CN111033331B - Phase difference plate with optical compensation function for flexible display - Google Patents

Abstract

The present invention provides a method for manufacturing a flexible retardation plate with an optical compensation function that does not cause defects such as wrinkles and cracks even when folded, and does not reflect external light in a colored state when folded. In the production method of the present invention, a horizontal alignment film is formed through coating, drying, and alignment treatment steps, a horizontal alignment liquid crystal cured film is formed through a coating, drying, and ultraviolet irradiation step, and a vertical alignment film is formed through a coating and drying step. Alignment film, through the process of coating, drying, and ultraviolet irradiation to form a vertical alignment liquid crystal cured film, by sequentially forming a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a method of vertical alignment liquid crystal cured film, manufactured for flexible displays The retardation plate with optical compensation function.

Description

Phase difference plate with optical compensation for flexible displays

technical field

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

Background technique

Flat panel displays such as organic EL image display devices generally have a flat image display surface. The image display surface of the flat panel display maintains a flat state regardless of when an image is displayed or when no image is displayed.

Such flat panel displays often use retardation plates. For example, in an organic EL image display device, in order to prevent light reflection from occurring at electrodes constituting the image display device, a circularly polarizing plate in which a retardation plate and a polarizing plate are combined is used.

Among such retardation plates, those exhibiting reverse wavelength dispersion are preferable from the viewpoint of exhibiting the same retardation performance in a wide wavelength range of visible light. As a retardation plate exhibiting reverse wavelength dispersibility, a retardation plate formed of a horizontally oriented liquid crystal cured film in which a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility is formed so as to extend along a horizontal direction is known. It is obtained by polymerizing and curing in an oriented state.

In addition, there is also a demand for a retardation plate with an optical compensation function, which has a function of compensating so as to exhibit the same optical performance as when viewed from the front direction when viewed from an oblique direction, as such a retardation plate with an optical compensation function. , Patent Document 1 [Japanese Unexamined Patent Publication No. 2015-163935 ] proposes a phase of a vertically aligned liquid crystal cured film that includes a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal compound that is polymerized and cured in a vertically aligned state. Bad board. This document also discloses that the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film are laminated only via an alignment film, or via a protective layer or the like. In addition, this document only discloses that the retardation plate with an optical compensation function described in this document can be used in a flat panel display.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2015-163935

SUMMARY OF THE INVENTION

The problem to be solved by the invention

On the other hand, as a display, a so-called flexible display that is foldable has also been developed. In a flexible display, a retardation plate with optical compensation will also be folded together with the display.

However, when defects such as wrinkles and cracks occur during folding, when the flexible display is unfolded again to display an image, the defective parts such as wrinkles and cracks become defects and damage the displayed image. In addition, when folded with the image displayed, the elevation angle of the folded portion (the angle formed by the film plane and the direction in which the viewer observes the screen) is very small, so that the optical performance cannot be sufficiently compensated, and the folded portion is in a colored state. The fact that external light is reflected also becomes a problem.

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

means of solving problems

The inventors of the present application have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention.

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

[1] A method for producing a retardation plate with an optical compensation function, wherein

A horizontal alignment film is formed through coating, drying, and alignment treatment steps,

A horizontally aligned liquid crystal cured film is formed through coating, drying, and ultraviolet irradiation processes,

Further through the coating and drying process, a vertical alignment film is formed,

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

Thereby, a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film are formed in this order.

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

[3] The method for producing a retardation plate with an optical compensation function according to any one of the above [1] to [2], wherein a horizontal alignment film formed of a photo alignment film and a horizontal alignment liquid crystal cured film are sequentially formed , vertical alignment film, vertical alignment liquid crystal curing film.

[4] The method for producing a retardation plate with an optical compensation function according to any one of the above [1] to [3], wherein a horizontal alignment film formed of a photo-alignment film containing a cinnamoyl group, a horizontal alignment film comprising a cinnamoyl group are sequentially formed Alignment liquid crystal cured film, vertical alignment film, vertical alignment liquid crystal cured film.

[5] The method for producing a retardation plate with an optical compensation function according to any one of the above [1] to [4], wherein a horizontal alignment film and a horizontal alignment liquid crystal cured film are formed in this order, and the film thickness is 1.0 μm The following vertical alignment films and vertical alignment liquid crystal cured films.

[6] The method for producing a retardation plate with an optical compensation function according to any one of the above [1] to [5], wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, and a vertical alignment film containing an Si element are sequentially formed Alignment film, vertical alignment liquid crystal cured film.

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

[8] The method for producing a retardation plate with an optical compensation function according to any one of the above [1] to [7], wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment film are sequentially formed. A method of aligning a liquid crystal cured film to produce a retardation plate with an optical compensation function, wherein the horizontally aligned liquid crystal cured film satisfies the following relation (1).

ReA(450)/ReA(550)＜1.00...(1)

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

ReA(λ)=(nxA(λ)-nyA(λ))×dA

Here, nxA(λ) represents the principal refractive index at the wavelength λ(nm) in the film plane of the horizontally aligned liquid crystal cured film, and nyA(λ) represents the in-plane orthogonal direction to nxA(λ), The refractive index at wavelength λ (nm), dA represents the thickness of the horizontally aligned liquid crystal cured film.

[9] The method for producing a retardation plate with an optical compensation function according to any one of the above [1] to [8], wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment film are sequentially formed. A method of aligning a liquid crystal cured film to produce a retardation plate with an optical compensation function, wherein the vertically aligned liquid crystal cured film satisfies the following relation (2).

RthC(450)/RthC(550)＜1.00...(2)

In the formula, RthC(λ) represents the retardation value in the thickness direction at the wavelength λnm of the vertically aligned liquid crystal cured film. The definition of the phase difference value RthC(λ) is as follows.

RthC(λ)=((nxC(λ)+nyC(λ))/2-nzC(λ))×dC

where nxC(λ) represents the principal refractive index at wavelength λ(nm) in the film plane of the vertically aligned liquid crystal cured film,

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

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

dC represents the thickness of the vertically aligned liquid crystal cured film.

It should be noted that when nxC(λ)=nyC(λ), nxC(λ) may be the refractive index in any direction in the film plane.

In addition, the present invention also includes the following aspects.

[10] A method for producing a retardation plate with an optical compensation function, wherein

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

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

Further through the coating, drying, and orientation treatment steps to form a horizontal alignment film,

A horizontally aligned liquid crystal cured film is formed through coating, drying, and ultraviolet irradiation processes,

Thereby, a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film are formed in this order.

[11] The method for producing a retardation plate with an optical compensation function according to the above [10], wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film having a film thickness of 1.0 μm or less, and a horizontal alignment film are sequentially formed Liquid crystal cured film.

[12] The method for producing a retardation plate with an optical compensation function according to the above [10] or [11], wherein a vertical alignment film, a vertical alignment liquid crystal cured film, and a horizontal alignment film formed of a photo alignment film are sequentially formed , Horizontal alignment liquid crystal cured film.

[13] The method for producing a retardation plate with an optical compensation function according to any one of the above [10] to [12], wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a cinnamoyl-containing film are formed in this order; The horizontal alignment film formed by the photo-alignment film, and the horizontal alignment liquid crystal cured film.

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

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

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

[17] The method for producing a retardation plate with an optical compensation function according to any one of the above [10] to [16], wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment film are sequentially formed. A method of aligning a liquid crystal cured film to produce a retardation plate with an optical compensation function, wherein the horizontally aligned liquid crystal cured film satisfies the following relation (3).

ReA(450)/ReA(550)＜1.00...(3)

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

ReA(λ)=(nxA(λ)-nyA(λ))×dA

Here, nxA(λ) represents the principal refractive index at the wavelength λ(nm) in the film plane of the horizontally aligned liquid crystal cured film, and nyA(λ) represents the in-plane orthogonal direction to nxA(λ), The refractive index at wavelength λ (nm), dA represents the thickness of the horizontally aligned liquid crystal cured film.

[18] The method for producing a retardation plate with an optical compensation function according to the above [1] to [17], wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film are sequentially formed Thus, a method of producing a retardation plate with an optical compensation function in which the vertically aligned liquid crystal cured film satisfies the following relation (4).

RthC(450)/RthC(550)＜1.00...(4)

In the formula, RthC(λ) represents the retardation value in the thickness direction at the wavelength λnm of the vertically aligned liquid crystal cured film. The definition of the phase difference value RthC(λ) is as follows.

RthC(λ)=((nxC(λ)+nyC(λ))/2-nzC(λ))×dC

where nxC(λ) represents the principal refractive index at wavelength λ(nm) in the film plane of the vertically aligned liquid crystal cured film,

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

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

dC represents the thickness of the vertically aligned liquid crystal cured film.

It should be noted that when nxC(λ)=nyC(λ), nxC(λ) may be the refractive index in any direction in the film plane.

Using the manufacturing method of the present invention, a retardation plate with an optical compensation function can be obtained, and an elliptically polarizing plate with an optical compensation function can be produced by stacking a polarizing plate on the retardation plate.

This elliptically polarizing plate with an optical compensation function is preferably used in, for example, an organic EL display device.

effect of invention

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

Detailed ways

[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 formed of a polymer containing a polymerizable liquid crystal compound. From the viewpoint that the thinning and wavelength dispersion characteristics of the horizontally aligned liquid crystal cured film can be arbitrarily designed, it is preferable to form the horizontally aligned liquid crystal cured film by a method of applying a polymerizable liquid crystal composition to a horizontally aligned liquid crystal cured film. On the film, the composition containing the polymerizable liquid crystal compound in the alignment state is polymerized by heating and/or light irradiation.

The three-dimensional refractive index ellipsoid formed by the horizontally aligned liquid crystal cured film may have biaxiality, but preferably has uniaxiality. In the case of the horizontally aligned liquid crystal cured film, it may be a horizontally aligned liquid crystal cured film formed from a polymer of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound in a relatively horizontally aligned liquid crystal cured film The state of being oriented in the horizontal direction in terms of the plane; it can also be a mixed orientation liquid crystal cured film or a tilted orientation liquid crystal cured film. The refractive indices nx, ny, and nz in the three directions of the refractive index ellipsoid formed by the alignment of the polymerizable liquid crystal may have nx>ny≈nz (referred to as positive A plate), or nx<ny≈ nz (called negative A plate) relationship. nx represents the principal refractive index in the direction parallel to the plane of the horizontally aligned liquid crystal cured film in the refractive index ellipsoid formed by the horizontally aligned liquid crystal cured film. ny represents the refractive index in the direction parallel to the plane of the horizontally aligned liquid crystal cured film and orthogonal to the nx direction in the refractive index ellipsoid formed by the horizontally aligned liquid crystal cured film. 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.

As the horizontally aligned liquid crystal cured film, any of rod-shaped polymerizable liquid crystals and disc-shaped polymerizable liquid crystals can be used, but rod-shaped polymerizable liquid crystals are preferred. When a 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 aligned liquid crystal cured film has optical anisotropy in the plane of the film, Re1(550), which is an in-plane retardation value with respect to light having a wavelength of 550 nm, preferably satisfies the optical properties represented by the following formula (21). In addition, for the horizontally aligned liquid crystal cured film, Re1 (450), which is an in-plane retardation value with respect to light with a wavelength of 450 nm, Re1 (550), which is an in-plane retardation value with respect to light with a wavelength of 550 nm, and light with a wavelength of 650 nm. The in-plane retardation value of , that is, Re1 (650) preferably also satisfies the optical properties shown by equations (22) and (23). It is more preferable that the horizontal alignment liquid crystal cured film satisfies the optical characteristics shown by following formula (21), following formula (22), and following formula (23).

120nm≤ReA(550)≤170nm...(21)

[In the formula, ReA(550) represents the in-plane retardation value (in-plane retardation) of the horizontally aligned liquid crystal cured film with respect to light having a wavelength of 550 nm. ]

ReA(450)/ReA(550)≤1.0...(22)

1.00≤ReA(650)/ReA(550)...(23)

[wherein, ReA(450) represents the in-plane retardation value of the horizontally aligned liquid crystal cured film with respect to light with a wavelength of 450 nm, and ReA(550) represents the in-plane phase of the horizontally aligned liquid crystal cured film with respect to light with a wavelength of 550 nm, respectively The difference value, ReA(650), represents the in-plane retardation value of the horizontally aligned liquid crystal cured film with respect to light having a wavelength of 650 nm. ]

When the in-plane retardation value ReA (550) of the horizontally aligned liquid crystal cured film exceeds the range of the formula (21), the following problem arises: an elliptically polarizing plate with an optical compensation function (which includes a retardation with an optical compensation function) is used. board), the hue on the front of the display turns red or blue. As a further preferable range of the in-plane retardation value, 130 nm≦ReA(550)≦160 nm. When "ReA(450)/ReA(550)" of a horizontally-aligned liquid crystal cured film exceeds 1.0, the ellipticity on the short wavelength side of the elliptically polarizing plate provided with this horizontally-aligned liquid crystal cured film deteriorates. When the ellipticity of the elliptically polarizing plate on the short-wavelength side is degraded to less than 1.0, there is a tendency that the function as an elliptically polarizing plate is impaired on the short-wavelength side when viewed from the front. The "ReA(450)/ReA(550)" is preferably 0.75 to 0.92, more preferably 0.77 to 0.87, and further preferably 0.79 to 0.85.

The in-plane retardation value of the horizontally aligned liquid crystal cured film can be adjusted by the thickness of the horizontally aligned liquid crystal cured film. Since the in-plane retardation value is determined by the following formula (24), in order to obtain a desired in-plane retardation value (ReA(λ): the in-plane retardation of the horizontally aligned liquid crystal cured film at the wavelength λ (nm) value), adjust the three-dimensional refractive index and film thickness dA. In addition, the three-dimensional refractive index depends on the molecular structure and orientation state of the polymerizable liquid crystal compound to be described later.

ReA(λ)=(nxA(λ)-nyA(λ))×dA (24)

[In the formula, in the refractive index ellipsoid formed by the horizontally aligned liquid crystal cured film, there is a relationship of nxA(λ)>nyA(λ)≈nzA(λ), and nxA(λ) means that it is parallel to the plane of the horizontally aligned liquid crystal cured film The principal refractive index of light with relative wavelength λ (nm) in the direction of . nyA(λ) represents the relative wavelength λ(nm) in the direction parallel to the plane of the horizontally aligned liquid crystal cured film and orthogonal to the direction of nxA(λ) in the refractive index ellipsoid formed by the horizontally aligned liquid crystal cured film the refractive index of light. dA represents the thickness of the horizontally aligned liquid crystal cured film. ]

The horizontally aligned liquid crystal cured film is preferably a polymer containing a composition of 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, especially a photopolymerizable functional group. The photopolymerizable functional group refers to a group that can participate in a polymerization reaction by utilizing an active radical, an acid, or the like generated by 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, and epoxyethyl group. , oxetanyl, etc. Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferable, and an acryloyloxy group is more preferable. The liquid crystallinity may be a thermotropic liquid crystal or a lyotropic liquid crystal, and the phase order structure may be a nematic liquid crystal or a smectic liquid crystal.

In the present invention, the polymerizable liquid crystal compound is preferably the following formula (I) from the viewpoint of exhibiting reverse wavelength dispersibility and satisfying the relationship of the above-mentioned formulas (21) and (22) or the later-described (31) and (32) the compound represented,

In formula (I), Ar represents a divalent aromatic group which may have a substituent. The aromatic group here refers to a group having a planar ring structure, and the number of π electrons contained in the ring structure is [4n+2] according to Huckel's rule indivual. Here, n represents an integer. When a ring structure is formed by including heteroatoms such as -N= and -S-, it also includes a case where the non-covalent electron pair on these heteroatoms satisfies the Huckel's rule and thus has aromaticity. The divalent aromatic group preferably contains at least one of a nitrogen atom, an oxygen atom, and a sulfur atom.

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

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

L ¹ , L ² , B ¹ and B ² 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, in the case of 2≦k+1, B ¹ and B ² , and 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. Here, 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. - can be replaced by -O-, -S-, -Si-. P ¹ and P ² independently represent a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group.

G ¹ and G ² are each independently preferably 1,4-phenylenediyl which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms. 1,4-cyclohexanediyl substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1,4-cyclohexanediyl substituted with a methyl group Phenyl, unsubstituted 1,4-phenylene, or unsubstituted 1,4-trans-cyclohexanediyl, especially preferably unsubstituted 1,4-phenylene, or unsubstituted 1 , 4-trans-cyclohexanediyl. In addition, it is preferable that at least one of G ¹ and G ² present in plural is a divalent alicyclic hydrocarbon group, and it is more preferable that G ¹ and G bonded to L ¹ or L ² At least one of ² is a divalent alicyclic hydrocarbon group.

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

From the viewpoint of exhibiting inverse wavelength dispersion, k and l are preferably in the range of 2≤k+l≤6, preferably k+l=4, and more preferably k=2 and l=2. When k=2 and l=2, since a symmetrical structure is obtained, it is more preferable.

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

Examples of the polymerizable group represented by P ¹ or P ² include epoxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, and acryloyloxy group. , methacryloyloxy, oxirane, and oxetanyl. Among these, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferable, and an acryloyloxy group is more preferable.

Ar preferably has at least one selected from the group consisting of an optionally substituted aromatic hydrocarbon ring, an optionally substituted aromatic heterocyclic ring, and an electron withdrawing group. As this aromatic hydrocarbon ring, a benzene ring, a naphthalene ring, an anthracene ring, etc. are mentioned, for example, A benzene ring and a naphthalene ring are preferable. Examples of the aromatic heterocyclic ring include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, and a triazine ring. , pyrroline ring, imidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, thienothiazole ring, oxazole ring, benzoxazole ring, and phenanthroline ring, etc. 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 benzothiazolyl group. In addition, when a nitrogen atom is included in Ar, the nitrogen atom preferably has π electrons.

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

As an aromatic group represented by Ar, the following groups are mentioned, for example.

In formulas (Ar-1) to (Ar-22), the symbol * represents a linking portion, and Z ⁰ , Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group, nitro group, alkylsulfinyl group with 1 to 12 carbon atoms, alkylsulfonyl group with 1 to 12 carbon atoms, carboxyl group, fluoroalkyl group with 1 to 12 carbon atoms, and fluoroalkyl group with 1 to 12 carbon atoms Alkoxy group, alkylthio group having 1 to 12 carbon atoms, N-alkylamino group having 1 to 12 carbon atoms, N,N-dialkylamino group having 2 to 12 carbon atoms, and N,N-dialkylamino group having 1 to 12 carbon atoms N-alkylsulfamoyl of 12 or N,N-dialkylsulfamoyl of 2 to 12 carbon atoms.

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

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

Y ¹ , Y ² and Y ³ each independently represent an aromatic hydrocarbon group or 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 group in Y ¹ , Y ² and Y ³ include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl, naphthyl, anthracenyl, phenanthryl, and biphenyl, and preferably phenyl and naphthalene. group, more preferably a phenyl group. Examples of the aromatic heterocyclic group include carbon atoms containing at least one hetero atom (nitrogen atom, oxygen atom, sulfur atom, etc.), such as a furyl group, a pyrrolyl group, a thienyl group, a pyridyl group, a thiazolyl group, and a benzothiazolyl group. The aromatic heterocyclic group of numbers 4 to 20 is preferably a furyl group, a thienyl group, a pyridyl group, a thiazolyl group, and a benzothiazolyl group.

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

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

Q ¹ and Q ² are preferably -NH-, -S-, -NR ^2' -, and -O-, and R ^2' is preferably a hydrogen atom. Among them, -S-, -O-, and -NH- are particularly preferred.

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

In the formulae (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. The aromatic heterocyclic group includes the aromatic heterocyclic group described above as an aromatic heterocyclic ring which Ar may have, for example, a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, and a pyrazine ring. Ring, pyrimidine ring, indole ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring, etc. The aromatic heterocyclic group may have a substituent. In addition, Y ¹ may form the above-mentioned substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group together with the nitrogen atom and Z ⁰ to which it is bonded. For example, a benzofuran ring, a benzothiazole ring, a benzoxazole ring, etc. are mentioned. In addition, the compound represented by the said formula (I) can be manufactured according to the method described in 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 two or more kinds are used in combination, the content of the compound represented by the above formula (I) is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and still more preferably 80 parts by mass or more with respect to 100 parts by mass of the polymerizable liquid crystal compound. .

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

The content of the polymerizable liquid crystal compound is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, and more preferably 90 to 98 parts by mass relative 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 a horizontally-aligned liquid crystal cured film to improve. Here, the solid content refers to the total amount of the components after removing the solvent from the composition.

As the solvent, a solvent capable of dissolving the polymerizable liquid crystal compound is preferable, and a solvent inactive to the polymerization reaction of the polymerizable liquid crystal compound is preferable. Examples of the solvent include water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2 - Alcohol solvents such as butoxyethanol and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate Ester solvents; 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; ethyl acetate Alicyclic hydrocarbon solvents such as 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 ; Dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone and other amide-based solvents, etc. These solvents may be used alone or in combination of two or more. However, the compound represented by the above formula (I) generally has a relatively large conjugated system, and therefore has low solubility in solvents. Among the solvents exemplified above, alcohol solvents, ester solvents, ketone solvents, and chlorine-containing solvents are preferably used , ether-based solvent, amide-based solvent, and aromatic hydrocarbon solvent, more preferably, ester solvent, ketone solvent, chlorine-containing solvent, ether-based solvent, and amide-based solvent are used.

50-98 mass parts are preferable with respect to 100 mass parts of polymerizable liquid crystal compositions, and, as for content of a solvent, 70-95 mass parts are more preferable. Therefore, the solid content in 100 parts by mass of the composition is preferably 2 to 50 parts by mass. When the solid content of a composition is 50 mass parts or less, since the viscosity of a composition falls, the thickness of a horizontally-aligned liquid crystal cured film becomes substantially uniform, and there exists a tendency for unevenness to become hard to generate|occur|produce in a horizontally-aligned liquid crystal cured film. The above-mentioned solid content can be appropriately determined in consideration of the thickness of the horizontally aligned liquid crystal cured film to be produced.

A polymerization initiator is a compound which can generate|occur|produce a reactive substance by the participation of heat or light, and can initiate a polymerization reaction of a polymerizable liquid crystal or the like. Examples of the reactive material include active materials such as radicals, cations, or anions. Among them, a photopolymerization initiator that reacts by light irradiation is preferable from the viewpoint of easy control of the reaction.

As a photoinitiator, a photoradical polymerization initiator, a photocationic polymerization initiator, etc. are mentioned. Examples of photoradical polymerization initiators include benzoin compounds, benzophenone compounds, benzil ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, triazine compounds, and the like, and examples of photocationic polymerization Examples of the initiator include onium salts such as aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts, iron-aromatic complexes, and the like.

Specifically, Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG manufactured by BASF Japan Co., Ltd. ), SEIKUOL BZ, SEIKUOL Z, SEIKUOL BEE (the above are manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by DOW Corporation), ADEKA Optomer SP-152, ADEKA Optomer SP -170, ADEKA Optomer N-1717, ADEKA Optomer N-1919, ADEKA ARKLS NCI-831, ADEKA ARKLSNCI-930 (the above are manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (the above are manufactured by Siber Hegner Corporation of Japan) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.), KAYARAD (registered trademark) series (manufactured by Nippon Kayaku Co., Ltd.), CYRACUREUVI series (manufactured by Dow Chemical Co., Ltd.), CPI series (manufactured by SAN-APRO Co., Ltd.), TAZ, BBI and DTS (the above are manufactured by Midori Chemical Co., Ltd.), RHODORSIL (registered trademark) (manufactured by Rhodia Co., Ltd.), and the like. The photopolymerization initiators may be used alone or in combination of two or more. Among these, photoradical polymerization initiators that generate radicals by light irradiation are preferred from the viewpoint of easy control of the reaction.

The photopolymerization initiator preferably has a maximum absorption wavelength in the range of 300 nm to 400 nm, more preferably in the range of 300 nm to 380 nm, from the viewpoint of fully utilizing the energy emitted from the light source and achieving excellent productivity. In addition, from the same viewpoint, an α-acetophenone-based polymerization initiator and an oxime-based photopolymerization initiator are preferable.

Examples of the α-acetophenone-based polymerization initiator include 2-methyl-2-morpholino-1-(4-methylthiophenyl)-1-propanone, 2-dimethylamino -1-(4-morpholinophenyl)-2-benzyl-1-butanone and 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylbenzene) ylmethyl)-1-butanone and the like, more preferably 2-methyl-2-morpholino-1-(4-methylthiophenyl)-1-propanone and 2-dimethylamino -1-(4-Morpholinophenyl)-2-benzyl-1-butanone. Commercially available products of the α-acetophenone compound include Irgacure 369, 379EG, 907 (the above are manufactured by BASF Japan Co., Ltd.), SEIKUOL BEE (manufactured by Seiko Chemical Corporation), and the like.

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

The addition amount of a photoinitiator is 0.1-30 mass parts normally with respect to 100 mass parts of polymerizable liquid crystal compounds, Preferably it is 1-20 mass parts, More preferably, it is 1-15 mass parts. Within the above range, the reaction of the polymerizable group proceeds sufficiently, and the alignment of the polymerizable liquid crystal compound is less likely to be disturbed.

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

Moreover, by using a photosensitizer, a photoinitiator can be made highly sensitive. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone; anthracenes and anthracenes having substituents such as alkyl ethers; phenothiazine; and rubrene. A photosensitizer can be used individually or in combination of 2 or more types. Content of a photosensitizer is 0.01-10 mass parts normally with respect to 100 mass parts of polymerizable liquid crystal compounds, Preferably it is 0.05-5 mass parts, More preferably, it is 0.1-3 mass parts.

The term "leveling agent" refers to an additive having a function of adjusting the fluidity of the polymerizable liquid crystal composition and making the layer obtained by coating the composition more flat, and examples thereof include silicone-based and polyacrylic acid such as silane coupling agents. Ester-based and perfluoroalkyl-based leveling agent. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all of the above are manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340 , KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE -502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBE-585, KBM-802, KBM-802 , KRM-803, KBE-846, KBE-9007 (all of the above are manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all of the above are Momentive High-tech Materials Japan Contract Co., Ltd.), Fluorinert (registered trademark) FC-72, Fluorinert FC-40, Fluorinert FC-43, Fluorinert FC-3283 (all of which are manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) R- 08. MEGAFAC R-30, MEGAFAC R-90, MEGAFAC F-410, MEGAFAC F-411, MEGAFAC F-443, MEGAFAC F-445, MEGAFAC F-470, MEGAFAC F-477, MEGAFAC F-479, MEGAFAC F-482 , MEGAFAC F-483 (all of the above are manufactured by DIC Co., Ltd.), EFTOP (trade name) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (all of the above are manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-105, KH-40, SA-100 (all of the above are manufactured by AGC Kiyomi Chemical Co., Ltd.), products Name E1830, trade name E5844 (manufactured by Daikin Institute of Fine Chemicals Co., Ltd.), BM-1000, BM-1100, BYK-352, BYK-353, and BYK- 361N (all trade names: manufactured by BM Chemie) and the like. A leveling agent can be used individually or in combination of 2 or more types.

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 content of a leveling agent exists in the said range, since there exists a tendency for the obtained horizontal alignment liquid crystal cured film to become smoother, it is preferable.

The polymerizable liquid crystal composition can be obtained by, for example, stirring the polymerizable liquid crystal compound and components other than the polymerizable liquid crystal compound such as additives at a predetermined temperature.

The horizontally aligned liquid crystal cured film can be obtained by applying the above-mentioned polymerizable liquid crystal composition on the horizontal alignment film described later, then removing the solvent, and applying heat and/or an active energy ray to contain the polymerizable liquid crystal in an aligned state. The polymerizable liquid crystal composition of the compound is cured.

As a method for 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, and reverse gravure coating method can be mentioned. method, CAP coating method, slit coating method, microgravure method, die coating method, inkjet method, etc. Moreover, the method etc. which apply|coat using a coating machine, such as a dip coater, a bar coater, and a spin coater, are mentioned. Among them, in the case of continuous coating by a roll-to-roll method, a coating method based on a microgravure method, an inkjet method, a slit coating method, or a die coating method is preferable.

As a method of removing the solvent (hereinafter, it may be referred to as solvent removal method A), for example, natural drying, ventilation drying, heating drying, drying under reduced pressure, and a method of combining these are exemplified. Among them, natural drying or heat drying is preferable. The drying temperature is preferably in the range of 0 to 200°C, more preferably in the range of 20 to 150°C, still more preferably in the range of 50 to 130°C. The drying time is preferably 10 seconds to 20 minutes, and more preferably 30 seconds to 10 minutes.

The active energy ray to be irradiated depends on the type of the polymerizable liquid crystal compound (in particular, the type of photopolymerizable functional group possessed by the polymerizable liquid crystal compound) and the type of the photopolymerization initiator (in the case of including a photopolymerization initiator) , and their amounts are appropriately selected. Specifically, one or more kinds of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-ray, α-ray, β-ray, and γ-ray can be mentioned. Among them, ultraviolet light is preferable from the viewpoint of easy control of the progress of the polymerization reaction and from the viewpoint of being able to use an apparatus that has been widely used in this field as a photopolymerization apparatus, and it is preferable to select it so that photopolymerization can be carried out by ultraviolet light. Types of polymerizable liquid crystal compounds.

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

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

When irradiated one or more times with such ultraviolet irradiation intensity, the cumulative light amount is 10 to 3,000 mJ/cm ² , preferably 50 to 2,000 mJ/cm ² , and more preferably 100 to 1,000 mJ/cm ² . When the accumulated light amount is below the above-mentioned lower limit, curing of the polymerizable liquid crystal compound may become insufficient, and good transferability may not be obtained. On the contrary, when the accumulated light quantity is more than the said upper limit, the retardation plate with an optical compensation function containing a horizontally-aligned liquid crystal cured film may be colored.

From the viewpoint of thinning the functional film, the thickness of the horizontally aligned liquid crystal cured film is preferably 5 μm or less, more preferably 3 μm or less, and further preferably 2.5 μm or less. Moreover, 0.1 micrometer or more is preferable, as for the minimum of the film thickness of a horizontal alignment liquid crystal cured film, 0.5 micrometer or more is more preferable, and 1.0 micrometer or more is still more preferable. The film thickness of the horizontally aligned liquid crystal cured film can be measured using an ellipsometer or a contact film thickness meter.

[Horizontal alignment film]

An alignment film is a film which has the alignment control force which orientates the polymerizable liquid crystal compound of a liquid crystal cured film in a predetermined direction. As an orientation process required to express an orientation control force, a rubbing process, a photo-orientation process, a light irradiation process, etc. are mentioned. In addition, various orientations such as vertical orientation, horizontal orientation, hybrid orientation, and oblique orientation can be controlled by the type of orientation film, rubbing conditions, and light irradiation conditions. Here, the horizontal alignment film is an alignment film having an alignment control force for aligning the polymerizable liquid crystal compound of the liquid crystal cured film in the horizontal direction. Therefore, by using a horizontal alignment film, a horizontal alignment liquid crystal film can be formed.

As an alignment film, it is preferable that it has solvent resistance that does not dissolve due to coating of the polymerizable liquid crystal composition, etc., and also has heat resistance to heat treatment for removing the solvent and orienting the polymerizable liquid crystal compound. sex.

A rubbing alignment film, a photo alignment film, a groove alignment film having a concavo-convex pattern and a plurality of grooves on the surface, etc. are mentioned as a horizontal alignment film which shows the alignment control force which orientates a horizontal alignment liquid crystal cured film in a horizontal direction. In the case of applying to a long roll-shaped film, for example, a photo-alignment film is preferable because the orientation direction can be easily controlled.

In the case of a rubbed alignment film, a composition containing an alignment polymer and a solvent (hereinafter, also referred to as a composition for forming a rubbed alignment film) is usually applied to a substrate or the like, and the solvent is removed to form a coating. The coating film is rubbed to impart orientation control force.

Examples of the oriented polymer include polyamides having amide bonds, gelatins, polyimides having imide bonds, and hydrolyzates thereof, that is, polyamic acid, polyvinyl alcohol, and alkyl-modified polyethylene. Alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylate. These oriented polymers can be used alone or in combination of two or more.

The concentration of the alignment polymer in the composition for forming a rubbed alignment film should just be a range in which the alignment polymer is completely dissolved in the solvent. 0.1-20 mass parts is preferable with respect to 100 mass parts of this composition, and, as for content of an orientation polymer, 0.1-10 mass parts is more preferable.

The composition for forming a rubbed alignment film is commercially available. As a commercial item, SUNEVER (registered trademark, manufactured by Nissan Chemical Industries, Ltd.), OPTMER (registered trademark, manufactured by JSR Corporation), etc. are mentioned.

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

As a method of a rubbing treatment, the method of making the said coating film and the rubbing roll wound with a rubbing cloth and rotating, for example, is mentioned. When performing the rubbing treatment, when masking is performed, a plurality of regions (patterns) having different alignment directions can be formed on the alignment film.

The photo-alignment film can usually be obtained by applying a composition (also referred to as a photo-alignment film-forming composition) containing a polymer or monomer having a photoreactive group and a solvent on a substrate or the like, After removing the solvent, polarized light (preferably polarized UV light) is irradiated. In the case of a photo-alignment film, the direction of the alignment control force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.

The photoreactive group refers to a group that generates alignment ability by light irradiation. Specifically, a group that participates in a photoreaction that becomes a source of alignment ability, such as an orientation-induced reaction of molecules by light irradiation, an isomerization reaction, a photodimerization reaction, a photocrosslinking reaction, or a photodecomposition reaction, can be mentioned. . As the photoreactive group, a group having an unsaturated bond, especially a double bond is preferable, and it is particularly preferable to have a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), A group of at least one selected from the group consisting of a nitrogen-nitrogen double bond (N=N bond) and a carbon-oxygen double bond (C=O bond).

Examples of the photoreactive group having a C=C bond include a vinyl group, a polyalkenyl group, a stilbene group, a stilbazole group, a stilbazolium group, a chalcone group, and a cinnamon group. Acyl. As a photoreactive group which has a C=N bond, the group which has structures, such as an aromatic Schiff base and an aromatic hydrazone, is mentioned, for example. Examples of the photoreactive group having an N=N bond include an azophenyl group, an azonaphthyl group, an aromatic heterocyclic azo group, a disazo group, a formazan group, and an oxidative group. A group of azobenzene structure. As a photoreactive group which has a C=O bond, a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group are mentioned, for example. These groups may have substituents such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, a haloalkyl group, and the like.

From the viewpoint of being excellent in orientation, a group participating in a photodimerization reaction or a photocrosslinking reaction is preferable. Among them, a photoreactive group that participates in a photodimerization reaction is preferable, and cinnamon is preferable from the viewpoint that the amount of polarized light irradiation required for alignment is small, and it is easy to obtain a photo-alignment film excellent in thermal stability and stability over time. Acyl and chalcone groups. As a polymer which has a photoreactive group, the polymer which has a cinnamoyl group in which the terminal part of this polymer side chain becomes a cinnamic acid structure or a cinnamate structure is especially preferable.

The content of the polymer or monomer having a photoreactive group can be adjusted according to the type of the polymer or monomer and the thickness of the target photo-alignment film, and relative to 100 parts by mass of the composition for forming a photo-alignment film, It is preferably at least 0.2 parts by mass or more, and more preferably in the range of 0.3 to 10 parts by mass.

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

In order to irradiate the polarized light, for example, the system of irradiating the polarized light directly to the product obtained by removing the solvent from the composition for photo-alignment film formation apply|coated to the base material etc. may be sufficient. In addition, it is preferable that the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably a wavelength in a wavelength region in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength in the range of 250 to 400 nm is particularly preferable. Examples of the light source for irradiating the polarized light include a xenon lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, and ultraviolet 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 luminous intensity of ultraviolet rays having a wavelength of 313 nm is high. Polarized UV light can be irradiated by irradiating light from the above-mentioned light source through an appropriate polarizing element. Examples of the polarizing element include polarizing filters, polarizing prisms such as Glan-Thompson and Glan-Taylor, and wire grids. Among them, a wire grid type polarizer is preferable from the viewpoints of increasing the area and resistance to heat.

In addition, when performing rubbing or polarized light irradiation, when shielding is performed, it is also possible to form a plurality of regions (patterns) in which the directions of liquid crystal alignment are different.

A groove alignment film is a film having a concavo-convex pattern or a plurality of grooves (grooves) on the film surface. When the 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 grooves.

As a method of obtaining a groove alignment film, a method of exposing the surface of the photosensitive polyimide film through an exposure mask having a slit having a pattern shape, and then performing development and rinsing treatment to form a concavo-convex pattern can be mentioned. ; A method of forming a UV-curable resin layer before curing on a plate-shaped original plate having grooves on the surface, moving the formed resin layer to a substrate, etc., and then curing; and, pressing the roll-shaped original plate with a plurality of grooves on A method of forming a film of a UV-curable resin before curing on a substrate, etc., thereby forming unevenness, and then curing; and the like.

The composition for horizontal alignment film formation, such as the said composition for rubbing alignment film formation, the said composition for photo-alignment film formation, etc. may contain the additive etc. exemplified in the horizontal alignment liquid crystal cured film in addition to a solvent.

From the viewpoint of thinning the retardation plate with an optical compensation function, the thickness of the horizontal alignment film is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.3 μm or less. In addition, the thickness of the horizontal alignment film is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, and particularly preferably 30 nm or more. The film thickness of the horizontal alignment film can be measured using an ellipsometer or a contact 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 formed of a polymer containing a polymerizable liquid crystal compound. From the viewpoint of being able to arbitrarily design the thinning and wavelength dispersion characteristics of the vertically aligned liquid crystal cured film, it is preferable to form the vertically aligned liquid crystal cured film by a method of applying a polymerizable liquid crystal composition to a vertically aligned liquid crystal cured film. On the film, the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound in the alignment state is polymerized by heating and/or light irradiation.

The three-dimensional refractive index ellipsoid formed by the vertically aligned liquid crystal cured film may have biaxiality, but preferably has uniaxiality. In the case of a vertically aligned liquid crystal cured film, it may be a vertically aligned liquid crystal cured film formed from a polymer of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound in a plane relative to the liquid crystal cured film The state of being oriented in the vertical direction; it may also be a hybrid alignment liquid crystal cured film or a tilt alignment liquid crystal cured film. The refractive indices nx, ny, and nz in the three directions of the refractive index ellipsoid formed by the alignment of the polymerizable liquid crystal may have nz>nx≈ny (referred to as positive C plate) or nz<nx≈ny (called the negative C plate). nx represents the principal 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 represents the refractive index in the direction parallel to the plane of the vertically aligned liquid crystal cured film and orthogonal to the nx direction in the refractive index ellipsoid formed by the vertically aligned liquid crystal cured film. In addition, when nx=ny, nx can take any direction in the plane of the vertical alignment liquid crystal cured film. nz represents the refractive index in the direction perpendicular to the plane of the vertically aligned liquid crystal cured film in the refractive index ellipsoid formed by the vertically aligned liquid crystal cured film.

Although either rod-shaped polymerizable liquid crystal and disc-shaped polymerizable liquid crystal can be used for the vertically aligned liquid crystal cured film, rod-shaped polymerizable liquid crystal is preferably used. When a rod-shaped polymerizable liquid crystal forms a vertical alignment liquid crystal cured film, the vertical alignment liquid crystal cured film becomes a positive C plate.

When the vertical alignment liquid crystal cured film is a positive C plate, it is preferable for the vertical alignment liquid crystal cured film that the retardation value in the thickness direction with respect to light of wavelength λ nm, that is, RthC(λ) satisfy the following formula (31) optical properties. In addition, it is also preferable to satisfy the optical properties represented by the following formulas (32) and (33). The vertically aligned liquid crystal cured film more preferably satisfies the optical properties represented by the following formula (31), the following formula (32), and the following formula (33).

-100nm≤RthC(550)≤-50nm...(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) represents the retardation value in the thickness direction with respect to light with a wavelength of 450 nm, RthC(550) represents the retardation value in the thickness direction with respect to light with a wavelength of 550 nm, and RthC(650) represents the relative wavelength The retardation value in the thickness direction of 650nm light.)

When the retardation value RthC (550) in the thickness direction of the vertical alignment liquid crystal cured film exceeds the range of the formula (31), the following problem arises: an elliptically polarizing plate with an optical compensation function (which contains a phase with an optical compensation function) is used. The slanted hue of the monitor of the difference plate) turns red or blue. A more preferable range of the retardation value in the thickness direction is −95 nm≦RthC(550)≦−55 nm, and a further preferable range is −90 nm≦RthC(550)≦−60 nm. When "RthC(450)/RthC(550)" of the vertical alignment liquid crystal cured film exceeds 1.0, the ellipticity of the elliptically polarizing plate provided with the vertical alignment liquid crystal cured film when viewed obliquely on the short wavelength side deteriorates. When the ellipticity of the elliptically polarizing plate on the short wavelength side is degraded to less than 1.0, there is a tendency that the function as an elliptically polarizing plate is impaired on the short wavelength side. "RthC(450)/RthC(550)" is preferably 0.75 to 0.92, more preferably 0.77 to 0.87, further preferably 0.79 to 0.85.

The retardation value in the thickness direction of the vertical alignment liquid crystal cured film can be adjusted by the thickness of the vertical alignment liquid crystal cured film. Since the retardation value in the thickness direction is determined by the following formula (34), in order to obtain the desired retardation value in the thickness direction (RthC(λ): the thickness direction of the vertically aligned liquid crystal cured film at the wavelength λ (nm) The retardation value) can be adjusted by adjusting the three-dimensional 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)

(in the formula, in the refractive index ellipsoid formed by the vertical alignment liquid crystal cured film, there is a relationship of nzC(λ)>nxC(λ)≈nyC(λ), in the formula, nzC(λ) indicates that the vertical alignment liquid crystal cured In the refractive index ellipsoid formed by the film, the refractive index of light with a wavelength of λ (nm) in the direction perpendicular to the plane of the vertical alignment liquid crystal cured film. nxC (λ) represents the refraction formed by the vertical alignment liquid crystal cured film In the rate ellipsoid, the maximum refractive index of light with a wavelength of λ (nm) in the direction parallel to the plane of the vertically aligned liquid crystal cured film. nyC (λ) represents the refractive index ellipsoid formed by the vertically aligned liquid crystal cured film , the refractive index of light of relative wavelength λ (nm) in the direction parallel to the plane of the vertical alignment liquid crystal cured film and perpendicular to the direction of the above-mentioned nxC. However, when nxC(λ)=nyC(λ), nxC(λ) ) represents the refractive index in an arbitrary direction parallel to the plane of the vertical alignment liquid crystal cured film. Here, dC represents the thickness of the vertical alignment liquid crystal cured film.)

The vertically aligned liquid crystal cured film is preferably a polymer of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound in a vertically aligned state as described above. The polymerizable liquid crystal compound forming the vertical alignment liquid crystal cured film is a liquid crystal compound having a polymerizable functional group, especially a photopolymerizable functional group. The photopolymerizable functional group refers to a group that can participate in a polymerization reaction by utilizing an active radical, an acid, or the like generated by 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, and epoxyethyl group. , oxetanyl, etc. Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferable, and an acryloyloxy group is more preferable. The liquid crystallinity may be a thermotropic liquid crystal or a lyotropic liquid crystal, and the phase order structure may be a nematic liquid crystal or a smectic liquid crystal.

As the polymerizable liquid crystal compound used for formation of the vertical alignment liquid crystal cured film, the compound represented by the above-mentioned formula (I) is preferably used. By using the compound represented by the formula (I), reverse wavelength dispersion can be exhibited, and the above-mentioned relationships (31) and (32) can be satisfied.

The polymerizable liquid crystal compound used for the vertical alignment liquid crystal cured film may be used alone or in combination of two or more. When two or more kinds are used in combination, the content of the compound represented by the formula (I) is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 80 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. above.

The composition for forming a vertical alignment liquid crystal cured film (hereinafter, also referred to as a polymerizable liquid crystal composition) used for the vertical alignment liquid crystal cured film may further contain a solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, Adhesion improver. These additives may be used alone or in combination of two or more.

The content of the polymerizable liquid crystal compound is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, and more preferably 90 to 98 parts by mass relative 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 a vertical alignment liquid crystal cured film to improve. Here, the solid content refers to the total amount of the components after removing the solvent from the composition.

As the solvent, a solvent capable of dissolving the polymerizable liquid crystal compound is preferable, and a solvent inactive to the polymerization reaction of the polymerizable liquid crystal compound is preferable. As a solvent, the same solvent as the solvent used for the composition for horizontal alignment liquid crystal cured film formation can be used.

50-98 mass parts are preferable with respect to 100 mass parts of polymerizable liquid crystal compositions, and, as for content of a solvent, 70-95 mass parts are more preferable. Therefore, the solid content in 100 parts by mass of the composition is preferably 2 to 50 parts by mass. When the solid content of the composition is 50 parts by mass or less, the viscosity of the composition decreases, so that the thickness of the vertical alignment liquid crystal cured film becomes substantially uniform, and unevenness tends to be less likely to occur in the vertical alignment liquid crystal cured film. The above-mentioned solid content can be appropriately determined in consideration of the thickness of the vertically aligned liquid crystal cured film to be produced.

A polymerization initiator is a compound which can generate|occur|produce a reactive substance by the participation of heat or light, and can initiate a polymerization reaction of a polymerizable liquid crystal or the like. Examples of the reactive material include active materials such as radicals, cations, or anions. Among them, a photopolymerization initiator that reacts by light irradiation is preferable from the viewpoint of easy control of the reaction. As a photoinitiator, the same initiator as the photoinitiator used for the composition for horizontal alignment liquid crystal cured film formation can be used.

The addition amount of a photoinitiator is 0.1-30 mass parts normally with respect to 100 mass parts of polymerizable liquid crystal compounds, Preferably it is 1-20 mass parts, More preferably, it is 1-15 mass parts. Within the above range, the reaction of the polymerizable group proceeds sufficiently, and the alignment of the polymerizable liquid crystal compound is less likely to be disturbed.

By blending a polymerization inhibitor, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. As a polymerization inhibitor, the same polymerization inhibitor as the polymerization inhibitor used for the composition for horizontal alignment liquid crystal cured film formation can be used. In order to polymerize the polymerizable liquid crystal compound without disturbing the orientation of the polymerizable liquid crystal compound, the content of the polymerization inhibitor is usually 0.01 to 10 parts by mass, preferably 0.1 to 100 parts by mass of the polymerizable liquid crystal compound. 5 parts by mass, more preferably 0.1 to 3 parts by mass. A polymerization inhibitor can be used individually or in combination of 2 or more types.

Moreover, by using a photosensitizer, a photoinitiator can be made highly sensitive. As a photosensitizer, the same photosensitizer as the photosensitizer used for the composition for horizontal alignment liquid crystal cured film formation 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 refers to an additive having a function of adjusting the fluidity of the polymerizable liquid crystal composition and making the layer obtained by coating the composition flatter, and the leveling agent used in the composition for forming a horizontally aligned liquid crystal cured film can be used. Leveling agent The same leveling agent.

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 content of a leveling agent exists in the said range, since there exists a tendency for the obtained vertical alignment liquid crystal cured film to be made smoother, it is preferable.

The polymerizable liquid crystal composition used for formation of a vertical alignment liquid crystal cured film can be obtained by stirring the polymerizable liquid crystal compound and components other than the polymerizable liquid crystal compound such as additives at a predetermined temperature, or the like.

The vertical alignment liquid crystal cured film can be obtained by applying the above-mentioned polymerizable liquid crystal composition on the vertical alignment film described later, then removing the solvent, and applying heat and/or an active energy ray to polymerize an alignment state. The polymerizable liquid crystal composition of the liquid crystal compound is cured.

The method of apply|coating a polymerizable liquid crystal composition on a vertical alignment film can use the method similar to the case of forming a horizontal alignment liquid crystal cured film.

As the method of removing the solvent, the same method as when forming a horizontally aligned liquid crystal cured film can be used.

The active energy ray to be irradiated depends on the type of the polymerizable liquid crystal compound (in particular, the type of photopolymerizable functional group possessed by the polymerizable liquid crystal compound) and the type of the photopolymerization initiator (in the case of including a photopolymerization initiator) , and their amounts are appropriately selected. Specifically, one or more kinds of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-ray, α-ray, β-ray, and γ-ray can be mentioned. Among them, ultraviolet light is preferable from the viewpoint of easy control of the progress of the polymerization reaction and from the viewpoint of being able to use an apparatus that has been widely used in this field as a photopolymerization apparatus, and it is preferable to select it so that photopolymerization can be carried out by ultraviolet light. Types of polymerizable liquid crystal compounds.

As a light source of the said active energy ray, the same light source as the light source used when forming a horizontal alignment liquid crystal cured film can be used.

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

When irradiated one or more times with such ultraviolet irradiation intensity, the cumulative light amount is 10 to 3,000 mJ/cm ² , preferably 50 to 2,000 mJ/cm ² , and more preferably 100 to 1,000 mJ/cm ² . When the accumulated light amount is below the above-mentioned lower limit, curing of the polymerizable liquid crystal compound may become insufficient, and good transferability may not be obtained. Conversely, when the accumulated light amount is more than the above-mentioned upper limit, the retardation plate with an optical compensation function including a vertically aligned liquid crystal cured film may be colored.

From the viewpoint of thinning the functional film, the film thickness of the vertically aligned liquid crystal cured film is preferably 3 μm or less, more preferably 2 μm or less, and further preferably 1.5 μm or less. In addition, the lower limit of the film thickness of the vertically aligned liquid crystal cured film is preferably 0.1 μm or more, more preferably 0.3 μm or more, and further preferably 0.5 μm or more. The film thickness of the vertical alignment liquid crystal cured film can be measured using an ellipsometer or a contact film thickness meter.

[Vertical Alignment Film]

An alignment film is a film which has the alignment control force which orientates the polymerizable liquid crystal compound of a liquid crystal cured film in a predetermined direction. In addition, various orientations such as vertical orientation, horizontal orientation, hybrid orientation, and oblique orientation can be controlled by the type of orientation film, rubbing conditions, and light irradiation conditions. Here, the vertical alignment film is an alignment film having an alignment control force for aligning the polymerizable liquid crystal compound of the liquid crystal cured film in the vertical direction. Therefore, by using a vertical alignment film, a vertical alignment liquid crystal film can be formed.

As the vertical alignment film, a material that reduces the surface tension of the surface of a substrate or the like is preferably used. Examples of such materials include the above-mentioned oriented polymers, for example, polyimide, polyamide, polyamic acid as a hydrolyzate thereof, fluorine-based polymers such as perfluoroalkyl groups, silane compounds, and condensation thereof. The polysiloxane compound obtained by the reaction. The vertical alignment film can be obtained by applying a composition containing such a material and a solvent, for example, the solvent exemplified in the section of the vertical alignment liquid crystal film (hereinafter, also referred to as a composition for vertical alignment film formation) on a substrate. On the material or the like, after removing the solvent, heating or the like is applied to the coating film.

When a silane compound is used in the vertical alignment film, it is preferable that the vertical alignment film contains Si element in the constituent elements from the viewpoints that the surface tension can be easily lowered and the adhesiveness of the layer adjacent to the vertical alignment film can be easily improved. For the film formed with the compound of element C, a silane compound can be suitably used. In the present invention, when the vertical alignment film is arranged between the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film, the vertical alignment film, the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film exhibit high adhesiveness, and it is possible to In a retardation plate with an optical compensation function, peeling at the interface between the layers is effectively suppressed or prevented.

As the silane compound, silicone-based such as the above-mentioned silane coupling agent can be preferably used, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxysilane) ) silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, 3-glycidoxypropyltrimethoxysilane, 3-ring Oxypropoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropane trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxysilane Oxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropylethoxydimethylsilane, and the like.

The silane compound may be an organosilicon monomer type or an organosilicon oligomer (polymer) type. When the silicone oligomer is shown in the form of a (monomer)-(monomer) copolymer, 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyl trimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer, and 3-mercaptopropyltriethoxysilane-tetraethoxysilane mercaptopropyl group-containing copolymers such as copolymers; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane Silane-tetramethoxysilane copolymer, and mercaptomethyl-containing copolymers such as mercaptomethyltriethoxysilane-tetraethoxysilane copolymer; 3-methacryloyloxypropyltrimethoxy Silane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane- Tetramethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane- Tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldiethoxy Silane-tetramethoxysilane copolymer and methacryloyloxypropyl group-containing copolymer such as 3-methacryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer ; 3-Acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropyl triethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxy Silane-tetramethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldiethoxysilane - Copolymers containing acryloyloxypropyl groups such as tetramethoxysilane copolymers and 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymers; vinyltrimethoxysilane Silane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane- Tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethyl Oxysilane-tetramethoxysilane copolymer and vinyl group-containing copolymer such as vinylmethyldiethoxysilane-tetraethoxysilane copolymer; 3-aminopropyltrimethoxysilane-tetra Methoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane Ethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyl Dimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethyl An oxysilane copolymer, an amino group-containing copolymer such as a 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer, and the like. The silane compound may be used alone or in combination of two or more. Moreover, a silane coupling agent etc. which are also sometimes used as a leveling agent can also be used.

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

The layer arranged in the lower layer is less likely to dissolve from the viewpoint of more easily improving the adhesiveness, the applicability of the composition for forming a vertically aligned liquid crystal cured film, and the method for producing a retardation plate with an optical compensation function described later. From the viewpoint of this, the vertical alignment film is preferably a film formed of a compound containing Si element, C element, and O element among the constituent elements. In addition, the number of carbon atoms of a substituent (preferably an alkyl group or an alkoxy group) including a Si atom-bonded C atom of the silane compound forming the vertical alignment film is preferably 1 to 30, and more preferably 2 to 25. , more preferably 3-20. That is, the ratio of Si element to C element (Si/C, molar ratio) is preferably 0.03 to 1.00, more preferably 0.04 to 0.50, and even more preferably 0.05 to 0.33. When the Si/C ratio is more than the above-mentioned lower limit, the coatability of the composition for forming a vertically aligned liquid crystal cured film is improved, and when the Si/C ratio is below the above-mentioned upper limit, the adhesiveness with the adjacent layer can be improved.

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

The composition for forming a vertical alignment film may contain, in addition to the solvent, additives and the like exemplified in the item 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 viewpoints of thinning the retardation plate with an optical compensation function and exhibiting the orientation control power. In addition, the film thickness of the vertical alignment film is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, and particularly preferably 30 nm or more. The film thickness of the vertical alignment film can be measured using an ellipsometer or a contact film thickness meter.

[Substrate]

The base material is a material used for coating the composition for forming an alignment film and the composition for forming a liquid crystal cured film, and may be a design in which the base material is peeled off and the film applied on the base material is transferred, or a base material may be The design that cannot be transferred due to the adhesion to the base material is preferably a design that can be transferred to the transfer target body and can be peeled off from the base material from the viewpoint of thinning. As such a base material, a glass base material and a film base material are mentioned, From the viewpoint of workability, a film base material is preferable, and a long roll-shaped film is more preferable from the viewpoint of being able to manufacture continuously. Examples of the resin constituting the film substrate include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; Methacrylate; polyacrylate; cellulose esters such as triacetyl cellulose, diacetyl cellulose and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyether Sulfone; polyether ketone; polyphenylene sulfide and polyphenylene ether and other plastics. The surface of the base material may be subjected to mold release treatment such as silicone treatment. As a commercially available cellulose ester base material, "FUJITACFILM" (made by Fuji Photo Film Co., Ltd.); "KC8UX2M", "KC8UY", and "KC4UY" (the above are made by Konica Minolto Opto Co., Ltd.), etc. are mentioned. Such a resin can be formed into a film by known means such as a solvent casting method and a melt extrusion method to form a base material.

Commercially available cyclic olefin resins include "Topas" (registered trademark) (manufactured by Ticona Corporation (Germany)), "ARTON" (registered trademark) (manufactured by JSR Corporation), and "ZEONOR" (registered trademark) , "ZEONEX" (registered trademark) (the above are manufactured by Japan ZEON Co., Ltd.), and "Apel" (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.). Commercially available cyclic olefin-based resin substrates can also be used. Examples of commercially available cyclic olefin resin substrates include "Escena" (registered trademark), "SCA40" (registered trademark) (the above are manufactured by Sekisui Chemical Industry Co., Ltd.), "ZEONORFILM" (registered trademark) ( OPTES Co., Ltd.) and "ARTONFILM" (registered trademark) (manufactured by JSR Corporation).

It is preferable that a base material is easy to laminate|stack a horizontal alignment liquid crystal cured film, a horizontal alignment film, a vertical alignment liquid crystal cured film, a vertical alignment film, and is easy to peel. The thickness of such a base material is 5-300 micrometers normally, Preferably it is 20-200 micrometers.

[Phase plate with optical compensation function]

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

The interlayer distance between the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film is 5 μm or less. ···(1)

A horizontal alignment film or a vertical alignment film is included between the layers of the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film. ···(2)

Satisfy the following relation

ReA(450)/ReA(550)<1.00...(3).

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

The definition of the phase difference value is as follows.

ReA(λ)=(nxA-nyA)×dA

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

Satisfy the following relation

RthC(450)/RthC(550)<1.00...(4).

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

RthC(λ)=((nxC+nyC)/2-nzC)×dC

Among them, nxC represents the principal refractive index in the film plane of the vertical alignment liquid crystal cured film, nyC represents the refractive index in the direction orthogonal to nxC in the same plane, nzC represents the refractive index of the vertical alignment liquid crystal cured film in the thickness direction, dC represents the thickness of the vertically aligned liquid crystal cured film.

It should be noted that when nxC=nyC, nxC may be the refractive index in any direction in the film plane.

The interlayer distance between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film is preferably 5 μm or less, more preferably 1 μm or less, still more preferably 0.5 μm or less, and particularly preferably 0.3 μm or less, as shown in formula (1). In addition, the thickness of the horizontal alignment film is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, and particularly preferably 30 nm or more.

The retardation plate with an optical compensation function preferably satisfies the following relational expression (5). In order to reduce the amount of light leakage near the wavelength of 550 nm in the oblique direction when an elliptically polarizing plate with an optical compensation function using a retardation plate with an optical compensation function is applied to a display, |R0(550)-R40(550)| The smaller the value, the better. The value of |R0(550)-R40(550)| is preferably less than 10 nm, more preferably 5 nm or less, still more preferably 4 nm or less, and particularly preferably 3 nm or less.

|R0(550)-R40(550)|＜10nm...(5)

Here, R0 (λ) represents the in-plane retardation value of the retardation plate with an optical compensation function including a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film. In addition, R40 represents the direction (fast axis direction) in the phase difference plate with the optical compensation function including the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film, around the direction orthogonal to the main refractive index direction in the film plane in the same plane. ) apparent phase difference when rotated 40°.

The retardation plate with an optical compensation function preferably satisfies the following relational expression (6). In order to reduce the amount of light leakage near the wavelength of 450 nm in the oblique direction when an elliptically polarizing plate with an optical compensation function using a retardation plate with an optical compensation function is used for a display, |R0(450)-R40(450)| The smaller the value, the better. The value of |R0(450)-R40(450)| is preferably less than 10 nm, more preferably 5 nm or less, still more preferably 4 nm or less, and particularly preferably 3 nm or less.

|R0(450)-R40(450)|＜10nm...(6)

Here, R0(λ) represents the in-plane retardation value of the retardation plate with an optical compensation function including a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film. In addition, R40 represents the direction (fast axis direction) in the phase difference plate with the optical compensation function including the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film, around the direction orthogonal to the main refractive index direction in the film plane in the same plane. ) apparent phase difference when rotated 40°.

In addition, it is preferable that the difference between the values represented by the relational expressions (5) and (6) satisfy the following relational expression (7).

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

In the case where the relational expression (7) is satisfied, when an elliptically polarizing plate with an optical compensation function using a retardation plate with an optical compensation function is applied to a display, the frontal and oblique reflection hues are close to black, so (7) is preferable. The value of is 3 nm or less, more preferably 2 nm or less, still more preferably 1 nm or less.

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

Specific examples of the difference between the average refractive indices of the layers include:

(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 the horizontal alignment film is included between the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured 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 vertical alignment liquid crystal cured film;

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

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

(3-b) the 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 many more.

The retardation plate with an optical compensation function of the present invention may include layers other than a horizontal alignment liquid crystal cured film, a horizontal alignment film, a vertical alignment liquid crystal cured film, and a vertical alignment film, and as a specific example thereof, other alignment liquid crystal curing may be mentioned. film, other alignment films, protective layers, etc. As another alignment liquid crystal cured film, the vertical alignment liquid crystal cured film, the horizontal alignment liquid crystal cured film, etc. which were exemplified above are mentioned, and the alignment film etc. which were exemplified above are mentioned as another alignment film.

The protective layer is preferably formed from a composition for forming a protective layer which usually contains a water-soluble polymer, that is, a polyfunctional acrylate (methacrylate), a urethane acrylate, Acrylic oligomers or polymers formed from polyester acrylates, epoxy acrylates, etc., polyvinyl alcohol, ethylene-vinyl alcohol copolymers, polyvinylpyrrolidone, starches, methyl cellulose, carboxymethyl cellulose, Sodium alginate, etc.; and solvents.

The solvent contained in the composition for forming a protective layer includes the same solvents as those exemplified above, and among them, from the viewpoint of not dissolving the layer forming the protective layer, it is preferably selected from water, an alcohol solvent, and an ether solvent at least one solvent from the group consisting of. Examples of the alcohol solvent include methanol, ethanol, butanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether. As an ether solvent, ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate are mentioned. Among them, ethanol, isopropanol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are preferable.

The film thickness of the protective layer is 0.1 μm to 10 μm, and 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, a vertical alignment film, and a vertically aligned liquid crystal cured film in this order, but preferably : A method of laminating a horizontal alignment film on a base material, then laminating a horizontal alignment liquid crystal cured film, further laminating a vertical alignment film, and then laminating a vertical alignment liquid crystal cured film (hereinafter, referred to as production method A); or, laminating on a base material The vertical alignment film is a method of laminating a vertical alignment liquid crystal cured film, further laminating a horizontal alignment film, and then laminating a horizontal alignment liquid crystal cured film (hereinafter, referred to as manufacturing method B). As the lamination method of a horizontal alignment liquid crystal cured film, a horizontal alignment film, a vertical alignment liquid crystal cured film, and a vertical alignment film, the formation method of each layer mentioned above can be used.

When a retardation plate with an optical compensation function is produced by the production method A or the production method B, there is a possibility that an alignment defect or an alignment defect may occur due to the alignment of the liquid crystal cured film disposed in the lower layer. That is, in the case of the manufacturing method A, since the vertical alignment liquid crystal cured film is laminated after laminating the horizontal alignment liquid crystal cured film in the lower layer, when the vertical alignment liquid crystal cured film is formed, it may be affected by the horizontal alignment liquid crystal cured film of the lower layer and may occur. Defective orientation and orientation defect; in the case of production method B, the vertical alignment liquid crystal cured film of the lower layer is similarly laminated after the vertical alignment liquid crystal cured film is laminated. Therefore, when the horizontal alignment liquid crystal cured film is formed, it may be cured by the vertical alignment liquid crystal of the lower layer. Due to the influence of the film, misorientation and orientation defects occur. Therefore, depending on 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 in order to form each layer to be laminated There are also cases in which changes in optical properties, poor orientation, and orientation defects occur by dissolving the lower layer. Therefore, the material, solvent, solid content concentration, coating method, film thickness, etc. contained in the composition used to form each layer to be laminated must be appropriately selected.

[Elliptical polarizer with optical compensation]

The retardation plate with an optical compensation function of the present invention is transferred by bonding with a transfer target body and peeling off the base material, or by laminating with an adhesive or the like in a state with a base material. The function of the retardation plate with an optical compensation function, that is, the optical properties thereof can be imparted to the transferred body, and an optical laminate to which the optical properties of the retardation plate with an optical compensation function are imparted can be produced. Among them, when laminated with a polarizing plate, an elliptically polarizing plate with an optical compensation function can be produced. In embodiment of this invention, it is preferable to laminate|stack so that the slow axis (optical axis) of a horizontal alignment liquid crystal cured film and the absorption axis of a polarizing plate may become substantially 45 degrees. The function as a circular polarizer can be obtained by laminating|stacking so that the slow axis (optical axis) of the optical film of this invention and the absorption axis of a polarizing plate may become substantially 45 degrees. In addition, what is called substantially 45 degrees is normally the range of 45±5 degrees.

[Subject to transfer]

Examples of the transfer object include: optical films of a single-layer structure, such as polarizers, retardation plates, brightness improvement films, anti-glare films, anti-reflection films, diffusion films, condensing films, etc.; optical films of a multilayer structure As the film, for example, a retardation plate and an elliptically polarizing plate, among these, a retardation plate, a retardation plate, a polarizing plate, and an elliptically polarizing plate can be preferably used. The optical laminate in the present invention can be used in image display devices such as liquid crystal display devices, organic electroluminescence (EL) display devices, inorganic electroluminescence (EL) display devices, touch panel display devices, electron emission display devices (field emission display devices) Display devices (FED, etc.), surface field emission display devices (SED)), electronic paper (display devices using electronic ink and electrophoretic elements), plasma display devices, projection display devices (grating light valve) ( GLV) display device, display device with digital micromirror device (DMD), etc.), piezoelectric ceramic display, etc., and can be suitably used for organic EL display device, touch panel display device and the like in particular.

[Polarizer]

The polarizer is formed of a polarizer having a polarizing function. As a polarizer, a stretched film to which a dye having absorption anisotropy is adsorbed, or a film to which a dye having absorption anisotropy is coated and oriented can be mentioned. As a dye which has absorption anisotropy, a dichroic dye is mentioned.

A stretched film to which a dye having absorption anisotropy is adsorbed is usually produced through the following steps: a step of uniaxially stretching a polyvinyl alcohol-based resin film; A step of dyeing so that the dichroic dye is adsorbed; a step of treating the polyvinyl alcohol-based resin film to which the dichroic dye is adsorbed with an aqueous boric acid solution; and a step of washing with water after the treatment with an aqueous boric acid solution. A polarizing plate can be obtained by bonding the polarizing plate obtained in this way to a transparent protective film. Examples of the dichroic dye include iodine and dichroic organic dyes. As a dichroic organic dye, the dichroic direct dye which consists of a disazo compound, such as C.I. Direct Red 39, and the dichroic direct dye which consists of compounds, such as trisazo and tetrazo, etc. are mentioned. As described above, the thickness of the polarizer obtained by uniaxially stretching the polyvinyl alcohol-based resin film, dyeing with a dichroic dye, boric acid treatment, washing with water, and drying is preferably 5 μm to 40 μm.

[binder]

As the adhesive, a pressure-sensitive adhesive, a drying-curable adhesive, and a chemically reactive adhesive can be mentioned. As a chemical reaction type adhesive agent, an active energy ray hardening type adhesive agent is mentioned, for example.

Pressure sensitive adhesives typically contain polymers and may also contain solvents. Examples of the polymer include acrylic polymers, silicone polymers, polyesters, polyurethanes, polyethers, and the like. Among them, acrylic adhesives containing acrylic polymers are excellent in optical transparency, moderate wettability, cohesive force, and adhesiveness, and are excellent in weather resistance, heat resistance, etc. Or under humidified conditions, floating, peeling, and the like do not easily occur, which is preferable.

The acrylic polymer is preferably a (meth)acrylate in which the alkyl group of the ester moiety is an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, or butyl, and (meth)acrylic acid, (meth)acrylic acid, and (meth)acrylic acid esters. Copolymers of (meth)acrylic monomers having functional groups such as hydroxyethyl acrylate.

The pressure-sensitive adhesive containing such a copolymer is excellent in adhesiveness, and does not produce adhesive residue or the like on the transfer target body when it is removed after being attached to the transfer target body, It can be removed relatively easily, so it is preferable. The glass transition temperature of the acrylic polymer is preferably 25°C or lower, and more preferably 0°C or lower. The mass average molecular weight of such an acrylic polymer is preferably 100,000 or more.

As a solvent, the solvent etc. mentioned above as a solvent are mentioned. The pressure sensitive adhesive may contain a light diffusing agent. The light-diffusing agent is an additive that imparts light-diffusing properties to the binder, and may be fine particles having a refractive index different from that of the polymer contained in the binder. As a light-diffusion agent, the fine particle which consists of an inorganic compound, and the fine particle which consists of an organic compound (polymer) are mentioned. Since many polymers contained in the binder as an active ingredient, including the acrylic polymer, have a refractive index of about 1.4 to 1.6, it is preferable to appropriately select from light diffusing agents having a refractive index of 1.2 to 1.8. The difference in refractive index between the polymer contained in the binder as an active ingredient and the light diffusing agent is usually 0.01 or more, and is preferably 0.01 to 0.2 from the viewpoints of brightness and displayability of the display device. The fine particles used as the light diffusing agent are preferably spherical and nearly monodisperse fine particles, and more preferably fine particles having an average particle diameter of 2 to 6 μm. Refractive index can be measured using conventional minimum deflection angle method or Abbe refractometer.

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

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

The dry-curable adhesive may contain a solvent. Examples of the dry-curable adhesive include a composition containing a polymer containing a monomer having a protic functional group such as a hydroxyl group, a carboxyl group, or an amino group, and an ethylenically unsaturated group, or a carbamate The acid ester polymer is a main component, and further contains a crosslinking agent or a curable compound such as a polyaldehyde, an epoxy compound, an epoxy resin, a melamine compound, a zirconia compound, and a zinc compound. Examples of polymers of monomers having protic functional groups such as hydroxyl groups, carboxyl groups, and amino groups and ethylenically unsaturated groups include ethylene-maleic acid copolymers, itaconic acid copolymers, acrylic acid copolymers, and acrylamide copolymers. products, saponified products of polyvinyl acetate, and polyvinyl alcohol-based resins.

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

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

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

As the epoxy resin, polyamide polyamine (which is obtained by mixing polyalkylene polyamines such as diethylenetriamine and triethylenetetramine) and dicarboxylic acids such as adipic acid can be mentioned. polyamide epoxy resin etc. obtained by reaction of acid) and epichlorohydrin. As a commercial item of the said polyamide epoxy resin, "SUMIREZRESIN (registered trademark) 650" and "SUMIREZRESIN 675" (the above are manufactured by SumikaChemtex Co., Ltd.), "WS-525" (Japan PMC Co., Ltd.) are mentioned. society), etc. When mixing an epoxy resin, the addition amount is 1-100 mass parts normally with respect to 100 mass parts of polyvinyl alcohol-type resin, Preferably it is 1-50 mass parts.

The thickness of the adhesive layer formed from the dry-curable adhesive is usually 0.001 to 5 μm, preferably 0.01 to 2 μm, and more preferably 0.01 to 0.5 μm. When the adhesive bond layer formed of the dry-curable adhesive agent is too thick, the appearance tends to be poor.

The active energy ray-curable adhesive may contain a solvent. The active energy ray-curable adhesive refers to an adhesive that is cured by being irradiated with an active energy ray. Examples of the active energy ray-curable adhesive include a cationically polymerizable adhesive containing an epoxy compound and a cationic polymerization initiator; and a radically polymerizable adhesive containing an acrylic curing component and a radical polymerization initiator. adhesives; adhesives that contain both a cationically polymerizable curing component such as an epoxy compound and a radically polymerizable curing component such as an acrylic compound, and also contain a cationic polymerization initiator and a radical polymerization initiator; and an adhesive that does not contain These polymerization initiators, adhesives cured by electron beam irradiation, and the like.

Among them, a radically polymerizable active energy ray-curable adhesive containing an acrylic curing component and a photoradical polymerization initiator, and a cationically polymerizable active energy ray-curable adhesive containing an epoxy compound and a photocationic polymerization initiator are preferable agent. 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 contain compounds other than the epoxy compound. As a compound other than an epoxy compound, an oxetane compound, an acrylic compound, etc. are mentioned.

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

The active energy ray-curable adhesive may further contain ion trapping agents, antioxidants, chain transfer agents, tackifiers, thermoplastic resins, fillers, flow regulators, plasticizers, defoaming agents, and the like.

In the present specification, an active energy ray is defined as an energy ray capable of decomposing a compound capable of generating an active species to generate an active species. Examples of such active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, alpha rays, beta rays, gamma rays, and electron beams, and ultraviolet rays and electron beams are preferred. Preferable ultraviolet irradiation conditions are the same as those of the above-mentioned polymerization of the polymerizable liquid crystal compound.

Example

Hereinafter, the present invention will be described more specifically with reference to examples. In addition, unless it is specifically limited, "%" and "part" in an example mean mass % and mass part. In addition, in the following Examples, the film thickness was measured using the ellipsometer M-220 by JASCO Corporation, or the contact film thickness meter (MH-15M by Nikon Corporation, Counter TC101, MS-5C). In addition, the retardation value Rth (λ) in the thickness direction, the in-plane retardation value Re (λ), and the apparent retardation value R40 (λ) when measured from the 40° direction were obtained using Oji Measuring Instruments Co., Ltd. KOBRA-WPR, Or measure and calculate with the Ellipsometer M-220 manufactured by JASCO Corporation. In addition, the ratio of Si/C can be calculated by elemental analysis of the vertical alignment film and measurement of surface constituent elements using X-ray photoelectric spectroscopy; or, when the structural formula of the compound used for the formation of the vertical alignment film is fully known can be calculated from the structural formula. In addition, AGF-B10 by Kasuga Electric Co., Ltd. was used as a corona treatment apparatus. The corona treatment can be appropriately performed when the composition is applied to a substrate. Using the above-mentioned corona treatment apparatus, it performed once under the conditions of an output of 0.3 kW and a treatment speed of 3 m/min.

[Example 1]

[Preparation of a composition for forming a horizontal alignment film]

As components, 5 parts of a photo-alignment material having the following structure (weight average molecular weight: 30,000) and 95 parts of cyclopentanone (solvent) were mixed, and the resulting mixture was stirred at 80° C. for 1 hour to obtain a horizontal alignment film formation. with composition.

[Preparation of composition for vertical alignment film formation]

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

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

To a mixture obtained by mixing the polymerizable liquid crystal compound A and the polymerizable liquid crystal compound B shown below at a mass ratio of 90:10, 1.0 part of a leveling agent (F-556; manufactured by DIC Corporation) and a polymerization initiator were added 6 parts of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)-1-butanone ("Irgacure 369 (Irg369)", manufactured by BASF JAPAN Co., Ltd.).

Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration might be 13%, and the composition was stirred at 80° C. for 1 hour to obtain a composition for forming a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film. Formative composition.

The polymerizable liquid crystal compound A was produced by the method described in JP-A No. 2010-31223. In addition, the polymerizable liquid crystal compound B was produced according to the method described in Japanese Unexamined Patent Application Publication No. 2009-173893. The respective molecular structures are shown below.

[Polymerizable Liquid Crystal Compound A]

[Polymerizable Liquid Crystal Compound B]

[Manufacture of polarizing plates]

A polyvinyl alcohol film having an average degree of polymerization of about 2,400, a degree of saponification of 99.9 mol% or more, and a thickness of 75 μm was immersed in pure water at 30°C, and then immersed in iodine/potassium iodide/water at a mass ratio of 0.02/2/100 at 30°C. , iodine dyeing (iodine dyeing process) was carried out. The polyvinyl alcohol film subjected to the iodine dyeing step was immersed in an aqueous solution having a mass ratio of potassium iodide/boric acid/water of 12/5/100 at 56.5°C, and boric acid treatment was performed (boric acid treatment step). The polyvinyl alcohol film subjected to the boric acid treatment process was washed with pure water at 8° C., and then dried at 65° C. to obtain a polarizer (thickness after stretching: 27 μm) in which iodine was adsorbed and oriented in polyvinyl alcohol. At this time, stretching is performed in the iodine dyeing process and the boric acid treatment process. The total draw ratio in this drawing was 5.3 times. The obtained polarizer and the saponified triacetyl cellulose film (KC4UYTAC 40 μm, manufactured by Konica Minolto Co., Ltd.) were bonded together with a nip roll through a water-based adhesive. While maintaining the tension of the obtained bonding product at 430 N/m, it was dried at 60° C. for 2 minutes to obtain a polarizing plate having a triacetyl cellulose film as a protective film on one side. It should be noted that the above-mentioned water-based adhesive is made by adding 3 parts of carboxyl-modified polyvinyl alcohol (manufactured by Kuraray, "Kuraray PovalKL318") and water-soluble polyamide epoxy resin (manufactured by Sumika Chemtex, "Sumirez") to 100 parts of water. Resin 650", prepared by 1.5 parts of an aqueous solution with a solid content concentration of 30%.

The optical properties of the obtained polarizing plate were measured. The measurement was performed using a spectrophotometer ("V7100", manufactured by JASCO Corporation) using the polarizer surface of the polarizing plate obtained above as an incident surface. The absorption axis of the polarizing plate is consistent with the stretching direction of the polyvinyl alcohol. The obtained polarizing plate has a visibility-corrected monomer transmittance of 42.1%, a visibility-corrected polarization degree of 99.996%, a monomer hue a of -1.1, and a monomer hue b is 3.7.

[Manufacture of a laminate including a base material, a horizontal alignment film, and a horizontal alignment liquid crystal cured film]

After corona treatment was performed on a COP film (ZF-14-50) manufactured by ZEON Co., Ltd., the composition for forming a horizontal alignment film was coated with a bar coater, dried at 80° C. for 1 minute, and a polarized UV light irradiation device was used. ("SPOT CURE SP-9", manufactured by Ushio Electric Co., Ltd.), under the conditions of cumulative light quantity at a wavelength of 313 nm: 100 mJ/cm ² , polarized UV exposure was performed at an axial angle of 45°. When the film thickness of the obtained horizontal alignment film was measured with an ellipsometer, it was 100 nm.

Next, the composition for forming a horizontally-aligned liquid crystal cured film was coated on the horizontally-aligned film by a bar coater, dried at 120° C. for 1 minute, and then applied with a high-pressure mercury lamp (“Unicure VB-15201BY-A”, Ushio Electric Co., Ltd. A horizontal alignment liquid crystal cured film was formed by irradiating ultraviolet rays (in a nitrogen atmosphere, the cumulative amount of light at a wavelength of 365 nm: 500 mJ/cm ² ), and a laminate comprising a substrate, a horizontal alignment film, and a horizontal alignment liquid crystal cured film was obtained. When the film thickness of the horizontally aligned liquid crystal cured film was measured with an ellipsometer, it was 2.3 μm.

[Measurement of Re of a Horizontally Aligned Liquid Crystal Cured Film]

For the in-plane retardation value ReA (λ) of the horizontally aligned liquid crystal cured film produced by the above method, after being attached to glass through an adhesive, the COP of the base material was peeled off, and then a measuring machine (“ KOBRA-WPR", manufactured by Oji Scientific Instruments Co., Ltd.) was measured. The results obtained by measuring the retardation value ReA(λ) at each wavelength are: ReA(450)=121nm, ReA(550)=142nm, ReA(650)=146nm, ReA(450)/ReA(550) =0.85.

[Manufacture of a laminate including a substrate, a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film]

After corona treatment was performed on the laminate including the substrate, the horizontal alignment film, and the horizontally aligned liquid crystal cured film produced by the above method, the composition for forming a vertical alignment film was coated with a bar coater, and dried at 80° C. for 1 minute. A vertical alignment film was obtained. When the film thickness of the obtained vertical alignment film was measured with an ellipsometer, it was 50 nm.

Furthermore, the composition for forming a vertical alignment liquid crystal cured film was coated on the vertical alignment film with a bar coater, dried at 120° C. for 1 minute, and then applied with a high pressure mercury lamp (“Unicure VB-15201BY-A”, Ushio Electric Co., Ltd. system) irradiated with ultraviolet rays (in a nitrogen atmosphere, the cumulative amount of light at a wavelength of 365 nm: 500 mJ/cm ² ) to form a vertical alignment liquid crystal cured film to obtain a substrate, a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, A laminated body of a vertically aligned liquid crystal cured film. The film thickness of the vertically aligned liquid crystal cured film was measured with an ellipsometer and found to be 1.2 μm. In addition, the interlayer distance of the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film was 50 nm. In addition, the constituent element ratio of the vertical alignment film was Si/C=0.33.

[Rth measurement of vertical alignment liquid crystal cured film]

In order to measure the Rth of the vertical alignment liquid crystal cured film, a vertical alignment film and a vertical alignment liquid crystal cured film were produced on a COP film (ZF-14-50) manufactured by ZEON Co., Ltd. by the same procedure as above, and were bonded through The vertical alignment liquid crystal cured film and glass were bonded together with an agent (pressure-sensitive adhesive 15 μm manufactured by Lintec), and after confirming that the COP had no retardation, the retardation value was measured by changing the incident angle of light to the sample with an ellipsometer. . In addition, the average refractive index at wavelengths λ of 450 nm and 550 nm was measured with a refractometer (manufactured by Atago Co., Ltd., "Multi-wavelength Abbe Refractometer DR-M4"). ReC calculated from the obtained film thickness, average refractive index, and measurement results of an ellipsometer are: RthC(450)=-63 nm, RthC(550)=-73 nm, RthC(450)/RthC(550)=0.85, respectively .

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

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 produced by the above method was interposed through an adhesive (pressure-sensitive adhesive 15 μm manufactured by Lintec Corporation). After bonding with glass, peeling off the COP to prepare a sample for measurement, and confirming that there is no retardation between the horizontal alignment film and the vertical alignment film, KOBRA-WPR is used to measure the retardation in the front direction of the retardation plate with an optical compensation function. The value R0 (λ) and the retardation value R40 (λ) at the time of tilting 40° around the fast axis of the horizontally aligned liquid crystal cured film were measured. From the obtained values of R0(λ) and R40(λ), calculate |R0(550)-R40(550)|, |R0(450)-R40(450)|, and |{R0(450)-R40(450 )}-{R0(550)-R40(550)}|, and the obtained results are shown in Table 1.

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

Each layer was coated on glass as described above, and the average refractive index of each layer was calculated using a refractometer (manufactured by Atago Co., Ltd., "Multi-wavelength Abbe Refractometer DR-M4") or elliptical polarization, and each layer was confirmed. The difference between the in-plane average refractive indices is 0.2 or less.

[Bendability test]

On the coating film surface side of the laminate including the substrate, the horizontal alignment film, the horizontal alignment liquid crystal cured film, the vertical alignment film, and the vertical alignment liquid crystal cured film produced by the above method, a glass plate with a thickness of 0.7 mm was placed so as to lie on the side of the coating film. The laminated body was bent 180 degrees so as to lie on the glass plate, and then the light of the fluorescent lamp was transmitted through a magnifying glass of 10 times, and the bent portion was observed to confirm the presence or absence of wrinkles and cracks. The results are shown in Table 1.

[Confirmation of the reflection hue of the curved part]

After corona treatment was performed on the coating film surface side of the laminate including the base material, the horizontal alignment film, the horizontal alignment liquid crystal cured film, the vertical alignment film, and the vertical alignment liquid crystal cured film produced by the above method, the absorption axis of the polarizing plate was adjusted. The angle formed by the slow axis of the horizontal alignment film was 45°, and it was bonded to the polarizing plate produced by the above method through an adhesive, and the base material was peeled off to produce an elliptically polarizing plate with an optical compensation function. After that, it was bonded to the aluminum foil via an adhesive, and was bent by 180° on the polarizing plate side so as to have a radius of 1 cm, and the reflection hue of the bent portion was visually observed. The results are shown in Table 1.

(Examples 2 and 3)

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

(Example 4)

0.5 wt % of polyimide ("SUNEVER SE-610", manufactured by Nissan Chemical Industry Co., Ltd.), 72.3 wt % of N-methyl-2-pyrrolidone, 18.1 wt % of 2-butoxyethanol, 9.1 wt % of % by weight of ethylcyclohexane and 0.01% by weight of DPHA (manufactured by Shin-Nakamura Chemical Co., Ltd.) were mixed to prepare a composition B for forming a vertical alignment film, and the composition B for forming a vertical alignment film was used. Example 1 A retardation plate with an optical compensation function was produced in the same manner, and the measurement of the retardation value, the bendability test, and the confirmation of the reflection hue of the bent portion were carried out. The results are shown in Table 1. In addition, the film thickness of the vertical alignment film was measured with an ellipsometer, and it was 0.2 micrometer. From this, it can be seen that the interlayer distance between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film is 0.2 μm. In addition, it was confirmed that when the composition for forming a vertical alignment liquid crystal cured film was applied, the vertical alignment film was corroded by the solvent, and an alignment defect and an alignment defect were locally generated.

(Example 5)

The base material was changed to a polyethylene terephthalate film (SP-PLR382050 manufactured by Lintec Co., Ltd., hereinafter abbreviated as "separator") subjected to mold release treatment, and the stacking order was changed to a vertical alignment film , the order of the vertical alignment liquid crystal cured film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film, a retardation plate with an optical compensation function was produced in the same manner as in Example 1, and the retardation value measurement, the bendability test, and the bending were carried out. The reflection hue of the part is confirmed. The results are shown in Table 1. In addition, when the film thickness of the horizontal alignment film was measured with an ellipsometer, it was 0.2 micrometer. From this, it can be seen that the interlayer distance between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film is 0.2 μm.

(Examples 6 and 7)

A phase with an optical compensation function was produced in the same manner as in Example 1, except that the values of RthC(450) and RthC(550) were changed as described in Table 1 by changing the film thickness of the vertically aligned liquid crystal cured film For the difference plate, the measurement of the retardation value, the bendability test, and the confirmation of the reflection hue of the bent portion were carried out. The results are shown in Table 1.

(Example 8)

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

(Preparation of composition (B) for vertical alignment liquid crystal cured film formation)

To the liquid crystal compound LC242 described below: Paliocolor LC242 (registered trademark of BASF Corporation), 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 might be 13% to obtain The composition (B) for vertical alignment liquid crystal cured film formation. The name of the obtained liquid crystal composition was made into "composition V".

Liquid crystal compound LC242: Paliocolor LC242 (registered trademark of BASF Corporation)

(Comparative Example 1)

After producing the laminate of the horizontal alignment film and the horizontal alignment liquid crystal cured film by the method described in Example 1, a laminate of the vertical alignment film and the vertical alignment liquid crystal cured film (Lintec company system). The obtained laminates were bonded to each other with an adhesive (pressure-sensitive adhesive 15 μm manufactured by Lintec), and the retardation value measurement, the bendability test, and the reflection hue confirmation of the bent portion were performed. The results are shown in Table 1.

[Table 1]

Reflection hue of the curved part: the case of black was marked with ◯, and the case where clear coloring was observed was marked with ×.

Bendability test: When no defect occurred, it was marked as ○;

By applying the manufacturing method of the present invention, a retardation plate with an optical compensation function can be obtained that can suppress defects such as wrinkles and cracks that are generated during bending.

Claims (16)

1. A method of manufacturing a retardation plate with an optical compensation function, wherein, A horizontal alignment film is formed through coating, drying, and alignment treatment steps, A horizontally aligned liquid crystal cured film is formed through coating, drying, and ultraviolet irradiation processes, Further through the coating and drying process, a vertical alignment film is formed, A vertical alignment liquid crystal cured film is formed through the steps of coating, drying, and ultraviolet irradiation, Thus, a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film are sequentially formed to manufacture a retardation plate with an optical compensation function, In the production method, the vertical alignment liquid crystal cured film obtained by polymerizing and curing the polymerizable liquid crystal compound in a vertically aligned state satisfies the following relations (1) and (2): -100nm≤RthC(550)≤-50nm…(1) RthC(450)/RthC(550)<1.00…(2) In the formula, RthC(λ) represents the retardation value in the thickness direction at the wavelength λnm of the vertically aligned liquid crystal cured film, and the definition of the retardation value RthC(λ) is as follows, RthC(λ)=((nxC(λ)+nyC(λ))/2-nzC(λ))×dC where nxC(λ) represents the principal refractive index at wavelength λ(nm) in the film plane of the vertically aligned liquid crystal cured film, nyC(λ) represents the refractive index at wavelength λ(nm) in the direction orthogonal to nxC(λ) in the same plane, nzC(λ) represents the refractive index at wavelength λ(nm) in the thickness direction of the vertically aligned liquid crystal cured film, dC represents the thickness of the vertically aligned liquid crystal cured film. 2 . The method for producing a retardation plate with an optical compensation function according to claim 1 , wherein a horizontal alignment film having a film thickness of 1.0 μm or less, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film are sequentially formed. 3 . membrane. 3. The method for producing a retardation plate with an optical compensation function according to claim 1 or 2, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal formed of a photo alignment film are sequentially formed Cured film. 4. The method for producing a retardation plate with an optical compensation function according to claim 1 or 2, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, and a vertical alignment film formed of a photo alignment film containing a cinnamoyl group are sequentially formed , Vertical alignment liquid crystal cured film. 5 . The method for producing a retardation plate with an optical compensation function according to claim 1 , wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film having a film thickness of 1.0 μm or less, and a vertical alignment film are sequentially formed. 6 . Liquid crystal cured film. 6. The method for producing a retardation plate with an optical compensation function according to claim 1 or 2, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film containing Si element, and a vertical alignment liquid crystal cured film are sequentially formed . 7. The method for producing a retardation plate with an optical compensation function according to claim 1 or 2, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film having Si/C elements of 0.03 to 1.00, Vertically aligned liquid crystal cured film. 8. The method for producing a retardation plate with an optical compensation function according to claim 1 or 2, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film, and a vertical alignment liquid crystal cured film are sequentially formed to produce the optical film with optical A method of compensating a functional retardation plate, wherein the horizontally aligned liquid crystal cured film satisfies the following relation (3): ReA(450)/ReA(550)<1.00…(3) In the formula, ReA(λ) represents the in-plane retardation value at the wavelength λnm of the horizontally aligned liquid crystal cured film, and the definition of the in-plane retardation value ReA(λ) is as follows, ReA(λ)=(nxA(λ)-nyA(λ))×dA Here, nxA(λ) represents the principal refractive index at the wavelength λ(nm) in the film plane of the horizontally aligned liquid crystal cured film, and nyA(λ) represents the in-plane orthogonal direction to nxA(λ), The refractive index at wavelength λ (nm), dA represents the thickness of the horizontally aligned liquid crystal cured film. 9. The manufacturing method of the retardation plate with optical compensation function, wherein, A vertical alignment film is formed through a coating and drying process, A vertical alignment liquid crystal cured film is formed through the steps of coating, drying, and ultraviolet irradiation, Further through the coating, drying, and orientation treatment steps to form a horizontal alignment film, A horizontally aligned liquid crystal cured film is formed through coating, drying, and ultraviolet irradiation processes, Thus, a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film are sequentially formed to manufacture a retardation plate with an optical compensation function, In the production method, the vertical alignment liquid crystal cured film obtained by polymerizing and curing the polymerizable liquid crystal compound in a vertically aligned state satisfies the following relations (1) and (2): -100nm≤RthC(550)≤-50nm…(1) RthC(450)/RthC(550)<1.00…(2) In the formula, RthC(λ) represents the retardation value in the thickness direction at the wavelength λnm of the vertically aligned liquid crystal cured film, and the definition of the retardation value RthC(λ) is as follows, RthC(λ)=((nxC(λ)+nyC(λ))/2-nzC(λ))×dC where nxC(λ) represents the principal refractive index at wavelength λ(nm) in the film plane of the vertically aligned liquid crystal cured film, nyC(λ) represents the refractive index at wavelength λ(nm) in the direction orthogonal to nxC(λ) in the same plane, nzC(λ) represents the refractive index at wavelength λ (nm) in the thickness direction of the vertically aligned liquid crystal cured film, dC represents the thickness of the vertically aligned liquid crystal cured film. 10 . The method for producing a retardation plate with an optical compensation function according to claim 9 , wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film having a film thickness of 1.0 μm or less, and a horizontal alignment liquid crystal cured film are sequentially formed. 11 . membrane. 11. The method for producing a retardation plate with an optical compensation function according to claim 9 or 10, wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film formed of a photo alignment film, and a horizontal alignment liquid crystal are sequentially formed Cured film. 12. The method for producing a retardation plate with an optical compensation function according to claim 9 or 10, wherein a vertical alignment film, a vertical alignment liquid crystal cured film, and a horizontal alignment film formed of a photo alignment film containing a cinnamoyl group are sequentially formed , Horizontal alignment liquid crystal cured film. 13. The method for producing a retardation plate with an optical compensation function according to claim 9 or 10, wherein a vertical alignment film having a film thickness of 1.0 μm or less, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment film are sequentially formed Liquid crystal cured film. 14. The method for producing a retardation plate with an optical compensation function according to claim 9 or 10, wherein a vertical alignment film containing Si element, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film are sequentially formed . 15. The method for producing a retardation plate with an optical compensation function according to claim 9 or 10, wherein a horizontal alignment film, a horizontal alignment liquid crystal cured film, a vertical alignment film having Si/C elements of 0.03 to 1.00, Vertically aligned liquid crystal cured film. 16. The method for producing a retardation plate with an optical compensation function as claimed in claim 9 or 10, wherein a vertical alignment film, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film are sequentially formed to produce the optical A method of compensating a functional retardation plate, wherein the horizontally aligned liquid crystal cured film satisfies the following relation (3): ReA(450)/ReA(550)<1.00…(3) In the formula, ReA(λ) represents the in-plane retardation value at the wavelength λnm of the horizontally aligned liquid crystal cured film, and the definition of the in-plane retardation value ReA(λ) is as follows, ReA(λ)=(nxA(λ)-nyA(λ))×dA Here, nxA(λ) represents the principal refractive index at wavelength λ(nm) in the film plane of the horizontally aligned liquid crystal cured film, and nyA(λ) represents the in-plane orthogonal direction to nxA(λ), The refractive index at wavelength λ (nm), dA represents the thickness of the horizontally aligned liquid crystal cured film.