Light-absorbing anisotropic film, laminate, optical device, and head-mounted display

Abstract

The present invention addresses the problem of providing, for example, a light-absorbing anisotropic film which has a curved surface part and in which the occurrence of unevenness in film thickness and cracking is suppressed. A light-absorbing anisotropic film according to the present invention has a curved surface part, said light-absorbing anisotropic film being obtained by fixing the alignment state of a liquid crystal composition that contains a liquid crystal compound, a dichroic substance, and a compound having a thiol group, wherein the angle θ formed by the transmittance center axis of the light-absorbing anisotropic film and the normal direction of the light-absorbing anisotropic film surface is 0° to 45°.

Description

Optically absorbing anisotropic film, laminate, optical device and head-mounted display

[0001] The present invention relates to an optically absorptive anisotropic film, a laminate, an optical device, and a head-mounted display.

[0002] Image display devices such as liquid crystal display devices and organic electroluminescence (hereinafter abbreviated as "EL") display devices are widely used as displays for smartphones, laptop computers, and the like. In recent years, these devices have become thinner and lighter, making them easier to carry, and as a result, they are increasingly being used in transportation such as trains and airplanes, as well as in public places such as libraries and restaurants. Therefore, due to the need to protect personal information, confidential information, and the like, there is a demand for technology that prevents others from peeking at the content displayed on the image display device.

[0003] For example, Patent Document 1 describes an optical film having a light absorption anisotropic layer in which the angle θ between the transmittance central axis and the normal direction of the layer surface is 0 to 45°, and a color-adjusting layer containing at least one organic dye compound ([Claim 1]), and also indicates that the film has suitability for curved surface processing (

[0253] ).

[0004] International Publication No. 2021 / 246441

[0005] The present inventors have studied the optical film described in Patent Document 1 and have found that providing a curved surface portion in the light absorption anisotropic layer may result in variations in film thickness or the occurrence of cracks, and therefore there is room for improvement in the suitability for curved surface processing.

[0006] Therefore, an object of the present invention is to provide an optically absorptive anisotropic film having a curved surface portion in which film thickness variation and crack occurrence are suppressed, and a laminate, an optical device, and a head-mounted display that include the optically absorptive anisotropic film.

[0007] As a result of intensive research to achieve the above object, the present inventors have found that an optically absorptive anisotropic film obtained by fixing the alignment state of a liquid crystal composition containing a liquid crystal compound, a dichroic substance, and a compound having a thiol group can suppress the occurrence of film thickness variations and cracks, and have completed the present invention. That is, the present inventors have found that the above object can be achieved by the following configuration.

[0008] [1] An optically absorptive anisotropic film having a curved surface, the optically absorptive anisotropic film being a film obtained by fixing the alignment state of a liquid crystal composition containing a liquid crystal compound, a dichroic substance, and a compound having a thiol group, wherein the angle θ between the central axis of transmittance of the optically absorptive anisotropic film and the normal direction to the surface of the optically absorptive anisotropic film is 0° or more and 45° or less. [2] The optically absorptive anisotropic film according to [1], wherein the compound containing a thiol group is a compound having two or more primary or secondary thiol groups per molecule. [3] The optically absorptive anisotropic film according to [1] or [2], wherein at least one of the thiol groups is a secondary thiol group. [4] The optically absorptive anisotropic film according to any one of [1] to [3], wherein the compound containing a thiol group has a thiol equivalent of 200 or less. [5] The optically absorptive anisotropic film according to any one of [1] to [4], wherein the content of the compound having a thiol group is 5 to 15 mass % relative to the total mass of the optically absorptive anisotropic film. [6] The optically absorptive anisotropic film according to any one of [1] to [5], wherein the curved surface shape of the curved surface portion is lenticular. [7] The optically absorptive anisotropic film according to any one of [1] to [6], wherein the minimum radius of curvature of the curved surface portion is 20 to 300 mm. [8] The optically absorptive anisotropic film according to any one of [1] to [7], wherein the dichroic substance is a mixture containing at least a dye compound having an absorption maximum in the wavelength range of 380 nm to less than 455 nm, a dye compound having an absorption maximum in the wavelength range of 455 nm to less than 560 nm, and a dye compound having an absorption maximum in the wavelength range of 560 nm to 700 nm. [9] The optically absorptive anisotropic film according to any one of [1] to [7], wherein the content of the dichroic substance in the optically absorptive anisotropic film is 20 to 650 mg / cm. ３

[10] The optically absorptive anisotropic film according to any one of [1] to [9], wherein the degree of orientation of the optically absorptive anisotropic film at a wavelength of 550 nm is 0.94 or more.

[11] The optically absorptive anisotropic film according to any one of [1] to

[10] , wherein the difference in the degree of orientation of the optically absorptive anisotropic film at wavelengths of 450 nm, 550 nm, and 650 nm is 0.025 or less.

[12] The optically absorptive anisotropic film according to any one of [1] to

[11] , wherein the haze value of the optically absorptive anisotropic film is 0.3% or less.

[13] A laminate comprising the optically absorptive anisotropic film according to any one of [1] to

[12] .

[14] An optical device comprising the optically anisotropic film according to any one of [1] to

[12] and a light guide plate having a diffractive element disposed on the surface.

[15] A head-mounted display comprising the optical device according to

[14] and an image display element.

[0009] According to the present invention, it is possible to provide an optically absorptive anisotropic film having a curved surface portion in which variations in film thickness and the occurrence of cracks are suppressed. Furthermore, according to the present invention, it is possible to provide a laminate, an optical device, and a head-mounted display having the optically absorptive anisotropic film.

[0010] Fig. 1 is a top view showing an example of the optically absorptive anisotropic film of the present invention, and Fig. 2 is a cross-sectional view taken along line AA in Fig. 1.

[0011] The present invention will be described in detail below. The following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the upper and lower limits. In this specification, the upper or lower limit of a numerical range described in stages may be replaced with the upper or lower limit of another numerical range described in stages. In addition, the upper or lower limit of a numerical range described in this specification may be replaced with a value shown in an example.

[0012] In this specification, parallel and perpendicular do not mean parallel and perpendicular in the strict sense, but rather mean a range of parallel ±5° and a range of perpendicular ±5°, respectively.

[0013] In addition, in this specification, for each component, a substance corresponding to the component may be used alone or in combination of two or more. Here, when two or more substances for each component are used in combination, the content of the component refers to the total content of the substances used in combination, unless otherwise specified.

[0014] In addition, in this specification, "(meth)acrylate" is a notation representing "acrylate" or "methacrylate", "(meth)acrylic" is a notation representing "acrylic" or "methacrylic", and "(meth)acryloyl" is a notation representing "acryloyl" or "methacryloyl".

[0015] In this specification, Re(λ) and Rth(λ) represent the in-plane retardation and the thickness direction retardation, respectively, at a wavelength λ. Unless otherwise specified, the wavelength λ is 550 nm. In the present invention, Re(λ) and Rth(λ) are values ​​measured at a wavelength λ using an AxoScan (manufactured by Axometrics). By inputting the average refractive index ((nx + ny + nz) / 3) and film thickness (d (μm)) into AxoScan, the following slow axis direction (°) is calculated: Re(λ) = R0(λ) Rth(λ) = ((nx + ny) / 2 - nz) × d. Note that R0(λ) is displayed as a numerical value calculated by AxoScan, but it means Re(λ).

[0016] In this specification, the refractive indices nx, ny, and nz are measured using an Abbe refractometer (NAR-4T, manufactured by Atago Co., Ltd.) with a sodium lamp (λ = 589 nm) as a light source. Wavelength dependency can be measured using a multi-wavelength Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.) in combination with an interference filter. Values ​​from the Polymer Handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can also be used. Examples of average refractive index values ​​for major optical films are listed below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), and polystyrene (1.59).

[0017] [Lightly absorbing anisotropic film] The lightly absorbing anisotropic film of the present invention is a lightly absorbing anisotropic film having a curved surface. The lightly absorbing anisotropic film of the present invention is a film obtained by fixing the alignment state of a liquid crystal composition containing a liquid crystal compound, a dichroic substance, and a compound having a thiol group. The lightly absorbing anisotropic film of the present invention is a film in which the angle θ between the transmittance central axis of the lightly absorbing anisotropic film and the normal direction to the surface of the lightly absorbing anisotropic film (hereinafter also referred to as "transmittance central axis angle θ") is 0° or more and 45° or less.

[0018] Here, the transmittance central axis of the optically absorbing anisotropic film refers to the direction that exhibits the highest transmittance when the transmittance is measured by changing the tilt angle (polar angle) and tilt direction (azimuth angle) relative to the normal direction of the optically absorbing anisotropic film surface. Specifically, the Mueller matrix at a wavelength of 550 nm is measured using an AxoScan (OPMF-2, manufactured by Axometrics). More specifically, during measurement, the azimuth angle at which the transmittance central axis is tilted is first found, and then, within a plane containing the normal direction of the optically absorbing anisotropic film along that azimuth angle (a plane containing the transmittance central axis and perpendicular to the film surface), the polar angle, which is the angle relative to the normal direction of the optically absorbing anisotropic film surface, is changed in 1° increments from -70 to 70°, and the Mueller matrix at a wavelength of 550 nm is measured, and the transmittance of the optically absorbing anisotropic film is derived. As a result, the direction with the highest transmittance is designated as the transmittance central axis. The transmittance central axis means the direction of the absorption axis (the direction of the long axis of the molecule) of the dichroic material contained in the optically absorptive anisotropic film.

[0019] Furthermore, with regard to the normal direction to the surface of the optically absorptive anisotropic film, the normal direction to the surface of the optically absorptive anisotropic film at the curved surface portion refers to the normal direction of the tangential plane that contacts the curved surface of the optically absorptive anisotropic film, i.e., the thickness direction of the optically absorptive anisotropic film.

[0020] As described above, in the present invention, an optically absorptive anisotropic film obtained by fixing the alignment state of a liquid crystal composition containing a liquid crystal compound, a dichroic substance, and a compound having a thiol group can suppress film thickness variations and cracking. The reason for this effect is unclear, but the inventors speculate as follows. First, the compound having a thiol group contained in the liquid crystal composition is thought to function as a chain transfer agent, causing a thiol-ene reaction with polymerizable groups (e.g., terminal double bonds) in other components. This facilitates uniform curing reaction deep into the optically absorptive anisotropic film, improving the film's ability to conform to curved surfaces and suppressing film thickness variations and cracking. Furthermore, an optically absorptive anisotropic film cured by the above-described thiol-ene reaction has a low volume shrinkage rate, which reduces residual stress in the optically absorptive anisotropic film and reduces weak points that could be the starting point for film damage when the optically absorptive anisotropic film is deformed. This is thought to have improved the ability of the optically absorptive anisotropic film to conform to the curved surface, thereby suppressing variations in film thickness and the occurrence of cracks.

[0021] [Curved Surface Portion] The optically absorptive anisotropic film of the present invention has a curved surface portion. Here, the term "curved surface portion" refers to a portion of a curved surface shape. The term "curved surface shape" refers to a shape having a curvature greater than 0, and includes a developable curved surface shape and a three-dimensional curved surface shape. A developable surface refers to a surface that can be developed into a plane without expanding or contracting each part of the surface. Examples of developable curved surfaces include surfaces corresponding to cylindrical surfaces, elliptical cylindrical surfaces, conical surfaces, and elliptical conical surfaces, and may be convex or concave curved surfaces. A three-dimensional curved surface refers to a curved surface that cannot be formed by deformation of a plane, i.e., a curved surface that is not developable. Examples of three-dimensional curved surfaces include surfaces corresponding to spherical surfaces and spheroidal surfaces, and surfaces corresponding to curved surfaces whose cross sections form parabolas or hyperbolas (e.g., paraboloids of revolution), and may be convex or concave curved surfaces.

[0022] In the present invention, the curved surface shape of the curved portion is preferably lenticular, because this enhances the usefulness of the optically absorptive anisotropic film of the present invention when used to cut out unnecessary stray light incident from an oblique direction and prevent ghost images, rainbow irregularities, etc. caused by the presence of stray light. Examples of lenticular curved shapes include spherical shapes, spheroidal shapes, and aspherical shapes, and they may be convex or concave lenticular shapes.

[0023] In addition, in the present invention, the minimum radius of curvature of the curved surface portion is preferably 20 to 300 mm, and more preferably 30 to 150 mm, because particularly useful effects are likely to be obtained when applied to AR glasses, etc.

[0024] FIG. 1 shows an example of an optically absorptive anisotropic film of the present invention. FIG. 1 is a top view of the optically absorptive anisotropic film, and FIG. 2 is a cross-sectional view taken along line A-A in FIG. 1. As shown in FIGS. 1 and 2, the optically absorptive anisotropic film 10 has a curved shape. More specifically, as shown in FIG. 2, the optically absorptive anisotropic film 10 has a shape (convex shape) that is convexly curved toward the upper side of the paper. In other words, the optically absorptive anisotropic film 10 has a convex shape that protrudes toward one surface. It can also be said that the optically absorptive anisotropic film 10 has a concave shape that is concave toward the other surface. While FIG. 1 shows an embodiment in which the shape of the optically absorptive anisotropic film when viewed in plan is pentagonal, the present invention is not limited to this embodiment, and the shape of the optically absorptive anisotropic film when viewed in plan may be rectangular, circular, or another shape.

[0025] [Transmittance central axis angle θ] As described above, the transmittance central axis angle θ of the optically absorptive anisotropic film of the present invention is 0° or more and 45° or less, preferably 0° or more and less than 45°, more preferably 0° or more and 35° or less, and even more preferably 0° or more and less than 35°.

[0026] [Liquid Crystal Composition] As described above, the optically absorptive anisotropic film of the present invention is a film obtained by fixing the alignment state of a liquid crystal composition containing a liquid crystal compound, a dichroic substance, and a compound having a thiol group. Hereinafter, the components contained in the liquid crystal composition will be described in detail.

[0027] <Liquid Crystal Compound> The liquid crystal composition contains a liquid crystal compound. This allows the dichroic material to be aligned with a higher degree of orientation while suppressing precipitation of the dichroic material. As the liquid crystal compound, either a polymer liquid crystal compound or a low molecular weight liquid crystal compound can be used, with a polymer liquid crystal compound being preferred because it allows for a higher degree of orientation. Furthermore, as the liquid crystal compound, a polymer liquid crystal compound and a low molecular weight liquid crystal compound may be used in combination. Here, the term "polymer liquid crystal compound" refers to a liquid crystal compound having a repeating unit in its chemical structure. The term "low molecular weight liquid crystal compound" refers to a liquid crystal compound having no repeating units in its chemical structure. Examples of polymer liquid crystal compounds include the thermotropic liquid crystal polymers described in JP 2011-237513 A and the polymer liquid crystal compounds described in paragraphs

[0012] to

[0042] of WO 2018 / 199096 A. Examples of low molecular weight liquid crystal compounds include those described in paragraphs

[0072] to

[0088] of JP 2013-228706 A, and among them, liquid crystal compounds exhibiting smectic properties are preferred. Examples of such liquid crystal compounds include those described in paragraphs

[0019] to

[0140] of WO 2022 / 014340 A, the disclosures of which are incorporated herein by reference. It should be noted that the liquid crystal compound is preferably a liquid crystal compound that does not exhibit dichroism in the visible light region.

[0028] The content of the liquid crystal compound is preferably 25 to 2000 parts by mass, more preferably 100 to 1300 parts by mass, and even more preferably 200 to 900 parts by mass, relative to 100 parts by mass of the content of the dichroic material described below. When the content of the liquid crystal compound is within the above range, the degree of orientation of the dichroic material is further improved. The liquid crystal compound may be contained alone, or two or more types may be contained. When two or more types of liquid crystal compounds are contained, the content of the liquid crystal compound refers to the total content of the liquid crystal compounds.

[0029] <Dichroic Material> The liquid crystal composition contains a dichroic material. Here, the dichroic material refers to a dye whose absorbance varies depending on the direction. The dichroic material may or may not exhibit liquid crystallinity.

[0030] The dichroic substance is not particularly limited, and examples thereof include visible light absorbing substances (dichroic dyes), luminescent substances (fluorescent substances, phosphorescent substances), ultraviolet absorbing substances, infrared absorbing substances, nonlinear optical substances, carbon nanotubes, and inorganic substances (e.g., quantum rods), and any conventionally known dichroic substance (dichroic dye) can be used. Specifically, for example, paragraphs

[0067] to

[0071] of JP 2013-228706 A, paragraphs

[0008] to

[0026] of JP 2013-227532 A, paragraphs

[0008] to

[0015] of JP 2013-209367 A, paragraphs

[0045] to

[0058] of JP 2013-14883 A, paragraphs

[0012] to

[0029] of JP 2013-109090 A, paragraphs

[0009] to

[0017] of JP 2013-101328 A, Paragraphs

[0051] to

[0065] of JP 2013-37353 A, paragraphs

[0049] to

[0073] of JP 2012-63387 A, paragraphs

[0016] to

[0018] of JP 11-305036 A, paragraphs

[0009] to

[0011] of JP 2001-133630 A, paragraphs

[0030] to

[0169] of JP 2011-215337 A, paragraphs

[0021] to

[0075] of JP 2010-106242 A, paragraphs

[0016] to

[0018] of JP 2010-215846 A

[0011] to

[0025] paragraphs,

[0017] to

[0069] paragraphs of JP 2011-048311 A,

[0013] to

[0133] paragraphs of JP 2011-213610 A,

[0074] to

[0246] paragraphs of JP 2011-237513 A,

[0005] to

[0051] paragraphs of JP 2016-006502 A,

[0014] to

[0032] paragraphs of JP 2018-053167 A, and

[0014] to

[0033] paragraphs of JP 2020-11716 A paragraphs

[0005] to

[0041] of International Publication No. 2016 / 060173, paragraphs

[0008] to

[0062] of International Publication No. 2016 / 136561, paragraphs

[0014] to

[0033] of International Publication No. 2017 / 154835, paragraphs

[0014] to

[0033] of International Publication No. 2017 / 154695, paragraphs

[0013] to

[0037] of International Publication No. 2017 / 195833, paragraphs

[0014] to

[0034] of International Publication No. 2018 / 164252,Examples include those described in paragraphs

[0021] to

[0030] of International Publication No. 2018 / 186503, paragraphs

[0043] to

[0063] of International Publication No. 2019 / 189345, paragraphs

[0043] to

[0085] of International Publication No. 2019 / 225468, paragraphs

[0050] to

[0074] of International Publication No. 2020 / 004106, and paragraphs

[0015] to

[0038] of International Publication No. 2021 / 044843.

[0031] As the dichroic substance, a dichroic azo dye compound is preferred. A dichroic azo dye compound refers to an azo dye compound whose absorbance varies depending on the direction. A dichroic azo dye compound may or may not exhibit liquid crystallinity. When a dichroic azo dye compound exhibits liquid crystallinity, it may exhibit either nematic or smectic properties. The temperature range in which the liquid crystal phase is exhibited is preferably room temperature (approximately 20 to 28°C) to 300°C, and more preferably 50 to 200°C from the viewpoints of handleability and manufacturing suitability.

[0032] In the present invention, from the viewpoint of adjusting color hue, it is preferable to use, as the dichroic substance, a mixture containing at least a dye compound (particularly, a dichroic azo dye compound) having an absorption maximum in a wavelength range of 380 nm or more and less than 455 nm, a dye compound (particularly, a dichroic azo dye compound) having an absorption maximum in a wavelength range of 455 nm or more and less than 560 nm, and a dye compound (particularly, a dichroic azo dye compound) having an absorption maximum in a wavelength range of 560 nm or more and less than 700 nm.

[0033] In the present invention, the dichroic substance preferably has a crosslinkable group, such as a cationically polymerizable group such as an epoxy group, an epoxycyclohexyl group, or an oxetanyl group; or a radically polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, or an allyl group.

[0034] The content of the dichroic substance contained in the optically absorptive anisotropic film is not particularly limited, but is preferably 3% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, and particularly preferably 10 to 30% by mass, relative to the total mass of the optically absorptive anisotropic film, because the degree of orientation of the optically absorptive anisotropic film formed is high. When multiple dichroic substances are used in combination, the total amount of the multiple dichroic substances is preferably within the above-mentioned range. Furthermore, the content of the dichroic substance contained in the optically absorptive anisotropic film is preferably 20 to 650 mg / cm, because the degree of orientation of the optically absorptive anisotropic film formed is high. ３ is preferably 25 to 500 mg / cm ３ is preferably 30 to 200 mg / cm ３ More preferably, it is 40 to 150 mg / cm ３ When a plurality of dichroic substances are used in combination, the total amount of the dichroic substances is preferably in the above-mentioned range. ３ ) can be obtained by measuring a solution in which a laminate having an optically absorptive anisotropic film is dissolved, or an extract obtained by immersing the laminate in a solvent, by high-performance liquid chromatography (HPLC), but the above method is not limited to this. Quantification can be performed by using the dichroic substance contained in the optically absorptive anisotropic film as a standard sample. One example of a method for calculating the content of the dichroic substance is to calculate the volume by multiplying the thickness of the optically absorptive anisotropic film obtained from a microscopic image of the cross section of the laminate by the area of ​​the optical laminate used to measure the amount of dye, and then dividing the volume by the amount of dye measured by HPLC to calculate the dye content.

[0035] <Compound Having a Thiol Group> The liquid crystal composition contains a compound having a thiol group (hereinafter also referred to as "thiol compound"). Here, the thiol compound is not particularly limited as long as it is a compound having one or more thiol groups (-SH) in the molecule. The class of the thiol group is not particularly limited, and may be, for example, primary, secondary, or tertiary. A thiol group having two hydrogen atoms bonded to the α-position (referring to the carbon atom to which the thiol group is bonded; the same applies hereinafter) is referred to as a primary thiol group, a thiol group having one hydrogen atom bonded to the α-position is referred to as a secondary thiol group, and a thiol group having no hydrogen atom bonded to the α-position is referred to as a tertiary thiol group.

[0036] In the present invention, the thiol compound is preferably a compound having two or more primary or secondary thiol groups per molecule, and more preferably a compound having 2 to 4 primary or secondary thiol groups per molecule, because this further suppresses variations in the film thickness of the curved surface portion and the occurrence of cracks.

[0037] In the present invention, for the reason that the storage stability of the liquid crystal composition is good, it is preferable that at least one of the thiol groups of the thiol compound is a secondary thiol group, and it is more preferable that all of the thiol groups present in the molecule of the thiol compound are secondary thiol groups.

[0038] In the present invention, for the reason that the occurrence of cracks and variations in film thickness on curved surface portions (particularly three-dimensional curved surfaces) are further suppressed, the thiol equivalent of the thiol compound, i.e., the mass (g / eq) of the thiol compound corresponding to 1 mol of thiol groups, is preferably 200 or less, more preferably 100 to 200, and even more preferably 100 to 150.

[0039] Examples of thiol compounds include primary thiol compounds such as 3-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, methoxybutyl-β-mercaptopropionate, stearyl-3-mercaptopropionate, ethylene glycol dimercaptopropionate, tetraethylene glycol bis(3-mercaptopropionate), 2,2-bis[[(3-mercaptopropionyl)oxy]methyl]trimethylenebis[3-mercaptopropionate]; secondary thiol compounds such as pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(2-(3-sulfanylbutanoyloxy)ethyl)-1,3,5-triazinane-2,4,6-trione, and trimethylolpropane tris(3-mercaptobutyrate); Examples include:

[0040] In the present invention, for the reasons of suppressing the occurrence of film thickness variations and cracks and simultaneously maintaining a high degree of orientation of the dichroic dye, the content of the thiol group compound is preferably 5 to 15 mass %, more preferably 6 to 12 mass %, based on the total mass of solids in the liquid crystal composition.

[0041] <Vertical Alignment Agent> The liquid crystal composition preferably contains a vertical alignment agent. Here, the vertical alignment agent refers to an additive having the function of aligning the liquid crystal compound in a direction perpendicular to the main plane of the optically absorptive anisotropic film. Note that "vertical alignment" does not require alignment at a strict 90° angle, but means alignment at an angle of 70 to 110°.

[0042] Examples of the vertical alignment agent include an ionic vertical alignment agent and a vertical alignment agent having a boronic acid group, and it is preferable to use an ionic vertical alignment agent and a vertical alignment agent having a boronic acid group in combination.

[0043] Suitable examples of the ionic vertical alignment agent include onium compounds represented by the following formula (B1).

[0044] In the formula (B1), ring A represents a quaternary ammonium ion consisting of a nitrogen-containing heterocycle, and X represents an anion. １ represents a divalent linking group. ２ represents a single bond or a divalent linking group. １ represents a divalent linking group having a 5-membered or 6-membered ring as a partial structure. Z represents a divalent linking group having an alkylene group having 2 to 20 carbon atoms as a partial structure. P １ and P ２ each independently represents a monovalent substituent having a polymerizable ethylenically unsaturated bond.

[0045] Ring A represents a quaternary ammonium ion consisting of a nitrogen-containing heterocycle. Examples of ring A include a pyridine ring, a picoline ring, a 2,2'-bipyridyl ring, a 4,4'-bipyridyl ring, a 1,10-phenanthroline ring, a quinoline ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazine ring, a triazole ring, and a tetrazole ring, and are preferably a quaternary imidazolium ion or a quaternary pyridinium ion.

[0046] X represents an anion. Examples of X include halogen anions (e.g., fluorine ion, chloride ion, bromide ion, iodide ion, etc.), sulfonate ions (e.g., methanesulfonate ion, trifluoromethanesulfonate ion, methyl sulfate ion, vinyl sulfonate ion, allyl sulfonate ion, p-toluenesulfonate ion, p-chlorobenzenesulfonate ion, p-vinylbenzenesulfonate ion, 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion, etc.), sulfate ion, carbonate ion, nitrate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, benzoate ion, p-vinylbenzoate ion, formate ion, trifluoroacetate ion, phosphate ion (e.g., hexafluorophosphate ion), hydroxide ion, etc. Preferred are halogen anions, sulfonate ions, and hydroxide ions. Particularly preferred are chloride ions, bromide ions, iodide ions, methanesulfonate ions, vinylsulfonate ions, p-toluenesulfonate ions, and p-vinylbenzenesulfonate ions.

[0047] L １ represents a divalent linking group. １ Examples of the group include an alkylene group, —O—, —S—, —CO—, and —SO ２ -, -NRa- (wherein Ra is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), an alkenylene group, an alkynylene group, or a divalent linking group having 1 to 20 carbon atoms formed in combination with an arylene group. １ is preferably -AL-, -O-AL-, -CO-O-AL-, or -O-CO-AL- having 1 to 10 carbon atoms, more preferably -AL- or -O-AL- having 1 to 10 carbon atoms, and most preferably -AL- or -O-AL- having 1 to 5 carbon atoms. AL represents an alkylene group.

[0048] L2 represents a single bond or a divalent linking group. ２ Examples of the group include an alkylene group, —O—, —S—, —CO—, and —SO ２-, -NRa- (wherein Ra is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), an alkenylene group, a divalent linking group having 1 to 10 carbon atoms formed in combination with an alkynylene group or an arylene group, a single bond, -O-, -O-CO-, -CO-O-, -O-AL-O-, -O-AL-O-CO-, -O-AL-CO-O-, -CO-O-AL-O-, -CO-O-AL-O-CO-, -CO-O-AL-CO-O-, -O-CO-AL-O-, -O-CO-AL-O-CO-, -O-CO-AL-CO-O-, and the like. AL represents an alkylene group. L2 is preferably a single bond, -AL-, -O-AL-, or -NRa-AL-O- having 1 to 10 carbon atoms, more preferably a single bond, -AL-, -O-AL-, or -NRa-AL-O- having 1 to 5 carbon atoms, and most preferably a single bond, or -O-AL- or -NRa-AL-O- having 1 to 5 carbon atoms.

[0049] Y １ represents a divalent linking group having a 5- or 6-membered ring as a partial structure. １ Examples of the aromatic ring include a cyclohexyl ring, an aromatic ring, a heterocyclic ring, etc. Examples of the aromatic ring include a benzene ring, an indene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, a biphenyl ring, and a pyrene ring, with a benzene ring, a biphenyl ring, and a naphthalene ring being particularly preferred. The heteroatom constituting the heterocycle is preferably a nitrogen atom, an oxygen atom, or a sulfur atom, and examples thereof include a furan ring, a thiophene ring, a pyrrole ring, a pyrroline ring, a pyrrolidine ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an imidazoline ring, an imidazolidine ring, a pyrazole ring, a pyrazoline ring, a pyrazolidine ring, a triazole ring, a furazan ring, a tetrazole ring, a pyran ring, a dioxane ring, a dithiane ring, a thiine ring, a pyridine ring, a piperidine ring, an oxazine ring, a morpholine ring, a thiazine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperazine ring, and a triazine ring. The heterocycle is preferably a 6-membered ring. Y １ The divalent linking group having a 5- or 6-membered ring as a partial structure, represented by the following formula (I), may further have a substituent (for example, the above-mentioned substituent W).

[0050] Y １ The divalent linking group represented by the formula (I) is preferably a divalent linking group having two or more 5- or 6-membered rings, and more preferably has a structure in which two or more rings are linked by a linking group. Examples of the linking group include L １ and L ２ Examples of the linking group include -C≡C-, -CH=CH-, -CH=N-, -N=CH-, and -N=N-.

[0051] Z represents a divalent linking group having an alkylene group having 2 to 20 carbon atoms as a partial structure and formed by combining -O-, -S-, -CO-, or -SO2-, and the alkylene group may have a substituent. Examples of the divalent linking group include an alkyleneoxy group and a polyalkyleneoxy group. The alkylene group represented by Z preferably has 2 to 16 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.

[0052] P1 and P2 each independently represent a monovalent substituent having a polymerizable ethylenically unsaturated group. Examples of the monovalent substituent having a polymerizable ethylenically unsaturated group include the following formulae (M-1) to (M-8). That is, the monovalent substituent having a polymerizable ethylenically unsaturated group may be a substituent consisting only of an ethenyl group, as in (M-8).

[0053]

[0054] In formulas (M-3) and (M-4), R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group. Among the formulas (M-1) to (M-8), (M-1), (M-2), and (M-8) are preferred, with (M-1) or (M-8) being more preferred. In particular, (M-1) is preferred as P1. Furthermore, (M-1) or (M-8) is preferred as P2. In compounds in which ring A is a quaternary imidazolium ion, P2 is preferably (M-8) or (M-1), and in compounds in which ring A is a quaternary pyridinium ion, P2 is preferably (M-1).

[0055] Examples of the onium compound represented by formula (B1) include the onium salts described in paragraphs

[0052] to

[0058] of JP-A No. 2012-208397, the onium salts described in paragraphs

[0024] to

[0055] of JP-A No. 2008-026730, and the onium salts described in JP-A No. 2002-37777.

[0056] As the ionic vertical alignment agent, in addition to the onium compound represented by the above formula (B1), for example, those described in paragraphs

[0017] to

[0029] of JP-A-2020-181150 can be mentioned.

[0057] A preferred example of the vertical alignment agent having a boronic acid group is a boronic acid compound represented by the following formula (B2).

[0058] In (B2) above, R １ and R ２ each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. ３ represents a substituent.

[0059] R １ and R ２ Examples of the aliphatic hydrocarbon group represented by one embodiment of the formula include substituted or unsubstituted linear or branched alkyl groups having 1 to 20 carbon atoms (e.g., methyl, ethyl, isopropyl, etc.), substituted or unsubstituted cyclic alkyl groups having 3 to 20 carbon atoms (e.g., cyclohexyl, etc.), and alkenyl groups having 2 to 20 carbon atoms (e.g., vinyl, etc.). １ and R ２ Examples of the aryl group represented by one embodiment of R include a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms (for example, a phenyl group, a tolyl group, etc.), and a substituted or unsubstituted naphthyl group having 10 to 20 carbon atoms. １ and R ２Examples of the heterocyclic group represented by one embodiment of R include substituted or unsubstituted 5- or 6-membered ring groups containing at least one heteroatom (e.g., nitrogen atom, oxygen atom, sulfur atom, etc.), and specific examples include a pyridyl group, an imidazolyl group, a furyl group, a piperidyl group, and a morpholino group. １ and R ２ may be linked together to form a ring, for example, R １ and R ２ The isopropyl groups may be linked to form a 4,4,5,5-tetramethyl-1,3,2-dioxaborolane ring.

[0060] R １ and R ２ is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or a ring formed by linking these groups, and more preferably a hydrogen atom.

[0061] R ３ is preferably a substituent containing a functional group capable of bonding to a (meth)acrylic group. Here, examples of the functional group capable of bonding to a (meth)acrylic group include a vinyl group, an acrylate group, a methacrylate group, an acrylamide group, a styryl group, a vinyl ketone group, a butadiene group, a vinyl ether group, an oxiranyl group, an aziridinyl group, and an oxetane group. Among these, a vinyl group, an acrylate group, a methacrylate group, a styryl group, an oxiranyl group, or an oxetane group is preferred, and a vinyl group, an acrylate group, an acrylamide group, or a styryl group is more preferred.

[0062] R ３is preferably a substituted or unsubstituted aliphatic hydrocarbon group, an aryl group, or a heterocyclic group having a functional group capable of bonding to a (meth)acrylic group. Examples of the aliphatic hydrocarbon group include a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms (e.g., methyl group, ethyl group, isopropyl group, n-propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, sec-butyl group, tert Examples of the aryl group include substituted or unsubstituted phenyl groups having 6 to 50 carbon atoms (e.g., phenyl, tolyl, styryl, 4-benzoyloxyphenyl, 4-phenoxycarbonylphenyl, 4-biphenyl, 4-(4-octyloxybenzoyloxy)phenoxycarbonylphenyl), and substituted or unsubstituted naphthyl groups having 10 to 50 carbon atoms (e.g., unsubstituted naphthyl).Examples of heterocyclic groups include substituted or unsubstituted 5- or 6-membered ring groups containing at least one heteroatom (e.g., nitrogen atom, oxygen atom, sulfur atom, etc.), and examples thereof include pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxazole, isoxazole, oxadiazole, thiazole, thiadiazole, indole, carbazole, benzofuran, dibenzofuran, thianaphthene, dibenzothiophene, indazole, benzimidazole, anthranil, benzisoxazole, benzoxazole, benzothiazole, purine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, quinoline, acridine, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthyridine, phenanthroline, pteridine, morpholine, and piperidine groups.

[0063] Examples of the boronic acid compound represented by formula (B2) include the boronic acid compounds represented by general formula (I) described in paragraphs 0023 to 0032 of JP-A No. 2008-225281. Preferred examples of the compound represented by formula (B2) include the compounds exemplified below.

[0064]

[0065] The content of any vertical alignment agent contained in the optically absorptive anisotropic film is preferably 1.0 to 7.0 parts by mass, more preferably 1.5 to 8.0 parts by mass, and even more preferably 2.5 to 6.0 parts by mass, relative to 100 parts by mass of the liquid crystal compound. The vertical alignment agent may be contained alone or in combination of two or more types. When two or more types of liquid crystal compounds are contained, the content of the vertical alignment agent refers to the total content of the vertical alignment agents.

[0066] <Solvent> The liquid crystal composition preferably contains a solvent from the viewpoint of workability and the like. Examples of the solvent include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, acetylacetone, etc.), ethers (e.g., dioxane, tetrahydrofuran, tetrahydropyran, dioxolane, tetrahydrofurfuryl alcohol, cyclopentyl methyl ether, dibutyl ether, etc.), aliphatic hydrocarbons (e.g., hexane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, tetralin, trimethylbenzene, etc.), halogenated carbons (e.g., dichloromethane, trichloromethane (chloroform), dichloroethane, dichlorobenzene, 1,1,2,2-tetrachloroethane, chlorotoluene, etc.), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, diethyl carbonate, ethyl acetoacetate, n-pentyl acetate, ethyl benzoate, benzyl benzoate, butyl carbitol acetate, diethylene glycol monoethyl ether acetate, Examples of suitable solvents include organic solvents such as ethanol, isopropanol, butanol, cyclohexanol, furfuryl alcohol, 2-ethylhexanol, octanol, benzyl alcohol, ethanolamine, ethylene glycol, propylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, phenols (e.g., phenol, cresol, etc.), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, 1,2-dimethoxyethane, etc.), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide, etc.), amides (e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc.), and heterocyclic compounds (e.g., pyridine, 2,6-lutidine, etc.), as well as water. These solvents may be used alone or in combination of two or more.

[0067] When the liquid crystal composition contains a solvent, the content of the solvent is preferably 60 to 99.5% by mass, more preferably 70 to 99% by mass, and particularly preferably 75 to 98% by mass, relative to the total mass (100% by mass) of the liquid crystal composition.

[0068] <Polymerization initiator> The liquid crystal composition may contain a polymerization initiator. There are no particular limitations on the polymerization initiator, but it is preferably a photosensitive compound, i.e., a photopolymerization initiator. As the photopolymerization initiator, various compounds can be used without particular limitations. Examples of photopolymerization initiators include α-carbonyl compounds (U.S. Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (U.S. Pat. No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compounds (U.S. Pat. No. 2,722,512), polynuclear quinone compounds (U.S. Pat. Nos. 3,046,127 and 2,951,758), and combinations of triarylimidazole dimers and p-aminophenyl ketones (U.S. Pat. No. 3,549,367). ), acridine and phenazine compounds (JP 60-105667 A and U.S. Pat. No. 4,239,850 A), oxadiazole compounds (U.S. Pat. No. 4,212,970 A), o-acyloxime compounds (JP 2016-27384 A

[0065] ), and acylphosphine oxide compounds (JP 63-40799 A, JP 5-29234 A, JP 10-95788 A, and JP 10-29997 A). Commercially available photopolymerization initiators can also be used, including Irgacure-184, Irgacure-907, Irgacure-369, Irgacure-651, Irgacure-819, Irgacure-OXE-01, and Irgacure-OXE-02 manufactured by BASF.

[0069] When the liquid crystal composition contains a polymerization initiator, the content of the polymerization initiator is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass, based on the total solid mass of the liquid crystal composition.

[0070] <Interfacial improver> The liquid crystal composition may contain an interfacial improver. There are no particular limitations on the interfacial improver, and polymer-based interfacial improvers and low-molecular-weight interfacial improvers can be used, such as the compounds described in paragraphs

[0253] to

[0293] of JP-A No. 2011-237513. Furthermore, fluorine (meth)acrylate polymers described in paragraphs

[0018] to

[0043] of JP-A No. 2007-272185 can also be used as interfacial improvers. Examples of the interface improver include compounds described in paragraphs

[0079] to

[0102] of JP-A-2007-069471, polymerizable liquid crystal compounds represented by formula (4) described in JP-A-2013-047204 (particularly compounds described in paragraphs

[0020] to

[0032] ), polymerizable liquid crystal compounds represented by formula (4) described in JP-A-2012-211306 (particularly compounds described in paragraphs

[0022] to

[0029] ), and liquid crystal alignment promoters represented by formula (4) described in JP-A-2002-129162 (particularly compounds described in paragraphs

[0032] to

[0032] ). The compounds described in paragraphs

[0076] to

[0078] and

[0082] to

[0084] of the present invention, the compounds represented by formulas (4), (II) and (III) described in JP-A-2005-099248 (particularly the compounds described in paragraphs

[0092] to

[0096] ), the compounds described in paragraphs

[0013] to

[0059] of Japanese Patent No. 4,385,997, the compounds described in paragraphs

[0018] to

[0044] of Japanese Patent No. 5,034,200, and the compounds described in paragraphs

[0019] to

[0038] of Japanese Patent No. 4,895,088 can also be used. The interfacial modifiers may be used alone or in combination of two or more.

[0071] When the liquid crystal composition contains an interfacial modifier, the content of the interfacial modifier is preferably 0.005 to 15% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.015 to 3% by mass, based on the total mass of the solid content of the liquid crystal composition. When multiple interfacial modifiers are used in combination, the total amount of the multiple interfacial modifiers is preferably in the above-mentioned range.

[0072] [Method for forming an optically absorptive anisotropic film] The method for forming an optically absorptive anisotropic film is not particularly limited, and examples thereof include a method comprising, in this order, a step of applying the above-described liquid crystal composition (hereinafter also referred to as "optically absorptive anisotropic film-forming composition") to form a coating film (hereinafter also referred to as "coating film formation step"), and a step of orienting the liquid crystalline component and dichroic substance contained in the coating film (hereinafter also referred to as "orientation step"). Note that the liquid crystalline component refers to a component that includes not only the above-described liquid crystal compound, but also the dichroic substance having liquid crystallinity, if the above-described dichroic substance has liquid crystallinity.

[0073] <Coating Film Forming Step> The coating film forming step is a step of forming a coating film by applying a composition for forming an optically absorptive anisotropic film. By using a composition for forming an optically absorptive anisotropic film containing the above-mentioned solvent, or by using a composition for forming an optically absorptive anisotropic film that has been converted into a liquid such as a molten liquid by heating, etc., it becomes easier to apply the composition for forming an optically absorptive anisotropic film. Specific examples of the coating method for the composition for forming an optically absorptive anisotropic film include known methods such as roll coating, gravure printing, spin coating, wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spraying, and inkjet printing.

[0074] In the present invention, the coating amount of the dichroic material in the coating film forming step is set to 15 mg / m because the optical effect (for example, viewing angle control) is enhanced. ２ It is preferable that the concentration is 50 to 1000 mg / m or more. ２ More preferably, it is 200 to 800 mg / m ２ It is more preferable that:

[0075] <Orientation Step> The orientation step is a step of orienting the liquid crystalline component contained in the coating film. This results in an optically absorbing anisotropic film. The orientation step may include a drying treatment. Components such as the solvent can be removed from the coating film by the drying treatment. The drying treatment may be performed by leaving the coating film at room temperature for a predetermined time (e.g., natural drying), or by heating and / or blowing air. Here, the liquid crystalline component contained in the composition for forming an optically absorbing anisotropic film may be aligned by the above-mentioned coating film formation step or drying treatment. For example, in an embodiment in which the composition for forming an optically absorbing anisotropic film is prepared as a coating liquid containing a solvent, the coating film is dried to remove the solvent from the coating film, thereby obtaining a coating film with optically absorbing anisotropy (i.e., an optically absorbing anisotropic film). When the drying treatment is performed at a temperature equal to or higher than the transition temperature of the liquid crystalline component contained in the coating film to a liquid crystal phase, the heat treatment described below may not be performed.

[0076] The transition temperature of the liquid crystalline component contained in the coating film to the liquid crystal phase is preferably 10 to 250°C, more preferably 25 to 190°C, from the viewpoint of manufacturability and the like. When the transition temperature is 10°C or higher, no cooling treatment or the like is required to lower the temperature to the temperature range in which the liquid crystal phase is exhibited, and this is preferable. Furthermore, when the transition temperature is 250°C or lower, high temperatures are not required even when the film is once converted to an isotropic liquid state at a temperature higher than the temperature range in which the liquid crystal phase is exhibited, and this is preferable because waste of thermal energy and deformation and deterioration of the substrate can be reduced.

[0077] The orientation step preferably includes a heat treatment. This allows the liquid crystalline component contained in the coating film to be oriented, and the coating film after the heat treatment can be suitably used as an optically absorptive anisotropic film. From the viewpoint of manufacturability, the heat treatment is preferably performed at a temperature of 10 to 250°C, more preferably 25 to 190°C. The heating time is preferably 1 to 300 seconds, more preferably 1 to 60 seconds.

[0078] The alignment step may include a cooling treatment carried out after the heating treatment. The cooling treatment is a treatment in which the coated film after heating is cooled to about room temperature (20 to 25°C). This allows the alignment of the liquid crystalline component contained in the coated film to be fixed. The cooling method is not particularly limited and can be carried out by a known method. By the above steps, an optically absorptive anisotropic film can be obtained. In this embodiment, drying treatment and heating treatment are mentioned as methods for aligning the liquid crystalline component contained in the coated film, but the method is not limited thereto and can be carried out by a known alignment treatment.

[0079] <Other Steps> The method for forming an optically absorbing anisotropic film may include a step of curing the optically absorbing anisotropic film (hereinafter also referred to as a "curing step") after the alignment step. For example, when the optically absorbing anisotropic film has a crosslinkable group (polymerizable group), the curing step is performed by heating and / or light irradiation (exposure). Among these, the curing step is preferably performed by light irradiation. Various light sources, such as infrared, visible light, or ultraviolet light, can be used as the light source for curing, but ultraviolet light is preferred. Furthermore, ultraviolet light may be irradiated while heating during curing, or ultraviolet light may be irradiated through a filter that transmits only specific wavelengths. When exposure is performed while heating, the heating temperature during exposure is preferably 25 to 140°C, although this depends on the transition temperature of the liquid crystal component contained in the liquid crystal film to the liquid crystal phase. Furthermore, exposure may be performed under a nitrogen atmosphere. When curing of the liquid crystal film proceeds by radical polymerization, exposure under a nitrogen atmosphere is preferred because inhibition of polymerization by oxygen is reduced.

[0080] In the present invention, the thickness of the optically absorptive anisotropic film is not particularly limited, but is preferably 1.5 μm or more, more preferably 2 to 10 μm, and even more preferably 2 to 8 μm, because this improves the light-shielding properties in oblique directions and increases the degree of orientation of the optically absorptive anisotropic film. Here, the thickness of the optically absorptive anisotropic film is measured by cutting the film with a microtome to prepare a cross-sectioned sample, and then observing the cross-section with a scanning electron microscope from the normal direction to the cross-section.

[0081] In the present invention, because the difference in the degree of orientation of the optically absorptive anisotropic film at wavelengths of 450 nm, 550 nm, and 650 nm can be suppressed when the film is applied to an image display device, it is preferable that the difference be 0.025 or less, more preferably 0.020 or less, and even more preferably 0.010 or less. Here, the degree of orientation of the optically absorptive anisotropic film at wavelengths of 450 nm, 550 nm, and 650 nm is calculated by the following method. Specifically, using an AxoScan (manufactured by Axometrics), the Mueller matrix is ​​measured in the in-plane slow axis direction at polar angles ranging from -70 to 70° at 5° intervals, and kx(λ), ky(λ), and kz(λ) are determined by fitting. Next, the absorption anisotropies Ao(λ) and Ae(λ) are calculated according to the following formulas (A) to (D), and the degree of orientation S is calculated according to the following formula (E). To(λ) = EXP{-4 x π x (kx(λ) + ky(λ)) / 2 x d / λ} (A) Te(λ) = EXP{-4 x π x kz(λ) x d / λ} (B) Ao(λ) = -log(To(λ)) (C) Ae(λ) = -log(Te(λ)) (D) Degree of orientation S(λ) = [Ao(λ) / Ae(λ) - 1] / [Ao(λ) / Ae(λ) + 2] (E) Here, d represents the film thickness (nm) of the optically absorptive anisotropic film, To(λ) and Te(λ) represent the transmittance, and Ao(λ) and Ae(λ) represent the absorbance. The difference in the degree of orientation (0.025 or less) specified in the above-mentioned requirement 3 refers to the maximum difference among the difference in the degree of orientation at wavelengths of 450 nm and 550 nm, the difference in the degree of orientation at wavelengths of 450 nm and 650 nm, and the difference in the degree of orientation at wavelengths of 550 nm and 650 nm.

[0082] In the present invention, the degree of orientation of the optically absorptive anisotropic film at a wavelength of 550 nm is preferably 0.94 or more, more preferably 0.95 to 1.00, and even more preferably 0.96 to 1.00, because the optically absorptive anisotropic film can absorb more polarized light incident on the film from a specific direction and achieve favorable optical performance. Here, the degree of orientation of the optically absorptive anisotropic film at a wavelength of 550 nm can be calculated by the method described above.

[0083] In addition, it is preferable to perform the heat treatment in the above-mentioned orientation step multiple times (particularly twice) because this makes it easier to make the difference in the degree of orientation of the optically absorptive anisotropic film at wavelengths of 450 nm, 550 nm, and 650 nm 0.025 or less. Furthermore, the cooling treatment performed between two heat treatments is preferably a treatment in which the coating film after the first heat treatment is cooled to about 30 to 45°C.

[0084] In the present invention, the haze value of the optically absorptive anisotropic film is preferably 0.3% or less, more preferably 0.2% or less, and even more preferably 0.1% or less, because this maintains a high degree of polarization of light passing through the optically absorptive anisotropic film and results in more favorable optical performance. Here, the haze value refers to the haze measured in accordance with JIS K7136:2000 "Method of determining haze for plastic transparent materials," and refers to the value measured using a haze meter (e.g., NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.)) in an environment of 25°C and a relative humidity of 55%.

[0085] Furthermore, it is preferable to perform the heat treatment in the orientation step multiple times (particularly twice) because this makes it easier to adjust the haze ratio of the optically absorptive anisotropic film to 0.3% or less. In particular, it is preferable to lower the temperature in the two heat treatments, more preferably to set it to 65 to 80°C.

[0086] [Laminate] The laminate of the present invention includes the optically absorptive anisotropic film of the present invention described above. The laminate of the present invention may also include at least one of a polarizer layer, an antireflection layer, and a retardation layer.

[0087] [Polarizer Layer] The polarizer layer is not particularly limited as long as it is a member capable of converting light into specific linearly polarized light, and conventionally known absorptive polarizers and reflective polarizers can be used. Examples of absorptive polarizers include iodine-based polarizers, dye-based polarizers using dichroic dyes, and polyene-based polarizers. Iodine-based polarizers and dye-based polarizers include coated polarizers and stretched polarizers, and either can be used. However, coated polarizers are preferred. In addition, methods for obtaining a polarizer by stretching and dyeing a laminated film having a polyvinyl alcohol layer formed on a substrate are described in Japanese Patent Nos. 5048120, 5143918, 4691205, 4751481, and 4751486. ​​These known techniques related to polarizers can also be preferably used. Examples of coated polarizers include those disclosed in WO2018 / 124198, WO2018 / 186503, WO2019 / 132020, WO2019 / 132018, WO2019 / 189345, JP2019-197168A, JP2019-194685A, and JP2019-139222A, and known techniques relating to these polarizers can also be preferably utilized. Examples of reflective polarizers that can be used include polarizers in which thin films with different birefringences are laminated, wire grid polarizers, and polarizers in which a cholesteric liquid crystal having a selective reflection region is combined with a quarter-wave plate. Among these, polyvinyl alcohol-based resins (-CH ２A polymer containing -CHOH- as a repeating unit. In particular, a polarizer containing at least one selected from the group consisting of polyvinyl alcohol and an ethylene-vinyl alcohol copolymer is preferred. Furthermore, from the viewpoint of imparting crack resistance, the polarizer may have depolarizing portions formed along opposing edges. Examples of depolarizing portions include those described in JP 2014-240970 A. The polarizer may also have non-polarizing portions arranged at predetermined intervals in the longitudinal direction and / or width direction. The non-polarizing portions are partially bleached portions. The arrangement pattern of the non-polarizing portions can be appropriately set depending on the purpose. For example, when the polarizer is cut (cut, punched, etc.) to a predetermined size for installation in an image display device of a predetermined size, the non-polarizing portions are arranged in positions corresponding to the camera portion of the image display device. Examples of arrangement patterns of non-polarizing portions include those described in JP 2016-27392 A.

[0088] [Antireflection Layer] The antireflection layer is not particularly limited, and a known antireflection layer can be used. Examples of the antireflection layer include the antireflection layers described in paragraphs 0108 to 0121 of WO 2016 / 047648, the contents of which are incorporated herein by reference.

[0089] [Retardation layer] There is no particular limitation on retardation layer, and known retardation layer can be used.For example, retardation layer can be stretched polycarbonate film, stretched norbornene polymer film, transparent film containing and oriented inorganic particles having birefringence such as strontium carbonate, thin film obtained by obliquely depositing inorganic dielectric on support, film that uniaxially oriented and fixed orientation of liquid crystal compound, etc.In addition, as retardation layer, film that uniaxially oriented and fixed orientation of the above-mentioned liquid crystal compound is preferred.

[0090] [Image Display Device] The image display device of the present invention is an image display device having the laminate of the present invention. The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic EL display panel, an inorganic EL display panel, and a plasma display panel.

[0091] [Laminate manufacturing method] The laminate manufacturing method of the present invention is not particularly limited.For example, the manufacturing method according to the first aspect can be a laminate manufacturing method comprising: a light absorption anisotropic film forming step of forming a light absorption anisotropic film on a temporary support, the light absorption anisotropic film being a film formed by fixing the alignment state of a liquid crystal composition containing a liquid crystal compound, a dichroic substance, and a compound having a thiol group, and the angle θ between the transmittance central axis of the film and the normal direction of the film surface is 0°C or more and 45° or less; after the light absorption anisotropic film forming step, the light absorption anisotropic film is transferred to a support, and the temporary support is peeled off; after the transfer step, the light absorption anisotropic film is pressed against a mold having a curved surface, and the light absorption anisotropic film is molded into a curved surface; That is, the manufacturing method according to the first aspect is a method in which, except for using a liquid crystal composition containing the above-mentioned thiol compound, a laminate having a support and an optically absorptive anisotropic film is produced by a conventionally known method, and then the optically absorptive anisotropic film is pressed against a mold having a curved portion, thereby forming a curved portion in the optically absorptive anisotropic film.

[0092] Furthermore, a production method according to the second aspect includes a method for producing a laminate, which includes a light absorption anisotropic film formation step of forming an optically absorptive anisotropic film on a support having a curved surface, the light absorption anisotropic film being a film formed by fixing the alignment state of a liquid crystal composition containing a liquid crystal compound, a dichroic substance, and a compound having a thiol group, wherein the angle θ between the transmittance central axis of the film and the normal direction to the film surface is 0° C. or more and 45° or less. That is, the production method according to the first aspect is the same as the conventionally known methods (e.g., the above-mentioned coating film formation step and alignment step) except that a support having a curved surface is used and a liquid crystal composition containing the above-mentioned thiol compound is used.

[0093] [Optical Device / Head-Mounted Display] The optical device of the present invention is an optical device having an optical filter including the laminate of the present invention described above and a light guide plate having a diffraction element disposed on the surface thereof. Also, the head-mounted display of the present invention is a head-mounted display having the optical device described above and an image display element.

[0094] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0095] Example 1 (1) Temporary Support A cellulose acylate film 1 (TAC substrate having a thickness of 40 μm; TG40, Fujifilm Corporation) was used as a temporary support after the surface thereof was saponified with an alkaline solution.

[0096] (2) Preparation of Alignment Film The following composition 1 for forming an alignment film was applied onto a cellulose acylate film 1. The temporary support on which the coating film was formed was dried with hot air at 145°C for 120 seconds to form an alignment film 1. The thickness of the alignment film 1 was 0.5 µm.

[0097] ------------------------------------------------------------------ Composition 1 for forming alignment film -------------------------------------------------- Polymer PA-1 (described below) 10.0 parts by mass Acid generator PAG-1 (described below) 0.83 parts by mass Stabilizer DIPEA (described below) 0.06 parts by mass Butyl acetate 100 parts by mass ------------------------------------------------------------------

[0098] Polymer PA-1

[0099] Acid generator PAG-1

[0100] Stabilizer DIPEA

[0101] (3) Preparation of Optically Absorbent Anisotropic Film An optically absorptive anisotropic film-forming composition 1 having the following composition was applied to the obtained TAC (triacetyl cellulose) film with an alignment film using a wire bar, heated at 120°C for 60 seconds, and then cooled to 35°C. The film was then heated at 75°C for 60 seconds and cooled again to room temperature. Thereafter, under nitrogen purging conditions (oxygen concentration 100 ppm or less), an LED (light emitting diode) lamp (center wavelength 365 nm) was used to illuminate the film from the normal direction at an illuminance of 200 mW / cm. ２ The optically absorptive anisotropic film 1 was formed on the alignment film by irradiating the film with light for 2 seconds under the irradiation conditions of 1. The film thickness of the optically absorptive anisotropic film 1 was 4.5 μm. The transmittance central axis angle θ of the formed optically absorptive anisotropic film 1 was measured by the method described above. The results are shown in Table 1 below.

[0102] 0.16 parts by mass of vertical alignment agent E-1 below; 0.16 parts by mass of vertical alignment agent E-2 below; 0.407 parts by mass of thiol compound (EHMP, manufactured by SC Organic Chemical Co., Ltd.); 0.007 parts by mass of surfactant F-1 below; 78.17 parts by mass of cyclopentanone Benzyl alcohol 8.69 parts by mass ----------------------------------------------------------------

[0103] Dichroic substance D-1

[0104] Dichroic substance D-2

[0105] Dichroic substance D-3

[0106] Polymer liquid crystal compound P-1

[0107] Liquid crystal compound L-1 (a mixture of the following liquid crystal compounds (RA), (RB), and (RC) in a mass ratio of 84:14:2)

[0108] Vertical alignment agent E-1

[0109] Vertical alignment agent E-2

[0110] Surfactant F-1

[0111] (4) Preparation of Protective Layer The surface of the obtained optically absorptive anisotropic film 1 was subjected to a corona treatment under conditions of 4.0 m / min, 440 W, and a clearance of 2.0 mm. Next, a protective layer-forming coating solution 1 having the following composition was applied to the corona-treated optically absorptive anisotropic film 1 using a wire bar to form a coating film. Next, the temporary support on which the coating film had been formed was dried with hot air at 60°C for 60 seconds and then with hot air at 100°C for 120 seconds to form protective layer 1. Thereafter, under nitrogen purging conditions (oxygen concentration 100 ppm or less), an LED lamp (center wavelength 365 nm) was used to illuminate the film normal direction at an illuminance of 200 mW / cm. ２ The protective layer 1 was formed on the optically absorbing anisotropic film 1 by irradiating the film for 2 seconds under the irradiation conditions of

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[0112] -------------------------------------------------- Coating liquid 1 for forming protective layer -------------------------------------------------- 3.80 parts by mass of modified polyvinyl alcohol PVA-1 shown below 0.20 parts by mass IRGACURE 2959 (manufactured by BASF) 0.08 parts by mass of dye compound G-1 shown below Water 70 parts by mass Methanol 30 parts by mass --------------------------------------------------

[0113] Modified polyvinyl alcohol PVA-1

[0114] Pigment compound G-1

[0115] (5) Curved Surface Processing of Optically Absorbing Anisotropic Film The protective layer 1 side of the optically absorbing anisotropic film 1 (layer structure: temporary support 1 / alignment film 1 / optically absorbing anisotropic film 1 / protective layer 1) was attached to a PMMA film via an adhesive sheet, and only the temporary support was peeled off to form the optically absorbing anisotropic film 2, which was then set in a molding device. At this time, the PMMA side was arranged on the upper side. The molding space in the molding device consists of boxes 1 and 2 separated by the optically absorbing anisotropic film 2, and in box 1 below the optically absorbing anisotropic film 2, a mold was prepared that resembled the surface shape of a smartphone cover glass (size: 65 mm x 140 mm, minimum radius of curvature of the three-dimensional curved surface of the rounded edge portion: 38 mm, minimum radius of curvature of the developable surface of the rounded edge portion: 38 mm) and was placed so that the curved surface of the rounded edge portion was facing up. Furthermore, a transparent window was installed at the top of box 2 above light-absorbing anisotropic film 2, and an IR light source for heating light-absorbing anisotropic film 2 was installed outside this window. Next, a vacuum pump was used to evacuate box 1 and box 2 to a pressure of 0.1 atmospheres or less. Next, as a step of heating light-absorbing anisotropic film 2, infrared rays were irradiated and light-absorbing anisotropic film 2 was heated to a temperature of 108°C. Next, as a step of pressing light-absorbing anisotropic film 2 against a mold and deforming it to the shape of the mold, gas was flowed into box 2 from a gas cylinder to pressurize it to 300 kPa, and light-absorbing anisotropic film 2 was pressure-bonded to the mold. Next, light-absorbing anisotropic film 2 was removed from the cover glass mold. This resulted in light-absorbing anisotropic film 2 having a curved surface.

[0116] Example 2 Laminate 2 was prepared in the same manner as in Example 1, except that composition 1 for forming an optically absorptive anisotropic film was replaced with composition 2 for forming an optically absorptive anisotropic film having the following composition. 0.16 parts by mass of the vertical alignment agent E-2 0.16 parts by mass of the vertical alignment agent E-2 0.407 parts by mass of thiol compound (BMPA, manufactured by SC Organic Chemical Co., Ltd.) 0.007 parts by mass of the surfactant F-1 0.007 parts by mass of the surfactant F-2 0.16 parts by mass of the vertical alignment agent E-3 0.16 parts by mass of the vertical alignment agent E-2 0.16 parts by mass of the vertical alignment agent E-3 0.16 parts by mass of the vertical alignment agent E-4 0.16 parts by mass of the vertical alignment agent E-5 0.16 parts by mass of the vertical alignment agent E-6 0.16 parts by mass of the vertical alignment agent E-7 0.16 parts by mass of the vertical alignment agent E-8 0.16 parts by mass of the vertical alignment agent E-9 0.16 parts by mass of the vertical alignment agent E-1 0.16 parts by mass of the vertical alignment agent E-2 ...1 0.16 parts by mass of the vertical alignment agent E-2 0.16 parts by mass of the vertical alignment agent E-3 0.16 parts by mass of the vertical alignment agent E-4 0.16 parts by mass of the vertical alignment agent E-5 0.16 parts by mass of the vertical alignment agent E-6 0.16 parts by mass of the vertical alignment agent E-7 0.16 parts by mass of the vertical alignment agent E-8 0.16 parts by mass of the vertical alignment agent E-9 0.16 parts by mass of the vertical alignment agent E-9 0.16 parts by mass of the vertical alignment agent E-9 0.16 parts by mass of the vertical alignment agent E-1 0.1 Benzyl alcohol 8.69 parts by mass ----------------------------------------------------------------

[0117] Example 3 Laminate 3 was prepared in the same manner as in Example 1, except that composition 1 for forming an optically absorptive anisotropic film was replaced with composition 3 for forming an optically absorptive anisotropic film having the following composition. ------------------------------------------------ Optical absorption anisotropic film-forming composition 3---------------------------------------------------------------- Dichroic material D-1: 0.69 parts by mass Dichroic material D-2: 0.17 parts by mass Dichroic material D-3: 1.13 parts by mass Polymer liquid crystal compound P-1: 8.67 parts by mass Liquid crystal compound L-1: 1.97 parts by mass IRGACUE OXE-2 (manufactured by BASF) 0.20 parts by mass Vertical alignment agent E-1: 0.16 parts by mass Vertical alignment agent E-2: 0.16 parts by mass Thiol compound (EGDMP, Anhui Royal Chemical Co., Ltd) 0.407 parts by mass Surfactant F-1: 0.007 parts by mass Cyclopentanone 78.17 parts by mass Benzyl alcohol 8.69 parts by mass --------------------------------------------------

[0118] Example 4 Laminate 4 was prepared in the same manner as in Example 1, except that composition 1 for forming an optically absorptive anisotropic film was replaced with composition 4 for forming an optically absorptive anisotropic film having the following composition. 0.16 parts by mass of the vertical alignment agent E-1; 0.16 parts by mass of the vertical alignment agent E-2; 0.407 parts by mass of thiol compound (PEMP, manufactured by SC Organic Chemical Co., Ltd.); 0.007 parts by mass of the surfactant F-1; 78.17 parts by mass of cyclopentanone. Benzyl alcohol 8.69 parts by mass ----------------------------------------------------------------

[0119] Example 5 Laminate 5 was prepared in the same manner as in Example 1, except that composition 1 for forming an optically absorptive anisotropic film was replaced with composition 5 for forming an optically absorptive anisotropic film having the following composition. ------------------------------------------------ Optical absorption anisotropic film-forming composition 5------------------------------------------------ 0.69 parts by mass of the dichroic material D-1 0.17 parts by mass of the dichroic material D-2 1.13 parts by mass of the dichroic material D-3 8.67 parts by mass of the polymer liquid crystal compound P-1 1.97 parts by mass of the liquid crystal compound L-1 0.20 parts by mass of IRGACUE OXE-2 (manufactured by BASF) 0.16 parts by mass of the vertical alignment agent E-1 0.16 parts by mass of the vertical alignment agent E-2 0.407 parts by mass of a thiol compound (Karenz MT BD1, manufactured by Resonac Co., Ltd.) 0.007 parts by mass of the surfactant F-1 Cyclopentanone 78.17 parts by mass Benzyl alcohol 8.69 parts by mass --------------------------------------------------

[0120] Example 6 Laminate 6 was prepared in the same manner as in Example 1, except that composition 1 for forming an optically absorptive anisotropic film was replaced with composition 6 for forming an optically absorptive anisotropic film having the following composition. ------------------------------------------------ Optical absorption anisotropic film-forming composition 6---------------------------------------------------------------- Dichroic material D-1 0.69 parts by mass Dichroic material D-2 0.17 parts by mass Dichroic material D-3 1.13 parts by mass Polymer liquid crystal compound P-1 8.67 parts by mass Liquid crystal compound L-1 1.97 parts by mass IRGACUE OXE-2 (manufactured by BASF) 0.20 parts by mass Vertical alignment agent E-1 0.16 parts by mass Vertical alignment agent E-2 0.16 parts by mass Thiol compound (Karenz MT TPMB, manufactured by Resonac Co., Ltd.) 0.407 parts by mass Surfactant F-1 0.007 parts by mass Cyclopentanone 78.17 parts by mass Benzyl alcohol 8.69 parts by mass --------------------------------------------------

[0121] Example 7 Laminate 7 was prepared in the same manner as in Example 1, except that composition 1 for forming an optically absorptive anisotropic film was replaced with composition 7 for forming an optically absorptive anisotropic film having the following composition. ------------------------------------------------ Optically absorptive anisotropic film-forming composition 7---------------------------------------------------------------- Dichroic material D-1 0.69 parts by mass Dichroic material D-2 0.17 parts by mass Dichroic material D-3 1.13 parts by mass Polymer liquid crystal compound P-1 8.67 parts by mass Liquid crystal compound L-1 1.97 parts by mass IRGACUE OXE-2 (manufactured by BASF) 0.20 parts by mass Vertical alignment agent E-1 0.16 parts by mass Vertical alignment agent E-2 0.16 parts by mass Thiol compound (Karenz MT TPMB, manufactured by Resonac Co., Ltd.) 0.840 parts by mass Surfactant F-1 0.007 parts by mass Cyclopentanone 78.17 parts by mass Benzyl alcohol 8.69 parts by mass --------------------------------------------------

[0122] Example 8 Laminate 8 was produced in the same manner as in Example 7, except that the mold used to curve the light-absorption anisotropic film was changed to a concave lens (diameter: 50 nmφ, radius of curvature: 52 mm).

[0123] Example 9 The composition for forming an alignment film 1 of Example 1 was applied onto the surface of a concave lens (diameter: 50 nmφ, radius of curvature: 52 mm) using a spin coater. After application, the lens was dried with hot air at 145°C for 120 seconds to form an alignment film. The thickness of the alignment film was 0.5 μm. Next, the composition for forming an optically absorptive anisotropic film 7 of Example 7 was applied onto the formed alignment film using a spin coater, heated at 120°C for 60 seconds, and then cooled to 35°C. Next, the composition was heated at 75°C for 60 seconds and cooled again to room temperature. Thereafter, under nitrogen purging conditions (oxygen concentration 100 ppm or less), an LED lamp (center wavelength 365 nm) was used to illuminate the film from directly above at an illuminance of 200 mW / cm. ２ An optically absorbing anisotropic film was produced on the alignment film by irradiating the film with light for 2 seconds under irradiation conditions of 4.0 m / min, 440 W, and a clearance of 2.0 mm, thereby forming an optically absorbing anisotropic film. The film thickness of the optically absorbing anisotropic film was 4.5 μm. Next, the surface of the obtained optically absorbing anisotropic film was subjected to corona treatment under conditions of 4.0 m / min, 440 W, and a clearance of 2.0 mm, and then the protective layer forming coating solution 1 of Example 1 was applied using a spin coater. Next, the support on which the coating film was formed was dried with hot air at 60°C for 60 seconds and then with hot air at 100°C for 120 seconds to form a protective layer. Thereafter, under nitrogen purging conditions (oxygen concentration 100 ppm or less), an LED lamp (center wavelength 365 nm) was used to illuminate the support from directly above at an illuminance of 200 mW / cm. ２ A protective layer was formed by irradiating the sample for 2 seconds under the irradiation conditions of 1.5 μm to form a laminate. The protective layer had a thickness of 0.5 μm. By the above operations, a lens-shaped optically absorptive anisotropic film sample was prepared.

[0124] Example 10 A laminate 10 was produced in the same manner as in Example 1, except that the composition 1 for forming an optically absorptive anisotropic film was replaced with the composition 10 for forming an optically absorptive anisotropic film having the following composition. ------------------------------------------------ Optically absorptive anisotropic film-forming composition 10------------------------------------------------ Dichroic substance D-4 (1.82 parts by mass) Dichroic substance D-5 (0.49 parts by mass) Dichroic substance D-6 (3.25 parts by mass) Polymer liquid crystal compound P-1 (18.21 parts by mass) Liquid crystal compound L-1 (4.13 parts by mass) IRGACUE 369 (manufactured by BASF) 1.67 parts by mass Vertical alignment agent E-1 (0.37 parts by mass) Vertical alignment agent E-2 (0.37 parts by mass) Thiol compound (Karenz MT TPMB, manufactured by Resonac Co., Ltd.) 1.94 parts by mass BYK-361N (BYK-Chemie) 0.084 parts by mass o-xylene 200 parts by mass ---------------------------------------------------

[0125] Dichroic substance D-4

[0126] Dichroic substance D-5

[0127] Dichroic substance D-6

[0128] Example 11 A laminate 11 was prepared in the same manner as in Example 1, except that the composition 1 for forming an optically absorptive anisotropic film was replaced with the composition 11 for forming an optically absorptive anisotropic film having the following composition. ------------------------------------------------ Optically absorptive anisotropic film-forming composition 11---------------------------------------------------------------- Dichroic material D-1 0.79 parts by mass Dichroic material D-2 0.21 parts by mass Dichroic material D-3 1.41 parts by mass Liquid crystal compound L-2 below 7.52 parts by mass Liquid crystal compound L-3 below 2.51 parts by mass IRGACUE 369 (manufactured by BASF) 0.73 parts by mass Thiol compound (Karenz MT TPMB, manufactured by Resonac Co., Ltd.) 0.843 parts by mass BYK-361N (BYK-Chemie) 0.036 parts by mass Cyclopentanone 78.13 parts by mass Benzyl alcohol 8.67 parts by mass ――――――――――――――――――――――――――――――

[0129] Liquid crystal compound L-2

[0130] Liquid crystal compound L-3

[0131] Example 12 A laminate 12 was prepared in the same manner as in Example 1, except that the composition 1 for forming an optically absorptive anisotropic film was replaced with the composition 12 for forming an optically absorptive anisotropic film having the following composition. ------------------------------------------------ Optically absorptive anisotropic film-forming composition 12---------------------------------------------------------------- Dichroic material D-4 0.78 parts by mass Dichroic material D-5 0.21 parts by mass Dichroic material D-6 1.39 parts by mass Liquid crystal compound L-2 7.39 parts by mass Liquid crystal compound L-3 2.46 parts by mass IRGACUE 369 (manufactured by BASF) 0.71 parts by mass Thiol compound (Karenz MT TPMB, manufactured by Resonac Co., Ltd.) 0.828 parts by mass BYK-361N (BYK-Chemie) 0.036 parts by mass o-xylene 87.02 parts by mass ----------------------------------------------------------------------------------

[0132] Comparative Example 1 A laminate H1 was produced in the same manner as in Example 1, except that the thiol compound was not blended in the composition 1 for forming an optically absorptive anisotropic film.

[0133] [Evaluation] The maximum absorption wavelength of the dichroic material used and the content of the dichroic material (mg / cm ３ ), and the degree of orientation of the optically absorptive anisotropic film measured by the above-mentioned method, the difference in the degree of orientation at each wavelength, and the haze value are shown in Table 1 below.

[0134] [Film Thickness Variation] The cross section of the curved surface of the prepared laminate was observed using a scanning electron microscope (SEM), and the film thickness of the optically absorptive anisotropic film was measured at any five points, and evaluated according to the following criteria.In Table 1 below, "developable surface" refers to the "developable surface (edge ​​portion) of the rounded edge cover glass," and "three-dimensional" refers to the "corner portion" of the rounded edge cover glass, and in the case of a concave lens, the entire surface is a three-dimensional curved surface.<Evaluation Criteria> A+: Thickness unevenness is less than 4% A: Thickness unevenness is 4% or more and less than 5% B: Thickness unevenness is 5% or more and less than 6% C: Thickness unevenness is 6% or more and less than 10% D: Thickness unevenness is 10% or more

[0135] [Cracks] The curved surface of the produced laminate was observed with a 10x magnifying glass, and the light-absorbing anisotropic film having a curved surface was evaluated according to the following criteria. <Evaluation criteria> A: No cracks were visible. B: Slight cracks were visible. C: Clear cracks were visible.

[0136] [Storage] The viscosity of the optically absorptive anisotropic film-forming compositions used in Examples 1 to 12 and Comparative Example 1 was measured immediately after preparation and after standing at room temperature (23°C) for one week, and evaluated according to the following criteria. <Evaluation criteria> A: Viscosity increase of 5% or less B: Viscosity increase of more than 5% but not more than 20%

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[0138] The results shown in Table 1 indicate that when a thiol compound is not blended into the composition for forming an optically absorptive anisotropic film (liquid crystal composition), variations in film thickness occur at the curved surface of the optically absorptive anisotropic film, and cracks also occur (Comparative Example 1). In contrast, when a thiol compound is blended into the composition for forming an optically absorptive anisotropic film (liquid crystal composition), variations in film thickness and the occurrence of cracks are suppressed at the curved surface of the optically absorptive anisotropic film (Examples 1 to 12). In particular, a comparison of Examples 1 to 4 indicates that when the thiol compound has two or more primary or secondary thiol groups per molecule, variations in film thickness and the occurrence of cracks at the curved surface are further suppressed. A comparison of Examples 3 and 5 indicates that when at least one of the thiol groups in the thiol compound is a secondary thiol group, the shelf life of the liquid crystal composition is improved. A comparison between Example 1 and Example 2 revealed that the occurrence of cracks on curved surfaces (particularly three-dimensional curved surfaces) and variations in film thickness were further suppressed when the thiol equivalent of the thiol compound was 200 or less. A comparison between Example 6 and Example 7 revealed that the content of the thiol group compound was 5 to 15 mass% with respect to the total mass of the optically absorptive anisotropic film, which further suppressed variations in film thickness and the occurrence of cracks, while simultaneously maintaining a high degree of orientation of the dichroic dye.

[0139] 10. Optically absorbing anisotropic film

Claims

1. An optically absorptive anisotropic film having a curved surface, the optically absorptive anisotropic film being a film formed by fixing the orientation state of a liquid crystal composition containing a liquid crystal compound, a dichroic substance, and a compound having a thiol group, and the angle θ between the central axis of transmittance of the optically absorptive anisotropic film and the normal direction to the surface of the optically absorptive anisotropic film is greater than or equal to 0° and less than or equal to 45°.

2. The optically absorptive anisotropic film according to claim 1, wherein the compound containing a thiol group is a compound having two or more primary or secondary thiol groups in one molecule.

3. The optically absorptive anisotropic film according to claim 2, wherein at least one of the thiol groups is a secondary thiol group.

4. The optically absorptive anisotropic film according to any one of claims 1 to 3, wherein the thiol equivalent of the compound containing a thiol group is 200 or less.

5. The optically absorptive anisotropic film described in any one of claims 1 to 3, wherein the content of the compound having a thiol group is 5 to 15 mass % relative to the total mass of the optically absorptive anisotropic film.

6. The optically absorptive anisotropic film according to any one of claims 1 to 3, wherein the curved surface shape of the curved portion is lenticular.

7. The optically absorptive anisotropic film according to any one of claims 1 to 3, wherein the minimum radius of curvature of the curved surface portion is 20 to 300 mm.

8. The optically absorptive anisotropic film according to any one of claims 1 to 3, wherein the dichroic substance is a mixture containing at least a dye compound having a maximum absorption wavelength in the wavelength range of 380 nm or more and less than 455 nm, a dye compound having a maximum absorption wavelength in the wavelength range of 455 nm or more and less than 560 nm, and a dye compound having a maximum absorption wavelength in the wavelength range of 560 nm or more and 700 nm or less.

9. The content of the dichroic material contained in the optically absorptive anisotropic film is 20 to 650 mg / cm ３ 4. The optically absorptive anisotropic film according to claim 1, wherein 10. The optically absorptive anisotropic film according to any one of claims 1 to 3, wherein the degree of orientation of the optically absorptive anisotropic film at a wavelength of 550 nm is 0.94 or more.

11. The optically absorptive anisotropic film according to any one of claims 1 to 3, wherein the difference in the degree of orientation of the optically absorptive anisotropic film at wavelengths of 450 nm, 550 nm and 650 nm is 0.025 or less.

12. The optically absorptive anisotropic film according to any one of claims 1 to 3, wherein the haze value of the optically absorptive anisotropic film is 0.3% or less.

13. A laminate comprising the optically absorptive anisotropic film according to any one of claims 1 to 3.

14. An optical device comprising the optically anisotropic film according to any one of claims 1 to 3 and a light guide plate having a diffractive element disposed on the surface thereof.

15. A head mounted display comprising the optical device according to claim 14 and an image display element.

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