Laminates and image display devices

Abstract

To provide a laminate containing a light-absorbing anisotropic layer sandwiched between adhesive layers, which has excellent resistance to moist heat, and an image display device using the same. [Solution] A laminate having an adhesive layer 1, a light-absorbing anisotropic layer, and an adhesive layer 2 in this order, wherein the light-absorbing anisotropic layer contains an organic dichroic substance, the thickness of the light-absorbing anisotropic layer is 5 μm or less, adhesive layer 1 and adhesive layer 2 are the adhesive layers in the laminate that are closest to the light-absorbing anisotropic layer, and H represented by the following formula (I) is 10.0 or less. H = (Thickness of adhesive layer 1 + Thickness of adhesive layer 2) / Total thickness of layers inside adhesive layer 1 and adhesive layer 2. Equation (I)

Description

[Technical Field]

[0001] This invention relates to a laminate and an image display device. [Background technology]

[0002] In recent years, organic electroluminescent (hereinafter abbreviated as "EL") display devices have become thinner, and there is a growing demand for even thinner components to be used in them. Organic EL display devices have high reflectivity, so circular polarizers consisting of a λ / 4 plate and a polarizer are used to prevent reflection of ambient light. However, there is a need to make these circular polarizers thinner as well. However, iodine polarizers, which are commonly used in circular polarizers, are made by dissolving or adsorbing iodine into a polymer material such as polyvinyl alcohol, and then stretching the resulting film in one direction at high magnification, making it difficult to achieve sufficient thinness.

[0003] Therefore, polarizing elements are being investigated that involve coating a dichroic azo dye onto a substrate such as a transparent film and aligning it using intermolecular interactions. For example, Patent Document 1 proposes a polarizing element having a high dichroic azo dye concentration and a high degree of polarization in a thin film. Furthermore, Patent Document 2 proposes a polarizing element with a high degree of orientation by using a specific liquid crystalline compound to enhance the crystallinity of a dichroic azo dye compound. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 5437744 [Patent Document 2] International Publication No. 2018 / 124198 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The present inventors have found that when a laminate is fabricated with a polarizing element (hereinafter also referred to as the "light-absorbing anisotropic layer") as described in Patent Documents 1 and 2, etc., having a layer structure in which the light-absorbing anisotropic layer is sandwiched between two adhesive layers for bonding with a picture display element, etc., wrinkles occur in the light-absorbing anisotropic layer when exposed to a high-temperature, high-humidity environment.

[0006] Therefore, the object of the present invention is to provide a laminate containing a light-absorbing anisotropic layer sandwiched between adhesive layers, which has excellent resistance to moist heat, and an image display device using the same. [Means for solving the problem]

[0007] As a result of diligent research to achieve the above objectives, the inventors of the present invention have found that, in a configuration in which a light-absorbing anisotropic layer containing an organic dichroic substance is sandwiched between adhesive layers, the objectives of the present invention can be achieved by appropriately controlling the total thickness of the adhesive layer and the total thickness of the layer sandwiched between the adhesive layers. In other words, we found that the above problem can be solved by the following configuration.

[0008] [1] A laminate having an adhesive layer 1, a light-absorbing anisotropic layer, and an adhesive layer 2 in this order, The light-absorbing anisotropic layer contains an organic dichroic substance, The thickness of the light-absorbing anisotropic layer is 5 μm or less. Adhesive layer 1 and adhesive layer 2 are, respectively, the adhesive layers located closest to the light-absorbing anisotropic layer in the laminate. A laminate in which H, represented by the following formula (I), is 10.0 or less. H = (Thickness of adhesive layer 1 + Thickness of adhesive layer 2) / Total thickness of layers inside adhesive layer 1 and adhesive layer 2. Equation (I)

[0009] [2] The laminate according to [1], wherein H represented by the above formula (I) is 6.0 or less. [3] The laminate according to [1] or [2], wherein H represented by formula (I) above is 4.0 or less. [4] The laminate according to any one of [1] to [3], wherein the storage modulus of at least one of the adhesive layer 1 and the adhesive layer 2 is 0.1 MPa or more. [5] The laminate according to [4], wherein the storage modulus of both adhesive layer 1 and adhesive layer 2 is 0.1 MPa or greater. [6] The laminate according to [4] or [5], wherein the storage modulus of at least one of the adhesive layer 1 and the adhesive layer 2 is 0.5 MPa or more. [7] The laminate according to [6], wherein the storage modulus of the adhesive layer 1 is 0.5 MPa or more. [8] The laminate according to [6], wherein the storage modulus of both adhesive layer 1 and adhesive layer 2 is 0.5 MPa or greater. [9] The laminate according to any one of [1] to [8], wherein the thickness of the adhesive layer 1 is 8 μm or less.

[10] The laminate according to any one of [1] to [9], wherein the thickness of the light-absorbing anisotropic layer is 0.8 μm or less.

[0010]

[11] The laminate according to any one of [1] to

[10] , wherein at least one of the adhesive layer 1 and the adhesive layer 2 contains a polymer having repeating units represented by the following formula (A). [ka] In the above formula (A), R 1 R represents a hydrogen atom or a methyl group. 2 This represents an alkyl group with 1 to 6 carbon atoms.

[0011]

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

[11] , having an adhesive layer 1, a light-absorbing anisotropic layer, a curable adhesive layer, an optical anisotropic layer, and an adhesive layer 2 in this order.

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

[12] , having an adhesive layer 1, an oxygen barrier layer, a curing layer, a light-absorbing anisotropic layer, a curing adhesive layer, an optical anisotropic layer, and an adhesive layer 2 in this order.

[14] The laminate according to

[13] , having an adhesive layer 1, an oxygen barrier layer, a curing layer, a light-absorbing anisotropic layer, a curing adhesive layer, an optical anisotropic layer, and an adhesive layer 2 adjacent to each other in this order.

[15] The laminate according to

[13] or

[14] , wherein the curable adhesive layer is an ultraviolet curable adhesive layer.

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

[15] , further comprising a surface protective layer on the side opposite to the side of the adhesive layer 1 that has the light-absorbing anisotropic layer.

[0012]

[17] The laminate has an image display element and any of the laminates described in [1] to

[16] . An image display device in which the image display element is positioned on the side opposite to the side of the adhesive layer 2 that has the light-absorbing anisotropic layer.

[18] The image display device according to

[17] , wherein the image display element is an organic EL display element. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a laminate containing a light-absorbing anisotropic layer sandwiched between adhesive layers, which has excellent resistance to moist heat, and an image display device using the same. [Brief explanation of the drawing]

[0014] [Figure 1] Figure 1 is a schematic cross-sectional view showing an example of the laminate of the present invention. [Figure 2] Figure 2 is a schematic cross-sectional view showing an example of the laminate of the present invention. [Modes for carrying out the invention]

[0015] The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In addition, in this specification, "parallel", "orthogonal", "horizontal", and "vertical" do not mean parallel, orthogonal, horizontal, and vertical in the strict sense, but rather mean a range of parallel ±10°, a range of orthogonal ±10°, horizontal ±10°, and vertical ±10°, respectively. In addition, in this specification, each component may be used alone as one kind of substance corresponding to each component, or two or more kinds may be used in combination. Here, when two or more kinds of substances are used in combination for each component, the content of that component refers to the total content of the combined substances, unless otherwise specified. In 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".

[0016] (In-plane average refractive index measurement method) The in-plane average refractive index is measured using a spectroscopic ellipsometer M-2000U manufactured by Woollam. The direction with the maximum refractive index in the plane is defined as the x-axis, the direction orthogonal to it is the y-axis, and the normal direction to the plane is the z-axis. The refractive indices in each direction are defined as n x , n y , n z . The in-plane average refractive index (n ave ) in the present invention is represented by the following formula (1). Formula (1) n ave =(n x +n y ) / 2

[0017] [Laminate] As shown in FIG. 1, the laminate (100) of the present invention is a laminate (100) having an adhesive layer 1 (1), a light absorption anisotropic layer (2), and an adhesive layer 2 (3) in this order. The light absorption anisotropic layer (2) contains an organic dichroic substance, the thickness of the light absorption anisotropic layer (2) is 5 μm or less, and the adhesive layer 1 (1) and the adhesive layer 2 (3) are adhesive layers at the positions closest to the light absorption anisotropic layer (2) in the laminate (100), respectively. The laminate is one in which H (hereinafter simply abbreviated as "H value"), represented by the following formula (I), is 10.0 or less. H = (Thickness of adhesive layer 1 + Thickness of adhesive layer 2) / Total thickness of layers inside adhesive layer 1 and adhesive layer 2. Equation (I) Here, "adhesive layer 1 and adhesive layer 2 are each located in the closest position to the light-absorbing anisotropic layer in the laminate" means that there are no other adhesive layers between adhesive layer 1 and adhesive layer 2. Therefore, for example, if the laminate of the present invention has three or more adhesive layers, adhesive layer 1 is the adhesive layer located in the closest position on the opposite side of the light-absorbing anisotropic layer from the side with adhesive 2, and adhesive layer 2 is the adhesive layer located in the closest position on the opposite side of the light-absorbing anisotropic layer from the side with adhesive 1.

[0018] In this invention, the H value is preferably 6.0 or less, and more preferably 4.0 or less, because it provides better resistance to moist heat. There is no particular lower limit, but it is usually 0.1 or higher.

[0019] The laminate (200) of the present invention is preferably a laminate having an adhesive layer 1, a light-absorbing anisotropic layer, a curable adhesive layer, an optical anisotropic layer, and an adhesive layer 2 in this order, for the reason that the H value can be reduced. Furthermore, for the reason that the H value can be reduced, the laminate (200) of the present invention is preferably a laminate having an adhesive layer 1 (1), an oxygen barrier layer (5), a cured layer (6), a light-absorbing anisotropic layer (2), a curable adhesive layer (7), an optical anisotropic layer (8), and an adhesive layer 2 (3) in this order, as shown in Figure 2, and more preferably a laminate having these layers adjacent to each other. Furthermore, for the sake of improving surface scratch resistance, it is preferable that the laminate (200) of the present invention has an additional surface protection layer (4) on the side of the adhesive layer 1 (1) opposite to the side having the light-absorbing anisotropic layer (2), as shown in Figure 2.

[0020] [Light-absorbing anisotropic layer] The light-absorbing anisotropic layer in the laminate of the present invention is a light-absorbing anisotropic layer containing an organic dichroic substance and having a thickness of 5 μm or less. In the present invention, the thickness of the light-absorbing anisotropic layer is preferably 0.1 to 5 μm, and more preferably 0.1 to 3 μm. In particular, for the reasons why the effects of the present invention are particularly pronounced, it is preferably 0.8 μm or less, and more preferably 0.1 to 0.8 μm. Furthermore, in the present invention, it is preferable that the light-absorbing anisotropic layer is formed using a composition containing an organic dichroic substance (hereinafter also referred to as the "composition for forming a light-absorbing anisotropic layer").

[0021] <Organic dichroic substances> There are no particular limitations on the organic dichroic substances used in the present invention. As the organic dichroic substance, a dichroic azo dye compound is preferred, and dichroic azo dye compounds commonly used in so-called coated polarizers can be used. The dichroic azo dye compound is not particularly limited, and conventionally known dichroic azo dyes can be used, but the compounds described below are preferred.

[0022] In this invention, a dichroic azo dye compound means a dye whose absorbance differs depending on the direction. The dichroic azo dye compound may or may not exhibit liquid crystalline properties. When a dichroic azo dye compound exhibits liquid crystalline properties, it may exhibit either nematic or smectic properties. The temperature range in which the liquid crystalline phase is exhibited is preferably room temperature (approximately 20°C to 28°C) to 300°C, and more preferably 50°C to 200°C from the viewpoint of handling and manufacturing suitability.

[0023] In the present invention, from the viewpoint of color adjustment, it is preferable that the light-absorbing anisotropic layer has at least one dye compound having a maximum absorption wavelength in the range of 560 to 700 nm (hereinafter also referred to as the "first dichroic azo dye compound") and at least one dye compound having a maximum absorption wavelength in the range of 455 nm or more and less than 560 nm (hereinafter also referred to as the "second dichroic azo dye compound"). More specifically, it is more preferable that it has at least a dichroic azo dye compound represented by formula (1) described later and a dichroic azo dye compound represented by formula (2) described later.

[0024] In the present invention, three or more dichroic azo dye compounds may be used in combination. For example, from the viewpoint of making the light-absorbing anisotropic layer closer to black, it is preferable to use a first dichroic azo dye compound, a second dichroic azo dye compound, and at least one dye compound having a maximum absorption wavelength in the range of 380 nm to less than 455 nm (preferably in the range of 380 to 454 nm) in combination (hereinafter also referred to as the "third dichroic azo dye compound").

[0025] In the present invention, it is preferable that the dichroic azo dye compound has a crosslinking group for the reason that it provides better resistance to pressure. Examples of crosslinkable groups include (meth)acryloyl groups, epoxy groups, oxetanyl groups, and styryl groups, with (meth)acryloyl groups being preferred.

[0026] (First dichroic azo dye compound) The first dichroic azo dye compound is preferably a compound having a chromophore as a core and side chains bound to the ends of the chromophore. Specific examples of chromophores include aromatic ring groups (e.g., aromatic hydrocarbon groups, aromatic heterocyclic groups) and azo groups. Structures having both aromatic ring groups and azo groups are preferred, and bis-azo structures having an aromatic heterocyclic group (preferably a thienothiazole group) and two azo groups are more preferred. The side chain is not particularly limited and may include groups represented by L3, R2, or L4 in formula (1) described below.

[0027] The first dichroic azo dye compound is preferably a dichroic azo dye compound having a maximum absorption wavelength in the range of 560 nm to 700 nm (more preferably 560 to 650 nm, and particularly preferably 560 to 640 nm) from the viewpoint of adjusting the color of the polarizer. In this specification, the maximum absorption wavelength (nm) of a dichroic azo dye compound is determined from the ultraviolet-visible light spectrum in the wavelength range of 380 to 800 nm, measured by a spectrophotometer using a solution of the dichroic azo dye compound dissolved in a good solvent.

[0028] In the present invention, the first dichroic azo dye compound is preferably a compound represented by the following formula (1) because it further improves the degree of orientation of the formed light-absorbing anisotropic layer.

[0029] [ka]

[0030] In formula (1), Ar1 and Ar2 each independently represent an optionally substituted phenylene group or an optionally substituted naphthylene group, with the phenylene group being preferred.

[0031] In formula (1), R1 represents a hydrogen atom, a linear or branched alkyl group which may have substituents having 1 to 20 carbon atoms, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylcarbonyl group, an alkyloxycarbonyl group, an acyloxy group, an alkylcarbonate group, an alkylamino group, an acylamino group, an alkylcarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an alkylsulfamoyl group, an alkylcarbamoyl group, an alkylsulfinyl group, an alkylureido group, an alkylphosphate amide group, an alkylimino group, or an alkylsilyl group. The -CH2- group constituting the above alkyl group may also be substituted with -O-, -CO-, -C(O)-O-, -OC(O)-, -Si(CH3)2-O-Si(CH3)2-, -N(R1')-, -N(R1')-CO-, -CO-N(R1')-, -N(R1')-C(O)-O-, -OC(O)-N(R1')-, -N(R1')-C(O)-N(R1')-, -CH=CH-, -C≡C-, -N=N-, -C(R1')=CH-C(O)-, or -OC(O)-O-. If R1 is a group other than a hydrogen atom, the hydrogen atoms in each group may be substituted with a halogen atom, a nitro group, a cyano group, -N(R1')2, an amino group, -C(R1')=C(R1')-NO2, -C(R1')=C(R1')-CN, or -C(R1')=C(CN)2. R1' represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. If multiple R1' elements exist in each group, they may be the same or different from one another.

[0032] In formula (1), R2 and R3 each independently represent a hydrogen atom, a linear or branched alkyl group which may have substituents having 1 to 20 carbon atoms, an alkoxy group, an acyl group, an alkyloxycarbonyl group, an alkylamide group, an alkylsulfonyl group, an aryl group, an arylcarbonyl group, an arylsulfonyl group, an aryloxycarbonyl group, or an arylamide group. The -CH2- constituting the above alkyl group may be substituted with -O-, -S-, -C(O)-, -C(O)-O-, -OC(O)-, -C(O)-S-, -SC(O)-, -Si(CH3)2-O-Si(CH3)2-, -NR2'-, -NR2'-CO-, -CO-NR2'-, -NR2'-C(O)-O-, -OC(O)-NR2'-, -NR2'-C(O)-NR2'-, -CH=CH-, -C≡C-, -N=N-, -C(R2')=CH-C(O)-, or -OC(O)-O-. If R2 and R3 are groups other than hydrogen atoms, the hydrogen atoms in each group may be substituted with halogen atoms, nitro groups, cyano groups, -OH groups, -N(R2')2, amino groups, -C(R2')=C(R2')-NO2, -C(R2')=C(R2')-CN, or -C(R2')=C(CN)2. R2' represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. If multiple R2' elements exist in each group, they may be identical or different from one another. R2 and R3 may bond to each other to form a ring, or R2 or R3 may bond to Ar2 to form a ring.

[0033] From the viewpoint of lightfastness, R1 is preferably an electron-withdrawing group, and R2 and R3 are preferably groups with low electron-donating properties. Specific examples of such groups include alkylsulfonyl groups, alkylcarbonyl groups, alkyloxycarbonyl groups, acyloxy groups, alkylsulfonylamino groups, alkylsulfamoyl groups, alkylsulfinyl groups, and alkylureido groups for R1, and groups with the following structures for R2 and R3. Note that the groups with the following structures are shown in formula (1) above in a form that includes the nitrogen atom to which R2 and R3 are bonded.

[0034] [ka]

[0035] Specific examples of the first dichroic azo dye compound are shown below, but are not limited to these.

[0036] [ka] JPEG2026116358000005.jpg161127JPEG2026116358000006.jpg1296

[0037] (Second dichroic azo dye compound) The second dichroic azo dye compound is a different compound from the first dichroic azo dye compound, specifically in that its chemical structure is different. The second dichroic azo dye compound is preferably a compound having a chromophore, which is the core of the dichroic azo dye compound, and a side chain bound to the end of the chromophore. Specific examples of chromophores include aromatic ring groups (e.g., aromatic hydrocarbon groups, aromatic heterocyclic groups) and azo groups. Structures having both aromatic hydrocarbon groups and azo groups are preferred, and bisazo or trisazo structures having an aromatic hydrocarbon group and two or three azo groups are more preferred. The side chain is not particularly limited and may include groups represented by R4, R5, or R6 in formula (2) described below.

[0038] The second dichroic azo dye compound is a dichroic azo dye compound having a maximum absorption wavelength in the range of 455 nm to less than 560 nm. From the viewpoint of adjusting the color of the polarizer, it is preferable that the dichroic azo dye compound has a maximum absorption wavelength in the range of 455 to 555 nm, and more preferably that it has a maximum absorption wavelength in the range of 455 to 550 nm. In particular, using a first dichroic azo dye compound with a maximum absorption wavelength of 560-700 nm and a second dichroic azo dye compound with a maximum absorption wavelength of 455 nm or more and less than 560 nm makes it easier to adjust the color of the polarizer.

[0039] The second dichroic azo dye compound is preferably the compound represented by formula (2) because it further improves the orientation of the polarizer.

[0040] [ka]

[0041] In equation (2), n represents either 1 or 2. In formula (2), Ar3, Ar4, and Ar5 each independently represent an optionally substituted phenylene group, an optionally substituted naphthylene group, or an optionally substituted heterocyclic group. The heterocyclic group may be either aromatic or non-aromatic. Atoms other than carbon that constitute an aromatic heterocyclic group include nitrogen, sulfur, and oxygen atoms. If an aromatic heterocyclic group has multiple atoms other than carbon that constitute the ring, these may be the same or different. Specific examples of aromatic heterocyclic groups include pyridylene (pyridine-diyl group), pyridazine-diyl group, imidazole-diyl group, thienylene (thiophene-diyl group), quinolylene (quinoline-diyl group), isoquinolylene (isoquinoline-diyl group), oxazole-diyl group, thiazole-diyl group, oxadiazole-diyl group, benzothiazole-diyl group, benzothiadiazole-diyl group, phthalimide-diyl group, thienothiazole-diyl group, thiazolothiazole-diyl group, thienothiophene-diyl group, and thienoxazole-diyl group.

[0042] In equation (2), the definition of R4 is the same as that of R1 in equation (1). In equation (2), the definitions of R5 and R6 are the same as those of R2 and R3 in equation (1), respectively.

[0043] From the viewpoint of lightfastness, R4 is preferably an electron-withdrawing group, and R5 and R6 are preferably groups with low electron-donating properties. Among these groups, a specific example when R4 is an electron-withdrawing group is the same as a specific example when R1 is an electron-withdrawing group, and a specific example when R5 and R6 are groups with low electron-donating properties is the same as a specific example when R2 and R3 are groups with low electron-donating properties.

[0044] Specific examples of the second type of dichroic azo dye compound are shown below, but are not limited to these.

[0045] [ka] JPEG2026116358000009.jpg155111JPEG2026116358000010.jpg160106JPEG2026116358000011.jpg167111

[0046] (Difference in logP values) The logP value is an index that expresses the hydrophilic and hydrophobic properties of a chemical structure. The absolute difference between the logP value of the side chain of the first dichroic azo dye compound and the logP value of the side chain of the second dichroic azo dye compound (hereinafter also referred to as the "logP difference") is preferably 2.30 or less, more preferably 2.0 or less, even more preferably 1.5 or less, and particularly preferably 1.0 or less. If the logP difference is 2.30 or less, the affinity between the first dichroic azo dye compound and the second dichroic azo dye compound increases, making it easier to form a sequence structure, and thus the degree of orientation of the light-absorbing anisotropic layer is further improved. Furthermore, if the first dichroic azo dye compound or the second dichroic azo dye compound has multiple side chains, it is preferable that at least one logP difference satisfies the above value. Here, the side chains of the first dichroic azo dye compound and the second dichroic azo dye compound refer to the groups that bind to the ends of the chromophore described above. For example, if the first dichroic azo dye compound is the compound represented by formula (1), then R1, R2, and R3 in formula (1) are the side chains, and if the second dichroic azo dye compound is the compound represented by formula (2), then R4, R5, and R6 in formula (2) are the side chains. In particular, if the first dichroic azo dye compound is the compound represented by formula (1) and the second dichroic azo dye compound is the compound represented by formula (2), it is preferable that at least one of the logP differences among the difference in logP values ​​between R1 and R4, the difference in logP values ​​between R1 and R5, the difference in logP values ​​between R2 and R4, and the difference in logP values ​​between R2 and R5 satisfies the above value.

[0047] Here, the logP value is an index that expresses the hydrophilic and hydrophobic properties of a chemical structure, and is sometimes called the hydrophilic / hydrophobic parameter. The logP value can be calculated using software such as ChemBioDraw Ultra or HSPiP (Ver. 4.1.07). It can also be determined experimentally by methods such as those described in OECD Guidelines for the Testing of Chemicals, Sections 1, Test No. 117. In this invention, unless otherwise specified, the value calculated by inputting the structural formula of the compound into HSPiP (Ver. 4.1.07) will be adopted as the logP value.

[0048] (Third dichroic azo dye compound) The third dichroic azo dye compound is a dichroic azo dye compound other than the first and second dichroic azo dye compounds, and specifically, it has a different chemical structure from the first and second dichroic azo dye compounds. If the light-absorbing anisotropic layer contains the third dichroic azo dye compound, it has the advantage of making it easier to adjust the color of the light-absorbing anisotropic layer. The maximum absorption wavelength of the third dichroic azo dye compound is 380 nm or more and less than 455 nm, with 385 to 454 nm being preferred. Specific examples of the third dichroic azo dye compound include compounds represented by formula (1) described in International Publication No. 2017 / 195833, other than the first dichroic azo dye compound and the second dichroic azo dye compound.

[0049] The following are specific examples of the third dichroic dye compound, but the present invention is not limited to these. In the following examples, n represents an integer from 1 to 10.

[0050] [ka]

[0051] [ka]

[0052] (Content of dichroic azo dye compounds) The content of the dichroic azo dye compound is preferably 15 to 30% by mass, more preferably 18 to 28% by mass, and even more preferably 20 to 26% by mass, relative to the total solid content mass of the light-absorbing anisotropic layer. If the content of the dichroic azo dye compound is within the above range, a light-absorbing anisotropic layer with a high degree of orientation can be obtained even when the light-absorbing anisotropic layer is made into a thin film. Therefore, a light-absorbing anisotropic layer with excellent flexibility can be easily obtained. Furthermore, if it exceeds 30% by mass, it becomes difficult to suppress internal reflection by the refractive index adjustment layer. The content of the first dichroic azo dye compound is preferably 40 to 90 parts by mass, and more preferably 45 to 75 parts by mass, based on 100 parts by mass of the total content of dichroic azo dye compounds in the light-absorbing anisotropic layer-forming composition. The content of the second dichroic azo dye compound is preferably 6 to 50 parts by mass, and more preferably 8 to 35 parts by mass, based on 100 parts by mass of the total content of dichroic azo dye compounds in the light-absorbing anisotropic layer-forming composition. The content of the third dichroic azo dye compound is preferably 3 to 35 parts by mass, and more preferably 5 to 30 parts by mass, based on the total content of the dichroic azo dye compound in the light-absorbing anisotropic layer-forming composition. The content ratio of the first dichroic azo dye compound, the second dichroic azo dye compound, and the third dichroic azo dye compound, which may be used as needed, can be arbitrarily set to adjust the color of the light-absorbing anisotropic layer. However, the content ratio of the second dichroic azo dye compound to the first dichroic azo dye compound (second dichroic azo dye compound / first dichroic azo dye compound) is preferably 0.1 to 10, more preferably 0.2 to 5, and particularly preferably 0.3 to 0.8 in molar terms. If the content ratio of the second dichroic azo dye compound to the first dichroic azo dye compound is within the above range, the degree of orientation can be increased.

[0053] <Liquid crystal compounds> The light-absorbing anisotropic layer-forming composition may contain a liquid crystalline compound. By including a liquid crystalline compound, the precipitation of organic dichroic substances (especially dichroic azo dye compounds) can be suppressed while the organic dichroic substances (especially dichroic azo dye compounds) can be oriented with a high degree of orientation. Liquid crystalline compounds are liquid crystalline compounds that do not exhibit dichroism. Both low-molecular-weight liquid crystalline compounds and high-molecular-weight liquid crystalline compounds can be used as liquid crystalline compounds, but high-molecular-weight liquid crystalline compounds are more preferable for obtaining a high degree of orientation. Here, "low-molecular-weight liquid crystalline compound" refers to a liquid crystalline compound that does not have repeating units in its chemical structure. "High-molecular-weight liquid crystalline compound" refers to a liquid crystalline compound that has repeating units in its chemical structure. Examples of low-molecular-weight liquid crystalline compounds include the liquid crystalline compounds described in Japanese Patent Publication No. 2013-228706. Examples of polymeric liquid crystalline compounds include the thermotropic liquid crystalline polymer described in Japanese Patent Publication No. 2011-237513. Furthermore, the polymeric liquid crystalline compound may have crosslinkable groups (e.g., acryloyl groups and methacryloyl groups) at its terminals. Liquid crystalline compounds may be used individually or in combination of two or more. The content of the liquid crystalline compound is preferably 100 to 600 parts by mass, more preferably 200 to 450 parts by mass, and even more preferably 250 to 400 parts by mass, based on the content of the organic dichroic substance (particularly dichroic azo dye compound) in the light-absorbing anisotropic layer-forming composition by 100 parts by mass. Having the liquid crystalline compound content within the above range further improves the degree of orientation of the light-absorbing anisotropic layer.

[0054] The liquid crystalline compound is preferably a polymer liquid crystalline compound containing a repeating unit represented by the following formula (3-1) (hereinafter also referred to as "repeating unit (3-1)"), because it exhibits a superior degree of orientation of organic dichroic substances (especially dichroic azo dye compounds).

[0055] [ka]

[0056] In formula (3-1) above, P1 represents the repeating main chain, 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.

[0057] In the repeating unit (3-1), it is preferable that the difference between the logP values ​​of P1, L1, and SP1 and the logP value of M1 is 4 or more. More preferably, it is 4.5 or more. Since the logP values ​​of the main chain, L1, and spacer groups and the log value of the mesogenic group are separated by a predetermined value or more, the compatibility between the structure from the main chain to the spacer group and the mesogenic group is low. This is presumed to increase the crystallinity of the polymeric liquid crystalline compound and increase the degree of orientation of the polymeric liquid crystalline compound. Thus, it is presumed that when the degree of orientation of the polymeric liquid crystalline compound is high, the compatibility between the polymeric liquid crystalline compound and organic dichroic substances (especially dichroic azo dye compounds) decreases (i.e., the crystallinity of the dichroic azo dye compound improves), and the degree of orientation of the dichroic azo dye compound improves. As a result, it is thought that the degree of orientation of the resulting light-absorbing anisotropic layer will be high.

[0058] Specifically, the main chain of the repeating unit represented by P1 can be, for example, a group represented by the following formulas (P1-A) to (P1-D), and among these, the group represented by the following formula (P1-A) is preferred from the viewpoint of the diversity of monomers used as raw materials and ease of handling.

[0059] [ka]

[0060] In equations (P1-A) to (P1-D), "*" represents the bonding position with L1 in equation (3-1). In the above equations (P1-A) to (P1-D), R 1 , R 2 , R 3 and R 4Each of these independently represents a hydrogen atom, a halogen atom, a cyano group, or a C1-C10 alkyl group, or a C1-C10 alkoxy group. The alkyl group may be a linear or branched alkyl group, or a cyclic alkyl group (cycloalkyl group). The number of carbon atoms in the alkyl group is preferably 1 to 5. The group represented by the above formula (P1-A) is preferably a unit of the partial structure of a poly(meth)acrylic acid ester obtained by polymerization of (meth)acrylic acid esters. The group represented by the above formula (P1-B) is preferably an ethylene glycol unit formed by ring-opening polymerization of the epoxy group of a compound having an epoxy group. The group represented by the above formula (P1-C) is preferably a propylene glycol unit formed by ring-opening polymerization of the oxetane group of a compound having an oxetane group. The group represented by the above formula (P1-D) is preferably a siloxane unit of a polysiloxane obtained by condensation polymerization of a compound having at least one of an alkoxysilyl group and a silanol group. Here, the compound having at least one of an alkoxysilyl group and a silanol group is a compound of the formula SiR 14 (OR 15 Examples include compounds having a group represented by )2-. In the formula, R 14 R in (P1-D) 14 It is synonymous with multiple R 15 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0061] L1 is a single bond or a divalent linking group. The divalent linking groups represented by L1 include -C(O)O-, -OC(O)-, -O-, -S-, and -C(O)NR 3 -, -NR 3 C(O)-, -SO2-, and -NR 3 R 4 - are some examples. In the formula, R 3 and R 4 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which may have substituents. When P1 is a group represented by formula (P1-A), L1 is preferably a group represented by -C(O)O- because it provides a better degree of orientation of the light absorption anisotropy layer. When P1 is a group represented by formulas (P1-B) to (P1-D), L1 is preferably a single bond because it results in a better degree of orientation of the light absorption anisotropy layer.

[0062] The spacer group represented by SP1 preferably includes at least one structure selected from the group consisting of oxyethylene structure, oxypropylene structure, polysiloxane structure, and fluorinated alkylene structure, due to reasons such as its tendency to exhibit liquid crystalline properties and the availability of raw materials. Here, the oxyethylene structure represented by SP1 is *-(CH2-CH2O) n1 A group represented by -* is preferred. In the formula, n1 represents an integer from 1 to 20, and * represents the bonding position with L1 or M1 in formula (3-1) above. n1 is preferably an integer from 2 to 10, more preferably an integer from 2 to 4, and most preferably 3, because it provides a better degree of orientation of the light absorption anisotropy layer. Furthermore, the oxypropylene structure represented by SP1 is *-(CH(CH3)-CH2O) because it exhibits a superior degree of orientation in the light-absorbing anisotropic layer. n2 A base represented by -* is preferred. In the formula, n2 represents an integer from 1 to 3, and * represents the bonding position with L1 or M1. Furthermore, the polysiloxane structure represented by SP1 is *-(Si(CH3)2-O) because it exhibits a superior degree of orientation in the light-absorbing anisotropic layer. n3 A base represented by -* is preferred. In the formula, n3 represents an integer between 6 and 10, and * represents the bonding position with L1 or M1. Furthermore, the alkylene fluoride structure represented by SP1 is *-(CF2-CF2) because it exhibits a superior degree of orientation in the light-absorbing anisotropic layer. n4 A base represented by -* is preferred. In the formula, n4 represents an integer between 6 and 10, and * represents the bonding position with L1 or M1.

[0063] The mesogenic group represented by M1 is the group that represents the main skeleton of liquid crystal molecules that contribute to liquid crystal formation. Liquid crystal molecules exhibit liquid crystalline properties, which is an intermediate state (mesophase) between the crystalline state and the isotropic liquid state. There are no particular restrictions on the mesogenic group; for example, refer to the description in "Flussige Kristalle in Tabellen II" (VEB Deutsche Verlag fur Grundstoff Industrie, Leipzig, 1984), especially pages 7 to 16, and the description in the Liquid Crystal Handbook (Maruzen, 2000), edited by the Liquid Crystal Handbook Editorial Committee, especially Chapter 3. As the mesogenic group, a group having at least one cyclic structure selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups is preferred. The mesogenic group preferably has aromatic hydrocarbon groups, more preferably has 2 to 4 aromatic hydrocarbon groups, and even more preferably has 3 aromatic hydrocarbon groups, because it provides a better degree of orientation of the light-absorbing anisotropic layer.

[0064] As for the mesogenic group, a group represented by the following formula (M1-A) or (M1-B) is preferred, and the group represented by formula (M1-B) is more preferred, from the viewpoint of exhibiting liquid crystalline properties, adjusting the liquid crystal phase transition temperature, availability of raw materials, and suitability for synthesis, as well as because it provides a superior degree of orientation of the light-absorbing anisotropic layer.

[0065] [ka]

[0066] 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 alkyl groups, alkyl fluoride groups, alkoxy groups, or substituents. The divalent group represented by A1 is preferably a 4- to 6-membered ring. Furthermore, the divalent group represented by A1 may be a monoring or a fused ring. * indicates the binding site with SP1 or T1.

[0067] Examples of the divalent aromatic hydrocarbon group represented by A1 include phenylene, naphthylene, fluorene-diyl, anthracene-diyl, and tetracene-diyl groups. From the viewpoint of the diversity of mesogenic skeleton design and the availability of raw materials, a phenylene or naphthylene group is preferred, with a phenylene group being more preferred.

[0068] The divalent heterocyclic group represented by A1 may be either aromatic or non-aromatic, but from the viewpoint of improving the degree of orientation, it is preferable that it be a divalent aromatic heterocyclic group. Atoms other than carbon that constitute a divalent aromatic heterocyclic group include nitrogen, sulfur, and oxygen atoms. If an aromatic heterocyclic group has multiple atoms other than carbon that constitute the ring, these may be the same or different. Specific examples of divalent aromatic heterocyclic groups include, for example, pyridylene (pyridine-diyl group), pyridazine-diyl group, imidazole-diyl group, thienylene (thiophene-diyl group), quinolylene (quinoline-diyl group), isoquinolylene (isoquinoline-diyl group), oxazole-diyl group, thiazole-diyl group, oxadiazole-diyl group, benzothiazole-diyl group, benzothiadiazole-diyl group, phthalimide-diyl group, thienothiazole-diyl group, thiazolothiazole-diyl group, thienothiophene-diyl group, and thienoxazole-diyl group.

[0069] Specific examples of the divalent alicyclic group represented by A1 include the cyclopentylene group and the cyclohexylene group.

[0070] In equation (M1-A), a1 represents an integer between 1 and 10. If a1 is 2 or greater, multiple A1s may be the same or different.

[0071] In formula (M1-B), A2 and A3 are each independently divalent groups selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups. Specific examples and preferred embodiments of A2 and A3 are the same as those for A1 in formula (M1-A), so their explanation is omitted. In formula (M1-B), a2 represents an integer from 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. a2 is preferably an integer of 2 or greater, and more preferably 2, because it results in a better degree of orientation of the light absorption anisotropy layer. In formula (M1-B), when a2 is 1, LA1 is a divalent linking group. When a2 is 2 or more, each of the multiple LA1s is independently either 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 preferable that one of the two LA1s is a divalent linking group and the other is a single bond, for a better degree of orientation of the light-absorbing anisotropic layer.

[0072] In formula (M1-B), the divalent linking group represented by LA1 is -O-, -(CH2) g -,-(CF2) g -, -Si(CH3)2-, -(Si(CH3)2O) g -,-(OSi(CH3)2) g -(g represents an integer from 1 to 10.), -N(Z)-, -C(Z)=C(Z')-, -C(Z)=N-, -N=C(Z)-, -C(Z)2-C(Z')2-, -C(O)-, -OC(O)-, -C(O)O-, -OC(O)O-, -N(Z) C(O)-, -C(O)N(Z)-, -C(Z)=C(Z')-C(O)O-, -OC(O)-C(Z)=C(Z')-, -C(Z)=N-, -N=C(Z)-, -C(Z)=C(Z')-C(O)N(Z'')-, -N(Z'')-C(O Examples include -C(Z)=C(Z')-, -C(Z)=C(Z')-C(O)-S-, -SC(O)-C(Z)=C(Z')-, -C(Z)=NN=C(Z')- (where Z, Z', and Z'' independently represent hydrogen, a C1-C4 alkyl group, a cycloalkyl group, an aryl group, a cyano group, or a halogen atom), -C≡C-, -N=N-, -S-, -S(O)-, -S(O)(O)-, -(O)S(O)O-, -O(O)S(O)O-, -SC(O)-, and -C(O)S-. Among these, -C(O)O- is preferred because it exhibits superior orientation of the light-absorbing anisotropic layer. LA1 may be a group formed by combining two or more of these groups.

[0073] An example of M1 is the following structure. In the example below, "Ac" represents an acetyl group.

[0074] [ka] [ka] [ka]

[0075] [ka] [ka] [ka] [ka]

[0076] Examples of terminal groups represented by T1 include hydrogen atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups, C1-C10 alkyl groups, C1-C10 alkoxy groups, C1-C10 alkylthio groups, C1-C10 alkoxycarbonyloxy groups, C1-C10 alkoxycarbonyl groups (ROC(O)-: R is an alkyl group), C1-C10 acyloxy groups, C1-C10 acylamino groups, C1-C10 alkoxycarbonylamino groups, C1-C10 sulfonylamino groups, C1-C10 sulfamoyl groups, C1-C10 carbamoyl groups, C1-C10 sulfinyl groups, and C1-C10 ureido groups and (meth)acryloyloxy group-containing groups. Examples of the (meth)acryloyloxy group-containing groups mentioned above include the group represented by -LA (where L represents a single bond or a linking group; specific examples of linking groups are the same as those for L1 and SP1 above; and A represents a (meth)acryloyloxy group). 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, because it provides a better degree of orientation of the light-absorbing anisotropic layer. These terminal groups may be further substituted with these groups or polymerizable groups described in Japanese Patent Application Publication No. 2010-244038. The number of atoms in the main chain of T1 is preferably 1 to 20, more preferably 1 to 15, even more preferably 1 to 10, and particularly preferably 1 to 7, because this results in a better degree of orientation of the light-absorbing anisotropic layer. The degree of orientation of the light-absorbing anisotropic layer is further improved when the number of atoms in the main chain of T1 is 20 or less. Here, "main chain" in T1 refers to the longest molecular chain bonded to M1, and hydrogen atoms are not counted in the number of atoms in the main chain of T1. For example, if T1 is an n-butyl group, the number of atoms in the main chain is 4, and if T1 is a sec-butyl group, the number of atoms in the main chain is 3.

[0077] The content of repeating units (3-1) is preferably 20 to 100% by mass relative to 100% by mass of the total repeating units of the polymeric liquid crystalline compound, because this results in a superior degree of orientation of the light-absorbing anisotropic layer. In this invention, the content of each repeating unit in the polymeric liquid crystalline compound is calculated based on the amount (mass) of each monomer used to obtain each repeating unit. The repeating unit (3-1) may be present alone or in combination of two or more types in the polymeric liquid crystalline compound. When the polymeric liquid crystalline compound contains two or more types of repeating units (3-1), there are advantages such as improved solubility of the polymeric liquid crystalline compound in the solvent and easier adjustment of the liquid crystal phase transition temperature. When two or more types of repeating units (3-1) are present, it is preferable that their total amount is within the above range.

[0078] When a polymeric liquid crystalline compound contains two types of repeating units (3-1), it is preferable that the terminal group represented by T1 in one repeating unit (repeating unit A) is an alkoxy group, and the terminal group represented by T1 in the other repeating unit (repeating unit B) is a group other than an alkoxy group, in order to obtain a superior degree of orientation of the light-absorbing anisotropic layer. In the repeating unit B described above, the terminal group represented by T1 is preferably an alkoxycarbonyl group, a cyano group, or a (meth)acryloyloxy group-containing group, and more preferably an alkoxycarbonyl group or a cyano group, because it provides a better degree of orientation of the light-absorbing anisotropic layer. The ratio (A / B) of the content of repeating unit A in the polymeric liquid crystalline compound to the content of repeating unit B in the polymeric liquid crystalline compound is preferably 50 / 50 to 95 / 5, more preferably 60 / 40 to 93 / 7, and even more preferably 70 / 30 to 90 / 10, for the reason that the degree of orientation of the light absorption anisotropy layer is superior.

[0079] <Repeating Unit (3-2)> The polymeric liquid crystalline compound of the present invention may further contain a repeating unit represented by the following formula (3-2) (hereinafter also referred to as "repeating unit (3-2)"). This offers advantages such as improved solubility of the polymeric liquid crystalline compound in solvents and easier adjustment of the liquid crystal phase transition temperature. The repeating unit (3-2) differs from the repeating unit (3-1) in that it does not have at least a mesogenic group. If the polymeric liquid crystalline compound contains repeating units (3-2), the polymeric liquid crystalline compound is a copolymer of repeating units (3-1) and repeating units (3-2) (it may also be a copolymer containing repeating units A and B), and may be any polymer such as a block polymer, an alternating polymer, a random polymer, or a graft polymer.

[0080] [ka]

[0081] In formula (3-2), P3 represents the repeating main chain, L3 represents a single bond or a divalent linking group, SP3 represents a spacer group, and T3 represents a terminal group. The specific examples of P3, L3, SP3, and T3 in equation (3-2) are the same as those of P1, L1, SP1, and T1 in equation (3-1) above. Here, in formula (3-2), T3 preferably has a polymerizable group from the viewpoint of improving the intensity of the light-absorbing anisotropic layer.

[0082] When repeating units (3-2) are present, the content is preferably 0.5 to 40% by mass, and more preferably 1 to 30% by mass, relative to 100% by mass of the total repeating units of the polymeric liquid crystalline compound. The repeating unit (3-2) may be present alone or in combination of two or more types in the polymeric liquid crystalline compound. When two or more types of repeating units (3-2) are present, it is preferable that their total amount is within the above range.

[0083] (Weight average molecular weight) The weight-average molecular weight (Mw) of the polymeric liquid crystalline compound is preferably between 1,000 and 500,000, and more preferably between 2,000 and 300,000, because it results in a superior degree of orientation of the light-absorbing anisotropic layer. If the Mw of the polymeric liquid crystalline compound is within the above range, the polymeric liquid crystalline compound becomes easier to handle. In particular, from the viewpoint of suppressing cracks during coating, the weight-average molecular weight (Mw) of the polymeric liquid crystalline compound is preferably 10,000 or more, and more preferably between 10,000 and 300,000. Furthermore, from the viewpoint of the temperature latitude of the degree of orientation, the weight-average molecular weight (Mw) of the polymeric liquid crystalline compound is preferably less than 10,000, and preferably between 2,000 and less than 10,000. Here, the weight-average molecular weight and number-average molecular weight in this invention are values ​​measured by gel permeation chromatography (GPC). • Solvent (eluent): N-methylpyrrolidone ·Device name: TOSOH HLC-8220GPC • Column: Three TOSOH TSKgelSuperAWM-H (6mm x 15cm) columns connected together are used. • Column temperature: 25℃ • Sample concentration: 0.1% by mass ·Flow rate: 0.35mL / min • Calibration curve: A calibration curve was used based on 7 samples of TOSOH TSK standard polystyrene with Mw=2,800,000 to 1,050 (Mw / Mn=1.03 to 1.06).

[0084] [Adhesive layer] The adhesive layer 1 and adhesive layer 2 (hereinafter, if there is no distinction between them, they will simply be abbreviated as "adhesive layer") of the laminate of the present invention are not particularly limited as long as they are adhesive layers that are normally used for bonding phase difference films or display elements. Furthermore, the thickness, material, etc., of adhesive layer 1 and adhesive layer 2 may be the same or different. Here, the adhesive contained in the adhesive layer is a viscoelastic material that exhibits adhesive properties simply by applying force after bonding, and does not include adhesives described later that exhibit adhesive properties through drying or reaction after bonding.

[0085] Examples of adhesives used in the adhesive layer include rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, and cellulose-based adhesives. Of these, acrylic adhesives (pressure-sensitive adhesives) are preferred from the viewpoint of transparency, weather resistance, and heat resistance.

[0086] In the present invention, it is preferable that at least one of the adhesive layer 1 and the adhesive layer 2 contains a polymer having repeating units represented by the following formula (A), in order to achieve better resistance to moist heat. [ka]

[0087] In the above formula (A), R 1 R represents a hydrogen atom or a methyl group. 2 This represents an alkyl group with 1 to 6 carbon atoms. Here, the alkyl group may be linear, branched, or cyclic, but specific examples of linear alkyl groups include methyl, ethyl, n-propyl, and butyl groups. Preferred branched alkyl groups are those having 3 to 6 carbon atoms, specifically, for example, isopropyl groups and tert-butyl groups. As for the cyclic alkyl group, alkyl groups having 3 to 6 carbon atoms are preferred, and specifically, examples include cyclopropyl group, cyclopentyl group, and cyclohexyl group.

[0088] The adhesive layer can be formed, for example, by applying an adhesive solution onto a release sheet, allowing it to dry, and then transferring it to the surface of the transparent resin layer; or by directly applying an adhesive solution to the surface of the transparent resin layer and allowing it to dry; and so on. The adhesive solution is prepared as a 10-40% by mass solution by dissolving or dispersing the adhesive in a solvent such as toluene or ethyl acetate. Coating methods can include roll coating methods such as reverse coating and gravure coating, spin coating, screen coating, fountain coating, dipping, and spraying.

[0089] Furthermore, suitable thin sheets such as synthetic resin films (e.g., polyethylene, polypropylene, polyethylene terephthalate), rubber sheets, paper, cloth, nonwoven fabrics, nets, foamed sheets, and metal foils can be used as constituent materials for the release sheet.

[0090] The storage modulus of the adhesive layer used in the present invention is preferably 0.1 MPa or higher, and more preferably 0.5 MPa or higher. It is preferable that either adhesive layer 1 or adhesive layer 2 satisfies the above storage modulus, and more preferably that both satisfy the above storage modulus. In the present invention, it is preferable that the storage modulus of the adhesive layer 1 is 0.5 MPa or higher, in order to improve pencil hardness.

[0091] Method for measuring the storage modulus of elasticity In this invention, the storage modulus refers to the value measured using a dynamic viscoelasticity measuring device (DVA-200) manufactured by IT Measurement Control Co., Ltd., under the conditions of a frequency of 1 Hz and a temperature of 25°C.

[0092] In the present invention, the thickness of the adhesive layer is not particularly limited, but it is preferably 1 to 50 μm, and more preferably 3 to 30 μm. In particular, the thickness of the adhesive layer 1 is preferably 8 μm or less, and more preferably 3 to 8 μm, because it improves pencil hardness.

[0093] [Adhesive layer] The laminate of the present invention may have an adhesive layer. The adhesive is not particularly limited as long as it exhibits adhesive properties through drying or reaction after bonding. Polyvinyl alcohol-based adhesives (PVA-based adhesives) develop their adhesive properties upon drying, making it possible to bond materials together. Specific examples of curing adhesives that exhibit adhesive properties through reaction include active energy ray curing adhesives such as (meth)acrylate adhesives and cationic polymerization curing adhesives. (Meth)acrylate refers to acrylate and / or methacrylate. Examples of curing components in (meth)acrylate adhesives include compounds having a (meth)acryloyl group and compounds having a vinyl group. Furthermore, compounds having epoxy groups or oxetanyl groups can also be used as cationic polymerization-curing adhesives. Compounds having epoxy groups are not particularly limited as long as they have at least two epoxy groups in their molecule, and various generally known curable epoxy compounds can be used. Examples of preferred epoxy compounds include compounds having at least two epoxy groups and at least one aromatic ring in their molecule (aromatic epoxy compounds), and compounds having at least two epoxy groups in their molecule, at least one of which is formed between two adjacent carbon atoms constituting an alicyclic ring (alicyclic epoxy compounds).

[0094] [Optical anisotropy layer] As described above, the laminate of the present invention may have an optically anisotropic layer. The present invention most preferably relates to a laminate for providing an anti-reflective function, in which case the optical anisotropy layer is preferably a λ / 4 plate. A λ / 4 plate is a plate that has the function of converting linearly polarized light of a specific wavelength to circularly polarized light (or circularly polarized light to linearly polarized light). It is a plate (phase difference film) in which the in-plane retardation Re(λ) at a specific wavelength λnm satisfies Re(λ)=λ / 4, and it is preferable to create it by adjusting the Re of a positive A plate to λ / 4. To improve color changes when viewed from an oblique direction and light leakage when displaying black, it is preferable to further combine it with a positive C plate. In this case, it is preferable to adjust so that the total Rth of the anti-reflective plate is close to zero. Anti-reflective plates are suitably used for anti-reflective applications in image display devices such as liquid crystal displays (LCDs), plasma display panels (PDPs), electroluminescent displays (ELDs), and cathode ray tube displays (CRTs), and can improve the contrast ratio of the displayed light. For example, an anti-reflective plate can be provided on the light extraction surface side of an organic EL display device. In this case, ambient light is linearly polarized by the polarizer, and then becomes circularly polarized after passing through the phase difference plate. When this is reflected by the metal electrodes of the organic EL panel, the circular polarization state is reversed, and when it passes through the phase difference plate again, it becomes linearly polarized with a 90° tilt from the incident state, and reaches the polarizer where it is absorbed. As a result, the influence of ambient light can be suppressed.

[0095] The optically anisotropic layer used in the present invention may be located between the light-absorbing anisotropic layer and the adhesive layer 2, or it may be located outside the adhesive layer 2. When the optically anisotropic layer is located between the light-absorbing anisotropic layer and the adhesive layer 2, it is preferable to use a curable adhesive layer, described later, rather than an adhesive layer, to bond the layers together.

[0096] The laminate of the present invention can be manufactured, for example, by bonding a light-absorbing anisotropic layer and optically anisotropic layers, namely a λ / 4 positive A plate and a positive C plate, using an adhesive or the like. If the optical anisotropy layer is composed of a λ / 4 positive A plate and a positive C plate, it may be bonded to the light-absorbing anisotropy layer on the side of the positive C plate, or it may be bonded to the light-absorbing anisotropy layer on the opposite side. Alternatively, the plates can be manufactured by directly forming λ / 4 positive A plates and positive C plates on a light-absorbing anisotropic layer. As described in Example 19 of Japanese Patent No. 6243869, it is also preferable to add an orientation layer between the light-absorbing anisotropic layer and the positive A plate. Furthermore, as described in Example 1 of Japanese Patent No. 6123563, it is also possible to add a protective layer between the light-absorbing anisotropic layer and the positive A plate. Alternatively, the light-absorbing anisotropic layer can be formed after the λ / 4 positive A plates and positive C plates have been formed.

[0097] The angle between the slow axis direction of the positive A plate of the anti-reflective plate and the absorption axis direction of the anisotropic light absorption layer is preferably in the range of 45°±10°. Regarding the optical properties of the positive A plate and the positive C plate, it is preferable that the wavelength dispersion of Re and Rth exhibits inverse dispersion, particularly from the viewpoint of suppressing color changes.

[0098] In the manufacture of the anti-reflective plate, it is preferable to include a step in which, for example, a light-absorbing anisotropic layer, a positive A plate, and a positive C plate are continuously laminated in a long length. The long anti-reflective plate is then cut to match the size of the screen of the image display device used.

[0099] The optically anisotropic layer is preferable in terms of flexibility because it can be made into a thin layer when formed from a liquid crystalline compound. Furthermore, from the viewpoint of light durability, it is preferable to include a layer formed using a composition containing a polymerizable liquid crystalline compound represented by formula (4), which will be described later. In the following, we will first describe in detail the components of the composition used to form the optically anisotropic layer (hereinafter also abbreviated as "composition for forming the optically anisotropic layer"), and then describe in detail the manufacturing method and properties of the optically anisotropic layer.

[0100] (Polymerizable liquid crystalline compound represented by formula (4)) The composition for forming an optically anisotropic layer contains a polymerizable liquid crystalline compound represented by formula (4). The polymerizable liquid crystalline compound represented by formula (4) is a compound that exhibits liquid crystalline properties.

[0101] [ka]

[0102] In the above formula (4), D 1 , D 2 , D 3 and D 4 These are, independently, single bonds, -CO-O-, -C(=S)O-, and -CR bonds. 1 R 2 -, -CR 1 R 2 -CR 3 R 4 -, -O-CR 1 R 2 -, -CR 1 R 2 -O-CR 3 R 4 -,-CO-O-CR 1 R 2 -, -O-CO-CR 1 R 2 -, -CR 1 R 2 -O-CO-CR 3 R 4 -, -CR 1 R 2 -CO-O-CR 3 R 4 -, -NR 1 -CR 2 R 3 -, or -CO-NR 1 - represents R 1 , R 2 , R 3 and R 4 Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. Also, in formula (4) above, SP 1 and SP 2 Each of these independently represents a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a divalent linking group in which one or more of the -CH2- groups constituting a linear or branched alkylene group having 1 to 12 carbon atoms are substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, where Q represents a substituent. Also, in equation (4) above, L 1 and L 2 Each of these independently represents a monovalent organic group, L 1 and L 2 At least one of them represents a polymerizable group. However, if Ar is an aromatic ring represented by the following formula (Ar-3), then L 1 and L 2 Furthermore, L in the following equation (Ar-3) 3 and L 4 At least one of them represents a polymerizable group.

[0103] In the above formula (4), SP 1 and SP 2 The linear or branched alkylene group having 1 to 12 carbon atoms shown is preferably, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a methylhexylene group, and a heptylene group. 1 and SP 2 As described above, this may be a divalent linking group in which one or more of the -CH2- groups constituting a linear or branched alkylene group having 1 to 12 carbon atoms are substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, and the substituent represented by Q is Y in formula (Ar-1) described later. 1 Examples of substituents that may be present include those similar to those that the molecule may have.

[0104] In the above formula (4), L 1 and L 2 Examples of monovalent organic groups include alkyl groups, aryl groups, and heteroaryl groups. The alkyl group may be linear, branched, or cyclic, but linear is preferred. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. Furthermore, the aryl group may be monocyclic or polycyclic, but monocyclic is preferred. The number of carbon atoms in the aryl group is preferably 6 to 25, and more preferably 6 to 10. Also, the heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the heteroaryl group are preferably a nitrogen atom, a sulfur atom, or an oxygen atom. The carbon number of the heteroaryl group is preferably 6 to 18, more preferably 6 to 12. Also, the alkyl group, aryl group, and heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the same substituents as those that the Y 1 in the formula (Ar-1) described later may have.

[0105] In the above formula (4), the polymerizable group represented by at least one of L 1 and L 2 is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferred. As the radical polymerizable group, generally known radical polymerizable groups can be used, and an acryloyl group or a methacryloyl group is preferred. In this case, it is generally known that the polymerization rate of the acryloyl group is fast, and from the viewpoint of improving productivity, the acryloyl group is preferred, but the methacryloyl group can also be used as a polymerizable group in the same manner. As the cationic polymerizable group, generally known cationic polymerizability can be used. Specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and a vinyloxy group can be mentioned. Among them, an alicyclic ether group or a vinyloxy group is preferred, and an epoxy group, an oxetanyl group, or a vinyloxy group is more preferred. Examples of particularly preferred polymerizable groups include the following. In the following formula, * represents the bonding position of the polymerizable group.

[0106]

Chemical formula

[0107] In the above formula (4), from the point that the thermal durability of the laminate is more excellent (hereinafter, also simply referred to as "the point where the effect of the present invention is more excellent"), L in the above formula (4)1 and L 2 are both preferably polymerizable groups, more preferably an acryloyl group or a methacryloyl group.

[0108] On the other hand, in the above formula (4), Ar represents any aromatic ring selected from the group consisting of the groups represented by the following formulas (Ar-1) to (Ar-5). In the following formulas (Ar-1) to (Ar-5), * represents D 1 or D 2 and represents the bonding position with.

[0109]

Chemical formula

[0110] Here, in the above formula (Ar-1), Q 1 represents N or CH, and Q 2 represents -S-, -O-, or -N(R 5 )-, R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y 1 represents an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms. R 5 Examples of the alkyl group having 1 to 6 carbon atoms represented by include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. Y 1 Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms represented by include aryl groups such as a phenyl group, a 2,6-diethylphenyl group, and a naphthyl group. Y 1 Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by include heteroaryl groups such as a thienyl group, a thiazolyl group, a furyl group, and a pyridyl group. In addition, examples of the substituent that Y 1 may have include an alkyl group, an alkoxy group, and a halogen atom. As alkyl groups, linear, branched, or cyclic alkyl groups having 1 to 18 carbon atoms are preferred, alkyl groups having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, and cyclohexyl group) are more preferred, alkyl groups having 1 to 4 carbon atoms are even more preferred, and methyl or ethyl groups are particularly preferred. As for the alkoxy group, for example, an alkoxy group having 1 to 18 carbon atoms is preferred, an alkoxy group having 1 to 8 carbon atoms (e.g., a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, etc.) is more preferred, an alkoxy group having 1 to 4 carbon atoms is even more preferred, and a methoxy group or an ethoxy group is particularly preferred. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms or chlorine atoms being preferred.

[0111] Also, in the above equations (Ar-1) to (Ar-7), Z 1 , Z 2 and Z 3 These are, independently, a hydrogen atom, a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group with 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, and -OR. 6 , -NR 7 R 8 , or -SR 9 Represents R 6 ~R 9 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Z 1 and Z 2 These may combine with each other to form an aromatic ring. As the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, alkyl groups having 1 to 15 carbon atoms are preferred, and alkyl groups having 1 to 8 carbon atoms are more preferred. Specifically, methyl, ethyl, isopropyl, tert-pentyl (1,1-dimethylpropyl), tert-butyl, or 1,1-dimethyl-3,3-dimethyl-butyl groups are even more preferred, and methyl, ethyl, or tert-butyl groups are particularly preferred. Examples of monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms include monocyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, methylcyclohexyl, and ethylcyclohexyl; monocyclic unsaturated hydrocarbon groups such as cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadiene; bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, tricyclo[5.2.1.0 2,6 ]decyl group, tricyclo[3.3.1.1 3,7 ] Decyl group, tetracyclo[6.2.1.1 3,6 .0 2,7 Examples include polycyclic saturated hydrocarbon groups such as dodecyl groups and adamantyl groups. Examples of monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl groups, 2,6-diethylphenyl groups, naphthyl groups, and biphenyl groups, with aryl groups having 6 to 12 carbon atoms (particularly phenyl groups) being preferred. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms, chlorine atoms, or bromine atoms being preferred. On the other hand, R 6 ~R 9 Examples of C1-C6 alkyl groups represented by include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl groups.

[0112] Furthermore, in the above formulas (Ar-2) and (Ar-3), A 1 and A 2 These are -O- and -N(R) independently of each other. 10 R represents a group selected from the group consisting of -, -S-, and -CO-. 10 represents a hydrogen atom or substituent. R 10 The substituent shown is Y in formula (Ar-1) above. 1 Examples of substituents that may be present include those similar to those that the molecule may have.

[0113] Furthermore, in the above formula (Ar-2), X represents a hydrogen atom or a nonmetal atom of Groups 14 to 16 that may have substituents attached. Furthermore, examples of nonmetallic atoms in groups 14-16 represented by X include oxygen atoms, sulfur atoms, substituted nitrogen atoms, and substituted carbon atoms. Examples of substituents include alkyl groups, alkoxy groups, alkyl-substituted alkoxy groups, cyclic alkyl groups, aryl groups (e.g., phenyl groups, naphthyl groups, etc.), cyano groups, amino groups, nitro groups, alkylcarbonyl groups, sulfo groups, and hydroxyl groups.

[0114] Also, in the above formula (Ar-3), D 5 and D 6 These are, independently, single bonds, -CO-O-, -C(=S)O-, and -CR bonds. 1 R 2 -, -CR 1 R 2 -CR 3 R 4 -, -O-CR 1 R 2 -, -CR 1 R 2 -O-CR 3 R 4 -,-CO-O-CR 1 R 2 -, -O-CO-CR 1 R 2 -, -CR 1 R 2 -O-CO-CR 3 R 4-, -CR 1 R 2 -CO-O-CR 3 R 4 -, -NR 1 -CR 2 R 3 -, or -CO-NR 1 - represents R 1 , R 2 , R 3 and R 4 Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.

[0115] Furthermore, in the above formula (Ar-3), SP 3 and SP 4 Each of these independently represents a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a divalent linking group in which one or more of the -CH2- groups constituting a linear or branched alkylene group having 1 to 12 carbon atoms are substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, where Q represents a substituent. As a substituent, Y in the above formula (Ar-1) is 1 Examples of substituents that may be present include those similar to those that the molecule may have.

[0116] Furthermore, in the above formula (Ar-3), L 3 and L 4 Each of these independently represents a monovalent organic group, L 3 and L 4 Furthermore, L in formula (4) above 1 and L 2 At least one of them represents a polymerizable group. As a monovalent organic group, L in formula (4) above is 1 and L 2 The same examples as those explained in [previous section] can be cited. Furthermore, the polymerizable group is L in formula (4) above. 1 and L 2 The same examples as those explained in [previous section] can be cited.

[0117] Furthermore, in the above formulas (Ar-4) to (Ar-7), Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles. Furthermore, in the above formulas (Ar-4) to (Ar-7), Ay represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have substituents, or an organic group having 2 to 30 carbon atoms which has at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles. Here, the aromatic rings in Ax and Ay may have substituents, or Ax and Ay may be bonded together to form a ring. Also, Q 3 This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which may have substituents. Examples of Ax and Ay are those described in paragraphs

[0039] to

[0095] of International Publication No. 2014 / 010325. Also, Q 3 Examples of C1-C6 alkyl groups represented by include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl groups, and as substituents, Y in the above formula (Ar-1) 1 Examples of substituents that may be present include those similar to those that the molecule may have.

[0118] Examples of such polymerizable liquid crystalline compounds (4) include compounds represented by general formula (1) described in Japanese Patent Publication No. 2010-084032 (particularly the compounds described in paragraphs

[0067] to

[0073] ), compounds represented by general formula (II) described in Japanese Patent Publication No. 2016-053709 (particularly the compounds described in paragraphs

[0036] to

[0043] ), and compounds represented by general formula (1) described in Japanese Patent Publication No. 2016-081035 (particularly the compounds described in paragraphs

[0043] to

[0055] ).

[0119] In addition, as such a polymerizable liquid crystalline compound (4), for example, compounds represented by the following formulas (1) to (22) are preferably mentioned. Specifically, as K (side chain structure) in the following formulas (1) to (22), compounds having the side chain structures shown in Table 1 and Table 2 below are respectively mentioned. In Table 1 and Table 2 below, "*" shown in the side chain structure of K represents the bonding position to the aromatic ring. In addition, in the following description, a compound represented by the following formula (1) and having the group shown as 1-1 in Table 1 below is denoted as "Compound (1-1-1)", and compounds having other structural formulas and groups are also denoted in the same manner. For example, a compound represented by the following formula (2) and having the group shown as 2-3 in Table 2 below can be denoted as "Compound (2-2-3)". In addition, in the side chain structures represented by 1-2 in Table 1 and 2-2 in Table 2 below, the groups adjacent to the acryloyloxy group and the methacryloyl group respectively represent a propylene group (a group in which a methyl group is substituted by an ethylene group), and represent a mixture of positional isomers having different positions of the methyl group.

[0120]

Chemical formula

[0121]

Table 1

[0122]

Table 2

[0123] The content of the polymerizable liquid crystalline compound represented by the formula (4) in the composition for forming an optically anisotropic layer is not particularly limited, but is preferably 50 to 100% by mass, more preferably 70 to 99% by mass, based on the total solid content in the composition for forming an optically anisotropic layer. Solid content refers to the components other than the solvent in the optically anisotropic layer-forming composition, and is calculated as solid content even if its properties are liquid.

[0124] The composition for forming an optically anisotropic layer may contain other components besides the polymerizable liquid crystalline compound represented by formula (4).

[0125] (liquid crystal compound) The composition for forming an optically anisotropic layer may contain other liquid crystalline compounds besides the polymerizable liquid crystalline compound represented by formula (4). Examples of other liquid crystalline compounds include known liquid crystalline compounds (rod-shaped liquid crystalline compounds and disc-shaped liquid crystalline compounds). The other liquid crystalline compounds may have polymerizable groups.

[0126] (polymerizable monomer) The composition for forming an optically anisotropic layer may contain a polymerizable liquid crystalline compound represented by formula (4) and other polymerizable monomers other than other liquid crystalline compounds having polymerizable groups. Among these, polymerizable compounds having two or more polymerizable groups (polyfunctional polymerizable monomers) are preferred in that they provide superior strength of the optically anisotropic layer. As the polyfunctional polymerizable monomer, polyfunctional radical polymerizable monomers are preferred. Examples of polyfunctional radical polymerizable monomers include the polymerizable monomers described in paragraphs

[0018] to

[0020] of Japanese Patent Application Publication No. 2002-296423. Furthermore, if the composition contains a polyfunctional polymerizable monomer, the content of the polyfunctional polymerizable monomer is preferably 1 to 50% by mass, and more preferably 2 to 30% by mass, relative to the total mass of the polymerizable liquid crystalline compound represented by formula (4).

[0127] (Polymerization initiator) The composition for forming an optically anisotropic layer may contain a polymerization initiator. As a polymerization initiator, a photopolymerization initiator that can initiate the polymerization reaction by ultraviolet irradiation is preferred. Examples of photopolymerization initiators include α-carbonyl compounds (as described in U.S. Patent Nos. 2,367,661 and 2,367,670), acyloin ethers (as described in U.S. Patent No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compounds (as described in U.S. Patent No. 2,722,512), polynuclear quinone compounds (as described in U.S. Patent Nos. 3,046,127 and 2,951,758), and combinations of triarylimidazole dimers and p-aminophenyl ketones (as described in U.S. Patent No. 3,549,367). Examples include acridine and phenazine compounds (as described in the specification), acridine and phenazine compounds (as described in Japanese Patent Publication No. 60-105667 and U.S. Patent No. 4,239850), oxadiazole compounds (as described in U.S. Patent No. 4,212970), O-acyloxime compounds (as described in Japanese Patent Publication No. 2016-27384

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

[0128] Oxime-type polymerization initiators are preferred as polymerization initiators.

[0129] (solvent) The composition for forming an optically anisotropic layer may contain a solvent, from the viewpoint of ease of forming the optically anisotropic layer. Examples of solvents include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone), ethers (e.g., dioxane and tetrahydrofuran), aliphatic hydrocarbons (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., toluene, xylene, and trimethylbenzene), halogenated carbons (e.g., dichloromethane, dichloroethane, dichlorobenzene, and chlorotoluene), esters (e.g., methyl acetate, ethyl acetate, and butyl acetate), water, alcohols (e.g., ethanol, isopropanol, butanol, and cyclohexanol), cellosolves (e.g., methyl cellosolve and ethyl cellosolve), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide), and amides (e.g., dimethylformamide, dimethylacetamide). These may be used individually or in combination of two or more.

[0130] (Leveling agent) The composition for forming an optically anisotropic layer may contain a leveling agent to maintain a smooth surface on the optically anisotropic layer. As leveling agents, fluorine-based or silicon-based leveling agents are preferred due to their high leveling effect relative to the amount added, and fluorine-based leveling agents are more preferred because they are less likely to cause blooming or bleeding. Examples of leveling agents include the compounds described in paragraphs

[0079] to

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

[0020] to

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

[0022] to [002 Examples include the compounds described in [9], liquid crystal alignment promoters represented by general formula (4) described in Japanese Patent Application Publication No. 2002-129162 (particularly the compounds described in paragraphs

[0076] to

[0078] and paragraphs

[0082] to

[0084] ), and compounds represented by general formula (4), (II) and (III) described in Japanese Patent Application Publication No. 2005-099248 (particularly the compounds described in paragraphs

[0092] to

[0096] ). These may also have the function of an alignment control agent as described later.

[0131] (Orientation control agent) The composition for forming an optically anisotropic layer may optionally contain an orientation control agent. Orientation control agents can create various orientation states, including homogeneous orientation, homeotropic orientation (vertical orientation), tilted orientation, hybrid orientation, and cholesteric orientation, and can also enable more uniform and precise control of specific orientation states.

[0132] As orientation control agents that promote homogeneous orientation, for example, low molecular weight orientation control agents and high molecular weight orientation control agents can be used. For low molecular weight orientation control agents, for example, reference can be given to paragraphs

[0009] to

[0083] of Japanese Patent Publication No. 2002-20363, paragraphs

[0111] to

[0120] of Japanese Patent Publication No. 2006-106662, and paragraphs

[0021] to

[0029] of Japanese Patent Publication No. 2012-211306, and this information is incorporated into the present specification. In addition, as the polymer orientation control agent, for example, paragraphs

[0021] to

[0057] of JP-A No. 2004-198511 and paragraphs

[0121] to

[0167] of JP-A No. 2006-106662 can be referred to, and this content is incorporated into the specification of the present application.

[0133] In addition, as the orientation control agent for forming or promoting homeotropic orientation, for example, a boronic acid compound and an onium salt compound can be mentioned. Specifically, paragraphs

[0023] to

[0032] of JP-A No. 2008-225281, paragraphs

[0052] to

[0058] of JP-A No. 2012-208397, paragraphs

[0024] to

[0055] of JP-A No. 2008-026730, and paragraphs

[0043] to

[0055] of JP-A No. 2016-193869, etc. The compounds described in can be referred to, and this content is incorporated into the specification of the present application.

[0134] When the orientation control agent is contained, the content is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content in the composition.

[0135] (Other components) The composition for forming an optically anisotropic layer may contain components other than the above-described components. For example, a surfactant, a tilt angle control agent, an orientation aid, a plasticizer, and a crosslinking agent can be mentioned.

[0136] (Method for producing an optically anisotropic layer) The method for producing an optically anisotropic layer is not particularly limited, and known methods can be mentioned. For example, the composition for forming an optically anisotropic layer is applied to a predetermined substrate (for example, a support layer described later) to form a coating film, and the obtained coating film is subjected to a curing treatment (irradiation with active energy rays (light irradiation treatment) and / or heat treatment) to produce a cured coating film (optically anisotropic layer). In addition, an orientation film described later may be used as necessary. The composition can be applied by known methods (e.g., wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, and die coating).

[0137] In the above method for producing the optically anisotropic layer, it is preferable to perform orientation treatment on the liquid crystalline compound contained in the coating film before performing curing treatment on the coating film. Orientation treatment can be performed by drying at room temperature (e.g., 20-25°C) or by heating. The liquid crystal phase formed by the orientation treatment can generally be transitioned by changes in temperature or pressure in the case of thermotropic liquid crystal compounds. In the case of lyotropic liquid crystal compounds, the transition can also be achieved by changing the composition ratio, such as the amount of solvent. If the orientation treatment is a heat treatment, the heating time (heat maturation time) is preferably 10 seconds to 5 minutes, more preferably 10 seconds to 3 minutes, and even more preferably 10 seconds to 2 minutes.

[0138] The curing treatment (irradiation with active energy rays (photoirradiation) and / or heat treatment) applied to the coating film, as described above, can also be described as an immobilization treatment to fix the orientation of the liquid crystalline compound. The immobilization treatment is preferably carried out by irradiation with active energy rays (preferably ultraviolet light), and the liquid crystal is immobilized by polymerization of the liquid crystalline compound.

[0139] (Characteristics of the optically anisotropic layer) The optically anisotropic layer is a film formed using the composition described above. The optical properties of the optically anisotropic layer are not particularly limited, but it is preferable that it functions as a λ / 4 plate. A λ / 4 plate is a plate that has the function of converting linearly polarized light of a specific wavelength to circularly polarized light (or circularly polarized light to linearly polarized light), and is a plate (optical anisotropic layer) in which the in-plane retardation Re(λ) at a specific wavelength λnm satisfies Re(λ)=λ / 4. This equation only needs to be achieved at any wavelength in the visible light range (for example, 550 nm), but it is preferable that the in-plane retardation Re(550) at a wavelength of 550 nm satisfies the relationship 110 nm ≤ Re(550) ≤ 160 nm, and more preferably 110 nm ≤ Re(550) ≤ 150 nm.

[0140] It is preferable that the in-plane retardation Re(450) measured at a wavelength of 450 nm in the optical anisotropic layer, the in-plane retardation Re(550) measured at a wavelength of 550 nm in the optical anisotropic layer, and the in-plane retardation Re(650) measured at a wavelength of 650 nm in the optical anisotropic layer satisfy the relationship Re(450) ≤ Re(550) ≤ Re(650). In other words, this relationship can be said to represent inverse wavelength dispersion.

[0141] The optically anisotropic layer may be an A plate or a C plate, but it is preferably a positive A plate. A positive A plate can be obtained, for example, by horizontally oriented a polymerizable liquid crystalline compound represented by formula (4).

[0142] The thickness of the optical anisotropy layer is not particularly limited, but from the viewpoint of thinning, 0.5 to 10 μm is preferred, and 1.0 to 5 μm is more preferred.

[0143] [Oriented layer] The laminate of the present invention may have an orientation layer. Methods for forming an orientation layer include, for example, rubbing treatment of the film surface with an organic compound (preferably a polymer), oblique deposition of an inorganic compound, formation of a layer having microgrooves, and accumulation of an organic compound (e.g., ω-tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearylate, etc.) by the Langmuir-Bludget method (LB film). Furthermore, orientation layers that exhibit orientation function upon application of an electric field, magnetic field, or light irradiation are also known. In particular, in this invention, an orientation layer formed by rubbing is preferred in terms of ease of controlling the pre-tilt angle of the orientation layer, but a photo-orientation layer formed by light irradiation is more preferred in terms of orientation uniformity, which is important for this invention.

[0144] <Rubbing-treated orientation layer> Numerous polymer materials are described in various publications and many commercially available products can be used for the orientation layer formed by the rubbing process. In this invention, polyvinyl alcohol or polyimide, and their derivatives are preferably used. For the orientation layer, refer to the description on pages 43, line 24 to 49, line 8 of International Publication WO01 / 88574A1. The thickness of the orientation layer is preferably 0.01 to 10 μm, and more preferably 0.01 to 2 μm.

[0145] [Curing adhesive layer] As described above, the laminate of the present invention may have a curable adhesive layer. The curable adhesive layer used in the present invention may be any commonly used curable adhesive layer, such as a water-reactive curable adhesive layer, a thermosetting adhesive layer, or an ultraviolet-curable adhesive layer, with the ultraviolet-curable adhesive layer being preferable. When forming a curable adhesive layer directly adjacent to a light-absorbing anisotropic layer, it is preferable to increase the degree of crosslinking of the curable adhesive layer from the viewpoint of suppressing dye diffusion from the light-absorbing anisotropic layer. To increase the degree of crosslinking of the curable adhesive layer, methods such as increasing the UV irradiation dose or increasing the proportion of highly reactive monomers can be suitably used. The UV irradiation dose is 100 mJ / cm². 2 ~1500 mJ / cm 2 It is preferable to set the range to 600 mJ / cm². 2 ~1200 mJ / cm² 2 It is more preferable to define it as a range. As an example of a highly reactive monomer, it is preferable to use CEL2021P (manufactured by Daicel Corporation) as a solid content of 50% or more, and more preferably 90% or more. Furthermore, it is preferable to make the curing adhesive layer thicker, preferably in the range of 0.1 μm to 8 μm, and more preferably in the range of 0.5 μm to 5 μm.

[0146] [Oxygen barrier layer] The laminate of the present invention may have an oxygen barrier layer for the purpose of improving the light resistance of the organic dichroic substance (particularly the dichroic azo dye compound) in the light-absorbing anisotropic layer. An "oxygen barrier layer" refers to an oxygen barrier membrane that has an oxygen barrier function, but in this invention, the oxygen permeability is 200 cc / m³. 2 This refers to oxygen barrier membranes with an oxygen level of / day / atm or lower. Furthermore, oxygen permeability is an index that represents the amount of oxygen passing through the membrane per unit time and per unit area. In this invention, the value measured using an oxygen concentration device (for example, MODEL3600 manufactured by Hack Ultra Analytical Corporation) under conditions of 25°C and 50% relative humidity is adopted. In this invention, the oxygen permeability is 100 cc / m³. 2 Preferably less than / day / atm, and 30cc / m 2 Less than / day / atm is more preferable, and 10cc / m 2 / day / atm or less is even more preferable, and 3cc / m 2 The most preferred option is / day / atm or below.

[0147] Specific examples of oxygen barrier layers include layers containing organic compounds such as polyvinyl alcohol, polyethylene vinyl alcohol, polyvinyl ether, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, cellulose ether, polyamide, polyimide, styrene / maleic acid copolymer, gelatin, vinylidene chloride, and cellulose nanofiber. Polyvinyl alcohol and polyethylene vinyl alcohol are preferred due to their high oxygen barrier capacity, with polyvinyl alcohol being particularly preferred.

[0148] Polymerizable compounds with high oxygen barrier function include polymerizable compounds with high hydrogen bonding and compounds with a large number of polymerizable groups per unit molecular weight. Examples of compounds with a large number of polymerizable groups per unit molecular weight include pentaerythritol tetra(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

[0149] Examples of polymerizable compounds with high hydrogen bonding properties include, for instance, compounds represented by the following formula, and among these, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, represented by CEL2021P below, is preferred.

[0150] [ka] JPEG2026116358000034.jpg20127

[0151] Furthermore, thin layers made of metal compounds (metal compound thin layers) can also be used. Any method that can form the desired thin layer can be used for forming the metal compound thin layer. For example, sputtering, vacuum deposition, ion plating, and plasma CVD (Chemical Vapor Deposition) are suitable, and specifically, the formation methods described in Japanese Patent No. 3400324, Japanese Patent Publication No. 2002-322561, and Japanese Patent Publication No. 2002-361774 can be employed.

[0152] The components contained in the thin layer of metal compound are not particularly limited as long as they can exhibit oxygen barrier function, but for example, oxides, nitrides, or oxidized nitrides containing one or more metals selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, or Ta can be used. Among these, oxides, nitrides, or oxidized nitrides of metals selected from Si, Al, In, Sn, Zn, and Ti are preferred, and metal oxides, nitrides, or oxidized nitrides selected from Si, Al, Sn, and Ti are particularly preferred. These may contain other elements as secondary components. Layers consisting of reaction products of aluminum compounds and phosphorus compounds, as described in Japanese Patent Publication No. 2016-40120 and Japanese Patent Publication No. 2016-155255, are also preferred.

[0153] Furthermore, the oxygen barrier layer may be in the form of a laminate of a layer containing the above-mentioned organic material and a thin layer of metal compound, as described in, for example, U.S. Patent No. 6,413,645, Japanese Patent Publication No. 2015-226995, Japanese Patent Publication No. 2013-202971, Japanese Patent Publication No. 2003-335880, Japanese Patent Publication No. 53-12953, and Japanese Patent Publication No. 58-217344, or it may be a hybrid layer of organic and inorganic compounds, as described in International Publication No. 2011 / 11836, Japanese Patent Publication No. 2013-248832, and Japanese Patent No. 3855004.

[0154] For layers containing organic compounds, the thickness of the oxygen barrier layer is preferably 0.1 to 10 μm, and more preferably 0.5 to 5.5 μm. For thin layers of metal compounds, the thickness of the oxygen barrier layer is preferably 5 nm to 500 nm, and more preferably 10 nm to 200 nm.

[0155] For example, it is also preferable to integrate functions by imparting oxygen barrier functionality to other functional layers such as refractive index adjustment layers, adhesive layers, and surface protection layers. It is particularly preferable that the adhesive layer between the refractive index adjustment layer and the surface protection layer film has oxygen barrier functionality.

[0156] [Hardened layer] As described above, the laminate of the present invention may have a cured layer. The cured layer used in the present invention is preferably a layer positioned in contact with the light-absorbing anisotropic layer, and is preferably a refractive index adjustment layer for so-called index matching, formed from a composition containing a compound having a crosslinkable group, and having an in-plane average refractive index of 1.55 or more and 1.70 or less at a wavelength of 550 nm.

[0157] The in-plane average refractive index of the refractive index adjustment layer may be within the above range, but is preferably 1.58 to 1.70, and more preferably 1.60 to 1.70.

[0158] The thickness of the refractive index adjustment layer is not particularly limited, but from the viewpoint of miniaturization, it is preferably 0.01 to 2.00 μm, more preferably 0.01 to 0.80 μm, and even more preferably 0.01 to 0.15 μm.

[0159] The types of components constituting the refractive index adjustment layer are not particularly limited as long as they contain compounds having crosslinking groups. The presence of crosslinking groups ensures the strength within the layer. Compounds that harden with light or heat, such as polymerizable compounds having (meth)acryloyl groups or epoxy groups, are preferred. Polymerizable liquid crystalline compounds are also preferred because they can obtain a high in-plane average refractive index. Furthermore, polymerizable liquid crystalline compounds have high potential for refractive index optimization with light-absorbing anisotropic layers that have in-plane refractive index anisotropy, as they allow for control of the refractive index anisotropy within the plane.

[0160] The refractive index adjusting layer may contain particles along with a compound having a crosslinking group. Examples of particles include organic particles, inorganic particles, and organic-inorganic composite particles containing organic and inorganic components. Examples of organic particles include styrene resin particles, styrene-divinylbenzene copolymer particles, acrylic resin particles, methacrylic resin particles, styrene-acrylic copolymer particles, styrene-methacrylic copolymer particles, melamine resin particles, and resin particles containing two or more of these. The components constituting inorganic particles include metal oxides, metal nitrides, metal oxynitrides, and elemental metals. Examples of metal atoms contained in the above-mentioned metal oxides, metal nitrides, metal oxynitrides, and elemental metals include titanium atoms, silicon atoms, aluminum atoms, cobalt atoms, and zirconium atoms. Specific examples of inorganic particles include alumina particles, alumina hydrate particles, silica particles, zirconia particles, and inorganic oxide particles such as clay minerals (e.g., smectite). Zirconia particles are preferred because they provide a high refractive index.

[0161] The average particle diameter is preferably 1 to 300 nm, and more preferably 10 to 200 nm. Within the above range, a cured product (transparent resin layer) can be obtained that exhibits excellent particle dispersibility, as well as superior high-temperature durability, moist heat durability, and transparency. Here, the average particle diameter can be determined from photographs obtained by observation using a TEM (transmission electron microscope) or SEM (scanning electron microscope). Specifically, the projected area of ​​the particle is determined, and the corresponding equivalent circle diameter (diameter of the circle) is taken as the average particle diameter. In this invention, the average particle diameter is the arithmetic mean of the equivalent circle diameters obtained for 100 particles. The particles may be spherical, needle-shaped, fibrous, columnar, or plate-shaped, among other shapes. The particle content in the refractive index adjustment layer is not particularly limited, but it is preferably 1 to 50% by mass, and more preferably 1 to 30% by mass, relative to the total mass of the refractive index adjustment layer, as this makes it easier to adjust the in-plane average refractive index of the refractive index adjustment layer.

[0162] The method for forming the refractive index adjustment layer is not particularly limited, but one method involves applying a refractive index adjustment layer-forming composition onto a polarizer and, if necessary, curing the coating film. The composition for forming a refractive index adjustment layer contains components that can constitute a refractive index adjustment layer, such as resins, monomers, and particles. Examples of resins and particles are as described above. Examples of monomers include photocurable compounds and thermosetting compounds (e.g., thermosetting resins). Preferred monomers are monofunctional polymerizable compounds containing one polymerizable group per molecule, and polyfunctional polymerizable compounds containing two or more identical or different polymerizable groups per molecule. The polymerizable compound may be a monomer, an oligomer, or a polymer such as a prepolymer. Examples of polymerizable groups include radical polymerizable groups and cationic polymerizable groups, with radical polymerizable groups being preferred. Examples of radical polymerizable groups include ethylenically unsaturated bonding groups. Examples of cationic polymerizable groups include epoxy groups and oxetane groups.

[0163] The refractive index adjustment layer formation composition may contain at least one of an interface modifier, a polymerization initiator, and a solvent. Examples of these components include the compounds exemplified as components that may be included in the light absorption anisotropy layer formation composition.

[0164] The method for applying the composition for forming the refractive index adjustment layer is not particularly limited, and the above-described method for applying the composition for forming the light absorption anisotropy layer can be used.

[0165] After applying the refractive index adjustment layer-forming composition, the coating film may be dried if necessary. Furthermore, if the refractive index adjustment layer forming composition contains a curable compound such as a monomer, the coating film may be cured after the refractive index adjustment layer forming composition has been applied. Curing treatments include photocuring and thermocuring, and the optimal conditions are selected depending on the material used.

[0166] When a polymerizable liquid crystalline compound is used as the compound having a crosslinking group, the compound is not particularly limited. Generally, liquid crystalline compounds can be classified into rod-shaped and disc-shaped types based on their shape. Furthermore, each of these types can be divided into low-molecular-weight and high-molecular-weight types. High-molecular-weight compounds generally refer to those with a degree of polymerization of 100 or more (Polymer Physics and Phase Transition Dynamics, by Masao Doi, p. 2, Iwanami Shoten, 1992). In the present invention, any liquid crystalline compound can be used, but it is preferable to use a rod-shaped liquid crystalline compound (hereinafter also abbreviated as "CLC") or a discotic liquid crystalline compound (hereinafter also abbreviated as "DLC"), and it is more preferable to use a rod-shaped liquid crystalline compound. Furthermore, two or more rod-shaped liquid crystalline compounds, two or more disc-shaped liquid crystalline compounds, or a mixture of rod-shaped liquid crystalline compounds and disc-shaped liquid crystalline compounds may also be used.

[0167] In the present invention, it is necessary to use a liquid crystalline compound having polymerizable groups for the immobilization of the above-mentioned liquid crystalline compound, and it is even more preferable that the liquid crystalline compound has two or more polymerizable groups in one molecule. If the liquid crystalline compound is a mixture of two or more types, it is preferable that at least one of the liquid crystalline compounds has two or more polymerizable groups in one molecule. Furthermore, after the liquid crystalline compound has been immobilized by polymerization, it is no longer necessary for it to exhibit liquid crystalline properties.

[0168] Furthermore, the type of polymerizable group is not particularly limited, but functional groups capable of addition polymerization are preferred, and polymerizable ethylenically unsaturated groups or cyclic polymerizable groups are preferred. More specifically, (meth)acryloyl groups, vinyl groups, styryl groups, and allyl groups are preferred, with (meth)acryloyl groups being more preferred. Note that (meth)acryloyl group refers to either a methacryloyl group or an acryloyl group.

[0169] As rod-shaped liquid crystalline compounds, for example, those described in claim 1 of Japanese Patent Publication No. 11-513019 or paragraphs

[0026] to

[0098] of Japanese Patent Application Publication No. 2005-289980 can be preferably used, and as discotic liquid crystalline compounds, for example, those described in paragraphs

[0020] to

[0067] of Japanese Patent Application Publication No. 2007-108732 or paragraphs

[0013] to

[0108] of Japanese Patent Application Publication No. 2010-244038 can be preferably used, but are not limited to these.

[0170] <Other ingredients> Other components included in the refractive index adjustment layer formation composition include, specifically, the polymerization initiator, surfactant, and solvent described above in the composition containing the dichroic azo dye compound (composition for forming a light-absorbing anisotropic layer).

[0171] <Formation method> The method for forming a refractive index adjustment layer using the above-described refractive index adjustment layer formation composition is not particularly limited, and includes a method comprising, in this order, a step of applying the above-described refractive index adjustment layer formation composition onto the above-described orientation layer or the above-described light absorption anisotropy layer according to the layer configuration to form a coated film (hereinafter also referred to as the "coated film formation step"), and a step of aligning the liquid crystalline components contained in the coated film (hereinafter also referred to as the "orientation step"). Here, the coating film formation step and orientation step are the same steps as those described in the method for forming the light-absorbing anisotropic layer described above.

[0172] [Surface protective layer] The laminate of the present invention may have a surface protective layer on the side opposite to the side of the adhesive layer 1 that has the light-absorbing anisotropic layer, that is, at the most visible position when used as part of a display device. The surface protection layer is not limited as long as it has a function to protect the surface, and may be a single layer or multiple layers. High hardness is preferable, but high resilience is also preferable. A low-reflectance layer that suppresses surface reflection occurring at the air interface is also preferable. One preferred embodiment is one having a support and / or a surface coating layer. The support and surface coating layer will be described below.

[0173] <Support> The surface protective layer preferably has a support, and more preferably has a transparent support. Here, "transparent" as used in this invention means that the transmittance of visible light is 60% or more, preferably 80% or more, and particularly preferably 90% or more. Examples of transparent supports include glass substrates and plastic substrates, with plastic substrates being preferred. Examples of plastics that make up plastic substrates include polyolefins such as polyethylene, polypropylene, and norbornene polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate; polyacrylic acid; cellulose esters such as triacetylcellulose (TAC), diacetylcellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; polyphenylene sulfide; polyphenylene oxide; and polyimide resins. In particular, cellulose esters, cyclic olefin resins, polyethylene terephthalate, and polymethacrylate esters are preferred due to their easy availability from the market and excellent transparency, while polyimide resins are preferred due to their excellent flexibility. Polyimides have a high refractive index, which can lead to a large refractive index gap. However, it is preferable to adjust the refractive index by methods such as incorporating silica particles. For more details on polyimides, please refer to International Publication No. 2018 / 062296 and International Publication No. 2018 / 062190.

[0174] The thickness of the transparent support is preferably thin enough to maintain strength and processability, while ensuring sufficient transparency and a mass that allows for practical handling. The thickness of the glass substrate is preferably 100 to 3000 μm, and more preferably 100 to 1000 μm. The thickness of the plastic substrate is preferably 5 to 300 μm, and more preferably 5 to 200 μm. Furthermore, when the laminate of the present invention is used as a circular polarizing plate (especially when used as a circular polarizing plate for mobile devices), the thickness of the transparent support is preferably about 5 to 100 μm.

[0175] <Surface coating layer> The surface coating layer may be at least one selected from the group consisting of an anti-reflective layer, an anti-glare layer, and a hard coat layer. A hard coat layer is preferred. Known layer materials can be used for these. Multiple layers may be laminated.

[0176] Unlike the anti-reflective coatings of so-called circular polarizers, which are composed of the optical anisotropy layer and the light absorption anisotropy layer mentioned above, an anti-reflective layer refers to a structure that reduces reflection using a structure that utilizes light interference. In its simplest configuration, the anti-reflective layer may consist only of a low refractive index layer. To further reduce reflectivity, it is preferable to construct the anti-reflective layer by combining a high refractive index layer and a low refractive index layer. Examples of configurations include a two-layer structure with a high refractive index layer and a low refractive index layer from bottom to top, or a three-layer structure with different refractive indices, such as a medium refractive index layer (a layer with a higher refractive index than the bottom layer and a lower refractive index than the high refractive index layer) / high refractive index layer / low refractive index layer, and configurations with even more anti-reflective layers have also been proposed. In particular, from the standpoint of durability, optical properties, cost, and productivity, it is preferable to have a medium refractive index layer / high refractive index layer / low refractive index layer on the hard coat layer in that order. Examples of configurations described in Japanese Patent Publication No. 8-122504, Japanese Patent Publication No. 8-110401, Japanese Patent Publication No. 10-300902, Japanese Patent Publication No. 2002-243906, and Japanese Patent Publication No. 2000-111706 are examples of such configurations. Furthermore, a three-layer anti-reflective film with excellent robustness against film thickness fluctuations is described in Japanese Patent Publication No. 2008-262187. When the above three-layer anti-reflective film is installed on the surface of an image display device, the average reflectance can be set to 0.5% or less, reflections can be significantly reduced, and an image with excellent three-dimensionality can be obtained. Furthermore, each layer may be given other functions, such as a low refractive index layer for stain resistance, a high refractive index layer for antistatic properties, an antistatic hard coat layer, or an anti-glare hard coat layer (e.g., Japanese Patent Publication No. 10-206603, Japanese Patent Publication No. 2002-243906, Japanese Patent Publication No. 2007-264113, etc.). On the other hand, as the hard coat layer, a hard coat using a silsesquioxane compound with a structure described in Japanese Patent Publication No. 2015-212353, Japanese Patent Publication No. 2017-008148, etc., can be suitably used.

[0177] [Photoalignment layer] In the present invention, it is preferable to utilize a photo-orientation layer containing a photoactive compound in order to improve the degree of orientation of organic dichroic substances (particularly dichroic azo dye compounds). The photo-alignment layer can be removed during the process of bonding the optically anisotropic layer and the light-absorbing anisotropic layer, but it is also preferable to leave it between the optically anisotropic layer and the light-absorbing anisotropic layer. In this case, from the viewpoint of the film strength of the laminate, it is preferable to form it from a compound having a crosslinking group. Preferred crosslinking groups are radical polymerizable groups and cationic polymerizable groups, with radical polymerizable groups being more preferable. Examples of radical polymerizable groups include ethylenically unsaturated bonding groups. Examples of cationic polymerizable groups include epoxy groups and oxetane groups. A dichroic azo dye compound photo-alignment layer refers to an alignment layer in which an alignment-regulating force is imparted by coating a substrate with a composition containing a compound having a photoreactive group and a solvent, and irradiating it with polarized light (preferably polarized UV). A photoreactive group is a group that generates liquid crystal alignment ability upon irradiation with light. Specifically, it is a photoreaction that is the origin of liquid crystal alignment ability, such as orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photodegradation reaction of molecules (called photoactive compounds) generated by irradiation with light. As a photoreactive group, those having unsaturated bonds, especially double bonds, are preferred, and groups having at least one selected from the group consisting of carbon-carbon double bonds (C=C bonds), carbon-nitrogen double bonds (C=N bonds), nitrogen-nitrogen double bonds (N=N bonds), and carbon-oxygen double bonds (C=O bonds) are more preferred.

[0178] Examples of photoreactive groups having a C=C bond include vinyl groups, polyene groups, stilbene groups, stilbazole groups, stilbazolium groups, chalcone groups, and cinnamoyl groups. Examples of photoreactive groups having a C=N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. Examples of photoreactive groups having a C=O bond include benzophenone groups, coumarin groups, anthraquinone groups, and maleimide groups. Examples of photoreactive groups having an N=N bond include azobenzene groups, azonaphthalene groups, aromatic heterocyclic azo groups, bisazo groups, and formazan groups, as well as groups with azoxybenzene as their basic structure. These groups may have substituents such as alkyl groups, alkoxy groups, allyl groups, allyloxy groups, cyano groups, alkoxycarbonyl groups, hydroxyl groups, sulfonic acid groups, or halogenated alkyl groups. In particular, cinnamoyl groups and azobenzene groups are preferred because they require relatively little polarized irradiation for photo-orientation, and they readily yield a photo-orientation layer with excellent thermal stability and chronological stability. Specific compounds are described in sections

[0211] to

[0263] of Japanese Patent Publication No. 5300776 and are preferably used.

[0179] A photo-alignment layer formed from the above material is subjected to linearly polarized or unpolarized irradiation to produce a photo-alignment layer. In this specification, "linearly polarized irradiation" and "unpolarized irradiation" refer to operations for causing a photoreaction in a photo-oriented material. The wavelength of light used varies depending on the photo-oriented 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 irradiation is preferably 200 nm to 700 nm, and ultraviolet light with a peak wavelength of 400 nm or less is more preferred.

[0180] Light sources used for light irradiation include commonly used light sources 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.

[0181] Methods for obtaining linearly polarized light include using polarizers (e.g., iodine polarizers, two-color dye polarizers, and wire grid polarizers), using prism-type elements (e.g., Grant-Thomson prisms) or reflective polarizers utilizing the Brewster angle, or using light emitted from a polarized laser light source. Alternatively, filters or wavelength conversion elements may be used to selectively irradiate only the light of the required wavelength.

[0182] When linearly polarized light is used, the light is irradiated from the top or back surface of the orientation layer, perpendicularly or obliquely to the surface of the orientation layer. The angle of incidence of the light varies depending on the photo-orientation material, but is preferably 0 to 90° (perpendicular), and preferably 40 to 90°. In the case of non-polarized light, the orientation layer is irradiated with non-polarized light from an oblique angle. 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.

[0183] If patterning is required, a method can be employed in which light irradiation using a photomask is performed the number of times necessary to create the pattern, or a method can be employed in which the pattern is written by laser scanning.

[0184] [Image display device] The image display device of the present invention comprises the laminate of the present invention described above and an image display element, wherein the image display element is arranged on the side opposite to the side of the adhesive layer 2 that has the light-absorbing anisotropic layer. The display elements used in the image display device of the present invention are not particularly limited and include, for example, liquid crystal cells, organic EL display panels, and plasma display panels. Of these, a liquid crystal cell or an organic EL display panel is preferred, and a liquid crystal cell is more preferred. In other words, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element, and preferably an organic EL display device using an organic EL display panel as a display element, and more preferably an organic EL display device.

[0185] [Organic EL display device] As an example of an organic EL display device, which is an image display device of the present invention, a preferred embodiment is one in which, from the viewing side, the laminate of the present invention described above and an organic EL display panel are arranged in this order. In this case, the laminate is arranged from the viewing side in the following order: a surface protective layer, an adhesive layer or tack layer as needed, an oxygen barrier layer, a refractive index adjusting layer, a light absorption anisotropy layer, an adhesive layer or tack layer as needed, and an optical anisotropy layer. Furthermore, an organic EL display panel is a display panel constructed using an organic EL element in which an organic light-emitting layer (organic electroluminescent layer) is sandwiched between electrodes (between the cathode and the anode). The configuration of the organic EL display panel is not particularly limited, and known configurations can be adopted.

[0186] [Other configurations] The adhesive layer and support used in the present invention may contain an ultraviolet absorber. The UV absorber is not particularly limited, and various known types can be used, but it is preferable that the transmittance of the adhesive layer be 0.1% or less in the wavelength range of 350 to 390 nm, 20 to 70% at 410 nm, and 90% or more in the wavelength range of 450 nm and above. It is even more preferable that the transmittance at a wavelength of 410 nm be 40 to 50%.

[0187] In the image display device of the present invention, if the curable adhesive layer is positioned on the viewing side of the light-absorbing anisotropic layer, it is preferable to include an ultraviolet absorber in the curable adhesive layer in order to improve the light resistance of the light-absorbing anisotropic layer. If the curable adhesive layer is an ultraviolet-curable adhesive layer, it is preferable to shift the wavelength for curing the ultraviolet-curable adhesive layer and the absorption wavelength of the ultraviolet absorber.

[0188] The oxygen barrier layer used in the present invention may contain a radical trapping agent. By including a radical trapping agent in the oxygen barrier layer, the light resistance of the light-absorbing anisotropic layer can be improved. Compounds having a TEMPO structure are preferred as radical trapping agents, and compounds having multiple TEMPO structures are even more preferred. Commercially available compounds that can be used include Benzoloxy-TEMPO, Acetamide-TEMPO, and Isothiocyanate-TEMPO (Tokyo Chemical Industries).

[0189] The light-absorbing anisotropic layer of the laminate of the present invention is preferable because it has high resistance to ammonia exposure when a dichroic azo dye compound is used.

[0190] A thinner adhesive layer with a higher storage modulus of elasticity is preferable for achieving higher pencil hardness. The adhesive layer adjacent to the surface film has a particularly significant impact. From the viewpoint of pencil hardness, it is preferable to use an adhesive with a high modulus of elasticity, such as a PVA adhesive, UV adhesive, or thermosetting adhesive, instead of using a conventional adhesive.

[0191] In the process of manufacturing the laminate of the present invention, multiple thin layers of several μm or less, including the light-absorbing anisotropic layer used in the present invention, are formed on a long substrate by coating, and in one of the subsequent processes, a step of peeling off the long substrate may occur. As a result of the stress generated at the edges during peeling, cracks may occur at the edges of the sample, which can become a source of dust. To solve this problem, it is effective to devise a peeling method that reduces the bending stress applied to the thin-layer laminate during peeling, but it is also effective to appropriately adjust the coating width and coating thickness of each layer. As an example of a preferred embodiment, in a configuration of a long support, orientation layer, light-absorbing anisotropic layer, hardened layer, and oxygen barrier layer, it is effective to make the coating width of the orientation layer wider than that of the other layers. In other words, it is preferable that there is a region on the long support where only the orientation layer exists at the edges. Furthermore, regarding the thickness of the orientation layer, from the viewpoint of cracking at the edges, 1 μm to 10 μm is preferred, and 2 μm to 5 μm is more preferred. [Examples]

[0192] The present invention will be described in more detail below based on the following examples. The materials, amounts used, proportions, processing content, processing procedures, etc., shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0193] [Example 1] <Preparation of Cellulose Acrylate Film 1> (Preparation of cellulose acylate-doped core layer) The following compositions were placed in a mixing tank and stirred to dissolve each component, preparing a cellulose acetate solution to be used as a cellulose acylate dope for the core layer. ------------------------------------------------------------------ Core layer cellulose acylate doped ------------------------------------------------------------------ • 100 parts by mass of cellulose acetate with an acetyl substitution degree of 2.88 • Examples in Japanese Patent Publication No. 2015-227955 12 parts by mass of the listed polyester compound B • Compound F below: 2 parts by mass • Methylene chloride (first solvent) 430 parts by mass • Methanol (second solvent) 64 parts by mass ------------------------------------------------------------------

[0194] Compound F [ka]

[0195] (Preparation of outer layer cellulose acylate dope) A cellulose acetate solution to be used as the outer layer cellulose acylate dope was prepared by adding 10 parts by mass of the following mat agent solution to 90 parts by mass of the above-mentioned core layer cellulose acylate dope.

[0196] ------------------------------------------------------------------ Mat solution ------------------------------------------------------------------ • Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass • Methylene chloride (first solvent) 76 parts by mass • Methanol (second solvent) 11 parts by mass • 1 part by mass of the above-mentioned core layer cellulose acylate doped ------------------------------------------------------------------

[0197] (Preparation of Cellulose Acrylate Film 1) After filtering the above-mentioned core layer cellulose acylate dope and the above-mentioned outer layer cellulose acylate dope through filter paper with an average pore size of 34 μm and a sintered metal filter with an average pore size of 10 μm, the core layer cellulose acylate dope and the outer layer cellulose acylate dope on both sides were simultaneously cast from the casting port onto a drum at 20°C (band casting machine). Next, the film was peeled off with a solvent content of approximately 20% by mass, and both ends in the width direction of the film were fixed with tenter clips. The film was then dried while being stretched transversely at a stretching ratio of 1.1 times. Subsequently, the film was further dried by transporting it between the rolls of a heat treatment apparatus to produce an optical film with a thickness of 40 μm, which was designated as cellulose acylate film 1. The in-plane retardation of the obtained cellulose acylate film 1 was 0 nm.

[0198] <Formation of photo-aligned layer PA1> The orientation layer forming coating liquid PA1, described later, was continuously applied onto the cellulose acylate film 1 using a wire bar. The support with the coated film was dried with 140°C hot air for 120 seconds, and then polarized ultraviolet light (10 mJ / cm²) was irradiated onto the coating film. 2 By using an ultra-high pressure mercury lamp, a photo-alignment layer PA1 was formed, and a TAC film with a photo-alignment layer was obtained. The thickness of the photo-alignment layer PA1 was 1.0 μm.

[0199] ------------------------------------------------------------------ (PA1 coating solution for forming an orientation layer) ------------------------------------------------------------------ • 100.00 parts by mass of the polymer PA-1 described below • Acid generator PAG-1: 5.00 parts by mass • The following acid generator CPI-110TF: 0.005 parts by mass Xylene 1220.00 parts by mass • Methyl isobutyl ketone 122.00 parts by mass ------------------------------------------------------------------

[0200] Polymer PA-1 [ka]

[0201] Acid Generator PAG-1 [ka]

[0202] Acid Generator CPI-110F [ka]

[0203] <Formation of light-absorbing anisotropic layer P1> The following light-absorbing anisotropic layer-forming composition P1 was continuously applied to the obtained photo-alignment layer PA1 using a wire bar to form a coated layer P1. Next, the coated layer P1 was heated at 140°C for 30 seconds, and then cooled to room temperature (23°C). Next, it was heated at 90°C for 60 seconds and then cooled again to room temperature. Subsequently, an illuminance of 200 mW / cm was measured using an LED lamp (center wavelength 365 nm). 2 By irradiating for 2 seconds under the specified irradiation conditions, a light-absorbing anisotropic layer P1 was fabricated on the photo-alignment layer PA1. The thickness of the light-absorbing anisotropic layer P1 was 0.4 μm.

[0204] ------------------------------------------------------------------ Composition of composition P1 for forming a light-absorbing anisotropic layer ------------------------------------------------------------------ • 0.36 parts by mass of the following dichroic substance D-1 • The following dichroic substance D-2: 0.53 parts by mass • The following dichroic substance D-3: 0.31 parts by mass • 3.58 parts by mass of the following polymeric liquid crystalline compound P-1 • Polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.050 parts by mass • 0.026 parts by mass of the following interface modifier F-1 • 0.026 parts by mass of the following interface modifier F-2 Cyclopentanone 45.00 parts by mass • Tetrahydrofuran 45.00 parts by mass Benzyl alcohol 5.00 parts by mass ------------------------------------------------------------------

[0205] D-1 [ka]

[0206] D-2 [ka]

[0207] D-3 [ka]

[0208] Polymer liquid crystal compound P-1 [ka]

[0209] Interface modifier F-1 [ka]

[0210] Interface modifier F-2 (molecular weight 8000) [ka]

[0211] <Formation of hardened layer N1> The following curing layer-forming composition N1 was continuously applied to the obtained light-absorbing anisotropic layer P1 using a wire bar to form a cured layer N1. Next, the hardened layer N1 was dried at room temperature, and then irradiated with a high-pressure mercury lamp at an illuminance of 28 mW / cm². 2 A cured layer N1 was fabricated on the light-absorbing anisotropic layer P1 by irradiating it for 15 seconds under the specified irradiation conditions. The thickness of the cured layer N1 was 0.05 μm (50 nm).

[0212] ------------------------------------------------------------------ Composition of composition N1 for hardening layer formation ------------------------------------------------------------------ • Mixture L1 of the following rod-shaped liquid crystalline compounds: 2.61 parts by mass • 0.11 parts by mass of the following modified trimethylolpropane triacrylate • 0.05 parts by mass of the following photopolymerization initiator I-1 • 0.21 parts by mass of the following interface modifier F-3 • Methyl isobutyl ketone 297 parts by mass ------------------------------------------------------------------

[0213] A mixture of rod-shaped liquid crystalline compounds L1 (the values ​​in the formula below represent mass percent, and R represents a group bonded by an oxygen atom). [ka]

[0214] Modified trimethylolpropane triacrylate [ka]

[0215] The following photopolymerization initiator I-1 [ka]

[0216] Surfactant F-3 [ka]

[0217] <Formation of oxygen barrier layer B1> A coating solution with the following composition was continuously applied to the cured layer N1 using a wire bar. Then, by drying with 100°C hot air for 2 minutes, a laminated film 1B was fabricated in which a 1.0 μm thick polyvinyl alcohol (PVA) layer was formed on the cured layer N1.

[0218] ------------------------------------------------------------------ Composition of oxygen barrier layer forming composition B1 ------------------------------------------------------------------ • 3.80 parts by mass of the following modified polyvinyl alcohol • Initiator Irg2959 0.20 parts by mass ·Water 70 parts by mass • Methanol 30 parts by mass ------------------------------------------------------------------

[0219] Modified polyvinyl alcohol [ka]

[0220] <Preparation of surface protective layer H1> As shown below, coating solutions for each layer were prepared, and each layer was formed to create the surface protective layer H1.

[0221] (Preparation of compositions for forming a hard coat layer) Trimethylolpropane triacrylate (Viscote #295 (manufactured by Osaka Organic Chemical Co., Ltd.)) (750.0 parts by mass), poly(glycidyl methacrylate) with a mass-average molecular weight of 15,000 (270.0 parts by mass), methyl ethyl ketone (730.0 parts by mass), cyclohexanone (500.0 parts by mass), and a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) (50.0 parts by mass) were mixed. The resulting mixture was filtered through a polypropylene filter with a pore size of 0.4 μm to prepare a composition for forming a hard coat layer.

[0222] (Preparation of composition A for forming an intermediate refractive index layer) A hard coating agent containing ZrO2 microparticles (Desolite Z7404 [refractive index 1.72, solid content concentration: 60% by mass, zirconium oxide microparticle content: 70% by mass (relative to solid content), average particle size of zirconium oxide microparticles: approximately 20 nm, solvent composition: methyl isobutyl ketone / methyl ethyl ketone = 9 / 1, manufactured by JSR Corporation]) (5.1 parts by mass), a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA) (1.5 parts by mass), a photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.) (0.05 parts by mass), methyl ethyl ketone (66.6 parts by mass), methyl isobutyl ketone (7.7 parts by mass), and cyclohexanone (19.1 parts by mass) were mixed. After thoroughly stirring the resulting mixture, it was filtered through a polypropylene filter with a pore size of 0.4 μm to prepare composition A for forming a medium refractive index layer.

[0223] (Preparation of composition B for forming a medium refractive index layer) A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA) (4.5 parts by mass), a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.) (0.14 parts by mass), methyl ethyl ketone (66.5 parts by mass), methyl isobutyl ketone (9.5 parts by mass), and cyclohexanone (19.0 parts by mass) were mixed. After thoroughly stirring the resulting mixture, it was filtered through a polypropylene filter with a pore size of 0.4 μm to prepare composition B for forming a medium refractive index layer.

[0224] A medium refractive index layer-forming composition was prepared by mixing appropriate amounts of medium refractive index layer-forming composition A and medium refractive index layer-forming composition B so that the refractive index becomes 1.62.

[0225] (Preparation of compositions for forming high refractive index layers) A hard coating agent containing ZrO2 microparticles (Desolite Z7404 [refractive index 1.72, solid content concentration: 60% by mass, zirconium oxide microparticle content: 70% by mass (relative to solid content), average particle size of zirconium oxide microparticles: approximately 20 nm, solvent composition: methyl isobutyl ketone / methyl ethyl ketone = 9 / 1, manufactured by JSR Corporation]) (15.7 parts by mass), methyl ethyl ketone (61.9 parts by mass), methyl isobutyl ketone (3.4 parts by mass), and cyclohexanone (1.1 parts by mass) were mixed. The resulting mixture was filtered through a polypropylene filter with a pore size of 0.4 μm to prepare a composition for forming a high refractive index layer.

[0226] (Preparation of compositions for forming low refractive index layers) (Synthesis of perfluoroolefin copolymer (1)) [ka] In the above structural formula, 50:50 represents the molar ratio.

[0227] Ethyl acetate (40 ml), hydroxyethyl vinyl ether (14.7 g), and dilauroyl peroxide (0.55 g) were charged into a 100 ml stainless steel autoclave with a stirrer. The system was degassed and replaced with nitrogen gas. Hexafluoropropylene (25 g) was then introduced into the autoclave and the temperature was raised to 65°C. The pressure inside the autoclave when the temperature reached 65°C was 0.53 MPa (5.4 kg / cm²). 2 The temperature was maintained and the reaction continued for 8 hours, until the pressure reached 0.31 MPa (3.2 kg / cm²). 2Heating was stopped when the temperature reached 0.5°C and the mixture was allowed to cool. Once the internal temperature had dropped to room temperature, the unreacted monomers were expelled, and the autoclave was opened to remove the reaction mixture. The obtained reaction mixture was added to a large excess of hexane, and the solvent was removed by decantation, and the precipitated polymer was collected. Furthermore, the obtained polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove any remaining monomers, and after drying, the polymer (28 g) was obtained. Next, 20 g of this polymer was dissolved in 100 ml of N,N-dimethylacetamide to obtain a solution. Then, under ice cooling, 11.4 g of acrylic acid chloride was added dropwise to the solution, and the mixture was stirred at room temperature for 10 hours. Ethyl acetate was added to the reaction mixture and washed with water to extract the organic phase. After concentration, the resulting polymer was reprecipitated with hexane to obtain perfluoroolefin copolymer (1) (19 g). The refractive index of the obtained polymer was 1.422.

[0228] (Preparation of sol solution a) In a reactor equipped with a stirrer and reflux condenser, methyl ethyl ketone (120 parts by mass), acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) (100 parts by mass), and diisopropoxyaluminum ethyl acetoacetate (trade name: Kelope EP-12, manufactured by Hope Pharmaceutical Co., Ltd.) (3 parts by mass) were added and mixed. Then, ion-exchanged water (31 parts by mass) was added, and the resulting solution was reacted at 61°C for 4 hours, after which it was cooled to room temperature to obtain sol a. The mass-average molecular weight of the compounds in the obtained sol solution a was 1620, and among the components larger than the oligomeric component, 100% were in the molecular weight range of 1000 to 20000. Furthermore, gas chromatography analysis showed that no residue of the starting material, acryloyloxypropyltrimethoxysilane, remained.

[0229] (Preparation of hollow silica particle dispersion) Hollow silica particle sol (isopropyl alcohol silica sol, CS60-IPA manufactured by Shokutai Kasei Kogyo Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20%, refractive index of silica particles 1.31) (500 parts by mass), acryloyloxypropyltrimethoxysilane (30.5 parts by mass), and diisopropoxyaluminum ethyl acetate (1.51 parts by mass) were mixed, and then ion-exchanged water (9 parts by mass) was added. Next, the obtained solution was reacted at 60°C for 8 hours, then cooled to room temperature, and acetylacetone (1.8 parts by mass) was added to obtain a dispersion. Subsequently, solvent replacement was performed by vacuum distillation at a pressure of 30 Torr while adding cyclohexanone to keep the silica content nearly constant, and finally, the concentration was adjusted to obtain a hollow silica particle dispersion with a solid content of 18.2% by mass. The residual amount of IPA (isopropyl alcohol) in the obtained dispersion was analyzed by gas chromatography and found to be less than 0.5%.

[0230] Using the obtained hollow silica particle dispersion and sol solution a, a composition with the following composition was mixed, and the resulting solution was stirred and then filtered through a polypropylene filter with a pore size of 1 μm to prepare a composition for forming a low refractive index layer.

[0231] -------------------------------------------------- (Composition of composition for forming a low refractive index layer) -------------------------------------------------- DPHA 14.5g PO-1 24.5g • Hollow silica particle dispersion 302.2g RMS-033 5.0g Irgacure 907 1.0g Methyl ethyl ketone 1750g Cyclohexanone 223.0g --------------------------------------------------

[0232] The compounds used in the above-mentioned low refractive index layer forming compositions are shown below. • PO-1: Perfluoroolefin copolymer (1) • DPHA: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) • RMS-033: Reactive silicone (manufactured by Gelest Co., Ltd.) • Irgacure 907: Photopolymerization initiator (manufactured by BASF)

[0233] (Preparation of the hard coat layer) A hard coat layer-forming composition was applied to support S1 (a 40 μm thick TAC substrate; TG40, Fujifilm Corporation) using a gravure coater. After drying the coating at 100°C, an illuminance of 400 mW / cm² was applied using a 160 W / cm² air-cooled metal halide lamp (manufactured by iGraphics Co., Ltd.) while purging with nitrogen to maintain an oxygen concentration of 1.0 volume% or less. 2 , irradiation amount 150mJ / cm 2 The coating was cured by irradiation with ultraviolet light, forming a 12 μm thick hard coat layer. The refractive index was 1.52.

[0234] An anti-reflective film was prepared by applying a medium refractive index layer-forming composition, a high refractive index layer-forming composition, and a low refractive index layer-forming composition, each adjusted to achieve the desired refractive index, onto the obtained hard coat layer using a gravure coater. The refractive index of each layer was measured by coating a glass plate with the composition for forming each layer to a thickness of approximately 4 μm and measuring it using a multi-wavelength Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.). Furthermore, the refractive index measured using the "DR-M2, M4 Interference Filter 546(e)nm Part Number: RE-3523" was adopted as the refractive index at a wavelength of 550nm. The film thickness of each layer was calculated using a reflectance spectrophotometer "FE-3000" (manufactured by Otsuka Electronics Co., Ltd.) after stacking the medium refractive index layer, high refractive index layer, and low refractive index layer in that order. The refractive index of each layer used in the calculation was the value derived from the Abbe refractometer mentioned above.

[0235] The drying conditions for the medium refractive index layer were 90°C for 30 seconds. For UV curing, a 180 W / cm² air-cooled metal halide lamp (manufactured by I-Graphics Co., Ltd.) was used while purging with nitrogen to maintain an atmosphere with an oxygen concentration of 1.0 volume% or less, with an illuminance of 300 mW / cm². 2 , irradiation amount 240mJ / cm 2 This was the irradiation dose. The refractive index of the medium refractive index layer after curing was 1.62, and the layer thickness was 60 nm.

[0236] The drying conditions for the high refractive index layer were 90°C for 30 seconds. For UV curing, a 240 W / cm² air-cooled metal halide lamp (manufactured by iGraphics Co., Ltd.) was used while purging with nitrogen to maintain an atmosphere with an oxygen concentration of 1.0 volume% or less, with an illuminance of 300 mW / cm². 2 , irradiation amount 240mJ / cm 2 The irradiation dose was set to [value missing]. The refractive index of the cured high-refractive-index layer was 1.72, and the layer thickness was 110 nm.

[0237] The drying conditions for the low refractive index layer were 90°C for 30 seconds. For UV curing, a 240 W / cm² air-cooled metal halide lamp (manufactured by I-Graphics Co., Ltd.) was used while purging with nitrogen to maintain an atmosphere with an oxygen concentration of 0.1 volume% or less, with an illuminance of 600 mW / cm². 2 , irradiation amount 600mJ / cm 2 The irradiation dose was set to [value missing]. The refractive index of the low refractive index layer after curing was 1.36, and the layer thickness was 90 nm. With this, the surface protective layer H1 has been fabricated.

[0238] <Preparation of adhesive sheets N1-N4> Next, acrylate polymers were prepared according to the following procedure. In a reaction vessel equipped with a condenser, a nitrogen inlet, a thermometer, and a stirring device, 95 parts by weight of butyl acrylate and 5 parts by weight of acrylic acid were polymerized by solution polymerization to obtain acrylate polymer A1 with an average molecular weight of 2 million and a molecular weight distribution (Mw / Mn) of 3.0.

[0239] Next, using the obtained acrylate polymer A1, acrylate adhesive compositions were prepared with the compositions shown in Table 3 below. The prepared compositions were applied to a separator film (hereinafter also referred to as "release film") surface-treated with a silicone-based release agent using a die coater, dried for 1 minute at 90°C, and for compositions containing a polyfunctional acrylate monomer and a photopolymerization initiator, ultraviolet light (UV) was irradiated under the following conditions to obtain acrylate-based adhesive sheets N1 to N4. The composition of the acrylate-based adhesive, the film thickness of the adhesive sheet, and the storage modulus are shown in Table 3 below. (UV irradiation conditions) Fusion Corporation Electrodeless Lamp H Bulb ·Illuminance 600mW / cm 2 , light intensity 150mJ / cm 2 UV irradiance and light intensity were measured using the "UVPF-36" manufactured by iGraphics.

[0240] [Table 3]

[0241] (A) Polyfunctional acrylate monomer: Tris(acryloyloxyethyl) isocyanurate, molecular weight = 423, trifunctional type (manufactured by Toagosei Co., Ltd., trade name "Arronix M-315") (B) Photopolymerization initiator: A mixture of benzophenone and 1-hydroxycyclohexylphenyl ketone in a 1:1 mass ratio, "Irgacure 500" manufactured by Ciba Specialty Chemicals. (C) Isocyanate-based crosslinking agent: Trimethylolpropane-modified tolylene diisocyanate ("Coronate L" manufactured by Nippon Polyurethane Co., Ltd.) (D) Silane coupling agent: 3-Glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. "KBM-403")

[0242] <Fabrication of the laminated structure in example 1> The oxygen barrier layer side of the laminated film 1B was bonded to the support side of the surface protective layer H1 using the adhesive sheet N1 as the adhesive layer 1. Furthermore, only the cellulose acylate film 1 was removed, and the removed surface was bonded to the adhesive sheet N1 as the adhesive layer 2 to form the laminate of fabrication example 1.

[0243] [Example 2] The oxygen barrier layer side of the laminated film 1B was bonded to the support side of the surface protective layer H1 using the adhesive sheet N2 as the adhesive layer 1. Furthermore, only the cellulose acylate film 1 was removed, and the removed surface was bonded to the adhesive sheet N2 as the adhesive layer 2 to form the laminate of fabrication example 2.

[0244] [Example 3] The oxygen barrier layer side of the laminated film 1B was bonded to the support side of the surface protective layer H1 using the adhesive sheet N2 as the adhesive layer 1. Furthermore, only the cellulose acylate film 1 was removed, and the removed surface was bonded to the adhesive sheet N1 as the adhesive layer 2 to form the laminate of fabrication example 3.

[0245] [Example 4] The laminate of Fabrication Example 4 was obtained using the same method as in Fabrication Example 3, except that the thickness of the photo-alignment layer of laminated film 1B was changed from 1 μm to 2 μm. When removing only cellulose acylate film 1, we grasped the cellulose acylate film side and peeled it off while preventing the other layers from bending, resulting in less jagged edges. Furthermore, by expanding the coating area of ​​only the orientation layer and narrowing the coating area of ​​the other layers, we confirmed that the jagged edges were further improved and a clean edge surface was achieved by creating an area on cellulose acylate film 1 where only the orientation layer was coated, at the edge parallel to the peeling direction.

[0246] [Example 5] In forming the light-absorbing anisotropic layer of the laminated film 1B of Fabrication Example 4, the laminate of Fabrication Example 5 was obtained using the same method as in Fabrication Example 4, except that the light-absorbing anisotropic layer forming composition P2 shown below was replaced with the light-absorbing anisotropic layer forming composition P2, and the thickness was changed from 0.4 μm to 0.8 μm.

[0247] ------------------------------------------------------------------ Composition of composition P2 for forming a light-absorbing anisotropic layer ------------------------------------------------------------------ • The following dichroic substance D-4: 0.36 parts by mass • The following dichroic substance D-5: 0.53 parts by mass • The following dichroic substance D-6: 0.31 parts by mass • 3.58 parts by mass of the above polymeric liquid crystalline compound P-1 • Polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.050 parts by mass • 0.026 parts by mass of the above-mentioned interface modifier F-1 Cyclopentanone 45.00 parts by mass • Tetrahydrofuran 45.00 parts by mass Benzyl alcohol 5.00 parts by mass ------------------------------------------------------------------

[0248] D-4 [ka]

[0249] D-5 [ka]

[0250] D-6 [ka]

[0251] Polymer liquid crystal compound P-1 [ka]

[0252] [Example 6] In forming the light-absorbing anisotropic layer of the laminated film 1B of Fabrication Example 1, the laminate of Fabrication Example 6 was obtained using the same method as in Fabrication Example 1, except that the light-absorbing anisotropic layer-forming composition P1 was changed to the light-absorbing anisotropic layer-forming composition P2 shown below, and the thickness was changed from 0.4 μm to 0.8 μm.

[0253] [Example 7] The laminate of Fabrication Example 7 was obtained using the same method as in Fabrication Example 4, except that the adhesive in adhesive layer 2 of Fabrication Example 4 was changed from N1 to N3.

[0254] [Example 8] The laminate of Fabrication Example 8 was obtained using the same method as in Fabrication Example 3, except that the thickness of the oxygen barrier layer of the laminated film 1B was changed from 1 μm to 2 μm.

[0255] [Example 9] <Formation of the photo-aligned layer PA2> The orientation layer forming coating liquid PA2, described later, was continuously applied onto the cellulose acylate film 1 using a wire bar. The support with the coated film was dried with 140°C hot air for 120 seconds, and then polarized ultraviolet light (10 mJ / cm²) was irradiated onto the coating film. 2 By using an ultra-high pressure mercury lamp, a 0.2 μm thick photo-alignment layer PA2 was formed, and a TAC film with a photo-alignment layer was obtained.

[0256] ------------------------------------------------------------------ (PA2 coating solution for forming an orientation layer) ------------------------------------------------------------------ 100.00 parts by mass of the following polymer PA-2 1.00 parts by mass of the above acid generator PAG-1 Isopropyl alcohol 16.50 parts by mass Butyl acetate 1072.00 parts by mass Methyl ethyl ketone 268.00 parts by mass ------------------------------------------------------------------

[0257] Polymer PA-2 [ka]

[0258] Acid Generator PAG-1 [ka]

[0259] <Fabrication of optically anisotropic layer (positive A plate A1)> Composition A-1, having the composition described later, was applied onto the photo-alignment layer PA2 using a bar coater. The coating formed on the photo-alignment layer PA2 was heated to 120°C with hot air, then cooled to 60°C, and then heated at a wavelength of 365 nm using a high-pressure mercury lamp at 100 mJ / cm² under a nitrogen atmosphere. 2 The coating is irradiated with ultraviolet light, followed by heating to 120°C while applying 500 mJ / cm² of UV light. 2 By irradiating the coating with ultraviolet light, the orientation of the liquid crystalline compound was fixed, and a TAC film A1 having a positive A plate A1 was fabricated. The thickness of positive A plate A1 was 2.5 μm, and Re(550) was 144 nm. Furthermore, positive A plate A1 satisfied the relationship Re(450) ≤ Re(550) ≤ Re(650). The ratio of Re(450) / Re(550) was 0.82.

[0260] ------------------------------------------------------------------ (Composition A1) ------------------------------------------------------------------ • Polymerizable liquid crystalline compound L-1: 43.50 parts by mass • Polymerizable liquid crystalline compound L-2: 43.50 parts by mass • Polymerizable liquid crystalline compound L-3: 8.00 parts by mass • Polymerizable liquid crystalline compound L-4: 5.00 parts by mass • Polymerization initiator PI-1: 0.55 parts by mass • Leveling agent T-1: 0.20 parts by mass Cyclopentanone 235.00 parts by mass ------------------------------------------------------------------

[0261] Polymerizable liquid crystal compound L-1 [ka]

[0262] Polymerizable liquid crystal compound L-2 [ka]

[0263] Polymerizable liquid crystal compound L-3 [ka]

[0264] Polymerizable liquid crystal compound L-4 [ka]

[0265] Polymerization initiator PI-1 [ka]

[0266] Leveling agent T-1 [ka]

[0267] <Fabrication of optically anisotropic layer (positive C plate C1)> The above-mentioned cellulose acylate film 1 was used as a temporary support. Cellulose acylate film 1 is passed through a dielectric heating roll at a temperature of 60°C, and after raising the film surface temperature to 40°C, an alkaline solution with the composition shown below is applied to one side of the film using a bar coater at a rate of 14 ml / m². 2 The sample was coated, heated to 110°C, and then transported for 10 seconds under a steam-type far-infrared heater manufactured by Noritake Co., Limited. Next, using the same bar coater, 3 ml / m² of pure water is applied to the film. 2 It was applied. Next, the film was washed with water using a fountain coater and dewatered with an air knife three times, and then transported to a 70°C drying zone for 10 seconds to dry, thereby producing an alkaline saponified cellulose acylate film 1.

[0268] ------------------------------------------------------------------ (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(CH2CH 2O ) 20 H) 1.0 parts by mass Propylene glycol 14.8 parts by mass ------------------------------------------------------------------

[0269] A coating solution 3 for forming an orientation layer, having the composition described below, was continuously applied onto the alkali-saponified cellulose acylate film 1 using a #8 wire bar. The resulting film was dried with 60°C hot air for 60 seconds, and then with 100°C hot air for 120 seconds to form an orientation layer with a thickness of 0.5 μm. ------------------------------------------------------------------ (Coating solution for forming an orientation layer 3) ------------------------------------------------------------------ Polyvinyl alcohol (manufactured by Kuraray, PVA103) 2.4 parts by mass Isopropyl alcohol 1.6 parts by mass 36 parts by mass of methanol 60 parts by mass of water ------------------------------------------------------------------

[0270] The positive C plate forming coating liquid C1, described later, is applied to the orientation layer, and the resulting coating film is aged at 60°C for 60 seconds, after which it is subjected to 70 mW / cm² under air. 2 Using an air-cooled metal halide lamp (manufactured by iGraphics Co., Ltd.), 1000 mJ / cm² 2 By irradiating with ultraviolet light and fixing its orientation, the liquid crystalline compound was vertically oriented, and a positive C plate C1 with a thickness of 0.5 μm was fabricated. The Rth(550) of the obtained positive C plate was -60 nm.

[0271] ------------------------------------------------------------------ (Positive C-plate formation coating solution C1) ------------------------------------------------------------------ • 80 parts by mass of the following liquid crystalline compound L-11 • 20 parts by mass of the following liquid crystalline compound L-12 • 1 part by mass of the following vertically distributed liquid crystalline compound activator (S01) • Ethylene oxide modified trimethylolpropane triacrylate (V#360, manufactured by Osaka Organic Chemical Co., Ltd.) 8 parts by mass • IrgaCure 907 (BASF) 3 parts by mass • Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass · 0.4 parts by mass of the following compound B03 · 170 parts by mass of methyl ethyl ketone · 30 parts by mass of cyclohexanone ―――――――――――――――――――――――――――――――――

[0272]

Chemical formula

[0273]

Chemical formula

[0274]

Chemical formula

[0275] <Preparation of UV Adhesive> The following UV adhesive composition was prepared. ───────────────────────────────── 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 · 2.25 parts by mass of the following CPI - 100P ─────────────────────────────────

[0276] CPI - 100P

Chemical formula

[0277] <Preparation of the laminate of Production Example 9> The oxygen barrier layer side of the laminated film 1B was bonded to the support side of the surface protective layer H1 using the adhesive sheet N2 as the adhesive layer 1. Next, only the cellulose acylate film 1 was removed, and the removed surface and the phase difference side of the positive A plate A1 were bonded together using the UV adhesive at a rate of 600 mJ / cm². 2 The parts were bonded using UV irradiation. The following tests used UV adhesive under similar conditions. At this time, the layers were bonded so that the angle between the absorption axis of the light-absorbing anisotropic layer and the slow-phase axis of the positive A plate A1 was 45°. 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 (the same applies to the following description). Next, the orientation layer and cellulose acylate film 1 on the positive A plate side were removed, and the removed surface and the phase difference side of the positive C plate C1 were bonded together using the UV adhesive to form a UV adhesive layer B. The thickness of the UV adhesive layer B was 3 μm. The laminate of positive A plate A1, UV adhesive layer B, and positive C plate C1 was an optically anisotropic layer with a thickness of 6.0 μm. Furthermore, the orientation layer on the positive C plate C1 side and the cellulose acylate film 1 were removed, and the removed surface was bonded to the adhesive sheet N4 as the adhesive layer 2 to form the laminate of fabrication example 9.

[0278] [Example 10] <Fabrication of laminated film 2B> Laminated film 2B was obtained using the same method as for laminated film 1B, except that the photo-alignment layer forming coating solution PA1 was changed to PA2 and a photo-alignment layer with a thickness of 0.2 μm was formed on laminated film 1B.

[0279] <Fabrication of the laminated structure in example 10> The oxygen barrier layer side of the laminated film 2B was bonded to the support side of the surface protection layer 1 using the adhesive sheet N2 as the adhesive layer 1. Next, the cellulose acylate film 1 and the photo-alignment layer were removed, and the removed surface was bonded to the phase difference side of the positive A plate A1 using the UV adhesive. At this time, the layers were bonded together such that the angle between the absorption axis of the light-absorbing anisotropic layer and the slow-phase axis of the positive A plate A1 was 45°. The thickness of the UV adhesive layer was 3 μm. Next, the orientation layer and cellulose acylate film 1 on the positive A plate A1 side were removed, and the removed surface and the phase difference side of the positive C plate C1 were bonded together using the UV adhesive to form a UV adhesive layer B. The thickness of the UV adhesive layer B was 3 μm. The laminate of positive A plate A1, UV adhesive layer B, and positive C plate C1 was an optically anisotropic layer with a thickness of 6.0 μm. Furthermore, the orientation layer on the positive C plate side and the cellulose acylate film 1 were removed, and the removed surface was bonded to the adhesive sheet N4 as the adhesive layer 2 to form the laminate of fabrication example 10.

[0280] [Example 11] In fabrication example 10, the laminate of fabrication example 11 was obtained in the same manner as in fabrication example 10, except that the adhesive sheet of adhesive layer 2 of fabrication example 10 was changed from N4 to N2.

[0281] [Example 12] <Fabrication of optically anisotropic layer (positive C plate C2)> Positive C plate C2 was obtained in the same manner as positive C plate C1, except that the orientation layer forming coating liquid 3 was replaced with the orientation layer forming coating liquid 4 described below.

[0282] (Preparation of coating solution 4 for orientation layer formation) -------------------------------------------------- Composition of coating liquid 4 for orientation layer formation -------------------------------------------------- • 3.80 parts by mass of the following modified polyvinyl alcohol • Initiator Irg2959 0.20 parts by mass ·Water 70 parts by mass • Methanol 30 parts by mass --------------------------------------------------

[0283] Modified polyvinyl alcohol [ka]

[0284] <Fabrication of the laminated body in example 12> The oxygen barrier layer side of the laminated film 2B was bonded to the support side of the surface protection layer 1 using the adhesive sheet N2 as the adhesive layer 1. Next, the cellulose acylate film 1 and the photo-alignment layer were removed, and the removed surface was bonded to the phase difference side of the positive A plate A1 using the UV adhesive. At this time, the layers were bonded together such that the angle between the absorption axis of the light-absorbing anisotropic layer and the slow-phase axis of the positive A plate A1 was 45°. The thickness of the UV adhesive layer was 3 μm. Next, the orientation layer and cellulose acylate film 1 on the positive A plate side were removed, and the removed surface and the phase difference side of the positive C plate C2 were bonded together using the UV adhesive to form a UV adhesive layer B. The thickness of the UV adhesive layer B was 3 μm. The laminate of positive A plate A1, UV adhesive layer B, and positive C plate C2 was an optically anisotropic layer with a thickness of 6.0 μm. Furthermore, the surface of the cellulose acylate film 1 on the positive C plate side was bonded to the adhesive sheet N4 as adhesive layer 2 to form the laminate of fabrication example 12.

[0285] [Example 13] <Fabrication of laminated film 3B> Laminated film 3B was obtained in the same manner as laminated film 1B, except that the photo-alignment layer forming coating solution PA1 was replaced with the photo-alignment layer forming coating solution PA3 described below, and a photo-alignment layer with a thickness of 0.3 μm was formed on laminated film 1B.

[0286] (Preparation of PA3 coating solution for photo-alignment layer formation) ------------------------------------------------------------------ (PA3 coating solution for forming an orientation layer) ------------------------------------------------------------------ 100.00 parts by mass of the above-mentioned polymer PA-1 5.00 parts by mass of the above acid generator PAG-1 0.005 parts by mass of the above acid generator CPI-110TF Isopropyl alcohol 16.50 parts by mass Butyl acetate 1072.00 parts by mass Methyl ethyl ketone 268.00 parts by mass ------------------------------------------------------------------

[0287] <Fabrication of the laminated structure in example 13> The oxygen barrier layer side of the laminated film 3B was bonded to the support side of the surface protection layer 1 using the adhesive sheet N1 as the adhesive layer 1. Furthermore, the adhesive sheet N1 was bonded to the surface of the cellulose acylate film 1 as the adhesive layer 2 to form the laminate of fabrication example 13.

[0288] [Example 14] <Formation of an oxygen barrier layer> A 40 μm thick TAC substrate (TG40, manufactured by Fujifilm Corporation) was subjected to saponification treatment, and then the oxygen barrier layer formation composition liquid B1 prepared above was applied using a wire bar. Subsequently, by drying with 100°C hot air for 2 minutes, a transparent support 1 was obtained on the TAC substrate with a 1.0 μm thick oxygen barrier layer formed on it.

[0289] <Formation of the photophosphoric layer> The above-mentioned orientation layer forming coating liquid PA3 was continuously applied to the oxygen barrier layer of the transparent support 1 using a wire bar. The support with the formed coating film was dried with 140°C hot air for 120 seconds, and then polarized ultraviolet light (10 mJ / cm²) was irradiated onto the coating film. 2 By using an ultra-high pressure mercury lamp, a photo-alignment layer PA3 was formed, and a TAC film 1 with a photo-alignment layer was obtained. The film thickness was 0.2 μm.

[0290] <Formation of the hardened layer> The above-mentioned curing layer-forming composition N1 was continuously applied to the obtained photo-alignment layer PA3 using a wire bar to form a curing layer N1. Next, the hardened layer N1 was dried at room temperature, and then irradiated with a high-pressure mercury lamp at an illuminance of 28 mW / cm². 2 A cured layer N1 was fabricated on the photo-aligned layer PA3 by irradiating it for 15 seconds under the specified irradiation conditions. The thickness of the cured layer N1 was 0.05 μm (50 nm).

[0291] <Formation of a light-absorbing anisotropic layer> The following light-absorbing anisotropic layer-forming composition P1 was continuously applied to the obtained cured layer N1 using a wire bar to form a coated layer P1. Next, the coated layer P1 was heated at 140°C for 30 seconds, and then cooled to room temperature (23°C). Next, it was heated at 90°C for 60 seconds and then cooled again to room temperature. Subsequently, an illuminance of 200 mW / cm was measured using an LED lamp (center wavelength 365 nm). 2 A light-absorbing anisotropic layer P1 was fabricated on the hardened layer N1 by irradiating it for 2 seconds under the specified irradiation conditions. The film thickness was 0.4 μm.

[0292] <Formation of a barrier layer> The barrier layer H1 was formed by continuously coating the obtained light-absorbing anisotropic layer P1 with the following barrier layer-forming composition H1 using a wire bar. Next, the barrier layer H1 was dried at room temperature, and then irradiated with a high-pressure mercury lamp at an illuminance of 28 mW / cm². 2 By irradiating under these conditions for 10 seconds, a barrier layer H1 was fabricated on the light-absorbing anisotropic layer P1, and a laminated film 1A was obtained. The thickness of the barrier layer H1 was 1.0 μm. -------------------------------------------------- Composition of barrier layer forming composition H1 -------------------------------------------------- • CEL2021P (manufactured by Daicel Corporation) 32 parts by mass • Polymerization initiator IRGACURE819 (BASF): 1 part by mass • CPI-100P (50% propylene carbonate solution) 2 parts by mass • Methyl ethyl ketone (MEK) 65 parts by mass --------------------------------------------------

[0293] <Fabrication of the laminated structure in example 14> The TG40 side of the laminated film 1A was bonded to the support side of the surface protection layer 1 using the adhesive sheet N2 as the adhesive layer 1. Furthermore, the adhesive sheet N1 was bonded to the surface of the barrier layer H1 as the adhesive layer 2 to form the laminate of fabrication example 14.

[0294] [Example 15] <Formation of an oxygen barrier layer> The oxygen barrier layer forming solution B1 prepared above was applied to the surface of a 40 μm thick TAC substrate (TG40, manufactured by Fujifilm Corporation) using a wire bar. Subsequently, by drying with 100°C hot air for 2 minutes, a transparent support 2 was obtained on the TAC substrate with a 1.0 μm thick oxygen barrier layer formed on it.

[0295] <Formation of the photophosphoric layer> The above-mentioned orientation layer forming coating liquid PA3 was continuously applied to the oxygen barrier layer of the transparent support 2 using a wire bar. The support with the formed coating film was dried with 140°C hot air for 120 seconds, and then polarized ultraviolet light (10 mJ / cm²) was irradiated onto the coating film. 2 A photo-alignment layer PA3 was formed by using an ultra-high pressure mercury lamp. The film thickness was 0.2 μm.

[0296] <Formation of the hardened layer> The above-mentioned curing layer-forming composition N1 was continuously applied to the obtained photo-alignment layer PA3 using a wire bar to form a curing layer N1. Next, the hardened layer N1 was dried at room temperature, and then irradiated with a high-pressure mercury lamp at an illuminance of 28 mW / cm². 2 A cured layer N1 was fabricated on the photo-aligned layer PA3 by irradiating it for 15 seconds under the specified irradiation conditions. The thickness of the cured layer N1 was 0.05 μm (50 nm).

[0297] <Formation of a light-absorbing anisotropic layer> The following light-absorbing anisotropic layer-forming composition P1 was continuously applied to the obtained cured layer N1 using a wire bar to form a coated layer P1. Next, the coated layer P1 was heated at 140°C for 30 seconds, and then cooled to room temperature (23°C). Next, it was heated at 90°C for 60 seconds and then cooled again to room temperature. Subsequently, an illuminance of 200 mW / cm was measured using an LED lamp (center wavelength 365 nm). 2 By irradiating under these conditions for 2 seconds, a light-absorbing anisotropic layer P1 with a thickness of 0.4 μm was fabricated on the cured layer N1, and a laminated film 2A was obtained.

[0298] <Fabrication of the laminated body in example 15> The side of the laminated film 2A with the light-absorbing anisotropic layer and the phase difference side of the positive A plate A1 were bonded together using the UV adhesive. At this time, the layers were bonded so that the angle between the absorption axis of the light-absorbing anisotropic layer and the slow-phase axis of the positive A plate A1 was 45°. 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 (the same applies to the following description). Next, the orientation layer and cellulose acylate film 1 on the positive A plate side were removed, and the removed surface and the phase difference side of the positive C plate C1 were bonded together using the UV adhesive to form a UV adhesive layer B. The thickness of the UV adhesive layer B was 3 μm. The laminate of positive A plate A1, UV adhesive layer B, and positive C plate C2 was an optically anisotropic layer with a thickness of 6.0 μm. Furthermore, TG40 was removed from the resulting laminate, and the removed surface and the support-side surface of the surface protection layer 1 were bonded together using the adhesive sheet N2 as the adhesive layer 1. Finally, the orientation layer on the positive C plate side and the cellulose acylate film 1 were removed, and the adhesive sheet N4 was bonded to the removed surface as the adhesive layer 2 to form the laminate of fabrication example 15.

[0299] [Example 16] <Formation of an oxygen barrier layer> The oxygen barrier layer forming solution B1 prepared above was applied to the surface of a 40 μm thick TAC substrate (TG40, manufactured by Fujifilm Corporation) using a wire bar. Subsequently, by drying with 100°C hot air for 2 minutes, a transparent support 2 was obtained on the TAC substrate with a 1.0 μm thick oxygen barrier layer formed on it.

[0300] <TAC film with orientation layer 2> The surface of the oxygen barrier layer of the transparent support 2 prepared above was subjected to a rubbing treatment to obtain a TAC film 2 with an orientation layer.

[0301] <Formation of the hardened layer> The curing layer-forming composition N1 described above was continuously applied to the orientation layer of the obtained orientation-forming TAC film 2 using a wire bar to form the curing layer N1. Next, the hardened layer N1 was dried at room temperature, and then irradiated with a high-pressure mercury lamp at an illuminance of 28 mW / cm². 2 A cured layer N1 was fabricated on the photo-aligned layer PA3 by irradiating it for 15 seconds under the specified irradiation conditions. The thickness of the cured layer N1 was 0.05 μm (50 nm).

[0302] <Formation of a light-absorbing anisotropic layer> The following light-absorbing anisotropic layer-forming composition P1 was continuously applied to the obtained cured layer N1 using a wire bar to form a coated layer P1. Next, the coated layer P1 was heated at 140°C for 30 seconds, and then cooled to room temperature (23°C). Next, it was heated at 90°C for 60 seconds and then cooled again to room temperature. Subsequently, an illuminance of 200 mW / cm was measured using an LED lamp (center wavelength 365 nm). 2By irradiating under these conditions for 2 seconds, a light-absorbing anisotropic layer P1 with a thickness of 0.4 μm was fabricated on the cured layer N1, and a laminated film 3A was obtained.

[0303] <Fabrication of the laminated body in example 16> The laminate of Fabrication Example 16 was obtained using the same method as in Fabrication Example 15, except that the laminated film 2A of the laminate of Fabrication Example 15 was changed to the laminated film 3A.

[0304] [evaluation] [Moist heat durability] The resulting laminate was cut to a size of 50 mm x 50 mm, the release film was peeled off, and the adhesive layer 2 was pressed onto a glass substrate (Corning Eagle XG). This glass substrate pressed sample was subjected to a durability test at 60°C and 90% humidity, and the sample was visually observed and evaluated according to the following criteria. The results are shown in Table 4 below. Although the cutting was done by punching, no delamination between layers was observed at the edges, and the shape was clean and straight. AA: No wrinkles appear even after more than 400 hours. A: Wrinkles appear between 100 hours and 400 hours. B: Wrinkles appear between 50 and 100 hours. C: Wrinkles appear in less than 50 hours.

[0305] [Table 4]

[0306] The results shown in Table 4 indicate that when the H value is greater than 10, the thermal resistance of the laminate is poor (Examples 1 and 6). In contrast, it was found that when the H value was 10 or less, the thermal resistance of the laminate was good (Examples 2-5 and 7-16). In particular, comparisons from these examples showed that when the H value was 4.0 or less, the thermal resistance was even better.

[0307] [Examples 17-26] <Fabrication of the laminated structure in example 17> The adhesive layer 2 and the phase difference side of the positive A plate A1 were bonded to the laminate of fabrication example 1. At this time, the layers were bonded together such that the angle between the absorption axis of the light-absorbing anisotropic layer and the slow-phase axis of the positive A plate A1 was 45°. Next, the orientation layer and cellulose acylate film 1 on the positive A plate side were removed, and the removed surface was bonded to the phase difference side of the positive C plate C1 using the UV adhesive. The thickness of the UV adhesive layer was 3 μm. Furthermore, the orientation layer on the positive C plate side and the cellulose acylate film 1 were removed, and the adhesive sheet N1 was bonded to the removed surface to form the laminate of fabrication example 17.

[0308] <Fabrication of laminated structures for examples 18-26> Laminates for fabrication examples 18-26 were fabricated using the same method as in fabrication example 17, with respect to the laminates for fabrication examples 2-8, 13, and 14.

[0309] [Examples 27 and 28] For the laminate of Fabrication Example 4, adhesive sheet N1 was bonded to the laminate as adhesive layer 1 instead of adhesive sheet N2, resulting in the laminate of Fabrication Example 27. This laminate of Fabrication Example 27 had H=8.7, which is within the scope of the present invention, and the result of the durability evaluation described above was evaluation B. The adhesive layer 2 and the cellulose acylate film 1 were bonded to the laminate of fabrication example 27 to form laminate 27B. On the other hand, the phase difference side of the positive A plate A1 and the phase difference side of the positive C plate C1 were bonded together using the UV adhesive. The thickness of the UV adhesive layer was 3 μm. Next, the orientation layer and cellulose acylate film 1 on the positive A plate A1 side were removed, and the removed surface and the cellulose acylate film 1 side of the laminate 27B were bonded together using the adhesive sheet N1. At this time, the layers were bonded together such that the angle between the absorption axis of the light-absorbing anisotropic layer and the slow-phase axis of the positive A plate A1 was 45°. Next, the orientation layer on the positive C plate C1 side and the cellulose acylate film 1 were removed, and the adhesive sheet N1 was bonded to the removed surface to form the laminate of fabrication example 28.

[0310] <Fabrication of Organic EL Display Devices> A Samsung Galaxy S4 equipped with an organic EL panel (organic EL display element) was disassembled, and the touch panel with a circular polarizer was peeled off from the organic EL display device. The circular polarizer was then peeled off from the touch panel, isolating the organic EL display element, touch panel, and circular polarizer. Next, the isolated touch panel was re-bonded to the organic EL display element, and then the laminates described in fabrication examples 9-12, 15-26, and 28 were bonded onto the touch panel with the adhesive layer facing the panel side to fabricate an organic EL display device, and it was confirmed that an anti-reflective effect was observed.

[0311] [Examples 29-32] <Preparation of adhesive sheets N5-N7> Next, acrylate polymers were prepared according to the following procedure. A reaction vessel equipped with a condenser, nitrogen inlet tube, thermometer, and stirrer was charged with a mixed solution of ethyl acetate (81.8 parts by mass), 2-ethylhexyl acrylate (69.0 parts by mass), 2-methoxyethyl acrylate (29.0 parts by mass), 2-hydroxybutyl acrylate (1.0 part by mass), and acrylic acid (1.0 part by mass) as a solvent. Polymerization was carried out by solution polymerization to prepare an ethyl acetate solution of acrylate polymer A2. The obtained acrylate-based polymer A2 had a weight-average molecular weight (Mw) of 2 million and a polystyrene-based molecular weight (Mw / Mn) of 5.8, as determined by GPC.

[0312] Next, using the obtained acrylate polymer A1 or acrylate polymer A2, acrylate adhesive compositions were prepared with the compositions shown in Table 5 below. The prepared compositions were applied to a separator film (hereinafter also referred to as "release film") surface-treated with a silicone-based release agent using a die coater, and dried for 1 minute at 90°C to obtain acrylate-based adhesive sheets N5 to N7. The composition of the acrylate-based adhesive, the film thickness of the adhesive sheet, and the storage modulus are shown in Table 5 below.

[0313] [Table 5]

[0314] (C) Isocyanate-based crosslinking agent: Trimethylolpropane-modified tolylene diisocyanate ("Coronate L" manufactured by Nippon Polyurethane Co., Ltd.) (D) Silane coupling agent: 3-Glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. "KBM-403")

[0315] <Fabrication of the laminated body in example 29> For the laminate of Fabrication Example 2, adhesive sheet N5 was bonded to the adhesive layer 2 instead of adhesive sheet N2, resulting in the laminate of Fabrication Example 29.

[0316] <Fabrication of the laminated body in example 30> For the laminate of Fabrication Example 2, adhesive sheet N6 was bonded to the adhesive layer 2 instead of adhesive sheet N2 to obtain the laminate of Fabrication Example 30.

[0317] <Fabrication of the laminated body in example 31> For the laminate of Fabrication Example 1, adhesive sheet N7 was bonded to the laminate as adhesive layer 2 instead of adhesive sheet N1, resulting in the laminate of Fabrication Example 31.

[0318] <Fabrication of the laminated body in example 32> For the laminate of Fabrication Example 9, adhesive sheet N7 was bonded to the laminate as adhesive layer 2 instead of adhesive sheet N4, resulting in the laminate of Fabrication Example 32.

[0319] [evaluation] [Moist heat durability] The obtained laminates 29-32 were cut to a size of 50 mm x 50 mm, the release film was peeled off, and the adhesive layer 2 was pressed onto a glass substrate (Corning Eagle XG). This glass substrate pressed sample was subjected to a durability test at 60°C and 90% humidity, and the sample was visually observed and evaluated in the same manner as above. The results are shown in Table 6 below.

[0320] [Table 6]

[0321] The results shown in Table 6 indicate that when the H value is greater than 10, the thermal resistance of the laminate is poor (Fabrication Example 31). In contrast, it was found that when the H value is 10 or less, the thermal durability of the laminate is good (Fabrication Examples 29, 30, and 32). In particular, from a comparison between Fabrication Example 29 and Fabrication Example 30, it was found that the durability is better when the adhesive constituting the adhesive layer 2 contains a polymer having repeating units represented by the above formula (A).

[0322] [Examples 33-36] <Preparation of adhesive sheets N8-N10> Using the acrylate polymer A1 described above, acrylate adhesive compositions were prepared with the compositions shown in Table 7 below. The prepared composition was applied to a separator film (hereinafter also abbreviated as "release film") surface-treated with a silicone-based release agent using a die coater, dried for 1 minute at 90°C, and irradiated with ultraviolet (UV) light under the same conditions as for adhesive sheet N1 to obtain acrylate-based adhesive sheets N8 to N10. The composition of the acrylate-based adhesive, the film thickness of the adhesive sheet, and the storage modulus are shown in Table 7 below.

[0323] [Table 7]

[0324] <Preparation of adhesive sheet N11> 70 parts of butyl acrylate, 30 parts of methyl acrylate, 4 parts of acrylic acid, 2 parts of N,N-dimethylmethacrylamide, 0.1 parts of azobisisobutyronitrile, and 120 parts of ethyl acetate were added. This was polymerized by solution polymerization to obtain a solution of acrylic copolymer 1 with a weight-average molecular weight of 1.5 million. Adhesive composition N11 was prepared by mixing 3 parts of Coronate L (polyisocyanate, manufactured by Nippon Polyurethane Industries Co., Ltd.), 0.2 parts of Aluminum Chelate A (aluminum trisacetylacetonate, manufactured by Kawaken Fine Chemicals Co., Ltd.), and 0.1 parts of KBM-803 (γ-mercaptopropylmethyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) with 100 parts of the solid content of copolymer solution 1. These compositions were applied to a separator film (hereinafter also referred to as "release film") surface-treated with a silicone-based release agent using a die coater, and dried for 1 minute at 90°C to produce an adhesive sheet N11 having an adhesive layer with a thickness of 15 μm. The storage modulus of the adhesive layer was 0.3 MPa.

[0325] <Fabrication of the laminated body in example 33> For the laminate of Fabrication Example 2, adhesive sheet N8 was bonded to the laminate of Fabrication Example 33 instead of adhesive sheet N2 as adhesive layer 1.

[0326] <Fabrication of the laminated body in example 34> For the laminate of Fabrication Example 2, adhesive sheet N9 was bonded to the laminate of Fabrication Example 34 instead of adhesive sheet N2 as adhesive layer 1.

[0327] <Fabrication of the laminated body in example 35> For the laminate of Fabrication Example 2, adhesive sheet N10 was bonded to the laminate of Fabrication Example 35 instead of adhesive sheet N2 as adhesive layer 1.

[0328] <Fabrication of the laminated body in example 36> For the laminate of Fabrication Example 2, adhesive sheet N11 was bonded to the adhesive layer 1 instead of adhesive sheet N2, resulting in the laminate of Fabrication Example 36.

[0329] [evaluation] [Moist heat durability] The obtained laminates 33-36 were cut to a size of 50 mm x 50 mm, the release film was peeled off, and the adhesive layer 2 was pressed onto a glass substrate (Corning Eagle XG). This glass substrate pressed sample was subjected to a durability test at 60°C and 90% humidity, and the sample was visually observed and evaluated in the same manner as above. As a result, all samples received a rating of B or higher, demonstrating the effectiveness of the present invention.

[0330] [Pencil hardness] As an indicator of scratch resistance, the pencil hardness test described in JIS K-5400 was performed. The obtained laminates 33-36 were cut to a size of 50 mm x 50 mm, the release film was peeled off, and the adhesive layer 2 was pressed onto a glass substrate (Corning Eagle XG). These samples were conditioned at 25°C and 60% RH for 2 hours. Then, using an HB test pencil, the surface with the hard coat layer was rubbed with a load of 4.9 N and evaluated according to the following criteria. The results are shown in Table 8 below. A: In the evaluation of n=5, all were undamaged. B: In the evaluation of n=5, there are 3 or more items with no damage and 4 or fewer items.

[0331] [Table 8]

[0332] As shown in Table 8, a comparison between fabrication example 34 and fabrication example 36 revealed that when the storage modulus of the adhesive layer 1 is 0.5 MPa or higher, the pencil hardness improves. Furthermore, a comparison of fabrication examples 33-35 revealed that pencil hardness improved when the thickness of the adhesive layer 1 was 8 μm or less. [Explanation of Symbols]

[0333] 100, 200 laminated 1 Adhesive layer 1 2. Light-absorbing anisotropic layer 3. Adhesive layer 2 4 Surface protective layer 5. Oxygen barrier layer 6 Hardened layer 7 Curing adhesive layer 8 Optical Anisotropy Layer 9. Adhesive layer

Claims

1. A laminate comprising, in this order: adhesive layer 1, triacetylcellulose substrate, photoalignment film, light-absorbing anisotropic layer, adhesive layer 2, and optical anisotropic layer, The aforementioned light-absorbing anisotropic layer contains an organic dichroic substance, The thickness of the aforementioned light-absorbing anisotropic layer is 5 μm or less. The adhesive layer 1 and the adhesive layer 2 are, respectively, the adhesive layers located in the laminate that are closest to the light-absorbing anisotropic layer. The photo-alignment film contains a copolymer having repeating units having photo-aligning groups and other repeating units, The in-plane retardation Re(450) measured at a wavelength of 450 nm of the optical anisotropic layer, the in-plane retardation Re(550) measured at a wavelength of 550 nm of the optical anisotropic layer, and the in-plane retardation Re(650) measured at a wavelength of 650 nm of the optical anisotropic layer satisfy the relationship Re(450) ≤ Re(550) ≤ Re(650), and the in-plane retardation Re(550) measured at a wavelength of 550 nm of the optical anisotropic layer satisfies the relationship 110 nm ≤ Re(550) ≤ 160 nm. A laminate in which H, represented by the following formula (I), is between 0.5 and 4.

0. H = (Thickness of adhesive layer 1 + Thickness of adhesive layer 2) / Total thickness of layers inside adhesive layer 1 and adhesive layer 2 Equation (I)

2. The laminate according to claim 1, wherein the storage modulus of at least one of the adhesive layer 1 and the adhesive layer 2 is 0.5 MPa or more.

3. The laminate according to claim 2, wherein the storage modulus of the adhesive layer 1 is 0.5 MPa or more.

4. The laminate according to claim 3, wherein the storage modulus of both the adhesive layer 1 and the adhesive layer 2 is 0.5 MPa or more.

5. The laminate according to any one of claims 1 to 4, wherein the storage modulus of the adhesive layer 2 is 0.7 MPa or more.

6. The laminate according to any one of claims 1 to 5, wherein the thickness of the light-absorbing anisotropic layer is 0.8 μm or less.

7. The laminate according to any one of claims 1 to 6, wherein at least one of the adhesive layer 1 and the adhesive layer 2 contains a polymer having repeating units represented by the following formula (A). 【Chemistry 1】 In the above formula (A), R １ R represents a hydrogen atom or a methyl group. ２ This represents an alkyl group having 1 to 6 carbon atoms.

8. The laminate according to any one of claims 1 to 7, wherein the optical anisotropy layer has a λ / 4 plate.

9. The laminate according to any one of claims 1 to 8, wherein the optical anisotropy layer has a λ / 4 plate, and the λ / 4 plate is inverse wavelength dispersive.

10. The laminate according to any one of claims 1 to 9, wherein the optical anisotropy layer comprises a λ / 4 plate and a positive C plate.

11. The laminate according to any one of claims 1 to 10, further comprising a surface protective layer on the side of the adhesive layer 1 opposite to the side having the light-absorbing anisotropic layer.

12. The laminate according to claim 11, wherein the surface protective layer has a support.

13. The laminate according to claim 12, wherein the support comprises an ultraviolet absorber.

14. The laminate according to any one of claims 1 to 13, wherein at least one of the adhesive layer 1 and the adhesive layer 2 contains an ultraviolet absorber.

15. The laminate comprises the laminate according to any one of claims 1 to 13 and an image display element, An image display device wherein the image display element is arranged on the side of the adhesive layer 2 opposite to the side having the light-absorbing anisotropic layer.

16. The image display device according to claim 15, wherein the image display element is an organic EL display element.

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