TWI838451B - Laminated body, elliptical polarizing plate, organic EL display device, and method for manufacturing elliptical polarizing plate - Google Patents

Abstract

The present invention provides a laminate including a vertically aligned liquid crystal cured film, which can be formed without a vertically aligned film and is formed by aligning a polymerizable liquid crystal compound with good precision in the vertical direction.

The laminate of the present invention comprises a vertically aligned liquid crystal cured film and a substrate, and the vertically aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition formed by curing a polymerizable liquid crystal compound in a state of being aligned in a direction perpendicular to the plane of the liquid crystal cured film. The vertically aligned liquid crystal cured film satisfies at least one of the following formulas (1) and (2), and satisfies at least one of the following formulas (3), (4), (5) and (6).

F(A)>F(C) (1)

Si(A)>Si(C) (2)

N(B)>N(C) (3)

P(B)>P(C) (4)

F(B)>F(C) (5)

Si(B)>Si(C) (6)

[In formulas (1) to (6), F(A) represents the presence ratio (atom%) of the fluorine element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate, F(B) represents the presence ratio (atom%) of the fluorine element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the substrate side, F(C) represents the presence ratio (atom%) of the fluorine element in the liquid crystal cured film at a point 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate, Si(A) represents the presence ratio (atom%) of the silicon element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate, Si(B) represents the presence ratio (atom%) of the silicon element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the substrate side, Si(C) represents the presence ratio (atom%) of the silicon element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the substrate side, [N(B) represents the existence ratio (atom%) of the silicon element in the liquid crystal cured film at the interface on the side opposite to the substrate, at a point 100nm in the thickness direction of the liquid crystal cured film side; N(C) represents the existence ratio (atom%) of the nitrogen element in the liquid crystal cured film at the interface on the side opposite to the substrate of the vertically aligned liquid crystal cured film, at a point 100nm in the thickness direction of the liquid crystal cured film side; P(B) represents the existence ratio (atom%) of the phosphorus element in the liquid crystal cured film at the interface on the side opposite to the substrate of the vertically aligned liquid crystal cured film; P(C) represents the existence ratio (atom%) of the phosphorus element in the liquid crystal cured film at the interface on the side opposite to the substrate of the vertically aligned liquid crystal cured film, at a point 100nm in the thickness direction of the liquid crystal cured film side].

Description

Laminated body, elliptical polarizing plate, organic EL display device, and method for manufacturing elliptical polarizing plate

The present invention relates to a laminate comprising a vertically aligned liquid crystal cured film and a substrate, an elliptical polarizer comprising the laminate, and an organic EL (Electroluminescence) display device. In addition, the present invention also relates to a polymerizable liquid crystal composition that can be used to form the laminate.

An elliptical polarizing plate is an optical component that is a laminate of polarizing plates and phase difference plates, and is used, for example, in an organic EL image display device or other device that displays images in a planar state to prevent light reflection in the electrodes that constitute the device. As a phase difference plate that constitutes the elliptical polarizing plate, a so-called λ/4 plate is generally used. As such a phase difference plate, there is a known one that includes a horizontally aligned liquid crystal cured film formed by polymerizing a polymerizable liquid crystal compound in a state of being aligned in a horizontal direction relative to the plane of the phase difference plate and curing it. It is also known that by further incorporating a vertically aligned liquid crystal cured film into an elliptical polarizing plate having a horizontally aligned liquid crystal cured film, the oblique color change during black display when the elliptical polarizing plate is used in an organic EL display device can be suppressed, and Patent Document 1 describes a laminate comprising a vertically aligned liquid crystal cured film formed on a vertically aligned film and a horizontally aligned liquid crystal cured film formed on a horizontally aligned film.

[Prior Art Literature] [Patent Literature]

[Patent document 1] Japanese Patent Publication No. 2015-163935

However, in the past, in order to manufacture a vertically aligned liquid crystal cured film, a vertically aligned film for aligning the polymerizable liquid crystal compound in the vertical direction was usually required. Therefore, the vertically aligned film must be formed before forming the vertically aligned liquid crystal cured film. In order to obtain a coating film using an alignment film forming composition and a liquid crystal cured film forming composition, at least two coating film forming steps are required, which easily reduces productivity. In contrast, in order to improve productivity, a method of forming a vertically aligned liquid crystal cured film without forming a vertically aligned film is required. However, when only the step of forming the vertically aligned film is omitted from the previous manufacturing steps of the vertically aligned liquid crystal cured film, there is a problem that the alignment of the vertically aligned liquid crystal cured film becomes insufficient.

Therefore, the purpose of the present invention is to provide a novel solution to the above-mentioned problem, that is, a laminate including a vertically aligned liquid crystal cured film, which can be formed without a vertically aligned film and is formed by aligning a polymerizable liquid crystal compound with good precision in the vertical direction, similar to the vertically aligned liquid crystal cured film formed on the vertically aligned film.

The inventors of the present invention have made great efforts to solve the above problems and have completed the present invention. That is, the present invention includes the following aspects.

[1] A laminate comprising a vertically aligned liquid crystal cured film and a substrate, wherein the vertically aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition, wherein the polymerizable liquid crystal composition is formed by curing a polymerizable liquid crystal compound in a state of being aligned in a direction perpendicular to the plane of the liquid crystal cured film, and the vertically aligned liquid crystal cured film satisfies at least one of the following formulas (1) and (2), and satisfies at least one of the following formulas (3), (4), (5) and (6).

F(A)>F(C) (1)

Si(A)>Si(C) (2)

N(B)>N(C) (3)

P(B)>P(C) (4)

F(B)>F(C) (5)

Si(B)>Si(C) (6)

[In formulas (1) to (6), F(A) represents the presence ratio (atom%) of the fluorine element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate, F(B) represents the presence ratio (atom%) of the fluorine element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the substrate side, F(C) represents the presence ratio (atom%) of the fluorine element in the liquid crystal cured film at a point 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate, Si(A) represents the presence ratio (atom%) of the silicon element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate, Si(B) represents the presence ratio (atom%) of the silicon element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the substrate side, Si(C) represents the presence ratio (atom%) of the silicon element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the substrate side, =N(B) represents the existence ratio (atom%) of the silicon element in the liquid crystal cured film at the interface on the side opposite to the substrate, at a point 100nm in the thickness direction of the liquid crystal cured film side; N(C) represents the existence ratio (atom%) of the nitrogen element in the liquid crystal cured film at the interface on the side opposite to the substrate, at a point 100nm in the thickness direction of the liquid crystal cured film side; P(B) represents the existence ratio (atom%) of the phosphorus element in the liquid crystal cured film at the interface on the side opposite to the substrate, and P(C) represents the existence ratio (atom%) of the phosphorus element in the liquid crystal cured film at the interface on the side opposite to the substrate, at a point 100nm in the thickness direction of the liquid crystal cured film side]

[2] A laminate as described in [1] above, wherein the vertically aligned liquid crystal cured film is adjacent to the substrate.

[3] The multilayer structure described in [1] or [2] above satisfies at least one of the above formulas (1) and (2), at least one of the above formulas (3) and (4), and at least one of the above formulas (5) and (6).

[4] A layered structure as described in any one of [1] to [3] above, which satisfies at least one of the above formulas (1) and (2), and satisfies at least three of the above formulas (3), (4), (5) and (6).

[5] A laminate as described in any one of [1] to [4] above, wherein the vertically aligned liquid crystal cured film further comprises a leveling agent.

[6] The laminate as described in [5] above, wherein the leveling agent contains fluorine element or silicon element.

[7] A laminate as described in any one of [1] to [6] above, wherein the vertically aligned liquid crystal cured film comprises an ionic compound containing non-metallic atoms.

[8] A laminate as described in any one of [1] to [7] above, wherein the vertically aligned liquid crystal cured film comprises an ionic compound containing non-metallic atoms, and the molecular weight of the ionic compound is greater than 100 and less than 10,000.

[9] A laminate as described in any one of [1] to [8] above, wherein the vertically aligned liquid crystal cured film comprises an ionic compound containing a phosphonium salt or an ammonium salt.

[10] A laminate as described in any one of [1] to [9] above, wherein the vertically aligned liquid crystal cured film comprises a non-ionic silane compound.

[11] A laminate as described in any one of [1] to [10] above, wherein the vertically aligned liquid crystal cured film comprises a non-ionic silane compound, and the non-ionic silane compound is a silane coupling agent.

[12] A laminate as described in any one of [1] to [11] above, wherein the vertically aligned liquid crystal cured film comprises a non-ionic silane compound and an ionic compound.

[13] A laminate as described in any one of [1] to [12] above, wherein the thickness of the vertically aligned liquid crystal cured film is greater than 0.3 μm and less than 5.0 μm.

[14] A laminate as described in any one of [1] to [13] above, wherein the vertically aligned liquid crystal cured film satisfies the following formula (7).

-150≦RthC(550)≦-30 (7)

[In formula (7), RthC(550) represents the phase difference in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550nm]

[15] A laminate as described in any one of [1] to [14] above, wherein the vertically aligned liquid crystal cured film satisfies the following formula (8).

RthC(450)/RthC(550)≦1.0 (8)

[In formula (8), RthC(450) represents the phase difference value of the vertical alignment liquid crystal cured film in the thickness direction at a wavelength of 450nm, and RthC(550) represents the phase difference value of the vertical alignment liquid crystal cured film in the thickness direction at a wavelength of 550nm]

[16] A laminate as described in any one of [1] to [15] above, further comprising a horizontally aligned phase difference film.

[17] The laminate as described in [16] above, wherein the horizontally aligned phase difference film is a horizontally aligned liquid crystal cured film formed by curing at least one polymerizable liquid crystal compound in a state of being horizontally aligned relative to the in-plane direction of the phase difference film.

[18] An elliptical polarizing plate comprising a laminate as described in [16] or [17] above and a polarizing film.

[19] The elliptical polarizing plate described in [18] above, wherein the angle between the phase axis of the horizontally aligned phase difference film constituting the laminate and the absorption axis of the polarizing film is 45±5°.

[20] An organic EL display device comprising an elliptical polarizing plate as described in [18] or [19] above.

[21] A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound having an absorbance of 0.10 or less at a wavelength of 350 nm, a leveling agent, and at least one selected from the group consisting of an ionic compound containing a non-metal atom and a non-ionic silane compound.

[22] The polymerizable liquid crystal composition described in [21] above comprises a polymerizable liquid crystal compound having an absorbance of 0.10 or less at a wavelength of 350 nm, a leveling agent, an ionic compound containing non-metal atoms, and a non-ionic silane compound.

[23] A polymerizable liquid crystal composition as described in [21] or [22] above, wherein the polymerizable liquid crystal compound having an absorbance of 0.10 or less at a wavelength of 350 nm is a polymerizable liquid crystal compound having a structure represented by formula (Y).

P11-B11-E11-B12-A11-B13 (Y)

[In formula (Y), P11 represents a polymerizable group; A11 represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group; B11 represents -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ¹⁶ -, -NR ¹⁶ -CO-, -CO-, -CS-, or a single bond; R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; B12 and B13 independently represent -C≡C-, -CH=CH-, -CH ₂ -CH ₂ -, -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -CH=N-, -N=CH-, -N=N-, -C(=O)-NR ¹⁶ -, -NR ¹⁶ -C(=O)-, -OCH ₂ -, -OCF2- _{, -CH2O- ,} -CF2O-, -CH=CH-C(=O)-O-, -OC(=O)-CH=CH-, -H, -C≡N or a single bond; E11 represents an alkanediyl group having 1 to 12 carbon atoms, the hydrogen atom contained in the alkanediyl group may be substituted by an alkoxy group having 1 to 5 carbon atoms, and the hydrogen atom contained in the alkoxy group may be substituted by a halogen atom; further, the _-CH2- constituting the alkanediyl group may be substituted by -O- or -CO-]

[24] A method for manufacturing an elliptical polarizing plate, wherein the elliptical polarizing plate is manufactured by peeling off a substrate from a laminate described in any one of [1] to [15], and then laminating the laminate peeled off from the substrate, a horizontally aligned phase difference film, and a polarizing film.

[25] The method described in [24], wherein the angle between the retarded axis of the horizontally aligned phase difference film constituting the laminate of the elliptical polarizer and the absorption axis of the polarizing film is 45±5°.

According to the present invention, a laminate including a vertically aligned liquid crystal cured film can be provided. The vertically aligned liquid crystal cured film can be formed without a vertically aligned film, and is formed by aligning a polymerizable liquid crystal compound with good precision in the vertical direction, similar to the vertically aligned liquid crystal cured film formed on the vertically aligned film.

1: Base material

2: Vertically aligned liquid crystal hardening film

11: Layered body

(A): Non-substrate side interface

(B): Substrate side interface

(C):Midpoint

FIG1 is a schematic cross-sectional view showing an example of the layer structure of the laminate of the present invention.

The laminate of the present invention includes a vertically aligned liquid crystal curing film and a substrate. FIG. 1 is not limited to this, but shows one aspect of the laminate of the present invention, showing the most basic layer structure of the laminate of the present invention. The laminate 11 shown in FIG. 1 is formed by laminating a substrate 1 and a vertically aligned liquid crystal curing film 2. In the laminate 11 shown in FIG. 1, the vertically aligned liquid crystal curing film 2 is directly formed on the substrate 1, and the substrate 1 and the vertically aligned liquid crystal curing film 2 exist adjacent to each other. In addition to the substrate and the vertically aligned liquid crystal curing film, the laminate of the present invention may also further include other layers.

In the present invention, the vertical alignment liquid crystal curing film can be formed on a substrate or on a layer without vertical alignment limiting force provided on the substrate through a layer with vertical alignment limiting force (hereinafter, also referred to as "vertical alignment film") or without a vertical alignment film. In the laminate of the present invention, the vertical alignment liquid crystal curing film can be formed without a vertical alignment film, so the number of manufacturing steps of the laminate is reduced, and the laminate can be manufactured with good productivity. That is, in the present invention, the vertical alignment liquid crystal curing film can be laminated on the substrate without a vertical alignment film, and the laminate of the present invention is preferably formed by the substrate and the vertical alignment liquid crystal curing film being adjacent to each other.

[Vertical alignment liquid crystal hardening film]

The vertically aligned liquid crystal cured film constituting the laminate of the present invention satisfies at least one of the following formulas (1) and (2), and satisfies at least one of the following formulas (3), (4), (5) and (6).

F(A)>F(C) (1)

Si(A)>Si(C) (2)

N(B)>N(C) (3)

P(B)>P(C) (4)

F(B)>F(C) (5)

Si(B)>Si(C) (6)

In formulas (1) to (6), F(A) represents the presence ratio (atom%) of the fluorine element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate, F(B) represents the presence ratio (atom%) of the fluorine element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the substrate side, F(C) represents the presence ratio (atom%) of the fluorine element in the liquid crystal cured film at a point 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate, Si(A) represents the presence ratio (atom%) of the silicon element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate, Si(B) represents the presence ratio (atom%) of the silicon element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the substrate side, and Si(C) represents the presence ratio (atom%) of the silicon element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the substrate side. The ratio of silicon in the liquid crystal cured film at the interface on the side opposite to the substrate, at a point 100 nm in the thickness direction on the liquid crystal cured film side (atom%), N(B) represents the ratio of nitrogen in the liquid crystal cured film at the interface on the substrate side of the vertically aligned liquid crystal cured film (atom%), N(C) represents the ratio of nitrogen in the liquid crystal cured film at the interface on the side opposite to the substrate on the liquid crystal cured film side, at a point 100 nm in the thickness direction, P(B) represents the ratio of phosphorus in the liquid crystal cured film at the interface on the substrate side of the vertically aligned liquid crystal cured film (atom%), P(C) represents the ratio of phosphorus in the liquid crystal cured film at the interface on the side opposite to the substrate on the liquid crystal cured film side, at a point 100 nm in the thickness direction on the liquid crystal cured film side.

The above formulas (1) to (6) serve as indicators of the presence of a segregation of specific elements in a vertically aligned liquid crystal cured film. F, Si, N, and P in formulas (1) to (6) represent fluorine, silicon, nitrogen, and phosphorus, respectively. As shown in FIG1 , (A) is the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate (hereinafter, also referred to as the "non-substrate side interface"), (B) is the interface of the vertically aligned liquid crystal cured film on the substrate side (hereinafter, also referred to as the "substrate side interface"), and (C) is a point 100 nm in the thickness direction on the side of the liquid crystal cured film from the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate (hereinafter, also referred to as the "midpoint"), which refers to the point at which the presence or absence of each element in the vertically aligned liquid crystal cured film is analyzed. Regarding the vertically aligned liquid crystal cured film constituting the laminate of the present invention, fluorine, silicon, nitrogen and phosphorus are segregated in a specific positional relationship in the vertically aligned liquid crystal cured film. Such segregation of specific elements refers to the presence of additives that function as leveling agents or vertical alignment promoters in the vertically aligned liquid crystal cured film in a specific positional relationship, and the surface energy of the liquid crystal cured film is controlled by the segregation, and electrostatic repulsion to the polymerizable liquid crystal compound can be exhibited. It is believed that the orientation restriction force that makes the polymerizable liquid crystal compound align in a direction perpendicular to the film plane of the liquid crystal cured film is exhibited, and a vertically aligned liquid crystal cured film in which the polymerizable liquid crystal compound is aligned in a direction perpendicular to the film plane can be formed without passing through a vertically aligned film. Furthermore, when the above-mentioned elements are segregated in the vertically aligned liquid crystal cured film constituting the laminate of the present invention, the segregation location is within a range of several tens of nm (maximum about 50 nm) from the two interfaces of the non-substrate side and the substrate side of the liquid crystal cured film, respectively. At a point more than 100 nm inward in the thickness direction from the non-substrate interface or the substrate interface of the liquid crystal cured film, regardless of whether there is segregation of the elements at the above-mentioned interface, almost no change in the existence ratio of the elements is observed.

The above formula (1) means that the existence ratio (atom%) of the fluorine element at the non-substrate side interface of the vertically aligned liquid crystal cured film is greater than the existence ratio (atom%) of the fluorine element at the midpoint, indicating that the fluorine element is segregated at the non-substrate side interface. The above formula (2) means that the existence ratio (atom%) of the silicon element at the non-substrate side interface of the vertically aligned liquid crystal cured film is greater than the existence ratio (atom%) of the silicon element at the midpoint, indicating that the silicon element is segregated at the non-substrate side interface. The segregation of the fluorine element and/or the silicon element at the non-substrate side interface of the vertically aligned liquid crystal cured film can be achieved, for example, by the liquid crystal cured film containing the following components (such as surfactants, etc.), which contain fluorine elements and/or silicon elements as constituent components and are easily segregated at the interface side of the non-substrate side. If the fluorine element and/or silicon element are concentrated on the interface of the non-substrate side of the liquid crystal cured film due to this component, the surface energy at the interface of the non-substrate side of the liquid crystal cured film is reduced, thereby showing a vertical alignment restraining force that makes the polymerizable liquid crystal compound align in a direction perpendicular to the film plane.

By making the vertically aligned liquid crystal cured film constituting the laminate of the present invention satisfy at least one of formula (1) and formula (2), the surface energy of the non-substrate side interface of the liquid crystal cured film is reduced, and the polymerizable liquid crystal compound is easily aligned in the vertical direction.

The vertically aligned liquid crystal cured film constituting the laminate of the present invention satisfies at least one of the above formulas (3), (4), (5) and (6). The above formula (3) means that the existence ratio (atom%) of the nitrogen element at the substrate side interface of the vertically aligned liquid crystal cured film is greater than the existence ratio (atom%) of the nitrogen element at the midpoint, indicating that the nitrogen element is concentrated at the substrate side interface. The above formula (4) means that the existence ratio (atom%) of the phosphorus element at the substrate side interface of the vertically aligned liquid crystal cured film is greater than the existence ratio (atom%) of the phosphorus element at the midpoint, indicating that the phosphorus element is concentrated at the substrate side interface. The above formula (5) means that the existence ratio (atom%) of the fluorine element at the substrate side interface of the vertically aligned liquid crystal cured film is greater than the existence ratio (atom%) of the fluorine element at the midpoint, indicating that the fluorine element is concentrated at the substrate side interface. The above formula (6) means that the existence ratio (atom%) of the silicon element at the interface on the substrate side of the vertically aligned liquid crystal cured film is greater than the existence ratio (atom%) of the silicon element at the midpoint, indicating that the silicon element is segregated at the interface on the substrate side. The segregation of nitrogen, phosphorus, fluorine and/or silicon at the interface on the substrate side of the vertically aligned liquid crystal cured film can be achieved, for example, by the liquid crystal cured film containing the following components (such as ionic compounds, etc.), which contain nitrogen, phosphorus, fluorine and/or silicon as constituent components and are easily segregated at the interface side on the substrate side. The mechanism of the vertical alignment restriction force using the presence of these component segregation is not clear, but it is speculated that since charged ionic compounds and uncharged polymerizable liquid crystal compounds usually have very different polarities, if such component segregation exists at the interface on the substrate side of the liquid crystal cured film, an electrostatic repulsion effect on the polymerizable liquid crystal compound is generated at the interface on the substrate side of the liquid crystal cured film where the above elements exist, and the polymerizable liquid crystal compound is arranged in a manner that reduces the contact area of the interface on the substrate side of the liquid crystal cured film, so that a vertical alignment restriction force that aligns the polymerizable liquid crystal compound in a direction perpendicular to the film plane can be expressed.

By satisfying at least one of the formulas (3), (4), (5) and (6) in the liquid crystal cured film, an electrostatic repulsion effect can be generated between the substrate-side interface of the liquid crystal cured film and the polymerizable liquid crystal compound, and the polymerizable liquid crystal compound is easily aligned in the vertical direction. In the present invention, by satisfying at least one of the formulas (3), (4), (5) and (6), a vertically aligned liquid crystal cured film having a vertically aligned restraining force for the polymerizable liquid crystal compound can be obtained, so the element that is segregated on the substrate-side interface side can be any one of nitrogen, phosphorus, fluorine or silicon. From the viewpoint that a vertically aligned liquid crystal cured film containing the above-mentioned specific element in a segregated state can be easily obtained by using a common ionic compound as described below, in the present invention, the vertically aligned liquid crystal cured film preferably satisfies at least one of formula (3) and formula (4), and satisfies at least one of formula (5) and formula (6), more preferably satisfies at least three of formula (3), (4), (5) and (6), and further preferably satisfies at least one of formula (3) and (4), and satisfies formula (5) and formula (6).

The vertically aligned liquid crystal cured film constituting the laminate of the present invention satisfies at least one of formulas (1) and (2), and satisfies at least one of formulas (3), (4), (5), and (6). By satisfying at least one of formulas (1) and (2), and at least one of formulas (3) to (6), the surface energy reduction effect at the non-substrate side interface of the liquid crystal cured film and the electrostatic repulsion effect at the substrate side interface of the liquid crystal cured film can be used to exhibit vertical alignment restriction force on the polymerizable liquid crystal compound from both interfaces of the liquid crystal cured film. Therefore, compared with the case where any one of formulas (1) to (6) is satisfied, or at least one of formulas (1) and (2) is satisfied, or at least one of formulas (3) to (6) is satisfied, the polymerizable liquid crystal compound can be aligned with higher precision in a direction perpendicular to the film plane of the liquid crystal cured film without a vertical alignment film.

In the present invention, the vertical alignment liquid crystal curing film can adopt the following aspects.

a) Satisfy at least one of formulas (1) and (2), at least one of formulas (3) and (4), and at least one of formulas (5) and (6).

b) Satisfy at least one of equations (1) and (2), and at least three of equations (3) to (6).

c) Satisfy at least one of equations (1) and (2), and at least one of equations (3) and (4), and further satisfy equations (5) and (6) at the same time.

In terms of the ease of aligning the polymerizable liquid crystal compound in the vertical direction, the above-mentioned state (b) is preferred, and in terms of the ease of aligning the polymerizable liquid crystal compound vertically with higher precision, the above-mentioned state (c) is more preferred.

When the vertically aligned liquid crystal cured film satisfies formula (1), the difference between the existence ratio (atom%) of the fluorine element at the interface on the non-substrate side represented by F(A) and the existence ratio (atom%) of the fluorine element at the midpoint represented by F(C) [F(A)-F(C)] is preferably 0.01 or more, more preferably 0.1 or more, and further preferably 0.5 or more. If the difference between F(A) and F(C) is greater than the above lower limit, a sufficient amount of fluorine element is concentrated on the interface side on the non-substrate side of the vertically aligned liquid crystal cured film, and the polymerizable liquid crystal compound is easily aligned in the vertical direction with good precision. The upper limit of the difference between F(A) and F(C) is not particularly limited, and is usually 50 or less, preferably 30 or less.

When the vertically aligned liquid crystal cured film satisfies formula (2), the difference between the existence ratio (atom%) of the silicon element at the interface on the non-substrate side represented by Si(A) and the existence ratio (atom%) of the silicon element at the midpoint represented by Si(C) [Si(A)-Si(C)] is preferably 0.01 or more, more preferably 0.05 or more, and further preferably 0.10 or more. If the difference between Si(A) and Si(C) is greater than the above lower limit, a sufficient amount of silicon element is concentrated on the interface side on the non-substrate side of the vertically aligned liquid crystal cured film, and the polymerizable liquid crystal compound is easily aligned in the vertical direction with good precision. The upper limit of the difference between Si(A) and Si(C) is not particularly limited, and is usually 50 or less, preferably 30 or less.

When the vertically aligned liquid crystal cured film satisfies formula (3), the difference between the existence ratio (atom%) of the nitrogen element at the interface on the substrate side represented by N(B) and the existence ratio (atom%) of the nitrogen element at the midpoint represented by N(C) [N(B)-N(C)] is preferably 0.001 or more, more preferably 0.01 or more, and further preferably 0.05 or more. If the difference between N(B) and N(C) is greater than the above lower limit, a sufficient amount of nitrogen element is concentrated on the substrate interface side of the vertically aligned liquid crystal cured film, and the polymerizable liquid crystal compound is easily aligned in the vertical direction with good precision. The upper limit of the difference between N(B) and N(C) is not particularly limited, and is usually 30 or less, preferably 10 or less.

When the vertically aligned liquid crystal cured film satisfies formula (4), the difference between the existence ratio (atom%) of the phosphorus element at the interface on the substrate side represented by P(B) and the existence ratio (atom%) of the phosphorus element at the midpoint represented by P(C) [P(B)-P(C)] is preferably 0.001 or more, more preferably 0.01 or more, and further preferably 0.05 or more. If the difference between P(B) and P(C) is greater than the above lower limit, a sufficient amount of phosphorus element is concentrated on the substrate interface side of the vertically aligned liquid crystal cured film, and the polymerizable liquid crystal compound is easily aligned in the vertical direction with good precision. The upper limit of the difference between P(B) and P(C) is not particularly limited, and is usually 30 or less, preferably 10 or less.

When the vertically aligned liquid crystal cured film satisfies formula (5), the difference between the existence ratio (atom%) of the fluorine element at the interface on the substrate side represented by F(B) and the existence ratio (atom%) of the fluorine element at the midpoint represented by F(C) [F(B)-F(C)] is preferably 0.01 or more, more preferably 0.05 or more, and further preferably 0.10 or more. If the difference between F(B) and F(C) is greater than the above lower limit, a sufficient amount of fluorine element is concentrated on the substrate interface side of the vertically aligned liquid crystal cured film, and the polymerizable liquid crystal compound is easily aligned in the vertical direction with good precision. The upper limit of the difference between F(B) and F(C) is not particularly limited, and is usually 50 or less, preferably 30 or less.

When the vertically aligned liquid crystal cured film satisfies formula (6), the difference between the existence ratio (atom%) of the silicon element at the interface on the substrate side represented by Si(B) and the existence ratio (atom%) of the silicon element at the midpoint represented by Si(C) [Si(B)-Si(C)] is preferably 0.01 or more, more preferably 0.05 or more, and further preferably 0.10 or more. If the difference between Si(B) and Si(C) is greater than the above lower limit, a sufficient amount of silicon element is concentrated on the substrate interface side of the vertically aligned liquid crystal cured film, and the polymerizable liquid crystal compound is easily aligned in the vertical direction with good precision. The upper limit of the difference between Si(B) and Si(C) is not particularly limited, and is usually 50 or less, preferably 30 or less.

In the present invention, when the same element (such as fluorine or silicon) is concentrated on both the non-substrate side interface and the substrate side interface of the vertically aligned liquid crystal cured film, the relationship between the existence ratio of the element at the non-substrate side interface and the existence ratio of the element at the substrate side interface is not particularly limited, and can be the same degree as each other, or one of them can be higher.

In the present invention, the above formulas (1) to (6) in the vertical alignment liquid crystal cured film can be controlled by adjusting the type of components containing fluorine and/or silicon as constituents and easily segregating on the interface side of the non-substrate side, or components containing nitrogen, phosphorus, fluorine and/or silicon as constituents and easily segregating on the interface side of the substrate side, the amount and combination of these, the composition of the composition for forming the vertical alignment liquid crystal cured film, the manufacturing conditions of the vertical alignment liquid crystal cured film, the type of the coated substrate or the surface treatment conditions, etc., according to the polymerizable liquid crystal compound used to constitute the vertical alignment liquid crystal cured film. For example, by selecting the leveling agent and/or non-ionic silane compound described below according to the polymerizable liquid crystal compound used, and adjusting the mixing amount thereof, a vertically aligned liquid crystal cured film satisfying formula (1) and/or (2) can be obtained. Also, by selecting the ionic compound described below according to the polymerizable liquid crystal compound used, and adjusting the mixing amount thereof, a vertically aligned liquid crystal cured film satisfying formula (3), (4), (5) and/or (6) can be obtained.

The ratio of each of the above elements in the vertical alignment liquid crystal cured film can be measured by X-ray photoelectron spectroscopy (XPS). For example, after analyzing the constituent elements of the interface on the non-substrate side of the vertical alignment liquid crystal cured film by XPS, etching can be performed from the non-substrate side interface, and the constituent elements in the liquid crystal cured film at a point 100nm in the thickness direction of the liquid crystal cured film from the non-substrate side interface can be analyzed by XPS. Then, the substrate is peeled off from the vertical alignment liquid crystal cured film used in the above analysis, and the constituent elements of the surface (substrate side interface) from which the substrate is peeled off can be analyzed by XPS. More detailed conditions such as XPS measurement conditions or etching conditions for analyzing the constituent elements of the intermediate point can be appropriately determined according to the measurement device, the sample to be measured, etc. For example, the conditions described in the following embodiment can be adopted.

The vertically aligned liquid crystal cured film constituting the laminate of the present invention is a cured product of the following polymerizable liquid crystal composition, which is formed by curing the polymerizable liquid crystal compound in a state of being aligned in a direction perpendicular to the plane of the liquid crystal cured film. In the present invention, the polymerizable liquid crystal composition used to form the above-mentioned vertically aligned liquid crystal cured film is composed of a component other than the polymerizable liquid crystal compound, and is used to make the obtained liquid crystal cured film have a partial presence of a specific element as represented by formulas (1) to (6).

In the present invention, it is preferred that the vertically aligned liquid crystal cured film constituting the laminate includes the following components, which include fluorine and/or silicon as constituent components and are easily segregated on the interface side of the non-substrate side. By including such components, a liquid crystal cured film satisfying formula (1) and/or formula (2) can be obtained. Due to such components, the fluorine and/or silicon elements are segregated on the interface of the non-substrate side of the liquid crystal cured film, thereby reducing the surface energy at the interface of the non-substrate side of the liquid crystal cured film, and exhibiting a vertical alignment restraining force that aligns the polymerizable liquid crystal compound in a direction perpendicular to the film plane. As a result, in the laminate of the present invention, there is no need to form a vertically aligned film, the manufacturing steps of the laminate are simplified, and the laminate can be manufactured with good productivity. As components that contain fluorine and/or silicon as constituents and are easily segregated on the interface side other than the substrate side, for example, there can be listed: leveling agents, non-ionic silane compounds, ionic compounds, etc.

In the present invention, the vertical alignment liquid crystal curing film preferably includes a leveling agent. The leveling agent has the function of adjusting the fluidity of the polymerizable liquid crystal composition to flatten the coating film obtained by coating the composition. Typical leveling agents include surfactants, etc. In the present invention, the fluorine element and/or the silicon element are easily concentrated on the non-substrate side interface of the liquid crystal curing film, so that the function as a leveling agent can be exerted, and from the perspective of showing a higher vertical alignment restriction force for the polymerizable liquid crystal compound, the vertical alignment liquid crystal curing film is more preferably included. At least one leveling agent selected from a leveling agent containing a silicon element (hereinafter, also referred to as a "polysilicone-based leveling agent") and a leveling agent containing a fluorine element (hereinafter, also referred to as a "fluorine-based leveling agent"). By including a leveling agent containing fluorine elements in the vertical alignment liquid crystal cured film, it is easy to satisfy formula (1), and by including a leveling agent containing silicon elements, it is easy to satisfy formula (2). As these leveling agents, only one type can be used, or two or more types can be used in combination.

As the leveling agent, a commercially available product can be used. For example, as silicone leveling agents and fluorine leveling agents, specifically, there are: DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all of the above are Dow Corning Toray Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all manufactured by Maitu Advanced Materials Japan Co., Ltd.), fluorinert (registered trademark) FC-72, same series FC-40, same series FC-43, same series FC-3283 (all manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) R-08, same series R-30, same series R-90, same series F-410, same series F-411, same series F-443, same series F-445, same series F-470, same series F-477, same series F-479, same series F-482, same series F-483, same series F-556 (all manufactured by DIC Co., Ltd.), Eftop (trade name) EF301, EF303 of the same series, EF351 of the same series, EF352 of the same series (all manufactured by Mitsubishi Materials Corporation), Surflon (registered trademark) S-381, S-382 of the same series, S-383 of the same series, S-393 of the same series, SC-101 of the same series, SC-105 of the same series, KH-40, SA-100 (all manufactured by AGC Seimi Chemical Co., Ltd.), trade name E1830, E5844 of the same series (manufactured by Daikin Precision Chemicals Laboratories, Ltd.), etc.

When the vertical alignment liquid crystal cured film contains a leveling agent, its content is preferably 0.001 mass parts or more, more preferably 0.01 mass parts or more, and further preferably 0.03 mass parts or more, and further preferably 5 mass parts or less, more preferably 3 mass parts or less, and further preferably 1.5 mass parts or less, relative to 100 mass parts of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition forming the vertical alignment liquid crystal cured film. If the content of the leveling agent is within the above range, the good coating property of the polymerizable liquid crystal composition can be maintained, and the vertical alignment of the polymerizable liquid crystal compound can be effectively promoted. Furthermore, when the vertical alignment liquid crystal cured film contains two or more leveling agents, the content of the above-mentioned leveling agent refers to the total content of all the leveling agents contained in the vertical alignment liquid crystal cured film.

In the present invention, the vertical alignment liquid crystal cured film preferably contains a non-ionic silane compound. The non-ionic silane compound usually has a tendency to segregate at the non-substrate side interface of the vertical alignment liquid crystal cured film. By including it, a liquid crystal cured film satisfying formula (2) can be obtained. If the polymerizable liquid crystal composition forming the vertical alignment liquid crystal cured film contains a non-ionic silane compound, the non-ionic silane compound can reduce the surface tension of the polymerizable liquid crystal composition and reduce the surface energy of the interface on the non-substrate side of the liquid crystal cured film, thereby increasing the vertical alignment restriction force on the polymerizable liquid crystal compound. In this way, the liquid crystal cured film can be formed by maintaining the vertical alignment state of the polymerizable liquid crystal compound. In particular, by including a non-ionic silane compound in addition to the above-mentioned leveling agent, the vertical alignment restriction force brought about by the above-mentioned effect can be more significantly manifested.

Non-ionic silane compounds are non-ionic compounds containing silicon. Examples of non-ionic silane compounds include silicone polymers such as polysilane, silicone oils and silicone resins, silicone oligomers, organic and inorganic silane compounds such as silsesquioxane and alkoxysilane (more specifically, silane coupling agents, etc.), and the like. Furthermore, the above-mentioned leveling agent containing silicon element is also equivalent to non-ionic silane compound in its molecular structure, but in the present invention, the leveling agent containing silicon element (polysilicone leveling agent) is distinguished from non-ionic silane compound in that it has significant leveling property (after applying the vertical alignment liquid crystal curing film composition on the substrate, it transfers to the surface to make the coating surface smooth). In order to show the leveling property, the polysilicone leveling agent usually has a larger molecular weight, preferably a weight average molecular weight of 1000 or more.

The non-ionic silane compound may be a polysiloxane monomer type or a polysiloxane oligomer (polymer) type. If the polysiloxane oligomer is represented in the form of a (monomer)-(monomer) copolymer, examples thereof include copolymers containing butylene propyl groups such as 3-butylene propyltrimethoxysilane-tetramethoxysilane copolymer, 3-butylene propyltrimethoxysilane-tetraethoxysilane copolymer, 3-butylene propyltriethoxysilane-tetramethoxysilane copolymer and 3-butylene propyltriethoxysilane-tetraethoxysilane copolymer; methyl trimethoxysilane-tetramethoxysilane copolymer, methyl trimethoxysilane-tetraethoxysilane copolymer, methyl triethoxysilane-tetramethoxysilane copolymer, and methyl triethoxysilane-tetraethoxysilane copolymer; 3-methacryloxypropyl trimethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropyl trimethoxysilane-tetramethoxysilane copolymer; 3-Methacryloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-Methacryloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-Methacryloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-Methacryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-Methacryloxypropyltriethoxysilane-tetraethoxysilane copolymer Methacryloyloxypropyl copolymers such as methyldiethoxysilane-tetramethoxysilane copolymer and 3-methacryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer; 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer; 3-acryloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-acryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer; vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinyl-containing copolymers such as vinyl silane-tetraethoxysilane copolymers, vinyl methyl diethoxysilane-tetramethoxysilane copolymers and vinyl methyl diethoxysilane-tetraethoxysilane copolymers; 3-aminopropyl trimethoxysilane-tetramethoxysilane copolymers, 3-aminopropyl trimethoxysilane-tetraethoxysilane copolymers, 3-aminopropyl triethoxysilane-tetramethoxysilane copolymers , 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer, etc. Such non-ionic silane compounds can be used alone or in combination of two or more. Among them, from the viewpoint of further improving the adhesion of the adjacent layer such as the substrate, the silane coupling agent is preferred.

Silane coupling agents are compounds containing silicon elements and having at least one functional group selected from the group consisting of vinyl, epoxy, styryl, methacryl, acryl, amino, isocyanurate, urea, hydroxyl, isocyanate, carboxyl, and hydroxyl groups at the terminal, and at least one alkoxysilyl group or silanol group. By appropriately selecting these functional groups, it is possible to impart specific effects such as improving the mechanical strength of the vertical alignment liquid crystal cured film, modifying the surface of the vertical alignment liquid crystal cured film, and improving the adhesion between the vertical alignment liquid crystal cured film and the adjacent layer (substrate, etc.). From the viewpoint of adhesion, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and another different reactive group (such as the above functional group). Furthermore, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and a polar group. If the silane coupling agent has at least one alkoxysilyl group and at least one polar group in its molecule, it is easier to improve the vertical alignment of the polymerizable liquid crystal compound and tends to significantly obtain a vertical alignment promotion effect. As polar groups, for example, epoxy groups, amino groups, isocyanurate groups, hydroxyl groups, carboxyl groups and hydroxyl groups can be listed. Furthermore, in order to control the reactivity of the silane coupling agent, the polar group can appropriately have a substituent or a protecting group.

Specific examples of the silane coupling agent include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, 3-glycidyloxypropyltrimethoxysilane, 3- Glycidyloxypropyl methyl dimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-chloropropyl methyl dimethoxysilane, 3-chloropropyl trimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane, 3-butylene propyl trimethoxysilane, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl triethoxysilane, 3-glycidyloxypropyl dimethoxymethyl silane and 3-glycidyloxypropyl ethoxydimethyl silane.

In addition, commercially available silane coupling agents include, for example, 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, K Silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd., such as BE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007.

When the vertical alignment liquid crystal cured film includes a non-ionic silane compound, its content is preferably 0.01 mass parts or more, more preferably 0.05 mass parts or more, and further preferably 0.1 mass parts or more, and further preferably 5 mass parts or less, more preferably 4 mass parts or less, and further preferably 3 mass parts or less, in the polymerizable liquid crystal composition forming the vertical alignment liquid crystal cured film. If the content of the non-ionic silane compound is within the above range, the good coating and alignment of the polymerizable liquid crystal composition can be maintained, and the vertical alignment of the polymerizable liquid crystal compound can be effectively promoted.

The vertically aligned liquid crystal cured film constituting the laminate of the present invention preferably contains the following components, which contain nitrogen, phosphorus, fluorine and/or silicon as constituent components and are easily segregated on the interface side of the substrate side. By including such components, a liquid crystal cured film satisfying formula (3), (4), (5) and/or (6) can be obtained. As the above-mentioned components that are easily segregated on the interface side of the substrate side, for example, ionic compounds containing nitrogen, phosphorus, fluorine and/or silicon can be listed. Since charged ionic compounds and uncharged polymerizable liquid crystal compounds generally have very different polarities, if nitrogen, phosphorus, fluorine and/or silicon are concentrated on the interface on the substrate side of the liquid crystal cured film due to such components, an electrostatic repulsion effect on the polymerizable liquid crystal compound is generated at the interface on the substrate side of the liquid crystal cured film where the above elements exist. In this way, the polymerizable liquid crystal compound is configured in a manner that reduces the contact area of the interface on the substrate side of the liquid crystal cured film, so that a vertical alignment restraining force that aligns the polymerizable liquid crystal compound in a direction perpendicular to the film plane can be exhibited.

In order to prevent alignment defects of polymerizable liquid crystal compounds from occurring, it is preferred that the vertical alignment liquid crystal cured film of the present invention contain ionic compounds containing non-metal atoms. Ionic compounds containing non-metal atoms tend to be concentrated at the interface on the substrate side in the vertical alignment liquid crystal cured film, and tend to be more significantly concentrated when the polarity of the substrate film is high, such as when a triacetyl cellulose film is used, or when a corona treatment, plasma treatment, excimer light irradiation treatment, etc. is performed on the substrate. In this way, when the ionic compound is concentrated at the interface on the substrate side in the vertical alignment liquid crystal cured film, an electrostatic repulsion effect is generated between the polymerizable liquid crystal compound without charge and the ionic compound with charge, which can show a vertical alignment restraining force that makes the polymerizable liquid crystal compound align in a direction perpendicular to the film plane. Furthermore, the vertical alignment liquid crystal cured film contains the above-mentioned leveling agent, especially the leveling agent containing silicon element or the leveling agent containing fluorine element or the non-ionic silane compound and the ionic compound containing non-metallic atoms, so that the vertical alignment restraining force of the polymerizable liquid crystal compound is exerted from both sides of the non-substrate side interface and the substrate side interface of the vertical alignment liquid crystal cured film, so that the polymerizable liquid crystal compound is easily aligned in the vertical direction, which can further improve its alignment accuracy.

As ionic compounds containing non-metallic atoms, for example, onium salts can be listed (more specifically, quaternary ammonium salts, tertiary cobalt salts, and quaternary phosphonium salts, etc., in which nitrogen atoms have negative charges). By including ammonium salts in the vertically aligned liquid crystal cured film, formula (3) is easily satisfied, and by including phosphonium salts, formula (4) is easily satisfied. Among these onium salts, quaternary onium salts are preferred from the perspective of further improving the vertical alignment of polymerizable liquid crystal compounds, and quaternary phosphonium salts or quaternary ammonium salts are more preferred from the perspective of improving the availability and mass production. The onium salt may have two or more quaternary onium salt sites in the molecule, and may also be an oligomer or a polymer.

The molecular weight of the ionic compound containing non-metal atoms is preferably greater than 100 and less than 10,000. If the molecular weight is within the above range, it is easy to improve the vertical alignment of the polymerizable liquid crystal compound while ensuring the coating property of the polymerizable composition. The molecular weight of the ionic compound containing non-metal atoms is more preferably less than 5000, and further preferably less than 3000.

As cationic components of ionic compounds containing non-metal atoms, for example, inorganic cations and organic cations can be listed. Among them, organic cations are preferred in terms of being less likely to produce alignment defects of polymerizable liquid crystal compounds. As organic cations, for example, imidazolium cations, pyridinium cations, ammonium cations, cobalt cations, and phosphonium cations can be listed.

Ionic compounds containing non-metallic atoms usually have counter anions. As anionic components that serve as counter ions for the above-mentioned cationic components, for example, inorganic anions and organic anions can be cited. Among them, organic anions are preferred in terms of being less likely to produce alignment defects in polymerizable liquid crystal compounds. By using anions containing fluorine elements in the molecular structure as counter anions, it is easy to satisfy formula (5). Furthermore, cations and anions do not necessarily have to correspond one to one.

Specifically, as anionic components, for example, the following can be cited.

Chloride anion [Cl ^- ], bromine anion [Br ^- ], iodine anion [I ^- ], tetrachloroaluminate anion [AlCl ₄ ^- ], heptachlorodialuminate anion [Al ₂ Cl ₇ ^- ], tetrafluoroborate anion [BF ₄ ^- ], hexafluorophosphate anion [PF ₆ ^- ], perchlorate anion [ClO ₄ ^- ], nitrate anion [NO ₃ ^- ], acetate anion [CH ₃ COO ^- ], trifluoroacetate anion [CF ₃ COO ^- ], fluorosulfonate anion [FSO ₃ ^- ], methanesulfonate anion [CH ₃ SO ₃ ^- ], trifluoromethanesulfonate anion [CF ₃ SO ₃ ^- ], p-toluenesulfonate anion [p-CH ₃ C ₆ H ₄ SO ₃ ^- ], bis(fluorosulfonyl)imide anion [(FSO ₂ ) ₂ N ^- ], bis(trifluoromethanesulfonyl)imide anion [(CF ₃ SO ₂ ) ₂ N ^- ], tris(trifluoromethanesulfonyl)methanide anion [(CF ₃ SO ₂ ) ₃ C ^- ], hexafluoroarsenate anion [AsF ₆ ^- ], hexafluoroantimonate anion [SbF ₆ ^- ], hexafluoronitric acid anion [NbF ₆ ^- ], hexafluorotibrate anion [TaF ₆ ^- ], dimethylphosphinate anion [(CH ₃ ) ₂ POO ^- ], fluoro(poly)hydrofluoride anion [F(HF) _n ^- ] (for example, n represents an integer of 1 to 3), dicyanamide anion [(CN) ₂ N ^- ], thiocyanate anion [SCN ^- ], perfluorobutanesulfonate anion [C ₄ F ₉ SO ₃ ^- ], bis(pentafluoroethanesulfonyl)imide anion [(C ₂ F ₅ SO ₂ ) ₂ N ^- ], perfluorobutyrate anion [C ₃ F ₇ COO ^- ], and (trifluoromethanesulfonyl)(trifluoromethanecarbonyl)imide anion [(CF ₃ SO ₂ )(CF ₃ CO)N ^- ].

Specific examples of ionic compounds containing non-metal atoms can be appropriately selected from the above-mentioned combinations of cationic components and anionic components. Specific compounds of the combination of cationic components and anionic components can be listed as follows.

(Pyridinium salt)

N-Hexylpyridinium hexafluorophosphate, N-octylpyridinium hexafluorophosphate, N-methyl-4-hexylpyridinium hexafluorophosphate, N-butyl-4-methylpyridinium hexafluorophosphate, N-octyl-4-methylpyridinium hexafluorophosphate, N-hexylpyridinium bis(fluorosulfonyl)imide, N-octylpyridinium bis(fluorosulfonyl)imide, N-methyl-4-hexylpyridinium bis(fluorosulfonyl)imide, N-butyl-4-methylpyridinium bis(fluorosulfonyl)imide, N-octyl-4-methylpyridinium bis(fluorosulfonyl)imide, N-hexylpyridinium bis(fluorosulfonyl)imide (Trifluoromethanesulfonyl)imide, N-octylpyridinium bis(trifluoromethanesulfonyl)imide, N-methyl-4-hexylpyridinium bis(trifluoromethanesulfonyl)imide, N-butyl-4-methylpyridinium bis(trifluoromethanesulfonyl)imide, N-octyl-4-methylpyridinium bis(trifluoromethanesulfonyl)imide, N-hexylpyridinium p-toluenesulfonate, N-octylpyridinium p-toluenesulfonate, N-methyl-4-hexylpyridinium p-toluenesulfonate, N-butyl-4-methylpyridinium p-toluenesulfonate, and N-octyl-4-methylpyridinium p-toluenesulfonate.

(Imidazolium salt)

1-Ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium p-toluenesulfonate, 1-butyl-3-methylimidazolium methanesulfonate, etc.

(Pyrrolidinium salt)

N-butyl-N-methylpyrrolidinium hexafluorophosphate, N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide, N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, N-butyl-N-methylpyrrolidinium p-toluenesulfonate, etc.

(Ammonium salt)

Tetrabutylammonium hexafluorophosphate, tetrabutylammonium bis(fluorosulfonyl)imide, tetrahexylammonium bis(fluorosulfonyl)imide, trioctylmethylammonium bis(fluorosulfonyl)imide, (2-hydroxyethyl)trimethylammonium bis(fluorosulfonyl)imide, tetrabutylammonium bis(trifluoromethanesulfonyl)imide, tetrahexylammonium bis(trifluoromethanesulfonyl)imide, trioctylmethylammonium bis(fluorosulfonyl)imide Methylammonium bis(trifluoromethanesulfonyl)imide, (2-hydroxyethyl)trimethylammonium bis(trifluoromethanesulfonyl)imide, tetrabutylammonium p-toluenesulfonate, tetrahexylammonium p-toluenesulfonate, trioctylmethylammonium p-toluenesulfonate, (2-hydroxyethyl)trimethylammonium p-toluenesulfonate, (2-hydroxyethyl)trimethylammonium dimethylphosphinate

1-(3-Trimethoxysilylpropyl)-1,1,1-tributylammoniumbis(trifluoromethanesulfonyl)imide, 1-(3-Trimethoxysilylpropyl)-1,1,1-trimethylammoniumbis(trifluoromethanesulfonyl)imide, 1-(3-Trimethoxysilylbutyl)-1,1,1-tributylammoniumbis(trifluoromethanesulfonyl)imide, 1-(3-Trimethoxysilylbutyl) -1,1,1-trimethylammonium bis(trifluoromethanesulfonyl)imide, N-{(3-triethoxysilylpropyl)aminomethyloxyethyl)}-N,N,N-trimethylammonium bis(trifluoromethanesulfonyl)imide, and N-[2-{3-(3-trimethoxysilylpropylamino)-1-oxopropoxy}ethyl]-N,N,N-trimethylammonium bis(trifluoromethanesulfonyl)imide.

(Phosphorus salt)

Tributyl (2-methoxyethyl) phosphonium bis (trifluoromethanesulfonyl) imide, tributyl methyl phosphonium bis (trifluoromethanesulfonyl) imide, 1,1,1-trimethyl-1-[(trimethoxysilyl) methyl] phosphonium bis (trifluoromethanesulfonyl) imide, 1,1,1-trimethyl-1-[2-(trimethoxysilyl) ethyl] phosphonium bis (trifluoromethanesulfonyl) imide, 1,1,1-trimethyl-1-[3-(trimethoxysilyl) propyl] phosphonium bis (trifluoromethanesulfonyl) imide 、1,1,1-trimethyl-1-[4-(trimethoxysilyl)butyl]phosphonium bis(trifluoromethanesulfonyl)imide, 1,1,1-tributyl-1-[(trimethoxysilyl)methyl]phosphonium bis(trifluoromethanesulfonyl)imide, 1,1,1-tributyl-1-[2-(trimethoxysilyl)ethyl]phosphonium bis(trifluoromethanesulfonyl)imide, and 1,1,1-tributyl-1-[3-(trimethoxysilyl)propyl]phosphonium bis(trifluoromethanesulfonyl)imide.

These ionic compounds containing non-metal atoms may be used alone or in combination of two or more.

As the ionic compound containing non-metallic atoms, phosphonium salts with alkyl groups, ammonium salts with alkyl groups, etc. are preferred, and as the counter anions thereof, counter anions with sulfonyl groups containing fluorine atoms such as fluorosulfonyl groups and trifluoroalkylsulfonyl groups are preferred. Furthermore, the alkyl groups in phosphonium salts with alkyl groups and ammonium salts with alkyl groups may have substituents such as hydroxyl groups or alkoxysilyl groups.

Among them, the preferred is an ionic compound containing a phosphonium salt or an ammonium salt having a positive charge on the nitrogen atom (including the above-mentioned pyridinium salt or imidazolium salt, etc.), and more preferred is an ionic compound containing a phosphonium salt or an ammonium salt in which an anion containing a fluorine element is used as a counter anion in the molecular structure.

From the perspective of further improving the vertical alignment of the polymerizable liquid crystal compound, the ionic compound containing non-metal atoms preferably has silicon and/or fluorine elements in the molecular structure of the cationic part. If the ionic compound containing non-metal atoms has silicon and/or fluorine elements in the molecular structure of the cationic part, it is easy to make the ionic compound segregate on the surface of the vertically aligned liquid crystal cured film. By including such an ionic compound containing non-metal atoms, it is easy to satisfy formula (5) and/or formula (6).

Among them, the ionic compound whose constituent elements are all non-metallic elements is preferably a salt containing ammonium cation or phosphonium cation and bis(trifluoromethanesulfonyl)imide having a (C1-C4) alkoxysilylalkyl group, and more preferably the following ionic compounds (I) to (III) and the like.

For example, the method of using a surfactant with a certain chain length of alkyl to treat the surface of the substrate to improve the alignment of the liquid crystal (for example, refer to Chapter 2 of "Liquid Crystal Handbook" - Alignment and Physical Properties of Liquid Crystal (published by Maruzen Co., Ltd.) etc.) can be applied to further improve the vertical alignment of the polymerizable liquid crystal compound. That is, by using an ionic compound with a certain chain length of alkyl to treat the surface of the substrate, the vertical alignment of the polymerizable liquid crystal compound can be effectively improved.

The ionic compound containing non-metal atoms preferably satisfies the following formula (9).

5<M<16 (9)

In formula (9), M is represented by the following formula (10).

M=(the number of covalent bonds from the atom with negative charge to the end of the molecular chain of the substituent with the largest number of covalent bonds directly bonded to the atom with negative charge to the end of the molecular chain) ÷ (the number of atoms with negative charge) (10)

By using ionic compounds that satisfy the above (9), the vertical alignment of polymerizable liquid crystal compounds can be effectively improved.

When there are two or more negatively charged atoms in the molecule of an ionic compound containing non-metal atoms, the number of covalent bonds from the number of negatively charged atoms considered as the base point to the nearest other negatively charged atom is set to the "number of covalent bonds from the negatively charged atom to the molecular chain terminal" described in the definition of M above. When an ionic compound containing non-metal atoms has two or more repeating units, the above M is calculated by considering the structural unit as one molecule. When an atom with a negative charge is incorporated into a ring structure, the number of covalent bonds to an atom with the same negative charge through the ring structure or to the end of a substituent bonded to the ring structure, whichever is greater, is set as the "number of covalent bonds from the atom with a negative charge to the end of the molecular chain" described in the definition of M above.

When the vertical alignment liquid crystal cured film contains an ionic compound containing non-metallic atoms, its content is preferably 0.01 mass parts or more, more preferably 0.1 mass parts or more, and further preferably 0.3 mass parts or more, and further preferably 5 mass parts or less, more preferably 4 mass parts or less, and further preferably 3 mass parts or less, in the polymerizable liquid crystal composition forming the vertical alignment liquid crystal cured film. If the content of the ionic compound containing non-metallic atoms is within the above range, the good coating and alignment of the polymerizable liquid crystal composition can be maintained, and the vertical alignment of the polymerizable liquid crystal compound can be effectively promoted.

In the case where the vertically aligned liquid crystal cured film includes both a non-ionic silane compound and an ionic compound containing non-metal atoms, the vertical alignment of the polymerizable liquid crystal compound is more easily promoted by the electrostatic interaction derived from the ionic compound and the surface tension reduction effect derived from the non-ionic silane compound. In this way, a liquid crystal cured film can be formed in which the polymerizable liquid crystal compound is vertically aligned with better precision. Therefore, in a preferred embodiment of the present invention, the vertically aligned liquid crystal cured film includes a non-ionic silane compound and an ionic compound containing non-metal atoms. Furthermore, by including a leveling agent, a non-ionic silane compound, and an ionic compound containing non-metal atoms in the vertically aligned liquid crystal cured film, the alignment accuracy of the polymerizable liquid crystal compound can be further improved. Therefore, in another preferred embodiment of the present invention, the vertical alignment liquid crystal curing film includes a leveling agent, a non-ionic silane compound, and an ionic compound containing non-metal atoms.

In the present invention, the vertical alignment liquid crystal cured film is a cured product of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound, and is a liquid crystal cured film formed by curing the polymerizable liquid crystal compound in a state of being aligned in a direction perpendicular to the film plane of the liquid crystal cured film. In the present invention, the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition forming the vertical alignment liquid crystal cured film refers to a liquid crystal compound having a polymerizable group. The polymerizable liquid crystal compound is not particularly limited, and for example, a polymerizable liquid crystal compound previously known in the field of phase difference film can be used.

The so-called polymerizable group refers to a group that can participate in the polymerization reaction by utilizing the active free radical or acid generated by the polymerization initiator. Examples of polymerizable groups include: vinyl, vinyloxy, 1-vinyl chloride, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, ethylene oxide, cyclobutylene, etc. Among them, free radical polymerizable groups are preferred, acryloxy, methacryloxy, vinyl, vinyloxy are more preferred, and acryloxy and methacryloxy are further preferred.

The liquid crystal properties exhibited by the polymerizable liquid crystal compound can be thermotropic liquid crystal or hydrotropic liquid crystal. In terms of being able to control the thickness of the dense film, thermotropic liquid crystal is preferred. In addition, the phase sequence structure of the thermotropic liquid crystal can be nematic liquid crystal or lamellar liquid crystal. The polymerizable liquid crystal compound can be used alone or in combination of two or more.

As polymerizable liquid crystal compounds, there can be listed polymerizable liquid crystal compounds that generally exhibit positive wavelength dispersion and polymerizable liquid crystal compounds that exhibit reverse wavelength dispersion. Only one polymerizable liquid crystal compound can be used, or two polymerizable liquid crystal compounds can be mixed and used. In a display device incorporating the obtained multilayer body, from the viewpoint of increasing the effect of suppressing the oblique reflection hue during black display, it is preferred to include a polymerizable liquid crystal compound that exhibits reverse wavelength dispersion. As polymerizable liquid crystal compounds, only one type can be used, or two or more types can be used in combination.

As a polymerizable liquid crystal compound showing reverse wavelength dispersion, a compound having the following characteristics (A) to (D) is preferred.

(A) Compounds that can form nematic or smectic phases.

(B) has π electrons in the long axis direction (a) of the polymerizable liquid crystal compound.

(C) It has π electrons in the direction that intersects with the long axis direction (a) [intersecting direction (b)].

(D) Let the total number of π electrons in the long axis direction (a) be N(πa), let the total number of molecular weights in the long axis direction be N(Aa), and the π electron density in the long axis direction (a) of the polymerizable liquid crystal compound defined by the following formula (i): D(πa)=N(πa)/N(Aa) (i)

The total number of π electrons in the cross direction (b) is N(πb), the total number of molecular weights in the cross direction (b) is N(Ab), and the π electron density in the cross direction (b) of the polymerizable liquid crystal compound is defined by the following formula (ii): D(πb)=N(πb)/N(Ab) (ii)

In the relationship of formula (iii), 0≦[D(πa)/D(πb)]<1 (iii)

[That is, the π electron density in the cross direction (b) is greater than the π electron density in the long axis direction (a)]. Moreover, as described above, the polymerizable liquid crystal compound having π electrons in the long axis and in the direction relative to the cross direction exhibits a T-shaped structure, for example.

In the above characteristics (A)~(D), the major axis direction (a) and the number of π electrons N are defined as follows.

‧ Long axis direction (a): For example, if the compound has a rod-like structure, it is the long axis direction of the rod.

‧The number of π electrons N(πa) existing in the long axis direction (a) does not include the π electrons that disappear due to polymerization reactions.

‧The number of π electrons N(πa) existing in the long axis direction (a) includes the total number of π electrons on the long axis and the π electrons coyochically connected to it, for example, the number of π electrons existing in the ring that satisfies the Huckel rule and is in the long axis direction (a).

‧The number of π electrons N(πb) existing in the cross direction (b) does not include the π electrons that disappear due to the polymerization reaction.

The polymerizable liquid crystal compound that satisfies the above conditions has a liquid crystal primary structure in the long axis direction. The liquid crystal primary structure exhibits a liquid crystal phase (nematic phase, smectic phase).

By applying a polymerizable liquid crystal compound satisfying the above (A) to (D) on a film (layer) forming a liquid crystal cured film and heating it to above the phase transition temperature, a nematic phase or a lamellar phase can be formed. Regarding the nematic phase or lamellar phase formed by the alignment of the polymerizable liquid crystal compound, it is usually aligned in a manner that the long axis directions of the polymerizable liquid crystal compound are parallel to each other, and the long axis direction becomes the alignment direction of the nematic phase. If such a polymerizable liquid crystal compound is made into a film and polymerized in a nematic phase or a lamellar phase state, a polymer film containing a polymer polymerized in a state of alignment along the long axis direction (a) can be formed. The polymer film absorbs ultraviolet light using π electrons in the long axis direction (a) and π electrons in the cross direction (b). Here, the absorption maximum wavelength of ultraviolet light absorbed by π electrons in the cross direction (b) is set to λbmax. λbmax is usually 300nm~400nm. The density of π electrons satisfies the above formula (iii), and the density of π electrons in the cross direction (b) is greater than that in the long axis direction (a), so that the absorption of linearly polarized ultraviolet light (wavelength λbmax) with a vibration plane along the cross direction (b) is greater than that of linearly polarized ultraviolet light (wavelength λbmax) with a vibration plane along the long axis direction (a) becomes a polymer film. The ratio (absorbance of linearly polarized ultraviolet light in the cross direction (b)/absorbance in the long axis direction (a)) is, for example, greater than 1.0, preferably greater than 1.2, and is usually less than 30, for example, less than 10.

The polymerizable liquid crystal compound having the above-mentioned characteristics usually exhibits reverse wavelength dispersion in most cases. As the polymerizable liquid crystal compound, for example, the compound represented by the following formula (X) can be cited.

In formula (X), Ar represents a divalent group having an aromatic group which may have a substituent. The so-called aromatic group referred to here refers to a group having a π electron number of [4n+2] in the ring structure according to Huckel's rule, for example, it may have two or more Ar groups as exemplified in (Ar-1) to (Ar-23) below through a divalent linking group. Here, n represents an integer. When a ring structure is formed by containing heteroatoms such as -N= or -S-, the following situation is also included: containing non-covalent bond electron pairs on the heteroatoms to satisfy Huckel's rule and have aromaticity. Among the aromatic groups, it is preferred to contain at least one of nitrogen atoms, oxygen atoms, and sulfur atoms. The number of aromatic groups contained in the divalent group Ar may be one or more. When there is one aromatic group, the divalent group Ar may be a divalent aromatic group which may have a substituent. When there are two or more aromatic groups contained in the divalent group Ar, the two or more aromatic groups may be bonded to each other using a single bond, -CO-O-, -O- or other divalent bonding groups.

^G1 and ^G2 each independently represent a divalent aromatic group or a divalent alicyclic alkyl group. Here, the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic alkyl group may be substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and the carbon atom constituting the divalent aromatic group or the divalent alicyclic alkyl group may be substituted by 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 represent integers of 0 to 3 independently and satisfy the relationship 1≦k+1. Here, when 2≦k+1, ^B1 and ^B2 , ^G1 and ^G2 may be the same or different from each other.

^E1 and ^E2 each independently represent an alkanediyl group having 1 to 17 carbon atoms, preferably an alkanediyl group having 4 to 12 carbon atoms. The hydrogen atom in the alkanediyl group may be substituted by a halogen atom, and the _-CH2- group in the alkanediyl group may be substituted by -O-, -S-, _-SiH2- or -C(=O)-.

^P1 and ^P2 independently represent a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group.

^G1 and ^G2 are each independently preferably a 1,4-phenylenediyl group which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, a 1,4-cyclohexanediyl group which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably a methyl-substituted 1,4-phenylenediyl group, an unsubstituted 1,4-phenylenediyl group, or an unsubstituted 1,4-trans-cyclohexanediyl group, and particularly preferably an unsubstituted 1,4-phenylenediyl group or an unsubstituted 1,4-trans-cyclohexanediyl group.

When there are plural ^G1 and ^G2 , at least one of them is preferably a divalent alicyclic hydrocarbon group, and at least one of ^G1 and ^G2 bonded to ^L1 or ^L2 is more preferably a divalent alicyclic hydrocarbon group.

^L1 and ^L2 are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, ^-S- , ^-Ra1OR2- , -Ra3COOR4-, -Ra5OCOR6-, Ra7OC= ^{OOR8- ,} -N=N-, ^-CRc = ^CRd- , or -C≡C-. Here, ^Ra1 to ^Ra8 are each independently a single bond, or an alkylene group ^{having 1} to 4 carbon atoms, and ^Rc and ^Rd are each a alkyl group having 1 to 4 carbon atoms or a hydrogen _atom . ^L1 and ^L2 are each independently more preferably a single bond, ^-OR2-1- , ^-CH2- _{, -CH2CH2-} ^{, -COOR4-1-} , or ^-OCOR6-1- . Here, ^Ra2-1 , ^Ra4-1 , and ^Ra6-1 each independently represent a single bond, _-CH2- , or _-CH2CH2- . ^L1 and ^L2 each independently represent preferably a _single bond, _-O- , _-CH2CH2- , -COO- _{, -COOCH2CH2-} , or -OCO-.

^B1 and ^B2 are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a9 OR ^a10 -, -R ^a11 COOR ^a12 -, -R ^a13 OCOR ^a14 -, or R ^a15 OC=OOR ^a16 -. Here, R ^a9 to R ^a16 are each independently a single bond, or an alkylene group having 1 to 4 carbon atoms. ^B1 and ^B2 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 are each independently a single bond, -CH ₂ -, or -CH ₂ CH ₂ -. ^B1 and ^B2 are each independently preferably _a single bond, -O-, _-CH2CH2- , _-COO- , _-COOCH2CH2- , _-OCO- , or _-OCOCH2CH2- .

From the perspective of showing anti-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. If k=2 and l=2, it becomes a symmetric structure, so it is better.

Examples of the polymerizable group represented by ^P1 or ^P2 include epoxy, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, ethylene oxide, and cyclobutylene. Among them, acryloxy, methacryloxy, vinyl, and vinyloxy are preferred, and acryloxy and methacryloxy are more preferred.

環、嘧啶環、三唑環、三

環、吡咯啉環、咪唑環、吡唑環、噻唑環、苯并噻唑環、噻吩并噻唑環、

唑環、苯并

唑環、及啡啉環等。其中，較佳為具有噻唑環、苯并噻唑環、或苯并呋喃環，進而較佳為具有苯并噻唑基。又，於Ar中包含氮原子之情形時，該氮原子較佳為具有π電子。 Ar preferably has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocyclic ring which may have a substituent, and an electron withdrawing group. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and the like, preferably a benzene ring and a naphthalene ring. 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 pyridine ring, and a pyridine ring.

Ring, pyrimidine ring, triazole ring, tri

ring, pyrroline ring, imidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, thienothiazole ring,

Azole, benzo

Among them, it is preferably a thiazole ring, a benzothiazole ring, or a benzofuran ring, and more preferably a benzothiazolyl group. In addition, when Ar contains a nitrogen atom, the nitrogen atom preferably has π electrons.

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

As the aromatic group represented by Ar, the following groups can be cited, for example.

In formula (Ar-1) to formula (Ar-23), the * symbol represents a linking portion, and ^Z0 , ^Z1 , and ^Z2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 12 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, an N-alkylamino group having 1 to 12 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylaminesulfonyl group having 1 to 12 carbon atoms, or an N,N-dialkylaminesulfonyl group having 2 to 12 carbon atoms. In addition, ^Z0 , ^Z1 , and ^Z2 may also include a polymerizable group.

^Q1 and ^Q2 each independently represent ^-CR2'R3'- , ^-S- , -NH-, ^-NR2'- , -CO- or -O-, and R2 ^' and R3 ^' each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

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

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

^W1 and ^W2 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 alkyl group in Y ¹ , Y ² and Y ³ include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl and other aromatic alkyl groups having 6 to 20 carbon atoms, preferably phenyl and naphthyl, and more preferably phenyl. Examples of the aromatic heterocyclic group include furanyl, pyrrolyl, thienyl, pyridyl, thiazolyl, benzothiazolyl and other aromatic heterocyclic groups having 4 to 20 carbon atoms and containing at least one hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom and the like, preferably furanyl, thienyl, pyridyl, thiazolyl, benzothiazolyl.

^Y1 , ^Y2 and ^Y3 may be independently substituted polycyclic aromatic alkyl groups or polycyclic aromatic heterocyclic groups. Polycyclic aromatic alkyl groups refer to condensed polycyclic aromatic alkyl groups or groups derived from aromatic aggregated rings. Polycyclic aromatic heterocyclic groups refer to condensed polycyclic aromatic heterocyclic groups or groups derived from aromatic aggregated rings.

^Z0 , ^Z1 and ^Z2 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. ^Z0 is further preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cyano group. ^Z1 and ^Z2 are further preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a cyano group. Furthermore, ^Z0 , ^Z1 and ^Z2 may also include a polymerizable group.

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

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

環、嘧啶環、吲哚環、喹啉環、異喹啉環、嘌呤環、吡咯啶環等。該芳香族雜環基可具有取代基。又，Y¹可為能夠與其所鍵結之氮原子及Z⁰一併進行上述取代之多環系芳香族烴基或多環系芳香族雜環基。例如可列舉：苯并呋喃環、苯并噻唑環、苯并

唑環等。 In formula (Ar-16) to (Ar-23), ^Y1 may form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and ^Z0 . Examples of the aromatic heterocyclic group include the aromatic heterocyclic rings that Ar may have and are described above, for example, pyrrole ring, imidazole ring, pyrroline ring, pyridine ring, pyrrol ...

ring, pyrimidine ring, indole ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidinyl ring, etc. The aromatic heterocyclic group may have a substituent. In addition, ^Y1 may be a polycyclic aromatic alkyl group or a polycyclic aromatic heterocyclic group capable of the above-mentioned substitution together with the nitrogen atom to which it is bonded and ^Z0 . For example, benzofuran ring, benzothiazole ring, benzo

Azole, etc.

Furthermore, in the present invention, as a polymerizable liquid crystal compound for forming a vertically aligned liquid crystal cured film, a polymerizable liquid crystal compound having an absorbance of 0.10 or less at a wavelength of 350 nm can be used. A polymerizable liquid crystal compound having an absorbance of 0.10 or less at a wavelength of 350 nm generally has a tendency to show positive wavelength dispersion. As such a polymerizable liquid crystal compound, for example, a compound having a structure represented by the following formula (Y) that generally has a tendency to show positive wavelength dispersion can be listed (hereinafter, also referred to as "polymerizable liquid crystal compound (Y)"). Furthermore, the absorbance of the polymerizable liquid crystal compound can be measured in a solvent using an ultraviolet-visible spectrophotometer, for example, the absorbance can be measured with reference to the method described in the embodiment. The solvent is one that can dissolve the polymerizable liquid crystal compound, for example, tetrahydrofuran, chloroform, etc. can be listed.

P11-B11-E11-B12-A11-B13- (Y)

[In formula (Y), P11 represents a polymerizable group; A11 represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group; B11 represents -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ¹⁶ -, -NR ¹⁶ -CO-, -CO-, -CS-, or a single bond; R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; B12 and B13 independently represent -C≡C-, -CH=CH-, -CH ₂ -CH ₂ -, -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -CH=N-, -N=CH-, -N=N-, -C(=O)-NR ¹⁶ -, -NR ¹⁶ -C(=O)-, -OCH ₂ -, -OCF2- _{, -CH2O- ,} -CF2O-, -CH=CH-C(=O)-O-, -OC(=O)-CH=CH-, -H, -C≡N or a single bond; E11 represents an alkanediyl group having 1 to 12 carbon atoms, the hydrogen atom contained in the alkanediyl group may be substituted by an alkoxy group having 1 to 5 carbon atoms, and the hydrogen atom contained in the alkoxy group may be substituted by a halogen atom; further, the _-CH2- constituting the alkanediyl group may be substituted by -O- or -CO-]

The number of carbon atoms in the aromatic alkyl group and the alicyclic alkyl group of A11 is preferably in the range of 3 to 18, more preferably in the range of 5 to 12, and particularly preferably 5 or 6. The hydrogen atom contained in the divalent alicyclic alkyl group and the divalent aromatic alkyl group represented by A11 may be substituted by a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group, and the hydrogen atom contained in the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be substituted by a fluorine atom. As A11, cyclohexane-1,4-diyl and 1,4-phenylene are preferred.

E11 is preferably a linear alkanediyl group having 1 to 12 carbon atoms. -CH ₂ - constituting the alkanediyl group may be substituted with -O-.

Specifically, there can be mentioned: methylene, ethylidene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9- _diyl , decane-1,10-diyl, undecane-1,11-diyl and dodecane-1,12-diyl; _-CH2 - _CH2 -O- _CH2 -CH2-, -CH2 _{- CH2-} O-CH2- _CH2 -O _{- CH2} - _CH2- and _-CH2 - _CH2 -O-CH2-CH2-O _{- CH2 -} CH2-O _{- CH2} - _CH2- , etc.

As B11, -O-, -S-, -CO-O-, and -O-CO- are preferred, and -CO-O- is more preferred.

As B12 and B13, -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -O-C(=O)-O- are preferred, respectively and independently. Among them, -O- or -O-C(=O)-O- is more preferred.

As the polymerizable group represented by P11, in terms of higher polymerization reactivity, especially higher photopolymerization reactivity, it is preferably a free radical polymerizable group or a cationic polymerizable group. In terms of easy handling and easier production of the liquid crystal compound itself, the polymerizable group is preferably a group represented by the following formula (P-11) to formula (P-15).

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

As specific examples of the groups represented by formula (P-11) to formula (P-15), the groups represented by the following formula (P-16) to formula (P-20) can be cited.

P11 is preferably a group represented by formula (P-14) to formula (P-20), and more preferably a vinyl group, a para-stilbene group, an epoxy group or an oxacyclobutyl group.

The group represented by P11-B11- is preferably an acryloxy group or a methacryloxy group.

As the polymerizable liquid crystal compound (Y), there can be listed compounds represented by formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI).

P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-B16-E12-B17-P12 (I)

P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-F11 (II)

P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-E12-B17-P12 (III)

P11-B11-E11-B12-A11-B13-A12-B14-A13-F11 (IV)

P11-B11-E11-B12-A11-B13-A12-B14-E12-B17-P12 (V)

P11-B11-E11-B12-A11-B13-A12-F11 (VI)

(In the formula, A11, B11~B13 and P11 have the same meanings as above, A12~A14 have the same meanings as A11 independently, B14~B16 have the same meanings as B12 independently, B17 has the same meaning as B11, E12 has the same meaning as E11, and P12 has the same meaning as P11.

F11 represents a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxyl group, a hydroxymethyl group, a formyl group, a sulfo group (-SO ₃ H), a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or a halogen atom; the -CH ₂ - group constituting the alkyl group and the alkoxy group may be substituted with -O-)

Specific examples of polymerizable liquid crystal compounds (Y) include: compounds having polymerizable groups among the compounds described in "3.8.6 Network structure (completely cross-linked type)" and "6.5.1 Liquid crystal material b. Polymerizable nematic liquid crystal material" of Liquid Crystal Handbook (edited by Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000), and polymerizable liquid crystals described in Japanese Patent Publication No. 2010-31223, Japanese Patent Publication No. 2010-270108, Japanese Patent Publication No. 2011-6360, and Japanese Patent Publication No. 2011-207765.

As specific examples of polymerizable liquid crystal compounds (Y), there can be listed compounds represented by the following formulas (I-1) to (I-4), (II-1) to (II-4), (III-1) to (III-26), (IV-1) to (IV-26), (V-1) to (V-2) and (VI-1) to (VI-6). In the following formulas, k1 and k2 independently represent integers of 2 to 12. Such polymerizable liquid crystal compounds (Y) are preferred in terms of ease of synthesis or ease of acquisition.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and further preferably 90 to 95 parts by mass, relative to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. If the content of the polymerizable liquid crystal compound is within the above range, it is more advantageous from the perspective of the alignment of the obtained liquid crystal cured film. Furthermore, in the present invention, the so-called solid content of the polymerizable liquid crystal composition refers to all components from the polymerizable liquid crystal composition excluding volatile components such as organic solvents. In addition, when the polymerizable liquid crystal composition contains more than two polymerizable liquid crystal compounds, it is preferred that the total content of all polymerizable liquid crystal compounds contained in the polymerizable liquid crystal composition is within the above range.

The polymerizable liquid crystal composition used in the formation of the vertical alignment liquid crystal cured film may contain additives such as solvents, polymerization initiators, antioxidants, and photosensitizers in addition to the vertical alignment promoter and polymerizable liquid crystal compound. These components may be used alone or in combination of two or more.

Since the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film is usually coated on a substrate or the like in a state of being dissolved in a solvent, it is preferably to contain a solvent. As the solvent, it is preferably a solvent that can dissolve the polymerizable liquid crystal compound, and it is preferably a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound. As the solvent, for example, alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl Ketone solvents such as methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; aliphatic hydrocarbon solvents such as ethyl cyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone, etc. These solvents can be used alone or in combination of two or more. Among them, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents and aromatic hydrocarbon solvents are preferred.

The content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by weight, and more preferably 70 to 95 parts by weight, relative to 100 parts by weight of the polymerizable liquid crystal composition. Therefore, the solid content in 100 parts by weight of the polymerizable liquid crystal composition is preferably 2 to 50 parts by weight. If the solid content is less than 50 parts by weight, the viscosity of the polymerizable liquid crystal composition decreases, so the thickness of the film becomes roughly uniform and is less likely to be uneven. The above solid content can be appropriately determined by considering the thickness of the liquid crystal cured film to be manufactured.

A polymerization initiator is a compound that can generate reactive species with the help of heat or light to start the polymerization reaction of a polymerizable liquid crystal compound. Reactive species include free radicals, cations, anions, and other active species. Among them, from the perspective of easy control of the reaction, a photopolymerization initiator that generates free radicals by light irradiation is preferred.

化合物、錪鹽及鋶鹽。具體而言，可列舉：Irgacure(註冊商標)907、Irgacure 184、Irgacure 651、Irgacure 819、Irgacure 250、Irgacure 369、Irgacure 379、Irgacure 127、Irgacure 2959、Irgacure 754、Irgacure 379EG(以上、BASF Japan股份有限公司製造)、Seikuol BZ、Seikuol Z、Seikuol BEE(以上、精工化學股份有限公司製造)、kayacure BP100(日本化藥股份有限公司製造)、kayacure UVI-6992(陶氏化學公司製造)、Adeka Optomer SP-152、Adeka Optomer SP-170、Adeka Optomer N-1717、Adeka Optomer N-1919、Adekaarc Luz NCI-831、Adekaarc Luz NCI-930(以上、ADEKA股份有限公司製造)、TAZ-A、TAZ-PP(以上、Nihon SiberHegner公司製造)及TAZ-104(三和化學公司製造)。 Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzoyl ketone compounds, α-hydroxy ketone compounds, α-amino ketone compounds, oxime compounds, tris(II) compounds, and the like.

compounds, iodine salts and cobalt salts. 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 (all manufactured by BASF Japan Co., Ltd.), Seikuol BZ, Seikuol Z, Seikuol BEE (all manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow Chemical Company), Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer N-1919, Adekaarc Luz NCI-831, Adekaarc Luz NCI-930 (all manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (all manufactured by Nihon SiberHegner Co., Ltd.) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.).

The photopolymerization initiator can fully utilize the energy emitted by the light source and has excellent productivity, so the maximum absorption wavelength is preferably 300nm~400nm, and more preferably 300nm~380nm. Among them, α-acetophenone-based polymerization initiators and oxime-based photopolymerization initiators are preferred.

Examples of the α-acetophenone compound include 2-methyl-2-morpholinyl-1-(4-methylthiosulfonylphenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutane-1-one, and 2-dimethylamino-1-(4-morpholinylphenyl)-2-(4-methylphenylmethyl)butane-1-one. More preferred examples include 2-methyl-2-morpholinyl-1-(4-methylthiosulfonylphenyl)propane-1-one and 2-dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutane-1-one. Commercially available products of α-acetophenone compounds include Irgacure 369, 379EG, 907 (all manufactured by BASF Japan Co., Ltd.) and Seikuol BEE (manufactured by Seiko Chemical Co., Ltd.).

化合物或咔唑化合物，就感度之觀點而言，更佳為包含肟酯結構之咔唑化合物。作為肟系光聚合起始劑，可列舉：1,2-辛二酮,1-[4-(苯硫基)-2-(O-苯甲醯基肟)]、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-1-(O-乙醯肟)等。作為肟酯系光聚合起始劑之市售品，可列舉：Irgacure OXE-01、 Irgacure OXE-02、Irgacure OXE-03(以上、BASF Japan股份有限公司製造)、Adeka Optomer N-1919、Adekaarc Luz NCI-831(以上、ADEKA股份有限公司製造)等。 Oxime-based photopolymerization initiators generate free radicals such as phenyl radicals or methyl radicals by irradiation with light. The free radicals are used to appropriately polymerize the polymerizable liquid crystal compound, and the oxime-based photopolymerization initiator that generates methyl radicals is preferred in terms of higher polymerization reaction initiation efficiency. In addition, from the perspective of more efficient polymerization, it is preferred to use a photopolymerization initiator that can efficiently utilize ultraviolet rays with a wavelength of more than 350 nm. As a photopolymerization initiator that can efficiently utilize ultraviolet rays with a wavelength of more than 350 nm, it is preferred to include a three-mercapto-oxime structure.

Compounds or carbazole compounds, from the viewpoint of sensitivity, are more preferably carbazole compounds containing an oxime ester structure. Examples of oxime-based photopolymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)], acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), etc. Examples of commercially available oxime-ester-based photopolymerization initiators include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (all manufactured by BASF Japan Co., Ltd.), Adeka Optomer N-1919, Adekaarc Luz NCI-831 (all manufactured by ADEKA Co., Ltd.), etc.

The content of the photopolymerization initiator is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. If it is within the above range, the reaction of the polymerizable group is fully carried out, and it is not easy to disrupt the alignment of the polymerizable liquid crystal compound.

By preparing an antioxidant, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. As an antioxidant, it can be a primary antioxidant selected from phenolic antioxidants, amine antioxidants, quinone antioxidants, and nitroso antioxidants, and it can also be a secondary antioxidant selected from phosphorus antioxidants and sulfur antioxidants. In order to polymerize the polymerizable liquid crystal compound without disrupting the orientation of the polymerizable liquid crystal compound, the content of the antioxidant is usually 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and further preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. Antioxidants can be used alone or in combination of two or more.

酮、9-氧硫

等

酮類；蒽及具有烷基醚等取代基之蒽類；啡噻

；紅螢烯。光敏劑可單獨使用或組合兩種以上而使用。關於光敏劑之含量，相對於聚合性液晶化合物100質量份，通常為0.01~10質量份，較佳為0.05~5質量份，進而較佳為0.1~3質量份。 In addition, by using a photosensitizer, the photopolymerization initiator can be made highly sensitive. Examples of photosensitizers include:

Ketone, 9-oxosulfur

wait

Ketones; anthracene and anthracene with alkyl ether substituents; phenanthrene

; Rubrene. The photosensitizer may be used alone or in combination of two or more. The content of the photosensitizer is generally 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and further preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound.

The polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film can be obtained by stirring the components that function as a leveling agent or a vertical alignment promoter and the polymerizable liquid crystal compound, and other components such as solvents or photopolymerization initiators at a specific temperature.

In the present invention, the vertically aligned liquid crystal cured film is preferably aligned with a higher degree of order along the vertical direction of the liquid crystal cured film. In the vertically aligned liquid crystal cured film, by making the polymerizable liquid crystal compound have a higher degree of order and aligning, when the laminate including the vertically aligned liquid crystal cured film is assembled into an organic EL display device, there is a tendency to have an excellent effect of suppressing the oblique reflection color phase change during black display. As an indicator of the higher alignment state of the polymerizable liquid crystal compound in the vertically aligned liquid crystal cured film and the degree of the oblique optical compensation effect during black display, the vertically aligned liquid crystal cured film preferably satisfies the following formula (7).

-150nm≦RthC(550)≦-30nm (7)

In formula (7), RthC(550) represents the phase difference value in the thickness direction of the vertical alignment liquid crystal cured film at a wavelength of 550nm. From the perspective of further improving the oblique reflection hue during black display, the phase difference value RthC(550) in the thickness direction of the vertical alignment liquid crystal cured film is preferably greater than -130nm, more preferably greater than -100nm, particularly preferably greater than -90nm, and more preferably less than -40nm, and further preferably less than -50nm.

Furthermore, in one embodiment of the present invention, the vertically aligned liquid crystal cured film satisfies the following formula (8).

RthC(450)/RthC(550)≦1.0 (8)

[In formula (8), RthC(λ) represents the phase difference value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of λ nm]

By satisfying the above formula (8), the reduction of the ellipticity can be suppressed on the short wavelength side in the laminate including the vertical alignment liquid crystal cured film, and the oblique reflection hue during black display can be improved. The value of RthC(450)/RthC(550) in the vertical alignment liquid crystal cured film is preferably 0.95 or less, more preferably 0.92 or less, and particularly preferably 0.9 or less, and more preferably 0.7 or more, more preferably 0.75 or more, and further preferably 0.8 or more.

The phase difference value RthC(λ) in the thickness direction of the vertical alignment liquid crystal cured film can be adjusted by the thickness dC of the vertical alignment liquid crystal cured film. The in-plane phase difference value is determined by the following formula: RthC(λ)=((nxC(λ)+nyC(λ))/2-nzC(λ))×dC

(Here, nxC(λ) represents the in-plane principal refractive index of the vertically aligned liquid crystal cured film at a wavelength of λ nm, nyC(λ) represents the refractive index in the direction orthogonal to nxC(λ) at a wavelength of λ nm, nzC(λ) represents the refractive index in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of λ nm, and when nxC(λ)=nyC(λ), nxC(λ) can be set to the refractive index in any direction in the film plane, and dC represents the film thickness of the vertically aligned liquid crystal cured film). Therefore, in order to obtain the required phase difference value RthC(λ) in the film thickness direction, it is only necessary to adjust the 3D refractive index and the film thickness dC. Furthermore, the 3D refractive index depends on the molecular structure and alignment state of the above-mentioned polymerizable liquid crystal compound.

As the substrate constituting the laminate of the present invention, a glass substrate or a film substrate can be cited. From the viewpoint of processability, a resin film substrate is preferred. As the resin constituting the film substrate, for example, polyolefins such as polyethylene, polypropylene, and norbornene polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate; polyacrylate; cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; plastics such as polyphenylene sulfide and polyphenylene ether can be cited. This type of resin can be formed into a substrate by known methods such as solvent casting and melt extrusion. The substrate surface can also be subjected to mold release treatment such as silicone treatment, corona treatment, plasma treatment, etc.

As the substrate, a commercially available product may be used. Examples of commercially available cellulose ester substrates include: cellulose ester substrates manufactured by Fujitac Film Co., Ltd., such as Fujitac Film; cellulose ester substrates manufactured by Konica Minolta Opto Co., Ltd., such as "KC8UX2M", "KC8UY", and "KC4UY", etc. Examples of commercially available cyclic olefin resins include: "Topas (registered trademark)" and the like, cyclic olefin resins manufactured by Ticona (Germany); "Arton (registered trademark)" and the like, cyclic olefin resins manufactured by JSR Co., Ltd.; "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)" and the like, cyclic olefin resins manufactured by Zeon Co., Ltd.; and "Apel (registered trademark)" and the like, cyclic olefin resins manufactured by Mitsui Chemicals Co., Ltd. A commercially available cyclic olefin resin substrate may also be used. Examples of commercially available cyclic olefin resin substrates include: "S-SINA (registered trademark)" and "SCA40 (registered trademark)" manufactured by Sekisui Chemical Industries, Ltd.; "Zeonor Film (registered trademark)" manufactured by Optronics Co., Ltd.; and "Arton Film (registered trademark)" manufactured by JSR Co., Ltd.

In the present invention, the substrate may also be something that can be finally peeled off from the laminate of the present invention.

From the perspectives of thinning the laminate, ease of substrate peeling, and substrate handling, the thickness of the substrate is usually 5~300μm, preferably 10~150μm.

The laminate of the present invention may also include layers other than the substrate and the vertical alignment liquid crystal cured film within the scope that will not affect the effect of the present invention. Such other layers include, for example, a curing resin layer, a hard coating layer, an adhesive layer, a base coating layer, etc., which are intended to improve or enhance the mechanical strength of the horizontal alignment phase difference film (horizontally aligned liquid crystal cured film), the horizontal alignment film, and the liquid crystal cured film.

In the present invention, a vertically aligned liquid crystal cured film that satisfies at least one of formulas (1) and (2) and satisfies at least one of formulas (3), (4), (5) and (6) can obtain a vertically aligned liquid crystal cured film without a vertically aligned film and in which the polymerizable liquid crystal compound is aligned in the vertical direction with higher precision. Therefore, in the present invention, a polymerizable liquid crystal composition that can form a vertically aligned liquid crystal cured film that satisfies at least one of the above formulas (1) and (2) and satisfies at least one of formulas (3), (4), (5) and (6) is also an object.

As such a polymerizable liquid crystal composition, there can be listed a polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound, a leveling agent, and at least one selected from the group consisting of an ionic compound containing non-metal atoms and a non-ionic silane compound. Preferably, it is a polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound, a leveling agent, an ionic compound containing non-metal atoms, and a non-ionic silane compound. As the polymerizable liquid crystal compound, it can be any one of a polymerizable liquid crystal compound with reverse wavelength dispersion and a polymerizable liquid crystal compound with positive wavelength dispersion. As the polymerizable liquid crystal compound, the leveling agent, the ionic compound containing non-metal atoms, and the non-ionic silane compound, the same ones as those exemplified above as those that can be included in the vertically aligned liquid crystal cured film constituting the laminate of the present invention can be used. Furthermore, the polymerizable liquid crystal composition may further include additives such as solvents, polymerization initiators, antioxidants, and photosensitizers. As these components, the same ones as those exemplified above as those that can be included in the vertically aligned liquid crystal cured film constituting the laminate of the present invention may be used.

In one embodiment of the present invention, the polymerizable liquid crystal composition of the present invention comprises a polymerizable liquid crystal compound having an absorbance of 0.10 or less at a wavelength of 350 nm, a leveling agent, and at least one selected from the group consisting of an ionic compound containing non-metal atoms and a non-ionic silane compound. In addition, in one embodiment of the present invention, the polymerizable liquid crystal composition of the present invention comprises a polymerizable liquid crystal compound having an absorbance of 0.10 or less at a wavelength of 350 nm, a leveling agent, an ionic compound containing non-metal atoms, and a non-ionic silane compound. The polymerizable liquid crystal compound having an absorbance of 0.10 or less at a wavelength of 350 nm in each of the above embodiments is preferably a polymerizable liquid crystal compound having a structure represented by the above formula (Y).

[Manufacturing method of laminated body]

The laminate of the present invention can be manufactured, for example, by a method comprising the following steps: a step of coating a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film containing a polymerizable liquid crystal compound on a substrate to obtain a coating; a step of drying the coating to form a dry coating; and a step of irradiating the dry coating with active energy rays to form a vertically aligned liquid crystal cured film.

The formation of the coating film of the polymerizable liquid crystal composition can be carried out, for example, by coating the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film on a substrate or on other layers such as a cured resin layer disposed on the substrate that does not have a vertically aligned restricting force.

As methods for applying the polymerizable liquid crystal composition on a substrate, there are known methods such as spin coating, extrusion coating, gravure coating, die coating, rod coating, smear coating, and printing such as flexographic coating.

Then, the solvent is removed by drying, etc., thereby forming a dry coating. As drying methods, natural drying, ventilation drying, heating drying, and reduced pressure drying can be listed. At this time, by heating the coating obtained from the polymerizable liquid crystal composition, the solvent can be dried and removed from the coating, and the polymerizable liquid crystal compound can be aligned in a direction perpendicular to the coating plane. The heating temperature of the coating can be appropriately determined in consideration of the polymerizable liquid crystal compound used and the material of the substrate forming the coating. In order to make the polymerizable liquid crystal compound undergo phase transition to the liquid crystal phase state, it is usually necessary to be a temperature above the liquid crystal phase transition temperature. In order to remove the solvent contained in the polymerizable liquid crystal composition and make the polymerizable liquid crystal compound into a vertical alignment state, for example, the temperature can be heated to a temperature above the liquid crystal phase transition temperature (smectic phase transition temperature or nematic phase transition temperature) of the polymerizable liquid crystal compound contained in the above polymerizable liquid crystal composition.

Furthermore, the liquid crystal phase transition temperature can be measured, for example, using a polarizing microscope equipped with a temperature control stage, or a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), etc. Furthermore, when two or more polymerizable liquid crystal compounds are combined and used as polymerizable liquid crystal compounds, the above phase transition temperature refers to a mixture of polymerizable liquid crystal compounds obtained by mixing all polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition in the same ratio as the composition in the polymerizable liquid crystal composition, and the temperature is measured in the same manner as when one polymerizable liquid crystal compound is used. Furthermore, it is generally known that the liquid crystal phase transition temperature of the polymerizable liquid crystal compound in the above polymerizable liquid crystal composition is also lower than the liquid crystal phase transition temperature of the polymerizable liquid crystal compound as a monomer.

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

Removal of solvent from the coating can be performed simultaneously with heating to a temperature above the liquid crystal phase transition temperature of the polymerizable liquid crystal compound, or can be performed separately. From the perspective of improving productivity, it is preferably performed simultaneously. Before heating to a temperature above the liquid crystal phase transition temperature of the polymerizable liquid crystal compound, a pre-drying step can be provided, which is used to appropriately remove the solvent in the coating under the condition that the polymerizable liquid crystal compound contained in the coating obtained from the polymerizable liquid crystal composition does not undergo polymerization. As drying methods in the pre-drying step, natural drying, ventilation drying, heating drying, and reduced pressure drying can be listed. The drying temperature (heating temperature) in the drying step can be appropriately determined according to the type of polymerizable liquid crystal compound used, the type of solvent or its boiling point and its amount, etc.

Then, in the obtained dry coating, the vertical alignment state of the polymerizable liquid crystal compound is maintained unchanged, and the polymerizable liquid crystal compound is polymerized to form a vertical alignment liquid crystal cured film. As the polymerization method, thermal polymerization or photopolymerization can be listed. From the perspective of easy control of the polymerization reaction, photopolymerization is preferred. In the photopolymerization, the light irradiated to the dry coating is appropriately selected according to the type of polymerization initiator contained in the dry coating, the type of polymerizable liquid crystal compound (especially the type of polymerizable group possessed by the polymerizable liquid crystal compound) and its amount. As a specific example, one or more lights selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α rays, β rays and γ rays or active electron beams can be listed. Among them, ultraviolet light is preferred in terms of easy control of the progress of the polymerization reaction or in terms of being widely used as a photopolymerization device in the field. It is preferred to use ultraviolet light to pre-select the type of polymerizable liquid crystal compound or polymerization initiator contained in the polymerizable liquid crystal composition in a manner that allows photopolymerization. In addition, during polymerization, an appropriate cooling method can be used to control the polymerization temperature by cooling the dried coating while irradiating the coating with light. By adopting such a cooling method, if the polymerization of the polymerizable liquid crystal compound is carried out at a lower temperature, a vertically aligned liquid crystal cured film can be properly formed even if a substrate with relatively low heat resistance is used. In addition, the polymerization reaction can be promoted by increasing the polymerization temperature within a range that does not cause adverse conditions caused by heat during light irradiation (such as deformation caused by heat of the substrate). During photopolymerization, a patterned cured film can also be obtained by masking or developing.

As the light source of the above-mentioned active energy line, there can be listed: low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, halogen lamp, carbon arc lamp, tungsten lamp, gallium lamp, excimer laser, LED light source emitting light in the wavelength range of 380~440nm, chemical lamp, black light lamp, microwave-excited mercury lamp, metal halide lamp, etc.

The intensity of ultraviolet irradiation is usually 10~3,000mW/cm ² . The intensity of ultraviolet irradiation is preferably within the wavelength range that is effective for activating the photopolymerization initiator. The 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, and further preferably 0.1 second to 1 minute. If the ultraviolet irradiation intensity is used once or multiple times, the cumulative light amount is 10~3,000mJ/cm ² , preferably 50~2,000mJ/cm ² , and more preferably 100~1,000mJ/cm ² .

The thickness of the vertical alignment liquid crystal cured film can be appropriately selected according to the display device to which it is applied, preferably 0.3μm or more and 5.0μm or less, more preferably 3.0μm or less, and further preferably 2.0μm or less.

[Horizontal alignment phase difference film]

The horizontal alignment phase difference film that can constitute the multilayer body of the present invention refers to a phase difference film that is aligned in a horizontal direction relative to the in-plane direction of the vertical alignment liquid crystal cured film, for example, it can be a stretched film or the following cured product (hereinafter, also referred to as "horizontally aligned liquid crystal cured film"), etc. The cured product is a cured product of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound, and the polymerizable liquid crystal compound is cured in a state of being aligned in a horizontal direction relative to the plane of the phase difference film.

In the present invention, the horizontally aligned phase difference film preferably satisfies the following formula (11).

ReA(450)/ReA(550)≦1.0 (11)

[In formula (11), ReA(λ) represents the in-plane phase difference value of the horizontal alignment phase difference film at a wavelength of λ nm, which is ReA(λ)=(nxA(λ)-nyA(λ))×dA (where nxA(λ) represents the principal refractive index at a wavelength of λ nm in the plane of the horizontal alignment phase difference film, nyA(λ) represents the refractive index at a wavelength of λ nm in the direction orthogonal to the direction of nxA in the same plane as nxA, and dA represents the film thickness of the horizontal alignment phase difference film)]

When the horizontally aligned phase difference film satisfies formula (11), the horizontally aligned phase difference film shows the so-called reverse wavelength dispersion property that the in-plane phase difference value under short wavelength becomes smaller than the in-plane phase difference value under long wavelength. By combining such a horizontally aligned phase difference film with the vertically aligned liquid crystal curing film, a laminate having excellent effect of improving the front and oblique reflection hue during black display when incorporated into an organic EL display device can be obtained. Due to the improvement of the reverse wavelength dispersion property, the effect of improving the reflection hue in the front direction of the horizontally aligned phase difference film can be further improved, so ReA(450)/ReA(550) is preferably 0.70 or more, more preferably 0.78 or more, and preferably 0.95 or less, more preferably 0.92 or less.

The above-mentioned in-plane phase difference value can be adjusted by the thickness dA of the horizontally aligned phase difference film. The in-plane phase difference value is determined by the above-mentioned formula ReA(λ)=(nxA(λ)-nyA(λ))×dA. Therefore, in order to obtain the required in-plane phase difference value (ReA(λ): the in-plane phase difference value of the horizontally aligned phase difference film at wavelength λ(nm)), it is only necessary to adjust the 3D refractive index and the film thickness dA.

Furthermore, the horizontally aligned phase difference film preferably satisfies the following formula (12).

120nm≦ReA(550)≦170nm (12)

[In formula (12), ReA(λ) has the same meaning as above]

If the in-plane phase difference ReA(550) of the horizontally aligned phase difference film is within the range of formula (12), the effect of improving the front reflection hue during black display (the effect of suppressing coloration) becomes significant when the laminate (elliptical polarizing plate) including the horizontally aligned phase difference film is applied to an organic EL display device. The further preferred range of the in-plane phase difference value is 130nm≦ReA(550)≦150nm.

In terms of being able to easily control the phase difference required for the phase difference film and being able to be thinned, the horizontal alignment phase difference film is preferably a horizontal alignment liquid crystal cured film. As a polymerizable liquid crystal compound for forming a horizontal alignment liquid crystal cured film, a polymerizable liquid crystal compound previously known in the field of phase difference films can be used. Specifically, the compounds represented by formula (X) and/or (Y) exemplified as polymerizable liquid crystal compounds that can be used in the formation of vertical alignment liquid crystal cured films can be used, among which a polymerizable liquid crystal compound showing so-called reverse wavelength dispersion is preferred, for example, the compound represented by the above formula (X) can be appropriately used. In the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film, the polymerizable liquid crystal compound can be used alone or in combination of two or more.

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

The polymerizable liquid crystal composition used in the formation of the horizontal alignment liquid crystal cured film may further include additives such as solvents, photopolymerization initiators, leveling agents, antioxidants, and photosensitizers in addition to polymerizable liquid crystal compounds. As these components, the same ones as those exemplified above as components that can be used in the vertical alignment liquid crystal cured film can be listed, and only one type can be used, or two or more types can be used in combination.

The polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film can be obtained by stirring a polymerizable liquid crystal compound and components other than the polymerizable liquid crystal compound such as a solvent or a photopolymerization initiator at a specific temperature.

The horizontal alignment liquid crystal cured film can be manufactured, for example, by a method comprising the following steps: a step of coating a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film on a substrate or a horizontal alignment film to obtain a coating; a step of drying the coating to form a dry coating; and a step of irradiating the dry coating with active energy rays to form a horizontal alignment liquid crystal cured film.

The formation of the coating film of the polymerizable liquid crystal composition can be performed, for example, by coating the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film on a substrate or a horizontal alignment film as described below. Here, as the substrate that can be used, the same as the substrate that can be used in the manufacture of the vertical alignment liquid crystal cured film and is exemplified above can be used.

Then, the solvent is removed by drying, etc., thereby forming a dry coating. As drying methods, natural drying, ventilation drying, heating drying, and reduced pressure drying methods can be listed. In terms of productivity, heating drying is preferred, and the heating temperature in this case is preferably capable of removing the solvent and is above the phase transition temperature of the polymerizable liquid crystal compound. The order or conditions in this step can be listed as the same as those that can be adopted in the method for manufacturing a vertically aligned liquid crystal curing film.

By irradiating the obtained dried coating with active energy rays (more specifically, ultraviolet rays, etc.), the polymerizable liquid crystal compound is kept aligned in a horizontal direction relative to the coating plane, and the polymerizable liquid crystal compound is polymerized to form a horizontally aligned liquid crystal cured film. As a polymerization method, the same method as that used in the method for manufacturing a vertically aligned liquid crystal cured film can be cited.

The thickness of the horizontal alignment liquid crystal curing film can be appropriately selected according to the display device used, preferably 0.2~5μm, more preferably 0.2~4μm, and further preferably 0.2~3μm.

By forming a coating of a polymerizable liquid crystal compound on a horizontal alignment film, the alignment of the polymerizable liquid crystal compound in the horizontal direction can be further improved. For example, when a horizontal alignment film is formed on a vertical alignment liquid crystal cured film constituting the laminate of the present invention, and a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film is coated thereon to obtain a horizontal alignment liquid crystal cured film, compared with a method in which a horizontal alignment liquid crystal cured film is formed on a substrate or disposed on a horizontal alignment film on the substrate and then attached to a vertical alignment liquid crystal cured film via an adhesive layer, etc., there is also an advantage that the manufacturing steps of the laminate can be simplified. The alignment film can be appropriately selected from materials having a horizontal alignment restricting force that allows the polymerizable liquid crystal compound to align in a horizontal direction relative to the coating plane. The alignment restriction force can be adjusted arbitrarily according to the type of alignment layer, surface state or friction conditions, etc. When formed by photo-aligned polymer, it can be adjusted arbitrarily according to polarized light irradiation conditions, etc.

As an alignment film, it is preferred to have solvent resistance that does not dissolve due to coating of the polymerizable liquid crystal composition, and to have heat resistance for removal of the solvent or the heat treatment of the alignment of the polymerizable liquid crystal compound described below. As alignment films, there are: alignment films comprising alignment polymers, optical alignment films and groove alignment films having a concave-convex pattern or multiple grooves on the surface, and stretching films extending in the alignment direction. From the perspective of the accuracy and quality of the alignment angle, optical alignment films are preferred.

唑、聚乙烯亞胺、聚苯乙烯、聚乙烯吡咯啶酮、聚丙烯酸及聚丙烯酸酯類。其中，較佳為聚乙烯醇。配向性聚合物可單獨使用或組合兩種以上而使用。 As the alignment polymer, for example, there can be mentioned: polyamides or gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule and polyamides as their hydrolyzates, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, poly

Polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylates. Among them, polyvinyl alcohol is preferred. The aligning polymer can be used alone or in combination of two or more.

An alignment film containing an alignment polymer can generally be obtained by applying a composition obtained by dissolving an alignment polymer in a solvent (hereinafter, sometimes referred to as an "alignment polymer composition") to a substrate and removing the solvent, or applying the alignment polymer composition to a substrate, removing the solvent, and rubbing (rubbing method). As the solvent, the same solvents as those exemplified above as solvents that can be used in the polymerizable liquid crystal composition can be listed.

The concentration of the alignment polymer in the alignment polymer composition can be within the range that the alignment polymer material can be completely dissolved in the solvent, preferably 0.1-20% in terms of solid content relative to the solution, and more preferably about 0.1-10%.

As the alignment polymer composition, commercially available alignment film materials can be used directly. Commercially available alignment film materials include: Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.), Optomer (registered trademark, manufactured by JSR Corporation), etc.

As a method for applying the alignable polymer composition to the substrate, the same methods as those exemplified as the method for applying the polymerizable liquid crystal composition to the substrate can be cited.

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

In order to impart an alignment restriction force to the alignment film, a friction treatment (rubbing method) may be performed as needed. As a method of imparting an alignment restriction force by the friction method, there can be cited a method of bringing an alignment polymer film formed on the surface of a substrate by applying an alignment polymer composition to a substrate and annealing it into contact with a friction roller that is wound around a rubbing cloth and rotates. During the friction treatment, if masking is performed, multiple regions (patterns) with different alignment directions can also be formed on the alignment film.

The photo-alignment film can be generally obtained by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter, also referred to as a "photo-alignment film forming composition") to a substrate, and irradiating the substrate with polarized light (preferably polarized UV) after removing the solvent. The photo-alignment film is also advantageous in that the direction of the alignment restraining force can be arbitrarily controlled by selecting the polarization direction of the polarized light irradiated.

The so-called photoreactive group refers to a group that generates liquid crystal alignment ability by light irradiation. Specifically, it can be listed as a group that participates in the photoreaction that is the origin of the liquid crystal alignment ability, such as the alignment induction or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction of the molecules generated by light irradiation. Among them, in terms of excellent alignment, the group that participates in dimerization reaction or photocrosslinking reaction is preferred. As the photoreactive group, it is preferred to have an unsaturated bond, especially a double bond, and it is particularly preferred to have at least one selected from the group consisting of a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond (N=N bond), and a carbon-oxygen double bond (C=O bond).

Examples of photoreactive groups having a C=C bond include vinyl, polyene, stilbene, styrylpyridyl, stilbazolium, chalcone, and cinnamyl groups. Examples of photoreactive groups having a C=N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. Examples of photoreactive groups having an N=N bond include azophenyl, azonaphthyl, aromatic heterocyclic azo, bisazo, formazan, and groups having an oxide azobenzene structure. Examples of photoreactive groups having a C=O bond include benzophenone, coumarin, anthraquinone, and cis-butylenediimide groups. These groups may have substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonic acid, halogenated alkyl, etc.

Among them, the photoreactive groups that participate in the photodimerization reaction are preferably cinnamyl and chalcone groups, which are relatively less polarized light irradiation required for photo-alignment and have excellent thermal stability or stability over time. As a polymer having a photoreactive group, it is particularly preferred that the terminal of the polymer side chain has a cinnamyl group such as a cinnamic acid structure.

By applying the photo-alignment film forming composition on a substrate, a photo-alignment inducing layer can be formed on the substrate. As the solvent contained in the composition, the same solvents as those exemplified above as solvents that can be used in the polymerizable liquid crystal composition can be listed, and can be appropriately selected according to the solubility of the polymer or monomer having a photoreactive group.

The content of the polymer or monomer having a photoreactive group in the photo-alignment film-forming composition can be appropriately adjusted according to the type of polymer or monomer or the thickness of the target photo-alignment film, preferably at least 0.2% by mass, more preferably in the range of 0.3-10% by mass, relative to the mass of the photo-alignment film-forming composition. In the range where the properties of the photo-alignment film are not significantly damaged, the photo-alignment film-forming composition may also include a polymer material or a photosensitizer such as polyvinyl alcohol or polyimide.

As a method for applying the photo-alignment film-forming composition to a substrate, the same method as the method for applying the aligning polymer composition to a substrate can be cited. As a method for removing the solvent from the applied photo-alignment film-forming composition, for example, natural drying method, ventilation drying method, heating drying method and reduced pressure drying method can be cited.

When irradiating with polarized light, the composition for forming a photo-alignment film coated on the substrate after removing the solvent can be directly irradiated with polarized light UV from the substrate side, so that the polarized light is transmitted and irradiated. In addition, the polarized light is preferably substantially parallel light. The wavelength of the irradiated polarized light is preferably in the wavelength range where the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) with a wavelength range of 250 to 400 nm is particularly preferred. As the light source used in the polarized light irradiation, there can be listed: xenon lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, KrF, ArF and other ultraviolet lasers, etc., and high pressure mercury lamp, ultra high pressure mercury lamp and metal halide lamp are more preferred. Among them, high pressure mercury lamp, ultra high pressure mercury lamp and metal halide lamp are more preferred because of the high intensity of ultraviolet light with a wavelength of 313nm. Polarized UV can be irradiated by irradiating light from the above light sources through an appropriate polarizing element. As the polarizing element, a polarizing filter, a polarizing prism such as Glenn-Thompson, Glenn-Taylor, or a wire-grid type polarizing element can be used.

Furthermore, if shielding is performed during rubbing or polarized light irradiation, multiple regions (patterns) with different liquid crystal alignment directions can also be formed.

A groove alignment film is a film with a concave-convex pattern or multiple grooves on the film surface. When a polymerizable liquid crystal compound is applied to a film having multiple straight grooves arranged at equal intervals, the liquid crystal molecules are aligned along the direction of the grooves.

As methods for obtaining a groove alignment film, there are the following methods: a method of exposing a photosensitive polyimide film surface through an exposure mask having narrow slits in a pattern shape, and then developing and rinsing to form a concave-convex pattern; a method of forming a layer of a UV curable resin before curing on a plate-shaped master having grooves on the surface, and then curing the formed resin layer after transferring it to a substrate; and a method of pressing a roll-shaped master having a plurality of grooves against a film of a UV curable resin before curing formed on a substrate to form concave-convex, and then curing it.

In the laminate of the present invention, the vertical alignment liquid crystal cured film and the horizontal alignment phase difference film can be laminated, for example, via an adhesive layer or a bonding agent layer. As the adhesive or bonding agent, those previously known in the field can be used. In addition, by coating a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film with a horizontal alignment film interposed therebetween on the vertical alignment liquid crystal cured film constituting the laminate of the present invention, a horizontal alignment phase difference film (horizontal alignment liquid crystal cured film) can be laminated on the vertical alignment liquid crystal cured film.

[Elliptical polarizing plate]

The present invention includes an elliptical polarizing plate comprising the laminate of the present invention and a polarizing film.

Polarizing film is a film with polarizing function, and examples thereof include stretched film adsorbed with a pigment having absorption anisotropy or film coated with a pigment having absorption anisotropy as a polarizing element. Examples of pigments having absorption anisotropy include dichroic pigments.

The film containing a stretched film adsorbed with a dye having absorption anisotropy as a polarizing element is usually prepared by the following method: a step of uniaxially stretching a polyvinyl alcohol resin film; a step of dyeing the polyvinyl alcohol resin film with a dichroic dye to adsorb the dichroic dye; a step of treating the polyvinyl alcohol resin film adsorbed with the dichroic dye with a boric acid aqueous solution; and a step of washing with water after the treatment with the boric acid aqueous solution, wherein at least one side of the polarizing element is sandwiched with a transparent protective film via an adhesive.

Polyvinyl alcohol resins can be obtained by saponifying polyvinyl acetate resins. As polyvinyl acetate resins, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, copolymers of vinyl acetate and other monomers copolymerizable therewith can be used. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

The saponification degree of polyvinyl alcohol resin is usually around 85~100 mol%, preferably above 98 mol%. Polyvinyl alcohol resin can be modified, for example, polyvinyl formal or polyvinyl alcohol acetal modified with aldehydes can also be used. The polymerization degree of polyvinyl alcohol resin is usually around 1,000~10,000, preferably in the range of 1,500~5,000.

The film made of this polyvinyl alcohol resin can be used as a polarizing film. The method of making the polyvinyl alcohol resin film is not particularly limited, and the film can be made by a known method. The film thickness of the polyvinyl alcohol film can be set to about 10~150μm, for example.

The uniaxial stretching of the polyvinyl alcohol resin film can be performed before, during, or after dyeing with a dichroic dye. When the uniaxial stretching is performed after dyeing, the uniaxial stretching can be performed before or during the boric acid treatment. Furthermore, the uniaxial stretching can be performed in these multiple stages. During the uniaxial stretching, the uniaxial stretching can be performed between rollers with different circumferential speeds, or the uniaxial stretching can be performed using a hot roller. Furthermore, the uniaxial stretching can be dry stretching performed in the atmosphere, or wet stretching performed using a solvent to swell the polyvinyl alcohol resin film. The stretching ratio is usually about 3 to 8 times.

The dyeing of the polyvinyl alcohol resin film with a dichroic dye is performed, for example, by immersing the polyvinyl alcohol resin film in an aqueous solution containing a dichroic dye.

As dichroic pigments, specifically, iodine or dichroic organic dyes can be used. As dichroic organic dyes, there can be cited dichroic direct dyes containing bis-azo compounds such as C.I.DIRECT RED 39 and dichroic direct dyes containing trisazo, tetrakis-azo and other compounds. The polyvinyl alcohol resin film is preferably immersed in water before dyeing.

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

On the other hand, when a dichroic organic dye is used as a dichroic pigment, a method of dyeing is usually adopted in which a polyvinyl alcohol-based resin film is immersed in an aqueous solution containing a water-soluble dichroic dye. Regarding the content of the dichroic organic dye in the aqueous solution, it is usually about 1×10 ^-4 ~10 mass parts per 100 mass parts of water, preferably 1×10 ^-3 ~1 mass part, and further preferably 1×10 ^-3 ~1×10 ^-2 mass parts. The aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing auxiliary. The temperature of the dichroic dye aqueous solution used in dyeing is usually about 20~80°C. In addition, the immersion time in the aqueous solution (dyeing time) is usually about 10~1,800 seconds.

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

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

After washing with water, a drying process is performed to obtain a polarizing element. The drying process can be performed using, for example, a hot air dryer or a far infrared heater. The temperature of the drying process is usually around 30~100°C, preferably 50~80°C. The drying process time is usually around 60~600 seconds, preferably 120~600 seconds. Through the drying process, the moisture content of the polarizing element is reduced to a practical level. The moisture content is usually around 5~20% by mass, preferably 8~15% by mass. If the moisture content is lower than 5% by mass, the flexibility of the polarizing element may be lost, and the polarizing element may be damaged or broken after drying. In addition, if the moisture content exceeds 20% by mass, the thermal stability of the polarizing element may deteriorate.

The thickness of the polarizing element obtained by uniaxially stretching the polyvinyl alcohol resin film, dyeing with a dichroic pigment, treating with boric acid, washing with water and drying is preferably 5 to 40 μm.

As a film coated with a pigment having absorption anisotropy, a film obtained by coating a composition containing a dichroic pigment having liquid crystal properties, or a composition containing a dichroic pigment and polymerizable liquid crystal, etc. can be cited. The film preferably has a protective film on one or both sides thereof. As the protective film, the same resin film as the substrate that can be used in the manufacture of a vertically aligned liquid crystal cured film can be cited.

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

As the above-mentioned film coated with a pigment having absorption anisotropy, specifically, there can be cited films described in Japanese Patent Laid-Open No. 2012-33249, etc.

A transparent protective film may be laminated on at least one side of the polarizing element obtained in the above manner, for example, via an adhesive layer. As the transparent protective film, the same transparent film as the resin film exemplified above as a substrate that can be used in the manufacture of a vertically aligned liquid crystal cured film may be used.

The elliptical polarizing plate of the present invention includes the laminate of the present invention, or the laminate obtained by removing the substrate from the laminate of the present invention and the polarizing film. For example, the elliptical polarizing plate of the present invention can be obtained by laminating the laminate of the present invention and the polarizing film through a bonding agent layer. In addition, the elliptical polarizing plate of the present invention can be obtained by laminating the laminate obtained by removing the substrate from the laminate of the present invention and the polarizing film.

In addition, the method for manufacturing an elliptical polarizing plate by peeling off the substrate from the laminate of the present invention and then laminating the laminate peeled off from the substrate, a horizontally aligned phase difference film, and a polarizing film is also one of the inventions of this case.

In one embodiment of the present invention, when the laminate of the present invention includes a horizontally aligned phase difference film and a polarizing film, it is preferred to laminate in such a way that the angle between the retardation axis (optical axis) of the horizontally aligned phase difference film constituting the laminate and the absorption axis of the polarizing film becomes 45±5°.

The elliptical polarizing plate of the present invention may have a structure similar to that of a conventional elliptical polarizing plate, or a polarizing film and a phase difference film. Examples of such a structure include: an adhesive layer (sheet) for attaching the elliptical polarizing plate to an organic EL or other display element, a protective film for protecting the surface of a polarizing film or a liquid crystal curing film from damage or contamination, etc.

The multilayer body and elliptical polarizer of the present invention can be used in various display devices.

The so-called display device is a device having a display element, including a light-emitting element or a light-emitting device as a light source. Examples of display devices include: liquid crystal display devices, organic electroluminescent (EL) display devices, inorganic electroluminescent (EL) display devices, touch panel display devices, electron emission display devices (such as field emission display devices (FED), surface field emission display devices (SED)), electronic paper (display devices using electronic ink or electrophoretic elements, plasma display devices, projection display devices (such as grating valve (GLV) display devices, display devices with digital micromirror devices (DMD)) and piezoelectric ceramic displays. Liquid crystal display devices also include transmissive liquid crystal display devices, semi-transmissive liquid crystal display devices, reflective liquid crystal display devices, etc. Any one of a 2D liquid crystal display device, a direct-view liquid crystal display device, and a projection liquid crystal display device. Such display devices may be display devices that display 2D images, or may be stereoscopic display devices that display 3D images. In particular, the elliptical polarizing plate of the present invention can be suitably used in organic electroluminescent (EL) display devices in terms of high alignment accuracy and excellent optical properties. The multilayer body of the present invention can be suitably used in liquid crystal display devices and touch panel display devices. By using the multilayer body or elliptical polarizing plate of the present invention, a display device that can easily realize thinning of the display device, has excellent optical properties, and can exhibit good image display characteristics can be obtained.

[Implementation example]

The present invention is described in more detail below by way of examples. In addition, "%" and "parts" in the examples refer to mass % and mass parts, respectively, unless otherwise specified.

1. Implementation Example 1 (1) Preparation of polymerizable liquid crystal compounds

A polymerizable liquid crystal compound (X1), a polymerizable liquid crystal compound (X2), and a polymerizable liquid crystal compound (X3) having the following molecular structures were prepared respectively. The polymerizable liquid crystal compound (X1) was prepared according to the method described in Japanese Patent Publication No. 2010-31223. In addition, the polymerizable liquid crystal compound (X2) was prepared according to the method described in Japanese Patent Publication No. 2009-173893. The polymerizable liquid crystal compound (X3) was prepared with reference to Japanese Patent Publication No. 2011-207765.

Polymerizable liquid crystal compound (X1)

1 mg of the polymerizable liquid crystal compound (X1) was dissolved in 50 mL of tetrahydrofuran to obtain a solution. The solution obtained as a sample for measurement was added to a measurement tank with an optical path length of 1 cm, and the sample for measurement was placed in an ultraviolet-visible spectrophotometer ("UV-2450" manufactured by Shimadzu Corporation) to measure the absorption spectrum. The wavelength of maximum absorbance was read from the obtained absorption spectrum, and the maximum absorption wavelength λ _max in the wavelength range of 300 to 400 nm was 350 nm.

The absorbance of the polymerizable liquid crystal compound (X2) at a wavelength of 350nm was measured according to the following method.

First, 1 mg of the polymerizable liquid crystal compound (X1) was dissolved in 50 mL of tetrahydrofuran to obtain a solution. The solution obtained as a test sample was added to a test tank with an optical path length of 1 cm, and the test sample was placed in an ultraviolet-visible spectrophotometer ("UV-2450" manufactured by Shimadzu Corporation) to measure the absorption spectrum. Based on the absorbance measurement at a wavelength of 350 nm of the obtained absorption spectrum, the result was confirmed to be less than 0.05.

A 1 mg/50 mL tetrahydrofuran solution of a polymerizable liquid crystal compound (X3) was prepared. The solution obtained as a test sample was added to a test tank with an optical path length of 1 cm, and the test sample was placed in an ultraviolet-visible spectrophotometer ("UV-2450" manufactured by Shimadzu Corporation) to measure the absorption spectrum. The wavelength of maximum absorbance was read from the obtained absorption spectrum, and the maximum absorption wavelength λ _max in the wavelength range of 300-400 nm was 354 nm.

(2) Preparation of polymerizable liquid crystal composition for forming vertically aligned liquid crystal cured film

A polymerizable liquid crystal compound (X1), a polymerizable liquid crystal compound (X2), and a polymerizable liquid crystal compound (X3) were mixed at a mass ratio of 83:14:3 to obtain a mixture. 1.5 mass parts of a leveling agent "F-556" (manufactured by DIC Corporation), 2.0 mass parts of an ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802, 0.5 mass parts of a silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.), and 4 mass parts of Irgacure OXE-03 (manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator were added to 100 mass parts of the obtained mixture. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80°C for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film.

(3) Manufacturing of vertically aligned liquid crystal curing film

After the COP film (ZF14-50) manufactured by Zeon Co., Ltd. of Japan was subjected to corona treatment, a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film was applied using a rod coater, and after heating at 120°C for 60 seconds, a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.) was used to irradiate the surface coated with the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film with ultraviolet light (cumulative light quantity at a wavelength of 365nm in a nitrogen atmosphere: 500mJ/ ^cm2 ) to form a vertical alignment liquid crystal cured film. The film thickness of the obtained vertical alignment liquid crystal cured film was measured using an elliptical polarimeter (M-220 manufactured by JASCO Corporation) and the result was 1.2μmm.

<Rth measurement of vertically aligned liquid crystal cured film>

The vertical alignment liquid crystal cured film surface of the laminated body including the substrate and the vertical alignment liquid crystal cured film prepared in the above order was subjected to corona treatment, and after being bonded to glass using a 25μm pressure-sensitive adhesive manufactured by LINTEC, the substrate was peeled off. The obtained laminated body including glass, adhesive and vertical alignment liquid crystal cured film was used to change the incident angle of light on the sample for measuring optical properties, and the phase difference value when tilted 40° to the center of the phase axis was measured using KOBRA-WPR manufactured by Oji Testing Instruments Co., Ltd.

The average refractive index at each wavelength was measured using an elliptical polarimeter M-220 manufactured by JASCO Corporation. The film thickness was measured using an Optical NanoGauge film thickness meter C12562-01 manufactured by Hamamatsu Photonics Co., Ltd. The 3D refractive index was calculated based on the above-mentioned front phase difference value, phase difference value when tilted 40° to the center of the phase axis, average refractive index, and film thickness values with reference to Oji Measuring Instrument Technical Data (http://www.oji-keisoku.co.jp/products/kobra/reference.html). Based on the obtained 3D refractive index, the optical properties of each vertically aligned liquid crystal cured film were calculated according to the following formula, and the values of Rth(450), Rth(550), and Rth(450)/Rth(550) were calculated. The results are shown in Table 5.

RthC(λ)=((nxC(λ)+nyC(λ))/2-nzC(λ))×dC

Furthermore, RthC(λ) represents the phase difference value in the thickness direction of the vertical alignment liquid crystal cured film at a wavelength of λ nm. In addition, nxC(λ) represents the in-plane principal refractive index of the vertical alignment liquid crystal cured film at a wavelength of λ nm, nyC(λ) represents the refractive index in the direction orthogonal to nxC(λ) in the plane at a wavelength of λ nm, and nzC(λ) represents the refractive index in the thickness direction of the vertical alignment liquid crystal cured film at a wavelength of λ nm. When nxC(λ)=nyC(λ), nxC(λ) can be set to the refractive index in any direction in the film plane, and dC represents the film thickness of the vertical alignment liquid crystal cured film.

<Orientation evaluation>

The vertically aligned liquid crystal cured film surface of the laminated body including the substrate and the vertically aligned liquid crystal cured film prepared in the above order was bonded to a 5×5cm×0.7mm thick glass via a pressure-sensitive adhesive (25μm) manufactured by LINTEC, and only the substrate was peeled off. The obtained sample was observed at a magnification of 200 times using a polarizing microscope ("BX-51" manufactured by Olympus Co., Ltd.), and the number of alignment defects in the field of view of 480μm×320μm was counted. Here, only the number of alignment defects caused by the sample for measurement was counted, and the number of defects caused by environmental foreign matter other than the sample was excluded and not counted. Based on the observation results using a polarizing microscope, the orientation of the multilayer (vertically aligned liquid crystal cured film) was evaluated based on the following evaluation criteria. If it is ○, it is judged that the orientation is excellent, and if it is △, it is judged that it is a good orientation that does not affect the optical properties. The results are shown in Table 9.

Evaluation criteria: ○ (very good): The number of alignment defects is 0 or more and 5 or less.

△ (good): The number of alignment defects is 6 or more and 20 or less.

× (poor): The number of alignment defects is 21 or more, or there is no alignment at all.

<Analysis of constituent elements>

Under the conditions listed in Table 1 below, XPS (K-Alpha+ manufactured by Thermo Fisher Scientific) was used to analyze the constituent elements of the interface on the side opposite to the substrate of the vertically aligned liquid crystal cured film (interface A on the non-substrate side of the vertically aligned liquid crystal cured film) in the laminate comprising the vertically aligned liquid crystal cured film and the substrate prepared by the above method.

Next, etching was performed using an Ar gas cluster ion beam under the etching conditions listed in Table 1 below from the interface on the side opposite to the substrate of the vertically aligned liquid crystal cured film, and element information was confirmed using XPS to confirm the etching time from the interface on the side opposite to the substrate to the interface on the substrate side, and then the element analysis information at a point 100nm from the interface on the side opposite to the substrate was extracted to confirm the constituent elements in the liquid crystal cured film at a point (midpoint C) 100nm in the thickness direction on the liquid crystal cured film side from the interface on the side opposite to the substrate of the vertically aligned liquid crystal cured film.

Finally, in the laminate including the vertical alignment liquid crystal cured film and the substrate, the vertical alignment liquid crystal cured film side was bonded to a separately prepared TAC film (KC4UY manufactured by Konica Minolta) via a pressure-sensitive adhesive (25μm) manufactured by LINTEC, and after peeling off the substrate COP film (ZF14-50) in the original laminate, the constituent elements of the substrate peeling side of the obtained sample (interface B on the substrate side of the vertical alignment liquid crystal cured film) were analyzed in the same way using XPS. The results are shown in Table 2.

2. Implementation Example 2

The preparation of the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film and the formation of the vertically aligned liquid crystal cured film were changed as described below, and the etching rate during the analysis of the constituent elements was changed to 100 sec × 35 times. In addition, the vertically aligned liquid crystal cured film was manufactured in the same manner as in Example 1, the constituent elements were confirmed, and the optical properties and alignment were evaluated. The results are shown in Tables 3 and 9.

(1) Preparation of polymerizable liquid crystal composition for forming vertically aligned liquid crystal cured film

To 100 parts by mass of the liquid crystal compound (X2), 0.25 parts by mass of a leveling agent "F-556" (manufactured by DIC Corporation), 2.0 parts by mass of an ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802, 0.5 parts by mass of a silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.), and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator were added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. By stirring the mixture at 80°C for 1 hour, a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was obtained.

(2) Production of vertically aligned liquid crystal curing film

After a COP film (ZF14-50) manufactured by Zeon Co., Ltd. of Japan was subjected to a corona treatment, a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film was coated using a rod coater, and after heating at 120°C for 60 seconds, a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.) was used to irradiate ultraviolet rays (cumulative light quantity at a wavelength of 365nm in a nitrogen atmosphere: 500mJ/ ^cm2 ) from the surface coated with the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film while maintaining the heating at 120°C, thereby forming a vertical alignment liquid crystal cured film. The film thickness of the obtained vertical alignment liquid crystal cured film was measured using an elliptical polarimeter (M-220 manufactured by JASCO Corporation), and the result was 0.6 μm.

3. Implementation Example 3

The preparation method of the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed to the following, and the etching rate during the analysis of the constituent elements was changed to 5 sec × 50 times. In addition, a vertically aligned liquid crystal cured film was manufactured in the same manner as in Example 1, the constituent elements were confirmed, and the optical properties and alignment were evaluated. The results are shown in Tables 4 and 9.

(1) Preparation of polymerizable liquid crystal composition for forming vertically aligned liquid crystal cured film

A polymerizable liquid crystal compound (X1) and a polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. To 100 parts by mass of the obtained mixture, 0.25 parts by mass of a leveling agent "F-556" (manufactured by DIC Corporation), 2.0 parts by mass of an ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802, 0.5 parts by mass of a silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.), and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator were added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added in such a way that the solid content concentration became 13%. The mixture was stirred at 80°C for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film.

4. Implementation Example 4

The preparation method of the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed to the following, and the etching rate during the analysis of the constituent elements was changed to 5 sec × 50 times. In addition, a vertically aligned liquid crystal cured film was manufactured in the same manner as in Example 1, the constituent elements were confirmed, and the optical properties and alignment were evaluated. The results are shown in Tables 5 and 9.

(1) Preparation of polymerizable liquid crystal composition for forming vertically aligned liquid crystal cured film

A polymerizable liquid crystal compound (X1) and a polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. To 100 parts by mass of the obtained mixture, 0.25 parts by mass of a leveling agent "F-556" (manufactured by DIC Corporation), 3.0 parts by mass of an ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802, 1.0 parts by mass of a silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.), and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator were added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added in such a manner that the solid content concentration became 13%. The mixture was stirred at 80°C for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film.

5. Implementation Example 5

The preparation method of the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed to the following, and the etching rate during the analysis of the constituent elements was changed to 50 sec × 100 times. In addition, a vertically aligned liquid crystal cured film was manufactured in the same manner as in Example 1, the constituent elements were confirmed, and the optical properties and alignment were evaluated. The results are shown in Tables 6 and 9.

(1) Preparation of polymerizable liquid crystal composition for forming vertically aligned liquid crystal cured film

A polymerizable liquid crystal compound (X1) and a polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. To 100 parts by mass of the obtained mixture, 1.00 parts by mass of a leveling agent "F-556" (manufactured by DIC Corporation), 2.0 parts by mass of an ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802, 0.5 parts by mass of a silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.), and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator were added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added in such a way that the solid content concentration became 13%. The mixture was stirred at 80°C for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film.

6. Implementation Example 6

The preparation method of the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed to the following, and the etching rate during the analysis of the constituent elements was changed to 5 sec × 50 times. In addition, a vertically aligned liquid crystal cured film was manufactured in the same manner as in Example 1, the constituent elements were confirmed, and the optical properties and alignment were evaluated. The results are shown in Tables 7 and 9.

(1) Preparation of polymerizable liquid crystal composition for forming vertically aligned liquid crystal cured film

A polymerizable liquid crystal compound (X1) and a polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. To 100 parts by mass of the obtained mixture, 0.10 parts by mass of a leveling agent "F-556" (manufactured by DIC Corporation), 1.5 parts by mass of an ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802, 0.25 parts by mass of a silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.), and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator were added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added in such a way that the solid content concentration became 13%. The mixture was stirred at 80°C for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film.

7. Comparison Example 1

The preparation of the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed as described below, and the etching rate during the analysis of the constituent elements was changed to 100 sec × 35 times. In addition, a vertically aligned liquid crystal cured film was manufactured in the same manner as Example 1, the constituent elements were confirmed, and the optical properties and alignment were evaluated. The results are shown in Tables 8 and 9.

(1) Preparation of polymerizable liquid crystal composition for forming vertically aligned liquid crystal cured film

0.25 parts by mass of leveling agent "F-556" (manufactured by DIC Corporation) and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator were added to 100 parts by mass of polymerizable liquid crystal compound (X1). Furthermore, N-methyl-2-pyrrolidone (NMP) was added in such a way that the solid content concentration became 13%. The mixture was stirred at 80°C for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film.

According to the present invention, it is confirmed that the orientation of the liquid crystal is excellent in a vertically aligned liquid crystal cured film with a specific element ratio (Examples 1 to 6).

Claims (22)

A laminate comprising a vertically aligned liquid crystal cured film and a substrate, wherein the vertically aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition formed by curing a polymerizable liquid crystal compound in a state of being aligned in a direction vertical to the plane of the liquid crystal cured film, wherein the vertically aligned liquid crystal cured film satisfies at least one of the following formulas (1') and (2'), and satisfies at least one of the following formulas (3'), (4'), (5') and (6'), 30≧F(A)-F(C)≧0.5 (1') 30≧Si(A)-Si(C)≧0.10 (2') 10≧N(B)-N(C)≧0.05 (3') 10≧P(B)-P(C)≧0.05 (4') 30≧F(B)-F(C)≧0.10 (5') 30≧Si(B)-Si(C)≧0.10 (6') [In formulas (1') to (6'), F(A) represents the presence ratio (atom%) of the fluorine element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate, F(B) represents the presence ratio (atom%) of the fluorine element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the substrate side, F(C) represents the presence ratio (atom%) of the fluorine element in the liquid crystal cured film at a point 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate, Si(A) represents the presence ratio (atom%) of the silicon element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate, Si(B) represents the presence ratio (atom%) of the silicon element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the substrate side, Si(C) represents the presence ratio (atom%) of the silicon element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the substrate side, The ratio of silicon in the liquid crystal cured film at the interface on the side opposite to the substrate, at a point 100 nm in the thickness direction of the liquid crystal cured film; N(B) represents the ratio of nitrogen in the liquid crystal cured film at the interface on the substrate side of the vertically aligned liquid crystal cured film; N(C) represents the ratio of nitrogen in the liquid crystal cured film at the interface on the side opposite to the substrate, at a point 100 nm in the thickness direction of the liquid crystal cured film; P(B) represents the ratio of phosphorus in the liquid crystal cured film at the interface on the substrate side of the vertically aligned liquid crystal cured film; P(C) represents the ratio of phosphorus in the liquid crystal cured film at the interface on the side opposite to the substrate, at a point 100 nm in the thickness direction of the liquid crystal cured film. As in claim 1, the laminated body, wherein the vertically aligned liquid crystal curing film exists adjacent to the substrate. For example, the multilayer of claim 1 or 2 satisfies at least one of the above formulas (1') and (2'), satisfies at least one of the above formulas (3') and (4'), and satisfies at least one of the above formulas (5') and (6'). For example, the multilayer of claim 1 or 2 satisfies at least one of the above formulas (1') and (2'), and satisfies at least three of the above formulas (3'), (4'), (5') and (6'). In the multilayer body of claim 1 or 2, the vertically aligned liquid crystal curing film further comprises a leveling agent. As in claim 5, the layered body, wherein the leveling agent contains fluorine or silicon. As in claim 1 or 2, the laminate, wherein the vertically aligned liquid crystal curing film comprises an ionic compound containing non-metallic atoms. The laminate of claim 1 or 2, wherein the vertically aligned liquid crystal curing film comprises an ionic compound containing non-metallic atoms, and the molecular weight of the ionic compound is greater than 100 and less than 10,000. A laminate as claimed in claim 1 or 2, wherein the vertically aligned liquid crystal curing film comprises an ionic compound containing a phosphonium salt or an ammonium salt. As in claim 1 or 2, the laminated body, wherein the vertically aligned liquid crystal curing film comprises a non-ionic silane compound. As in claim 1 or 2, the laminate, wherein the vertically aligned liquid crystal curing film comprises a non-ionic silane compound, and the non-ionic silane compound is a silane coupling agent. As in claim 1 or 2, the laminated body, wherein the vertically aligned liquid crystal curing film comprises a non-ionic silane compound and an ionic compound. In the multilayer body of claim 1 or 2, the thickness of the vertically aligned liquid crystal cured film is greater than 0.3 μm and less than 5.0 μm. A laminate as claimed in claim 1 or 2, wherein the vertically aligned liquid crystal cured film satisfies the following formula (7), -150≦RthC(550)≦-30 (7) [In formula (7), RthC(550) represents the phase difference value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 550nm]. The laminate of claim 1 or 2, wherein the vertically aligned liquid crystal cured film satisfies the following formula (8), RthC(450)/RthC(550)≦1.0 (8) [In formula (8), RthC(450) represents the phase difference value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 450nm, and RthC(550) represents the phase difference value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 550nm]. The multilayer body of claim 1 or 2 further comprises a horizontally aligned phase difference film. As in claim 16, the horizontally aligned phase difference film is a horizontally aligned liquid crystal cured film formed by curing at least one polymerizable liquid crystal compound in a state of being horizontally aligned relative to the in-plane direction of the phase difference film. An elliptical polarizing plate, comprising a laminate as claimed in claim 16 or 17, and a polarizing film. For example, in the elliptical polarizing plate of claim 18, the angle between the phase delay axis of the horizontally aligned phase difference film constituting the laminate and the absorption axis of the polarizing film is 45±5°. An organic EL display device comprising an elliptical polarizing plate as claimed in claim 18 or 19. A method for manufacturing an elliptical polarizing plate, wherein the laminate according to any one of claims 1 to 15 is peeled off from a substrate, and then the laminate peeled off from the substrate, a horizontally aligned phase difference film, and a polarizing film are stacked to manufacture the elliptical polarizing plate. As in the method of claim 21, the angle between the retardation axis of the horizontally aligned phase difference film constituting the laminate of the elliptical polarizer and the absorption axis of the polarizing film is 45±5°.