Light-absorbing anisotropic film, manufacturing method thereof, laminate, and image display device

Abstract

The purpose of the present invention is to provide a light-absorbing anisotropic film that exhibits excellent tightness of black when used in an image display device, a manufacturing method thereof, and a laminate and an image display device having the light-absorbing anisotropic film. The light-absorbing anisotropic film of the present invention comprises a dichroic substance and a liquid crystal compound, at least a part of the dichroic substance forms an array structure, and where an average value of the length of the long axis of the array structure observed in a region A from one surface to 150 nm in the film thickness direction in a cross section observed with a scanning transmission electron microscope is denoted by Ltop, and an average value of the length of the long axis of the array structure observed in a region B from the other surface to 150 nm in the film thickness direction is denoted by Llow, the following formula (1-1) and / or formula (1-2) is satisfied.　Ltop ≤ 35 nm (1-1) Llow ≤ 35 nm (1-2)

Description

Optically absorptive anisotropic film, its manufacturing method, laminate, and image display device

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

[0002] Optically absorptive anisotropic films are used in a wide variety of applications. For example, organic electroluminescence (EL) display devices have a structure using metal electrodes, which reflect external light, sometimes resulting in reduced contrast and glare. Therefore, polarizing plates having optically absorptive anisotropic films have been used to suppress the adverse effects of external light reflection. For example, Patent Document 1 discloses a polarizing plate having a polarizing layer (optically absorptive anisotropic film) formed from a composition containing a dichroic dye (dichroic material) and a liquid crystal compound.

[0003] Japanese Patent Application Laid-Open No. 2020-023153

[0004] On the other hand, in recent years, organic EL display devices have been required to have excellent black density in the front direction in order to further improve image quality. Note that "excellent black density" means that when the image display device displays black, the coloring of black is suppressed.

[0005] In this situation, the present inventors produced an organic EL display device having the polarizing plate described in Patent Document 1 and evaluated its black depth, and found that it did not necessarily meet the standards currently required.

[0006] In view of the above, the present invention aims to provide an optically absorptive anisotropic film that exhibits excellent black density when used in an image display device, a method for producing the same, and a laminate and an image display device that include the optically absorptive anisotropic film.

[0007] As a result of extensive research into the above-mentioned problems, the present inventors have found that the deepness of black can be improved by forming an array structure of dichroic materials in a film and reducing the size of the array structure near the surface of the film, and have arrived at the present invention. That is, the present inventors have found that the above-mentioned problems can be solved by the following configuration.

[0008] (1) An optically absorptive anisotropic film containing a dichroic substance and a liquid crystal compound, wherein at least a part of the dichroic substance forms an ordered structure, and wherein, in a cross section observed with a scanning transmission electron microscope, when the average value of the length of the major axes of the ordered structure observed in a region A extending 150 nm from one surface in the film thickness direction is Ltop, and when the average value of the length of the major axes of the ordered structure observed in a region B extending 150 nm from the other surface in the film thickness direction is Llow, the optically absorptive anisotropic film satisfies at least one of the following formulas (1-1) and (1-2): Ltop≦35 nm (1-1) Llow≦35 nm (1-2) (2) The optically absorptive anisotropic film according to (1), wherein, when the average value of the length of the major axes of the ordered structure observed in a region C extending 150 nm from the center in the film thickness direction is Lmid, the optically absorptive anisotropic film according to (1), satisfies at least one of the following formulas (2-1) and (2-2): (2-1) Ltop / Lmid<0.87 (2-2) (3) The optically absorptive anisotropic film according to (1) or (2) above, which satisfies the following formula (3-1): Lmid>40 nm (3-1) (4) The optically absorptive anisotropic film according to any one of (1) to (3) above, which contains a unevenly distributed substance that is unevenly distributed in at least one of the region A and the region B. (5) The optically absorptive anisotropic film according to (4) above, in which the weight-average molecular weight of the unevenly distributed substance is 1,000 or more. (6) A method for producing the optically absorptive anisotropic film according to any one of (1) to (5) above, comprising: a coating film forming step of applying a composition for forming an optically absorptive anisotropic film, containing a dichroic substance and a liquid crystal compound, onto an alignment film to form a coating film; and an alignment step of orienting the dichroic substance contained in the coating film to obtain the optically absorptive anisotropic film. (7) The production method according to (6) above, wherein the alignment step includes a step of exposing the coating film under atmospheric pressure. (8) The production method according to (6) or (7) above, wherein the alignment step includes a step of exposing the coating film to ultraviolet light not containing light of 330 nm or more. (9) A laminate comprising the optically absorptive anisotropic film according to any one of (1) to (5) above and a λ / 4 plate. (10) An image display device comprising the optically absorptive anisotropic film according to any one of (1) to (5) above.

[0009] As will be described below, the present invention can provide an optically absorptive anisotropic film that exhibits excellent black density when used in an image display device, a method for producing the same, and a laminate and an image display device that include the optically absorptive anisotropic film.

[0010] 1 is a schematic partial cross-sectional view of an optically anisotropically absorbing film 100 which is one embodiment of the optically anisotropically absorbing film of the present invention.

[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. Furthermore, in this specification, parallel, perpendicular, horizontal, and vertical do not mean parallel, perpendicular, horizontal, and vertical in the strict sense, respectively, but rather mean a range of parallel ±10°, perpendicular ±10°, horizontal ±10°, and vertical ±10°, respectively. Furthermore, in this specification, each component may be a single substance corresponding to each 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 that component refers to the total content of the substances used in combination, unless otherwise specified. Furthermore, for an optically absorptive anisotropic film, excellent black density, durability, heat resistance, and orientation are also referred to as "excellent effects of the present invention." In addition, in this specification, "(meth)acrylate" is a notation representing "acrylate" or "methacrylate", "(meth)acrylic" is a notation representing "acrylic" or "methacrylic", and "(meth)acryloyl" is a notation representing "acryloyl" or "methacryloyl".

[0012] [1] Optically Absorbent Anisotropic Film The optically absorptive anisotropic film of the present invention is an optically absorptive anisotropic film containing a dichroic material and a liquid crystal compound, wherein at least a part of the dichroic material forms an ordered structure, and wherein, in a cross section observed with a scanning transmission electron microscope, the average length of the major axes of the ordered structure observed in a region A extending from one surface to 150 nm in the film thickness direction is defined as Ltop, and the average length of the major axes of the ordered structure observed in a region B extending from the other surface to 150 nm in the film thickness direction is defined as Llow, where Ltop is the average length of the major axes of the ordered structure observed in a region B extending from the other surface to 150 nm in the film thickness direction, and the optically absorptive anisotropic film (hereinafter also referred to as "the film of the present invention") satisfies at least one of the following formulas (1-1) and (1-2): Ltop≦35 nm (1-1) Llow≦35 nm (1-2)

[0013] The film of the present invention has such a structure, and is therefore believed to be able to solve the above-mentioned problems of the present invention. Although the reason for this is not clear, it is presumed that the film of the present invention has a small size of the array structure near the surface, which makes it difficult for external light to be scattered when it is incident thereon.

[0014] In the film of the present invention, dichroic substances may be bonded to each other, liquid crystal compounds may be bonded to each other, or a dichroic substance and a liquid crystal compound may be bonded to each other via a crosslinkable group, a polymerizable group, or the like.

[0015] In the following, the arrangement structure will be explained first, and then each component contained in the film will be explained.

[0016] [Array Structure] In the optically absorptive anisotropic film of the present invention, at least a portion of the dichroic material described above forms an array structure. Here, the array structure refers to a state in which the dichroic material aggregates in the optically absorptive anisotropic film, and the molecules of the dichroic material are periodically arranged in the aggregate. The array structure may be formed solely by the dichroic material, or by a liquid crystal compound and a dichroic material. The array structure may be formed by one type of dichroic material, or by multiple types of dichroic materials. The optically absorptive anisotropic film may contain a mixture of array structures formed by one type of dichroic material and another type of dichroic material. When the optically absorptive anisotropic film contains multiple types of dichroic materials, all of the multiple types of dichroic materials contained in the optically absorptive anisotropic film may form an array structure, or only some of the dichroic materials may form an array structure.

[0017] [Array structure size]

[0018] [Region A, Region B, and Region C] First, Region A, Region B, and Region C of the optically anisotropic absorbing film of the present invention will be described. FIG. 1 is a schematic partial cross-sectional view of an optically anisotropic absorbing film 100, which is one embodiment of the optically anisotropic absorbing film of the present invention. As shown in FIG. 1, Region A is a region from one surface a to 150 nm in the film thickness direction. Region B is a region from the other surface b to 150 nm in the film thickness direction. Region C is a region of the central 150 nm in the film thickness direction, in other words, a region consisting of a region from the center c in the film thickness direction to 75 nm in the film thickness direction (surface a) and a region from the center c in the film thickness direction to 75 nm in the film thickness direction (surface b).

[0019] In this specification, when the optically absorptive anisotropic film is prepared by applying an optically absorptive anisotropic film-forming composition containing a dichroic substance and a liquid crystal compound to a substrate (e.g., an alignment film), the region on the coated surface side is referred to as region A, and the region on the substrate side is referred to as region B.

[0020] [Formulas (1-1) and (1-2)] In a cross section observed with a scanning transmission electron microscope, the film of the present invention satisfies at least one of the following formulas (1-1) and (1-2), where Ltop is the average length L of the major axes of the ordered structure observed in a region A extending from one surface to 150 nm in the film thickness direction, and Llow is the average length L of the major axes of the ordered structure observed in a region B extending from the other surface to 150 nm in the film thickness direction. Ltop≦35 nm (1-1) Llow≦35 nm (1-2)

[0021] Ltop and Llow are each independently preferably 30 nm or less, more preferably 25 nm or less, for reasons of better effects of the present invention, etc. Although the lower limit values ​​of Ltop and Llow are not particularly limited, for reasons of better effects of the present invention, they are each independently preferably 5 nm or more, more preferably 7 nm or more, and even more preferably 10 nm or more.

[0022] <Means>

[0023] (Formula (1-1)) As a means for making the optically absorptive anisotropic film satisfy the formula (1-1), for example, in the production method of the present invention (coating film formation step, orientation step) described below, a method can be mentioned in which a surfactant and a substance having a high affinity with the surfactant (for example, a small Log P value (octanol / water partition coefficient)) and a high molecular weight (for example, Mw of 1,000 or more) are further added to the optically absorptive anisotropic film-forming composition. In this case, in the formed coating film, the surfactant is unevenly distributed toward the coating surface, and accordingly, the substance is unevenly distributed in region A on the coating surface side due to its affinity with the surfactant. In other words, the substance functions as a unevenly distributed substance unevenly distributed in region A. Then, the uneven distribution of the unevenly distributed substance with a high molecular weight in region A increases the viscosity of region A, and the rate of formation of the arrangement structure of the dichroic material in region A decreases. As a result, an optically absorptive anisotropic film having a small size (Ltop) of the arrangement structure in region A is obtained. The value of Ltop can be further adjusted by the type, molecular weight, amount added, etc. of the unevenly distributed substance.

[0024] Another method for making the optically absorptive anisotropic film satisfy the formula (1-1) is, for example, a method of exposing the coating film to short-wavelength UV (preferred embodiment 2) which will be described later.

[0025] (Formula (1-2)) As a means for making the optically absorptive anisotropic film satisfy formula (1-2), for example, in the production method of the present invention described below, a method can be given in which a substance having a small ΔSP value (difference in solubility parameters) with respect to the substrate (e.g., alignment film) onto which the composition is applied and a high molecular weight (e.g., Mw of 1,000 or more) is further added to the optically absorptive anisotropic film-forming composition. In this case, in the formed coating film, the substance is unevenly distributed in region B on the substrate side due to its affinity with the substrate. That is, the substance functions as a unevenly distributed substance unevenly distributed in region B. The uneven distribution of the unevenly distributed substance with a high molecular weight in region B increases the viscosity of region B, and the rate at which the arrangement structure of the dichroic material in region B is formed decreases. As a result, an optically absorptive anisotropic film having a small size (L low ) of the arrangement structure in region B is obtained. The value of L low can be further adjusted by the type, molecular weight, amount added, etc. of the unevenly distributed substance.

[0026] Another method for making the optically absorptive anisotropic film satisfy the formula (1-2) is, for example, a method of exposing the coating film in the atmosphere (preferred embodiment 1) which will be described later.

[0027] [Formulas (2-1) and (2-2)] For the reasons why the effects of the present invention (particularly durability and heat resistance) are superior, the film of the present invention preferably satisfies at least one of the following formulas (2-1) and (2-2), where Lmid is the average value of the length of the major axes of the ordered structure observed in a region C of the central 150 nm in the film thickness direction in a cross section observed with a scanning transmission electron microscope. The definitions of Ltop and Llow are as described above. Ltop / Lmid<0.87 (2-1) Llow / Lmid<0.87 (2-2)

[0028] For reasons of obtaining better effects of the present invention (particularly durability and heat resistance), Ltop / Lmid and Llow / Lmid are each independently preferably 0.70 or less, more preferably 0.60 or less, and even more preferably 0.50 or less. There are no particular restrictions on the lower limit values ​​of Ltop / Lmid and Llow / Lmid, but for reasons of obtaining better effects of the present invention, they are each independently preferably 0.10 or more, more preferably 0.20 or more, and even more preferably 0.30 or more.

[0029] <Means> Examples of means for making the optically absorptive anisotropic film satisfy formula (2-1) or formula (2-2) include means similar to those for making the above-mentioned formula (1-1) or formula (1-2) satisfy. That is, by making Ltop and Llow relatively smaller than Lmid, an optically absorptive anisotropic film satisfying formula (2-1) or formula (2-2) can be obtained.

[0030] [Formula (3-1)] The film of the present invention preferably satisfies the following formula (3-1) for the reason that the effects of the present invention (particularly durability and heat resistance) are more excellent. The definition of Lmid is as described above. Lmid>40 nm (3-1)

[0031] Lmid is preferably 50 nm or more for reasons of better effects of the present invention (particularly durability and heat resistance). There is no particular upper limit for Lmid, but for reasons of better effects of the present invention, it is preferably 100 nm or less, and more preferably 80 nm or less.

[0032] <Means> As a means for making the optically absorptive anisotropic film satisfy the formula (3-1), for example, the manufacturing method of the present invention described below can be mentioned.

[0033] [Observation of Cross Section] Next, observation of a cross section using a scanning transmission electron microscope will be described. In the present invention, observation of a cross section using a scanning transmission electron microscope (hereinafter also referred to as "STEM") is specifically performed as follows. First, an optically absorbing anisotropic film is cut in the film thickness direction using an ultramicrotome to prepare an ultrathin section with a thickness of 100 nm. Next, the ultrathin section is placed on a grid with a carbon support film for STEM observation. Thereafter, the grid is placed in a scanning transmission electron microscope, and the cross section is observed at an electron beam acceleration voltage of 30 kV.

[0034] [Measurement of the length L of the major axis] The length L of the major axis of the array structure is specifically measured as follows. First, as described above, the cross section of the optically absorbing anisotropic film is observed by STEM, and the captured image is analyzed to create a frequency histogram, and the maximum frequency and the standard deviation of the frequency distribution are determined. Next, the frequency that is 1.3 times the standard deviation on the dark side from the maximum frequency is set as a threshold. Next, an image is created in which the brightness is binarized using this threshold, and the binarized dark region is approximated as an ellipse, and the length of the major axis of the approximated ellipse is taken as the length L of the major axis of the array structure. The length L of the major axis of such an array structure may be measured using known image processing software. An example of the image processing software is the image processing software "ImageJ." The image analysis described above is performed for each region (region A, region B, region C), and arbitrarily selected non-overlapping 13.58 μm ２ area, 3 locations (total 40 μm ２ ) and extract and count the array structures that satisfy L≧5 nm. The counting of such array structures is performed on arbitrarily selected non-overlapping 40 μm ２ (13.58 μm ２ The measurement is carried out at 10 locations in the region (13.58 μm × 3). Then, for each region, the average value of the length of the long axis of the array structure at the 10 measurement locations is calculated, and these average values ​​are designated as Ltop (region A), Llow (region B), and Lmid (region C), respectively. Note that the measurement is actually carried out at 13.58 μm ２×3=40.74 μm ２ However, in the present invention, the fraction is rounded down and the value is set to "40 μm" for convenience. ２ It is called "Hatari".

[0035] [Dichroic Material] The dichroic material contained in the film of the present invention is not particularly limited, and examples thereof 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), and any conventionally known dichroic material (dichroic dye) can be used. 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 2013-014883 A, paragraphs

[0012] to

[0029] of JP 2013-109090 A, paragraphs

[0009] to [ 0017] paragraph, paragraphs

[0051] to

[0065] of JP 2013-037353 A, paragraphs

[0049] to

[0073] of JP 2012-063387 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], paragraphs

[0011] to

[0025] of JP 2010-215846 A, paragraphs

[0017] to

[0069] of JP 2011-048311 A, paragraphs

[0013] to

[0133] of JP 2011-213610 A, paragraphs

[0074] to

[0246] of JP 2011-237513 A, paragraphs

[0005] to

[0051] of JP 2016-006502 A, [000 5] to

[0041] paragraphs, WO2016 / 136561, paragraphs

[0008] to

[0062] , WO2017 / 154835, paragraphs

[0014] to

[0033] , WO2017 / 154695, paragraphs

[0014] to

[0033] , WO2017 / 195833, paragraphs

[0013] to

[0037] , and WO2018 / 164252, paragraphs

[0014] to

[0034] .

[0036] The film of the present invention may use two or more dichroic substances in combination. For example, from the viewpoint of making the resulting optically absorptive anisotropic film closer to black, it is preferable to use a combination of at least one dichroic substance having a maximum absorption wavelength in the wavelength range of 370 nm or more and less than 500 nm and at least one dichroic substance having a maximum absorption wavelength in the wavelength range of 500 nm or more and less than 700 nm.

[0037] The dichroic substance may have a crosslinkable group, such as a (meth)acryloyl group, an epoxy group, an oxetanyl group, or a styryl group, and among these, a (meth)acryloyl group is preferred because it provides superior effects of the present invention.

[0038] [Content] In the film of the present invention, the content of the dichroic substance is preferably 2 to 80 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 15 to 40 parts by mass, relative to 100 parts by mass of the liquid crystal compound described below, for reasons of better achieving the effects of the present invention, etc. Furthermore, in the film of the present invention, the content of the dichroic substance is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass, for reasons of better achieving the effects of the present invention, etc.

[0039] [Liquid Crystal Compound] The liquid crystal compound contained in the film of the present invention can be either a polymer liquid crystal compound or a low molecular weight liquid crystal compound. Since this increases the degree of orientation of the dichroic material, it is preferable to use a polymer 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 that does not have a 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 smectic liquid crystal compounds being preferred.

[0040] In addition, a polymer liquid crystal compound and a low molecular weight liquid crystal compound may be used in combination as the liquid crystal compound. When a polymer liquid crystal compound and a liquid crystal compound are used in combination, the ratio of the polymer liquid crystal compound to the total liquid crystal compound is preferably 30 to 85% by mass, more preferably 45 to 80% by mass, and even more preferably 60 to 75% by mass, for reasons such as better effects of the present invention.

[0041] [Preferred embodiment] As the liquid crystal compound, a polymer liquid crystal compound containing a repeating unit represented by the following formula (1) (hereinafter also abbreviated as "repeating unit (1)") is preferred, since it results in a higher degree of orientation of the dichroic substance.

[0042]

[0043] In the above formula (1), P1 represents the main chain of the repeating unit, L1 represents a single bond or a divalent linking group, SP1 represents a spacer group, M1 represents a mesogenic group, and T1 represents a terminal group.

[0044] Examples of the main chain of the repeating unit represented by P1 include groups represented by the following formulae (P1-A) to (P1-D). Among these, the group represented by the following formula (P1-A) is preferred in terms of the variety of monomers that can be used as raw materials and ease of handling.

[0045]

[0046] In the above formulas (P1-A) to (P1-D), "*" represents the bonding position with L1 in the above formula (1). １ , R ２ , R ３ and R ４each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. The alkyl group may be a linear or branched alkyl group, or an alkyl group having a cyclic structure (cycloalkyl group). The alkyl group preferably has 1 to 5 carbon atoms. The group represented by formula (P1-A) is preferably a unit of a partial structure of a poly(meth)acrylic acid ester obtained by polymerization of a (meth)acrylic acid ester. The group represented by formula (P1-B) is preferably an ethylene glycol unit formed by ring-opening polymerization of an 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 an 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 represented by the formula SiR ４ (OR ５ ) ２ In the formula, R ４ is R in (P1-D) ４ and plural R ５ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0047] In the above formula (1), L1 is a single bond or a divalent linking group. Examples of the divalent linking group represented by L1 include —C(O)O—, —O—, —S—, and —C(O)NR ６ -, -SO ２ - and -NR ６ R ７ In the formula, R ６ and R ７each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. When P1 is a group represented by formula (P1-A), L1 is preferably a group represented by -C(O)O-, since this will result in a higher degree of orientation of the dichroic material. When P1 is a group represented by formulas (P1-B) to (P1-D), L1 is preferably a single bond, since this will result in a higher degree of orientation of the dichroic material.

[0048] In the above formula (1), the spacer group represented by SP1 preferably contains at least one structure selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure, and a fluorinated alkylene structure, in view of the ease of exhibiting liquid crystallinity and the availability of raw materials. Here, the oxyethylene structure represented by SP1 is a structure represented by *-(CH ２ -CH ２ O) ｎ１ In the formula, n1 represents an integer of 1 to 20, and * represents the bonding position with L1 or M1 in the above formula (1). n1 is preferably an integer of 2 to 10, more preferably an integer of 2 to 4, and most preferably 3, in order to further increase the degree of orientation of the dichroic material. In addition, the oxypropylene structure represented by SP1 is preferably a group represented by *-(CH(CH ３ )-CH ２ O) ｎ２ In the formula, n2 represents an integer of 1 to 3, and * represents the bonding position with L1 or M1. In addition, the polysiloxane structure represented by SP1 is preferably a group represented by *-(Si(CH ３ ) ２ -O) ｎ３ In the formula, n3 represents an integer of 6 to 10, and * represents the bonding position with L1 or M1. In addition, the fluorinated alkylene structure represented by SP1 is preferably *-(CF ２ -CF ２ ) ｎ４ A group represented by -* is preferred, in which n4 represents an integer of 6 to 10, and * represents the bonding position to L1 or M1.

[0049] In the above formula (1), the mesogenic group represented by M1 is a group that represents the main skeleton of the liquid crystal molecule that contributes to the formation of liquid crystals. The liquid crystal molecules exhibit liquid crystallinity, which is an intermediate state (mesophase) between a crystalline state and an isotropic liquid state. There are no particular limitations on the mesogenic group, and reference can be made, for example, to "FlussigeKristalle in Tablellen II" (VEB Deutsche Verlag fur Grundstoff Industrie, Leipzig, 19th edition, 2000), particularly the description in Chapter 3. As the mesogenic group, for example, a group having at least one cyclic structure selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group is preferred. The mesogenic group preferably has an aromatic hydrocarbon group, more preferably has 2 to 4 aromatic hydrocarbon groups, and even more preferably has 3 aromatic hydrocarbon groups, in order to increase the degree of orientation of the dichroic substance.

[0050] As the mesogenic group, from the viewpoints of liquid crystallinity expression, adjustment of the liquid crystal phase transition temperature, availability of raw materials and suitability for synthesis, and of a higher degree of orientation of the dichroic substance, a group represented by the following formula (M1-A) or (M1-B) is preferred, and a group represented by formula (M1-B) is more preferred.

[0051]

[0052] In formula (M1-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 an alkyl group, a fluorinated alkyl group, an alkoxy group, or a substituent. The divalent group represented by A1 is preferably a 4- to 6-membered ring. In addition, the divalent group represented by A1 may be a monocyclic ring or a fused ring. * indicates the bonding position with SP1 or T1.

[0053] Examples of the divalent aromatic hydrocarbon group represented by A1 include a phenylene group, a naphthylene group, a fluorene-diyl group, an anthracene-diyl group, and a tetracene-diyl group. From the viewpoints of the diversity of mesogenic skeleton designs and the availability of raw materials, a phenylene group or a naphthylene group is preferred, and a phenylene group is more preferred.

[0054] The divalent heterocyclic group represented by A1 may be either aromatic or non-aromatic, but a divalent aromatic heterocyclic group is preferred because it increases the degree of orientation of the dichroic material. Examples of atoms other than carbon constituting the divalent aromatic heterocyclic group include nitrogen atoms, sulfur atoms, and oxygen atoms. When the aromatic heterocyclic group has multiple atoms constituting the ring other than carbon, these atoms may be the same or different. Examples of divalent aromatic heterocyclic groups 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.

[0055] Examples of the divalent alicyclic group represented by A1 include a cyclopentylene group and a cyclohexylene group.

[0056] In formula (M1-A), a1 represents an integer of 1 to 10. When a1 is 2 or more, multiple A1s may be the same or different.

[0057] In formula (M1-B), A2 and A3 are each independently a divalent group selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group. Specific examples and preferred embodiments of A2 and A3 are the same as those of A1 in formula (M1-A), and therefore their description will be omitted. In formula (M1-B), a2 represents an integer of 1 to 10. When a2 is 2 or greater, multiple A2s may be the same or different, multiple A3s may be the same or different, and multiple LA1s may be the same or different. In order to increase the degree of orientation of the dichroic material, a2 is preferably an integer of 2 or greater, and more preferably 2. In formula (M1-B), when a2 is 1, LA1 is a divalent linking group. When a2 is 2 or greater, multiple LA1s are each independently a single bond or a divalent linking group, and at least one of the multiple LA1s is a divalent linking group. When a2 is 2, it is preferred that one of the two LA1's is a divalent linking group and the other is a single bond, since this will result in a higher degree of orientation of the dichroic substance.

[0058] In formula (M1-B), examples of the divalent linking group represented by LA1 include —O—, —(CH ２ ) ｇ -, - (CF ２ ) ｇ -, -Si(CH ３ ) ２ -, -(Si(CH ３ ) ２ O) ｇ -, -(OSi(CH ３ ) 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 a hydrogen atom, a C1 to 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-. Of these, -C(O)O- is preferred because it further increases the degree of orientation of the dichroic substance. LA1 may be a group formed by combining two or more of these groups.

[0059] In the above formula (1), examples of the terminal group represented by T1 include a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkoxycarbonyloxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms (ROC(O)-: R is an alkyl group), an acyloxy group having 1 to 10 carbon atoms, an acylamino group having 1 to 10 carbon atoms, an alkoxycarbonylamino group having 1 to 10 carbon atoms, a sulfonylamino group having 1 to 10 carbon atoms, a sulfamoyl group having 1 to 10 carbon atoms, a carbamoyl group having 1 to 10 carbon atoms, a sulfinyl group having 1 to 10 carbon atoms, a ureido group having 1 to 10 carbon atoms, and a (meth)acryloyloxy group-containing group. Examples of the (meth)acryloyloxy group-containing group include a group represented by -LA (wherein L represents a single bond or a linking group. Specific examples of the linking group are the same as those of L1 and SP1 described above. A represents a (meth)acryloyloxy group).

[0060] T1 is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably a methoxy group, in that the degree of orientation of the dichroic material is increased. These terminal groups may be further substituted with these groups or with the polymerizable groups described in JP-A-2010-244038.

[0061] T1 is preferably a polymerizable group, since this improves the adhesion between the polarizer (light absorption anisotropic film) and the optically anisotropic layer and improves the cohesive strength of the film. The polymerizable group is preferably a radically polymerizable group or a cationically polymerizable group. As the radically polymerizable group, a commonly known radically polymerizable group can be used, and an acryloyl group or a methacryloyl group is preferred. In this case, it is known that the polymerization rate of an acryloyl group is generally fast, and an acryloyl group is preferred from the viewpoint of improving productivity, but a methacryloyl group can also be used as the polymerizable group. As the cationically polymerizable group, a commonly known cationic polymerizable group can be used, and examples thereof 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 more preferred.

[0062] <Molecular Weight> The weight-average molecular weight (Mw) of the polymeric liquid crystal compound containing the repeating unit represented by formula (1) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. When the Mw of the polymeric liquid crystal compound is within the above range, the polymeric liquid crystal compound is easy to handle. In particular, from the viewpoint of suppressing cracking during application, the weight-average molecular weight (Mw) of the polymeric liquid crystal compound is preferably 10,000 or more, more preferably 10,000 to 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 crystal compound is preferably less than 10,000, and preferably 2,000 or more but less than 10,000.

[0063] In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured by gel permeation chromatography (GPC). Solvent (eluent): N-methylpyrrolidone Apparatus name: TOSOH HLC-8220GPC Column: Three TOSOH TSKgel Super AWM-H (6 mm x 15 cm) columns connected together Column temperature: 25°C Sample concentration: 0.1% by mass Flow rate: 0.35 mL / min Calibration curve: A calibration curve using seven samples of TSK standard polystyrene manufactured by TOSOH with Mw = 2,800,000 to 1,050 (Mw / Mn = 1.03 to 1.06) was used.

[0064] [Content] In the film of the present invention, the content of the liquid crystal compound is preferably 50% by mass or more, more preferably 70% by mass or more, for reasons of better effects of the present invention, etc. The upper limit of the content of the liquid crystal compound is not particularly limited, but is preferably 95% by mass or less, for reasons of better effects of the present invention, etc.

[0065] [Other Components] The film of the present invention may contain other components in addition to the above-mentioned dichroic material and liquid crystal compound. Such other components include a ubiquitous substance, a polymerization initiator, a surfactant, etc.

[0066] [Unevenly distributed substance] In one preferred embodiment, the membrane of the present invention contains an unevenly distributed substance that is unevenly distributed in at least one of region A and region B, because this reduces Ltop and Llow and improves the effects of the present invention. The unevenly distributed substance may be present in a region other than region A and region B (for example, region C). Specific examples and preferred embodiments of the unevenly distributed substance are described below.

[0067] <Content> In the film of the present invention, the content of the unevenly distributed substance is preferably 0.5 mass% or more, more preferably 1.0 mass% or more, and even more preferably 1.5 mass% or more, because Ltop and Llow become smaller and the effects of the present invention are more excellent. In the film of the present invention, the content of the unevenly distributed substance is preferably 3.0 mass% or less, and more preferably 2.5 mass% or less, because the effects of the present invention are more excellent.

[0068] [Thickness] The thickness of the optically absorptive anisotropic film is not particularly limited, but is preferably 300 to 8000 nm, more preferably 450 to 5000 nm, and even more preferably 1000 to 3000 nm, for reasons such as better effects of the present invention. The thickness of the optically absorptive anisotropic film refers to the average thickness of the optically absorptive anisotropic film. The average thickness is determined by measuring the thickness at any five or more locations on the optically absorptive anisotropic film and calculating the arithmetic average.

[0069] [2] Manufacturing method of optically absorbing anisotropic film There are no particular limitations on the method for manufacturing the optically absorbing anisotropic film of the present invention described above. However, because the obtained optically absorbing anisotropic film has better effects of the present invention, a manufacturing method including the following steps (hereinafter also referred to as "manufacturing method of the present invention") is preferred. Hereinafter, when the obtained optically absorbing anisotropic film has better effects of the present invention, it will also be simply referred to as "the effects of the present invention are excellent." (1) Coating film forming step: A step of forming a coating film by applying a composition for forming an optically absorbing anisotropic film containing a dichroic material and a liquid crystal compound onto an alignment film. (2) Orientation step: A step of obtaining an optically absorbing anisotropic film by orienting the dichroic material contained in the coating film.

[0070] Each step will be described below.

[0071] [Coating Film Forming Step] The coating film forming step is a step of forming a coating film (coating film) by applying a light-absorbing anisotropic film-forming composition containing a dichroic substance and a liquid crystal compound onto an alignment film. Using a light-absorbing anisotropic film-forming composition containing a solvent, or using a light-absorbing anisotropic film-forming composition that has been converted into a liquid such as a molten liquid by heating, etc., makes it easy to apply the light-absorbing anisotropic film-forming composition onto the alignment film. Examples of methods for applying the light-absorbing anisotropic film-forming composition include known methods such as roll coating, gravure printing, spin coating, wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spraying, and inkjet printing.

[0072] [Composition for forming an optically absorptive anisotropic film] The composition for forming an optically absorptive anisotropic film used in the coating film formation step is a composition containing a dichroic substance and a liquid crystal compound (hereinafter also referred to as the "composition of the present invention"). The composition of the present invention may contain other components in addition to the dichroic substance and the liquid crystal compound. Such other components include a ubiquitous substance, a polymerization initiator, a surfactant, a solvent, etc.

[0073] <Dichroic Substance> The composition of the present invention contains a dichroic substance. Specific examples and preferred embodiments of the dichroic substance are as described above.

[0074] (Content) In the composition of the present invention, the content of the dichroic substance is preferably 2 to 80 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 40 parts by mass, relative to 100 parts by mass of the liquid crystal compound, for reasons of better achieving the effects of the present invention, etc. Furthermore, in the composition of the present invention, the content of the dichroic substance is preferably 1 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, of the total solid content, for reasons of better achieving the effects of the present invention, etc.

[0075] In this specification, the term "solid content" refers to the components in the composition excluding the solvent, and specific examples of the solid content include a liquid crystal compound, a dichroic substance, a unevenly distributed substance, a polymerization initiator, and a surfactant.

[0076] <Liquid Crystal Compound> The composition of the present invention contains a liquid crystal compound. Specific examples and preferred embodiments of the liquid crystal compound are as described above.

[0077] In the composition of the present invention, the content of the liquid crystal compound is preferably 50% by mass or more, and more preferably 70% by mass or more, of the total solid content, for reasons of better effects of the present invention, etc. The upper limit of the content of the liquid crystal compound is not particularly limited, but is preferably 95% by mass or less of the total solid content, for reasons of better effects of the present invention, etc.

[0078] <Unevenly Distributed Substance> In one preferred embodiment, the composition of the present invention contains an unevenly distributed substance, because this reduces Ltop and Llow and improves the effects of the present invention. The unevenly distributed substance is preferably a polymer from the viewpoints of sufficiently increasing the viscosity of the region in the coating film where the unevenly distributed substance is unevenly distributed and enhancing phase separation, and its weight-average molecular weight (Mw) is preferably 1,000 or more, more preferably 5,000 or more. There is no particular upper limit to the Mw of the unevenly distributed substance, but because this improves the effects of the present invention, it is preferably 10,000,000 or less, more preferably 1,000,000 or less.

[0079] From the viewpoint of orientation, it is preferable that the unevenly distributed substance does not contain a low surface energy structure (for example, a fluorine atom or a siloxane structure) that is contained in a general surfactant.

[0080] Specific examples of unevenly distributed substances include polyalkylene oxides (particularly polyethylene oxides), epoxy resins (particularly cresol novolac type epoxy resins), and the like.

[0081] (Content) When the composition of the present invention contains unevenly distributed substance, the content of unevenly distributed substance is preferably 0.5 mass % or more in the total solid content, from the viewpoint of sufficiently increasing the viscosity of the area where unevenly distributed substance is unevenly distributed in the coating film, more preferably 1.0 mass % or more, and even more preferably 1.5 mass % or more.In the film of the present invention, the content of unevenly distributed substance is preferably 3.0 mass % or less in the total solid content, more preferably 2.5 mass % or less, because the effect of the present invention is more excellent.

[0082] <Polymerization initiator> The composition of the present invention preferably contains a polymerization initiator because the effects of the present invention are more excellent. There are no particular restrictions on the polymerization initiator, but because the effects of the present invention are more excellent, a photosensitive compound, i.e., a photopolymerization initiator, is preferred. As the photopolymerization initiator, various compounds can be used without particular restrictions. Examples of photopolymerization initiators include α-carbonyl compounds (see U.S. Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (see U.S. Pat. No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compounds (see U.S. Pat. No. 2,722,512), polynuclear quinone compounds (see U.S. Pat. Nos. 3,046,127 and 2,951,758), and a combination of triarylimidazole dimer and p-aminophenyl ketone (see U.S. Pat. No. 3,549,367). detailed description), acridine and phenazine compounds (JP 60-105667 A and U.S. Pat. No. 4,239,850 A), oxadiazole compounds (U.S. Pat. No. 4,212,970 A), o-acyloxime compounds (JP 2016-027384 A,

[0065] ), and acylphosphine oxide compounds (JP 63-040799 A, JP 5-029234 A, JP 10-095788 A, and JP 10-029997 A).

[0083] (Content) When the composition of the present invention contains a polymerization initiator, the content of the polymerization initiator is preferably 0.01 to 30 parts by mass, and more preferably 0.1 to 15 parts by mass, relative to 100 parts by mass of the total of the dichroic substance and the liquid crystal compound, for reasons such as better effects of the present invention.

[0084] <Surfactant> The composition of the present invention preferably contains a surfactant, because the effects of the present invention are more excellent. By including a surfactant, the smoothness of the coated surface is improved, the degree of alignment is further improved, and repelling and unevenness are suppressed, thereby improving in-plane uniformity. As the surfactant, because the effects of the present invention are more excellent, one that horizontally aligns the dichroic material and the liquid crystal compound on the coated surface is preferred. Examples of the surfactant include the compounds described in paragraphs

[0155] to

[0170] of WO 2016 / 009648 and the compounds (horizontal alignment agents) described in paragraphs

[0253] to

[0293] of JP 2011-237513 A.

[0085] (Content) When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 5 parts by mass, and more preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the total of the dichroic substance and the liquid crystal compound.

[0086] <Solvent> From the viewpoint of workability, the composition of the present invention 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.

[0087] (Content) When the composition of the present invention contains a solvent, the content of the solvent is preferably 80 to 99 mass %, and more preferably 83 to 97 mass %, relative to the total mass of the composition, for reasons such as the fact that the effects of the present invention are more excellent.

[0088] [Alignment Film] The alignment film may be any film capable of aligning (e.g., horizontally aligning) the liquid crystal compound contained in the composition of the present invention. 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, forming a layer with microgrooves, or accumulating 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.

[0089] (1) Rubbed Alignment Film Polymer materials used for alignment films formed by rubbing treatment are described in numerous literature, and many commercially available products are available. In the present invention, polyvinyl alcohol or polyimide, and derivatives thereof, are preferably used. For details of alignment films, see WO 2001 / 88574 A1, page 43, line 24 to page 49, line 8. The thickness of the alignment film is preferably 0.01 to 10 μm, and more preferably 0.01 to 1 μm.

[0090] (2) Photo-alignment film Photo-alignment materials used for alignment films formed by light irradiation are described in many documents. In the present invention, for example, azo compounds described in JP-A-2006-285197, JP-A-2007-76839, JP-A-2007-138138, JP-A-2007-094071, JP-A-2007-121721, JP-A-2007-140465, JP-A-2007-156439, JP-A-2007-133184, JP-A-2009-109831, Japanese Patent No. 3883848, Japanese Patent No. 4151746, azo compounds described in JP-A-2002-229039, Preferred examples include aromatic ester compounds described in JP-A Nos. 2002-265541 and 2002-317013, maleimide and / or alkenyl-substituted nadimide compounds having a photoalignment unit described in JP-A Nos. 4205195 and 4205198, and photocrosslinkable polyimides, polyamides, or esters described in JP-A Nos. 2003-520878 and 2004-529220, or JP-A No. 4162850. Azo compounds, photocrosslinkable polyimides, polyamides, or esters are more preferred.

[0091] 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.

[0092] 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 ethylenically unsaturated double bond-containing 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, or a group having an ethylenically unsaturated double bond is 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.

[0093] 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.

[0094] 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.

[0095] As a means for obtaining linearly polarized light, a method using a polarizer (e.g., an iodine polarizer, a dichroic material polarizer, and a wire grid polarizer), a method using a prism-based 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.

[0096] 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.

[0097] 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 beam scanning can be used.

[0098] [Orientation Step] The orientation step is a step of orienting the dichroic substance contained in the coating film. This results in the optically absorptive anisotropic film of the present invention. It is believed that in the orientation step, the dichroic substance is oriented along the liquid crystal compound oriented by the orientation film. The orientation step may include a drying treatment. Components such as the solvent can be removed from the coating film by the drying treatment. The drying treatment may be performed by leaving the coating film at room temperature for a predetermined time (e.g., natural drying), or by heating and / or blowing air. Here, the dichroic substance contained in the optically absorptive anisotropic film-forming composition may be aligned by the above-described coating film-forming step or drying treatment. For example, in an embodiment in which the optically absorptive anisotropic film-forming composition is prepared as a coating liquid containing a solvent, the coating film may be dried to remove the solvent from the coating film, thereby aligning the dichroic substance contained in the coating film, thereby obtaining the optically absorptive anisotropic film of the present invention.

[0099] The orientation step preferably includes a heat treatment. This further aligns the dichroic material contained in the coating film, resulting in a higher degree of orientation in the resulting optically absorptive anisotropic film. From the standpoint 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.

[0100] The heat treatment is preferably carried out in multiple stages at different heating temperatures, and more preferably, the first stage of heat treatment (e.g., 140°C, 10 seconds) is followed by cooling to approximately room temperature (20 to 25°C), and then the second and subsequent stages of heat treatment (e.g., 50 to 100°C, 15 seconds) are carried out at a temperature lower than that of the first stage of heat treatment (e.g., 40 to 90°C lower). It is presumed that the first stage of heat treatment causes the dichroic material to assume a nematic orientation state (unintentionally present alignment structure is melted), and then the second stage of heat treatment forms the desired alignment structure of the dichroic material.

[0101] 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, and the degree of orientation of the resulting optically absorptive anisotropic film is increased. The cooling method is not particularly limited and can be carried out by a known method. The optically absorptive anisotropic film of the present invention can be obtained by the above steps.

[0102] [Other Steps] The manufacturing method of the present invention may include a step of curing the optically absorptive anisotropic film (hereinafter also referred to as a "curing step") after the alignment step. The curing step is carried out, for example, by heating and / or light irradiation (exposure). Among these, the curing step is preferably carried out by light irradiation. Various light sources such as infrared light, visible light, or ultraviolet light can be used as the light source used for curing, but ultraviolet light is preferred. Furthermore, ultraviolet light may be irradiated while heating during curing, or ultraviolet light may be irradiated through a filter that transmits only specific wavelengths. Furthermore, exposure may be carried out in a nitrogen atmosphere. When the curing of the optically absorptive anisotropic film proceeds by radical polymerization, exposure in a nitrogen atmosphere is preferred because inhibition of polymerization by oxygen is reduced.

[0103] [Preferred Embodiment 1] One preferred embodiment of the manufacturing method of the present invention is an embodiment (preferred embodiment 1) in which the orientation step includes a step of exposing the coating film formed in the coating film formation step to air (atmospheric atmosphere) (hereinafter also referred to as an "atmospheric exposure step"). When the coating film is exposed to air, radicals are deactivated in the region on the coating surface side (region A), making polymerization difficult, while polymerization proceeds in the region on the alignment film side (region B) (half cure). As a result, the viscosity of region B increases, the rate of formation of the alignment structure of the dichroic material in region B decreases, and an optically absorptive anisotropic film with a small size (L low ) of the alignment structure in region B is obtained. The value of L low can be further adjusted by the exposure conditions (illuminance, exposure time, etc.).

[0104] For reasons such as better effects of the present invention, the atmospheric exposure step is preferably carried out after the first stage of heat treatment described above and cooling to about room temperature, but before the second stage of heat treatment.

[0105] In the atmospheric exposure step, the illuminance is set to 1 to 300 mW / cm because the effects of the present invention are more excellent. ２ is preferably 10 to 250 mW / cm ２ More preferably, it is 20 to 200 mW / cm ２ It is more preferable that:

[0106] In the atmospheric exposure step, the exposure time is preferably 0.05 to 10 seconds, more preferably 0.07 to 5 seconds, and even more preferably 0.1 to 2 seconds, for reasons such as better effects of the present invention.

[0107] [Preferred Embodiment 2] Another preferred embodiment of the manufacturing method of the present invention is an embodiment (preferred embodiment 2) in which the orientation step includes a step of exposing the coating film formed in the coating film formation step to ultraviolet light not containing light of 330 nm or longer (hereinafter also referred to as "short-wavelength UV") (hereinafter also referred to as "short-wavelength UV exposure step"). When the coating film is exposed to short-wavelength UV, polymerization proceeds in the region on the coating surface side (region A) (half-cure), whereas polymerization proceeds less in the region on the orientation film side (region B) because the short-wavelength UV is less likely to penetrate. As a result, the viscosity of region A increases, the rate of formation of the alignment structure of the dichroic material in region A decreases, and an optically absorptive anisotropic film with a small size (Ltop) of the alignment structure in region A is obtained. The value of Ltop can be further adjusted by the exposure conditions (illuminance, exposure time, etc.).

[0108] As a method for generating short wavelength UV, for example, UV exposure through a short pass filter can be mentioned.

[0109] For reasons such as better effects of the present invention, the short-wavelength UV exposure step is preferably carried out after the first-stage heating treatment described above and cooling to about room temperature, but before the second-stage heating treatment.

[0110] In the short wavelength UV exposure step, the illuminance is set to 1 to 500 mW / cm because the effects of the present invention are more excellent. ２ is preferably 10 to 400 mW / cm ２ More preferably, it is 20 to 300 mW / cm ２ It is more preferable that:

[0111] In the atmospheric exposure step, the exposure time is preferably 0.05 to 10 seconds, more preferably 0.07 to 5 seconds, and even more preferably 0.1 to 2 seconds, for reasons such as better effects of the present invention.

[0112] [3] Laminate The laminate of the present invention is a laminate having the optically absorptive anisotropic film of the present invention described above. The laminate of the present invention may have a film (layer) other than the film of the present invention. Examples of such a film (layer) include a protective layer, an alignment film, a substrate, and an optically anisotropic film. When the laminate of the present invention is used in an image display device, it is preferable that the protective layer side is placed on the viewing side (light incident side). By placing the surface with a low polarization degree (surface with a low refractive index) on the protective layer side, the refractive index difference between the optically absorptive anisotropic film and the protective layer is reduced, and internal reflection can be further suppressed.

[0113] [Lightly Absorbent Anisotropic Film] The lightly absorptive anisotropic film of the present invention included in the laminate of the present invention is as described above, and therefore further description thereof will be omitted.

[0114] [Protective Layer] The protective layer is not particularly limited, but examples thereof include an oxygen-blocking layer and a UV (ultraviolet) absorbing layer, and an oxygen-blocking layer is preferred because it provides better effects of the present invention.

[0115] [Oxygen Barrier Layer] The oxygen barrier layer is an oxygen barrier film with oxygen barrier function. In this specification, oxygen barrier function is not limited to a state in which oxygen is completely blocked, but also includes a state in which oxygen is slightly passed depending on the desired performance. Specific examples of oxygen barrier layers include layers containing organic compounds such as polyvinyl alcohol, modified polyvinyl alcohol, polyethylene vinyl alcohol, polyvinyl ether, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, cellulose ether, polyamide, polyimide, styrene / maleic acid copolymer, gelatin, vinylidene chloride, and cellulose nanofibers. Polyacrylic acid, polyvinyl alcohol, or modified polyvinyl alcohol is preferred because it provides superior effects of the present invention. In addition to the organic compound, the oxygen barrier layer may further contain a light resistance improver to further improve light resistance. When the oxygen barrier layer contains a light resistance improver, the content of the light resistance improver is preferably 0.1 to 5.0% by mass, more preferably 0.3 to 3.0% by mass, based on the total mass of the oxygen barrier layer. The thickness of the oxygen-blocking layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5.5 μm, for reasons such as the fact that the effects of the present invention are more excellent.

[0116] The refractive index of the protective layer at a wavelength of 550 nm is preferably 1.40 to 1.60, more preferably 1.45 to 1.55, for reasons of better effects of the present invention, etc. Here, the refractive index of the protective layer at a wavelength of 550 nm can be measured in the same manner as the average refractive index of the above-mentioned optically absorptive anisotropic film.

[0117] [Alignment Film] The alignment film of the laminate of the present invention is the same as the alignment film used in the above-mentioned method for producing an optically absorptive anisotropic film, and therefore, description thereof will be omitted.

[0118] [Substrate] The laminate of the present invention may have a substrate on the side of the alignment film opposite the optically absorptive anisotropic film. The substrate can be selected depending on the application of the optically absorptive anisotropic film, and examples thereof include glass and polymer films. 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 one in which the exhibiting property has been reduced by molecular modification as described in WO 2000 / 26705. The average visible light transmittance of the substrate is preferably 80% or more.

[0119] [Optically Anisotropic Film] The laminate of the present invention preferably has an optically anisotropic film (optically anisotropic layer). Here, the term "optically anisotropic film" refers to any film that generates a retardation, such as a stretched polymer film or a retardation film having an optically anisotropic layer containing an oriented liquid crystalline compound on a support. The orientation direction of the liquid crystalline compound contained in the optically anisotropic layer is not particularly limited, and examples thereof include horizontal, vertical, and twisted orientation relative to the film surface. Specific functions of the optically anisotropic film include, for example, a λ / 4 plate and a λ / 2 plate. The optically anisotropic layer may be composed of multiple layers. For details of an optically anisotropic layer composed of multiple optically anisotropic layers, see, for example, paragraphs

[0008] to

[0053] of JP-A-2014-209219. Such an optically anisotropic film and the above-mentioned light absorption anisotropic film may be provided in contact with each other, or another layer may be provided between them. Such layers include the above-mentioned alignment film, and an adhesive layer or bonding layer for ensuring adhesion.

[0120] The laminate of the present invention preferably uses a λ / 4 plate as the optically anisotropic film, and preferably has a λ / 4 plate on the side of the alignment film opposite to the light absorption anisotropic film.Here, the "λ / 4 plate" refers to 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, as an embodiment in which the λ / 4 plate has a single layer structure, specifically, a retardation film having an optically anisotropic layer having a λ / 4 function on a support, etc. can be mentioned.Also, as an embodiment in which the λ / 4 plate has a multilayer structure, specifically, a broadband λ / 4 plate formed by laminating a λ / 4 plate and a λ / 2 plate can be mentioned.The λ / 4 plate may be one that uses a reverse dispersion liquid crystal compound and has a wavelength dispersion of the retardation Re of reverse dispersion. Here, the wavelength dispersion of reverse dispersion means that Re(λ) and Rth(λ) become larger values ​​as the wavelength λ increases, and at this time, the retardation Re(λ) satisfies the following formulas (Re-1) and (Re-2). Formula (Re-1): Re(450) / Re(550)< 1.0 Formula (Re-2): Re(650) / Re(550)> 1.0 If the wavelength dispersion of the retardation Re has the wavelength dispersion of reverse dispersion, it is possible to reduce the reflection of external light in all wavelength ranges of visible light and suppress the coloring of reflected light, which is preferable.

[0121] [4] Image Display Device The image display device of the present invention is an image display device having the above-described optically absorptive anisotropic film (polarizer) of the present invention. The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (organic EL) display panel, and a plasma display panel. Among these, a liquid crystal cell or an organic EL display panel is preferred, and an organic EL display panel is more preferred. That is, the 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 an organic EL display device.

[0122] [Liquid Crystal Display Device] A liquid crystal display device, which is an example of the display device of the present invention, is a liquid crystal display device having the above-mentioned laminate of the present invention (however, not including a λ / 4 plate) and a liquid crystal cell. In the present invention, of the laminates provided on both sides of the liquid crystal cell, it is preferable to use the laminate of the present invention as the polarizing element on the front side (viewing side), and it is more preferable to use the laminate of the present invention as the polarizing elements on the front side and rear side. The liquid crystal cell constituting the liquid crystal display device will be described in detail below.

[0123] [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, rod-shaped liquid crystal molecules (rod-shaped liquid crystal compounds) are aligned substantially horizontally when no voltage is applied, and are further aligned with a twist angle of 60 to 120 degrees. TN mode liquid crystal cells are most commonly used in color TFT liquid crystal display devices, and are described in many literatures. 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 (described in Japanese Patent Application Laid-Open No. 2-176625) in which rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied and substantially horizontally when voltage is applied, as well as (2) multi-domain VA mode (MVA mode (Multi-domain Vertical Alignment)) liquid crystal cells (described in SID97, Digest of Tech. Papers (Proceedings) 28 (1997) 845) in which VA mode is multi-domain aligned to widen the viewing angle, and (3) n-ASM (Axially Symmetrically Aligned) mode in which rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied and substantially horizontally aligned when voltage is applied. These include (3) liquid crystal cells of an IPS mode (described in Proceedings of the Japan Liquid Crystal Discussion Society, Vols. 58-59 (1998)) and (4) a SURVIVAL mode liquid crystal cell (presented at LCD (Liquid Crystal Display) International 98). The liquid crystal cell may be of any of a PVA (Patterned Vertical Alignment) type, an optical alignment type, and a PSA (Polymer-Sustained Alignment) type. Details of these modes are described in Japanese Patent Laid-Open Publication No. 2006-215326 and Japanese Patent Laid-Open Publication No. 2008-538819. In an IPS mode liquid crystal cell, rod-shaped liquid crystal molecules are aligned substantially parallel to the substrates, and when an electric field parallel to the substrate surfaces is applied, the liquid crystal molecules respond in a planar manner.In the IPS mode, a black display is achieved when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are perpendicular to each other. Methods of using an optical compensation sheet to reduce light leakage during black display in an oblique direction and improve the viewing angle are disclosed in JP-A Nos. 10-54982, 11-202323, 9-292522, 11-133408, 11-305217, and 10-307291.

[0124] [Organic EL Display Device] An organic EL display device, which is one example of the display device of the present invention, preferably has, from the viewing side, the above-described laminate of the present invention (preferably including a λ / 4 plate) and an organic EL display panel. In this case, the laminate is preferably arranged in the following order from the viewing side: a protective layer, a light absorption anisotropic film, an alignment film, and a λ / 4 plate. The organic EL display panel is a display panel configured using organic EL elements in which an organic light-emitting layer (organic electroluminescence layer) is sandwiched between electrodes (between a cathode and an anode). The configuration of the organic EL display panel is not particularly limited, and a known configuration may be used.

[0125] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0126] [Example 1]

[0127] [Preparation of Transparent Support] The following composition was charged into a mixing tank and stirred to prepare a cellulose acetate solution to be used as a cellulose acylate dope for the core layer. -------------------------------- Core Layer Cellulose Acylate Dope------------------------------------------------ - 100 parts by mass of cellulose acetate having an acetyl substitution degree of 2.88 - 12 parts by mass of polyester compound B described in the examples of JP 2015-227955 A - 2 parts by mass of compound F below - 430 parts by mass of methylene chloride (first solvent) - 64 parts by mass of methanol (second solvent)------------------------------------------------

[0128] Compound F

[0129]

[0130] To 90 parts by weight of the above-mentioned cellulose acylate dope for the core layer, 10 parts by weight of the following matting agent solution was added to prepare a cellulose acetate solution to be used as the cellulose acylate dope for the outer layer.

[0131] Matting agent solution - Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass Methylene chloride (first solvent) 76 parts by mass Methanol (second solvent) 11 parts by mass The above-mentioned cellulose acylate dope for the core layer 1 part by mass

[0132] The core layer cellulose acylate dope and the outer layer cellulose acylate dope were filtered through a filter paper with an average pore size of 34 μm and a sintered metal filter with an average pore size of 10 μm, and then the core layer cellulose acylate dope and the outer layer cellulose acylate dope on both sides were simultaneously cast onto a drum at 20°C from a casting nozzle (band caster). Next, when the solvent content in the film was approximately 20% by mass, the film on the drum was peeled off, and both ends of the film in the width direction were fixed with tenter clips, and the film was stretched in the transverse direction at a draw ratio of 1.1 times while being dried. The resulting film was then transported between the rolls of a heat treatment device and further dried to produce a transparent support with a thickness of 40 μm, which was designated as cellulose acylate film A1.

[0133] [Formation of Photo-Alignment Film B1] A composition for forming a photo-alignment film, which will be described later, was continuously applied onto the cellulose acylate film A1 using a wire bar. The support on which the coating film was formed was dried with hot air at 140°C for 120 seconds, and then the coating film was irradiated with polarized ultraviolet light (10 mJ / cm ２ , using an ultra-high pressure mercury lamp) to form a photo-alignment film B1, and a TAC (triacetyl cellulose) film with a photo-alignment film was obtained. The film thickness of the photo-alignment film B1 was 0.25 μm. ---------------------------------------------------------------- Composition for forming photo-alignment film ---------------------------------------------------------------- - 100.00 parts by mass of polymer PA-1 shown below - 8.25 parts by mass of acid generator PAG-1 shown below - 0.6 parts by mass of stabilizer DIPEA shown below - 1126.60 parts by mass of xylene - 125.18 parts by mass of methyl isobutyl ketone ----------------------------------------------------------------

[0134] Polymer PA-1 (wherein the numerical value for each repeating unit represents the content (% by mass) of each repeating unit relative to all repeating units)

[0135]

[0136] Acid generator PAG-1

[0137]

[0138] Stabilizer DIPEA

[0139]

[0140] [Preparation of Optically Absorbent Anisotropic Film C1]

[0141] <Coating Film Forming Step> A composition for forming an optically absorptive anisotropic film having the following composition was continuously coated on the obtained photoalignment film B1 using a wire bar to form a coating film.

[0142] <Orientation Step> Next, the coating film was heated at 140°C for 15 seconds and cooled to room temperature (23°C). Next, the coating film was heated at 75°C for 60 seconds and cooled to room temperature again. Thereafter, an LED (light emitting diode) lamp (center wavelength 365 nm) was used to illuminate the coating film at an illuminance of 200 mW / cm. ２ The photo-alignment film B1 was irradiated for 2 seconds under the irradiation conditions of 1.8 μm to form a light absorption anisotropic film C1 (polarizer) (thickness: 1.8 μm) on the photo-alignment film B1.

[0143] The transmittance of the optically absorptive anisotropic film C1 in the wavelength range of 280 to 780 nm was measured using a spectrophotometer, and the average visible light transmittance was 42%. The absorption axis of the optically absorptive anisotropic film C1 was perpendicular to the width direction of the cellulose acylate film A1.

[0144] In the optically absorptive anisotropic film C1, the surfactant is unevenly distributed near the surface on the coated surface side, and accordingly, polyethylene oxide (PEO), which has a high affinity for the surfactant (low Log P value (octanol / water partition coefficient)), is also unevenly distributed in region A on the coated surface side.

[0145] 0.69 parts by mass of the first dichroic substance Dye-C1 described below 0.14 parts by mass of the second dichroic substance Dye-M1 described below 0.25 parts by mass of the third dichroic substance Dey-Y1 described below 3.16 parts by mass of the liquid crystal compound (L-1) described below 1.40 parts by mass of the rod-shaped liquid crystal compound (L-2) described below 0.18 parts by mass of polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.12 parts by mass of polyethylene oxide (Mw=100,000) 0.01 parts by mass of the surfactant (F-1) described below 91.86 parts by mass of cyclopentanone・Benzyl alcohol 2.36 parts by mass ----------------------------------------------------------------

[0146] Dichroic substance Dye-C1

[0147]

[0148] Dichroic substance Dye-M1

[0149]

[0150] Dichroic substance Dye-Y1

[0151]

[0152] Liquid crystal compound (L-1) (In the formula, the numerical values ​​("59", "15", "26") shown for each repeating unit represent the content (% by mass) of each repeating unit relative to all repeating units.)

[0153]

[0154] Rod-shaped liquid crystal compound (L-2) (wherein the numerical value for each compound represents the content (% by mass) of each compound relative to the total amount of all compounds.)

[0155]

[0156] Surfactant (F-1) (In the formula, the numerical value shown for each repeating unit represents the content (% by mass) of each repeating unit relative to all repeating units.)

[0157]

[0158] [Formation of Oxygen Barrier Layer D1] Coating liquid D1 having the following composition was continuously applied onto the optically absorptive anisotropic film C1 using a wire bar. This was then dried with hot air at 80°C for 5 minutes to obtain a laminate having an oxygen barrier layer D1 made of polyvinyl alcohol (PVA) with a thickness of 1.0 µm, i.e., a laminate CP1 having a cellulose acylate film A1 (transparent support), a photo-alignment film B1, an optically absorptive anisotropic film C1, and an oxygen barrier layer D1 adjacent to each other in this order. ------------------------------------------------Composition of coating liquid D1 for forming oxygen barrier layer------------------------------------------------ 3.80 parts by mass of modified polyvinyl alcohol shown below 0.20 parts by mass of initiator Irgacure 2959 Water 70 parts by mass Methanol 30 parts by mass

[0159] Modified polyvinyl alcohol (wherein the numerical value for each repeating unit represents the content (% by mass) of each repeating unit relative to all repeating units)

[0160] [Preparation of TAC Film Having Positive A Plate] A coating solution E1 for forming a photo-alignment film having the following composition was continuously coated on the above-mentioned cellulose acylate film A1 using a wire bar. The support on which the coating film was formed was dried with hot air at 140°C for 120 seconds, and then the coating film was irradiated with polarized ultraviolet light (10 mJ / cm ２ , using an ultra-high pressure mercury lamp) to form a photo-alignment film E1 with a thickness of 0.2 μm, thereby obtaining a TAC film with a photo-alignment film.

[0161] -------------------------------------------------- Coating liquid E1 for forming photoalignment film -------------------------------------------------- Polymer PA-2 (described below) 100.00 parts by mass Acid generator PAG-1 (described above) 5.00 parts by mass Acid generator CPI-110TF (described 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

[0162] Acid generator CPI-110TF

[0163]

[0164] Polymer PA-2 (wherein the numerical value for each repeating unit represents the content (% by mass) of each repeating unit relative to all repeating units)

[0165]

[0166] 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 nm, thereby fixing the alignment of the liquid crystal compound, and a TAC film having 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.

[0167] -------------------------------- 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 --------------------------------

[0168] Polymerizable liquid crystal compound LA-1 (tBu represents a tertiary butyl group)

[0169]

[0170] Polymerizable liquid crystal compound LA-2

[0171]

[0172] Polymerizable liquid crystal compound LA-3

[0173]

[0174] Polymerizable liquid crystal compound LA-4 (Me represents a methyl group)

[0175]

[0176] Polymerization initiator PI-1

[0177]

[0178] Leveling agent T-1 (wherein the numerical value for each repeating unit represents the content (% by mass) of each repeating unit relative to all repeating units)

[0179]

[0180] [Preparation of TAC Film Having Positive C-Plate H1] The above-described cellulose acylate film A1 was used as a temporary support. The cellulose acylate film A1 was passed through a dielectric heating roll at a temperature of 60°C to raise the surface temperature of the film to 40°C, and then an alkaline solution having the composition shown below was applied to one side of the film using a bar coater in an amount of 14 ml / m. ２ The film was heated to 110°C and transported for 10 seconds under a steam-type far-infrared heater manufactured by Noritake Co., Ltd. Next, pure water was applied to the film at a rate of 3 ml / m using the same bar coater. ２ Next, after repeating washing with water using a fountain coater and draining with an air knife three times, the film was transported to a drying zone at 70° C. for 10 seconds and dried to prepare an alkali-saponified cellulose acylate film A1.

[0181] ---------------------------------------------------------------- (Alkaline solution) ---------------------------------------------------------------- Potassium hydroxide 4.7 parts by mass Water 15.8 parts by mass Isopropanol 63.7 parts by mass Fluorine-containing surfactant SF-1 (C １４ H ２９ O (CH ２ CH ２ O) ２０ H) 1.0 part by mass Propylene glycol 14.8 parts by mass

[0182] A coating solution G1 for forming a photo-alignment film having the following composition was continuously applied onto the above-mentioned alkaline saponification-treated cellulose acylate film A1 using a #8 wire bar. The obtained film was dried with hot air at 60°C for 60 seconds and then with hot air at 100°C for 120 seconds to form a photo-alignment film G1.

[0183] ------------------------------------------------------------------ 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 ------------------------------------------------------------------

[0184] 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 film with ultraviolet light of 1000 nm to vertically align the liquid crystal compound, thereby producing a TAC film having a positive C-plate H1 with a thickness of 0.5 μm. The Rth(550) of the obtained positive C-plate was −60 nm.

[0185] -------------------------------- Coating liquid H1 for forming a 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 vertically aligning liquid crystal compound 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 --------------------------------

[0186] Liquid crystal compound LC-1

[0187]

[0188] Liquid crystal compound LC-2

[0189]

[0190] Vertically aligning liquid crystal compound S01

[0191]

[0192] Compound B03 (wherein the numerical value for each repeating unit represents the content (% by mass) of each repeating unit relative to all repeating units.)

[0193]

[0194] [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.

[0195] 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.

[0196] -------------------------------------------------- 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 --------------------------------------------------

[0197] -------------------------------------------------- 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 --------------------------------------------------

[0198] (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.)

[0199] [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

[0200] CPI-100P

[0201]

[0202] [Preparation of Laminate CPAC1] The retardation side of the TAC film having the positive A plate F1 and the retardation side of the TAC film having the positive C plate H1 were bonded to each other with the UV adhesive composition at 600 mJ / cm ２ The laminates were bonded together by UV irradiation. The thickness of the UV adhesive layer was 3 μm. The surfaces to be bonded with the UV adhesive were each subjected to corona treatment. Next, the photo-alignment film E1 and cellulose acylate film A1 on the positive A plate F1 side were removed to obtain a retardation plate AC1. The layer structure of the retardation plate AC1 was a positive A plate F1, a UV adhesive layer, a positive C plate H1, a photo-alignment film G1, and a cellulose acylate film A1. The oxygen-blocking layer D1 side of the laminate CP1 was bonded to the support side of a low-reflection surface film CV-LC5 (manufactured by Fujifilm Corporation) using the pressure-sensitive adhesive N1. Next, only the cellulose acylate film A1 contained in the laminate CP1 was removed, and the removed surface was bonded to the positive A plate F1 side of the retardation plate AC1 using the pressure-sensitive adhesive N1. Next, the photo-alignment film G1 and cellulose acylate film A1 on the positive C-plate H1 side of the retardation plate AC1 were removed to prepare a laminate CPAC1. The laminate CPAC1 was attached so that the absorption axis of the optically absorptive anisotropic film C1 and the slow axis of the positive A-plate F1 formed an angle of 45°. The laminate CPAC1 had a layer structure consisting of a low-reflection surface film CV-LC5, an adhesive layer N1, an oxygen-blocking layer D1, an optically absorptive 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.

[0203]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0059]

[0061]

[0059]

[0062]

[0059]

[0063]

[0059]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098] [009 ...

[0204] [Fabrication of Organic EL Display Device (Display Device 2)] After fabricating the optically absorptive anisotropic film C1, a cellulose acylate film A was bonded to the surface of the optically absorptive anisotropic film C1 opposite to the photo-alignment film B1, and then the cellulose acylate film A on the photo-alignment film B1 side was removed to form an oxygen-blocking layer D1 on the photo-alignment film B1. A laminate CP2 was obtained, comprising a cellulose acylate film A1 (transparent support), an optically absorptive anisotropic film C1, a photo-alignment film B1, and an oxygen-blocking layer D1 adjacent to each other in this order, following the same procedure as for the laminate CP1 described above. An organic EL display device (Display Device 2) was then fabricated following the same procedure as for the display device 1, except that the laminate CP2 was used instead of the laminate CP1.

[0205] [Example 2] Organic EL display devices (display device 1, display device 2) were produced in the same manner as in Example 1, except that compositions for forming optically absorptive anisotropic films having the following compositions were used as the optically absorptive anisotropic film-forming compositions.

[0206] In the optically absorptive anisotropic film C1, EPICLON N-695 has a small ΔSP value (difference in solubility parameter) with respect to the photo-alignment film B1, and therefore is unevenly distributed in region B on the photo-alignment film B1 side.

[0207] ------------------------------------------------ Composition of composition for forming optically absorptive anisotropic film (Example 2)---------------------------------------------------------------- First dichroic substance Dye-C1: 0.69 parts by mass Second dichroic substance Dye-M1: 0.14 parts by mass Third dichroic substance Dey-Y1: 0.25 parts by mass Liquid crystal compound (L-1): 3.16 parts by mass Rod-like liquid crystal compound (L-2): 1.40 parts by mass Polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.18 parts by mass EPICLON N-695 (manufactured by DIC) 0.12 parts by mass Surfactant (F-1): 0.01 parts by mass Cyclopentanone: 91.86 parts by mass・Benzyl alcohol 2.36 parts by mass ----------------------------------------------------------------

[0208] EPICLON N-695 (cresol novolac epoxy resin) (Mw=2,100) manufactured by DIC Corporation

[0209] [Example 3] Organic EL display devices (display device 1, display device 2) were produced in the same manner as in Example 1, except that compositions for forming optically absorptive anisotropic films having the following compositions were used as the compositions for forming optically absorptive anisotropic films.

[0210] In the optically absorptive anisotropic film C1, polyethylene oxide (PEO) is unevenly distributed in region A on the coated surface side, as in Example 1, and EPICLON N-695 is unevenly distributed in region B on the photo-alignment film B1 side, as in Example 2.

[0211] ------------------------------------------------ Composition of composition for forming optically absorptive anisotropic film (Example 3)---------------------------------------------------------------- First dichroic substance Dye-C1: 0.69 parts by mass Second dichroic substance Dye-M1: 0.14 parts by mass Third dichroic substance Dey-Y1: 0.25 parts by mass Liquid crystal compound (L-1): 3.16 parts by mass Rod-shaped liquid crystal compound (L-2): 1.40 parts by mass Polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.18 parts by mass Polyethylene oxide (Mw=100,000): 0.12 parts by mass EPICLON N-695 (manufactured by DIC Corporation) 0.12 parts by mass 0.01 parts by mass of the above surfactant (F-1) 91.86 parts by mass of cyclopentanone 2.36 parts by mass of benzyl alcohol

[0212] Example 4 Organic EL display devices (display device 1, display device 2) were produced in the same manner as in Example 1, except that the optically absorptive anisotropic film C1 was produced as follows.

[0213] [Preparation of Optically Absorbent Anisotropic Film C1]

[0214] <Coating Film Forming Step> A composition for forming an optically anisotropic film having the following composition was continuously coated on the photo-alignment film B1 using a wire bar to form a coating film.

[0215] <Orientation Step> Next, the coating film was heated at 140°C for 15 seconds and then cooled to room temperature (23°C). Next, an LED (light emitting diode) lamp (center wavelength 365 nm) was used to illuminate the coating film at an illuminance of 10 mW / cm. ２ The coating film was then heated at 75°C for 60 seconds and cooled to room temperature again. Thereafter, the coating film was irradiated with light at an illuminance of 200 mW / cm using an LED (light emitting diode) lamp (center wavelength 365 nm).２ The photo-alignment film B1 was irradiated for 2 seconds under the irradiation conditions of 1.8 μm to form a light absorption anisotropic film C1 (polarizer) (thickness: 1.8 μm) on the photo-alignment film B1.

[0216] The transmittance of the optically absorptive anisotropic film C1 was measured in the wavelength range of 280 to 780 nm using a spectrophotometer, and the average visible light transmittance was 42%. The absorption axis of the optically absorptive anisotropic film C1 was perpendicular to the width direction of the cellulose acylate film A1.

[0217] ---------------------------------------------------------------------------- Composition of the composition for forming an optically absorptive anisotropic film (Examples 4 to 7)---------------------------------------------------------------- First dichroic substance Dye-C1: 0.69 parts by mass Second dichroic substance Dye-M1: 0.14 parts by mass Third dichroic substance Dey-Y1: 0.25 parts by mass Liquid crystal compound (L-1): 3.16 parts by mass Rod-like liquid crystal compound (L-2): 1.40 parts by mass Polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.18 parts by mass Surfactant (F-1): 0.01 parts by mass Cyclopentanone: 91.86 parts by mass Benzyl alcohol: 2.36 parts by mass ----------------------------------------------------------------------------------

[0218] Example 5 Organic EL display devices (display device 1, display device 2) were produced in the same manner as in Example 1, except that the optically absorptive anisotropic film C1 was produced as follows.

[0219] [Preparation of Optically Absorbent Anisotropic Film C1]

[0220] <Coating Film Forming Step> A composition for forming an optically anisotropic film having the same composition as in Example 4 was continuously applied onto the photo-alignment film B1 using a wire bar to form a coating film.

[0221] <Orientation Step> Next, the coating film was heated at 140°C for 15 seconds and then cooled to room temperature (23°C). Next, an LED (light emitting diode) lamp (center wavelength 365 nm) was used to illuminate the coating film at an illuminance of 20 mW / cm. ２ The coating film was then heated at 75°C for 60 seconds and cooled to room temperature again. Thereafter, the coating film was irradiated with light from an LED (light emitting diode) lamp (center wavelength 365 nm) at an illuminance of 200 mW / cm. ２ The photo-alignment film B1 was irradiated for 2 seconds under the irradiation conditions of 1.8 μm to form a light absorption anisotropic film C1 (polarizer) (thickness: 1.8 μm) on the photo-alignment film B1.

[0222] The transmittance of the optically absorptive anisotropic film C1 was measured in the wavelength range of 280 to 780 nm using a spectrophotometer, and the average visible light transmittance was 42%. The absorption axis of the optically absorptive anisotropic film C1 was perpendicular to the width direction of the cellulose acylate film A1.

[0223] Example 6 Organic EL display devices (display device 1, display device 2) were produced in the same manner as in Example 1, except that the optically absorptive anisotropic film C1 was produced as follows.

[0224] [Preparation of Optically Absorbent Anisotropic Film C1]

[0225] <Coating Film Forming Step> A composition for forming an optically anisotropic film having the same composition as in Example 4 was continuously applied onto the photo-alignment film B1 using a wire bar to form a coating film.

[0226] <Orientation Step> Next, the coating film was heated at 140°C for 15 seconds and then cooled to room temperature (23°C). Next, using a high-pressure mercury lamp equipped with a 310 nm short-pass filter, the coating film was irradiated with light at an illuminance of 50 mW / cm ２ The coating film was then heated at 75°C for 60 seconds and cooled to room temperature again. Thereafter, an LED (light emitting diode) lamp (center wavelength 365 nm) was used to irradiate the coating film with an illuminance of 200 mW / cm. ２ The photo-alignment film B1 was irradiated for 2 seconds under the irradiation conditions of 1.8 μm to form a light absorption anisotropic film C1 (polarizer) (thickness: 1.8 μm) on the photo-alignment film B1.

[0227] The transmittance of the optically absorptive anisotropic film C1 was measured in the wavelength range of 280 to 780 nm using a spectrophotometer, and the average visible light transmittance was 42%. The absorption axis of the optically absorptive anisotropic film C1 was perpendicular to the width direction of the cellulose acylate film A1.

[0228] Example 7 Organic EL display devices (display device 1, display device 2) were produced in the same manner as in Example 1, except that the optically absorptive anisotropic film C1 was produced as follows.

[0229] [Preparation of Optically Absorbent Anisotropic Film C1]

[0230] <Coating Film Forming Step> A composition for forming an optically anisotropic film having the same composition as in Example 4 was continuously applied onto the photo-alignment film B1 using a wire bar to form a coating film.

[0231] <Orientation Step> Next, the coating film was heated at 140°C for 15 seconds and cooled to room temperature (23°C). Next, using a high-pressure mercury lamp equipped with a 310 nm short-pass filter, the coating film was irradiated with light at an illuminance of 10 mW / cm ２ The coating film was then heated at 75°C for 60 seconds and cooled to room temperature again. Thereafter, an LED (light emitting diode) lamp (center wavelength 365 nm) was used to irradiate the coating film with an illuminance of 200 mW / cm. ２ An optically absorptive anisotropic film C1 (polarizer) (thickness: 1.8 μm) was prepared on the photo-alignment film B1 by irradiating the film with light under the irradiation conditions of 1.0 μm for 2 seconds. The transmittance of the optically absorptive anisotropic film C1 in the wavelength range of 280 to 780 nm was measured using a spectrophotometer, and the average visible light transmittance was 42%. The absorption axis of the optically absorptive anisotropic film C1 was perpendicular to the width direction of the cellulose acylate film A1.

[0232] [Example 8] Organic EL display devices (display device 1, display device 2) were produced in the same manner as in Example 4, except that in producing the optically absorptive anisotropic film C1, compositions for forming an optically absorptive anisotropic film having the following compositions were used as the optically absorptive anisotropic film-forming composition.

[0233] 0.44 parts by mass of the first dichroic substance Dye-C2 described below; 0.14 parts by mass of the second dichroic substance Dye-M1; 0.25 parts by mass of the third dichroic substance Dey-Y1; 3.16 parts by mass of the liquid crystal compound (L-1); 1.40 parts by mass of the rod-shaped liquid crystal compound (L-2); 0.18 parts by mass of polymerization initiator IRGACUREOXE-02 (manufactured by BASF); 0.01 parts by mass of the surfactant (F-1); 91.86 parts by mass of cyclopentanone・Benzyl alcohol 2.36 parts by mass ----------------------------------------------------------------

[0234] Dichroic substance Dye-C2

[0235]

[0236] [Example 9] Organic EL display devices (display device 1, display device 2) were produced in the same manner as in Example 6, except that in producing the optically absorptive anisotropic film C1, a composition for forming an optically absorptive anisotropic film having the same composition as in Example 8 was used.

[0237] [Example 10] Organic EL display devices (display device 1, display device 2) were produced in the same manner as in Example 4, except that in producing the optically absorptive anisotropic film C1, compositions for forming an optically absorptive anisotropic film having the following compositions were used as the optically absorptive anisotropic film-forming composition.

[0238] 0.26 parts by mass of the first dichroic substance Dye-C1 0.77 parts by mass of the first dichroic substance Dye-C2 0.25 parts by mass of the second dichroic substance Dye-M1 0.04 parts by mass of the third dichroic substance Dey-Y2 described below 3.16 parts by mass of the liquid crystal compound (L-1) 1.40 parts by mass of the rod-shaped liquid crystal compound (L-2) 0.18 parts by mass of polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.01 parts by mass of the surfactant (F-1) Cyclopentanone 91.86 parts by mass ・Benzyl alcohol 2.36 parts by mass ----------------------------------------------------------------

[0239] Dichroic substance Dey-Y2

[0240]

[0241] [Example 11] Organic EL display devices (display device 1, display device 2) were produced in the same manner as in Example 6, except that in producing the optically absorptive anisotropic film C1, a composition for forming an optically absorptive anisotropic film having the same composition as in Example 10 was used.

[0242] [Example 12] Organic EL display devices (display device 1, display device 2) were produced in the same manner as in Example 6, except that in producing the optically absorptive anisotropic film C1, compositions for forming an optically absorptive anisotropic film having the following compositions were used.

[0243] -------------------------------- Composition of composition for forming optically absorptive anisotropic film (Example 12)------------------------------------------------ 0.26 parts by mass of the first dichroic substance Dye-C1 0.77 parts by mass of the first dichroic substance Dye-C2 0.25 parts by mass of the second dichroic substance Dye-M1 0.04 parts by mass of the third dichroic substance Dey-Y2 3.42 parts by mass of the following liquid crystal compound (L-3) 1.14 parts by mass of the following liquid crystal compound (L-4) 0.18 parts by mass of polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.01 parts by mass of the above surfactant (F-1) 91.86 parts by mass of cyclopentanone・Benzyl alcohol 2.36 parts by mass ----------------------------------------------------------------

[0244] Liquid crystal compound (L-3)

[0245]

[0246] Liquid crystal compound (L-4)

[0247]

[0248] [Comparative Example 1] Organic EL display devices (display device 1, display device 2) were produced in the same manner as in Example 1, except that the composition for forming an optically absorptive anisotropic film of Example 4 was used as the composition for forming an optically absorptive anisotropic film.

[0249] [Observation of Alignment Structure] For each example of the optically absorptive anisotropic film C1, Ltop, Llow, and Lmid were measured by the method described above. As described above, the photo-alignment film B1 side is region B (Llow), and the opposite side to the photo-alignment film B1 is region A (Ltop). The results are shown in Table 1.

[0250] [Evaluation] The fabricated organic EL display devices were evaluated as follows.

[0251] [Deepness of Black] The display screens of the prepared organic EL display devices (Display Device 1, Display Device 2) were set to black display, and fluorescent light was shone on them from the front, and the reflected light was observed. Then, the deepness of black was evaluated based on the following criteria. The results are shown in Table 1. In practice, it is preferable that at least one of Display Device 1 and Display Device 2 is A or B, and A is more preferable. A: Black, with no visible coloring. B: Slight red coloring is visible, but acceptable. C: Clear red coloring is visible, and unacceptable.

[0252] [Durability] Of Display Device 1 and Display Device 2, the display device with the better evaluation of tight black was left to stand for 500 hours in an environment of 80°C and a relative humidity of less than 10%. Thereafter, the display screen of the organic EL display device was set to black display, and the reflected light was observed when a fluorescent lamp was projected from the front. Durability was then evaluated based on the following criteria. In practical terms, A or B is preferable, and A is more preferable. A: Black, with no visible coloring. B: Slight coloring is visible, but acceptable. C: Coloring is clearly visible, and unacceptable.

[0253]

[0254] As can be seen from Table 1, all of Examples 1 to 12, which satisfied at least one of formula (1-1) and formula (1-2), exhibited excellent tightness of black. Furthermore, a comparison of Examples 1 to 12 revealed that Examples 1 to 4 and Examples 6 to 12, which satisfied formula (3-1), exhibited excellent durability. Furthermore, a comparison of Examples 1 to 12 revealed that Examples 1 to 6 and Examples 8 to 12, in which at least one of Ltop and Llow was 30 nm or less, exhibited even more excellent tightness of black.

[0255] On the other hand, in Comparative Example 1, which did not satisfy both the formula (1-1) and the formula (1-2), the density of black was insufficient.

[0256] a One surface b Other surface c Center in film thickness direction A Region A B Region B C Region C 100 Optically absorbing anisotropic film

Claims

1. A light absorption anisotropic film containing a dichroic substance and a liquid crystal compound, wherein at least a part of the dichroic substance forms an array structure, in a cross-section observed by a scanning transmission electron microscope, when the average value of the major axis lengths of the array structures observed in region A from one surface to 150 nm in the film thickness direction is Ltop, and the average value of the major axis lengths of the array structures observed in region B from the other surface to 150 nm in the film thickness direction is Llow, a light absorption anisotropic film that satisfies at least one of the following formula (1-1) and the following formula (1-2). Ltop ≤ 35 nm (1-1) Llow ≤ 35 nm (1-2)

2. In a cross-section observed by a scanning transmission electron microscope, when the average value of the major axis lengths of the array structures observed in region C of 150 nm in the center in the film thickness direction is Lmid, the light absorption anisotropic film according to Claim 1, which satisfies at least one of the following formula (2-1) and the following formula (2-2). Ltop / Lmid < 0.87 (2-1) Llow / Lmid < 0.87 (2-2)

3. In a cross-section observed by a scanning transmission electron microscope, when the average value of the major axis lengths of the array structures observed in region C of 150 nm in the center in the film thickness direction is Lmid, the light absorption anisotropic film according to Claim 1, which satisfies the following formula (3-1). Lmid > 40 nm (3-1)

4. The light absorption anisotropic film according to Claim 1, containing a preferentially distributed substance preferentially distributed in at least one of the region A and the region B.

5. The light absorption anisotropic film according to Claim 4, wherein the weight average molecular weight of the preferentially distributed substance is 1000 or more.

6. A method for manufacturing the light absorption anisotropic film according to any one of Claims 1 to 5, including a coating film forming step of forming a coating film by coating a composition for forming a light absorption anisotropic film containing a dichroic substance and a liquid crystal compound on an alignment film, and an alignment step of obtaining a light absorption anisotropic film by aligning the dichroic substance contained in the coating film.

7. The manufacturing method according to Claim 6, wherein the alignment step includes a step of exposing the coating film in the atmosphere.

8. The manufacturing method according to Claim 6, wherein the alignment step includes a step of exposing the coating film with ultraviolet light containing no light of 330 nm or more.

9. A laminate having the light absorption anisotropic film according to any one of Claims 1 to 5 and a λ / 4 plate.

10. An image display device having the light absorption anisotropic film according to any one of Claims 1 to 5.