etc. are mentioned.

The polyester-based ionomer-type urethane resin referred to herein is a urethane resin having a polyester skeleton, and a resin having a small amount of ionic components (hydrophilic components) introduced therein. Since the ionomer-type urethane resin is emulsified in water without using an emulsifying agent to form an emulsion, it can be used as a water-based point adhesive. When using a polyester ionomer-type urethane resin, it is effective to blend a water-soluble epoxy compound as a crosslinking agent.

As an epoxy resin, polyamide epoxy obtained by reacting epichlorohydrin with polyamide polyamine obtained by reaction of polyalkylene polyamine such as diethylene triamine or triethylene tetramine and dicarboxylic acid such as adipic acid And resins. As commercially available products of such polyamide epoxy resins, "Sumirez Resin (registered trademark) 650" and "Sumirez Resin 675" (above, manufactured by Sumika Chemtex Co., Ltd.), "WS-525" (manufactured by Nippon PMC Co., Ltd.), etc. Can be lifted. When mixing an epoxy resin, the addition amount is 1-100 mass parts normally with respect to 100 mass parts of polyvinyl alcohol-type resins, Preferably it is 1-50 mass parts.

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

The active energy ray-curable adhesive may contain a solvent. The active energy ray-curable adhesive is an adhesive that is cured by irradiation with active energy rays. Examples of the active energy ray-curable adhesive include a cationic polymerizable adhesive containing an epoxy compound and a cationic polymerization initiator, a radical polymerizable adhesive containing an acrylic curing component and a radical polymerization initiator, and a cationic polymerizable curing component such as an epoxy compound, and And adhesives containing both of a radically polymerizable curing component such as an acrylic compound and further containing a cationic polymerization initiator and a radical polymerization initiator, and an adhesive that is cured by irradiating an electron beam without including these polymerization initiators. .

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

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

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

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

Example

Hereinafter, the present invention will be described in more detail by examples. In addition, "%" and "part" in the example mean mass% and mass parts unless otherwise specified. In addition, in the following examples, the film thickness was measured using an ellipsometer M-220 manufactured by Nippon Spectroscopic Co., Ltd., or a contact film thickness meter (MH-15M manufactured by Nikon, 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 in the 40 ° direction are manufactured by Oji Scientific Instruments Co., Ltd. KOBRA-WPR, or Nippon Spectroscopic Co., Ltd. It was measured and calculated using the ellipsometer M-220 of. In addition, the Si / C ratio can be calculated from elemental analysis of a vertical alignment film, measurement of a surface constituent element using X-ray photoelectron spectroscopy, or from a structural formula when all of the structural formulas of a compound used to form a vertical alignment film are known. have. Moreover, AGF-B10 manufactured by Kasuga Electric Co., Ltd. was used as the corona treatment device. Corona treatment can be appropriately performed when applying the composition to the substrate. Using the said corona treatment apparatus, it performed once under the conditions of an output of 0.3 kPa and a processing speed of 3 m / min.

[Example 1]

[Preparation of composition for forming horizontal alignment film]

A composition for forming a horizontal alignment film was obtained by mixing 5 parts of a photo-alignment material having the following structure (weight average molecular weight: 30000) and 95 parts of cyclopentanone (solvent) as a component and stirring the obtained mixture at 80 ° C for 1 hour.

[Preparation of composition for forming vertical alignment film]

The silane coupling agent "KBE-9103" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in a mixed solvent in which ethanol and water were mixed at a ratio of 9: 1 (mass ratio) to obtain a composition for forming a vertical alignment film having a solid content of 0.5%.

[Preparation of composition for forming horizontally oriented liquid crystal cured film and composition for forming vertically oriented liquid crystal cured film]

For the mixture in which the polymerizable liquid crystal compound A and the polymerizable liquid crystal compound B shown below are mixed in a mass ratio of 90:10, a leveling agent (F-556; manufactured by DIC) is 1.0 part, and 2-dimethyl as a polymerization initiator. 6 parts of amino-2-benzyl-1- (4-morpholinophenyl) butan-1-one ("Irgacure 369 (Irg369)", manufactured by BASF Japan Co., Ltd.) was added.

Further, by adding N-methyl-2-pyrrolidone (NMP) so that the solid content concentration becomes 13% and stirring at 80 ° C for 1 hour, the composition for forming a horizontally aligned liquid crystal cured film and for forming a vertically aligned liquid crystal cured film are added. The composition was obtained.

The polymerizable liquid crystal compound A was prepared by the method described in JP 2010-31223 A. Moreover, the polymerizable liquid crystal compound B was produced in accordance with the method described in JP 2009-173893 A. Each molecular structure is shown below.

[Polymerizable Liquid Crystal Compound A]

[Polymerizable Liquid Crystal Compound B]

[Production of polarizing plate]

After the polyvinyl alcohol film having an average polymerization degree of about 2,400 and a saponification degree of 99.9 mol% or more and a thickness of 75 μm was immersed in pure water at 30 ° C., at 30 ° C. in an aqueous solution having a mass ratio of iodine / potassium iodide / water of 0.02 / 2/100. Iodine staining was performed by immersion (iodine dyeing process). The polyvinyl alcohol film subjected to the iodine dyeing process was immersed in an aqueous solution having a potassium iodide / boric acid / water mass ratio of 12/5/100 at 56.5 ° C to carry out boric acid treatment (boric acid treatment step). The polyvinyl alcohol film which had been 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 thick after stretching) in which iodine was 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 such stretching was 5.3 times. The obtained polarizer and the saponified triacetyl cellulose film (KC4UYTAC 40 µm, manufactured by Konica Minolta) were pasted together with a nip roll through a water-based adhesive. The obtained composite was dried at 60 ° C. for 2 minutes while maintaining the tension at 430 N / m to obtain a polarizing plate having a triacetylcellulose film as a protective film on one side. In addition, the water-based adhesive was added to 100 parts of water, 3 parts of carboxyl group-modified polyvinyl alcohol (manufactured by Kurare, `` Kurarefoval KL318 ''), and water-soluble polyamide epoxy resin (manufactured by Sumika Chemtex, `` Smirez Resin 650 '', An aqueous solution having a solid content concentration of 30%] was added and prepared.

Optical properties were measured for the obtained polarizing plate. The measurement was performed with a spectrophotometer ("V7100" manufactured by Nippon Spectroscopy) using the polarizer face of the polarizing plate obtained above as an incident surface. The absorption axis of the polarizing plate was coincident with the stretching direction of the polyvinyl alcohol, and the obtained polarizing plate had a single-visibility transmittance of 42.1%, a visibility-corrected polarization of 99.996%, a single color of -1.1 and a single color of b of 3.7.

[Production of laminate composed of substrate, horizontal alignment film, and horizontal alignment liquid crystal cured film]

After performing a corona treatment on the COP film (ZF-14-50) manufactured by Nippon Xeon Co., Ltd., the composition for forming a horizontal alignment film was applied with a bar coater, dried at 80 ° C for 1 minute, and a polarized UV irradiation device ("SPOT CURE SP-9 ”, manufactured by Ushio Electric Co., Ltd.), and subjected to polarized UV exposure at an axial angle of 45 ° at an integrated light amount 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 horizontally oriented liquid crystal cured film was applied to a horizontally oriented film using a bar coater, dried at 120 ° C. for 1 minute, and then a high pressure mercury lamp (“Unicure VB-15201BY-A”, Ushio Electric Co., Ltd.) Manufactured) to form a horizontally aligned liquid crystal cured film by irradiating ultraviolet rays (in a nitrogen atmosphere, a cumulative amount of light at a wavelength of 365 nm: 500 mJ / cm 2), which is composed of a substrate, a horizontally aligned film, and a horizontally aligned liquid crystal cured film. A laminate was obtained. It was 2.3 micrometers when the film thickness of the horizontally-oriented liquid crystal cured film was measured with the ellipsometer.

[Re measurement of horizontally aligned liquid crystal cured film]

The in-plane retardation value ReA (λ) of the horizontally oriented liquid crystal cured film produced by the above method was adhered to the glass through an adhesive, followed by peeling off of the COP as a base material ("KOBRA-WPR" manufactured by Oji Measurement Instruments Co., Ltd.) It was measured by. As a result of measuring the phase difference value ReA (λ) at each wavelength, ReA (450) = 121 nm, ReA (550) = 142 nm, ReA (650) = 146 nm, ReA (450) / ReA (550) = 0.85.

[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 the corona treatment was performed on the laminate formed of the substrate, horizontal alignment film, and horizontal alignment liquid crystal cured film prepared by the above-described method, the composition for forming a vertical alignment film was applied with a bar coater, dried at 80 ° C. for 1 minute, and then vertical alignment film. Got It was 50 nm when the film thickness of the obtained vertical alignment film was measured with the ellipsometer.

Further, a composition for forming a vertically oriented liquid crystal cured film was applied to a vertically oriented film using a bar coater, dried at 120 ° C. for 1 minute, and then a high pressure mercury lamp (“Unicure VB-15201BY-A” manufactured by Ushio Electric Co., Ltd.) was used. By using ultraviolet radiation (in a nitrogen atmosphere, the total amount of light at a wavelength of 365 nm: 500 mJ / cm 2), a vertically aligned liquid crystal cured film is formed to form a substrate, horizontally aligned film, horizontally aligned liquid crystal cured film, vertically aligned film, vertical A laminate composed of an alignment liquid crystal cured film was obtained. It was 1.2 micrometers when the film thickness of the vertically-oriented liquid crystal cured film was measured with the ellipsometer. Moreover, the distance between the layers of the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film was 50 nm. Moreover, the structural element ratio of the vertical alignment film was Si / C = 0.33.

[Rth Measurement of Vertically Oriented 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 were prepared on the COP film (ZF-14-50) manufactured by Nippon Xeon Co., Ltd. in the same order as above, and the vertically aligned liquid crystal cured film was an adhesive. After bonding with glass via (Lintec's pressure-sensitive adhesive 15 μm) and confirming that there was no phase difference in the COP, the phase difference value was measured by changing the incident angle of light to the sample with an ellipsometer. Incidentally, the average refractive index at wavelengths λ of 450 nm and 550 nm was measured using a refractometer (Atago Co., Ltd., "Multi-wavelength Abbe refractometer DR-M4"). ReC calculated from the obtained film thickness, the average refractive index, and the measurement results of the ellipsometer are RthC (450) = -63 nm, RthC (550) = -73 nm, and RthC (450) / RthC (550) = 0.85.

[Measurement of R0 and R40 of a laminate (a retardation plate with an optical compensation function) composed of a horizontally aligned liquid crystal cured film, a vertically aligned film, and a vertically aligned liquid crystal cured film]

A laminate composed of a substrate, a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertically aligned liquid crystal cured film prepared by the above method was bonded to glass through an adhesive (a pressure sensitive adhesive manufactured by Lintec, 15 μm), and the COP was peeled off. After preparing the sample for measurement, after confirming that there was no phase difference in the horizontal alignment film and the vertical alignment film, the phase difference value R0 (λ) in the front direction of the retardation plate with an optical compensation function, and the axis of progress of the horizontally aligned liquid crystal cured film were centered. The phase difference value R40 (λ) when inclined at 40 ° was 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 {R0 (550)-R40 (550)} |.

 [Difference in average refractive index in plane of each layer]

Each layer was applied onto glass according to the above method, and the average refractive index of each layer was calculated using a refractive index meter (manufactured by Atago Co., Ltd., `` multi-wavelength Abbe refractometer DR-M4 '') or an ellipsometer, and the in-plane of each layer was calculated. It was confirmed that the difference in average refractive index was 0.2 or less.

[Flexibility test]

A glass plate having a thickness of 0.7 mm is placed on the coated film side of a laminate made of the above-described substrate, a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertically aligned liquid crystal cured film, and stretched on the glass plate so that the laminate is 180 degrees. After bending, the bent portion was observed by transmitting the light of a fluorescent lamp using a loupe 10 times, and the presence or absence of wrinkles or cracks was confirmed. Table 1 shows the results.

[Check the reflection color of the bend]

After performing the corona treatment on the coating film side of the laminate comprising the base material, 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 and the slow axis of the horizontal alignment film are formed. It was bonded to the polarizing plate manufactured by the above-described method through an adhesive so that the angle was 45 °, and the substrate was peeled to prepare an elliptical polarizing plate with an optical compensation function. Then, it was adhered to the aluminum foil through an adhesive, and bent 180 ° to a radius of 1 cm on the polarizer side, and the reflection color of the bent portion was visually observed. Table 1 shows the results.

(Examples 2 and 3)

A retardation plate with an optical compensation function was produced in the same manner as in Example 1, except that the film thickness of the vertical alignment film was changed as shown in Table 1, and retardation value measurement, flexural test, and reflection color confirmation of the bent portion were performed. Table 1 shows the results.

(Example 4)

0.5% by weight of polyimide ("Sunever SE-610" manufactured by Nissan Chemical Industries, Ltd.), 72.3% by weight of N-methyl-2-pyrrolidone, 18.1% by weight of 2-butoxyethanol, 9.1% by weight Ethylcyclohexane and 0.01% by weight of DPHA (manufactured by Shin-Nakamura Chemical) were mixed to prepare composition B for forming a vertical alignment film, and optical compensation was performed in the same manner as in Example 1 except that the composition B for forming a vertical alignment film was used. A retardation plate with a function was prepared, and retardation value measurement, flexural test, and reflection color confirmation of the bent portion were performed. Table 1 shows the results. Moreover, it was 0.2 micrometers when the film thickness of the vertical alignment film was measured with the ellipsometer. In this regard, the distance between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film was 0.2 µm. Moreover, when apply | coating the composition for forming a vertically-oriented liquid crystal cured film, it was confirmed that the vertically-aligned film was invaded with a solvent, and an orientation defect or an orientation defect partially occurred.

(Example 5)

The substrate was changed to a polyethylene terephthalate film (released by Lintec Co., Ltd., SP-PLR382050, hereinafter referred to as "separator") subjected to a release treatment, and the lamination order was a vertical alignment film, a vertical alignment liquid crystal cured film, and a horizontal A retardation plate with an optical compensation function was prepared in the same manner as in Example 1 except that the alignment film and the horizontally aligned liquid crystal cured film were changed in order, and retardation value measurement, flexural test, and reflection color confirmation of the bent portion were performed. Table 1 shows the results. Moreover, it was 0.2 micrometers when the film thickness of the horizontal alignment film was measured with the ellipsometer. In this regard, the 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)

A retardation plate with an optical compensation function was prepared in the same manner as in Example 1, except that the values of RthC 450 and RthC 550 were changed as shown in Table 1 by changing the film thickness of the vertically aligned liquid crystal cured film, The retardation value was measured, the bendability test, and the reflection color of the bent portion was checked. Table 1 shows the results.

(Example 8)

The composition for forming a vertically oriented liquid crystal cured film was changed to the composition for forming a vertically oriented liquid crystal cured film (B) described below, and the drying temperature after applying the composition for forming a vertically oriented liquid crystal cured film (B) was 120 ° C. A retardation plate with an optical compensation function was prepared in the same manner as described in Example 1 except that the temperature was changed to 80 ° C, and a retardation value measurement, flexural test, and reflection color confirmation of the bent portions were performed. Table 1 shows the results.

(Adjustment of composition (B) for forming a vertically oriented liquid crystal cured film)

To the liquid crystal compound LC242 described below: PaliocolorLC242 (registered trademark of BASF), 0.1 part of leveling agent F-556 and 3 parts of polymerization initiator Irg369 were added, and cyclopentanone was added so that the solid content concentration was 13%, A composition (B) for forming a vertically aligned liquid crystal cured film was obtained. The obtained liquid crystal composition is named "Composition V".

Liquid crystal compound LC242: PaliocolorLC242 (BASF registered trademark)

(Comparative Example 1)

After the laminate of the horizontal alignment film and the horizontal alignment liquid crystal cured film was prepared by the method described in Example 1, a vertical alignment film and a vertical alignment liquid crystal cured film laminate (manufactured by Lintec) were separately prepared on the COP. . The obtained laminates were bonded together using a pressure-sensitive adhesive (15 µm pressure-sensitive adhesive manufactured by Lintec), and retardation value measurement, bending test, and reflection color confirmation of the bent portions were performed. Table 1 shows the results.

Bend reflection color: In the case of black, it is designated as ○, and when coloring is clearly confirmed, it is set as ×.

Flexibility test: When the problem does not occur, ○, and when a problem such as wrinkles or cracks occurs is set to ×.

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

Claims (18)

A horizontal alignment film is formed through a coating, drying, and alignment treatment process.
After applying, drying, and irradiating ultraviolet rays, a horizontally oriented liquid crystal cured film is formed,
In addition, a vertical alignment layer is formed through a coating and drying process.
By forming a vertically aligned liquid crystal cured film through coating, drying, and ultraviolet irradiation processes,
The manufacturing method of the phase difference 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. According to claim 1,
A method of manufacturing a phase difference plate with an optical compensation function in which a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film having a film thickness of 1.0 µm or less are formed in this order. The method according to any one of claims 1 to 2,
The manufacturing method of the phase difference 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 vertically aligned liquid crystal cured film which consists of a photo-alignment film in this order. The method according to any one of claims 1 to 3,
A method of manufacturing a retardation plate with an optical compensation function that forms a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film made of a photo-alignment film containing a cinnamoyl group in this order. The method according to any one of claims 1 to 4,
A manufacturing method of a phase difference plate with an optical compensation function in which a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film with a thickness of 1.0 µm or less, and a vertical alignment liquid crystal cured film are formed in this order. The method according to any one of claims 1 to 5,
The manufacturing method of the phase difference plate with an optical compensation function which forms 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 in this order. The method according to any one of claims 1 to 6,
A method of manufacturing a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film having an Si / C element of 0.03 to 1.00, and a vertical alignment liquid crystal cured film in this order. The method according to any one of claims 1 to 7,
A method of manufacturing 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 to produce a retardation plate with an optical compensation function, wherein the horizontal alignment liquid crystal cured film satisfies the following relationship (1) Manufacturing method of retardation plate with function.
ReA (450) / ReA (550) <1.00… (One)
In the formula, ReA (λ) represents the in-plane retardation value at a wavelength λ nm of the horizontally oriented liquid crystal cured film. The definition of the in-plane retardation value ReA (λ) is as follows.
ReA (λ) = (nxA (λ)-nyA (λ)) × dA
However, nxA (λ) is the main refractive index in the film plane of the horizontally oriented liquid crystal cured film, the main refractive index at wavelength λ (nm), and nyA (λ) is the direction orthogonal to nxA (λ) in the same plane. As the refractive index, the refractive index at the wavelength λ (nm), and dA represents the thickness of the horizontally oriented liquid crystal cured film, respectively. The method according to any one of claims 1 to 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, wherein the vertical alignment liquid crystal cured film satisfies the following relationship (2) Manufacturing method of retardation plate with function.
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 oriented 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
However, nxC (λ) is the main refractive index in the film plane of the vertically oriented liquid crystal cured film, and the main refractive index at wavelength λ (nm),
nyC (λ) is a refractive index in the direction orthogonal to nxC (λ) in the same plane, and the refractive index at wavelength λ (nm),
nzC (λ) is the refractive index in the thickness direction of the vertically aligned liquid crystal cured film, and the refractive index at wavelength λ (nm),
dC represents the thickness of the vertically oriented liquid crystal cured film, respectively. A vertical alignment film is formed through a coating and drying process,
A vertical alignment liquid crystal cured film is formed through coating, drying, and ultraviolet irradiation processes,
In addition, a horizontal alignment film is formed through a process of coating, drying, and alignment,
By forming a horizontally oriented liquid crystal cured film through coating, drying, and ultraviolet irradiation processes,
The manufacturing method of the phase difference plate with an optical compensation function which forms a vertical alignment film, a vertically aligned liquid crystal cured film, a horizontally aligned film, and a horizontally aligned liquid crystal cured film in this order. The method of claim 10,
A manufacturing method of a phase difference plate with an optical compensation function in which 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 of claim 10 or 11,
A method of manufacturing a retardation plate with an optical compensation function that forms a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film composed of a photo alignment film, and a horizontal alignment liquid crystal cured film in this order. The method according to any one of claims 10 to 12,
A method for 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 composed of a photo-alignment film containing cinnamoyl groups, and a horizontal alignment liquid crystal cured film are formed in this order. The method according to any one of claims 10 to 13,
A method for manufacturing a phase difference 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 having a film thickness of 1.0 µm or less are formed in this order. The method according to any one of claims 10 to 14,
The manufacturing method of the phase difference plate with an optical compensation function which forms 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 in this order. The method according to any one of claims 10 to 15,
A method of manufacturing a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film having an Si / C element of 0.03 to 1.00, and a vertical alignment liquid crystal cured film in this order. The method according to any one of claims 10 to 16,
A method of manufacturing 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 to produce a retardation plate with an optical compensation function, wherein the horizontal alignment liquid crystal cured film satisfies the following relationship (3) Manufacturing method of retardation plate with function.
ReA (450) / ReA (550) <1.00… (3)
In the formula, ReA (λ) represents the in-plane retardation value at a wavelength λ nm of the horizontally oriented liquid crystal cured film. The definition of the in-plane retardation value ReA (λ) is as follows.
ReA (λ) = (nxA (λ)-nyA (λ)) × dA
However, nxA (λ) is the main refractive index in the film plane of the horizontally oriented liquid crystal cured film, and nyA (λ) is the refractive index in the direction orthogonal to the same plane as nxA (λ). As, the refractive index at wavelength λ (nm), and dA represents the thickness of the horizontally aligned liquid crystal cured film, respectively. The method according to any one of claims 10 to 17,
A method of manufacturing 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 to produce a retardation plate with an optical compensation function, wherein the vertical alignment liquid crystal cured film satisfies the following relationship (4) Manufacturing method of retardation plate with function.
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 oriented 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
However, nxC (λ) is the main refractive index in the film plane of the vertically oriented liquid crystal cured film, and the main refractive index at wavelength λ (nm),
nyC (λ) is a refractive index in the direction orthogonal to nxC (λ) in the same plane, and the refractive index at wavelength λ (nm),
nzC (λ) is the refractive index in the thickness direction of the vertically aligned liquid crystal cured film, and the refractive index at wavelength λ (nm),
dC represents the thickness of the vertically oriented liquid crystal cured film, respectively.