TW201936661A - Vertically aligned liquid crystal cured film - Google Patents

Abstract

A vertically aligned liquid crystal cured film which is aligned in a vertical direction with respect to an in-plane direction and which includes at least one compound selected from the group consisting of non-ionic silane compounds and ionic compounds.

Description

Vertical alignment liquid crystal hardened film

The invention relates to a vertically aligned liquid crystal cured film, a laminate, an elliptical polarizing plate, and an organic EL (Electroluminescence) 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 planar state (such as an organic EL display device), it is used to prevent light reflection on electrodes constituting the device. In this elliptically polarizing plate, a so-called λ / 4 plate is used as a phase difference plate.
As the retardation plate used for the elliptically polarizing plate, it is preferable that those exhibiting inverse wavelength dispersion have the same retardation performance in a wider wavelength range of visible light. As a retardation plate exhibiting reverse wavelength dispersion, there is known a retardation plate including a horizontal alignment liquid crystal hardened by polymerizing and curing a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion in a state of being aligned in the horizontal direction membrane.
In addition, a polarizing plate with an optical compensation function is also required, which has a function of compensating in such a manner as to exhibit the same optical performance as when viewed from the front direction even when viewed from the oblique direction. Examples of such a polarizing plate with an optical compensation function include a horizontally aligned liquid crystal cured film having reverse wavelength dispersion, and further a vertically aligned liquid crystal cured film obtained by polymerizing and curing a polymerizable liquid crystal compound in a vertically aligned state. . Furthermore, among the vertically-aligned liquid crystal cured films, Patent Document 1 also proposes a vertically-aligned liquid crystal cured film using a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility.
[Prior Technical Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-57646

[Problems to be solved by the invention]

However, since the molecular center of gravity of the liquid crystal compound exhibiting reverse wavelength dispersion is unstable, only the liquid crystal compound will generate a large number of alignment defects and is not easy to be vertically aligned. Therefore, when manufacturing a vertical alignment liquid crystal cured film, an alignment film for vertical alignment is required. However, in this case, a step of forming an alignment film for vertical alignment is necessary, so there is a problem of reduced productivity.

The present invention has been completed in view of the above-mentioned problems, and its object is to provide a composition capable of forming a vertical alignment liquid crystal cured film that suppresses the occurrence of alignment defects even without an alignment film.
[Technical means to solve the problem]

The inventor of the present invention conducted intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention includes the following aspects.
[1] A vertically-aligned liquid crystal cured film, which is aligned in a vertical direction with respect to the in-plane direction, and includes at least one selected from the group consisting of nonionic silane compounds and ionic compounds.
[2] The vertical alignment liquid crystal cured film as described in [1], wherein the nonionic silane compound is a silane coupling.
[3] The vertical alignment liquid crystal cured film according to [1] or [2], wherein the nonionic silane compound is a silane coupling agent having an alkoxysilane group and a polar group.
[4] The vertically-aligned liquid crystal cured film as described in any one of [1] to [3], in which all elements constituting the ionic compound are non-metallic elements.
[5] The vertical alignment liquid crystal cured film as described in any one of [1] to [4], wherein the molecular weight of the ionic compound is 100 or more and 10000 or less.
[6] The vertical alignment liquid crystal cured film as described in any one of [1] to [5], which satisfies the following relational expression (1):
-150 nm ≦ RthC (550) ≦ -30 nm (1)
[In relation (1), RthC (550) represents the phase difference value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm].
[7] The vertical alignment liquid crystal cured film as described in any one of [1] to [6], which satisfies the following relational expression (2):
RthC (450) / RthC (550) ≦ 1 (2)
[In relation (2), RthC (450) represents the phase difference of the thickness of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and RthC (550) represents the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm Phase difference value].
[8] A laminate including a base material and a vertical alignment liquid crystal cured film as described in any one of [1] to [7], and the vertical alignment liquid crystal cured film is adjacent to the base material.
[9] A laminate including the vertical alignment liquid crystal cured film as described in [1] to [7], and a film aligned horizontally with respect to the in-plane direction of the vertical alignment liquid crystal cured film.
[10] The laminate as described in [9], which satisfies the following relational expression (3):
ReA (450) / ReA (550) ≦ 1.00 (3)
[In relation (3), ReA (450) represents the in-plane retardation value of the film aligned horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and ReA (550) represents the relative The in-plane retardation value of the film aligned horizontally on the film surface of the vertically aligned liquid crystal cured film at a wavelength of 550 nm].
[11] The laminate according to any one of [9] or [10], which satisfies the following relational expression (4):
| R0 (550) －R40 (550) | ≦ 10 nm (4)
[In relation (4), R0 (550) represents the in-plane phase difference of the laminate at a wavelength of 550 nm, and R40 (550) represents the rotation of the laminate by 40 ° around the phase-advancing axis of the film aligned in the horizontal direction Phase difference at 550 nm].
[12] The laminate as described in any one of [9] to [11], which satisfies the following relational expression (5):
| R0 (450) －R40 (450) | ≦ 10 nm (5)
[In relation (5), R0 (450) represents the in-plane phase difference of the laminate at a wavelength of 450 nm, and R40 (450) represents when the laminate rotates 40 ° around the phase-advancing axis of the film oriented in the horizontal direction Phase difference at 450 nm].
[13] The laminate as described in any one of [9] to [12], which satisfies the following relational expression (6):
| {R0 (450) －R40 (450)} － {R0 (550) －R40 (550)} | ≦ 3 nm (6)
[In relation (6), R0 (450) represents the in-plane phase difference of the laminate at a wavelength of 450 nm, R0 (550) represents the in-plane phase difference of the laminate at a wavelength of 550 nm, R40 (450) Represents the phase difference value at a wavelength of 450 nm when the layered body rotates 40 ° around the phase-advancing axis of the film oriented in the horizontal direction, R40 (550) means that the layered body rotates 40 ° around the phase-advancing axis of the film oriented in the horizontal direction The phase difference at a wavelength of 550 nm].
[14] The laminate as described in any one of [9] to [13], wherein the film aligned 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.
[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 aligned 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 elliptical polarizing plate as described in [15] or [16], wherein the angle formed by the retardation axis of the film oriented horizontally and the absorption axis of the polarizing film is 45 ± 5 °.
[18] The elliptically polarizing plate as described in any one of [15] to [17], wherein the polarizing film includes a horizontally aligned liquid crystal cured film B aligned horizontally with respect to the film plane of the polarizing film, and the horizontally aligned liquid crystal The cured film B contains a dichroic pigment.
[19] The elliptically polarizing plate according to [18], wherein the dichroic dye has an azo group.
[20] The elliptically polarizing plate as described in [18] or [19], wherein the horizontal alignment liquid crystal cured film B-based liquid crystal compound is cured in a state of a smectic phase aligned horizontally with respect to the in-plane direction of the film. Into a hardened film.
[21] An organic EL display device comprising the elliptically polarizing plate as described in any one of [15] to [20].
[Effect of invention]

According to the present invention, it is possible to provide a vertical alignment liquid crystal cured film that suppresses the occurrence of alignment defects even without an alignment film.

Hereinafter, the embodiments of the present invention will be described in detail. In addition, in this specification, acrylic acid and methacrylic acid may be called "(meth) acrylic acid". In addition, sometimes "system" is added after the compound name to collectively refer to the compound and its derivatives. When "system" is added after the compound name to indicate the polymer name, it means that 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 is implemented after polymerization Chemically modified polymers.

<Vertical alignment liquid crystal cured film>
The vertical alignment liquid crystal cured film of the present invention is aligned in the vertical direction with respect to the in-plane direction, and includes at least one selected from the group consisting of nonionic silane compounds and ionic compounds. The vertically aligned liquid crystal cured film is aligned in the vertical direction with respect to the in-plane direction. That is, it includes a liquid crystal compound and / or a polymer of a liquid crystal compound in a state of being aligned in the vertical direction with respect to the in-plane direction of the vertically aligned liquid crystal cured film. The three-dimensional refractive index ellipsoid forming the vertically aligned liquid crystal hardened film may have biaxiality, but preferably has uniaxiality.

The vertical alignment liquid crystal cured film of the present invention suppresses the occurrence of alignment defects even if there is no alignment film. The reason is presumed as follows. The vertical alignment liquid crystal cured film of the present invention includes at least one selected from the group consisting of nonionic silane compounds and ionic compounds. In the production of a liquid crystal cured film, when a composition for forming a vertically aligned liquid crystal cured film is applied to a substrate to form a coated film, and the coated film is heated and dried to form a dry coating, the dry coating is The affinity of the ionic silane compound and the liquid crystal compound and / or the affinity of the ionic compound and the liquid crystal compound may be caused by the presence of the ionic compound on the surface of the substrate and / or on the surface side of the dry coating (away from the surface of the substrate Side) There is a distribution of nonionic silane compounds. Such a distribution will increase the vertical alignment restricting force, so there is a tendency for the liquid crystal compound to align in the vertical direction relative to the substrate surface in the dry coating. Therefore, the cured film can be formed while keeping the liquid crystal compound vertically aligned. Therefore, it is considered that the vertical alignment liquid crystal cured film of the present invention suppresses the occurrence of alignment defects even if there is no alignment film. As at least one selected from the group consisting of a nonionic silane compound and an ionic compound, three types of nonionic silane compounds, ionic compounds, and nonionic silane compounds and ionic compounds can be mentioned. Although only one of the nonionic silane compound and the ionic compound has the effect of increasing the vertical alignment restricting force, from the viewpoint of further increasing the vertical alignment restricting force, it is preferable to include both the nonionic silane compound and the ion Sexual compounds.

From the viewpoint of suppressing the deterioration of the oblique reflection hue of a display equipped with an elliptical polarizing plate containing a vertically aligned liquid crystal hardened film (for example, the problem of confirming coloration such as red and blue in the oblique hue of the display),
The vertically aligned liquid crystal cured film preferably satisfies the following relationship (1):
-150 nm ≦ RthC (550) ≦ -30 nm (1)
[In relation (1), RthC (550) represents the phase difference value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm].
From the viewpoint of further suppressing the deterioration of the oblique reflection hue of the above display, the phase difference 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 more preferably- Above 80 nm-below 40 nm.

The phase difference 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 determined by 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 main refractive index of the vertically aligned liquid crystal cured film in the film surface at a wavelength of 550 nm, and nyC (550) represents the direction orthogonal to nxC (550) in the same plane The refractive index of the wavelength of 550 nm, nzC (550) represents the refractive index of the wavelength of 550 nm in the thickness direction of the vertically aligned liquid crystal cured film, dC represents the film thickness of the vertically aligned liquid crystal cured film]
Therefore, in order to obtain the desired phase difference value RthC (550) in the thickness direction, the three-dimensional refractive index and film thickness dC may be adjusted. Furthermore, the three-dimensional refractive index depends on the molecular structure and alignment of the liquid crystal compound. In addition, in the case of nxC (550) = nyC (550), nxC (550) can be set as the refractive index in any direction in the film plane.

Also, from the viewpoint of suppressing the decrease in the ellipticity when viewed obliquely from the short-wavelength side of the elliptically polarizing plate containing a vertically aligned liquid crystal cured film,
The vertically aligned liquid crystal cured film preferably satisfies the following relationship (2):
RthC (450) / RthC (550) ≦ 1 (2)
[In relation (2), RthC (450) represents the phase difference of the thickness of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and RthC (550) represents the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm Phase difference value].
From the viewpoint of further suppressing the reduction of the ellipticity, the RthC (450) / RthC (550) of the vertically aligned liquid crystal cured film is more preferably 0.95 or less, and further preferably 0.90 or less. In addition, the phase difference values RthC (450) and RthC (550) in the thickness direction of the vertically aligned liquid crystal cured film can also be adjusted by the thickness dC of the vertically aligned liquid crystal cured film.

From the viewpoint of thinning, 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, further preferably 2.0 μm or less, and particularly preferably 1.5 μm or less. In addition, the lower limit of the film thickness of the vertical alignment liquid crystal cured film is preferably 0.1 μm or more, more preferably 0.3 μm or more, and still 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 film thickness meter.

[1. Nonionic Silane Compound]
In this specification, the nonionic silane compound is a nonionic compound containing Si element. The non-ionic silane compound can fully enhance the vertical alignment of the liquid crystal compound (I) -1 in the production of the vertical alignment liquid crystal cured film, and further improve the vertical alignment of the liquid crystal compound by combining with the ionic compound. In addition, the nonionic silane compound tends to reduce the surface tension of the composition for forming a vertically-aligned liquid crystal cured film, thereby improving the wettability of the composition to the substrate. As the nonionic silane compound, for example, silicone polymers such as polysilane, polysiloxane resins such as polysiloxane oil and polysiloxane resin, and polysiloxane oligomers, sesquisiloxane, and Organic inorganic silane compounds such as alkoxysilanes (more specifically, silane coupling agents, etc.).

The non-ionic silane compound may be a polysiloxane monomer type or a polysiloxane oligomer (polymer) type. If the polysiloxane oligomer is represented in the form of (monomer)-(monomer) copolymer, it may include: 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyl Copolymer of trimethoxysilane-tetraethoxysilane, 3-mercaptopropyltriethoxysilane-tetramethoxysilane, and 3-mercaptopropyltriethoxysilane-tetraethoxysilane Mercaptopropyl-containing copolymers; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxy Silane-tetramethoxysilane copolymers, and mercaptomethyl-containing copolymers such as mercaptomethyltriethoxysilane-tetraethoxysilane copolymers; 3-methacryloxypropyl trimethyl Oxysilane-tetramethoxysilane copolymer, 3-methacryloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane -Tetramethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-Tetraethoxysilane copolymer, 3-methacryloxypropyl Dimethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropyl Methacrylic acid, such as methyldiethoxysilane-tetramethoxysilane copolymer and 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer Copolymer of acetyl propyl; 3-propyl propyl propyl trimethoxy silane-tetramethoxy silane copolymer, 3- propyl propyl propyl trimethoxy silane-tetraethoxy silane copolymer , 3-Propylene oxypropyl triethoxy silane-tetramethoxy silane copolymer, 3- Propyl acetyl propyl triethoxy silane-tetraethoxy silane copolymer, 3- Propylene oxy silane Propyl propyl methyl dimethoxy silane-tetramethoxy silane copolymer, 3-propenyl propyl methyl dimethoxy silane-tetraethoxy silane copolymer, 3-propene acetyl propane Propylene-containing ethoxypropane-containing copolymers such as methyl methyl diethoxy silane-tetramethoxy silane copolymer and 3-propene acetyl propyl methyl diethoxy silane-tetraethoxy silane copolymer Ji Gong Thing; vinyl trimethoxysilane-tetramethoxysilane copolymer, vinyl trimethoxysilane-tetraethoxysilane copolymer, vinyl triethoxysilane-tetramethoxysilane copolymer, vinyl Triethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, Vinyl methyl diethoxy silane-tetramethoxy silane copolymer and vinyl methyl diethoxy silane-tetraethoxy silane copolymer and other vinyl-containing copolymers; 3-amino group Propyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxy Silane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-amino group Propylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-amine Propyl methyl diethoxy silane-- amine-containing copolymer of tetraethyl orthosilicate or the like of the copolymer and the like. These nonionic silane compounds may be used alone or in combination of two or more. In addition, a silane-containing compound exemplified by the leveling agent can also be used. Among these nonionic silane compounds, from the viewpoint of further improving adhesion, a silane coupling agent is preferred.

The silane coupling agent has a terminal group selected from the group consisting of vinyl group, epoxy group, styryl group, methacryl group, acryl group, amine group, isocyanurate group, urea group, mercapto group, isocyanate group, carboxyl group, Compounds containing at least one kind of functional group such as hydroxyl group and at least one alkoxysilyl group or silanol group containing Si element. By properly 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 modified, and the adhesion to the layer (such as a substrate) adjacent to the vertically aligned liquid crystal cured film can be imparted Special effects such as improvement. From the viewpoint of further improving adhesion, the silane coupling agent is preferably a silane coupling agent having an alkoxysilane group and another different reactive group (for example, the above-mentioned functional group). The silane coupling agent is further preferably a silane coupling agent having an alkoxysilane group and a polar group. If the silane coupling agent has at least one alkoxysilane group and at least one polar group in its molecule, the vertical alignment of the liquid crystal compound is further improved, and the vertical alignment promotion effect can be obviously obtained. Examples of polar groups include epoxy groups, amine groups, isocyanurate groups, mercapto groups, carboxyl groups, and hydroxyl groups. Furthermore, in order to control the reactivity of the silane coupling agent, the polar group may have a substituent or a protective group as appropriate.

Examples of the silane coupling agent include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri (2-methoxyethoxy) silane, and N- (2-aminoethyl)- 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethyl Oxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methyl Acryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- Glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylethoxydimethylsilane.

Examples of commercially available silane coupling agents include KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403 , KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE -9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007 silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.

The content of the nonionic silane compound is usually 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 4% by mass, and more preferably the solid content of the composition for forming a vertically aligned liquid crystal cured film. It is 0.1% by mass to 3% by mass. If the content of the nonionic silane compound is 0.01% by mass or more relative to the solid content of the composition, the vertical alignment of the liquid crystal compound is further improved, and if the content of the nonionic silane compound is relative to the solid content of the composition If the component contains 5 mass% or less, the coating property of the composition is not easily reduced.

[2. Ionic compounds]
The vertical alignment of the liquid crystal compound (I) -1 can be fully improved by the ionic compound in the production of the vertical alignment liquid crystal cured film. By combining with the nonionic silane compound, the vertical alignment of the liquid crystal compound (I) -1 can be achieved Alignment is further improved.

Examples of the ionic compound include onium salts (more specifically, quaternary ammonium salts having a positive charge on a nitrogen atom, tertiary ammonium salts, and quaternary phosphonium salts having a positive charge on a phosphorus atom, etc.). Among these onium salts, from the viewpoint of further improving the vertical alignment of the liquid crystal compound (I) -1, it is preferably a quaternary onium salt, and further preferably from the viewpoint of improving the availability and mass productivity It is a fourth-grade phosphonium salt or a fourth-grade ammonium salt. The onium salt may have two or more quaternary onium salt sites in the molecule, and may also be an oligomer or polymer.

From the viewpoint of further improving the vertical alignment of the liquid crystal compound (I) -1, the molecular weight of the ionic compound is preferably 100 or more. From the viewpoint of further improving the coating properties of the composition for forming a vertical alignment liquid crystal cured film, the molecular weight of the ionic compound is preferably 10,000 or less, more preferably 5000 or less, and still more preferably 3000 or less. From the viewpoint of further improving the vertical alignment of the liquid crystal compound (I) -1 and further improving the coatability of the composition, the molecular weight of the ionic compound is more preferably 100 or more and 10,000 or less.

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

On the other hand, ionic compounds generally have counter anions. Examples of the anion component that becomes the counter ion of the above-mentioned cationic component include inorganic anions and organic anions. Among these anion components, from the viewpoint of suppressing the occurrence of alignment defects of the liquid crystal compound, organic anions are preferred. In addition, the cation and the anion need not correspond one-to-one. Examples of the anionic component include the following.
Chloride anions [Cl ^-],
Bromide anion [Br ^-],
Iodide anion [I ^-],
Tetrachloroaluminate anion [AlCl ₄ ^-],
Heptachlor aluminum anions [Al ₂ Cl ₇ ^-],
Tetrafluoroborate anion [BF ₄ ^-],
Hexafluorophosphate anions [PF ₆ ^-],
Perchlorate anion [ClO ₄ ^-],
Nitrate anions [NO ₃ ^-],
Acetate anion [CH ₃ COO ^-],
Trifluoroacetic acid anion [CF ₃ COO ^-],
Fluorosulfonic acid anion [FSO ₃ ^-],
Methanesulfonate anion [CH ₃ SO ₃ ^-],
Trifluoromethanesulfonic acid anion [CF ₃ SO ₃ ^-],
P-toluenesulfonate anion _{[p-CH 3 C 6 H} 4 SO 3 -],
Bis (fluoromethyl sulfonylurea) imide anion ^{_{[(FSO 2) 2 N -}} ],
Bis (trifluoromethanesulfonyl XI) imide anion _{[(CF 3 SO 2) 2} N -],
Tris (trifluoromethanesulfonyl XI) methane anion _{[(CF 3 SO 2) 3} C -],
Hexafluoroarsenate anion [AsF ₆ ^-],
Hexafluoroantimonate anion [SbF ₆ ^-],
Niobium hexafluorophosphate anion [NbF ₆ ^-],
Tantalum hexafluorophosphate anion [TaF ₆ ^-],
Dimethyl phosphinate anion ^{_{[(CH 3) 2 POO -}} ],
(Poly) Hydrogen Fluoride anion ^{_{[F (HF) n -]}} ( for example, n represents an integer of 1 to 3),
Dicyanimide anion ^{_{[(CN) 2 N -]}} ,
Thiocyanate anion [SCN ^-],
Perfluorobutane sulfonate anion ^{_{[C 4 F 9 SO 3 -}} ],
Bis (pentafluoroethane sulfonylurea) imide anion _{[(C2F 5 SO 2) 2} N -],
Perfluoro butyrate anion ^{_{[C 3 F 7 COO -]}} , and
(Trifluoromethanesulfonyl acyl) (trifluoromethane-carbonyl) acyl imide anion _{[(CF 3 SO 2) (} CF 3 CO) N -].

As a specific example of the ionic compound, it can be appropriately selected from the combination of the above-mentioned cationic component and anionic component. As specific compounds in which the cationic component and the anionic component are combined, the following can be mentioned.

(Pyridinium salt)
N-hexylpyridinium hexafluorophosphate,
N-octylpyridinium hexafluorophosphate,
N-methyl-4-hexylpyridinium hexafluorophosphate,
N-butyl-4-methylpyridinium hexafluorophosphate,
N-octyl-4-methylpyridinium hexafluorophosphate,
Bis (fluorosulfonyl) imide 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 (trifluoromethanesulfonyl) 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,
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,
Bis (fluorosulfonyl) imide 1-ethyl-3-methylimidazolium,
Bis (trifluoromethanesulfonyl) imide 1-ethyl-3-methylimidazolium,
1-ethyl-3-methylimidazolium p-toluenesulfonate,
1-Butyl-3-methylimidazolium methanesulfonate, etc.

(Pyrrolidinium salt)
N-butyl-N-methylpyrrolidinium hexafluorophosphate,
Bis (fluorosulfonyl) imide N-butyl-N-methylpyrrolidinium,
Bis (trifluoromethanesulfonyl) imide N-butyl-N-methylpyrrolidinium,
P-toluenesulfonic acid N-butyl-N-methylpyrrolidinium and so on.

(Ammonium salt)
Tetrabutylammonium hexafluorophosphate,
Bis (fluorosulfonyl) imide tetrabutylammonium,
Bis (fluorosulfonyl) imide tetrahexylammonium,
Bis (fluorosulfonyl) imide trioctylmethylammonium,
Bis (fluorosulfonyl) imide (2-hydroxyethyl) trimethylammonium,
Bis (trifluoromethanesulfonyl) imide tetrabutylammonium,
Bis (trifluoromethanesulfonyl) imide tetrahexylammonium,
Bis (trifluoromethanesulfonyl) imide trioctylmethylammonium,
Bis (trifluoromethanesulfonyl) imide (2-hydroxyethyl) trimethylammonium,
Tetrabutylammonium p-toluenesulfonate,
Tetrahexylammonium p-toluenesulfonate,
Trioctylmethyl ammonium p-toluenesulfonate,
P-toluenesulfonic acid (2-hydroxyethyl) trimethylammonium,
Dimethylphosphinic acid (2-hydroxyethyl) trimethylammonium,
Bis (trifluoromethanesulfonyl) imide 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) aminemethyloxyethyl)}-N, N, N-trimethylammonium, and bis (tris (Fluorosulfonamide) imine N- [2- {3- (3-trimethoxysilylpropylamino) -1-oxopropoxy} ethyl] -N, N, N-trimethyl Ammonium.

(Phosphonium salt)
Bis (trifluoromethanesulfonyl) imide 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, and bis (trifluoromethanesulfonyl) imide 1, 1,1-tributyl-1- [3- (trimethoxysilyl) propyl] phosphonium.

These plasma compounds may be used alone or in combination of two or more. In addition, from the viewpoint of further improving the vertical alignment of the liquid crystal compound, the ionic compound preferably has Si element and / or F element in the molecular structure of the cation site.
The reason is that if the ionic compound has Si element and / or F element in the molecular structure of the cation site, the ionic compound can be segregated to the surface of the vertically aligned liquid crystal cured film. Among the ionic compounds, ionic compounds composed of non-metallic elements as a whole (preferably, the following ionic compounds (1) to (3), etc.) are preferred.

(Ionic compound (1))
[Chem 1]

(Ionic compound (2))
[Chem 2]

(Ionic compound (3))
[Chemical 3]

As a method of improving the vertical alignment of the liquid crystal compound, for example, a method of treating the surface of the substrate with a surfactant having an alkyl group with a long chain length to a certain extent can be cited. This method is described, for example, in Chapter 2 of the "Liquid Crystal Handbook", the alignment and physical properties of liquid crystals (issued by Maruzen Co., Ltd.). The method of improving the vertical alignment of the liquid crystal compound by the surfactant can be applied to ionic compounds. That is, as a method of improving the vertical alignment of the liquid crystal compound, for example, a method of treating the surface of the substrate with an ionic compound having an alkyl group with a long chain length to a certain extent can be cited. More specifically, from the viewpoint of improving the vertical alignment of the liquid crystal compound, the ionic compound preferably satisfies the following formula (10).
5 ＜ M ＜ 16 (10)
In formula (10), M is represented by the following formula (11).
M = (number of covalent bonds from the atom with positive charge to the end of the molecular chain from the atom with positive charge to the substituent with the most covalent bonds to the end of the molecular chain among the substituents directly bonded to the atom with positive charge) ÷ (Number of atoms with positive charge) (11)

Furthermore, when there are more than two positively charged atoms in the molecule of the ionic compound, the substituent with more than two positively charged atoms will start from the positively charged atom as the base point Calculated, the number of covalent bonds to the nearest positively charged atom is taken 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. In addition, when the ionic compound is an oligomer or polymer having two or more repeating units, the structural unit is regarded as one molecule, and the above M is calculated. When atoms with positive charges are incorporated into the ring structure, the number of covalent bonds through the ring structure to the atoms with positive charges, or to the end of the substituents bonded to the ring structure Those with a larger number of valence bonds are referred to as "the number of covalent bonds from the atom with a positive charge to the end of the molecular chain" described in the definition of M above.

The content of the ionic compound is usually 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, and still more preferably 0.1 to 3% by mass relative to the solid content of the composition for forming a vertically aligned liquid crystal cured film. . If 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 if the content of the ionic compound is 5 relative to the solid content of the composition Below mass%, the applicability of the composition is not likely to decrease.

[3. Liquid crystal compound]
Examples of the liquid crystal compound that can form the vertical alignment liquid crystal cured film of the present invention include the following formula (I) -1:
[Chem 4]

[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 1 and 4 positions of the 6-membered ring are combined with L ¹ and L ² bonding,
L ¹ and L ² are independently a single bond or a divalent linking group,
G ¹ and G ² independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, and the hydrogen atoms contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group may be independently replaced by halogen atoms, carbon Alkyl group having 1 to 4 carbon atoms, fluoroalkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, cyano group, or nitro group, the divalent aromatic group and the divalent alicyclic hydrocarbon group The carbon atoms contained can be independently replaced by oxygen atoms, sulfur atoms, or nitrogen atoms,
* Indicating key bonding]
Liquid crystal compound of the indicated structure (hereinafter, sometimes referred to as liquid crystal compound (I) -1).

Liquid crystal compound (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 The 1, 4 bits are bonded to L ¹ and L ² , so there is a tendency to form a T-shaped structure. Compounds having such a structure generally have a tendency to show reverse wavelength dispersion. Therefore, the liquid crystal compound (I) -1 exhibits reverse wavelength dispersion. On the other hand, since the liquid crystal compound (I) -1 has a T-shaped structure, it is generally not easy to perform vertical alignment when alone. In the production of the vertical alignment liquid crystal cured film, the vertical alignment of the liquid crystal compound (I) -1 can be sufficiently improved by including the non-ionic silane compound or the ionic compound in the composition for forming the vertical alignment liquid crystal cured film. Furthermore, the composition for forming a vertical alignment 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 unit of the ring structure possessed by Ar is a single ring. For example, in the following liquid crystal compounds A, (A) -2, and (A) -3, Ar has four, two, and three ring structures, respectively. Two or more ring structures can be condensed by two or more single rings adjacent to each other, or more than two single rings can be bonded to each other through a chemical bond, or more than two single rings can not be condensed and do not pass through a chemical bond adjacent. Hereinafter, the first aspect may be described as a condensation type, the second aspect may be described as a bonding type, and the third aspect may be described as a spiral ring type. In addition, a condensed ring (polycyclic ring) formed by condensing a single ring and a single ring through a chemical bond may be bonded to each other, or a polycyclic ring and a polycyclic ring may be bonded to each other through a chemical bond. Hereinafter, such a form is sometimes referred to as a bonding condensation type. The following liquid crystal compounds A, (A) -2, and (A) -3 are respectively a bonding condensation type, a condensation type, and a bonding type. The chemical bond that bonds two or more rings in the bonding type and the bonding condensation type may include, for example, a conjugated double bond (more specifically, -C = C- and -C = N-, etc.) and a carbonyl group The spreading bond or base of the conjugated system in general.

Examples of monocyclic rings include monocyclic hydrocarbon rings (more specifically, cycloalkane rings, benzene rings, etc.) and monocyclic heterocycles. Examples of monocyclic heterocycles include 5-membered heterocycles (more specifically, pyrrole ring, furan ring, thiophene ring, oxazole ring, imidazole ring, pyrazole ring, thiazole ring, triazole ring, Pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, etc.), and 6-membered heterocyclic ring (more specifically, pyridine ring, pyridine ring, pyrimidine ring, thi ring, piperidine ring, etc.). The polycyclic ring is a structure having a ring structure of 2 or more rings. The ring structure may be an aromatic ring or a hydrocarbon ring. Examples of polycyclic rings include those containing condensed rings and monocyclic heterocycles. The condensed ring is, for example, a ring formed by condensing two or more monocyclic rings of the same kind among these single rings, and a ring formed by condensing two or more monocyclic rings of different kinds. Examples of the condensed ring include polycyclic hydrocarbon rings (more specifically, naphthalene rings, anthracene rings, and phenanthrene rings), and polycyclic heterocycles (more specifically, quinoline rings and quinolines). Porphyrin ring, benzofuran ring, benzothiophene ring, stilbene ring, indole ring, carbazole ring, benzimidazole ring, benzothiazole ring, thienothiazole ring, benzoxazole ring, 1,3-benzene Dithiol ring, morpholine ring, etc.). Among these condensed rings, from the viewpoint of exhibiting inverse wavelength dispersion characteristics, a polycyclic structure is preferred, and a polycyclic heterocyclic structure is more preferred.

Monocyclic and polycyclic rings may have substituents. Examples of the substituents that the monocyclic ring and the polycyclic ring may have include, for example, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. Group, alkyl polyalkenyl group, cyano group, or amine group, the carbon atom in the substituent can be further replaced by an oxygen atom, a nitrogen atom, or a sulfur atom (in this case, the hydrogen atom bonded to the carbon atom It can be increased or decreased according to the valence of the replaced atom). Among these substituents, the spatial diffusion of the conjugated system can be expanded like an imino group, an alkyl polyalkenyl group, a cyano group, a hydroxyl group, and an amine group. These substituents may be further substituted.

Examples of the 6-membered ring which Ar has include a benzene ring and a cyclohexane ring. The 6-membered ring may contain hetero atoms as ring member atoms. Examples of the condensed ring containing a 6-membered ring include quinoline ring, quinoline ring, benzofuran ring, benzothiophene ring, stilbene ring, indole ring, carbazole ring, benzimidazole ring, benzothiazole Ring, thienothiazole ring, benzoxazole ring, 1,3-benzenedithiol ring, and morpholine ring.

From the viewpoint of further improving the reverse wavelength dispersion of the polarizing plate, Ar preferably represents a divalent group including a ring structure having one or more sulfur atoms as ring member atoms. From the viewpoint of further improving the reverse wavelength dispersion, Ar preferably represents a divalent group represented by the following formula. ＊ Indicating bonding key.
[Chemical 5]

In the above formula, X ₁ , X ₂ , and X ₃ are independently selected from any one of CR _1X , R _2X , NR _3X , sulfur atom, and oxygen atom. R _1X , R _2X , and R _3X each independently represent a hydrogen atom or a C 1-4 alkyl group.
U contains at least one ring structure, and examples of the ring structure include structures including the single ring and / or multiple rings described in paragraphs 0041 to 0043,
Y may be any substituent. From the viewpoint of improving the inverse wavelength dispersion, it is preferable to include at least one ring structure. Examples of the ring structure include the single ring described in paragraphs 0041 to 0043 and / Or multi-ring structure.
L ₁₀ is a divalent linking group, representing a single bond, -O-CO-O-, -N = N-, -C≡C-, -CR _a = CR _b- , -CH = NN = CH-, or- CR _c = N-.
L ₁₁ is a divalent linking group and represents 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 = NN = 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 independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the carbon atom in the alkyl group may be substituted with a nitrogen atom, an oxygen atom, or a sulfur atom (in this case, according to The atomic valence number appropriately increases or decreases the number of hydrogen atoms).
Z represents a nonmetallic atom of Group 14 to Group 16 to which a hydrogen atom or a substituent can be bonded. From the viewpoint of improving the inverse wavelength dispersion, Z preferably has a structure selected from the group consisting of: expansion of the spatial diffusion of the conjugated system (more specifically, double bond sites, triple bond sites, and those satisfying Huckel's law Aromatic rings, heterocycles, etc.), and at least one kind selected from the group consisting of 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, methylene, ethylidene, propylidene, butylidene, etc.), R ^c And R ^d independently represent a C 1-4 alkyl group (more specifically, a methyl group, an ethyl group, a propyl group, a butyl group, etc.) or a hydrogen atom.

L ¹ and L ² preferably independently represent 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-. More preferably, L ¹ and L ² independently represent a single bond, -OR ^a2-1- , -CH _2- , -CH ₂ CH _2- , ^{-COOR a4-1-} , or OCOR ^a6-1- . Here, R ^a2-1 , R ^a4-1 and R ^a6-1 each independently represent a single bond, -CH _2- , or -CH ₂ CH _2- . L ¹ and L ² preferably further independently 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 phenylenediyl and naphthylylenediyl. 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 a C 1-4 alkyl group. The divalent aromatic group may have a hetero atom (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 cyclopentadiyl, cyclohexanediyl, and cycloheptadiyl. The divalent alicyclic hydrocarbon group may be substituted with a substituent such as a halogen atom and a C 1-4 alkyl group.

In this specification, the aromatic group refers to a group having a planar ring structure, and the number of π electrons possessed by the ring structure is [4n + 2] (n represents a positive integer of 1 or more) according to Huckel's law. When heteroatoms such as -N = and S- are used as ring members to form a ring structure, non-covalent bond electron pairs including these heteroatoms also satisfy Huckel's law and are aromatic The situation of ethnicity.

G ¹ and G ^{2 are} preferably independently 1,4-phenylenediyl, which can be substituted by at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms. 1,4-cyclohexanediyl substituted by at least one substituent selected from the group consisting of halogen atoms and alkyl groups having 1 to 4 carbon atoms, more preferably 1,4-phenylene disubstituted with methyl Group, unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4-transcyclohexanediyl, preferably unsubstituted 1,4-phenylenediyl, or unsubstituted Substituted 1,4-trans cyclohexanediyl. Further, it is preferred that at least one of the plurality of G ¹ and G ² is a divalent alicyclic hydrocarbon group, and it is more preferred that at least 1 of G ¹ and G ² bonded to L ¹ or L ² is A divalent alicyclic hydrocarbon group.

The liquid crystal compound (I) -1 preferably has a maximum absorption in the region of wavelength 260-400 nm. In the case where the liquid crystal compound (I) -1 has an aromatic group having a hetero atom or a structure in which the conjugated system is expanded, the absorption in the near-ultraviolet region shifts toward the long wavelength side compared to the benzene ring, so in many cases It has a maximum absorption in the wavelength region of 260 nm or more. If it has a maximum absorption in the wavelength region of 260 nm or more, it is preferable from the viewpoint of improving the inverse wavelength dispersion. In addition, when there is a maximum absorption in a wavelength region greater than the wavelength of 400 nm, coloring may occur, so the liquid crystal compound (I) -1 preferably has a maximum absorption in the region below the wavelength of 400 nm. Furthermore, from the viewpoint of further improving the wavelength dispersion, it is more preferable that the region with a wavelength of 280 nm or more and 400 nm or less has maximum absorption, and it is more preferable that the region with a wavelength of 300 nm or more and 400 nm or less have maximum absorption.

The liquid crystal compound (I) -1 preferably has the following formula (I) -2:
[化 6]

The liquid crystal compound of the structure shown (hereinafter, it may be described as liquid crystal compound (I) -2).

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 at the 1 and 4 positions of the 6-membered ring, L ¹ and L ² bonding,
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, and the hydrogen atoms contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group may be independently replaced by Halogen atom, alkyl group having 1 to 4 carbon atoms, fluoroalkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, cyano group, or nitro group, the divalent aromatic group and the divalent lipid The carbon atoms contained in the cyclic hydrocarbon group may be independently replaced by oxygen atoms, sulfur atoms, or nitrogen atoms,
* Indicates bonding key.

Of formula (I) Ar in the ^{-2, L 1, L 2,} G 1, and G ^2, respectively of formula (I) Ar -1 in the same ^{L 1, L 2, G 1} , G ² and meanings.

B ¹ preferably represents 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-. More preferably, L ¹ and L ² independently represent a single bond, -OR ^a2-1- , -CH _2- , -CH ₂ CH _2- , ^{-COOR a4-1-} , or -OCOR ^a6-1- . Here, R ^a2-1 , R ^a4-1 , and R ^a6-1 each independently represent a single bond, -CH _2- , or -CH ₂ CH _2- . L ¹ and L ² preferably further independently 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 phenylenediyl and naphthalenediyl. 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 a C 1-4 alkyl group. Examples of the divalent alicyclic hydrocarbon group represented by G ³ include cyclopentadiyl, cyclohexanediyl, and cycloheptadiyl. 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} preferably independently 1,4-phenylenediyl which may be substituted by at least one substituent selected from the group consisting of halogen atoms and alkyl groups having 1 to 4 carbon atoms, and may be selected from halogen 1,4-cyclohexanediyl substituted by at least one substituent in the group consisting of an atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1,4-phenylenediyl substituted with methyl, unsubstituted Substituted 1,4-phenylenediyl, or unsubstituted 1,4-transcyclohexanediyl, preferably unsubstituted 1,4-phenylenediyl, or unsubstituted 1 , 4-transcyclohexanediyl.

The liquid crystal compound (I) -1 more preferably has the following formula (I) -3:
[化 7]

The liquid crystal compound of the structure shown (hereinafter, it may be described as liquid crystal compound (I) -3).

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 at the 1 and 4 positions of the 6-membered ring L ¹ and L ² bonding,
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, and the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted It 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 divalent aromatic group or the divalent The carbon atoms contained in the alicyclic hydrocarbon group may be replaced with oxygen atoms, sulfur atoms, or nitrogen atoms,
* Indicates bonding key.

Ar in the formula ^{(I) -3, L 1,} L 2, G 1, and G ^2, respectively of formula (I) Ar -1 in the same ^{L 1, L 2, G 1} , G ² and meanings. 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 preferably represents 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-. More preferably, L ¹ and L ² independently represent a single bond, -OR ^a2-1- , -CH _2- , -CH ₂ CH _2- , ^{-COOR a4-1-} , or -OCOR ^a6-1- . Here, R ^a2-1 , R ^a4-1 , and R ^a6-1 each independently represent a single bond, -CH _2- , or -CH ₂ CH _2- . L ¹ and L ² preferably further independently 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 phenylenediyl and naphthalenediyl. 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 a C 1-4 alkyl group. Examples of the divalent alicyclic hydrocarbon group represented by G ³ include cyclopentadiyl, cyclohexanediyl, and cycloheptadiyl. 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 which may be substituted with at least one substituent selected from the group consisting of halogen atoms and alkyl groups having 1 to 4 carbon atoms, and may be selected from halogen atoms and carbon atoms. 1,4-cyclohexanediyl substituted by at least one substituent in the group consisting of alkyl groups of 1 to 4 is more preferably 1,4-phenylenediyl substituted by methyl, unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4-transcyclohexanediyl, particularly preferably unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4- Transcyclohexanediyl.

The liquid crystal compound (I) -1 may have one or more polymerizable groups. In the present specification, a polymerizable group refers to a group that can participate in polymerization by an active species such as an active radical generated from a photopolymerization initiator or an acid. Examples of the polymerizable group include epoxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, propenyl oxy group, methacryl oxy group, epoxy group Ethyl, and oxetanyl. Among these polymerizable groups, acryloxy and methacryloxy are preferred. In this specification, the liquid crystal compound (I) -1 having a polymerizable group can form a polymer by polymerization reaction.

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

(Liquid Crystal Compound A)
[Chem 8]

(Liquid crystal compound (A) -2)
[化 9]

(Liquid crystal compound (A) -3)
[化 10]

(Liquid crystal compound (A) -4)
[化 11]

(Liquid crystal compound (A) -5)
[Chem 12]

The content of the liquid crystal compound (I) -1 (when plural liquid crystal compounds are included) is preferably 50 to 99.5 relative to 100 parts by mass of the solid content of the composition for forming a vertically aligned liquid crystal cured film The part by mass is more preferably 60 to 99 parts by mass, and still more preferably 70 to 99 parts by mass. In this specification, the mass of the solid content of the composition refers to the total mass of the components after removing the solvent from the composition.

[Manufacturing method of vertical alignment liquid crystal cured film]
The vertical alignment liquid crystal cured film is a cured product of the vertical alignment liquid crystal cured film forming composition. The manufacturing method of the vertical alignment liquid crystal cured film includes: a coating film forming step, which applies a composition for forming a vertical alignment liquid crystal cured film to a substrate, and forms a coating film on the substrate; a dry coating film forming step, which enables The coating film is dried to form a dry coating; and a hardened film forming step, which irradiates the dry coating with active energy rays to form a vertically aligned liquid crystal hardened film. The laminated body manufactured by this manufacturing method consists of a base material and a vertically-aligned liquid crystal cured film. The case where the liquid crystal compound has one or more polymerizable groups and the composition further includes a photopolymerization initiator will be described as an example.

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

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

(Step of forming a cured film)
In the step of forming a cured film, for example, a dry film is irradiated with active energy rays (more specifically, ultraviolet rays, etc.) using a light irradiation device to form a vertically aligned liquid crystal cured film. The liquid crystal compound maintains a liquid crystal state aligned perpendicular to the plane of the substrate in the dry coating. By irradiating the dried film with active energy rays, the liquid crystal compound maintains the vertically aligned liquid crystal state and undergoes photopolymerization. Thereby, a vertically aligned liquid crystal cured film can be directly formed on the substrate.

(Other steps: Vertical alignment film formation step)
As described above, the vertical alignment liquid crystal cured film can be formed directly on the substrate without forming an alignment film. On the other hand, the manufacturing method of the vertical alignment liquid crystal cured film can further improve the alignment of the vertical alignment liquid crystal cured film, and further includes the step of forming a vertical alignment film for forming the vertical alignment film. In this case, the vertical alignment liquid crystal cured film is indirectly formed on the substrate via the vertical alignment film.

The vertical alignment film forming step is a step performed before the coating film forming step to form a vertical alignment film. Here, an example of a method of 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, for example, a printing apparatus is applied with a composition for forming a vertical alignment film on a substrate to form a second coating film. The composition for forming a vertical alignment film includes, for example, the following alignment polymer and the above-mentioned solvent. In the second dry coating film forming step, for example, the second coating film is heated using a heating device to dry the second coating film to form a second dry coating film. In the case where a step of curing by UV irradiation is further required, the second dry coating is irradiated with UV using a UV irradiation device and hardened to form a vertical alignment film. When the manufacturing method of the vertical alignment liquid crystal cured film includes a vertical alignment film forming step, a vertical alignment liquid crystal cured film is formed on the vertical alignment film.

(Composition for forming vertical alignment liquid crystal cured film)
The composition for forming a vertical alignment liquid crystal cured film includes, for example, either or both of a nonionic silane compound or an ionic compound, and additives added as needed. 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. One type of these additives may be used alone, or two or more types may be used in combination. The composition can be obtained by agitating any or both of the nonionic silane compound or ionic compound, and other components added as needed at a specific temperature, etc., and dispersing or dissolving these components substantially uniformly .

(Solvent)
The composition for forming a vertical alignment liquid crystal cured film is usually applied to a substrate or the like in a state of being dissolved in a solvent, and therefore preferably contains a solvent. Examples of the solvent include water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxy Alcohol solvents such as ethanol and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate Solvents; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatics such as pentane, hexane, and heptane Hydrocarbon solvents; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorinated solvents such as chloroform and chlorobenzene; dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2- Amidyl solvents such as 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-based 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 mass, and more preferably 70 to 95 parts by mass with respect to 100 parts by mass of the composition for forming a vertically aligned liquid crystal cured film. Therefore, the content of the solid content in 100 parts by mass of the composition is preferably 2 to 50 parts by mass. If the solid content of the composition is 50 parts by mass or less, the viscosity of the composition becomes low, so that the thickness of the vertically aligned liquid crystal cured film becomes substantially uniform, and it is not easy to cause unevenness of the vertically aligned liquid crystal cured film. The above-mentioned solid content component can be appropriately determined in consideration of the thickness of the vertical alignment liquid crystal cured film to be produced.

(Photopolymerization initiator)
The composition for forming a vertical alignment liquid crystal cured film may include a photopolymerization initiator for the purpose of allowing the polymerization reaction to proceed. In this specification, the photopolymerization initiator provides an active species that absorbs active energy rays to start the polymerization reaction. Regarding the photopolymerization initiator, when a curable composition hardened by radical polymerization, such as (meth) acrylate or (meth) acrylate carbamate, is used as the curable material, light can be used As a radical polymerization initiator, when a curable composition hardened by cationic polymerization, such as an epoxy compound or an oxetane compound, is used as the curable composition, a photo-cationic polymerization initiator can be used.

Examples of the photopolymerization initiator include photoradical polymerization initiators and photocationic polymerization initiators. Examples of the photo radical polymerization initiator include benzoin compounds, benzophenone compounds, benzophenone compounds, α-hydroxyketone compounds, α-aminoketone compounds, and tri-compounds. Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic iodonium salts, and aromatic cerium salts, and iron-aromatic hydrocarbon 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 379 Photopolymerization initiators manufactured by BASF Japan Co., Ltd .; photopolymerization initiators manufactured by Seiko Chemical Co., Ltd. such as SEIKUOL BZ, SEIKUOL Z, and SEIKUOL BEE; Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), And photopolymerization initiators 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 Arkls NCI-831, Adeka Arkls Photopolymerization initiators manufactured by ADEKA Corporation such as NCI-930; photopolymerization initiators manufactured by Nihon Siber Hegner such as TAZ-A and TAZ-PP; Sanwa Chemical companies such as TAZ-104 Photopolymerization initiators manufactured; Photopolymerization initiators manufactured by Nippon Kayaku Co., Ltd. such as Kayarad (registered trademark) series; Dow Chemical Co., Ltd. such as Cyracure UVI series The photopolymerization initiator manufactured by the company; the photopolymerization initiator manufactured by San-Apro Co., Ltd. such as CPI series; the photopolymerization initiator manufactured by Midori Kagaku Co., Ltd. such as TAZ, BBI, and DTS; A photopolymerization initiator manufactured by Rhodia Co., Ltd. such as RHODORSIL (registered trademark). One type of these photopolymerization initiators may be used alone, or two or more types may be used in combination. The photopolymerization initiator can be appropriately selected and used according to the materials used.

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

Examples of the α-acetophenone-based polymerization initiator include 2-methyl-2-olinyl-1- (4-methylthiophenyl) propane-1-one and 2-dimethylamino -1- (4-Polinylphenyl) -2-benzylbutane-1-one (2-dimethylamino-2-benzyl-1- (4-olinylphenyl) butane-1 -Ketone), and 2-dimethylamino-1- (4-olinylphenyl) -2- (4-methylphenylmethyl) butane-1-one. The α-acetophenone-based polymerization initiator is preferably 2-methyl-2-olinyl-1- (4-methylthiophenyl) propane-1-one, and 2-dimethylamino- 1- (4-Polinylphenyl) -2-benzylbutane-1-one. Examples of commercially available products of α-acetophenone compounds include α-acetophenone-based polymerization initiators manufactured by BASF Japan Co., Ltd. such as Irgacure 369, 379EG, and 907, and Seiko Chemicals such as SEIKUOL BEE. The α-acetophenone-based polymerization initiator manufactured by the company.

The oxime-based photopolymerization initiator can generate free radicals by irradiating light. By this radical, the composition for forming a vertical alignment liquid crystal cured film in the deep part of the coating film is polymerized well. Further, from the viewpoint of more efficiently performing the polymerization reaction in the deep part of the coating film, it is preferable to use an oxime-based photopolymerization initiator that can efficiently use ultraviolet rays with a wavelength of 350 nm or more. As the oxime-based photopolymerization initiator that can efficiently use ultraviolet rays with a wavelength of 350 nm or more, for example, a tri compound and an oxime ester type carbazole compound are preferably listed, and from the viewpoint of sensitivity, for example, an oxime ester is more preferably listed Type carbazole compound. Examples of the oxime ester type carbazole compound include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyl oxime)], and 1- [9-B Yl-6- (2-methylbenzyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyl oxime). Examples of commercially available products of oxime ester-type carbazole compounds include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 and the like, oxime ester-type carbazole compounds manufactured by BASF Japan Co., Ltd., and Adeka Optomer N -1919, oxime ester type carbazole compound manufactured by ADEKA Corporation, such as Adeka Arkls NCI-831.

When the solid content contained in the composition for forming a vertically-aligned liquid crystal cured film (after removing the content of the solvent from the composition) is set to 100 parts by mass, the content of the photopolymerization initiator is usually preferably from 0.1 to 20 The part by mass is more preferably 0.5 to 10 parts by mass, and still more preferably 1 to 7 parts by mass. If the photopolymerization initiator is 0.1 to 20 parts by mass relative to 100 parts by mass of the composition, the polymerization reaction can easily proceed sufficiently.

(Leveling agent)
The leveling agent can adjust the coating property of the composition for forming a vertical alignment liquid crystal hardened film, that is, to adjust the fluidity of the composition for coating to make the surface of the layer obtained by coating the composition flatter as It is added to the composition for the purpose. Examples of the leveling agent include polysiloxane-based leveling agents such as silane coupling agents, polyacrylate-based leveling agents, and fluoroalkyl-based leveling agents. Among these leveling agents, from the viewpoint of further improving the vertical alignment of the liquid crystal compound, polysiloxane-based leveling agents and fluoroalkyl-based leveling agents are preferred.

Examples of commercially available leveling agents include DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, and FZ2123 leveling agents manufactured by Toray Dow Corning Co., Ltd .; KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM- 502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBE-585, KBM-802, KBM-802, KBM-803, KBE-846, and KBE-9007 leveling agents manufactured by Shin-Etsu Chemical Industry Co., Ltd .; TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446 , TSF4452, and leveling agent manufactured by Momentive Performance Materials Japan LLC such as TSF4460; Fluorinert (registered trademark) FC-72, Fluorinert FC-40, Fluorinert FC-43, and Sumitomo 3M such as Fluorinert FC-3283 (Share) Leveling agent manufactured; MEGAFAC (registered trademark) R-08, MEGAFAC R-30, MEGAFAC R-90, MEGAFAC F-410, MEGAFAC F-411, MEGAFAC F-443, MEGAFAC F-4 45. Levelers made by DIC (shares) such as MEGAFAC F-470, MEGAFAC F-477, MEGAFAC F-479, MEGAFAC F-482, MEGAFAC F-483, MEGAFAC F-556; Eftop (trade name) EF301 , Eftop EF303, Eftop EF351, and Eftop EF352 and other leveling agents manufactured by Mitsubishi Materials Electronic Chemicals (shares); Surflon (registered trademark) S-381, Surflon S-382, Surflon S-383, Surflon S-393, Leveling agent manufactured by AGC SEIMI CHEMICAL (share) such as Surflon SC-101, Surflon SC-105, KH-40, and SA-100; Daikin Precision Chemicals (trade name) such as trade name E1830, trade name E5844 Leveling agent manufactured by the research institute; leveling agent (trade names are BM) manufactured by Chemie, such as BM-1000, BM-1100, BYK-352, BYK-353, and BYK-361N. These leveling agents can be used alone or in combination of two or more.

The content of the leveling agent in the solid content of the composition for forming a vertical alignment liquid crystal cured film is usually preferably 0.001 to 3% by mass, more preferably 0.01 to 3% by mass, and still more preferably 0.1 to 3% by mass. If the content of the leveling agent in the solid content of the composition is 0.001 to 3% by mass, the applicability of the composition is further improved.

<Laminate>
The laminate includes the above-mentioned vertical alignment liquid crystal cured film. The laminate may further include 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 The following film is aligned in the horizontal direction with respect to the in-plane direction of the vertical alignment liquid crystal cured film (hereinafter, sometimes referred to as a horizontal alignment film). Examples of the structure of the laminate include a laminate including the above-mentioned vertical alignment liquid crystal cured film, a horizontal alignment film and a horizontal alignment film, a laminate including the above-mentioned vertical alignment liquid crystal cured film and a substrate, and the above-mentioned vertical alignment liquid crystal cured film 、 Horizontal alignment film, laminated body of horizontal alignment film and base material. However, in the present invention, even if there is no alignment film for vertical alignment, a vertical alignment liquid crystal cured film can be formed, and therefore the laminate may not have 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 may be adjacent to the base material. In addition, the vertical alignment liquid crystal cured film adjacent to the substrate produced by the above method may transfer only the vertical alignment liquid crystal cured film through the adhesive layer, remove the substrate, and manufacture the laminate.

[Substrate]
Examples of the base material include a glass base material and a film base material. From the viewpoint of processability, a film base material is preferable, and in terms of enabling continuous production, a long roll-shaped film is more preferable. Examples of the resin constituting the film substrate include polyolefins such as polyethylene, polypropylene, and olefin-reducing polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; Acrylates; Polyacrylates; Cellulose esters such as triacetyl cellulose, diethyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polystyrene; polyether碸; polyether ketone; plastics such as polyphenylene sulfide and polyphenylene ether. The bonding surface of the substrate and the adhesive layer can be subjected to release treatment such as polysiloxane treatment. Examples of commercially available cellulose ester substrates include cellulose ester substrates manufactured by Fuji Film Co., Ltd. such as FUJITAC film; Konica Minolta Opto shares such as "KC8UX2M", "KC8UY", and "KC4UY" Cellulose ester substrate manufactured by Co., Ltd. Such a resin can be formed into a base material by a known method such as a solvent casting method or a melt extrusion method.

Examples of commercially available cyclic olefin resins include cyclic olefin resins manufactured by Ticona Corporation (Germany) such as "Topas (registered trademark)" and JSR Co., Ltd. such as "ARTON (registered trademark)". Cyclic olefin resin manufactured; Zeon Corporation (ZEONOR (registered trademark)) and ZEONEX (registered trademark) and other cyclic olefin resins manufactured by Zeon Corporation; `` Apel '' (registered trademark) and the like Cyclic olefin resin manufactured by Mitsui Chemicals Co., Ltd. A commercially available cyclic olefin resin base material can also be used. Examples of commercially available cyclic olefin resin base materials include cyclic olefin resin base materials manufactured by Sekisui Chemical Industry Co., Ltd., such as "S-SINA (registered trademark)" and "SCA40 (registered trademark)"; Cyclic olefin resin base material manufactured by Optes Corporation, such as "Zeonor Film (registered trademark)"; cyclic olefin resin base material manufactured by JSR Corporation, such as "ARTON Film (registered trademark)".

The base material preferably has a thickness that allows easy lamination and peeling of the layers. The thickness of such a substrate is usually 5 to 300 μm, preferably 10 to 150 μm.

[Vertical Alignment Film]
The alignment film is a film having an alignment restricting force that aligns the liquid crystal compound of the liquid crystal cured film in a specific direction. Regarding the formation method of the alignment film, various alignments such as vertical alignment, horizontal alignment, mixed alignment, and inclined alignment can be controlled by the type of alignment film material, rubbing conditions, or light irradiation conditions. The process of expressing the alignment-limiting force in this way is called the alignment process. Among them, the vertical alignment film is an alignment film having an alignment restricting force that aligns the liquid crystal compound in the vertical direction. By using a vertical alignment film, a vertical alignment liquid crystal cured film can be formed.

The vertical alignment film preferably has solvent resistance that does not dissolve by application of the composition for forming a vertical alignment liquid crystal cured film, etc., and has heat resistance to heat treatment for removing the solvent or aligning the liquid crystal compound.

The vertical alignment film is preferably a material that reduces the surface tension of the surface of the substrate or the like. Examples of such materials include aligning polymers, such as polyimide, polyamide, polyamic acid as a hydrolyzate thereof, and fluorine-based polymers of perfluoroalkyl groups, silane compounds, and The polysiloxane compound obtained by the condensation reaction. The vertical alignment film can be applied to a substrate or the like by applying a composition (hereinafter also referred to as a composition for forming a vertical alignment film) containing such a material and a solvent, for example, a solvent exemplified in the vertical alignment liquid crystal cured film. After the solvent is removed, the coating film is heated and the like.

When a silane compound is used for the vertical alignment film, the vertical alignment film preferably has constituent elements including Si element and C element from the viewpoint of easily reducing the surface tension and easily improving the adhesion to the layer adjacent to the vertical alignment film The film of the compound can use a silane compound well. As the silane compound, the nonionic silane compound or the ionic compound containing silane as exemplified in the above-mentioned ionic compound can be used. By using these silane compounds, the vertical alignment restriction force can be improved. These silane compounds can be used alone or in combination of two or more, or can be mixed with other materials. In the case where the silane compound is a nonionic silane compound, from the viewpoint of easily improving the vertical alignment restricting force, a silane compound having an alkyl group at the molecular terminal is preferred, and more preferably an alkyl group having 3 to 30 carbon atoms Silane compounds.

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

[Alignment film for horizontal alignment]
The horizontal alignment film has an alignment restricting force that aligns the liquid crystal compound in the horizontal direction. When the composition for forming a horizontal alignment liquid crystal cured film is formed on the horizontal alignment film, the horizontal alignment film can form the horizontal alignment state of the horizontal alignment liquid crystal cured film. The alignment restricting force can be arbitrarily adjusted by, for example, the type, surface state, and friction conditions of the alignment film, and when it is formed of a photo-alignment polymer, it can be arbitrarily adjusted by polarized light irradiation conditions and the like. The process of expressing the alignment-limiting force in this way is called the alignment process.

The horizontal alignment film preferably has solvent resistance that does not dissolve due to application of the liquid crystal composition or the like, and has heat resistance to heat treatment for removing the solvent or aligning the liquid crystal compound.

Examples of the horizontal alignment film include a rubbing alignment film, a light alignment film, and a groove alignment film having a concave-convex pattern or a plurality of grooves on the surface. For example, when it is applied to a long roll-shaped film, in terms of being able to easily control the alignment direction, a light alignment film is preferred.

The friction alignment film can generally be formed by applying a composition containing an alignment polymer and a solvent (hereinafter, sometimes referred to as a composition for forming a friction alignment film) to a substrate, removing the solvent, and forming a coating film. The coating film is rubbed to give alignment restricting force.

Examples of the aligning polymer include polyamidoamines having an amide bond or gelatins, polyimides having an amide imide bond, and polyamic acid, polyvinyl alcohol, and alkyl modification as hydrolyzates thereof Polyvinyl alcohol, polyacrylamide, polyoxazole, polyethylenimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylates. These alignment polymers may be used alone or in combination of two or more.

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

As a commercially available product of the composition for forming a friction alignment film, for example, a composition for forming a friction alignment film manufactured by Nissan Chemical Industry Co., Ltd. such as Sunever (registered trademark), and JSR such as Optimer (registered trademark) (Strand) A composition for forming a friction alignment film.

As a method of the rubbing treatment, for example, a method of bringing the above-mentioned coating film into contact with a rubbing roller wound with a rubbing cloth and rotating is mentioned. During the rubbing treatment, if masking is performed, a plurality of regions (patterns) with different alignment directions can also be formed on the alignment film.

The photo-alignment film can usually be applied to a substrate by applying a composition (hereinafter, sometimes referred to as a photo-alignment film-forming composition) containing a polymer or monomer having a photoreactive group and a solvent, and after removing the solvent, irradiating It is obtained by polarized light (preferably polarized UV). The light alignment film can arbitrarily control the direction of the alignment limiting force by selecting the polarization direction of the irradiated polarized light.

The photoreactive group refers to a group that generates alignment ability by light irradiation. Specifically, examples include photoreactions such as the alignment induction reaction, isomerization reaction, photodimerization reaction, photocrosslinking reaction, or photolysis reaction of molecules generated by light irradiation, which are the origins of the alignment ability. base. As the photoreactive group, a group having an unsaturated bond, especially a double bond is preferred, and a group selected from a carbon-carbon double bond (C = C bond) and a carbon-nitrogen double bond (C = N bond) is particularly preferred. , A nitrogen-nitrogen double bond (N = N bond), and a carbon-oxygen double bond (C = O bond) group of at least one double bond group.

Examples of the photoreactive group having a C = C bond include a vinyl group, a polyalkenyl group, a stilbene group, a stilbene group, a stilbazolium group, a chalcone group, and a cinnamyl group. Examples of the photoreactive group having a C = N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. Examples of the photoreactive group having an N = N bond include azophenyl group, azonaphthyl group, aromatic heterocyclic azo group, disazo group, mesityl group, and those having an oxyazobenzene structure base. Examples of the photoreactive group having a C = O bond include a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group. Such groups may have substituents such as alkyl groups, alkoxy groups, aryl groups, allyloxy groups, cyano groups, alkoxycarbonyl groups, hydroxyl groups, sulfonic acid groups, and halogenated alkyl groups.

The group participating in the photodimerization reaction or photocrosslinking reaction is preferable in terms of excellent alignment. Among them, a photoreactive group participating in a photodimerization reaction is preferred, and it is preferable in terms of relatively small amount of polarized light irradiation required for alignment, and easy to obtain a photoalignment film having excellent thermal stability or stability over time. Cinnamon acyl group and chalcone group. As the polymer having a photoreactive group, it is particularly preferable that the terminal part of the side chain of the polymer has a cinnamic acid structure or a cinnamic acid ester structure.

The content of the polymer or monomer having a photoreactive group can be adjusted according to the type of polymer or monomer or the thickness of the target optical alignment film, and it is preferably set to 100 parts by mass of the composition for forming the optical alignment film. It is 0.2 mass parts or more, More preferably, it is 0.3-10 mass parts.

When polarized light is irradiated, for example, the polarized light may be directly irradiated after removing the solvent from the composition for forming an optical alignment film coated on the substrate. Moreover, it is preferable that the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably a wavelength region in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet) in the wavelength range of 250 to 400 nm is particularly preferred. Examples of light sources that irradiate 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 preferred because of their greater luminous intensity at 313 nm. By irradiating light from the light source through an appropriate polarizing element, polarized UV can be irradiated. Examples of the polarizing element include polarizing filters, polarizing filters such as Gran-Thomson and Gran-Taylor, and wire grids. Among these polarizing elements, a wire grid is preferred from the viewpoint of large area and heat resistance.

In addition, when rubbing or polarized light irradiation, if shielding is performed, a plurality of regions (patterns) with different liquid crystal alignment directions can also be formed.

A groove alignment film is a film having a concave-convex pattern or a plurality of grooves (grooves) on the surface of the film. In the case of applying the composition to a film having a plurality of linear grooves arranged at equal intervals, the liquid crystal compound is aligned in the direction along the groove.

As a method of obtaining a groove alignment film, a method of forming a concave-convex pattern by developing and rinsing the surface of the photosensitive polyimide film after exposing it through an exposure mask having a slit with a pattern shape; A method of forming a UV-hardening resin layer before hardening on a plate-shaped master having grooves on the surface, transferring the formed resin layer to a substrate, and hardening; and UV-curing resin before hardening formed on the substrate The film presses a roll-shaped master having a plurality of grooves to form irregularities, and then a method of hardening is performed.

From the standpoints of achieving thin film formation and showing alignment limitation, the thickness of the horizontal alignment film is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.3 μm or less. In addition, the thickness of the horizontal alignment film is preferably 1 nm or more, more preferably 5 nm or more, and further preferably 10 nm or more, and particularly preferably 30 nm or more. The film thickness of the horizontal alignment film can be measured using an ellipsometer or a contact film thickness meter.

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

(Horizontal alignment liquid crystal cured film A)
In this specification, the horizontally aligned liquid crystal cured film A is a polymerized liquid crystal compound that is cured in a state of being aligned in the 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 a liquid crystal compound (I) -1 having at least one polymerizable group. Furthermore, in this specification, the horizontally aligned liquid crystal cured film included in the laminate of the present invention is called horizontally aligned liquid crystal cured film A, and the horizontally aligned liquid crystal cured film included in the polarizing film of the following polarizing plate is called horizontal The liquid crystal cured film B is aligned to distinguish each.

(Manufacturing method of horizontal alignment liquid crystal cured film A)
A cured product of a horizontally aligned liquid crystal cured film A-based composition (hereinafter sometimes referred to as a composition for forming a horizontally aligned liquid crystal cured film A). The manufacturing method of the horizontal alignment liquid crystal cured film A is different from the manufacturing method of the vertical alignment liquid crystal cured film, except that it is formed on the horizontal alignment film. As an example of a method for manufacturing the horizontal alignment liquid crystal cured film A, it includes: a coating step, which applies the composition on the horizontal alignment film prepared in advance to form a coating film; and a dry coating film forming step, which makes the coating film Drying to form a dry coating; and a hardened film forming step, which irradiates the dry coating with active energy rays to form a horizontally aligned liquid crystal hardened film.

(Stretch film)
Examples of the stretched film include stretched films containing polycarbonate resin. As a commercially available stretch film, for example, a stretch film manufactured by Teijin Co., Ltd. such as "PURE-ACE (registered trademark) WR" can be cited. The stretched film can usually be obtained by stretching the base film. As a method of stretching the base film, for example, a winding body obtained by winding the base film into a roll is prepared, the base film is continuously wound out from the winding body, and the rolled base film is transported to heating furnace. The set temperature of the heating furnace is preferably in the range from the glass transition temperature of the base film to the glass transition temperature + 50 ° C. In the heating furnace, the substrate film is extended in the transport direction or in a direction orthogonal to the transport direction. During stretching, the conveying direction or tension is adjusted, and uniaxial stretching, biaxial stretching, or diagonal stretching thermal stretching is performed at an angle to any angle. The direction of the slow phase axis of the stretched film differs according to the stretching method, and the slow phase axis or the optical axis is determined according to the stretching method. The stretched film and the laminate of the present invention can be adhered via an adhesive layer.

In the laminated body of the present invention, from the viewpoint of suppressing the decrease in the ellipticity of the elliptically polarizing plate provided with the laminated body on the short wavelength side, the horizontal alignment film constituting the laminated body preferably satisfies the following relationship (3):
ReA (450) / ReA (550) ≦ 1 (3)
[In relation (3), ReA (450) represents the in-plane retardation value of the film aligned horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and ReA (550) represents the relative The in-plane retardation value of the film aligned in the horizontal direction of the vertically aligned liquid crystal cured film toward the horizontal direction at a wavelength of 550 nm].
From the viewpoint of further suppressing the decrease in ellipticity, ReA (450) / ReA (550) is more preferably 0.95 or less, and still more preferably 0.90 or less.
Also, from the viewpoint of improving the ellipticity of the elliptically polarizing plate provided with a laminate, it is preferable to satisfy the following (3) -2:
120 nm ≦ ReA (550) ≦ 170 nm (3) -2.
From the viewpoint of improving the ellipticity of an elliptically polarizing plate provided with a laminate, it is preferably 130 nm ≦ ReA (550) ≦ 160 nm.

Among the laminates described in the present invention, a laminate including a vertically aligned liquid crystal cured film and a film aligned horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film reduces the frontal phase difference value and self-oblique From the viewpoint of the difference in phase difference value, that is, from the viewpoint of suppressing the deterioration of the oblique reflection hue of the display including the elliptically polarizing plate of the laminate, it is preferable to satisfy the following relational expression (4):
| R0 (550) －R40 (550) | ≦ 10 nm (4)
[In relation (4), R0 (550) represents the in-plane retardation value of the laminate at a wavelength of 550 nm, and R40 (550) represents the alignment in the horizontal direction around the above-mentioned in-plane direction relative to the vertically aligned liquid crystal cured film The phase difference value at a wavelength of 550 nm when the film's phase axis is rotated by 40 °].
From the viewpoint of further suppressing the deterioration of the oblique reflection hue, it is more preferably 8 nm or less, and further preferably 4 nm or less.

Among the laminates described in the present invention, a laminate including a vertically aligned liquid crystal cured film and a film aligned horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film suppresses a display equipped with an elliptically polarizing plate including the laminate From the viewpoint of the deterioration of the oblique reflection hue, it is preferable to satisfy the following relational expression (5):
| R0 (450) －R40 (450) | ≦ 10 nm (5)
[In relation (5), R0 (450) represents the in-plane retardation value of the laminate at a wavelength of 450 nm, and R40 (450) represents the alignment in the horizontal direction around the above-mentioned in-plane direction with respect to the vertically aligned liquid crystal cured film The phase difference at a wavelength of 450 nm when the film's phase-advancing axis is rotated by 40 °].
From the viewpoint of further suppressing the deterioration of the oblique reflection hue, it is more preferably 8 nm or less, and further preferably 4 nm or less.

Among the laminates described in the present invention, a laminate including a vertically-aligned liquid crystal cured film and a film aligned horizontally with respect to the in-plane direction of the vertically-aligned liquid crystal cured film suppresses a display equipped with an elliptically polarizing plate including the laminate From the viewpoint of the deterioration of the oblique reflection hue, it is preferable to satisfy the following relational expression (6):
| {R0 (450) －R40 (450)} － {R0 (550) －R40 (550)} | ≦ 3 nm (6)
[In relation (6), R0 (450) represents the in-plane phase difference of the laminate at a wavelength of 450 nm, R0 (550) represents the in-plane phase difference of the laminate at a wavelength of 550 nm, R40 (450) Represents the phase difference value at a wavelength of 450 nm when the phase advancement axis of the film aligned horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film is rotated by 40 °, and R40 (550) represents the liquid crystal with respect to the vertical alignment The phase difference value at a wavelength of 550 nm when the in-plane direction of the cured film is rotated by 40 ° in the direction of the phase advancement axis of the film aligned horizontally].
From the viewpoint of further suppressing the deterioration of the oblique reflection hue, it is more preferably 2 nm or less, and further preferably 1 nm or less.

[Manufacturing method of laminate]
The manufacturing method of the laminate of the present invention includes a step of forming a vertically aligned liquid crystal cured film. The step of forming a vertically aligned liquid crystal cured film is the above-mentioned method of manufacturing a vertically aligned liquid crystal cured film. According to the method for manufacturing a vertically-aligned liquid crystal cured film described above, it is possible to manufacture a laminate composed of a substrate and a vertically-aligned liquid crystal cured film, and a laminate composed of a substrate, an alignment film, and a vertically-aligned liquid crystal cured film.
When the laminate has a film that is aligned horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film, the manufacturing method of the laminate further includes a step of laminating the film or a step of forming a horizontally aligned liquid crystal cured film A. The step of attaching the stretched film is to stick the stretched film to, for example, a vertically aligned liquid crystal cured film using an adhesive. The manufacturing method of the laminated body provided with the horizontally aligned liquid crystal cured film A can be manufactured by, for example, bonding a vertically aligned liquid crystal cured film and a horizontally aligned liquid crystal cured film via an adhesive layer, or a horizontally aligned film and a horizontally aligned liquid crystal cured film A can be formed On the vertical alignment liquid crystal hardened film. In addition, a vertically aligned liquid crystal cured film may be formed on the stretched film or the horizontally aligned liquid crystal cured film A.

[Adhesive]
Examples of the adhesive include pressure-sensitive adhesives, dry-curing adhesives, and chemical reaction adhesives. Examples of the chemical reaction type adhesive include active energy ray hardening type adhesives.

The pressure-sensitive adhesive usually contains a polymer, and may also contain a solvent. Examples of the polymer include acrylic polymers, polysiloxane polymers, polyesters, polyurethanes, and polyethers. Among these pressure-sensitive adhesives, pressure-sensitive adhesives containing acrylic polymers have excellent optical transparency, moderate wettability or cohesive force, excellent adhesion, and higher weather resistance or heat resistance. And, under the condition of heating or humidification, it is not easy to cause bulging or peeling, so it is preferred.

As the acrylic polymer, for example, a (meth) acrylic acid ester with (meth) acrylic acid or (meth) acrylic acid or (meth) acrylic acid or (meth) acrylic acid or an alkyl group having a carbon number of 1 to 20 such as a methyl group, an ethyl group or a butyl group in the ester portion is preferably Copolymers of (meth) acrylic monomers with functional groups such as hydroxyethyl methacrylate.

Since the pressure-sensitive adhesive containing such a copolymer has excellent adhesiveness, even if it is removed after being attached to the transfer body, it can be removed relatively easily without leaving a paste residue on the transfer body. Better. The glass transition temperature of the acrylic polymer is preferably 25 ° C or lower, and more preferably 0 ° C or lower. The mass average molecular weight of such acrylic polymer is preferably 100,000 or more.

As the solvent, for example, the solvents listed as the above-mentioned solvents can be cited. The pressure-sensitive adhesive may also contain a light diffusing agent. The light diffusing agent is an additive that imparts light diffusibility to the pressure-sensitive adhesive, as long as it is a fine particle having a refractive index different from that of the polymer contained in the pressure-sensitive adhesive. Examples of the light diffusing agent include fine particles containing inorganic compounds and fine particles containing organic compounds (polymers). Including acrylic polymers, most of the polymers included in the pressure-sensitive adhesive as an active ingredient have a refractive index of about 1.4 to 1.6. Therefore, it is preferable to appropriately select a light diffusing agent having a refractive index of 1.2 to 1.8. The difference in refractive index between the polymer and the light diffusing agent contained in the pressure-sensitive adhesive as an effective component is usually 0.01 or more, and from the viewpoint of the brightness and displayability of the display device, it is preferably 0.01 to 0.2. The fine particles used as the light diffusing agent are preferably spherical fine particles, especially close to monodisperse fine particles, and more preferably fine particles having an average particle diameter of 2 to 6 μm. The refractive index is measured by the general minimum angle method or Abbe refractometer.

Examples of fine particles containing inorganic compounds include aluminum oxide (refractive index 1.76) and silicon oxide (refractive index 1.45). Examples of fine particles containing organic compounds (polymers) include melamine particles (refractive index 1.57), polymethyl methacrylate particles (refractive index 1.49), and methyl methacrylate / styrene copolymer resin particles (refractive index) 1.50 ～ 1.59), polycarbonate particles (refractive index 1.55), polyethylene particles (refractive index 1.53), polystyrene particles (refractive index 1.6), polyvinyl chloride particles (refractive index 1.46), and silicone particles (Refractive index 1.46). The content of the light diffusing agent is usually 3 to 30 parts by mass relative to 100 parts by mass of the polymer.

The thickness of the pressure-sensitive adhesive is determined according to its adhesion, etc., so it is not particularly limited, but it is usually 1 μm to 40 μm. From the aspects of workability and durability, the thickness is preferably 3 μm to 25 μm, and more preferably 5 μm to 20 μm. By setting the thickness of the adhesive layer formed by the pressure-sensitive adhesive to 5 μm to 20 μm, it is possible to maintain the brightness when viewing the display device from the front or from the oblique direction, and it is not easy to cause blooming of the displayed image or blurry.

The dry-curing adhesive may also contain a solvent. Examples of dry-curing adhesives include compositions containing a polymer of a monomer having a protonic functional group such as a hydroxyl group, a carboxyl group, or an amine group and an ethylenically unsaturated group, or a carbamate The polymer is a main component, and further contains a crosslinking agent or hardening compound such as polyaldehyde, epoxy compound, epoxy resin, melamine compound, zirconia compound, and zinc compound. Examples of the polymer having a monomer having a protonic functional group such as a hydroxyl group, a carboxyl group, or an amine group and an ethylenically unsaturated group include ethylene-maleic acid copolymer, itaconic acid copolymer, acrylic copolymer, and propylene Acetylamine copolymer, saponified polyvinyl acetate, and polyvinyl alcohol resin.

Examples of the polyvinyl alcohol-based resin include polyvinyl alcohol, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, ethoxylated polyvinyl alcohol, and hydroxymethyl modified polyhydric alcohol. Vinyl alcohol, and amine modified polyvinyl alcohol. The content of the polyvinyl alcohol-based resin in the water-based adhesive is generally 1 to 10 parts by mass, preferably 1 to 5 parts by mass relative to 100 parts by mass of water.

As the urethane resin, for example, a polyester ionomer type urethane resin can be mentioned. The polyester ionic polymer urethane resin referred to here is a urethane resin having a polyester skeleton, and a resin in which a small amount of ionic component (hydrophilic component) is introduced. The ionic polymer urethane resin does not use an emulsifier and is emulsified in water to become an emulsion, so it can be made into an aqueous adhesive. In the case of using a polyester-based ionic polymer urethane resin, it is effective to prepare a water-soluble epoxy compound as a crosslinking agent.

Examples of the epoxy resin include polyamide obtained by reacting epichlorohydrin with a polyalkylene polyamine such as diethylenetriamine or triethylenetetraamine, and a dicarboxylic acid such as adipic acid. Polyamide epoxy resin obtained by reacting polyamine. Examples of commercially available products of this polyamide epoxy resin include "Sumirez Resin (registered trademark) 650" and "Sumirez Resin 675" manufactured by Sumika Chemtex Co., Ltd., and "WS-" manufactured by Japan PMC Co., Ltd. 525 ". In the case of blending epoxy resin, its content is usually 1 to 100 parts by mass, preferably 1 to 50 parts by mass relative to 100 parts by mass of the polyvinyl alcohol-based resin.

From the viewpoint of suppressing the appearance of poor appearance, the thickness of the adhesive layer formed of the dry-curing adhesive is usually 0.001 to 5 μm, preferably 0.01 to 2 μm, and more preferably 0.01 to 0.5 μm.

The active energy ray-curable adhesive may also contain a solvent. Active energy ray hardening adhesive refers to an adhesive that is hardened by the irradiation of active energy rays. Examples of the active energy ray-curable adhesive include cationic polymerizable adhesives containing epoxy compounds and cationic polymerization initiators, and radical polymerizable adhesives containing acrylic curing components and radical polymerization initiators. , An adhesive containing a cationic polymerizable hardening component such as an epoxy compound and a radical polymerizable hardening component such as an acrylic compound and further containing a cationic polymerization initiator and a radical polymerization initiator, and not containing These polymerization initiators are adhesives hardened by irradiation with electron beams.

Among these active energy ray-curable adhesives, it is preferably a radically polymerizable active energy ray-curable adhesive containing an acrylic curing component and a photo radical polymerization initiator, and an epoxy compound and a photo cation Cationic polymerizable active energy ray hardening type adhesive for polymerization initiator. 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 photo-radical polymerization initiator and photo-cationic polymerization initiator include the above-mentioned photo-radical polymerization initiators and photo-cationic polymerization initiator. The content of the radical polymerization initiator and the cationic polymerization initiator is usually 0.5 to 20 parts by mass, and preferably 1 to 15 parts by mass relative to 100 parts by mass of the active energy ray hardening type adhesive.

The active energy ray-curable adhesive may further contain an ion scavenger, antioxidant, chain transfer agent, adhesion-imparting agent, thermoplastic resin, filler, flow regulator, plasticizer, and defoaming agent.

<Elliptical Polarizer>
The elliptically polarizing plate includes the above-mentioned laminate and polarizing film. The elliptically polarizing plate may further include an arbitrary layer (more specifically, a protective layer, an adhesive, etc.) as needed. The laminate and the polarizing film are adhered by an adhesive, for example.

FIG. 1 is a schematic cross-sectional view showing an example of the layer configuration of an elliptically polarizing plate. The elliptical 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 A 5, an adhesive 7, and a vertical alignment liquid crystal cured film 9. The angle formed by the retardation axis of the horizontally aligned liquid crystal cured film A 5 and the absorption axis of the polarizing film 11 is 45 ± 5 °.

(Polarizing film)
The polarizing film is a film having a polarizing function. As the polarizing film, for example, a film containing a dichroic dye and aligned in the horizontal direction with respect to the film surface of the polarizing film (more specifically, an extended film adsorbed with a dichroic dye (hereinafter, sometimes referred to as a polarizing film A), and a horizontally aligned liquid crystal cured film B (hereinafter sometimes referred to as polarizing film B) containing a dichroic dye, etc.). From the viewpoint of thinning the elliptically polarizing plate, it is preferable that the horizontal alignment liquid crystal cured film B containing a dichroic dye is used. The dichroic pigment means a pigment that exhibits absorption anisotropy, and has a property that the absorbance of the molecule of the dichroic pigment in the long axis direction is different from the absorbance in the short axis direction.

(Horizontal alignment 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 a polarizing film B) containing a dichroic dye and a polymerizable liquid crystal compound (B). The horizontal alignment liquid crystal cured film B contains a dichroic dye, and is a liquid crystal cured film obtained by curing the polymerizable liquid crystal compound (B) in a state of being aligned horizontally with respect to the in-plane direction.

The horizontally aligned liquid crystal cured film B is preferably a cured film obtained by curing the polymerizable liquid crystal compound (B) 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 showing a nematic liquid crystal phase or a thermotropic liquid crystal compound showing a smectic liquid crystal phase. When a polarizing function is exhibited as a cured film by a polymerization reaction, the liquid crystal state displayed by the polymerizable liquid crystal compound is preferably a smectic phase, and a higher-order smectic phase is more preferable from the viewpoint of high performance. Among them, it is more preferable to form 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 a higher order smectic liquid crystal compound of smectic L phase, and further preferably a higher order smectic liquid crystal compound forming smectic B phase, smectic F phase or smectic I phase. If the liquid crystal phase formed by the polymerizable liquid crystal compound (B) is the high-order smectic phase, a polarizing film with higher polarization performance can be manufactured. In addition, in the X-ray diffraction measurement, a polarizing film having a higher polarizing performance as described above can obtain a Bragg wave peak derived from a six-phase or crystalline equivalent higher-order structure. The Bragg wave peak is derived from the peak of the periodic structure of molecular alignment, and a film with a periodic interval of 3 to 6 Å can be obtained. From the viewpoint of obtaining higher polarization characteristics, the horizontally aligned liquid crystal cured film B is preferably a polymer containing a polymerizable liquid crystal compound (B) polymerized in a smectic phase. Furthermore, the following polymerizability possessed by the polymerizable liquid crystal compound (B) may be in an unpolymerized state or a polymerized state in the horizontal alignment liquid crystal cured film B. That is, the horizontally aligned liquid crystal cured film B can be used in the polymerizable liquid crystal compound (B) (monomer), the polymerizable liquid crystal compound (B) oligomer, the polymerizable liquid crystal compound (B) polymer, and combinations of these Contains in any state. The polymerizability of the polymerizable liquid crystal compound (B) is preferably in an unpolymerized state based on 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). When this polymerizable liquid crystal can be used alone, it can also be used in combination of 2 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. Here, the divalent aromatic group or the divalent alicyclic hydrocarbon group The contained hydrogen atom may be substituted with a halogen atom, a C 1-4 alkyl group, a C 1-4 fluoroalkyl group, a C 1-4 alkoxy group, a cyano group, or a nitro group, constituting the 2 The carbon atom of the valent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. Among them, at least one of X ¹ , X ² , and X ³ represents 1,4-phenylene which may have a substituent, or cyclohexane-1,4-diyl which may have a substituent.
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 independently represent a C 1-20 alkanediyl group which may have a substituent, and -CH ₂ -constituting the alkanediyl group may be substituted with -O-, -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 represents 1,4-phenylene which may have a substituent, or cyclohexane-1 which may have a substituent 4-diyl. In particular, X ¹ and X ³ preferably represent a cyclohexane-1,4-diyl group which may have a substituent, and the cyclohexane-1,4-diyl group is further preferably transcyclohexane-1, 4-diyl. Examples of the optionally substituted substituents of 1,4-phenylene which may have a substituent or cyclohexane-1,4-diyl which may have a substituent include methyl, ethyl, and butyl. The C 1-4 alkyl groups, cyano groups, and halogen atoms such as chlorine and fluorine atoms. 1,4-phenylene which may have a substituent, or cyclohexane-1,4-diyl which may have a substituent is preferably 1,4-phenylene and cyclohexane-1,4-diyl . In addition, 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 is a different structure. In the case where at least one of X ¹ , X ² and X ³ has a different structure, there is a tendency to easily express smectic liquid crystallinity.

Y ¹ and Y ² each independently preferably represent a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - CH 2 CH 2 O -, - COO -, - OCO -, - N = N -, - CR ^a = CR ^b- , -C≡C- or CR ^a = N-, R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y ¹ and Y ^{2 more} preferably independently represent -CH ₂ CH _2- , -COO-, -OCO-, or a single bond. In addition, when X ¹ , X ² and X ³ all have the same structure, it is preferable that Y ¹ and Y ² are different bonding systems from each other. In the case where Y ¹ and Y ² are different bonding methods from each other, there is a tendency to easily express smectic liquid crystallinity.

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

Examples of C 1-20 alkanediyl represented by V ¹ and V ² include methylene, ethylidene, propane-1,3-diyl, butane-1,3-diyl and butane Alkane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane Alkane-1,10-diyl, tetradecane-1,14-diyl, and eicosane-1,20-diyl. V ¹ and V ² preferably represent an alkanediyl group having 2 to 12 carbon atoms, and more preferably represent a linear alkanediyl group having 6 to 12 carbon atoms. When V ¹ and V ² represent a linear alkanediyl group having 6 to 12 carbon atoms, there is a tendency for the alignment of the polymerizable liquid crystal compound (B) to be improved, and the smectic liquid crystallinity tends to be easily expressed.
Examples of the optionally substituted substituents of the C 1-20 alkanediyl which may have a substituent include a cyano group, a halogen atom such as a chlorine atom and a fluorine atom, but the alkanediyl group is preferably Substitution is more preferably unsubstituted and linear alkanediyl.

U ¹ and U ^{2 both} preferably represent a polymerizable group, and more preferably both represent a photopolymerizable group. Since the polymerizable liquid crystal compound (B) having a photopolymerizable group can be polymerized at a lower temperature than the thermally polymerizable group, it can form a polymer in a state where the order of the liquid crystal is higher, which is advantageous in this respect. .

The polymerizable groups represented by U ¹ and U ² may be the same as or different from each other, preferably the same. Examples of the polymerizable group include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloyloxy, methacryloyloxy, ethylene oxide, And oxetanyl. Among these photopolymerizable groups, preferred are acryloxy, methacryloxy, ethyleneoxy, oxirane, and oxetanyl, and more preferably methacryloxy , And propylene oxy.

Examples of such a polymerizable liquid crystal compound (B) include polymerizable liquid crystal compounds represented by the following formulas (1-1) to (1-23).
[Chem 13]

[化 14]

[化 15]

[Chem 16]

Among the above-mentioned polymerizable liquid crystal compounds, it is preferably selected from the group consisting of formula (1-2), formula (1-3), formula (1-4), formula (1-6), formula (1-7), and formula At least one of the group consisting of the compounds represented by (1-8), formula (1-13), formula (1-14) and formula (1-15). The polymerizable liquid crystal compound may be used alone or in combination of two or more.

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

As long as the composition containing the polymerizable liquid crystal compound (B) does not impair the effect of the present invention, it may contain other liquid crystal compounds than the polymerizable liquid crystal compound (B). From the viewpoint of obtaining a polarizing film having a high degree of alignment, The ratio 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 or more, and still more preferably 90% by mass or more.

In addition, 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), or it may be All are polymerizable liquid crystal compounds (B). By combining a plurality of polymerizable liquid crystal compounds, the liquid crystallinity can be temporarily maintained at a temperature below the liquid crystal-crystal phase transition temperature.

The content rate of the polymerizable liquid crystal compound (B) in the composition containing the polymerizable liquid crystal compound (B) is preferably 40 to 99.9% by mass relative to the solid content of the composition containing the polymerizable liquid crystal compound (B). It is more preferably 60 to 99% by mass, and still more preferably 70 to 99% by mass. If the content rate of the polymerizable liquid crystal compound (B) is within the above range, the alignment of the liquid crystal compound tends to increase. In addition, the solid content component means the total amount of components after removing the solvent from the polymerizable liquid crystal composition.

(Dichroic pigment)
The dichroic pigment refers to a pigment having 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 pigment preferably has the characteristic of absorbing visible light, and more preferably has an absorption maximum wavelength (λ _MAX ) in the wavelength range of 380-680 nm. Examples of dichroic dyes include iodine and dichroic organic dyes. Examples of the dichroic organic dye include acridine dye, pigment, cyanine dye, naphthalene dye, azo dye, and anthraquinone dye. Among these dichroic organic dyes, azo pigments are preferred. Examples of the azo dye include monoazo dye, disazo dye, triazo dye, tetraazo dye, and stilbene azo dye. Among these azo pigments, disazo pigments and triazo pigments are preferred. The dichroic organic dyes can be used alone or in combination of two or more. In order to obtain absorption in the visible light, it is preferable to use more than three dichroic pigments, and more preferably to combine more than three kinds of couples. Use of nitrogen pigments. The polyvinyl alcohol-based resin film is preferably immersed in water before dyeing.

Examples of the azo dye 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 independently represent 1,4-phenylene, naphthalene-1,4-diyl which may have a substituent, or a divalent heterocyclic group which may have a substituent, T ¹ and T ² independently represents an electron-withdrawing group or an electron-withdrawing group, and is located at a position substantially 180 ° relative to the azo bond plane; p represents an integer of 0 to 4; when p represents an integer of 2 or more, plural A ² may be the same or different from each other. In the range where the azo pigment shows absorption in the visible region, -N = N- bond can be replaced by -C = C- bond, -COO- bond, -NHCO- bond, or -N = CH- bond]

Examples of the substituents optionally possessed by 1,4-phenylene, naphthalene-1,4-diyl, and divalent heterocyclic groups represented by A ¹ , A ² , and A ³ include, for example, methyl, C1-C4 alkyl groups such as ethyl and butyl; C1-C4 alkoxy groups such as methoxy, ethoxy and butoxy; trifluoromethyl and the like Fluoroalkyl having 1 to 4 carbon atoms; cyano group; nitro group; halogen atom such as chlorine atom and fluorine atom; substituted amine group such as amino group, diethylamino group and pyrrolidinyl group or unsubstituted Amine group (substituted amine group refers to an amine group having 1 or 2 alkyl groups having 1 to 6 carbon atoms, or 2 substituted alkyl groups bonded to each other to form an alkyldiyl group having 2 to 8 carbon atoms) Amino group; unsubstituted amine group is -NH ₂ ). In addition, examples of the C 1-6 alkyl group include a methyl group, an ethyl group, and a hexyl group. Examples of alkanediyl having 2 to 8 carbon atoms include ethylidene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, and pentane- 1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, and octane-1,8-diyl. In order to be included in a high-order liquid crystal structure such as smectic liquid crystal, A ¹ , A ² and A ³ preferably represent unsubstituted or hydrogen atoms are substituted with methyl or methoxy 1,4-benzyl , Or a divalent heterocyclic group, p preferably represents an integer of 0 to 2. Among them, p is 1 and at least two of the three structures of A ¹ , A ² and A ³ are 1,4-phenylene, which is better in terms of both the simplicity of molecular synthesis and higher performance .

Examples of the divalent heterocyclic group include quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole, and benzoxazole, each obtained by removing two hydrogen atoms. Basis. In the case where A ² represents a divalent heterocyclic group, it is preferable that the molecular bond angle becomes substantially 180 °, specifically, a benzothiazole structure or benzo formed by condensation of two 5-membered rings Imidazole structure and benzoxazole structure.

T ¹ and T ² independently represent an electron-withdrawing group or an electron-withdrawing group, preferably an electron-withdrawing group or an electron-withdrawing group having different structures from each other, further preferably T ¹ represents an electron-withdrawing group and T ² represents an electron-withdrawing group In the case of radicals, or T ¹ represents an electron-pushing radical and T ² represents an electron-pulling radical. Specifically, T ¹ and T ^{2 are} preferably independently an alkyl group having 1 to 8 carbons, an alkoxy group having 1 to 8 carbons, a cyano group, a nitro group, and having 1 or 2 carbons. The substituted amine group of the alkyl group of 6 and the two substituted alkyl groups are bonded to each other to form a C2-C8 alkanediyl amine group and a trifluoromethyl group. Among them, in order to be included in a high-order liquid crystal structure such as smectic liquid crystal, it must be a structure with a smaller repulsive volume of molecules, so it is preferably a C 1-6 alkyl group and a C 1-6 alkoxy group Group, a cyano group, a substituted amine group having one or two alkyl groups having 1 to 6 carbon atoms, and two substituted alkyl groups are bonded to each other to form an alkyldiyl group having 2 to 8 carbon atoms.

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

[化 17]

[Chemical 18]

In formulas (2-1) to (2-8),
B ¹ to B ³⁰ 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 amine group (substituted amine Groups and unsubstituted amine groups are as defined above), chlorine atom, or trifluoromethyl group. Also, from the viewpoint of obtaining higher polarizing 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 preferably independently represent a hydrogen atom or a methyl group, and more preferably represent a hydrogen atom.
n1 to n4 independently represent integers of 0 to 2.
When n1 represents 2, the plurality of B ² may be the same or different from each other,
When n2 represents 2, the plurality of B ⁶ may be the same or different from each other,
When n3 represents 2, the plurality of B ⁹ may be the same or different from each other,
When n4 represents 2, the plurality of B ¹⁴ may be the same or different from each other.

As the anthraquinone pigment, compounds represented by formula (2-9) are preferred.

[Chem 19]

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

As the pigment, the compound represented by formula (2-10) is preferred.

[化 20]

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

As the acridine dye, a compound represented by formula (2-11) is preferred.

[化 21]

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

In formula (2-9), formula (2-10) and formula (2-11), examples of the alkyl group having 1 to 4 carbon atoms represented by R ^x include methyl, ethyl, propyl and butyl Base, pentyl, and hexyl. In the formula (2-9), formula (2-10) and formula (2-11), examples of the aryl group having 6 to 12 carbon atoms represented by R ^x include phenyl, tolyl, and xylene Base, and naphthyl.

As the cyanine pigment, compounds represented by formula (2-12) and compounds represented by formula (2-13) are preferred.

[化 22]

[In formula (2-12),
D ¹ and D ² independently represent the base represented by any one of formula (2-12a) to formula (2-12d);
[化 23]

n5 represents an integer from 1 to 3]

[化 24]

[In formula (2-13),
D ³ and D ⁴ independently represent the bases represented by any of formula (2-13a) to formula (2-13h);
[化 25]

n6 represents an integer from 1 to 3]

From the viewpoint of obtaining good light absorption characteristics, the content of the dichroic organic dye (the total amount when plural types are included) is usually 0.1 to 100 parts by mass of the polymerizable liquid crystal compound (B) 30 parts by mass, preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass. If the content of the dichroic organic dye is 0.1 parts by mass or more relative to 100 parts by mass of the polymerizable liquid crystal compound (B), the light absorption of the dichroic organic dye tends to be sufficient to obtain sufficient polarizing performance. If the content of the dichroic organic dye is 30 parts by mass or less with respect to 100 parts by mass of the polymerizable liquid crystal compound (B), the alignment of the polymerizable liquid crystal compound is less likely to be hindered.

(Stretched film adsorbed with dichroic pigments)
A transparent protective film may be provided on at least one side of the stretched film to which the dichroic pigment is adsorbed. A film containing an extended film adsorbed with a dichroic dye as a polarizing element is usually manufactured by sandwiching a transparent protective film through an adhesive on at least one side of the polarizing element. The polarizing element is manufactured through the following steps: The step of uniaxial stretching of the alcohol-based resin film, the step of adsorbing the dichroic pigment by dyeing the polyvinyl alcohol-based resin film with dichroic pigments, and the polyethylene adsorbed with dichroic pigments using aqueous boric acid The step of treating the alcohol-based resin film, and the step of washing with water after the treatment with the boric acid aqueous solution.

The polyvinyl alcohol-based resin is obtained by saponifying the polyvinyl acetate-based resin. As the polyvinyl acetate-based resin, for example, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and other monomers copolymerizable therewith can also be used. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and propylene amides having ammonium groups.

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

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

The uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before dyeing with dichroic dyes, simultaneously with dyeing, or after dyeing. In the case of uniaxial stretching after dyeing, the uniaxial stretching may be performed before boric acid treatment, or may be performed in boric acid treatment. Furthermore, uniaxial extension can also be performed in these plural stages. When uniaxial stretching is performed, it may be uniaxially stretched between rolls having different peripheral speeds, or it may be uniaxially stretched using a hot roller. The uniaxial stretching may be dry stretching in the atmosphere, or wet stretching using a solvent to swell the polyvinyl alcohol-based resin film. The stretching magnification is usually about 3 to 8 times.

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

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

On the other hand, when a dichroic organic dye is used as a dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye for dyeing is generally used. The content of the dichroic organic dye in the aqueous solution is usually about 1 × 10 ^-4 to 10 parts by mass relative to 100 parts by mass of water, preferably 1 × 10 ^-3 to 1 part by mass, and more preferably 1 × 10 ^-3 to 1 × 10 ^-2 parts by mass. The aqueous solution may also contain inorganic salts 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. In addition, the immersion time (dyeing time) of the aqueous solution is usually about 10 to 1,800 seconds.

The boric acid treatment after dyeing with a dichroic pigment can usually be performed by immersing the dyed polyvinyl alcohol-based resin film in a boric acid aqueous solution. The content of boric acid in the aqueous solution of boric acid is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass relative to 100 parts by mass of water. When iodine is used as the dichroic pigment, the aqueous solution of boric acid preferably contains potassium iodide. In this case, the content of potassium iodide is usually about 0.1 to 15 parts by mass relative to 100 parts by mass of water, preferably 5 to 12 Quality parts. 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 boric acid treatment is usually 50 ° C or higher, preferably 50 to 85 ° C, and more preferably 60 to 80 ° C.

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

After washing with water, a drying treatment is performed to obtain a polarizing element. The drying process can be performed using, for example, a hot air dryer or a far-infrared heater. The temperature of the drying process is usually 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. By drying, the moisture content of the polarizing element is reduced to a practical level. The 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 polarizing element may be lost, and the polarizing element may be damaged or broken after it is dried. Moreover, if the moisture content is higher than 20% by weight, there is a possibility that the thermal stability of the polarizing element will deteriorate.

The thickness of the polarizing element obtained by uniaxially stretching the polyvinyl alcohol-based resin film, dyeing with a dichroic pigment, 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 above-mentioned elliptically polarizing plate. As a preferable aspect of the organic EL display device, for example, a device in which an elliptically polarizing plate is bonded to an organic EL panel via an adhesive is mentioned.
[Example]

Hereinafter, the present invention will be described more specifically by examples. In addition, "%" and "parts" in the examples mean mass% and mass parts, unless otherwise specified.

[Preparation of Liquid Crystal Compound]
The liquid crystal compound A is manufactured according to the method described in Japanese Patent Laid-Open No. 2010-31223. Moreover, the liquid crystal compound B is manufactured according to the method described in Japanese Patent Laid-Open No. 2009-173893. The molecular structures of liquid crystal compound A and liquid crystal compound B are shown below.

(Liquid Crystal Compound A)
[化 26]

(Liquid Crystal Compound B)
[化 27]

[test methods]
(Calculation method of the ratio of maximum absorption wavelength to maximum absorbance)
A 1 mg / 50 mL tetrahydrofuran solution of liquid crystal compound A was prepared as a sample for measurement. Put the measurement sample into the 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. In addition, the control system is set to the solvent of only the measurement sample. From the obtained absorption spectrum, the wavelength at which the maximum absorption is read is set as the maximum absorption wavelength λ _max . Furthermore, the maximum absorption wavelength of the liquid crystal compound A in the region with a wavelength of 260 nm or more and 400 nm or less is read from the obtained absorption spectrum. Furthermore, when there is a complex maximum absorption wavelength in a region with a wavelength of 260 nm or more and 400 nm or less, the wavelength with the highest absorbance among the complex maximum absorption wavelengths is set to λ _max . Table 1 shows the maximum absorption wavelengths obtained.

[Preparation of ionic compounds]
The ionic compound (1) is manufactured according to the method described in Japanese Patent Application No. 2016-514802. Moreover, the ionic compound (2) and the ionic compound (3) are manufactured according to the method described in Japanese Patent Laid-Open No. 2013-28586 or Japanese Patent Laid-Open No. 2013-199509. The structural formulas of the ionic compounds (1) to (3) are shown below.

(Ionic compound (1))
[Chem 28]

(Ionic compound (2))
[化 29]

(Ionic compound (3))
[化 30]

<Example 1>
[Preparation of composition (A-1) for forming vertical alignment liquid crystal cured film]
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 as a photopolymerization initiator are added -6 parts by mass of (4-linylphenyl) butane-1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan Co., Ltd.). Furthermore, 3-triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was added as a silane compound to become 0.5%. KBE-9103 "), the ionic compound (1) is added so as to become 2.0%.

N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80 ° C. for 1 hour, thereby obtaining a composition (A-1) for forming a vertically-aligned liquid crystal cured film (hereinafter sometimes referred to as composition (A-1)). In addition, it was confirmed that the silane compound ("KBE-9103" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) reacted with the solvent or moisture in the environment in the composition (A-1) to hydrolyze to generate an amine group as a polar group.

[Manufacturing method of vertical alignment liquid crystal cured film (A-1)]
Using a corona treatment device ("AGF-B10" manufactured by Kasuga Electric Co., Ltd.) to the amorphous cycloolefin polymer film (COP film) as a substrate (Zeon corporation "ZF-14-23") Perform corona treatment once under the conditions of output 0.3 kW and treatment speed 3 m / min. A bar coater was used to apply the composition (A-1) to the surface of the substrate subjected to the corona treatment to form a coating film. The coating film was dried at 120 ° C. for 1 minute to form a dry film. Then, using a high-pressure mercury lamp ("UNICURE VB-15201BY-A" manufactured by Niuwei Electric Co., Ltd.), the dry film was irradiated with ultraviolet light under a nitrogen atmosphere and under a condition of a cumulative light intensity 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) is formed.

[Optical characteristics of vertical alignment liquid crystal cured film (A-1)]
The obtained vertical alignment liquid crystal cured film (A-1) was bonded to glass via an adhesive (pressure-sensitive adhesive 15 μm manufactured by LINTEC) to prepare a sample for measuring optical characteristics.

(Measurement of phase difference)
It was confirmed that the ZF-14-23 base material is an optically isotropic film with a retardation value of 1 nm or less at a wavelength of 550 nm, which does not affect the measured value of a sample for measuring optical characteristics. Then, using a measuring machine ("KOBRA-WPR" manufactured by Oji Measurement Co., Ltd.), the angle of incidence of light on the sample for measuring optical characteristics was changed to measure the phase difference value.

(Measurement of average refractive index)
The average refractive index at wavelengths λ = 450 nm and 550 nm was measured using a refractive index meter (“Multiwavelength Abbe Refractometer DR-M4” manufactured by Atago Co., Ltd.). The Rth calculated from the obtained film thickness, average refractive index, and measurement results of the measuring machine ("KOBRA-WPR" manufactured by Oji Measuring Equipment Co., Ltd.) are Rth (450) =-60 nm, Rth (550) = -70 nm, Rth (450) / Rth (550) = 0.85.

(Alignment evaluation of alignment liquid crystal cured film)
A polarizing microscope ("BX-51" manufactured by Olympus Co., Ltd.) was used to observe at a magnification of 200 times, and the number of alignment defects in a field of view of 480 μm × 320 μm was counted. Here, only the number of alignment defects due to the measurement sample is counted, and the number of defects due to environmental foreign objects other than the optical characteristic sample is excluded and not counted. Based on the results of observation with a polarizing microscope, the alignment of the vertically aligned liquid crystal cured film (A-1) was evaluated based on the following evaluation criteria. A, B, and C were judged to be excellent in alignment. As shown in Table 1, the vertical alignment liquid crystal cured film (A-1) produced using the composition (A-1) has an alignment of A.
(Evaluation criteria)
A (very good): The number of alignment defects is 0 or more and 3 or less.
B (very good): The number of alignment defects is 4 or more and 10 or less.
C (good): The number of alignment defects is 11 or more and 50 or less.
D (Poor): There are more than 51 alignment defects or no alignment at all.

<Examples 2 to 9 and 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 changed to the type of the base material, the type and addition amount of the silane compound, and the type and addition of the ionic compound described in Table 1. Except for this amount, the compositions (A) of Examples 2 to 9, Example 20, Example 21, and Comparative Example 1 were prepared in the same manner as the preparation method of the composition (A-1) of Example 1, respectively (A -2) to (A-9), (A-20), (A-21), and (B-1). Change the composition (A-1) to the compositions (A-2) to (A-9), (A-20), (A-21), and (B-1), and further change the film of the coating film The thickness is changed so as to become the phase difference value shown in Table 1. Except for this, in the same manner as in the manufacturing method of the vertically-aligned liquid crystal cured film (A-1) of Example 1, Examples 2 to 4 were prepared, respectively. 9. Vertically aligned liquid crystal cured films (A-2) to (A-9), (A-20), (A-21), and (B-1) of Example 20, Example 21, and Comparative Example 1. . In addition, in the same manner as in Example 1, a sample for optical characteristic measurement was prepared, and the phase difference value, average refractive index, and alignment were evaluated. The results are shown in Table 1.

<Example 10>
Change the base material from COP film ("ZF-14-23" manufactured by Zeon Corporation) to polyethylene terephthalate with protective layer (hereinafter, sometimes referred to as PET with protective layer), In addition, the PET substrate was peeled off during the measurement of the optical characteristics to prepare a sample, and otherwise, a vertical alignment liquid crystal cured film (A-) was prepared in the same manner as the preparation method of the vertical alignment liquid crystal cured film (A-1) in Example 1. 10). In addition, in the same manner as in Example 1, a sample for optical characteristic measurement was prepared, and the phase difference value, average refractive index, and alignment were evaluated. The results are shown in Table 1. Hereinafter, a method for preparing PET with a protective layer will be described.

[Preparation of composition for forming protective layer]
50 parts of dipentaerythritol hexaacrylate ("ARONIX (registered trademark) M-403" multifunctional acrylate manufactured by East Asia Synthetic Co., Ltd.) and 50 parts of acrylate resin ("Ebecryl 4858" manufactured by Daicel-UCB Co., Ltd.) 50 Parts, and 3 parts of 2-methyl-1 [4- (methylthio) phenyl] -2-olinylpropane-1-one ("Irgacure (registered trademark) 907" manufactured by Ciba Specialty Chemicals) dissolved in In 250 parts of isopropyl alcohol, a solution was prepared. The obtained solution was set as the composition for protective layer formation.

[Manufacture of PET with protective layer]
Using a bar coater, a composition for forming a protective layer was coated on a PET film (thickness: 38 μm) to form a coating film. The coating film was dried at 50 ° C for 1 minute to form a dry coating. Using a high-pressure mercury lamp ("UNICURE VB-15201BY-A" manufactured by Niuwei Electric Co., Ltd.), the dry coating was irradiated with ultraviolet light under a nitrogen atmosphere and a cumulative light amount of 400 mJ / cm ² at a wavelength of 365 nm. As a result, PET with a protective layer containing acrylic resin is formed. In addition, according to the optical property measurement method described in Example 1, after bonding to glass via an adhesive and peeling off the PET film, the phase difference value of the protective layer at a wavelength of 550 nm was measured. The result was 1 nm or less, which was confirmed to be optical Isotropic membrane. Furthermore, the film thickness of the formed protective layer was measured using an ellipsometer, and the result was 2 μm.

<Example 11>
The composition of the liquid crystal compound of Example 1 was changed from liquid crystal compound A / liquid crystal compound B = 90% / 10% to liquid crystal compound (A) -2 100%, in addition to the composition (A- 1) In the same manner as the method for preparing the vertical alignment liquid crystal cured film (A-1), the composition (A-11) of Example 11 and the vertical alignment liquid crystal cured film (A-11) were prepared, respectively. The liquid crystal compound (A) -2 was prepared with reference to Japanese Patent Laid-Open No. 2016-81035. The liquid crystal compound (A) -2 is represented by the following formula (A) -2. In addition, in the same manner as in Example 1, a sample for measurement was prepared, and the phase difference value, average refractive index, and alignment were evaluated. Furthermore, the ratio of the maximum absorption wavelength and the maximum absorbance of the liquid crystal compound (A) -2 was calculated in the same manner as in Example 1. The results are shown in Table 1.
[化 31]

<Example 12>
The composition of the liquid crystal compound of Example 1 was changed from liquid crystal compound A / liquid crystal compound B = 90% / 10% to liquid crystal compound (A) -3 100%, in addition to the composition (A- 1) In the same manner as the method for preparing the vertical alignment liquid crystal cured film (A-1), the composition (A-12) of Example 12 and the vertical alignment liquid crystal cured film (A-12) were prepared respectively. The liquid crystal compound (A) -3 was prepared with reference to International Patent Publication No. 2015/025793. The liquid crystal compound (A) -3 is represented by the following formula (A) -3. In addition, in the same manner as in Example 1, a sample for optical characteristic measurement was prepared, and the phase difference value, average refractive index, and alignment were evaluated. Furthermore, the ratio of the maximum absorption wavelength and the maximum absorbance of the liquid crystal compound (A) -3 was calculated in the same manner as in Example 1. The results are shown in Table 1.
[化 32]

<Example 13>
The composition of the liquid crystal compound of Example 1 was changed from liquid crystal compound A / liquid crystal compound B = 90% / 10% to liquid crystal compound (A) -4 100%, in addition to the composition (A- 1) In the same manner as the method for preparing the vertical alignment liquid crystal cured film (A-1), the composition (A-13) of Example 11 and the vertical alignment liquid crystal cured film (A-13) were prepared, respectively. The liquid crystal compound (A) -4 was prepared with reference to Japanese Patent Laid-Open No. 2011-207765. The liquid crystal compound (A) -4 is represented by the following formula (A) -4. In addition, in the same manner as in Example 1, a sample for optical characteristic measurement was prepared, and the phase difference value, average refractive index, and alignment were evaluated. Furthermore, the ratio of the maximum absorption wavelength and the maximum absorbance of the liquid crystal compound (A) -4 was calculated in the same manner as in Example 1. The results are shown in Table 1.
[化 33]

<Example 14>
The composition of the liquid crystal compound of Example 1 was changed from liquid crystal compound A / liquid crystal compound B = 90% / 10% to liquid crystal compound (A) -5 100%, and the composition (A- 1) The composition (A-14) of Example 14 and the vertical alignment liquid crystal cured film (A-14) were prepared in the same manner as the method for preparing the vertical alignment liquid crystal cured film (A-1). The liquid crystal compound (A) -5 was prepared with reference to Japanese Patent Laid-Open No. 2010-31223. The liquid crystal compound (A) -5 is represented by the following formula (A) -5. In addition, in the same manner as in Example 1, a sample for optical characteristic measurement was prepared, and the phase difference value, average refractive index, and alignment were evaluated. Furthermore, the ratio of the maximum absorption wavelength and the maximum absorbance of the liquid crystal compound (A) -5 was calculated in the same manner as in Example 1. The results are shown in Table 1.
[化 34]

<Example 15>
The silane compound of Example 1 was changed from 3-triethoxysilane-N- (1,3-dimethyl-butylene) propylamine ("KBE-9103" manufactured by Shin-Etsu Chemical Co., Ltd.) It is 3-glycidoxypropyltriethoxysilane ("KBE-403" manufactured by Shin-Etsu Chemical Co., Ltd.). In addition, it is aligned with the composition (A-1) and vertical alignment of Example 1. In the same manner as the preparation method of the liquid crystal cured film (A-1), the composition (A-15) of Example 15 and the vertical alignment liquid crystal cured film (A-15) were prepared separately. In addition, in the same manner as in Example 1, a sample for optical characteristic measurement was prepared, and the phase difference value, average refractive index, and alignment were evaluated. The results are shown in Table 1.

<Example 16>
[Manufacture of Polarizing Film A]
After immersing the polyvinyl alcohol film (average degree of polymerization about 2,400, saponification degree 99.9 mol% or more, thickness 75 μm) in pure water at 30 ℃, the mass ratio of iodine / potassium iodide / water at 30 ℃ is 0.02 / A 2/100 aqueous solution was subjected to iodine staining (iodine staining step). The polyvinyl alcohol film subjected to the iodine dyeing step was immersed in an aqueous solution with a mass ratio of 12/5/100 of potassium iodide / boric acid / water at 56.5 ° C for boric acid treatment (boric acid treatment step). The polyvinyl alcohol film subjected to the boric acid treatment step was washed with pure water at 8 ° C, and then dried at 65 ° C to obtain a polarizing element (thickness 27 μm after extension) made of iodine adsorbed and aligned with polyvinyl alcohol. At this time, extension is performed in the iodine dyeing step and the boric acid treatment step. The total stretching magnification in this stretching is 5.3 times. The obtained polarizing element and the saponification-treated triacetyl cellulose film ("KC4UYTAC" 40 μm manufactured by Konica Minolta) were bonded via a water-based adhesive using a nip roller. The tension of the obtained patch was maintained at 430 N / m, and dried at 60 ° C for 2 minutes to obtain a polarizing film having a triacetyl cellulose film as a protective film on one side. In addition, the above-mentioned water-based adhesive agent is added with 3 parts of carboxyl-modified polyvinyl alcohol ("Kuraray Poval KL318" manufactured by Kuraray) and water-soluble polyamide epoxy resin ("Sumirez Resin" manufactured by Sumika Chemtex) to 100 parts of water 650 ", an aqueous solution with a solid content concentration of 30%) prepared in 1.5 parts.

[Determination of Optical Properties of Polarizing Film A]
The optical characteristics of the obtained polarizing film A were measured. The measurement was carried out using a spectrophotometer ("V7100" manufactured by Japan Spectroscopy) using the polarizing element surface of the polarizing film A obtained above as an incident surface. The absorption axis of the polarizing film is consistent with the extension direction of the polyvinyl alcohol. The obtained polarizing film has a visual acuity correction monomer transmittance of 42.1%, a visual acuity correction polarized degree of 99.996%, a monomer hue a of -1.1, and The hue b is 3.7.

[Preparation of composition for forming horizontal alignment film]
5 parts of the photo-alignment material (weight average molecular weight: 30000) of the following structure was mixed with 95 parts of cyclopentanone as a solvent, and the obtained mixture was stirred at 80 ° C. for 1 hour, thereby obtaining a combination for forming a horizontal alignment film Thing.
[化 35]

[Preparation of composition for forming horizontal alignment 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- (as a polymerization initiator were added 6 parts of 4-linylphenyl) butane-1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan Co., Ltd.). In addition, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The composition for forming the horizontal alignment liquid crystal cured film A was obtained by stirring at 80 ° C for 1 hour.

[Manufacture of horizontal alignment liquid crystal cured film A]
Corona treatment was performed on the COP film ("ZF-14-50" manufactured by Zeon Corporation). Thereafter, the composition for forming a horizontal alignment film is 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 coating. A polarized UV irradiation device ("SPOT CURE SP-9" manufactured by Niuwei Electric Co., Ltd.) was used to obtain a level of polarized UV exposure under the conditions of a cumulative light amount of 100 mJ / cm ² at a wavelength of 313 nm and an axis angle of 45 °. Alignment membrane. The thickness of the obtained horizontal alignment film was measured using an ellipsometer, and the result was 100 nm.

Then, using a bar coater, the composition for forming the horizontal alignment liquid crystal cured film A was applied to the horizontal alignment film to form a coating film. The coated film was dried at 120 ° C for 1 minute to form a dry film. Using a high-pressure mercury lamp ("UNICURE VB-15201BY-A" manufactured by Niuwei Electric Co., Ltd.), under a nitrogen atmosphere and at a cumulative light intensity of 500 mJ / cm ² at a wavelength of 365 nm, irradiate the dried film with ultraviolet rays. This forms a horizontally aligned liquid crystal cured film A. A laminate including a base material, a horizontal alignment film, and a horizontal alignment liquid crystal cured film A was obtained. The film thickness of the horizontally aligned liquid crystal cured film A was measured using an ellipsometer, and the result was 2.3 μm.

[Re measurement of horizontal alignment liquid crystal cured film A]
After the laminate is bonded to the glass via an adhesive, the COP film as a substrate is peeled off. Thereby, the horizontal alignment liquid crystal cured film A for Re measurement was obtained. Using a measuring machine ("KOBRA-WPR" manufactured by Oji Measuring Equipment Co., Ltd.), the in-plane phase difference value ReA (λ) of the horizontal alignment liquid crystal cured film A was measured. The results of measuring the phase difference 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 the laminate including the horizontally aligned liquid crystal cured film A and the 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 passed through an adhesive (pressure-sensitive adhesive 15 μm manufactured by LINTEC) By laminating, 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 laminate, and it was bonded to glass via an adhesive to obtain a laminate for measuring the phase difference value. After confirming that there is no phase difference between the COP film and the horizontal alignment film, use a measuring machine ("KOBRA-WPR" manufactured by Oji Measuring Equipment Co., Ltd.) to measure the phase difference value R0 in the front direction of the laminate for measuring the phase difference value. (λ), and the phase difference value R40 (λ) (λ = 450 nm and 550 nm) when the horizontal alignment liquid crystal cured film A is inclined by 40 ° as the center. Table 2 shows the measurement results. Calculate | R0 (550) －R40 (550) |, | R0 (450) －R40 (450) |, based on the obtained values of R0 (λ) and R40 (λ) (λ = 450 nm and 550 nm) And | {R0 (450) －R40 (450)}-{R0 (550) －R40 (550)} |. The results are shown in Table 3.

[Evaluation of Hue of Oblique Reflection]
The layered body (including the layered body of the horizontally aligned liquid crystal cured film A and the vertically aligned liquid crystal cured film (A-1)) and the polarizing film A produced by the above method are aligned with the horizontally aligned liquid crystal cured film A with the absorption axis of the polarizing film The angle formed by the late phase axis becomes 45 °, the lamination is carried out through the adhesive, the base material is peeled off, and an elliptical polarizing plate with optical compensation function is produced. After that, it is pasted on the aluminum foil via an adhesive, and the oblique reflection hue of the elliptical polarizing plate is visually observed from the direction of the elevation angle 45 ° and the azimuth angle 0 to 360 °. Based on the results of visual observation, the oblique reflection hue was evaluated based on the following evaluation criteria. The results are shown in Table 3.
(Evaluation criteria)
A (good): Black was visually confirmed.
B (Poor): Visually confirm the obvious coloring.

<Examples 17 and 18>
The phase difference value was measured in the same manner as in Example 16 except that the thickness of the vertical alignment liquid crystal cured film was changed, and the values of RthC (450) and RthC (550) were changed as described in Table 2. , Confirmation of oblique reflection hue. The results are shown in Table 2 and Table 3.

<Example 19>
The phase difference was implemented in the same manner as in Example 16, except that the polarizing film A was changed to a polarizing film B made of a horizontally aligned liquid crystal cured film B and a dichroic dye prepared by the method shown below. Value measurement and evaluation of oblique reflection hue. The results are shown in Table 2 and Table 3.

[Preparation of composition for forming polarizing film B]
The following components were mixed and stirred at 80 ° C. for 1 hour, thereby obtaining a composition for forming a polarizing film B including the polymerizable liquid crystal compound (B) and the dichroic dye. As the dichroic pigment, the azo pigment described in the examples of Japanese Patent Laid-Open No. 2013-101328 is used. The polymerizable liquid crystal compounds represented by formulas (1-6) and (1-7) as the polymerizable liquid crystal compound (B) are based on lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996) manufacturing method.
Polymerizable liquid crystal compound (B):
[化 36]

75 servings
[化 37]

25 copies of dichroic pigment 1:
Polyazo pigment: compound (1-8) 2.5 parts
[化 38]

Compound (1-5) 2.5 parts
[化 39]

Compound (1-16) 2.5 servings
[化 40]

Polymerization initiator:
2-Dimethylamino-2-benzyl-1- (4-olinylphenyl) butane-1-one (Irgacure 369; manufactured by Ciba Specialty Chemicals) 6 parts of leveling agent:
Polyacrylate compound ("BYK-361N" manufactured by BYK-Chemie)
1.2 parts solvent: 250 parts o-xylene

[Manufacture of Polarizing Film B]
(Production of horizontal alignment film)
Corona treatment was carried out on triacetyl cellulose film (TAC) ("KC4UY" manufactured by Konica Minolta). Then, using a bar coater, the horizontal alignment film forming composition was applied to the surface of the TAC subjected to the corona treatment 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 Niuwei Electric Co., Ltd.), the polarized UV exposure of the dried coating was performed under the conditions of a cumulative light intensity of 100 mJ / cm ² and an axis angle of 90 ° to obtain horizontal alignment. membrane. Using an ellipsometer to measure the thickness of the obtained horizontal alignment film, the result was 150 nm.

(Manufacture of horizontal alignment liquid crystal cured film B)
Furthermore, the composition for polarizing film B formation was applied to the horizontal alignment film using a bar coater 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 are aligned is obtained. After naturally cooling the dried coating film to room temperature (25 ° C), a high-pressure mercury lamp ("UNICURE VB-15201BY-A" manufactured by Niuwei Electric Co., Ltd.) was used under a nitrogen atmosphere at a wavelength of 365 nm and a wavelength of 365 nm Under the condition of a cumulative light intensity of 1000 mJ / cm ² , ultraviolet light is irradiated to polymerize the polymerizable liquid crystal compound (B) to produce a polarizing film having a horizontally aligned liquid crystal cured film B containing a dichroic dye.

[Measurement of Polarization Degree of Polarizing Film B and Monomer Transmission Rate]
The polarization degree and the monomer transmittance of the obtained polarizing film B were measured as follows. Used in a spectrophotometer ("UV-3150" manufactured by Shimadzu Corporation) with a support for polarizing elements, using a two-beam method at a wavelength of 380 to 680 nm at 2 nm steps The transmittance (T ¹ ) in the transmission axis direction and the transmittance (T ² ) in the absorption axis direction were measured. Using the following formulas (p) and (q), the monomer transmittance and polarization at each wavelength were calculated. Furthermore, the visual acuity correction was performed by the 2 degree field of view (C light source) of Japanese Industrial Standard JIS Z 8701, and the visual acuity correction monomer transmittance (Ty) and the visual acuity correction polarization (Py) were calculated. As a result, the monomer transmittance was 42%, the degree of polarization is 97%, which is confirmed to be a useful value as a polarizing film.
Monomer transmission rate (%) = (T ¹ + T ² ) / 2 (p)
Polarization (%) = {(T ^1- T ² ) / (T ¹ + T ² )} × 100 (q)

<Comparative example 2>
Except that the vertical alignment film and the vertical alignment liquid crystal cured film shown below were produced, samples were prepared in the same manner as in Example 16, and the measurement of the phase difference value and the evaluation of the oblique reflection hue were carried out. The results are shown in Table 2 and Table 3.

(Preparation of composition (B) for forming vertical alignment film)
Mix 0.5% polyimide ("Sunever SE-610" manufactured by Nissan Chemical Industry Co., Ltd.), 72.3% N-methyl-2-pyrrolidone, 18.1% 2-butoxyethanol, 9.1 % Ethylcyclohexane, and 0.01% DPHA (dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate) (manufactured by Shin Nakamura Chemical Co., Ltd.) to produce a composition (B) for forming a vertical alignment film.

(Preparation of composition (B) for forming vertical alignment liquid crystal cured film)
To the liquid crystal compound LC242 represented by the following formula (LC242): Paliocolor LC242 (registered trademark of BASF), 0.1 part of a leveling agent ("F-556" manufactured by DIC) and 3 parts of a polymerization initiator Irg369 are added to Cyclopentanone was added so that the solid content concentration became 13%, and these were mixed to obtain a composition (B) for forming a vertical alignment liquid crystal cured film.
Liquid crystal compound LC242: PaliocolorLC242 (registered trademark of BASF company)
[化 41]

(Manufacture of vertical alignment liquid crystal cured film)
The COP film (Zeon corporation, Inc. "ZF-14-23") as a substrate was subjected to corona treatment. Using a bar coater, the COP film subjected to the corona treatment was coated with the bar coater to apply the composition (B) for forming a vertical alignment film to form a coating film. The coated film was dried at 80 ° C for 1 minute to obtain a vertical alignment film. The thickness of the obtained vertical alignment film was measured using an ellipsometer, and the result was 0.2 μm. Next, the composition (B) for forming a vertical alignment liquid crystal cured film was applied on the prepared vertical alignment film to form a coating film. The coating film was dried at 80 ° C for 1 minute to form a dry coating. After that, the high-pressure mercury lamp ("UNICURE VB-15201BY-A" manufactured by Niuwei Electric Co., Ltd.) was used to irradiate the dry film with ultraviolet light under a nitrogen atmosphere and a cumulative light intensity of 500 mJ / cm ² at a wavelength of 365 nm. To form a vertically aligned liquid crystal cured film. The thickness of the obtained vertical alignment liquid crystal cured film was 0.5 μm.

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

[Table 1]

The vertical alignment liquid crystal cured films (A-1) to (A-15) of Examples 1 to 15 are cured products of compositions (A-1) to (A-15), respectively. The compositions (A-1) to (A-15) contain 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 are non-ionic silane compounds. The alignment of the vertically aligned liquid crystal cured films (A-1) to (A-15) of Examples 1 to 15 was evaluated as either A or B. In addition, the vertical alignment liquid crystal cured film (A-20) of Example 20 is a cured product of the composition (A-20). Composition (A-20) contains an ionic compound. The vertical alignment liquid crystal cured film (A-21) of Example 21 is a cured product of the composition (A-21). Composition (A-21) contains a nonionic silane compound. The alignment evaluation of the vertical alignment liquid crystal cured film (A-20) of Example 20 and the vertical alignment liquid crystal cured film (A-21) of Example 21 were both C.

The alignment liquid crystal cured film (B-1) of Comparative Example 1 is a cured product of the composition (B-1). Composition (B-1) does not contain nonionic silane compounds and ionic compounds. The alignment of the vertical alignment liquid crystal cured film (B-1) of Comparative Example 1 was evaluated as D.

From the above, it can be seen that the vertically aligned liquid crystal cured films (A-1) to (A-15), (A-20), and (A-21) of Examples 1 to 15 and the aligned liquid crystal cured film (B) of Comparative Example 1 -1) In comparison, the alignment is excellent.

The elliptical polarizing plates of Examples 16 to 19 include a vertical alignment liquid crystal cured film, a horizontal alignment film, a horizontal alignment liquid crystal cured film A, and a polarizing film produced using the composition (A-1). The oblique reflection hues of the elliptical polarizing plates of Examples 16 to 19 are all A.

The elliptical polarizing plate of Comparative Example 2 includes a vertical alignment liquid crystal cured film, a horizontal alignment film, a horizontal alignment liquid crystal cured film A, and a polarizing film produced using the composition (B-2). Composition (B-2) contains liquid crystal compound LC242. Ar of the liquid crystal compound is a divalent group having one ring structure, and is not a compound included in the liquid crystal compound represented by formula (I) -1. The oblique reflection hue of the elliptical polarizing plate of Comparative Example 2 is B.

From the above, it can be seen that the elliptical polarizing plates of Examples 16 to 19 are superior to the elliptical polarizing plate of Comparative Example 2 in oblique reflection hue.

[Table 2]

[table 3]

1‧‧‧ Base material

3‧‧‧Horizontal alignment film

5‧‧‧Horizontal alignment liquid crystal cured film A

7‧‧‧ Adhesive layer

9‧‧‧ Vertical alignment liquid crystal hardened film

11‧‧‧ Polarizing film

13‧‧‧Protective layer

15‧‧‧Layered body

20‧‧‧Elliptical polarizing plate

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

Claims (21)

A vertically aligned liquid crystal cured film, which is aligned in a vertical direction with respect to an in-plane direction, and includes at least one selected from the group consisting of nonionic silane compounds and ionic compounds. The vertical alignment liquid crystal cured film according to claim 1, wherein the nonionic silane compound is a silane coupling agent. The vertical alignment liquid crystal cured film according to claim 1 or 2, wherein the nonionic silane compound is a silane coupling agent having an alkoxysilane group and a polar group. The vertical alignment liquid crystal cured film according to any one of claims 1 to 3, wherein all the elements constituting the ionic compound are non-metallic elements. The vertical alignment liquid crystal cured film according to any one of claims 1 to 4, wherein the molecular weight of the ionic compound is 100 or more and 10000 or less. The vertical alignment liquid crystal cured film according to any one of claims 1 to 5, which satisfies the following relationship (1): -150 nm ≦ RthC (550) ≦ -30 nm (1) [In relation (1), RthC (550) represents the phase difference value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm]. If the vertical alignment liquid crystal cured film of any one of claims 1 to 6, it satisfies the following relationship (2): RthC (450) / RthC (550) ≦ 1 (2) [In relation (2), RthC (450) represents the phase difference of the thickness of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and RthC (550) represents the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm Phase difference value]. A laminate having a base material and a vertical alignment liquid crystal cured film according to any one of claims 1 to 7, and The vertical alignment liquid crystal cured film is adjacent to the substrate. A laminate including a vertically aligned liquid crystal cured film according to claims 1 to 7 and a film aligned in a horizontal direction with respect to the in-plane direction of the vertically aligned liquid crystal cured film. If the layered body of claim 9, it satisfies the following relationship (3): ReA (450) / ReA (550) ≦ 1.00 (3) [In relation (3), ReA (450) represents the in-plane retardation value of the film aligned horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and ReA (550) represents the relative The in-plane retardation value of the film aligned horizontally on the film surface of the vertically aligned liquid crystal cured film at a wavelength of 550 nm]. If the laminate of any one of claims 9 or 10, it satisfies the following relationship (4): | R0 (550) －R40 (550) | ≦ 10 nm (4) [In relation (4), R0 (550) represents the in-plane phase difference of the laminate at a wavelength of 550 nm, and R40 (550) represents the rotation of the laminate by 40 ° around the phase-advancing axis of the film aligned in the horizontal direction Phase difference at 550 nm]. If the laminate of any one of claims 9 to 11 satisfies the following relationship (5): | R0 (450) －R40 (450) | ≦ 10 nm (5) [In relation (5), R0 (450) represents the in-plane phase difference of the laminate at a wavelength of 450 nm, and R40 (450) represents when the laminate rotates 40 ° around the phase-advancing axis of the film oriented in the horizontal direction Phase difference at 450 nm]. If the laminate of any one of claims 9 to 12 satisfies the following relationship (6): | {R0 (450) －R40 (450)} － {R0 (550) －R40 (550)} | ≦ 3 nm (6) [In relation (6), R0 (450) represents the in-plane phase difference of the laminate at a wavelength of 450 nm, R0 (550) represents the in-plane phase difference of the laminate at a wavelength of 550 nm, R40 (450) Represents the phase difference value at a wavelength of 450 nm when the layered body rotates 40 ° around the phase-advancing axis of the film oriented in the horizontal direction, R40 (550) represents the layered body rotates 40 ° around the phase-advancing axis of the film oriented in the horizontal direction The phase difference at a wavelength of 550 nm]. The laminate according to any one of claims 9 to 13, wherein the film aligned 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. An elliptically polarizing plate comprising the laminate according to any one of claims 9 to 14, and a polarizing film. The elliptically polarizing plate according to claim 15, wherein the film aligned 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. An elliptical polarizer according to claim 15 or 16, wherein the angle formed by the retardation axis of the film oriented horizontally and the absorption axis of the polarizing film is 45 ± 5 °. The elliptical polarizing plate according to any one of claims 15 to 17, wherein the polarizing film includes a horizontally aligned liquid crystal cured film B aligned in a horizontal direction with respect to the film plane of the polarizing film, and the horizontally aligned liquid crystal cured film B includes two Color pigments. The elliptically polarizing plate according to claim 18, wherein the dichroic pigment has an azo group. The elliptically polarizing plate according to claim 18 or 19, wherein the above-mentioned horizontally aligned liquid crystal cured film B is a cured film obtained by curing a liquid crystal compound in a smectic phase aligned horizontally with respect to the in-plane direction of the film. An organic EL display device including the elliptically polarizing plate according to any one of claims 15 to 20.