Optical film, viewing angle control system, and image display device

Abstract

The present invention addresses the problem of providing: a viewing angle control system that provides an image which is bright and clearly visible from a desired direction, that blocks the light of the image from other directions, and that can sufficiently restrict reflected glare onto window glass or the like; a display device; and an optical film for the same. An optical film according to the present invention includes a light-absorbing anisotropic layer formed from a liquid crystal composition containing a thermotropic liquid crystalline compound, a dichroic substance, and an interface improving agent, wherein the content of the dichroic substance is at least 10.0 mass% relative to the total solid mass of the liquid crystal composition and the angle θ between the transmittance center axis of the light-absorbing anisotropic layer and the normal direction of the surface of the optical film is at least 5° and less than 45°.

Description

[Technical Field]

[0001] The present invention relates to an optical film, a viewing angle control 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 light emitted upward from the display screen reflects onto the windshield or other surfaces, interfering with driving. To solve this problem, for example, Patent Document 1 proposes a method that uses a first polarizer having an absorption axis in its plane and a second polarizer (light-absorbing anisotropic layer) in which the absorption axis of an organic dichroic dye is oriented at 0° to 45° with respect to the normal direction. Here, the first polarizer can be the polarizer on the viewing side of a liquid crystal display device. In this method, only light from the image in a specific direction is transmitted, and the transmission of light at other angles is blocked, so that the image can be observed by an observer in the desired direction, but the image cannot be seen from other directions, such as the direction of a window. [Prior art documents] [Patent Documents]

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

[0004] However, the above viewing angle control method still has a problem: while the light transmittance is insufficient when viewed from the direction in which the image is to be visible, resulting in inadequate visibility, the light transmittance is not sufficiently reduced when viewed from other directions, i.e., in the direction in which the screen is to be obscured, so the screen cannot be completely shielded.

[0005] For example, with the conventional viewing angle control methods described above, in automotive applications (such as applications to in-car displays), the screen is difficult to see from directions where it is important to accurately and quickly view the screen and obtain information, such as from the direction of the driver or passenger. In addition, the screen is slightly visible from directions where reflections on the window glass should be eliminated, resulting in insufficient reflection prevention. This situation was undesirable from a safety standpoint for an in-car display system.

[0006] Therefore, the object of the present invention is to provide a viewing angle control system, a display device, and an optical film therefor that can provide a bright and easy-to-view image from a desired direction, while blocking the light from the image from other directions and sufficiently limiting reflections on window glass and the like. [Means for solving the problem]

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

[0008] [1] An optical film comprising a light-absorbing anisotropic layer formed from a liquid crystal composition containing a thermotropic liquid crystal compound, a dichroic substance, and an interface modifier, The content of the above-mentioned dichroic substance is 10.0% by mass or more relative to the total solid content mass of the above-mentioned liquid crystal composition. An optical film in which the angle θ between the transmittance center axis of the above-mentioned light-absorbing anisotropic layer and the normal direction of the optical film surface is 5° or more and less than 45°. [2] The optical film according to [1], wherein the content of the dichroic substance is 15.0% by mass or more with respect to the total solid content mass of the liquid crystal composition. [3] The optical film according to [1] or [2], wherein the mixed liquid crystal degrade temperature ΔTL, defined by formula (T) described later, is 0.1 to 10.0°C. [4] The optical film according to any one of [1] to [3], further comprising an orientation layer containing an azo compound, polyvinyl alcohol, or polyimide on the above light-absorbing anisotropic layer. [5] A visual angle control system having an optical film described in any one of [1] to [4] and a polarizer, The above polarizer has an absorption axis in its plane, A visual angle control system in which the angle φ between the direction in which the transmittance center axis of the light absorption anisotropy layer of the optical film is orthogonally projected onto the optical film surface and the absorption axis of the polarizer is 0° or more and less than 85°, greater than 95° and less than 265°, or greater than 275° and 360° or less. [6] An image display device having the viewing angle control system described in [5] arranged on at least one main surface of the display panel. [7] The image display device according to [6], wherein the light-absorbing anisotropic layer is arranged on the viewing side of the polarizer. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a viewing angle control system, a display device, and an optical film therefor that can provide a bright and easy-to-view image from a desired direction, while blocking the light from the image from other directions and sufficiently limiting reflection on window glass. More specifically, the optical film of the present invention can precisely control the viewing angle, and when used in in-vehicle displays, it can sufficiently suppress image reflections on window glass, etc., while providing a bright and easily visible image to the driver. [Brief explanation of the drawing]

[0010] [Figure 1] Figure 1 is a schematic cross-sectional view showing an example of an embodiment of the liquid crystal display device of the present invention. [Figure 2] Figure 2 is a schematic cross-sectional view showing an example of an embodiment of the viewing angle control system using the optical film of the present invention. [Figure 3] Figure 3 shows the relationship between the direction of the transmittance center axis of the light absorption anisotropy layer and the position of the absorption axis of the polarizer within the image display device 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. In this specification, "parallel" and "orthogonal" do not mean parallel or orthogonal in the strict sense, but rather a range of ±5° from parallel or orthogonal. In this specification, the terms "liquid crystal composition" and "liquid crystal compound" conceptually include substances that no longer exhibit liquid crystal properties due to curing or other reasons. In this specification, visible light refers to electromagnetic waves with wavelengths between 380 and 800 nm, 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." In this specification, the solid content of a liquid crystal composition refers to the components that can form a light-absorbing anisotropic layer, after the solvent has been removed from the liquid crystal composition, and is considered solid content even if its properties are liquid.

[0012] 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), and Examples of substituents include ammonium 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 heteroarylazo 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).

[0013] [ka]

[0014] 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.

[0015] 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").

[0016] 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-(g represents an integer of 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' and Z'' each 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"). A hydrogen atom of the above alkylene group and a hydrogen atom of the heterocyclic group may be substituted with 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 H ', -NZ H C(O)NZ H 'OZ H '', -SH, -SZ H , -C(S)Z H , -C(O)SZ H , -SC(O)Z H , (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).

[0017] [Optical film] The optical film of the present invention is an optical film comprising a light-absorbing anisotropic layer formed from a liquid crystal composition containing a thermotropic liquid crystal compound, a dichroic substance, and an interface modifier, wherein the dichroic substance is 10.0% by mass or more of the total solid content mass of the liquid crystal composition. The angle θ between the transmittance center axis of the light-absorbing anisotropic layer and the normal direction of the optical film surface is 5° or more and less than 45°. The mechanism by which the viewing angle control system and display device using the optical film of the present invention can provide a bright and easy-to-view image from a desired direction, while blocking the light from the image from other directions and sufficiently limiting reflection on window glass, is not entirely clear, but the inventors speculate as follows. The optical film of the present invention, by containing a light-absorbing anisotropic layer containing a thermotropic liquid crystalline compound, a dichroic substance, and an interface modifier, controls the orientation direction of the dichroic substance, providing a bright and easily viewable image from a desired direction, while blocking light from other directions and sufficiently limiting reflection on window glass. Furthermore, it is believed that the above effect can be further enhanced if the dichroic substance is 10.0% by mass or more relative to the total solid content mass of the liquid crystal composition. Furthermore, the ability of the viewing angle control system and display device using the optical film of the present invention to provide a bright and easy-to-view image from a desired direction, while blocking the light from other directions and sufficiently limiting reflection on window glass, is also referred to as "the effect of the present invention." The following describes the layers that an optical film may contain.

[0018] [Light-absorbing anisotropic layer] In the present invention, the light-absorbing anisotropic layer is formed from a liquid crystal composition containing a thermotropic liquid crystal compound, a dichroic substance, and an interface modifier, wherein the content of the dichroic substance is 10.0% by mass or more relative to the total solid content mass of the liquid crystal composition. Furthermore, in the present invention, the light-absorbing anisotropic layer has an angle θ between the transmittance center axis of the light-absorbing anisotropic layer and the normal direction of the optical film surface that is 5° or more and less than 45°. Hereinafter, the angle between the transmittance center axis of the light-absorbing anisotropic layer and the normal direction of the optical film surface will also be called the "tilt angle". By setting θ within the above range, the light transmittance toward the observer of the image is increased, improving image visibility, while simultaneously reducing transmittance in other directions to suppress reflections on window glass, etc. θ is preferably 5° or more and less than 35°.

[0019] 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 light region in a desired direction, and it is even more preferable to orient the dichroic substance using the orientation of a liquid crystalline compound. As an example, a light-absorbing anisotropic layer can be provided in which at least one type of dichroic substance is oriented in a gradient direction with respect to the film normal direction. The tilt orientation of the dichroic material in the light-absorbing anisotropic layer from the film normal direction (normal direction of the optical film surface) can be confirmed by measuring the angle θ (hereinafter also called the "tilt angle θ") of the axis where transmittance is maximized (hereinafter also called the "transmittance center axis"). Specifically, using a wavelength in the absorption region of the dichroic material (for example, the visible wavelength region; specifically, a wavelength of 650 nm is preferred), polarized light parallel to the direction of the orthogonal projection of the transmittance center axis of the light-absorbing anisotropic layer onto the film surface is incident on the optical film, and the transmittance is measured by tilting the sample from the normal direction (i.e., θz=0°) to in-plane (i.e., θz=90° and -90°) (let's call this T3). Specifically, the transmittance is measured by tilting at 0.5° increments. Similarly, the transmittance of an optical film without a light-absorbing anisotropic layer is measured (let's call this T4). T3 / T4 is calculated, and the θz at which this value is maximized is determined. If the θz at which the above T3 / T4 is maximized does not coincide with 0° (normal), it can be determined that the dichroic material is oriented at an angle from the optical film normal direction. In other words, it can be determined that the transmittance center axis of the light-absorbing anisotropic layer is tilted with respect to the normal direction of the optical film surface, and the θz at which the above T3 / T4 is maximized corresponds to the angle between the transmittance center axis of the light-absorbing anisotropic layer and the normal direction of the optical film surface. The transmittance center axis mentioned above refers to the direction with the highest transmittance when the transmittance is measured while varying the tilt angle (polar angle) and tilt direction (azimuth angle) of the main surface of the light-absorbing anisotropic film relative to the normal direction. As described above, when measuring the angle between the transmittance center axis of the light-absorbing anisotropic layer and the normal direction of the optical film surface, first, the direction in which the transmittance center axis is tilted relative to the normal of the surface of the light-absorbing anisotropic film is first found. More specifically, a sample of the light-absorbing anisotropic film is cut into, for example, a 4cm square, and the obtained sample is placed on the sample stage of an optical microscope (for example, Nikon Corporation, product name "ECLIPSE E600 POL") with a linear polarizer placed on the light source side. Next, using a multi-channel spectrometer (for example, Ocean Optics, product name "QE65000"), the absorbance of the sample at a wavelength of 650nm is monitored while rotating the sample stage clockwise by 1° at a time, and the direction in which the absorbance is maximum is confirmed. The angle θ is determined based on the direction in which the absorbance is maximized within the plane of the sample.

[0020] 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 the methods for fabricating dichroic polarizing elements described in Japanese Patent Publication No. 11-305036 and Japanese Patent Publication No. 2002-90526, and in the methods for fabricating 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 fabricate the light-absorbing anisotropic layer used in the present invention. For example, by utilizing guest-host liquid crystal cell technology, the dichroic material can be oriented to the desired orientation as described above in conjunction with the orientation of the host liquid crystal. Specifically, by mixing a guest dichroic material with a rod-shaped liquid crystalline compound that will serve as the host liquid crystal, oriented the host liquid crystal, and oriented the molecules of the dichroic material in accordance with the orientation of its liquid crystal molecules, thereby fixing the orientation state, the light-absorbing anisotropic layer used in this invention can be fabricated.

[0021] 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. Furthermore, by impregnating a polymer film with a dichroic substance and orienting the dichroic substance along the orientation of the polymer molecules in the polymer film, a polymer film that satisfies the light absorption characteristics required for the light absorption anisotropy layer used in the present invention can be produced. Specifically, this can be done by coating a solution of the dichroic substance onto the surface of the polymer film and allowing it to penetrate the film. The orientation of the dichroic substance can be adjusted by the orientation of the polymer chains in the polymer film, their properties (chemical and physical properties of the polymer chains or the functional groups they possess), the coating method, etc. Details of this method are described in Japanese Patent Application Publication No. 2002-90526.

[0022] The light-absorbing anisotropic layer used in the present invention preferably has a transmittance of 60% or less (transmittance at a wavelength of 650 nm) tilted 30° from the transmission axis center axis (transmittance at a wavelength of 650 nm), more preferably 50% or less, and even more preferably 45% or less. This makes it possible to increase the contrast between the illuminance at the transmittance center axis and the illuminance in the direction offset from the transmittance center axis, thereby narrowing the viewing angle sufficiently.

[0023] The light-absorbing anisotropic layer used in the present invention preferably has a transmittance of 65% or more along the transmission axis center (transmittance at a wavelength of 650 nm), 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.

[0024] 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. The color of optical films containing dichroic substances is usually controlled by adjusting the amount of dichroic substance added to the film. However, achieving a neutral color in both the frontal and oblique directions is sometimes not possible by simply adjusting the amount of dichroic substance added. One factor that prevents achieving a neutral color in both the frontal and oblique directions is a low degree of orientation at 420 nm. By increasing the degree of orientation at 420 nm, it is possible to achieve a neutral color in both the frontal and oblique directions.

[0025] In this specification, the degree of orientation at a wavelength of λnm shall be defined as follows. Using the AxoScan OPMF-1 (OptoScience Co., Ltd.), the Mueller matrix at wavelength λnm is measured at each pole angle, changing the pole angle (angle with respect to the normal direction of the optical absorption anisotropy layer) in 5° increments from 0 to 90°, and the minimum transmittance (Tmin) is derived. Next, after removing the effect of surface reflection, the Tmin at the pole angle where Tmin is highest is defined as Tm(0), and the Tmin at the direction where the pole angle is increased by another 40° from the pole angle with the highest Tmin is defined as Tm(40). Absorbance is calculated from the obtained Tm(0) and Tm(40) using the following formula to calculate A(0) and A(40). A = -log(Tm) Here, Tm represents transmittance and A represents absorbance. From the calculated A(0) and A(40), the degree of orientation S at the wavelength λnm is calculated using the following formula. S=(4.6×A(40)-A(0)) / (4.6×A(40)+2×A(0)) In this specification, the term "degree of orientation of the light-absorbing anisotropic layer" simply refers to the degree of orientation of compounds, etc., contained in the light-absorbing anisotropic layer, and is not limited to the measurement method described above.

[0026] Furthermore, the optical anisotropic absorption layer of the present invention may be constructed by laminating multiple optical anisotropic absorption layers or a phase difference layer so as to satisfy the transmittance tilted 30° from the transmission axis and the transmittance along the transmission axis. By laminating multiple optical anisotropic absorption layers with different transmission axis axes, the width of the region with high transmittance can be adjusted. In addition, when a phase difference layer is laminated, the transmission and light-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, and an O plate can be used. The thickness of the phase difference layer is preferably as thin as possible from the viewpoint of thinning the viewing angle control system, as long as it does not impair the optical properties, mechanical properties, and manufacturability. Specifically, 1 to 150 μm is preferred, 1 to 70 μm is more preferred, and 1 to 30 μm is even more preferred.

[0027] [Liquid crystal composition] The liquid crystal composition used for forming the photoisotropic absorption layer of the present invention contains an interface modifier, a thermotropic liquid crystal compound, and a dichroic substance. The liquid crystal composition of the present invention may also contain a polymerization initiator, a polymerizable compound, and an additive. The components included in and potentially included in the liquid crystal composition of the present invention will be described below.

[0028] <Interface modifier> The interface modifier is preferably a compound that is easily concentrated on at least one surface of the light-absorbing anisotropic layer when forming a light-absorbing anisotropic layer using a liquid crystal composition, and so-called surfactants are preferred. As the interface modifier (preferably a surfactant), compounds having hydrophobic groups in the molecule are more preferred, and compounds having both hydrophilic and hydrophobic groups in the molecule are preferred. The interface modifier may be a low-molecular-weight compound or a high-molecular-weight compound, but high-molecular-weight compounds are preferred, high-molecular-weight compounds having repeating units with hydrophobic groups are more preferred, and high-molecular-weight compounds having repeating units with hydrophobic groups and repeating units with hydrophilic groups are even more preferred. The hydrophobic group is preferably a group having a fluorine atom or a silicon atom, and is a perfluoroalkyl group (-(CF2)n -CF3) or perfluoroalkylene group (-(CF2)) n -) is preferred. The number of carbon atoms in the perfluoroalkyl group or perfluoroalkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 3 to 8. It is also preferable that one of the bonds of the perfluoroalkylene group is bonded to a hydrogen atom. That is, as a hydrophobic group, -(CF2) n Groups represented by -Z (where Z represents a hydrogen atom or a fluorine atom) are also preferred. Examples of hydrophilic groups include carboxylic acid groups and hydroxyl groups.

[0029] The interface modifier preferably has a repeating unit represented by formula (A). The repeating unit represented by formula (A) corresponds to a repeating unit having a hydrophobic group.

[0030] [ka]

[0031] In formula (A), R 1 represents a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 3 carbon atoms, and more preferably 1 carbon atom. L 1 This represents a single bond or a divalent linking group. Examples of divalent linking groups include the divalent linking groups represented by LW mentioned above. X represents a hydrophobic group. The definition of a hydrophobic group is as described above. The content of the repeating units represented by formula (A) is not particularly limited, but is preferably 5.0 to 95.0% by mass, and more preferably 10.0 to 90.0% by mass, relative to the total repeating units of the interface modifier.

[0032] The interface modifier preferably has a repeating unit represented by formula (B). The repeating unit represented by formula (B) corresponds to a repeating unit having a hydrophilic group.

[0033] [ka]

[0034] In formula (B), R 2 represents a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 3 carbon atoms, and more preferably 1 carbon atom. L 2 This represents a single bond or a divalent linking group. Examples of divalent linking groups include the divalent linking groups represented by LW mentioned above. Y represents a hydrophilic group. The definition of a hydrophilic group is as described above. The content of the repeating units represented by formula (B) is not particularly limited, but is preferably 5.0 to 95.0% by mass, and more preferably 10.0 to 90.0% by mass, relative to the total repeating units of the interface modifier.

[0035] The interface modifier may have repeating units other than the repeating unit represented by formula (A) and the repeating unit represented by formula (B) described above. Other repeating units include, for example, repeating units having an aromatic ring. Repeating units having an aromatic ring preferably have a mesogenic group. The mesogenic group will be described in detail later.

[0036] While there are no particular limitations on the interface modifier, polymer-based interface modifiers and low-molecular-weight interface modifiers can be used, and compounds described in paragraphs

[0253] to

[0293] of Japanese Patent Application Publication No. 2011-237513 can be used. Furthermore, as an interface modifier, fluorine (meth)acrylate polymers described in paragraphs

[0018] to

[0043] of Japanese Patent Publication No. 2007-272185 can also be used. Furthermore, other interface modifiers include the compounds described in paragraphs

[0079] to

[0102] of Japanese Patent Publication No. 2007-069471, polymerizable liquid crystal compounds represented by formula (4) described in Japanese Patent Publication No. 2013-047204 (particularly the compounds described in paragraphs

[0020] to

[0032] ), polymerizable liquid crystal compounds represented by formula (4) described in Japanese Patent Publication No. 2012-211306 (particularly the compounds described in paragraphs

[0022] to

[0029] ), and liquid crystal alignment promoters represented by formula (4) described in Japanese Patent Publication No. 2002-129162 (particularly [00 Examples include the compounds described in paragraphs 76-78 and 0082-0084, as well as the compounds represented by formulas (4), (II), and (III) described in Japanese Patent Application Publication No. 2005-099248 (particularly the compounds described in paragraphs 0092-0096), the compounds described in paragraphs 0013-0059 of Japanese Patent No. 4385997, the compounds described in paragraphs 0018-0044 of Japanese Patent No. 5034200, and the compounds described in paragraphs 0019-0038 of Japanese Patent No. 4895088. Multiple interfacial modifiers listed above can also be used in combination.

[0037] The interface modifier is preferably such that the mixed liquid crystal degrade temperature ΔTL, defined by the following formula (T), is 0.1 to 10.0°C, more preferably 0.1 to 7.0°C, and even more preferably 0.1 to 3.5°C.

[0038] ΔTL = T1 - T2 (T)

[0039] In formula (T), T1 represents the liquid-liquid crystal phase transition temperature of a liquid crystal composition without an interface modifier, and T2 represents the liquid-liquid crystal phase transition temperature of a mixture obtained by mixing 10.0 parts by mass of an interface modifier with 100 parts by mass of a liquid crystal composition without an interface modifier. More specifically, T1 corresponds to the liquid-liquid crystal phase transition temperature, measured using a composition obtained by removing the interface modifier from the liquid crystal composition used to form the light-absorbing anisotropic layer. The liquid-liquid crystal phase transition temperature of the above liquid crystal composition is measured using the solid content obtained by removing the solvent from the liquid crystal composition. That is, the solvent is removed from the above liquid crystal composition, the resulting solid content is heated to a liquid state, and then subjected to a cooling treatment to measure the temperature at which it transitions from the liquid to the liquid crystal phase as the liquid-liquid crystal phase transition temperature. Furthermore, T2 corresponds to the liquid-liquid crystal phase transition temperature measured using a mixture obtained by mixing 10.0 parts by mass of a predetermined interface improver with 100 parts by mass of the composition excluding the interface improver used in the measurement of T1, and following the same procedure as for T1. The specific procedure for measuring the mixed liquid crystal deceleration temperature ΔTL described above is shown in the Examples section below.

[0040] According to the liquid crystal composition of the present invention (particularly a liquid crystal composition in which the mixed liquid crystal decomposition temperature ΔTL is within the above range), the tilt angle fluctuation due to the maturation temperature is small and the in-plane uniformity is superior, and when used in an in-vehicle display or the like, it is possible to provide a bright and easily visible image to the driver while sufficiently suppressing image reflections on window glass and the like. The details of this reason are still unclear, but the inventors speculate that it is due to the following reasons.

[0041] In the light-absorbing anisotropic layer of the present invention, the dichroic material is oriented in a skewed direction with respect to the film normal direction. As described above, in order to achieve both good visibility from the direction in which the image is to be visible and good light shielding from other directions, it is preferable to have sufficient absorption in the light-absorbing anisotropic layer, and the content of the dichroic material, as described later, is 10.0% by mass or more with respect to the total solid content mass of the liquid crystal composition. In such light-absorbing anisotropic layers, even slight differences in tilt angle within the plane are easily visible as unevenness; therefore, tilt angle control near the air interface of liquid crystalline compounds and dichroic materials is necessary. When a liquid crystal composition is coated and oriented on a film to form a light-absorbing anisotropic layer, the tilt angle near the air interface may fluctuate due to the influence of interface modifiers, temperature, and other factors. In particular, in a light-absorbing anisotropic layer formed by oriented a liquid crystal composition containing a high concentration of dichroic substances, such fluctuations in the tilt angle near the air interface significantly affect the direction of the transmittance center axis of the entire light-absorbing layer. Therefore, it is preferable to keep the fluctuations in the tilt angle near the air interface small. The interface modifier is thought to be concentrated near the air interface of the light-absorbing anisotropic layer. In liquid crystal compositions, the miscibility / immisapplication state between the interface modifier and the liquid crystalline compound and dichroic substance may change due to temperature and liquid crystal phase transitions, and this change is thought to cause fluctuations in the tilt angle θ near the air interface. Therefore, a small ΔTL indicates that the affinity between the liquid crystalline compound and dichroic substance and the interface modifier is low, and the miscibility / immisapplication change with temperature is small, so the tilt angle does not fluctuate easily with temperature, and the tilt angle is easy to control.

[0042] The content of the interface modifier is preferably 0.005 to 15% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.015 to 3% by mass, relative to the total solid content (100% by mass) of the liquid crystal composition, from the viewpoint of achieving superior effects of the present invention. When multiple interface modifiers are used in combination, it is preferable that the total amount of the multiple interface modifiers is within the above range.

[0043] <Thermotropic liquid crystal compounds> The liquid crystal composition used for forming the photo-anisotropic absorption layer of the present invention includes a thermotropic liquid crystal compound. A thermotropic liquid crystal compound is a liquid crystal compound that undergoes a transition to a liquid crystal phase in response to temperature changes. The thermotropic liquid crystal compound may exhibit either a nematic phase or a smectic phase, but it is preferable that it exhibits at least a nematic phase because this results in a higher degree of orientation of the photo-absorption anisotropic layer and makes haze less observable (better haze). The temperature range in which the nematic phase is observed is preferably room temperature (23°C) to 450°C, as this results in a higher degree of orientation of the light-absorbing anisotropic layer and less observation of haze. From the viewpoint of handling and manufacturing suitability, a temperature range of 40°C to 400°C is more preferable. Thermotropic liquid crystalline compounds can generally be classified into rod-shaped and disc-shaped types based on their shape. The liquid crystal composition of the present invention preferably contains a rod-shaped liquid crystalline compound. Furthermore, the rod-shaped liquid crystalline compound is preferably a liquid crystalline compound that does not exhibit dichroism in the visible light region.

[0044] Both low-molecular-weight liquid crystalline compounds and high-molecular-weight liquid crystalline compounds can be used as rod-shaped liquid crystalline compounds. Here, "low-molecular-weight liquid crystalline compounds" refer to liquid crystalline compounds that do not have repeating units in their chemical structure. "High-molecular-weight liquid crystalline compounds" refer to liquid crystalline compounds that have repeating units in their chemical structure. Examples of thermotropic 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 compounds described in Japanese Patent Publication No. 2011-237513. Furthermore, the polymeric liquid crystalline compounds may have crosslinkable groups (e.g., acryloyl groups and methacryloyl groups) at their terminals.

[0045] The rod-shaped liquid crystalline compounds may be used individually or in combination of two or more. The rod-shaped liquid crystalline compound preferably contains a polymer liquid crystalline compound, and more preferably contains both a polymer liquid crystalline compound and a low-molecular-weight liquid crystalline compound, in order to achieve superior effects of the present invention.

[0046] The rod-shaped liquid crystalline compound preferably contains 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 phase exhibited by the rod-shaped liquid crystalline compound may be a nematic phase or a smectic phase, and the rod-shaped liquid crystalline compound may exhibit both a nematic phase and a smectic phase, but it is preferable that it exhibits at least a nematic phase. The smectic phase may be a higher-order smectic phase. The higher-order smectic phases referred to here are smectic phase B, smectic phase D, smectic phase E, smectic phase F, smectic phase G, smectic phase H, smectic phase I, smectic phase J, smectic phase K, and smectic phase L, among which smectic phase B, smectic phase F, or smectic phase I are preferred. The temperature range in which the nematic phase is observed is preferably room temperature (23°C) to 450°C, as this results in a higher degree of orientation of the light-absorbing anisotropic layer and less observation of haze. From the viewpoint of handling and manufacturing suitability, 40°C to 400°C is more preferable. When the smectic liquid crystal phase exhibited by a liquid crystalline compound is one of these higher-order smectic liquid crystal phases, a light-absorbing anisotropic layer with a higher degree of orientational order can be fabricated. Furthermore, a light-absorbing anisotropic layer fabricated from such a higher-order smectic liquid crystal phase yields Bragg peaks originating from higher-order structures such as the hexatic phase and crystalline phase in X-ray diffraction measurements. The Bragg peaks mentioned above are peaks originating from the planar periodic structure of molecular orientation, and according to the liquid crystal composition of the present invention, a light-absorbing anisotropic layer with a periodic interval of 3.0 to 5.0 Å can be obtained.

[0047] [ka]

[0048] 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 aryl group. The following are crosslinkable groups represented by formulas (P1) to (P-30): a reylsulfonylamino 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 heteroarylazo 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 at least one of Q1 and Q2 is preferably a crosslinkable group represented by the following formula.

[0049] [ka]

[0050] 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 aryloxycarbonyl groups. R represents a ruamino 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 heteroarylazo 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. 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).

[0051] 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.

[0052] 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.

[0053] 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.

[0054] [ka]

[0055] 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. The divalent group represented by A1 is preferably a 4- to 15-membered ring. Furthermore, the divalent group represented by A1 may be a monoring or a fused ring. * indicates a connection position with S1 or S2.

[0056] 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.

[0057] The divalent heterocyclic group represented by A1 may be either aromatic or non-aromatic, but a divalent aromatic heterocyclic group is preferred from the viewpoint of improving the degree of orientation. Atoms other than carbon that constitute a divalent 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 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.

[0058] [ka]

[0059] 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 to 16 which may have substituents, Jx represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles, Jy represents an organic group having 2 to 30 carbon atoms having a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have substituents, or 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 to 6 carbon atoms which may have substituents.

[0060] 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 equation (II-2), J1 and J2 are -NR 21 When representing -, R 21 As substituents, for example, refer to the descriptions in paragraphs

[0035] to

[0045] of Japanese Patent Publication No. 2008-107767, which are incorporated herein by reference. In formula (II-2), if E is a nonmetal atom of group 14 to 16 which may have substituents attached, then =O, =S, =NR', or =C(R')R' is preferred. R' represents a substituent, and as substituents, refer to paragraphs

[0035] to

[0045] of Japanese Patent Application Publication No. 2008-107767 for example, -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.

[0061] 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.

[0062] In equation (MG-A), a1 represents an integer between 2 and 10. Multiple A1s may be the same or different.

[0063] 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. For reasons that the effects of the present invention are superior, a2 of 2 or more is more preferable. In formula (MG-B), LA1 is either a single bond or a divalent linking group. However, if a2 is 1, LA1 is a divalent linking group, and if a2 is 2 or more, 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.

[0064] 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 described above.

[0065] [ka]

[0066] [ka] JPEG0007926918000010.jpg18992

[0067] [ka] JPEG0007926918000012.jpg116132 JPEG0007926918000013.jpg13683 JPEG0007926918000014.jpg13287

[0068] <Low molecular liquid crystal compounds> 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, cyclopentylene, phenylene, naphthylene, fluorene-diyl, pyridine-diyl, pyridazine-diyl, thiophene-diyl, oxazole-diyl, thiazole-diyl, and thienothiophene-diyl groups, with the number of cyclic structures preferably being 2 to 10, and more preferably 3 to 7. 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 the above formulas (P1) to (P30). 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, or oxetanyl groups.

[0069] The preferred embodiments of the divalent spacer groups S1 and S2 are the same as those described above for SPW, so their explanation will be omitted. When using a low-molecular-weight liquid crystalline compound that exhibits a smectic phase, 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.

[0070] 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, solubility can be improved and the phase transition temperature of the liquid crystal composition can be adjusted.

[0071] 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.

[0072] [ka] JPEG0007926918000016.jpg204112 JPEG0007926918000017.jpg174148JPEG0007926918000018.jpg197148

[0073] [ka] JPEG0007926918000020.jpg150126 JPEG0007926918000021.jpg215130

[0074] <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.

[0075] (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)").

[0076] [ka]

[0077] 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.

[0078] 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.

[0079] [ka]

[0080] 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 14 Each 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 the substructure of a poly(meth)acrylic acid ester obtained by polymerization of (meth)acrylic acid esters. 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, the compound having at least one of an alkoxysilyl group and a silanol group is a compound of formula SiR 14 (OR 15 Examples include compounds having a group represented by )2-. In the formula, R 14 R in equation (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.

[0081] 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 17 Each of these independently represents a C1-C6 alkyl group which may have a hydrogen atom or a substituent (for example, the substituent W mentioned above). In a specific example of a divalent linking group, the left bond is bonded to PC1 and the right bond is bonded to SP1. If PC1 is the group represented by formula (P1-A), then L1 is -C(O)O- or -C(O)NR 16 A base represented by - is preferred. When PC1 is a group represented by formulas (P1-B) to (P1-D), L1 is preferably a single bond.

[0082] 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 that the group includes 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 that includes at least one structure selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure, and a fluorinated alkylene structure, due to reasons such as its tendency to exhibit liquid crystalline properties and the 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 even more preferably an integer from 2 to 4. Furthermore, the oxypropylene structure represented by SP1 is *-(CH(CH3)-CH2O) n2 A base represented by -* is preferred. In the formula, n2 represents an integer from 1 to 3, and * represents the bond position with L1 or MG1. Furthermore, the polysiloxane structure represented by SP1 is *-(Si(CH3)2-O) n3 A base represented by -* is preferred. In the formula, n3 represents an integer from 6 to 10, and * represents the bond position with L1 or MG1. Furthermore, the alkylene fluoride structure represented by SP1 is *-(CF2-CF2) n4 A base represented by -* is preferred. In the formula, n4 represents an integer from 6 to 10, and * represents the bond position with L1 or MG1.

[0083] 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 of these groups include, independently, a hydrogen atom, a substituted or unsubstituted C1-C10 alkyl group, a cycloalkyl group, or an aryl group, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 alkylthio group, a C1-C10 alkoxycarbonyloxy group, a C1-C10 acyloxy group, a C1-C10 acylamino group, a C1-C10 alkoxycarbonyl group, a C1-C10 alkoxycarbonylamino group, a C1-C10 sulfonylamino group, a C1-C10 sulfamoyl group, a C1-C10 carbamoyl group, a C1-C10 sulfinyl group, a C1-C10 ureido group, and a crosslinking group-containing group. 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. 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. 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 light absorption 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.

[0084] 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, a light-absorbing anisotropic layer with good orientation can be obtained. If the content of repeating units (1) is 100% by mass or less, a light-absorbing anisotropic layer with good orientation can be obtained. The repeating unit (1) may be present as a single unit or as two or more units in the polymeric liquid crystalline compound. If two or more repeating units (1) are present, the content of the repeating unit (1) refers to the total content of the repeating unit (1).

[0085] -logP value- In equation (1), it is preferable that 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, more preferably 4.25 or more, and even more preferably 4.5 or more, from the viewpoint of further improving the orientation of the light absorption anisotropy layer. 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 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.

[0086] As mentioned above, logP1 refers to the logP values ​​of PC1, L1, and SP1. "LogP values ​​of PC1, L1, and SP1" means the logP value of the structure PC1, L1, and SP1 as a whole, and 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 equation (1) into the software described above. However, when calculating logP1, for the part of the series of structural formulas from PC1 to SP1 that is represented by the group PC1, 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 the group that can become PC1 after polymerization of the monomer used to obtain the repeating unit represented by formula (1) may be used. Here, specific examples of the latter (groups that can become PC1) are as follows: When PC1 is obtained by polymerization of (meth)acrylic acid esters, 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 Rs 2 At least one of them represents an alkyl group.

[0087] logP1 can be lower than or higher than logP2, provided that the difference between it and logP2 is 4 or greater. 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. When PC1 in formula (1) is obtained by polymerization of (meth)acrylic acid ester and logP1 is lower than logP2, the logP value of SP1 in formula (1) is preferably 0.7 or less, and more preferably 0.5 or less. On the other hand, when PC1 in formula (1) is obtained by polymerization of (meth)acrylic acid ester and logP1 is higher than logP2, the logP value of SP1 in formula (1) 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.

[0088] (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 light-absorbing anisotropic layer formed using it is improved compared to when it contains only either repeating unit (21) or repeating unit (22). The details of the reason for this are not clear, but it is generally presumed to be as follows. In other words, it is presumed that the opposite dipole moments generated in repeating units (21) and (22) interact intermolecularly, strengthening the interaction of the mesogenic groups in the short axis direction, resulting in a more uniform orientation of the liquid crystal. Consequently, the order of the liquid crystal is expected to increase. This also improves the orientation of the dichroic material, and is therefore presumed to increase the degree of orientation of the formed light-absorbing anisotropic layer. The repeating units (21) and (22) above may be the repeating units represented by formula (1) above.

[0089] The repeating unit (21) has a mesogenic group and an electron-withdrawing group with a σp value greater than 0 located at the end of the mesogenic group. The electron-withdrawing group described above is located at the terminal end of the mesogenic group and is a group with 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 described above is preferably 0.3 or higher, and more preferably 0.4 or higher, as greater than 0 results in a higher degree of orientation of the light-absorbing anisotropic layer. The upper limit of the σp value of the electron-withdrawing group described above is preferably 1.2 or lower, and more preferably 1.0 or lower, as this provides excellent uniformity of orientation.

[0090] The σp value is Hammett's substituent constant σp value (also simply abbreviated as "σp value"), which numerically represents the effect of substituents 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, Hammett's 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 values ​​for each group are those given in the reference "Hansch et al., Chemical Reviews, 1991, Vol, 91, No. 2, 165-195". For groups for which the Hammett substituent constant σp value is not given in the above reference, 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.

[0091] 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. However, a repeating unit represented by the following formula (LCP-21) is preferred because it results in a higher degree of orientation of the light-absorbing anisotropic layer.

[0092] [ka]

[0093] 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.

[0094] 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 linear or branched alkylene groups 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 fluorinated alkylene structure, due to reasons such as its tendency to exhibit liquid crystalline properties and the availability of raw materials.

[0095] 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 light-absorbing 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.

[0096] 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, an acyl group (specifically, *-C(O)R E a group represented by ), an acyloxy group (specifically, *-OC(O)R E a group represented by ), an isocyanate group (-N=C(O)), *-C(O)N(R F )2, a halogen atom, and alkyl groups substituted with any of these groups (preferably having 1 to 20 carbon atoms). In each of the above groups, * represents the bonding position to SP21B. R E represents an alkyl group having 1 to 20 carbon atoms (preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms). R F each 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 preferably a group represented by *-C(O)O-R E , a (meth)acryloyloxy group, a cyano group, or a nitro group, from the viewpoint that the effect of the present invention is more exhibited.

[0097] The content of the repeating unit (21) is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less, relative to the total repeating units (100% by mass) of the polymer liquid crystalline compound, from the viewpoint that the polymer liquid crystalline compound and the dichroic substance can be uniformly aligned while maintaining a high degree of alignment of the light absorption anisotropic layer. The lower limit of the content of the repeating unit (21) is preferably 1% by mass or more, more preferably 3% by mass or more, relative to the total repeating units (100% by mass) of the polymer liquid crystalline compound, from the viewpoint that the effect of the present invention is more exhibited. In the present invention, the content of each repeating unit contained in the polymer liquid crystalline compound is calculated based on the charged amount (mass) of each monomer used to obtain each repeating unit. The repeating unit (21) may be present as a single unit or as two or more units in the polymeric liquid crystalline compound. When the polymeric liquid crystalline compound contains two or more 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 repeating units (21) are present, it is preferable that their total amount is within the above range.

[0098] When two or more 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 light-absorbing 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, or oxetanyl groups. In this case, from the viewpoint of balancing the curability and orientation of the light-absorbing anisotropic layer, it is preferable that the content of repeating units (21) containing 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.

[0099] An example of a repeating unit (21) is shown below, but the repeating unit (21) is not limited to the repeating unit shown below.

[0100] [ka] JPEG0007926918000026.jpg164118

[0101] Furthermore, regarding the composition (content ratio) of the repeating units (21) and (22), and the electron-donating and electron-withdrawing properties of the terminal groups, it is preferable to lower the content ratio of the repeating units (21) when the electron-withdrawing properties of the electron-withdrawing groups of the repeating units (21) are strong (i.e., the σp value is large), as this increases the degree of orientation of the light-absorbing anisotropic layer. Conversely, it is preferable to increase the content ratio of the repeating units (21) when the electron-withdrawing properties of the electron-withdrawing groups of the repeating units (21) are weak (i.e., the σp value is close to 0), as this increases the degree of orientation of the light-absorbing anisotropic layer. Although the details of this reason are not clear, it is generally estimated as follows: It is presumed that intermolecular interactions due to an appropriate dipole moment act within the polymeric liquid crystalline compound, resulting in a more uniform orientation of the liquid crystals. Consequently, the degree of order in the liquid crystals increases, and the degree of orientation of the light-absorbing anisotropic 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 even more preferably 0.055 to 0.125. If the above product is within the above range, the degree of orientation of the light-absorbing anisotropic layer will be higher.

[0102] Each 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 repeating units (22) in the polymeric liquid crystalline compound allows for uniform orientation of the polymeric liquid crystalline compound and the dichroic substance. The mesogenic group is a group that represents the main backbone of liquid crystal molecules that contribute to liquid crystal formation. The details are as described later in formula (LCP-22) by MG, and specific examples are also as described therein. The above-mentioned group is located at the terminal end of a mesogenic group and is a group with a σp value of 0 or less. Examples of the above-mentioned group (a group with a σp value of 0 or less) include a hydrogen atom with a σp value of 0, and the group represented by T22 in the formula (LCP-22) described later (an electron-donating group) with a σp value less than 0. Specific examples of the above-mentioned group with a σp value less than 0 (an electron-donating group) are the same as T22 in the formula (LCP-22) described later. The σp value of the above group is preferably less than 0, more preferably -0.1 or less, and even more 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.

[0103] 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 viewpoint of achieving greater uniformity of liquid crystal orientation, the repeating unit represented by the following formula (PCP-22) is preferred over the repeating unit represented by the above formula (LCP-21).

[0104] [ka]

[0105] 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.

[0106] 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, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and alkylamino groups having 1 to 10 carbon atoms. The degree of orientation of the light-absorbing anisotropic layer is further improved when the number of atoms in the main chain of T22 is 20 or less. Here, the "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 main chain of T22. 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.

[0107] An example of a repeating unit (22) is shown below, but the repeating unit (22) is not limited to the repeating unit shown below.

[0108] [ka] JPEG0007926918000029.jpg157123

[0109] 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 results in a higher degree of orientation of the light-absorbing anisotropic layer. Specifically, in order to increase the degree of orientation of the light-absorbing anisotropy layer, it is preferable that at least one of the following conditions be met: SP21A of formula (LCP-21) and SP22 of formula (LCP-22) have the same structure; MG21 of formula (LCP-21) and MG22 of formula (LCP-22) have the same structure; and L21 of formula (LCP-21) and L22 of 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.

[0110] The content of repeating units (22) is preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more, relative to the total repeating units (100% by mass) of the polymeric liquid crystalline compound, in order to obtain 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, in order to improve the degree of orientation. The repeating unit (22) may be present as a single unit or as two or more units in the polymeric liquid crystalline compound. When the polymeric liquid crystalline compound contains two or more repeating units (22), 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 repeating units (22) are present, it is preferable that their total amount is within the above range.

[0111] (Repeating unit (3)) Polymeric liquid crystalline compounds can contain repeating units (3) that do not contain mesogens, from the viewpoint of improving solubility in general-purpose 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. In other words, the presence of non-mesogenic repeating units (3) in the molecular chain of the polymeric liquid crystalline compound improves solubility because it allows solvents to penetrate the polymeric liquid crystalline compound more easily, but the non-mesogenic repeating units (3) are thought to reduce the degree of orientation. On the other hand, it is presumed that the small molecular weight of the above repeating units makes it less likely for the orientation of the repeating units (1), (21), or (22) containing the mesogenic group to be disrupted, thereby suppressing the decrease in the degree of orientation.

[0112] The repeating unit (3) described above is preferably a repeating unit with a molecular weight of 280 or less. The molecular weight of repeating unit (3) does not refer to the molecular weight of the monomer used to obtain repeating unit (3), but rather to the molecular weight of 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 preferably 280 or less, more preferably 180 or less, and even more preferably 100 or less. The lower limit of the molecular weight of the repeating unit (3) is usually 40 or more, and preferably 50 or more. If the molecular weight of the repeating unit (3) is 280 or less, a light-absorbing anisotropic layer with excellent solubility of polymeric liquid crystalline compounds and a high degree of orientation can be obtained. On the other hand, if the molecular weight of 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 the polymeric liquid crystal compound easily, which may reduce the solubility of the polymeric liquid crystal compound.

[0113] 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)").

[0114] -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-ylmethacrylate (e.g., 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], dienes (e.g.) (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 Examples include 2-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 [56.1]. 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 acid compounds, esters or amides derived therefrom, acrylonitrile, methacrylonitrile, or aromatic vinyl compounds are preferred. Other monomers that can be used include, for example, the compounds described in Research Disclosure No. 1955 (July 1980).

[0115] 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.

[0116] [ka]

[0117] -Repeating Unit (3-2)- In the repeating unit (3-2), specific examples of crosslinkable groups include the groups represented by the above formulas (P1) to (P30), 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, or oxetanyl groups being more preferred. The repeating unit (3-2) is preferably the repeating unit represented by the following formula (3) because it is easy to polymerize.

[0118] [ka]

[0119] 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.

[0120] The following shows specific examples of repeating units (3-2) and their molecular weights (Mw), but the present invention is not limited to these specific examples.

[0121] [ka] JPEG0007926918000033.jpg106122

[0122] The content of repeating units (3) is preferably less than 14% by mass, more preferably 7% by mass or less, and even 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 light-absorbing anisotropic 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. The repeating unit (3) may be present as a single unit or as two or more units in the polymeric liquid crystalline compound. When two or more repeating units (3) are present, it is preferable that their total amount is within the above range.

[0123] (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. In other words, the inclusion of such a flexible structure with long molecular chains facilitates entanglement among the molecular chains constituting the polymeric liquid crystalline compound, thereby suppressing aggregate breakdown of the light-absorbing anisotropic layer (specifically, breakdown of the light-absorbing anisotropic layer itself). As a result, it is presumed that the adhesion between the light-absorbing anisotropic layer and the underlying layer (e.g., substrate or orientation layer) is improved. Furthermore, the decrease in planar uniformity is thought to be caused by 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 the inclusion of a flexible structure with long molecular chains in the polymeric liquid crystalline compound suppresses the precipitation of the dichroic substance, resulting in a light-absorbing anisotropic layer with excellent planar uniformity. Here, excellent planar uniformity means that there are few orientation defects caused by the liquid crystal composition containing the polymeric liquid crystalline compound being repelled on the underlying layer (e.g., substrate or orientation layer).

[0124] The repeating unit (4) described above is the repeating unit represented by the following formula (4).

[0125] [ka]

[0126] 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.

[0127] Specific examples and preferred embodiments of PC4 are the same as those of PC1 in formula (1), so their explanation will be omitted.

[0128] For L4, a single bond is preferred in order to better demonstrate the effects of the present invention.

[0129] In formula (4), SP4 represents an alkylene group having 10 or more main chain atoms. Provided that one or more -CH2- groups constituting the alkylene group represented by SP4 may be substituted by the above-mentioned "SP-C", and 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-, it is preferably substituted with at least one group selected from the group consisting of. Provided that R 21 to R 28 each independently represent 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, a hydrogen atom contained in one or more -CH2- groups constituting the alkylene group represented by SP4 may be substituted by the above-mentioned "SP-H".

[0130] The number of main chain atoms of SP4 is 10 or more, and from the viewpoint of obtaining a light absorption anisotropic layer with more excellent adhesion and / or surface uniformity, 15 or more is preferable, and 19 or more is more preferable. Further, the upper limit of the number of main chain atoms of SP2 is preferably 70 or less, more preferably 60 or less, and still more preferably 50 or less, from the viewpoint of obtaining a light absorption anisotropic layer with more excellent orientation degree. Here, the "main chain" in SP4 means a partial structure necessary for directly linking L4 and T4, and the "number of main chain atoms" means the number of atoms constituting the partial structure. In other words, the "main chain" in SP4 is a partial structure that minimizes the number of atoms linking L4 and T4. For example, when SP4 is a 3,7-dimethyldecanyl group, the number of main chain atoms is 10, and when SP4 is a 4,6-dimethyldodecanyl group, the number of main chain atoms is 12. Further, in the following formula (4-1), the inside of the frame represented by the dotted rectangle corresponds to SP4, and the number of main chain atoms of SP4 (corresponding to the total number of atoms circled by the dotted line) is 11.

[0131] [ka]

[0132] 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, more preferably 15 to 80, even more preferably 25 to 70, and particularly preferably 25 to 60, in order to obtain an excellent light-absorbing anisotropic layer depending on the degree of orientation.

[0133] It is preferable that the one or more -CH2- groups constituting the alkylene group represented by SP4 are replaced by the aforementioned "SP-C" groups, as this provides excellent adhesion and planar uniformity, resulting in a light-absorbing anisotropic layer. Furthermore, when there are multiple -CH2- groups constituting the alkylene group represented by SP4, it is more preferable that only a portion of the multiple -CH2- groups are replaced by the aforementioned "SP-C" group, as this allows for a light-absorbing anisotropic layer with superior adhesion and planar uniformity.

[0134] Among "SP-C", -O-, -S-, -N(R 21 )-, -C(=O)-, -C(=S)-, -C(R 22 )=C(R 23 )-, alkynylene group, -Si(R 24 )(R 25 )-, -N=N-, -C(R 26 )=NN=C(R 27 )-,-C(R 28 At least one group selected from the group consisting of -O- and -N(R)2- is preferred, as it provides excellent light absorption anisotropy due to adhesion and planar uniformity. 21 At least one group selected from the group consisting of -, -C(=O)- and S(=O)2- is more preferably -O-, -N(R 21 At least one group selected from the group consisting of )- and C(=O)- is particularly preferred. However, R 21 ~R 28Each of these 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. In particular, SP4 is preferably a group comprising at least one selected from the group consisting of an oxyalkylene structure in which one or more -CH2- constituting the alkylene group are replaced by -O-, an ester structure in which one or more -CH2-CH2- constituting the alkylene group are replaced by -O- and C(=O)-, and a urethane bond in which one or more -CH2-CH2-CH2- constituting the alkylene group are replaced by -O-, -C(=O)- and NH-.

[0135] The hydrogen atoms in one or more -CH2- groups that make up the alkylene group represented by SP4 may be replaced by the aforementioned "SP-H". In this case, it is sufficient that one or more hydrogen atoms in -CH2- are replaced by "SP-H". That is, only one hydrogen atom in -CH2- may be replaced by "SP-H", or all (2) hydrogen atoms in -CH2- may be replaced by "SP-H". "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, and is 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.

[0136] 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 those for 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 formulas (P1) to (P30) being preferred). The preferred CL is 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. 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 even more preferably 6 (i.e., when the epoxycycloalkyl group is an epoxycyclohexyl group) from the viewpoint of achieving superior effects of the present invention. 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 because they exhibit superior effects of the present invention. The alkyl group used as a substituent for the oxetanyl group may be linear or branched, but a linear configuration is preferred because it exhibits superior effects of the present invention. 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.

[0137] 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.

[0138] [ka] JPEG0007926918000037.jpg125101

[0139] 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, a light-absorbing anisotropic layer with superior adhesion can be obtained. If the content of repeating units (4) is 20% by mass or less, a light-absorbing anisotropic layer with superior planar uniformity can be obtained. The repeating unit (4) may be present alone or in combination of two or more types in the polymeric liquid crystalline compound. If two or more types of repeating units (4) are present, the content of the repeating unit (4) refers to the total content of the repeating units (4).

[0140] (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 the repeating units (5) can improve planar uniformity while suppressing a decrease in the degree of orientation is presumed to be as follows. The repeating unit (5) is a unit introduced into the polymeric liquid crystalline compound by polymerizing the polyfunctional monomer. Therefore, it is thought that the polymeric liquid crystalline compound contains high molecular weight molecules that form a three-dimensional crosslinked structure by the repeating unit (5). However, since the content of the repeating unit (5) is small, the content of high molecular weight molecules containing the repeating unit (5) is considered to be small. It is presumed that the presence of a small amount of high molecular weight material forming this three-dimensional crosslinked structure suppresses the repulsion of the liquid crystal composition, resulting in a light-absorbing 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 compounds was small.

[0141] The repeating unit (5) introduced by polymerizing the above polyfunctional monomer is preferably a repeating unit represented by the following formula (5).

[0142] [ka]

[0143] 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.

[0144] PC5A and PC5B may be the same group or different groups, but it is preferable that they be the same group in that the degree of orientation of the light absorption anisotropy layer is further improved. L5A and L5B may both be single bonds, the same group, or different groups. However, from the viewpoint of improving the degree of orientation of the light absorption anisotropy layer, it is preferable that they are both single bonds or the same group, and more preferable that they are the same group. SP5A and SP5B may both be single bonds, the same group, or different groups. However, from the viewpoint of improving the degree of orientation of the light absorption anisotropy layer, it is preferable that they are both single bonds or the same group, and more preferable that they are the same group. 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.

[0145] a and b are each independent integers of 0 or 1, and are preferably 1 from the viewpoint of further improving the orientation of the light-absorbing anisotropic layer. a and b may be the same or different, but it is preferable that both be 1, as this improves the degree of orientation of the light-absorbing anisotropic layer. The sum of a and b is preferably 1 or 2 (i.e., the repeating unit represented by formula (5) has a mesogenic group), and more preferably 2, from the viewpoint of improving the degree of orientation of the light-absorbing anisotropic layer.

[0146] -(MG5A) a -(MG5B) b -The substructure represented by - preferably has a cyclic structure in that it further improves the orientation of the light-absorbing anisotropy layer.In this case, -(MG5A2) a -(MG5B) b The number of annular structures in the substructure represented by - is preferably two or more, more preferably 2 to 8, even more preferably 2 to 6, and particularly preferably 2 to 4. The mesogenic groups represented by MG5A and MG5B each preferably contain one or more cyclic structures, more preferably 2 to 4, more preferably 2 to 3, and even more preferably 2, from the viewpoint of further improving the orientation of the light-absorbing anisotropic layer. Specific examples of cyclic structures include aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups, with aromatic hydrocarbon groups and alicyclic groups being preferred among these. MG5A and MG5B may be the same group or different groups, but it is preferable that they be the same group in that the degree of orientation of the light absorption anisotropy layer is further improved.

[0147] As for the mesogenic groups represented by MG5A and MG5B, the mesogenic group MG in the above formula (LC) is preferred because it is superior in terms 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.

[0148] In particular, for the repeating unit (5), it is preferable that PC5A and PC5B are the same group, both L5A and L5B are a single bond or the same group, both SP5A and SP5B are a single bond or the same group, and MG5A and MG5B are the same group. This further improves the degree of orientation of the light absorption anisotropic layer.

[0149] The content of the repeating unit (5) is preferably 10% by mass or less, more preferably 0.001 to 5% by mass, and still more preferably 0.05 to 3% by mass, based on the total content (100% by mass) of all repeating units contained in the polymer liquid crystalline compound. The repeating unit (5) may be contained alone in the polymer liquid crystalline compound, or two or more kinds thereof may be contained. When two or more kinds of the repeating unit (5) are contained, the total amount thereof is preferably within the above range.

[0150] (Star-shaped polymer) The polymer liquid crystalline compound may be a star-shaped polymer. The star-shaped polymer in the present invention means a polymer having three or more polymer chains extending from a core as a starting point, and is specifically represented by the following formula (6). The star-shaped polymer represented by formula (6) as the polymer liquid crystalline compound can form a light absorption anisotropic layer with a high degree of orientation while having high solubility (excellent solubility in a solvent).

[0151]

Chemical Formula

[0152] In formula (6), n A represents an integer of 3 or more, and an integer of 4 or more is preferable. n A The upper limit of is not limited thereto, but is usually 12 or less, preferably 6 or less. A plurality of PIs each independently represent a polymer chain containing any one of the repeating units represented by the above formulas (1), (21), (22), (3), (4) and (5). Provided that at least one of the plurality of PIs represents a polymer chain containing the repeating unit represented by the above formula (1). A represents the atomic group that forms the core of the star-shaped polymer. Specific examples of A include the structure obtained by removing a hydrogen atom from the thiol group of a polyfunctional thiol compound described in paragraphs

[0052] to

[0058] of Japanese Patent Publication No. 2011-074280, paragraphs

[0017] to

[0021] of Japanese Patent Publication No. 2012-189847, paragraphs

[0012] to

[0024] of Japanese Patent Publication No. 2013-031986, and paragraphs

[0118] to

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

[0153] The number of thiol groups in the polyfunctional thiol compound from which A is derived is preferably 3 or more, and more preferably 4 or more. The upper limit of the number of thiol groups in the polyfunctional thiol compound is usually 12 or less, and preferably 6 or less. Specific examples of polyfunctional thiol compounds are shown below.

[0154] [ka] JPEG0007926918000041.jpg122131

[0155] From the viewpoint of improving the degree of orientation, the polymeric liquid crystalline compound may be a thermotropic liquid crystal and a crystalline polymer.

[0156] (crystalline polymer) The above-mentioned polymeric liquid crystalline compound may also be a crystalline polymer. Crystalline polymers are polymers that exhibit a transition to a crystalline layer in response to temperature changes. Crystalline polymers may also exhibit a glass transition in addition to a transition to a crystalline layer. Crystalline polymers are preferable because they exhibit a higher degree of orientation of the light-absorbing anisotropic layer and less observable haze. Therefore, polymeric liquid crystalline compounds that undergo a transition from the crystalline phase to the liquid crystal phase when heated (a glass transition may occur in between) or polymeric liquid crystalline compounds that undergo a transition to the crystalline phase (a glass transition may occur in between) when the temperature is lowered after becoming liquid crystal by heating are preferred.

[0157] The presence or absence of crystallinity in polymeric liquid crystalline compounds is evaluated as follows. Two anisotropic light-absorbing layers of an optical microscope (Nikon ECLIPSE E600 POL) are positioned orthogonally to each other, and a sample stage is placed between the two layers. A small amount of the polymer liquid crystalline compound is placed on a glass slide, and the 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 polymer liquid crystalline compound exhibits liquid crystalline properties, causing the polymer liquid crystalline compound to become liquid crystalline. After the polymer 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 polymer liquid crystalline compound exhibits multiple liquid crystalline phases (e.g., nematic phase and smectic phase), all transition temperatures are also recorded. 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) (an empty aluminum pan is used as a reference). Heat the polymeric liquid crystalline compound to the temperature at which it exhibits the liquid crystal phase, and then hold the temperature for 1 minute. After that, measure the calorimetry while cooling at a rate of 10°C / min. Confirm the exothermic peak from the obtained calorimetry spectrum. As a result, if an exothermic peak is observed at a temperature other than the liquid crystal phase transition temperature, that exothermic peak is due to crystallization, and the polymer liquid crystalline compound can be said to be crystalline. On the other hand, if no exothermic peaks are observed at temperatures other than the liquid crystal phase transition temperature, it can be said that the polymer liquid crystalline compound does not possess crystallinity.

[0158] The method for obtaining the 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.

[0159] -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 less, even more preferably -20°C to less than 120°C, and most preferably 95°C or less, as this results in a higher degree of orientation of the light-absorbing 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. The crystallization temperature is the temperature of the exothermic peak due to crystallization in the DSC described above.

[0160] (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). • 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).

[0161] The polymer liquid crystalline compound may exhibit either a nematic phase or a smectic phase, but preferably exhibits at least a nematic phase. The temperature range for exhibiting a nematic phase is preferably 0 to 450°C, and more preferably 30 to 400°C from the viewpoint of handleability and production suitability.

[0162] (Content) The content of the thermotropic liquid crystalline compound (preferably a rod-like liquid crystalline compound) is preferably 10 to 97% by mass, more preferably 40 to 95% by mass, and still more preferably 50 to 95% by mass, relative to the total solid content (100% by mass) of the liquid crystal composition, from the viewpoint that the effect of the present invention is more excellent. When the thermotropic liquid crystalline compound (preferably a rod-like liquid crystalline compound) contains a polymer liquid crystalline compound, the content of the polymer liquid crystalline compound is preferably 10 to 99% by mass, more preferably 30 to 95% by mass, and still more preferably 50 to 90% by mass, relative to the total mass (100 parts by mass) of the thermotropic liquid crystalline compound (preferably a rod-like liquid crystalline compound). When the thermotropic liquid crystalline compound (preferably a rod-like liquid crystalline compound) contains a low-molecular-weight liquid crystalline compound, the content of the low-molecular-weight liquid crystalline compound is preferably 1 to 90% by mass, more preferably 5 to 70% by mass, and still more preferably 10 to 60% by mass, relative to the total mass (100 parts by mass) of the thermotropic liquid crystalline compound (preferably a rod-like liquid crystalline compound). When the thermotropic liquid crystalline compound (preferably a rod-like liquid crystalline compound) contains both a polymer liquid crystalline compound and a low-molecular-weight liquid crystalline compound, the mass ratio of the content of the low-molecular-weight liquid crystalline compound to the content of the polymer liquid crystalline compound (low-molecular-weight liquid crystalline compound / polymer liquid crystalline compound) is preferably 5 / 95 to 70 / 30, and more preferably 10 / 90 to 50 / 50, from the viewpoint that the effect of the present invention is more excellent. Here, the "solid content in the liquid crystal composition" refers to components excluding the solvent, and specific examples of the solid content include the aforementioned rod-like liquid crystalline compound, the dichroic substance described below, a polymerization initiator, an interface modifier, and the like.

[0163] <Dichroic Substance> The liquid crystal composition of the present invention 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.

[0164] Dichroic materials are not particularly limited and include visible light absorbing materials (dichroic dyes), luminescent materials (fluorescent materials, phosphorescent materials), ultraviolet absorbing materials, infrared absorbing materials, nonlinear optical materials, carbon nanotubes, and inorganic materials (e.g., quantum rods). Conventionally known dichroic materials (dichroic dyes) can be used. Specifically, for example, paragraphs

[0067] to

[0071] of JP 2013-228706, paragraphs

[0008] to

[0026] of JP 2013-227532, paragraphs

[0008] to

[0015] of JP 2013-209367, paragraphs

[0045] to

[0058] of JP 2013-14883, paragraphs

[0012] to

[0029] of JP 2013-109090, paragraphs

[0009] to

[0017] of JP 2013-101328, and paragraphs

[0051] to

[0017] of JP 2013-37353. Paragraph

[0065] , paragraphs

[0049] to

[0073] of JP 2012-63387, paragraphs

[0016] to

[0018] of JP 11-305036, paragraphs

[0009] to

[0011] of JP 2001-133630, paragraphs

[0030] to

[0169] of JP 2011-215337, paragraphs

[0021] to

[0075] of JP 2010-106242, paragraphs

[0011] to

[0025] of JP 2010-215846, paragraphs

[0017] to

[006] of JP 2011-048311 9) paragraph, paragraphs

[0013] to

[0133] of JP 2011-213610, paragraphs

[0074] to

[0246] of JP 2011-237513, paragraphs

[0005] to

[0051] of JP 2016-006502, paragraphs

[0014] to

[0032] of JP 2018-053167, paragraphs

[0014] to

[0033] of JP 2020-11716, paragraphs

[0005] to

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

[0008] to [ Examples include paragraph

[0062] , paragraphs

[0014] to

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

[0014] to

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

[0013] to

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

[0014] to

[0034] of International Publication No. 2018 / 164252, paragraphs

[0021] to

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

[0043] to

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

[0165] In the present invention, two or more dichroic materials may be used in combination. For example, from the viewpoint of making the formed light-absorbing anisotropic layer closer to black, it is preferable to use in combination at least one dichroic material having a maximum absorption wavelength in the range of 370 to 550 nm and at least one dichroic material having a maximum absorption wavelength in the range of 500 to 700 nm.

[0166] The content of the dichroic substance is 10.0% by mass or more, preferably 15.0% by mass or more, relative to the total solid content (100.0% by mass) of the liquid crystal composition. Furthermore, the content of the dichroic substance relative to the total solid content of the liquid crystal composition is preferably 10 to 70% by mass, more preferably 13.0 to 60.0% by mass, even more preferably 15.0 to 50.0% by mass, particularly preferably 15.0 to 30.0% by mass, and most preferably 15.0 to 20.0% by mass, from the viewpoint of achieving superior effects of the present invention. When multiple dichroic substances are used in combination, it is preferable that the total amount of the multiple dichroic substances is within the above range.

[0167] <Solvent> From the viewpoint of workability and other factors, the liquid crystal composition of the present invention preferably contains a solvent. Examples of solvents include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone), ethers (e.g., dioxane, tetrahydrofuran, tetrahydropyran, dioxolane, tetrahydrofurfuryl alcohol, and cyclopentyl methyl ether), aliphatic hydrocarbons (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., benzene, toluene, xylene, and trimethylbenzene), and halogenated carbons (e.g., dichloromethane, trichloromethane (chloroform), dichloroethane, dichlorobenzene, and chloromethyl ether). Examples of organic solvents include esters (e.g., methyl acetate, ethyl acetate, and butyl acetate, diethyl carbonate), alcohols (e.g., ethanol, isopropanol, butanol, and cyclohexanol), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, and 1,2-dimethoxyethane), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide), amides (e.g., dimethylformamide and dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone), and heterocyclic compounds (e.g., pyridine), as well as water. These solvents may be used individually or in combination of two or more.

[0168] Of these solvents, organic solvents are preferred because they result in a higher degree of orientation of the formed light-absorbing anisotropic layer and thus improved heat resistance, and halogenated carbons, ethers, or ketones are more preferred.

[0169] When the liquid crystal composition contains a solvent, the solvent content is preferably 60 to 99.5% by mass, more preferably 70 to 99% by mass, and particularly preferably 75 to 98% by mass, relative to the total mass (100% by mass) of the liquid crystal composition, because this increases the degree of orientation of the formed light-absorbing anisotropic layer and improves heat resistance.

[0170] <Polymerization initiator> The liquid crystal composition of the present invention may contain a polymerization initiator. There are no particular restrictions on the polymerization initiator, but it is preferably a photosensitive compound, i.e., a photopolymerization initiator. Various compounds can be used as photopolymerization initiators without particular limitations. 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. 4,239850), oxadiazole compounds (U.S. Patent No. 4,212970), o-acyloxime compounds (paragraph

[0065] of Japanese Patent Publication No. 2016-027384), and acylphosphine oxide compounds (Japanese Patent Publication No. 63-040799, Japanese Patent Publication No. 5-029234, Japanese Patent Publication No. 10-095788 and Japanese Patent Publication No. 10-029997). 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.

[0171] When a liquid crystal composition contains a polymerization initiator, the amount of polymerization initiator is preferably 0.01 to 30% by mass, and more preferably 0.1 to 15% by mass, relative to the total solid content (100% by mass) of the liquid crystal composition, because this results in a higher degree of orientation of the formed light-absorbing anisotropic layer and improved heat resistance.

[0172] <Polymerizable compound> The liquid crystal composition of the present invention may contain polymerizable compounds. Examples of polymerizable compounds include compounds containing acrylates (for example, (meth)acrylate monomers). When the liquid crystal composition of the present invention contains polymerizable compounds, the content of the polymerizable compound is preferably 0.5 to 50% by mass, and more preferably 1.0 to 40% by mass, relative to the total solid content (100% by mass) of the liquid crystal composition, from the viewpoint of achieving superior effects of the present invention.

[0173] The liquid crystal composition of the present invention may contain other additives. Examples of additives include alignment agents that assist in the orientation of the liquid crystal composition, specifically boronic acid compounds and onium salts.

[0174] As the boronic acid compound, the compound represented by formula (30) is preferred.

[0175] Formula (30) [ka]

[0176] In formula (30), R 1 and R 2 Each of these independently represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R 3 This represents a substituent containing a (meth)acrylic group. Specific examples of boronic acid compounds include the boronic acid compounds represented by general formula (I) described in paragraphs

[0023] to

[0032] of Japanese Patent Publication No. 2008-225281. The following compounds are also preferred as boronic acid compounds.

[0177] [ka]

[0178] As the onium salt, the compound represented by formula (31) is preferred.

[0179] Formula (31) [ka]

[0180] In formula (31), ring A represents a quaternary ammonium ion consisting of a nitrogen-containing heterocycle. X represents an anion. 1 This represents a divalent linking group. 2 This represents a single bond or a divalent linking group. 1 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. P 1 and P 2 Each of these independently represents a monovalent substituent having a polymerizable ethylenically unsaturated bond. Specific examples of onium salts include the onium salt described in paragraphs

[0052] to

[0058] of Japanese Patent Publication No. 2012-208397, the onium salt described in paragraphs

[0024] to

[0055] of Japanese Patent Publication No. 2008-026730, and the onium salt described in Japanese Patent Publication No. 2002-037777.

[0181] The content of alignment agents in the liquid crystal composition, specifically the content of liquid dichroic substances, is preferably 0.1 to 40% by mass, and more preferably 0.3 to 20% by mass, relative to the total solid content (100% by mass) of the liquid crystal composition. The alignment agents may be used alone or in combination of two or more types. When two or more alignment agents are used, it is preferable that their total amount is within the above range.

[0182] [Transparent base film] The optical film 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 base film, known transparent resin films, transparent resin plates, and transparent resin sheets can be used, and there are no particular limitations. As the transparent resin film, 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, and (meth)acrylonitrile film can be used.

[0183] 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 typically 20 to 100 μm. In the present invention, it is particularly preferable that the transparent substrate film is a cellulose ester film and has a film thickness of 20 to 70 μm.

[0184] [Orientation layer] The optical film of the present invention may have an orientation layer. Preferably, the orientation layer is arranged adjacent to a light-absorbing anisotropy layer. Preferably, the orientation layer is provided between the transparent substrate film and the light-absorbing anisotropy layer. The alignment layer can be any layer as long as it can bring the thermotropic liquid crystalline compound (preferably a rod-shaped liquid crystalline compound) and the dichroic substance contained in the liquid crystal composition of the present invention into a desired orientation state on the alignment layer. Means for providing an orientation layer include rubbing treatment of the film surface with an organic compound (preferably a polymer, such as polyvinyl alcohol and polyimide), oblique deposition of an inorganic compound, formation of a layer having microgrooves, and accumulation of an organic compound (e.g., ω-tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearylate) by the Langmuir-Bludget method (LB film). Furthermore, orientation layers that exhibit orientation function by applying an electric field, a magnetic field, or light irradiation are also known. Among these, in the present invention, an orientation layer formed by rubbing treatment is preferred from the viewpoint of ease of controlling the pre-tilt angle of the orientation layer, and a photo-orientation layer formed by light irradiation is also preferred from the viewpoint of uniformity of orientation. When tilting the orientation axis, for example, this can be achieved by irradiating a photo-orientation layer, such as an azo compound or a cinnamoyl compound, with UV light from an oblique direction, and as a result, it becomes possible to tilt the transmission axis center with respect to the normal direction of the film. Furthermore, the orientation layer may also function as a barrier layer, as will be discussed later. The alignment layer may consist of two or more layers, and one or more of the two or more alignment layers may be alignment liquid crystal layers containing a liquid crystal compound.

[0185] The thickness of the light-absorbing anisotropic layer is not particularly limited, but from the viewpoint of miniaturization and weight reduction, 100 to 8000 nm is preferred, and 300 to 5000 nm is more preferred.

[0186] [Method for forming a light-absorbing anisotropic layer] The method for forming the light-absorbing anisotropic layer is not particularly limited, and examples include 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 "orientation step"). Furthermore, the term "liquid crystallinity component" includes not only the thermotropic liquid crystallinity compounds mentioned above, but also, if the dichroic substance mentioned above also possesses liquid crystallinity, the component also includes the dichroic substance that is liquid crystallinity.

[0187] [Coating film formation process] The coating film formation process involves applying a light-absorbing anisotropic layer-forming composition to form a coating film. 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, it becomes easier to apply the light-absorbing anisotropic layer-forming composition. Specific examples of known methods for applying the light-absorbing anisotropic layer-forming composition include, for example, roll coating, gravure printing, spin coating, wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spray coating, and inkjet coating.

[0188] [Orientation process] The orientation process 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 process. The drying process can remove components such as solvents from the coating film. The drying process may be carried out by leaving the coating film at room temperature for a predetermined time (e.g., natural drying), or by heating and / or blowing air. Here, the liquid crystalline components contained in the light-absorbing anisotropic layer-forming composition may be oriented by the coating film formation process or drying treatment described above. For example, in an embodiment in which the light-absorbing anisotropic layer-forming composition is prepared as a coating solution containing a solvent, a coating film with light-absorbing anisotropy (i.e., a light-absorbing anisotropic layer) is obtained by drying the coating film to remove the solvent from the coating film. If the drying process is carried out at a temperature above the transition temperature of the liquid crystalline components in the coated film to the liquid crystal phase, the heat treatment described later may not be necessary.

[0189] 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 transitioning to 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.

[0190] 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 after heat treatment suitable for use as a light-absorbing anisotropic film. For heat treatment, a temperature of 10 to 250°C is preferred, and 25 to 190°C is more preferred, from the standpoint of suitability for manufacturing. The heating time is preferably 1 to 300 seconds, and 1 to 60 seconds is more preferred.

[0191] The orientation step may include a cooling process performed after the heat treatment. The cooling process involves cooling the heated coating film to room temperature (approximately 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. By following the above steps, a light-absorbing anisotropic layer can be obtained. In this embodiment, drying treatment and heat treatment are mentioned 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.

[0192] [Other processes] The method for forming a light-absorbing anisotropic layer may include a step of curing the light-absorbing anisotropic layer after the orientation step (hereinafter also referred to as the "curing step"). The curing process 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 process 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. Furthermore, ultraviolet light may be irradiated while heating during curing, or ultraviolet light may be irradiated through a filter that transmits only specific wavelengths. When exposure is performed while heating, the heating temperature during exposure depends on the transition temperature of the liquid crystalline component in the light-absorbing anisotropic layer to the liquid crystal phase, but is preferably 25 to 140°C. Furthermore, exposure may be performed under a nitrogen atmosphere. When the curing of the light-absorbing anisotropic layer proceeds by radical polymerization, exposure under a nitrogen atmosphere is preferable because it reduces the inhibition of polymerization by oxygen.

[0193] [Patterning of light-absorbing anisotropic layers] The light-absorbing anisotropic layer used in this invention can be a light-absorbing anisotropic layer having region A and region B in its plane, with different transmittance center axes in each region. 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 the transmittance of regions C and D is different when tilted 30° from the transmittance center axis in the direction normal to the film surface in a plane encompassing the transmittance center axis and the normal to the film surface. In this case, it is preferable that the light-absorbing anisotropic layer has a transmittance of 50% or less when tilted 30° from the transmittance center axis in the direction normal to the film surface in region C, and a transmittance of 80% or more when tilted 30° from the transmittance center axis in the direction normal to the film surface in region D. By performing the patterning described above, it becomes possible to strengthen or weaken the viewing angle dependency in certain areas. This allows for the display of highly confidential information only in areas where the viewing angle dependency is strengthened. Furthermore, by controlling the viewing angle dependency for each display position in the display device, it becomes possible to create designs with superior aesthetics. Moreover, 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.

[0194] [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 layer, 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 within 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.

[0195] [Visual Angle Control System] The visual angle control system of the present invention preferably comprises the optical film and a polarizer. One embodiment of the visual angle control system of the present invention will be described with reference to Figure 2. The viewing angle control system 9 shown in Figure 2 has, from the viewing side, a barrier layer 1, a light-absorbing anisotropy layer 2, an alignment liquid crystal layer 3, an alignment layer 4, and a TAC film 5 in that order. A polarizer (not shown) is placed on the opposite side of the TAC film 5 from the alignment layer 4. In Figure 2, the barrier layer 1, the light-absorbing anisotropy layer 2, the alignment liquid crystal layer 3, the alignment layer 4, and the TAC film 5 constitute an optical film. The above embodiment includes an alignment liquid crystal layer 3, but an embodiment without the alignment liquid crystal layer 3 is also possible. Furthermore, the embodiment without the alignment liquid crystal layer 3 may have the barrier layer 1, alignment layer 4, light absorption anisotropy layer 2, and TAC film 5 in this order from the viewing side. Furthermore, although the above embodiment includes the TAC film 5, the TAC film 5 may be one of the other layers described later. Furthermore, as described above, the barrier layer 1 may also have the function of the orientation layer 4, in which case the barrier layer 1, the light-absorbing anisotropy layer 2, and the TAC film 5 may be arranged in this order from the viewing side. The layers that the visual angle control system of the present invention may include are described below.

[0196] [Barrier layer] The viewing angle control system of the present invention preferably also includes 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 layers contained in the optical film 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.

[0197] [Refractive index adjustment layer] In the viewing angle control system of the present invention, the above-mentioned light-absorbing anisotropic layer has a dichroic material, and internal reflection due to the high refractive index of the light-absorbing anisotropic layer may be a problem. In such cases, it is preferable to have a refractive index adjustment layer. The refractive index adjustment layer is a layer arranged in contact with the light-absorbing anisotropic layer, and it is preferable that the in-plane average refractive index at a wavelength of 550 nm is 1.55 or more and 1.70 or less. It is preferable that the above refractive index adjustment layer is a layer for performing so-called index matching.

[0198] [Polarizer] The polarizer used in the visual angle control system of the present invention is not particularly limited as long as it is a component that has the function of converting light into a specific linear polarization, and conventionally known polarizers can be used.

[0199] Suitable polarizers include iodine-based polarizers, dye-based polarizers utilizing dichroic dyes, and polyene-based polarizers. Iodine-based and dye-based polarizers include coated polarizers and stretched polarizers, both of which are applicable. For coated polarizers, polarizers in which dichroic dyes are oriented using the orientation of liquid crystalline compounds are preferred, while for stretched polarizers, polarizers made by adsorbing iodine or a dichroic dye onto polyvinyl alcohol and then stretching the material 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 those described in Japanese Patent Publication No. 5048120, No. 5143918, No. 5048120, No. 4691205, No. 4751481, and No. 4751486, and these known technologies related to polarizers can also be preferably utilized.

[0200] In particular, polarizers containing polyvinyl alcohol-based resin (polymers containing -CH2-CHOH- as repeating units, especially 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.

[0201] In the present invention, the thickness of the polarizer is not particularly limited, but is preferably 3 to 60 μm, more preferably 5 to 20 μm, and even more preferably 5 to 10 μm.

[0202] The light-absorbing anisotropic layer and the polarizer layer of the present invention may be laminated via an adhesive or bonding agent, or the orientation layer and the light-absorbing layer may be directly coated onto the polarizer and then laminated. In the viewing angle control system of the present invention, in Figure 3, the angle φ between the plane containing the transmittance center axis direction 22 of the light absorption anisotropy layer 20 and the normal to the film surface (normal to the light absorption anisotropy layer 23) (i.e., the plane containing the direction obtained by orthogonally projecting the transmittance center axis direction 22 of the light absorption anisotropy layer 20 of the optical film onto the optical film surface (direction indicated by φ1) and the normal to the film surface) and the absorption axis direction 24 of the polarizer 21 (direction indicated by φ2) is preferably 0° or more and less than 85°, greater than 95° and less than 265°, or greater than 275° and 360° or less, and more preferably 45° or more and less than 85°, greater than 95° and 135° or less, 225° or more and less than 265°, or greater than 275° and 315° or less.

[0203] [Adhesive layer] The visual angle control system of the present invention may have an adhesive layer, which is preferably a transparent, optically isotropic adhesive similar to those used in ordinary image display devices, and is usually a pressure-sensitive adhesive.

[0204] In addition to the base material (adhesive), conductive particles, and thermally expandable particles used as needed, the adhesive layer in 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.

[0205] 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.

[0206] The adhesive layer can be formed by methods such as directly applying a coating liquid containing a base material, conductive particles, and optionally thermally expandable particles, additives, and a solvent onto a support for the protective member and pressing it onto the support via a release liner, or by applying a 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 support for the protective member.

[0207] 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 material, 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.

[0208] [Adhesive layer] The visual angle control system of the present invention may have an adhesive layer, and the adhesive used in the adhesive layer develops its adhesive properties through drying and reaction after bonding. Polyvinyl alcohol-based adhesives (PVA-based adhesives) develop their adhesive properties upon drying, making it possible to bond materials together. 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 the molecule, and various generally known curable 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). In particular, from the viewpoint of resistance to heat deformation, UV-curing adhesives that harden with UV irradiation are preferably used.

[0209] Each layer of the adhesive layer and tack layer may be treated with an ultraviolet absorber such as a salicylic acid ester compound, benzophenol compound, benzotriazole compound, cyanoacrylate compound, or nickel complex salt compound to give it ultraviolet absorption capabilities.

[0210] The adhesive layer or bonding layer can be attached to the film by any suitable method. Examples include preparing an adhesive solution of about 10-40% by weight by dissolving or dispersing a 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 directly attaching it to the film by any suitable deployment method such as casting or coating; and forming an adhesive layer on a separator and transferring it, similar to the above.

[0211] The adhesive layer or bonding layer can be provided on one or both sides of the film as a superimposed layer of layers with 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.

[0212] Furthermore, the protective film may undergo surface modification treatment to improve adhesion or other properties before the application of adhesives or tacks. Specific examples of such treatments include corona treatment, plasma treatment, primer treatment, and saponification treatment.

[0213] [Other layers] To control the angle dependence of the viewing angle, the light-absorbing anisotropic layer used in the present invention can also be used in combination with an optically anisotropic film or photorotators. 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.

[0214] [Image display device] The image display device in the present invention can be a liquid crystal display device, an organic EL display device, or other display device, but here we will explain using a liquid crystal display device as an example. As shown in Figure 1, the liquid crystal display device 100 of the present invention is a liquid crystal display device that comprises, from the viewing side, an optical film 101 of the present invention, a viewing-side polarizer 102, a liquid crystal cell 103, a backlight-side polarizer 104, and a backlight 105 in this order, and the optical film contains a light-absorbing anisotropic layer. In the above embodiment, the viewing angle control system is composed of the optical film 101 and the viewing-side polarizer 102.

[0215] In this invention, the direction of the polarizer's absorption axis is sometimes referred to as the vertical direction or the horizontal direction. However, in the normal state of using a liquid crystal display device, the direction of the edge of the liquid crystal display device that is close to the vertical direction is referred to as the vertical direction, and the direction of the edge of the liquid crystal display device that is close to the horizontal direction is referred to as the horizontal direction.

[0216] The display element used in the image display device including the optical film of the present invention is not particularly limited, and examples include liquid crystal cells, organic electroluminescent (hereinafter abbreviated as "EL") display panels, and plasma display panels. Of these, liquid crystal cells or organic EL display panels are preferred. That is, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as the display element, or an organic EL display device using an organic EL display panel as the display element. A preferred example of a liquid crystal display device, which is an image display device of the present invention, is one having the light-absorbing anisotropic layer, polarizer, and liquid crystal cell described above. More preferably, it is a liquid crystal display device having the viewing angle control system and liquid crystal cell described above. In this invention, it is preferable to use the viewing angle control system of the present invention as the polarizing element on the front side or the barrier side among the polarizing elements provided on both sides of the liquid crystal cell, and it is also possible to use the viewing angle control system of the present invention as both the front side and the rear side polarizing elements. The following provides a detailed description of the liquid crystal cells that make up a liquid crystal display device.

[0217] Some image display devices are thin and can be molded into curved surfaces. The light-absorbing anisotropic layer used in this invention is thin and easily bendable, making it suitable for use in image display devices with curved display surfaces. Furthermore, some image display devices have a pixel density exceeding 250 ppi, enabling high-definition display. The light-absorbing anisotropic layer used in the present invention can be suitably applied to such high-definition image display devices without causing moiré patterns.

[0218] The following provides a detailed description of the liquid crystal cells and organic EL display devices that constitute liquid crystal display devices.

[0219] [Liquid crystal cell] The 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 a 60-120° angle. TN mode liquid crystal cells are the most widely used in color TFT (Thin Film Transistor) liquid crystal display devices and are described in numerous publications. 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. 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.

[0220] [Organic EL display device] As an example of an organic EL display device, which is an image display device of the present invention, a preferred configuration is one in which, from the viewing side, a light-absorbing anisotropic layer, a λ / 4 plate, and an organic EL display panel are arranged in this order. In this case, it is preferable that the organic EL display device is arranged in the following order from the viewing side: substrate, an optional alignment layer, a light-absorbing anisotropy layer, an optional barrier layer, a λ / 4 plate, and an organic EL display panel. A λ / 4 plate is a phase difference plate that can convert between linearly polarized light and circularly polarized or elliptically polarized light, and known types can be used. Furthermore, an organic EL display panel is a display panel constructed using an organic EL element in which an organic light-emitting layer (organic electroluminescent layer) is sandwiched between electrodes (between the cathode and the anode). The configuration of the organic EL display panel is not particularly limited, and known configurations can be adopted. [Examples]

[0221] The present invention will be described in more detail below based on the following examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0222] [Fabrication and evaluation of optical films] An optical film having a light-absorbing anisotropic layer in which dichroic material is oriented in a gradient was fabricated to have the configuration shown in the table below. A representative example of the optical film manufacturing method used in Example 1 will be described.

[0223] [Preparation of transparent support 1] 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 orientation layer forming coating solution 1 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 obtain an orientation layer coating film. Furthermore, the orientation layer coating film was rubbed to form an orientation layer E, and an orientation layer-coated transparent support 1 was obtained. The film thickness was 0.5 μm.

[0224] -------------------------------------------------- (Coating solution for forming an orientation layer 1) -------------------------------------------------- • 3.80 parts by mass of the following modified polyvinyl alcohol PVA-1 • Initiator Irg2959 0.20 parts by mass ·Water 70 parts by mass • Methanol 30 parts by mass --------------------------------------------------

[0225] PVA-1 [ka]

[0226] <Preparation of composition liquid F1 for forming photo-alignment layer> The components were mixed to achieve the following composition, dissolved for 1 hour while stirring, and then filtered through a 0.45 μm filter to obtain the photo-alignment layer formation composition solution F1. -------------------------------------------------- Composition liquid F1 for forming photo-alignment layer -------------------------------------------------- • The following photo-aligning material F1: 0.3 parts by mass 2-Butoxyethanol 41.6 parts by mass • Dipropylene glycol monomethyl ether 41.6 parts by mass ·Pure water 16.5 parts by mass --------------------------------------------------

[0227] [ka]

[0228] The following photo-alignment layer forming solution F1 was applied to the alignment layer E of the transparent support 1 with the alignment layer described above, and dried at 60°C for 2 minutes to obtain the transparent support 1 with the photo-alignment layer coating. The obtained photo-alignment layer coating was exposed to ultraviolet light (irradiation dose 2000 mJ / cm²) using an ultraviolet exposure apparatus. 2 The photo-alignment layer F was formed by irradiating the material from an extreme angle of 15°, and a transparent support 1 with a photo-alignment layer of 0.03 μm thickness was obtained. The azimuth angle of the ultraviolet irradiation direction was set to coincide with the rubbing direction of the alignment layer E. Furthermore, the above-mentioned photo-alignment material F1 is an azo compound.

[0229] [Fabrication of light-absorbing anisotropic layers] A photo-alignment layer F was formed on the photo-alignment layer F of the fabricated transparent support 1 with a photo-alignment layer by applying the following photo-absorption anisotropy layer formation composition P1 with a wire bar. The photo-absorption anisotropy layer formation composition P1 corresponds to the liquid crystal composition described above. Next, the coated layer P1 was heated at 120°C for 30 seconds, and then cooled to 100°C. Subsequently, an illuminance of 200 mW / cm² was measured using an LED lamp (center wavelength 365 nm) at room temperature (25°C). 2 An optical film was obtained by irradiating the photo-alignment layer F with ultraviolet light for 2 seconds under the specified irradiation conditions, thereby creating a light-absorbing anisotropic layer P1-A on the photo-alignment layer F. Furthermore, a coating layer P1 is prepared on the photo-alignment layer F of the transparent support 1 with a photo-alignment layer, which was prepared in the same manner as above. The prepared coating layer P1 is heated at 120°C for 30 seconds, cooled to 70°C, and illuminated at room temperature (25°C) with an LED lamp (center wavelength 365nm) at an illuminance of 200mW / cm². 2 By irradiating with ultraviolet light for 2 seconds under these irradiation conditions, a light-absorbing anisotropic layer P1-B was fabricated on the photo-alignment layer F, and an optical film was obtained.

[0230] ------------------------------------------------------------------ Composition of composition P1 for forming a light-absorbing anisotropic layer ------------------------------------------------------------------ ·Liquid crystal compound L1 4.405 parts by mass ·Liquid crystal compound L3 2.304 parts by mass ·Dichroic substance Y1 0.407 parts by mass ·Dichroic substance M1 0.068 parts by mass ·Dichroic substance C1 0.712 parts by mass • Polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.102 parts by mass • Interface modifier B1 0.003 parts by mass Cyclopentanone 82.800 parts by mass • Tetrahydrofuran 9,200 parts by mass ------------------------------------------------------------------

[0231] [ka] JPEG0007926918000048.jpg12131

[0232] [Measurement of mixed liquid crystal temperature drop] Two linear polarizers in an optical microscope (Nikon Corporation, product name "ECLIPSE E600 POL") were set up so that their absorption axes were perpendicular to each other. A composition was prepared by removing the interface modifier from the light-absorbing anisotropic layer-forming composition P1 of Example 1, and then adding the interface modifier in an amount of 10.0 parts by mass per 100.0 parts by mass of solids in the composition without the interface modifier. A glass slide containing the prepared composition was placed on a sample stage positioned between two linear polarizers, and the solvent was dried by leaving it at 70°C for 30 minutes. This glass slide was heated on a hot plate at a temperature 5°C higher than the liquid-liquid crystal phase transition temperature for 5 seconds. The temperature at which the transition from liquid to liquid crystal phase (T2) occurred was measured while the temperature was cooled at a rate of 5°C / min. Furthermore, using a composition obtained by removing the interface modifier from the light-absorbing anisotropic layer formation composition P1, the temperature (T1) at which the transition from liquid to liquid crystal phase occurs was measured in the same manner, and ΔTL = T1 - T2 was calculated.

[0233] [Temperature stability evaluation in the axial direction of transmittance] A 4cm x 4cm sample was cut from the fabricated optical film containing the light-absorbing anisotropic layer P1-A. The cut sample was set in a JASCO V-670 / ARMN-735 (manufactured by JASCO Corporation) so that the direction of orthogonal projection of the transmittance center axis onto the film surface was horizontal. For this film, linearly polarized light with a wavelength of 650nm, which is parallel to the direction of orthogonal projection of the transmittance center axis onto the film surface and vibrates horizontally, was used, and the transmittance T3-A was measured in the range of θ = -70 to 70°, with θ = 0° being the normal direction of the optical film, while changing the incident direction in 0.5° increments. The incident direction was changed within the plane containing the normal of the optical film and the transmittance center axis. Similarly, the transmittance T3-B of an optical film having a light-absorbing anisotropic layer P1-B was measured. Furthermore, the transmittance T4 of a transparent support 1 with a photo-alignment layer was measured. From the above measurement results, T3-A / T4 and T3-B / T4 were calculated, and the angles at which these values ​​were maximized were defined as θA and θB, respectively. The absolute value Δθ of the difference between θA and θB was then calculated. Δθ was evaluated based on the following criteria. Δθ is considered a parameter related to the temperature stability of the tilt angle, and a smaller Δθ is preferable for controlling the tilt angle. A: Δθ is less than 7° B: Δθ is 7° or greater and less than 12° C: Δθ is 12° or greater

[0234] [Evaluation of Transmittance Contrast of Optical Films] In the same manner as the measurement of the temperature stability in the axial direction of transmittance, the maximum value Tmax and minimum value Tmin of transmittance were measured using an optical film having a light-absorbing anisotropic layer P1-A, and the transmittance ratio Tm = Tmax / Tmin was calculated. Based on the Tm value, the transmittance contrast was evaluated according to the following criteria. A:Tm is 140 or higher B:Tm is less than 140, or 50 or more. C:Tm is less than 50

[0235] [Examples 1-9 and Comparative Examples 1-2] Optical films for Examples 2-9 and Comparative Examples 1-2 were obtained in the same manner as in Example 1, except that the composition of composition P1 for forming the orientation layer and the light absorption anisotropy layer was changed to the composition shown in Table 1 below. The obtained optical films and compositions were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1. In Table 1, if the orientation layer column is "E", it indicates that no photo-orientation layer F was formed, and instead, a photo-absorbing anisotropic layer was formed on the orientation layer E of the transparent support 1 with orientation layer. In Table 1, if the orientation layer column is "G", it indicates that a photo-absorbing anisotropic layer was formed on the orientation layer G of the transparent support 2 with orientation layer described below.

[0236] [Preparation of transparent support 2] A glass substrate (Central Glass Co., Ltd., blue plate glass, size 300mm x 300mm, thickness 1.1mm) was washed with an alkaline detergent, then washed with pure water, and the glass substrate was dried. The orientation film-forming composition G described below was applied to a dried glass substrate using a #4 bar. The applied orientation film-forming composition 1 was dried at 80°C for 15 minutes, then heated at 250°C for 1 hour to form a coating film on the glass substrate. The coating film was rubbed to form an orientation layer G, and a transparent support 2 with an orientation layer was obtained. Note that SE-130, described below, is a polyimide.

[0237] ------------------------------------------------------------------ Composition of composition G for aligning film formation ------------------------------------------------------------------ • SE-130 (product name, manufactured by Nissan Chemical Corporation) 2.0 parts by mass • N-methylpyrrolidone 98.0 parts by mass ------------------------------------------------------------------

[0238] The components indicated by symbols in Table 1, excluding those already listed, are summarized below. The numbers in parentheses next to each repeating unit indicate the content (mass %) of that repeating unit relative to the total repeating units in each polymer.

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[0241] In Table 1, the "tilt angle" (the angle between the transmittance center axis of the anisotropic light absorption layer and the normal direction of the optical film surface) is shown as measured by the method described above. In Table 1, the "Total Dichroic Substance Content" column shows the total content of dichroic substances relative to the solid content of the light-absorbing anisotropic layer-forming composition.

[0242] [Table 1]

[0243] From the results in Table 1, a comparison of Examples 2 to 9 confirmed that the evaluation of Δθ was superior when ΔTL was between 0.1 and 7.0°C (more preferably between 0.1 and 3.5°C). A comparison of Examples 3 and 4 confirmed that when the composition for forming a light-absorbing anisotropic layer contains a polymeric liquid crystalline compound, the evaluation of Tm is superior. A comparison of Examples 8 and 9 confirmed that when the interface modifier is a polymer compound, the evaluation of Δθ is superior.

[0244] [Evaluation of the visual angle control system] The viewing angle control system was evaluated using the optical films of each example and comparative example according to the procedure described below. The evaluation method for the viewing angle control system using the optical film of Example 3 will be described below as a representative example.

[0245] [Formation of barrier layer B1] The barrier layer-forming composition B1 described below was applied to the light-absorbing anisotropic layer P1 prepared in Example 3 using a wire bar, and dried at 80°C for 5 minutes to form a barrier coating layer B1. Next, the barrier coating layer B1 was subjected to an illuminance of 150 mW / cm using an LED lamp (center wavelength 365 nm) in an environment with an oxygen concentration of 100 ppm and a temperature of 60°C. 2 A barrier layer B1 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 B1 was 1.0 μm.

[0246] ------------------------------------------------------------------ Composition of barrier layer forming composition B1 ------------------------------------------------------------------ • 3.80 parts by mass of the above-mentioned modified polyvinyl alcohol PVA-1 ·IRGACURE2959 0.20 parts by mass ·Water 70.00 parts by mass • Methanol 30.00 parts by mass ------------------------------------------------------------------

[0247] <Fabrication of laminate A1> 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 surface of the polarizer exposed on the polarizing plate 1 described above and the surface of the light-absorbing anisotropic layer of the light-absorbing anisotropic film prepared in Example 3 described above were corona-treated, and then laminated using the PVA adhesive 1 described below to produce laminate A1. At this time, the lamination was carried out so that the angle between the direction in which the transmittance center axis of the light-absorbing anisotropic layer is orthogonally projected onto the film surface and the absorption axis of the polarizer was 80°.

[0248] (Preparation of PVA adhesive 1) PVA adhesive 1 was obtained by dissolving 20 parts of methylolmelamine in pure water at a temperature of 30°C with 100 parts of a polyvinyl alcohol-based resin containing acetoacetyl groups (average degree of polymerization: 1200, degree of saponification: 98.5 mol, degree of acetoacetylation: 5 mol%), and adjusting the solid content concentration to 3.7% to prepare an aqueous solution.

[0249] <Fabrication of Image Display Device B1> An iPad Air (registered trademark, hereinafter the same) Wi-Fi model 16GB (manufactured by Apple), which is an IPS mode liquid crystal display device, was disassembled and the liquid crystal cell was removed. The laminate A1 prepared above was attached to the surface from which the viewing-side polarizing plate had been peeled off the liquid crystal cell, with the polarizing plate 1 side facing the liquid crystal cell side, using the adhesive sheet 1 described below. At this time, the absorption axis direction of the polarizing plate 1 was aligned with the longitudinal direction of the liquid crystal screen. After bonding to the liquid crystal cell, it was reassembled to create an image display device B1.

[0250] (Preparation of adhesive sheet 1) Acrylate polymers were prepared according to the following procedure. In a reaction vessel equipped with a condenser, a nitrogen inlet, a thermometer, and a stirring device, 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.

[0251] Next, the obtained acrylate polymer A1 (100 parts by mass), Coronate L (75% by mass ethyl acetate solution of trimethylolpropane adduct of tolylene diisocyanate, number of isocyanate groups per molecule: 3, manufactured by Nippon Polyurethane Industry Co., Ltd.) (1.0 part by mass), and silane coupling agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) (0.2 parts by mass) were mixed, and finally ethyl acetate was added to make the total solid content concentration 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 (adhesive sheet 1). The film thickness was 25 μm and the storage modulus was 0.1 MPa.

[0252] [Reflection evaluation] The image display device B1, fabricated using the above procedure, was fixed in an upright position so that the display screen was perpendicular to the ground. Furthermore, a 2mm thick glass plate was placed at an angle perpendicular to the display screen and the ground, on the opposite side from the direction in which the transmittance center axis of the light absorption anisotropy layer faces. In addition, the room was made dark, and with a sample image displayed on the display, the reflection of the image on the glass and the brightness of the image when viewed from the transmittance center axis direction were visually evaluated in the dark room. No reflection was observed on the glass, and a bright image was visible when viewed from the transmittance center axis direction.

[0253] When the optical films used in the other embodiments besides Example 3 were evaluated in the same manner as described above, no reflections on the glass were observed, and a bright image was visible when viewed from the direction of the transmittance center axis. Furthermore, when an optical film with a superior evaluation of Δθ was used, reflections were suppressed even more effectively across the entire displayed image. Additionally, when an optical film with a superior evaluation of Tm was used, a brighter image was visible. On the other hand, when the optical film used in the comparative example was evaluated using the same procedure as described above, reflections on the glass were visible. [Explanation of Symbols]

[0254] 100 LCD display device 101 Optical Film 102 Viewing-side polarizer 103 LCD cell 104 Backlight polarizer 105 Backlight 1. Barrier layer 2. Light-absorbing anisotropic layer 3. Alignment liquid crystal layer 4. Orientation layer 5 TAC Film 9. View Angle Control System 20 Light-absorbing anisotropic layer 21 Polarizer 22 Transmittance central axis direction (polar angle θ) 23 Normal to the light-absorbing anisotropic layer 24 Polarizer absorption axis

Claims

1. An optical film comprising a light-absorbing anisotropic layer formed from a liquid crystal composition containing a thermotropic liquid crystal compound, a dichroic substance, and an interface modifier, The content of the dichroic substance is 10.0% by mass or more relative to the total solid content mass of the liquid crystal composition. The angle θ between the transmittance center axis of the light-absorbing anisotropic layer and the normal direction of the optical film surface is 5° or more and less than 45°. An optical film having repeating units represented by formula (A) as the interface modifier. 【Chemistry 1】 In formula (A), R1 represents a hydrogen atom or an alkyl group. In formula (A), L1 represents a single bond or a divalent linking group. In formula (A), X represents a hydrophobic group having a fluorine atom or a silicon atom.

2. The optical film according to claim 1, wherein the content of the dichroic substance is 15.0% by mass or more with respect to the total solid content mass of the liquid crystal composition.

3. The optical film according to claim 1 or 2, wherein the mixed liquid crystal degrade temperature ΔTL, defined by the following formula (T), is 0.1 to 10.0°C. ΔTL = T1 - T2 (T) In formula (T), T1 is the liquid-liquid crystal phase transition temperature of the liquid crystal composition without the interface modifier, and T2 is the liquid-liquid crystal phase transition temperature of a mixture obtained by mixing 10.0 parts by mass of the interface modifier with 100 parts by mass of the liquid crystal composition without the interface modifier.

4. The optical film according to any one of claims 1 to 3, further comprising an orientation layer containing an azo compound, polyvinyl alcohol, or polyimide on the light-absorbing anisotropic layer.

5. The optical film according to any one of claims 1 to 4, wherein the thermotropic liquid crystalline compound comprises a repeating unit represented by the following formula (1). 【Chemistry 2】 In formula (1), PC1 represents a repeating main chain, L1 represents a single bond or a divalent linking group, SP1 represents a spacer group, MG1 represents a mesogenic group, and T1 represents a terminal group.

6. A visual angle control system comprising an optical film according to any one of claims 1 to 5 and a polarizer, The polarizer has an absorption axis in its plane, A visual angle control system in which the angle φ between the direction in which the transmittance center axis of the light absorption anisotropy layer of the optical film is orthogonally projected onto the optical film surface and the absorption axis of the polarizer is 0° or more and less than 85°, greater than 95° and less than 265°, or greater than 275° and 360° or less.

7. An image display device in which the viewing angle control system according to claim 6 is arranged on at least one main surface of the display panel.

8. The image display device according to claim 7, wherein the light-absorbing anisotropic layer is arranged on the viewing side with respect to the polarizer.

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