JP7443413B2 - Vertical alignment liquid crystal cured film - Google Patents

Description

The present invention relates to a vertically aligned liquid crystal cured film, a laminate, an elliptically polarizing plate, and an organic EL display device.

An elliptically polarizing plate is an optical member in which a polarizing plate and a retardation plate are laminated. For example, in a device that displays an image in a flat state (for example, an organic EL display device), it prevents light reflection at the electrodes that make up the device. It is used to prevent In this elliptically polarizing plate, a so-called λ/4 plate is used as the retardation plate.
As a retardation plate used in such an elliptically polarizing plate, one exhibiting reverse wavelength dispersion is preferable in that it exhibits equivalent retardation performance over a wide wavelength range of visible light. As a retardation plate exhibiting reverse wavelength dispersion, a retardation plate consisting of a horizontally aligned liquid crystal cured film that is polymerized and cured in a horizontally oriented state of a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion is known. .
Furthermore, there is also a need for a polarizing plate with an optical compensation function, which has a compensation function so that the optical performance when viewed from an oblique direction is the same as when viewed from the front. As such a polarizing plate with an optical compensation function, one is known that further includes a vertically aligned liquid crystal cured film in which a polymerizable liquid crystal compound is polymerized and cured in a vertically aligned state, in addition to a horizontally aligned liquid crystal cured film having reverse wavelength dispersion. It is being Furthermore, among these vertically aligned liquid crystal cured films, a vertically aligned liquid crystal cured film using a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion is proposed in Patent Document 1.

Japanese Patent Application Publication No. 2015-57646

However, since the molecular center of gravity of a liquid crystal compound exhibiting reverse wavelength dispersion is unstable, a large number of alignment defects occur with the liquid crystal compound alone, making it difficult to achieve vertical alignment. For this reason, an alignment film for vertical alignment is required to fabricate a vertically aligned liquid crystal cured film. However, in that case, a step of forming an alignment film for vertical alignment is required, resulting in a problem of reduced productivity.

The present invention has been made in view of the above problems, and its purpose is to provide a vertically aligned liquid crystal cured film in which the occurrence of alignment defects is suppressed even without an alignment film.

The present inventor has 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 vertically aligned liquid crystal cured film oriented in a direction perpendicular to the in-plane direction and containing at least one selected from the group consisting of a nonionic silane compound and an ionic compound.
[2] The vertically aligned liquid crystal cured film according to [1], wherein the nonionic silane compound is a silane coupling agent.
[3] The vertically aligned liquid crystal cured film according to [1] or [2], wherein the nonionic silane compound is a silane coupling agent having an alkoxysilyl group and a polar group.
[4] The vertically aligned liquid crystal cured film according to any one of [1] to [3], wherein all of the elements constituting the ionic compound are nonmetallic elements.
[5] The vertically aligned liquid crystal cured film according to any one of [1] to [4], wherein the ionic compound has a molecular weight of 100 or more and 10,000 or less.
The following relational expression (1):
-150nm≦RthC(550)≦-30nm...(1)
[In relational expression (1), RthC (550) indicates the retardation value in the thickness direction at a wavelength of 550 nm of the vertically aligned liquid crystal cured film]
The vertically aligned liquid crystal cured film according to any one of [1] to [5], which satisfies the following.
[7] The following relational expression (2):
RthC(450)/RthC(550)≦1...(2)
[In relational expression (2), RthC (450) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and RthC (550) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. ]
The vertically aligned liquid crystal cured film according to any one of [1] to [6], which satisfies the following.
[8] Comprising a base material and the vertically aligned liquid crystal cured film according to any one of [1] to [7],
A laminate, wherein the vertically oriented cured film is adjacent to the substrate.
[9] A laminate comprising the vertically aligned liquid crystal cured film according to [1] to [7] and a film oriented in a direction horizontal to the in-plane direction of the vertically aligned liquid crystal cured film.
[10] The following relational expression (3):
ReA(450)/ReA(550)≦1.00...(3)
[In relational expression (3), ReA (450) represents the in-plane retardation value at a wavelength of 450 nm of the film oriented in the horizontal direction with respect to the in-plane direction of the vertically aligned liquid crystal cured film, and ReA (550) represents the in-plane retardation value at a wavelength of 450 nm. Shows the in-plane retardation value at a wavelength of 550 nm of a film oriented in the horizontal direction with respect to the film surface of a vertically oriented liquid crystal cured film]
The laminate according to [9], which satisfies the following.
[11] The following relational expression (4):
|R0(550)-R40(550)|≦10nm...(4)
[In relational expression (4), R0 (550) indicates the in-plane retardation value of the laminate at a wavelength of 550 nm, and R40 (550) indicates the value around the fast axis direction of the film oriented in the horizontal direction of the laminate. Shows the phase difference value at a wavelength of 550 nm when rotated by 40 degrees]
The laminate according to any one of [9] and [10], which satisfies the following.
[12] The following relational expression (5):
|R0(450)-R40(450)|≦10nm...(5)
[In relational expression (5), R0 (450) indicates the in-plane retardation value of the laminate at a wavelength of 450 nm, and R40 (450) indicates the value around the fast axis direction of the film oriented in the horizontal direction of the laminate. Shows the phase difference value at a wavelength of 450 nm when rotated by 40 degrees]
The laminate according to any one of [9] to [11], which satisfies the following.
[13] The following relational expression (6):
|{R0(450)-R40(450)}-{R0(550)-R40(550)}|≦3nm...(6)
[In relational expression (6), R0 (450) represents the in-plane retardation value of the laminate at a wavelength of 450 nm, R0 (550) represents the in-plane retardation value of the laminate at a wavelength of 550 nm, and R40 ( 450) indicates the retardation value at a wavelength of 450 nm when the film oriented in the horizontal direction of the laminate is rotated by 40° around the fast axis direction, and R40 (550) indicates the retardation value at a wavelength of 450 nm when the film is oriented in the horizontal direction of the laminate. Shows the retardation value at a wavelength of 550 nm when the film is rotated by 40° around the fast axis direction]
The laminate according to any one of [9] to [12], which satisfies the following.
[14] The laminate according to any one of [9] to [13], wherein the film oriented in the horizontal direction with respect to the film surface of the vertically aligned liquid crystal cured film is a horizontally aligned liquid crystal cured film A.
[15] An elliptically polarizing plate comprising the laminate according to any one of [9] to [14] and a polarizing film.
[16] The elliptically polarizing plate according to [15], wherein the film oriented in the horizontal direction with respect to the film surface of the vertically aligned liquid crystal cured film is the horizontally aligned liquid crystal cured film A.
[17] The elliptically polarizing plate according to [15] or [16], wherein the angle between the slow axis of the horizontally oriented film and the absorption axis of the polarizing film is 45±5°.
[18] The polarizing film includes a horizontally oriented liquid crystal cured film B oriented horizontally with respect to the film plane of the polarizing film, and the horizontally oriented liquid crystal cured film B contains a dichroic dye, [15] [17] The elliptically polarizing plate according to any one of [17].
[19] The elliptically polarizing plate according to [18], wherein the dichroic dye has an azo group.
[20] The horizontally aligned liquid crystal cured film B is a cured film cured in a smectic phase state in which the liquid crystal compound is aligned horizontally with respect to the in-plane direction of the film, according to [18] or [19]. Elliptical polarizer.
[21] An organic EL display device comprising the elliptically polarizing plate according to any one of [15] to [20].

According to the present invention, it is possible to provide a vertically aligned liquid crystal cured film in which the occurrence of alignment defects is suppressed even without an alignment film.

FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of an elliptically polarizing plate of the present invention.

Embodiments of the present invention will be described in detail below. Note that in this specification, acrylic and methacrylic are sometimes referred to as "(meth)acrylic." In addition, "system" may be added after the compound name to comprehensively refer to the compound and its derivatives. When a polymer name is expressed by adding "system" after the compound name, the repeating unit of the polymer is derived from the compound or its derivative, or the repeating unit derived from the compound or its derivative has undergone chemical modification etc. after polymerization. It means that it is a polymer that has been subjected to

<Vertical alignment liquid crystal cured film>
The vertically aligned liquid crystal cured film of the present invention is aligned in a direction perpendicular to the in-plane direction and contains at least one selected from the group consisting of a nonionic silane compound and an ionic compound. The vertically aligned liquid crystal cured film is aligned in a direction perpendicular to the in-plane direction. That is, it contains a liquid crystal compound and/or a polymer of a liquid crystal compound that is aligned in a direction perpendicular to the in-plane direction of the vertically aligned liquid crystal cured film. The three-dimensional refractive index ellipsoid formed by the vertically aligned liquid crystal cured film may have biaxiality, but preferably has uniaxiality.

In the vertically aligned liquid crystal cured film of the present invention, the occurrence of alignment defects is suppressed even without an alignment film. The reason is assumed to be as follows. The vertically aligned liquid crystal cured film of the present invention contains at least one selected from the group consisting of a nonionic silane compound and an ionic compound. In the production of a cured liquid crystal film, when a composition for forming a vertically aligned liquid crystal cured film is applied to a substrate to form a coating film, and the coating film is heated and dried to form a dry film, non-ionic Due to the affinity between the silane compound and the liquid crystal compound and/or the affinity between the ionic compound and the liquid crystal compound, the ionic compound exists on the surface side of the substrate and/or the surface side of the dry film (from the surface of the substrate This results in a distribution in which the nonionic silane compound is present on the far side). Such a distribution increases the ability to regulate vertical alignment, so that the liquid crystal compound tends to align in the direction perpendicular to the substrate surface within the dried film. Therefore, a cured film can be formed while maintaining the state in which the liquid crystal compound is vertically aligned. Therefore, it is considered that the vertically aligned liquid crystal cured film of the present invention suppresses the occurrence of alignment defects even without an alignment film. At least one selected from the group consisting of nonionic silane compounds and ionic compounds includes three embodiments: nonionic silane compounds, ionic compounds, and nonionic silane compounds and ionic compounds. Although either a nonionic silane compound or an ionic compound alone has the effect of increasing the vertical alignment regulating force, from the viewpoint of further increasing the vertical alignment regulating force, it is preferable to include both a nonionic silane compound and an ionic compound. Preferably.

A vertically aligned liquid crystal cured film can be used to prevent deterioration of the oblique reflection hue of a display equipped with an elliptically polarizing plate containing a vertically aligned liquid crystal cured film (for example, a problem in which coloring such as red and blue is observed in the oblique hue of the display). ), from the perspective of suppressing
The following relational expression (1):
-150nm≦RthC(550)≦-30nm...(1)
[In relational expression (1), RthC (550) indicates the retardation value in the thickness direction at a wavelength of 550 nm of the vertically aligned liquid crystal cured film]
It is preferable to satisfy the following. The retardation value RthC (550) in the thickness direction of the vertically aligned liquid crystal cured film is more preferably -100 nm or more and -40 nm or less, and -80 nm or more, from the viewpoint of further suppressing deterioration of the oblique reflection hue of the display. It is more preferably -40 nm or less.

The retardation value RthC (550) in the thickness direction 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 phase difference value is calculated using the following formula (1-2):
RthC(550)=[(nxC(550)+nyC(550))/2-nzC(550)]×dC...(1-2)
[In formula (1-2), nxC(550) represents the principal refractive index at a wavelength of 550 nm in the film plane of the vertically aligned liquid crystal cured film, and nyC(550) represents the direction perpendicular to nxC(550) in the same plane. nzC (550) indicates the refractive index at a wavelength of 550 nm in the thickness direction of the vertically aligned liquid crystal cured film, and dC indicates the film thickness of the vertically aligned liquid crystal cured film]
Therefore, in order to obtain the desired thickness direction retardation value RthC (550), the three-dimensional refractive index and the film thickness dC may be adjusted. Note that the three-dimensional refractive index depends on the molecular structure and orientation of the above-mentioned liquid crystal compound. Furthermore, when nxC(550)=nyC(550), nxC(550) can be a refractive index in any direction within the film plane.

In addition, the vertically aligned liquid crystal cured film has the following characteristics:
The following relational expression (2):
RthC(450)/RthC(550)≦1...(2)
[In relational expression (2), RthC (450) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and RthC (550) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. ]
It is preferable to satisfy the following. From the viewpoint of further suppressing the decrease in the ellipticity, RthC(450)/RthC(550) of the vertically aligned liquid crystal cured film is more preferably 0.95 or less, and even more preferably 0.90 or less. . Further, the retardation value RthC (450) in the thickness direction of the vertically aligned liquid crystal cured film can be adjusted by the thickness dC of the vertically aligned liquid crystal cured film, similarly to RthC (550).

The upper limit of the film thickness of the vertically aligned liquid crystal cured film is preferably 3 μm or less, more preferably 2.5 μm or less, even more preferably 2.0 μm or less, particularly preferably 1.5 μm or less, from the viewpoint of thinning the film. . Further, the lower limit of the film thickness of the vertically aligned liquid crystal cured film is preferably 0.1 μm or more, more preferably 0.3 μm or more, and even more preferably 0.4 μm or more. The film thickness of the vertically aligned liquid crystal cured film can be measured using an ellipsometer or a contact type film thickness meter.

[1. Nonionic silane compound]
In this specification, a nonionic silane compound is a compound that is nonionic and contains Si element. In the production of a vertically aligned liquid crystal cured film, the nonionic silane compound sufficiently improves the vertical alignment of liquid crystal compound (I)-1, and when combined with an ionic compound, further improves the vertical alignment of the liquid crystal compound. be able to. In addition, the nonionic silane compound can easily lower the surface tension of the composition for forming a vertically aligned liquid crystal cured film, and can improve the wettability of the composition to the substrate. 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 (more specifically examples include silane coupling agents, etc.).

The nonionic silane compound may be of the silicone monomer type or may be of the silicone oligomer (polymer) type. Silicone oligomers are expressed in the form of (monomer)-(monomer) copolymers: 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, Copolymers containing mercaptopropyl groups, such as propyltriethoxysilane-tetramethoxysilane copolymers, and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymers; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymers, mercaptomethyltrimethoxysilane- Copolymers containing mercaptomethyl groups, such as tetraethoxysilane 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-methacryloyloxypropylmethyldimethoxy Silane-tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-methacryloyloxypropylmethyldiethoxysilane-tetra Copolymers containing methacryloyloxypropyl groups such as ethoxysilane copolymers; 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymers, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymers, 3-acryloyloxypropyltriethoxysilane -Tetramethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3- Copolymers containing acryloyloxypropyl groups, such as acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymers and 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymers; vinyltrimethoxysilane-tetramethoxysilane copolymers, vinyl Trimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinyl Copolymers containing vinyl groups such as methyldiethoxysilane-tetramethoxysilane copolymers and vinylmethyldiethoxysilane-tetraethoxysilane copolymers; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymers, 3-aminopropyltrimethoxysilane -tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyl Examples thereof include amino group-containing copolymers such as dimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer. These nonionic silane compounds may be used alone or in combination of two or more. Furthermore, silane-containing compounds exemplified in the section on leveling agents can also be used. Among these nonionic silane compounds, silane coupling agents are preferred from the viewpoint of further improving adhesion.

The silane coupling agent has a terminal group selected from the group consisting of vinyl group, epoxy group, styryl group, methacrylic group, acrylic group, amino group, isocyanurate group, ureido group, mercapto group, isocyanate group, carboxy group, and hydroxy group. It is a compound containing an Si element and having at least one functional group such as those mentioned above and at least one alkoxysilyl group or silanol group. By appropriately selecting these functional groups, the mechanical strength of the vertically aligned liquid crystal cured film can be improved, the surface of the vertically aligned liquid crystal cured film can be improved, and the relationship between the vertically aligned liquid crystal cured film and an adjacent layer (e.g., the base material) can be improved. It is possible to impart unique effects such as improved adhesion. From the viewpoint of further improving adhesion, the silane coupling agent preferably has an alkoxysilyl group and another different reactive group (for example, the above-mentioned functional group). Further, the silane coupling agent preferably has 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 of the liquid crystal compound is further improved, and the effect of promoting vertical alignment is significantly obtained. Examples of the polar group include an epoxy group, an amino group, an isocyanurate group, a mercapto group, a carboxy group, and a hydroxy group. Incidentally, the polar group may have an appropriate substituent or protective group in order to control the reactivity of the silane coupling agent.

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-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylethoxydimethylsilane are mentioned. It will be done.

In addition, commercially available silane coupling agents include, for example, KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403. , KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE Silane coupling agents manufactured by 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. can be mentioned.

The content of the nonionic silane compound is usually preferably 0.01% by mass to 5% by mass, and preferably 0.05% by mass to 4% by mass, based on the solid content of the composition for forming a vertically aligned liquid crystal cured film. %, and even more preferably 0.1% by mass to 3% by mass. When the content of the nonionic silane compound is 0.01% by mass or more based on the solid content of the composition, the vertical alignment of the liquid crystal compound is further improved, and the content of the nonionic silane compound is 0.01% by mass or more based on the solid content of the composition. When it is contained in an amount of 5% by mass or less based on the solid content of the composition, the coating properties of the composition are unlikely to deteriorate.

[2. Ionic compounds]
In the production of a vertically aligned liquid crystal cured film, the ionic compound can sufficiently improve the vertical alignment of liquid crystal compound (I)-1, and when combined with a nonionic silane compound, the vertical alignment of liquid crystal compound (I)-1 can be improved. can further improve performance.

Examples of ionic compounds include onium salts (more specifically, quaternary ammonium salts and tertiary sulfonium salts in which the nitrogen atom has a positive charge, and quaternary phosphonium salts in which the phosphorus atom has a positive charge). salt, etc.). Among these onium salts, quaternary onium salts are preferred from the viewpoint of further improving the vertical alignment of liquid crystal compound (I)-1, and quaternary phosphonium salts or quaternary onium salts are preferred from the viewpoint of improving availability and mass production. More preferred are quaternary ammonium salts. The onium salt may have two or more quaternary onium salt sites in the molecule, and may be an oligomer or a polymer.

The molecular weight of the ionic compound is preferably 100 or more from the viewpoint of further improving the vertical alignment of liquid crystal compound (I)-1. In addition, the molecular weight of the ionic compound is preferably 10,000 or less, more preferably 5,000 or less, and 3,000 or less, from the viewpoint of further improving the coating properties of the composition for forming a vertically aligned liquid crystal cured film. is even more preferable. The molecular weight of the ionic compound is more preferably 100 or more and 10,000 or less from the viewpoint of further improving the vertical alignment of liquid crystal compound (I)-1 and further improving the coating properties of the composition.

Examples of the cation component of the ionic compound include inorganic cations and organic cations. Among the cationic components of these ionic compounds, organic cations are preferred from the viewpoint of suppressing the occurrence of alignment defects in the liquid crystal compound. Examples of organic cations include imidazolium cations, pyridinium cations, ammonium cations, sulfonium cations, and phosphonium cations.

On the other hand, ionic compounds generally have a counter anion. Examples of the anion component serving as a counter ion to the cation component include inorganic anions and organic anions. Among these anion components, organic anions are preferred from the viewpoint of suppressing the occurrence of alignment defects in the liquid crystal compound. Further, cations and anions do not necessarily have to have a one-to-one correspondence. Examples of anionic components 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 anion [F(HF) _n ⁻ ] (for example, n represents an integer from 1 to 3),
Dicyanamide anion [(CN) ₂ N ^- ],
Thiocyananion [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 can be appropriately selected from the above combinations of cationic components and anionic components. Specific examples of compounds that are 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, etc.

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

(ammonium salt)
Tetrabutylammonium hexafluorophosphate,
Tetrabutylammonium bis(fluorosulfonyl)imide,
Tetrahexylammonium bis(fluorosulfonyl)imide,
trioctylmethylammonium bis(fluorosulfonyl)imide,
(2-hydroxyethyl)trimethylammonium bis(fluorosulfonyl)imide,
Tetrabutylammonium bis(trifluoromethanesulfonyl)imide,
Tetrahexylammonium bis(trifluoromethanesulfonyl)imide,
trioctylmethylammonium bis(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 may be used alone or in combination of two or more. Moreover, from the viewpoint of further improving the vertical alignment of the liquid crystal compound, it is preferable that the ionic compound has Si element and/or F element in the molecular structure of the cation site. This is because when the ionic compound has Si element and/or F element in the molecular structure of the cation site, the ionic compound can be segregated on the surface of the vertically aligned liquid crystal cured film. Among these ionic compounds, ionic compounds whose constituent elements are all nonmetallic elements (more specifically, the following ionic compounds (1) to (3), etc.) are preferred.

（イオン性化合物（２））

（イオン性化合物（３））

(Ionic compound (1))

(Ionic compound (2))

(Ionic compound (3))

An example of a method for improving the vertical alignment of a liquid crystal compound is a method of treating the surface of a substrate using a surfactant having an alkyl group with a relatively long chain length. This method is described, for example, in "Liquid Crystal Handbook", Chapter 2: Orientation and Physical Properties of Liquid Crystals (published by Maruzen Co., Ltd.). The method of improving the vertical alignment of a liquid crystal compound using a surfactant as described above can be applied to ionic compounds. That is, a method for improving the vertical alignment of a liquid crystal compound includes, for example, a method of treating the surface of a substrate using an ionic compound having an alkyl group with a relatively long chain length. More specifically, the ionic compound preferably satisfies the following formula (10) from the viewpoint of improving the vertical alignment of the liquid crystal compound.
5<M<16...(10)
In formula (10), M is represented by the following formula (11).
M = (number of covalent bonds from the positively charged atom to the molecular chain end of the substituent that has 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)...(11)

In addition, when there are two or more positively charged atoms in the molecule of an ionic compound, substituents having two or more positively charged atoms are counted from the positively charged atom considered as the base point. The number of covalent bonds from the nearest other 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. Furthermore, when the ionic compound is an oligomer or polymer having two or more repeating units, the above M is calculated by considering the constituent unit as one molecule. If an atom with a positive charge is incorporated into a ring structure, the number of covalent bonds through the ring structure to the atom with the same positive charge, or to the end of a substituent bonded to the ring structure. Among the number of covalent bonds, the one with a 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" as described in the definition of M above.

The content of the ionic compound is usually preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, based on the solid content of the composition for forming a vertically aligned liquid crystal cured film. It is preferably 0.1 to 3% by mass, and more preferably 0.1 to 3% by mass. When the content of the ionic compound is 0.01% by mass or more in the solid content of the composition, the vertical alignment of the liquid crystal compound is further improved, and the content of the ionic compound is 0.01% by mass or more in the solid content of the composition. On the other hand, when the amount is 5% by mass or less, the coating properties of the composition are less likely to deteriorate.

・・・（Ｉ）－１
［式（Ｉ）－１中、Ａｒは、２つ以上の環構造を有する２価の基を表し、該２つ以上の環構造のうちの１つが６員環であり、該６員環の１位及び４位でＬ^１及びＬ^２と結合し、
Ｌ^１及びＬ^２は、それぞれ独立に、単結合又は二価の連結基を表し、
Ｇ^１及びＧ^２は、それぞれ独立に、二価の芳香族基又は二価の脂環式炭化水素基を表し、該二価の芳香族基及び該二価の脂環式炭化水素基に含まれる水素原子は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のフルオロアルキル基、炭素数１～４のアルコキシ基、シアノ基、又はニトロ基で置換されていてもよく、該二価の芳香族基及び該二価の脂環式炭化水素基に含まれる炭素原子は、それぞれ独立に、酸素原子、硫黄原子、又は窒素原子で置換されていてもよく、
＊は結合手を表す］
で表される構造を有する液晶化合物（以下、液晶化合物（Ｉ）－１と記載することがある）が挙げられる。 [3. Liquid crystal compound]
Examples of the liquid crystal compound that can form the vertically aligned liquid crystal cured film of the present invention include the following formula (I)-1:

...(I)-1
[In formula (I)-1, Ar represents a divalent group having two or more ring structures, one of the two or more ring structures is a 6-membered ring, and the 6-membered ring Combines with L ¹ and L ² at the 1st and 4th positions,
L ¹ and L ² each independently represent a single bond or a divalent linking group,
G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, and G 1 and G 2 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, and Each hydrogen atom is independently substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The carbon atoms contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group may be each independently substituted with an oxygen atom, a sulfur atom, or a nitrogen atom,
*represents a bond]
Examples include liquid crystal compounds having the structure represented by (hereinafter sometimes referred to as liquid crystal compound (I)-1).

Liquid crystal compound (I)-1 has formula (I)-1 in which Ar represents a divalent group having two or more ring structures, and one of the two or more ring structures is a 6-membered ring. Since it bonds with L ¹ and L ² at the 1 and 4 positions of the 6-membered ring, it tends to form a T-shaped structure. Compounds having such a structure generally tend to exhibit reverse wavelength dispersion. Therefore, liquid crystal compound (I)-1 exhibits reverse wavelength dispersion. On the other hand, since liquid crystal compound (I)-1 has a T-shaped structure, it is usually difficult to vertically align it alone. In the production of a vertically aligned liquid crystal cured film, the composition for forming a vertically aligned liquid crystal cured film contains a nonionic silane compound or an ionic compound to sufficiently improve the vertical alignment of liquid crystal compound (I)-1. I can do it. The composition for forming a vertically aligned liquid crystal cured film preferably contains both a nonionic silane compound and an ionic compound.

Ar represents a divalent group having two or more ring structures. In this specification, the ring structure unit of Ar is a monocyclic ring. For example, in liquid crystal compounds A, (A)-2, and (A)-3 described below, Ar has four, two, and three ring structures, respectively. In the two or more ring structures, two or more monocycles may be fused and adjacent to each other, two or more monocycles may be bonded to each other via a chemical bond, or two or more monocycles may be bonded to each other through a chemical bond. They may be adjacent to each other without being condensed or via a chemical bond. Hereinafter, the first aspect may be described as a condensed type, the second aspect as a bonded type, and the third aspect as a spirocyclic type. Further, a monocycle and a condensed ring (polycycle) formed by condensing monocycles may be bonded to each other via a chemical bond, or a polycycle and a polycycle may be bonded to each other via a chemical bond. Hereinafter, such an embodiment may be referred to as a bond condensation type. Liquid crystal compounds A, (A)-2, and (A)-3 described below are of a bond condensation type, a condensation type, and a bond type, respectively. The chemical bond that connects two or more rings in the bonded type and the bonded condensed type is, for example, a conjugated double bond (more specifically, -C=C- and -C=N-, etc.) and a carbonyl group. may contain bonds or groups that extend the spatial extent of the conjugated system.

Examples of the monocycle include monocyclic hydrocarbon rings (more specifically, cycloalkane rings, benzene rings, etc.) and monocyclic heterocycles. Examples of the monocyclic heterocycle include, for example, a 5-membered heterocycle (more specifically, a pyrrole ring, a furan ring, a thiophene ring, an oxazole ring, an imidazole ring, a pyrazole ring, a thiazole ring, and a triazole ring. ring, pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, etc.), and 6-membered heterocycles (more specifically, pyridine ring, pyrazine ring, pyrimidine ring, thiazine ring, piperidine ring, etc.). A polycyclic ring is a structure having two or more rings, and the ring structure may be an aromatic ring or a hydrocarbon ring. Examples of polycyclic rings include those containing fused rings and monocyclic heterocycles. Among these monocycles, the fused ring is, for example, a ring in which two or more monocycles of the same type are fused together, and a ring in which two or more monocycles of different types are fused together. Examples of condensed rings include polycyclic hydrocarbon rings (more specifically, naphthalene rings, anthracene rings, phenanthrene rings, etc.), and polycyclic heterocycles (more specifically, quinoline rings, quinoxaline ring, benzofuran ring, benzothiophene ring, fluorene ring, indole ring, carbazole ring, benzimidazole ring, benzothiazole ring, thienothiazole ring, benzoxazole ring, 1,3-benzodithiol ring, phenanthroline ring, etc.) can be mentioned. Among these condensed rings, a polycyclic structure is preferred from the viewpoint of exhibiting reverse wavelength dispersion characteristics, and a polycyclic heterocyclic structure is more preferred.

Monocyclic and polycyclic rings may have substituents. Examples of substituents that monocycles and polycycles may have include hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, and alkoxy groups having 1 to 20 carbon atoms. group, imino group, alkapolyenyl group, cyano group, or amino group, and the carbon atom in the substituent may be substituted with an oxygen atom, nitrogen atom, or sulfur atom ( In this case, the number of hydrogen atoms bonded to the carbon atom may be increased or decreased depending on the valence of the substituted atom). Among these substituents, an imino group, an alkapolyenyl group, a cyano group, a hydroxy group, and an amino group may expand the spatial extent of the conjugated system. These substituents may be further substituted.

Examples of the 6-membered ring possessed by Ar include a benzene ring and a cyclohexane ring. The 6-membered ring may contain a heteroatom as a ring member atom. Examples of the fused ring containing a 6-membered ring include a quinoline ring, a quinoxaline ring, a benzofuran ring, a benzothiophene ring, a fluorene ring, an indole ring, a carbazole ring, a benzimidazole ring, a benzothiazole ring, a thienothiazole ring, a benzoxazole ring, Examples include a 1,3-benzodithiol ring and a phenanthroline ring.

上記式中、Ｘ_１、Ｘ_２、及びＸ_３は、それぞれ独立に、ＣＲ_１Ｘ、Ｒ_２Ｘ、ＮＲ_３Ｘ、硫黄原子、及び酸素原子のいずれかから選択される。Ｒ_１Ｘ、Ｒ_２Ｘ、及びＲ_３Ｘは、それぞれ独立に、水素原子又は炭素数１～４のアルキル基を示す。
Ｕは、少なくとも１つの環構造を含み、該環構造としては前述の段落００４１～００４３に記載の単環及び／又は多環を含む構造が挙げられ、
Ｙは、任意の置換基であってもよいが、逆波長分散性を向上させる観点から少なくとも１つ以上の環構造を含むことが好ましく、該環構造としては前述の段落００４１～００４３に記載の単環及び／又は多環を含む構造が挙げられる。
Ｌ_１０は、二価の連結基であって、単結合、－Ｏ－ＣＯ－Ｏ－、－Ｎ＝Ｎ－、－Ｃ≡Ｃ－、－ＣＲ_a＝ＣＲ_b－、－ＣＨ＝Ｎ－Ｎ＝ＣＨ－、又は－ＣＲ_c＝Ｎ－を表す。
Ｌ_１１は、二価の連結基であって、単結合、－ＣＯ－、－ＣＯＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＣＨ＝ＣＨ－ＣＯＯ－、－ＣＨ＝ＣＨ－ＯＣＯ－、－ＣＨ_２ＣＨ_２－ＣＯＯ－、－ＣＨ_２ＣＨ_２－ＯＣＯ－、－ＣＨ_２－ＣＯＯ－、－ＣＨ_２－ＯＣＯ－、－Ｎ＝Ｎ－、－Ｃ≡Ｃ－、－ＣＲ_d＝ＣＲ_e－、－ＣＨ＝Ｎ－Ｎ＝ＣＨ－、－ＣＲ_f＝Ｎ－、－ＣＲ_g＝Ｎ－ＮＲ_h－、－Ｎ＝Ｎ－ＣＲ_iＲ_j－、－Ｎ＝ＣＲ_k－ＣＲ_lＲ_m－、－Ｎ＝ＣＲ_n－ＮＲ_o－、－ＣＲ_p＝ＣＲ_q－ＮＲ_r－、又は－ＣＲ_sＲ_t－Ｎ_u＝ＣＲ_x－を表す。ここで、Ｒ_ｃ～Ｒ_ｇは、それぞれ独立に、水素原子又は炭素数１～１０のアルキル基を示し、該アルキル基中の炭素原子は窒素原子、酸素原子、硫黄原子で置換されていても良い（この場合、原子価数に合わせて適宜水素原子数が増減される）。
Ｚは、水素原子又は置換基が結合していてもよい第１４～１６族の非金属原子を表す。Ｚは、逆波長分散性を向上させる観点から、共役系の空間的広がりを拡張させるような構造（より具体的には、２重結合部位、３重結合部位、並びにヒュッケル則を満たす芳香環及び複素環等）、並びに窒素原子及び硫黄原子から選ばれる原子からなる群から選択される少なくとも一つ以上を有することが好ましい。 From the viewpoint of further improving the reverse wavelength dispersion of the polarizing plate, Ar preferably represents a divalent group containing a ring structure having one or more sulfur atoms as ring member atoms. From the viewpoint of further improving reverse wavelength dispersion, Ar preferably represents a divalent group represented by the following formula. * indicates a bond.

In the above formula, X ₁ , X ₂ , and X ₃ are each independently selected from CR _{1X ,} R _2X , NR _3X , a sulfur atom, and an oxygen atom. R _1X , R _2X and R _3X each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
U contains at least one ring structure, and the ring structure includes the monocyclic and/or polycyclic structures described in paragraphs 0041 to 0043 above,
Y may be any substituent, but from the viewpoint of improving reverse wavelength dispersion, it is preferable to include at least one ring structure, and the ring structure includes the ring structures described in paragraphs 0041 to 0043 above. Examples include structures containing monocyclic rings and/or polycyclic rings.
L ₁₀ is a divalent linking group, and is a single bond, -O-CO-O-, -N=N-, -C≡C-, -CR _a =CR _b -, -CH=N-N =CH-, or -CR _c =N-.
L ₁₁ is a divalent linking group, and is a single bond, -CO-, -COO-, -O-CO-O-, -CO-NH-, -CH=CH-COO-, -CH=CH -OCO-, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -CH ₂ -COO-, -CH ₂ -OCO-, -N=N-, -C≡C-, -CR _d = CR _e -, -CH=N-N=CH-, -CR _f =N-, -CR _g =N-NR _h -, -N=N-CR _i R _j -, -N=CR _k - CR _l R _m -, -N=CR _n -NR _o -, -CR _p = CR _q -NR _r -, or -CR _s R _t -N _u = CR _x -. Here, R _c to R _g each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a carbon atom in the alkyl group may be substituted with a nitrogen atom, an oxygen atom, or a sulfur atom. Good (in this case, the number of hydrogen atoms is increased or decreased as appropriate according to the valence number).
Z represents a hydrogen atom or a nonmetallic atom of Groups 14 to 16 to which a substituent may be bonded. From the viewpoint of improving reverse wavelength dispersion, Z is a structure that expands the spatial extent of the conjugated system (more specifically, a double bond site, a triple bond site, and an aromatic ring that satisfies Huckel's rule). It is preferable to have at least one selected from the group consisting of atoms selected from nitrogen atoms and sulfur atoms.

Examples of the divalent linking group represented by L ¹ and L ² include 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 -, and -C≡C-. Here, R ^a1 to R ^a8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms (more specifically, a methylene group, an ethylene group, a propylene group, a butylene group, etc.), and R ^c and R ^d each independently represent an alkyl group having 1 to 4 carbon atoms (more specifically, a methyl group, ethyl group, propyl group, butyl group, etc.) or a hydrogen atom.

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-. 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 - represents. 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 each independently more preferably represent a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, or OCO-.

Examples of the divalent aromatic group represented by G ¹ and G ² include a phenylenediyl group and a naphthylenediyl group. The divalent aromatic group may be substituted with a substituent such as a halogen atom (more specifically, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 4 carbon atoms. The divalent aromatic group may have a heteroatom (more specifically, an oxygen atom, a sulfur atom, a nitrogen atom, etc.) as a ring member atom. Examples of the divalent alicyclic hydrocarbon group represented by G ¹ and G ² include a cyclopentanediyl group, a cyclohexanediyl group, and a cycloheptanediyl group. The divalent alicyclic hydrocarbon group may be substituted with a substituent such as a halogen atom and an alkyl group having 1 to 4 carbon atoms.

In this specification, the aromatic group refers to a group having a planar cyclic structure, in which the number of π electrons in the cyclic structure is [4n+2] according to Huckel's rule (n is a positive number of 1 or more). (indicates an integer). When a ring structure is formed by including heteroatoms such as -N= and S- as ring member atoms, it satisfies Huckel's rule including the non-covalently bonded electron pairs on these heteroatoms and has aromaticity. Including cases.

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, and more preferably a 1,4-cyclohexanediyl group 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. Furthermore, at least one of the plurality of G ¹ and G ² is preferably a divalent alicyclic hydrocarbon group, and at least one of G ¹ and G ² bonded to L ¹ or L ² More preferably, one is a divalent alicyclic hydrocarbon group.

Liquid crystal compound (I)-1 preferably has maximum absorption in the wavelength range of 260 to 400 nm. When the liquid crystal compound (I)-1 has an aromatic group having a hetero atom or a structure in which a conjugated system is extended, the absorption in the near-ultraviolet region shifts to the long wavelength side compared to a benzene ring, so that it has a structure of 260 nm or more. It often has maximum absorption in the wavelength region of 260 nm or more, and it is preferable to have maximum absorption in the wavelength region of 260 nm or more from the viewpoint of improving reverse wavelength dispersion. Furthermore, if the liquid crystal compound (I)-1 has maximum absorption in a wavelength region larger than 400 nm, coloring may occur, so it is preferable that liquid crystal compound (I)-1 has maximum absorption in a wavelength region of 400 nm or less. Furthermore, from the viewpoint of further improving wavelength dispersion, it is more preferable to have maximum absorption in a wavelength range of 280 nm or more and 400 nm or less, and even more preferably to have maximum absorption in a wavelength range of 300 nm or more and 400 nm or less.

・・・（Ｉ）－２
で表される構造を有する液晶化合物（以下、液晶化合物（Ｉ）－２と記載することがある）であることが好ましい。 Liquid crystal compound (I)-1 has the following formula (I)-2:

...(I)-2
A liquid crystal compound having a structure represented by (hereinafter sometimes referred to as liquid crystal compound (I)-2) is preferable.

In formula (I)-2, Ar represents a divalent group having two or more ring structures, one of the two or more ring structures is a 6-membered ring, and one of the 6-membered rings Combines with L ¹ and L ² at the position and 4 position,
L ¹ , L ² and B ¹ each independently represent a single bond or a divalent linking group,
G ¹ , G ² , and G ³ each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group; The hydrogen atoms contained in the hydrogen group are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The carbon atoms contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group may each be independently substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. It's okay,
* represents a bond.

Ar, L ¹ , L ² , G ¹ and G ² in formula (I)-2 have the same meanings as Ar, L ¹ , L ² , G ¹ and G ² in formula (I)-1, respectively. be.

B ¹ is 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-. 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 - represents. 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 each independently more preferably represent a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, or OCO-.

Examples of the divalent aromatic group represented by G ³ include a phenylenediyl group and a naphthylenediyl group. The divalent aromatic group may be substituted with a substituent such as a halogen atom (more specifically, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 4 carbon atoms. Examples of the divalent alicyclic hydrocarbon group represented by G ³ include a cyclopentanediyl group, a cyclohexanediyl group, and a cycloheptanediyl group. The divalent alicyclic hydrocarbon group may be substituted with a substituent such as a halogen atom or an alkyl group having 1 to 4 carbon atoms.

G ³ is 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 halogen atom and a 1,4-cyclohexanediyl group optionally substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, more preferably a 1,4-cyclohexanediyl group substituted with a methyl group. A phenylenediyl group, an unsubstituted 1,4-phenylenediyl group, or an unsubstituted 1,4-trans-cyclohexanediyl group, particularly preferably an unsubstituted 1,4-phenylenediyl group or an unsubstituted 1 , 4-trans-cyclohexanediyl group.

・・・（Ｉ）－３
で表される構造を有する液晶化合物（以下、液晶化合物（Ｉ）－３と記載することがある）であることがより好ましい。 Liquid crystal compound (I)-1 has the following formula (I)-3:

...(I)-3
A liquid crystal compound having a structure represented by (hereinafter sometimes referred to as liquid crystal compound (I)-3) is more preferable.

In formula (I)-3, Ar represents a divalent group having two or more ring structures, one of the two or more ring structures is a 6-membered ring, and one of the 6-membered rings Combines with L ¹ and L ² at the position and 4 position,
L ¹ , L ² , B ¹ , and B ² each independently represent a single bond or a divalent linking group,
G ¹ , G ² , G ³ , and G ⁴ each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group; The hydrogen atom contained in the cyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The carbon atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom,
* indicates a bond.

Ar, L ¹ , L ² , G ¹ and G ² in formula (I)-3 have the same meanings as Ar, L ¹ , L ² , G ¹ and G ² in formula (I)-1, respectively. be. B ¹ and G ³ in formula (I)-3 have the same meanings as B ¹ and G ³ in formula (I)-2, respectively.

B ² is 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-. 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 - represents. 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 each independently more preferably represent a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, or OCO-.

Examples of the divalent aromatic group represented by G ⁴ include a phenylenediyl group and a naphthylenediyl group. The divalent aromatic group may be substituted with a substituent such as a halogen atom (more specifically, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 4 carbon atoms. Examples of the divalent alicyclic hydrocarbon group represented by G ³ include a cyclopentanediyl group, a cyclohexanediyl group, and a cycloheptanediyl group. The divalent alicyclic hydrocarbon group may be substituted with a substituent such as a halogen atom or an alkyl group having 1 to 4 carbon atoms.

G ⁴ is 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 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 alkyl groups of ~4, more preferably a 1,4-phenylenediyl group substituted with a methyl group, An unsubstituted 1,4-phenylenediyl group or an unsubstituted 1,4-trans-cyclohexanediyl group, particularly preferably an unsubstituted 1,4-phenylenediyl group or an unsubstituted 1,4-trans - cyclohexanediyl group.

Liquid crystal compound (I)-1 may have one or more polymerizable groups. In this specification, a polymerizable group refers to a group that can participate in a polymerization reaction by active species such as active radicals and acids generated from a photopolymerization initiator. Examples of the polymerizable group include epoxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, and oxetanyl group. . Among these polymerizable groups, acryloyloxy groups and methacryloyloxy groups are preferred. In this specification, the liquid crystal compound (I)-1 having a polymerizable group can form a polymer through a polymerization reaction.

Examples of the liquid crystal compound (I)-1 include liquid crystal compounds having structures represented by formulas (A)-1 to (A)-5.

・・・（Ａ）－１
（液晶化合物（Ａ）－２）

・・・（Ａ）－２
（液晶化合物（Ａ）－３）

・・・（Ａ）－３
（液晶化合物（Ａ）－４）

・・・（Ａ）－４
（液晶化合物（Ａ）－５）

・・・（Ａ）－５ (Liquid crystal compound A)

...(A)-1
(Liquid crystal compound (A)-2)

...(A)-2
(Liquid crystal compound (A)-3)

...(A)-3
(Liquid crystal compound (A)-4)

...(A)-4
(Liquid crystal compound (A)-5)

...(A)-5

The content of liquid crystal compound (I)-1 (if multiple types of liquid crystal compounds are included, the total content) is 50 to 99 parts by mass based on 100 parts by mass of the solid content of the composition for forming a vertically aligned liquid crystal cured film. The amount is preferably .5 parts by weight, more preferably 60 to 99 parts by weight, and even more preferably 70 to 99 parts by weight. As used herein, the mass of the solid content of the composition refers to the total mass of the components of the composition excluding the solvent.

[Method for manufacturing vertically aligned liquid crystal cured film]
The vertical alignment liquid crystal cured film is a cured product of a composition for forming a vertical alignment liquid crystal cured film. The method for producing a vertically aligned liquid crystal cured film includes a coating film forming step in which a composition for forming a vertically aligned liquid crystal cured film is applied to a base material and a coated film is formed on the base material, and a coated film is dried to form a dry film. The method includes a dry film forming step and a cured film forming step of irradiating the dry film with active energy rays to form a vertically aligned liquid crystal cured film. The laminate produced by this production method is composed of a base material and a vertically aligned liquid crystal cured film. A case where the liquid crystal compound has one or more polymerizable groups and the composition further contains a photopolymerization initiator will be described as an example.

(Coating film formation process)
In the coating film forming step, the composition is applied to a base material using, for example, a printing device to form a coating film on the base material. Examples of the coating method include gravure coating, die coating, and printing methods such as flexography.

(Dry film formation process)
In the dry film forming step, the coating film is dried using, for example, a heating device to form a dry film. After the coating film is heated and the solvent in the coating film is removed, the liquid crystal compound is vertically aligned and converted into a dry film. The heating temperature is preferably such that the solvent can be removed and is higher than the phase transition temperature of the liquid crystal compound.

(Cured film formation process)
In the cured film forming step, for example, a light irradiation device is used to irradiate the dry film with active energy rays (more specifically, ultraviolet rays, etc.) to form a vertically aligned liquid crystal cured film. The liquid crystal compound maintains a liquid crystal state aligned perpendicularly to the plane of the substrate in the dry film. By irradiating the dry film with active energy rays, the liquid crystal compound maintains a vertically aligned liquid crystal state and photopolymerizes. Thereby, a vertically aligned liquid crystal cured film can be formed directly on the base material.

(Other processes: Vertical alignment film formation process)
As already explained, the vertically aligned liquid crystal cured film can be formed directly on the substrate without forming an alignment film. Meanwhile, the method for producing a vertically aligned cured liquid crystal film may further include a vertically aligned film forming step of forming a vertically aligned film in order to further improve the orientation of the vertically aligned liquid crystal cured film. In such a case, the vertically aligned liquid crystal cured film is indirectly formed on the base material via the vertically aligned film.

The vertical alignment film forming process is a process performed before the coating film forming process, and forms a vertical alignment film. Here, an example of a method for forming a vertical alignment film will be described. The alignment film forming step includes a second coating film forming step, a second dry coating forming step, and an alignment film forming step.
In the second coating film forming step, the composition for forming a vertical alignment film is applied onto the substrate using, for example, a printing device to form a second coating film. The composition for forming a vertical alignment film includes, for example, an alignment polymer described below and the above-mentioned solvent. In the second dry film forming step, for example, a heating device is used to heat the second coating film to dry the second coating film, thereby forming a second dry film. If a further step of curing by UV irradiation is required, a UV irradiation device is used to irradiate and cure the second dry film to form a vertical alignment film. When the method for manufacturing a vertically aligned liquid crystal cured film includes a vertically aligned film forming step, a vertically aligned liquid crystal cured film is formed on the vertically aligned film.

(Composition for forming vertically aligned liquid crystal cured film)
The composition for forming a vertically aligned liquid crystal cured film contains, for example, one or both of a nonionic silane compound and an ionic compound, and additives added as necessary. Examples of additives include liquid crystal compounds, photopolymerization initiators, leveling agents, solvents, polymerization inhibitors, and adhesion improvers. Examples of the liquid crystal compound include liquid crystal compound (I)-1. These additives may be used alone or in combination of two or more. The composition is made by stirring, etc., one or both of the nonionic silane compound and the ionic compound, and other components as necessary, at a predetermined temperature to disperse these components substantially uniformly. Or it can be obtained by dissolving it.

(solvent)
The composition for forming a vertically aligned liquid crystal cured film is usually applied to a substrate etc. in a state dissolved in a solvent, so it preferably contains a solvent. Examples of solvents include water; methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether. ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl Ketone solvents such as isobutylketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; cycloaliphatic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl- Examples include amide solvents such as 2-imidazolidinone. These solvents may be used alone or in combination of two or more. Among these solvents, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents, and aromatic hydrocarbon solvents are preferred. These solvents may be used alone or in combination of two or more.

The content of the solvent is preferably 50 to 98 parts by weight, more preferably 70 to 95 parts by weight, based on 100 parts by weight of the composition for forming a vertically aligned liquid crystal cured film. Therefore, the solid content in 100 parts by mass of the composition is preferably 2 to 50 parts by mass. When the solid content of the composition is 50 parts by mass or less, the viscosity of the composition is low, so the thickness of the vertically aligned liquid crystal cured film becomes approximately uniform, and unevenness is less likely to occur in the vertically aligned liquid crystal cured film. Tend. The above-mentioned solid content can be appropriately determined in consideration of the thickness of the vertically aligned liquid crystal cured film to be manufactured.

(Photopolymerization initiator)
The composition for forming a vertically aligned liquid crystal cured film may contain a photopolymerization initiator for the purpose of advancing the polymerization reaction. As used herein, a photopolymerization initiator provides an active species that absorbs active energy rays and initiates a polymerization reaction. A photo-radical polymerization initiator can be used when a curable composition that is cured by radical polymerization, such as (meth)acrylate or urethane (meth)acrylate, is used as a curable material. A cationic photopolymerization initiator can be used when a curable composition, such as an epoxy compound or an oxetane compound, is used as the curable composition.

Examples of the photopolymerization initiator include radical photopolymerization initiators and cationic photopolymerization initiators. Examples of the photoradical polymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, and triazine compounds. Examples of the photocationic polymerization initiator include aromatic diazonium salts, onium salts such as aromatic iodonium salts and aromatic sulfonium salts, and iron-arene complexes. Examples of the photopolymerization initiator include Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, and Irgacure 379EG. photopolymerization initiators manufactured by BASF Japan Co., Ltd.; photopolymerization initiators manufactured by Seiko Kagaku Co., Ltd. such as Seiqual BZ, Seiqual Z, and Seiqual BEE; Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.); and photoinitiators manufactured by Dow such as Kayacure UVI-6992; ADEKA OPTOMER SP-152, ADEKA OPTOMER SP-170, ADEKA OPTOMER N-1717, ADEKA OPTOMER N-1919, ADEKA ARCLES NCI Photopolymerization initiators made by ADEKA Co., Ltd. such as -831, ADEKA Arkles NCI-930; photopolymerization initiators made by Nippon Siberhegner Co., Ltd. such as TAZ-A, and TAZ-PP; such as TAZ-104. Photopolymerization initiators manufactured by Sanwa Chemical Co., Ltd.; photopolymerization initiators manufactured by Nippon Kayaku Co., Ltd. such as the Kayarad (registered trademark) series; photopolymerization initiators manufactured by Dow Chemical Co., Ltd. such as Cylacure UVI series; CPI series photopolymerization initiators manufactured by Sun-Apro Co., Ltd. such as; photopolymerization initiators manufactured by Midori Kagaku Co., Ltd. such as TAZ, BBI, and DTS; photopolymerization initiators manufactured by Rhodia Co., Ltd. such as RHODORSIL (registered trademark); can be mentioned. These photopolymerization initiators may be used alone or in combination of two or more. The photopolymerization initiator can be appropriately selected and used depending on the material used.

The maximum absorption wavelength of the photopolymerization initiator is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm, since the photopolymerization initiator can fully utilize the energy emitted from the light source and has excellent productivity. Among these photopolymerization initiators, α-acetophenone polymerization initiators and oxime photopolymerization initiators are preferred.

Examples of α-acetophenone polymerization initiators include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2 -benzylbutan-1-one (2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one), and 2-dimethylamino-1-(4-morpholinophenyl)-2-( 4-methylphenylmethyl)butan-1-one is mentioned. The α-acetophenone polymerization initiators are 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzyl. Butan-1-one is preferred. Commercially available α-acetophenone compounds include α-acetophenone polymerization initiators manufactured by BASF Japan Co., Ltd. such as Irgacure 369, 379EG, and 907, and α-acetophenone polymerization initiators manufactured by Seiko Kagaku Co., Ltd. such as Seiqual BEE. Examples include polymerization initiators.

Oxime-based photopolymerization initiators generate radicals when irradiated with light. Due to these radicals, polymerization of the composition for forming a vertically aligned liquid crystal cured film in the deep part of the coating film progresses suitably. Furthermore, from the viewpoint of more efficiently advancing the polymerization reaction deep in the coating film, it is preferable to use an oxime-based photopolymerization initiator that can efficiently utilize ultraviolet rays with a wavelength of 350 nm or more. Examples of oxime-based photopolymerization initiators that can efficiently utilize ultraviolet light with a wavelength of 350 nm or more include triazine compounds and oxime ester type carbazole compounds, and from the viewpoint of sensitivity, oxime esters are more preferred. type carbazole compounds. Examples of oxime ester type carbazole compounds include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], and ethanone, 1-[9-ethyl-6-(2 -methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime). Commercially available oxime ester type carbazole compounds include, for example, oxime ester type carbazole compounds manufactured by BASF Japan Co., Ltd. such as Irgacure OXE-01, Irgacure OXE-02, and Irgacure OXE-03, and ADEKA Optomer N-1919, Examples include oxime ester type carbazole compounds manufactured by ADEKA Corporation, such as ADEKA Arkles NCI-831.

The content of the photopolymerization initiator is usually 0 when the solid content (excluding the solvent content in the composition) contained in the composition for forming a vertically aligned liquid crystal cured film is 100 parts by mass. The amount is preferably from .1 to 20 parts by weight, more preferably from 0.5 to 10 parts by weight, and even more preferably from 1 to 7 parts by weight. When the amount of the photopolymerization initiator is 0.1 to 20 parts by mass based on 100 parts by mass of the composition, the polymerization reaction can proceed sufficiently easily.

(Leveling agent)
The purpose of the leveling agent is to adjust the coating properties of the composition for forming a vertically aligned liquid crystal cured film, that is, to adjust the fluidity of the composition for coating, and to improve the layer surface obtained by coating the composition. It may be added to the composition for the purpose of flattening it. Examples of the leveling agent include silicone leveling agents such as silane coupling agents, polyacrylate leveling agents, and fluoroalkyl leveling agents. Among these leveling agents, silicone-based leveling agents and fluoroalkyl-based leveling agents are preferred from the viewpoint of further improving the vertical alignment of the liquid crystal compound.

As a commercially available leveling agent, for example, DC3PA, SH7PA, DC11PA, SH28PA, SH30PA, ST8600, ST8600, SH8400, SH8400, SH8700, and FZ2123, such as FZ2123. Selection; KP321, KP323, KP324 , KP326, KP340, KP341, -503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBE-585, KBM-802 Shin-Etsu Chemical Co., Ltd. leveling agents such as , KBM-802, KBM-803, KBE-846, and KBE-9007; TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 Fluorinert® leveling agents manufactured by Momentive Performance Materials Japan LLC; such as Fluorinert® FC-72, Fluorinert® FC-40, Fluorinert® FC-43, and Fluorinert® FC-3283 manufactured by Sumitomo 3M Ltd. Leveling agent: Megafac (registered trademark) R-08, R-30, R-90, F-410, F-411, F-443, F-445, F-470, F Leveling agents manufactured by DIC Corporation such as -477, F-479, F-482, F-483, and F-556; F-TOP (trade name) EF301, EF303, EF351, and EF352 Leveling agents manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; Surflon (registered trademark) S-381, S-382, S-383, S-393, SC-101, SC-105, KH- 40, and leveling agents manufactured by AGC Seimi Chemical Co., Ltd. such as SA-100; leveling agents manufactured by Daikin Fine Chemical Laboratories Co., Ltd. such as product names E1830 and E5844; BM-1000, BM-1100, BYK-352 , BYK-353, and BYK-361N (all trade names: BM) manufactured by Chemie. These leveling agents may be used alone or in combination of two or more.

Generally, the content of the leveling agent in the solid content of the composition for forming a vertically aligned liquid crystal cured film is preferably 0.001 to 3% by mass, more preferably 0.01 to 3% by mass, and 0.1% by mass. ~3% by mass is more preferred. When the content of the leveling agent in the solid content of the composition is 0.001 to 3% by mass, the coating properties of the composition are further improved.

<Laminated body>
The laminate includes the vertically aligned liquid crystal cured film. The laminate includes a base material, an alignment film for vertical alignment (hereinafter sometimes referred to as a vertical alignment film), an alignment film for horizontal alignment (hereinafter sometimes referred to as a horizontal alignment film), an adhesive layer, And/or it may further include a film (hereinafter sometimes referred to as a horizontally oriented film) oriented in a horizontal direction with respect to the in-plane direction of the vertically oriented cured liquid crystal film described below. The structure of the laminate includes, for example, a laminate including the vertically aligned liquid crystal cured film, a horizontal alignment film, and a horizontal alignment film, a laminate including the vertically aligned liquid crystal cured film and a base material, and the vertically aligned liquid crystal cured film. A laminate including a film, a horizontally oriented film, a horizontally oriented film, and a base material is mentioned. However, in the present invention, a vertical alignment cured liquid crystal film can be formed without an alignment film for vertical alignment, so the laminate does not need to include a vertical alignment film. For example, when the laminate includes a base material and a vertically aligned liquid crystal cured film, the vertically aligned liquid crystal cured film can be adjacent to the base material. Further, for the vertically aligned liquid crystal cured film adjacent to the base material created by the above-described method, a laminate can also be produced by transferring only the vertically aligned liquid crystal cured film via an adhesive layer and removing the base material.

〔Base material〕
Examples of the base material include a glass base material and a film base material, and a film base material is preferable from the viewpoint of processability, and a long roll-shaped film is more preferable from the viewpoint of continuous production. Examples of the resin constituting the film base material include polyolefins such as polyethylene, polypropylene, and norbornene polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate ester; polyacrylate ester; triacetyl cellulose; Cellulose esters such as diacetyl cellulose and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; plastics such as polyphenylene sulfide and polyphenylene oxide. The surface of the base material to be bonded to the adhesive layer may be subjected to a release treatment such as silicone treatment. Commercially available cellulose ester base materials include, for example, cellulose ester base materials manufactured by Fuji Photo Film Co., Ltd. such as Fuji Tac film; manufactured by Konica Minolta Opto Co., Ltd. such as "KC8UX2M", "KC8UY", and "KC4UY"; Examples include cellulose ester base materials. Such a resin can be formed into a film by a known method such as a solvent casting method or a melt extrusion method to form a base material.

Commercially available cyclic olefin resins include, for example, cyclic olefin resins manufactured by Ticona (Germany) such as "Topas (registered trademark)"; cyclic olefin resins 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 resins such as “APEL” (registered trademark) Examples include cyclic olefin resin manufactured by Kagaku Corporation. A commercially available cyclic olefin resin base material can also be used. Commercially available cyclic olefin resin base materials include cyclic olefin resin base materials manufactured by Sekisui Chemical Co., Ltd. such as "Escina (registered trademark)" and "SCA40 (registered trademark)"; "Zeonor Film (registered trademark)" Examples include cyclic olefin resin base materials manufactured by Optes Co., Ltd.; and cyclic olefin resin base materials manufactured by JSR Corporation such as "Arton Film (registered trademark)".

The base material preferably has a thickness that allows each layer to be easily laminated and peeled off. The thickness of such a base material is usually 5 to 300 μm, preferably 10 to 150 μm.

[Vertical alignment film]
The alignment film is a film that has an alignment regulating force that aligns the liquid crystal compound of the cured liquid crystal film in a predetermined direction. Regarding the method for forming the alignment film, various alignments such as vertical alignment, horizontal alignment, hybrid alignment, and tilted alignment can be controlled depending on the type of alignment film material, rubbing conditions, and light irradiation conditions. The process of exerting the alignment regulating force in this manner is called alignment process. Among these, the vertical alignment film is an alignment film that has alignment regulating power to align the liquid crystal compound in the vertical direction. Therefore, by using a vertical alignment film, a vertical alignment liquid crystal film can be formed.

The vertical alignment film preferably has a solvent resistance that does not dissolve when the composition for forming a vertical alignment liquid crystal cured film is applied, etc., and also has heat resistance in heat treatment for removing the solvent and aligning the liquid crystal compound.

For the vertical alignment film, it is preferable to use a material that lowers the surface tension of the surface of the base material or the like. Examples of such materials include oriented polymers such as polyimide, polyamide, polyamic acid which is a hydrolyzate thereof, fluorine-based polymers of perfluoroalkyl, silane compounds, and polysiloxane compounds obtained by condensation reactions thereof. Can be mentioned. The vertical alignment film is produced by applying a composition (hereinafter also referred to as a composition for forming a vertical alignment film) containing such materials and a solvent, such as the solvents listed in the section of the vertical alignment liquid crystal cured film, onto a base material or the like. It can be obtained by coating, removing the solvent, and then subjecting the coated film to heating or the like.

When using a silane compound for the vertical alignment film, the vertical alignment film contains Si element and C element as constituent elements from the viewpoint of easily lowering the surface tension and increasing the adhesion with the layer adjacent to the vertical alignment film. A film containing a compound containing is preferable, and a silane compound can be suitably used. As the silane compound, the aforementioned nonionic silane compounds and silane-containing ionic compounds as exemplified in the section on ionic compounds can be used, and by using these silane compounds, vertical alignment can be controlled. You can increase your power. These silane compounds may be used alone, in combination of two or more, or in combination with other materials. When the silane compound is a nonionic silane compound, a silane compound having an alkyl group at the end of the molecule is preferable, and a silane compound having an alkyl group having 3 to 30 carbon atoms is more preferable from the viewpoint of easily increasing the vertical alignment control force. .

The thickness of the vertical alignment film is preferably 5 μm or less, more preferably 3 μm or less, still more preferably 2 μm or less, preferably 1 nm or more, and more preferably 5 nm or less, from the viewpoint of expressing alignment regulating force. or more, more preferably 10 nm or more, particularly preferably 30 nm or more. The thickness of the vertical alignment film can be measured using an ellipsometer or a contact thickness meter.

[Alignment film for horizontal alignment]
The horizontal alignment film has an alignment regulating force that aligns the liquid crystal compound in the horizontal direction. The horizontal alignment film can form the horizontal alignment state of a horizontal alignment liquid crystal cured film when the composition for forming a horizontal alignment liquid crystal cured film is formed on the horizontal alignment film. The alignment regulating force can be arbitrarily adjusted, for example, by the type of alignment film, surface condition, and rubbing conditions, and if it is formed from a photo-alignable polymer, it can be arbitrarily adjusted by the polarized light irradiation conditions, etc. Is possible. The process of exerting the alignment regulating force in this manner is called alignment process.

The horizontal alignment film preferably has a solvent resistance that does not dissolve when the liquid crystal composition is applied, etc., and also has heat resistance during heat treatment for removing the solvent and aligning the liquid crystal compound.

Examples of the horizontal alignment film include a rubbed alignment film, a photo alignment film, and a groove alignment film having an uneven pattern or a plurality of grooves on the surface. For example, when applied to a long roll-shaped film, a photo-alignment film is preferred because the orientation direction can be easily controlled.

A rubbed alignment film is usually formed by applying a composition containing an alignment polymer and a solvent (hereinafter sometimes referred to as a composition for forming a rubbed alignment film) to a base material, and then removing the solvent to form a coating film. However, by rubbing the coating film, alignment regulating force can be imparted.

Examples of oriented polymers include polyamides and gelatins having amide bonds, polyimides having imide bonds, and polyamic acid which is a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, and polystyrene. , polyvinylpyrrolidone, polyacrylic acid, and polyacrylic esters. These oriented polymers may be used alone or in combination of two or more.

The concentration of the oriented polymer in the composition for forming a rubbed alignment film may be within a range where the oriented polymer is completely dissolved in the solvent. The content of the oriented polymer is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the composition for forming a rubbed alignment film.

Commercially available rubbing alignment film forming compositions include, for example, rubbing alignment film forming compositions manufactured by Nissan Chemical Industries, Ltd. such as Sunever (registered trademark), and JSR (registered trademark) such as Optomer (registered trademark). For example, a composition for forming a rubbed alignment film manufactured by Co., Ltd. is used.

Examples of the rubbing treatment include a method in which the coating film is brought into contact with a rotating rubbing roll around which a rubbing cloth is wound. If masking is performed when performing the rubbing process, a plurality of regions (patterns) with different orientation directions can be formed on the alignment film.

A photo-alignment film is usually produced by coating a base material with a composition containing a polymer or monomer having a photo-reactive group and a solvent (hereinafter sometimes referred to as a composition for forming a photo-alignment film), and then removing the solvent. It is obtained by subsequently irradiating with polarized light (preferably polarized UV). The optical alignment film can arbitrarily control the direction of the alignment regulating force by selecting the polarization direction of the polarized light to be irradiated.

The photoreactive group refers to a group that exhibits orientation ability when irradiated with light. Specifically, groups that participate in photoreactions that are the origin of orientation ability, such as molecular orientation-inducing reactions, isomerization reactions, photodimerization reactions, photocrosslinking reactions, and photodecomposition reactions, which are caused by light irradiation, can be mentioned. The photoreactive group is preferably a group having an unsaturated bond, especially a double bond, such as a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), or a nitrogen-nitrogen double bond. Particularly preferred is a group having at least one double bond selected from the group consisting of a double bond (N=N bond) and a carbon-oxygen double bond (C=O bond).

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

A group that participates in a photodimerization reaction or a photocrosslinking reaction is preferable because it has excellent orientation. Among these, photoreactive groups that participate in photodimerization reactions are preferable, and cinnamoyl groups are preferable because the amount of polarized light irradiation required for alignment is relatively small and it is easy to obtain a photoalignment film with excellent thermal stability and stability over time. and chalcone groups are preferred. As the polymer having a photoreactive group, one having a cinnamoyl group such that the end portion of the polymer side chain has a cinnamic acid structure or a cinnamic acid ester structure is particularly preferred.

The content of the polymer or monomer having a photoreactive group can be adjusted depending on the type of polymer or monomer and the desired thickness of the photoalignment film, and is 0.2 parts by mass per 100 parts by mass of the composition for forming a photoalignment film. It is preferably at least 0.3 parts by mass, more preferably 0.3 to 10 parts by mass.

The polarized light may be irradiated, for example, by directly irradiating the polarized light onto the photo-alignment film-forming composition coated on the substrate, from which the solvent has been removed. Further, it is 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 a photoreactive group of a polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) in the wavelength range of 250 to 400 nm is particularly preferred. Examples of light sources that emit the polarized light include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and ultraviolet lasers such as KrF and ArF. Among these light sources, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferable because they emit high ultraviolet light with a wavelength of 313 nm. Polarized UV can be irradiated by passing the light from the light source through a suitable polarizing element. Examples of polarizing elements include polarizing filters, polarizing prisms such as Glan-Thompson and Glan-Taylor, and wire grids. Among these polarizing elements, a wire grid is preferable from the viewpoint of large area and heat resistance.

Note that by performing masking when performing rubbing or polarized light irradiation, it is also possible to form a plurality of regions (patterns) in which the directions of liquid crystal alignment are different.

A groove alignment film is a film having an uneven pattern or a plurality of grooves on the film surface. When a composition is applied to a film having a plurality of linear grooves arranged at equal intervals, the liquid crystal compound is oriented in the direction along the grooves.

The groove alignment film can be obtained by exposing the surface of a photosensitive polyimide film to light through an exposure mask having pattern-shaped slits, followed by development and rinsing to form a concavo-convex pattern, and by using a plate with grooves on the surface. A method of forming a layer of uncured UV curable resin on a shaped master, transferring the formed resin layer to a base material, and then curing it; Examples include a method in which a rolled master having a plurality of grooves is pressed against each other to form irregularities, and then hardened.

The thickness of the horizontal alignment film is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.3 μm or less, from the viewpoint of realizing thin film formation and exerting alignment regulating power. Further, the thickness of the horizontal alignment film is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, and particularly preferably 30 nm or more. The thickness of the horizontal alignment film can be measured using an ellipsometer or a contact thickness meter.

[Film oriented in the horizontal direction with respect to the in-plane direction of the vertically oriented liquid crystal cured film]
In this specification, a film oriented in a direction horizontal to the in-plane direction of a vertically oriented cured liquid crystal film (hereinafter sometimes referred to as a horizontally oriented film) is a retardation film. Examples of the horizontally oriented film include a stretched film and a horizontally oriented liquid crystal cured film A. The optical properties of the horizontally oriented film can be adjusted by the orientation state of the polymerizable liquid crystal compound or the stretching method. From the viewpoint of making the horizontally oriented film thinner, the horizontally oriented liquid crystal cured film A is preferred.

(Horizontally aligned liquid crystal cured film A)
In this specification, the horizontally aligned liquid crystal cured film A is a liquid crystal cured film in which a polymerizable liquid crystal compound is oriented in a horizontal direction with respect to the in-plane direction of the vertically aligned liquid crystal cured film. In the horizontally aligned liquid crystal cured film A, the optical axis of the polymerizable liquid crystal compound is aligned in the horizontal direction with respect to the in-plane direction of the vertically aligned liquid crystal cured film. Examples of the polymerizable liquid crystal compound include liquid crystal compound (I)-1 having at least one polymerizable group. In this specification, the horizontally aligned liquid crystal cured film included in the laminate of the present invention is referred to as horizontally aligned liquid crystal cured film A, and the horizontally aligned liquid crystal cured film included in the polarizing film of the polarizing plate described below is referred to as horizontally aligned liquid crystal cured film. They are referred to as membrane B to distinguish them from each other.

(Method for manufacturing horizontally aligned liquid crystal cured film A)
The horizontally aligned liquid crystal cured film A is a cured product of a composition (hereinafter sometimes referred to as a composition for forming a horizontally aligned liquid crystal cured film A). The method for manufacturing the horizontally aligned liquid crystal cured film A is different from the above-described method for manufacturing the vertically aligned liquid crystal cured film in that it is formed on the horizontally aligned film. An example of the method for manufacturing the horizontally aligned liquid crystal cured film A includes a coating step of coating the composition on a horizontally aligned film prepared in advance to form a coated film, and a drying step of drying the coated film to form a dry film. The method includes a film forming step and a cured film forming step of irradiating the dried film with active energy rays to form a horizontally aligned liquid crystal cured film.

(Stretched film)
Examples of the stretched film include stretched films made of polycarbonate resin. Examples of commercially available stretched films include stretched films manufactured by Teijin Ltd., such as "Pure Ace (registered trademark) WR". A stretched film is usually obtained by stretching a base film. As a method for stretching the base film, for example, a roll body in which the base film is wound around a roll is prepared, the base film is continuously unwound from the roll body, and the unrolled base film is stretched. The material film is transported to a heating furnace. The temperature setting of the heating furnace is preferably in the range from near the glass transition temperature of the base film to glass transition temperature +50°C. In a heating furnace, the base film is stretched in the transport direction or in a direction perpendicular to the transport direction. When stretching, the conveyance direction and tension are adjusted, and the film is tilted at an arbitrary angle, and hot stretching processing such as uniaxial stretching, biaxial stretching, or diagonal stretching is performed. The direction of the retardation axis of a stretched film varies depending on the stretching method, and the retardation axis or optical axis is determined depending on the stretching method. The stretched film and the laminate of the present invention can be bonded together via an adhesive layer.

The laminate of the present invention has the following relational expression (3):
ReA(450)/ReA(550)≦1...(3)
[In relational expression (3), ReA (450) represents the in-plane retardation value at a wavelength of 450 nm of the film oriented in the horizontal direction with respect to the in-plane direction of the vertically aligned liquid crystal cured film, and ReA (550) represents the in-plane retardation value at a wavelength of 450 nm. Indicates the in-plane retardation value at a wavelength of 550 nm of a film oriented in the horizontal direction with respect to the in-plane direction of the vertically aligned liquid crystal cured film]
It is preferable to satisfy the following. From the viewpoint of further suppressing a decrease in ellipticity, ReA(450)/ReA(550) is more preferably 0.95 or less, and even more preferably 0.90 or less.
In addition, from the viewpoint of improving the ellipticity of an elliptically polarizing plate including a laminate, the following (3)-2:
120nm≦ReA(550)≦170nm...(3)-2
It is preferable to satisfy the following. From the viewpoint of improving the ellipticity of the elliptically polarizing plate including the laminate, preferably 130 nm≦ReA(550)≦160 nm.

Among the laminates according to the present invention, a laminate including a vertically oriented liquid crystal cured film and a film oriented in the horizontal direction with respect to the in-plane direction of the vertically oriented liquid crystal cured film has a retardation value in the front direction and From the viewpoint of reducing the difference in the retardation value of , that is, from the viewpoint of suppressing deterioration of the oblique reflection hue of a display equipped with an elliptically polarizing plate including the laminate, the following relational expression (4):
|R0(550)-R40(550)|≦10nm...(4)
[In relational expression (4), R0 (550) indicates the in-plane retardation value of the laminate at a wavelength of 550 nm, and R40 (550) indicates the in-plane retardation value of the laminate at a wavelength of 550 nm, and R40 (550) indicates the in-plane retardation value of the laminate at a wavelength of 550 nm. Shows the retardation value at a wavelength of 550 nm when the oriented film is rotated by 40° around the fast axis direction]
It is preferable to satisfy the following. From the viewpoint of further suppressing deterioration of the oblique reflection hue, the thickness is more preferably 8 nm or less, and even more preferably 4 nm or less.

Among the laminates according to the present invention, a laminate including a vertically oriented liquid crystal cured film and a film oriented in a horizontal direction with respect to the in-plane direction of the vertically oriented liquid crystal cured film is provided with an elliptically polarizing plate including the laminate. From the viewpoint of suppressing the deterioration of the oblique reflection hue of the display, the following relational expression (5):
|R0(450)-R40(450)|≦10nm...(5)
[In relational expression (5), R0 (450) indicates the in-plane retardation value of the laminate at a wavelength of 450 nm, and R40 (450) indicates the in-plane retardation value of the vertically aligned liquid crystal cured film aligned in the horizontal direction with respect to the in-plane direction. Shows the retardation value at a wavelength of 450 nm when the film is rotated by 40° around the fast axis direction]
It is preferable to satisfy the following. From the viewpoint of further suppressing deterioration of the oblique reflection hue, the thickness is more preferably 8 nm or less, and even more preferably 4 nm or less.

Among the laminates according to the present invention, a laminate including a vertically oriented liquid crystal cured film and a film oriented in a horizontal direction with respect to the in-plane direction of the vertically oriented liquid crystal cured film is provided with an elliptically polarizing plate including the laminate. From the perspective of suppressing the deterioration of the oblique reflection hue of the display, the following relational expression (6):
|{R0(450)-R40(450)}-{R0(550)-R40(550)}|≦3nm...(6)
[In relational expression (6), R0 (450) indicates the in-plane retardation value of the laminate at a wavelength of 450 nm, R0 (550) indicates the in-plane retardation value of the laminate at a wavelength of 550 nm, and R40 (450) indicates the retardation value at a wavelength of 450 nm when the film oriented horizontally to the in-plane direction of the vertically aligned liquid crystal cured film is rotated by 40° around the fast axis direction, and R40 (550) is , shows the retardation value at a wavelength of 550 nm when the film is rotated by 40° around the fast axis direction of the film oriented in the horizontal direction with respect to the in-plane direction of the vertically oriented liquid crystal cured film]
It is preferable to satisfy the following. From the viewpoint of further suppressing deterioration of the oblique reflection hue, the thickness is more preferably 2 nm or less, and even more preferably 1 nm or less.

[Method for manufacturing laminate]
The method for manufacturing a laminate of the present invention includes a step of forming a vertically aligned liquid crystal cured film. The vertical alignment liquid crystal cured film forming step is a method for manufacturing the above-mentioned vertical alignment liquid crystal cured film. By the method for producing a vertically aligned liquid crystal cured film as described above, it is possible to produce a laminate composed of a base material and a vertically aligned liquid crystal cured film, and a laminate composed of a base material, an alignment film, and a vertically aligned liquid crystal cured film. can.
When the laminate includes a film oriented horizontally with respect to the in-plane direction of the vertically oriented liquid crystal cured film, the method for producing the laminate further includes a stretched film bonding step or a horizontally oriented liquid crystal cured film A forming step. In the stretched film bonding step, the stretched film is bonded to, for example, a vertically aligned liquid crystal cured film using an adhesive. A method for manufacturing a laminate including a horizontally aligned liquid crystal cured film A may be, for example, by bonding a vertically aligned liquid crystal cured film and a horizontally aligned liquid crystal cured film via an adhesive layer, or by bonding a horizontally aligned liquid crystal cured film and a horizontally aligned liquid crystal cured film. The horizontally aligned liquid crystal cured film A may be formed on the vertically aligned liquid crystal cured film. Further, a vertically aligned liquid crystal cured film may be formed on the stretched film or on the horizontally aligned liquid crystal cured film A.

[Adhesive]
Examples of adhesives include pressure-sensitive adhesives, dry-setting adhesives, and chemically reactive adhesives. Examples of chemically reactive adhesives include active energy ray-curable adhesives.

Pressure-sensitive adhesives typically contain a polymer and may also contain a solvent. Examples of the polymer include acrylic polymers, silicone polymers, polyesters, polyurethanes, and polyethers. Among these pressure-sensitive adhesives, pressure-sensitive adhesives containing acrylic polymers have excellent optical transparency, moderate wettability and cohesive strength, excellent adhesive properties, and are also weather and heat resistant. It is preferable because it has high properties such as high elasticity and is difficult to cause lifting or peeling under conditions of heating or humidification.

Examples of acrylic polymers include (meth)acrylates in which the alkyl group in the ester moiety is an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, or butyl; (meth)acrylic acid and hydroxyethyl ( A copolymer with a (meth)acrylic monomer having a functional group such as meth)acrylate is preferred.

Pressure-sensitive adhesives containing such copolymers have excellent adhesive properties, and can be removed relatively easily after being attached to a transfer object without leaving adhesive residue on the transfer object. This is preferable because it can be removed. The glass transition temperature of the acrylic polymer is preferably 25°C or lower, more preferably 0°C or lower. The mass average molecular weight of such an acrylic polymer is preferably 100,000 or more.

Examples of the solvent include the solvents listed above as the solvent. The pressure sensitive adhesive may contain a light diffusing agent. The light diffusing agent is an additive that imparts light diffusivity to the pressure-sensitive adhesive, and may be fine particles having a refractive index different from the refractive index of the polymer contained in the pressure-sensitive adhesive. Examples of the light diffusing agent include fine particles made of an inorganic compound and fine particles made of an organic compound (polymer). Most of the polymers contained as active ingredients in pressure-sensitive adhesives, including acrylic polymers, have a refractive index of about 1.4 to 1.6, so light diffusion with a refractive index of 1.2 to 1.8 It is preferable to select an appropriate one from among these agents. The refractive index difference between the polymer contained as an active ingredient in the pressure-sensitive adhesive and the light diffusing agent is usually 0.01 or more, and from the viewpoint of brightness and display performance of the display device, the difference in refractive index is 0.01 to 0.2. preferable. The fine particles used as the light diffusing agent are preferably spherical fine particles, particularly nearly monodisperse fine particles, and more preferably fine particles having an average particle size of 2 to 6 μm. The refractive index is measured by the common minimum deviation method or Abbe refractometer.

Examples of fine particles made of inorganic compounds include aluminum oxide (refractive index 1.76) and silicon oxide (refractive index 1.45). Examples of fine particles made of organic compounds (polymers) include melamine beads (refractive index 1.57), polymethyl methacrylate beads (refractive index 1.49), methyl methacrylate/styrene copolymer resin beads (refractive index 1. .50 to 1.59), polycarbonate beads (refractive index 1.55), polyethylene beads (refractive index 1.53), polystyrene beads (refractive index 1.6), polyvinyl chloride beads (refractive index 1.46), and silicone resin beads (refractive index 1.46). The content of the light diffusing agent is usually 3 to 30 parts by weight based on 100 parts by weight of the polymer.

The thickness of the pressure-sensitive adhesive is determined depending on its adhesion strength, etc., and is not particularly limited, but is usually 1 μm to 40 μm. In terms of workability, durability, etc., the thickness is preferably 3 μm to 25 μm, more preferably 5 μm to 20 μm. By setting the thickness of the adhesive layer formed from the pressure-sensitive adhesive to 5 μm to 20 μm, brightness is maintained when the display device is viewed from the front or from an angle, and the display image does not bleed or blur. It can be made difficult.

The dry-setting adhesive may contain a solvent. Examples of dry-setting adhesives include a polymer of a monomer having a protic functional group such as a hydroxyl group, a carboxyl group, or an amino group and an ethylenically unsaturated group, or a urethane polymer as a main component; Further examples include compositions containing crosslinking agents or curable compounds such as polyhydric aldehydes, epoxy compounds, epoxy resins, melamine compounds, zirconia compounds, and zinc compounds. Examples of polymers of monomers having a protic functional group such as a hydroxyl group, a carboxyl group, or an amino group and an ethylenically unsaturated group include ethylene-maleic acid copolymers, itaconic acid copolymers, and acrylic acid copolymers. , acrylamide copolymers, saponified products of polyvinyl acetate, and polyvinyl alcohol-based resins.

Examples of the polyvinyl alcohol resin include polyvinyl alcohol, partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, methylol group-modified polyvinyl alcohol, and amino group-modified polyvinyl alcohol. Can be mentioned. The content of polyvinyl alcohol resin in the water-based adhesive is usually 1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of water.

Examples of the urethane resin include polyester-based ionomer type urethane resins. The polyester-based ionomer type urethane resin referred to herein is a urethane resin having a polyester skeleton into which a small amount of an ionic component (hydrophilic component) is introduced. Such an ionomer-type urethane resin emulsifies in water to form an emulsion without using an emulsifier, and therefore can be used as a water-based adhesive. When using a polyester ionomer type urethane resin, it is effective to blend a water-soluble epoxy compound as a crosslinking agent.

Examples of the epoxy resin include polyamide epoxy resins obtained by reacting epichlorohydrin with a polyamide polyamine obtained by reacting a polyalkylene polyamine such as diethylene triamine or triethylene tetramine with a dicarboxylic acid such as adipic acid. Examples of commercially available polyamide epoxy resins include "Sumirezu Resin (registered trademark) 650" and "Sumirezu Resin 675" manufactured by Sumika Chemtex Co., Ltd., and "WS-525" manufactured by Nippon PMC Co., Ltd. It will be done. When blending an epoxy resin, its content is usually 1 to 100 parts by weight, preferably 1 to 50 parts by weight, per 100 parts by weight of the polyvinyl alcohol resin.

The thickness of the adhesive layer formed from the dry solidifying adhesive is usually 0.001 to 5 μm, preferably 0.01 to 2 μm, from the viewpoint of suppressing appearance defects, and Preferably it is 0.01 to 0.5 μm.

The active energy ray curable adhesive may contain a solvent. An active energy ray-curable adhesive is an adhesive that hardens upon irradiation with active energy rays. Examples of active energy ray-curable adhesives include cationically polymerizable adhesives containing an epoxy compound and a cationic polymerization initiator, radically polymerizable adhesives containing an acrylic curing component and a radical polymerization initiator, Adhesives containing both a cationically polymerizable curing component such as an epoxy compound and a radically polymerizable curing component such as an acrylic compound, and further containing a cationic polymerization initiator and a radical polymerization initiator; Examples include adhesives that do not contain a polymerization initiator and are cured by electron beam irradiation.

Among these active energy ray-curable adhesives, radically polymerizable active energy ray-curable adhesives containing an acrylic curing component and a radical photopolymerization initiator, and those containing an epoxy compound and a cationic photopolymerization initiator. A cationically polymerizable active energy ray-curable adhesive is preferred. Examples of the acrylic curing component include (meth)acrylates such as methyl (meth)acrylate and hydroxyethyl (meth)acrylate, and (meth)acrylic acid. The active energy ray-curable adhesive containing an epoxy compound may further contain a compound other than the epoxy compound. Examples of compounds other than epoxy compounds include oxetane compounds and acrylic compounds.

Examples of the radical photopolymerization initiator and the cationic photopolymerization initiator include the above-mentioned radical photopolymerization initiator and cationic photopolymerization initiator. The content of the radical polymerization initiator and the cationic polymerization initiator is usually 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the active energy ray-curable adhesive.

Active energy ray-curable adhesives further contain ion trapping agents, antioxidants, chain transfer agents, tackifiers, thermoplastic resins, fillers, flow regulators, plasticizers, and antifoaming agents. It's okay.

<Elliptically polarizing plate>
The elliptically polarizing plate includes the laminate and a polarizing film. The elliptically polarizing plate may further include an arbitrary layer (more specifically, a protective layer, an adhesive, etc.) as necessary. The laminate and the polarizing film are adhered to each other via, for example, an adhesive.

FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of an elliptically polarizing plate. The elliptically polarizing plate 20 shown in FIG. 1 is composed of a laminate 15, an adhesive 7, a polarizing film 11, and a protective layer 13. The laminate 15 is composed of a base material 1, a horizontal alignment film 3, a horizontal alignment liquid crystal cured film A5, an adhesive 7, and a vertical alignment liquid crystal cured film 9. The angle between the slow axis of the horizontally aligned liquid crystal cured film A5 and the absorption axis of the polarizing film 11 is 45±5°.

(polarizing film)
A polarizing film is a film that has a polarizing function. As a polarizing film, for example, a film containing a dichroic dye and oriented in the horizontal direction with respect to the film surface of the polarizing film (more specifically, a stretched film on which a dichroic dye is adsorbed (hereinafter referred to as polarizing film A) ), and a horizontally aligned liquid crystal cured film B (hereinafter sometimes referred to as polarizing film B) containing a dichroic dye. From the viewpoint of making the elliptically polarizing plate thinner, a horizontally aligned liquid crystal cured film B containing a dichroic dye is preferred. A dichroic dye refers to a dye that exhibits absorption anisotropy and has a property that the absorbance in the long axis direction of the dichroic dye molecule is different from the absorbance in the short axis direction.

(Horizontally aligned liquid crystal cured film B)
The horizontally aligned liquid crystal cured film B is a cured product of a composition (hereinafter sometimes referred to as a composition for forming polarizing film B) containing a dichroic dye and a polymerizable liquid crystal compound (B). The horizontally oriented liquid crystal cured film B is a liquid crystal cured film containing a dichroic dye and cured in a state in which the polymerizable liquid crystal compound (B) is oriented in the horizontal direction with respect to the in-plane direction.

The horizontally oriented liquid crystal cured film B is preferably a cured film in which the polymerizable liquid crystal compound (B) is cured in a smectic phase aligned horizontally with respect to the in-plane direction of the film. That is, when the polymerizable liquid crystal compound (B) is a thermotropic liquid crystal, it may be a thermotropic liquid crystal compound exhibiting a nematic liquid crystal phase or a thermotropic liquid crystal compound exhibiting a smectic liquid crystal phase. . When exhibiting a polarizing function as a cured film through a polymerization reaction, the liquid crystal state exhibited by the polymerizable liquid crystal compound is preferably a smectic phase, and a higher smectic phase is more preferable from the viewpoint of improving performance. Among them, higher-order smectic liquid crystal compounds forming smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase or smectic L phase are used. More preferred are higher-order smectic liquid crystal compounds that form a smectic B phase, a smectic F phase, or a smectic I phase. When the liquid crystal phase formed by the polymerizable liquid crystal compound (B) is one of these higher-order smectic phases, a polarizing film with higher polarizing performance can be manufactured. In addition, a polarizing film having such high polarization performance can obtain a Bragg peak derived from a higher-order structure such as a hexatic phase or a crystal phase in X-ray diffraction measurement. The Bragg peak is a peak derived from the periodic structure of molecular orientation, and a film having a periodic interval of 3 to 6 Å can be obtained. It is preferable that the horizontally aligned liquid crystal cured film B contains a polymer of the polymerizable liquid crystal compound (B) polymerized in a smectic phase state from the viewpoint of obtaining higher polarization characteristics. In addition, the below-mentioned polymerizable group that the polymerizable liquid crystal compound (B) has may be in an unpolymerized state or a polymerized state in the horizontally aligned liquid crystal cured film B. That is, the horizontally aligned liquid crystal cured film B is made of any of the following: polymerizable liquid crystal compound (B) (monomer), oligomer of polymerizable liquid crystal compound (B), polymer of polymerizable liquid crystal compound (B), and combinations thereof. may be included. The polymerizable group that the polymerizable liquid crystal compound (B) has is preferably in an unpolymerized state in the horizontally aligned liquid crystal cured film B.

Specific examples of the polymerizable liquid crystal compound (B) include compounds represented by the following formula (B). The polymerizable liquid crystal may be used alone or in combination of two or more types.

U ¹ -V ¹ -W ¹ -X ¹ -Y ¹ -X ² -Y ² -X ³ -W ² -V ² -U ² (B)
[In formula (B),
X ¹ , X ² , and X ³ each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group; The hydrogen atom contained in the cyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The carbon atoms constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. However, at least one of X ¹ , X ² , and X ³ is a 1,4-phenylene group that may have a substituent, or a cyclohexane-1,4- Represents a diyl group.
Y ¹ , Y ² , W ¹ , and W ² each independently represent a single bond or a divalent linking group.
V ¹ and V ² each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - constituting the alkanediyl group is -O-, - It may be substituted with CO-, -S- or NH-.
U ¹ and U ² each independently represent a polymerizable group or a hydrogen atom, and at least one of U ¹ and U ² represents a polymerizable group.

In the polymerizable liquid crystal compound (B), at least one of X ¹ , X ² , and X ³ is a 1,4-phenylene group that may have a substituent, or a 1,4-phenylene group that may have a substituent. Represents a good cyclohexane-1,4-diyl group. In particular, it is preferable that X ¹ and X ³ represent a cyclohexane-1,4-diyl group which may have a substituent, and the cyclohexane-1,4-diyl group is a trans-cyclohexane-1,4-diyl group. More preferably, it represents a 1,4-diyl group. Examples of optional substituents of the 1,4-phenylene group that may have a substituent or the cyclohexane-1,4-diyl group that may have a substituent include, for example, a methyl group. Examples include alkyl groups having 1 to 4 carbon atoms such as , ethyl group, and butyl group, cyano group, and halogen atoms such as chlorine atom and fluorine atom. The 1,4-phenylene group which may have a substituent or the cyclohexane-1,4-diyl group which may have a substituent is preferably a 1,4-phenylene group and a cyclohexane-1,4-diyl group. It is a xane-1,4-diyl group. Moreover, when Y ¹ and Y ² have the same structure, it is preferable that at least one of X ¹ , X ² and X ³ has a different structure. When at least one of X ¹ , X ² and X ³ has a different structure, smectic liquid crystallinity tends to occur easily.

Y ¹ and Y ² each independently represent a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ O-, -COO-, -OCO-, -N=N-, - It is preferable to represent CR ^a =CR ^b -, -C≡C-, or CR ^a =N-, and R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is more preferable that Y ¹ and Y ² each independently represent -CH ₂ CH ₂ -, -COO-, -OCO-, or a single bond. Moreover, when X ¹ , X ² and X ³ all have the same structure, it is preferable that Y ¹ and Y ² have different bonding methods. When Y ¹ and Y ² have different bonding methods, smectic liquid crystallinity tends to occur easily.

W ¹ and W ² each independently preferably represent a single bond, -O-, -S-, -COO-, or OCO-, and more preferably each independently represent a single bond or O- .

Examples of the alkanediyl group having 1 to 20 carbon atoms represented by V ¹ and V ² include methylene group, ethylene group, propane-1,3-diyl group, butane-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, decane-1,10-diyl group , tetradecane-1,14-diyl group, and icosane-1,20-diyl group. V ¹ and V ² preferably represent an alkanediyl group having 2 to 12 carbon atoms, more preferably a linear alkanediyl group having 6 to 12 carbon atoms. When V ¹ and V ² represent linear alkanediyl groups having 6 to 12 carbon atoms, the orientation of the polymerizable liquid crystal compound (B) tends to be improved and smectic liquid crystallinity is likely to be exhibited.
Examples of the optional substituents of the alkanediyl group having 1 to 20 carbon atoms which may have a substituent include a cyano group and halogen atoms such as chlorine and fluorine atoms. The diyl group is preferably unsubstituted, and more preferably an unsubstituted linear alkanediyl group.

Both U ¹ and U ² preferably represent a polymerizable group, and more preferably both represent a photopolymerizable group. The polymerizable liquid crystal compound (B) having a photopolymerizable group can be polymerized under lower temperature conditions than a thermally polymerizable group, and therefore is advantageous in that the liquid crystal can form a polymer with a higher degree of order.

The polymerizable groups represented by U ¹ and U ² may be the same or different, but are preferably the same. 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 these photopolymerizable groups, acryloyloxy, methacryloyloxy, vinyloxy, oxiranyl, and oxetanyl groups are preferred, and methacryloyloxy and acryloyloxy groups are more preferred.

Examples of such polymerizable liquid crystal compounds (B) include polymerizable liquid crystal compounds represented by the following formulas (1-1) to (1-23).

Among the exemplified polymerizable liquid crystal compounds, formula (1-2), formula (1-3), formula (1-4), formula (1-6), formula (1-7), formula (1-8) ), formula (1-13), formula (1-14) and formula (1-15). One type of polymerizable liquid crystal compound may be used alone, or two or more types may be used in combination.

The polymerizable liquid crystal compound (B) is, for example, manufactured by Lub et al., Recl. Trav. Chim. It can be produced by the known method described in Pays-Bas, 115, 321-328 (1996), or Japanese Patent No. 4719156.

The composition containing the polymerizable liquid crystal compound (B) may contain other liquid crystal compounds other than the polymerizable liquid crystal compound (B) as long as the effects of the present invention are not impaired. The proportion of the polymerizable liquid crystal compound (B) to the total mass of all liquid crystal compounds contained in the composition containing the polymerizable liquid crystal compound (B) is preferably 51% by mass or more, more preferably 70% by mass. It is at least 90% by mass, more preferably at least 90% by mass.

Furthermore, when the composition containing the polymerizable liquid crystal compound (B) contains two or more types of polymerizable liquid crystal compounds (B), at least one of them may be a polymerizable liquid crystal compound (B: exemplified compound). , all of which may be the polymerizable liquid crystal compound (B). By combining multiple polymerizable liquid crystal compounds, it may be possible to temporarily maintain liquid crystallinity even at temperatures below the liquid crystal-crystal phase transition temperature.

The content of the polymerizable liquid crystal compound (B) in the composition containing the polymerizable liquid crystal compound (B) is preferably 40 to 99.9 mass based on the solid content of the composition containing the polymerizable liquid crystal compound (B). %, more preferably 60 to 99% by mass, still more preferably 70 to 99% by mass. When the content of the polymerizable liquid crystal compound (B) is within the above range, the orientation of the liquid crystal compound tends to be high. Note that the solid content refers to the total amount of components excluding the solvent from the polymerizable liquid crystal composition.

(dichroic dye)
A dichroic dye refers to a dye that has a property that the absorbance in the long axis direction of the molecule is different from the absorbance in the short axis direction. The dichroic dye preferably has the property of absorbing visible light, and more preferably has a maximum absorption wavelength (λ _MAX ) in the wavelength range of 380 to 680 nm. Examples of dichroic dyes include iodine and dichroic organic dyes. Examples of dichroic organic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes, and anthraquinone dyes. Among these dichroic organic dyes, azo dyes are preferred. Examples of azo dyes include monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes, and stilbene azo dyes. Among these azo dyes, bisazo dyes and trisazo dyes are preferred. Dichroic organic dyes may be used alone or in combination of two or more types, but in order to obtain absorption in the entire visible light range, three or more types of dichroic dyes may be used. It is preferable to use them in combination, and it is more preferable to use them in combination of three or more types of azo dyes. It is preferable that the polyvinyl alcohol resin film is immersed in water before being dyed.

Examples of azo dyes include compounds represented by formula (I).
T ¹ -A ¹ (-N=NA ² ) _p -N=NA ³ -T ² (I)
[In formula (I),
A ¹ , A ² , and A ³ are each independently a 1,4-phenylene group that may have a substituent, a naphthalene-1,4-diyl group, or a substituent. It represents a divalent heterocyclic group, and T ¹ and T ² each independently represent an electron-withdrawing group or an electron-emitting group, and are located at substantially 180° with respect to the azo bond plane. p represents an integer from 0 to 4. When p represents an integer of 2 or more, a plurality of ^A2 's may be the same or different from each other. The -N=N- bond may be replaced with a -C=C- bond, -COO- bond, -NHCO- bond, or -N=CH- bond within the range where the azo dye exhibits absorption in the visible region. ]

Examples of optional substituents on the 1,4-phenylene group, naphthalene-1,4-diyl group, and divalent heterocyclic group represented by A ¹ , A ² , and A ³ include methyl group, ethyl group, , and alkyl groups having 1 to 4 carbon atoms such as butyl groups; alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, and butoxy groups; 1 to 4 carbon atoms such as trifluoromethyl groups; Fluorinated alkyl group; cyano group; nitro group; halogen atom such as chlorine atom and fluorine atom; substituted or unsubstituted amino group such as amino group, diethylamino group and pyrrolidino group (substituted amino group refers to the number of carbon atoms Refers to an amino group having one or two alkyl groups having 1 to 6 carbon atoms, or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms.Unsubstituted amino The group is -NH ₂ ). Note that examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, and a hexyl group. Examples of the alkanediyl group having 2 to 8 carbon atoms include ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group. Examples include diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, and octane-1,8-diyl group. In order to incorporate it into a highly ordered liquid crystal structure such as a smectic liquid crystal, A ¹ , A ² and A ³ are unsubstituted or 1,4-phenylene groups in which the hydrogen atom is substituted with a methyl group or a methoxy group, or It is preferable to represent a divalent heterocyclic group, and p is preferably an integer of 0 to 2. Among them, p is 1 and at least two of the three structures A ¹ , A ² and A ³ are 1,4-phenylene groups, which provides both ease of molecular synthesis and high performance. More preferred.

Examples of the divalent heterocyclic group include groups obtained by removing two hydrogen atoms from a heterocyclic ring such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole, and benzoxazole. . When A ² represents a divalent heterocyclic group, a structure in which the molecular bond angle is substantially 180° is preferable, and specifically, a benzothiazole structure or a benzimidazole structure in which two 5-membered rings are fused. , and benzoxazole structures are more preferred.

T ¹ and T ² each independently represent an electron-withdrawing group or an electron-releasing group, preferably representing an electron-withdrawing group or an electron-releasing group with mutually different structures, T ¹ represents an electron-withdrawing group, and T ² More preferably, it represents an electron-emitting group, or when T ¹ represents an electron-emitting group and T ² represents an electron-withdrawing group. Specifically, T ¹ and T ² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms. Preferred are a substituted amino group having one or two substituted amino groups, an amino group in which two of the substituted alkyl groups bond to each other to form an alkanediyl group having 2 to 8 carbon atoms, and a trifluoromethyl group. Among them, in order to be included in a highly ordered liquid crystal structure such as a smectic liquid crystal, the structure needs to have a smaller excluded volume of molecules. group, a cyano group, a substituted amino group having one or two alkyl groups having 1 to 6 carbon atoms, and an amino group in which two of the substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms. Groups are preferred.

Examples of such azo dyes include azo dyes represented by the following formulas (2-1) to (2-8).

In formulas (2-1) to (2-8),
B ¹ to B ³⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, a nitro group, a substituted or unsubstituted amino group (substituted amino group and The definition of the unsubstituted amino group is as described above), a chlorine atom, or a trifluoromethyl group. In addition, from the viewpoint of obtaining high polarization performance when combined with smectic liquid crystal, B ² , B ⁶ , B ⁹ , B ¹⁴ , B ¹⁸ , B ¹⁹ , B ²² , B ²³ , B ²⁴ , B ²⁷ , B ²⁸ , and B ²⁹ each independently preferably represent a hydrogen atom or a methyl group, and more preferably represent a hydrogen atom.
n1 to n4 each independently represent an integer of 0 to 2.
When n1 represents 2, the plurality of ^B2 's may be the same or different,
When n2 represents 2, the plurality of ^B6s may be the same or different,
When n3 represents 2, multiple ^B9s may be the same or different,
When n4 represents 2, the plurality of ^B14s may be the same or different.

The anthraquinone dye is preferably a compound represented by formula (2-9).

[In formula (2-9),
R ¹ to R ⁸ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

The oxazine dye is preferably a compound represented by formula (2-10).

[In formula (2-10),
R ⁹ to R ¹⁵ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

The acridine dye is preferably a compound represented by formula (2-11).

[In formula (2-11),
R ¹⁶ to R ²³ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

In formula (2-9), formula (2-10) and formula (2-11), the alkyl group having 1 to 4 carbon atoms represented by R ^x includes, for example, a methyl group, an ethyl group, a propyl group, Mention may be made of butyl, pentyl, and hexyl groups. In formula (2-9), formula (2-10) and formula (2-11), the aryl group having 6 to 12 carbon atoms represented by R ^x includes, for example, a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

The cyanine dye is preferably a compound represented by formula (2-12) or a compound represented by formula (2-13).

ｎ５は１～３の整数を表す。］ [In formula (2-12),
D ¹ and D ² each independently represent a group represented by any one of formulas (2-12a) to (2-12d).

n5 represents an integer from 1 to 3. ]

ｎ６は１～３の整数を表す。］ [In formula (2-13),
D ³ and D ⁴ each independently represent a group represented by any one of formulas (2-13a) to (2-13h).

n6 represents an integer from 1 to 3. ]

From the viewpoint of obtaining good light absorption characteristics, the content of the dichroic organic dye (or the total amount when multiple types are included) is usually 0.1 parts by mass per 100 parts by mass of the polymerizable liquid crystal compound (B). ~30 parts by weight, preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight. When the content of the dichroic organic dye is 0.1 part by mass or more based on 100 parts by mass of the polymerizable liquid crystal compound (B), the light absorption of the dichroic organic dye is sufficient, and sufficient polarization performance is achieved. tends to be obtained. When the content of the dichroic organic dye is 30 parts by mass or less based on 100 parts by mass of the polymerizable liquid crystal compound (B), the alignment of the polymerizable liquid crystal compound is less likely to be inhibited.

(Stretched film with dichroic dye adsorbed)
At least one of the stretched films adsorbing the dichroic dye may be provided with a transparent protective film. A film containing a stretched film with a dichroic dye adsorbed thereon as a polarizer is usually produced through a process of uniaxially stretching a polyvinyl alcohol resin film, or by dyeing the polyvinyl alcohol resin film with a dichroic dye. At least one surface of a polarizer manufactured through a step of adsorbing a dye, a step of treating a polyvinyl alcohol resin film with a dichroic dye adsorbed with an aqueous boric acid solution, and a step of washing with water after treatment with an aqueous boric acid solution. It is made by sandwiching a transparent protective film between the two using an adhesive.

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

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

A film made of such a polyvinyl alcohol resin is used as a raw film of a polarizing film. The method of forming a polyvinyl alcohol resin into a film is not particularly limited, and any known method can be used to form the film. The thickness of the polyvinyl alcohol base film can be, for example, about 10 to 150 μm.

Uniaxial stretching of the polyvinyl alcohol resin film can be performed before, simultaneously with, or after dyeing with a dichroic dye. When uniaxial stretching is performed after dyeing, this uniaxial stretching may be performed before or during the boric acid treatment. Moreover, it is also possible to perform uniaxial stretching in these plural steps. In the uniaxial stretching, it may be uniaxially stretched between rolls having different circumferential speeds, or it may be uniaxially stretched using hot rolls. Further, the 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 stretching ratio is usually about 3 to 8 times.

Staining of a polyvinyl alcohol resin film with a dichroic dye is carried out, for example, by immersing the polyvinyl alcohol resin film in an aqueous solution containing the dichroic dye.

When using iodine as a dichroic dye, a method is usually employed in which a polyvinyl alcohol resin film is immersed in an aqueous solution containing iodine and potassium iodide for dyeing. 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. Further, 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 (staining time) in this aqueous solution is usually about 20 to 1,800 seconds.

On the other hand, when using a dichroic organic dye as the dichroic dye, a method of dyeing by immersing a polyvinyl alcohol 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 x 10 ^-4 to 10 parts by weight, preferably 1 x 10 -3 to 1 part by weight, and more preferably about 1 x 10 ^-4 to 1 part by weight, per 100 parts by weight 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 (staining time) in this aqueous solution is usually about 10 to 1,800 seconds.

The boric acid treatment after dyeing with a dichroic dye can usually be carried out by immersing the dyed polyvinyl alcohol resin film in an aqueous boric acid solution. The content of boric acid in this boric acid aqueous solution is usually about 2 to 15 parts by weight, preferably 5 to 12 parts by weight, based on 100 parts by weight 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 this case is usually 0.1 to 100 parts by mass of water. The amount 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, and more preferably 200 to 400 seconds. The temperature of the boric acid treatment is usually 50°C or higher, preferably 50 to 85°C, more preferably 60 to 80°C.

The polyvinyl alcohol resin film treated with boric acid is usually washed with water. The water washing treatment can be performed, for example, by immersing a boric acid-treated polyvinyl alcohol resin film in water. The temperature of water in the 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 process is performed to obtain a polarizer. The drying process can be performed using, for example, a hot air dryer or a far-infrared heater. The temperature of the drying treatment 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 weight, preferably 8 to 15% by weight. If the moisture content is less than 5% by weight, the flexibility of the polarizer is lost and the polarizer may be damaged or broken after drying. Furthermore, if the moisture content exceeds 20% by weight, 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.

<Organic EL display device>
The organic EL display device includes the elliptically polarizing plate. A preferred embodiment of the organic EL display device includes, for example, a device in which an elliptically polarizing plate is bonded to an organic EL panel via an adhesive.

Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, "%" and "parts" in the examples mean % by mass and parts by mass, respectively, unless otherwise specified.

[Preparation of liquid crystal compound]
Liquid crystal compound A was produced according to the method described in JP-A-2010-31223. Furthermore, liquid crystal compound B was produced according to the method described in JP-A No. 2009-173893. The molecular structures of liquid crystal compound A and liquid crystal compound B are shown below.

(Liquid crystal compound A)

(Liquid crystal compound B)

[Measuring method]
(Calculation method of maximum absorption wavelength and maximum absorbance ratio)
A 1 mg/50 mL tetrahydrofuran solution of liquid crystal compound A was prepared and used as a measurement sample. A measurement sample was placed in a measurement cell with an optical path length of 1 cm. The measurement sample was set in an ultraviolet-visible spectrophotometer ("UV-2450" manufactured by Shimadzu Corporation), and the absorption spectrum was measured. Note that the reference was only the solvent of the measurement sample. The wavelength at which the maximum absorption occurs was read from the obtained absorption spectrum, and this was defined as the maximum absorption wavelength λ _max . Furthermore, the maximum absorption wavelength of liquid crystal compound A in the wavelength range of 260 nm or more and 400 nm or less was read from the obtained absorption spectrum. In addition, when a plurality of maximum absorption wavelengths exist in the wavelength range of 260 nm or more and 400 nm or less, the wavelength with the highest absorbance among the plurality of maximum absorption wavelengths was defined as λ _max . Table 1 shows the maximum absorption wavelengths obtained.

[Preparation of ionic compound]
Ionic compound (1) was produced according to the method described in Japanese Patent Application No. 2016-514802. In addition, the ionic compound (2) and the ionic compound (3) were produced according to the method described in JP-A No. 2013-28586 or JP-A No. 2013-199509. The structural formulas of ionic compounds (1) to (3) are shown below.

（イオン性化合物（２））

（イオン性化合物（３））

(Ionic compound (1))

(Ionic compound (2))

(Ionic compound (3))

<Example 1>
[Preparation of composition for forming vertically aligned liquid crystal cured film (A-1)]
Liquid crystal compound A and liquid crystal compound B were mixed at a mass ratio of 90:10 to obtain a mixture. To 100 parts by mass of the obtained mixture, 1.5 parts by mass of a leveling agent ("F-556" manufactured by DIC Corporation) and 2-dimethylamino-2-benzyl-1-(4- 6 parts by mass of morpholinophenyl)butan-1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan Ltd.) were added. In addition, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine ("KBE-9103" manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane compound was added to ionic Compound (1) was further added to give a concentration of 2.0%.

N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. By stirring at 80° C. for 1 hour, a composition (A-1) for forming a vertically aligned liquid crystal cured film (hereinafter sometimes referred to as composition (A-1)) was obtained. In addition, the silane compound (KBE-9103 manufactured by Shin-Etsu Chemical Co., Ltd.) reacts with the solvent and moisture in the environment in the composition (A-1), and hydrolysis proceeds, and the amino group, which is a polar group, is I confirmed that it is generated.

[Method for producing vertically aligned liquid crystal cured film (A-1)]
Using a corona treatment device (“AGF-B10” manufactured by Kasuga Denki Co., Ltd.), amorphous cycloolefin polymer film (COP film) (Nippon Zeon Co., Ltd. “ZF-14-23”) was treated as a base material. , Corona treatment was performed once under conditions of an output of 0.3 kW and a processing speed of 3 m/min. Composition (A-1) was applied to the surface of the corona-treated substrate using a bar coater to form a coating film. The coating film was dried at 120° C. for 1 minute to form a dry film. Next, the dried film was irradiated with ultraviolet rays using a high-pressure mercury lamp (Unicure VB-15201BY-A manufactured by Ushio Inc.) under conditions of a nitrogen atmosphere and a cumulative light amount of 500 mJ/cm ² at a wavelength of 365 nm. As a result, a vertically aligned liquid crystal cured film (A-1) (film thickness: 1.0 μm) was formed.

[Optical properties of vertically aligned liquid crystal cured film (A-1)]
The obtained vertically aligned liquid crystal cured film (A-1) was bonded to glass via an adhesive (pressure-sensitive adhesive manufactured by Lintec, 15 μm) to prepare a sample for measuring optical properties.

(Measurement of phase difference value)
The base material ZF-14-23 is an optically isotropic film with a retardation value of 1 nm or less at a wavelength of 550 nm, and it was confirmed that the measured values of the sample for measuring optical properties were not affected. Subsequently, using a measuring device ("KOBRA-WPR" manufactured by Oji Keizoku Co., Ltd.), the phase difference value was measured by changing the angle of incidence of light on the sample for measuring optical properties.

(Measurement of average refractive index)
The average refractive index at wavelengths λ=450 nm and 550 nm was measured using a refractometer (“Multi-wavelength Abbe refractometer DR-M4” manufactured by Atago Co., Ltd.). Rth calculated from the obtained film thickness, average refractive index, and measurement results of a measuring device ("KOBRA-WPR" manufactured by Oji Scientific Instruments Co., Ltd.) is Rth (450) = -60 nm, Rth (550) = -70 nm, and Rth(450)/Rth(550)=0.85.

(Orientation evaluation of oriented liquid crystal cured film)
It was observed using a polarizing microscope ("BX-51" manufactured by Olympus Corporation) at a magnification of 200 times, and the number of orientation defects was counted in a field of view of 480 μm x 320 μm. Here, only the number of orientation defects caused by the measurement sample was counted, and the number of defects caused by environmental foreign substances other than the optical property sample was excluded and not counted. From the observation results with a polarizing microscope, the orientation of the vertically aligned liquid crystal cured film (A-1) was evaluated based on the following evaluation criteria. Samples A, B, and C were judged to have excellent orientation. As shown in Table 1, the orientation of the vertically aligned liquid crystal cured film (A-1) prepared using the composition (A-1) was A.
(Evaluation criteria)
A (very good): The number of orientation defects is 0 or more and 3 or less.
B (very good): The number of orientation defects is 4 or more and 10 or less.
C (Good): The number of orientation defects is 11 or more and 50 or less.
D (Bad): 51 or more orientation defects or no orientation at all.

<Examples 2 to 9, Example 20, Example 21, Comparative Example 1>
The base material of Example 1, 0.5% of the silane compound, and 2 parts of the ionic compound (2) were added to the base material type, the type and amount of the silane compound, and the type and addition of the ionic compound listed in Table 1. Examples 2 to 9, Example 20, Example 21, and Comparative Example 1 composition (A-2 ) to (A-9), (A-20), (A-21), and (B-1) were prepared, respectively. Composition (A-1) was changed to compositions (A-2) to (A-9), (A-20), (A-21), and (B-1), and the film thickness of the coating film was further changed. Examples 2 to 9 and Examples 2 to 9 were prepared in the same manner as the method for producing the vertically aligned liquid crystal cured film (A-1) of Example 1, except that the retardation values were changed to have the retardation values shown in Table 1. 20, Example 21, and vertically aligned liquid crystal cured films (A-2) to (A-9), (A-20), (A-21), and (B-1) of Comparative Example 1 were produced, respectively. . In addition, a sample for measuring optical properties was prepared in the same manner as in Example 1, and the retardation value, average refractive index, and orientation were evaluated. The results are shown in Table 1.

<Example 10>
The base material was changed from COP film (ZF-14-23 manufactured by Zeon Corporation) to polyethylene terephthalate with a protective layer (hereinafter sometimes referred to as PET with a protective layer), and when measuring optical properties. A vertically aligned liquid crystal cured film (A-10) was prepared in the same manner as the method for preparing the vertically aligned liquid crystal cured film (A-1) in Example 1, except that the PET base material was peeled off to prepare a sample. . In addition, a sample for measuring optical properties was prepared in the same manner as in Example 1, and the retardation value, average refractive index, and orientation were evaluated. The results are shown in Table 1. Hereinafter, a method for preparing PET with a protective layer will be explained.

[Preparation of composition for forming protective layer]
50 parts of dipentaerythritol hexaacrylate (“Aronix (registered trademark) M-403” polyfunctional acrylate manufactured by Toagosei Co., Ltd.), 50 parts of acrylate resin (“Evecryl 4858” manufactured by Daicel UCB Corporation), and 2-methyl 3 parts of -1[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("Irgacure (registered trademark) 907" manufactured by Ciba Specialty Chemicals) were dissolved in 250 parts of isopropanol, and the solution was Prepared. The obtained solution was used as a composition for forming a protective layer.

[Production of PET with protective layer]
The composition for forming a protective layer was applied onto a PET film (thickness: 38 μm) using a bar coater to form a coating film. The coating film was dried at 50° C. for 1 minute to form a dry film. Using a high-pressure mercury lamp (Unicure VB-15201BY-A manufactured by Ushio Inc.), the dried film was irradiated with ultraviolet rays in a nitrogen atmosphere and at a wavelength of 365 nm with an integrated light intensity of 400 mJ/cm ² . As a result, PET with a protective layer made of acrylic resin was formed. In addition, according to the method for measuring optical properties described in Example 1, the retardation value of the protective layer at a wavelength of 550 nm was measured after laminating it to glass via an adhesive and peeling off the PET film, and it was 1 nm or less. It was confirmed that the film was optically isotropic. Further, the thickness of the formed protective layer was measured with an ellipsometer and was found to be 2 μm.

・・・（Ａ）－２ <Example 11>
The composition (A-1) and the composition of Example 1 except that the composition of the liquid crystal compound of Example 1 was changed from liquid crystal compound A/liquid crystal compound B = 90%/10% to 100% of liquid crystal compound (A)-2. The composition (A-11) of Example 11 and the vertically aligned liquid crystal cured film (A-11) were prepared in the same manner as the method for preparing the vertically aligned liquid crystal cured film (A-1). Liquid crystal compound (A)-2 was prepared with reference to JP-A-2016-81035. Liquid crystal compound (A)-2 is represented by the following formula (A)-2. In addition, a measurement sample was prepared in the same manner as in Example 1, and the retardation value, average refractive index, and orientation were evaluated. Furthermore, the ratio of the maximum absorption wavelength and maximum absorbance of liquid crystal compound (A)-2 was also calculated in the same manner as in Example 1. The results are shown in Table 1.

...(A)-2

・・・（Ａ）－３ <Example 12>
The composition (A-1) and the composition of Example 1 except that the composition of the liquid crystal compound of Example 1 was changed from liquid crystal compound A/liquid crystal compound B = 90%/10% to 100% of liquid crystal compound (A)-3. The composition (A-12) of Example 12 and the vertically aligned liquid crystal cured film (A-12) were prepared in the same manner as the method for preparing the vertically aligned liquid crystal cured film (A-1). Liquid crystal compound (A)-3 was prepared with reference to International Patent Publication No. 2015/025793. Liquid crystal compound (A)-3 is represented by the following formula (A)-3. In addition, a sample for measuring optical properties was prepared in the same manner as in Example 1, and the retardation value, average refractive index, and orientation were evaluated. Furthermore, the ratio of the maximum absorption wavelength and maximum absorbance of liquid crystal compound (A)-3 was also calculated in the same manner as in Example 1. The results are shown in Table 1.

...(A)-3

・・・（Ａ）－４ <Example 13>
The composition (A-1) and the composition of Example 1 except that the composition of the liquid crystal compound of Example 1 was changed from Liquid Crystal Compound A/Liquid Crystal Compound B = 90%/10% to 100% of Liquid Crystal Compound (A)-4. The composition (A-13) of Example 11 and the vertically aligned liquid crystal cured film (A-13) were prepared in the same manner as the method for preparing the vertically aligned liquid crystal cured film (A-1). Liquid crystal compound (A)-4 was prepared with reference to JP-A-2011-207765. Liquid crystal compound (A)-4 is represented by the following formula (A)-4. In addition, a sample for measuring optical properties was prepared in the same manner as in Example 1, and the retardation value, average refractive index, and orientation were evaluated. Furthermore, the ratio of the maximum absorption wavelength and maximum absorbance of liquid crystal compound (A)-4 was also calculated in the same manner as in Example 1. The results are shown in Table 1.

...(A)-4

・・・（Ａ）－５
<Example 14>
The composition (A-1) and the composition of Example 1 except that the composition of the liquid crystal compound of Example 1 was changed from liquid crystal compound A/liquid crystal compound B = 90%/10% to 100% of liquid crystal compound (A)-5. The composition (A-14) of Example 14 and the vertically aligned liquid crystal cured film (A-14) were prepared in the same manner as the method for preparing the vertically aligned liquid crystal cured film (A-1). Liquid crystal compound (A)-5 was prepared with reference to JP-A-2010-31223. Liquid crystal compound (A)-5 is represented by the following formula (A)-5. In addition, a sample for measuring optical properties was prepared in the same manner as in Example 1, and the retardation value, average refractive index, and orientation were evaluated. Furthermore, the ratio of the maximum absorption wavelength and maximum absorbance of liquid crystal compound (A)-5 was also calculated in the same manner as in Example 1. The results are shown in Table 1.

...(A)-5

<Example 15>
The silane compound of Example 1 was converted from 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine (“KBE-9103” manufactured by Shin-Etsu Chemical Co., Ltd.) to 3-glycidoxypropyltriethoxysilane ( Example 1 was prepared in the same manner as the preparation method of the composition (A-1) and the vertically aligned liquid crystal cured film (A-1) of Example 1, except for changing to "KBE-403" manufactured by Shin-Etsu Chemical Co., Ltd. A composition of No. 15 (A-15) and a vertically aligned liquid crystal cured film (A-15) were prepared.In addition, samples for measuring optical properties were prepared in the same manner as in Example 1, and the retardation value, average refraction The ratio and orientation were evaluated.The results are shown in Table 1.

<Example 16>
[Manufacture of polarizing film A]
After immersing a polyvinyl alcohol film (average degree of polymerization of about 2,400, degree of saponification of 99.9 mol% or more, thickness 75 μm) in pure water at 30°C, the mass ratio of iodine/potassium iodide/water was 0. Iodine dyeing was carried out by immersing it in an aqueous solution of .02/2/100 at 30°C (iodine dyeing process). The polyvinyl alcohol film that had undergone the iodine dyeing process was immersed at 56.5°C in an aqueous solution with a mass ratio of potassium iodide/boric acid/water of 12/5/100 to perform boric acid treatment (boric acid treatment process). ). After washing the polyvinyl alcohol film that had undergone the boric acid treatment process with pure water at 8°C, it was dried at 65°C to obtain a polarizer (thickness 27 μm after stretching) in which iodine was adsorbed and oriented in polyvinyl alcohol. . At this time, stretching was performed in the iodine dyeing step and the boric acid treatment step. The total stretching ratio in this stretching was 5.3 times. The obtained polarizer and a saponified triacetyl cellulose film (“KC4UYTAC” 40 μm, manufactured by Konica Minolta) were bonded together with a nip roll via a water-based adhesive. While maintaining the tension of the obtained bond at 430 N/m, it was dried at 60° C. for 2 minutes to obtain a polarizing film having a triacetyl cellulose film as a protective film on one side. The water-based adhesive contains 100 parts of water, 3 parts of carboxyl group-modified polyvinyl alcohol (Kuraray Poval KL318, manufactured by Kuraray), water-soluble polyamide epoxy resin (Sumiraze Resin 650, manufactured by Sumika Chemtex), solid content concentration. 30% aqueous solution).

[Measurement of optical properties of polarizing film A]
The optical properties of the obtained polarizing film A were measured. The measurement was carried out using a spectrophotometer ("V7100" manufactured by JASCO Corporation) using the polarizer surface of the polarizing film A obtained above as the incident surface. The absorption axis of the polarizing film coincides with the stretching direction of polyvinyl alcohol, and the resulting polarizing film has a visibility-corrected single transmittance of 42.1%, a visibility-corrected polarization degree of 99.996%, and a single hue a. -1.1, and the single hue b was 3.7.

[Preparation of composition for forming horizontal alignment film]
A horizontal alignment film was formed by mixing 5 parts of a photo-alignable material (weight average molecular weight: 30,000) with the following structure and 95 parts of cyclopentanone as a solvent, and stirring the resulting mixture at 80°C for 1 hour. A composition for use was obtained.

[Preparation of composition for forming horizontally aligned liquid crystal cured film A]
Liquid crystal compound A and liquid crystal compound B were mixed at a mass ratio of 90:10 to obtain a mixture. To 100 parts by mass of the obtained mixture, 1.0 part of a leveling agent ("F-556" manufactured by DIC Corporation) and 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl) as a polymerization initiator were added. ) 6 parts of butan-1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan Ltd.) was added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. By stirring at 80° C. for 1 hour, a composition for forming a horizontally aligned liquid crystal cured film A was obtained.

[Manufacture of horizontally aligned liquid crystal cured film A]
Corona treatment was performed on a COP film (“ZF-14-50” manufactured by Nippon Zeon Co., Ltd.). Thereafter, a horizontal alignment film forming composition was applied using a bar coater to form a coating film. The coating film was dried at 80° C. for 1 minute to form a dry film. Using a polarized UV irradiation device (“SPOT CURE SP-9” manufactured by Ushio Inc.), polarized UV exposure was performed under the conditions of an integrated light amount of 100 mJ/cm ² at a wavelength of 313 nm and an axis angle of 45° to form a horizontal alignment film. Obtained. The thickness of the obtained horizontal alignment film was measured with an ellipsometer and was found to be 100 nm.

Subsequently, the composition for forming a horizontally aligned liquid crystal cured film A was applied to the horizontally aligned film using a bar coater to form a coated film. The coating film was dried at 120° C. for 1 minute to form a dry film. By irradiating the dried film with ultraviolet rays using a high-pressure mercury lamp (Unicure VB-15201BY-A manufactured by Ushio Inc.) under conditions of a nitrogen atmosphere and a cumulative light intensity of 500 mJ/cm ² at a wavelength of 365 nm, A horizontally aligned liquid crystal cured film A was formed. A laminate consisting of a base material, a horizontally aligned film, and a horizontally aligned liquid crystal cured film A was obtained. The thickness of the horizontally aligned liquid crystal cured film A was measured with an ellipsometer and found to be 2.3 μm. Met.

[Re measurement of horizontally aligned liquid crystal cured film A]
After bonding the laminate to glass via an adhesive, the COP film serving as the base material was peeled off. As a result, a horizontally aligned liquid crystal cured film A for Re measurement was obtained. The in-plane retardation value ReA (λ) of the horizontally aligned liquid crystal cured film A was measured using a measuring device (“KOBRA-WPR” manufactured by Oji Scientific Instruments Co., Ltd.). The measurement results of the retardation value ReA (λ) at each wavelength (450 nm, 550 nm, and 650 nm) are: ReA (450) = 121 nm, ReA (550) = 142 nm, ReA (650) = 146 nm, and ReA (450) / ReA(550)=0.85.

[Measurement of R0 and R40 of a laminate consisting of a horizontally aligned liquid crystal cured film A and a vertically aligned liquid crystal cured film]
The horizontally aligned liquid crystal cured film A produced by the above method and the vertically aligned liquid crystal cured film (A-1) produced by the method of Example 1 were bonded together via an adhesive (pressure sensitive adhesive manufactured by Lintec, 15 μm). Then, a laminate including a horizontally aligned liquid crystal cured film A and a vertically aligned liquid crystal cured film (A-1) was produced. Furthermore, one COP film used as a base material was peeled from the same laminate and bonded to glass via an adhesive to obtain a laminate for retardation value measurement. After confirming that there is no retardation in the COP film and the horizontal alignment film, the retardation value R0 (λ) in the front direction of the laminate for retardation value measurement and the fast axis of the horizontal alignment liquid crystal cured film A are determined. The retardation value R40 (λ) (λ = 450 nm and 550 nm) when tilted at 40° from the center was measured using a measuring device (“KOBRA-WPR” manufactured by Oji Scientific Instruments Co., Ltd.). The measurement results are shown in Table 2. From the obtained values of R0(λ) and R40(λ) (λ=450nm and 550nm), |R0(550)-R40(550)|, |R0(450)-R40(450)|, and |{R0 (450)-R40(450)}-{R0(550)-R40(550)}| was calculated. The results are shown in Table 3.

[Evaluation of oblique reflection hue]
The laminate produced by the above method (the laminate containing the horizontally oriented liquid crystal cured film A and the vertically oriented liquid crystal cured film (A-1)) and the polarizing film A are connected to the absorption axis of the polarizing film A and the horizontally oriented liquid crystal cured film. They were laminated via an adhesive so that the angle formed with the slow axis of A was 45°, and the base material was peeled off to produce an elliptically polarizing plate with an optical compensation function. Thereafter, it was attached to aluminum foil via an adhesive, and the oblique reflection hue of the elliptically polarizing plate was visually observed from an elevation angle of 45° and an azimuth angle of 0 to 360°. The oblique reflection hue was evaluated based on the following evaluation criteria from the results of visual observation. The results are shown in Table 3.
(Evaluation criteria)
A (Good): Black color is visually confirmed.
B (Bad): Clear coloration is visually confirmed.

<Examples 17 and 18>
The retardation value measurement was carried out in the same manner as in Example 16, except that the values of RthC (450) and RthC (550) were changed as shown in Table 2 by changing the film thickness of the vertically aligned liquid crystal cured film. Oblique reflection hue confirmation was carried out. The results are shown in Tables 2 and 3.

<Example 19>
The retardation value was the same as in Example 16, except that the polarizing film A was changed to a polarizing film B containing a dichroic dye and a horizontally aligned liquid crystal cured film B oriented in the horizontal direction, which was prepared by the method shown below. Measurement and evaluation of oblique reflection hue were performed. The results are shown in Tables 2 and 3.

７５部

２５部
二色性色素１：
ポリアゾ色素；化合物（１－８） ２．５部

化合物（１－５） ２．５部

化合物（１－１６） ２．５部

重合開始剤；
２－ジメチルアミノ－２－ベンジル－１－（４－モルホリノフェニル）ブタン－１－オン（イルガキュア３６９；チバスペシャルティケミカルズ社製） ６部
レベリング剤；
ポリアクリレート化合物（ＢＹＫ－Ｃｈｅｍｉｅ社製「ＢＹＫ－３６１Ｎ」）
１．２部
溶剤；o-キシレン ２５０部 [Preparation of composition for forming polarizing film B]
A composition for forming polarizing film B containing a polymerizable liquid crystal compound (B) and a dichroic dye was obtained by mixing the following components and stirring at 80° C. for 1 hour. As the dichroic dye, an azo dye described in Examples of JP-A No. 2013-101328 was used. The polymerizable liquid crystal compounds represented by formulas (1-6) and (1-7) as the polymerizable liquid crystal compound (B) are described by Lub et al. , Recl. Trav. Chim. It was produced according to the method described in Pays-Bas, 115, 321-328 (1996).
Polymerizable liquid crystal compound (B):

75 copies

25 parts dichroic dye 1:
Polyazo dye; compound (1-8) 2.5 parts

Compound (1-5) 2.5 parts

Compound (1-16) 2.5 parts

Polymerization initiator;
2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemicals) 6 parts Leveling agent;
Polyacrylate compound (“BYK-361N” manufactured by BYK-Chemie)
1.2 parts Solvent; o-xylene 250 parts

[Manufacture of polarizing film B]
(Preparation of horizontal alignment film)
Corona treatment was performed on triacetyl cellulose film (TAC) (“KC4UY” manufactured by Konica Minolta). Next, using a bar coater, the composition for forming a horizontal alignment film was applied to the corona-treated TAC surface to form a coating film. The coated film was dried at 80° C. for 1 minute to form a dry film. Using a polarized UV irradiation device (“SPOT CURE SP-7” manufactured by Ushio Inc.), the dried film was exposed to polarized UV at an integrated light intensity of 100 mJ/cm ² and an axis angle of 90° to achieve horizontal alignment. A membrane was obtained. The thickness of the obtained horizontal alignment film was measured using an ellipsometer and was found to be 150 nm.

(Preparation of horizontally aligned liquid crystal cured film B)
Furthermore, using a bar coater, the composition for forming polarizing film B was applied to the horizontal alignment film to form a coating film. Thereafter, the coating film was dried for 1 minute in a drying oven set at 120°C. As a result, a dried coating film in which the polymerizable liquid crystal compound (B) and the dichroic dye were oriented was obtained. After naturally cooling this dry coating film to room temperature (25°C), using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Inc.), under a nitrogen atmosphere, the cumulative amount of light at wavelengths of 365 nm and 365 nm was measured. The polymerizable liquid crystal compound (B) was polymerized by irradiation with ultraviolet rays at 1000 mJ/cm ² to produce a polarizing film having a horizontally aligned liquid crystal cured film B containing a dichroic dye.

[Measurement of polarization degree and single transmittance of polarizing film B]
The degree of polarization and single transmittance of the obtained polarizing film B were measured as follows. The transmittance in the transmission axis direction (T ¹ ) and the transmittance in the absorption axis direction (T ² ) were measured using a spectrophotometer ("UV-3150" manufactured by Shimadzu Corporation) with a folder with a polarizer set. , was measured in a wavelength range of 380 to 680 nm in 2 nm steps using the double beam method. The single transmittance and degree of polarization at each wavelength were calculated using the following formulas (p) and (q). Furthermore, visibility correction was performed using the 2-degree field of view (C light source) of Japanese Industrial Standard JIS Z 8701, and the visibility correction single transmittance (Ty) and visibility correction polarization degree (Py) were calculated. 42%, and the degree of polarization was 97%, which were confirmed to be useful values as a polarizing film.
Single transmittance (%) = (T ¹ + T ² )/2...(p)
Degree of polarization (%) = {(T ¹ - T ² )/(T ¹ + T ² )}×100...(q)

<Comparative example 2>
Samples were prepared in the same manner as in Example 16, except that the vertical alignment film and vertical alignment liquid crystal cured film shown below were prepared, and the retardation value was measured and the oblique reflection hue was evaluated. The results are shown in Tables 2 and 3.

(Preparation of vertical alignment film forming composition (B))
0.5% polyimide ("Sunever SE-610" manufactured by Nissan Chemical Industries, Ltd.), 72.3% N-methyl-2-pyrrolidone, 18.1% 2-butoxyethanol, 9.1% ethyl A vertical alignment film forming composition (B) was prepared by mixing cyclohexane and 0.01% DPHA (manufactured by Shin Nakamura Chemical).

(Preparation of composition (B) for forming a vertically aligned liquid crystal cured film)
0.1 part of a leveling agent ("F-556" manufactured by DIC Corporation) and 3 parts of a polymerization initiator Irg369 were added to the liquid crystal compound LC242 represented by the following formula (LC242): Paliocolor LC242 (registered trademark of BASF Corporation). , cyclopentanone was added so that the solid content concentration was 13%, and these were mixed to obtain a composition (B) for forming a vertically aligned liquid crystal cured film.
Liquid crystal compound LC242: Paliocolor LC242 (registered trademark of BASF)

(Preparation of vertically aligned liquid crystal cured film)
Corona treatment was performed on a COP film (Nippon Zeon Co., Ltd. "ZF-14-23") as a base material. Using a bar coater, the composition for forming a vertical alignment film (B) was applied to a COP film subjected to corona treatment to form a coating film. The coating film was dried at 80° C. for 1 minute to obtain a vertically aligned film. The thickness of the obtained vertical alignment film was measured with an ellipsometer and was found to be 0.2 μm. Subsequently, the composition (B) for forming a vertical alignment liquid crystal cured film was applied onto the produced vertical alignment film to form a coating film. The coating film was dried at 80° C. for 1 minute to form a dry film. Thereafter, the dried film was irradiated with ultraviolet rays using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Inc.) in a nitrogen atmosphere and at a cumulative light intensity of 500 mJ/cm ² at a wavelength of 365 nm. A vertically aligned liquid crystal cured film was formed. The thickness of the obtained vertically aligned liquid crystal cured film was 0.5 μm.

In Table 1, the column "addition amount" of the silane compound and the "addition amount" of the ionic compound each indicate the addition amount (unit: weight %) with respect to the composition for forming a vertically aligned liquid crystal cured film, respectively. The numbers in the column Ratio of Liquid Crystal Compounds and the letters in parentheses indicate the ratio of the amounts of the added liquid crystal compounds. For example, 90/10 (A/B) indicates that the mass ratio (liquid crystal compound A/liquid crystal compound B) is 90/10.

The vertically aligned liquid crystal cured films (A-1) to (A-15) of Examples 1 to 15 were cured products of compositions (A-1) to (A-15), respectively. Compositions (A-1) to (A-15) contained the silane compound KBE-9103 or KBE-403 and any one of the ionic compounds (1) to (3). Silane compounds KBE-9103 and KBE-403 were nonionic silane compounds. The orientation evaluation of the vertically aligned liquid crystal cured films (A-1) to (A-15) of Examples 1 to 15 was either A or B. Further, the vertically aligned liquid crystal cured film (A-20) of Example 20 was a cured product of the composition (A-20). Composition (A-20) contained an ionic compound. The vertically aligned liquid crystal cured film (A-21) of Example 21 was a cured product of the composition (A-21). Composition (A-21) contained a nonionic silane compound. The alignment evaluation of the vertically aligned liquid crystal cured film of Example 20 (A-20) and the vertically aligned liquid crystal cured film of Example 21 (A-21) was C.

The oriented liquid crystal cured film (B-1) of Comparative Example 1 was a cured product of the composition (B-1). Composition (B-1) did not contain a nonionic silane compound or an ionic compound. The orientation evaluation of the vertically aligned liquid crystal cured film (B-1) of Comparative Example 1 was D.

From the above, the vertically aligned liquid crystal cured films (A-1) to (A-15), (A-20), and (A-21) of Examples 1 to 15 are the aligned liquid crystal cured films of Comparative Example 1 (B It is clear that the orientation is superior to that of -1).

The elliptically polarizing plates of Examples 16 to 19 included a vertically aligned liquid crystal cured film prepared using composition (A-1), a horizontal alignment film, a horizontally aligned liquid crystal cured film A, and a polarizing film. . The oblique reflection hues of the elliptically polarizing plates of Examples 16 to 19 were all A.

The elliptically polarizing plate of Comparative Example 2 included a vertically aligned liquid crystal cured film prepared using composition (B-2), a horizontally aligned film, a horizontally aligned liquid crystal cured film A, and a polarizing film. Composition (B-2) contained liquid crystal compound LC242. Ar of the liquid crystal compound was a divalent group having one ring structure, and was not a compound included in the liquid crystal compound represented by formula (I)-1. The oblique reflection hue of the elliptically polarizing plate of Comparative Example 2 was B.

From the above, it is clear that the elliptically polarizing plates of Examples 16 to 19 are superior to the elliptically polarizing plate of Comparative Example 2 in terms of oblique reflection hue.

DESCRIPTION OF SYMBOLS 1... Base material, 3... Horizontal alignment film, 5... Horizontal alignment liquid crystal cured film A, 7... Adhesive layer, 9... Vertical alignment liquid crystal cured film, 11... Polarizing film, 13... Protective layer, 15... Laminate, 20... Elliptically polarizing plate

Claims (14)

A laminate comprising a base material and a vertically aligned liquid crystal cured film, the vertically aligned liquid crystal cured film being adjacent to the base material,
The vertically aligned liquid crystal cured film is aligned in a direction perpendicular to the in-plane direction and contains a nonionic silane compound,
The nonionic silane compound has an alkoxysilyl group and at least one polar group selected from an epoxy group, an amino group, an isocyanurate group, a mercapto group, a carboxy group, and a hydroxy group,
The vertically aligned liquid crystal cured film further includes an ionic compound,
The content of the ionic compound is 0.01 to 5% by mass based on the solid content of the composition for forming a vertically aligned liquid crystal cured film,
the cationic component of the ionic compound is selected from imidazolium cations, pyridinium cations, ammonium cations, sulfonium cations, and phosphonium cations,
The following relational expression (1):
-150nm≦RthC(550)≦-30nm...(1)
[In relational expression (1), RthC (550) indicates the retardation value in the thickness direction at a wavelength of 550 nm of the vertically aligned liquid crystal cured film]
and the following relational expression (2):
RthC(450)/RthC(550)≦0.95...(2)
[In relational expression (2), RthC (450) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and RthC (550) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. ]
The filling,
A laminate, wherein the vertically aligned liquid crystal cured film has a thickness of 0.1 μm or more and 3 μm or less. The laminate according to claim 1, wherein the base material has a thickness of 5 to 300 μm. The laminate according to claim 1 or 2 , further comprising a film oriented in a direction horizontal to the in-plane direction of the vertically oriented cured liquid crystal film. The film oriented in the horizontal direction with respect to the in-plane direction of the vertically oriented liquid crystal cured film satisfies the following relational formula (3):
ReA(450)/ReA(550)≦1.00...(3)
[In relational expression (3), ReA (450) represents the in-plane retardation value at a wavelength of 450 nm of the film oriented in the horizontal direction with respect to the in-plane direction of the vertically aligned liquid crystal cured film, and ReA (550) represents the in-plane retardation value at a wavelength of 450 nm. Shows the in-plane retardation value at a wavelength of 550 nm of a film oriented in the horizontal direction with respect to the film surface of a vertically oriented liquid crystal cured film]
The laminate according to claim 3 , which satisfies the following. The following relational expression (4):
|R0(550)-R40(550)|≦10nm...(4)
[In relational expression (4), R0 (550) indicates the in-plane retardation value of the laminate at a wavelength of 550 nm, and R40 (550) indicates the value around the fast axis direction of the film oriented in the horizontal direction of the laminate. Shows the phase difference value at a wavelength of 550 nm when rotated by 40 degrees]
The laminate according to claim 3 or 4 , which satisfies the following. The following relational expression (5):
|R0(450)-R40(450)|≦10nm...(5)
[In relational expression (5), R0 (450) indicates the in-plane retardation value of the laminate at a wavelength of 450 nm, and R40 (450) indicates the value around the fast axis direction of the film oriented in the horizontal direction of the laminate. Shows the phase difference value at a wavelength of 450 nm when rotated by 40 degrees]
The laminate according to any one of claims 3 to 5 , which satisfies the following. The following relational expression (6):
|{R0(450)-R40(450)}-{R0(550)-R40(550)}
｜≦3nm...(6)
[In relational expression (6), R0 (450) represents the in-plane retardation value of the laminate at a wavelength of 450 nm, R0 (550) represents the in-plane retardation value of the laminate at a wavelength of 550 nm, and R40 ( 450) indicates the retardation value at a wavelength of 450 nm when the film oriented in the horizontal direction of the laminate is rotated by 40° around the fast axis direction, and R40 (550) indicates the retardation value at a wavelength of 450 nm when the film is oriented in the horizontal direction of the laminate. Shows the retardation value at a wavelength of 550 nm when the film is rotated by 40 degrees around the fast axis direction]
The laminate according to any one of claims 3 to 6 , which satisfies the following. The laminate according to any one of claims 3 to 7 , wherein the film oriented in the horizontal direction with respect to the film surface of the vertically oriented cured liquid crystal film is a horizontally oriented cured liquid crystal film A. An elliptically polarizing plate comprising the laminate according to any one of claims 3 to 8 and a polarizing film. The elliptically polarizing plate according to claim 9 , wherein the angle between the slow axis of the horizontally oriented film and the absorption axis of the polarizing film is 45±5°. 11. The polarizing film includes a horizontally oriented liquid crystal cured film B oriented horizontally with respect to the film plane of the polarizing film, and the horizontally oriented liquid crystal cured film B contains a dichroic dye. elliptically polarizing plate. The elliptically polarizing plate according to claim 11 , wherein the dichroic dye has an azo group. The elliptically polarizing plate according to claim 11 or 12 , wherein the horizontally aligned liquid crystal cured film B is a cured film in which the liquid crystal compound is cured in a smectic phase state aligned horizontally with respect to the in-plane direction of the film. An organic EL display device comprising the elliptically polarizing plate according to any one of claims 9 to 13 .