KR20200118822A - Vertically aligned liquid crystal cured film - Google Patents

Abstract

A vertically aligned liquid crystal cured film oriented in a direction perpendicular to the in-plane direction, and comprising at least one selected from the group consisting of a nonionic silane compound and an ionic compound.

Description

Vertically aligned liquid crystal cured film

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

The elliptically polarizing plate is an optical member in which a polarizing plate and a retardation plate are stacked, for example, in a device that displays an image in a planar state (for example, an organic EL display device), to prevent light reflection from an electrode constituting the device. It is being used for. In this elliptically polarizing plate, a so-called λ/4 plate is used as the retardation plate.

As a retardation plate used for such an elliptically polarizing plate, it is preferable to exhibit reverse wavelength dispersion from the viewpoint of exhibiting equivalent retardation performance in a wide wavelength range of visible light. As a retardation plate exhibiting reverse wavelength dispersion, a retardation plate comprising a horizontally aligned liquid crystal cured film obtained by polymerization and curing a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion in a horizontal direction is known.

Further, even when viewed from an oblique direction, a polarizing plate provided with an optical compensation function having a function of compensating to exhibit the same optical performance as when viewed from the front direction is also required. As a polarizing plate to which such an optical compensation function is provided, it is known to further include a vertically aligned liquid crystal cured film obtained by polymerization and curing a polymerizable liquid crystal compound in a vertically aligned state together with a horizontally aligned liquid crystal cured film having reverse wavelength dispersion. Moreover, among this vertically aligned liquid crystal cured film, a vertically aligned liquid crystal cured film using a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion is proposed in Patent Document 1.

Japanese Unexamined Patent Publication No. 2015-57646

However, since a liquid crystal compound exhibiting reverse wavelength dispersion has an unstable molecular center of gravity, it is difficult to vertically align the liquid crystal compound alone because many alignment defects occur. For this reason, in production of a vertically aligned liquid crystal cured film, an alignment film for vertical alignment is required. However, in that case, there is a problem that a step of forming an alignment film for vertical alignment is required, and thus productivity is lowered.

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

The inventor of the present invention came to complete the present invention as a result of earnestly examining in order to solve the above problems. That is, the following aspects are included in this invention.

[1] A vertically aligned liquid crystal cured film which is oriented in a direction perpendicular to the in-plane direction and contains at least one selected from the group consisting of a nonionic silane compound and an ionic compound.

[2] The vertically aligned liquid crystal cured film according to [1], wherein the nonionic silane compound is a silane coupling agent.

[3] The vertically aligned liquid crystal cured film according to [1] or [2], wherein the nonionic silane compound is a silane coupling agent having an alkoxysilyl group and a polar group.

[4] The vertically aligned liquid crystal cured film according to any one of [1] to [3], wherein all of the elements constituting the ionic compound are non-metallic elements.

[5] The vertically aligned liquid crystal cured film according to any one of [1] to [4], wherein the molecular weight of the ionic compound is 100 or more and 10000 or less.

The following relational formula (1):

-150 nm ≤ RthC(550) ≤ -30 nm...(1)

[In relational formula (1), RthC(550) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm]

The vertically aligned liquid crystal cured film according to any one of [1] to [5], which satisfies.

[7] The following relational equation (2):

RthC(450)/RthC(550) ≤ 1...(2)

[In the relational formula (2), RthC(450) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and RthC(550) is the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. Represents the phase difference value]

The vertically aligned liquid crystal cured film according to any one of [1] to [6], which satisfies.

[8] comprising the substrate and the vertically aligned liquid crystal cured film according to any one of [1] to [7],

A laminate in which the vertically oriented cured film is adjacent to the substrate.

[9] A laminate comprising the vertically aligned liquid crystal cured film according to [1] to [7], and a film oriented horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film.

[10] The following relational equation (3):

ReA(450)/ReA(550) ≤ 1.00...(3)

[In the relational formula (3), ReA(450) represents the in-plane retardation value at a wavelength of 450 nm of the film oriented horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film, and ReA(550) is the vertically aligned liquid crystal The in-plane retardation value at a wavelength of 550 nm of the film oriented horizontally with respect to the film surface of the cured film is shown.]

The laminate according to [9] that satisfies.

[11] The following relational equation (4):

｜R0(550)-R40(550)｜ ≤ 10 nm···(4)

[In the relational formula (4), R0(550) represents the in-plane retardation value of the laminate at a wavelength of 550 nm, and R40(550) is 40 around the fast axis direction of the film oriented in the horizontal direction of the laminate. Denotes a retardation value at a wavelength of 550 nm when rotated.]

The laminate according to any one of [9] or [10], which satisfies.

[12] The following relational equation (5):

｜ R0(450)-R40(450)｜ ≤ 10 nm···(5)

[In the relational expression (5), R0(450) represents the in-plane retardation value of the laminate at a wavelength of 450 nm, and R40(450) is 40 around the fast axis direction of the film oriented in the horizontal direction of the laminate. The retardation value at a wavelength of 450 nm when rotated is shown.]

The laminate according to any one of [9] to [11] that satisfies.

[13] The following relational equation (6):

｜{R0(450)-R40(450)}-{R0(550)-R40(550)}｜ ≤ 3 nm···(6)

[In the relational formula (6), R0(450) represents the in-plane retardation value of the laminate at a wavelength of 450 nm, R0(550) represents the in-plane retardation value of the laminate at a wavelength of 550 nm, and R40 (450) represents a retardation value at a wavelength of 450 nm when rotated by 40° around the fast axis direction of the film oriented in the horizontal direction of the laminate, and R40 (550) represents the retardation value in the horizontal direction of the laminate. The retardation value at a wavelength of 550 nm when rotated by 40° around the fast axis direction of the oriented film is shown.]

The laminate according to any one of [9] to [12], which satisfies.

[14] The laminate according to 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 a horizontally aligned liquid crystal cured film A.

[15] An elliptically polarizing plate comprising the laminate according to any one of [9] to [14] and a polarizing film.

[16] The elliptically polarizing plate according to [15], wherein the film aligned in the horizontal direction with respect to the film surface of the vertically aligned liquid crystal cured film is a horizontally aligned liquid crystal cured film A.

[17] The elliptically polarizing plate according to [15] or [16], wherein an angle formed by the slow axis of the horizontally oriented film and the absorption axis of the polarizing film is 45±5°.

[18] The polarizing film includes a horizontally 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 contains a dichroic dye. The elliptically polarizing plate according to any one of [17].

[19] The elliptically polarizing plate according to [18], in which the dichroic dye has an azo group.

[20] The elliptically polarizing plate according to [18] or [19], wherein the horizontally aligned liquid crystal cured film B is a cured film obtained by curing in a smectic phase state in which the liquid crystal compound is oriented horizontally with respect to the in-plane direction of the film.

[21] An organic EL display device comprising the elliptically polarizing plate according to any one of [15] to [20].

According to the present invention, even if there is no alignment film, it is possible to provide a vertically aligned liquid crystal cured film in which the occurrence of alignment defects is suppressed.

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

Hereinafter, an embodiment of the present invention will be described in detail. In addition, in this specification, acrylic and methacrylic may be called "(meth)acryl". Further, "system" is added after the compound name, and the compound and its derivatives are sometimes referred to generically. When the polymer name is indicated by adding ``system'' after the compound name, the repeating unit of the polymer is derived from a compound or a derivative thereof, or a polymer subjected to chemical modification after polymerization on the repeating unit derived from the compound or its derivative. it means.

<Vertical alignment liquid crystal cured film>

The vertically aligned liquid crystal cured film of the present invention is oriented in a direction perpendicular to the in-plane direction, and contains at least one selected from the group consisting of a nonionic silane compound and an ionic compound. The vertically aligned liquid crystal cured film is aligned in a direction perpendicular to the in-plane direction. That is, it contains a liquid crystal compound and/or a polymer of a liquid crystal compound in a state of being aligned in a direction perpendicular to the in-plane direction of the vertically aligned liquid crystal cured film. Although the three-dimensional refractive index ellipsoid formed by the vertically aligned liquid crystal cured film may have biaxiality, it is preferable to have uniaxiality.

Even if the vertically aligned liquid crystal cured film of the present invention does not have an alignment film, generation of alignment defects is suppressed. The reason is estimated as follows. The vertically aligned liquid crystal cured film of the present invention contains at least one selected from the group consisting of a nonionic silane compound and an ionic compound. In the production of a liquid crystal cured film, when a composition for forming a vertically aligned liquid crystal cured film is applied to a substrate to form a coating film, and the coating film is heated and dried to form a dry film, in the dry film, a nonionic silane compound and a liquid crystal compound are formed. From the affinity and/or the affinity of the ionic compound and the liquid crystal compound, the ionic compound is present on the surface of the substrate and/or the nonionic silane compound is present on the surface side of the dry film (the side away from the substrate surface). Causes distribution. Since such a distribution increases the vertical alignment regulating force, the liquid crystal compound tends to align in a direction perpendicular to the substrate surface in the dry film. For this reason, a cured film can be formed by maintaining the state in which the liquid crystal compound is vertically aligned. Therefore, in the vertically aligned liquid crystal cured film of the present invention, it is considered that the occurrence of alignment defects is suppressed 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 aspects of a nonionic silane compound, an ionic compound, and a nonionic silane compound and an ionic compound can be mentioned. Although the nonionic silane compound and the ionic compound have the effect of increasing the vertical orientation regulating power by only either one, it is preferable to contain the nonionic silane compound and the ionic compound together from the viewpoint of further enhancing the vertical orientation regulating power.

The vertically aligned liquid crystal cured film is a deterioration of the four-way reflection color of a display provided with an elliptically polarizing plate including a vertically-oriented liquid crystal cured film (for example, a problem in which coloring such as red and blue is observed in all four colors of the display ) From the viewpoint of suppressing,

The following relational formula (1):

-150 nm ≤ RthC(550) ≤ -30 nm...(1)

[In relational formula (1), RthC(550) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm]

It is desirable to satisfy. The retardation value RthC (550) in the thickness direction of the vertically aligned liquid crystal cured film is more preferably -100 nm or more and -40 nm or less, and -80 nm or more -40 from the viewpoint of further suppressing the deterioration of the oblique reflection color of the display. More preferably, it is less than or equal to nm.

The retardation value RthC(550) in the thickness direction of the vertically aligned liquid crystal cured film can be adjusted by the thickness dC of the vertically aligned liquid crystal cured film. The in-plane retardation value is the following formula (1-2):

RthC(550) = [(nxC(550) + nyC(550))/2-nzC(550)] × dC...(1-2)

[In formula (1-2), nxC(550) represents the principal refractive index of a wavelength of 550 nm in the film plane of the vertically aligned liquid crystal cured film, and nyC(550) is in a direction orthogonal to nxC(550) in the same plane. Represents the refractive index of wavelength 550 nm, nzC (550) represents the refractive index of the wavelength 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]

From the point determined by, in order to obtain the retardation value RthC(550) in the desired thickness direction, the three-dimensional refractive index and the film thickness dC may be adjusted. In addition, the three-dimensional refractive index depends on the molecular structure and orientation of the liquid crystal compound described above. Moreover, when nxC(550) = nyC(550), nxC(550) can be made into a refractive index in an arbitrary direction in the film plane.

In addition, the vertically aligned liquid crystal cured film is from the viewpoint of suppressing a decrease in the ellipticity when viewed from all directions on the short wavelength side in the elliptically polarizing plate containing the vertically aligned liquid crystal cured film,

The following relational formula (2):

RthC(450)/RthC(550) ≤ 1...(2)

[In the relational formula (2), RthC(450) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and RthC(550) is the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. Represents the phase difference value]

It is desirable to satisfy. From the viewpoint of further suppressing the decrease in the ellipticity, the RthC(450)/RthC(550) of the vertically aligned liquid crystal cured film is more preferably 0.95 or less, and still more preferably 0.90 or less. In addition, the retardation value RthC (450) in the thickness direction of the vertically aligned liquid crystal cured film can be adjusted by the thickness dC of the vertically aligned liquid crystal cured film, similarly to the RthC (550).

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, still more preferably 2.0 µm or less, and particularly preferably 1.5 µm or less. Further, the lower limit of the film thickness of the vertically aligned liquid crystal cured film is preferably 0.1 µm or more, more preferably 0.3 µm or more, and 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.

[One. Nonionic silane compound]

In this specification, the nonionic silane compound is a compound that is nonionic and contains an Si element. The nonionic silane compound sufficiently improves the vertical alignment of the liquid crystal compound (I)-1 in production of a vertically aligned liquid crystal cured film, and can further improve the vertical alignment of the liquid crystal compound by combination with an ionic compound. In addition, the nonionic silane compound tends to lower the surface tension of the composition for forming a vertically aligned liquid crystal cured film, and can improve the wettability of the composition to the substrate. Nonionic silane compounds include, for example, silicon polymers such as polysilane, silicone resins such as silicone oils and silicone resins, and organo-inorganic silane compounds such as silicone oligomers, silsesquioxane, and alkoxysilanes (more specifically Silver, a silane coupling agent, etc.) are mentioned.

The nonionic silane compound may be of a silicone monomer type or a silicone oligomer (polymer) type. If the silicone oligomer is represented in the form of (monomer)-(monomer) copolymer, 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer , Copolymers containing a mercaptopropyl group such as 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer, and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer; Mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer, and mercaptomethyltri Mercaptomethyl group-containing copolymers such as ethoxysilane-tetraethoxysilane copolymer; 3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropyltrier Oxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-methacryloyloxypropylmethyl Methacryloyloxypropyl group-containing copolymers such as diethoxysilane-tetraethoxysilane copolymer; 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane- Tetramethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-acryloyl Oxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane A copolymer containing an acryloyloxypropyl group such as a copolymer; Vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer Polymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane-tetramethoxysilane copolymer, and vinylmethyldiethoxysilane-tetrae Vinyl group-containing copolymers such as oxysilane copolymers; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3- Aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyl And amino group-containing copolymers such as methyldiethoxysilane-tetramethoxysilane copolymer and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer. These nonionic silane compounds may be used individually by 1 type, or may be used in combination of 2 or more types. Moreover, a silane-containing compound illustrated in the term of a leveling agent can also be used. Among these nonionic silane compounds, a silane coupling agent is preferable from the viewpoint of further improving adhesion.

The silane coupling agent is in the group consisting of a vinyl group, an epoxy group, a styryl group, a methacryl group, an acrylic group, an amino group, an isocyanurate group, a ureide group, a mercapto group, an isocyanate group, a carboxyl group, and a hydroxy group at the terminal. It is a compound containing a Si element having at least one selected functional group and at least one alkoxysilyl group or silanol group. By appropriately selecting these functional groups, peculiar effects such as improvement of the mechanical strength of the vertically aligned liquid crystal cured film, surface modification of the vertically aligned liquid crystal cured film, and improvement of the adhesion between the vertically aligned liquid crystal cured film and the adjacent layer (for example, substrate) are provided. It is possible to do. The silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and another different reactive group (eg, the functional group) from the viewpoint of further improving the adhesion. Moreover, it is preferable that a silane coupling agent is a silane coupling agent which has an alkoxysilyl group and a polar group. When the silane coupling agent has at least one alkoxysilyl group and at least one polar group in its molecule, the vertical alignment property of the liquid crystal compound is further improved, and the effect of promoting vertical alignment is remarkably obtained. Examples of the polar group include an epoxy group, an amino group, an isocyanurate group, a mercapto group, a carboxyl group, and a hydroxy group. Further, the polar group may appropriately have a substituent or a protecting group in order to control the reactivity of the silane coupling agent.

Examples of the silane coupling agent include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tris (2-methoxyethoxy) silane, N-(2-aminoethyl) -3-aminopropylmethyldimethoxy Silane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propyl Amine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltri Ethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylethoxydimethylsilane.

In addition, as a commercially available silane coupling agent, for example, KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM- 403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, Shin-Etsu Chemical Industries Co., Ltd. silane coupling agents such as KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007 Can be lifted.

The content rate of the nonionic silane compound is usually preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 4% by mass, and 0.1% by mass with respect to the solid content of the composition for forming a vertically aligned liquid crystal cured film. It is more preferable that it is-3 mass %. When the content rate of the nonionic silane compound is 0.01% by mass or more with respect to the solid content of the composition, the vertical alignment property of the liquid crystal compound is further improved, and when the content rate of the nonionic silane compound is 5% by mass or less based on the solid content of the composition, the It is difficult to lower the coatability of the composition.

[2. Ionic compound]

The ionic compound sufficiently improves the vertical alignment of the liquid crystal compound (I)-1 in production of the vertically aligned liquid crystal cured film, and further improves the vertical alignment of the liquid crystal compound (I)-1 by combination with a nonionic silane compound. Can be improved.

As an ionic compound, for example, an onium salt (more specifically, a quaternary ammonium salt having a positive charge of nitrogen valence, a tertiary sulfonium salt, and a quaternary phosphonium salt having a positive charge of phosphorus valency) Etc.). Among these onium salts, a quaternary onium salt is preferable from the viewpoint of further improving the vertical alignment of the liquid crystal compound (I)-1, and from the viewpoint of improving availability and mass production, a quaternary phosphonium salt or a fourth Grade ammonium salts are more preferred. The onium salt may have two or more quaternary onium salt sites in the molecule, and may be oligomers or polymers.

The molecular weight of the ionic compound is preferably 100 or more from the viewpoint of further improving the vertical orientation of the liquid crystal compound (I)-1. In addition, the molecular weight of the ionic compound is preferably 10000 or less, more preferably 5000 or less, and still more preferably 3000 or less, from the viewpoint of further improving the coatability of the composition for forming a vertically aligned liquid crystal cured film. The molecular weight of the ionic compound is more preferably 100 or more and 10000 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.

As a cation component of an ionic compound, an inorganic cation and an organic cation are mentioned, for example. Among the cation components of these ionic compounds, organic cation is preferable from the viewpoint of suppressing the occurrence of alignment defects in the liquid crystal compound. As an organic cation, imidazolium cation, pyridinium cation, ammonium cation, sulfonium cation, and phosphonium cation are mentioned, for example.

On the other hand, ionic compounds generally have counter anions. Examples of the anion component that becomes the counter ion of the cation component include an inorganic anion or an organic anion. Among these anionic components, organic anions are preferred from the viewpoint of suppressing the occurrence of alignment defects in the liquid crystal compound. In addition, cation and anion do not necessarily have to be a one-to-one correspondence. As an anion component, the following things are mentioned, for example.

Chloride anion [Cl ^-],

Bromide anion [Br ^-],

Iodide anion [I ^- ],

Tetrachloroaluminate anion [AlCl ₄ ^- ],

Heptachlorodialuminate anion [Al ₂ Cl ₇ ^- ],

Tetrafluoroborate anion [BF ₄ ^- ],

Hexafluorophosphate anion [PF ₆ ^- ],

Perchlorate anion [ClO ₄ ^- ],

Nitrate anion [NO ₃ ^- ],

Acetate anion [CH ₃ COO ^-],

Trifluoroacetate anion [CF ₃ COO ^-],

Fluorosulfonate anion [FSO ₃ ^- ],

Methanesulfonate anion [CH ₃ SO ₃ ^- ],

Trifluoromethanesulfonate anion [CF ₃ SO ₃ ^- ],

p-toluenesulfonate anion [p-CH ₃ C ₆ H ₄ SO ₃ ^- ],

Bis (fluoroalkyl sulfonyl) imide anion [(FSO _{2) 2} N ^-],

Bis (trifluoromethane sulfonyl) imide anion _{[(CF 3 SO 2) 2 N} - ], tris (trifluoromethane sulfonyl) bumetanide anion _{[(CF 3 SO 2) 3 C} - ],

Hexafluoro-acetoxy carbonate anion [AsF ₆ ^-],

Hexafluoroantimonate anion [SbF ₆ ^- ],

Hexafluoroniobate anion [NbF ₆ ^- ],

Hexafluorotantalate anion [TaF ₆ ^- ],

Dimethyl phosphinate anion [(CH _{3) 2} POO ^-],

(Poly) hydrofluorofluoride anion [F(HF) _n ^- ] (for example, n represents an integer of 1 to 3),

Dicyanamide anion [(CN) ₂ N ^- ],

Thiocyanion [SCN ^- ],

Perfluorobutanesulfonate anion [C ₄ F ₉ SO ₃ ^- ],

Bis (ethanesulfonyl pentafluorophenyl) imide anion _{[(C 2 F 5 SO 2)} 2 N - ],

Perfluoro butanoate anion [C ₃ F ₇ COO ^-], and

(Trifluoromethanesulfonyl) (trifluoromethanecarbonyl) imideanion [(CF ₃ SO ₂ )(CF ₃ CO)N ^- ].

Specific examples of the ionic compound can be appropriately selected from the combination of the cation component and the anion component. As a compound which is a specific combination of a cation component and an anion component, 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,

N-hexylpyridinium bis(fluorosulfonyl)imide,

N-octylpyridinium bis(fluorosulfonyl)imide,

N-methyl-4-hexylpyridinium bis(fluorosulfonyl)imide,

N-butyl-4-methylpyridinium bis(fluorosulfonyl)imide,

N-octyl-4-methylpyridinium bis(fluorosulfonyl)imide,

N-hexylpyridinium bis(trifluoromethanesulfonyl)imide,

N-octylpyridinium bis(trifluoromethanesulfonyl)imide,

N-methyl-4-hexylpyridinium bis(trifluoromethanesulfonyl)imide,

N-butyl-4-methylpyridinium bis(trifluoromethanesulfonyl)imide, N-octyl-4-methylpyridinium bis(trifluoromethanesulfonyl)imide,

N-hexylpyridinium p-toluenesulfonate,

N-octylpyridinium p-toluenesulfonate,

N-methyl-4-hexylpyridinium p-toluenesulfonate,

N-butyl-4-methylpyridinium p-toluenesulfonate, and

N-octyl-4-methylpyridinium p-toluenesulfonate.

(Imidazolium salt)

1-ethyl-3-methylimidazolium hexafluorophosphate,

1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide,

1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide,

1-ethyl-3-methylimidazolium p-toluenesulfonate,

1-butyl-3-methylimidazolium methanesulfonate, etc.

(Pyrrolidinium salt)

N-butyl-N-methylpyrrolidinium hexafluorophosphate,

N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide,

N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide,

N-butyl-N-methylpyrrolidinium p-toluenesulfonate and the like.

(Ammonium salt)

Tetrabutylammonium hexafluorophosphate,

Tetrabutylammonium bis(fluorosulfonyl)imide,

Tetrahexylammonium bis(fluorosulfonyl)imide,

Trioctylmethylammonium bis(fluorosulfonyl)imide,

(2-hydroxyethyl) trimethylammonium bis(fluorosulfonyl)imide,

Tetrabutylammonium bis(trifluoromethanesulfonyl)imide,

Tetrahexylammonium bis(trifluoromethanesulfonyl)imide,

Trioctylmethylammonium bis(trifluoromethanesulfonyl)imide,

(2-hydroxyethyl)trimethylammonium bis(trifluoromethanesulfonyl)imide,

Tetrabutylammonium p-toluenesulfonate,

Tetrahexylammonium p-toluenesulfonate,

Trioctylmethylammonium p-toluenesulfonate,

(2-hydroxyethyl) trimethylammonium p-toluenesulfonate,

(2-hydroxyethyl) trimethylammonium dimethylphosphinate,

1-(3-trimethoxysilylpropyl)-1,1,1-tributylammonium bis(trifluoromethanesulfonyl)imide,

1-(3-trimethoxysilylpropyl)-1,1,1-trimethylammonium bis(trifluoromethanesulfonyl)imide,

1-(3-trimethoxysilylbutyl)-1,1,1-tributylammonium bis(trifluoromethanesulfonyl)imide,

1-(3-trimethoxysilylbutyl)-1,1,1-trimethylammonium bis(trifluoromethanesulfonyl)imide,

N-{(3-triethoxysilylpropyl)carbamoyloxyethyl)}-N,N,N-trimethylammonium bis(trifluoromethanesulfonyl)imide, and

N-[2-{3-(3-trimethoxysilylpropylamino)-1-oxopropoxy}ethyl]-N,N,N-trimethylammonium bis(trifluoromethanesulfonyl)imide.

(Phosphonium salt)

Tributyl (2-methoxyethyl) phosphonium bis (trifluoromethanesulfonyl) imide,

Tributylmethylphosphoniumbis(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]phosphoniumbis(trifluoromethanesulfonyl)imide,

1,1,1-trimethyl-1-[4-(trimethoxysilyl)butyl]phosphonium bis(trifluoromethanesulfonyl)imide,

1,1,1-tributyl-1-[(trimethoxysilyl)methyl]phosphonium bis(trifluoromethanesulfonyl)imide,

1,1,1-tributyl-1-[2-(trimethoxysilyl)ethyl]phosphonium bis(trifluoromethanesulfonyl)imide, and

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

These ionic compounds may be used individually, respectively, or may be used in combination of 2 or more types. Further, from the viewpoint of further improving the vertical alignment of the liquid crystal compound, it is preferable that the ionic compound has a Si element and/or an F element in the molecular structure of the cation moiety.

This is because if the ionic compound has a Si element and/or an F element in the molecular structure of the cation moiety, the ionic compound can be segregated on the surface of the vertically aligned liquid crystal cured film. Among these ionic compounds, ionic compounds (more specifically, the following ionic compounds (1) to (3), etc.) in which all constituting elements are non-metallic elements are preferable.

(Ionic compound (1))

[Formula 1]

(Ionic compound (2))

[Formula 2]

(Ionic compound (3))

[Formula 3]

As a method of improving the vertical orientation of the liquid crystal compound, for example, a method of treating the surface of a substrate using a surfactant having an alkyl group having a long chain length to some extent is exemplified. This method is described, for example, in Chapter 2 of the "Liquid Crystal Handbook", the orientation and physical properties of liquid crystals (published by Maruzen Corporation). In this way, the method of improving the vertical alignment of the liquid crystal compound with a surfactant can be applied to an ionic compound. 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 using an ionic compound having an alkyl group having a long chain length to some extent is exemplified. More specifically, it is preferable that an ionic compound satisfies the following formula (10) from a viewpoint of improving the vertical alignment property of a liquid crystal compound.

In formula (10), M is represented by following formula (11).

M = (the number of covalent bonds from the positively charged atom to the molecular chain end of the substituent with the largest number of covalent bonds to the molecular chain end among the substituents directly bonded on the positively charged atom) ÷ (plus Number of atoms with charge)...(11)

In addition, when there are two or more atoms with positive charge in the molecule of the ionic compound, for a substituent having two or more atoms with positive charge, count from the atom with positive charge considered as the starting point and the nearest The number of covalent bonds to an atom having another positive charge is referred to as “the number of covalent bonds from an atom having a positive charge to the end of the molecular chain” described in the definition of M. In addition, when the ionic compound is an oligomer or polymer having two or more repeating units, the structural unit is considered as one molecule, and the M is calculated. When an atom having a positive charge is inserted into the ring structure, the number of covalent bonds until reaching an atom having the same positive charge via the ring structure, or a covalent bond to the end of the substituent bonded to the ring structure In water, the more covalent bond number is defined as "the number of covalent bonds from the positively charged atom to the molecular chain terminal" described in the definition of M.

The content rate of the ionic compound is usually preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, and still more 0.1 to 3% by mass with respect to the solid content of the composition for forming a vertically aligned liquid crystal cured film. desirable. When the content rate of the ionic compound is 0.01% by mass or more in the solid content of the composition, the vertical orientation of the liquid crystal compound is further improved, and when the content rate of the ionic compound is 5% by mass or less with respect to the solid content of the composition, the coating properties of the composition It is difficult to degrade.

[3. Liquid crystal compound]

As a liquid crystal compound capable of forming the vertically aligned liquid crystal cured film of the present invention, for example, the following formula (I)-1:

[Formula 4]

[In formula (I)-1, Ar represents a divalent group having two or more cyclic structures, and one of the two or more cyclic structures is a 6-membered ring, and L at the 1 position and 4 positions of the 6 membered ring Combines with ¹ and L ² ,

L ¹ and L ² each independently represent a single bond or a divalent linking group,

G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, and the hydrogen atoms contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group are each independently a halogen atom, It may be substituted with a C1-C4 alkyl group, a C1-C4 fluoroalkyl group, a C1-C4 alkoxy group, a cyano group, or a nitro group, and is contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group. Each carbon atom may be independently substituted with an oxygen atom, a sulfur atom, or a nitrogen atom,

* Represents a bond hand]

A liquid crystal compound having a structure represented by (hereinafter, it may be described as a liquid crystal compound (I)-1) is mentioned.

In the liquid crystal compound (I)-1, in formula (I)-1, Ar represents a divalent group having two or more cyclic structures, and one of the two or more cyclic structures is a six-membered ring, and Since it binds to L ¹ and L ² at positions ¹ and 4, it tends to take a T-shaped structure. Compounds having such a structure generally tend to exhibit reverse wavelength dispersion. Accordingly, the liquid crystal compound (I)-1 exhibits reverse wavelength dispersion. On the other hand, since liquid crystal compound (I)-1 has a T-shaped structure, it is usually difficult to vertically align alone. In production of a vertically aligned liquid crystal cured film, the vertical alignment of the liquid crystal compound (I)-1 can be sufficiently improved by the composition for forming a vertically aligned liquid crystal cured film containing a nonionic silane compound or an ionic compound. In addition, the composition for forming a vertically aligned liquid crystal cured film preferably contains a nonionic silane compound and an ionic compound together.

Ar represents a divalent group having two or more ring structures. In this specification, the unit of the cyclic structure of Ar is a monocyclic. For example, in liquid crystal compounds A, (A)-2, and (A)-3 described later, Ar has 4, 2, and 3 ring structures, respectively. Two or more ring structures may be adjacent to each other by condensation of two or more monocyclic rings, two or more monocyclic rings may be bonded to each other through a chemical bond, or two or more monocyclic rings may be adjacent to each other without condensation and without a chemical bond. Hereinafter, the first aspect is described as a condensed type, the second aspect is described as a bonded type, and the third aspect is sometimes described as a spirocyclic type. Moreover, a monocyclic ring and a condensed ring (dari) in which a monocyclic ring is condensed may be bonded to each other via a chemical bond, or a polycyclic ring and a polycyclic ring may be bonded to each other via a chemical bond. Hereinafter, such an aspect may be described as a bonded condensation type. The liquid crystal compounds A, (A)-2, and (A)-3 described later are a bonded condensation type, a condensed type, and a bonded type, respectively. Chemical bonds that bond two or more rings in the bonded type and bonded condensation type are, for example, conjugated double bonds (more specifically, -C=C- and -C=N-, etc.) and a carbonyl group. You may include bonds or groups that expand the spatial expansion of the conjugated system.

As a monocyclic ring, a monocyclic hydrocarbon ring (more specifically, a cycloalkane ring, a benzene ring, etc.), and a monocyclic heterocyclic ring are mentioned, for example. As a monocyclic hetero ring, for example, a 5-membered heterocyclic ring (more specifically, a pyrrole ring, a furan ring, a thiophene ring, an oxazole ring, an imidazole ring, a pyrazole ring, a thiazole ring, A triazole ring, a pyrrolidine ring, a tetrahydrofuran ring, and a tetrahydrothiophene ring, etc.), and a heterocycle of a 6-membered ring (more specifically, a pyridine ring, a pyrazine ring, a pyrimidine ring, a thiazine ring, And piperidine ring, etc.). The bridge is a structure having two or more ring structures, and the ring structure may be an aromatic ring or a hydrocarbon ring. Examples of the polycyclic ring include those containing a condensed ring and a monocyclic heterocyclic ring. Condensed rings are, for example, a ring obtained by condensing two or more monocyclic rings of the same type among these monocyclic rings, and a ring obtained by condensing two or more monocyclic rings of different types. As the condensed ring, for example, a polycyclic hydrocarbon ring (more specifically, a naphthalene ring, an anthracene ring, and a phenanthrene ring, etc.), and a polycyclic hetero ring (more specifically, a quinoline ring, quinoxaline Ring, benzofuran ring, benzothiophene ring, fluorene ring, indole ring, carbazole ring, benzoimidazole ring, benzothiazole ring, thienothiazole ring, benzoxazole ring, 1,3-benzodithiol ring , And a phenanthroline ring, etc.). Among these condensed rings, a polycyclic structure is preferable, and a polycyclic heterocyclic structure is more preferable from the viewpoint of expressing reverse wavelength dispersion characteristics.

Monocyclic and dagori may have a substituent. Examples of the substituent which monocyclic and polycyclic may have include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and these substituents further include a cyano group, an imino group, and an alkapoly It may have an enyl group, a cyano group, or an amino group, and the carbon atom in the substituent may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom (in this case, the hydrogen atom bonded to the carbon atom is the valence of the substituted atom It may be increased or decreased according to). Among these substituents, the spatial expansion of the conjugated system may be expanded, such as an imino group, an alkapolyenyl group, a cyano group, a hydroxy group, and an amino group. These substituents may also be substituted.

As 6-membered ring which Ar has, a benzene ring and a cyclohexane ring are mentioned, for example. The 6-membered ring may contain a hetero atom as a ring member atom. As a condensed ring including a 6-membered ring, for example, a quinoline ring, a quinoxaline ring, a benzofuran ring, a benzothiophene ring, a fluorene ring, an indole ring, a carbazole ring, a benzoimidazole ring, a benzothiazole Ring, thienothiazole ring, benzoxazole ring, 1,3-benzodithiol ring, and phenanthroline ring.

Ar preferably represents a divalent group containing a ring structure having at least one sulfur atom as a reducing atom from the viewpoint of further improving the reverse wavelength dispersion of the polarizing plate. Ar preferably represents a divalent group represented by the following formula from the viewpoint of further improving reverse wavelength dispersion. * Represents a bond hand.

[Formula 5]

In the above formula, X ₁ , X ₂ , and X ₃ are each independently selected from CR _1X , R _2X , NR _3X , a sulfur atom, and an oxygen atom. R _1X , R _2X , and R _3X each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

U contains at least one ring structure, and examples of the ring structure include monocyclic and/or polycyclic structures described in paragraphs <0192> to <0201> described above,

Y may be an arbitrary substituent, but it is preferable to include at least one or more cyclic structures from the viewpoint of improving reverse wavelength dispersion, and the cyclic structures include monocyclics described in paragraphs <0192> to <0201> described above, and / Or a structure containing a polycyclic ring is mentioned.

L ₁₀ is a divalent linking group, 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, 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 each 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, Accordingly, the number of hydrogen atoms is appropriately increased or decreased).

Z represents a hydrogen atom or a non-metal atom of Group 14 to 16 which may be bonded to a substituent.

Z is a structure that expands the spatial expansion of the conjugated system from the viewpoint of improving the reverse wavelength dispersion (more specifically, a double bonding site, a triple bonding site, and an aromatic ring satisfying the Huckel rule and a heterocyclic ring, etc. ), and at least one selected from the group consisting of an atom selected from a nitrogen atom and a sulfur atom.

As the divalent linking group represented by L ¹ and L ² , for example, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a1 OR ^a2 -, -R ^a3 COOR ^a4 -, -R ^a5 OCOR ^a6 -, R ^a7 OC=OOR ^a8 -, -N=N-, -CR ^c =CR ^d -, and -C≡C-. Here, R ^a1 to R ^a8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms (more specifically, a methylene group, an ethylene group, a propylene group, a butylene group, etc.), and R ^c and R ^d each independently represents a C1-C4 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 are each independently, preferably, a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a1 OR ^a2 -, -R ^a3 COOR ^a4 -, -R ^a5 OCOR ^a6 -, R ^a7 OC=OOR ^a8 -, -N=N-, -CR ^c =CR ^d -, or -C≡C-. L ¹ and L ² are each independently, more preferably, a single bond, -OR ^a2-1 -, -CH ₂ -, -CH ₂ CH ₂ -, -COOR ^a4-1 -, or OCOR ^a6-1 -Represents. Here, R ^a2-1 , R ^a4-1 , and R ^a6-1 each independently represent a single bond, -CH ₂ -, or -CH ₂ CH ₂ -. Each of L ¹ and L ² independently represents a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, or OCO-.

As a divalent aromatic group represented by G ¹ and G ² , a phenylenediyl group and a naphthylylenediyl group are mentioned, for example. The divalent aromatic group may be substituted with a substituent such as a halogen atom (more specifically, a fluorine atom, a chlorine atom, and a bromine atom) or an alkyl group having 1 to 4 carbon atoms. The divalent aromatic group may have a hetero atom (more specifically, an oxygen atom, a sulfur atom, and a nitrogen atom) as a reducing atom. As a divalent alicyclic hydrocarbon group represented by G ¹ and G ² , a cyclopentanediyl group, a cyclohexanediyl group, and a cycloheptanediyl group are mentioned, for example. The divalent alicyclic hydrocarbon group may be substituted with a substituent such as a halogen atom and an alkyl group having 1 to 4 carbon atoms.

In the present specification, an aromatic group is a group having a planarity of a cyclic structure, and the number of π electrons in the cyclic structure is [4n + 2] according to Huckel's rule (n represents a positive integer of 1 or more). When a cyclic structure is formed by including heteroatoms such as -N= and S- as reducing atoms, the Huckel rule is satisfied by including non-covalent electron pairs on these hetero atoms, and aromaticity is also included.

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

It is preferable that the liquid crystal compound (I)-1 has a maximum absorption in a region having a wavelength of 260 to 400 nm. When the liquid crystal compound (I)-1 has an aromatic group having a hetero atom or a structure that expands the conjugated system, the absorption in the near-ultraviolet region is shifted toward the longer wavelength side compared to the benzene ring, so it has maximum absorption in the wavelength region of 260 nm or more. In many cases, such maximum absorption in a wavelength region of 260 nm or more is preferable from the viewpoint of improving reverse wavelength dispersion. In addition, when it has maximum absorption in a wavelength region greater than 400 nm in wavelength, since coloring may occur, it is preferable that the liquid crystal compound (I)-1 has maximum absorption in a region having a wavelength of 400 nm or less. In addition, from the viewpoint of further improving the wavelength dispersion, it is more preferable to have maximum absorption in a region of 280 nm or more and 400 nm or less, and even more preferably in a region of 300 nm or more and 400 nm or less.

Liquid crystal compound (I)-1 is the following formula (I)-2:

[Formula 6]

It is preferably a liquid crystal compound having a structure represented by (hereinafter, it may be described as a liquid crystal compound (I)-2).

In formula (I)-2, Ar represents a divalent group having two or more cyclic structures, one of the two or more cyclic structures is a 6-membered ring, and L ¹ at the 1 position and 4 positions of the 6 membered ring And L ² combined with,

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 are each independently , A halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, the divalent aromatic group and the divalent alicyclic type The carbon atoms contained in the hydrocarbon group may each independently be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom,

* Represents a bond hand.

Formula (I) -2 of the Ar, L ^1, L ^2, G ^1, and G ² has the formula (I) -1 of Ar, L ^1, L ^2, G ^1, G ^2, and each agrees with.

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

As a divalent aromatic group represented by G ³ , a phenylenediyl group and a naphthylylenediyl group are mentioned, for example. The divalent aromatic group may be substituted with a substituent such as a halogen atom (more specifically, a fluorine atom, a chlorine atom, and a bromine atom) or an alkyl group having 1 to 4 carbon atoms. As a divalent alicyclic hydrocarbon group represented by G ³ , a cyclopentanediyl group, a cyclohexanediyl group, and a cycloheptanediyl group are mentioned, for example. 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.

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

Liquid crystal compound (I)-1 is the following formula (I)-3:

[Formula 7]

It is more preferable that it is a liquid crystal compound (hereinafter, it may be described as liquid crystal compound (I)-3) having a structure represented by.

In formula (I)-3, Ar represents a divalent group having two or more cyclic structures, and one of the two or more cyclic structures is a 6-membered ring, and L ¹ at the 1 position and 4 positions of the 6 membered ring And L ² combined with,

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 is, It may be substituted with a halogen atom, a C1-C4 alkyl group, a C1-C4 fluoroalkyl group, a C1-C4 alkoxy group, a cyano group, or a nitro group, its divalent aromatic group, or its divalent alicyclic hydrocarbon The carbon atom contained in the group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom,

* Represents a bond hand.

Formula (I) -3 it is of Ar, L ^1, L ^2, G ^1, and G ² has the formula (I) -1 of Ar, L ^1, L ^2, G ^1, G ^2, and each agrees with. Formula (I) -3 of B ¹ and G ³ are, respectively, formula (I) -2 of the B ¹ and G ³ and consent.

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

As the divalent aromatic group represented by G ⁴ , a phenylenediyl group or a naphthylylenediyl group can be mentioned, for example. The divalent aromatic group may be substituted with a substituent such as a halogen atom (more specifically, a fluorine atom, a chlorine atom, and a bromine atom) or an alkyl group having 1 to 4 carbon atoms. As a divalent alicyclic hydrocarbon group represented by G ³ , a cyclopentanediyl group, a cyclohexanediyl group, and a cycloheptanediyl group are mentioned, for example. 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, a halogen atom and an alkyl group having 1 to 4 carbon atoms which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms. 1,4-cyclohexanediyl group which may be substituted with at least one substituent selected from the group consisting of, more preferably a 1,4-phenylenediyl group substituted with a methyl group, or an unsubstituted 1,4-phenylenediyl group , Or an unsubstituted 1,4-trans-cyclohexanediyl group, and particularly preferably an unsubstituted 1,4-phenylenediyl group, or an unsubstituted 1,4-trans-cyclohexanediyl group.

The liquid crystal compound (I)-1 may have one or more polymerizable groups. In the present specification, the polymerizable group refers to a group capable of participating in the polymerization reaction by an active radical generated from a photoinitiator or an active species such as an acid. Examples of the polymerizable group include an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxyranyl group, and A cetanyl group is mentioned. Among these polymerizable groups, it is preferable that they are an acryloyloxy group and a methacryloyloxy group. In this specification, the liquid crystal compound (I)-1 having a polymerizable group can form a polymer by a polymerization reaction.

As a liquid crystal compound (I)-1, a liquid crystal compound which has a structure represented by Formula (A)-1-Formula (A)-5 is mentioned, for example.

(Liquid Crystal Compound A)

[Formula 8]

(Liquid Crystal Compound (A)-2)

[Formula 9]

(Liquid Crystal Compound (A)-3)

[Formula 10]

(Liquid Crystal Compound (A)-4)

[Formula 11]

(Liquid Crystal Compound (A)-5)

[Formula 12]

The content of the liquid crystal compound (I)-1 (in the case of containing a plurality of liquid crystal compounds, the sum of the contents) is preferably 50 to 99.5 parts by mass with respect to 100 parts by mass of the solid content of the composition for forming a vertically aligned liquid crystal cured film. And, it is more preferable that it is 60-99 mass parts, and it is still more preferable that it is 70-99 mass parts. In the present specification, the mass of the solid content of the composition refers to the total mass of the components in which the solvent has been removed from the composition.

[Method of manufacturing vertically aligned liquid crystal cured film]

The vertically aligned liquid crystal cured film is a cured product of the composition for forming a vertically aligned liquid crystal cured film. The production method of the vertically aligned liquid crystal cured film includes a coating film forming step of applying a composition for forming a vertically aligned liquid crystal cured film to a substrate to form a coating film on the substrate, and a dry film forming step of drying the coated film to form a dry film. And a cured film forming step of irradiating a dry film with an active energy ray to form a vertically aligned liquid crystal cured film. The laminate produced by the present production method is constituted by a substrate 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 is described as an example.

(Coating film formation process)

In the coating film forming process, for example, using a printing device, the composition is applied to a substrate to form a coating film on the substrate. As a method of applying, for example, a printing method such as a gravure coating method, a die coating method, and a flexo method may be mentioned.

(Dry film formation process)

In the dry film forming step, for example, a heating device is used to dry the coated film to form a dry film. After the coating film is heated and the solvent in the coating film is removed, the liquid crystal compound is vertically aligned and converted into a dry film. It is preferable that the heating temperature can remove a solvent and is more than the phase transition temperature of a liquid crystal compound.

(Cured film formation process)

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

(Other process: vertical alignment film formation process)

As already explained, the vertically aligned liquid crystal cured film can be formed directly on the substrate without forming an alignment film. On the other hand, the manufacturing method of a vertically aligned liquid crystal cured film may further include a vertical alignment film forming step of forming a vertically aligned film for the purpose of further improving the alignment of the vertically aligned liquid crystal cured film. In this case, the vertically aligned liquid crystal cured film is indirectly formed on the substrate via the vertically aligned film.

The vertical alignment film formation process is a process performed before the coating film formation process, and forms a vertical alignment film. Here, an example of a method of forming a vertical alignment layer will be described. The alignment film formation process includes a 2nd coating film formation process, a 2nd dry coating formation process, and an alignment film formation process.

In the 2nd coating film formation process, a 2nd coating film is formed by coating the composition for vertical alignment film formation on a base material using, for example, a printing apparatus. The composition for forming a vertical alignment film contains, for example, an alignment polymer described later and the solvent described above. In the 2nd dry film formation process, a 2nd coating film is heated by using a heating device, for example, and a 2nd coating film is dried, and a 2nd dry film is formed. In addition, when a step of curing by UV irradiation is necessary, a vertical alignment film is formed by irradiating UV to the second dry film and curing it using a UV irradiation device. When the production method of the vertically aligned liquid crystal cured film includes a vertical alignment film forming step, a vertically aligned liquid crystal cured film is formed on the vertically aligned liquid crystal film.

(Composition for vertically aligned liquid crystal cured film formation)

The composition for forming a vertically aligned liquid crystal cured film contains, for example, either or both of a nonionic silane compound or an ionic compound, and an additive to be added as necessary. As an additive, a liquid crystal compound, a photoinitiator, a leveling agent, a solvent, a polymerization inhibitor, and an adhesion improving agent are mentioned, for example. As a liquid crystal compound, a liquid crystal compound (I)-1 is mentioned, for example. These additives may be used individually by 1 type, or may be used in combination of 2 or more types. The composition can be obtained by substantially uniformly dispersing or dissolving these components by stirring any one or both of a nonionic silane compound or an ionic compound and, if necessary, other components at a predetermined temperature.

(menstruum)

Since the composition for forming a vertically aligned liquid crystal cured film is usually applied to a substrate or the like in a state dissolved in a solvent, it is preferable to contain a solvent. Examples of the solvent include water; Alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; 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; Chlorine-containing solvents such as chloroform and chlorobenzene; And amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone. These solvents may be used individually by 1 type, or may be used in combination of 2 or more types. Among these solvents, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents, and aromatic hydrocarbon solvents are preferred. These solvents may be used individually by 1 type, or may be used in combination of 2 or more types.

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. When the solid content of the composition is 50 parts by mass or less, since the viscosity of the composition is lowered, the thickness of the vertically aligned liquid crystal cured film becomes substantially uniform, and there is a tendency that nonuniformity is less likely to occur in the vertically aligned liquid crystal cured film. The solid content may be appropriately determined in consideration of the thickness of the vertically aligned liquid crystal cured film to be produced.

(Photopolymerization initiator)

The composition for forming a vertically aligned liquid crystal cured film may contain a photoinitiator for the purpose of advancing a polymerization reaction. In the present specification, the photoinitiator absorbs active energy rays and provides an active species that initiates a polymerization reaction. The photopolymerization initiator can be used in the case of using a curable composition cured by radical polymerization, for example, (meth)acrylate or urethane (meth)acrylate as a curable material, and cured by cationic polymerization When using the curable composition described above, for example, an epoxy compound or an oxetane compound as the curable composition, a photocationic polymerization initiator can be used.

As a photoinitiator, a photoradical polymerization initiator and a photocationic polymerization initiator are mentioned, for example. Examples of the photoradical polymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, and triazine compounds. As a photocationic polymerization initiator, an onium salt, such as an aromatic diazonium salt, an aromatic iodonium salt, and an aromatic sulfonium salt, and an iron-arene complex, are mentioned, for example. As a photopolymerization initiator, for example, Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure Photopolymerization initiators manufactured by BASF Japan, such as 379, Irgacure 127, Irgacure 2959, Irgacure 754, and Irgacure 379EG; Photopolymerization initiators manufactured by Seiko Chemical Co., Ltd., such as Seikol BZ, Seikol Z, and Seikol BEE, photopolymerization manufactured by Dow Corporation such as Kayacure BP100 (manufactured by Nippon Explosives Corporation), and Kayacure UVI-6992 Initiator; Corporations such as Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer N-1919, Adeka Arcles NCI-831, Adeka Arcles NCI-930 Photoinitiators manufactured by ADEKA; Photoinitiators manufactured by Nippon Siberhegner, such as TAZ-A and TAZ-PP; A photoinitiator manufactured by Sanwa Chemical Co., such as TAZ-104; A photoinitiator manufactured by Nippon Explosives Co., Ltd. like the Kayarard (registered trademark) series; Photoinitiators manufactured by Dow Chemical Co., such as Cyracure UVI series; Photoinitiators manufactured by San-Apro Co., Ltd. like the CPI series; Photoinitiators manufactured by Midori Chemical Co., Ltd. such as TAZ, BBI, and DTS; A photoinitiator manufactured by Rhodia Corporation such as RHODORSIL (registered trademark) can be mentioned. These photoinitiators may be used individually by 1 type, or may be used in combination of 2 or more types. The photoinitiator can be appropriately selected and used according to the material to be used.

Since the photoinitiator can sufficiently utilize the energy emitted from the light source and is excellent in productivity, the maximum absorption wavelength of the photoinitiator is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm. Among these photoinitiators, α-acetophenone-based polymerization initiators and oxime-based photoinitiators are preferred.

As an α-acetophenone-based polymerization initiator, for example, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4- Morpholinophenyl)-2-benzylbutan-1-one (2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one), and 2-dimethylamino-1-( 4-morpholinophenyl)-2-(4-methylphenylmethyl)butan-1-one. α-acetophenone-based polymerization initiators are 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, and 2-dimethylamino-1-(4-morpholinophenyl) )-2-Benzylbutan-1-one is preferred. As commercially available products of α-acetophenone compounds, α-acetophenone-based polymerization initiators manufactured by BASF Japan Co., Ltd. such as Irgacure 369, 379EG, and 907, and α-acetophenone manufactured by Seiko Chemical Co., Ltd. such as Seikol BEE Non-system polymerization initiators, etc. are mentioned.

The oxime photoinitiator generates a radical by irradiation with light. Polymerization of the composition for forming a vertically aligned liquid crystal cured film in the core portion of the coating film preferably proceeds by this radical. Moreover, it is preferable to use an oxime type photoinitiator which can efficiently utilize ultraviolet rays of 350 nm or more in wavelength from a viewpoint of making the polymerization reaction in the deep part of a coating film advance more efficiently. As an oxime photoinitiator that can efficiently use ultraviolet rays with a wavelength of 350 nm or more, preferably, a triazine compound and an oxime ester carbazole compound can be mentioned, and from the viewpoint of sensitivity, for example, more Preferably, an oxime ester type carbazole compound is mentioned. Examples of the oxime ester carbazole compound include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], and ethanone, 1-[9-ethyl -6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) is mentioned. As a commercial product of the oxime ester carbazole compound, for example, an oxime ester carbazole compound manufactured by BASF Japan Co., Ltd. such as Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03, and ADEKA Co., Ltd. oxime ester type carbazole compounds such as Adeka Optomer N-1919 and Adeka Arcles NCI-831 are mentioned.

When the content of the photoinitiator is made into 100 parts by mass of the solid content (excluding the content of the solvent in the composition) contained in the composition for forming a vertically aligned liquid crystal cured film, it is usually preferably 0.1 to 20 parts by mass, and 0.5 It is more preferable that it is -10 mass parts, and it is still more preferable that it is 1-7 mass parts. When the photoinitiator is 0.1 to 20 parts by mass per 100 parts by mass of the composition, the polymerization reaction is likely to proceed sufficiently.

(Leveling agent)

The leveling agent is applied to the composition for the purpose of adjusting the applicability of the composition for forming a vertically aligned liquid crystal cured film, i.e., adjusting the fluidity of the composition to be applied, and making the layer surface obtained by applying the composition more flat. You may add it. Examples of the leveling agent include silicone-based leveling agents such as silane coupling agents, polyacrylate-based leveling agents, and fluoroalkyl-based leveling agents. Among these leveling agents, a silicone-based leveling agent and a fluoroalkyl-based leveling agent are preferable from the viewpoint of further improving the vertical alignment of the liquid crystal compound.

Commercially available leveling agents include, for example, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, and leveling agents manufactured by Toray Dow Corning, such as FZ2123; 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- Shin-Etsu Chemical Co., Ltd. leveling agent, such as 585, KBM-802, KBM-802, KBM-803, KBE-846, and KBE-9007; Momentive Performance Materials Japan joint company manufacturing leveling agents such as TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460; Leveling agents manufactured by Sumitomo 3M, such as fluorinert (registered trademark) FC-72, copper FC-40, copper FC-43, and FC-3283; Megapak (registered trademark) R-08, East R-30, East R-90, East F-410, East F-411, East F-443, East F-445, East F-470, East F-477, Leveling agent manufactured by DIC Co., Ltd. such as F-479, F-482, F-483, and F-556; Leveling agents manufactured by Mitsubishi Matreal Electronics Chemicals Co., Ltd. such as FTOP (brand name) EF301, copper EF303, copper EF351, and copper EF352; AGC Seimi Chemicals such as Suflon (registered trademark) S-381, S-382, S-383, S-393, SC-101, SC-105, KH-40, and SA-100 ( Note) Manufacturing leveling agent; Daikin Fine Chemical Laboratory Co., Ltd. manufacturing leveling agent like brand name E1830 and copper E5844; Chemie's leveling agents (all brand names: BM) such as BM-1000, BM-1100, BYK-352, BYK-353, and BYK-361N are mentioned. These leveling agents may be used individually by 1 type, or may be used in combination of 2 or more types.

The leveling agent 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 in the solid content of the composition for forming a vertically aligned liquid crystal cured film. When the content rate of the leveling agent in the solid content of the composition is 0.001 to 3% by mass, the coating property of the composition is further improved.

<Laminate>

The layered product includes the vertically aligned liquid crystal cured film. The laminate is a substrate, an alignment film for vertical alignment (hereinafter, it may be described as a vertical alignment film), an alignment film for horizontal alignment (hereinafter, may be described as a horizontal alignment film), an adhesive layer, and/or described later. You may further provide a film oriented horizontally with respect to the in-plane direction of the said vertically aligned liquid crystal cured film (hereinafter, it may be described as a horizontal alignment film). As a configuration of a laminate, for example, a laminate comprising the vertically aligned liquid crystal cured film, a horizontal alignment film and a horizontal alignment film, a laminate provided with the vertically aligned liquid crystal cured film and a substrate, and the vertically aligned liquid crystal cured A layered product including a film, a horizontal alignment film, a horizontal alignment film, and a base material is mentioned. However, in the present invention, since a vertically aligned liquid crystal cured film can be formed even without an alignment film for vertical alignment, the laminate does not need to have a vertical alignment film. For example, when the laminate includes a substrate and a vertically aligned liquid crystal cured film, the vertically aligned liquid crystal cured film may be adjacent to the substrate. Moreover, the vertically aligned liquid crystal cured film adjacent to the base material produced by the above-described method may transfer only the vertically aligned liquid crystal cured film through an adhesive layer, and remove the base material to produce a laminate.

〔materials〕

Examples of the substrate include a glass substrate and a film substrate, and a film substrate is preferable from the viewpoint of processability, and a long roll-shaped film is more preferable because it can be continuously produced. Examples of the resin constituting the film base material include polyolefins such as polyethylene, polypropylene, and norbornene-based polymer; Cyclic olefin resin; Polyvinyl alcohol; Polyethylene terephthalate; Polymethacrylic acid ester; Polyacrylic acid ester; Cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; Polyethylene naphthalate; Polycarbonate; Polysulfone; Polyethersulfone; Polyether ketone; And plastics such as polyphenylene sulfide and polyphenylene oxide. A release treatment such as silicone treatment may be applied to the bonding surface of the substrate with the adhesive layer. Examples of commercially available cellulose ester substrates include cellulose ester substrates manufactured by Fuji Photo Film Co., Ltd. such as Fuji Tak film; Cellulose ester base materials manufactured by Konica Minolta Opto, such as "KC8UX2M", "KC8UY", and "KC4UY" are mentioned. Such a resin can be formed into a film by a known means such as a solvent casting method or a melt extrusion method, and can be used as a substrate.

Examples of commercially available cyclic olefin resins include cyclic olefin resins manufactured by Ticona (Germany) such as "Topas (registered trademark)"; Cyclic olefin resins manufactured by JSR Corporation such as "Aton (registered trademark)"; Cyclic olefin resins manufactured by Nippon Xeon Co., Ltd., such as "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)"; Cyclic olefin resins manufactured by Mitsui Chemicals Co., Ltd. such as "Apel" (registered trademark) are mentioned. A commercially available cyclic olefin resin substrate can also be used. As commercially available cyclic olefin resin substrates, Sekisui Chemical Industries Co., Ltd. cyclic olefin resin substrates such as "Sushina (registered trademark)" and "SCA40 (registered trademark)"; Cyclic olefin-based resin substrates manufactured by Optes, such as "Zeonor Film (registered trademark)"; Cyclic olefin resin base materials manufactured by JSR Corporation such as "Aton Film (registered trademark)" are mentioned.

It is preferable that the base material has a thickness in which each layer is easily laminated and peelable. 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 regulating force for aligning the liquid crystal compound of the liquid crystal cured film in a predetermined direction. Regarding the method of forming the alignment layer, various alignments such as vertical alignment, horizontal alignment, hybrid alignment, and oblique alignment can be controlled according to the type of alignment layer material, rubbing conditions, and light irradiation conditions. The treatment for expressing the orientation regulating force in this way is referred to as orientation treatment. Among these, the vertical alignment film is an alignment film having an alignment regulating force for aligning the liquid crystal compound in the vertical direction. For this reason, by using a vertical alignment film, a vertical alignment liquid crystal film can be formed.

It is preferable that the vertical alignment film has a solvent resistance that does not dissolve by application of a composition for forming a vertically aligned liquid crystal cured film or the like, and also has heat resistance in heat treatment for removal of the solvent or alignment of the liquid crystal compound.

It is preferable to apply a material that lowers the surface tension of the surface of the substrate or the like as the vertical alignment film. Examples of such materials include oriented polymers such as polyimide, polyamide, polyamic acid as a hydrolyzate thereof, and fluorine-based polymers of perfluoroalkyl, silane compounds, and polysiloxane compounds obtained by condensation reactions thereof. have.

In the vertical alignment film, a composition containing such a material and a solvent, for example, a solvent exemplified in the section of a vertically aligned liquid crystal cured film (hereinafter, also referred to as a composition for forming a vertical alignment film) is applied onto a substrate, etc., and the solvent is removed. After that, it can be obtained by heating or the like to the coating film.

In the case of using a silane compound for the vertical alignment layer, the surface tension is easily lowered and the vertical alignment layer contains a compound containing Si elements and C elements as constituent elements from the viewpoint of increasing adhesion with the layer adjacent to the vertical alignment layer. A film to be formed is preferable, and a silane compound can be preferably used. As the silane compound, the nonionic silane compound described above, the silane-containing ionic compound exemplified in the section of the ionic compound, etc. can be used, and the vertical orientation regulating force can be enhanced by using these silane compounds. These silane compounds may be used individually by 1 type, may be used in combination of 2 or more types, and may be used by mixing with other materials. When the silane compound is a nonionic silane compound, a silane compound having an alkyl group at the molecular terminal is preferable, and a silane compound having an alkyl group having 3 to 30 carbon atoms is more preferable from the viewpoint of increasing the vertical orientation regulating force.

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

[Orientation film for horizontal alignment]

The horizontal alignment film has an alignment regulating force for aligning the liquid crystal compound in the horizontal direction. The horizontal alignment film can form the horizontal alignment state of the horizontal alignment liquid crystal cured film when the composition for horizontal alignment liquid crystal cured film formation is formed on the horizontal alignment film. The orientation regulating force can be arbitrarily adjusted according to, for example, the kind of the alignment film, the surface condition, and the rubbing condition, and when formed of a photo-alignable polymer, it can be arbitrarily adjusted by polarization irradiation conditions or the like. The treatment for expressing the orientation regulating force in this way is referred to as orientation treatment.

It is preferable that the horizontal alignment film has solvent resistance that does not dissolve by application of a liquid crystal composition or the like, and also has heat resistance in heat treatment for removal of the solvent or alignment of the liquid crystal compound.

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

The rubbing alignment film is usually oriented by applying a composition containing an oriented polymer and a solvent (hereinafter, it may be described as a composition for forming a rubbing alignment film) to a substrate, removing the solvent to form a coating film, and rubbing the coating film. It can impart regulatory power.

As an orientation polymer, for example, polyamide or gelatin having an amide bond, polyimide having an imide bond, and a hydrolyzate thereof such as polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxa Sol, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid esters are mentioned. These orientation polymers may be used individually by 1 type, or may be used in combination of 2 or more types.

The concentration of the alignment polymer in the composition for forming a rubbing alignment film may be within a range in which the alignment polymer is fully used in a solvent. The content of the oriented 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 rubbing alignment film.

As a commercial item of the composition for forming a rubbing alignment film, for example, a composition for forming a rubbing alignment film manufactured by Nissan Chemical Industries, Ltd. such as Sunever (registered trademark), and a composition for forming a rubbing alignment film manufactured by Optmer (registered trademark), manufactured by JSR Corporation The composition for forming a rubbing alignment film is mentioned.

As a method of the rubbing treatment, for example, a method in which the rubbing cloth is wound and the coating film is brought into contact with a rotating rubbing roll is mentioned. When performing a rubbing treatment, if masking is performed, a plurality of regions (patterns) having different orientation directions may be formed in the orientation film.

In the photo-alignment film, a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter, it may be described as a composition for forming a photo-alignment film) is applied to the base material, and after removing the solvent, polarization (preferably, It is obtained by irradiating polarized light UV). The photoalignment film can arbitrarily control the direction of the orientation regulating force by selecting the polarization direction of polarized light to be irradiated.

The photoreactive group refers to a group that generates orientation ability by irradiation with light. Specifically, a group involved in a photoreaction which is the origin of an orientation ability such as a molecular orientation-causing reaction, isomerization reaction, photodimerization reaction, photocrosslinking reaction, or photodecomposition reaction caused by light irradiation is mentioned. As the photoreactive group, a group having an unsaturated bond, particularly a double bond, is preferable, and a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond (N=N Bond), and a group having at least one double bond selected from the group consisting of a carbon-oxygen double bond (C=O bond).

As a photoreactive group which has a C=C bond, a vinyl group, a polyene group, a stilbene group, a stilbazole group, a stilbazolium group, a chalcone group, and a cinnamoyl group are mentioned, for example. As a photoreactive group having a C=N bond, a group having a structure such as an aromatic cipro base and an aromatic hydrazone can be exemplified. Examples of the photoreactive group having an N=N bond include an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group, a formazane group, and a group having an azoxybenzene structure. As a photoreactive group which has a C=O bond, a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group are mentioned, for example. These groups may have substituents such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.

The group involved in the photo-dimerization reaction or the photo-crosslinking reaction is preferable from the viewpoint of excellent orientation. Among them, the photoreactive group involved in the light dimerization reaction is preferred, and the amount of polarization irradiation required for alignment is relatively small, and since it is easy to obtain a photoalignment film excellent in thermal stability and time-lapse stability, cinnamoyl group and chalcone group desirable. As the polymer having a photoreactive group, it is particularly preferable that the terminal portion of the side chain of the polymer has a cinnamoyl group which becomes 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 the polymer or monomer or the thickness of the target photoalignment film, and it is preferably 0.2 parts by mass or more with respect to 100 parts by mass of the composition for forming a photoalignment film. , 0.3 to 10 parts by mass is more preferable.

In order to irradiate polarized light, for example, from the composition for forming a photoalignment film applied on the substrate, the solvent may be directly irradiated with polarized light. In addition, the polarized light is preferably substantially parallel light. The wavelength of polarized light to be irradiated is preferably a wavelength range in which the photoreactive group of a polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) in the region of wavelength 250 to 400 nm is particularly preferred. Examples of the light source for irradiating the polarized light include a xenon lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, and an ultraviolet laser such as KrF and ArF. Among these light sources, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferable because of their large luminous intensity of ultraviolet rays having a wavelength of 313 nm. Polarized UV can be irradiated by irradiating light from the light source through an appropriate polarizing element. Examples of the polarizing element include a polarizing filter, a polarizing prism such as Glen Thompson, and Glen Taylor, and a wire grid. Among these polarizing elements, a wire grid is preferable from the viewpoint of a large area and resistance to heat.

In addition, when performing rubbing or polarization irradiation, when masking is performed, a plurality of regions (patterns) having different directions of liquid crystal alignment may be formed.

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

As a method of obtaining the grooved alignment film, a method of forming an uneven pattern by performing development and rinsing treatment after exposure through an exposure mask having a pattern-shaped slit on the surface of the photosensitive polyimide film, and on a plate-shaped disc having grooves on the surface, A method of forming a layer of UV-cured resin before curing, transferring the formed resin layer to a substrate, and then curing, and a roll-shaped disc having a plurality of grooves is pressed against the film of the UV-cured resin formed on the substrate before curing. And a method of forming and then curing.

The film thickness of the horizontal alignment film is preferably 1 µm or less, more preferably 0.5 µm or less, and still more preferably 0.3 µm or less from the viewpoint of achieving a thin film and expressing an orientation regulating force. Moreover, the film thickness of the horizontal alignment film is 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 horizontal alignment film can be measured using an ellipsometer or a contact film thickness meter.

[Film oriented horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film]

In this specification, the film oriented horizontally with respect to the in-plane direction of a vertically aligned liquid crystal cured film (hereinafter, it may be described as a horizontal alignment film) is a retardation film. As a horizontal alignment film, a stretched film and a horizontal alignment liquid crystal cured film A are mentioned, for example.

The optical properties 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 preferable.

(Horizontal alignment liquid crystal cured film A)

In this specification, the horizontally aligned liquid crystal cured film A is a liquid crystal cured film cured in a state in which a 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. In the horizontally aligned liquid crystal cured film A, the optical axis of the polymerizable liquid crystal compound is aligned horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film. As a polymerizable liquid crystal compound, the liquid crystal compound (I)-1 which has at least 1 polymerizable group is mentioned, for example. In addition, in this specification, the horizontally aligned liquid crystal cured film included in the laminate of the present invention is referred to as a horizontally aligned liquid crystal cured film A, and the horizontally aligned liquid crystal cured film included in the polarizing film of a polarizing plate described later is referred to as a horizontally aligned liquid crystal cured film B. , Distinguish each.

(Production method of horizontally aligned liquid crystal cured film A)

The horizontally aligned liquid crystal cured film A is a cured product of a composition (hereinafter, it may be described 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 differs from the manufacturing method of the vertical alignment liquid crystal cured film mentioned above in the point of forming on a horizontal alignment film. Examples of the manufacturing method of the horizontally aligned liquid crystal cured film A include a coating step of forming a coating film by applying the composition on a horizontal alignment film prepared in advance, a dry film forming step of drying the coated film to form a dry film, It includes a cured film forming step of irradiating the dry film with an active energy ray to form a horizontally aligned liquid crystal cured film.

(Stretched film)

As a stretched film, a stretched film made of a polycarbonate resin is mentioned, for example. As a commercially available stretched film, a stretched film manufactured by Teijin Corporation such as "Pure Ace (registered trademark) WR" is mentioned, for example. A stretched film is usually obtained by stretching a base film. As a method of stretching the base film, for example, a roll-up body in which a base film is wound on a roll is prepared, the base film is continuously unwound from the winding, and the unwound base film is conveyed to a heating furnace. The setting temperature of the heating furnace is preferably in the range of the vicinity of the glass transition temperature of the base film to the glass transition temperature + 50°C. In a heating furnace, it stretches in the conveyance direction of a base film, or the direction orthogonal to a conveyance direction. When stretching, the conveying direction or tension is adjusted and the inclination is made at an arbitrary angle to perform thermal stretching treatment of uniaxial stretching, biaxial stretching, or oblique stretching. The direction of the retardation axis of the stretched film is different depending on the stretching method, and the retardation axis or the optical axis is determined according to the stretching method. The stretched film and the laminate of the present invention can be bonded through an adhesive layer.

From the viewpoint of suppressing a decrease in the ellipticity on the short wavelength side in the elliptically polarizing plate provided with the laminate, the laminate of the present invention, the following relational formula (3):

ReA(450)/ReA(550) ≤ 1...(3)

[In the relational formula (3), ReA(450) represents the in-plane retardation value at a wavelength of 450 nm of the film oriented horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film, and ReA(550) is the vertically aligned liquid crystal The in-plane retardation value at a wavelength of 550 nm of the film oriented horizontally with respect to the in-plane direction of the cured film is shown.]

It is desirable to satisfy. 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.

In addition, from the viewpoint of improving the ellipticity of the elliptically polarizing plate including the laminate, the following (3)-2: 120 nm ≤ ReA(550) ≤ 170 nm ... (3)-2

It is desirable to satisfy. From the viewpoint of improving the ellipticity of the elliptically polarizing plate provided with the laminate, it is preferably 130 nm≦ReA(550)≦160 nm.

Among the laminates described in the present invention, the laminate comprising a vertically aligned liquid crystal cured film and a film oriented horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film is a retardation value in the front direction and a retardation from all directions. From the viewpoint of reducing the difference in values, that is, from the viewpoint of suppressing the deterioration of the oblique reflection color of a display including an elliptically polarizing plate including the laminate, the following relational expression (4):

｜R0(550)-R40(550)｜ ≤ 10 nm···(4)

[In relational formula (4), R0(550) represents the in-plane retardation value of the laminate at a wavelength of 550 nm, and R40 (550) is a film oriented horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film The retardation value at a wavelength of 550 nm when rotated by 40° around the fast axis direction of is shown.]

It is desirable to satisfy. From the viewpoint of further suppressing the deterioration of the tetragonal reflection hue, it is more preferably 8 nm or less, and even more preferably 4 nm or less.

Among the laminates described in the present invention, the laminate comprising a vertically aligned liquid crystal cured film and a film oriented in a horizontal direction with respect to the in-plane direction of the vertically aligned liquid crystal cured film is all directions of a display including an elliptically polarizing plate comprising the laminated body. From the viewpoint of suppressing the deterioration of the reflected color, the following relational expression (5):

｜R0(450)-R40(450)｜ ≤ 10 nm...(5)

[In the relational formula (5), R0 (450) represents the in-plane retardation value of the laminate at a wavelength of 450 nm, and R40 (450) represents the film oriented horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film. The retardation value at a wavelength of 450 nm when rotated by 40° around the fast axis direction is shown.]

It is desirable to satisfy. From the viewpoint of further suppressing the deterioration of the tetragonal reflection hue, it is more preferably 8 nm or less, and even more preferably 4 nm or less.

Among the laminates described in the present invention, the laminate comprising a vertically aligned liquid crystal cured film and a film oriented in a horizontal direction with respect to the in-plane direction of the vertically aligned liquid crystal cured film is all directions of a display including an elliptically polarizing plate comprising the laminated body. From the viewpoint of suppressing the deterioration of the reflected color, the following relational expression (6):

｜{R0(450)-R40(450)}-{R0(550)-R40(550)}｜ ≤ 3 nm···(6)

[In the relational formula (6), R0(450) represents the in-plane retardation value of the laminate at a wavelength of 450 nm, R0(550) represents the in-plane retardation value of the laminate at a wavelength of 550 nm, and R40 (450) ) Represents a retardation value at a wavelength of 450 nm when rotated by 40° around the fast axis direction of the film oriented horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film, and R40(550) is the above Represents the retardation value at a wavelength of 550 nm when rotated by 40° around the fast axis direction of the film oriented horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film.]

It is desirable to satisfy. From the viewpoint of further suppressing the deterioration of the tetragonal reflection hue, it is more preferably 2 nm or less, and even more preferably 1 nm or less.

[Method of manufacturing laminate]

The manufacturing method of the layered product of this invention includes a vertically aligned liquid crystal cured film formation process. The vertically aligned liquid crystal cured film forming process is a production method of the vertically aligned liquid crystal cured film described above. By the method for producing a vertically aligned liquid crystal cured film described above, 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 can be produced.

When the laminated body includes a film oriented horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film, the production method of the laminate further includes a stretched film bonding step or a horizontally aligned liquid crystal cured film A forming step. The stretched film bonding step attaches a stretched film to a vertically aligned liquid crystal cured film, for example, using an adhesive agent. The manufacturing method of the layered product provided with the horizontally aligned liquid crystal cured film A may be produced by bonding a vertically aligned liquid crystal cured film and a horizontally aligned liquid crystal cured film through an adhesive layer, for example, and a horizontal alignment film and a horizontally aligned liquid crystal cured film You may form A on a vertically aligned liquid crystal cured film. Further, a vertically aligned liquid crystal cured film may be formed on the stretched film or on the horizontally aligned liquid crystal cured film A.

[Adhesive]

As an adhesive agent, a pressure-sensitive adhesive, a dry solidifying adhesive, and a chemical reaction adhesive are mentioned, for example. As a chemically reactive adhesive, an active energy ray-curable adhesive is mentioned, for example.

The pressure-sensitive adhesive usually contains a polymer and may contain a solvent. Examples of the polymer include acrylic polymers, silicone polymers, polyesters, polyurethanes, and polyethers. Among these pressure-sensitive adhesives, pressure-sensitive adhesives containing acrylic polymers are excellent in optical transparency, have moderate wettability or cohesiveness, are excellent in adhesiveness, and, furthermore, have high weather resistance and heat resistance, and are lifted under conditions of heating or humidification. It is preferable because it is difficult to cause or peeling.

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

The pressure-sensitive adhesive containing such a copolymer is preferable because it has excellent adhesiveness and can be removed relatively easily without causing glue residue or the like on the transfer object even when it is removed after bonding to the transfer object. The glass transition temperature of the acrylic polymer is preferably 25°C or less, and more preferably 0°C or less. It is preferable that the mass average molecular weight of such an acrylic polymer is 100,000 or more.

As a solvent, the solvent illustrated as said solvent is mentioned, for example. The pressure-sensitive adhesive may contain a light diffusing agent. The light diffusing agent is an additive that imparts light diffusing property to the pressure-sensitive adhesive, and may be fine particles 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 composed of an inorganic compound and fine particles composed of an organic compound (polymer). Including acrylic polymers, many of the polymers contained in the pressure-sensitive adhesive as an active ingredient have a refractive index of about 1.4 to 1.6, so it is preferable to appropriately select from light diffusing agents having a refractive index of 1.2 to 1.8. The difference in refractive index between the polymer and the light diffusing agent contained in the pressure-sensitive adhesive as an active ingredient is usually 0.01 or more, and from the viewpoint of brightness and displayability of the display device, 0.01 to 0.2 is preferable. The fine particles used as the light diffusing agent are preferably spherical fine particles and fine particles close to monodisperse, and more preferably fine particles having an average particle diameter of 2 to 6 µm. The refractive index is measured by a general minimum declination method or an Abbe refractometer.

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

The thickness of the pressure-sensitive adhesive is not particularly limited because it is determined depending on the adhesive force or the like, but is usually 1 µm to 40 µm. From the viewpoints 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 from the pressure-sensitive adhesive to 5 µm to 20 µm, brightness can be maintained when the display device is viewed from the front or viewed from an inclination, and it is difficult to cause blur or blur on the display.

The dry solidifying adhesive may contain a solvent. As a dry-solidifying adhesive, for example, a polymer of a monomer having a protic functional group and an ethylenically unsaturated group such as a hydroxyl group, a carboxyl group, or an amino group, or a urethane polymer as a main component, and a polyhydric aldehyde, an epoxy compound, or an epoxy A composition containing a crosslinking agent or curable compound such as a resin, a melamine compound, a zirconia compound, and a zinc compound can be mentioned.

As a polymer of a monomer having a protic functional group such as a hydroxyl group, a carboxyl group or an amino group and an ethylenically unsaturated group, for example, ethylene-maleic acid copolymer, itaconic acid copolymer, acrylic acid copolymer, acrylamide copolymer, polyvinyl acetate Saponified products and polyvinyl alcohol-based resins.

Examples of the polyvinyl alcohol-based resin include polyvinyl alcohol, partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol, carboxyl group modified polyvinyl alcohol, acetoacetyl group modified polyvinyl alcohol, methylol group modified polyvinyl alcohol, and And amino group-modified polyvinyl alcohol. The content of the polyvinyl alcohol-based resin in the water-based adhesive agent is usually 1 to 10 parts by mass, and preferably 1 to 5 parts by mass with respect to 100 parts by mass of water.

As the urethane resin, a polyester-based ionomer type urethane resin is mentioned, for example. The polyester-based ionomer type urethane resin referred to herein is a urethane resin having a polyester skeleton, and is a resin into which a small amount of ionic component (hydrophilic component) is introduced. Since such an ionomer-type urethane resin is emulsified in water without using an emulsifier to become an emulsion, it can be used as an aqueous adhesive. When using a polyester-based ionomer-type urethane resin, it is effective to blend a water-soluble epoxy compound as a crosslinking agent.

As an epoxy resin, a polyamide polyamine obtained by reacting a polyalkylene polyamine such as diethylenetriamine or triethylenetetramine with a dicarboxylic acid such as adipic acid, and a polyamide polyamine obtained by reacting epichlorohydrin Resin, etc. are mentioned. Commercially available products of such polyamide epoxy resins include, for example, "Sumirez Resin (registered trademark) 650" and "Sumirez Resin 675" manufactured by Sumika Chemtex Co., Ltd., and "WS-525" manufactured by Nippon PMC Corporation. I can. In the case of blending an epoxy resin, the content is usually 1 to 100 parts by mass, preferably 1 to 50 parts by mass with respect to 100 parts by mass of the polyvinyl alcohol-based resin.

The thickness of the pressure-sensitive adhesive layer formed from the dry solidifying adhesive is usually 0.001 to 5 µm, preferably 0.01 to 2 µm, more preferably 0.01 to 0.5 µm, from the viewpoint of suppressing the occurrence of appearance defects. .

The active energy ray-curable adhesive may contain a solvent. An active energy ray-curable adhesive is an adhesive that cures by receiving irradiation with an active energy ray. Examples of the active energy ray-curable adhesive include cationic polymerizable adhesives containing an epoxy compound and a cation polymerization initiator, radical polymerizable adhesives containing an acrylic curing component and a radical polymerization initiator, and cationic polymerization such as an epoxy compound. An adhesive containing both a hardening component and a radically polymerizable hardening component such as an acrylic compound, and further containing a cation polymerization initiator and a radical polymerization initiator, and an adhesive cured by irradiating an electron beam without containing these polymerization initiators Can be mentioned.

Among these active energy ray-curable adhesives, a radically polymerizable active energy ray-curable adhesive containing an acrylic curing component and a photo-radical polymerization initiator, and a cationic polymerizable active energy ray-curable adhesive containing an epoxy compound and a photo-cationic polymerization initiator desirable. 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 compounds other than the epoxy compound. As a compound other than an epoxy compound, an oxetane compound and an acrylic compound are mentioned, for example.

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

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

<Elliptical polarizing plate>

The elliptically polarizing plate contains the said laminated body and a polarizing film. The elliptically polarizing plate may further contain an arbitrary layer (more specifically, a protective layer, an adhesive agent, etc.) as needed. The laminated body and the polarizing film are bonded, for example, through an adhesive agent.

1 is a schematic cross-sectional view showing an example of a layer structure of an elliptically polarizing plate. The elliptically polarizing plate 20 shown in FIG. 1 is composed of a laminate 15, an adhesive 7, a polarizing film 11, and a protective layer 13. The layered product 15 is constituted by 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 slow 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 a polarizing film, for example, a film containing a dichroic dye and oriented horizontally with respect to the film surface of the polarizing film (more specifically, a stretched film adsorbed with a dichroic dye (hereinafter referred to as polarizing film A) May be), and a horizontally aligned liquid crystal cured film B containing a dichroic dye (hereinafter, it may be described as a polarizing film B) and the like). From the viewpoint of thinning the elliptically polarizing plate, a horizontally aligned liquid crystal cured film B containing a dichroic dye is preferable. The dichroic dye refers to a dye that exhibits absorption anisotropy and has a property of different absorbance in the major axis direction of the molecule of the dichroic dye and the absorbance in the minor axis direction.

(Horizontal alignment liquid crystal cured film B)

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

It is preferable that the horizontally aligned liquid crystal cured film B is a cured film cured in the state of a smectic phase in which the polymerizable liquid crystal compound (B) is oriented 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 expressing the polarization function as a cured film by polymerization reaction, the liquid crystal state exhibited by the polymerizable liquid crystal compound is preferably a smectic phase, and more preferably a high-order smectic phase from the viewpoint of high performance. Among them, Smectic B Phase, Smectic D Phase, Smectic E Phase, Smectic F Phase, Smectic G Phase, Smectic H Phase, Smectic I Phase, Smectic J Phase, Smectic K Phase or Smectic A higher order Smectic liquid crystal compound forming the L phase is more preferable, and a higher order Smectic liquid crystal compound forming the Smectic B phase, the Smectic F phase, or the Smectic I phase is more preferable. If the liquid crystal phase formed by the polymerizable liquid crystal compound (B) is such a high-order smectic phase, a polarizing film having higher polarization performance can be produced. Further, such a polarizing film having high polarization performance is one in which Bragg peaks derived from higher order structures such as a hexatic phase or a crystal phase are obtained in X-ray diffraction measurement. The Bragg peak is a peak derived from a periodic structure of molecular orientation, and a film having a periodic interval of 3 to 6 Å can be obtained. The horizontally aligned liquid crystal cured film B is preferable from the viewpoint of obtaining higher polarization characteristics to contain a polymer of the polymerizable liquid crystal compound (B) polymerized in a smectic phase state. In addition, the polymerizable group described later in the polymerizable liquid crystal compound (B) may be in a state of unpolymerized or polymerized in the horizontally aligned liquid crystal cured film B. That is, the horizontally aligned liquid crystal cured film B is contained in any of the polymerizable liquid crystal compound (B) (monomer), the oligomer of the polymerizable liquid crystal compound (B), the polymer of the polymerizable liquid crystal compound (B), and combinations thereof You can do it. It is preferable that the polymerizable group which the polymerizable liquid crystal compound (B) has is in a state of non-polymerization in the horizontally aligned liquid crystal cured film B.

As a polymerizable liquid crystal compound (B), the compound etc. which are specifically represented by following formula (B) are mentioned. The polymerizable liquid crystal may be used alone or in combination of two or more.

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 represents a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group is a halogen atom or an alkyl group having 1 to 4 carbon atoms , May be substituted with a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, and the carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group is an oxygen atom, It may be substituted with a sulfur atom or a nitrogen atom. However, at least one of X ¹ , X ² , and X ³ represents a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group 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 each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ -constituting the alkanediyl group is -O-, -CO-, -S -Or NH- may be substituted.

Each of U ¹ and U ² independently represents a polymerizable group or a hydrogen atom, and at least one of U ¹ and U ² represents a polymerizable group.

In the polymerizable liquid crystal compound (B), at least one of X ¹ , X ² , and X ³ is 1,4-phenylene group which may have a substituent, or cyclohexane-1,4- which may have a substituent. It represents a diyl group. In particular, it is preferable that X ¹ and X ³ represent a cyclohexane-1,4-diyl group which may have a substituent, and the cyclohexane-1,4-diyl group is trans-cyclohexane-1,4-di It is more desirable to display a diary. As a substituent optionally having a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent, for example, 1 to 1 carbon atoms such as a methyl group, an ethyl group, and a butyl group And a halogen atom such as an alkyl group of 4, a cyano group, and a chlorine atom and a fluorine atom. The 1,4-phenylene group which may have a substituent or the cyclohexane-1,4-diyl group which may have a substituent is preferably a 1,4-phenylene group and a cyclohexane-1,4-diyl group. . Moreover, when Y ¹ and Y ² have the same structure, it is preferable that at least one of X ¹ , X ² and X ³ is a different structure. When at least one of X ¹ , X ² and X ³ has a different structure, smectic liquid crystal properties tend to be easily expressed.

Y ¹ and Y ² are each independently a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ O-, -COO-, -OCO-, -N=N-,- It is preferable to represent CR ^a =CR ^b -, -C≡C- or CR ^a =N-, and each of R ^a and R ^b independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y ¹ and Y ² are each independently more preferably -CH ₂ CH ₂ -, -COO-, -OCO-, or a single bond. In addition, when all of X ¹ , X ² and X ³ have the same structure, it is preferable that Y ¹ and Y ² are different bonding methods. When Y ¹ and Y ² are mutually different bonding methods, smectic liquid crystal properties tend to be easily expressed.

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

Examples of the alkanediyl group having 1 to 20 carbon atoms represented by V ¹ and V ² include methylene group, ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1, 4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, A tetradecane-1,14-diyl group, and an icosan-1,20-diyl group.

V ¹ and V ² preferably represent an alkanediyl group having 2 to 12 carbon atoms, more preferably a linear alkanediyl group having 6 to 12 carbon atoms. When V ¹ and V ² represent a linear C 6 to C 12 alkanediyl group, the orientation of the polymerizable liquid crystal compound (B) is improved, and smectic liquid crystal properties tend to be easily expressed.

Examples of the substituents that an alkanediyl group having 1 to 20 carbon atoms which may have a substituent optionally has, for example, a cyano group and a halogen atom such as a chlorine atom and a fluorine atom, but the alkanediyl group is unsubstituted It is preferable, and it is more preferable that it is an unsubstituted and linear alkanediyl group.

It is preferable that both U ¹ and U ² represent a polymerizable group, and it is more preferable that both represent a photopolymerizable group. The polymerizable liquid crystal compound (B) having a photopolymerizable group is advantageous in that a polymer can be formed in a state in which the liquid crystal is more orderly, since it can be polymerized under conditions of a lower temperature than the thermal polymerizable group.

Although the polymerizable groups represented by U ¹ and U ² may be the same or different from each other, the same is preferable. As a polymerizable group, for example, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, and oxetanyl Can be raised. Among these photopolymerizable groups, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferable, and a methacryloyloxy group and an acryloyloxy group are more preferable.

As such a polymerizable liquid crystal compound (B), a polymerizable liquid crystal compound represented by the following formula (1-1)-(1-23) is mentioned, for example.

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

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

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

The composition containing the polymerizable liquid crystal compound (B) may contain other liquid crystal compounds other than the polymerizable liquid crystal compound (B), as long as the effect of the present invention is not impaired, but from the viewpoint of obtaining a polarizing film with high alignment order 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, and more preferably 70% by mass. It is not less than 90% by mass, more preferably not less than 90% by mass.

Moreover, when the composition containing a 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: exemplary compound), and all of them The polymerizable liquid crystal compound (B) may be used. By combining a plurality of polymerizable liquid crystal compounds, liquid crystal properties may be temporarily maintained even at a temperature equal to or lower than the liquid crystal-crystal phase transition temperature in some cases.

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 mass% with respect to the solid content of the composition containing the polymerizable liquid crystal compound (B). , More preferably, it is 60 to 99 mass%, More preferably, it is 70 to 99 mass%. When the content ratio of the polymerizable liquid crystal compound (B) is within the above range, the orientation of the liquid crystal compound tends to increase. In addition, the solid content means the total amount of components from which the solvent was removed from the polymerizable liquid crystal composition.

(Dichroic pigment)

The dichroic dye refers to a dye having a property different from the absorbance in the major axis direction of the molecule and the absorbance in the minor axis direction. As a dichroic dye, it is preferable to have a characteristic of absorbing visible light, and more preferably to have an absorption maximum wavelength (λ _MAX ) in a wavelength range of 380 to 680 nm. As a dichroic dye, iodine and a dichroic organic dye are mentioned, for example. As a dichroic organic dye, an acridine dye, an oxazine dye, a cyanine dye, a naphthalene dye, an azo dye, and an anthraquinone dye are mentioned, for example. Among these dichroic organic dyes, an azo dye is preferable. As an azo dye, a monoazo dye, a bis azo dye, a tris azo dye, a tetrakis azo dye, and a stilbenazo dye are mentioned, for example. Among these azo dyes, preferred are bis azo dyes and tris azo dyes. Dichroic organic dyes may be used singly or in combination of two or more, but in order to obtain absorption in the entire visible light, it is preferable to use three or more dichroic dyes in combination. It is more preferable to use the above azo dyes in combination. It is preferable that the polyvinyl alcohol-based resin film is subjected to immersion treatment in water before dyeing treatment.

As an azo dye, the compound represented by Formula (I) is mentioned, for example.

T ¹ -A ¹ (-N=NA ² ) _p -N=NA ³ -T ² (I)

[In formula (I),

A ¹ , A ² , and A ³ each independently represent a 1,4-phenylene group which may have a substituent, a naphthalene-1,4-diyl group, or a divalent heterocyclic group which may have a substituent, and T ^{Each of 1} and T ² independently represents an electron withdrawing group or an electron emitter, and has a position of substantially 180° with respect to the azo bonding surface. p represents the integer of 0-4. When p represents an integer of 2 or more, a plurality of A ² may be the same or different. The -N=N- bond may be substituted with a -C=C- bond, -COO- bond, -NHCO- bond, or -N=CH- bond in the range in which the azo dye absorbs in the visible region.]

Examples of the substituents which A ¹ , A ² , and A ³ represent 1,4-phenylene group, naphthalene-1,4-diyl group, and divalent heterocyclic group optionally include, for example, methyl group, ethyl group, and butyl group. An alkyl group having the same carbon number of 1 to 4; Alkoxy groups having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group; A C1-C4 fluorinated alkyl group such as a trifluoromethyl group; Cyano group; Nitro group; Halogen atoms such as chlorine atom and fluorine atom; A substituted or unsubstituted amino group such as an amino group, diethylamino group and pyrrolidino group (a substituted amino group is an amino group having 1 or 2 alkyl groups having 1 to 6 carbon atoms, or two substituted alkyl groups bonded to each other to have 2 to 8 carbon atoms. It means an amino group which forms an alkanediyl group of. The unsubstituted amino group is -NH ₂ .) is mentioned. Moreover, as a C1-C6 alkyl group, a methyl group, an ethyl group, and a hexyl group are mentioned, for example. Examples of the alkanediyl group having 2 to 8 carbon atoms include ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5 -Diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, and octane-1,8-diyl group are mentioned. In order to be incorporated in a high-order liquid crystal structure such as Smectic liquid crystal, A ¹ , A ² and A ³ represent a 1,4-phenylene group in which unsubstituted or hydrogen atoms are substituted with a methyl group or a methoxy group, or a divalent heterocyclic group. It is preferable, and it is preferable that p represents an integer of 0-2. Among them, p is 1, and it is more preferable that at least two of the three structures of A ¹ , A ^2, and A ³ are 1,4-phenylene groups in terms of simplicity in molecular synthesis and high performance. .

As a divalent heterocyclic group, for example, two hydrogen atoms are removed from a heterocycle such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzoimidazole, oxazole, and benzoxazole. Can be raised. When A ² represents a divalent heterocyclic group, a structure in which the molecular bonding angle is substantially 180° is preferable, and specifically, a benzothiazole structure in which two five-membered rings are condensed, a benzoimidazole structure, and The benzoxazole structure is more preferable.

T ¹ and T ² each independently represent an electron withdrawing group or an electron emitter, preferably representing an electron withdrawing group or an electron emitter of different structures, T ¹ representing an electron withdrawing group, and T ² representing an electron emitter. The case, or the case where T ¹ represents an electron emitter and T ² represents an electron withdrawing group is more preferable. Specifically, T ¹ and T ² are each independently a C 1 to C 8 alkyl group, a C 1 to C 8 alkoxy group, a cyano group, a nitro group, a substitution having 1 or 2 C 1 to C 6 alkyl groups An amino group, an amino group in which two substituted alkyl groups thereof are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms, and a trifluoromethyl group are preferable. Among them, in order to be contained in a high-order liquid crystal structure such as a smectic liquid crystal, a structure having a smaller exclusion volume of molecules is required. A substituted amino group having one or two alkyl groups of from 6 to 6, and an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms are preferable.

As such azo dye, an azo dye represented by the following formulas (2-1) to (2-8) is mentioned, for example.

[Formula 17]

[Formula 18]

In formulas (2-1) to (2-8),

B ¹ to B ³⁰ are each independently a hydrogen atom, a C 1 to C 6 alkyl group, a C 1 to C 6 alkoxy group, a cyano group, a nitro group, a substituted or unsubstituted amino group (definition of a substituted amino group and an unsubstituted amino group Is the same as above), a chlorine atom, or a trifluoromethyl group.

In addition, from the viewpoint of obtaining high polarization performance when combined with Smectic liquid crystal, B ² , B ⁶ , B ⁹ , B ¹⁴ , B ¹⁸ , B ¹⁹ , B ²² , B ²³ , B ²⁴ , B ²⁷ , B ²⁸ , And B ²⁹ each independently represent a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

Each of n1 to n4 independently represents the integer of 0 to 2.

When n1 represents 2, a plurality of B ² may be the same as or different from each other,

When n2 represents 2, a plurality of B ⁶ may be the same as or different from each other,

When n3 represents 2, a plurality of B ⁹ may be the same as or different from each other,

When n4 represents 2, a plurality of B ¹⁴ may be the same as or different from each other.

As the anthraquinone dye, a compound represented by formula (2-9) is preferable.

[Formula 19]

[In formula (2-9),

Each of R ¹ to R ⁸ independently represents a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x , or a halogen atom.

R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.]

As the oxazine dye, a compound represented by formula (2-10) is preferable.

[Formula 20]

[In formula (2-10),

Each of R ⁹ to R ¹⁵ independently represents a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x , or a halogen atom.

R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.]

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

[Formula 21]

[In formula (2-11),

R ¹⁶ to R ²³ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x , or a halogen atom.

R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.]

In formulas (2-9), (2-10), and (2-11), examples of the alkyl group having 1 to 4 carbon atoms represented by R ^x include methyl group, ethyl group, propyl group, butyl group, pen And a tyl group and a hexyl group. In formulas (2-9), (2-10) and (2-11), examples of the aryl group having 6 to 12 carbon atoms represented by R ^x include phenyl group, toluyl group, xylyl group, and naphe. Tilc is mentioned.

As the cyanine dye, a compound represented by formula (2-12) and a compound represented by formula (2-13) are preferred.

[Formula 22]

[In formula (2-12),

D ¹ and D ² each independently represent a group represented by any one of formulas (2-12a) to (2-12d).

[Formula 23]

n5 represents the integer of 1-3.]

[Formula 24]

[In formula (2-13),

D ³ and D ⁴ each independently represent a group represented by any of formulas (2-13a) to (2-13h).

[Formula 25]

n6 represents the integer of 1-3.]

The content of the dichroic organic dye (in the case of containing a plurality of types, the total amount) is usually 0.1 to 30 parts by mass, preferably based on 100 parts by mass of the polymerizable liquid crystal compound (B) from the viewpoint of obtaining good light absorption characteristics. Is 1 to 20 parts by mass, more preferably 3 to 15 parts by mass. When the content of the dichroic organic dye is 0.1 parts by mass or more with respect to 100 parts by mass of the polymerizable liquid crystal compound (B), light absorption of the dichroic organic dye becomes sufficient, and sufficient polarization performance tends to be obtained. When 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 orientation of the polymerizable liquid crystal compound is hardly inhibited.

(Stretched film with dichroic dye adsorbed)

A transparent protective film may be provided on at least one of the stretched films to which the dichroic dye was adsorbed. A film comprising a stretched film to which a dichroic dye is adsorbed as a polarizer is usually a step of uniaxially stretching a polyvinyl alcohol-based resin film, and the dichroic dye is adsorbed by dyeing a polyvinyl alcohol-based resin film with a dichroic dye. Transparency protection by interposing an adhesive on at least one side of the polarizer manufactured through the process of preparing, treating the polyvinyl alcohol-based resin film adsorbed with a dichroic dye with an aqueous boric acid solution, and washing with water after treatment with an aqueous boric acid solution It is produced by sandwiching it with a film.

Polyvinyl alcohol-based resin is obtained by saponifying a polyvinyl acetate-based resin. As the polyvinyl acetate resin, for example, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and another monomer copolymerizable therewith is used.

Other monomers copolymerizable with vinyl acetate include, for example, unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

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

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

The uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before, simultaneously with, or after dyeing with a dichroic dye. When uniaxial stretching is performed after dyeing, this uniaxial stretching may be performed before boric acid treatment or during boric acid treatment. In addition, it is also possible to uniaxially stretch in a plurality of these steps. At the time of uniaxial stretching, it may be stretched uniaxially between rolls having different circumferential speeds, or uniaxially stretched using a hot roll. Further, uniaxial stretching may be dry stretching performed in the air, or wet stretching performed in a state in which the polyvinyl alcohol-based resin film is swollen using a solvent. The draw ratio is usually about 3 to 8 times.

Dyeing of a polyvinyl alcohol-based resin film with a dichroic dye is performed, for example, by a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a dichroic dye.

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

On the other hand, when a dichroic organic dye is used as the dichroic dye, a method of dyeing by immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye is usually employed.

The content of the dichroic organic dye in this aqueous solution is, per 100 parts by mass of water, usually about 1 × 10 ^-4 to 10 parts by mass, preferably 1 × 10 ^-3 to 1 part by mass, more preferably It is 1 × 10 ^-3 to 1 × 10 ^-2 parts by mass. This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing aid. The temperature of the dichroic dye aqueous solution used for dyeing is usually about 20 to 80°C. Moreover, the immersion time (dyeing time) in this aqueous solution is usually about 10 to 1,800 seconds.

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

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

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

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

<Organic EL display device>

An organic EL display device includes the above 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 through an adhesive is mentioned.

Example

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

[Preparation of liquid crystal compound]

The liquid crystal compound A was prepared according to the method described in JP 2010-31223 A. Moreover, liquid crystal compound B was manufactured according to the method described in Japanese Unexamined-Japanese-Patent No. 2009-173893.

Below, the molecular structures of liquid crystal compound A and liquid crystal compound B are shown, respectively.

(Liquid Crystal Compound A)

(Liquid Crystal Compound B)

[How to measure]

(Calculation method of ratio of maximum absorption wavelength and maximum absorbance)

A 1 mg/50 mL tetrahydrofuran solution of liquid crystal compound A was prepared, and it was set as a sample for measurement. A measurement sample was placed in a measurement cell having 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 reference was used only as the solvent of the sample for measurement. From the obtained absorption spectrum, the wavelength used as the maximum absorption was read, and this was taken as the maximum absorption wavelength λ _max . Further, from the obtained absorption spectrum, the maximum absorption wavelength of the liquid crystal compound A in a region of 260 nm or more and 400 nm or less was read. In addition, when a plurality of maximum absorption wavelengths exist in a region of 260 nm or more and 400 nm or less, the wavelength having the highest absorbance among the plurality of maximum absorption wavelengths was set to λ _max . Table 1 shows the obtained maximum absorption wavelength.

[Preparation of ionic compounds]

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

(Ionic compound (1))

(Ionic compound (2))

(Ionic compound (3))

<Example 1>

[Preparation of composition for vertically aligned liquid crystal cured film formation (A-1)]

The liquid crystal compound A and the liquid crystal compound B were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the obtained mixture, 1.5 parts by mass of a leveling agent ("F-556" manufactured by DIC) and 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane- as a photoinitiator 6 parts by mass of 1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan) were added. Moreover, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine ("KBE-9103" manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane compound was 0.5%, so that the ionic compound (1 ) Was further added so as to be 2.0%.

N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%.

By stirring at 80°C for 1 hour, the vertically aligned liquid crystal cured film-forming composition (A-1) (hereinafter, it may be described as a composition (A-1)) was obtained. In addition, it was confirmed that the silane compound ("KBE-9103" manufactured by Shin-Etsu Chemical Co., Ltd.) reacted with a solvent or moisture in the environment in the composition (A-1) to proceed with hydrolysis, thereby generating an amino group as a polar group.

[Production method of vertically aligned liquid crystal cured film (A-1)]

Using a corona treatment apparatus ("AGF-B10" manufactured by Kasuga Electric Corporation), an amorphous cycloolefin polymer film (COP film) as a base material (Nippon Xeon Co., Ltd.``ZF-14-23'') was treated with an output of 0.3 kW. Corona treatment was carried out once under conditions of a speed of 3 m/min. Using a bar coater, the composition (A-1) was applied to the surface of the substrate subjected to corona treatment to form a coating film. The coating film was dried at 120° C. for 1 minute to form a dry film. Next, using a high-pressure mercury lamp ("Unicure VB-15201BY-A" manufactured by Ushio Electric Co., Ltd.), the dried film was irradiated with ultraviolet rays under a nitrogen atmosphere and conditions of an accumulated light amount of 500 mJ/cm 2 in a wavelength of 365 nm. . As a result, a vertically aligned liquid crystal cured film (A-1) (film thickness: 1.0 µm) was formed.

[Optical properties of vertically aligned liquid crystal cured film (A-1)]

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

(Measurement of phase difference value)

ZF-14-23 as a base material was an optically isotropic film having a retardation value of 1 nm or less at a wavelength of 550 nm, and it was confirmed that no influence was observed on the measured value of the sample for measuring optical properties. Subsequently, the phase difference value was measured by changing the incident angle of light to the sample for measuring optical properties using a measuring device ("KOBRA-WPR" manufactured by Oji Measurement Corporation).

(Measurement of average refractive index)

The average refractive index in wavelength λ = 450 nm and 550 nm was measured using a refractometer ("Multi-wavelength Abbe refractometer DR-M4" manufactured by Atago Corporation). The obtained film thickness, the average refractive index, and the Rth calculated from the measurement result of the measuring instrument ("KOBRA-WPR" manufactured by Oji Measuring Instruments Co., Ltd.) are respectively Rth(450) = -60 nm and Rth(550) = -70 nm, Rth(450)/Rth(550) = 0.85.

(Evaluation of orientation of orientation liquid crystal cured film)

Using a polarization microscope ("BX-51" manufactured by Olympus Corporation), it observed under conditions of 200 times magnification, and the number of orientation defects in a field of view of 480 µm x 320 µm was counted. Here, only the number of orientation defects caused by the measurement sample was counted, and the number of defects caused by environmental foreign matters other than the optical characteristic sample was not counted. From the observation result with a polarizing microscope, the orientation of the vertically aligned liquid crystal cured film (A-1) was evaluated based on the following evaluation criteria. It was judged that A and B and C were excellent in orientation. As shown in Table 1, the orientation of the vertically aligned liquid crystal cured film (A-1) produced from the composition (A-1) was A.

(Evaluation standard)

A (very good): The number of orientation defects is 0 or more and 3 or less.

B (very good): The number of orientation defects is 4 or more and 10 or less.

C (good): The number of orientation defects is 11 or more and 50 or less.

D (bad): 51 or more orientation defects, or no orientation at all.

<Examples 2 to 9 and Example 20, Example 21, Comparative Example 1>

Except for changing the substrate of Example 1, 0.5% of the silane compound, and 2 parts of the ionic compound (2) to the type of the substrate shown in Table 1, the type and amount of the silane compound, and the type and amount of the ionic compound. In the same manner as in the preparation method of the composition (A-1) of Example 1, the compositions (A-2) to (A-9), (A) of Examples 2 to 9, Example 20, Example 21, and Comparative Example 1 -20), (A-21), and (B-1) were each prepared. By changing the composition (A-1) to the compositions (A-2) to (A-9), (A-20), (A-21), and (B-1), by changing the film thickness of the coating film Except having changed so that it might become the retardation value shown in Table 1, it carried out similarly to the manufacturing method of the vertically aligned liquid crystal cured film (A-1) of Example 1, and Examples 2-9, Examples 20, Example 21, and Vertically aligned liquid crystal cured films (A-2) of Comparative Example 1 to (A-9), (A-20), (A-21), and (B-1) were produced, respectively. Further, in the same manner as in Example 1, a sample for measuring optical properties was prepared, and the retardation value, average refractive index, and orientation were evaluated. Table 1 shows the results.

<Example 10>

The substrate was changed from a COP film ("ZF-14-23" manufactured by Nippon Xeon Co., Ltd.) to polyethylene terephthalate with a protective layer (hereinafter sometimes referred to as PET with a protective layer), and when measuring optical properties In the same manner as in the preparation method of the vertically aligned liquid crystal cured film (A-1) of Example 1, except that the PET substrate was peeled off to prepare a sample, a vertically aligned liquid crystal cured film (A-10) was prepared. Further, in the same manner as in Example 1, a sample for measuring optical properties was prepared, and the retardation value, average refractive index, and orientation were evaluated. Table 1 shows the results. Hereinafter, a method of preparing PET with a protective layer will be described.

[Preparation of the composition for forming a protective layer]

50 parts of dipentaerythritol hexaacrylate ("Aronix (registered trademark) M-403" polyfunctional acrylate) manufactured by Dong-A Synthetic Co., Ltd.) and 50 parts of acrylate resin ("Evecryl 4858" manufactured by Daicel Yushibi Corporation) Wow, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one (Chiba Specialty Chemicals "Irgacure (registered trademark) 907") 3 parts to 250 parts of isopropanol It was dissolved and a solution was prepared. The obtained solution was used as a composition for forming a protective layer.

[Production of PET with protective layer]

Using a bar coater, the composition for forming a protective layer was applied onto a PET film (38 µm in thickness) to form a coating film. The coating film was dried at 50° C. for 1 minute to form a dry film. Using a high-pressure mercury lamp ("Unicure VB-15201BY-A" manufactured by Ushio Electric Co., Ltd.), ultraviolet rays were irradiated to the dry film under a nitrogen atmosphere and conditions of a cumulative amount of light of 400 mJ/cm 2 at a wavelength of 365 nm. As a result, PET with a protective layer made of acrylic resin was formed. In addition, according to the optical property measurement method described in Example 1, after bonding to glass through a pressure-sensitive adhesive and peeling off the PET film, the retardation value at the wavelength of 550 nm of the protective layer was measured to be 1 nm or less. It confirmed that it was an isotropic film. Moreover, it was 2 micrometers when the film thickness of the formed protective layer was measured with an ellipsometer.

<Example 11>

Composition (A-1) of Example 1 and vertical alignment except having changed the composition of the liquid crystal compound of Example 1 from liquid crystal compound A/liquid crystal compound B = 90%/10% to 100% of liquid crystal compound (A)-2 It carried out similarly to the preparation method of a liquid crystal cured film (A-1), and produced the composition (A-11) of Example 11 and a vertically aligned liquid crystal cured film (A-11), respectively. The liquid crystal compound (A)-2 was prepared with reference to Japanese Patent Laid-Open No. 2016-81035. Liquid crystal compound (A)-2 is represented by following formula (A)-2. Further, in the same manner as in Example 1, a sample for measurement was prepared, and the retardation value, average refractive index, and orientation were evaluated. In addition, the ratio of the maximum absorption wavelength and the maximum absorbance of the liquid crystal compound (A)-2 was also calculated in the same manner as in Example 1. Table 1 shows the results.

<Example 12>

Composition (A-1) of Example 1 and vertical alignment except having changed the composition of the liquid crystal compound of Example 1 from liquid crystal compound A/liquid crystal compound B = 90%/10% to 100% of liquid crystal compound (A)-3 It carried out similarly to the preparation method of the liquid crystal cured film (A-1), and produced the composition (A-12) of Example 12 and the vertically aligned liquid crystal cured film (A-12), respectively. Liquid crystal compound (A)-3 was prepared with reference to International Patent Publication No. 2015/025793. Liquid crystal compound (A)-3 is represented by following formula (A)-3. Further, in the same manner as in Example 1, a sample for measuring optical properties was prepared, and the retardation value, average refractive index, and orientation were evaluated. In addition, the ratio of the maximum absorption wavelength and the maximum absorbance of the liquid crystal compound (A)-3 was also calculated in the same manner as in Example 1. Table 1 shows the results.

<Example 13>

Composition (A-1) of Example 1 and vertical alignment except having changed the composition of the liquid crystal compound of Example 1 from liquid crystal compound A/liquid crystal compound B = 90%/10% to 100% of liquid crystal compound (A)-4 It carried out similarly to the preparation method of the liquid crystal cured film (A-1), and produced the composition (A-13) of Example 11 and the vertically aligned liquid crystal cured film (A-13), respectively. The liquid crystal compound (A)-4 was prepared by referring to JP2011-207765A. Liquid crystal compound (A)-4 is represented by following formula (A)-4. Further, in the same manner as in Example 1, a sample for measuring optical properties was prepared, and the retardation value, average refractive index, and orientation were evaluated. In addition, the ratio of the maximum absorption wavelength and the maximum absorbance of the liquid crystal compound (A)-4 was also calculated in the same manner as in Example 1. Table 1 shows the results.

<Example 14>

Composition (A-1) of Example 1 and vertical alignment except having changed the composition of the liquid crystal compound of Example 1 from liquid crystal compound A/liquid crystal compound B = 90%/10% to 100% of liquid crystal compound (A)-5 It carried out similarly to the preparation method of a liquid crystal cured film (A-1), and produced the composition (A-14) of Example 14 and a vertically aligned liquid crystal cured film (A-14), respectively. The liquid crystal compound (A)-5 was prepared with reference to JP 2010-31223 A. Liquid crystal compound (A)-5 is represented by following formula (A)-5. Further, in the same manner as in Example 1, a sample for measuring optical properties was prepared, and the retardation value, average refractive index, and orientation were evaluated. In addition, the ratio of the maximum absorption wavelength and the maximum absorbance of the liquid crystal compound (A)-5 was also calculated in the same manner as in Example 1. Table 1 shows the results.

<Example 15>

The silane compound of Example 1 was prepared from 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine (Shin-Etsu Chemical Co., Ltd. "KBE-9103") to 3-glycidoxypropyltrie. Except having changed to oxysilane (the Shin-Etsu Chemical Co., Ltd. product "KBE-403", it carried out similarly to the preparation method of the composition (A-1) of Example 1 and the vertically aligned liquid crystal cured film (A-1), respectively, and carried out. The composition (A-15) and the vertically aligned liquid crystal cured film (A-15) of Example 15 were produced. Further, in the same manner as in Example 1, a sample for measuring optical properties was prepared, and a retardation value, an average refractive index, and an orientation property The results are shown in Table 1.

<Example 16>

[Production of polarizing film A]

After immersing a polyvinyl alcohol film (average degree of polymerization of about 2,400, degree of saponification of 99.9 mol% or more, thickness of 75 μm) in pure water at 30° C., in an aqueous solution having a mass ratio of iodine/potassium iodide/water of 0.02/2/100 at 30° C. Iodine dyeing was performed by immersing in (iodine dyeing process). The polyvinyl alcohol film subjected to the iodine dyeing step was immersed in an aqueous solution having a mass ratio of potassium iodide/boric acid/water of 12/5/100 at 56.5°C to perform boric acid treatment (boric acid treatment step). After washing the polyvinyl alcohol film which passed through the boric acid treatment process with 8 degreeC pure water, it dried at 65 degreeC, and the polarizer (27 micrometers in thickness after extending|stretching) in which iodine is adsorbed and oriented to polyvinyl alcohol was obtained. At this time, stretching was performed in an iodine dyeing process and a boric acid treatment process. The total draw ratio in such stretching was 5.3 times. The obtained polarizer and the saponified triacetylcellulose film ("KC4UYTAC" by Konica Minolta 40 µm) were bonded together with a nip roll via a water-based adhesive. It dried at 60 degreeC for 2 minutes, maintaining the tension|tensile_strength of the obtained bonding material at 430 N/m, and obtained the polarizing film which has a triacetyl cellulose film as a protective film on one side. In addition, the water-based adhesive is 100 parts of water, 3 parts of carboxyl group-modified polyvinyl alcohol (``Kuraray Poval KL318'' manufactured by Kuraray), and a water-soluble polyamide epoxy resin (``Sumirez Resin 650'' manufactured by Sumica Chemtex, solid content concentration) It prepared by adding 1.5 parts of 30% aqueous solution).

[Measurement of optical properties of polarizing film A]

Optical properties were measured about the obtained polarizing film A. The measurement was performed with a spectrophotometer ("V7100" manufactured by Nippon Spectroscopy) using the polarizer surface of the polarizing film A obtained above as the incident surface. The absorption axis of the polarizing film coincided with the stretching direction of the polyvinyl alcohol, and the luminous sensitivity corrected single transmittance of the obtained polarizing film was 42.1%, the luminous intensity corrected polarization degree was 99.996%, the single color a was -1.1, and the single color b was 3.7.

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

A composition for horizontal alignment film formation was obtained by mixing 5 parts of the photoalignable material (weight average molecular weight: 30000) of the following structure and 95 parts of cyclopentanone as a solvent, and stirring the obtained mixture at 80 degreeC for 1 hour.

[Preparation of composition for forming horizontally aligned liquid crystal cured film A]

The liquid crystal compound A and the liquid crystal compound B were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the obtained mixture, 1.0 part of a leveling agent ("F-556" manufactured by DIC) and 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1-as a polymerization initiator On (BASF Japan Co., Ltd. "Irgacure (registered trademark) 369 (Irg369)") 6 parts were added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. The composition for horizontal alignment liquid crystal cured film A formation was obtained by stirring at 80 degreeC for 1 hour.

[Production of horizontally aligned liquid crystal cured film A]

Corona treatment was performed on a COP film ("ZF-14-50" manufactured by Nippon Xeon Corporation). Thereafter, a composition for forming a horizontal alignment film was applied using a bar coater to form a coating film. The coating film was dried at 80°C for 1 minute to form a dry film. Using a polarized UV irradiation device ("SPOT CURE SP-9" manufactured by Ushio Electric Co., Ltd.), polarized UV exposure was performed under conditions of an integrated light amount of 100 mJ/cm 2 and an axis angle of 45° at a wavelength of 313 nm to form a horizontal alignment film. Got it. When the film thickness of the obtained horizontal alignment film was measured with an ellipsometer, it was 100 nm.

Subsequently, the composition for horizontal alignment liquid crystal cured film A formation was applied to the horizontal alignment film using a bar coater to form a coating film. The coating film was dried at 120° C. for 1 minute to form a dry film. Using a high-pressure mercury lamp ("Unicure VB-15201BY-A" manufactured by Ushio Electric Co., Ltd.), under a nitrogen atmosphere and conditions of a cumulative amount of light of 500 mJ/cm 2 in a wavelength of 365 nm, by irradiating the dried film with ultraviolet rays, horizontal An aligned liquid crystal cured film A was formed. A laminate comprising a substrate, a horizontal alignment film, and a horizontal alignment liquid crystal cured film A was obtained. When the film thickness of the horizontally aligned liquid crystal cured film A was measured with an ellipsometer, it was 2.3 µm.

[Re measurement of horizontally aligned liquid crystal cured film A]

After the laminate was bonded to the glass through an adhesive, the COP film as the substrate was peeled off.

Thereby, the horizontally aligned liquid crystal cured film A for Re measurement was obtained. The in-plane retardation value ReA(λ) of the horizontally aligned liquid crystal cured film A was measured using a measuring device ("KOBRA-WPR" manufactured by Oji Measuring Equipment Co., Ltd.). The measurement result of the retardation value ReA(λ) at each wavelength (450 nm, 550 nm, and 650 nm) is ReA(450) = 121 nm, ReA(550) = 142 nm, ReA(650) = 146 nm , And ReA(450)/ReA(550) = 0.85.

[Measurement of R0 and R40 of a laminate comprising a horizontally aligned liquid crystal cured film A and a vertically aligned liquid crystal cured film]

The horizontally aligned liquid crystal cured film A prepared by the above method and the vertically aligned liquid crystal cured film (A-1) prepared by the method of Example 1 were bonded through an adhesive (pressure-sensitive adhesive 15 μm manufactured by Lintec Co., Ltd.), and horizontally aligned A laminate comprising the liquid crystal cured film A and the vertically aligned liquid crystal cured film (A-1) was produced.

Moreover, one COP film used as a base material was peeled from the same laminated body, and it bonded with glass through an adhesive, and the laminated body for phase difference value measurement was obtained. After confirming that there is no retardation in the COP film and the horizontal alignment film, the retardation value R0 (λ) in the front direction of the layered product for measuring the retardation value and the fast axis of the horizontally aligned liquid crystal cured film A are inclined by 40°. The retardation value R40(λ) (λ = 450 nm and 550 nm) was measured using a measuring instrument ("KOBRA-WPR" manufactured by Oji Measuring Instruments Co., Ltd.). Table 2 shows the measurement results. From the obtained values of R0(λ) and R40(λ) (λ = 450 nm and 550 nm), ｜R0(550)-R40(550)｜, ｜R0(450)-R40(450)｜, and ｜(R0 (450)-R40(450)}-{R0(550)-R40(550)}| was calculated. Table 3 shows the results.

〔Evaluation of all-reflective color〕

The layered product produced by the above method (a layered product including a horizontally aligned liquid crystal cured film A and a vertically aligned liquid crystal cured film (A-1)) and a polarizing film A, the absorption axis of the polarizing film A and the horizontally aligned liquid crystal cured film A It was bonded through an adhesive so that the angle formed by the slow axis of was 45°, and the base material was peeled to prepare an elliptically polarizing plate with an optical compensation function. Thereafter, it was bonded to the aluminum foil through the pressure-sensitive adhesive, and the oblique reflection color of the elliptically polarizing plate was visually observed from the direction of elevation angle of 45° and azimuth angle of 0 to 360°. From the observation result with the naked eye, the four-way reflection color was evaluated based on the following evaluation criteria. Table 3 shows the results.

(Evaluation standard)

A (Good): Black is seen with the naked eye.

B (bad): Clear coloration is observed with the naked eye.

<Examples 17 and 18>

In the same manner as in Example 16, except that the values of RthC (450) and RthC (550) were changed as described in Table 2 by changing the film thickness of the vertically aligned liquid crystal cured film, the phase difference value was measured and the oblique reflection color was checked in the same manner as in Example 16. I did. The results are shown in Tables 2 and 3.

<Example 19>

Measurement of the retardation value in the same manner as in Example 16, except that the polarizing film A was changed to a horizontally aligned liquid crystal cured film B and a polarizing film B containing a dichroic dye aligned in the horizontal direction produced by the method shown below, And evaluation of the color of the four-way reflection. The results are shown in Tables 2 and 3.

[Preparation of composition for forming polarizing film B]

The following components were mixed and stirred at 80° C. for 1 hour to obtain a composition for forming a polarizing film B containing a polymerizable liquid crystal compound (B) and a dichroic dye. As the dichroic dye, the azo dye described in Examples of JP 2013-101328 A was used. The polymerizable liquid crystal compounds represented by formulas (1-6) and (1-7) as the polymerizable liquid crystal compound (B) are described in lub et al., Recl. Trav. Chim. It was prepared according to the method described in Pays-Bas, 115, 321-328 (1996).

Polymerizable liquid crystal compound (B):

Dichroic Pigment 1:

Polyazo dyes; 2.5 parts of compound (1-8)

2.5 parts of compound (1-5)

2.5 parts of compound (1-16)

Polymerization initiator;

2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by Chiba Specialty Chemicals) 6 parts

Leveling agent;

1.2 parts of polyacrylate compound ("BYK-361N" manufactured by BYK-Chemie)

Solvent; o-xylene 250 parts

[Production of polarizing film B]

(Preparation of horizontal alignment film)

Corona treatment was performed on the triacetyl cellulose film (TAC) ("KC4UY" manufactured by Konica Minolta). Next, the composition for horizontal alignment film formation was applied to the corona-treated TAC surface using a bar coater to form a coating film. The coating film was dried at 80°C for 1 minute to form a dry film. Using a polarized UV irradiation apparatus ("SPOT CURE SP-7" manufactured by Ushio Electric Co., Ltd.), polarized UV exposure was performed on the dried film under conditions of an accumulated light amount of 100 mJ/cm 2 and an axial angle of 90° to obtain a horizontal alignment film. When the film thickness of the obtained horizontal alignment film was measured with an ellipsometer, it was 150 nm.

(Production of horizontally aligned liquid crystal cured film B)

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

[Measurement of polarization degree of polarizing film B and single transmittance]

The polarization degree of the obtained polarizing film B and the single transmittance were measured as follows. The transmittance in the direction of the transmission axis (T ¹ ) and the transmittance in the direction of the absorption axis (T ² ) were measured using a device in which a folder with a polarizer attached to a spectrophotometer (``UV-3150'' manufactured by Shimadzu Corporation) was used, and a double beam method was used. It measured in the wavelength range of 380-680 nm by 2 nm step. Using the following formulas (p) and (q), the single transmittance and the degree of polarization at each wavelength were calculated. In addition, the luminous sensitivity was corrected according to the 2-degree field of view (C light source) of Japanese Industrial Standard JIS Z 8701, and the luminous intensity corrected single transmittance (Ty) and the luminous intensity corrected polarization degree (Py) were calculated. The degree of polarization was 97%, and it confirmed that it was a useful value as a polarizing film.

^Single transmittance (%) = (T ¹ + T ² )/2...(p)

Polarization degree (%) = {(T ¹ -T ² )/(T ¹ + T ² )} × 100...(q)

<Comparative Example 2>

Except having produced the vertical alignment film and the vertically aligned liquid crystal cured film shown below, a sample was produced in the same manner as in Example 16, and the phase difference value was measured and the oblique reflection hue was evaluated. The results are shown in Tables 2 and 3.

(Preparation of composition (B) for vertical alignment film formation)

0.5% of polyimide (Nissan Chemical Industry Co., Ltd. "Sunever SE-610"), 72.3% of N-methyl-2-pyrrolidone, 18.1% of 2-butoxyethanol, 9.1% of ethylcyclohexane, and 0.01% of DPHA (manufactured by Shin-Nakamura Chemical) was mixed to prepare a vertical alignment film-forming composition (B).

(Preparation of composition (B) for vertically aligned liquid crystal cured film formation)

Liquid crystal compound LC242 represented by the following formula (LC242): 0.1 part of a leveling agent ("F-556" manufactured by DIC) and 3 parts of a polymerization initiator Irg369 were added to PaliocolorLC242 (registered trademark by BASF), and the solid content concentration was 13% Cyclopentanone was added so that it might become, and these were mixed, and the composition for vertical alignment liquid crystal cured film formation (B) was obtained.

Liquid crystal compound LC242: PaliocolorLC242 (registered trademark of BASF)

(Preparation of vertically aligned liquid crystal cured film)

Corona treatment was performed on the COP film (Nippon Xeon Co., Ltd. "ZF-14-23") as a substrate. Using a bar coater, the composition (B) for vertical alignment film formation was applied to the COP film subjected to corona treatment using a bar coater to form a coating film. The coating film was dried at 80°C for 1 minute to obtain a vertical alignment film. When the film thickness of the obtained vertical alignment film was measured with an ellipsometer, it was 0.2 micrometer. Subsequently, the composition (B) for vertical alignment liquid crystal cured film formation was applied on the produced vertical alignment film, and a coating film was formed. The coating film was dried at 80° C. for 1 minute to form a dry film. After that, using a high-pressure mercury lamp (Ushio Electric Co., Ltd. "Unicure VB-15201BY-A"), the dried film is irradiated with ultraviolet rays under a nitrogen atmosphere and conditions of a cumulative amount of light of 500 mJ/cm 2 at a wavelength of 365 nm. Thus, a vertically aligned liquid crystal cured film was formed. The film thickness of the obtained vertically aligned liquid crystal cured film was 0.5 µm.

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

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

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

From the above, the vertically aligned liquid crystal cured films (A-1) to (A-15), (A-20), and (A-21) of Examples 1 to 15 are the alignment liquid crystal cured films (B Compared with -1), it is clear that orientation is excellent.

The elliptically polarizing plates of Examples 16-19 contained a vertically aligned liquid crystal cured film, a horizontal alignment film, a horizontally aligned liquid crystal cured film A, and a polarizing film produced using the composition (A-1). All the four-way reflection hues of the elliptically polarizing plates of Examples 16 to 19 were A.

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

From the above, it is clear that the elliptically polarizing plates of Examples 16 to 19 are superior to the elliptically polarizing plates of Comparative Example 2 in a four-way reflection color.

1: description
3: horizontal alignment layer
5: horizontally aligned liquid crystal cured film A
7: adhesive layer
9: vertically aligned liquid crystal cured film
11: polarizing film
13: protective layer
15: laminate
20: elliptically polarizing plate

Claims (21)

A vertically aligned liquid crystal cured film oriented in a direction perpendicular to the in-plane direction, and comprising at least one selected from the group consisting of a nonionic silane compound and an ionic compound. The method of claim 1,
The vertically aligned liquid crystal cured film, wherein the nonionic silane compound is a silane coupling agent. The method according to claim 1 or 2,
The vertically aligned liquid crystal cured film, wherein the nonionic silane compound is a silane coupling agent having an alkoxysilyl group and a polar group. The method according to any one of claims 1 to 3,
The vertically aligned liquid crystal cured film, wherein all of the elements constituting the ionic compound are non-metallic elements. The method according to any one of claims 1 to 4,
A vertically aligned liquid crystal cured film having a molecular weight of 100 or more and 10000 or less of the ionic compound. The method according to any one of claims 1 to 5,
The following relational formula (1):
-150 nm ≤ RthC(550) ≤ -30 nm...(1)
[In relational formula (1), RthC(550) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm]
A vertically aligned liquid crystal cured film satisfying. The method according to any one of claims 1 to 6,
The following relational formula (2):
RthC(450)/RthC(550) ≤ 1...(2)
[In the relational formula (2), RthC(450) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and RthC(550) is the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. Represents the phase difference value]
A vertically aligned liquid crystal cured film satisfying. Equipped with a substrate and the vertically aligned liquid crystal cured film according to any one of claims 1 to 7,
A laminate in which the vertically oriented cured film is adjacent to the substrate. A laminate comprising the vertically aligned liquid crystal cured film according to claim 1, and a film oriented horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film. The method of claim 9,
The following relational equation (3):
ReA(450)/ReA(550) ≤ 1.00...(3)
[In the relational formula (3), ReA(450) represents the in-plane retardation value at a wavelength of 450 nm of the film oriented horizontally with respect to the in-plane direction of the vertically aligned liquid crystal cured film, and ReA(550) is the vertically aligned liquid crystal The in-plane retardation value at a wavelength of 550 nm of the film oriented horizontally with respect to the film surface of the cured film is shown.]
To satisfy the laminate. The method of claim 9 or 10,
The following relational equation (4):
｜R0(550)-R40(550)｜ ≤ 10 nm···(4)
[In the relational formula (4), R0(550) represents the in-plane retardation value of the laminate at a wavelength of 550 nm, and R40(550) is 40 around the fast axis direction of the film oriented in the horizontal direction of the laminate. Denotes a retardation value at a wavelength of 550 nm when rotated.]
To satisfy the laminate. The method according to any one of claims 9 to 11,
The following relational formula (5):
｜R0(450)-R40(450)｜ ≤ 10 nm...(5)
[In the relational formula (5), R0(450) represents the in-plane retardation value of the laminate at a wavelength of 450 nm, and R40(450) is 40 around the fast axis direction of the film oriented in the horizontal direction of the laminate. The retardation value at a wavelength of 450 nm when rotated is shown.]
To satisfy the laminate. The method according to any one of claims 9 to 12,
The following relational equation (6):
｜{R0(450)-R40(450)}-{R0(550)-R40(550)}｜ ≤ 3 nm···(6)
[In the relational formula (6), R0(450) represents the in-plane retardation value of the laminate at a wavelength of 450 nm, R0(550) represents the in-plane retardation value of the laminate at a wavelength of 550 nm, and R40 (450) represents a retardation value at a wavelength of 450 nm when rotated by 40° around the fast axis direction of the film oriented in the horizontal direction of the laminate, and R40 (550) represents the retardation value in the horizontal direction of the laminate. The retardation value at a wavelength of 550 nm when rotated by 40° around the fast axis direction of the oriented film is shown.]
To satisfy the laminate. The method according to any one of claims 9 to 13,
A laminate in which the film aligned in the horizontal direction with respect to the film surface of the vertically aligned liquid crystal cured film is a horizontally aligned liquid crystal cured film A. An elliptically polarizing plate comprising the laminate according to any one of claims 9 to 14 and a polarizing film. The method of claim 15,
An elliptically polarizing plate wherein the film aligned in the horizontal direction with respect to the film surface of the vertically aligned liquid crystal cured film is a horizontally aligned liquid crystal cured film A. The method of claim 15 or 16,
An angle formed by the slow axis of the horizontally oriented film and the absorption axis of the polarizing film is 45±5°. The method according to any one of claims 15 to 17,
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 contains a dichroic dye. The method of claim 18,
An elliptically polarizing plate in which the dichroic dye has an azo group. The method of claim 18 or 19,
The horizontally aligned liquid crystal cured film B is an elliptically polarizing plate which is a cured film cured in a smectic phase state in which a liquid crystal compound is oriented horizontally with respect to the in-plane direction of the film. An organic EL display device comprising the elliptically polarizing plate according to any one of claims 15 to 20.

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