Laminate, reflection prevention system, and image display device

Abstract

The problem addressed by the present invention is to provide a laminate which, for an image reflected on a nearby object (for example, window glass), can reduce changes in hue from an original image, in particular suppress a shift in hue of the reflected image in the reddish direction, and which can suppress the reflected image from becoming too conspicuous, and to provide an antireflection system and an image display device comprising said laminate. The laminate according to the present invention comprises a polarizer having an absorbing axis in the in-plane direction, a light absorbing anistropic layer containing a crystalline compound and a dichroic substance, and a linear polarization conversion layer. The transmittance central axis of the light absorbing anistropic layer and the normal of the layer plane of the light absorbing anistropic layer form an angle of 0-45°.

Description

[Technical Field]

[0001] This invention relates to a laminate, an anti-reflection system, and an image display device. [Background technology]

[0002] When using in-car displays such as car navigation systems, there is a problem in that the light emitted upward from the display screen reflects onto the windshield and other surfaces, interfering with driving. To solve these problems, for example, Patent Document 1 discloses a viewing angle control system having a polarizer (light-absorbing anisotropic layer) containing a dichroic substance and having an angle between the absorption axis and the normal to the film surface of 0° to 45°. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Patent No. 4902516 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] The present inventors investigated the viewing angle control system described in Patent Document 1 and found that it reduces reflections on the window glass (windshield) located above the in-vehicle display. However, they found that the hue of the remaining reflected images changes significantly from the original color to reddish, greenish, or bluish tones, resulting in a problem where the reflected images with reduced brightness become noticeable again. In particular, they found that a change towards reddish tones is highly noticeable to the human eye and is especially undesirable, while a change towards bluish tones is relatively more acceptable to the human eye.

[0005] The inventors of this invention conducted a thorough analysis of this phenomenon and found the cause to be as follows. First, the second polarizer described in Patent Document 1 uses a liquid crystalline compound along with an absorbing dichroic substance, and the absorbing dichroic substance is oriented in a specific direction by utilizing the guest-host effect of the liquid crystalline compound. Typically, the birefringence of the liquid crystalline compound and absorbing dichroic substance used here has wavelength dispersion, which causes light with different polarization characteristics, such as S-polarization and P-polarization, to be emitted from the surface of the anti-reflection film for each wavelength. Furthermore, window glass surfaces reflect S-polarized light more strongly than P-polarized light in the incident angle region around the Brewster angle, which results in a change in the color of the reflected image. For example, if red S-polarized light and green to blue P-polarized light are emitted from the surface of an anti-reflective film, the reflected image will have a reddish hue because the S-polarized light is reflected more strongly.

[0006] The object of the present invention is to provide a laminate that can reduce the hue change of reflected images on the surroundings (e.g., window glass) relative to the original image, and in particular suppress the hue shift toward red in the reflected image, thereby suppressing the visibility of the reflected image, as well as a reflection prevention system and an image display device having this laminate. [Means for solving the problem]

[0007] The inventors have found that the above problem can be solved by the following configuration.

[0008] [1] A polarizer having an absorption axis in the in-plane direction, a light-absorbing anisotropic layer containing a liquid crystalline compound and a dichroic substance, and a linear polarization conversion layer, A laminate in which the angle between the transmittance center axis of the light-absorbing anisotropic layer and the normal to the layer plane of the light-absorbing anisotropic layer is between 0° and 45°. [2] The laminate according to [1], wherein the content of the dichroic substance is 5% by mass or more relative to the total solid content mass of the light-absorbing anisotropic layer. [3] The laminate according to [1] or [2], wherein the linear polarization conversion layer is a C plate. [4] The laminate according to [3], wherein the C plate is a negative C plate. [5] The laminate according to [1] or [2], wherein the linear polarization conversion layer is a λ / 2 plate or a λ / 4 plate. [6] The laminate according to [1] or [2], wherein the linear polarization conversion layer is a polarization depolarization layer. [7] The laminate according to [6], wherein the depolarization layer is a randomly oriented liquid crystal layer. [8] The laminate according to [6], wherein the depolarizing layer is a layer containing fine particles. [9] The laminate according to [6], wherein the depolarization layer contains a liquid crystalline compound and a dichroic substance, and the liquid crystalline compound is randomly oriented in the layer.

[10] The linear polarization conversion layer is a polarizer having an absorption axis in the in-plane direction, The laminate according to [1] or [2], wherein the angle φ between the direction obtained by orthogonally projecting the transmittance central axis of the light absorption anisotropy layer onto the layer plane of the light absorption anisotropy layer and the absorption axis of the polarizer, which is a linear polarization conversion layer, is 85° to 95°.

[11] The laminate according to [1] or [2], wherein the linear polarization conversion layer is a phase difference layer with an in-plane retardation value of 6000 nm or more, measured at a wavelength of 550 nm.

[12] The laminate according to

[11] , wherein the phase difference layer is a PET film.

[13] A laminate according to any one of [1] to

[12] , having a B plate between a polarizer and a light-absorbing anisotropic layer.

[14] An anti-reflection system having a laminate as described in any of [1] to

[13] .

[15] An image display device having a laminate as described in any of [1] to

[13] . [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a laminate, an anti-reflection system, and an image display device that can reduce the hue change of reflected images on the surroundings (e.g., window glass) relative to the original image, and in particular suppress the hue shift toward red in the reflected image, thereby suppressing the visibility of the reflected image. Furthermore, the laminate of the present invention is useful as a laminate for preventing reflections when laminated on an in-vehicle display, and can prevent driver error caused by images reflected on the window glass, thereby contributing to safe driving of the vehicle. [Brief explanation of the drawing]

[0010] [Figure 1] Figure 1 is a schematic cross-sectional view showing an example of an embodiment of the image display device with reflection prevention system of the present invention. [Figure 2] Figure 2 shows a microscopic image of the randomly oriented liquid crystal layer used as the linear polarization conversion layer in the present invention, observed under crossed nicol conditions with a polarizing microscope. [Figure 3] Figure 3 is a schematic diagram of the evaluation system for reflected images on window glass. [Figure 4] Figure 4 is a schematic cross-sectional view of a light-absorbing anisotropic film, which is part of an embodiment of the present invention. [Figure 5] Figure 5 is a schematic cross-sectional view of a linear polarization conversion film, which is part of an embodiment of the present invention. [Modes for carrying out the invention]

[0011] The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. Furthermore, in this specification, "parallel" and "orthogonal" do not mean parallel and orthogonal in the strict sense, but rather mean a range of ±5° parallel and ±5° orthogonal, respectively.

[0012] Furthermore, in this specification, the terms "liquid crystal composition" and "liquid crystal compound" also include, conceptually, substances that no longer exhibit liquid crystal properties due to curing or other reasons.

[0013] Furthermore, in this specification, each component may be represented by a single substance or by a combination of two or more substances. When two or more substances are used in combination for each component, the content of that component refers to the total content of the combined substances unless otherwise specified. In this specification, "(meth)acrylate" refers to "acrylate" or "methacrylate," "(meth)acrylic" refers to "acrylic" or "methacrylic," and "(meth)acryloyl" refers to "acryloyl" or "methacryloyl."

[0014] [Substituent W] The substituent W used herein represents the following group: Substituents W include, for example, halogen atoms, C1-C20 alkyl groups, C1-C20 halogenated alkyl groups, C1-C20 cycloalkyl groups, C1-C10 alkylcarbonyl groups, C1-C10 alkyloxycarbonyl groups, C1-C10 alkylcarbonyloxy groups, C1-C10 alkylamino groups, alkylaminocarbonyl groups, C1-C20 alkoxy groups, C1-C20 alkenyl groups, C1-C20 alkynyl groups, C1-C20 aryl groups, heterocyclic groups (also called heterocyclic groups), cyano groups, hydroxyl groups, nitro groups, carboxyl groups, aryloxy groups, silyloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, amino groups (including anilino groups), Examples of substituents include ammonia groups, acylamino groups, aminocarbonylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, sulfamoylamino groups, alkyl or arylsulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfamoyl groups, sulfo groups, alkyl or arylsulfinyl groups, alkyl or arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl or heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, phosphono groups, silyl groups, hydrazino groups, ureido groups, boronic acid groups (-B(OH)2), phosphat groups (-OPO(OH)2), sulfat groups (-OSO3H), and other known substituents. Further details regarding the substituents are described in paragraph

[0023] of Japanese Patent Publication No. 2007-234651. Furthermore, the substituent W may be a group represented by the following formula (W1).

[0015] [ka]

[0016] In formula (W1), LW represents a single bond or a divalent linking group, SPW represents a divalent spacer group, Q represents Q1 or Q2 in formula (LC) described later, and * represents the bond position.

[0017] The divalent linking groups represented by LW are -O- and -(CH2). g -,-(CF2) g -, -Si(CH3)2-, -(Si(CH3)2O) g -,-(OSi(CH3)2) g -(g represents an integer from 1 to 10.), -N(Z)-, -C(Z)=C(Z')-, -C(Z)=N-, -N=C(Z)-, -C(Z)2-C(Z')2-, -C(O)-, -OC(O)-, -C(O)O-, -OC(O)O-, -N(Z)C(O)-, -C(O) N(Z)-, -C(Z)=C(Z')-C(O)O-, -OC(O)-C(Z)=C(Z')-, -C(Z)=N-, -N=C(Z )-, -C(Z)=C(Z')-C(O)N(Z")-, -N(Z")-C(O)-C(Z)=C(Z')-, -C(Z)=C(Z Examples include -C(O)-S-, -SC(O)-C(Z)=C(Z')-, -C(Z)=NN=C(Z')- (where Z, Z', and Z'' independently represent hydrogen, a C1-C4 alkyl group, a cycloalkyl group, an aryl group, a cyano group, or a halogen atom), -C≡C-, -N=N-, -S-, -S(O)-, -S(O)(O)-, -(O)S(O)O-, -O(O)S(O)O-, -SC(O)-, and -C(O)S-. LW may also be a group formed by combining two or more of these groups (hereinafter abbreviated as "LC").

[0018] Examples of divalent spacer groups represented by SPW include linear, branched, or cyclic alkylene groups having 1 to 50 carbon atoms, or heterocyclic groups having 1 to 20 carbon atoms. The carbon atoms in the above alkylene group and heterocyclic group are -O-, -Si(CH3)2-, and -(Si(CH3)2O). g -,-(OSi(CH3)2) g-(where g represents an integer from 1 to 10), -N(Z)-, -C(Z)=C(Z’)-, -C(Z)=N-, -N=C(Z)-, -C(Z)2-C(Z’)2-, -C(O)-, -OC(O)-, -C(O)O-, -O-C(O)O-, -N(Z)C(O)-, -C(O)N(Z)-, -C(Z)=C(Z’)-C(O)O-, -O-C(O)-C(Z)=C(Z’)-, -C(Z)=N-, -N=C(Z)-, -C(Z)=C(Z’)-C(O)N(Z”)-, -N(Z”)-C(O)-C(Z)=C(Z’)-, -C(Z)=C(Z’)-C(O)-S-, -S-C(O)-C(Z)=C(Z’)-, -C(Z)=N-N=C(Z’)-(Z, Z’, Z” independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, a cyano group, or a halogen atom), -C≡C-, -N=N-, -S-, -C(S)-, -S(O)-, -SO2-, -(O)S(O)O-, -O(O)S(O)O-, -SC(O)-, and -C(O)S-, and may be substituted with a group formed by combining two or more of these groups (hereinafter also abbreviated as "SP-C"). The hydrogen atoms of the above-mentioned alkylene group and the hydrogen atoms of the heterocyclic group are a halogen atom, a cyano group, -Z H , -OH, -OZ H , -COOH, -C(O)Z H , -C(O)OZ H , -OC(O)Z H , -OC(O)OZ H , -NZ H Z H ’, -NZ H C(O)Z H ’, -NZ H C(O)OZ H ’, -C(O)NZ H Z H ’, -OC(O)NZ H Z [[ID=3३]] H ’, -NZ H C(O)NZ H ’OZ H ’’, -SH, -SZ H , -C(S)Z H , -C(O)SZ H , -SC(O)Z H , and may be substituted (hereinafter also abbreviated as "SP-H"). Here, ZH , Z H ' represents an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or -L-CL (L represents a single bond or a divalent linking group. Specific examples of divalent linking groups are the same as those for LW and SPW described above. CL represents a crosslinking group, such as the group represented by Q1 or Q2 in formula (LC) described below, with the crosslinking groups represented by formulas (P1) to (P30) described below being preferred).

[0019] [Laminated structure] The laminate of the present invention comprises a polarizer having an absorption axis in the in-plane direction, a light-absorbing anisotropic layer containing a liquid crystalline compound and a dichroic substance, and a linear polarization conversion layer. Furthermore, in the laminate of the present invention, the angle between the transmittance center axis of the light-absorbing anisotropic layer and the normal to the layer plane of the light-absorbing anisotropic layer (hereinafter abbreviated as "transmittance center axis axis direction (polar angle)") is 0° or more and 45° or less.

[0020] Here, the transmittance center axis refers to the direction that exhibits the highest transmittance when the transmittance is measured while varying the tilt angle (polar angle) and tilt direction (azimuth angle) relative to the normal direction of the surface of the light-absorbing anisotropic layer. Specifically, the Müller matrix at a wavelength of 550 nm is measured using an AxoScan OPMF-1 (OptoScience Co., Ltd.). More specifically, during the measurement, the azimuth angle at which the transmittance center axis is tilted is first found. Then, within a plane containing the normal direction of the optical absorption anisotropy layer along that azimuth angle (a plane containing the transmittance center axis and perpendicular to the layer surface), the polar angle, which is the angle between the normal direction of the optical absorption anisotropy layer surface, is changed in 1° increments from -70 to 70°, and the Müller matrix at a wavelength of 550 nm is measured, and the transmittance of the optical absorption anisotropy layer is derived. As a result, the direction with the highest transmittance is defined as the transmittance center axis. The transmittance center axis refers to the direction of the absorption axis (the long axis direction of the molecule) of the dichroic substance contained in the light absorption anisotropy layer.

[0021] [Linear polarization conversion layer] The linear polarization conversion layer in the laminate of the present invention is a layer located on the viewing side (the position that becomes the viewing side when the laminate of the present invention is used in an image display device; the same applies hereinafter) of the light absorption anisotropy layer described later, and is a layer that converts some or all of the linear polarization components coming from the viewing side surface of the light absorption anisotropy layer into natural light (random polarization), circular polarization, elliptic polarization, other linear polarization with different vibration directions, and low-intensity linear polarization. The relationship between the linear polarization conversion layer and the converted light is as follows: if a depolarization layer is used in the linear polarization conversion layer, it is converted to natural light (random polarization); if a λ / 4 plate (HWP) is used in the linear polarization conversion layer, it is converted to circularly polarized or elliptically polarized light; if a λ / 2 plate (HWP) is used in the linear polarization conversion layer, it is converted to linearly polarized light with a different vibration direction than the original; and if a polarizer is used in the linear polarization conversion layer, it is converted to linearly polarized light with the same vibration direction but different light intensity. Here, "depolarization layer" refers to a layer that has the function of converting some or all of linearly polarized light into natural light (randomly polarized light). Furthermore, a "λ / 4 plate" refers to a phase difference layer in which the in-plane phase difference is approximately 1 / 4 of the wavelength. Specifically, it refers to a phase difference layer in which the in-plane phase difference Re(550) at a wavelength of 550 nm is between 110 nm and 160 nm. Furthermore, a "λ / 2 plate" refers to a phase difference layer in which the in-plane phase difference is approximately half the wavelength. Specifically, it refers to a phase difference layer in which the in-plane phase difference Re(550) at a wavelength of 550 nm is between 220 nm and 320 nm.

[0022] In this invention, a so-called super-birefringent film having a large phase difference of several thousand nanometers or more can also be used for the linear polarization conversion layer. Examples of such ultrabirefringent films include phase difference layers (phase difference films) with an in-plane retardation value of 6000 nm or more measured at a wavelength of 550 nm, and specifically, polyethylene terephthalate (PET) film is a preferred example. Furthermore, since a polyester film with a thickness of several tens of micrometers can be used as the super-birefringent film, it can also be used as a support within the anti-reflection system. Here, the in-plane retardation value refers to the value measured using an AxoScan OPMF-1 (manufactured by OptoScience Co., Ltd.) with light at the measurement wavelength. Specifically, by inputting the average refractive index ((Nx+Ny+Nz) / 3) and film thickness (d(μm)) into the AxoScan OPMF-1, Slow axis direction (°) Re(λ)=R0(λ) Rth(λ)=((nx+ny) / 2-nz)×d This is calculated. Note that R0(λ) is a value displayed by the AxoScan OPMF-1, and it means Re(λ).

[0023] In this invention, a C plate can also be used as the linear polarization conversion layer. Here, there are two types of C plates: positive C plates and negative C plates. Positive C plates satisfy the relationship shown in equation (C1) below, and negative C plates satisfy the relationship shown in equation (C2) below. Note that positive C plates show a negative Rth value, and negative C plates show a positive Rth value. When a negative C plate or a positive C plate is used as a linear polarization conversion layer, it does not affect the polarization state of light emitted from the display in the forward direction, but it does change the polarization state of light emitted at an angle, thereby changing only the hue and brightness of the reflected image on a window glass at an angle. Formula (C1) nz>nx≒ny Formula (C2) nz <nx≒ny Furthermore, the above "≒" includes not only cases where the two are completely identical, but also cases where they are substantially identical. "Substantially identical" means, for example, that (nx-ny)×d (where d is the thickness of the film) is between 0 and 10 nm, preferably between 0 and 5 nm, which is included in "nx≒ny".

[0024] Furthermore, in this invention, a B plate can also be used for the linear polarization conversion layer. When a B-plate is used as a linear polarization conversion layer, it is also possible to change the hue and brightness of the reflected image on a window glass that is in a specific direction relative to the display. Here, a B-plate refers to a biaxial optical element in which refractive indices nx, ny, and nz are different values ​​from each other.

[0025] Furthermore, in the present invention, the linear polarization conversion layer can be an optical anisotropic layer containing a liquid crystalline compound and having a liquid crystal orientation pattern in which the orientation of the optical axis derived from the liquid crystalline compound changes while continuously rotating along at least one direction in the plane.

[0026] In the present invention, it is preferable to use a polarizer having an absorption axis in the in-plane direction as the linear polarization conversion layer, in order to further suppress the hue shift toward the reddish direction of the reflected image, and to set it so that the angle φ between the direction in which the transmittance center axis of the light absorption anisotropy layer is orthogonally projected onto the layer plane of the light absorption anisotropy layer and the absorption axis of the polarizer as the linear polarization conversion layer is 85° to 95°. The polarizer used as the linear polarization conversion layer is the same as the polarizer found in the laminate of the present invention (described later).

[0027] When using a birefringent phase difference layer in the linear polarization conversion layer, various phase difference layers can be selected by considering the polarization state of light emitted from the surface of the light absorption anisotropy layer, the birefringence of the phase difference layer, alignment film, support, etc. located on the opposite side of the light absorption anisotropy layer (the position that becomes the display element side when the laminate of the present invention is used in an image display device), the direction of the window glass to be controlled, and the optical properties of the surface of the window glass, etc.

[0028] Furthermore, in addition to using a single linear polarization conversion layer, multiple types may be used in combination. Furthermore, the linear polarization conversion layer may be further modified by applying a new layer through coating and drying, transfer, etc., or it may be used in conjunction with a support, barrier layer, or other layers, with these layers also possessing the function of a linear polarization conversion layer.

[0029] <Depolarizing layer> As a depolarization layer, which is one embodiment of a linear polarization conversion layer, any method is acceptable as long as the depolarization layer has the ability to convert some or all of the linearly polarized light into natural light (random polarization). For example, a randomly oriented liquid crystal layer and a layer containing fine particles are preferred, and among these, a randomly oriented liquid crystal layer is preferred from the viewpoint of easily obtaining depolarization ability and easily obtaining a transparent layer while avoiding whitening caused by domains in the layer.

[0030] (Randomly oriented liquid crystal layer) A randomly oriented liquid crystal layer (hereinafter also referred to as a "randomly oriented liquid crystal layer") refers to a liquid crystal state such as the nematic phase or smectic phase in which the orientation direction of the liquid crystalline compound is randomly oriented in various directions. A randomly oriented liquid crystal layer in the nematic phase is more preferable. A randomly oriented liquid crystal layer can be fabricated by providing a liquid crystal layer containing a photopolymerizable group and a photopolymerization initiator on a support that has not undergone any orientation treatment such as rubbing, heating the layer as needed to bring it into a liquid crystal state (nematic phase, smectic phase, etc.), and then fixing its orientation state by ultraviolet exposure. Figure 2 shows a microscopic image of a randomly oriented liquid crystal layer fabricated by this method, observed under crossed nicol conditions using a polarizing microscope.

[0031] Examples of randomly oriented liquid crystal layers include layers containing liquid crystalline compounds and dichroic substances, in which the liquid crystalline compounds are randomly oriented. With such a layer, it is possible to form a randomly oriented liquid crystal layer near the air interface of the light-absorbing anisotropic layer simultaneously with (i.e., in a continuous procedure with) the formation of the light-absorbing anisotropic layer described later.

[0032] (Layer containing fine particles) A layer containing fine particles is a layer in which depolarization occurs due to a certain degree of light scattering within the layer. Examples of fine particles that can be used include inorganic particles such as silica, alumina, zircon, and zirconia, as well as organic fine particles such as acrylic resin, melamine resin, and polyamide resin. The particles can be of various sizes, ranging from approximately 0.1 to 3 μm in diameter. Furthermore, the microparticles can be of various shapes, such as spherical, rod-shaped, or fibrous. These can also be used in combination to adjust the degree of polarization reduction.

[0033] (others) Another example of a depolarization layer, which is one form of a linear polarization conversion layer, is a depolarization layer fabricated by adding multiple types of incompatible optically anisotropic materials and separating their phases.

[0034] [Light-absorbing anisotropic layer] The light-absorbing anisotropic layer of the laminate of the present invention is a light-absorbing anisotropic layer containing a liquid crystalline compound and a dichroic substance. While various low-molecular-weight liquid crystals and polymer liquid crystals can be used as the liquid crystalline compound, it is preferable that at least a portion of the compound contains polymer liquid crystal to obtain a good orientation state for the dichroic material within the light-absorbing anisotropic layer. Furthermore, using polymer liquid crystals makes it possible to keep the difference in tilt angle of the liquid crystalline compound at the air-side interface and the support-side interface of the light-absorbing anisotropic layer relatively small, which is also preferable for obtaining good viewing angle characteristics.

[0035] To control the light transmission direction of a light-absorbing anisotropic layer, it is preferable to orient a dichroic substance having absorption in the visible region in a desired direction, and it is even more preferable to orient the dichroic substance using the orientation of a liquid crystalline compound. An example is a light-absorbing anisotropic layer in which at least one dichroic substance is oriented perpendicularly or obliquely with respect to the film normal direction.

[0036] When controlling the orientation direction of the light-absorbing anisotropic layer used in the present invention, an orientation film adjacent to the light-absorbing anisotropic layer can also be used. For a photo-orientation layer, such as azobenzene dyes or polyvinyl cinnamate, ultraviolet light is irradiated from an oblique direction at an angle to the normal direction of the photo-orientation layer to generate anisotropy with a gradient relative to the normal direction of the photo-orientation layer. By orienting the light-absorbing anisotropic layer on top of this, the dichroic substances in the light-absorbing anisotropic layer can also be oriented.

[0037] Furthermore, instead of a photo-alignment layer, a liquid crystal layer with hybrid oriented liquid crystalline compounds can be used as an alignment film to control the orientation direction of the light-absorbing anisotropy layer. In this invention, this will hereafter be referred to as a "graded liquid crystal alignment film." There are no particular limitations on the method for determining the orientation azimuth angle of the graded liquid crystal alignment film, but the orientation direction of the graded liquid crystal alignment film can be controlled by providing a rubbing-treated polyvinyl alcohol layer, a rubbing-treated polyimide layer, or a photo-alignment film adjacent to the orientation layer on the opposite side from the light-absorbing anisotropy layer.

[0038] Techniques for orienting dichroic materials in a desired direction can be based on techniques for fabricating polarizers using dichroic materials and techniques for fabricating guest-host liquid crystal cells. For example, techniques used in methods for manufacturing dichroic polarizing elements described in Japanese Patent Publication No. 11-305036 and Japanese Patent Publication No. 2002-90526; and methods for manufacturing guest-host type liquid crystal display devices described in Japanese Patent Publication No. 2002-99388 and Japanese Patent Publication No. 2016-27387; can also be used to manufacture the light-absorbing anisotropic layer used in the present invention.

[0039] For example, by utilizing guest-host liquid crystal cell technology, the molecules of a dichroic substance can be aligned to the desired orientation as described above, in conjunction with the orientation of the host liquid crystal. Specifically, a light-absorbing anisotropic layer used in the present invention can be fabricated by mixing a guest dichroic substance with a rod-shaped liquid crystalline compound that acts as a host liquid crystal, aligning the host liquid crystal, and aligning the molecules of the dichroic substance along the orientation of the liquid crystal molecules, thereby fixing the orientation state. Figure 4 shows a schematic cross-sectional view of a light-absorbing anisotropic film (reference numeral 1: barrier layer, reference numeral 2: light-absorbing anisotropic layer, reference numeral 3: barrier layer / PVA alignment film, reference numeral 4: TAC support) having a light-absorbing anisotropic layer in which the dichroic substance (reference numeral 12: dichroic dye D-1, reference numeral 13: dichroic dye D-2, reference numeral 14: dichroic dye D-3) is vertically oriented due to the guest-host effect of liquid crystal molecules 11.

[0040] To prevent variations in the light absorption properties of the light-absorbing anisotropic layer used in the present invention due to the operating environment, it is preferable to fix the orientation of the dichroic material by forming chemical bonds. For example, the orientation can be fixed by promoting polymerization of the host liquid crystal, the dichroic material, or optionally added polymerizable component.

[0041] Alternatively, a guest-host type liquid crystal cell itself, having a liquid crystal layer containing at least a dichroic substance and a host liquid crystal on a pair of substrates, may be used as the light-absorbing anisotropic layer in the present invention. The orientation of the host liquid crystal (and the orientation of the associated dichroic substance molecules) can be controlled by an alignment film formed on the inner surface of the substrate, and unless external stimuli such as an electric field are applied, the orientation state is maintained, and the light-absorbing characteristics of the light-absorbing anisotropic layer used in the present invention can be kept constant.

[0042] The light-absorbing anisotropic layer used in the present invention preferably has a transmittance of 60% or less, more preferably 50% or less, and even more preferably 45% or less, when tilted 30° from the transmittance center axis (referring to the transmittance at a wavelength of 550 nm; the same applies hereinafter). This makes it possible to increase the contrast between the transmittance center and the illuminance in directions offset from the transmittance center, and to sufficiently narrow the viewing angle.

[0043] The light-absorbing anisotropic layer used in the present invention preferably has a transmittance of 65% or more along the transmittance center axis, more preferably 75% or more, and even more preferably 85% or more. This increases the illuminance at the center of the viewing angle of the image display device, thereby improving visibility.

[0044] Furthermore, in order to achieve a neutral color in the frontal direction, it is preferable that the degree of orientation of the light-absorbing anisotropic layer at 420 nm is 0.93 or higher. Here, the color control of the light-absorbing anisotropic layer containing a dichroic substance is usually performed by adjusting the amount of dichroic substance added to the light-absorbing anisotropic layer. However, it was found that achieving a neutral color in both the front and oblique directions cannot be done by adjusting the amount of dichroic substance added alone. It was discovered that the reason why the color in both the front and oblique directions could not be made neutral was the low degree of orientation at 420 nm, and that by increasing the degree of orientation at 420 nm, the color in both the front and oblique directions could be made neutral.

[0045] Furthermore, the optical anisotropic absorption layer used in the present invention may be formed by laminating multiple optical anisotropic absorption layers with different transmittance centers or by laminating a phase difference layer, so as to satisfy the transmittance tilted 30° from the transmittance center axis and the transmittance along the transmittance center axis. By stacking multiple optically anisotropic absorption layers with different transmittance central axes, the width of the region with high transmittance can be adjusted.

[0046] In the present invention, it is preferable that the above-mentioned light-absorbing anisotropic layer is a light-absorbing anisotropic layer formed from a light-absorbing anisotropic layer-forming composition (hereinafter also referred to as "light-absorbing anisotropic layer-forming composition") containing a liquid crystalline compound and a dichroic substance. Furthermore, the composition for forming a light-absorbing anisotropic layer may contain a solvent, a polymerization initiator, a polymerizable compound, an interface modifier, and other additives. The following explains each component.

[0047] <Liquid crystal compounds> The composition for forming a light-absorbing anisotropic layer contains a liquid crystalline compound. Liquid crystal compounds can generally be classified into rod-shaped and disc-shaped types based on their shape. Furthermore, the liquid crystalline compound is preferably one that does not exhibit dichroism in the visible region. In the following explanation, "a higher degree of orientation of the formed light-absorbing anisotropic layer" is also referred to as "a superior effect of the present invention."

[0048] As the liquid crystalline compound, either a low-molecular-weight liquid crystalline compound or a high-molecular-weight liquid crystalline compound can be used. Here, "low molecular weight liquid crystalline compounds" refers to liquid crystalline compounds that do not have repeating units in their chemical structure. Furthermore, "polymeric liquid crystalline compounds" refer to liquid crystalline compounds that have repeating units in their chemical structure. Examples of low-molecular-weight liquid crystalline compounds include the liquid crystalline compounds described in Japanese Patent Publication No. 2013-228706. Examples of polymeric liquid crystalline compounds include the thermotropic liquid crystalline polymer described in Japanese Patent Publication No. 2011-237513. Furthermore, the polymeric liquid crystalline compound may have crosslinkable groups (e.g., acryloyl groups and methacryloyl groups) at its terminals.

[0049] The liquid crystalline compound is preferably a rod-shaped liquid crystalline compound, and more preferably a polymer liquid crystalline compound, because the effects of the present invention are more easily manifested in this case.

[0050] Liquid crystalline compounds may be used individually or in combination of two or more. The liquid crystalline compound preferably includes a polymer liquid crystalline compound, and more preferably includes both a polymer liquid crystalline compound and a low molecular weight liquid crystalline compound, in order to achieve superior effects of the present invention.

[0051] The liquid crystalline compound preferably includes a liquid crystalline compound represented by formula (LC) or a polymer thereof. The liquid crystalline compound represented by formula (LC) or a polymer thereof is a compound that exhibits liquid crystalline properties. The liquid crystalline property may be in the nematic phase or the smectic phase, or it may exhibit both the nematic phase and the smectic phase, but it is preferable that it exhibits at least the nematic phase. The smectic phase may be a higher-order smectic phase. The higher-order smectic phases referred to here are smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase, and smectic L phase, and among these, smectic B phase, smectic F phase, and smectic I phase are preferred. When the smectic liquid crystal phase exhibited by the liquid crystalline compound is one of these higher-order smectic liquid crystal phases, it is preferable that an optically anisotropic layer with a higher degree of orientation order can be produced. Furthermore, optically anisotropic layers fabricated from such highly oriented smectic liquid crystal phases yield Bragg peaks originating from higher-order structures such as hexatic and crystalline phases in X-ray diffraction measurements. These Bragg peaks are peaks derived from the periodic plane structure of molecular orientation, and according to the optically anisotropic layer formation composition of the present invention, an optically anisotropic layer with a periodic interval of 3.0 to 5.0 Å can be obtained.

[0052] [ka]

[0053] In formula (LC), Q1 and Q2 are independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, a heterocyclic group (or heterocyclic group), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group (including anilino group), an ammonia group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl or Q1 represents an arylsulfonylamino group, a mercapto alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a phosphono group, a silyl group, a hydrazino group, a ureido group, a boronic acid group (-B(OH)2), a phosphat group (-OPO(OH)2), a sulfat group (-OSO3H), or a crosslinkable group represented by the following formulas (P1) to (P-30), and preferably at least one of Q1 and Q2 is a crosslinkable group represented by the following formula.

[0054] [ka]

[0055] In formulas (P-1) to (P-30), R PThis includes hydrogen atoms, halogen atoms, linear, branched, or cyclic alkylene groups with 1 to 10 carbon atoms, alkyl halides with 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, alkenyl groups with 1 to 20 carbon atoms, alkynyl groups with 1 to 20 carbon atoms, aryl groups with 1 to 20 carbon atoms, heterocyclic groups (also called heterocyclic groups), cyano groups, hydroxyl groups, nitro groups, carboxyl groups, aryloxy groups, silyloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, amino groups (including anilino groups), ammonia groups, acylamino groups, aminocarbonylamino groups, alkoxycarbonylamino groups, and aryloxycarbon The R represents a nyamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (-B(OH)2), phosphat group (-OPO(OH)2), or sulfat group (-OSO3H), and multiple R P These may be the same or different.

[0056] Preferred crosslinkable groups include radical polymerizable groups or cationic polymerizable groups. Preferred radical polymerizable groups include the vinyl group represented by formula (P-1), the butadiene group represented by formula (P-2), the (meth)acrylic group represented by formula (P-4), the (meth)acrylamide group represented by formula (P-5), the vinyl acetate group represented by formula (P-6), the fumarate ester group represented by formula (P-7), the styryl group represented by formula (P-8), the vinylpyrrolidone group represented by formula (P-9), the maleic anhydride group represented by formula (P-11), or the maleimide group represented by formula (P-12). Preferred cationic polymerizable groups include the vinyl ether group represented by formula (P-18), the epoxy group represented by formula (P-19), or the oxetanyl group represented by formula (P-20).

[0057] In formula (LC), S1 and S2 each independently represent a divalent spacer group, and preferred embodiments of S1 and S2 include the same structure as SPW in formula (W1) above, so their explanation is omitted.

[0058] In formula (LC), MG represents a mesogenic group, which will be described later. The mesogenic group represented by MG is a group that represents the main skeleton of a liquid crystal molecule that contributes to liquid crystal formation. Liquid crystal molecules exhibit liquid crystalline properties, which is an intermediate state (mesophase) between the crystalline state and the isotropic liquid state. There are no particular restrictions on the mesogenic group; for example, refer to the description in "Flussige Kristalle in Tabellen II" (VEB Deutsche Verlag fur Grundstoff Industrie, Leipzig, 1984), especially pages 7 to 16, and the description in the Liquid Crystal Handbook (Maruzen, 2000), edited by the Liquid Crystal Handbook Editorial Committee, especially Chapter 3. The mesogenic group represented by MG preferably contains 2 to 10 cyclic structures, and more preferably 3 to 7. Specific examples of cyclic structures include aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups.

[0059] As for the mesogenic group represented by MG, a group represented by the following formula (MG-A) or formula (MG-B) is preferred, and the group represented by formula (MG-B) is more preferred, from the viewpoint of the emergence of liquid crystalline properties, adjustment of the liquid crystal phase transition temperature, availability of raw materials, and suitability for synthesis, as well as the effects of the present invention.

[0060] [ka]

[0061] In formula (MG-A), A1 is a divalent group selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups. These groups may be substituted with substituents such as substituent W, which will be described later. The divalent group represented by A1 is preferably a 4- to 15-membered ring. Furthermore, the divalent group represented by A1 may be a monocyclic or fused ring.

[0062] * indicates a connection position with S1 or S2.

[0063] Examples of divalent aromatic hydrocarbon groups represented by A1 include phenylene, naphthylene, fluorene-diyl, anthracene-diyl, and tetracene-diyl groups. From the viewpoint of the diversity of mesogenic skeleton design and the availability of raw materials, phenylene and naphthylene groups are preferred.

[0064] The divalent heterocyclic group represented by A1 may be either aromatic or non-aromatic, but from the viewpoint of improving the degree of orientation, it is preferable to be a divalent aromatic heterocyclic group. Examples of atoms other than carbon that constitute the divalent aromatic heterocyclic group include nitrogen, sulfur, and oxygen atoms. If the aromatic heterocyclic group has multiple atoms other than carbon that constitute the ring, these may be the same or different. Specific examples of divalent aromatic heterocyclic groups include, for example, pyridylene (pyridine-diyl group), pyridazine-diyl group, imidazole-diyl group, thienylene (thiophene-diyl group), quinolylene (quinoline-diyl group), isoquinolylene (isoquinoline-diyl group), oxazole-diyl group, thiazole-diyl group, oxadiazole-diyl group, benzothiazole-diyl group, benzothiadiazole-diyl group, phthalimide-diyl group, thienothiazole-diyl group, thiazolothiazole-diyl group, thienothiophene-diyl group, and thienoxazole-diyl group, as well as structures (II-1) to (II-4) below.

[0065] [ka]

[0066] In equations (II-1) to (II-4), D1 is -S-, -O-, or NR 11 - represents R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Y1 represents an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 3 to 12 carbon atoms, and Z1, Z2, and Z3 independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, or -NR. 12 R 13 or -SR 12 Z1 and Z2 may be bonded to each other to form an aromatic ring or an aromatic heterocycle, R 12 and R 13 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and J1 and J2 independently represent -O- and -NR, respectively.21 -(R 21 ) represents a hydrogen atom or substituent. ), represents a group selected from the group consisting of -S- and C(O)-, E represents a hydrogen atom or a nonmetal atom of group 14-16 which may have substituents, Jx represents an organic group having 2-30 carbon atoms having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles, Jy represents a hydrogen atom, an alkyl group having 1-6 carbon atoms which may have substituents, or an organic group having 2-30 carbon atoms having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles, the aromatic rings of Jx and Jy may have substituents, Jx and Jy may be bonded to form a ring, and D2 represents a hydrogen atom or an alkyl group having 1-6 carbon atoms which may have substituents.

[0067] In formula (II-2), if Y1 is an aromatic hydrocarbon group having 6 to 12 carbon atoms, it may be monocyclic or polycyclic. If Y1 is an aromatic heterocyclic group having 3 to 12 carbon atoms, it may be monocyclic or polycyclic. In formula (II-2), J1 and J2 are -NR 21 When representing -, R 21 For substituents, see, for example, paragraphs 0035 to 0045 of Japanese Patent Publication No. 2008-107767, which are incorporated into this specification. In formula (II-2), if E is a nonmetal atom of group 14 to 16 to which substituents may be attached, then =O, =S, =NR', =C(R')R' are preferred. R' represents a substituent, and for substituents, see, for example, paragraphs

[0035] to

[0045] of Japanese Patent Publication No. 2008-107767, -NZ A1 Z A2 (Z A1 and Z A2 Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group. ) is preferred.

[0068] Specific examples of the divalent alicyclic group represented by A1 include the cyclopentylene group and the cyclohexylene group, and the carbon atoms may be substituted with -O-, -Si(CH3)2-, -N(Z)- (where Z represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, a cyano group, or a halogen atom), -C(O)-, -S-, -C(S)-, -S(O)-, and -SO2-, or groups formed by combining two or more of these groups.

[0069] In equation (MG-A), a1 represents an integer between 2 and 10. Multiple A1s may be the same or different.

[0070] In formula (MG-B), A2 and A3 are each independently divalent groups selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups. Specific examples and preferred embodiments of A2 and A3 are the same as those of A1 in formula (MG-A), so their explanation is omitted. In formula (MG-B), a2 represents an integer from 1 to 10, and multiple A2s may be the same or different, and multiple LA1s may be the same or different. It is more preferable that a2 is 2 or greater for superior effects of the present invention. In formula (MG-B), LA1 is a single bond or a divalent linking group. However, when a2 is 1, LA1 is a divalent linking group, and when a2 is 2 or greater, at least one of the multiple LA1s is a divalent linking group. In formula (MG-B), the divalent linking group represented by LA1 is the same as that of LW, so its explanation is omitted.

[0071] Specific examples of MG include the following structure, in which hydrogen atoms on aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups may be substituted with the substituent W mentioned above.

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] (Low molecular liquid crystal compound) When the liquid crystalline compound represented by formula (LC) is a low-molecular-weight liquid crystalline compound, preferred embodiments of the cyclic structure of the mesogenic group MG include cyclohexylene group, cyclopentylene group, phenylene group, naphthylene group, fluorene-diyl group, pyridine-diyl group, pyridazine-diyl group, thiophene-diyl group, oxazole-diyl group, thiazole-diyl group, thienothiophene-diyl group, and the like, with 2 to 10 cyclic structures being preferred, and 3 to 7 being more preferred.

[0076] Preferred embodiments of the substituent W in the mesogenic structure include halogen atoms, alkyl halides, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, C1-C10 alkoxy groups, C1-C10 alkylcarbonyl groups, C1-C10 alkyloxycarbonyl groups, C1-C10 alkylcarbonyloxy groups, amino groups, C1-C10 alkylamino groups, alkylaminocarbonyl groups, and groups in the above formula (W1) where LW is a single bond, SPW is a divalent spacer group, and Q is a crosslinkable group represented by (P1) to (P30) above. Preferred crosslinkable groups include vinyl groups, butadiene groups, (meth)acrylic groups, (meth)acrylamide groups, vinyl acetate groups, fumarate ester groups, styryl groups, vinylpyrrolidone groups, maleic anhydride, maleimide groups, vinyl ether groups, epoxy groups, and oxetanyl groups.

[0077] The preferred embodiments of the divalent spacer groups S1 and S2 are the same as those described for SPW above, so their explanation is omitted. When using a low-molecular-weight liquid crystalline compound exhibiting smectic properties, the number of carbon atoms in the spacer group (or the number of atoms if these carbons are replaced with "SP-C") is preferably 6 or more, and more preferably 8 or more.

[0078] When the liquid crystalline compound represented by formula (LC) is a low-molecular-weight liquid crystalline compound, multiple low-molecular-weight liquid crystalline compounds may be used in combination, preferably 2 to 6 types, and more preferably 2 to 4 types. By using low-molecular-weight liquid crystalline compounds in combination, it is possible to improve solubility and adjust the phase transition temperature of the composition for forming a light-absorbing anisotropic layer.

[0079] Specific examples of low-molecular-weight liquid crystalline compounds include those represented by the following formulas (LC-1) to (LC-77), but low-molecular-weight liquid crystalline compounds are not limited to these.

[0080] [ka] JPEG0007835725000010.jpg150118 JPEG0007835725000011.jpg131120 JPEG0007835725000012.jpg56165 JPEG0007835725000013.jpg185162 JPEG0007835725000014.jpg166154

[0081] [ka] JPEG0007835725000016.jpg125123 JPEG0007835725000017.jpg101143 JPEG0007835725000018.jpg132137

[0082] (Polymer liquid crystal compound) The polymeric liquid crystalline compound is preferably a homopolymer or copolymer containing repeating units as described later, and may be any polymer such as a random polymer, block polymer, graft polymer, or star polymer.

[0083] (Repeating unit (1)) The polymeric liquid crystalline compound preferably contains a repeating unit represented by formula (1) (hereinafter also referred to as "repeating unit (1)").

[0084] [ka]

[0085] In formula (1), PC1 represents the repeating main chain, L1 represents a single bond or a divalent linking group, SP1 represents a spacer group, MG1 represents the mesogenic group MG in formula (LC) above, and T1 represents a terminal group.

[0086] Examples of the main chain of the repeating unit represented by PC1 include the groups represented by formulas (P1-A) to (P1-D), and among these, the group represented by the following formula (P1-A) is preferred from the viewpoint of the diversity of monomers used as raw materials and ease of handling.

[0087] [ka]

[0088] In equations (P1-A) to (P1-D), "*" represents the bond position with L1 in equation (1). In equations (P1-A) to (P1-D), R 11 , R 12 , R 13 , R 14Each of these independently represents a hydrogen atom, a halogen atom, a cyano group, or a C1-C10 alkyl group, or a C1-C10 alkoxy group. The alkyl group may be a linear or branched alkyl group, or a cyclic alkyl group (cycloalkyl group). The number of carbon atoms in the alkyl group is preferably 1 to 5. The group represented by formula (P1-A) is preferably a unit of a partial structure of a poly(meth)acrylic acid ester obtained by polymerization of (meth)acrylic acid ester. The group represented by formula (P1-B) is preferably an ethylene glycol unit formed by ring-opening polymerization of the epoxy group of a compound having an epoxy group. The group represented by formula (P1-C) is preferably a propylene glycol unit formed by ring-opening polymerization of the oxetane group of a compound having an oxetane group. The group represented by formula (P1-D) is preferably a siloxane unit of a polysiloxane obtained by condensation polymerization of a compound having at least one of an alkoxysilyl group and a silanol group. Here, as a compound having at least one of an alkoxysilyl group and a silanol group, the formula SiR 14 (OR 15 Examples include compounds having a group represented by )2-. In the formula, R 14 R in (P1-D) 14 It is synonymous with multiple R 15 Each of these independently represents either a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0089] The divalent linking group represented by L1 is a divalent linking group similar to LW in the above formula (W1), and preferred embodiments include -C(O)O-, -OC(O)-, -O-, -S-, and -C(O)NR. 16 -, -NR 16 C(O)-, -S(O)2-, and -NR 16 R 17 - are some examples. In the formula, R 16 and R 17Each of these independently represents a C1-C6 alkyl group which may have a hydrogen atom or a substituent (e.g., substituent W as described above). In a specific example of a divalent linking group, the left-hand bond is linked to PC1 and the right-hand bond is linked to SP1. When PC1 is a group represented by formula (P1-A), L1 is -C(O)O- or -C(O)NR 16 A group represented by - is preferred. If PC1 is a group represented by formulas (P1-B) to (P1-D), then L1 is a single bond.

[0090] The spacer group represented by SP1 represents the same groups as S1 and S2 in the above formula (LC), and from the viewpoint of orientation, it is preferable to have a group containing at least one structure selected from the group consisting of oxyethylene structure, oxypropylene structure, polysiloxane structure and alkylene fluoride structure, or a linear or branched alkylene group having 2 to 20 carbon atoms. However, the alkylene group may include -O-, -S-, -O-CO-, -CO-O-, -O-CO-O-, -O-CNR- (where R represents an alkyl group having 1 to 10 carbon atoms), or -S(O)2-. The spacer group represented by SP1 is more preferably a group containing at least one structure selected from the group consisting of oxyethylene structure, oxypropylene structure, polysiloxane structure and alkylene fluoride structure, due to reasons such as ease of exhibiting liquid crystalline properties and availability of raw materials. Here, the oxyethylene structure represented by SP1 is *-(CH2-CH2O) n1 A base represented by -* is preferred. In the formula, n1 represents an integer from 1 to 20, and * represents the bonding position with L1 or MG1. For reasons that the effects of the present invention are superior, n1 is preferably an integer from 2 to 10, more preferably an integer from 2 to 6, and most preferably from 2 to 4.

[0091] Furthermore, the oxypropylene structure represented by SP1 is preferably a group represented by *-(CH(CH3)-CH2O)n2-*. In the formula, n2 represents an integer from 1 to 3, and * represents the bonding position with L1 or MG1. Furthermore, the polysiloxane structure represented by SP1 is preferably a group represented by *-(Si(CH3)2-O)n3-*. In the formula, n3 represents an integer from 6 to 10, and * represents the bonding position with L1 or MG1. Furthermore, the alkylene fluoride structure represented by SP1 is preferably a group represented by *-(CF2-CF2)n4-*. In the formula, n4 represents an integer from 6 to 10, and * represents the bonding position with L1 or MG1.

[0092] The terminal groups represented by T1 include hydrogen, halogen, cyano, nitro, hydroxyl, -SH, carboxyl, boronic acid, -SO3H, -PO3H2, and -NR. 11 R 12 (R 11 and R 12 Examples include C1-C10 alkyl groups, cycloalkyl groups, or aryl groups (where each represents independently a hydrogen atom or a substituted or unsubstituted C1-C10 alkyl group, cycloalkyl group, or aryl group), C1-C10 alkyl groups, C1-C10 alkoxy groups, C1-C10 alkylthio groups, C1-C10 alkoxycarbonyloxy groups, C1-C10 acyloxy groups, C1-C10 acylamino groups, C1-C10 alkoxycarbonyl groups, C1-C10 alkoxycarbonylamino groups, C1-C10 sulfonylamino groups, C1-C10 sulfamoyl groups, C1-C10 carbamoyl groups, C1-C10 sulfinyl groups, and C1-C10 ureido groups, crosslinking group-containing groups, etc.

[0093] Examples of the crosslinkable group-containing groups include the -L-CL group described above. L represents a single bond or a linking group. Specific examples of linking groups are the same as those described above for LW and SPW. CL represents a crosslinkable group, and examples include the group represented by Q1 or Q2 above, with the group represented by formulas (P1) to (P30) above being preferred. Furthermore, T1 may be a group formed by combining two or more of these groups.

[0094] For T1, a carbon-1 to carbon-10 alkoxy group is preferred, a carbon-1 to carbon-5 alkoxy group is more preferred, and a methoxy group is even more preferred, for reasons that the effects of the present invention are superior. These terminal groups may be further substituted with these groups or with polymerizable groups described in Japanese Patent Application Publication No. 2010-244038.

[0095] The number of atoms in the main chain of T1 is preferably 1 to 20, more preferably 1 to 15, even more preferably 1 to 10, and particularly preferably 1 to 7, for reasons that the effects of the present invention are superior. When the number of atoms in the main chain of T1 is 20 or less, the degree of orientation of the optical anisotropy layer is further improved. Here, "main chain" in T1 refers to the longest molecular chain bonded to M1, and hydrogen atoms are not counted in the number of atoms in the main chain of T1. For example, when T1 is an n-butyl group, the number of atoms in the main chain is 4, and when T1 is a sec-butyl group, the number of atoms in the main chain is 3.

[0096] The content of repeating units (1) is preferably 40 to 100% by mass, and more preferably 50 to 95% by mass, relative to the total repeating units (100% by mass) of the polymeric liquid crystalline compound. If the content of repeating units (1) is 40% by mass or more, an excellent optical anisotropy layer can be obtained due to good orientation. If the content of repeating units (1) is 100% by mass or less, an excellent optical anisotropy layer can be obtained due to good orientation. Repeating units (1) may be present as a single type or as two or more types in the polymeric liquid crystalline compound. If two or more types of repeating units (1) are present, the above content of repeating units (1) refers to the total content of repeating units (1).

[0097] (logP value) In equation (1), the difference (|logP1-logP2|) between the logP values ​​of PC1, L1, and SP1 (hereinafter also referred to as "logP1") and the logP value of MG1 (hereinafter also referred to as "logP2") is 4 or more, and from the viewpoint of further improving the orientation of the optical anisotropy layer, it is preferably 4.25 or more, and more preferably 4.5 or more. Furthermore, from the viewpoint of adjusting the liquid crystal phase transition temperature and suitability for synthesis, the upper limit of the above difference is preferably 15 or less, more preferably 12 or less, and even more preferably 10 or less. Here, the logP value is an index that expresses the hydrophilic and hydrophobic properties of the chemical structure, and is sometimes called the hydrophilic-hydrophobic parameter. The logP value can be calculated using software such as ChemBioDraw Ultra or HSPiP (Ver.4.1.07). It can also be determined experimentally by methods such as those in OECD Guidelines for the Testing of Chemicals, Sections 1, Test No. 117. In this invention, unless otherwise specified, the logP value is the value calculated by inputting the structural formula of the compound into HSPiP (Ver. 4.1.07).

[0098] As mentioned above, logP1 refers to the logP values ​​of PC1, L1, and SP1. "LogP values ​​of PC1, L1, and SP1" refers to the logP value of the structure of PC1, L1, and SP1 as a whole, and is not the sum of the individual logP values ​​of PC1, L1, and SP1. Specifically, logP1 is calculated by inputting the series of structural formulas from PC1 to SP1 in formula (1) into the software. However, when calculating logP1, for the group represented by PC1 in the series of structural formulas from PC1 to SP1, the structure of the group represented by PC1 itself (for example, formulas (P1-A) to (P1-D) mentioned above) may be used, or the structure of a group that can become PC1 after polymerization of the monomer used to obtain the repeating unit represented by formula (1) may be used. Here, a specific example of the latter (a group that can become PC1) is as follows: When PC1 is obtained by polymerization of (meth)acrylic acid ester, CH2=C(R 1 )- represents the group (R 1) represents a hydrogen atom or a methyl group. Furthermore, if PC1 is obtained by polymerization of ethylene glycol, it is ethylene glycol, and if PC1 is obtained by polymerization of propylene glycol, it is propylene glycol. Furthermore, if PC1 is obtained by polycondensation of silanol, it is silanol (formula Si(R 2 A compound represented by )3(OH). Multiple R 2 Each of these independently represents a hydrogen atom or an alkyl group. However, multiple R 2 At least one of them represents an alkyl group.

[0099] logP1 may be lower than or higher than logP2, as long as the difference between it and logP2 is 4 or more. Here, the logP value of a typical mesogenic group (logP2 as described above) tends to be in the range of 4 to 6. In this case, if logP1 is lower than logP2, the value of logP1 is preferably 1 or less, and more preferably 0 or less. On the other hand, if logP1 is higher than logP2, the value of logP1 is preferably 8 or more, and more preferably 9 or more. If PC1 in formula (1) above is obtained by polymerization of (meth)acrylic acid ester and logP1 is lower than logP2, the logP value of SP1 in formula (1) above is preferably 0.7 or less, and more preferably 0.5 or less. On the other hand, if PC1 in formula (1) above is obtained by polymerization of (meth)acrylic acid ester and logP1 is higher than logP2, the logP value of SP1 in formula (1) above is preferably 3.7 or more, and more preferably 4.2 or more. Examples of structures with a logP value of 1 or less include oxyethylene structures and oxypropylene structures. Examples of structures with a logP value of 6 or more include polysiloxane structures and alkylene fluorides.

[0100] (Repeating units (21) and (22)) From the viewpoint of improving the degree of orientation, it is preferable that the polymeric liquid crystalline compound contains repeating units having electron-donating and / or electron-withdrawing properties at its ends. More specifically, it is more preferable that it contains repeating units (21) having a mesogenic group and an electron-withdrawing group with a σp value greater than 0 at its end, and repeating units (22) having a mesogenic group and a group with a σp value of 0 or less at its end. In this way, when the polymeric liquid crystalline compound contains repeating units (21) and repeating units (22), the degree of orientation of the optically anisotropic layer formed using it is improved compared to when it contains only either repeating unit (21) or repeating unit (22). The details of this reason are not clear, but it is generally estimated as follows: That is, the opposite dipole moments generated in repeating units (21) and repeating units (22) interact intermolecularly, strengthening the interaction of the mesogenic group in the short axis direction, which is thought to make the orientation of the liquid crystal more uniform, and as a result the degree of order of the liquid crystal is increased. This improves the orientation of the dichroic material, and it is presumed that the degree of orientation of the formed optically anisotropic layer will be high. The repeating units (21) and (22) above may be the repeating units represented by formula (1) above.

[0101] Each repeating unit (21) comprises a mesogenic group and an electron-withdrawing group located at the end of the mesogenic group with a σp value greater than 0. The electron-withdrawing group is located at the end of the mesogenic group and has a σp value greater than 0. Examples of electron-withdrawing groups (groups with a σp value greater than 0) include the group represented by EWG in formula (LCP-21) described later, and specific examples are similar. The σp value of the electron-withdrawing group is preferably 0.3 or greater, and more preferably 0.4 or greater, from the viewpoint that greater orientation of the optically anisotropic layer is achieved. The upper limit of the σp value of the electron-withdrawing group is preferably 1.2 or less, and more preferably 1.0 or less, from the viewpoint that uniformity of orientation is excellent.

[0102] The σp value is the Hammett substituent constant σp value (also simply abbreviated as "σp value"), which numerically represents the effect of the substituent on the acid dissociation equilibrium constant of substituted benzoic acid. It is a parameter that indicates the strength of the electron-withdrawing and electron-donating properties of the substituent. In this specification, the Hammett substituent constant σp value refers to the substituent constant σ when the substituent is located at the para position of benzoic acid. In this specification, the Hammett substituent constant σp value for each group is adopted from the values ​​described in the literature "Hansch et al., Chemical Reviews, 1991, Vol, 91, No. 2, 165-195". For groups for which the Hammett substituent constant σp value is not shown in the above literature, the Hammett substituent constant σp value can be calculated using the software "ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08)" based on the difference between the pKa of benzoic acid and the pKa of a benzoic acid derivative with a substituent at the para position.

[0103] The repeating unit (21) is not particularly limited as long as it has a mesogenic group and an electron-withdrawing group with a σp value greater than 0 located at the end of the mesogenic group in its side chain, but it is preferable that the repeating unit be represented by the following formula (LCP-21) in order to achieve a higher degree of orientation of the optically anisotropic layer.

[0104] [ka]

[0105] In formula (LCP-21), PC21 represents the repeating main chain, more specifically the same structure as PC1 in formula (1) above; L21 represents a single bond or a divalent linking group, more specifically the same structure as L1 in formula (1) above; SP21A and SP21B each independently represent a single bond or a spacer group, with a specific example of the spacer group representing the same structure as SP1 in formula (1) above; MG21 represents a mesogenic structure, more specifically the mesogenic group MG in formula (LC) above; and EWG represents an electron-withdrawing group with a σp value greater than 0.

[0106] The spacer groups represented by SP21A and SP21B represent groups similar to those of formulas S1 and S2 above, and preferably include at least one structure selected from the group consisting of oxyethylene structure, oxypropylene structure, polysiloxane structure, and alkylene fluoride structure, or a linear or branched alkylene group having 2 to 20 carbon atoms. However, the alkylene group may include -O-, -O-CO-, -CO-O-, or -O-CO-O-. The spacer group represented by SP1 preferably includes at least one structure selected from the group consisting of oxyethylene structure, oxypropylene structure, polysiloxane structure, and alkylene fluoride structure, due to its ease of exhibiting liquid crystalline properties and the availability of raw materials.

[0107] SP21B is preferably a single bond or a linear or branched alkylene group having 2 to 20 carbon atoms. However, the alkylene group may include -O-, -O-CO-, -CO-O-, or -O-CO-O-. Among these, the spacer group represented by SP21B is preferably a single bond because it results in a higher degree of orientation of the optically anisotropic layer. In other words, the repeating unit 21 preferably has a structure in which the electron-withdrawing group EWG in formula (LCP-21) is directly bonded to the mesogenic group MG21 in formula (LCP-21). When the electron-withdrawing group is directly bonded to the mesogenic group in this way, it is presumed that intermolecular interactions due to an appropriate dipole moment work more effectively in the polymeric liquid crystalline compound, resulting in a more uniform orientation of the liquid crystal. As a result, the order of the liquid crystal is increased, and the degree of orientation is considered to be higher.

[0108] EWG represents electron-withdrawing groups with a σp value greater than 0. Examples of electron-withdrawing groups with a σp value greater than 0 include ester groups (specifically, *-C(O)OR E (represented by), (meth)acryloyl group, (meth)acryloyloxy group, carboxyl group, cyano group, nitro group, sulfo group, -S(O)(O)-OR E ,-S(O)(O)-R E -OS(O)(O)-R E , acyl group (specifically, *-C(O)R E(The group represented by ), acyloxy group (specifically, *-OC(O)R E Groups represented by , isocyanate groups (-N=C(O)), *-C(O)N(R F )2, halogen atoms, and alkyl groups substituted with these groups (preferably having 1 to 20 carbon atoms) are examples. In each of the above groups, * indicates the bond position with SP21B. R E R represents an alkyl group having 1 to 20 carbon atoms (preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms). F Each of these independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms). Among the above groups, EWG is preferred because it allows the effects of the present invention to be more fully realized. E A group represented by , a (meth)acryloyloxy group, or a cyano group or a nitro group is preferred.

[0109] The content of repeating units (21) is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 45% by mass or less, relative to the total repeating units (100% by mass) of the polymer liquid crystalline compound, in order to maintain a high degree of orientation of the optically anisotropic layer while uniformly oriented the polymer liquid crystalline compound and the dichroic substance. The lower limit of the content of repeating units (21) is preferably 1% by mass or more, and more preferably 3% by mass or more, relative to the total repeating units (100% by mass) of the polymer liquid crystalline compound, in order to better exhibit the effects of the present invention. In the present invention, the content of each repeating unit in the polymeric liquid crystalline compound is calculated based on the amount (mass) of each monomer used to obtain each repeating unit. The repeating unit (21) may be present alone or in combination of two or more types in the polymeric liquid crystalline compound. When the polymeric liquid crystalline compound contains two or more types of repeating units (21), there are advantages such as improved solubility of the polymeric liquid crystalline compound in the solvent and easier adjustment of the liquid crystal phase transition temperature. When two or more types of repeating units (21) are present, it is preferable that their total amount is within the above range.

[0110] When two or more types of repeating units (21) are included, repeating units (21) that do not contain crosslinking groups in the EWG and repeating units (21) that contain polymerizable groups in the EWG may be used in combination. This further improves the curability of the optically anisotropic layer. Preferred crosslinking groups include vinyl groups, butadiene groups, (meth)acrylic groups, (meth)acrylamide groups, vinyl acetate groups, fumarate ester groups, styryl groups, vinylpyrrolidone groups, maleic anhydride, maleimide groups, vinyl ether groups, epoxy groups, and oxetanyl groups. In this case, from the viewpoint of balancing the curability and orientation of the optically anisotropic layer, it is preferable that the content of repeating units (21) that contain polymerizable groups in the EWG is 1 to 30% by mass relative to the total repeating units (100% by mass) of the polymeric liquid crystalline compound.

[0111] An example of a repeating unit (21) is shown below, but the repeating unit (21) is not limited to the repeating unit shown below.

[0112] [ka]

[0113] The inventors diligently investigated the composition (content ratio) and electron-donating and electron-withdrawing properties of the terminal groups of repeating units (21) and (22). As a result, they found that when the electron-withdrawing properties of the electron-withdrawing group of repeating unit (21) are strong (i.e., when the σp value is large), lowering the content ratio of repeating unit (21) increases the degree of orientation of the optically anisotropic layer. Conversely, when the electron-withdrawing properties of the electron-withdrawing group of repeating unit (21) are weak (i.e., when the σp value is close to 0), increasing the content ratio of repeating unit (21) increases the degree of orientation of the optically anisotropic layer.

[0114] Although the details of this reason are not clear, it is generally estimated as follows: It is presumed that the intermolecular interactions due to an appropriate dipole moment in the polymeric liquid crystalline compound result in a more uniform orientation of the liquid crystal, and as a result the degree of order of the liquid crystal increases, and the degree of orientation of the optical anisotropy layer increases. Specifically, the product of the σp value of the electron-withdrawing group (EWG in formula (LCP-21)) in the repeating unit (21) and the content ratio (by mass) of the repeating unit (21) in the polymeric liquid crystalline compound is preferably 0.020 to 0.150, more preferably 0.050 to 0.130, and particularly preferably 0.055 to 0.125. If the above product is within the above range, the degree of orientation of the optical anisotropy layer will be higher.

[0115] The repeating unit (22) has a mesogenic group and a group with a σp value of 0 or less located at the end of the mesogenic group. The presence of the repeating unit (22) in the polymeric liquid crystalline compound allows for uniform orientation of the polymeric liquid crystalline compound and dichroic substances. The mesogenic group is a group that represents the main skeleton of the liquid crystal molecule that contributes to liquid crystal formation, and its details are as described by MG in formula (LCP-22) below, with the same specific examples. The above group is located at the end of the mesogenic group and has a σp value of 0 or less. Examples of the above group (a group with a σp value of 0 or less) include a hydrogen atom with a σp value of 0, and a group represented by T22 in formula (LCP-22) below with a σp value less than 0 (an electron-donating group). Specific examples of the above group with a σp value less than 0 (an electron-donating group) are the same as T22 in formula (LCP-22) below. The σp value of the above group is preferably less than 0, more preferably -0.1 or less, and particularly preferably -0.2 or less, as this provides superior uniformity of orientation. The lower limit of the σp value of the above group is preferably -0.9 or higher, and more preferably -0.7 or higher.

[0116] The repeating unit (22) is not particularly limited as long as it has a mesogenic group and a group with a σp value of 0 or less located at the end of the mesogenic group in its side chain. However, from the standpoint of achieving greater uniformity in the orientation of the liquid crystal, it is preferable that the repeating unit is not one represented by the above formula (LCP-21) but rather one represented by the following formula (PCP-22).

[0117] [ka]

[0118] In formula (LCP-22), PC22 represents the repeating main chain, more specifically the same structure as PC1 in formula (1) above; L22 represents a single bond or a divalent linking group, more specifically the same structure as L1 in formula (1) above; SP22 represents a spacer group, more specifically the same structure as SP1 in formula (1) above; MG22 represents a mesogenic structure, more specifically the same structure as the mesogenic group MG in formula (LC) above; and T22 represents an electron-donating group with a Hammett substituent constant σp value less than 0.

[0119] T22 represents an electron-donating group with a σp value less than 0. Examples of electron-donating groups with a σp value less than 0 include hydroxyl groups, C1-C10 alkyl groups, C1-C10 alkoxy groups, and C1-C10 alkylamino groups. The degree of orientation of the optically anisotropic layer is further improved when the number of atoms in the T22 main chain is 20 or less. Here, "main chain" in T22 refers to the longest molecular chain bonded to MG22, and hydrogen atoms are not counted in the number of atoms in the T22 main chain. For example, if T22 is an n-butyl group, the number of atoms in the main chain is 4, and if T22 is a sec-butyl group, the number of atoms in the main chain is 3.

[0120] An example of a repeating unit (22) is shown below, but the repeating unit (22) is not limited to the repeating unit shown below.

[0121] [ka]

[0122] It is preferable that repeating units (21) and (22) share some structural similarities. The more similar the structures of the repeating units are, the more uniformly the liquid crystals are expected to align. This increases the degree of orientation of the optical anisotropy layer. Specifically, in order to increase the degree of orientation of the optical anisotropy layer, it is preferable that at least one of the following conditions be met: SP21A in formula (LCP-21) and SP22 in formula (LCP-22) have the same structure; MG21 in formula (LCP-21) and MG22 in formula (LCP-22) have the same structure; and L21 in formula (LCP-21) and L22 in formula (LCP-22) have the same structure. It is preferable that at least one of these conditions be met, more preferably two or more, and particularly preferably all of them be met.

[0123] The content of repeating units (22) is preferably 50% by mass or more, more preferably 55% by mass or more, and particularly preferably 60% by mass or more, relative to the total repeating units (100% by mass) of the polymeric liquid crystalline compound, from the viewpoint of excellent uniformity of orientation. The upper limit of the content of repeating units (22) is preferably 99% by mass or less, and more preferably 97% by mass or less, relative to the total repeating units (100% by mass) of the polymeric liquid crystalline compound, from the viewpoint of improving the degree of orientation. Repeating units (22) may be present as one type alone or as two or more types in the polymeric liquid crystalline compound. When the polymeric liquid crystalline compound contains two or more types of repeating units (22), there are advantages such as improved solubility of the polymeric liquid crystalline compound in solvents and easier adjustment of the liquid crystal phase transition temperature. When two or more types of repeating units (22) are present, it is preferable that their total amount is within the above range.

[0124] (Repeating unit (3)) Polymeric liquid crystalline compounds can contain repeating units (3) that do not contain mesogens, from the viewpoint of improving solubility in common solvents. In particular, in order to improve solubility while suppressing a decrease in the degree of orientation, it is preferable that the repeating units (3) that do not contain mesogens have a molecular weight of 280 or less. The reason why including repeating units with a molecular weight of 280 or less that do not contain mesogens can improve solubility while suppressing a decrease in the degree of orientation is presumed to be as follows: That is, when a polymeric liquid crystalline compound contains repeating units (3) that do not contain mesogens in its molecular chain, the solvent can easily penetrate into the polymeric liquid crystalline compound, thus improving solubility, but it is thought that the non-mesogenic repeating units (3) reduce the degree of orientation. However, it is presumed that because the molecular weight of the above repeating units is small, the orientation of the repeating units (1), (21), or (22) containing the mesogenic group is less likely to be disrupted, and a decrease in the degree of orientation can be suppressed.

[0125] The repeating unit (3) described above is preferably a repeating unit with a molecular weight of 280 or less. The molecular weight of the repeating unit (3) does not refer to the molecular weight of the monomer used to obtain the repeating unit (3), but rather to the molecular weight of the repeating unit (3) in the state in which it is incorporated into the polymeric liquid crystalline compound by polymerization of the monomer. The molecular weight of the repeating unit (3) is 280 or less, preferably 180 or less, and more preferably 100 or less. The lower limit of the molecular weight of the repeating unit (3) is usually 40 or more, and more preferably 50 or more. If the molecular weight of the repeating unit (3) is 280 or less, an optically anisotropic layer with excellent solubility of the polymeric liquid crystalline compound and a high degree of orientation can be obtained. On the other hand, if the molecular weight of the repeating unit (3) exceeds 280, it may disrupt the liquid crystal orientation of the repeating unit (1), repeating unit (21), or repeating unit (22), resulting in a lower degree of orientation. In addition, the solvent may not be able to penetrate into the polymeric liquid crystalline compound easily, which may reduce the solubility of the polymeric liquid crystalline compound.

[0126] Specific examples of repeating units (3) include repeating units that do not contain crosslinking groups (e.g., ethylenically unsaturated groups) (hereinafter also referred to as "repeating unit (3-1)") and repeating units that contain crosslinking groups (hereinafter also referred to as "repeating unit (3-2)").

[0127] • Repeating unit (3-1) Specific examples of monomers used in the polymerization of the repeating unit (3-1) include acrylic acid [72.1], α-alkylacrylic acids (e.g., methacrylic acid [86.1], itaconic acid [130.1]), and esters and amides derived therefrom (e.g., Ni-propylacrylamide [113.2], Nn-butylacrylamide [127.2], Nt-butylacrylamide [127.2], N,N-dimethylacrylamide [99.1], N-methylmethacrylamide [99.1], acrylamide [71.1], methacrylamide [85.1]). Diacetone acrylamide [169.2], acryloylmorpholine [141.2], N-methylolacrylamide [101.1], N-methylolmethacrylamide [115.1], methyl acrylate [86.0], ethyl acrylate [100.1], hydroxyethyl acrylate [116.1], n-propyl acrylate [114.1], i-propyl acrylate [114.2], 2-hydroxypropyl acrylate [130.1], 2-methyl-2-nitropropyl acrylate [173.2], n-butyl acrylate

[128] .2], i-butyl acrylate [128.2], t-butyl acrylate [128.2], t-pentyl acrylate [142.2], 2-methoxyethyl acrylate [130.1], 2-ethoxyethyl acrylate [144.2], 2-ethoxyethoxyethyl acrylate [188.2], 2,2,2-trifluoroethyl acrylate [154.1], 2,2-dimethylbutyl acrylate [156.2], 3-methoxybutyl acrylate [158.2], ethyl carbitol acrylate [188.2], phenoxyethyl acrylate [192.2], n-pentyl acrylate [142.2], n-hexyl acrylate [156.2], cyclohexyl acrylate [154.2], cyclopentyl acrylate [140.2], benzyl acrylate [162.2], n-octyl acrylate [184.3], 2-ethylhexyl acrylate [184.3], 4-methyl-2-propylpentyl acrylate [198.3], methyl methacrylate [100.1], 2,2,2-trifluoroethyl methacrylate [168.1], hydroxyethyl methacrylate [130.1], 2-hydroxypropyl methacrylate [144.2], n-butyl methacrylate [142.2], i-butyl methacrylate [142.2], sec-butyl methacrylate [142.2], n-octyl methacrylate [198.3], 2-ethylhexyl methacrylate [198.3], 2-methoxyethyl methacrylate [144.2], 2-ethoxyethyl methacrylate [158.2], benzyl methacrylate [176.2], 2-norbornyl methyl methacrylate [194.3], 5-norbornene-2-i Methyl methacrylate [194.3], dimethylaminoethyl methacrylate [157.2]), vinyl esters (e.g., vinyl acetate [86.1]), esters derived from maleic acid or fumaric acid (e.g., dimethyl maleate [144.1], diethyl fumarate [172.2]), maleimides (e.g., N-phenylmaleimide [173.2]), maleic acid [116.1], fumaric acid [116.1], p-styrene sulfonic acid [184.1], acrylonitrile [53.1], methacrylonitrile [67.1], diethyl methacrylate N-sulfur compounds (e.g., butadiene [54.1], cyclopentadiene [66.1], isoprene [68.1]), aromatic vinyl compounds (e.g., styrene [104.2], p-chlorostyrene [138.6], t-butylstyrene [160.3], α-methylstyrene [118.2]), N-vinylpyrrolidone [111.1], N-vinyloxazolidone [113.1], N-vinylsuccinimide [125.1], N-vinylformamide [71.1], N-vinyl-N-methylformamide [85.1], N-vinylacetamide [85. 1], N-vinyl-N-methylacetamide [99.1], 1-vinylimidazole [94.1], 4-vinylpyridine [105.2], vinylsulfonic acid [108.1], sodium vinylsulfonate [130.2], sodium allylsulfonate [144.1], sodium methallylsulfonate [158.2], vinylidene chloride [96.9], vinyl alkyl ethers (e.g., methyl vinyl ether [58.1]), ethylene [28.0], propylene [42.1], 1-butene [56.1], and isobutene [56.Examples include [1]. The numbers in brackets [ ] represent the molecular weight of the monomer. The above monomers may be used individually or in combination of two or more. Among the above monomers, acrylic acid, α-alkylacrylic acids, esters and amides derived therefrom, acrylonitrile, methacrylonitrile, and aromatic vinyl compounds are preferred. Other monomers that can be used include, for example, the compounds described in Research Disclosure No. 1955 (July 1980).

[0128] The following shows specific examples of repeating units (3-1) and their molecular weights, but the present invention is not limited to these specific examples.

[0129] [ka]

[0130] • Repeating units (3-2) In the repeating unit (3-2), specific examples of crosslinkable groups include the groups represented by P1 to P30 above, with vinyl groups, butadiene groups, (meth)acrylic groups, (meth)acrylamide groups, vinyl acetate groups, fumarate ester groups, styryl groups, vinylpyrrolidone groups, maleic anhydride, maleimide groups, vinyl ether groups, epoxy groups, and oxetanyl groups being more preferred. The repeating unit (3-2) is preferably a repeating unit represented by the following formula (3) because it is easy to polymerize.

[0131] [ka]

[0132] In formula (3) above, PC32 represents the repeating main chain, more specifically the same structure as PC1 in formula (1) above; L32 represents a single bond or a divalent linking group, more specifically the same structure as L1 in formula (1) above; and P32 represents the crosslinking group represented by formulas (P1) to (P30) above.

[0133] The following shows specific examples of repeating units (3-2) and their weight-average molecular weight (Mw), but the present invention is not limited to these specific examples.

[0134] [ka]

[0135] The content of repeating units (3) is less than 14% by mass, preferably 7% by mass or less, and more preferably 5% by mass or less, relative to the total repeating units (100% by mass) of the polymeric liquid crystalline compound. The lower limit of the content of repeating units (3) is preferably 2% by mass or more, and more preferably 3% by mass or more, relative to the total repeating units (100% by mass) of the polymeric liquid crystalline compound. If the content of repeating units (3) is less than 14% by mass, the degree of orientation of the optical anisotropy layer is further improved. If the content of repeating units (3) is 2% by mass or more, the solubility of the polymeric liquid crystalline compound is further improved. Repeating units (3) may be present as a single type or as two or more types in the polymeric liquid crystalline compound. If two or more types of repeating units (3) are present, it is preferable that their total amount is within the above range.

[0136] (Repeating unit (4)) Polymeric liquid crystalline compounds can contain repeating units (4) with long, flexible molecular chains (SP4 in equation (4) described later) to improve adhesion and planar uniformity. The reason for this is presumed to be as follows: By including such long, flexible molecular chains, entanglement between the molecular chains constituting the polymeric liquid crystalline compound becomes more likely, suppressing aggregate breakdown of the optically anisotropic layer (specifically, breakdown of the optically anisotropic layer itself). As a result, it is presumed that the adhesion between the optically anisotropic layer and the underlying layer (e.g., substrate or alignment film) is improved. Furthermore, the decrease in planar uniformity is thought to be due to the low compatibility between the dichroic substance and the polymeric liquid crystalline compound. That is, if the compatibility between the dichroic substance and the polymeric liquid crystalline compound is insufficient, it is thought that planar defects (orientation defects) will occur with the precipitated dichroic substance as a nucleus. In contrast, it is presumed that by including long, flexible molecular chains in the polymeric liquid crystalline compound, the precipitation of the dichroic substance is suppressed, resulting in an optically anisotropic layer with excellent planar uniformity. Here, "excellent planar uniformity" means that there are few orientation defects caused by the light-absorbing anisotropic layer-forming composition containing the polymer liquid crystalline compound being repelled on the underlying layer (e.g., substrate or orientation film).

[0137] The repeating unit (4) described above is the repeating unit represented by the following formula (4).

[0138] [ka]

[0139] In formula (4) above, PC4 represents a repeating main chain, more specifically a structure similar to PC1 in formula (1) above; L4 represents a single bond or a divalent linking group, more specifically a structure similar to L1 in formula (1) above (a single bond is preferred); SP4 represents an alkylene group with 10 or more atoms in the main chain; and T4 represents a terminal group, more specifically a structure similar to T1 in formula (1) above.

[0140] Specific examples and preferred embodiments of PC4 are the same as those of PC1 in formula (1), so their explanation will be omitted.

[0141] As L4, a single bond is preferable from the viewpoint that the effects of the present invention are more exerted.

[0142] In formula (4), SP4 represents an alkylene group having 10 or more carbon atoms in the main chain. However, one or more -CH2- constituting the alkylene group represented by SP4 may be replaced by the above-mentioned "SP-C". In particular, -O-, -S-, -N(R 21 )-, -C(=O)-, -C(=S)-, -C(R 22 )=C(R 23 )-, an alkynylene group, -Si(R 24 )(R 25 )-, -N=N-, -C(R 26 )=N-N=C(R 27 )-, -C(R 28 )=N- and S(=O)2- are preferably replaced by at least one group selected from the group consisting of. However, R 21 ~R 28 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group or a linear or branched alkyl group having 1 to 10 carbon atoms. Further, the hydrogen atom contained in one or more -CH2- constituting the alkylene group represented by SP4 may be replaced by the above-mentioned "SP-H".

[0143] The number of atoms in the main chain of SP4 is 10 or more, preferably 15 or more, and more preferably 19 or more, since an optically anisotropic layer with superior adhesion and planar uniformity can be obtained. The upper limit of the number of atoms in the main chain of SP2 is preferably 70 or less, more preferably 60 or less, and particularly preferably 50 or less, since an optically anisotropic layer with superior orientation can be obtained. Here, "main chain" in SP4 means the substructure necessary to directly link L4 and T4, and "number of atoms in the main chain" means the number of atoms constituting the above substructure. In other words, the "main chain" in SP4 is the substructure with the shortest number of atoms linking L4 and T4. For example, the number of atoms in the main chain when SP4 is a 3,7-dimethyldecanyl group is 10, and the number of atoms in the main chain when SP4 is a 4,6-dimethyldodecanyl group is 12. Furthermore, in equation (4-1) below, the area within the dotted rectangle corresponds to SP4, and the number of atoms in the main chain of SP4 (corresponding to the total number of atoms enclosed by the dotted circles) is 11.

[0144] [ka]

[0145] The alkylene group represented by SP4 may be linear or branched. The number of carbon atoms in the alkylene group represented by SP4 is preferably 8 to 80, 15 to 80, more preferably 25 to 70, and particularly preferably 25 to 60, from the standpoint of obtaining an optically anisotropic layer with an excellent degree of orientation.

[0146] It is preferable that one or more -CH2- groups constituting the alkylene group represented by SP4 are replaced by the aforementioned "SP-C" group, in order to obtain an optically anisotropic layer with excellent adhesion and planar uniformity. Furthermore, if there are multiple -CH2- groups constituting the alkylene group represented by SP4, it is even more preferable that only some of the multiple -CH2- groups are replaced by the aforementioned "SP-C" group, in order to obtain an optically anisotropic layer with excellent adhesion and planar uniformity.

[0147] Among "SP-C", -O-, -S-, -N(R 21)-, -C(=O)-, -C(=S)-, -C(R 22 )=C(R 23 )-, an alkynylene group, -Si(R 24 )(R 25 )-, -N=N-, -C(R 26 )=N-N=C(R 27 )-, -C(R 28 )=N- and at least one group selected from the group consisting of S(=O)2- are preferred. From the viewpoint that an optically anisotropic layer excellent in adhesion and planar uniformity can be obtained, at least one group selected from the group consisting of -O-, -N(R 21 )-, -C(=O)- and S(=O)2- is more preferred, and at least one group selected from the group consisting of -O-, -N(R 21 )- and C(=O)- is particularly preferred.

[0148] Particularly, SP4 is preferably a group containing at least one selected from the group consisting of an oxyalkylene structure in which one or more -CH2- constituting an alkylene group are replaced by -O-, an ester structure in which one or more -CH2-CH2- constituting an alkylene group are replaced by -O- and C(=O)-, and a urethane bond in which one or more -CH2-CH2-CH2- constituting an alkylene group are replaced by -O-, -C(=O)- and NH-.

[0149] The hydrogen atom contained in one or more -CH2- constituting the alkylene group represented by SP4 may be replaced by the aforementioned "SP-H". In this case, it is sufficient that one or more of the hydrogen atoms contained in -CH2- are replaced by "SP-H". That is, only one of the hydrogen atoms contained in -CH2- may be replaced by "SP-H", or all (two) of the hydrogen atoms contained in -CH2- may be replaced by "SP-H".

[0150] "SP-H" is preferably at least one group selected from the group consisting of a halogen atom, a cyano group, a nitro group, a hydroxyl group, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 1 to 10 carbon atoms, and a halogenated alkyl group having 1 to 10 carbon atoms. It is even more preferably at least one group selected from the group consisting of a hydroxyl group, a linear alkyl group having 1 to 10 carbon atoms, and a branched alkyl group having 1 to 10 carbon atoms.

[0151] As described above, T4 represents a terminal group similar to T1, and is preferably a hydrogen atom, a methyl group, a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a boronic acid group, an amino group, a cyano group, a nitro group, a phenyl group which may have a substituent, or -L-CL (L represents a single bond or a divalent linking group. Specific examples of divalent linking groups are the same as LW and SPW described above. CL represents a crosslinking group, and examples include the group represented by Q1 or Q2 above, with the crosslinking group represented by formula (P1) to (P30) being preferred). The CL is preferably a vinyl group, a butadiene group, a (meth)acrylic group, a (meth)acrylamide group, a vinyl acetate group, a fumarate ester group, a styryl group, a vinylpyrrolidone group, maleic anhydride, a maleimide group, a vinyl ether group, an epoxy group, or an oxetanyl group.

[0152] The epoxy group may be an epoxycycloalkyl group, and the number of carbon atoms in the cycloalkyl portion of the epoxycycloalkyl group is preferably 3 to 15, more preferably 5 to 12, and particularly preferably 6 (i.e., when the epoxycycloalkyl group is an epoxycyclohexyl group) from the viewpoint of achieving superior effects of the present invention.

[0153] Examples of substituents for the oxetanyl group include alkyl groups having 1 to 10 carbon atoms, and alkyl groups having 1 to 5 carbon atoms are preferred in terms of superior effects of the present invention. The alkyl group as a substituent for the oxetanyl group may be linear or branched, but it is preferable that it be linear in terms of superior effects of the present invention.

[0154] Examples of substituents on the phenyl group include boronic acid groups, sulfonic acid groups, vinyl groups, and amino groups. Boronic acid groups are preferred because they exhibit superior effects compared to the present invention.

[0155] Specific examples of the repeating unit (4) include the following structure, but the present invention is not limited to these. In the following specific examples, n1 represents an integer of 2 or more, and n2 represents an integer of 1 or more.

[0156] [ka]

[0157] The content of repeating units (4) is preferably 2 to 20% by mass, and more preferably 3 to 18% by mass, relative to the total repeating units (100% by mass) of the polymeric liquid crystalline compound. If the content of repeating units (4) is 2% by mass or more, an optically anisotropic layer with superior adhesion can be obtained. If the content of repeating units (4) is 20% by mass or less, an optically anisotropic layer with superior planar uniformity can be obtained. Repeating units (4) may be present as a single type or as two or more types in the polymeric liquid crystalline compound. If two or more types of repeating units (4) are present, the above content of repeating units (4) refers to the total content of repeating units (4).

[0158] (Repeating unit (5)) From the viewpoint of planar uniformity, polymeric liquid crystalline compounds may contain repeating units (5) introduced by polymerizing polyfunctional monomers. In particular, in order to improve planar uniformity while suppressing a decrease in the degree of orientation, it is preferable to include 10% by mass or less of these repeating units (5) introduced by polymerizing polyfunctional monomers. The reason why including 10% by mass or less of repeating units (5) can improve planar uniformity while suppressing a decrease in the degree of orientation is presumed to be as follows: Repeating units (5) are units introduced into polymeric liquid crystalline compounds by polymerizing polyfunctional monomers. Therefore, it is thought that polymeric liquid crystalline compounds contain high molecular weight molecules that form a three-dimensional crosslinked structure by repeating units (5). Here, since the content of repeating units (5) is small, it is thought that the content of high molecular weight molecules containing repeating units (5) is small.

[0159] It is presumed that the presence of a small amount of high molecular weight material forming a three-dimensional crosslinked structure suppressed the repulsion of the light-absorbing anisotropic layer-forming composition, resulting in an optically anisotropic layer with excellent planar uniformity. Furthermore, it is presumed that the effect of suppressing the decrease in the degree of orientation was maintained because the content of high molecular weight material was small.

[0160] The repeating unit (5) introduced by polymerizing the above polyfunctional monomer is preferably a repeating unit represented by the following formula (5).

[0161] [ka]

[0162] In formula (5), PC5A and PC5B represent the repeating main chain, more specifically the same structure as PC1 in formula (1) above; L5A and L5B represent single or divalent linking groups, more specifically the same structure as L1 in formula (1) above; SP5A and SP5B represent spacer groups, more specifically the same structure as SP1 in formula (1) above; MG5A and MG5B represent mesogenic structures, more specifically the same structure as the mesogenic group MG in formula (LC) above; and a and b represent integers of 0 or 1.

[0163] PC5A and PC5B may be the same group or different groups, but it is preferable that they be the same group in order to further improve the orientation of the optical anisotropy layer. L5A and L5B may both be single bonds, the same group or different groups, but it is preferable that they are single bonds or the same group, and more preferably the same group, in order to further improve the orientation of the optical anisotropy layer. SP5A and SP5B may both be single bonds, the same group or different groups, but it is preferable that they are single bonds or the same group, and more preferably the same group, in order to further improve the orientation of the optical anisotropy layer. Here, in formula (5), "identical groups" means that the chemical structure is the same regardless of the orientation in which each group is bonded. For example, if SP5A is *-CH2-CH2-O-** (where * represents the bond position with L5A and ** represents the bond position with MG5A) and SP5B is *-O-CH2-CH2-** (where * represents the bond position with MG5B and ** represents the bond position with L5B), then they are considered the same groups.

[0164] a and b are each an integer of 0 or 1, and are preferably 1 from the viewpoint of further improving the orientation of the optical anisotropy layer. a and b may be the same or different, but are preferably both 1 from the viewpoint of further improving the orientation of the optical anisotropy layer. The sum of a and b is preferably 1 or 2 from the viewpoint of further improving the orientation of the optical anisotropy layer (i.e., the repeating unit represented by formula (5) has a mesogenic group), and more preferably 2.

[0165] -(MG5A) a -(MG5B) b -The substructure represented by - preferably has an annular structure in that the degree of orientation of the optical anisotropy layer is further improved.In this case, -(MG5A2) a -(MG5B) bThe number of cyclic structures in the substructure represented by - is preferably two or more, more preferably two to eight, even more preferably two to six, and particularly preferably two to four. The mesogenic groups represented by MG5A and MG5B each independently preferably contain one or more cyclic structures, preferably two to four, more preferably two to three, and particularly preferably two, from the viewpoint of further improving the orientation of the optically anisotropic layer. Specific examples of cyclic structures include aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups, among which aromatic hydrocarbon groups and alicyclic groups are preferred. MG5A and MG5B may be the same group or different groups, but it is preferable that they be the same group from the viewpoint of further improving the orientation of the optically anisotropic layer.

[0166] The mesogenic groups represented by MG5A and MG5B are preferably the mesogenic group MG in the above formula (LC) because they offer superior effects from the viewpoints of liquid crystalline properties, adjustment of the liquid crystal phase transition temperature, availability of raw materials, and suitability for synthesis, as well as the effects of the present invention.

[0167] In particular, it is preferable that the repeating unit (5) has the same group as PC5A and PC5B, L5A and L5B are both single-bonded or the same group, SP5A and SP5B are both single-bonded or the same group, and MG5A and MG5B are the same group. This further improves the degree of orientation of the optically anisotropic layer.

[0168] The content of repeating units (5) is preferably 10% by mass or less, more preferably 0.001 to 5% by mass, and even more preferably 0.05 to 3% by mass, relative to the total content of repeating units (100% by mass) of the polymeric liquid crystalline compound. Repeating units (5) may be present as a single type or as two or more types in the polymeric liquid crystalline compound. When two or more types of repeating units (5) are present, it is preferable that their total amount is within the above range.

[0169] (Star-shaped polymer) The polymeric liquid crystalline compound may be a star polymer. The star polymer in the present invention means a polymer having three or more polymer chains extending from a core, and specifically, it is represented by the following formula (6). The star polymer represented by the formula (6) as the polymeric liquid crystalline compound can form an optically anisotropic layer with a high degree of orientation while having high solubility (excellent solubility in a solvent).

[0170]

Chemical formula

[0171] In formula (6), n A represents an integer of 3 or more, and an integer of 4 or more is preferable. The upper limit value of n A is not limited thereto, but is usually 12 or less, and 6 or less is preferable. Each of the plurality of PIs independently represents a polymer chain containing any one of the repeating units represented by the above formulas (1), (21), (22), (3), (4), and (5). However, at least one of the plurality of PIs represents a polymer chain containing the repeating unit represented by the above formula (1). A represents an atomic group serving as the core of the star polymer. Specific examples of A include the structures obtained by removing hydrogen atoms from the thiol groups of the polyfunctional thiol compounds described in paragraphs

[0052] to

[0058] of JP-A No. 2011-074280, paragraphs

[0017] to

[0021] of JP-A No. 2012-189847, paragraphs

[0012] to

[0024] of JP-A No. 2013-031986, paragraphs

[0118] to

[0142] of JP-A No. 2014-104631, etc. In this case, A and PI are bonded by a sulfide bond.

[0172] The number of thiol groups of the polyfunctional thiol compound from which A is derived is preferably 3 or more, and more preferably 4 or more. The upper limit value of the number of thiol groups of the polyfunctional thiol compound is usually 12 or less, and 6 or less is preferable. Specific examples of the polyfunctional thiol compound are shown below.

[0173]

Chemical formula

[0174] From the perspective of improving the degree of orientation, the polymeric liquid crystalline compound may be a thermotropic liquid crystal and a crystalline polymer.

[0175] (Thermotropic liquid crystal) A thermotropic liquid crystal is a liquid crystal that exhibits a transition to a liquid crystal phase with a change in temperature. A specific compound is a thermotropic liquid crystal and may exhibit either a nematic phase or a smectic phase. However, from the reasons that the degree of orientation of the optically anisotropic layer becomes higher and haze becomes more difficult to observe (haze becomes better), it is preferable to exhibit at least a nematic phase. The temperature range showing the nematic phase is preferably from room temperature (23 °C) to 450 °C because the degree of orientation of the optically anisotropic layer becomes higher and haze becomes more difficult to observe, and more preferably from 40 °C to 400 °C from the viewpoints of handling and manufacturing suitability.

[0176] (Crystalline polymer) A crystalline polymer is a polymer that exhibits a transition to a crystalline layer with a change in temperature. The crystalline polymer may exhibit a glass transition in addition to the transition to the crystalline layer. The crystalline polymer is preferably a polymeric liquid crystalline compound having a transition from a crystalline phase to a liquid crystal phase (there may be a glass transition in between) when heated, or a polymeric liquid crystalline compound having a transition to a crystalline phase (there may be a glass transition in between) when the temperature is lowered after being in a liquid crystal state by heating, because the degree of orientation of the optically anisotropic layer becomes higher and haze becomes more difficult to observe.

[0177] The crystallinity of polymeric liquid crystalline compounds is evaluated as follows: Two optically anisotropic layers of an optical microscope (Nikon ECLIPSE E600 POL) are positioned orthogonally to each other, and a sample stage is placed between the two optically anisotropic layers. A small amount of the polymeric liquid crystalline compound is placed on a glass slide, and the glass slide is placed on a hot stage on the sample stage. While observing the state of the sample, the temperature of the hot stage is raised to the temperature at which the polymeric liquid crystalline compound exhibits liquid crystalline properties, causing the polymeric liquid crystalline compound to become liquid crystalline. After the polymeric liquid crystalline compound becomes liquid crystalline, the behavior of the liquid crystalline phase transition is observed while gradually lowering the temperature of the hot stage, and the temperature of the liquid crystalline phase transition is recorded. If the polymeric liquid crystalline compound exhibits multiple liquid crystalline phases (e.g., nematic phase and smectic phase), all of its transition temperatures are also recorded.

[0178] Next, place approximately 5 mg of a polymeric liquid crystalline compound sample in an aluminum pan, cover it, and set it in a differential scanning calorimeter (DSC) (using an empty aluminum pan as a reference). Heat the polymeric liquid crystalline compound to the temperature at which it exhibits the liquid crystal phase, and then maintain the temperature for 1 minute. After that, measure the calorimetry while cooling at a rate of 10°C / min. Check the exothermic peak from the obtained calorimetry spectrum. If an exothermic peak is observed at temperatures other than the liquid crystal phase transition temperature, then that exothermic peak is due to crystallization, and the polymeric liquid crystalline compound is considered to be crystalline. On the other hand, if no exothermic peak is observed at temperatures other than the liquid crystal phase transition temperature, then the polymeric liquid crystalline compound is considered to be non-crystalline.

[0179] The method for obtaining a crystalline polymer is not particularly limited, but as a specific example, a method using a polymeric liquid crystalline compound containing the repeating unit (1) is preferred, and among these, a method using a preferred embodiment of the polymeric liquid crystalline compound containing the repeating unit (1) is more preferred.

[0180] ·Crystallization temperature The crystallization temperature of the polymeric liquid crystalline compound is preferably -50°C to less than 150°C, more preferably 120°C or lower, even more preferably -20°C to less than 120°C, and most preferably 95°C or lower, as this results in a higher degree of orientation of the optically anisotropic layer and less observation of haze. From the viewpoint of reducing haze, the crystallization temperature of the polymeric liquid crystalline compound is preferably less than 150°C. Note that the crystallization temperature is the temperature of the exothermic peak due to crystallization in the DSC described above.

[0181] (molecular weight) The weight-average molecular weight (Mw) of the polymeric liquid crystalline compound is preferably between 1,000 and 500,000, and more preferably between 2,000 and 300,000, from the viewpoint of achieving superior effects of the present invention. If the Mw of the polymeric liquid crystalline compound is within the above range, the polymeric liquid crystalline compound becomes easier to handle. In particular, from the viewpoint of suppressing cracks during coating, the weight-average molecular weight (Mw) of the polymeric liquid crystalline compound is preferably 10,000 or more, and more preferably between 10,000 and 300,000. Furthermore, from the viewpoint of the temperature latitude of the degree of orientation, the weight-average molecular weight (Mw) of the polymeric liquid crystalline compound is preferably less than 10,000, and preferably between 2,000 and less than 10,000. Here, the weight-average molecular weight and number-average molecular weight in this invention are values ​​measured by gel permeation chromatography (GPC).

[0182] • Solvent (eluent): N-methylpyrrolidone ·Device name: TOSOH HLC-8220GPC • Column: Three TOSOH TSKgelSuperAWM-H (6mm x 15cm) columns connected together are used. • Column temperature: 25℃ • Sample concentration: 0.1% by mass ·Flow rate: 0.35mL / min • Calibration curve: A calibration curve was used based on 7 samples of TOSOH TSK standard polystyrene with Mw=2,800,000 to 1,050 (Mw / Mn=1.03 to 1.06).

[0183] The liquid crystalline properties of the polymer liquid crystalline compound may be either nematic or smectic, but it is preferable that it exhibits at least nematic properties. The temperature range in which the nematic phase is exhibited is preferably 0°C to 450°C, and from the viewpoint of handling and manufacturing suitability, it is preferably 30°C to 400°C.

[0184] The content of the liquid crystalline 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, based on the content of the dichroic substance in the light-absorbing anisotropic layer-forming composition. A content of the liquid crystalline compound within the above range further improves the polarizer orientation. The liquid crystalline compound may be present as a single compound or as two or more compounds. If two or more liquid crystalline compounds are present, the above content of the liquid crystalline compound refers to the total content of the liquid crystalline compounds.

[0185] <Dichroic substances> The composition for forming a light-absorbing anisotropic layer further contains a dichroic substance. In this invention, a dichroic substance refers to a dye whose absorbance differs depending on the direction. The dichroic substance may or may not exhibit liquid crystalline properties. Dichroic materials are not particularly limited and include visible light absorbing materials (dichroic dyes, dichroic azo compounds), luminescent materials (fluorescent materials, phosphorescent materials), ultraviolet absorbing materials, infrared absorbing materials, nonlinear optical materials, carbon nanotubes, inorganic materials (e.g., quantum rods), and conventionally known dichroic materials (dichroic dyes) can be used.

[0186] Preferably used dichroic substances are organic dichroic dye compounds, with dichroic azo dye compounds being more preferred. The dichroic azo dye compound is not particularly limited, and conventionally known dichroic azo dyes can be used, but the compounds described below are preferably used.

[0187] In the present invention, the dichroic azo dye compound means a dye having different absorbances depending on the direction. The dichroic azo dye compound may exhibit liquid crystallinity or may not exhibit liquid crystallinity. When the dichroic azo dye compound exhibits liquid crystallinity, it may exhibit either nematicity or smecticity. The temperature range showing the liquid crystal phase is preferably from room temperature (about 20°C to 28°C) to 300°C, and more preferably from 50°C to 200°C from the viewpoints of handling property and manufacturing suitability.

[0188] In the present invention, from the viewpoint of color tone adjustment, the light absorption anisotropic layer preferably has at least one dye compound (hereinafter also abbreviated as "first dichroic azo dye compound") having a maximum absorption wavelength in the range of 560 to 700 nm, and at least one dye compound (hereinafter also abbreviated as "second dichroic azo dye compound") having a maximum absorption wavelength in the range of more than 455 nm and less than 560 nm. Specifically, it is more preferable to have at least a dichroic azo dye compound represented by the formula (1) described later and a dichroic azo dye compound represented by the formula (2) described later.

[0189] In the present invention, three or more kinds of dichroic azo dye compounds may be used in combination. For example, from the viewpoint of making the light absorption anisotropic layer closer to black, it is preferable to use in combination the first dichroic azo dye compound, the second dichroic azo dye compound, and at least one dye compound (hereinafter also abbreviated as "third dichroic azo dye compound") having a maximum absorption wavelength in the range of 380 nm or more and less than 455 nm.

[0190] In the present invention, from the viewpoint of better pressure resistance, it is preferable that the dichroic azo dye compound has a crosslinkable group. Specific examples of the crosslinkable group include, for example, (meth)acryloyl group, epoxy group, oxetanyl group, styryl group, etc. Among them, the (meth)acryloyl group is preferable.

[0191] (First dichroic azo dye compound) The first dichroic azo dye compound is preferably a compound having a chromophore as a core and side chains attached to the ends of the chromophore. Specific examples of the chromophore include aromatic ring groups (e.g., aromatic hydrocarbon groups, aromatic heterocyclic groups) and azo groups, with a structure having both an aromatic ring group and an azo group being preferred, and a bis-azo structure having an aromatic heterocyclic group (preferably a thienothiazole group) and two azo groups being more preferred. The side chain is not particularly limited and may include groups represented by L3, R2, or L4 of formula (1) described later.

[0192] The first dichroic azo dye compound is a dichroic azo dye compound having a maximum absorption wavelength in the range of 560 nm to 700 nm. From the viewpoint of adjusting the color of the polarizer, it is preferable that the dichroic azo dye compound has a maximum absorption wavelength in the range of 560 to 650 nm, and more preferably that it has a maximum absorption wavelength in the range of 560 to 640 nm. The maximum absorption wavelength (nm) of the dichroic azo dye compound in this specification is determined from the ultraviolet-visible light spectrum in the range of 380 to 800 nm measured by a spectrophotometer using a solution of the dichroic azo dye compound dissolved in a good solvent.

[0193] In the present invention, the first dichroic azo dye compound is preferably a compound represented by the following formula (1) because it further improves the degree of orientation of the formed light-absorbing anisotropic layer.

[0194] [ka]

[0195] In formula (1), Ar1 and Ar2 each independently represent an optionally substituted phenylene group or an optionally substituted naphthylene group, with the phenylene group being preferred.

[0196] In formula (1), R1 represents a hydrogen atom, a linear or branched alkyl group which may have substituents having 1 to 20 carbon atoms, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylcarbonyl group, an alkyloxycarbonyl group, an acyloxy group, an alkylcarbonate group, an alkylamino group, an acylamino group, an alkylcarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an alkylsulfamoyl group, an alkylcarbamoyl group, an alkylsulfinyl group, an alkylureido group, an alkylphosphate amide group, an alkylimino group, or an alkylsilyl group. The -CH2- groups constituting the above alkyl groups may be substituted with -O-, -CO-, -C(O)-O-, -OC(O)-, -Si(CH3)2-O-Si(CH3)2-, -N(R1')-, -N(R1')-CO-, -CO-N(R1')-, -N(R1')-C(O)-O-, -OC(O)-N(R1')-, -N(R1')-C(O)-N(R1')-, -CH=CH-, -C≡C-, -N=N-, -C(R1')=CH-C(O)-, or -OC(O)-O-. If R1 is a group other than a hydrogen atom, the hydrogen atom in each group may be substituted with a halogen atom, a nitro group, a cyano group, -N(R1')2, an amino group, -C(R1')=C(R1')-NO2, -C(R1')=C(R1')-CN, or -C(R1')=C(CN)2. R1' represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. If there are multiple R1' in each group, they may be the same or different from one another.

[0197] In formula (1), R2 and R3 each independently represent a hydrogen atom, a linear or branched alkyl group which may have substituents having 1 to 20 carbon atoms, an alkoxy group, an acyl group, an alkyloxycarbonyl group, an alkylamide group, an alkylsulfonyl group, an aryl group, an arylcarbonyl group, an arylsulfonyl group, an aryloxycarbonyl group, or an arylamide group. The -CH2- constituting the above alkyl group may be substituted with -O-, -S-, -C(O)-, -C(O)-O-, -OC(O)-, -C(O)-S-, -SC(O)-, -Si(CH3)2-O-Si(CH3)2-, -NR2'-, -NR2'-CO-, -CO-NR2'-, -NR2'-C(O)-O-, -OC(O)-NR2'-, -NR2'-C(O)-NR2'-, -CH=CH-, -C≡C-, -N=N-, -C(R2')=CH-C(O)-, or -OC(O)-O-. If R2 and R3 are groups other than a hydrogen atom, the hydrogen atom in each group may be substituted with a halogen atom, a nitro group, a cyano group, an -OH group, -N(R2')2, an amino group, -C(R2')=C(R2')-NO2, -C(R2')=C(R2')-CN, or -C(R2')=C(CN)2. R2' represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. If there are multiple R2' groups in each group, they may be the same or different from each other. R2 and R3 may bond to each other to form a ring, or R2 or R3 may bond to Ar2 to form a ring.

[0198] From the viewpoint of lightfastness, R1 is preferably an electron-withdrawing group, and R2 and R3 are preferably groups with low electron-donating properties. Specific examples of such groups include alkylsulfonyl groups, alkylcarbonyl groups, alkyloxycarbonyl groups, acyloxy groups, alkylsulfonylamino groups, alkylsulfamoyl groups, alkylsulfinyl groups, and alkylureido groups as R1, and groups with the following structures as R2 and R3. Note that the groups with the following structures are shown in formula (1) above in a form that includes the nitrogen atom to which R2 and R3 are bonded.

[0199] [ka]

[0200] Specific examples of the first dichroic azo dye compound are shown below, but are not limited to these.

[0201] [ka] JPEG0007835725000037.jpg161127 JPEG0007835725000038.jpg14101

[0202] (Second dichroic azo dye compound) The second dichroic azo dye compound is a different compound from the first dichroic azo dye compound, specifically in its chemical structure. The second dichroic azo dye compound is preferably a compound having a chromophore, which is the core of the dichroic azo dye compound, and side chains attached to the ends of the chromophore. Specific examples of the chromophore include aromatic ring groups (e.g., aromatic hydrocarbon groups, aromatic heterocyclic groups) and azo groups, with a structure having both aromatic hydrocarbon groups and azo groups being preferred, and a bis-azo or tris-azo structure having an aromatic hydrocarbon group and two or three azo groups being more preferred. The side chain is not particularly limited, and examples include groups represented by R4, R5, or R6 in formula (2) described later.

[0203] The second dichroic azo dye compound is a dichroic azo dye compound having a maximum absorption wavelength in the range of 455 nm to less than 560 nm. From the viewpoint of adjusting the color of the polarizer, it is preferable that the dichroic azo dye compound has a maximum absorption wavelength in the range of 455 to 555 nm, and more preferably that it has a maximum absorption wavelength in the range of 455 to 550 nm. In particular, using a first dichroic azo dye compound with a maximum absorption wavelength of 560 to 700 nm and a second dichroic azo dye compound with a maximum absorption wavelength of 455 nm to less than 560 nm makes it easier to adjust the color of the polarizer.

[0204] The second dichroic azo dye compound is preferably the compound represented by formula (2) because it further improves the orientation of the polarizer.

[0205] [ka]

[0206] In formula (2), n represents 1 or 2. In formula (2), Ar3, Ar4, and Ar5 each independently represent an optionally substituted phenylene group, an optionally substituted naphthylene group, or an optionally substituted heterocyclic group. The heterocyclic group may be aromatic or non-aromatic. Examples of atoms other than carbon that constitute an aromatic heterocyclic group include nitrogen, sulfur, and oxygen atoms. If an aromatic heterocyclic group has multiple atoms other than carbon that constitute the ring, these may be the same or different. Specific examples of aromatic heterocyclic groups include pyridylene (pyridine-diyl group), pyridazine-diyl group, imidazole-diyl group, thienylene (thiophene-diyl group), quinolylene (quinoline-diyl group), isoquinolylene (isoquinoline-diyl group), oxazole-diyl group, thiazole-diyl group, oxadiazole-diyl group, benzothiazole-diyl group, benzothiadiazole-diyl group, phthalimide-diyl group, thienothiazole-diyl group, thiazolothiazole-diyl group, thienothiophene-diyl group, and thienoxazole-diyl group.

[0207] In equation (2), the definition of R4 is the same as that of R1 in equation (1). In equation (2), the definitions of R5 and R6 are the same as those of R2 and R3 in equation (1), respectively.

[0208] From the viewpoint of lightfastness, it is preferable that R4 is an electron-withdrawing group, and that R5 and R6 are groups with low electron-donating properties. Among such groups, specific examples when R4 is an electron-withdrawing group are the same as specific examples when R1 is an electron-withdrawing group, and specific examples when R5 and R6 are groups with low electron-donating properties are the same as specific examples when R2 and R3 are groups with low electron-donating properties.

[0209] Specific examples of the second type of dichroic azo dye compound are shown below, but are not limited to these.

[0210] [ka] JPEG0007835725000041.jpg155111 JPEG0007835725000042.jpg160105 JPEG0007835725000043.jpg168111

[0211] (Difference in logP values) The logP value is an index that expresses the hydrophilic and hydrophobic properties of a chemical structure. The absolute difference between the logP value of the side chain of the first dichroic azo dye compound and the logP value of the side chain of the second dichroic azo dye compound (hereinafter also referred to as the "logP difference") is preferably 2.30 or less, more preferably 2.0 or less, even more preferably 1.5 or less, and particularly preferably 1.0 or less. If the logP difference is 2.30 or less, the affinity between the first dichroic azo dye compound and the second dichroic azo dye compound increases, making it easier to form a sequence structure, and thus the degree of orientation of the light-absorbing anisotropic layer is further improved.

[0212] Furthermore, if the first dichroic azo dye compound or the second dichroic azo dye compound has multiple side chains, it is preferable that at least one logP difference satisfies the above value. Here, the side chains of the first dichroic azo dye compound and the second dichroic azo dye compound refer to the groups that are attached to the ends of the chromophore described above. For example, if the first dichroic azo dye compound is the compound represented by formula (1), then R1, R2, and R3 in formula (1) are the side chains, and if the second dichroic azo dye compound is the compound represented by formula (2), then R4, R5, and R6 in formula (2) are the side chains. In particular, when the first dichroic azo dye compound is a compound represented by formula (1) and the second dichroic azo dye compound is a compound represented by formula (2), it is preferable that at least one of the logP differences among the difference in logP values ​​between R1 and R4, the difference in logP values ​​between R1 and R5, the difference in logP values ​​between R2 and R4, and the difference in logP values ​​between R2 and R5 satisfies the above value.

[0213] Here, the logP value is an index that expresses the hydrophilic and hydrophobic properties of a chemical structure, and is sometimes called the hydrophilic / hydrophobic parameter. The logP value can be calculated using software such as ChemBioDraw Ultra or HSPiP (Ver. 4.1.07). It can also be determined experimentally by methods such as those described in OECD Guidelines for the Testing of Chemicals, Sections 1, Test No. 117. In this invention, unless otherwise specified, the value calculated by inputting the structural formula of the compound into HSPiP (Ver. 4.1.07) will be adopted as the logP value.

[0214] (Third dichroic azo dye compound) The third dichroic azo dye compound is a dichroic azo dye compound other than the first and second dichroic azo dye compounds, and specifically, it has a different chemical structure from the first and second dichroic azo dye compounds. A composition for forming a light-absorbing anisotropic layer has the advantage of easily adjusting the color of the light-absorbing anisotropic layer. The maximum absorption wavelength of the third dichroic azo dye compound is 380 nm or more and less than 455 nm, with 385 to 454 nm being preferred.

[0215] The third dichroic azo dye compound preferably contains a dichroic azo dye represented by the following formula (6).

[0216] [ka]

[0217] In formula (6), A and B each independently represent a crosslinking group. In formula (6), a and b each independently represent 0 or 1. In terms of superior orientation at 420 nm, it is preferable that both a and b are 0. In formula (6), when a=0, L1 represents a monovalent substituent, and when a=1, L1 represents a single bond or a divalent linking group. Also, when b=0, L2 represents a monovalent substituent, and when b=1, L2 represents a single bond or a divalent linking group. In formula (6), Ar1 represents an (n1+2) valent aromatic hydrocarbon group or heterocyclic group, Ar2 represents an (n2+2) valent aromatic hydrocarbon group or heterocyclic group, and Ar3 represents an (n3+2) valent aromatic hydrocarbon group or heterocyclic group. In formula (6), R1, R2, and R3 each independently represent a monovalent substituent. If n1≧2, multiple R1s may be identical or different from each other; if n2≧2, multiple R2s may be identical or different from each other; and if n3≧2, multiple R3s may be identical or different from each other. In equation (6), k represents an integer from 1 to 4. If k≧2, multiple Ar2s may be identical or different from each other, and multiple R2s may be identical or different from each other. In equation (6), n1, n2, and n3 each independently represent an integer from 0 to 4. However, if k=1, then n1+n2+n3≧0, and if k≧2, then n1+n2+n3≧1.

[0218] In formula (6), examples of the crosslinkable groups represented by A and B include the polymerizable groups described in paragraphs

[0040] to

[0050] of Japanese Patent Application Publication No. 2010-244038. Among these, acryloyl groups, methacryloyl groups, epoxy groups, oxetanyl groups, and styryl groups are preferred from the viewpoint of improving reactivity and synthetic suitability, and acryloyl groups and methacryloyl groups are more preferred from the viewpoint of further improving solubility.

[0219] In equation (6), when a=0, L1 represents a monovalent substituent, and when a=1, L1 represents a single bond or a divalent linking group. Also, when b=0, L2 represents a monovalent substituent, and when b=1, L2 represents a single bond or a divalent linking group.

[0220] The monovalent substituents represented by L1 and L2 are preferably groups introduced to enhance the solubility of dichroic substances, or electron-donating or electron-withdrawing groups introduced to adjust the color tone as a dye. For example, the substituents are alkyl groups (preferably C1-C20, more preferably C1-C12, and particularly preferably C1-C8 alkyl groups, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, and cyclohexyl groups), alkenyl groups (preferably C2-C20, more preferably C2-C12, and particularly preferably C2-C8 alkenyl groups, for example, Examples include vinyl groups, allyl groups, 2-butenyl groups, 3-pentenyl groups, etc.), alkynyl groups (preferably alkynyl groups having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, such as propargyl groups and 3-pentinyl groups), and aryl groups (preferably aryl groups having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenyl groups, 2,6-diethylphenyl groups, and 3,5-ditrifluoromethylphenyl groups). Examples include groups such as the methylamino group, naphthyl group, and biphenyl group), substituted or unsubstituted amino groups (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example, unsubstituted amino groups, methylamino groups, dimethylamino groups, diethylamino groups, anilino groups, etc.), alkoxy groups (preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, for example, methoxy groups, ethoxy groups, butoxy groups, etc.), oxycarbonyl groups ( Preferably having 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and particularly preferably 2 to 10 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a phenoxycarbonyl group, etc.), an acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms, for example, an acetoxy group and a benzoyloxy group, etc.), an acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms,Examples include acetylamino groups and benzoylamino groups), alkoxycarbonylamino groups (preferably having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms, for example, methoxycarbonylamino groups), aryloxycarbonylamino groups (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, for example, phenyloxycarbonylamino groups), sulfonylamino groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms) (particularly preferably having 1 to 6 carbon atoms, for example, a methanesulfonylamino group, a benzenesulfonylamino group, etc.), a sulfamoyl group (particularly preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example, a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, a phenylsulfamoyl group, etc.), a carbamoyl group (particularly preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, an unsubstituted carbamoyl group, a methylcarbamoyl group) Examples include diethylcarbamoyl groups, phenylcarbamoyl groups, etc.), alkylthio groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms, for example, methylthio groups, ethylthio groups, etc.), arylthio groups (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms, for example, phenylthio groups), sulfonyl groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms, for example, mesyl groups) Examples include tosyl groups, sulfinyl groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, methanesulfinyl groups, benzenesulfinyl groups, etc.), ureido groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, unsubstituted ureido groups, methylureido groups, phenylureido groups, etc.), phosphate amide groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms,For example, diethyl phosphate amide group, phenyl phosphate amide group, etc. can be used. Heterocyclic groups (preferably heterocyclic groups having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, for example heterocyclic groups having heteroatoms such as nitrogen, oxygen, or sulfur atoms, for example imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl groups, etc.), silyl groups (preferably silyl groups having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably silyl groups having 3 to 24 carbon atoms, for example trimethylsilyl, triphenylsilyl, etc.), halogen atoms (for example fluorine, chlorine, bromine, or iodine atoms), hydroxyl groups, mercapto groups, cyano groups, nitro groups, hydroxamic acid groups, sulfino groups, hydrazino groups, imino groups, and azo groups can be used.

[0221] These substituents may be further substituted by other substituents. Furthermore, if there are two or more substituents, they may be the same or different. Also, where possible, they may be bonded to each other to form a ring. An example of a group in which the above substituents are further substituted by other substituents is a group in which an alkoxy group is substituted with an alkyl group, R B -(OR A ) na -A base can be listed. Here, in the formula, R A R represents an alkylene group with 1 to 5 carbon atoms. B L1 represents an alkyl group having 1 to 5 carbon atoms, and na represents an integer from 1 to 10 (preferably 1 to 5, more preferably 1 to 3). Among these, the monovalent substituents represented by L1 and L2 include alkyl groups, alkenyl groups, alkoxy groups, and groups in which these groups are further substituted by these groups (for example, the R groups mentioned above). B -(OR A ) na -Groups are preferred, alkyl groups, alkoxy groups, and groups in which these groups are further substituted by these groups (for example, the R groups mentioned above) B -(OR A ) na -Base) is more preferable.

[0222] Examples of divalent linking groups represented by L1 and L2 include -O-, -S-, -CO-, -COO-, -OCO-, -O-CO-O-, and -CO-NR. N -, -O-CO-NR N -, -NR N -CO-NR N Examples include -, -SO2-, -SO-, alkylene groups, cycloalkylene groups, and alkenylene groups, as well as groups formed by combining two or more of these groups. Among these, groups formed by combining an alkylene group with one or more groups selected from the group consisting of -O-, -COO-, -OCO-, and -O-CO-O- are preferred. Here, R N R represents a hydrogen atom or an alkyl group. N If there are multiple R N They may be the same or different from each other.

[0223] From the viewpoint of further improving the solubility of dichroic substances, the number of atoms in at least one of the main chains of L1 and L2 is preferably 3 or more, more preferably 5 or more, even more preferably 7 or more, and particularly preferably 10 or more. Furthermore, the upper limit of the number of atoms in the main chain is preferably 20 or less, and more preferably 12 or less.

[0224] On the other hand, from the viewpoint of further improving the orientation of the light-absorbing anisotropic layer, it is preferable that the number of atoms in at least one of the main chains of L1 and L2 be 1 to 5. Here, if A exists in formula (6), the "main chain" in L1 refers to the part necessary to directly connect the "O" atoms that connect to L1 and "A", and the "number of atoms in the main chain" refers to the number of atoms that make up the above part. Similarly, if B exists in formula (6), the "main chain" in L2 refers to the part necessary to directly connect the "O" atoms that connect to L2 and "B", and the "number of atoms in the main chain" refers to the number of atoms that make up the above part. Note that the "number of atoms in the main chain" does not include the number of atoms in the branched chain, which will be described later. Also, if A does not exist, the "number of atoms in the main chain" in L1 refers to the number of atoms in L1 excluding the branched chain. If B does not exist, the "number of atoms in the main chain" in L2 refers to the number of atoms in L2 excluding the branched chain.

[0225] Specifically, in equation (D1) below, the number of atoms in the L1 main chain is 5 (the number of atoms in the dotted box on the left side of equation (D1) below), and the number of atoms in the L2 main chain is 5 (the number of atoms in the dotted box on the right side of equation (D1) below). Also, in equation (D10) below, the number of atoms in the L1 main chain is 7 (the number of atoms in the dotted box on the left side of equation (D10) below), and the number of atoms in the L2 main chain is 5 (the number of atoms in the dotted box on the right side of equation (D10) below).

[0226] [ka]

[0227] L1 and L2 may have branched chains. Here, if A is present in formula (6), the "branched chain" in L1 refers to the portion other than the portion necessary to directly connect the "O" atom that connects to L1 in formula (6) and "A". Similarly, if B is present in formula (6), the "branched chain" in L2 refers to the portion other than the portion necessary to directly connect the "O" atom that connects to L2 in formula (6) and "B". Furthermore, if A is not present in formula (6), the "branched chain" in L1 refers to the portion other than the longest atomic chain (i.e., the main chain) extending from the "O" atom that connects to L1 in formula (6). Similarly, if B is not present in formula (6), the "branched chain" in L2 refers to the portion other than the longest atomic chain (i.e., the main chain) extending from the "O" atom that connects to L2 in formula (6). Preferably, the number of atoms in the branched chain is 3 or less. Having three or fewer atoms in the branched chain offers advantages such as improved orientation of the light-absorbing anisotropic layer. Note that the number of hydrogen atoms is not included in the number of atoms in the branched chain.

[0228] In formula (6), Ar1 represents an (n1+2)-valent (for example, trivalent when n1 is 1), Ar2 represents an (n2+2)-valent (for example, trivalent when n2 is 1), and Ar3 represents an (n3+2)-valent (for example, trivalent when n3 is 1) aromatic hydrocarbon group or heterocyclic group. Here, Ar1 to Ar3 can be rephrased as a divalent aromatic hydrocarbon group or divalent heterocyclic group substituted with n1 to n3 substituents (R1 to R3 described later). The divalent aromatic hydrocarbon group represented by Ar1 to Ar3 may be a monocyclic or have a fused ring structure of two or more rings. From the viewpoint of improving solubility, the number of rings in the divalent aromatic hydrocarbon group is preferably 1 to 4, more preferably 1 to 2, and even more preferably 1 (i.e., a phenylene group).

[0229] Specific examples of divalent aromatic hydrocarbon groups include phenylene, azulene-diyl, naphthylene, fluorene-diyl, anthracene-diyl, and tetracene-diyl groups. From the viewpoint of improving solubility, phenylene and naphthylene groups are preferred, with phenylene being more preferred. Specific examples of the third dichroic dye compound are shown below, but the present invention is not limited to these. In the following examples, n represents an integer from 1 to 10.

[0230] [ka]

[0231] [ka]

[0232] In terms of excellent orientation at 420 nm, a structure in which the third dye does not have radical polymerizable groups is preferred. For example, the following structure can be cited.

[0233] [ka] JPEG0007835725000049.jpg12119

[0234] The third dichroic azo dye compound is more preferably a dichroic substance having a structure represented by the following formula (1-1), as it exhibits particularly excellent orientation at 420 nm.

[0235] [ka]

[0236] In equation (1-1), the definitions of R1, R3, R4, R5, n1, n3, L1, and L2 are the same as those of R1, R3, R4, R5, n1, n3, L1, and L2 in equation (1), respectively. 21 and R 22The definitions of each are independently synonymous with R2 in equation (1). In equation (1-1), the definitions of n21 and n22 are independently synonymous with n2 in equation (1). n1+n21+n22+n3≧1, and n1+n21+n22+n3 is preferably 1 to 9, and more preferably 1 to 5.

[0237] Specific examples of dichroic substances are shown below, but the present invention is not limited to these.

[0238] [ka]

[0239] [ka]

[0240] [ka]

[0241] (Content of dichroic substances) The content of the dichroic substance is preferably 5% by mass or more, more preferably 5 to 30% by mass, even more preferably 15 to 28% by mass, and particularly preferably 20 to 30% by mass, relative to the total solid content mass of the light-absorbing anisotropic layer. If the content of the dichroic substance (especially organic dichroic dye compounds) is within the above range, a light-absorbing anisotropic layer with a high degree of orientation can be obtained even when the light-absorbing anisotropic layer is made into a thin film. Therefore, a light-absorbing anisotropic layer with excellent flexibility can be easily obtained.

[0242] From the perspective of increasing the contrast between illuminance at the center of the viewing angle and illuminance in directions offset from the center of the viewing angle, the content of dichroic substances per unit area should be 0.2 g / m². 2 Preferably, it is 0.3 g / m 2 It is more preferable that the amount be greater than or equal to 0.5 g / m 2 It is preferable that the amount be greater than or equal to the above. There is no particular upper limit, but it is usually 1.0 g / m 2 It is often used in the following cases.

[0243] The content of the first dichroic azo dye compound is preferably 40 to 90 parts by mass, and more preferably 45 to 75 parts by mass, based on 100 parts by mass of the total content of dichroic substances in the light-absorbing anisotropic layer-forming composition. The content of the second dichroic azo dye compound is preferably 6 to 50 parts by mass, and more preferably 8 to 35 parts by mass, based on 100 parts by mass of the total content of dichroic substances in the light-absorbing anisotropic layer-forming composition. The content of the third dichroic azo dye compound is preferably 3 to 35 parts by mass, and more preferably 5 to 30 parts by mass, based on 100 parts by mass of the dichroic azo dye compound in the light-absorbing anisotropic layer-forming composition.

[0244] The content ratio of the first dichroic azo dye compound, the second dichroic azo dye compound, and the third dichroic azo dye compound, which may be used as needed, can be arbitrarily set to adjust the color of the light-absorbing anisotropic layer. However, the content ratio of the second dichroic azo dye compound to the first dichroic azo dye compound (second dichroic azo dye compound / first dichroic azo dye compound) is preferably 0.1 to 10, more preferably 0.2 to 5, and particularly preferably 0.3 to 0.8 in molar terms. If the content ratio of the second dichroic azo dye compound to the first dichroic azo dye compound is within the above range, the degree of orientation can be increased.

[0245] <Interface modifier> The light-absorbing anisotropic layer-forming composition may contain an interface modifier. As the interface modifier, the interface modifiers described in the Examples section below can be used. When the composition for forming a light-absorbing anisotropic layer contains an interface modifier, the content of the interface modifier is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total of the dichroic substance and the liquid crystalline compound in the composition for forming a light-absorbing anisotropic layer.

[0246] <Polymerizable compound> The composition for forming a light-absorbing anisotropic layer may contain polymerizable compounds. Examples of polymerizable compounds include compounds containing acrylates (e.g., acrylate monomers). In this case, the light-absorbing anisotropic layer contains polyacrylate obtained by polymerizing the above-mentioned acrylate-containing compound. Examples of polymerizable compounds include the compound described in paragraph 0058 of Japanese Patent Application Publication No. 2017-122776. When the composition for forming a light-absorbing anisotropic layer contains a polymerizable compound, the content of the polymerizable compound is preferably 3 to 20 parts by mass per 100 parts by mass of the total of the dichroic substance and the liquid crystalline compound in the composition for forming a light-absorbing anisotropic layer.

[0247] <Vertical Orienting Agent> The light-absorbing anisotropic layer-forming composition may optionally contain a vertical alignment agent. Examples of vertical alignment agents include boronic acid compounds and onium salts.

[0248] As the boronic acid compound, the compound represented by formula (30) is preferred.

[0249] Formula (30) [ka]

[0250] In formula (30), R1 and R2 each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R3 represents a substituent including a (meth)acrylic group. Specific examples of boronic acid compounds include those represented by general formula (I) as described in paragraphs 0023 to 0032 of Japanese Patent Application Publication No. 2008-225281.

[0251] The following compounds are also preferred as boronic acid compounds.

[0252] [ka]

[0253] As the onium salt, the compound represented by formula (31) is preferred.

[0254] Formula (31)

[0255] [ka]

[0256] In formula (31), ring A represents a quaternary ammonium ion consisting of a nitrogen-containing heterocycle. X represents an anion. L1 represents a divalent linking group. L2 represents a single bond or a divalent linking group. Y1 represents a divalent linking group having a 5- or 6-membered ring as a substructure. Z represents a divalent linking group having 2 to 20 alkylene groups as a substructure. P1 and P2 each independently represent a monovalent substituent having a polymerizable ethylenically unsaturated bond. Specific examples of onium salts include the onium salts described in paragraphs 0052 to 0058 of Japanese Patent Publication No. 2012-208397, the onium salts described in paragraphs 0024 to 0055 of Japanese Patent Publication No. 2008-026730, and the onium salts described in Japanese Patent Publication No. 2002-37777.

[0257] The content of the vertical alignment agent in the composition is preferably 0.1 to 400% by mass, and more preferably 0.5 to 350% by mass, based on the total mass of the liquid crystalline compound. The vertical alignment agent may be used alone or in combination of two or more types. When two or more types of vertical alignment agents are used, it is preferable that their total amount is within the above range.

[0258] <Leveling agent> The composition for forming a light-absorbing anisotropic layer preferably contains the following leveling agent. When the composition for forming a light-absorbing anisotropic layer contains a leveling agent, surface roughness caused by drying air on the surface of the light-absorbing anisotropic layer is suppressed, and the dichroic substances in the light-absorbing anisotropic layer are oriented more uniformly. The leveling agent is not particularly limited, but a leveling agent containing fluorine atoms (fluorine-based leveling agent) or a leveling agent containing silicon atoms (silicon-based leveling agent) is preferred, and a fluorine-based leveling agent is more preferred.

[0259] Examples of fluorine-based leveling agents include fatty acid esters of polycarboxylic acids in which a portion of the fatty acid is substituted with a fluoroalkyl group, and polyacrylates having fluoro substituents. In particular, when rod-shaped compounds are used as the dichroic substance and liquid crystalline compound, leveling agents containing repeating units derived from the compound represented by formula (40) are preferred because they promote the vertical orientation of the dichroic substance and liquid crystalline compound.

[0260] Formula (40)

[0261] [ka]

[0262] R0 represents a hydrogen atom, a halogen atom, or a methyl group. L represents a divalent linking group. L is preferably an alkylene group having 2 to 16 carbon atoms, and any non-adjacent -CH2- in the alkylene group may be substituted with -O-, -COO-, -CO-, or -CONH-. n represents an integer from 1 to 18.

[0263] A leveling agent having repeating units derived from a compound represented by formula (40) may further contain other repeating units. Examples of other repeating units include repeating units derived from a compound represented by formula (41).

[0264] Formula (41) [ka]

[0265] R11 represents a hydrogen atom, a halogen atom, or a methyl group. X represents an oxygen atom, a sulfur atom, or -N(R13)-. R13 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R12 represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic group. The alkyl group preferably has 1 to 20 carbon atoms. The alkyl group may be linear, branched, or cyclic. Optional substituents on the alkyl group include a poly(alkylene oxy) group and a polymerizable group. The definition of a polymerizable group is as described above.

[0266] When the leveling agent contains repeating units derived from a compound represented by formula (40) and repeating units derived from a compound represented by formula (41), the content of repeating units derived from the compound represented by formula (40) is preferably 10 to 90 mol%, and more preferably 15 to 95 mol%, relative to the total repeating units contained in the leveling agent. When the leveling agent contains repeating units derived from a compound represented by formula (40) and repeating units derived from a compound represented by formula (41), the content of repeating units derived from the compound represented by formula (41) is preferably 10 to 90 mol%, and more preferably 5 to 85 mol%, relative to the total repeating units contained in the leveling agent.

[0267] Furthermore, as a leveling agent, there are also leveling agents that contain repeating units derived from the compound represented by formula (42) instead of the repeating units derived from the compound represented by formula (40) described above.

[0268] Formula (42) [ka]

[0269] R2 represents a hydrogen atom, a halogen atom, or a methyl group. L2 represents a divalent linking group. n represents an integer from 1 to 18.

[0270] Specific examples of leveling agents include the compounds exemplified in paragraphs 0046 to 0052 of Japanese Patent Publication No. 2004-331812, and the compounds described in paragraphs 0038 to 0052 of Japanese Patent Publication No. 2008-257205.

[0271] The content of the leveling agent in the composition is preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass, based on the total mass of the liquid crystalline compound. The leveling agent may be used alone or in combination of two or more types. When two or more leveling agents are used, it is preferable that their total amount is within the above range.

[0272] <Polymerization initiator> The composition for forming a light-absorbing anisotropic layer preferably contains a polymerization initiator. There are no particular restrictions on the polymerization initiator, but it is preferable that it be a photosensitive compound, i.e., a photopolymerization initiator. Various compounds can be used as photopolymerization initiators without particular restrictions. Examples of photopolymerization initiators include α-carbonyl compounds (US Patent Nos. 2,367,661 and 2,367,670), acyloin ethers (US Patent No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compounds (US Patent No. 2,722,512), polynuclear quinone compounds (US Patent Nos. 3,046,127 and 2,951,758), and combinations of triarylimidazole dimers and p-aminophenyl ketones (US Patent No. 3,549,367). Examples include acridine and phenazine compounds (Japanese Patent Publication No. 60-105667 and U.S. Patent No. 4239850), oxadiazole compounds (U.S. Patent No. 4212970), o-acyloxime compounds (Japanese Patent Publication No. 2016-27384

[0065] ), and acylphosphine oxide compounds (Japanese Patent Publication No. 63-40799, Japanese Patent Publication No. 5-29234, Japanese Patent Publication No. 10-95788 and Japanese Patent Publication No. 10-29997).

[0273] Commercially available photopolymerization initiators can also be used, including BASF's Irgacure-184, Irgacure-907, Irgacure-369, Irgacure-651, Irgacure-819, Irgacure-OXE-01, and Irgacure-OXE-02.

[0274] When the composition for forming a light-absorbing anisotropic layer contains a polymerization initiator, the amount of polymerization initiator is preferably 0.01 to 30 parts by mass, and more preferably 0.1 to 15 parts by mass, based on 100 parts by mass of the total of the dichroic substance and the liquid crystalline compound in the composition for forming a light-absorbing anisotropic layer. A polymerization initiator content of 0.01 parts by mass or more results in good durability of the light-absorbing anisotropic film, while a content of 30 parts by mass or less results in better orientation of the light-absorbing anisotropic film. The polymerization initiator may be used alone or in combination of two or more types. When two or more polymerization initiators are included, it is preferable that their total amount is within the above range.

[0275] <Solvent> From the viewpoint of workability and other factors, compositions for forming light-absorbing anisotropic layers preferably contain a solvent. Examples of solvents include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopetantanone, cyclohexanone, etc.), ethers (e.g., dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, cyclopentyl methyl ether, tetrahydropyran, dioxolane, etc.), aliphatic hydrocarbons (e.g., hexane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, trimethylbenzene, etc.), halogenated carbons (e.g., dichloromethane, trichloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), and esters (e.g., methyl acetate, ethyl acetate, butyl acetate, etc.). Examples of solvents include organic solvents such as ethyl lactate, alcohols (e.g., ethanol, isopropanol, butanol, cyclohexanol, isopentyl alcohol, neopentyl alcohol, diacetone alcohol, benzyl alcohol, 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, N-methylimidazole, etc.), as well as water. These solvents may be used individually or in combination of two or more. Of these solvents, ketones (especially cyclopentanone and cyclohexanone), ethers (especially tetrahydrofuran, cyclopentyl methyl ether, tetrahydropyran, and dioxolane), and amides (especially dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and N-ethylpyrrolidone) are preferred from the viewpoint of taking advantage of their excellent solubility.

[0276] When the light-absorbing anisotropic layer-forming composition contains a solvent, the solvent content is preferably 80 to 99% by mass, more preferably 83 to 97% by mass, and particularly preferably 85 to 95% by mass, based on the total mass of the light-absorbing anisotropic layer-forming composition. The solvent may be used alone or in combination of two or more types. When two or more solvents are included, it is preferable that their total amount is within the above range.

[0277] <Method for forming a light-absorbing anisotropic layer> The method for forming the light-absorbing anisotropic layer is not particularly limited, and includes a method comprising, in this order, a step of applying the above-mentioned light-absorbing anisotropic layer forming composition to form a coated film (hereinafter also referred to as the "coated film forming step"), and a step of aligning the liquid crystalline components and dichroic substances contained in the coated film (hereinafter also referred to as the "alignment step"). Note that the liquid crystalline components include not only the liquid crystalline compounds mentioned above, but also, if the above-mentioned dichroic substances are liquid crystalline, components that are liquid crystalline.

[0278] (Coating film formation process) The coating film formation process involves applying a light-absorbing anisotropic layer-forming composition to form a coating film. Applying the light-absorbing anisotropic layer-forming composition becomes easier by using a light-absorbing anisotropic layer-forming composition containing the aforementioned solvent, or by using a light-absorbing anisotropic layer-forming composition that has been made into a liquid such as a molten liquid by heating or other means. Specific examples of methods for applying the light-absorbing anisotropic layer-forming composition 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.

[0279] (Orientation process) The orientation step is a step in which the liquid crystalline components contained in the coated film are oriented. This results in a light-absorbing anisotropic layer. The orientation step may include a drying treatment. The drying treatment can remove components such as solvents from the coated film. The drying treatment may be carried out by leaving the coated film at room temperature for a predetermined time (e.g., natural drying), or by heating and / or blowing air. Here, the liquid crystalline components contained in the composition for forming the light-absorbing anisotropic layer may be oriented by the coating film formation step or drying treatment described above. For example, in an embodiment in which the composition for forming the light-absorbing anisotropic layer is prepared as a coating solution containing a solvent, a coating film with light-absorbing anisotropy (i.e., a light-absorbing anisotropic film) is obtained by drying the coated film and removing the solvent from the coated film. If the drying treatment is carried out at a temperature above the transition temperature of the liquid crystalline components contained in the coated film to the liquid crystal phase, the heat treatment described later may not be performed.

[0280] The transition temperature of the liquid crystalline component in the coated film to the liquid crystal phase is preferably 10 to 250°C, and more preferably 25 to 190°C, from the viewpoint of manufacturing suitability. A transition temperature of 10°C or higher is preferable because it eliminates the need for cooling treatment to lower the temperature to the temperature range in which the liquid crystal phase is observed. Furthermore, a transition temperature of 250°C or lower is preferable because it eliminates the need for high temperatures even when creating an isotropic liquid state at a temperature higher than the temperature range in which the liquid crystal phase is observed, thereby reducing the waste of thermal energy and the deformation and deterioration of the substrate.

[0281] The orientation step preferably includes a heat treatment. This allows the liquid crystalline components contained in the coated film to be oriented, making the coated film suitable for use as a light-absorbing anisotropic film after heat treatment. The heat treatment temperature is preferably 10 to 250°C, and more preferably 25 to 190°C, from the viewpoint of manufacturing suitability, etc. The heating time is preferably 1 to 300 seconds, and more preferably 1 to 60 seconds.

[0282] The orientation step may include a cooling treatment performed after the heat treatment. The cooling treatment is a process of cooling the heated coating film to room temperature (20-25°C). This fixes the orientation of the liquid crystalline components contained in the coating film. The cooling method is not particularly limited and can be carried out by known methods. A light-absorbing anisotropic film can be obtained through the above steps. In this embodiment, drying treatment and heat treatment are given as methods for aligning the liquid crystalline components contained in the coating film, but the method is not limited to these and can be carried out by known orientation treatments.

[0283] (Other processes) The method for forming a light-absorbing anisotropic layer may include a step of curing the light-absorbing anisotropic layer (hereinafter also referred to as the "curing step") after the orientation step described above. The curing step is carried out by heating and / or light irradiation (exposure), for example, if the light-absorbing anisotropic layer has crosslinkable groups (polymerizable groups). Among these, it is preferable that the curing step be carried out by light irradiation. Various light sources can be used for curing, such as infrared light, visible light, or ultraviolet light, but ultraviolet light is preferred. In addition, 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 carried out while heating, the heating temperature during exposure is preferably 25 to 140°C, although this depends on the transition temperature of the liquid crystal components contained in the liquid crystal film to the liquid crystal phase. Furthermore, exposure may be carried out under a nitrogen atmosphere. When curing of the liquid crystal film proceeds by radical polymerization, exposure under a nitrogen atmosphere is preferable because it reduces inhibition of polymerization by oxygen.

[0284] The thickness of the light-absorbing anisotropic layer is not particularly limited, but from the viewpoint of miniaturization and weight reduction, it is preferably 100 to 8000 nm, and more preferably 300 to 5000 nm.

[0285] <Patterning of light-absorbing anisotropic layers> The light-absorbing anisotropic layer used in this invention can have regions A and B within its surface, and each region can have a different transmittance center axis. By controlling the light-emitting pixels by patterning each pixel of the liquid crystal, it becomes possible to switch the center of the narrow field of view. Furthermore, the light-absorbing anisotropic layer used in the present invention may have regions C and D in its plane, and in regions C and D, the transmittance at a 30° angle from the transmittance center axis in the direction normal to the transmittance center axis is different in the plane encompassing the transmittance center axis and the normal to the surface of the light-absorbing anisotropic layer. In this case, it is preferable that the transmittance at a 30° angle from the transmittance center axis in the direction normal to the transmittance center of region C is 50% or less, and the transmittance at a 30° angle from the transmittance center axis in the direction normal to the transmittance center of region D is 80% or more. By performing the patterning described above, it becomes possible to strengthen or weaken the viewing angle dependence in certain areas. This allows for the display of highly confidential information only in areas where the viewing angle dependence is strengthened. Furthermore, by controlling the viewing angle dependence of the display device on a per-display position basis, it becomes possible to create designs with superior aesthetics. In addition, by controlling the light-emitting pixels through patterning for each pixel of the liquid crystal, it becomes possible to switch between narrow and wide viewing angles.

[0286] (Pattern formation method) There are no limitations on the method for forming a patterned optical anisotropy layer having two or more different regions in a plane, and various known methods, such as those described in publication WO2019 / 176918, can be used. Examples include a method for forming a pattern by changing the irradiation angle of ultraviolet light irradiated onto the photo-alignment film, a method for controlling the thickness of the patterned optical anisotropy layer in a plane, a method for unevenly distributing dichroic dye compounds in the patterned optical anisotropy layer, and a method for post-processing an optically uniform patterned optical anisotropy layer. Methods for controlling the thickness of the patterned light-absorbing anisotropic layer in a plane include using lithography, using imprinting, and forming the patterned light-absorbing anisotropic layer on a substrate with an uneven structure. A method for unevenly distributing the dichroic dye compound in the patterned light-absorbing anisotropic layer is to extract the dichroic dye by solvent immersion (bleaching). Furthermore, a method for post-processing an optically uniform patterned light-absorbing anisotropic layer is to cut a portion of the flat light-absorbing anisotropic layer by laser processing or the like.

[0287] [Polarizer] The polarizer in the laminate of the present invention is a polarizer having an absorption axis in the in-plane direction. Such polarizers are not particularly limited as long as they are materials that have the function of converting light into a specific linear polarization, and conventionally known polarizers can be used. Furthermore, when the laminate of the present invention is used in an image display device, the polarizer may be the polarizer on the viewing side of a liquid crystal display device or a polarizer included in a circular polarizer of an organic electroluminescent (hereinafter abbreviated as "EL") display device.

[0288] As polarizers, iodine-based polarizers, dye-based polarizers utilizing dichroic dyes, and polyene-based polarizers can be used. Iodine-based and dye-based polarizers include coated polarizers and stretched polarizers, both of which are applicable. For coated polarizers, polarizers in which dichroic organic dyes are oriented using the orientation of liquid crystalline compounds are preferred, and for stretched polarizers, polarizers made by adsorbing iodine or a dichroic dye onto polyvinyl alcohol and then stretching it are preferred. Furthermore, as a method for obtaining a polarizer by stretching and dyeing a laminated film in which a polyvinyl alcohol layer is formed on a substrate, examples include Japanese Patent No. 5048120, Japanese Patent No. 5143918, Japanese Patent No. 5048120, Japanese Patent No. 4691205, Japanese Patent No. 4751481, and Japanese Patent No. 4751486, and these known technologies related to polarizers can also be preferably used.

[0289] In particular, polarizers containing polyvinyl alcohol-based resin (polymers containing -CH2-CHOH- as repeating units; at least one selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymers) are preferred because they are readily available and have excellent polarization properties.

[0290] In the present invention, the thickness of the polarizer is not particularly limited, but is preferably 3 μm to 60 μm, more preferably 5 μm to 20 μm, and even more preferably 5 μm to 10 μm.

[0291] In the present invention, the light-absorbing anisotropic layer and the polarizer may be laminated via an adhesive or bonding agent, or the light-absorbing anisotropic layer may be directly coated onto the polarizer after forming an alignment film, as described later, on it.

[0292] Furthermore, in the present invention, the angle φ between the plane encompassing the transmittance center axis of the light absorption anisotropy layer and the normal to the layer plane of the light absorption anisotropy layer, and the absorption axis of the polarizer is preferably 45° to 90°, more preferably 80° to 90°, and even more preferably 88° to 90°. The closer the above angle is to 90°, the easier it is to create illumination contrast between the direction in which the image display device is easy to see and the direction in which it is difficult to see.

[0293] [Retardation layer] The laminate of the present invention may have a phase difference layer different from the linear polarization conversion layer and the light absorption anisotropy layer described above. By stacking such phase difference layers, the transmission and shielding performance can be controlled by controlling the phase difference value and the optical axis direction. As the phase difference layer, a positive A plate, a negative A plate, a positive C plate, a negative C plate, a B plate, an O plate, etc., can be used. The thickness of the phase difference layer is preferably as thin as possible from the viewpoint of miniaturizing the viewing angle control system, as long as it does not impair the optical properties, mechanical properties, and manufacturability. Specifically, it is preferably 1 to 150 μm, more preferably 1 to 70 μm, and even more preferably 1 to 30 μm. In particular, the laminate of the present invention preferably has a B plate between the polarizer (excluding the polarizer as a linear polarization conversion layer) and the light absorption anisotropy layer.

[0294] [Orientation film] The laminate of the present invention may also have an alignment film provided adjacent to the above-described light-absorbing anisotropic layer. The alignment layer is provided to control the orientation direction of the light-absorbing anisotropic layer. Examples of alignment films include layers of polyvinyl alcohol and polyimide, with or without rubbing treatment; and photo-alignment films of polyvinyl cinnamate and azo dyes, with or without polarized exposure treatment. Furthermore, as an alignment film, for example, a coating solution can be applied and dried on a hybrid-oriented liquid crystal layer to provide light absorption anisotropy. In this case, the transmittance center axis of the light absorption anisotropy layer is tilted in accordance with the tilt angle of the liquid crystal molecules on the surface of the hybrid-oriented liquid crystal layer, making it possible to tilt the transmittance center axis of the light absorption anisotropy layer diagonally.

[0295] [Protective layer] In the view of improving the durability of the light-absorbing anisotropic layer, the laminate of the present invention preferably has a protective layer as an adjacent layer to the light-absorbing anisotropic layer. The protective layer can be any known material, but a resin film is preferred. Examples of resin films include acrylic resin film, cellulose ester resin film, polyethylene terephthalate resin film, polyvinyl alcohol resin film, polycarbonate resin film, and modified resin films thereof.

[0296] Furthermore, the protective layer may undergo surface modification treatment to improve adhesion or other properties before the application of adhesives or bonding agents. Specific examples of such treatments include corona treatment, plasma treatment, primer treatment, and saponification treatment.

[0297] [Transparent base film] The laminate of the present invention may have a transparent substrate film. The transparent substrate film is preferably positioned on the side of the light-absorbing anisotropic layer opposite to the side where the protective layer is provided. As the transparent substrate film, known transparent resin films, transparent resin plates, transparent resin sheets, etc., can be used, and there are no particular limitations. Suitable transparent resin films include cellulose acylate films (e.g., cellulose triacetate film (refractive index 1.48), cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film), polyethylene terephthalate film, polyethersulfone film, polyacrylic resin film, polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyetherketone film, (meth)acrylonitrile film, etc.

[0298] Among these, cellulose acylate film is preferred because it has high transparency, low optical birefringence, is easy to manufacture, and is commonly used as a protective film for polarizing plates, and cellulose triacetate film is particularly preferred. The thickness of the transparent substrate film is usually 20 μm to 100 μm. In the present invention, it is particularly preferred that the transparent substrate film is a cellulose ester film and has a film thickness of 20 to 70 μm.

[0299] [Barrier layer] The laminate of the present invention preferably also has a barrier layer along with the light-absorbing anisotropic layer. Here, the barrier layer is also called a gas barrier layer (oxygen barrier layer) and has the function of protecting the polarizing element of the present invention from gases such as oxygen in the atmosphere, moisture, or compounds contained in adjacent layers. For information regarding the barrier layer, see, for example, paragraphs

[0014] to

[0054] of Japanese Patent Publication No. 2014-159124, paragraphs

[0042] to

[0075] of Japanese Patent Publication No. 2017-121721, paragraphs

[0045] to

[0054] of Japanese Patent Publication No. 2017-115076, paragraphs

[0010] to

[0061] of Japanese Patent Publication No. 2012-213938, and paragraphs

[0021] to

[0031] of Japanese Patent Publication No. 2005-169994.

[0300] [Refractive index adjustment layer] From the viewpoint of suppressing internal reflection caused by the dichroic substance contained in the above-mentioned light-absorbing anisotropic layer, it is preferable that the laminate of the present invention may contain a refractive index adjustment layer as needed. The refractive index adjustment layer is a layer positioned in contact with the light absorption anisotropy layer, and its in-plane average refractive index at a wavelength of 550 nm is between 1.55 and 1.70. It is preferable that this refractive index adjustment layer is for performing so-called index matching.

[0301] [Adhesive layer] The laminate of the present invention may be formed by bonding the above-described layers together via an adhesive layer. The adhesive layer in this invention is preferably a transparent, optically isotropic adhesive similar to those used in conventional image display devices, and is typically a pressure-sensitive adhesive.

[0302] In addition to the base material (adhesive), conductive particles, and thermally expandable particles used as needed, the adhesive layer of the present invention may also contain appropriate additives such as crosslinking agents (e.g., isocyanate-based crosslinking agents, epoxy-based crosslinking agents, etc.), tackifiers (e.g., rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenolic resins, etc.), plasticizers, fillers, antioxidants, surfactants, ultraviolet absorbers, light stabilizers, and antioxidants.

[0303] The thickness of the adhesive layer is typically 20 to 500 μm, preferably 20 to 250 μm. If it is less than 20 μm, the required adhesive strength and reworkability may not be obtained, and if it exceeds 500 μm, the adhesive may ooze or seep out from the peripheral edges of the image display device.

[0304] The adhesive layer can be formed by any suitable method, such as directly applying a coating liquid containing a base material, conductive particles, and optionally thermally expandable particles, additives, and solvents onto the protective member support 110 and pressing it down via a release liner; or applying the coating liquid onto a suitable release liner (such as release paper) to form a thermally expandable adhesive layer and then pressing and transferring it onto the protective member support 110.

[0305] In addition, as a protective member, for example, a configuration in which conductive particles are added to the structure of a heat-removable adhesive sheet described in Japanese Patent Publication No. 2003-292916 can be applied. Alternatively, as a protective member, a commercially available product such as "Riva Alpha" manufactured by Nitto Denko Corporation, in which conductive particles are scattered on the surface of the adhesive layer, may be used.

[0306] [Adhesive layer] The laminate of the present invention may be formed by bonding the above-described layers together via an adhesive layer. The adhesive layer in this invention exhibits adhesive properties through drying or reaction after bonding. Polyvinyl alcohol-based adhesives (PVA-based adhesives) exhibit adhesive properties upon drying, enabling bonding of materials. Specific examples of curing adhesives that exhibit adhesive properties through reaction include active energy ray curing adhesives such as (meth)acrylate adhesives and cationic polymerization curing adhesives. (Meth)acrylate refers to acrylate and / or methacrylate. Examples of curing components in (meth)acrylate adhesives include compounds having a (meth)acryloyl group and compounds having a vinyl group. Compounds having epoxy groups or oxetanyl groups can also be used as cationic polymerization curing adhesives. Compounds having epoxy groups are not particularly limited as long as they have at least two epoxy groups in their molecule; various generally known curing epoxy compounds can be used. Examples of preferred epoxy compounds include compounds having at least two epoxy groups and at least one aromatic ring in the molecule (aromatic epoxy compounds), and compounds having at least two epoxy groups in the molecule, at least one of which is formed between two adjacent carbon atoms constituting an alicyclic ring (alicyclic epoxy compounds). Among these, UV-curable adhesives that harden with UV irradiation are preferred from the viewpoint of resistance to heat deformation.

[0307] Each of the above-mentioned adhesive and bonding layers may be given ultraviolet absorption capabilities by methods such as treating them with ultraviolet absorbers such as salicylic acid ester compounds, benzophenol compounds, benzotriazole compounds, cyanoacrylate compounds, or nickel complex salt compounds.

[0308] The adhesive layer and bonding layer described above can be attached by any suitable method. For example, an adhesive solution of about 10 to 40% by weight can be prepared by dissolving or dispersing the base polymer or its composition in a solvent consisting of a suitable solvent such as toluene or ethyl acetate, either alone or in a mixture thereof, and then attaching it directly to the film by any suitable deployment method such as casting or coating, or a method in which an adhesive layer is formed on a separator and then transferred, similar to the above.

[0309] Adhesive layers or bonding layers can be provided on one or both sides of the film as superimposed layers of different compositions or types. Furthermore, when provided on both sides, the adhesive layers on the front and back of the film can have different compositions, types, or thicknesses.

[0310] [Other layers] In order to control the angle dependence of the viewing angle, the laminate of the present invention may also be used in combination with an optically anisotropic film or photorotators, in addition to the light-absorbing anisotropic layer used in the present invention. For example, it is preferable to use an optically anisotropic resin film made of a polymer containing carbonate, cycloolefin, cellulose acylate, methyl methacrylate, styrene, maleic anhydride, etc., as the transparent substrate film.

[0311] [Anti-reflection system] The reflection prevention system of the present invention is a reflection prevention system having the laminate of the present invention. As described above, in the reflection prevention system of the present invention, when the transmittance center axis of the light absorption anisotropy layer is inclined with respect to the normal to the layer plane of the light absorption anisotropy layer, the angle φ between the plane encompassing the transmittance center axis and the normal to the layer plane of the light absorption anisotropy layer and the absorption axis of the polarizer is preferably 45° to 90°, more preferably 80° to 90°, and even more preferably 88° to 90°. The closer the above angle is to 90°, the easier it is to create illumination contrast between the direction in which the image display device is easy to see and the direction in which it is difficult to see. Furthermore, if the transmittance center axis of the light-absorbing anisotropic layer is parallel to the normal of the layer plane of the light-absorbing anisotropic layer, the preferred embodiment is not particularly limited to the above-described embodiment.

[0312] [Image display device] The image display device of the present invention is an image display device having the laminate of the present invention described above. The image display device in the present invention can be an organic EL display device, a liquid crystal display device, or other display devices, but here we will explain using an organic EL display device as an example. As shown in Figure 1, the image display device 100 with the reflection prevention system of the present invention is an image display device that comprises, from the viewing side, at least a linear polarization conversion layer 101, a light absorption anisotropy layer 102, a polarizer 103, and an organic EL image display device 104 in this order.

[0313] [Image display element] The display elements used in the image display device of the present invention are not particularly limited and include, for example, liquid crystal cells, organic EL display panels, and plasma display panels. Of these, liquid crystal cells or organic EL display panels are preferred. In other words, the image display device of the present invention is preferably a liquid crystal display device using liquid crystal cells as the display element, or an organic EL display device using an organic EL display panel as the display element. A liquid crystal display device, which is an example of the image display device of the present invention, is preferably an embodiment having the light-absorbing anisotropic layer, polarizer, and liquid crystal cell of the present invention as described above. More preferably, it is a liquid crystal display device having the laminate and liquid crystal cell of the present invention as described above. In the present invention, it is preferable to use the laminate of the present invention as the front or rear polarizing element among the polarizing elements provided on both sides of the liquid crystal cell, and it is also possible to use the laminate of the present invention as both the front and rear polarizing elements.

[0314] Some image display devices are thin and can be molded to curved surfaces. The optical anisotropic absorption layer used in this invention is thin and easily bendable, so it can be suitably applied to image display devices with curved display surfaces. Furthermore, some image display devices have a pixel density exceeding 250 ppi, enabling high-definition display. The optical anisotropic absorption layer used in this invention can be suitably applied to such high-definition image display devices without causing moiré patterns.

[0315] The following provides a detailed description of the liquid crystal cells that make up a liquid crystal display device.

[0316] <Liquid crystal cell> Liquid crystal cells used in liquid crystal display devices are preferably in VA (Vertical Alignment) mode, OCB (Optically Compensated Bend) mode, IPS (In-Plane-Switching) mode, or TN (Twisted Nematic) mode, but are not limited to these. In TN mode liquid crystal cells, when no voltage is applied, the rod-shaped liquid crystal molecules are substantially horizontally oriented and further twisted to 60-120°. TN mode liquid crystal cells are most widely used in color TFT (Thin Film Transistor) liquid crystal display devices and are described in numerous publications.

[0317] In VA mode liquid crystal cells, rod-shaped liquid crystalline molecules are substantially oriented vertically when no voltage is applied. VA mode liquid crystal cells include (1) narrowly defined VA mode liquid crystal cells in which rod-shaped liquid crystalline molecules are substantially oriented vertically when no voltage is applied and substantially oriented horizontally when voltage is applied (described in Japanese Patent Publication No. 2-176625), (2) multi-domain liquid crystal cells (MVA mode) in which the VA mode is multi-domain to expand the viewing angle (described in SID97, Digest of tech.Papers (Proceedings) 28 (1997) 845), (3) liquid crystal cells in a mode (n-ASM mode) in which rod-shaped liquid crystalline molecules are substantially oriented vertically when no voltage is applied and twisted multi-domain orientation when voltage is applied (described in the Proceedings of the Japan Liquid Crystal Symposium 58-59 (1998)), and (4) SURVIVAL mode liquid crystal cells (presented at LCD International 98). Furthermore, it may be any of the following types: PVA (Patterned Vertical Alignment), Optical Alignment, or PSA (Polymer-Sustained Alignment). Details of these modes are described in detail in Japanese Patent Publication No. 2006-215326 and Japanese Patent Publication No. 2008-538819.

[0318] In IPS mode liquid crystal cells, rod-shaped liquid crystal molecules are oriented substantially parallel to the substrate, and when an electric field parallel to the substrate surface is applied, the liquid crystal molecules respond in a planar manner. In IPS mode, black is displayed when no electric field is applied, and the absorption axes of the pair of upper and lower polarizers are orthogonal. Methods for reducing light leakage when displaying black at an oblique angle and improving the viewing angle using an optical compensation sheet are disclosed in Japanese Patent Publication No. 10-54982, Japanese Patent Publication No. 11-202323, Japanese Patent Publication No. 9-292522, Japanese Patent Publication No. 11-133408, Japanese Patent Publication No. 11-305217, and Japanese Patent Publication No. 10-307291, among others. [Examples]

[0319] The present invention will be described in more detail below with reference to examples. The materials, reagents, amounts and proportions of substances, and procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

[0320] [Example 1] [Fabrication of light-absorbing anisotropic film P1] A light-absorbing anisotropic film P1 having a light-absorbing anisotropic layer with oriented dyes was prepared by the following procedure.

[0321] <Fabrication of a transparent support 1 with a barrier layer and PVA orientation film> The surface of a cellulose acylate film 1 (TAC substrate with a thickness of 40 μm; TG40, Fujifilm Corporation) used as a support was saponified with an alkaline solution, and the following coating solution for barrier layer and PVA film formation was applied thereon using a wire bar. The support with the coating film 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 barrier layer and PVA orientation film 1, obtaining a transparent support 1 with a barrier layer and PVA orientation film. The thickness of the barrier layer and PVA orientation film 1 was 0.5 μm.

[0322] ------------------------------------------------------------------ (Coating solution for forming a barrier layer and PVA alignment film) ------------------------------------------------------------------ • 3.80 parts by mass of the following modified polyvinyl alcohol • Initiator Irg2959 0.20 parts by mass ·Water 70 parts by mass • Methanol 30 parts by mass ------------------------------------------------------------------

[0323] Modified polyvinyl alcohol [ka]

[0324] <Formation of light-absorbing anisotropic layer P1> The following light-absorbing anisotropic layer-forming composition P1 was applied to the obtained barrier layer / PVA alignment film 1 using a wire bar to form a coating. Next, the coating was heated at 120°C for 60 seconds and then cooled to room temperature (23°C). After further heating at 80°C for 60 seconds, it was cooled to room temperature. Subsequently, the light-absorbing anisotropic layer P1 was formed on the barrier layer / PVA alignment film 1 by irradiating it for 1 second using an LED lamp (center wavelength 365 nm) at an irradiation condition of 200 mW / cm2.

[0325] ------------------------------------------------------------------ (Composition P1 for forming a light-absorbing anisotropic layer) ------------------------------------------------------------------ • The following dichroic substance D-1: 0.63 parts by mass • The following dichroic substance D-2: 0.17 parts by mass • The following dichroic substance D-3: 1.13 parts by mass • 8.18 parts by mass of the following polymeric liquid crystalline compound P-1 • Polymerization initiator IRGACUREOXE-02 (BASF) 0.16 parts by mass • Compound E-1 (listed below): 0.12 parts by mass • Compound E-2 (listed below): 0.12 parts by mass • Surfactant F-1 (listed below): 0.005 parts by mass Cyclopentanone 85.00 parts by mass Benzyl alcohol 4.50 parts by mass ------------------------------------------------------------------

[0326] Dichroic substance D-1 [ka]

[0327] Dichroic substance D-2 [ka]

[0328] Dichroic substance D-3 [ka]

[0329] Polymer liquid crystal compound P-1 [ka]

[0330] Compound E-1 [ka]

[0331] Compound E-2 [ka]

[0332] Surfactant F-1 [ka]

[0333] <Formation of barrier layer 1> The following barrier layer-forming coating solution was applied to the fabricated light-absorbing anisotropic layer P1 using a wire bar and dried at 80°C for 5 minutes. The resulting coating film was then subjected to an illuminance of 150 mW / cm² using an LED lamp (center wavelength 365 nm) in an environment of 100 ppm oxygen concentration and 60°C. 2 A barrier layer 1 was formed on the light-absorbing anisotropic layer P1 by irradiation for 2 seconds under the specified irradiation conditions. The thickness of the barrier layer 1 was 1.0 μm.

[0334] Based on the above, a light-absorbing anisotropic film P1 was obtained.

[0335] ------------------------------------------------------------------ (Coating solution for forming a barrier layer) ------------------------------------------------------------------ • 3.80 parts by mass of the above-mentioned modified polyvinyl alcohol • Initiator Irg2959 0.20 parts by mass ·Water 70 parts by mass • Methanol 30 parts by mass ------------------------------------------------------------------

[0336] [Fabrication of linear polarization conversion film Q1] A linear polarization conversion film Q1 having a randomly oriented liquid crystal layer as a linear polarization conversion layer was fabricated by the following procedure. The layer structure of the linear polarization conversion film Q1 is as shown in Figure 5 (reference numeral 21: linear polarization conversion layer, reference numeral 22: orientation auxiliary layer, reference numeral 23: barrier layer, reference numeral 24: TAC support).

[0337] <Fabrication of transparent support 2 with barrier layer> The surface of a cellulose acylate film 1 (TAC substrate with a thickness of 40 μm; TG40, Fujifilm Corporation) was saponified with an alkaline solution, and the following barrier layer forming coating solution was applied thereon using a wire bar. The support with the coated film was dried with 60°C hot air for 60 seconds, and then with 100°C hot air for 120 seconds to form a barrier layer 2, obtaining a transparent support 2 with a barrier layer. The thickness of the barrier layer 2 was 0.5 μm.

[0338] ------------------------------------------------------------------ (Coating solution for forming a barrier layer) ------------------------------------------------------------------ • 3.80 parts by mass of the above-mentioned modified polyvinyl alcohol • Initiator Irg2959 0.20 parts by mass ·Water 70 parts by mass • Methanol 30 parts by mass ------------------------------------------------------------------

[0339] <Formation of Orientation Auxiliary Layer 1> The orientation auxiliary layer forming composition 1 described below was applied onto the barrier layer 2 using a wire bar. The support with the formed coating was dried with 140°C hot air for 120 seconds, and then exposed to unpolarized (natural light) ultraviolet light at 1000 mJ / cm² at room temperature. 2 An orientation auxiliary layer 1 was formed by irradiation (using an ultra-high pressure mercury lamp). The thickness of the orientation auxiliary layer 1 was 0.25 μm. ------------------------------------------------------------------ (Composition for forming an orientation auxiliary layer 1) ------------------------------------------------------------------ • 10.0 parts by mass of the polymer PA-1 below • Acid generator PAG-1: 0.83 parts by mass • Stabilizer DIPEA 0.06 parts by mass Xylene 113 parts by mass • 12 parts by mass of methyl isobutyl ketone ------------------------------------------------------------------

[0340] Polymer PA-1 (In the formula, the numerical values ​​listed for each repeating unit represent the content (mass %) of each repeating unit relative to the total number of repeating units.)

[0341] [ka]

[0342] Acid Generator PAG-1

[0343] [ka]

[0344] Stabilizer DIPEA

[0345] [ka]

[0346] <Formation of linear polarization conversion layer 1> The random orientation liquid crystal layer formation composition 1 described below was applied onto the alignment auxiliary layer 1 using a wire bar. The support on which the coated film was formed was dried with hot air at 120°C for 120 seconds, and then 200 mJ / cm² was applied to the coated film at a temperature of 60°C. 2 A randomly aligned liquid crystal layer 1 was formed by irradiation with ultraviolet light (using an ultra-high pressure mercury lamp). In this embodiment, the obtained randomly aligned liquid crystal layer 1 was used as a linear polarization conversion layer 1. Figure 2 shows an image of the obtained randomly aligned liquid crystal layer 1 observed under crossed nicol conditions using a polarizing microscope. The thickness of the obtained randomly aligned liquid crystal layer 1 was approximately 2 μm. Furthermore, it was previously confirmed that the randomly aligned liquid crystal layer 1 exhibits a nematic phase liquid crystal state at 60°C by observing the liquid crystal phase at varying temperatures using a hot stage for microscopy (Mettler Toledo) and a polarizing microscope.

[0347] ------------------------------------------------------------------ (Composition 1 for forming a randomly aligned liquid crystal layer) ------------------------------------------------------------------ • 10.0 parts by mass of the following low molecular weight liquid crystalline compound M-1 • Photopolymerization initiator Irg907: 0.60 parts by mass • 0.40 parts by mass of the polymerizable compound M-2 listed below. • Surfactant F-2 (listed below): 0.03 parts by mass Methyl ethyl ketone 39.0 parts by mass ------------------------------------------------------------------

[0348] Low molecular liquid crystal compound M-1 [ka]

[0349] Polymerizable compound M-2

Chemistry

[0350] Surfactant F-2

Chemistry

[0351] 〔Fabrication of laminate A1〕 A polarizer 1 with a thickness of 8 μm and one side of the polarizer exposed was fabricated in the same manner as the polarizer 02 with a single-sided protective film described in International Publication No. 2015 / 166991. The exposed surface of the polarizer of the polarizer 1 and the surface of the fabricated light absorption anisotropic film P1 were corona-treated, and the polarizer and the barrier layer 1 of the light absorption anisotropic film P1 were bonded using the following PVA adhesive 1. At this time, the angle formed by the plane including the transmission rate central axis of the light absorption anisotropic layer and the normal line of the film surface and the absorption axis of the polarizer was 90°. Furthermore, the support surface of the same light absorption anisotropic film P1 and the linearly polarized light conversion layer 1 surface of the linearly polarized light conversion film Q1 were also bonded using the PVA adhesive 1 in the same manner as above to obtain a laminate A1.

[0352] <Preparation of PVA adhesive 1> To 100 parts of a polyvinyl alcohol-based resin containing an acetoacetyl group (average degree of polymerization: 1200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%), 20 parts of methylol melamine was dissolved in pure water under temperature conditions of 30 °C to prepare an aqueous solution adjusted to a solid content concentration of 3.7%.

[0353] 〔Fabrication of image display device B1 with anti-reflection system〕 A Samsung Galaxy S4 equipped with an organic EL panel (organic EL display element) was disassembled. The touch panel with a circular polarizer was peeled off the organic EL display device, and the circular polarizer was further peeled off the touch panel. The organic EL display element, touch panel, and circular polarizer were then isolated, and the isolated circular polarizer was re-bonded to the organic EL display element. Laminate A1 was then laminated onto the re-bonded circular polarizer using the adhesive sheet described below. At this time, the lamination was carried out so that the transmission axes of the polarizer in the circular polarizer and the polarizer in laminate A1 were parallel. Thus, an image display device B1 with an anti-reflection system was fabricated. The layer structure of the obtained image display device B1 from the viewing side, excluding adhesives and sealants, is shown in Table 1 below.

[0354] <Creating Adhesive Sheet 1> An acrylate polymer was prepared according to the following procedure. In a reaction vessel equipped with a condenser, a nitrogen inlet, a thermometer, and a stirrer, 95 parts by weight of butyl acrylate and 5 parts by weight of acrylic acid were polymerized by solution polymerization to obtain acrylate polymer A1 with an average molecular weight of 2 million and a molecular weight distribution (Mw / Mn) of 3.0.

[0355] Next, 100 parts by mass of the obtained acrylate polymer A1 was mixed with 1.0 part by mass of Coronate L (a 75% by mass ethyl acetate solution of trimethylolpropane adduct of tolylene diisocyanate, with 3 isocyanate groups per molecule, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 0.2 parts by mass of silane coupling agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.). Finally, ethyl acetate was added to achieve a total solid content concentration of 10% by mass to prepare an adhesive-forming composition. This composition was applied to a separator film surface-treated with a silicone-based release agent using a die coater and dried at 90°C for 1 minute to obtain an acrylate-based adhesive sheet. The film thickness was 25 μm and the storage modulus was 0.1 MPa.

[0356] [Example 2] An image display device B2 with an anti-reflection system was fabricated in the same manner as in Example 1, except that plate B was fabricated as described below, and laminate A2 was fabricated instead of laminate A1.

[0357] [Preparation of Plate B] Various phase difference layers used in the embodiments of the present invention were fabricated as follows.

[0358] <Extrusion molding> Cycloolefin resin ARTON G7810 (JSR Corporation) was dried at 100°C for more than 2 hours and then melt-extruded at 280°C using a twin-screw compounding extruder. At this time, a screen filter, a gear pump, and a leaf disc filter were placed in this order between the extruder and the die, and these were connected by melt piping. The extruded film was cast onto a triple cast roll set to 180°C, 175°C, and 170°C, yielding an unstretched film 1 with a width of 900 mm and a thickness of 320 μm.

[0359] <Stretching / heat setting> The unstretched film 1 being transported was subjected to a stretching process and a heat-setting process in the following manner.

[0360] (a) Longitudinal extension An unstretched film 1 was stretched longitudinally under the following conditions while being transported using a roll-to-roll longitudinal stretcher with an aspect ratio (L / W) of 0.2. <Condition> Preheating temperature: 170°C, Stretching temperature: 170°C, Stretching ratio: 155% (b) Lateral stretching The longitudinally stretched film was then stretched transversely under the following conditions while being transported using a tenter. <Condition> Preheating temperature: 170°C, Stretching temperature: 170°C, Stretching ratio: 80%

[0361] (c) Heat fixation Following the stretching process, the stretched film was held at both ends with tenter clips to maintain a constant width (within a range of expansion or contraction of 3%), and then heat-treated and heat-fixed under the following conditions. Heat setting temperature: 165℃, heat setting time: 30 seconds The preheating temperature, stretching temperature, and heat-fixing temperature are the average values ​​of measurements taken at five points in the width direction using a radiation thermometer.

[0362] <winding> After heat setting, both ends were trimmed, and the film was wound under a tension of 25 kg / m to obtain a film roll with a width of 1340 mm and a length of 2000 m. The obtained stretched film had a Re of 160 nm, an Rth of 390 nm, an Nz coefficient of 2.9, a slow axis in the MD direction, and a film thickness of 80 μm. This was designated as plate B.

[0363] [Fabrication of laminate A2] Using the same method as for polarizing plate 02 with a protective film on one side described in International Publication No. 2015 / 166991, a polarizing plate 1 was fabricated with a polarizer thickness of 8 μm and one side of the polarizer exposed. The exposed polarizer surface of polarizing plate 1 and the surface of plate B, which was prepared as described above, were corona-treated and bonded together using the PAV bonding method described above. At this time, the orientation was determined so that the longitudinal extension direction of plate B and the absorption axis of the polarizer were parallel before bonding. Next, the back side of the B plate, to which the polarizer was bonded, was corona-treated, and the surface of the B plate and the surface of the fabricated light-absorbing anisotropic film P1 were bonded together using the PVA adhesive 1 described above. At this time, the angle between the plane encompassing the transmittance center axis of the light-absorbing anisotropic layer and the normal to the film surface and the absorption axis of the polarizer was 90°. Furthermore, the support surface of the same light-absorbing anisotropic film P1 and the linear polarization conversion layer 1 surface of the linear polarization conversion film Q1 were bonded together using PVA adhesive 1 in the same manner as described above to obtain laminate A2.

[0364] [Example 3] An image display device B3 with an anti-reflection system was fabricated in the same manner as in Example 1, except that a linear polarization conversion film Q2 having a depolarization layer made of a fine particle-containing layer prepared as described below was used instead of the linear polarization conversion film Q1.

[0365] [Fabrication of linear polarization conversion film Q2] Except for using the fine particle-containing layer 1 prepared as described below as the linear polarization conversion layer 2, the linear polarization conversion film Q2 was fabricated in the same manner as the linear polarization conversion film Q1, following the linear polarization conversion film Q2 procedure.

[0366] <Formation of linear polarization conversion layer 2> The following fine particle-containing layer-forming composition 1 was applied onto the orientation auxiliary layer 1 using a wire bar. The support on which the coated film was formed was dried with hot air at 120°C for 120 seconds, and then 200 mJ / cm² was applied to the coated film at a temperature of 60°C. 2 A microparticle-containing layer 1 was formed by irradiation with ultraviolet light (using an ultra-high pressure mercury lamp). The obtained microparticle-containing layer 1 was used as the linear polarization conversion layer 2 in this example. The thickness of the obtained microparticle-containing layer was approximately 2 μm. The fabricated microparticle-containing layer had slight haze, indicating that light scattering was occurring.

[0367] -------------------------------------------------- (Fine particle-containing layer forming composition 1) -------------------------------------------------- • 3.80 parts by mass of the above-mentioned modified polyvinyl alcohol • Organosilica sol IPA-ST-ZL 3.80 parts by mass • Initiator Irg2959 0.20 parts by mass ·Water 70 parts by mass • Methanol 30 parts by mass --------------------------------------------------

[0368] [Example 4] An image display device B4 with an anti-reflection system was fabricated in the same manner as in Example 1, except that a λ / 4 plate (QWP) was used instead of the linear polarization conversion film Q1. However, the λ / 4 plate was used by bonding it so that the angle between its slow axis and the polarizer was 45°. Furthermore, the λ / 4 plate used here was prepared according to the following procedure.

[0369] <Fabrication of λ / 4 plate (QWP)> (1) Preparation of cellulose acylate film (Preparation of cellulose ester solution A-1) The following compositions were placed in a mixing tank and stirred while heating to dissolve each component, thereby preparing cellulose ester solution A-1. ------------------------------------------------------------------ Composition of Cellulose Ester Solution A-1 ------------------------------------------------------------------ • Cellulose acetate (acetylation degree 2.86) 100 parts by mass • Methylene chloride (first solvent) 320 parts by mass • Methanol (second solvent) 83 parts by mass • 1-Butanol (third solvent) 3 parts by mass Triphenylphosphate 7.6 parts by mass • Biphenyldiphenyl phosphate 3.8 parts by mass ------------------------------------------------------------------

[0370] (Preparation of mat agent dispersion B-1) The following compositions were placed in a disperser and stirred to dissolve each component, thereby preparing mat agent dispersion B-1. ------------------------------------------------------------------ Composition of mat agent dispersion B-1 ------------------------------------------------------------------ • Silica particle dispersion (average particle size 16nm) "AEROSIL R972", Manufactured by Nippon Aerosil Co., Ltd. 10.0 parts by mass • Methylene chloride 72.8 parts by mass • Methanol 3.9 parts by mass • Butanol 0.5 parts by mass • Cellulose ester solution A-1: ​​10.3 parts by mass ------------------------------------------------------------------

[0371] (Preparation of UV absorber solution C-1) The following compositions were placed in a separate mixing tank and stirred while heating to dissolve each component, thereby preparing UV absorber solution C-1. ------------------------------------------------------------------ Composition of UV absorber solution C-1 ------------------------------------------------------------------ • UV absorber (UV-1 below) 10.0 parts by mass • UV absorber (UV-2 below) 10.0 parts by mass Methylene chloride 55.7 parts by mass • 10 parts by mass of methanol • Cellulose ester solution A-1: ​​12.9 parts by mass • Butanol 1.3 parts by mass ------------------------------------------------------------------

[0372] [ka]

[0373] (Preparation of cellulose ester film) A mixture of 94.6 parts by mass of cellulose acylate solution A-1 and 1.3 parts by mass of matting agent dispersion B-1 was prepared. To this mixture, ultraviolet absorber solution C-1 was added so that the amount of ultraviolet absorber (UV-1) and ultraviolet absorber (UV-2) was 1.0 part by mass each per 100 parts by mass of cellulose acylate. The mixture was heated and thoroughly stirred to dissolve each component, thereby preparing a dope. The resulting dope was heated to 30°C and cast through a casting gieser onto a mirror-finished stainless steel support drum with a diameter of 3 m. The surface temperature of the support was set to -5°C, and the coating width was 1470 mm. The cast dope film was then dried over the drum with 34°C drying air for 150 m. 3The film was dried by applying heat for 1 minute and peeled off the drum when the residual solvent content was 150%. During peeling, it was stretched by 15% in the transport direction (longitudinal direction). Subsequently, the film was transported while gripping both ends in the width direction (direction perpendicular to the casting direction) with a pin tenter (a pin tenter as shown in Figure 3 of Japanese Patent Publication No. 4-1009), and no stretching treatment was performed in the width direction. Furthermore, it was dried by transporting it between the rolls of a heat treatment apparatus to produce a cellulose acylate film (T1). The residual solvent content of the produced long cellulose acylate film (T1) was 0.2%, the thickness was 60 μm, and the Re and Rth at 550 nm were 0.8 nm and 40 nm, respectively.

[0374] (2) Fabrication of phase difference plate (Alkaline saponification treatment) The aforementioned cellulose acylate film (T1) is passed through a dielectric heating roll at a temperature of 60°C to raise the film surface temperature to 40°C. Then, an alkaline solution with the composition shown below is applied to the band surface of the film using a bar coater at a rate of 14 ml / m². 2 The material was coated and then transported for 10 seconds under a steam-type far-infrared heater manufactured by Noritake Co., Ltd., heated to 110°C. Subsequently, using the same bar coater, 3 ml / m of pure water was applied. 2 The film was then coated. Next, it was washed with water using a fountain coater and dewatered with an air knife three times, and then transported to a 70°C drying zone for 10 seconds to dry, thereby producing an alkaline saponified cellulose acylate film. ------------------------------------------------------------------ Alkaline solution composition ------------------------------------------------------------------ • Potassium hydroxide 4.7 parts by mass ·Water 15.8 parts by mass Isopropanol 63.7 parts by mass • Surfactant SF-1:C 14 H 29 O(CH2CH2O) 20 H 1.0 parts by mass • Propylene glycol 14.8 parts by mass ------------------------------------------------------------------

[0375] (Formation of orientation film) An orientation film coating solution (A) with the following composition was continuously applied to the surface of a cellulose acylate film (T1) that had undergone alkali saponification using a #14 wire bar. It was dried with 60°C hot air for 60 seconds, and then with 100°C hot air for 120 seconds. The degree of saponification of the modified polyvinyl alcohol used was 96.8%. ------------------------------------------------------------------ Composition of the alignment film coating solution (A) ------------------------------------------------------------------ • 10 parts by mass of the following modified polyvinyl alcohol ·Water 308 parts by mass • Methanol 70 parts by mass Isopropanol 29 parts by mass • Photopolymerization initiator (Irgacure 2959, manufactured by BASF) 0.8 parts by mass ------------------------------------------------------------------

[0376] [ka]

[0377] (Formation of the optically anisotropic layer (Q)) The orientation film prepared as described above was subjected to a continuous rubbing process. At this time, the longitudinal direction of the long film and the transport direction were parallel, and the angle between the rotation axis of the rubbing roller and the longitudinal direction of the film was 45° (counterclockwise).

[0378] An optically anisotropic layer coating solution (A) containing a rod-shaped liquid crystal compound with the composition described below was continuously coated onto the prepared alignment film using a #2.2 wire bar. The film transport speed (V) was set to 26 m / min. To dry the solvent of the coating solution and mature the orientation of the rod-shaped liquid crystal compound, it was heated with 60°C hot air for 60 seconds and then irradiated with UV at 60°C to fix the orientation of the liquid crystal compound. The thickness of the optically anisotropic layer (Q) was 0.8 μm. The average inclination angle of the long axis of the rod-shaped liquid crystal compound with respect to the film surface was 0°, confirming that the liquid crystal compound was oriented horizontally with respect to the film surface. Furthermore, the angle of the slow phase axis was perpendicular to the rotation axis of the rubbing roller, and was 45° clockwise when the longitudinal direction of the film was set to 0°. Furthermore, the phase differences Re(550) and Rth(550) at a wavelength of 550 nm, measured using AxoScan OPMF-1 (OptoScience Co., Ltd.), were Re(550) = 120 nm and Rth(550) = 105 nm, respectively. ------------------------------------------------------------------ Composition of optically anisotropic layer coating solution (A) ------------------------------------------------------------------ • 80 parts by mass of the following rod-shaped liquid crystal compound (A) • 20 parts by mass of the following rod-shaped liquid crystal compound (B) • Photopolymerization initiator (Irgacure 907, manufactured by BASF) 3 parts by mass • Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass • 0.3 parts by mass of the following fluorine-based polymer (FP1) • Methyl ethyl ketone 193 parts by mass • Cyclohexanone 50 parts by mass ------------------------------------------------------------------

[0379] [ka]

[0380] The prepared λ / 4 plates were immersed in a 1.5 mol / liter sodium hydroxide solution at 55°C, and then thoroughly rinsed with water to remove the sodium hydroxide. Next, they were immersed in a 0.005 mol / liter dilute sulfuric acid solution at 35°C for 1 minute, and then thoroughly rinsed with water to remove the dilute sulfuric acid solution. Finally, the samples were thoroughly dried at 120°C.

[0381] [Example 5] An image display device B5 with an anti-reflection system was fabricated in the same manner as in Example 1, except that a λ / 2 plate (HWP) was used instead of the linear polarization conversion film Q1. However, the λ / 2 plate was used by bonding it so that the angle between its slow axis and the polarizer was 45°. Furthermore, the λ / 2 plate used here was a λ / 2 plate fabricated according to the following procedure.

[0382] <Fabrication of λ / 2 plate (HWP)> (1) Preparation of cellulose acylate film The cellulose acylate film was prepared in the same manner as in Example 4 (1) Preparation of Cellulose Acylate Film. The prepared long cellulose acylate film (T2) had a residual solvent content of 0.2%, a thickness of 60 μm, and Re and Rth at 550 nm were 0.8 nm and 40 nm, respectively.

[0383] (2) Fabrication of phase difference plate (Alkaline saponification treatment) The aforementioned cellulose acylate film (T2) was subjected to alkaline saponification treatment using the same procedure as in Example 4 (alkaline saponification treatment).

[0384] (Formation of orientation film) An orientation film was formed on the surface of the cellulose acylate film (T2) that had undergone alkali saponification treatment, using the same procedure as in Example 4 (Formation of Orientation Film). The degree of saponification of the modified polyvinyl alcohol used was 96.8%.

[0385] (Formation of optically anisotropic layer (H)) The orientation film prepared as described above was subjected to a continuous rubbing process. At this time, the longitudinal direction of the long film and the transport direction were parallel, and the angle between the rotation axis of the rubbing roller and the longitudinal direction of the film was 45° (clockwise).

[0386] An optically anisotropic layer coating solution (B) containing a discotic liquid crystal compound with the composition described below was continuously coated onto the prepared alignment film using a #5.0 wire bar. The film transport speed (V) was set to 26 m / min. To dry the solvent of the coating solution and mature the orientation of the discotic liquid crystal compound, the film was heated with 115°C hot air for 90 seconds, followed by 80°C hot air for 60 seconds, and then UV irradiation was performed at 80°C to fix the orientation of the liquid crystal compound. The thickness of the optically anisotropic layer (H) was 2.0 μm. The average inclination angle of the disc surface of the DLC compound with respect to the film surface was 90°, confirming that the discotic liquid crystal compound was oriented perpendicular to the film surface. Furthermore, the angle of the slow axis was parallel to the rotation axis of the rubbing roller, and was 45° clockwise when the longitudinal direction of the film was considered 0°. Furthermore, the phase difference Re(550) and Rth(550) at a wavelength of 550 nm, measured using AxoScan OPMF-1 (OptoScience Co., Ltd.), were Re(550) = 250 nm and Rth(550) = -70 nm, respectively. ------------------------------------------------------------------ Composition of optically anisotropic layer coating solution (B) ------------------------------------------------------------------ • 80 parts by mass of the following discotic liquid crystal compound (A) • 20 parts by mass of the following discotic liquid crystal compound (B) • Ethylene oxide-modified trimethylolpropane triacrylate (V#360, manufactured by Osaka Organic Chemical Co., Ltd.) 10 parts by mass • Photopolymerization initiator (Irgacure 907, manufactured by BASF) 3 parts by mass • 0.9 parts by mass of the following pyridinium salt (A) • 0.08 parts by mass of the following boronic acid-containing compound • 0.6 parts by mass of the following polymer (A) • 0.3 parts by mass of the following fluorine-based polymer (FP2) • Methyl ethyl ketone 183 parts by mass • Cyclohexanone 40 parts by mass ------------------------------------------------------------------

[0387] [ka] JPEG0007835725000078.jpg45148

[0388] The prepared λ / 2 plates were immersed in a 1.5 mol / liter sodium hydroxide solution at 55°C, and then thoroughly rinsed with water to remove the sodium hydroxide. Next, they were immersed in a 0.005 mol / liter dilute sulfuric acid solution at 35°C for 1 minute, and then thoroughly rinsed with water to remove the dilute sulfuric acid solution. Finally, the samples were thoroughly dried at 120°C.

[0389] [Example 6] An image display device B6 with an anti-reflection system was fabricated in the same manner as in Example 1, except that a polarizer (polarizer 2) prepared as described above was used instead of the linear polarization conversion film Q1. However, the polarizer was used by bonding it so that its absorption axis was parallel to the absorption axis of polarizer 1 used in the laminate A6.

[0390] [Example 7] An image display device B7 with an anti-reflection system was fabricated in the same manner as in Example 1, except that the linear polarization conversion film Q1 was not used, and instead of the light absorption anisotropy film P1, a light absorption anisotropy film P2 having a linear polarization conversion layer and light absorption anisotropy was fabricated by the following procedure, and further laminated so that the support side of the light absorption anisotropy film P2 faces the organic EL display device side.

[0391] [Fabrication of light-absorbing anisotropic film P2] A barrier layer / PVA alignment film 1, a light-absorbing anisotropic layer P1, and a barrier layer 1 were formed on a support in the same manner as the light-absorbing anisotropic film P1 of Example 1.

[0392] Furthermore, the orientation auxiliary layer forming composition 1 is applied to the barrier layer 1 using a wire bar, the formed coating is dried with 140°C hot air for 120 seconds, and then, at room temperature, the coating is exposed to unpolarized (natural light) ultraviolet light at a rate of 1000 mJ / cm². 2 An orientation auxiliary layer 2 was formed by irradiation (using an ultra-high pressure mercury lamp). The thickness of the orientation auxiliary layer 2 was 0.25 μm.

[0393] Furthermore, the above-mentioned random orientation liquid crystal layer forming composition 1 is applied onto the alignment auxiliary layer 2 using a wire bar, the formed coating is dried with hot air at 120°C for 120 seconds, and then 200 mJ / cm² is applied to the coating at a temperature of 60°C. 2 A randomly aligned liquid crystal layer was formed by irradiating it with ultraviolet light (using an ultra-high pressure mercury lamp). Based on the above experiments, a light-absorbing anisotropic film P2 was fabricated.

[0394] [Example 8] An image display device B8 with an anti-reflection system was fabricated in the same manner as in Example 1, except that a light-absorbing anisotropic film P3, prepared by the following procedure, was used instead of the light-absorbing anisotropic film P1.

[0395] [Fabrication of light-absorbing anisotropic film P3] A barrier layer / PVA alignment film 1 was formed on a support in the same manner as in Example 1. The formed barrier layer / PVA alignment film was then rubbed, and the following tilted liquid crystal alignment film forming composition 1 was applied thereon using a wire bar. The coating was then heated with 120°C hot air for 30 seconds to form a dry film. Afterward, a high-pressure mercury lamp was used to irradiate the film at an illuminance of 200 mW / cm². 2 A tilted liquid crystal alignment film was fabricated by irradiating it for 1 second under the specified irradiation conditions. The thickness of the fabricated tilted liquid crystal alignment film was 0.60 μm.

[0396] ------------------------------------------------------------------ (Composition 1 for forming tilted liquid crystal alignment film) ------------------------------------------------------------------ • The following low molecular weight liquid crystalline compound M-1: 9.57 parts by mass • Polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.41 parts by mass • 0.026 parts by mass of the above surfactant F-1 • Cyclopentanone 66 parts by mass • 66 parts by mass of tetrahydrofuran ------------------------------------------------------------------

[0397] Low molecular liquid crystal compound M-1 [ka]

[0398] The following light-absorbing anisotropic layer-forming composition P2 was applied to the fabricated tilted liquid crystal alignment film using a wire bar, and the coating was heated with 120°C hot air for 30 seconds, after which it was cooled to room temperature. Subsequently, it was reheated at 80°C for 60 seconds and cooled again to room temperature. After that, an illuminance of 200 mW / cm was applied using an LED lamp (center wavelength 365 nm). 2 A light-absorbing anisotropic layer P2 was fabricated by irradiating it for 1 second under the specified irradiation conditions. The thickness of the fabricated light-absorbing anisotropic layer P2 was 2.1 μm.

[0399] ------------------------------------------------------------------ (Composition P2 for forming a light-absorbing anisotropic layer) ------------------------------------------------------------------ • 0.74 parts by mass of the above dichroic substance D-1 • 0.33 parts by mass of the above dichroic substance D-2 • 1.10 parts by mass of the above dichroic substance D-3 • 4.32 parts by mass of the above polymeric liquid crystalline compound P-1 • 3.17 parts by mass of the above low molecular weight liquid crystalline compound M-1 • Polymerization initiator IRGACUREOXE-02 (BASF) 0.317 parts by mass • 0.010 parts by mass of the above surfactant F-2 Cyclopentanone 51.4 parts by mass Tetrahydrofuran 51.4 parts by mass ------------------------------------------------------------------

[0400] <Formation of barrier layer 2> The above-mentioned barrier layer forming solution was applied to the fabricated light-absorbing anisotropic layer P2 using a wire bar and dried at 80°C for 5 minutes. The resulting coating film was then subjected to an illuminance of 150 mW / cm² using an LED lamp (center wavelength 365 nm) in an environment of 100 ppm oxygen concentration and 60°C. 2 A barrier layer 2 was formed on the light-absorbing anisotropic layer P2 by irradiation for 2 seconds under the specified irradiation conditions. The thickness of the barrier layer 2 was 1.0 μm. Based on the above experiments, a light-absorbing anisotropic film P3 was fabricated.

[0401] [Example 9] An image display device B9 with an anti-reflection system was fabricated in the same manner as in Example 1, except that a linear polarization conversion film Q1 was not used, and a light absorption anisotropic film P4, prepared by the following procedure, was used instead of the light absorption anisotropic film P1.

[0402] [Fabrication of light-absorbing anisotropic film P4] The light-absorbing anisotropic film P4 was prepared in the same manner as the light-absorbing anisotropic film P1 of Example 1, except that a super-birefringent polyester film (Cosmoshine SRF, manufactured by Toyobo, 80 μm thick) was used as both a linear polarization conversion layer and a support, instead of the cellulose acylate film 1 as the support. However, when preparing the laminate A9, the layers were bonded so that the slow phase axis of the Cosmoshine SRF was at a 45° angle with respect to the slow phase axis of the polarizer.

[0403] [Example 10] An image display device B10 with an anti-reflection system was fabricated in the same manner as in Example 1, except that instead of the linear polarization conversion film Q1, a laminate A10 was used, which was made by stacking two linear polarization conversion films Q3-1 and Q3-2, which correspond to negative C plates, prepared by the following procedure.

[0404] [Fabrication of linear polarization conversion films Q3-1 and Q3-2] <Composition for forming negative C plates> The following negative C plate formation compositions were prepared, and a homogeneous solution was obtained. ------------------------------------------------------------------ Composition for forming negative C plates ------------------------------------------------------------------ • 80 parts by mass of the following discotic liquid crystalline compound CA-1 • 20 parts by mass of the following discotic liquid crystalline compound CA-2 • 5.6 parts by mass of the following discotic liquid crystalline compound DB-1 • 5.6 parts by mass of the polymerizable monomer CS1 listed below. • 0.2 parts by mass of the following polymer CC-1 • Polymerization initiator (Irgacure 907, manufactured by BASF) 3 parts by mass • Toluene 170 parts by mass • Methyl ethyl ketone 73 parts by mass ------------------------------------------------------------------

[0405] Discotic liquid crystalline compound CA-1 (1,3,5-substituted benzene-type polymerizable discotic liquid crystalline compound) [ka]

[0406] Discotic liquid crystalline compound CA-2 (1,3,5-substituted benzene-type polymerizable discotic liquid crystalline compound) [ka]

[0407] Discotic liquid crystalline compound CB-1 (polymerizable triphenylene-type discotic liquid crystalline compound) [ka]

[0408] Polymerizable monomer CS1 [ka]

[0409] Polymer CC-1 (The copolymerization ratio of the chemical structural formula is indicated in mass percent below.) [ka]

[0410] As a support, a commercially available cellulose triacetate film (Fujitac ZRD40, manufactured by Fujifilm Corporation) was used without saponification treatment. The negative C plate forming composition described above was coated onto the surface of the support, and the solvent was dried by continuously heating from room temperature to 100°C. The coated layer was then heated for approximately 90 seconds in a 100°C drying zone, and then cooled to 60°C before being subjected to a 300 mJ / cm³ treatment under air. 2 A linear polarization conversion film Q3-1 was obtained by UV exposure. After cooling to room temperature, the orientation state was observed, and it was found that the discotic liquid crystalline compound was horizontally oriented without defects. The Rth(550) was 327 nm and the Re was 1 nm.

[0411] Similarly, by adjusting the coating thickness of the negative C plate forming composition, a linear polarization conversion film Q3-2 with an Rth (550) of 361 nm and an Re of 1 nm was also fabricated. As described above, since Q3-1 and Q3-2 are used in a two-layer stack, the entire film can be considered as a linear polarization conversion film equivalent to a negative C plate with an Rth of 688 nm and an Re of 2 nm.

[0412] [Example 11] An image display device B11 with an anti-reflection system was fabricated in the same manner as in Example 2, except that instead of linear polarization conversion film Q1, two linear polarization conversion films Q3-1 and Q3-2 similar to those in Example 10 were stacked to form a laminate A11, and the phase difference of the B plate was changed to Re(550)=160nm and Rth(550)=390nm.

[0413] [Example 12] An image display device B12 with an anti-reflection system was fabricated in the same manner as in Example 1, except that a linear polarization conversion film was not used, and composition P3 for forming a light absorption anisotropy layer was used instead of composition P1 for forming a light absorption anisotropy layer of a light absorption anisotropy film, and the film thickness was adjusted to 4 μm.

[0414] ------------------------------------------------------------------ (Composition P3 for forming a light-absorbing anisotropic layer) ------------------------------------------------------------------ • 0.63 parts by mass of the above dichroic substance D-1 • 0.17 parts by mass of the above dichroic substance D-2 • 1.13 parts by mass of the above dichroic substance D-3 • 8.18 parts by mass of the above polymeric liquid crystalline compound P-1 • Polymerization initiator IRGACUREOXE-02 (BASF) 0.16 parts by mass • 0.12 parts by mass of the above compound E-1 • 0.12 parts by mass of the above compound E-2 • Surfactant F-3 (listed below): 0.01 parts by mass Cyclopentanone 85.00 parts by mass Benzyl alcohol 4.50 parts by mass ------------------------------------------------------------------

[0415] Surfactant F-3 [ka]

[0416] When 2 μm thick sections were collected from the fabricated light-absorbing anisotropic layer using a microtome and observed on a polarizing microscope, it was confirmed that extinction occurred at the interface with the support side. On the other hand, since no extinction occurred at the air-side interface, it was confirmed that a randomly oriented liquid crystal layer acting as a linear polarization conversion layer was formed on the air-side interface.

[0417] [Example 13] An image display device B13 with an anti-reflection system was manufactured in the same manner as in Example 1, except that polarizing plate 1 was replaced with a coated polarizing plate manufactured as described below.

[0418] [Preparation of transparent supports] The following compositions were added to a mixing tank and stirred to prepare a cellulose acetate solution to be used as a cellulose acylate dope for the core layer. ------------------------------------------------------------------ Core layer cellulose acylate doped ------------------------------------------------------------------ • 100 parts by mass of cellulose acetate with an acetyl substitution degree of 2.88 • Example of preparation for Japanese Patent Publication No. 2015-227955 12 parts by mass of the listed polyester compound B • Compound G below: 2 parts by mass • Methylene chloride (first solvent) 430 parts by mass • Methanol (second solvent) 64 parts by mass ------------------------------------------------------------------

[0419] Compound G [ka]

[0420] A cellulose acetate solution to be used as the outer layer cellulose acylate dope was prepared by adding 10 parts by mass of the following mat agent solution to 90 parts by mass of the above core layer cellulose acylate dope.

[0421] ------------------------------------------------------------------ Mat solution ------------------------------------------------------------------ • Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass • Methylene chloride (first solvent) 76 parts by mass • Methanol (second solvent) 11 parts by mass • 1 part by mass of the above-mentioned core layer cellulose acylate doped ------------------------------------------------------------------

[0422] The core layer cellulose acylate dope and the outer layer cellulose acylate dope were filtered using filter paper with an average pore size of 34 μm and a sintered metal filter with an average pore size of 10 μm. Then, the core layer cellulose acylate dope and the outer layer cellulose acylate dope on both sides were simultaneously cast into three layers from the casting port onto a drum at 20°C (band casting machine). Next, the film was peeled off the drum when the solvent content in the film was approximately 20% by mass. Both ends of the film in the width direction were fixed with tenter clips, and the film was dried while being stretched transversely at a stretching ratio of 1.1 times. Subsequently, the obtained film was further dried by transporting it between rolls in a heat treatment apparatus to produce a transparent support with a thickness of 40 μm, which was designated as cellulose acylate film A1.

[0423] [Formation of photo-aligned film B1] The photo-alignment film-forming composition described later was continuously applied onto the cellulose acylate film A1 using a wire bar. The support with the coated film was dried with 140°C hot air for 120 seconds, and then polarized ultraviolet light (10 mJ / cm²) was irradiated onto the coating film. 2 By using an ultra-high pressure mercury lamp, a photo-alignment film B1 was formed, and a TAC (triacetylcellulose) film with the photo-alignment film was obtained. The thickness of the photo-alignment film B1 was 0.25 μm. ------------------------------------------------------------------ Composition for forming photo-alignment film ------------------------------------------------------------------ • 100.00 parts by mass of the polymer PA-1 below • Acid generator PAG-1: 8.25 parts by mass • Stabilizer DIPEA 0.6 parts by mass Xylene 1126.60 parts by mass • Methyl isobutyl ketone 125.18 parts by mass ------------------------------------------------------------------

[0424] Polymer PA-1 (In the formula, the numerical values ​​listed for each repeating unit represent the content (mass %) of each repeating unit relative to the total number of repeating units.) [ka]

[0425] Acid Generator PAG-1 [ka]

[0426] Stabilizer DIPEA [ka]

[0427] [Fabrication of the light-absorbing anisotropic layer C1] A light-absorbing anisotropic layer-forming composition C1 with the following composition was continuously applied to the obtained photo-alignment film B1 using a wire bar to form a coating film. Next, the coating was heated at 140°C for 15 seconds, followed by a heating treatment at 80°C for 5 seconds, and then cooled to room temperature (23°C). Next, the coating was heated at 75°C for 60 seconds and then cooled again to room temperature. Subsequently, an illuminance of 200 mW / cm was measured using an LED (light-emitting diode) lamp (center wavelength 365 nm, half-width 10 nm). 2 By irradiating the photo-aligned film B1 for 2 seconds under the specified irradiation conditions, a light-absorbing anisotropic layer C1 (polarizer) (thickness: 2.0 μm) was fabricated on the photo-aligned film B1. The transmittance of the light-absorbing anisotropic layer C1 was measured using a spectrophotometer in the wavelength range of 280 to 780 nm, and the average visible light transmittance was 42%. The degree of orientation was measured as described below, and the degree of orientation at 650 nm was 0.97.

[0428] <Evaluation of Orientation> With a linear polarizer inserted into the light source side of an optical microscope (Nikon Corporation, product name "ECLIPSE E600 POL"), the optical absorption anisotropy layer C1 was set on the sample stage, and the absorbance of the optical absorption anisotropy layer C1 in the wavelength range of 400 to 700 nm was measured using a multi-channel spectrometer (Ocean Optics, product name "QE65000"), and the degree of orientation was calculated using the following formula. Orientation degree: S=[(Az0 / Ay0)-1] / [(Az0 / Ay0)+2] Az0: Absorbance of the light-absorbing anisotropic layer C1 for polarization in the direction of absorption axis Ay0: Absorbance of the light-absorbing anisotropic layer C1 for polarization in the polarization axis direction.

[0429] The absorption axis of the light-absorbing anisotropic layer C1 was in the plane of the light-absorbing anisotropic layer C1 and perpendicular to the width direction of the cellulose acylate film A1.

[0430] ------------------------------------------------------------------ Composition C1 for forming a light-absorbing anisotropic layer ------------------------------------------------------------------ • 0.59 parts by mass of the following first dichroic substance, Dye-C1 • 0.14 parts by mass of the second dichroic substance, Dye-M1, as described below. • 0.25 parts by mass of the third dichroic substance Dye-Y1 described below. • 3.27 parts by mass of the following liquid crystalline compound L-1 • 1.44 parts by mass of the following liquid crystalline compound L-2 • 0.06 parts by mass of the adhesion-improving agent A-1 listed below. • Polymerization initiator IRGACUREOXE-02 (BASF) 0.18 parts by mass • Surfactant F-4 (listed below): 0.030 parts by mass Cyclopentanone 91.70 parts by mass Benzyl alcohol 2.35 parts by mass ------------------------------------------------------------------

[0431] Dichroic substance Dye-C1 [ka]

[0432] Dichroic substance Dye-M1 [ka]

[0433] Dichroic substance Dye-Y1 [ka]

[0434] Liquid crystal compound L-1 (In the formula, the numerical values ​​indicated for each repeating unit ("59", "15", "26") represent the content (mass %) of each repeating unit relative to the total number of repeating units.) [ka]

[0435] Liquid crystal compound L-2 [ka]

[0436] Adhesion enhancer A-1 [ka]

[0437] Surfactant F-4 (In the formula, the numerical values ​​listed for each repeating unit represent the content (mass %) of each repeating unit relative to the total number of repeating units.) [ka]

[0438] [Formation of oxygen barrier layer D1] A coating solution D1 for forming an oxygen barrier layer, with the following composition, was continuously applied to the light-absorbing anisotropic layer C1 using a wire bar. Then, it was dried with 80°C hot air for 5 minutes, followed by UV irradiation (300 mJ / cm²). 2 Using an ultra-high pressure mercury lamp, a laminate was obtained in which an oxygen barrier layer D1 made of polyvinyl alcohol (PVA) with a thickness of 1.0 μm was formed, i.e., a coated polarizing plate comprising a cellulose acylate film A1 (transparent support), a photo-alignment film B1, a light-absorbing anisotropic layer C1, and an oxygen barrier layer D1 arranged adjacently in this order.

[0439] ------------------------------------------------------------------ Oxygen barrier layer forming coating solution D1 ------------------------------------------------------------------ • 3.30 parts by mass of the following modified polyvinyl alcohol • Initiator Irg2959 0.20 parts by mass • Surfactant F-5: 0.0018 parts by mass ·Water 74.1 parts by mass • Methanol 22.4 parts by mass ------------------------------------------------------------------

[0440] Modified polyvinyl alcohol [ka]

[0441] Surfactant F-5 [ka]

[0442] [Example 14] A laminate of polarizing plate 1, B plate, and light-absorbing anisotropic film P1 was fabricated using the same procedure as in Example 2. Next, a λ / 4 plate, prepared using the same procedure as in Example 4, was bonded to the support surface of the fabricated laminate in the same manner as in Example 4 to create laminate A14. Next, an image display device B14 with an anti-reflection system was fabricated using the same procedure as in Example 4.

[0443] The fabricated B plate had a Re of 160 nm, an Rth of 390 nm, an Nz coefficient of 2.9, a slow axis in the MD direction, and a film thickness of 80 μm.

[0444] The phase difference Re(550) and Rth(550) of the fabricated λ / 4 plate at a wavelength of 550 nm were Re(550) = 120 nm and Rth(550) = 105 nm, respectively.

[0445] [Example 15] A laminate of polarizing plate 1, B plate, and light-absorbing anisotropic film P1 was fabricated using the same procedure as in Example 2. Next, a λ / 2 plate, prepared using the same procedure as in Example 5, was bonded to the support surface of the fabricated laminate using the same method as in Example 5 to create laminate A15. Next, an image display device B15 with an anti-reflection system was fabricated using the same procedure as in Example 5.

[0446] The fabricated B plate had a Re of 160 nm, an Rth of 390 nm, an Nz coefficient of 2.9, a slow axis in the MD direction, and a film thickness of 80 μm.

[0447] The phase difference Re(550) and Rth(550) of the fabricated λ / 2 plate at a wavelength of 550 nm were Re(550) = 250 nm and Rth(550) = -70 nm, respectively.

[0448] [Comparative Example 1] Based on Example 1, an image display device with an anti-reflection system was fabricated in the same manner as in Example 1, except that the linear polarization conversion film Q1 was not used.

[0449] [Performance evaluation] (1) Evaluation of the central axis of transmittance The transmittance central axis angle θ was measured using the method described above for each fabricated light-absorbing anisotropic film. Since the layers other than the light-absorbing anisotropic layer in each light-absorbing anisotropic film do not exhibit absorption anisotropy, the transmittance central axis angle θ calculated above can be interpreted as the value of the light-absorbing anisotropic layer in each light-absorbing anisotropic film. The results are shown in Table 1 below.

[0450] (2) Evaluation of an image evaluation device with a reflection prevention system The image evaluation device with reflection prevention system that was fabricated was installed within the reflection image evaluation system shown in Figure 3, in order to evaluate the reflected image on the window glass. The image evaluation device displayed a white image (R256, G256, B256) across its entire surface. The hue of the reflected image on the surface of an acrylic plate, which was installed in place of window glass, was evaluated by sensory perception to determine its color (redness, greenness, blueness). Similarly, the color observed by directly viewing the display was also evaluated. At this time, the reflected image was observed from an oblique angle of approximately 30° with respect to a straight line extending from the center of the image display device toward the front of the acrylic plate, as shown in Figure 3, and from an oblique angle of approximately 20° with respect to the plane of the acrylic plate. The results are shown in Table 1 below.

[0451] [Sensory evaluation criteria] The color tones of the image reflected on the acrylic plate and the color tones of the image observed on the display without the acrylic plate were evaluated subjectively according to the following criteria.

[0452] A: The image has a neutral gray color. B: The image has a slightly reddish tint, but it is within an acceptable range. C: The image has a relatively strong bluish tint, but it is not reddish, so it is within an acceptable range. D: The image is strongly reddish and is outside the acceptable range.

[0453] The overall evaluation, which takes into account the color of the image reflected on the acrylic panel, the color of the image when the display is observed directly without reflection on the acrylic panel, and light leakage in oblique directions, was evaluated according to the following criteria.

[0454] A+: A highly desirable and problem-free result in practical terms. A: A practically acceptable and problem-free result. B: A result that is perfectly acceptable in practical terms. C: In practical terms, there are some issues, but it is acceptable. D: A result that presents practically unacceptable problems.

[0455] [Table 1]

[0456] It can be seen that the laminates having linear polarization conversion layers according to Examples 1 to 15 of the present invention improve the problem of reflections on window glass appearing reddish. In particular, the results from Examples 2, 11, 14, and 15 are especially favorable because the brightness of the reflected image is also suppressed by further using a B plate. [Explanation of Symbols]

[0457] 1. Barrier layer 2. Light-absorbing anisotropic layer 3. Barrier layer and PVA alignment film 4 TAC support 11 Liquid crystal molecules 12 Dichroic dye D-1 13 Dichroic dye D-2 14 Dichroic dye D-3 21 Linear Polarization Conversion Layer 22 Orientation auxiliary layer 23 Barrier layer 24 TAC support 100 Image display device with anti-reflection system 101 Linear Polarization Conversion Layer 102 Light-absorbing anisotropic layer 103 Polarizer 104 Organic EL Image Display Device 105 Anti-reflection system

Claims

1. An image display device having a laminate and a display element in this order from the viewing side, The laminate comprises, from the viewing side, a linear polarization conversion layer, a light absorption anisotropy layer containing a liquid crystalline compound and a dichroic substance, and a polarizer having an absorption axis in the in-plane direction, in this order. An image display device in which the angle between the transmittance center axis of the light-absorbing anisotropic layer and the normal to the layer plane of the light-absorbing anisotropic layer is 0° or more and 45° or less.

2. The image display device according to claim 1, wherein the content of the dichroic substance is 5% by mass or more with respect to the total solid content mass of the light-absorbing anisotropic layer.

3. The image display device according to claim 1 or 2, wherein the linear polarization conversion layer is a C plate.

4. The image display device according to claim 3, wherein the C plate is a negative C plate.

5. The image display device according to claim 1 or 2, wherein the linear polarization conversion layer is a λ / 2 plate or a λ / 4 plate.

6. The image display device according to claim 1 or 2, wherein the linear polarization conversion layer is a polarization depolarization layer.

7. The image display device according to claim 6, wherein the depolarization layer is a randomly oriented liquid crystal layer.

8. The image display device according to claim 6, wherein the depolarization layer is a layer containing fine particles.

9. The image display device according to claim 6, wherein the depolarization layer contains a liquid crystalline compound and a dichroic substance, and the liquid crystalline compound is randomly oriented in the layer.

10. The linear polarization conversion layer is a polarizer having an absorption axis in the in-plane direction, The image display device according to claim 1 or 2, wherein the angle φ between the direction obtained by orthogonally projecting the transmittance center axis of the light absorption anisotropy layer onto the layer plane of the light absorption anisotropy layer and the absorption axis of the polarizer which is the linear polarization conversion layer is 85° to 95°.

11. The image display device according to claim 1 or 2, wherein the linear polarization conversion layer is a phase difference layer having an in-plane retardation value of 6000 nm or more measured at a wavelength of 550 nm.

12. The image display device according to claim 11, wherein the phase difference layer is a PET film.

13. The image display device according to any one of claims 1 to 12, further comprising a B plate between the polarizer and the light-absorbing anisotropic layer.

Images