Light-absorption-anisotropic layer, method for manufacturing light-absorption-anisotropic layer, laminate, and image display device

Abstract

The present invention addresses the problem of providing a light-absorption-anisotropic layer in which the occurrence of haze is suppressed, and a method for manufacturing the same, and to provide a laminate and an image display device in which the light-absorption-anisotropic layer is used. This light-absorption-anisotropic layer contains a dichroic material and a liquid crystal compound, wherein the light-absorption-anisotropic layer satisfies expression (1) during measurement of an X-ray diffraction pattern thereof by an in-plane diffraction method when diffracted X-rays are measured in the measurement ranges below to determine the diffraction angle 2θmax and the rotation angle φmax at which the peak intensity is at maximum, I(φmax) being the peak intensity of diffracted X-rays at the diffraction angle 2θmax and the rotation angle φmax, and I(φmax – 10) being the peak intensity of diffracted X-rays at the diffraction angle 2θmax and a rotation angle φmax -10°.　Measurement ranges:　•Rotation angle φ in in-plane direction of light-absorption-anisotropic layer: 0-180° •Diffraction angle 2θ: 0-10° Expression (1): I(φmax) / I(φmax – 10) ≥ 1.6

Description

Optically absorptive anisotropic layer, method for producing optically absorptive anisotropic layer, laminate, and image display device

[0001] The present invention relates to an optically absorptive anisotropic layer, a method for producing an optically absorptive anisotropic layer, a laminate, and an image display device.

[0002] Conventionally, when functions such as attenuation, polarization, scattering, or light blocking of irradiated light, including laser light or natural light, were required, devices operating on different principles for each function were used. Therefore, products corresponding to the above functions were also manufactured using different manufacturing processes for each function. For example, in image display devices (e.g., liquid crystal display devices), linear or circular polarizers are used to control the optical rotation or birefringence of the display. Also, in organic light-emitting diodes (OLEDs), circular polarizers are used to prevent reflection of external light.

[0003] Although iodine has been widely used as a dichroic material in these polarizers, polarizers using an organic dye as a dichroic material instead of iodine have also been studied. For example, Patent Document 1 describes a polarizing layer (light absorption anisotropic layer) formed from a composition containing a polymerizable smectic liquid crystal compound and a dichroic dye (see claim 1).

[0004] Japanese Patent Application Laid-Open No. 2019-049758

[0005] The present inventors have studied the light absorption anisotropic layer described in Patent Document 1 and have found that haze occurs and there is room for improvement.

[0006] Therefore, an object of the present invention is to provide an optically absorptive anisotropic layer in which the generation of haze is suppressed, a method for producing the same, and a laminate and an image display device using the same.

[0007]

[0009] As a result of extensive research aimed at achieving the above object, the present inventors have found that an optically absorptive anisotropic layer in which the peak intensities of diffracted X-rays at predetermined positions (two positions) satisfy a specific relationship when an X-ray diffraction pattern is measured by an in-plane diffraction method can suppress the generation of haze, and have completed the present invention. That is, the present inventors have found that the above object can be achieved by the following configuration.

[0008] [1] An optically absorptive anisotropic layer containing a dichroic substance and a liquid crystal compound, wherein when the optically absorptive anisotropic layer is irradiated with X-rays and an X-ray diffraction pattern is measured by an in-plane diffraction method, the diffracted X-rays are measured in the following measurement region to determine the diffraction angle 2θmax and rotation angle φmax at which the peak intensity is maximum, and the peak intensity of the diffracted X-rays at the diffraction angle 2θmax and rotation angle φmax is defined as I(φmax), and the peak intensity of the diffracted X-rays at the diffraction angle 2θmax and rotation angle φmax-10° is defined as I(φmax-10), the optically absorptive anisotropic layer satisfies the relationship of the following formula (1): Measurement range: Rotation angle φ in the in-plane direction of the optically absorptive anisotropic layer: 0 to 180° Diffraction angle 2θ: 0 to 10° Formula (1): I(φmax) / I(φmax-10)≧1.6 [2] The optically absorptive anisotropic layer according to [1], wherein, when the optically absorptive anisotropic layer is fixed at a rotation angle φmax-90° and the diffraction angle 2θ is measured in a range of more than 10° to 30°, a diffracted X-ray peak is observed that exhibits a peak intensity of I(φmax)×0.2 or more. [3] The optically absorptive anisotropic layer according to [1] or [2], wherein the optically absorptive anisotropic layer is formed using a liquid crystal composition containing a dichroic substance, a liquid crystal compound, and a monofunctional compound, and wherein the molecular length D1 (Å) of the liquid crystal compound in the major axis direction and the molecular length D2 (Å) of the monofunctional compound in the major axis direction satisfy the relationship of the following formula (2): Formula (2): 0.2×D1≦D2≦0.45×D1 [4] The optically absorptive anisotropic layer according to any one of [1] to [3], wherein the dichroic substance comprises at least two dichroic substances having a maximum absorption wavelength in the wavelength range of 550 to 700 nm. [5] A method for producing the optically absorptive anisotropic layer according to any one of [1] to [4], comprising a step of irradiating a liquid crystal composition layer containing a dichroic substance, a liquid crystal compound, and a monofunctional compound with ultraviolet light in air to form an optically absorptive anisotropic layer. [6] The method for producing the optically absorptive anisotropic layer according to [5], comprising a step of irradiating the optically anisotropic layer after the optically absorptive anisotropic layer formation step with ultraviolet light in nitrogen. [7] A laminate comprising the optically absorptive anisotropic layer according to any one of [1] to [4], and a λ / 4 plate provided on the optically absorptive anisotropic layer.[8] An image display device comprising the optically absorptive anisotropic layer according to any one of [1] to [4] or the laminate according to claim 7.

[0009] According to the present invention, it is possible to provide an optically absorptive anisotropic layer in which the generation of haze is suppressed, a method for producing the same, and a laminate and an image display device using the same.

[0010] FIG. 1 is a schematic conceptual diagram for explaining a measurement region when measuring an X-ray diffraction pattern of an optically absorptive anisotropic layer by in-plane diffraction.

[0011] The present invention will be described in detail below. The following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In this specification, each component may be a single substance corresponding to the component, or two or more substances may be used in combination. Here, when two or more substances are used in combination for each component, the content of the component refers to the total content of the substances used in combination, unless otherwise specified.

[0012] [Lightly Absorbing Anisotropic Layer] The lightly absorptive anisotropic layer of the present invention is a lightly absorptive anisotropic layer containing a dichroic substance and a liquid crystal compound. Furthermore, when irradiating the light with X-rays and measuring the X-ray diffraction pattern by in-plane diffraction, the lightly absorptive anisotropic layer of the present invention first measures the diffracted X-rays in the measurement region described below to determine the diffraction angle 2θmax and rotation angle φmax at which the peak intensity is maximum. Next, when the peak intensity of the diffracted X-rays at the diffraction angle 2θmax and rotation angle φmax is defined as I(φmax), and the peak intensity of the diffracted X-rays at the diffraction angle 2θmax and rotation angle φmax-10° is defined as I(φmax-10), the relationship of the following formula (1) is satisfied. The peak at which the peak intensity is maximum is also abbreviated as "peak P1." Measurement range: Rotation angle φ in the in-plane direction of the light absorption anisotropic layer: 0 to 180° Diffraction angle 2θ: 0 to 10° Formula (1): I(φmax) / I(φmax−10)≧1.6

[0013] Fig. 1 is a schematic conceptual diagram illustrating a measurement region when measuring the X-ray diffraction pattern of an optically absorptive anisotropic layer by in-plane diffraction. As shown in Fig. 1, in measuring the X-ray diffraction pattern by in-plane diffraction, incident X-rays 4 are incident at an incident angle substantially parallel to the surface of the optically absorptive anisotropic layer 1 (more than 0° and less than 1°), and the diffraction angle 2θ of diffracted X-rays 6 (the angle between reflected X-rays 5 and the diffracted X-rays) is measured with a detector to evaluate the regularity of the alignment structure (diffraction plane 2) of liquid crystal compound 2.

[0014] In the present invention, the value of the peak intensity measured under the following conditions is used in the measurement of the diffracted X-rays in the measurement region described above. In the measurement of the diffracted X-rays in the measurement region described above, the measurement range of the diffraction angle 2θ (0 to 10°) may be measured at intervals of 0.008° with the rotation angle φ in the in-plane direction of the optically absorptive anisotropic layer fixed at any angle between 0 and 180°, or the measurement range of the diffraction angle 2θ (0 to 180°) may be measured at intervals of 1° with the measurement range of the diffraction angle 2θ fixed at any angle between 0 and 10°. <Measurement Conditions> Incident X-ray source: CuKα ray Reference (0°) position of the rotation angle φ: position of the optically anisotropic layer when the X-rays are first incident Reference (180°) position of the rotation angle φ: position obtained by rotating the optically absorptive anisotropic layer 180° clockwise from the 0° position Measurement interval of the rotation angle φ: 1° Measurement interval of the diffraction angle 2θ: 0.008°

[0015] As described above, the optically absorptive anisotropic layer of the present invention satisfies the above formula (1) when its X-ray diffraction pattern is measured by in-plane diffraction, thereby suppressing the generation of haze. The reason for this effect is not clear in detail, but the inventors speculate as follows. First, in measuring the X-ray diffraction pattern by in-plane diffraction, as described above, the optically absorptive anisotropic layer is rotated to a predetermined position in the in-plane direction, and the diffraction angle 2θ of the diffracted X-rays is measured with a detector to evaluate the regularity of the structure. Therefore, depending on the rotation position of the optically absorptive anisotropic layer, it is not possible to correctly evaluate the presence of an ordered structure that does not diffract incident X-rays (i.e., disordered alignment of the liquid crystal compound). The inventors speculate that this disordered alignment of the liquid crystal compound is the cause of the generation of haze in the optically absorptive anisotropic layer. In contrast, in the present invention, I(φmax-10) is also measured at a position shifted by 10° in rotation angle from the rotation angle and diffraction angle showing the maximum intensity I(φmax), and it is considered that the generation of haze in the optically absorptive anisotropic layer is suppressed because I(φmax) and I(φmax-10) satisfy the above formula (1), i.e., I(φmax-10) derived from the ordered structure caused by disordered alignment of the liquid crystal compound is small to a certain extent.

[0016] In the present invention, for the reason that the occurrence of haze is further suppressed, it is preferable that when the optically absorptive anisotropic layer is fixed at a position of a rotation angle φmax-90° (i.e., a position rotated 90° counterclockwise from the position of the rotation angle φmax) and the diffraction angle 2θ is measured in the range of more than 10° and not more than 30°, a diffracted X-ray peak (hereinafter also abbreviated as "peak P2") exhibiting a peak intensity of I(φmax)×0.2 or more is observed. In the measurement of the diffracted X-ray of peak P2, the value of the peak intensity measured under the following conditions is adopted. <Measurement conditions> Incident X-ray source: CuKα radiation Measurement interval of diffraction angle 2θ: 0.008°

[0017] As described above, the optically absorptive anisotropic layer of the present invention is an optically absorptive anisotropic layer containing a dichroic substance and a liquid crystal compound, and is preferably a layer in which the alignment states of the liquid crystal compound and the dichroic substance are fixed. The dichroic substance, the liquid crystal compound, and any optional components contained in the optically absorptive anisotropic layer of the present invention will be described below.

[0018] <Dichroic Material> In the present invention, the dichroic material refers to a dye whose absorbance varies depending on the direction. The dichroic material may or may not exhibit liquid crystallinity.

[0019] The dichroic substance is not particularly limited, and examples thereof include visible light absorbing substances (dichroic dyes), luminescent substances (fluorescent substances, phosphorescent substances), ultraviolet absorbing substances, infrared absorbing substances, nonlinear optical substances, carbon nanotubes, and inorganic substances (e.g., quantum rods), and any conventionally known dichroic substance (dichroic dye) can be used. Specifically, for example, paragraphs

[0067] to

[0071] of JP 2013-228706 A, paragraphs

[0008] to

[0026] of JP 2013-227532 A, paragraphs

[0008] to

[0015] of JP 2013-209367 A, paragraphs

[0045] to

[0058] of JP 2013-14883 A, paragraphs

[0012] to

[0029] of JP 2013-109090 A, paragraphs

[0009] to

[0017] of JP 2013-101328 A, Paragraphs

[0051] to

[0065] of JP 2013-37353 A, paragraphs

[0049] to

[0073] of JP 2012-63387 A, paragraphs

[0016] to

[0018] of JP 11-305036 A, paragraphs

[0009] to

[0011] of JP 2001-133630 A, paragraphs

[0030] to

[0169] of JP 2011-215337 A, paragraphs

[0021] to

[0075] of JP 2010-106242 A, paragraphs

[0016] to

[0018] of JP 2010-215846 A

[0011] to

[0025] paragraphs,

[0017] to

[0069] paragraphs of JP 2011-048311 A,

[0013] to

[0133] paragraphs of JP 2011-213610 A,

[0074] to

[0246] paragraphs of JP 2011-237513 A,

[0005] to

[0051] paragraphs of JP 2016-006502 A,

[0014] to

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

[0014] to

[0033] paragraphs of JP 2020-11716 A paragraphs

[0005] to

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

[0008] to

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

[0014] to

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

[0014] to

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

[0013] to

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

[0014] to

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

[0021] to

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

[0043] to

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

[0043] to

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

[0050] to

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

[0015] to

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

[0020] As the dichroic substance, a dichroic azo dye compound is preferred. A dichroic azo dye compound refers to an azo dye compound whose absorbance varies depending on the direction. A dichroic azo dye compound may or may not exhibit liquid crystallinity. When a dichroic azo dye compound exhibits liquid crystallinity, it may exhibit either nematic or smectic properties. The temperature range in which the liquid crystal phase is exhibited is preferably room temperature (approximately 20 to 28°C) to 300°C, and more preferably 50 to 200°C from the viewpoints of handleability and manufacturing suitability.

[0021] In the present invention, it is preferable to use at least two kinds of dichroic substances having maximum absorption wavelengths in the wavelength range of 550 to 700 nm, because this can suppress precipitation of the dichroic substances when the composition for forming an optically absorptive anisotropic layer described below is aged.

[0022] The upper limit of the content of the dichroic material contained in the optically absorptive anisotropic layer is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on the total mass of the optically absorptive anisotropic layer. The lower limit is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more. The content of the dichroic material contained in the optically absorptive anisotropic layer is preferably 20 to 400 mg / cm because the degree of orientation of the optically absorptive anisotropic layer formed is high. ３ is preferably 30 to 200 mg / cm ３ More preferably, it is 40 to 150 mg / cm ３ When a plurality of dichroic substances are used in combination, the total amount of the dichroic substances is preferably in the above-mentioned range. ３The dichroic substance content can be obtained by measuring a solution in which a laminate having an optically absorbing anisotropic layer is dissolved or an extract obtained by immersing an optical laminate in a solvent using high-performance liquid chromatography (HPLC), but is not limited to the above methods. Quantification can be performed using the dichroic substance contained in the optically absorbing anisotropic layer as a standard sample. One example of a method for calculating the content of the dichroic substance is to calculate the volume by multiplying the thickness of the optically absorbing anisotropic layer obtained from a microscopic image of the cross section of the laminate by the area of ​​the laminate used to measure the dye amount, and then dividing the volume by the amount of dye measured by HPLC to calculate the dye content.

[0023] <Liquid Crystal Compound> The liquid crystal compound contained in the light absorption anisotropic layer can be either a polymer liquid crystal compound or a low molecular weight liquid crystal compound. Here, "polymer liquid crystal compound" refers to a liquid crystal compound having a repeating unit in its chemical structure. Furthermore, "low molecular weight liquid crystal compound" refers to a liquid crystal compound having no repeating unit in its chemical structure. Examples of polymer liquid crystal compounds include the thermotropic liquid crystal polymers described in JP 2011-237513 A and the polymer liquid crystal compounds described in paragraphs

[0012] to

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

[0072] to

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

[0019] to

[0140] of WO 2022 / 014340, the disclosures of which are incorporated herein by reference.

[0024] In the present invention, the liquid crystal compound contained in the light absorption anisotropic layer is preferably a liquid crystal compound exhibiting a smectic liquid crystal state (hereinafter also abbreviated as "smectic liquid crystal compound").

[0025] Examples of the smectic phase include a smectic A phase and a smectic C phase, but may also be a higher order smectic phase (e.g., a smectic B phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase, a smectic L phase, etc.). In addition to the smectic phase, a nematic phase may also be exhibited.

[0026] In addition, in the present invention, it is preferable that the liquid crystal compound is a liquid crystal compound that exhibits any one of the liquid crystal states of smectic B phase, E phase, F phase, G phase, H phase, I phase, J phase, K phase and L phase, because this improves the degree of orientation of the light absorption anisotropic layer.

[0027] As the smectic liquid crystal compound, a compound represented by the following formula (I) or (II) is preferred, and it is more preferred to use compounds represented by the following formulas (I) and (II) in combination: Formula (I) Q1-V1-SP1-X1-(Ma-La)na-X2-SP2-V2-Q2 Formula (II) Q1-V1-SP1-X1-(Ma-La)na-Q3

[0028] In the above formulas (I) and (II), Q1 and Q2 each independently represent a polymerizable group, and Q3 represents a hydrogen atom or a substituent. Furthermore, V1, V2, X1, and X2 each independently represent a single bond or a divalent linking group. Furthermore, SP1 and SP2 each independently represent a divalent spacer group. Furthermore, na represents an integer of 2 to 10. Furthermore, Ma represents an aromatic ring, an aliphatic ring, or a heterocycle which may have a substituent. However, multiple Ma may be the same or different. Furthermore, La represents a single bond or a divalent linking group. However, multiple La may be the same or different.

[0029] The polymerizable group represented by one embodiment of Q1 and Q2 is preferably a radically polymerizable group (radical polymerizable group) or a cationically polymerizable group (cationically polymerizable group). As the radically polymerizable group, known radically polymerizable groups can be used, and preferred examples include an acryloyloxy group or a methacryloyloxy group. In this case, the polymerization rate of an acryloyloxy group is generally known to be fast, and from the viewpoint of improving productivity, an acryloyloxy group is preferred, but a methacryloyloxy group can also be used as the polymerizable group. As the cationically polymerizable group, known cationically polymerizable groups can be used, and specific examples include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and a vinyloxy group. Among these, an alicyclic ether group or a vinyloxy group is preferred, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferred. Particularly preferred examples of the polymerizable group include polymerizable groups represented by any of the following formulas (P-1) to (P-20):

[0030]

[0031] In the above formulas (I) and (II), examples of the divalent linking group represented by one embodiment of V1, V2, X1, X2, and La include —O—, —(CH ２ ) ｇ -, - (CF ２ ) ｇ -, -Si(CH ３ ) ２ -, -(Si(CH ３ ) ２ O) ｇ -, -(OSi(CH ３ ) ２ ) ｇ - (wherein 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 Examples of such divalent linking groups include -N=C(Z')- (Z, Z', and Z" each independently represent a hydrogen atom, 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-, -S(O)-, -S(O)(O)-, -(O)S(O)O-, -O(O)S(O)O-, -SC(O)-, and -C(O)S-. V1, V2, X1, X2, and La may be a group formed by combining two or more of these groups. Among these divalent linking groups, -CO-, -O-, -S-, -C(=S)-, -C(Z)(Z')-, -C(Z)=C(Z')-, -N(Z)-, or a divalent linking group formed by a combination of two or more of these is preferred.

[0032] In the above formulas (I) and (II), examples of the divalent spacer group represented by SP1 and SP2 include a linear, branched, or cyclic alkylene group having 1 to 50 carbon atoms, or a heterocyclic group having 1 to 20 carbon atoms. The carbon atoms of the alkylene group and the heterocyclic group may be bonded to each other by -O-, -Si(CH ３ ) ２ -, -(Si(CH ３ ) ２ O) ｇ -, -(OSi(CH ３ ) ２ ) ｇ - (wherein 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-, -OC(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 a hydrogen atom, 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)-, -SO ２ The hydrogen atoms of the alkylene groups and the heterocyclic groups 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 , wherein Z Ｈ , Z Ｈ' and Z" each independently represent an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or -L-Q (L represents a single bond or a divalent linking group. Specific examples of the divalent linking group are the same as those of V1 described above. Q represents a crosslinkable group, and examples thereof include the polymerizable groups that are preferred embodiments of Q1 or Q2 described above, with the polymerizable groups represented by formulas (P-1) to (P-20) described above being preferred). The divalent spacer group represented by SP1 and SP2 is preferably a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, or -CH ２ It is preferred that one or more of the -'s be substituted with -O-, -S-, -NH-, -N(Z)-, or -CO- to form a divalent linking group.

[0033] In the above formulas (I) and (II), Ma represents an aromatic ring, an aliphatic ring, or a heterocycle, which may have a substituent, and is preferably a 4- to 15-membered ring. Ma may be a monocycle or a condensed ring, and multiple Ma may be the same or different. Examples of the aromatic ring represented by Ma include a phenylene group, a naphthylene group, a fluorene-diyl group, an anthracene-diyl group, and a tetracene-diyl group, and from the viewpoints of the diversity of mesogen skeleton designs and the availability of raw materials, a phenylene group or a naphthylene group is preferred. Examples of the aliphatic ring represented by Ma include a cyclopentylene group and a cyclohexylene group, and the carbon atom is selected from the group consisting of -O-, -Si(CH ３ ) ２ -, -N(Z)- (Z represents a hydrogen atom, 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 -SO ２-, or a group consisting of a combination of two or more of these groups. Atoms other than carbon that constitute the heterocycle represented by Ma include a nitrogen atom, a sulfur atom, and an oxygen atom. When the heterocycle has multiple atoms other than carbon that constitute the ring, these atoms may be the same or different. Specific examples of the heterocycle include a pyridylene group (pyridine-diyl group), a pyridazine-diyl group, an imidazole-diyl group, a thienylene (thiophene-diyl group), a quinolylene group (quinoline-diyl group), an isoquinolylene group (isoquinoline-diyl group), an oxazole-diyl group, a thiazole-diyl group, an oxadiazole-diyl group, a benzothiazole-diyl group, a benzothiadiazole-diyl group, a phthalimido-diyl group, a thienothiazole-diyl group, a thiazolothiazole-diyl group, a thienothiophene-diyl group, and a thienoxazole-diyl group, as well as the following structures (II-1) to (II-4).

[0034]

[0035] In formulas (II-1) to (II-4), D １ is —S—, —O—, or NR １１ represents -, and R １１ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. １ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms. １ , Z ２ and Z ３ each independently represents a hydrogen atom, 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 where Z １ and Z ２ may be bonded to each other to form an aromatic ring or an aromatic heterocycle, R １２ and R １３ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. １ and A ２are each independently —O—, —NR ２１ - (R ２１ represents a hydrogen atom or a substituent. ), -S-, and -CO- represent a group selected from the group consisting of. E represents a hydrogen atom or a non-metallic atom of Groups 14 to 16 which may have a substituent bonded thereto. Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles, Ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles, the aromatic rings of Ax and Ay may have a substituent, and Ax and Ay may be bonded to form a ring. D ２ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

[0036] In formula (II-2), Y １ When Y is an aromatic hydrocarbon group having 6 to 12 carbon atoms, it may be monocyclic or polycyclic. １ When A is an aromatic heterocyclic group having 3 to 12 carbon atoms, it may be a monocyclic or polycyclic ring. １ and A ２ But, -NR ２１ When - represents R ２１ For the substituent, see, for example, paragraphs

[0035] to

[0045] of JP-A-2008-107767, the contents of which are incorporated herein by reference. In formula (II-2), when X is a non-metallic atom of Groups 14 to 16 which may have a substituent bonded thereto, ═O, ═S, ═NR', or ═C(R')R' is preferred. R' represents a substituent, and for the substituent, see, for example, paragraphs

[0035] to

[0045] of JP-A-2008-107767, with a nitrogen atom being preferred.

[0037] Regarding MA in the above formulas (I) and (II), examples of the substituent that the aromatic ring, aliphatic ring, or heterocycle may have include, for example, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl 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 (also referred to as a heterocyclic group), a cyano group, a hydroxy group, a nitro group, a carboxy 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 an anilino group), Ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imido group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (-B(OH) ２ ), phosphato group (—OPO(OH) ２ ), sulfato group (—OSO ３ H), and other known substituents. Details of the substituents are described in paragraph

[0023] of JP-A-2007-234651.

[0038] In the above formulas (I) and (II), na represents an integer of 2 to 10, preferably an integer of 2 to 8, and more preferably an integer of 2 to 5.

[0039] In the above formula (II), examples of the substituent represented by one embodiment of Q3 include the same substituents as those which the aromatic ring, aliphatic ring, or heterocycle may have, as explained in relation to Ma in the above formula (I). Among these, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms is preferable.

[0040] Examples of smectic liquid crystal compounds include those described in paragraphs

[0033] to

[0039] of JP-A No. 2008-19240, paragraphs

[0037] to

[0041] of JP-A No. 2008-214269, and paragraphs

[0033] to

[0040] of JP-A No. 2006-215437, the descriptions of which are incorporated herein by reference.

[0041] In the present invention, the content of the liquid crystal compound is preferably from 50 to 99% by mass, more preferably from 75 to 95% by mass, based on the total mass of the light absorption anisotropic layer.

[0042] <Liquid Crystal Composition> The optically absorptive anisotropic layer of the present invention is preferably formed using a liquid crystal composition containing the above-described dichroic substance and liquid crystal compound (hereinafter also abbreviated as "optically absorptive anisotropic layer-forming composition").

[0043] (Monofunctional Compound) The composition for forming an optically absorptive anisotropic layer preferably contains a monofunctional compound that satisfies the relationship of the following formula (2) in relation to the above-mentioned liquid crystal compound, for the reason that the generation of haze is further suppressed. That is, it is preferable that the molecular length D1 (Å) in the long axis direction of the above-mentioned liquid crystal compound and the molecular length D2 (Å) in the long axis direction of the monofunctional compound satisfy the relationship of the following formula (2). By satisfying the following formula (2), free volume is created between the molecules of the liquid crystal compound, and the presence of this free volume can suppress alignment disturbance that may occur when the composition for forming an optically absorptive anisotropic layer is cured, and as a result, it is thought that the generation of haze can be further suppressed. Formula (2): 0.2×D1≦D2≦0.45×D1

[0044] Here, the molecular length D1 (Å) in the long axis direction of the liquid crystal compound and the molecular length D2 (Å) in the long axis direction of the monofunctional compound refer to values ​​calculated by the following procedure: (1) Identify the structure of the compound to be calculated (target compound). (2) Save the ChemDraw file containing the chemical formula of the target compound in "MDLMolfile format." (3) Open the saved MDLMolfile format file in a molecular modeling application (e.g., Winmostar) and optimize the structure using a simple molecular force field method. (4) Calculate the interatomic distance at both ends of the target compound after structural optimization as the molecular length.

[0045] Such a monofunctional compound is preferably a non-liquid crystal compound, more preferably a compound having a polymerizable group, and even more preferably a compound having a polymerizable group and a molecular weight of not more than 500. Here, examples of the polymerizable group include those similar to those described for Q1 in formula (I) above, and particularly preferred are polymerizable groups represented by any of formulas (P-1) to (P-20) above.

[0046] (Solvent) From the viewpoint of workability, the composition for forming the optically absorptive anisotropic layer preferably contains a solvent. Examples of the solvent include organic solvents such as ketones, ethers, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated carbons, esters, alcohols, cellosolves, cellosolve acetates, sulfoxides, amides, and heterocyclic compounds, as well as water. These solvents may be used alone or in combination of two or more. Among these solvents, organic solvents are preferred, and halogenated carbons or ketones are more preferred.

[0047] When the composition for forming an optically absorptive anisotropic layer contains a solvent, the content of the solvent is preferably 80 to 99 mass %, more preferably 83 to 97 mass %, and even more preferably 85 to 95 mass %, based on the total mass of the composition for forming an optically absorptive anisotropic layer.

[0048] (Polymerization Initiator) The composition for forming an optically absorptive anisotropic layer may contain a polymerization initiator. The polymerization initiator is not particularly limited, but is preferably a photosensitive compound, i.e., a photopolymerization initiator. Commercially available photopolymerization initiators such as Irgacure 184, Irgacure 907, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure OXE-01, and Irgacure OXE-02, manufactured by BASF, can also be used. The polymerization initiators may be used alone or in combination of two or more. When the composition for forming an optically absorptive anisotropic layer contains a polymerization initiator, the content of the polymerization initiator is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the composition for forming an optically absorptive anisotropic layer.

[0049] [Method for manufacturing optically absorbing anisotropic layer] The method for manufacturing an optically absorbing anisotropic layer of the present invention is a method for manufacturing an optically absorbing anisotropic layer for manufacturing the optically absorbing anisotropic layer of the present invention described above, and includes an optically absorbing anisotropic layer-forming step of irradiating a liquid crystal composition layer containing a dichroic substance, a liquid crystal compound, and a monofunctional compound with ultraviolet (UV) rays in air to form an optically absorbing anisotropic layer.

[0050] Here, the "liquid crystal composition layer containing a dichroic material, a liquid crystal compound, and a monofunctional compound" is not particularly limited as long as it is a liquid crystal composition layer formed using a liquid crystal composition (composition for forming an optically absorptive anisotropic layer) containing the above-mentioned dichroic material, liquid crystal compound, and monofunctional compound, and examples thereof include a coating film formed by applying the above-mentioned composition for forming an optically absorptive anisotropic layer onto an alignment film described below. Examples of methods for applying the composition for forming an optically absorptive anisotropic layer include known methods such as roll coating, gravure printing, spin coating, wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spraying, and inkjet printing.

[0051] The alignment film may be any film that aligns the liquid crystal component contained in the composition for forming the optically absorptive anisotropic layer. It can be formed by methods such as rubbing an organic compound (preferably a polymer) onto the film surface, oblique vapor deposition of an inorganic compound, formation of a layer with microgrooves, or deposition of an organic compound (e.g., ω-tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearate) using the Langmuir-Blodgett method (LB film). Furthermore, alignment films that exhibit alignment function upon application of an electric field, a magnetic field, or light irradiation are also known. Among these, in the present invention, alignment films formed by rubbing are preferred in terms of ease of control of the pretilt angle of the alignment film, and photo-alignment films formed by light irradiation are also preferred in terms of uniformity of alignment.

[0052] Photo-alignment compounds used in photo-alignment films are described in many documents, etc. In the present invention, for example, azo compounds described in JP-A Nos. 2006-285197, 2007-76839, 2007-138138, 2007-94071, 2007-121721, 2007-140465, 2007-156439, 2007-133184, 2009-109831, Japanese Patent Nos. 3883848 and 4151746, and azo compounds described in JP-A No. 2002-229039 are used. Preferred examples include the aromatic ester compounds described in JP-A Nos. 2002-265541 and 2002-317013, maleimide and / or alkenyl-substituted nadimide compounds having a photoalignment unit, photocrosslinkable silane derivatives described in Japanese Patent Nos. 4205195 and 4205198, and photocrosslinkable polyimides, polyamides, or esters described in Japanese Patent Publication Nos. 2003-520878, 2004-529220, or Japanese Patent No. 4162850. Azo compounds, photocrosslinkable polyimides, polyamides, or esters are more preferred.

[0053] Among these, it is preferable to use a photosensitive compound having a photoreactive group that undergoes at least one of dimerization and isomerization under the action of light as the photoalignment compound. Examples of the photoreactive group include a group having a cinnamic acid (cinnamoyl) structure (skeleton), a group having a coumarin structure (skeleton), a group having a chalcone structure (skeleton), a group having a benzophenone structure (skeleton), and a group having an anthracene structure (skeleton). Among these groups, a group having a cinnamoyl structure and a group having a coumarin structure are preferred, and a group having a cinnamoyl structure is more preferred.

[0054] The photosensitive compound having the photoalignable group may further have a crosslinkable group. The crosslinkable group is preferably a thermally crosslinkable group that undergoes a curing reaction under the action of heat, or a photocrosslinkable group that undergoes a curing reaction under the action of light, and may be a crosslinkable group having both a thermally crosslinkable group and a photocrosslinkable group. Examples of the crosslinkable group include an epoxy group, an oxetanyl group, -NH-CH ２ Examples of the group include at least one selected from the group consisting of a group represented by -O-R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a group having an ethylenically unsaturated double bond, and a blocked isocyanate group. Among these, an epoxy group, an oxetanyl group, and a group having an ethylenically unsaturated double bond are preferred. A three-membered cyclic ether group is also called an epoxy group, and a four-membered cyclic ether group is also called an oxetanyl group. Specific examples of the group having an ethylenically unsaturated double bond include a vinyl group, an allyl group, a styryl group, an acryloyl group, and a methacryloyl group, with an acryloyl group or a methacryloyl group being preferred.

[0055] A photo-alignment film formed from the above materials is irradiated with linearly polarized or non-polarized light to produce a photo-alignment film. In this specification, "linearly polarized light irradiation" and "non-polarized light irradiation" refer to operations for causing a photoreaction in the photo-alignment material. The wavelength of the light used varies depending on the photo-alignment material used, and is not particularly limited as long as it is the wavelength necessary for the photoreaction. The peak wavelength of the light used for photoirradiation is preferably 200 nm to 700 nm, and ultraviolet light with a peak wavelength of 400 nm or less is more preferred.

[0056] Examples of light sources used for light irradiation include commonly used light sources, such as lamps such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, and carbon arc lamps, various lasers [e.g., semiconductor lasers, helium-neon lasers, argon ion lasers, helium-cadmium lasers, and YAG (yttrium aluminum garnet) lasers], light-emitting diodes, and cathode ray tubes.

[0057] As a means for obtaining linearly polarized light, a method using a polarizing plate (e.g., an iodine polarizing plate, a dichroic dye polarizing plate, and a wire grid polarizing plate), a method using a prism element (e.g., a Glan-Thompson prism) or a reflective polarizer utilizing the Brewster angle, or a method using light emitted from a polarized laser light source can be employed. Alternatively, a filter or a wavelength conversion element may be used to selectively irradiate only light of a required wavelength.

[0058] In the case of linearly polarized light, the light is irradiated from the top or back surface of the alignment film perpendicularly or obliquely to the surface of the alignment film. The incident angle of the light varies depending on the photo-alignment material, but is preferably 0 to 90° (perpendicular), and more preferably 40 to 90°. In the case of non-polarized light, the alignment film is irradiated with non-polarized light obliquely. The incident angle is preferably 10 to 80°, more preferably 20 to 60°, and even more preferably 30 to 50°. The irradiation time is preferably 1 to 60 minutes, and more preferably 1 to 10 minutes.

[0059] When patterning is required, a method of irradiating light using a photomask the number of times required to form a pattern, or a method of writing a pattern by laser light scanning can be used.

[0060] The method for producing an optically absorbing anisotropic layer according to the present invention is characterized by the inclusion of an optically absorbing anisotropic layer-forming step in which the liquid crystal composition layer described above is irradiated with ultraviolet light in air to form an optically absorbing anisotropic layer. By curing the layer with ultraviolet light in air, a hardened film can be formed while alleviating curing distortion, which is believed to suppress alignment disturbances that may occur during curing and, as a result, to suppress the occurrence of haze. The method for ultraviolet light irradiation is not particularly limited, as long as it is carried out in air containing oxygen, and methods similar to conventionally known ultraviolet light irradiation (exposure) methods can be used.

[0061] The method for producing an optically absorptive anisotropic layer of the present invention preferably includes a step of irradiating the optically absorptive anisotropic layer after the above-mentioned optically absorptive anisotropic layer formation step with ultraviolet light under nitrogen, because this improves the durability of the optically absorptive anisotropic layer.

[0062] In the method for producing an optically absorptive anisotropic layer of the present invention, it is preferable that the optically absorptive anisotropic layer formation step includes a step of aligning the liquid crystal component contained in the liquid crystal composition layer (hereinafter also referred to as the "alignment step") before irradiating the liquid crystal composition layer with ultraviolet light in air.

[0063] The alignment step is a step of orienting the liquid crystal components (especially the dichroic material) contained in the liquid crystal composition layer. In the alignment step, it is considered that the dichroic material is oriented along the liquid crystal compound oriented by the alignment film. The alignment step may include a drying treatment. The drying treatment can remove components such as the solvent from the coating film. The drying treatment may be performed by leaving the coating film at room temperature for a predetermined time (for example, natural drying), or by heating and / or blowing air.

[0064] The orientation step preferably includes a heat treatment. This further aligns the dichroic material contained in the coating film, thereby increasing the degree of orientation of the dichroic material. From the viewpoint of manufacturability, the heat treatment is preferably performed at a temperature of 10 to 250°C, more preferably 25 to 190°C. The heating time is preferably 1 to 300 seconds, more preferably 1 to 60 seconds.

[0065] The orientation step may include a cooling treatment carried out after the heating treatment. The cooling treatment is a treatment in which the coated film after heating is cooled to about room temperature (20 to 25°C). This further fixes the orientation of the dichroic material contained in the coated film, thereby increasing the degree of orientation of the dichroic material. The cooling method is not particularly limited and can be carried out by a known method.

[0066] [Laminate] The laminate of the present invention is a laminate having the optically absorbing anisotropic layer of the present invention described above and a λ / 4 plate provided on the optically absorbing anisotropic layer. The laminate of the present invention preferably has a substrate, and more preferably has a substrate, an optically absorbing anisotropic layer, and a λ / 4 plate in this order. The laminate of the present invention preferably has a barrier layer, and more preferably has an optically absorbing anisotropic layer, a barrier layer, and a λ / 4 plate in this order. The laminate of the present invention may also have an alignment film between the substrate and the optically anisotropic layer. Each layer constituting the laminate of the present invention will be described below.

[0067] [Substrate] The substrate can be selected depending on the application of the optically anisotropic layer, and examples include glass and polymer films. The light transmittance of the substrate is preferably 80% or more. When a polymer film is used as the substrate, it is preferable to use an optically isotropic polymer film. Specific examples and preferred embodiments of the polymer are described in paragraph

[0013] of JP-A No. 2002-22942. Furthermore, even if a conventionally known polymer is prone to exhibiting birefringence, such as polycarbonate or polysulfone, it is also possible to use a polymer whose exhibitability has been reduced by molecular modification as described in WO 2000 / 26705.

[0068] [Optically Anisotropic Layer] The optically anisotropic layer is as described above, and therefore the description thereof will be omitted.

[0069] [λ / 4 Plate] A "λ / 4 plate" is a plate having a λ / 4 function, specifically a plate having the function of converting linearly polarized light of a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light). For example, specific examples of a λ / 4 plate having a single-layer structure include a stretched polymer film and a retardation film having an optically anisotropic layer having a λ / 4 function on a support, and specific examples of a λ / 4 plate having a multi-layer structure include a broadband λ / 4 plate formed by laminating a λ / 4 plate and a λ / 2 plate. The λ / 4 plate and the optically anisotropic layer may be provided in contact with each other, or another layer may be provided between the λ / 4 plate and the optically anisotropic layer. Examples of such layers include an adhesive layer or bonding layer for ensuring adhesion, and a barrier layer.

[0070] [Barrier Layer] When the laminate of the present invention has a barrier layer, the barrier layer is preferably provided between the optically anisotropic layer and the λ / 4 plate. When a layer other than the barrier layer (for example, an adhesive layer or a bonding layer) is provided between the optically anisotropic layer and the λ / 4 plate, the barrier layer can be provided, for example, between the optically anisotropic layer and the other layer. The barrier layer is also called a gas barrier layer (oxygen barrier layer), and has the function of protecting the optically anisotropic layer from gases such as oxygen in the atmosphere, moisture, or compounds contained in adjacent layers. For the barrier layer, reference can be made to the descriptions in paragraphs

[0014] to

[0054] of JP 2014-159124 A, paragraphs

[0042] to

[0075] of JP 2017-121721 A, paragraphs

[0045] to

[0054] of JP 2017-115076 A, paragraphs

[0010] to

[0061] of JP 2012-213938 A, and paragraphs

[0021] to

[0031] of JP 2005-169994 A.

[0071] [Alignment Film] The laminate of the present invention may have an alignment film between the substrate and the optically anisotropic layer. Examples of the alignment film include the same films as those described in the method for producing the light-absorption anisotropic layer of the present invention.

[0072] [Image display device] The image display device of the present invention has the optically anisotropic layer of the present invention described above or the laminate of the present invention described above. The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as "EL") display panel, and a plasma display panel. Among these, a liquid crystal cell or an organic EL display panel is preferred, and a liquid crystal cell is more 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, and more preferably a liquid crystal display device.

[0073] [Liquid Crystal Display Device] A preferred example of a liquid crystal display device, which is an example of the image display device of the present invention, is an embodiment having the above-described optically anisotropic layer and a liquid crystal cell. More preferably, the liquid crystal display device has the above-described laminate (excluding a λ / 4 plate) and a liquid crystal cell. In the present invention, of the optically anisotropic layers (laminates) provided on both sides of the liquid crystal cell, it is preferable to use the optically anisotropic layer (laminate) of the present invention as the front-side polarizing element, and it is more preferable to use the optically anisotropic layer (laminate) of the present invention as the front-side and rear-side polarizing elements. The liquid crystal cell constituting the liquid crystal display device will be described in detail below.

[0074] <Liquid Crystal Cell> The liquid crystal cell used in the liquid crystal display device is preferably, but not limited to, a VA (Vertical Alignment) mode, an OCB (Opticaly Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode. In a TN mode liquid crystal cell, when no voltage is applied, rod-shaped liquid crystal molecules are aligned substantially horizontally and further twisted at an angle of 60 to 120°. TN mode liquid crystal cells are most commonly used as color TFT (Thin Film Transistor) liquid crystal displays, and are described in numerous literature. In a VA mode liquid crystal cell, rod-shaped liquid crystal molecules are aligned substantially 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 crystal molecules are aligned substantially vertically when no voltage is applied and substantially horizontally when voltage is applied (described in JP-A-2-176625), (2) multi-domain VA mode liquid crystal cells (described in SID97, Digest of Tech. Papers (Proceedings) 28 (1997) 845) in order to widen the viewing angle (MVA mode liquid crystal cells), (3) n-ASM mode liquid crystal cells in which rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied and substantially horizontally when voltage is applied (described in Proceedings of the Japan Liquid Crystal Symposium 58-59 (1998)), and (4) SURVIVAL mode liquid crystal cells (announced at LCD International 98). Furthermore, any of PVA (Patterned Vertical Alignment) type, optical alignment type, and PSA (Polymer-Sustained Alignment) type may be used. Details of these modes are described in Japanese Patent Laid-Open No. 2006-215326 and Japanese Patent Laid-Open No. 2008-538819. In an IPS mode liquid crystal cell, rod-shaped liquid crystal molecules are aligned substantially parallel to the substrates, and the liquid crystal molecules respond in a planar manner when an electric field parallel to the substrate surface is applied. In the IPS mode, a black display is achieved when no electric field is applied, and the absorption axes of a pair of upper and lower polarizing plates are perpendicular to each other.Methods of using an optical compensation sheet to reduce light leakage in oblique directions during black display and improve the viewing angle are disclosed in JP-A Nos. 10-54982, 11-202323, 9-292522, 11-133408, 11-305217, and 10-307291.

[0075] [Organic EL Display Device] An organic EL display device, which is an example of the image display device of the present invention, preferably has, from the viewer's side, an optically anisotropic layer, a λ / 4 plate, and an organic EL display panel. A more preferred embodiment has, from the viewer's side, the above-mentioned laminate having a λ / 4 plate and an organic EL display panel, in this order. In this case, the laminate is arranged in the following order from the viewer's side: a substrate, an optional alignment film, an optically anisotropic layer, an optional barrier layer, and a λ / 4 plate. The organic EL display panel is a display panel constructed using organic EL elements in which an organic light-emitting layer (organic electroluminescence layer) is sandwiched between electrodes (cathode and anode). The configuration of the organic EL display panel is not particularly limited, and any known configuration may be used.

[0076] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0077] Example 1 Preparation of Photo-Alignment Film Two parts by mass of the photo-alignment polymer PA1 described below and 98 parts by mass of o-xylene were mixed, and the resulting mixture was stirred at 80°C for 1 hour to obtain a composition for forming a photo-alignment film. The composition was then applied by a bar coating method and dried at 120°C to obtain a dried film. This dried film was then irradiated with polarized UV light to obtain a photo-alignment film. The polarized UV treatment was carried out using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Inc.) at an intensity of 100 mJ measured at a wavelength of 365 nm.

[0078] Photo-orientable polymer PA1:

[0079] [Preparation of Optically Absorbent Anisotropic Layer] The following components were mixed and stirred at 80° C. for 1 hour to obtain a composition 1 for forming an optically absorptive anisotropic layer. ------------------------------------------------ Composition 1 for forming optically absorptive anisotropic layer-------------------------------- 75 parts by mass of liquid crystal compound L1 shown below 25 parts by mass of liquid crystal compound L2 shown below 3 parts by mass of dichroic substance A1 shown below 3 parts by mass of dichroic substance A2 shown below 1 part by mass of dichroic substance A3 shown below 1 part by mass of dichroic substance A4 shown below 6 parts of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure 369, manufactured by BASF) 1.2 parts of polyacrylate compound (BYK-361N, manufactured by BYK-Chemie) 250 parts of o-xylene------------------------------------------------ Among these dichroic substances, dichroic substances A3 and A4 have maximum absorption wavelengths in the wavelength range of 550 to 700 nm.

[0080] Next, the composition 1 for forming an optically absorptive anisotropic layer was applied onto the photoalignment film PA1 using a slot die coater to form a coating film. The coating film was then transported through a ventilated drying oven set at 110°C for 2 minutes to remove the solvent, and then rapidly cooled to form a dry coating film (liquid crystal composition layer). Then, ultraviolet light of 500 mJ / cm was applied using a high-pressure mercury lamp under an air atmosphere. ２ After irradiating with ultraviolet light (365 nm standard), a high-pressure mercury lamp was used under a nitrogen atmosphere to irradiate the sample with ultraviolet light at 500 mJ / cm ２ (365 nm standard) to cure the polymerizable liquid crystal contained in the dried film, thereby producing an optically absorbing anisotropic layer. The curing process in Example 1 is also abbreviated as "exposure under air → N2 exposure."

[0081] Example 2 The curing process during the formation of the optically absorptive anisotropic layer was carried out in an air atmosphere by irradiating ultraviolet light at 1000 mJ / cm using a high-pressure mercury lamp. ２ An optically absorptive anisotropic layer was prepared in the same manner as in Example 1, except that the curing process in Example 2 was performed by irradiating the film with light at 365 nm (reference wavelength) and curing the film. The curing process in Example 2 is also abbreviated as "exposure in air."

[0082] Example 3 A composition further containing 6 parts by mass of the following monofunctional compound M1 was used as the composition 1 for forming an optically absorptive anisotropic layer. The curing process during the formation of the optically absorptive anisotropic layer was carried out in a nitrogen atmosphere by irradiating the composition with ultraviolet light at 1000 mJ / cm using a high-pressure mercury lamp. ２ An optically absorptive anisotropic layer was produced in the same manner as in Example 1, except that the curing process in Example 3 was performed by irradiating the film with light at 365 nm (reference wavelength) and curing the film. The curing process in Example 3 is also abbreviated as "exposure under N2".

[0083] Example 4 An optically absorptive anisotropic layer was prepared in the same manner as in Example 3, except that the following monofunctional compound M2 was used instead of the following monofunctional compound M1.

[0084] Example 5 An optically absorptive anisotropic layer was prepared in the same manner as in Example 1, except that the optically absorptive anisotropic layer-forming composition 1 was a composition further containing 6 parts by mass of the monofunctional compound M1 shown below.

[0085] [Example 6] An optically absorptive anisotropic layer was prepared in the same manner as in Example 1, except that the composition for forming an optically absorptive anisotropic layer 1 contained 2 parts by mass of dichroic material A3 and did not contain dichroic material A4.

[0086] Examples 7 and 8 Optically absorptive anisotropic layers were prepared in the same manner as in Example 1, except that the liquid crystal compounds shown in Table 1 below were used instead of the liquid crystal compounds L1 and L2.

[0087] [Comparative Example 1] A photo-alignment film was produced in the same manner as in Example 1. Then, a composition 1 for forming an optically absorptive anisotropic layer was prepared in the same manner as in Example 1. Next, the composition 1 for forming an optically absorptive anisotropic layer prepared above was applied onto the photo-alignment film produced above by a bar coating method, and an optically absorptive anisotropic layer (polarizer layer) was produced by the method described in paragraph

[0192] of Patent Document 1 (JP 2019-049758 A).

[0088] [Evaluation] (1) Diffraction angle 2θ and I(φmax) / I(φmax-10) For the prepared optically absorptive anisotropic layers, X-ray diffraction patterns were observed by in-plane diffraction using the method described above. The measurement results of the diffraction angles 2θ of peaks P1 and P2, as well as the calculation results of "I(φmax) / I(φmax-10)", which is the left-hand side of the above formula (1), are shown in Table 1 below. It was confirmed that peak P2 observed in Examples 1 to 7 exhibited a peak intensity of 0.2 or more times I(φmax), which is the peak intensity of peak P1.

[0089] (2) Haze The prepared light absorption anisotropic layer was observed for light scattering when fluorescent light was transmitted through it. Haze performance was evaluated based on the following criteria. The evaluation results are shown in Table 1 below. <Evaluation criteria> AA: Transparent, no visible light scattering. A: Very slight light scattering, but not visible. B: Slight light scattering, but acceptable. C: Light scattering, visible, not acceptable.

[0090] (3) Durability The prepared optically absorptive anisotropic layer was left in an environment of 80°C for 500 hours, and then the change in transmittance was observed. Durability was evaluated based on the following criteria. The results are shown in Table 1 below. <Evaluation criteria> A: Almost no change in transmittance was visible. B: There was a slight change in transmittance, but it was acceptable. C: There was a large change in transmittance, and it was unacceptable.

[0091] (4) Precipitation The precipitation of the dichroic material when the composition for forming an optically absorptive anisotropic layer was allowed to stand at room temperature was evaluated based on the following criteria. The evaluation results are shown in Table 1 below. A rating of C or higher is considered to be at a practically acceptable level. <Evaluation criteria> A: No precipitation of the dye occurs even after 7 days. B: No precipitation is observed after 3 days, but precipitation is observed after 7 days. C: No precipitation is observed after 1 day, but precipitation is observed after 3 days. D: Precipitation is observed after 1 day.

[0092]

[0093] The structures of the liquid crystal compounds, dichroic materials and monofunctional compounds in Table 1 above are shown below.

[0094] Liquid crystal compound L1

[0095] Liquid crystal compound L2

[0096] Liquid crystal compound L3

[0097] Liquid crystal compound L4

[0098] Liquid crystal compound L5

[0099] liquid crystal compound L6

[0100] Dichroic substance A1

[0101] Dichroic substance A2

[0102] Dichroic substance A3

[0103] Dichroic substance A4

[0104] Monofunctional compound M1

[0105] Monofunctional compound M2

[0106] The results shown in Table 1 indicate that when the value of I(φmax) / I(φmax-10) is less than 1.6, haze occurs, and the precipitation of the dichroic material is poor when the composition for forming an optically absorptive anisotropic layer is aged at room temperature (Comparative Example 1). In contrast, when the value of I(φmax) / I(φmax-10) is 1.6 or greater, the generation of haze is suppressed (Examples 1 to 8). In particular, a comparison between Example 1 and Example 2 indicates that durability is improved when ultraviolet irradiation (exposure) is performed in air and then ultraviolet irradiation (exposure) is performed in nitrogen during the curing process. Furthermore, a comparison between Example 1 and Example 5 indicates that the incorporation of a monofunctional compound satisfying the relationship of the above formula (2) further suppresses the generation of haze. Furthermore, a comparison between Example 1 and Example 6 revealed that the use of at least two dichroic substances having absorption maxima in the wavelength range of 550 to 700 nm can suppress the precipitation of the dichroic substances over time in the composition for forming an optically absorptive anisotropic layer. Furthermore, a comparison between Example 1 and Example 8 revealed that the occurrence of haze is further suppressed when not only Peak P1 but also Peak P2 is observed.

[0107] [Preparation of Positive A Plate] The coating solution E1 for forming a photo-alignment film having the following composition was continuously applied with a wire bar, and then dried with hot air at 140°C for 120 seconds. Subsequently, the coating film was irradiated with polarized ultraviolet light (10 mJ / cm ２ By using an ultra-high pressure mercury lamp, a photo-alignment film E1 having a thickness of 0.2 μm was formed.

[0108] -------------------------------------------------- Coating liquid E1 for forming photoalignment film -------------------------------------------------- Polymer PA-2 (shown below) 100.00 parts by mass Acid generator PAG-1 (shown below) 5.00 parts by mass Acid generator CPI-110TF (shown below) 0.005 parts by mass Isopropyl alcohol 16.50 parts by mass Butyl acetate 1072.00 parts by mass Methyl ethyl ketone 268.00 parts by mass --------------------------------------------------

[0109] Polymer PA-2

[0110] Acid generator PAG-1

[0111] Acid generator CPI-110TF

[0112] Composition F1 having the following composition was applied onto the photo-alignment film E1 using a bar coater. The coating film formed on the photo-alignment film E1 was heated to 120°C with hot air, then cooled to 60°C, and then irradiated with 100 mJ / cm2 at a wavelength of 365 nm using a high-pressure mercury lamp under a nitrogen atmosphere. ２ The coating film was irradiated with ultraviolet light of 500 mJ / cm 2 while being heated to 120°C. ２ The coating film was irradiated with ultraviolet light of 1000 kJ / cm 2 , thereby fixing the alignment of the liquid crystal compound, and a positive A plate F1 was produced. The thickness of the positive A plate F1 was 2.5 μm, and the Re(550) was 144 nm. The positive A plate also satisfied the relationship Re(450)≦Re(550)≦Re(650). The Re(450) / Re(550) was 0.82.

[0113] ------------------------------------------------- Composition F1 ------------------------------------------------- 43.50 parts by mass of polymerizable liquid crystal compound LA-1 described below 43.50 parts by mass of polymerizable liquid crystal compound LA-2 described below 8.00 parts by mass of polymerizable liquid crystal compound LA-3 described below 5.00 parts by mass of polymerizable liquid crystal compound LA-4 described below 0.55 parts by mass of polymerization initiator PI-1 described below 0.20 parts by mass of leveling agent T-1 described below 235.00 parts by mass of cyclopentanone ------------------------------------------------

[0114] Polymerizable liquid crystal compound LA-1 (tBu represents a tertiary butyl group)

[0115] Polymerizable liquid crystal compound LA-2

[0116] Polymerizable liquid crystal compound LA-3

[0117] Polymerizable liquid crystal compound LA-4 (Me represents a methyl group)

[0118] Polymerization initiator PI-1

[0119] Leveling agent T-1

[0120] [Preparation of TAC film with positive C plate H1] A coating solution G1 for forming a photo-alignment film having the following composition was applied using a bar coater, and then dried with hot air at 60°C for 60 seconds and then with hot air at 100°C for 120 seconds to form a photo-alignment film G1.

[0121] ------------------------------------------------------------------ Coating liquid G1 for forming photo-alignment film -------------------------------------------------- Polyvinyl alcohol (PVA103, manufactured by Kuraray) 2.4 parts by mass Isopropyl alcohol 1.6 parts by mass Methanol 36 parts by mass Water 60 parts by mass ------------------------------------------------------------------

[0122] A coating solution H1 for forming a positive C plate having the following composition was applied onto the photo-alignment film G1, and the resulting coating film was aged at 60° C. for 60 seconds, and then irradiated with 70 mW / cm 2 ２ An air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used, and the light output was 1000 mJ / cm ２ The alignment state was fixed by irradiating the liquid crystal compound with ultraviolet light of 1000 nm to vertically align the liquid crystal compound, thereby producing a positive C plate H1 having a thickness of 0.5 μm. The Rth(550) of the obtained positive C plate was −60 nm.

[0123] -------------------------------- Coating liquid H1 for forming positive C-plate -------------------------------- 80 parts by mass of the following liquid crystal compound LC-1 20 parts by mass of the following liquid crystal compound LC-2 1 part by mass of the following vertical alignment liquid crystal compound promoter S01 8 parts by mass of ethylene oxide-modified trimethylolpropane triacrylate (V#360, manufactured by Osaka Organic Chemical Co., Ltd.) 3 parts by mass of Irgacure 907 (manufactured by BASF) 1 part by mass of Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) 0.4 parts by mass of the following compound B03 170 parts by mass of methyl ethyl ketone 30 parts by mass of cyclohexanone --------------------------------

[0124] Liquid crystal compound LC-1

[0125] Liquid crystal compound LC-2

[0126] Vertical alignment liquid crystal compound promoter S01

[0127] Compound B03

[0128] [Preparation of Pressure-Sensitive Adhesives N1 and N2] Next, an acrylate polymer was prepared according to the following procedure: In a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer, and a stirrer, 95 parts by mass of butyl acrylate and 5 parts by mass of acrylic acid were polymerized by solution polymerization to obtain an acrylate polymer (NA1) having an average molecular weight of 2,000,000 and a molecular weight distribution (Mw / Mn) of 3.0.

[0129] Next, using the obtained acrylate polymer (NA1), acrylate-based pressure-sensitive adhesives were prepared with the following compositions. These compositions were applied using a die coater to separate films that had been surface-treated with a silicone-based release agent, dried for 1 minute in an environment at 90°C, and irradiated with ultraviolet (UV) rays under the following conditions to obtain the following acrylate-based pressure-sensitive adhesives N1 and N2 (adhesive layers). The compositions and film thicknesses of the acrylate-based pressure-sensitive adhesives are shown below. <UV irradiation conditions> Fusion Inc. electrodeless lamp H bulb Illuminance 600 mW / cm ２ , light intensity 150mJ / cm ２ UV illuminance and light quantity were measured using "UVPF-36" manufactured by Eye Graphics.

[0130] -------------------------------------------------- Acrylate adhesive N1 (film thickness 15 μm) -------------------------------------------------- Acrylate polymer (NA1) 100 parts by mass - (A) Multifunctional acrylate monomer (described below) 11.1 parts by mass - (B) Photopolymerization initiator (described below) 1.1 parts by mass - (C) Isocyanate crosslinking agent (described below) 1.0 part by mass - (D) Silane coupling agent (described below) 0.2 parts by mass --------------------------------------------------

[0131] -------------------------------------------------- Acrylate adhesive N2 (film thickness 25 μm) -------------------------------------------------- Acrylate polymer (NA1) 100 parts by mass - Isocyanate crosslinking agent (C) below 1.0 part by mass - Silane coupling agent (D) below 0.2 parts by mass --------------------------------------------------

[0132] (A) Polyfunctional acrylate monomer: tris(acryloyloxyethyl) isocyanurate, molecular weight = 423, trifunctional (manufactured by Toagosei Co., Ltd., trade name "Aronix M-315") (B) Photopolymerization initiator: a 1:1 mass ratio mixture of benzophenone and 1-hydroxycyclohexylphenyl ketone, "Irgacure 500" manufactured by Ciba Specialty Chemicals (C) Isocyanate crosslinking agent: trimethylolpropane-modified tolylene diisocyanate ("Coronate L" manufactured by Nippon Polyurethane Co., Ltd.) (D) Silane coupling agent: 3-glycidoxypropyltrimethoxysilane ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.)

[0133] [Preparation of UV adhesive] A UV adhesive composition was prepared having the following composition: UV adhesive composition ------------------------------------------------ CEL2021P (manufactured by Daicel Corporation) 70 parts by mass 1,4-butanediol diglycidyl ether 20 parts by mass 2-ethylhexyl glycidyl ether 10 parts by mass CPI-100P 2.25 parts by mass

[0134] CPI-100P

[0135] [Preparation of Laminate CPAC1] The positive A plate F1 and the positive C plate H1 were laminated together using the UV adhesive composition at 600 mJ / cm ２The plates were laminated together by UV irradiation. The thickness of the UV adhesive layer was 3 μm. The surfaces to be laminated with the UV adhesive were each subjected to corona treatment. Next, the support of the photo-alignment film E1 on the positive A plate F1 side was removed to produce a retardation plate AC1. The optically absorptive anisotropic layer prepared in Example 1 was laminated to the support side of a low-reflection surface film CV-LC5 (manufactured by Fujifilm Corporation) using the above-mentioned adhesive N1. Next, the support included in the optically absorptive anisotropic layer prepared in Example 1 was removed, and the removed surface was laminated to the positive A plate F1 side of the retardation plate AC1 using the above-mentioned adhesive N1. Next, the support on the positive C plate H1 side included in the retardation plate AC1 was removed to produce a laminate CPAC1. The laminate was laminated so that the angle between the absorption axis of the optically absorptive anisotropic film C1 included in the laminate CPAC1 and the slow axis of the positive A plate F1 was 45°. The layer structure of the laminate CPAC1 is a low-reflection surface film CV-LC5, an adhesive layer N1, an oxygen-blocking layer D1, a light-absorbing anisotropic film C1, a photo-alignment film B1, an adhesive layer N1, a positive A plate F1, a UV adhesive layer, and a positive C plate H1.

[0136] A SAMSUNG GALAXY S5 equipped with an organic EL panel (organic EL display element) was disassembled, the touch panel with the circular polarizer was peeled off from the organic EL display device, and the circular polarizer was further peeled off from the touch panel to separate the organic EL display element, the touch panel, and the circular polarizer. Subsequently, the separated touch panel was reattached to the organic EL display element, and the positive C plate 1 side of the laminate CPAC1 prepared above was attached to the touch panel in a manner that prevented air from entering, thereby producing an image display device.

[0137] When an image was displayed using the image display device prepared above, no light scattering was visible from either the front or oblique directions.

[0138] 1 Light absorption anisotropic layer 2 Liquid crystal compound 3 Diffraction surface 4 Incident X-ray 5 Reflected X-ray 6 Diffracted X-ray

Claims

1. A light absorbing anisotropic layer containing a dichroic substance and a liquid crystal compound, The optically absorptive anisotropic layer satisfies the relationship of the following formula (1) when, in irradiating the optically absorptive anisotropic layer with X-rays and measuring an X-ray diffraction pattern by an in-plane diffraction method, the diffracted X-rays are measured in the following measurement region to determine the diffraction angle 2θmax and rotation angle φmax at which the peak intensity is maximum, and the peak intensity of the diffracted X-rays at the diffraction angle 2θmax and rotation angle φmax is defined as I(φmax), and the peak intensity of the diffracted X-rays at the diffraction angle 2θmax and rotation angle φmax-10° is defined as I(φmax-10): Measurement area: Rotation angle φ in the in-plane direction of the light absorbing anisotropic layer: 0 to 180° Diffraction angle 2θ: 0 to 10° Formula (1): I(φmax) / I(φmax-10) ≧ 1.6

2. 2. The optically absorptive anisotropic layer according to claim 1, wherein when the optically absorptive anisotropic layer is fixed at a position of a rotation angle φmax-90° and a diffraction angle 2θ is measured in a range of more than 10° and not more than 30°, a diffracted X-ray peak showing a peak intensity of I(φmax)×0.2 or more is observed.

3. the light absorbing anisotropic layer is formed using a liquid crystal composition containing a dichroic substance, a liquid crystal compound, and a monofunctional compound, 3. The optically absorptive anisotropic layer according to claim 1, wherein a molecular length D1 (Å) of the liquid crystal compound in the long axis direction and a molecular length D2 (Å) of the monofunctional compound in the long axis direction satisfy the following formula (2): Formula (2): 0.2×D1 ≦ D2 ≦ 0.45×D1

4. 3. The optically absorptive anisotropic layer according to claim 1, wherein the dichroic material comprises at least two kinds of dichroic materials having maximum absorption wavelengths in the wavelength range of 550 to 700 nm.

5. A method for producing the optically absorptive anisotropic layer according to claim 1 or 2, comprising the steps of: A method for producing an optically absorptive anisotropic layer, comprising: a step of irradiating a liquid crystal composition layer containing a dichroic substance, a liquid crystal compound, and a monofunctional compound with ultraviolet light in air to form an optically absorptive anisotropic layer.

6. 6. The method for producing an optically absorptive anisotropic layer according to claim 5, further comprising the step of irradiating the optically absorptive anisotropic layer after the optically absorptive anisotropic layer forming step with ultraviolet light in a nitrogen atmosphere.

7. 3. A laminate comprising the optically absorptive anisotropic layer according to claim 1 or 2, and a λ / 4 plate provided on the optically absorptive anisotropic layer.

8. 3. An image display device comprising the optically absorptive anisotropic layer according to claim 1.