JP7302974B2 - Laminate, elliptically polarizing plate and polymerizable liquid crystal composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate comprising a vertically aligned liquid crystal cured film and a substrate, an elliptically polarizing plate comprising the laminate, and an organic EL display device. It also relates to a polymerizable liquid crystal composition that can be used to form the laminate.

An elliptically polarizing plate is an optical member in which a polarizing plate and a retardation plate are laminated. is used to prevent A so-called λ/4 plate is generally used as a retardation plate that constitutes the elliptically polarizing plate. As such a retardation plate, a retardation plate composed of a horizontally aligned liquid crystal cured film obtained by polymerizing and curing a polymerizable liquid crystal compound in a state of being aligned in the horizontal direction with respect to the plane of the retardation plate is known. . Further, by incorporating a vertically aligned liquid crystal cured film into an elliptical polarizer provided with a horizontally aligned liquid crystal cured film, oblique hue change during black display when the elliptical polarizer is used in an organic EL display device can be suppressed. Patent Document 1 describes a laminate including a vertically aligned liquid crystal cured film formed on a vertical alignment film and a horizontally aligned liquid crystal cured film formed on a horizontal alignment film. ing.

JP 2015-163935 A

Conventionally, however, a vertical alignment film for vertically aligning a polymerizable liquid crystal compound is generally required to produce a vertically aligned liquid crystal cured film. For this reason, it is necessary to form a vertical alignment film before forming the cured vertically aligned liquid crystal film. There is a problem that a film forming process is required and productivity tends to decrease. On the other hand, in order to improve productivity, a method of forming a vertically aligned liquid crystal cured film without forming a vertical alignment film is desired. If only the step of forming the alignment film is omitted, there is a problem that the alignment of the vertically aligned liquid crystal cured film becomes insufficient.

Therefore, the present invention provides a novel solution to the above problems, that is, it can be formed without a vertical alignment film, and a polymerizable liquid crystal compound is formed in the same manner as the vertically aligned liquid crystal cured film formed on the vertical alignment film. It is an object of the present invention to provide a laminate including a vertically aligned liquid crystal cured film in which is aligned in the vertical direction with high accuracy.

The inventors of the present invention have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention includes the following aspects.
[1] A laminate including a vertically aligned liquid crystal cured film and a substrate,
The vertically aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition cured in a state in which the polymerizable liquid crystal compound is 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 at least one of the following formulas (3), (4), (5) and (6) A laminate that satisfies one.
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 abundance ratio (atom%) of fluorine element in the liquid crystal cured film at the interface on the opposite side of the base material of the vertically aligned liquid crystal cured film,
F (B) represents the abundance ratio (atom%) of the fluorine element in the cured liquid crystal film at the interface of the cured vertically aligned liquid crystal film on the substrate side,
F(C) represents the abundance ratio (atom%) of the fluorine element in the cured liquid crystal film at a point of 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film on the opposite side of the substrate to the cured liquid crystal film side. ,
Si (A) represents the abundance ratio (atom%) of the silicon element in the cured liquid crystal film at the interface on the side opposite to the substrate of the cured vertically aligned liquid crystal film,
Si (B) represents the abundance ratio (atom%) of the silicon element in the liquid crystal cured film at the interface on the substrate side of the vertically aligned liquid crystal cured film,
Si (C) represents the abundance ratio (atom%) of the silicon element in the cured liquid crystal film at a point of 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film on the opposite side of the substrate to the cured liquid crystal film side. ,
N (B) represents the abundance ratio (atom%) of the nitrogen element in the cured liquid crystal film at the interface on the substrate side of the cured vertically aligned liquid crystal film,
N(C) represents the abundance ratio (atom%) of the nitrogen element in the cured liquid crystal film at a point of 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film on the opposite side of the substrate to the cured liquid crystal film side. ,
P (B) represents the abundance ratio (atom%) of the phosphorus element in the liquid crystal cured film at the substrate side interface of the vertically aligned liquid crystal cured film,
P (C) represents the abundance ratio (atom%) of the phosphorus element in the cured liquid crystal film at a point of 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film on the side opposite to the base material to the cured liquid crystal film side. . ]
[2] The laminate according to [1] above, wherein the vertically aligned liquid crystal cured film and the substrate are adjacent to each other.
[3] At least one of the formulas (1) and (2) is satisfied, at least one of the formulas (3) and (4) is satisfied, and the formulas (5) and (6) are satisfied. The laminate according to the above [1] or [2], which satisfies at least one of:
[4] satisfying at least one of the formulas (1) and (2) and at least three of the formulas (3), (4), (5) and (6), The laminate according to any one of [1] to [3].
[5] The laminate according to any one of [1] to [4], wherein the vertically aligned liquid crystal cured film contains a leveling agent.
[6] The laminate according to any one of [1] to [5], wherein the leveling agent contains elemental fluorine or elemental silicon.
[7] The laminate according to any one of [1] to [6], wherein the vertically aligned liquid crystal cured film contains an ionic compound composed of non-metallic atoms.
[8] The vertically aligned liquid crystal cured film according to any one of [1] to [7] above, wherein the cured film contains an ionic compound composed of non-metallic atoms, and the molecular weight of the ionic compound is 100 or more and 10,000 or less. laminate.
[9] The laminate according to any one of [1] to [8], wherein the vertically aligned liquid crystal cured film contains an ionic compound composed of a phosphonium salt or an ammonium salt.
[10] The laminate according to any one of [1] to [9], wherein the vertically aligned liquid crystal cured film contains a nonionic silane compound.
[11] The laminate according to any one of [1] to [10] above, wherein the vertically aligned liquid crystal cured film contains a nonionic silane compound, and the nonionic silane compound is a silane coupling agent.
[12] The laminate according to any one of [1] to [11], wherein the vertically aligned liquid crystal cured film contains a nonionic silane compound and an ionic compound.
[13] The laminate according to any one of [1] to [12], wherein the thickness of the vertically aligned liquid crystal cured film is 0.3 μm or more and 5.0 μm or less.
[14] The laminate according to any one of [1] to [13], wherein the vertically aligned liquid crystal cured film satisfies the following formula (7).
-150≤RthC(550)≤-30 (7)
[In the formula (7), RthC(550) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. ]
[15] The laminate according to any one of [1] to [14], wherein the vertically aligned liquid crystal cured film satisfies the following formula (8).
RthC(450)/RthC(550)≤1.0 (8)
[In the formula (8), RthC (450) represents the thickness direction retardation value of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and RthC (550) is the thickness direction retardation value of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. indicates ]
[16] The laminate according to any one of [1] to [15], further comprising a horizontally oriented retardation film.
[17] The above [16], wherein the horizontally aligned retardation film is a horizontally aligned liquid crystal cured film obtained by curing in a state in which at least one polymerizable liquid crystal compound is aligned horizontally with respect to the in-plane direction of the retardation film. ].
[18] An elliptically polarizing plate comprising the laminate according to [16] or [17] above, and a polarizing film.
[19] The elliptically polarizing plate according to [18] above, wherein the slow axis of the horizontally aligned retardation film constituting the laminate and the absorption axis of the polarizing film form an angle of 45±5°.
[20] An organic EL display comprising the elliptically polarizing plate of [18] or [19].
[21] Polymerization containing at least one selected from the group consisting of a polymerizable liquid crystal compound having an absorbance of 0.10 or less at a wavelength of 350 nm, a leveling agent, and an ionic compound consisting of nonmetallic atoms and a nonionic silane compound liquid crystal composition.
[22] The polymerizable liquid crystal composition according to [21] above, comprising 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 composed of nonmetallic atoms, and a nonionic silane compound. thing.
[23] The polymerization according to [21] or [22] above, wherein the polymerizable liquid crystal compound having an absorbance at a wavelength of 350 nm of 0.10 or less is a polymerizable liquid crystal compound containing a structure represented by formula (Y). liquid crystal composition.
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 is -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ¹⁶ -, -NR ¹⁶ -CO-, -CO-, - represents CS- or a single bond. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
B12 and B13 each independently represent -C≡C-, -CH=CH-, -CH ₂ -CH ₂ -, -O-, -S-, -C(=O)-, -C(=O ) -O-, -O-C(=O)-, -O-C(=O)-O-, -CH=N-, -N=CH-, -N=N-, -C(=O ) -NR ¹⁶ -, -NR ¹⁶ -C(=O)-, -OCH ₂ -, -OCF ₂ -, -CH ₂ O-, -CF ₂ O-, -CH=CH-C(=O)- represents 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 with an alkoxy group having 1 to 5 carbon atoms, and the hydrogen atom contained in the alkoxy group may be substituted with a halogen atom. -CH ₂ - constituting the alkanediyl group may be replaced with -O- or -CO-. ]

According to the present invention, a vertically aligned liquid crystal in which a polymerizable liquid crystal compound can be formed without a vertical alignment film and in which a polymerizable liquid crystal compound is precisely aligned in the vertical direction similarly to the vertically aligned liquid crystal cured film formed on the vertical alignment film. A laminate including the cured film can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows an example of the layer structure of the laminated body of this invention.

The laminate of the present invention includes a vertically aligned liquid crystal cured film and a substrate. FIG. 1 shows one embodiment of the laminate of the present invention, although not limited thereto, and shows the most basic layer structure of the laminate of the present invention. A laminate 11 shown in FIG. 1 is formed by laminating a substrate 1 and a vertically aligned liquid crystal cured film 2 . In the laminate 11 shown in FIG. 1, the vertically aligned liquid crystal cured film 2 is formed directly on the substrate 1, and the substrate 1 and the vertically aligned liquid crystal cured film 2 are adjacent to each other. The laminate of the present invention may comprise other layers in addition to the substrate and the vertically aligned liquid crystal cured film.

In the present invention, the vertically aligned liquid crystal cured film is provided on the substrate or on the substrate with or without a layer having a vertical alignment regulating force (hereinafter also referred to as a “vertical alignment film”). It can be formed on a layer that does not have a vertical alignment regulating force. In the laminate of the present invention, since the vertically aligned liquid crystal cured film can be formed without a vertically aligned film, the number of steps for manufacturing the laminate is reduced, and the laminate can be manufactured with high productivity. That is, in the present invention, the vertically aligned liquid crystal cured film can be laminated on the base material without interposing the vertically aligned liquid crystal film, and in the laminate of the present invention, the base material and the vertically aligned liquid crystal cured film are present adjacent to each other. It is preferable to

[Vertical alignment liquid crystal cured 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 the following formulas (3), (4), (5) and (6) ) at least one of
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 abundance ratio (atom%) of fluorine element in the liquid crystal cured film at the interface on the opposite side of the base material of the vertically aligned liquid crystal cured film,
F (B) represents the abundance ratio (atom%) of the fluorine element in the cured liquid crystal film at the interface of the cured vertically aligned liquid crystal film on the substrate side,
F(C) represents the abundance ratio (atom%) of the fluorine element in the cured liquid crystal film at a point of 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film on the opposite side of the substrate to the cured liquid crystal film side. ,
Si (A) represents the abundance ratio (atom%) of the silicon element in the cured liquid crystal film at the interface on the side opposite to the substrate of the cured vertically aligned liquid crystal film,
Si (B) represents the abundance ratio (atom%) of the silicon element in the liquid crystal cured film at the interface on the substrate side of the vertically aligned liquid crystal cured film,
Si (C) represents the abundance ratio (atom%) of the silicon element in the cured liquid crystal film at a point of 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film on the opposite side of the substrate to the cured liquid crystal film side. ,
N (B) represents the abundance ratio (atom%) of the nitrogen element in the cured liquid crystal film at the interface on the substrate side of the cured vertically aligned liquid crystal film,
N(C) represents the abundance ratio (atom%) of the nitrogen element in the cured liquid crystal film at a point of 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film on the opposite side of the substrate to the cured liquid crystal film side. ,
P (B) represents the abundance ratio (atom%) of the phosphorus element in the liquid crystal cured film at the substrate side interface of the vertically aligned liquid crystal cured film,
P (C) represents the abundance ratio (atom%) of the phosphorus element in the cured liquid crystal film at a point of 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film on the side opposite to the base material to the cured liquid crystal film side. .

The above formulas (1) to (6) serve as indices indicating the uneven distribution of specific elements in the vertically aligned liquid crystal cured film. F, Si, N and P in formulas (1) to (6) represent elemental fluorine, elemental silicon, elemental nitrogen and elemental phosphorus, respectively. As shown in FIG. 1, (A) is the interface of the vertically aligned liquid crystal cured film on the opposite side of the substrate (hereinafter also referred to as "non-substrate side interface"), and (B) is the vertically aligned liquid crystal cured film. 100 nm in the thickness direction from the interface on the opposite side of the substrate of the vertically aligned liquid crystal cured film to the liquid crystal cured film side. (hereinafter also referred to as "intermediate point"), which means the point where the presence or absence of each element in the vertically aligned liquid crystal cured film is analyzed. In the vertically aligned liquid crystal cured film constituting the laminate of the present invention, fluorine element, silicon element, nitrogen element and phosphorus element are unevenly distributed in the vertically aligned liquid crystal cured film in a specific positional relationship. Such uneven distribution of specific elements means that additives that function as leveling agents and vertical alignment accelerators in the vertically aligned liquid crystal cured film are unevenly distributed in a specific positional relationship. It is possible to control the surface energy of the cured film and develop electrostatic repulsive force against the polymerizable liquid crystal compound. As a result, an alignment control force that aligns the polymerizable liquid crystal compound in the direction perpendicular to the film plane of the cured liquid crystal film is developed, and the polymerizable liquid crystal compound is aligned in the direction perpendicular to the film plane without passing through the vertical alignment film. It is considered that an oriented vertically aligned liquid crystal cured film can be formed. When the above elements are unevenly distributed in the vertically aligned liquid crystal cured film constituting the laminate of the present invention, the unevenly distributed positions are several tens of nm (maximum is about 50 nm), and at a point that is 100 nm or more in the thickness direction from the non-substrate interface of the liquid crystal cured film or the substrate interface, regardless of the uneven distribution of each element at the interface, each element Almost no change in abundance ratio is observed.

The above formula (1) means that the abundance ratio (atom%) of the fluorine element at the non-substrate side interface of the vertically aligned liquid crystal cured film is higher than the abundance ratio (atom%) of the fluorine element at the intermediate point, This indicates that the fluorine element is unevenly distributed at the interface on the non-substrate side. The above formula (2) means that the abundance ratio (atom%) of the silicon element at the non-substrate side interface of the vertically aligned liquid crystal cured film is higher than the abundance ratio (atom%) of the silicon element at the intermediate point, This indicates that the silicon element is unevenly distributed at the interface on the non-substrate side. The uneven distribution of the fluorine element and/or the silicon element at the non-substrate side interface of the vertically aligned liquid crystal cured film is caused, for example, by the liquid crystal cured film containing fluorine element and/or silicon element as a constituent and This can be achieved by including a component that tends to segregate (for example, a surfactant, etc.). When the fluorine element and / or silicon element is unevenly distributed at the interface on the non-substrate side of the cured liquid crystal film due to such a component, the surface energy at the interface on the non-substrate side of the cured liquid crystal film is reduced, resulting in the polymerizable liquid crystal. A vertical alignment regulating force for aligning the compound in the direction perpendicular to the film plane can be developed.

When the vertically aligned liquid crystal cured film constituting the laminate of the present invention satisfies at least one of the formulas (1) and (2), the surface energy of the non-substrate side interface of the cured liquid crystal film becomes low. , 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 abundance ratio (atom%) of the nitrogen element at the substrate-side interface of the vertically aligned liquid crystal cured film is greater than the abundance ratio (atom%) of the nitrogen element at the intermediate point. This indicates that the nitrogen element is unevenly distributed at the material side interface. The above formula (4) means that the abundance ratio (atom%) of the phosphorus element at the substrate-side interface of the vertically aligned liquid crystal cured film is greater than the abundance ratio (atom%) of the phosphorus element at the intermediate point. This indicates that the phosphorus element is unevenly distributed at the interface on the material side. The above formula (5) means that the abundance ratio (atom%) of the fluorine element at the substrate-side interface of the vertically aligned liquid crystal cured film is higher than the abundance ratio (atom%) of the fluorine element at the intermediate point. This indicates that the fluorine element is unevenly distributed at the material side interface. The above formula (6) means that the abundance ratio (atom%) of the silicon element at the substrate-side interface of the vertically aligned liquid crystal cured film is greater than the abundance ratio (atom%) of the silicon element at the intermediate point. This indicates that the silicon element is unevenly distributed at the interface on the material side. The uneven distribution of nitrogen element, phosphorus element, fluorine element and/or silicon element at the substrate side interface of the vertically aligned liquid crystal cured film is, for example, that the liquid crystal cured film comprises nitrogen element, phosphorus element, fluorine element and/or silicon element. It can be realized by including a component (for example, an ionic compound, etc.) which is included as a component and tends to segregate on the interface side of the substrate side. Although the mechanism by which these components are unevenly distributed to exert the vertical alignment regulating force is not clear, there is usually a large difference in polarity between charged ionic compounds and uncharged polymerizable liquid crystal compounds. is unevenly distributed at the substrate-side interface of the liquid crystal cured film, an electrostatic repulsion effect occurs against the polymerizable liquid crystal compound at the substrate-side interface of the liquid crystal cured film where the element is present, and the polymerizable liquid crystal compound is the base of the liquid crystal cured film. It is presumed that the vertical alignment regulating force for aligning the polymerizable liquid crystal compound in the direction perpendicular to the film plane can be developed because it is arranged so that the contact area with respect to the material side interface becomes small.

By the liquid crystal cured film satisfying at least one of the formulas (3), (4), (5) and (6), static is formed between the substrate-side interface of the liquid crystal cured film and the polymerizable liquid crystal compound. An electric repulsion effect can be produced, and the polymerizable liquid crystal compound can be 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 vertical alignment regulating force for a polymerizable liquid crystal compound is obtained. Therefore, the element unevenly distributed on the side of the substrate-side interface may be nitrogen, phosphorus, fluorine or silicon. From the viewpoint of easily obtaining a vertically aligned liquid crystal cured film containing the uneven distribution of the specific element using a general ionic compound as described later, in the present invention, the vertically aligned liquid crystal cured film is represented by formula (3) and formula Preferably, at least one of (4) is satisfied and at least one of formulas (5) and (6) is satisfied, and formulas (3), (4), (5) and (6) ), more preferably at least one or more of formulas (3) and (4), and more preferably formulas (5) and (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 formulas (3), (4), (5) and (6) satisfy at least one of By satisfying at least one of the formulas (1) and (2) and at least one of the formulas (3) to (6), the surface energy at the non-substrate side interface of the cured liquid crystal film and the electrostatic repulsion effect at the interface of the cured liquid crystal film on the substrate side, the vertical alignment regulating force for the polymerizable liquid crystal compound can be expressed from both interfaces of the cured liquid crystal film. Therefore, when any one of the formulas (1) to (6) is satisfied, at least one of the formulas (1) and (2), or at least one of the formulas (3) to (6) The polymerizable liquid crystal compound can be aligned with higher accuracy in the direction perpendicular to the film plane of the cured liquid crystal film without a vertical alignment film, compared to the case where one condition is satisfied.

In the present invention, the vertically aligned liquid crystal cured film can take the following aspects.
a) satisfies at least one of formulas (1) and (2), satisfies at least one of formulas (3) and (4), and satisfies at least one of formulas (5) and (6) fulfill one.
b) satisfies at least one of formulas (1) and (2) and satisfies at least three of formulas (3)-(6);
c) satisfying at least one of equations (1) and (2) and at least one of equations (3) and (4), and simultaneously satisfying equations (5) and (6) Fulfill.
The above aspect (b) is preferable because the polymerizable liquid crystal compound is easily aligned in the vertical direction, and the above aspect (c) is more preferable because the polymerizable liquid crystal compound is easily aligned vertically with higher accuracy. .

When the vertically aligned liquid crystal cured film satisfies the formula (1), the abundance ratio (atom%) of the fluorine element at the non-substrate side interface indicated by F(A) and the fluorine element at the midpoint indicated by F(C) The difference [F(A)-F(C)] from the abundance ratio (atom %) of is preferably 0.01 or more, more preferably 0.1 or more, and still more preferably 0.5 or more. When the difference between F(A) and F(C) is at least the above lower limit, a sufficient amount of fluorine element is unevenly distributed on the interface side of the vertically aligned liquid crystal cured film on the non-substrate side, and the polymerizable liquid crystal compound is formed. It becomes easy to align in the vertical direction with high accuracy. 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 the formula (2), the abundance ratio (atom%) of the silicon element at the non-substrate side interface represented by Si (A) and the silicon element at the midpoint represented by Si (C) The difference [Si(A)-Si(C)] from the abundance ratio (atom %) of is preferably 0.01 or more, more preferably 0.05 or more, and still more preferably 0.10 or more. When the difference between Si (A) and Si (C) is at least the above lower limit, a sufficient amount of silicon element is unevenly distributed on the interface side of the vertically aligned liquid crystal cured film on the non-substrate side, and the polymerizable liquid crystal compound is formed. It becomes easy to align in the vertical direction with high accuracy. 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 the formula (3), the abundance ratio (atom%) of the nitrogen element at the substrate side interface indicated by N(B) and the nitrogen element at the midpoint indicated by N(C) The difference [N(B)-N(C)] from the abundance ratio (atom %) is preferably 0.001 or more, more preferably 0.01 or more, and still more preferably 0.05 or more. When the difference between N (B) and N (C) is at least the above lower limit, a sufficient amount of nitrogen element is unevenly distributed on the substrate interface side of the vertically aligned liquid crystal cured film, and the polymerizable liquid crystal compound moves in the vertical direction. It becomes easy to orient accurately. 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 the formula (4), the abundance ratio (atom%) of the phosphorus element at the substrate side interface indicated by P (B) and the phosphorus element at the intermediate point indicated by P (C) The difference [P(B)-P(C)] from the abundance ratio (atom %) is preferably 0.001 or more, more preferably 0.01 or more, and still more preferably 0.05 or more. When the difference between P (B) and P (C) is at least the above lower limit, a sufficient amount of phosphorus element is unevenly distributed on the substrate interface side of the vertically aligned liquid crystal cured film, and the polymerizable liquid crystal compound is vertically aligned. It becomes easy to orient accurately. 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 the formula (5), the abundance ratio (atom%) of the fluorine element at the substrate side interface indicated by F (B) and the fluorine element at the intermediate point indicated by F (C) The difference [F(B)-F(C)] from the abundance ratio (atom %) is preferably 0.01 or more, more preferably 0.05 or more, and still more preferably 0.10 or more. When the difference between F(B) and F(C) is at least the above lower limit, a sufficient amount of fluorine element is unevenly distributed on the substrate interface side of the vertically aligned liquid crystal cured film, and the polymerizable liquid crystal compound is vertically aligned. It becomes easy to orient accurately. 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 the formula (6), the abundance ratio (atom%) of the silicon element at the substrate side interface represented by Si (B) and the content of the silicon element at the midpoint represented by Si (C) The difference [Si(B)-Si(C)] from the abundance ratio (atom %) is preferably 0.01 or more, more preferably 0.05 or more, and still more preferably 0.10 or more. When the difference between Si (B) and Si (C) is at least the above lower limit, a sufficient amount of silicon element is unevenly distributed on the substrate interface side of the vertically aligned liquid crystal cured film, and the polymerizable liquid crystal compound is vertically aligned. It becomes easy to orient accurately. 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 (for example, fluorine element or silicon element) is unevenly distributed at both the non-substrate side interface and the substrate side interface of the vertically aligned liquid crystal cured film, the abundance ratio of the element at the non-substrate side interface and the abundance ratio of the element at the substrate-side interface is not particularly limited, and may be approximately the same or higher.

In the present invention, the above formulas (1) to (6) in the vertically aligned liquid crystal cured film respectively contain fluorine element and / or silicon element depending on the polymerizable liquid crystal compound used for constituting the vertically aligned liquid crystal cured film. It contains components that are likely to segregate on the interface side of the non-substrate side, and components that include nitrogen element, phosphorus element, fluorine element and/or silicon element as constituent components and are likely to segregate on the interface side of the substrate side. It can be controlled by adjusting the type, their compounding amount and combination, the composition of the vertically aligned liquid crystal cured film forming composition, the manufacturing conditions for the vertically aligned liquid crystal cured film, the type of substrate to be coated, the surface treatment conditions, etc. can. For example, depending on the polymerizable liquid crystal compound to be used, a leveling agent and/or a nonionic silane compound as described later are selected, and by adjusting their compounding amounts, formulas (1) and/or (2) are obtained. It is possible to obtain a vertically aligned liquid crystal cured film that satisfies the requirements. Further, for example, depending on the polymerizable liquid crystal compound to be used, by selecting an ionic compound as described later and adjusting the blending amount thereof, formulas (3), (4), (5) and / or (6) ) can be obtained.

The ratio of each element in the vertically aligned liquid crystal cured film can be measured by an X-ray photoelectron spectroscopy (XPS) method. For example, after analyzing the constituent elements of the non-substrate side interface of the vertically aligned liquid crystal cured film by XPS, etching is performed from the non-substrate side interface, and 100 nm in the thickness direction of the liquid crystal cured film from the non-substrate side interface. The constituent elements in the liquid crystal cured film at the point are similarly analyzed by XPS, then the substrate is peeled off from the vertically aligned liquid crystal cured film used for the analysis, and the surface (substrate side interface) from which the substrate is peeled. Elements can be analyzed by XPS. More detailed conditions such as XPS measurement conditions and etching conditions for analyzing constituent elements at intermediate points can be appropriately determined according to the measurement apparatus, the sample to be measured, etc. Conditions described in the examples may be employed.

The vertically aligned liquid crystal cured film constituting the laminate of the present invention is a cured product of a polymerizable liquid crystal composition cured in a state in which the polymerizable liquid crystal compound is aligned in a direction perpendicular to the plane of the liquid crystal cured film. In the present invention, the polymerizable liquid crystal composition for forming the vertically aligned liquid crystal cured film is, in addition to the polymerizable liquid crystal compound, such that the obtained liquid crystal cured film is represented by formulas (1) to (6). It is configured to contain a component for providing maldistribution of a specific element.

In the present invention, the vertically aligned liquid crystal cured film constituting the laminate preferably contains fluorine element and/or silicon element as constituent components, and contains a component that tends to segregate on the interface side on the non-substrate side. By containing such a component, a cured liquid crystal film satisfying formula (1) and/or formula (2) can be obtained. Due to such components, the fluorine element and / or silicon element are unevenly distributed at the interface on the non-substrate side of the cured liquid crystal film, so that the surface energy at the interface on the non-substrate side of the cured liquid crystal film can be reduced. A vertical alignment regulating force for aligning the polymerizable liquid crystal compound in the direction perpendicular to the film plane can be developed. Accordingly, in the laminate of the present invention, it is not necessary to form a vertical alignment film, the production process of the laminate is simplified, and the laminate can be produced with good productivity. Examples of components that contain elemental fluorine and/or elemental silicon and are likely to segregate on the interface side of the non-substrate side include leveling agents, nonionic silane compounds, and ionic compounds.

In the present invention, the vertically aligned liquid crystal cured film preferably contains a leveling agent. The leveling agent has the function of adjusting the fluidity of the polymerizable liquid crystal composition and leveling the coating film obtained by applying the composition, and typical leveling agents include surfactants and the like. . In the present invention, the fluorine element and/or the silicon element are likely to be unevenly distributed at the non-substrate side interface of the cured liquid crystal film, and while functioning as a conventional leveling agent, it exhibits a high vertical alignment regulating force for the polymerizable liquid crystal compound. From the viewpoint that the cured film of the vertically aligned liquid crystal can It is more preferred to include at least one selected leveling agent. The vertically aligned liquid crystal cured film easily satisfies formula (1) by containing a leveling agent containing fluorine element, and easily satisfies formula (2) by containing a leveling agent containing silicon element. These leveling agents may be used alone or in combination of two or more.

A commercially available product may be used as the leveling agent. For example, specific examples of silicone-based leveling agents and fluorine-based leveling agents include DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, and FZ2123 (all of which are manufactured by 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-444 6, TSF4452, TSF4460 (all manufactured by Momentive Performance Materials Japan G.K.), fluorinert (registered trademark) FC-72, FC-40, FC-43, FC-3283 (all Sumitomo 3M ( Co., Ltd.), Megafac (registered trademark) R-08, R-30, R-90, F-410, F-411, F-443, F-445, F-470, F-477, F-479, F-482, F-483, F-556 (all manufactured by DIC Corporation), F-top (trade name) EF301, EF303, EF351, EF352 (all manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Surflon (registered trademark) S-381, S-382, S-383, S-393, SC-101, SC-105, KH-40, SA-100 (all of which are manufactured by AGC Seimi Chemical Co., Ltd.), trade names E1830 and E5844 (manufactured by Daikin Fine Chemicals Laboratory Co., Ltd.), and the like.

When the vertically aligned liquid crystal cured film contains a leveling agent, the content is preferably 0.001 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film. Above, more preferably 0.01 parts by mass or more, still more preferably 0.03 parts by mass or more, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 1.5 parts by mass or less is. When the content of the leveling agent is within the above range, it is possible to effectively promote vertical alignment of the polymerizable liquid crystal compound while maintaining good applicability of the polymerizable liquid crystal composition. When the cured vertically aligned liquid crystal film contains two or more leveling agents, the content of the leveling agent means the total content of all leveling agents contained in the cured vertically aligned liquid crystal film.

Moreover, in the present invention, the vertically aligned liquid crystal cured film preferably contains a nonionic silane compound. A nonionic silane compound generally tends to segregate at the interface on the non-substrate side of a vertically aligned liquid crystal cured film. When the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film contains a nonionic silane compound, the nonionic silane compound reduces the surface tension of the polymerizable liquid crystal composition, and the non-substrate side of the liquid crystal cured film Since the surface energy of the interface can be lowered, the vertical alignment regulating force for the polymerizable liquid crystal compound can be enhanced. As a result, the cured liquid crystal film can be formed while maintaining the vertically aligned state of the polymerizable liquid crystal compound. In particular, by including a nonionic silane compound in addition to the leveling agent described above, the vertical alignment regulating force due to the above-described effect is exhibited more remarkably.

A nonionic silane compound is a compound that is nonionic and contains the element silicon. Nonionic silane compounds include, for example, silicon polymers such as polysilanes, silicone resins such as silicone oils and silicone resins, and organic and inorganic silane compounds such as silicone oligomers, silsessiloxanes and alkoxysilanes (more specifically, , a silane coupling agent, etc.) and the like. The leveling agent containing the silicon element described above corresponds to a nonionic silane compound in terms of its molecular structure. It is distinguished from nonionic silane compounds in that it has the effect of smoothing the surface of the coating film by migrating to the surface after the cured film composition for vertically aligned liquid crystal is applied to the substrate. Moreover, the nonionic silane compound having leveling properties generally has a large molecular weight, preferably a weight-average molecular weight of 1,000 or more, in order to develop leveling properties.

The nonionic silane compound may be of the silicone monomer type or of the silicone oligomer (polymer) type. In the form of (monomer)-(monomer) copolymer, the silicone oligomers are 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercapto Mercaptopropyl group-containing copolymers such as propyltriethoxysilane-tetramethoxysilane copolymer and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetra Mercaptomethyl group-containing copolymers such as ethoxysilane copolymers, mercaptomethyltriethoxysilane-tetramethoxysilane copolymers and mercaptomethyltriethoxysilane-tetraethoxysilane copolymers; 3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymers, 3 -Methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane- Tetramethoxysilane Copolymer, 3-Methacryloyloxypropylmethyldimethoxysilane-Tetraethoxysilane Copolymer, 3-Methacryloyloxypropylmethyldiethoxysilane-Tetramethoxysilane Copolymer and 3-Methacryloyloxypropylmethyldiethoxysilane-Tetraethoxysilane Copolymer 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetramethoxy Silane Copolymer, 3-Acryloyloxypropyltriethoxysilane-Tetraethoxysilane Copolymer, 3-Acryloyloxypropylmethyldimethoxysilane-Tetramethoxysilane Copolymer, 3-Acryloyloxypropylmethyldimethoxysilane-Tetraethoxysilane Copolymer, 3-Acryloyloxypropyl acryloyloxypropyl group-containing copolymers such as methyldiethoxysilane-tetramethoxysilane copolymer and 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer; vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane- Tetraethoxysilane Copolymer, Vinyltriethoxysilane-Tetramethoxysilane Copolymer, Vinyltriethoxysilane-Tetraethoxysilane Copolymer, Vinylmethyldimethoxysilane-Tetramethoxysilane Copolymer, Vinylmethyldimethoxysilane-Tetraethoxysilane Copolymer, Vinylmethyldiethoxysilane - vinyl group-containing copolymers such as tetramethoxysilane copolymer and vinylmethyldiethoxysilane-tetraethoxysilane copolymer; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer; , 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxy and amino group-containing copolymers such as silane copolymers, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymers and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymers. These nonionic silane compounds may be used singly or in combination of two or more. Among them, a silane coupling agent is preferable from the viewpoint of further improving adhesion with an adjacent layer such as a base material.

The silane coupling agent is terminally selected from the group consisting of vinyl, epoxy, styryl, methacryl, acryl, amino, isocyanurate, ureido, mercapto, isocyanate, carboxyl, and hydroxyl groups. and at least one alkoxysilyl group or silanol group. By appropriately selecting these functional groups, it is possible to improve the mechanical strength of the vertically aligned liquid crystal cured film, modify the surface of the vertically aligned liquid crystal cured film, and adhere the vertically aligned liquid crystal cured film to adjacent layers (substrates, etc.). It is possible to impart unique effects such as improved properties. From the viewpoint of adhesion, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and another different reactive group (for example, the functional group described above). Furthermore, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and a polar group. When the silane coupling agent has at least one alkoxysilyl group and at least one polar group in its molecule, the vertical alignment property of the polymerizable liquid crystal compound can be more easily improved, and the effect of promoting vertical alignment can be significantly obtained. There is a tendency. Polar groups include, for example, epoxy groups, amino groups, isocyanurate groups, mercapto groups, carboxyl groups and hydroxy groups. In addition, the polar group may have an appropriate substituent or protective group in order to control the reactivity of the silane coupling agent.

Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltri Methoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane and 3-glycidoxypropylethoxydimethylsilane are mentioned.

Further, 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, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE - Silane coupling agents from Shin-Etsu Chemical Co., Ltd. such as 9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007 are mentioned.

When the vertically aligned liquid crystal cured film contains a nonionic silane compound, the content thereof is 100 of the polymerizable liquid crystal compound normally contained in the polymerizable liquid crystal composition in the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film. With respect to parts by mass, it is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4 parts by mass. It is not more than 3 parts by mass, more preferably not more than 3 parts by mass. When the content of the nonionic silane compound is within the above range, it is possible to effectively promote vertical alignment of the polymerizable liquid crystal compound while maintaining good applicability and alignment of the polymerizable liquid crystal composition. can.

The vertically aligned liquid crystal cured film constituting the laminate of the present invention preferably contains a nitrogen element, a phosphorus element, a fluorine element and/or a silicon element as constituent components, and preferably contains a component that tends to segregate on the interface side of the substrate side. . By containing such components, it is possible to obtain a cured liquid crystal film that satisfies formulas (3), (4), (5) and/or (6). An ionic compound having an electric charge and a polymerizable liquid crystal compound having no electric charge usually have a large difference in polarity. Therefore, due to such components, nitrogen element, phosphorus element, and fluorine are present at the interface of the cured liquid crystal film on the substrate side. If the element and/or the silicon element are unevenly distributed, an electrostatic repulsion effect is produced against the polymerizable liquid crystal compound at the substrate-side interface of the cured liquid crystal film where the element is present. As a result, the polymerizable liquid crystal compound tries to be arranged so that the contact area becomes smaller with respect to the substrate-side interface of the cured liquid crystal film, so that the vertical alignment control force aligns the polymerizable liquid crystal compound in the direction perpendicular to the film plane. can be expressed.

Examples of components that contain nitrogen element, phosphorus element, fluorine element and/or silicon element as constituent components and that are likely to segregate on the interface side of the substrate side include ionic compounds, but the alignment defect of the polymerizable liquid crystal compound can be exemplified. In the present invention, the vertically aligned liquid crystal cured film preferably contains an ionic compound composed of non-metallic atoms because it tends to be difficult to occur. Ionic compounds composed of non-metal atoms tend to be unevenly distributed at the interface on the side of the substrate in the vertically aligned liquid crystal cured film. When the material is subjected to corona treatment, plasma treatment, excimer light irradiation treatment, etc., there is a tendency for it to be more prominently unevenly distributed. In this way, when the ionic compound is unevenly distributed at the interface on the substrate side in the vertically aligned liquid crystal cured film, an electrostatic repulsion effect occurs between the uncharged polymerizable liquid crystal compound and the charged ionic compound, resulting in polymerization. It is possible to develop a vertical alignment regulating force that aligns the liquid crystal compound in the direction vertical to the film plane. Furthermore, the vertically aligned liquid crystal cured film contains an ionic compound composed of non-metal atoms together with the above-described leveling agent, particularly a leveling agent containing silicon element or a leveling agent containing fluorine element, or a nonionic silane compound. Since the vertical alignment control force acts on the polymerizable liquid crystal compound from both the non-substrate side interface and the substrate side interface of the cured film, the polymerizable liquid crystal compound is easily aligned in the vertical direction, and the alignment accuracy can be further improved. can.

Examples of ionic compounds composed of non-metal atoms include onium salts (more specifically, quaternary ammonium salts and tertiary sulfonium salts in which the nitrogen atom has a positive charge, and phosphorus atoms have a positive charge). quaternary phosphonium salts, etc.). When the vertically aligned liquid crystal cured film contains an ammonium salt, it easily satisfies the formula (3), and when it contains a phosphonium salt, it easily satisfies the formula (4). Among these onium salts, quaternary onium salts are preferred from the viewpoint of further improving the vertical alignment properties of the polymerizable liquid crystal compound, and from the viewpoint of improving availability and mass productivity, quaternary phosphonium salts or quaternary onium salts are preferred. Ammonium salts are more preferred. The onium salt may have two or more quaternary onium salt sites in the molecule, and may be an oligomer or polymer.

The molecular weight of the ionic compound composed of non-metallic atoms is preferably 100 or more and 10,000 or less. When the molecular weight is within the above range, it is easy to improve the vertical alignment property of the polymerizable liquid crystal compound while ensuring the applicability of the polymerizable composition. The molecular weight of the ionic compound composed of nonmetallic atoms is more preferably 5,000 or less, more preferably 3,000 or less.

Examples of cationic components of ionic compounds composed of nonmetallic atoms include inorganic cations and organic cations. Among them, organic cations are preferable because they hardly cause alignment defects in the polymerizable liquid crystal compound. Examples of organic cations include imidazolium cations, pyridinium cations, ammonium cations, sulfonium cations and phosphonium cations.

Ionic compounds consisting of non-metallic atoms generally have a counter anion. Examples of the anion component that serves as a counterion for the cation component include inorganic anions and organic anions. Among them, an organic anion is preferable because it hardly causes an alignment defect of the polymerizable liquid crystal compound. By using an anion containing a fluorine element in its molecular structure as a counter anion, it becomes easier to satisfy the formula (5). Note that cations and anions do not necessarily have to correspond one-to-one.

Specific examples of the anion component include the following.
chloride anion [Cl ⁻ ],
bromide anion [Br ⁻ ],
iodide 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 ⁻ ],
hexafluoroniobate anion [NbF ₆ ⁻ ],
hexafluorotantalate anion [TaF ₆ ⁻ ],
dimethylphosphinate anion [(CH ₃ ) ₂ POO ⁻ ],
(poly)hydrofluorofluoride anions [F(HF) _n ⁻ ] (for example, n represents an integer of 1 to 3),
dicyanamide anion [(CN) ₂ N ⁻ ],
thiocyan anion [SCN ^- ],
perfluorobutanesulfonate anion [C ₄ F ₉ SO ₃ ⁻ ],
bis(pentafluoroethanesulfonyl)imide anion [(C ₂ F ₅ SO ₂ ) ₂ N ⁻ ],
perfluorobutanoate anion [C ₃ F ₇ COO ⁻ ], and (trifluoromethanesulfonyl)(trifluoromethanecarbonyl)imide anion [(CF ₃ SO ₂ )(CF ₃ CO)N ⁻ ].

Specific examples of the ionic compound composed of non-metallic atoms can be appropriately selected from combinations of the above cationic components and anionic components. Examples of compounds that are specific combinations of cationic components and anionic components include the following.

(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(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 and the like.

(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 and the like.

(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(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-tributylammonium bis(trifluoromethanesulfonyl)imide,
1-(3-trimethoxysilylpropyl)-1,1,1-trimethylammonium bis(trifluoromethanesulfonyl)imide,
1-(3-trimethoxysilylbutyl)-1,1,1-tributylammonium bis(trifluoromethanesulfonyl)imide,
1-(3-trimethoxysilylbutyl)-1,1,1-trimethylammonium bis(trifluoromethanesulfonyl)imide,
N-{(3-triethoxysilylpropyl)carbamoyloxyethyl)}-N,N,N-trimethylammonium bis(trifluoromethanesulfonyl)imide, and N-[2-{3-(3-trimethoxysilylpropylamino )-1-oxopropoxy}ethyl]-N,N,N-trimethylammonium bis(trifluoromethanesulfonyl)imide.

(Phosphonium salt)
tributyl(2-methoxyethyl)phosphonium bis(trifluoromethanesulfonyl)imide,
tributylmethylphosphonium 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 composed of nonmetallic atoms may be used alone or in combination of two or more. Among them, ionic compounds composed of phosphonium salts or ammonium salts having a positive charge on the nitrogen atom (including the aforementioned pyridinium salts, imidazolium salts, etc.) are preferable, and an anion containing a fluorine element in the molecular structure is used as a counter anion. An ionic compound consisting of a phosphonium salt or an ammonium salt is more preferred.

From the viewpoint of further improving the vertical alignment property of the polymerizable liquid crystal compound, the ionic compound composed of non-metal atoms preferably has a silicon element and/or a fluorine element in the molecular structure of the cation site. If the ionic compound composed of non-metal atoms has silicon element and/or fluorine element in the molecular structure of the cation site, the ionic compound is easily segregated on the surface of the vertically aligned liquid crystal cured film. By containing such an ionic compound composed of nonmetallic atoms, it becomes easier to satisfy formula (5) and/or formula (6). Among them, the following ionic compounds (I) to (III) are preferred as ionic compounds whose constituent elements are all non-metallic elements.

（イオン性化合物（ＩＩ））

（イオン性化合物（ＩＩＩ））

(Ionic compound (I))

(Ionic compound (II))

(Ionic compound (III))

In addition, for example, a method of treating the surface of a substrate with a surfactant having an alkyl group having a relatively long chain length to improve the orientation of liquid crystals (for example, "Liquid Crystal Handbook" Chapter 2 Alignment and physical properties of liquid crystals (published by Maruzen Co., Ltd.), etc.) can be applied to improve the vertical alignment of the polymerizable liquid crystal compound. That is, by treating the base material surface with an ionic compound having an alkyl group with a relatively long chain length, the vertical orientation of the polymerizable liquid crystal compound can be effectively improved.

Specifically, the ionic compound composed of non-metallic atoms preferably satisfies the following formula (9).
5<M<16 (9)
In formula (9), M is represented by the following formula (10).
M = (Number of covalent bonds from the positively charged atom to the molecular chain end of the substituent with the largest number of covalent bonds to the molecular chain end among the substituents directly bonded to the positively charged atom ) ÷ (number of atoms with positive charge) (10)
When the ionic compound satisfies the above (9), the vertical alignment property of the polymerizable liquid crystal compound can be effectively improved.

In addition, when there are two or more atoms with a positive charge in the molecule of an ionic compound composed of non-metallic atoms, the positive charge that is considered as a base point for a substituent that has two or more atoms with a positive charge The number of covalent bonds from the atom having a to another nearest positively charged atom is defined as the “number of covalent bonds from the positively charged atom to the end of the molecular chain” described in the definition of M above. When the ionic compound composed of nonmetallic atoms is an oligomer or polymer having two or more repeating units, the above M is calculated considering the constituent unit as one molecule. When a positively charged atom is incorporated into a ring structure, the number of covalent bonds through the ring structure to the same positively charged atom, or to the end of a substituent attached to the ring structure. Among the number of covalent bonds, the one with the larger number of covalent bonds is defined as "the number of covalent bonds from the positively charged atom to the end of the molecular chain" described in the definition of M above.

When the vertically aligned liquid crystal cured film contains an ionic compound composed of non-metal atoms, the content thereof in the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film is usually the polymerizable liquid crystal composition contained in the polymerizable liquid crystal composition. With respect to 100 parts by mass of the liquid crystal compound, it is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.3 parts by mass or more, and preferably 5 parts by mass or less. It is preferably 4 parts by mass or less, more preferably 3 parts by mass or less. When the content of the ionic compound composed of non-metallic atoms is within the above range, the vertical alignment of the polymerizable liquid crystal compound is effectively promoted while maintaining good applicability and alignment of the polymerizable liquid crystal composition. can be made

When the vertically aligned liquid crystal cured film contains both a nonionic silane compound and an ionic compound composed of non-metallic atoms, the electrostatic interaction derived from the ionic compound and the decrease in surface tension derived from the nonionic silane compound. As a result, the vertical alignment of the polymerizable liquid crystal compound is facilitated. This makes it possible to form a cured liquid crystal film in which the polymerizable liquid crystal compound is more precisely vertically aligned. Therefore, in a preferred embodiment of the present invention, the vertically aligned liquid crystal cured film contains a nonionic silane compound and an ionic compound composed of nonmetallic atoms. Furthermore, by including a leveling agent, a nonionic silane compound, and an ionic compound composed of non-metallic 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 vertically aligned liquid crystal cured film contains an ionic compound consisting of a leveling agent, a nonionic silane compound and nonmetallic atoms.

In the present invention, the cured vertically aligned liquid crystal film is a cured product of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound, and the polymerizable liquid crystal compound is oriented perpendicular to the film plane of the cured liquid crystal film. It is a cured liquid crystal film obtained by curing in a state of orientation. In the present invention, the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film means a liquid crystal compound having a polymerizable group. The polymerizable liquid crystal compound is not particularly limited, and for example, conventionally known polymerizable liquid crystal compounds in the field of retardation films can be used.

A polymerizable group is a group that can participate in a polymerization reaction by an active radical generated from a polymerization initiator, an acid, or the like. Examples of the polymerizable group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group and oxetanyl group. Among them, a radically polymerizable group is preferred, an acryloyloxy group, a methacryloyloxy group, a vinyl group and a vinyloxy group are more preferred, and an acryloyloxy group and a methacryloyloxy group are even more preferred.

The liquid crystallinity exhibited by the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a lyotropic liquid crystal, but the thermotropic liquid crystal is preferable in that it enables precise film thickness control. Further, the phase-ordered structure of the thermotropic liquid crystal may be nematic liquid crystal or smectic liquid crystal. A polymerizable liquid crystal compound can be used individually or in combination of 2 or more types.

The polymerizable liquid crystal compound generally includes a polymerizable liquid crystal compound that exhibits normal wavelength dispersion and a polymerizable liquid crystal compound that exhibits reverse wavelength dispersion, and it is also possible to use only one type of polymerizable liquid crystal compound. Alternatively, both kinds of polymerizable liquid crystal compounds can be mixed and used. From the viewpoint of increasing the effect of suppressing the oblique reflection hue during black display in a display device incorporating the obtained laminate, it is preferable that a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion is included. As the polymerizable liquid crystal compound, only one type may be used, or two or more types may be used in combination.

The polymerizable liquid crystal compound exhibiting reverse wavelength dispersion is preferably a compound having the following characteristics (A) to (D).
(A) A compound capable of forming a nematic phase or a smectic phase.
(B) The polymerizable liquid crystal compound has π electrons along the longitudinal direction (a).
(C) It has π electrons in a direction crossing the major axis direction (a) [intersecting direction (b)].
(D) A polymerizable liquid crystal compound defined by the following formula (i), where N (πa) is the sum of π electrons present in the major axis direction (a), and N (Aa) is the sum of the molecular weights present in the major axis direction. π electron density in the long axis direction (a) of
D(πa)=N(πa)/N(Aa) (i)
and a polymerizable liquid crystal compound defined by the following formula (ii), where N(πb) is the sum of π electrons present in the cross direction (b), and N(Ab) is the sum of the molecular weights present in the cross direction (b). π electron density in the cross direction (b) of
D(πb)=N(πb)/N(Ab) (ii)
is the formula (iii)
0≦[D(πa)/D(πb)]<1 (iii)
[that is, the π electron density in the cross direction (b) is higher than the π electron density in the long axis direction (a)]. Further, as described above, a polymerizable liquid crystal compound having π electrons on the long axis and in the direction crossing it has, for example, a T-shaped structure.

In the features (A) to (D) above, the major axis direction (a) and the number of π electrons N are defined as follows.
- The long axis direction (a) is, for example, the long axis direction of a rod-like structure in the case of a compound having a rod-like structure.
- The number of π electrons N (πa) present in the major axis direction (a) does not include π electrons that disappear due to the polymerization reaction.
The number of π electrons N (πa) present along the major axis direction (a) is the total number of π electrons on the major axis and the π electrons conjugated therewith, for example, present along the major axis direction (a) It includes the number of π electrons present in a ring that satisfies Hückel's rule.
- The number of π electrons N (πb) existing in the cross direction (b) does not include π electrons that disappear due to the polymerization reaction.
A polymerizable liquid crystal compound satisfying the above has a mesogenic structure in the major axis direction. A liquid crystal phase (nematic phase, smectic phase) is expressed by this mesogenic structure.

Forming a nematic phase or a smectic phase by applying a polymerizable liquid crystal compound that satisfies the above (A) to (D) onto a film (layer) that forms a liquid crystal cured film and heating it to a phase transition temperature or higher. is possible. In the nematic phase or smectic phase formed by aligning the polymerizable liquid crystal compound, the long axis directions of the polymerizable liquid crystal compound are usually oriented parallel to each other, and the long axis direction is the alignment direction of the nematic phase. becomes. When such a polymerizable liquid crystal compound is made into a film and polymerized in a nematic phase or smectic phase, a polymer film composed of a polymer oriented in the major axis direction (a) can be formed. . This polymer film absorbs ultraviolet rays by π electrons in the long axis direction (a) and π electrons in the cross direction (b). Let λbmax be the absorption maximum wavelength of ultraviolet rays absorbed by π electrons in the cross direction (b). λbmax is typically between 300 nm and 400 nm. The density of π electrons satisfies the above formula (iii), and the π electron density in the cross direction (b) is higher than the π electron density in the major axis direction (a). is greater than the absorption of linearly polarized UV light (wavelength: λbmax) having a plane of vibration in the major axis direction (a). The ratio (absorbance in cross direction (b) of linearly polarized ultraviolet rays/absorbance in long axis direction (a)) is, for example, more than 1.0, preferably 1.2 or more, usually 30 or less, for example 10 or less. is.

Polymerizable liquid crystal compounds having the above properties generally exhibit reverse wavelength dispersion in many cases. Specific examples thereof include compounds represented by the following formula (X).

In formula (X), Ar represents a divalent group having an optionally substituted aromatic group. The aromatic group as used herein refers to a ring structure having [4n+2] number of π electrons according to Hückel's rule, and is exemplified by (Ar-1) to (Ar-23) described later. You may have two or more such Ar groups via a divalent linking group. Here, n represents an integer. In the case where a ring structure is formed by including heteroatoms such as -N= and -S-, the non-covalently bonded electron pairs on these heteroatoms satisfy Hückel's rule and have aromaticity. At least one or more of a nitrogen atom, an oxygen atom and a sulfur atom are preferably contained in the aromatic group. The number of aromatic groups contained in the divalent group Ar may be one, or two or more. When there is one aromatic group, the divalent group Ar may be an optionally substituted divalent aromatic group. When the number of aromatic groups contained in the divalent group Ar is two or more, the two or more aromatic groups are bonded to each other with a divalent linking group such as a single bond, -CO-O-, -O-. may be
G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom contained in the divalent aromatic group or divalent alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a carbon may be substituted with an alkoxy group, cyano group or nitro group having a number of 1 to 4, and the carbon atoms constituting the divalent aromatic group or divalent alicyclic hydrocarbon group are an oxygen atom or a sulfur atom; Alternatively, it may be substituted with a nitrogen atom.
L ¹ , L ² , B ¹ and B ² are each independently a single bond or a divalent linking group.
k and l each independently represents an integer of 0 to 3 and satisfies the relationship 1≦k+l. Here, when 2≦k+l, B ¹ and B ² and G ¹ and G ² may be the same or different from each other.
E ¹ and E ² each independently represent an alkanediyl group having 1 to 17 carbon atoms, wherein an alkanediyl group having 4 to 12 carbon atoms is more preferred. A hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and —CH ₂ — contained in the alkanediyl group is —O—, —S—, —SiH ₂ —, —C It may be substituted with (=O)-.
P ¹ and P ² independently represent a polymerizable group or a hydrogen atom, at least one of which is a polymerizable group.

G ¹ and G ² are each independently preferably a 1,4-phenylenediyl group optionally substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms. , a 1,4-cyclohexanediyl group optionally substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1 substituted with a methyl group ,4-phenylenediyl group, unsubstituted 1,4-phenylenediyl group or unsubstituted 1,4-trans-cyclohexanediyl group, particularly preferably unsubstituted 1,4-phenylenediyl group or unsubstituted It is a substituted 1,4-trans-cyclohexanediyl group.
At least one of G ¹ and G ² present in plurality is preferably a divalent alicyclic hydrocarbon group, and at least one of G ¹ and G ² bonded to L ¹ or L ² is more preferably a divalent alicyclic hydrocarbon group.

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

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

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, from the viewpoint of exhibiting reverse wavelength dispersion. It is preferable that k=2 and l=2 because of the symmetrical structure.

Polymerizable groups represented by P ¹ or P ² include epoxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group and oxiranyl group. , and oxetanyl groups. Among them, an acryloyloxy group, a methacryloyloxy group, a vinyl group and a vinyloxy group are preferred, and an acryloyloxy group and a methacryloyloxy group are more preferred.

Ar preferably has at least one selected from an optionally substituted aromatic hydrocarbon ring, an optionally substituted aromatic heterocyclic ring, and an electron-withdrawing group. Examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, anthracene ring and the like, with benzene ring and naphthalene ring being preferred. Examples of the aromatic heterocyclic ring include furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazole ring, triazine ring, pyrroline ring, imidazole ring, and pyrazole ring. , thiazole ring, benzothiazole ring, thienothiazole ring, oxazole ring, benzoxazole ring, and phenanthroline ring. Among them, it preferably has a thiazole ring, a benzothiazole ring, or a benzofuran ring, and more preferably has a benzothiazole group. Moreover, when a nitrogen atom is contained in Ar, the nitrogen atom preferably has a π electron.

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, still more preferably 14 or more, and particularly It is preferably 16 or more. Also, it is preferably 30 or less, more preferably 26 or less, and still more preferably 24 or less.

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

In formulas (Ar-1) to (Ar-23), * represents a linking moiety, and Z ⁰ , Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, or an alkyl having 1 to 12 carbon atoms. 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, alkylthio group having 1 to 12 carbon atoms, N-alkylamino group having 1 to 12 carbon atoms, N,N-dialkylamino group having 2 to 12 carbon atoms, N-alkylsulfamoyl group having 1 to 12 carbon atoms or carbon represents an N,N-dialkylsulfamoyl group of numbers 2 to 12; Moreover, Z ⁰ , Z ¹ and Z ² may contain a polymerizable group.

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

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

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

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

Examples of the aromatic hydrocarbon group for Y ¹ , Y ² and Y ³ include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl group, naphthyl group, anthryl group, phenanthryl group and biphenyl group. , is preferably a naphthyl group, more preferably a phenyl group. The aromatic heterocyclic group includes a C4-20 group containing at least one heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group and a benzothiazolyl group. An aromatic heterocyclic group can be mentioned, and a furyl group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group are preferable.

Y ¹ , Y ² and Y ³ may each independently be an optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group. A polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly. A polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.

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

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

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

In formulas (Ar-16) to (Ar-23), Y ¹ may form an aromatic heterocyclic group together with the nitrogen atom to which it is attached and Z ⁰ . Examples of the aromatic heterocyclic group include those described above as the aromatic heterocyclic ring that Ar may have, and examples thereof include pyrrole ring, imidazole ring, pyrroline ring, pyridine ring, pyrazine ring, pyrimidine ring, indole ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring and the like. This aromatic heterocyclic group may have a substituent. In addition, Y ¹ , together with the nitrogen atom and Z ⁰ to which it is attached, may be the aforementioned optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group. Examples include benzofuran ring, benzothiazole ring, benzoxazole ring and the like.

In the present invention, a polymerizable liquid crystal compound having an absorbance of 0.10 or less at a wavelength of 350 nm may be used as the polymerizable liquid crystal compound forming the 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 generally tends to exhibit positive wavelength dispersion. As such a polymerizable liquid crystal compound, for example, a compound containing a structure represented by the following formula (Y), which generally tends to exhibit positive wavelength dispersion (hereinafter also referred to as "polymerizable liquid crystal compound (Y)" ). 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 by referring to the method described in Examples. The solvent is a solvent capable of dissolving the polymerizable liquid crystal compound, and examples thereof include tetrahydrofuran and chloroform.

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 is -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ¹⁶ -, -NR ¹⁶ -CO-, -CO-, - represents CS- or a single bond. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
B12 and B13 each independently represent -C≡C-, -CH=CH-, -CH ₂ -CH ₂ -, -O-, -S-, -C(=O)-, -C(=O ) -O-, -O-C(=O)-, -O-C(=O)-O-, -CH=N-, -N=CH-, -N=N-, -C(=O ) -NR ¹⁶ -, -NR ¹⁶ -C(=O)-, -OCH ₂ -, -OCF ₂ -, -CH ₂ O-, -CF ₂ O-, -CH=CH-C(=O)- represents 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 with an alkoxy group having 1 to 5 carbon atoms, and the hydrogen atom contained in the alkoxy group may be substituted with a halogen atom. -CH ₂ - constituting the alkanediyl group may be replaced with -O- or -CO-. ]

The number of carbon atoms in the aromatic hydrocarbon group and alicyclic hydrocarbon group of A11 is preferably in the range of 3 to 18, more preferably in the range of 5 to 12, particularly 5 or 6. preferable. A hydrogen atom contained in the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group represented by A11 is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, It may be substituted with a cyano group or a nitro group, and hydrogen atoms contained in the C1-6 alkyl group and the C1-6 alkoxy group may be substituted with a fluorine atom. A11 is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group.

E11 is preferably a linear alkanediyl group having 1 to 12 carbon atoms. —CH ₂ — constituting the alkanediyl group may be replaced with —O—.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane -1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group and dodecane-1,12- Linear alkanediyl groups having 1 to 12 carbon atoms such as diyl groups; -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O- CH ₂ -CH ₂ - and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ - and the like.
B11 is preferably -O-, -S-, -CO-O- or -O-CO-, and more preferably -CO-O-.
B12 and B13 each independently represent -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -OC (=O)-O- is preferred, and -O- or -OC(=O)-O- is more preferred.

［式（Ｐ－１１）～（Ｐ－１５）中、
Ｒ^１７～Ｒ^２１はそれぞれ独立に、炭素数１～６のアルキル基または水素原子を表わす。］ As the polymerizable group represented by P11, a radically polymerizable group or a cationically polymerizable group is preferable in terms of high polymerization reactivity, particularly photopolymerization reactivity, and handling is easy, and the production of the liquid crystal compound itself is also easy. Therefore, the polymerizable group is preferably a group represented by the following formulas (P-11) to (P-15).

[In the 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. ]

Specific examples of the groups represented by formulas (P-11) to (P-15) include groups represented by the following formulas (P-16) to (P-20).

P11 is preferably a group represented by formulas (P-14) to (P-20), more preferably a vinyl group, a p-stilbene group, an epoxy group or an oxetanyl group.
More preferably, the group represented by P11-B11- is an acryloyloxy group or a methacryloyloxy group.

Examples of the polymerizable liquid crystal compound (Y) include 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 are as defined above;
A12-A14 are each independently synonymous with A11, B14-B16 are each independently synonymous with B12, B17 is synonymous with B11, E12 is synonymous with E11, P12 is synonymous with P11 be.
F11 is 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 hydroxy group, a methylol 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, and —CH ₂ — constituting the alkyl group and the alkoxy group may be replaced with —O— good. )

Specific examples of the polymerizable liquid crystal compound (Y) are described in "3.8.6 Network (completely crosslinked type)" in Liquid Crystal Handbook (Liquid Crystal Handbook Editing Committee, published by Maruzen Co., Ltd. on October 30, 2000). , Compounds having a polymerizable group among the compounds described in "6.5.1 Liquid crystal material b. Polymerizable nematic liquid crystal material", JP 2010-31223, JP 2010-270108, JP Polymerizable liquid crystals described in JP-A-2011-6360 and JP-A-2011-207765 can be mentioned.

Specific examples of the polymerizable liquid crystal compound (Y) include the following formulas (I-1) to (I-4), formulas (II-1) to (II-4), formulas (III-1) to formulas (III-26), formulas (IV-1) to (IV-26), formulas (V-1) to (V-2) and formulas (VI-1) to (VI-6) compound. In the following formula, k1 and k2 each independently represent an integer of 2-12. These polymerizable liquid crystal compounds (Y) are preferable in terms of ease of synthesis or availability.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film is, for example, 70 to 99.5 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition, It is preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, still more preferably 90 to 95 parts by mass. When the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the cured liquid crystal film to be obtained. In the present invention, the solid content of the polymerizable liquid crystal composition means all components excluding volatile components such as organic solvents from the polymerizable liquid crystal composition. Further, when the polymerizable liquid crystal composition contains two or more polymerizable liquid crystal compounds, the total content of all the polymerizable liquid crystal compounds contained in the polymerizable liquid crystal composition is preferably within the above range.

The polymerizable liquid crystal composition used for forming the vertically aligned liquid crystal cured film further contains additives such as a solvent, a polymerization initiator, an antioxidant, and a photosensitizer, in addition to the vertical alignment accelerator and the polymerizable liquid crystal compound. You can stay. Each of 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 applied onto a substrate or the like in a state of being dissolved in a solvent, it preferably contains a solvent. As the solvent, a solvent capable of dissolving the polymerizable liquid crystal compound is preferable, and a solvent inert to the polymerization reaction of the polymerizable liquid crystal compound is preferable. Examples of solvents include water, alcohols such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol and propylene glycol monomethyl ether. Solvent; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone ketone solvents; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents; chlorine-containing solvents such as chloroform and chlorobenzene; amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP) and 1,3-dimethyl-2-imidazolidinone; be done. These solvents can be used alone or in combination of two or more. Among these, 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, more preferably 70 to 95 parts by weight, per 100 parts by weight of the polymerizable liquid crystal composition. Therefore, the solid content in 100 parts by mass of the polymerizable liquid crystal composition is preferably 2 to 50 parts by mass. When the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition is low, so that the thickness of the film becomes substantially uniform and unevenness tends to be less likely to occur. The solid content can be appropriately determined in consideration of the thickness of the cured liquid crystal film to be produced.

A polymerization initiator is a compound capable of initiating a polymerization reaction of a polymerizable liquid crystal compound or the like by generating reactive species with the contribution of heat or light. Reactive species include active species such as radicals or cations or anions. Among them, a photopolymerization initiator that generates radicals by light irradiation is preferable from the viewpoint that reaction control is easy.

Examples of photopolymerization initiators include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, oxime compounds, triazine compounds, iodonium salts and sulfonium 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 (above, BASF Japan Corporation ), Seikuol BZ, Seikuol Z, Seikuol BEE (manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adeka Optomer SP- 152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer N-1919, Adeka Arkles NCI-831, Adeka Arkles NCI-930 (manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ -PP (manufactured by Nihon SiberHegner Co., Ltd.) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.).

Since the photopolymerization initiator can fully utilize the energy emitted from the light source and is excellent in productivity, it is preferable that the maximum absorption wavelength is 300 nm to 400 nm, more preferably 300 nm to 380 nm. Polymerization initiators and oxime photopolymerization initiators are preferred.

α-Acetophenone compounds include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1 -one and 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)butan-1-one and the like, more preferably 2-methyl-2-morpholino-1-( 4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one. Commercially available α-acetophenone compounds include Irgacure 369, 379EG, and 907 (manufactured by BASF Japan Ltd.) and Seikuol BEE (manufactured by Seiko Kagaku Co., Ltd.).

Oxime-based photopolymerization initiators generate radicals such as phenyl radicals and methyl radicals when irradiated with light. Polymerization of the polymerizable liquid crystal compound favorably proceeds by these radicals, and among them, an oxime-based photopolymerization initiator that generates methyl radicals is preferable because of its high initiation efficiency of the polymerization reaction. Moreover, from the viewpoint of allowing the polymerization reaction to proceed more efficiently, it is preferable to use a photopolymerization initiator capable of efficiently utilizing ultraviolet rays having a wavelength of 350 nm or more. As a photopolymerization initiator capable of efficiently utilizing ultraviolet light having a wavelength of 350 nm or more, a triazine compound or a carbazole compound containing an oxime structure is preferable, and a carbazole compound containing an oxime ester structure is more preferable from the viewpoint of sensitivity. Examples of oxime photopolymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) and the like. Commercially available oxime ester photopolymerization initiators include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (manufactured by BASF Japan Ltd.), Adeka Optomer N-1919, and Adeka Arkles NCI-831. (above, manufactured by ADEKA Corporation) and the like.

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 with respect to 100 parts by mass of the polymerizable liquid crystal compound. is. Within the above range, the reaction of the polymerizable group proceeds sufficiently and the orientation of the polymerizable liquid crystal compound is less likely to be disturbed.

By adding an antioxidant, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. The antioxidant may be a primary antioxidant selected from phenol antioxidants, amine antioxidants, quinone antioxidants, and nitroso antioxidants, or may be a phosphorus antioxidant and a sulfur antioxidant. It may be a secondary antioxidant selected from system antioxidants. In order to polymerize the polymerizable liquid crystal compound without disturbing the alignment of the polymerizable liquid crystal compound, the content of the antioxidant is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. Yes, preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass. An antioxidant can be used individually or in combination of 2 or more types.

Moreover, a photoinitiator can be made highly sensitive by using a photosensitizer. Examples of photosensitizers include xanthones such as xanthone and thioxanthone; anthracenes having substituents such as anthracene and alkyl ether; phenothiazine; and rubrene. A photosensitizer can be used individually or in combination of 2 or more types. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. 3 parts by mass.

The polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film contains a component that functions as a leveling agent or a vertical alignment accelerator, a polymerizable liquid crystal compound, and other components such as a solvent and a photopolymerization initiator. It can be obtained by stirring at temperature.

In the present invention, the vertically aligned liquid crystal cured film is preferably aligned with a high degree of order in the vertical direction of the liquid crystal cured film. In the vertically aligned liquid crystal cured film, the polymerizable liquid crystal compound is oriented with a high degree of order. It tends to be excellent in the effect of suppressing reflection hue change. The vertically aligned liquid crystal cured film satisfies the following formula (7) as an index representing the high alignment state of the polymerizable liquid crystal compound in the vertically aligned liquid crystal compound and indicating the degree of the oblique optical compensation effect during black display. preferable.
−150 nm≦RthC(550)≦−30 nm (7)
In formula (7), RthC(550) represents the retardation value in the film thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. From the viewpoint of further improving the oblique reflection hue during black display, the film thickness direction retardation value RthC(550) of the vertically aligned liquid crystal cured film is more preferably −130 nm or more, more preferably −100 nm or more, and particularly It is preferably −90 nm or more, more preferably −40 nm or less, and still more preferably −50 nm or less.

In one aspect 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 a retardation value in the film thickness direction of the vertically aligned liquid crystal cured film at a wavelength of λnm. ]
By satisfying the above formula (8), it is possible to suppress the decrease in ellipticity on the short wavelength side in the laminate containing the cured film for vertically aligned liquid crystal, and to improve the oblique reflection hue during black display. . The value of RthC(450)/RthC(550) in the vertically aligned liquid crystal cured film is more preferably 0.95 or less, still more preferably 0.92 or less, and particularly preferably 0.9 or less. is 0.7 or more, more preferably 0.75 or more, and still more preferably 0.8 or more.

The thickness direction retardation value RthC(λ) of the vertically aligned liquid crystal cured film can be adjusted by the thickness dC of the vertically aligned liquid crystal cured film. The in-plane retardation value is given by the following formula:
RthC(λ)=((nxC(λ)+nyC(λ))/2−nzC(λ))×dC
(Wherein, nxC (λ) is the in-plane principal refractive index of the vertically aligned liquid crystal cured film at the wavelength λnm, nyC (λ) is the refraction in the plane perpendicular to nxC (λ) at the wavelength λnm index, nzC(λ) indicates the refractive index in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of λnm, and when nxC(λ) = nyC(λ), nxC(λ) is an arbitrary value in the film plane. It can be the refractive index of the direction, and dC indicates the thickness of the vertically aligned liquid crystal cured film)
Therefore, in order to obtain a desired retardation value RthC(λ) in the thickness direction, the three-dimensional refractive index and the thickness dC should be adjusted. The three-dimensional refractive index depends on the molecular structure and alignment state of the polymerizable liquid crystal compound described above.

Examples of the substrate constituting the laminate of the present invention include glass substrates and film substrates, and resin film substrates are preferable from the viewpoint of workability. Examples of resins constituting the film substrate include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; Cellulose esters such as diacetyl cellulose and cellulose acetate propionate; polyethylene naphthalates; polycarbonates; polysulfones; polyethersulfones; polyetherketones; Such a resin can be used as a base material by forming a film by known means such as a solvent casting method and a melt extrusion method. The substrate surface may be subjected to surface treatment such as release treatment such as silicone treatment, corona treatment, plasma treatment and the like.

A commercially available product may be used as the substrate. Commercially available cellulose ester substrates include, for example, cellulose ester substrates manufactured by Fuji Photo Film Co., Ltd. such as Fujitac Film; and cellulose ester base materials. Commercially available cyclic olefin resins include, for example, cyclic olefin resins manufactured by Ticona (Germany) such as "Topas (registered trademark)"; cyclic olefins manufactured by JSR Corporation such as "Arton (registered trademark)"; Cyclic olefin resins manufactured by Nippon Zeon Co., Ltd. such as "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)"; Mitsui such as "APEL" (registered trademark) A cyclic olefin-based resin manufactured by Kagaku Co., Ltd. can be mentioned. A commercially available cyclic olefin resin base material can also be used. Examples of commercially available cyclic olefin resin substrates include cyclic olefin resin substrates manufactured by Sekisui Chemical Co., Ltd. such as “Escina (registered trademark)” and “SCA40 (registered trademark)”; Optes Co., Ltd. cyclic olefin resin base material such as "; JSR Co., Ltd. cyclic olefin resin base material such as "Arton Film (registered trademark)".

In the present invention, the substrate may be one that can be finally peeled from the laminate of the present invention.
The thickness of the substrate is usually 5 to 300 μm, preferably 10 to 150 μm, from the viewpoints of thickness reduction of the laminate, easiness of peeling of the substrate, handleability of the substrate, and the like.

The laminate of the present invention may contain layers other than the substrate and the vertically aligned liquid crystal cured film as long as the effects of the present invention are not affected. Such other layers include, for example, a horizontal alignment retardation film (horizontal alignment liquid crystal cured film), a horizontal alignment film, a cured resin for the purpose of reinforcing the mechanical strength of the liquid crystal cured film layer, hard coat layer, adhesive layer, primer layer, and the like.

In the present invention, a vertically aligned liquid crystal satisfying at least one of formulas (1) and (2) and at least one of formulas (3), (4), (5) and (6) As for the cured film, a vertically aligned liquid crystal cured film in which the polymerizable liquid crystal compound is vertically aligned with high precision can be obtained without a vertical alignment film. Therefore, the present invention satisfies at least one of the above formulas (1) and (2) and satisfies at least one of the formulas (3), (4), (5) and (6) A polymerizable liquid crystal composition capable of forming a vertically aligned liquid crystal cured film is also targeted.

Such a polymerizable liquid crystal composition includes a polymerizable liquid crystal compound, a leveling agent, and at least one selected from the group consisting of an ionic compound composed of non-metal atoms and a nonionic silane compound. A polymerizable liquid crystal composition containing a polymerizable liquid crystal compound, a leveling agent, an ionic compound composed of nonmetallic atoms, and a nonionic silane compound is preferred. The polymerizable liquid crystal compound may be either a reverse wavelength dispersion polymerizable liquid crystal compound or a normal wavelength dispersion polymerizable liquid crystal compound. As the polymerizable liquid crystal compound, the leveling agent, the ionic compound composed of non-metallic atoms, and the nonionic silane compound, those exemplified above can be included in the vertically aligned liquid crystal cured film constituting the laminate of the present invention. A similar one can be used. Furthermore, the polymerizable liquid crystal composition may further contain additives such as solvents, polymerization initiators, antioxidants and photosensitizers. As these components, the same components as those previously exemplified as those which can be contained in the vertically aligned liquid crystal cured film constituting the laminate of the present invention can be used.

In one aspect 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 an ionic compound and a nonionic A polymerizable liquid crystal composition containing at least one selected from the group consisting of silane compounds. In one aspect of the present invention, the polymerizable liquid crystal composition of the present invention includes 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 comprising a nonmetallic atom, and a nonionic A polymerizable liquid crystal composition containing a 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 containing the structure represented by the above formula (Y).

[Method for manufacturing laminate]
The laminate of the present invention is, for example,
A step of applying 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 film;
drying the coating to form a dry coating; and
It can be produced by a method including a step of irradiating a dried coating film with an active energy ray to form a vertically aligned liquid crystal cured film.

Formation of the coating film of the polymerizable liquid crystal composition is performed, for example, on the base material or on another layer such as a cured resin layer having no vertical alignment control force provided on the base material. can be performed by applying the polymerizable liquid crystal composition of .

Examples of methods for applying the polymerizable liquid crystal composition to a substrate or the like include coating methods such as spin coating, extrusion, gravure coating, die coating, bar coating, and applicator methods, and printing methods such as flexography. and other known methods.

Then, a dry coating film is formed by removing the solvent by drying or the like. Drying methods include natural drying, ventilation drying, heat drying, and reduced pressure drying. At this time, by heating the coating film obtained from the polymerizable liquid crystal composition, the solvent can be removed from the coating film by drying, and the polymerizable liquid crystal compound can be oriented in the direction perpendicular to the plane of the coating film. The heating temperature of the coating film can be appropriately determined in consideration of the polymerizable liquid crystal compound to be used and the material of the base material forming the coating film. A temperature above the phase transition temperature is usually required. In order to bring the polymerizable liquid crystal compound into a vertically aligned state while removing the solvent contained in the polymerizable liquid crystal composition, for example, the liquid crystal phase transition temperature (smectic phase transition temperature) of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition temperature or nematic phase transition temperature).
The liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), or the like. Further, when two or more kinds of polymerizable liquid crystal compounds are used in combination, the phase transition temperature is obtained by polymerization in which all the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition are mixed in the same ratio as the composition in the polymerizable liquid crystal composition. It means a temperature measured using a mixture of polymerizable liquid crystal compounds in the same manner as in the case of using one type of polymerizable liquid crystal compound. It is generally known that the liquid crystal phase transition temperature of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition may be lower than the liquid crystal phase transition temperature of the polymerizable liquid crystal compound itself.

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

The removal of the solvent from the coating film may be carried out simultaneously with the heating of the polymerizable liquid crystal compound to the liquid crystal phase transition temperature or higher, or may be carried out separately. Before heating to the liquid crystal phase transition temperature or higher of the polymerizable liquid crystal compound, the solvent in the coating film is moderately added under conditions in which the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition is not polymerized. A pre-drying step may be provided for removal. Examples of the drying method in the preliminary drying step include a natural drying method, a ventilation drying method, a heat drying method and a reduced pressure drying method, and the drying temperature (heating temperature) in the drying step depends on the type of polymerizable liquid crystal compound used, the can be determined as appropriate according to the type of , its boiling point, its amount, and the like.

Next, in the obtained dried coating film, the polymerizable liquid crystal compound is polymerized while maintaining the vertical alignment state of the polymerizable liquid crystal compound, thereby forming a vertically aligned liquid crystal cured film. Examples of the polymerization method include a thermal polymerization method and a photopolymerization method, and the photopolymerization method is preferable from the viewpoint of easy control of the polymerization reaction. In photopolymerization, the light irradiated to the dry coating film includes the type of polymerization initiator contained in the dry coating film, the type of polymerizable liquid crystal compound (especially the type of polymerizable group possessed by the polymerizable liquid crystal compound), and It is appropriately selected according to the amount. Specific examples thereof include at least one kind of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays and γ-rays, and active electron beams. Among them, ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction and that a widely used photopolymerization apparatus in the field can be used. It is preferable to select the types of the polymerizable liquid crystal compound and the polymerization initiator contained in the polymerizable liquid crystal composition. The polymerization temperature can also be controlled by light irradiation while cooling the dry coating film with an appropriate cooling means at the time of polymerization. By adopting such a cooling means and polymerizing the polymerizable liquid crystal compound at a lower temperature, a vertically aligned liquid crystal cured film can be properly formed even if a base material having relatively low heat resistance is used. It is also possible to accelerate the polymerization reaction by raising the polymerization temperature within a range in which problems caused by heat during light irradiation (such as deformation of the base material due to heat) do not occur. A patterned cured film can also be obtained by performing masking or development during photopolymerization.

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

The UV irradiation intensity is usually 10 to 3,000 mW/cm ² . The ultraviolet irradiation intensity is preferably in the wavelength range effective for activation of the photopolymerization initiator. The light irradiation time is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, still more preferably 0.1 seconds to 1 minute. be. When irradiated once or multiple times with such an irradiation intensity of ultraviolet rays, the cumulative amount of light is 10 to 3,000 mJ/cm ² , preferably 50 to 2,000 mJ/cm ² , more preferably 100 to 1,000 mJ/cm. ² .

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

[Horizontal alignment retardation film]
The horizontally aligned retardation film that can constitute the laminate of the present invention means a retardation film aligned horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film, for example, a stretched film or a polymerizable liquid crystal compound A cured product of a polymerizable liquid crystal composition containing a cured product obtained by curing the polymerizable liquid crystal compound in a state aligned in the horizontal direction with respect to the retardation film plane (hereinafter, "horizontally aligned liquid crystal cured film" Also called) and so on.

In the present invention, the horizontally oriented retardation film preferably satisfies the following formula (11).
ReA(450)/ReA(550)≤1.0 (11)
[In the formula (11), ReA (λ) represents the in-plane retardation value of the horizontally aligned retardation film at a wavelength λ nm, ReA (λ) = (nxA (λ) - nyA (λ)) × dA ( In the formula, nxA (λ) represents the principal refractive index at wavelength λnm in the plane of the horizontally aligned retardation film, and nyA (λ) is the wavelength λnm in the direction perpendicular to the direction of nxA in the same plane as nxA. represents the refractive index of, dA represents the film thickness of the horizontally aligned retardation film)]

When the horizontally aligned retardation film satisfies the formula (11), the horizontally aligned retardation film has an in-plane retardation value at a short wavelength smaller than an in-plane retardation value at a long wavelength, so-called reverse wavelength dispersion show gender. By combining such a horizontally aligned retardation film with the vertically aligned liquid crystal cured film, it is possible to obtain a laminate having an excellent effect of improving frontal and oblique reflection hues during black display when incorporated in an organic EL display device. can. ReA(450)/ReA(550) is preferably 0.70 or more, more preferably 0.70 or more, because the reverse wavelength dispersion is improved and the effect of improving the reflection hue in the front direction of the horizontally aligned retardation film can be further enhanced. is 0.78 or more, preferably 0.95 or less, more preferably 0.92 or less.

The in-plane retardation value can be adjusted by the thickness dA of the horizontally oriented retardation film. Since the in-plane retardation value is determined by the above formula ReA (λ) = (nxA (λ) - nyA (λ)) x dA, the desired in-plane retardation value (ReA (λ): wavelength λ ( In order to obtain the in-plane retardation value of the horizontally aligned retardation film in nm)), the three-dimensional refractive index and the film thickness dA should be adjusted.

Moreover, it is preferable that the horizontally oriented retardation film satisfies the following formula (12).
120 nm≦ReA(550)≦170 nm (12)
[In formula (12), ReA(λ) has the same meaning as above]
When the in-plane retardation ReA (550) of the horizontally aligned retardation film is within the range of formula (12), the laminate (elliptically polarizing plate) containing the horizontally aligned retardation film is applied to an organic EL display device. The effect of improving the front reflection hue during black display (the effect of suppressing coloring) becomes remarkable. A more preferable range of the in-plane retardation value is 130 nm≦ReA(550)≦150 nm.

The horizontally aligned retardation film is preferably a horizontally aligned liquid crystal cured film because the desired retardation of the retardation film can be easily controlled and the film can be made thinner. As the polymerizable liquid crystal compound for forming the horizontally aligned liquid crystal cured film, conventionally known polymerizable liquid crystal compounds in the field of retardation films can be used. Specifically, compounds represented by the formulas (X) and/or (Y) exemplified as polymerizable liquid crystal compounds that can be used for forming a vertically aligned liquid crystal cured film can be used. A polymerizable liquid crystal compound exhibiting properties is preferable, and for example, a compound represented by the above formula (X) can be preferably used. In the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film, the polymerizable liquid crystal compounds may 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 for forming the horizontally aligned liquid crystal cured film is, for example, 70 to 99.5 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. , preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, still more preferably 90 to 95 parts by mass. If the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the resulting cured liquid crystal film.

In addition to the polymerizable liquid crystal compound, the polymerizable liquid crystal composition used for forming the horizontally aligned liquid crystal cured film further contains additives such as a solvent, a photoinitiator, a leveling agent, an antioxidant, and a photosensitizer. You can Examples of these components include those exemplified above as components that can be used in the vertically aligned liquid crystal cured film, and each may be used alone or in combination of two or more. .

A 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 and a photopolymerization initiator, at a predetermined temperature. .

The horizontal alignment liquid crystal cured film is, for example,
a step of applying a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film on a substrate or a horizontally aligned film to obtain a coating film;
drying the coating to form a dry coating; and
It can be produced by a method including a step of irradiating a dried coating film with an active energy ray to form a horizontally aligned liquid crystal cured film.

The coating film of the polymerizable liquid crystal composition can be formed, for example, by coating the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film on a substrate or on a horizontal alignment film as described below. . As the substrate that can be used here, the same substrates as those exemplified above as the substrate that can be used in the production of the vertically aligned liquid crystal cured film can be used.

Then, the solvent is removed by drying or the like to form a dry coating film. Drying methods include natural drying, ventilation drying, heat drying, and reduced pressure drying. Heat drying is preferable from the aspect of productivity, and the heating temperature in that case is preferably equal to or higher than the phase transition temperature of the polymerizable liquid crystal compound at which the solvent can be removed. Procedures and conditions in such steps are the same as those that can be employed in the method for producing a vertically aligned liquid crystal cured film.

The obtained dried coating film is irradiated with an active energy ray (more specifically, ultraviolet rays, etc.), and the polymerizable liquid crystal compound is irradiated while maintaining the state in which the polymerizable liquid crystal compound is aligned in the horizontal direction with respect to the plane of the coating film. is polymerized to form a horizontally aligned liquid crystal cured film. Examples of the polymerization method include the same methods as those that can be employed in the method for producing a vertically aligned liquid crystal cured film.

The thickness of the horizontally aligned liquid crystal cured film can be appropriately selected according to the display device to be applied, and is preferably 0.2 to 5 μm, more preferably 0.2 to 4 μm, and still more preferably 0.2 to 3 μm. .

By forming the coating film of the polymerizable liquid crystal compound on the horizontal alignment film, the horizontal alignment of the polymerizable liquid crystal compound can be further improved. For example, a horizontal alignment film is formed on the vertically aligned liquid crystal cured film constituting the laminate of the present invention, and the polymerizable liquid crystal composition for forming the horizontally aligned liquid crystal cured film is applied thereon to obtain a horizontally aligned liquid crystal cured film. In the case, compared with a method of forming a horizontally aligned liquid crystal cured film on a base material or on a horizontally aligned film provided on the base material, and later laminating the vertically aligned liquid crystal cured film via an adhesive layer or the like. , there is also the advantage that the manufacturing process of the laminate can be simplified. The alignment film can be appropriately selected from materials having a horizontal alignment regulating force for aligning the polymerizable liquid crystal compound in the horizontal direction with respect to the plane of the coating film. The orientation regulating force can be arbitrarily adjusted by the type of orientation layer, surface condition, rubbing conditions, etc., and in the case of being formed from a photo-orientable polymer, it can be arbitrarily adjusted by polarized irradiation conditions. It is possible.

The alignment film preferably has solvent resistance so that it does not dissolve when the polymerizable liquid crystal composition is applied or the like, and also has heat resistance during heat treatment for removing the solvent and for aligning the polymerizable liquid crystal compound, which will be described later. Examples of the alignment film include an alignment film containing an alignment polymer, a photo-alignment film, a groove alignment film having an uneven pattern or a plurality of grooves on the surface, a stretched film stretched in the orientation direction, etc., and the precision of the orientation angle and the A photo-alignment film is preferable from the viewpoint of quality.

Examples of the oriented polymer include polyamides and gelatins having an amide bond in the molecule, polyimide having an imide bond in the molecule and its hydrolysates such as polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, poly Oxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid esters. Among them, polyvinyl alcohol is preferred. Orientation polymer can be used individually or in combination of 2 or more types.

An oriented film containing an oriented polymer is usually produced by applying a composition in which an oriented polymer is dissolved in a solvent (hereinafter sometimes referred to as an "oriented polymer composition") to a substrate and removing the solvent, or It can be obtained by applying an oriented polymer composition to a substrate, removing the solvent, and rubbing (rubbing method). Examples of the solvent include the same solvents as those previously exemplified as solvents that can be used in the polymerizable liquid crystal composition.

The concentration of the oriented polymer in the oriented polymer composition may be within a range in which the oriented polymer material can be completely dissolved in the solvent. 0.1 to 10% is more preferable.

A commercially available alignment film material may be used as it is as the alignment polymer composition. Commercially available alignment film materials include Sanever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optomer (registered trademark, manufactured by JSR Corporation).

Examples of the method for applying the oriented polymer composition to the substrate include the same methods as those exemplified as the method for applying the polymerizable liquid crystal composition to the substrate.

Methods for removing the solvent contained in the oriented polymer composition include natural drying, ventilation drying, heat drying, and vacuum drying.

In order to impart an alignment regulating force to the alignment film, a rubbing treatment can be performed as necessary (rubbing method). As a method for imparting an alignment regulating force by a rubbing method, a rubbing cloth is wound around a rotating rubbing roll, and an orienting polymer composition is applied to the substrate and then annealed to form an orientation polymer composition on the substrate surface. A method of contacting a film of an oriented polymer can be mentioned. A plurality of regions (patterns) with different alignment directions can be formed in the alignment film by masking during the rubbing process.

A photo-alignment film is usually formed by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter also referred to as a "composition for forming a photo-alignment film") to a substrate, and removing the solvent and then polarizing the film. (preferably polarized UV). The photo-alignment film is also advantageous in that the direction of the alignment regulating force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarized light.

A photoreactive group refers to a group that exhibits liquid crystal alignment ability upon irradiation with light. Specific examples include groups involved in photoreactions that cause liquid crystal alignment ability, such as orientation induction of molecules caused by light irradiation, isomerization reactions, dimerization reactions, photocrosslinking reactions, photodecomposition reactions, and the like. Among them, a group involved in a dimerization reaction or a photocrosslinking reaction is preferable from the viewpoint of excellent orientation. As the photoreactive group, a group having an unsaturated bond, particularly a double bond is preferable, and a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond Groups having at least one selected from the group consisting of a heavy bond (N=N bond) and a carbon-oxygen double bond (C=O bond) are particularly preferred.

Photoreactive groups having a C═C bond include vinyl groups, polyene groups, stilbene groups, stilbazole groups, stilbazolium groups, chalcone groups and cinnamoyl groups. Photoreactive groups having a C═N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. The photoreactive group having an N=N bond includes an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group, a formazan group, and a group having an azoxybenzene structure. Photoreactive groups having a C=O bond include benzophenone, coumarin, anthraquinone and maleimide groups. These groups may have substituents such as alkyl groups, alkoxy groups, aryl groups, allyloxy groups, cyano groups, alkoxycarbonyl groups, hydroxyl groups, sulfonic acid groups, and halogenated alkyl groups.

Among them, a photoreactive group that participates in a photodimerization reaction is preferable, the amount of polarized light irradiation required for photoalignment is relatively small, and a photoalignment film having excellent thermal stability and stability over time can be easily obtained. Cinnamoyl and chalcone groups are preferred. As the polymer having a photoreactive group, a polymer having a cinnamoyl group having a cinnamic acid structure at the end of the polymer side chain is particularly preferred.

A photo-alignment inducing layer can be formed on a substrate by applying the composition for forming a photo-alignment film onto the substrate. The solvent contained in the composition includes the same solvents as those previously exemplified as solvents that can be used in the polymerizable liquid crystal composition, and is appropriately selected depending on the solubility of the polymer or monomer having a photoreactive group. can do.

The content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be appropriately adjusted depending on the type of polymer or monomer and the thickness of the desired photo-alignment film. It is preferably at least 0.2% by mass, more preferably in the range of 0.3 to 10% by mass. The composition for forming a photo-alignment film may contain a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer, as long as the properties of the photo-alignment film are not significantly impaired.

The method of applying the photo-alignment film-forming composition to the substrate includes the same method as the method of applying the orienting polymer composition to the substrate. Examples of methods for removing the solvent from the coated composition for forming a photo-alignment film include natural drying, ventilation drying, heat drying, and vacuum drying.

In order to irradiate polarized light, the composition for forming a photo-alignment film coated on the substrate, from which the solvent has been removed, is directly irradiated with polarized UV light. A format in which the light is irradiated may also be used. Moreover, it is particularly preferable that the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in a wavelength range in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb the light energy. Specifically, UV (ultraviolet rays) with a wavelength in the range of 250 to 400 nm is particularly preferred. Examples of the light source used for the polarized irradiation include a xenon lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, and an ultraviolet light laser such as KrF or ArF. preferable. Among these, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferable because of their high emission intensity of ultraviolet rays having a wavelength of 313 nm. Polarized UV can be emitted by passing the light from the light source through a suitable polarizer. As such a polarizer, a polarizing filter, a polarizing prism such as Glan-Thompson or Glan-Taylor, or a wire grid type polarizer can be used.

A plurality of regions (patterns) having different liquid crystal alignment directions can be formed by masking during rubbing or polarized light irradiation.

A groove alignment film is a film having an uneven pattern or a plurality of grooves on its surface. When a polymerizable liquid crystal compound is applied to a film having a plurality of linear grooves arranged at regular intervals, liquid crystal molecules are aligned along the grooves.

As a method for obtaining a grooved alignment film, after exposure through an exposure mask having pattern-shaped slits on the surface of a photosensitive polyimide film, development and rinsing are performed to form an uneven pattern, and a plate having grooves on the surface. A method of forming a UV curable resin layer before curing on a shaped master, transferring the formed resin layer to a substrate and then curing, and a UV curable resin film before curing formed on the substrate, A method of pressing a roll-shaped master plate having a plurality of grooves to form irregularities, and then curing the same may be used.

In the laminate of the present invention, the vertically aligned liquid crystal cured film and the horizontally aligned retardation film can be laminated via, for example, a pressure-sensitive adhesive layer or an adhesive layer. As the pressure-sensitive adhesive or adhesive, those conventionally known in the art can be used. Further, by applying a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film on the vertically aligned liquid crystal cured film constituting the laminate of the present invention through the horizontal alignment film, horizontal alignment is performed on the vertically aligned liquid crystal cured film. A retardation film (horizontally aligned liquid crystal cured film) can be laminated.

[Elliptical polarizing plate]
The present invention includes an elliptically polarizing plate comprising the laminate of the present invention and a polarizing film.
A polarizing film is a film having a polarizing function, and includes a stretched film to which a dye having anisotropic absorption is adsorbed, a film including a film coated with a dye having anisotropic absorption as a polarizer, and the like. Dyes having absorption anisotropy include, for example, dichroic dyes.

A film containing, as a polarizer, a stretched film to which a dye having anisotropic absorption is adsorbed is usually produced by uniaxially stretching a polyvinyl alcohol resin film and dyeing the polyvinyl alcohol resin film with a dichroic dye. At least a polarizer manufactured through a step of adsorbing a dichroic dye, a step of treating a polyvinyl alcohol resin film to which the dichroic dye is adsorbed with an aqueous boric acid solution, and a step of washing with water after the treatment with the aqueous boric acid solution. It is produced by sandwiching a transparent protective film on one side with an adhesive interposed therebetween.

A polyvinyl alcohol-based resin is obtained by saponifying a polyvinyl acetate-based resin. Polyvinyl acetate-based resins include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate with other monomers copolymerizable therewith. Other monomers copolymerizable with vinyl acetate include, for example, unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

The degree of saponification of the polyvinyl alcohol resin is usually about 85 to 100 mol %, preferably 98 mol % or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. The degree of polymerization of the polyvinyl alcohol resin is generally about 1,000 to 10,000, preferably 1,500 to 5,000.

A film obtained by forming such a polyvinyl alcohol-based resin is used as a raw film for a polarizing film. The method for forming a film from the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method. The film thickness of the polyvinyl alcohol-based raw film can be, for example, about 10 to 150 μm.

The uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before dyeing with a dichroic dye, simultaneously with dyeing, or after dyeing. When uniaxial stretching is performed after dyeing, this uniaxial stretching may be performed before boric acid treatment or during boric acid treatment. It is also possible to carry out uniaxial stretching in these multiple stages. In the uniaxial stretching, the film may be uniaxially stretched between rolls having different circumferential speeds, or may be uniaxially stretched using hot rolls. Uniaxial stretching may be dry stretching in which the film is stretched in the atmosphere, or wet stretching in which the polyvinyl alcohol resin film is stretched in a swollen state using a solvent. The draw ratio is usually about 3 to 8 times.

Dyeing a 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.

Specifically, iodine or a dichroic organic dye is used as the dichroic dye. Dichroic organic dyes include C.I. I. Examples include dichroic direct dyes composed of disazo compounds such as DIRECT RED 39, and dichroic direct dyes composed of compounds such as trisazo and tetrakisazo. The polyvinyl alcohol-based resin film is preferably immersed in water before being dyed.

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

On the other hand, when a dichroic organic dye is used as the dichroic dye, a method of dyeing by immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye is usually employed. The content of the dichroic organic dye in this aqueous solution is usually about 1×10 ⁻⁴ to 10 parts by mass, preferably 1×10 ⁻³ to 1 part by mass, more preferably about 1×10 −3 to 1 part by mass, per 100 parts by mass of water. is 1×10 ⁻³ to 1×10 ⁻² parts by mass. This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing aid. The temperature of the dichroic dye aqueous solution used for dyeing is usually about 20 to 80°C. The immersion time (dyeing time) in this aqueous solution is usually about 10 to 1,800 seconds.

Boric acid treatment after dyeing with a dichroic dye can usually be performed by a method of immersing a dyed polyvinyl alcohol-based resin film in an aqueous boric acid solution. The content of boric acid in the boric acid aqueous solution is usually 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 boric acid aqueous solution preferably contains potassium iodide, and the content of potassium iodide in that case is usually 0.1 to 0.1 per 100 parts by mass of water. It is about 15 parts by mass, preferably 5 to 12 parts by mass. The immersion time in the boric acid aqueous solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, more preferably 200 to 400 seconds. The temperature of boric acid treatment is usually 50°C or higher, preferably 50 to 85°C, more preferably 60 to 80°C.

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

After washing with water, a drying treatment is performed to obtain a polarizer. The drying treatment can be performed using, for example, a hot air dryer or a far-infrared heater. The drying temperature is usually about 30 to 100°C, preferably 50 to 80°C. The drying time is usually about 60 to 600 seconds, preferably 120 to 600 seconds. The drying process reduces the moisture content of the polarizer to a practical level. Its moisture content is usually about 5 to 20% by mass, preferably 8 to 15% by mass. If the moisture content is less than 5% by mass, the flexibility of the polarizer is lost, and the polarizer may be damaged or broken after drying. Moreover, when the moisture content exceeds 20% by mass, the thermal stability of the polarizer may deteriorate.

The thickness of the polarizer obtained by subjecting the polyvinyl alcohol resin film to uniaxial stretching, dyeing with a dichroic dye, boric acid treatment, washing with water and drying is preferably 5 to 40 μm.

Examples of the film coated with a dye having anisotropic absorption include a film obtained by coating a composition containing a dichroic dye having liquid crystallinity or a composition containing a dichroic dye and a polymerizable liquid crystal. mentioned. The film preferably has a protective film on one or both sides thereof. Examples of the protective film include the same resin films as the base material that can be used in the production of the vertically aligned liquid crystal cured film.

It is preferable that the film coated with the dye having anisotropic absorption is thin, 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 20 μm or less, preferably 5 μm or less, more preferably 0.5 to 3 μm.

Specific examples of the film coated with a dye having absorption anisotropy include films described in JP-A-2012-33249.

A transparent protective film may be laminated on at least one surface of the polarizer thus obtained, for example, via an adhesive layer. As the transparent protective film, the same transparent film as the resin film exemplified above as the base material that can be used in the production of the vertically aligned liquid crystal cured film can be used.

The elliptically polarizing plate of the present invention comprises the laminate of the present invention, or a laminate obtained by removing the substrate from the laminate of the present invention and a polarizing film. and a polarizing film via an adhesive layer or the like, the elliptically polarizing plate of the present invention can be obtained. Further, the elliptically polarizing plate of the present invention can be obtained by laminating the laminate obtained by removing the base material from the laminate of the present invention and a polarizing film.

In one aspect of the present invention, when the laminate of the present invention containing a horizontally aligned retardation film and a polarizing film are laminated, the slow axis (optical axis) and polarized light of the horizontally aligned retardation film constituting the laminate It is preferable to laminate so that the angle formed with the absorption axis of the film is 45±5°.

The elliptically polarizing plate of the present invention may have a structure like a conventional general elliptically polarizing plate, or a polarizing film and a retardation film. As such a configuration, for example, an adhesive layer (sheet) for bonding an elliptically polarizing plate to a display element such as an organic EL or the like, a polarizing film or a liquid crystal cured film used for the purpose of protecting the surface from scratches and stains protection film, etc.

The laminate and elliptically polarizing plate of the present invention can be used in various display devices.
A display device is a device having a display element, and includes a light-emitting element or a light-emitting device as a light source. Examples of display devices include liquid crystal displays, organic electroluminescence (EL) displays, inorganic electroluminescence (EL) displays, touch panel displays, electron emission displays (e.g. field emission displays (FED), surface field emission displays). (SED)), electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection display device (e.g. grating light valve (GLV) display device, display device having digital micromirror device (DMD) ) and piezoelectric ceramic displays, etc. Liquid crystal display devices include transmissive liquid crystal display devices, semi-transmissive liquid crystal display devices, reflective liquid crystal display devices, direct view liquid crystal display devices, projection liquid crystal display devices, and the like. The display device may be a display device for displaying a two-dimensional image, or a stereoscopic display device for displaying a three-dimensional image. The laminate of the present invention can be suitably used for organic electroluminescence (EL) display devices due to its high optical properties and excellent optical properties, and the laminate of the present invention can be suitably used for liquid crystal display devices and touch panel display devices. Alternatively, by using an elliptically polarizing plate, it is possible to obtain a display device that can easily realize a thin display device, has excellent optical characteristics, and exhibits excellent image display characteristics.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples. Unless otherwise specified, "%" and "parts" in the examples mean % by mass and parts by mass, respectively.

1. 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. Polymerizable liquid crystal compound (X1) was produced according to the method described in JP-A-2010-31223. Further, the polymerizable liquid crystal compound (X2) was produced according to the method described in JP-A-2009-173893. Polymerizable liquid crystal compound (X3) was prepared with reference to JP-A-2011-207765.

Polymerizable liquid crystal compound (X1)

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

Polymerizable liquid crystal compound (X2)

The absorbance of the polymerizable liquid crystal compound (X2) at a wavelength of 350 nm was measured according to the following method.
First, 1 mg of polymerizable liquid crystal compound (X1) was dissolved in 50 mL of tetrahydrofuran to obtain a solution. The solution obtained as a measurement sample is placed in a measurement cell with an optical path length of 1 cm, and the measurement sample is set in an ultraviolet-visible spectrophotometer ("UV-2450" manufactured by Shimadzu Corporation) to measure the absorption spectrum. When the absorbance at a wavelength of 350 nm was measured from the obtained absorption spectrum, it was confirmed to be 0.05 or less.

Polymerizable liquid crystal compound (X3)

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

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

Ionic compound A:

(3) Production of vertically aligned liquid crystal cured film COP film (ZF14-50) manufactured by Nippon Zeon Co., Ltd. After corona treatment, a polymerizable liquid crystal composition for vertically aligned liquid crystal cured film formation was applied using a bar coater. After heating at 120 ° C. for 60 seconds, a polymerizable liquid crystal composition for forming a cured film of a vertically aligned liquid crystal using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Inc.) while being heated to 120 ° C. A vertically aligned liquid crystal cured film was formed by irradiating the surface coated with ultraviolet rays (in a nitrogen atmosphere, an integrated amount of light at a wavelength of 365 nm: 500 mJ/cm ² ). The film thickness of the obtained vertically aligned liquid crystal cured film was measured with an ellipsometer (M-220 manufactured by JASCO Corporation) and found to be 1.2 μmm.

<Measurement of Rth of vertically aligned liquid crystal cured film>
Corona treatment was performed on the surface of the vertically aligned liquid crystal cured film of the laminate composed of the base material and the vertically aligned liquid crystal cured film prepared by the above procedure, and after bonding to glass via a 25 μm pressure-sensitive adhesive manufactured by Lintec, the substrate was applied. Peeled off the material. For the obtained laminate consisting of the glass, the adhesive, and the vertically aligned liquid crystal cured film, using KOBRA-WPR manufactured by Oji Scientific Instruments Co., Ltd., the front retardation was measured by changing the incident angle of light to the sample for optical property measurement. and a phase difference value when tilted at 40° about the fast axis center.
The average refractive index at each wavelength was measured using an ellipsometer M-220 manufactured by JASCO Corporation. The film thickness was measured using an Optical NanoGauge film thickness gauge C12562-01 manufactured by Hamamatsu Photonics K.K. From the values of the front retardation value, the retardation value when tilted at 40° about the fast axis, the average refractive index, and the film thickness, Oji Scientific Instruments technical data (http://www.oji-keisoku.co .jp/products/kobra/reference.html) to calculate the three-dimensional refractive index. From the obtained three-dimensional 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. . Table 5 shows the results.
RthC(λ)=((nxC(λ)+nyC(λ))/2−nzC(λ))×dC
RthC(λ) represents the retardation value in the film thickness direction of the vertically aligned liquid crystal cured film at a wavelength of λnm. Further, nxC(λ) is the in-plane principal refractive index of the vertically aligned liquid crystal cured film at wavelength λnm, nyC(λ) is the refractive index in the direction perpendicular to nxC(λ) at wavelength λnm, and nzC( λ) indicates 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) is the refractive index in any direction in the film plane. and dC indicates the film thickness of the vertically aligned liquid crystal cured film.

<Orientation evaluation>
The vertically aligned liquid crystal cured film surface of the laminate composed of the base material and the vertically aligned liquid crystal cured film prepared by the above procedure is applied to a glass of 5 × 5 cm × thickness 0.7 mm via a pressure-sensitive adhesive (25 μm) manufactured by Lintec. After bonding, only the substrate was peeled off. The resulting sample was observed using a polarizing microscope (“BX-51” manufactured by Olympus Corporation) at a magnification of 200 times, and the number of orientation defects in a field of view of 480 μm×320 μm was counted. Here, only the number of orientation defects caused by the measurement sample was counted, and the number of defects caused by environmental foreign matter other than the sample was excluded and not counted. Based on the results of observation with a polarizing microscope, the orientation of the laminate (cured film of vertically aligned liquid crystal) was evaluated based on the following evaluation criteria. If ◯, it was judged that the orientation was excellent, and if △, it was judged that the orientation was so good that the optical characteristics were not affected. Table 9 shows the results.
Evaluation criteria:
◯ (very good): The number of orientation defects is 0 or more and 5 or less.
Δ (Good): The number of orientation defects is 6 or more and 20 or less.
x (bad): 21 or more orientation defects, or no orientation at all.

<Analysis of constituent elements>
In the laminate composed of the vertically aligned liquid crystal cured film and the substrate prepared by the above method, the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate (non-substrate side interface A of the vertically aligned liquid crystal cured film) was analyzed by XPS (K-Alpha+ manufactured by Thermo Fisher Scientific) under the conditions shown in Table 1 below.
Next, from the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate, elemental information was confirmed by XPS while performing etching with an Ar gas cluster ion beam under the etching conditions shown in Table 1 below. After confirming the etching time from the interface on the opposite side to the interface on the substrate side, by extracting the elemental analysis information at the 100 nm point from the interface on the side opposite to the substrate, the vertically aligned liquid crystal cured film Constituent elements in the cured liquid crystal film were confirmed at a point (midpoint C) of 100 nm in the thickness direction from the interface on the opposite side of the base material to the cured liquid crystal film side.
Finally, a TAC film (KC4UY manufactured by Konica Minolta, Inc.) was separately prepared on the vertically aligned liquid crystal cured film side of the laminate composed of the vertically aligned liquid crystal cured film and the base material with a pressure-sensitive adhesive (25 μm) manufactured by Lintec Co., Ltd. , and after peeling off the base COP film (ZF14-50) in the original laminate, the structure of the base side peeled surface side of the obtained sample (base side interface B of the vertically aligned liquid crystal cured film) Elements were similarly analyzed by XPS. Table 2 shows the results.

2. Example 2
Except for changing the preparation of the polymerizable liquid crystal composition for forming the vertically aligned liquid crystal cured film and the formation of the vertically aligned liquid crystal cured film as follows, and changing the etching rate to 100 sec × 35 times when analyzing the constituent elements. produced a vertically aligned liquid crystal cured film in the same manner as in Example 1, confirmed the constituent elements, and evaluated the optical properties and orientation. Tables 3 and 9 show the results.

(1) Preparation of polymerizable liquid crystal composition for forming cured film of vertically aligned liquid crystal Liquid crystal compound (X2) 100 parts by weight, leveling agent "F-556" (manufactured by DIC) 0.25 parts by weight, Patent application 2016 2.0 parts by mass of ionic compound A (molecular weight: 645) prepared with reference to No. 514802, 0.5 parts by mass of silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.), photopolymerization initiation As an agent, 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (manufactured by BASF Japan Ltd., "Irgacure (registered trademark) 369 (Irg369)") was added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 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.

(2) Preparation of vertically aligned liquid crystal cured film After performing corona treatment on COP film (ZF14-50) manufactured by Zeon Corporation, a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was applied using a bar coater. After heating at 120 ° C. for 60 seconds, a polymerizable liquid crystal composition for forming a cured film of a vertically aligned liquid crystal using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Inc.) while being heated to 120 ° C. A vertically aligned liquid crystal cured film was formed by irradiating the surface coated with ultraviolet rays (in a nitrogen atmosphere, an integrated amount of light at a wavelength of 365 nm: 500 mJ/cm ² ). The film thickness of the obtained vertically aligned liquid crystal cured film was measured with an ellipsometer (M-220 manufactured by JASCO Corporation) and found to be 0.6 μm.

3. Example 3
The procedure was the same as in Example 1, except that the method for preparing the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed as follows, and that the etching rate was changed to 5 sec × 50 times when analyzing the constituent elements. A vertically aligned liquid crystal cured film was produced using the method, the constituent elements were confirmed, and the optical properties and orientation were evaluated. Tables 4 and 9 show the results.

(1) Preparation of polymerizable liquid crystal composition for forming cured film of vertically aligned liquid crystal The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the resulting mixture, 0.25 parts by mass of leveling agent "F-556" (manufactured by DIC), ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802. 2.0 parts by mass, silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass, 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl as a photopolymerization initiator ) 6 parts by mass of butan-1-one (manufactured by BASF Japan Ltd. “Irgacure (registered trademark) 369 (Irg369)”) was added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 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. Example 4
The procedure was the same as in Example 1, except that the method for preparing the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed as follows, and that the etching rate was changed to 5 sec × 50 times when analyzing the constituent elements. A vertically aligned liquid crystal cured film was produced using the method, the constituent elements were confirmed, and the optical properties and orientation were evaluated. Tables 5 and 9 show the results.

(1) Preparation of polymerizable liquid crystal composition for forming cured film of vertically aligned liquid crystal The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the resulting mixture, 0.25 parts by mass of leveling agent "F-556" (manufactured by DIC), ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802. 3.0 parts by mass, silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0 parts by mass, 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl as a photopolymerization initiator ) 6 parts by mass of butan-1-one (manufactured by BASF Japan Ltd. “Irgacure (registered trademark) 369 (Irg369)”) was added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 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. Example 5
The procedure was the same as in Example 1, except that the method for preparing the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed as follows, and that the etching rate was changed to 50 sec × 100 times when analyzing the constituent elements. A vertically aligned liquid crystal cured film was produced using the method, the constituent elements were confirmed, and the optical properties and orientation were evaluated. Tables 6 and 9 show the results.

(1) Preparation of polymerizable liquid crystal composition for forming cured film of vertically aligned liquid crystal The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the resulting mixture, 1.00 parts by mass of leveling agent "F-556" (manufactured by DIC), ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802. 2.0 parts by mass, silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass, 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl as a photopolymerization initiator ) 6 parts by mass of butan-1-one (manufactured by BASF Japan Ltd. “Irgacure (registered trademark) 369 (Irg369)”) was added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 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. Example 6
The procedure was the same as in Example 1, except that the method for preparing the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed as follows, and that the etching rate was changed to 5 sec × 50 times when analyzing the constituent elements. A vertically aligned liquid crystal cured film was produced using the method, the constituent elements were confirmed, and the optical properties and orientation were evaluated. Tables 7 and 9 show the results.

(1) Preparation of polymerizable liquid crystal composition for forming cured film of vertically aligned liquid crystal The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the resulting mixture, 0.10 parts by mass of leveling agent "F-556" (manufactured by DIC), ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802. 1.5 parts by mass, silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.25 parts by mass, 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl as a photopolymerization initiator ) 6 parts by mass of butan-1-one (manufactured by BASF Japan Ltd. “Irgacure (registered trademark) 369 (Irg369)”) was added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 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. Comparative example 1
In the same manner as in Example 1, except that the preparation of the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed as follows, and the etching rate was changed to 100 sec × 35 times in the analysis of the constituent elements. An oriented liquid crystal cured film was produced, the constituent elements were confirmed, and the optical properties and orientation were evaluated. Tables 8 and 9 show the results.

(1) Preparation of polymerizable liquid crystal composition for forming cured film of vertically aligned liquid crystal Polymerizable liquid crystal compound (X1) 100 parts by mass, leveling agent “F-556” (manufactured by DIC) 0.25 parts by mass, light 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (manufactured by BASF Japan Ltd. "Irgacure (registered trademark) 369 (Irg369)") was added as a polymerization initiator. . Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 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 was confirmed that a vertically aligned liquid crystal cured film having a predetermined element ratio exhibits excellent liquid crystal orientation (Examples 1 to 6).

1: Substrate 2: Vertically aligned liquid crystal cured film 11: Laminate (A): Non-substrate side interface (B): Substrate side interface (C): Midpoint

Claims (20)

A laminate including a vertically aligned liquid crystal cured film and a substrate,
The vertically aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition cured in a state in which the polymerizable liquid crystal compound is 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 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 abundance ratio (atom%) of fluorine element in the liquid crystal cured film at the interface on the opposite side of the base material of the vertically aligned liquid crystal cured film,
F (B) represents the abundance ratio (atom%) of the fluorine element in the cured liquid crystal film at the interface of the cured vertically aligned liquid crystal film on the substrate side,
F(C) represents the abundance ratio (atom%) of the fluorine element in the cured liquid crystal film at a point of 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film on the opposite side of the substrate to the cured liquid crystal film side. ,
Si (A) represents the abundance ratio (atom%) of the silicon element in the cured liquid crystal film at the interface on the side opposite to the substrate of the cured vertically aligned liquid crystal film,
Si (B) represents the abundance ratio (atom%) of the silicon element in the liquid crystal cured film at the interface on the substrate side of the vertically aligned liquid crystal cured film,
Si (C) represents the abundance ratio (atom%) of the silicon element in the cured liquid crystal film at a point of 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film on the opposite side of the substrate to the cured liquid crystal film side. ,
N (B) represents the abundance ratio (atom%) of the nitrogen element in the cured liquid crystal film at the interface on the substrate side of the cured vertically aligned liquid crystal film,
N(C) represents the abundance ratio (atom%) of the nitrogen element in the cured liquid crystal film at a point of 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film on the opposite side of the substrate to the cured liquid crystal film side. ,
P (B) represents the abundance ratio (atom%) of the phosphorus element in the liquid crystal cured film at the substrate side interface of the vertically aligned liquid crystal cured film,
P (C) represents the abundance ratio (atom%) of the phosphorus element in the cured liquid crystal film at a point of 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film on the side opposite to the base material to the cured liquid crystal film side. . ] 2. The laminate according to claim 1, wherein the vertically aligned liquid crystal cured film and the substrate are adjacent to each other. At least one of the formulas (1′) and (2′) is satisfied, at least one of the formulas (3′) and (4′) is satisfied, and the formulas (5′) and ( 3. Laminate according to claim 1 or 2, satisfying at least one of 6'). satisfying at least one of the formulas (1′) and (2′) and satisfying at least three of the formulas (3′), (4′), (5′) and (6′) The laminate according to any one of claims 1 to 3, which fills the 5. The laminate according to any one of claims 1 to 4, wherein the vertically aligned liquid crystal cured film contains a leveling agent. 6. The laminate according to claim 5, wherein the leveling agent contains elemental fluorine or elemental silicon. 7. The laminate according to any one of claims 1 to 6, wherein the vertically aligned liquid crystal cured film contains an ionic compound composed of non-metallic atoms. 8. The laminate according to any one of claims 1 to 7, wherein the vertically aligned liquid crystal cured film contains an ionic compound composed of non-metallic atoms, and the molecular weight of the ionic compound is 100 or more and 10,000 or less. 9. The laminate according to any one of claims 1 to 8, wherein the vertically aligned liquid crystal cured film contains an ionic compound comprising a phosphonium salt or an ammonium salt. 10. The laminate according to any one of claims 1 to 9, wherein the vertically aligned liquid crystal cured film contains a nonionic silane compound. 11. The laminate according to any one of claims 1 to 10, wherein the vertically aligned liquid crystal cured film contains a nonionic silane compound, and the nonionic silane compound is a silane coupling agent. 12. The laminate according to any one of claims 1 to 11, wherein the vertically aligned liquid crystal cured film contains a nonionic silane compound and an ionic compound. 13. The laminate according to any one of claims 1 to 12, wherein the thickness of the vertically aligned liquid crystal cured film is 0.3 µm or more and 5.0 µm or less. 14. The laminate according to any one of claims 1 to 13, wherein the vertically aligned liquid crystal cured film satisfies the following formula (7).
-150≤RthC(550)≤-30 (7)
[In the formula (7), RthC(550) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. ] 15. The laminate according to any one of claims 1 to 14, wherein the vertically aligned liquid crystal cured film satisfies the following formula (8).
RthC(450)/RthC(550)≤1.0 (8)
[In the formula (8), RthC (450) represents the thickness direction retardation value of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and RthC (550) is the thickness direction retardation value of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. indicates ] The laminate according to any one of claims 1 to 15, further comprising a horizontally oriented retardation film. The horizontally aligned retardation film is a horizontally aligned liquid crystal cured film obtained by curing in a state in which at least one polymerizable liquid crystal compound is horizontally aligned with respect to the in-plane direction of the retardation film, according to claim 16. laminate. An elliptically polarizing plate comprising the laminate according to claim 16 or 17 and a polarizing film. 19. The elliptically polarizing plate according to claim 18, wherein the angle between the slow axis of the horizontally aligned retardation film constituting the laminate and the absorption axis of the polarizing film is 45±5°. An organic EL display comprising the elliptically polarizing plate according to claim 18 or 19.

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